METALATIONS BY ORGANOLITHIUM COMPOUNDS 3. M. MALLAN AND R. L. BEBB Central Research Laboratory, The Firestone Tire and Rubber Company, Akron, Ohio 4431 7 Received Janlrary 3, 1969
contents I. Introduction 11. History and General Scope of Metalation
111.
IV.
V.
VI.
VII.
A. History B. Metalating Agents C. Complexes of Metalating Agents D. Structure of Organolithium Compounds Solvents Properties of the Compounds Metalated A. Hydrocarbon Acidity B. Derivatives C. Color of Metaiated Compounds D. Mechanism and Kinetics Types of Compounds Metalated A. Metalation of Hydrocarbons B. Metalation of Oxygen Compounds C. Metalation of Sulfur Compounds D. Metalation of Nitrogen Compounds E. Metalation of Mixed Heterocyclic Compounds F. Metalation of Group IVA Compounds G. Metalation of Haloorganic Compounds H. Metalation of Metallocenes 1. Metalation of Phosphorus Compounds J. Metalation of Organoboron Compounds Summary and General Trends in Organolithium Research Glossary and Tables
pounds by organolithium compounds. The term metalation is used in its broadest sense to describe a substitution reaction in which an acidic hydrogen is replaced by a metal t o produce a true organometallic compound. This review covers only those reactions which utilize an organolithium reagent as the metalating agent, as illustrated for the reaction between ethyllithium (1) and fluorene (2). All references to the use of organolithium reagents as catalytic agents, as in the polymerization of olefins, and additions across the double bond, as in the azomethine linkage in pyridines, have been omitted. Also omitted are all examples where the lithium becomes attached to an atom other than a group IVA element, Le., carbon, silicon, tin, germanium, and lead. Metalations by organolithium reagents were reviewed by Gilmans and covered the literature through 1952; reviews on other aspects of lithium chemistry are also available.6-19 It is the purpose of this review to emphasize the advances made since that time, t o define the present state of the art, and to indicate areas for further basic research. The literature from 1952 through 1966 has been surveyed. A few references, in which the experimental details, procedures, and products were too obscure to be reported accurately, have been intentionally omitted.
693 693 693 694 695 695 696 698 698 699 699 699 701 701 702 705 708 710 711 712 713 713 714
If. History and General Scope of Metalation
714 715
A. HISTORY
I . Introduction
Schlenk and BergmannZofirst reported a metalation reaction in 1928 after they discovered that ethyllithium (1) reacts with fluorene (2) by replacing an acidic hydrogen to produce fluor-
Metalation by organolithium compounds has become increasingly important in many areas of chemistry. A table of patents listing the catalytic applications of lithium for polymerization reactions gives an idea of their industrial importance, and the great impact of organolithium compounds on the synthetic rubber industry cannot be overlooked.2-4 Academic interest in the field of metalation by organolithium compounds has centered on three main areas: the position of metalation ; the mechanism, including structure and kinetic studies; and the synthetic methods involved. In the earlier years covered by this review, the position of metalation was of primary importance; the present trends emphasize mechanistic studies. The synthetic utility remains important throughout the entire period covered. This review is limited to the inetalation of organic com-
(5) H. Gilman and J. W. Morton, Jr., Org. Reactions, 8, 258 (1954). (6) E. A. Braude, Progr. Org. Chem., 3, 172 (1955). (7) T. L. Brown, Aduan. Organometal. Chem., 3, 365 (1965). (8) G. E. Coats, “Organometallic Compounds,” 2nd ed (revised), John Wiley and Sons, Inc., New York, N. Y., 1960. (9) R. E. Dessy, Chem. Eng. News, 41, 136 (1963). (10) R. E. Dessy and W. Kitching, Adran. Organomeral. Chem., 4, 267 ( 1966). (11) R. E. Dcssy and F. P u l i k , J . Chem. Educ., 40, 1S5 (1963). (12) C.G. Eberhardt, Organometal. Chem. Rer., 1, 491 (1966). (13) J . 0. Edwards and R. G. Pearsoii, J . A m . Chem. Sor., 84, 16
( 1962).
(14) J. J. Eisch and H. Gilmm, Adcan. Inorg. Chem. Radiochem., 2 , 61 (1960). (15) D. L. Es!nay, Advances in Chemistry Series, No. 23, Americdil Chemical Society, Washington, D. C., 1959, p 46. (16) H . Gilman, Bull. SOC.Chim. France, 1356 (1963). (17) R. G. Jones and H. Giiman, Chem. Reo., 54, 835 (2954). (18) J. Vidal and Y . Chauvin, Reo. Inst. France Petrole Ann. Combust. Liquides, 19, 1218 (1964). (19) J. Vidal and Y. Chauvin, ibid., 19, 1319 (1964). (20) W. Schlenk and E. Bergmann, AWL, 463, 98 (1928).
(1) C. W. Kamienski, 2nd. Eng. Chem., 57, 38 (1965).
(2) J. H. Harwood, “Industrial Applications of the Organometallic Compounds,” Reinhold Publishing Corp., New York, N. Y., 1963. (3) F. W. Stavely, et al., 2nd. Eng. Chem., 48, 778 (1956). (4) R. S. Steams and L. E. Forman, J. Polymer Sci., 41, 381 (1959).
693
J. M. Mallan and R. L Bebb
694
m d
2
+
CYHG
H’ ‘Li 3
enyllithium (3) and ethane (4). This reaction has been expanded during the years to include most compounds which contain an acidic hydrogen. The reaction is not restricted to those compounds which contain a classical acidic hydrogen, since the metalation of phenyllithium (5) has been reported. z 1
h+& Li
5
The most commonly used procedure to determine the concentration of organolithium compounds is the Gilman double titration.5 The method has been studied extensively,16gn-31 since there are inherent difficulties associated with any analysis where the compound under consideration cannot easily be obtained in standardized quantities. Gilman has published a study of the efficiency of various allylic halides used in the titratiomZ9Certain compounds, such as alkoxides, are known to give erroneous analytical results, and some organolithium compounds, such as methyl- and phenyllithium, are particularly difficult to determine by this method. Several procedures have been reported to avoid these difficulties. 3 z , 3 3 The preparation of previously unknown organolithium compounds, either in solution or in the crystalline state, has been one of the more recent advances in this field of chemistry. Table 111, including some of these new compounds and their method of preparation, appears at the end of this review. The transmetalation reaction, as exemplified by the preparation of vinyllithium (7)from tetravinyltin (6), is used very effectively for the preparation of many of these new compounds. 34,35 The product organolithium can be filtered away from the precipitated tetraphenyltin (S), and used either in
I
Li
Ziegler’s discoveryzzthat alkyl halides will react with lithium metal in ether or benzene to yield organolithium compounds has made these reagents readily available, and the work of Gilman and others has demonstrated the great synthetic utility of the metalation r e a c t i ~ n . ~ ’ ~
B. METALATING AGENTS The most commonly used metalating agents are butyl- and phenyllithium. While these are not the most reactive organolithium compounds, they are the most readily available. Butyllithium is more frequently used because it is the more reactive of the two. In addition, butane, the secondary product of the metalation, escapes from the reaction medium as a gas and thus tends to drive the reaction toward completion, leading to higher yields of metalated product. The other less common organolithium compounds are considered individually in a later section. The successful preparation of an organolithium reagent is dependent upon all the usual precautionary conditions employed in organometallic reactions. u Butyllithium in ether is usually prepared in 80-95% yield from butyl chloride and lithium metal containing 0.05% sodium. Several studies have been initiated to determine the effect of a purer grade metal on the yield. When lithium containing 0.005 % sodium was used, the yield decreased to about 50 %, a precipitate formed, the lithium became dull instead of shiny, and the temperature was extremely difficult to control.z3 Addition of several pieces of sodium to such a reaction mixture had no effect. Several workers demonstrated that at least 0.02 sodium, intimately mixed with the lithium, was essential for the reaction t o proceed n 0 r m a l l y . ~ ~ -In ~ 5 addition, retention of configuration is reported to be proportional to the amount of sodium present in the lithium. z6 (21) D. Bryce-Smith and E. E. Turner, J . Chem. Soc., 861 (1953). (22) K. Ziegler and H. Colonius, Ann., 479, 135 (1930). (23) J. A. Beel, W. G. Koch, G. E. Tomasi, D. E. Hermansen, and P . Fleetwood, J . Org. Chem., 24,2036 (1959). (24) K. C. Eberly, U. S. Patent 3,122,592; Chem. Abstr., 60, 13270 (19 64). (25) C. W. Kamienski and D. L. Esmay, J . Org. Chem., 25, 1807 (1960). (26) H. M. Walborsky and M. S. Aronoff, J . Organometal. Chem., 4, 418 (1965).
(CHZ=CH)$n 6
PhLi
4CH2=CHLi
hydrocarbon
or ether
7
+ PhSn 8
solution or further purified. Another advantage to this method of preparation is that the product organolithium is obtained free from lithium halide. Benzyllithium has been exceedingly diacult to prepare by any of the usual techniques.36,37For example, reaction of benzyl chloride with lithium metal results mainly in the coupling product, b i b e n ~ y l , ~and * metalation of toluene with butyllithium produces only small yields of the desired organometallic compound. 38 Gilman exploited the cleavage of benzylic ethers (9) by lithium metal in THF to provide the first Li
PhCHzOCHa+PhCH2Li THF
+ CHaOLi
10
9
practical preparation of benzyllithium 39 Benzyllithium has also been prepared by the transmetalation reaction between tribenzyltin chloride (11) and methyllithium (12). 40
+
ether
(PhCH2)&3nC1 4MeLi +3PhCH2Li 11 12 10
+ MeSn + LiCl
(27) D. E. Applequist and D. F. O’Brien, J . Am. Chem. SOC.,85, 743 (1963). (28) K. C. Eberly, J. Org. Chem., 26, 1309 (1961). (29) H. Gilman and F. K. Cartledge, J . Organometal. Chem., 2, 447 (1964). (30) H. Gilman, F. K. Cartledge, and S.-Y. Sim, ibid., 1, 8 (1963). (31) C. W. Kamienski and D. L. Esmay, J . Org. Chem., 25, 115 (1960). (32) P. F. Collins, C. W. Kamienski, D. L. Esmay, and R. B. Ellestad, Anal. Chem., 33, 468 (1961). (33) H. 0. House and W. L. Respess, J . Organometal. Chem., 4, 95 (1965). (34) D. Seyferth and M. A. Weiner, J . Am. Chem. SOC.,84, 361 (1962). (35) D. Seyferth, M. A. Weiner, L. G. Vaughan, G. Raab, D. E. Welch, H. M. Cohen, and D. L. Alleston, Bull. SOC.Chim. France, 1364 (1963). (36) H. Gilman and H. A. McNinch, J . Org. Chem., 26, 3723 (1961). (37) H. Gilman, H. A. McNinch, and D. Wittenberg, ibid., 23, 2044 (1958). (38) H. Gilman and R. D. Gorsich, J . Am. Chem. SOC.,77,3134 (1955). (39) H. Gilman and G. L. Schwebke, J . Org. Chem., 27, 4259 (1962). (40) D. Seyferth, R. Suzuki, C . 3. Murphy, and C. R. Sabet, J. Organometal. Chem., 2,431 (1964).
Metalations by Organolithium Compounds
695
Metalation of toluene by the butyllithium-TMEDA (tetramethylethylenediamine) (16) complex, 41742 which results in a quantitative yield of benzyllithium-TMEDA within minutes, is currently the most efficient method to prepare benzyllithium. Triphenylsilyllithium (14) can readily be prepared via tnLi
SiF4
+ PhMgBr +PhaSiF+ PhaSiLi THE’ 13
and may even contain lithium halide in a ternary complex, depending upon the mode of preparation. Many of these complexes have been isolated and studied.60 The most interesting complexes, from the synthetic standpoint, are formed from organolithium compounds and tertiary amines. The addition of triethylenediamine (DABCO), (15) in benzene to butyllithium in hydrocarbon produces a
14
phenylsilyl fluoride (13). 4 3 This procedure provides easy access t o this versatile metalating agent. Gilman has also shown that 14 can be prepared from triphenylsilyl chloride and lithium metal in THF. 4 4
C. COMPLEXES OF METALATING AGENTS
mN
N
u
CHB-N
N-CH, I
I
DABCO 15 16
Organolithium compounds form coordination complexes crystalline precipitate of the butyllithium-DABCO comwith various materials including neutral Lewis bases, ethers, plex.66r57Many of these complexes can serve as metalating amines, alkoxides, and lithium halides. 121 45--68 In this comagents for compounds which are not ordinarily metalated. plexed form, the compounds exhibit remarkably different For example, toluene is not easily metalated by butyllithium, characteristics depending upon the complexing agent. For but is attacked quantitatively by butyllithium-TMEDA, 41842 example, solid complexes of butyllithium-lithium halide5Sp66 and in at least 85% yield by butyllithium-DABC0.60 Even are inert in hydrocarbon solution, but upon addition of ether powdered lithium metal reacts with diamines to give a complex they are regenerated to conventional organolithium comwhich is capable of metalating certain hydrocarbons?’ pounds. While cyclic amines, such as DABCO (15), lead to crystalComplexesare also formed with e t h e r s a n d d i o ~ a n a t e s ~ ~line ~ ~ ~ precipitates, ~~~~~~ open-chain ditertiary amines, such as TMEDA (tetramethylethylenediamine) (16), produce stable (41) A. W. Langer, Jr., Trans. N . Y . Acad. Sci., 27, 741 (1965). complexes which are soluble in hydrocarbons; 41,42 thus both (42) A. W. Langer, Jr., Polymer Preprints, Vol. 7, No. 1, American solid and solution forms of the complexes are available. Chemical Society Division of Polymer Chemistry, Jan 1966, p 132. (43) G. Marr and D. E. Webster, J . Organometal. Chem., 2,93 (1964). (44) H. Zeiss, “Organometallic Chemistry,” Reinhold Publishing Corp., New York, N. Y., 1960. (45) T. L. Brown, D. W. Dickerhoof, and D. A. Bafus, J . Am. Chem. Soc., 84, 1371 (1962). (46) T. L. Brown, R. L. Gerteis, D. A. Bafus, and J. A. Ladd, ibid., 86, 2135 (1964). (47) T. L. Brown, J. A. Ladd, and G . N. Newman, J. Organometal. Chem., 3, 1 (1965). (48) Z. K. Cheema, G. W. Gibson, and J. F. Eastham, J . Am. Chem. Soc., 85, 3517 (1963). (49) J. A. Dixon, P. A. Gwinner, and D. C. Lini, ibid., 87, 1379 (1965). (50) G. G. Eberhardt and W. A. Butte, J . Org. Chem., 29, 2928 (1964). (51) W. H. Glaze and G. M. A d a m , J . Am. Chem. Soc., 88, 4653 (1966). (52) W. H. Glaze, J. Lin, and E. G. Felton, J . Org. Chem., 31, 2643 (1966). (53) W. H. Glaze and R. West, J. Am. Chem. Soc., 82,4437 (1960). (54) L. Lochmann, J. Pospisil, J. Vodnansky, J. Trekoval, and D. Lim, Collect. Czech. Chem. Commun., 30, 2187 (1965); Chem. Abstr., 63, 7027 (1965). (55) G. A. Razuvaev, G. G. Petukhov, R. F. Galiulina, and T. N. Brevnova, J . Gen. Chem. USSR,31, 2187 (1961). (56) C. G. Screttas, Ph.D. Thesis, University of Tennessee, 1966. (57) C. G. Screttas and J. F. Eastham. J . Am. Chem. SOC.,87, 3276 ( 1965). (58) F. A. Settle, M. Haggerty, and J. F. Eastham, ibid., 86, 2076 (1964). (59) T. V. Talalaeva, M. M. Nad, and K. A. Kocheshkov, Dokl. Akad. Nauk SSSR, 109, 101 (1956); Chem. Abstr., 51, 1962 (1957). (60) T. V. Talalaeva, A. N. Rodionov, and K. A. Kocheshkov, Proc. Acad. Scr. USSR,140,985 (1961). (61) R. Waack and M. A. Doran, J . Am. Chem. Soc., 85, 2861 (1963). (62) R. Waack and M. A. Doran, ibid., 85, 4042 (1963). (63) R. Waack and M. A. Doran, Chem. Ind. (London), 496 (1964). (64) R. Waack and P. West, J . Organometal. Chem., 5, 188 (1966). (65) M. Weiner and R. West, J. Am. Chem. SOC.,85. 485 (1963). (66) R. West and W. H. Glaze, U. S. Patent 3,082,264; Chem. Abstr., 59, 3956 (1963). (67) H. J. S. Winkler and H. Winkler, J . Am. Chem. Soc., 88, 964 (1966). (68) H. J. S. Winkler and H. Winkler, ibid., 88, 969 (1966). (69) A. N. Rodionov, T. V. Talalaeva, D. N. Shigorin, and K. A. Kocheshkov, Proc. Acad. SCLUSSR,136, 65 (1961). (70) T. V. Talalaeva, A. N. Rodionov, and K. A. Kocheshkov, Izv. Akad. Nauk SSSR, Old. Khim. Nauk, 1990 (1961); Chem. Abstr., 56, 10173 (1962).
D. STRUCTURE OF ORGANOLITHIUM COMPOUNDS Since the initial discovery that organolithium compounds are polymeric, many studies have been directed toward elucidating their structure. Clearly, the structure must be at least partially understood before kinetic and mechanistic studies attain much significance. The general subject of structure has been reviewed? and only the more significant facts will be considered here. All of the organolithium compounds studied so far are polymeric. The only reported exception to this, lithiomethyltrimethylsilane? has been refuted by other workers?@-75 The apparent degree of polymerization varies with both the solvent and the structure and, in general, is higher for straightchain than for branched-chain compounds. This suggests that steric hindrance is an important factor in determining the polymeric form. It is interesting to note, then, that the nalkyllithiums above n-propyl are l i q ~ i d s . ~ jThe ~ 6 degree of polymerization (n) is summarized in Table 17- 41, 4*~46--48,77--8* for some of the more common organolithiums. Organolith(71) 0. F. Beumel, Jr., and R. F. Harris, J. Org. Chem., 30, 814 (1965). (72) J. W. Connolly and G. Urry, Znorg. Chem., 2, 645 (1963). (73) R. H. Baney and R. J. Krager, ibid., 3, 1657 (1964). (74) G. E. Hartwell and T. L. Brown, ibid., 3, 1656 (1964). (75) G. E. Hartwell and T. L. Brown, ibid., 5, 1257 (1966). (76) R. T. Sanderson, J . Am. Chem. Soc., 77, 4531 (1955). (77) T. L. Brown and M. T. Rogers, ibid., 79, 1859 (1957). (78) M. T. Rogers and T. L. Brown, J . Phus. Chem., 61, 366 (1957). (79 K. B. Piotrovskii and M. P. Ronina, Dokl. Akad. Nauk S S S R , 112, 737 (1957); Chem. Abstr., 52, 3476 (1958). (80) D. Margerison and J. P. Newport, Trans. Faraday SOC.,59, 2058 (1963). (81) T . V. Talalaeva, A. N. Rodionov, and K. A. Kocheshkov, Proc. Acad. Sci. USSR, 154,47 (1964). (82) M. Weiner, G . Vogel, and R. West, Inorg. Chem., 1, 654 (1962).
J. M. Mallan and R...I Bebb
696
Table I Degree of Polymerization (n) of Some Organolithium Compounds Comoound
Ethyllithium
n-Butyllithium n-ButyllithiumTMEDA complex t-Butyllithium Phenyllithium
Solcent
n
Cyclohexane Benzene Benzene Hydrocarbon Diethyl ether Cyclohexane
6 6 2 6 2 (solvated) 6 6
80
Benzene Diethyl ether Hydrocarbon
2 6 1
19 81 41, 42
n-Hexane Benzene Hydrocarbon Diethyl ether
4 4 4 2
82 82 80 81
Benzene ~.
Ref 7, 47 46, 11,78 79 80 48 80
pounds are actually caused by alkoxide formation. 4 5 - 1 0 2 9 1 0 8 Other complex physical measurements have also been reported.58~IO9 The thermal stability of organolithium compounds has been the subject of several studies. Most organolithium compounds decompose on heating to lithium hydride and an unsaturated molecule. For example, butyllithium forms lithium hydride, 1-butene, n-butane, and resinl10 on thermal decomposition. A free-radical mechanism for this process has been excluded. ll1, 1 1 2 The products of pyrolysis of several organolithium compounds have also been determined,s1#52,113114 as well as their stereochemical stability at higher temperatures. l5-
111. Solvents
The role of the solvent in organometallic reactions is exceedingly complex. A complete discussion of the present state of ium compounds are also polymeric in the vapor phase45’54,83 knowledge regarding solvation is well beyond the scope of this review, but some of the more salient features are included. and in the solid ~ t a t e . ~ ~ s 8 ~ Ethers, such as diethyl ether and tetrahydrofuran (THF), and The paucity of physical measurements on organolithium hydrocarbons, such as pentane and hexane, are the most compounds is largely a result of the difficulty in obtaining pure commonly used solvents for organolithium reactions. l8 compounds and the great care which must be exercised in Dioxane and the “glymes” (ethylene glycol ethers) have ochandling these compounds t o prevent decomposition. Only Acetals are not usually satisfactory recently have heat of formation,@Sg viscosity and density,@ casionally been used. and have had only limited use.12o,l Z 1 and crystal structure84 ~ 8 5 , 8 9measurements been reported. In general, organometallic reactions proceed more rapidly Instrumental measurements have been used extensively to in ethereal solvents than in hydrocarbons. 22,n-12t-1*6 The determine various properties of organolithium compounds. accelerated rate effects are attributed to the much greater solFor example, temperature d e p e n d e n ~ e , exchange ~ ~ ~ ~ ~ ~revating properties of the ethers through complex formation actions,ga-Q7and complex f o r m a t i 0 n ~ ~have * 6 ~ all been studied between the ether and the metal. Such complexes are solvated by nmr. Bonding inferences have been obtained through nmr9* dimers1Z4 of higher reactivity than the original polymeric and ir studies,45~~Q,n,99-102 as well as through association forms which exist in hydrocarbon solution. In addition, comdata.64~1Oa-1m It should be carefully observed that many of plexing tends t o loosen, or ionize, the carbon-lithium bond, the early ir frequencies reported for organolithium comleading to over-all lower energy requirements in the transition state.lnV1” (83) J. Berkowitz, D. A. Bafus, and T.L. Brown, J. Phys. Chem., 65, In hydrocarbon solvents, where organolithium compounds 1380 (1961). are present in polymeric form, depolymerization to dimers or (84) H. Dietrich, Z . Naturforsch., 14B, 739 (1959). (85) H. Dietrich, Acra Crysf., 16, 681 (1963). monomers may be required before appreciable reaction be(86) P. A. Fowell and C. T.Mortimer, J. Chern. Soc., 3793 (1961). (87) Yu. A. Lebedev, E. A, Miroshnichenko, and A. M. Chaikin, Proc. Acad. Sci. USSR, 145, 751 (1962). (108) C. W. Kamienski and D. H. Lewis, J. Org. Chem., 30, 3498 (1965). (88) D. H. Lewis, W. S. Leonhardt, and C. W. Kamienski, Chimia (Aarau), 18, 134 (1964); Chem. Abstr., 61, 1881 (1964). (89) E. Weiss and E. A. C. Lucken, J. Organometal. Chem., 2, 197 (1964). (90) T. L. Brown and J. A. Ladd, ibid., 2, 373 (1964). (91) L. M. Seitz and T. L. Brown, J . Am. Chem. SOC.,88.2174 (1966). (92) R. Waack, M. A. Doran, and P. E. Stevenson, ibid., 88, 2109 (1966). (93) G. Fraenkel, D. G. Adams, and J. Williams, Tetrahedron Letters, 767 (1963). (94) G. E. Hartwell and T. L. Brown, J . Am. Chem. Soc., 88, 4625 (1966). (95) C. S. Johnson, Jr., M. A. Weiner, J. S. Waugh, and D. Seyferth, &id., 83. 1306 (1961). (96) L. M. Sei& and T. L. Brown, ibid., 88, 4140 (1966). (97) K. C. Williams and T. L. Brown, ibid., 88,4134 (1966). (98) R. Waack, M. A. Doran, E. B. Baker, and G. A. Olah, ibid., 88, 1272 (1966). (99) H. P. Fritz and R. Schneider, Chem. Ber., 93, 1171 (1960), (100) A. N. Rodionov, D. N. Shigorin, T. V. Talalaeva, and K. A. Kocheshltov, Proc. Acad. Sci. USSR, 143, 175 (1962). (101) A. N. Rodionov, V. N. Vasil’eva, T. V. Talalaeva, D. N. Shigorin, E. N . Gur’yanova, and I sulfur > nitrogen in increasing order of reactivity prevails. Phenoxathiin (125) is readily monometalated by butyllith-
*’*
123 n = 1,2,3,or 4 the nitrogen. Hauser has reported37gthat systems (123) with an odd number, Le., n = 1 or 3, of CH2 groups in a chain can be ortho lithiated, whereas those where n is a n even number cannot be metalated. These results are in conflict with the reported ortho lithiation of P-phenethyldimethylamine. Hauser has demonstrated that a-phenylpropyldimethylamine, n = 3, is metalated on the benzylic carbon379 and that @,pdimethyl-/3-phenylethyl)dimethylamine is metalated at the ortho position.
(373) W. H. Puterbaugh and C. R. Hauser, J. Am. Chem. SOC.,85, 2467 (1963). (374) F. N. Jones, R, L. Vaulx, and C. R. Hauser, J. Org. Chem., 289 3461 (1963). (375) F. N.Jones M. F. Zinn, and C . R. Hauser, ibid., 28, 663 (1963). (376) R. L. Gay, T. F. Crimmins, and C. R. Hauser, Chem. Znd. (London), 1635 (1966). (377) N. S. Narasimhan and A. C . Ranade, Tetrahedron Letters, 4145 (1965). (378) W. H. Puterbaugh and C . R. Hauser, J. Org. Chem., 29, 853 (1964). (379) R. L. Vaulx, F. N. Jones, and C . R. Hauser, ibid., 30, 58 (1965). (380) N.S. Narasimhan and A. C . Ranade, Tetrahedron Letters, 603 (1966).
Li I
ium in the 4 position, ortho to the o ~ y g e n However, . ~ ~ ~ ~ dimetalation leads to a mixture of products. After carbonation, both the 4,6-diacids and the 1,Bdiacids are obtained in a ratio of 4 :1. 384*386 Under more severe conditions, the sulfur moiety is cleaved and, after carbonation, the product is o-phenoxybenzoic acid.= When the sulfur is further activated, as in phenoxathiin 10-dioxide, the sulfone takes precedence over the oxygen, and metalation occurs in the 1 position, ortho to the sulfone. 386 Monometalation of phenoxazine (126) has been reported, H
126
I
Li
(381) R. L. Vaulx, F. N. Jones, and C. R. Hauser, J. Org. Chem., 29, 1387 (1964). (382) R. L. Vaulx, W. H. Puterbaugh, and C . R. Hauser, ibid., 29, 3514 (1964). (383) S. H.Eidt, Iowa State Coll. J. Sci., 31, 397 (1957). (384) H. Gilman and S. H. Eidt, J. Am. Chem. Soc., 78, 2633 (1956). (385) D.A. Shirley and E. A. Lehto, ibid., 77, 1841 (1955). (386) H.Gilman and S . H. Eidt, ibid., 78, 3848 (1956).
Metalations by Organolithium Compounds
711
and the metal enters ortho to the oxygen. 284 Metalation of the sydnones (127) has also been accomplished, and in this case
Ph-N-CH, I I H--Ny+=O
B ~ L ~ Bh-X-CHLi
1
H--N,O,C=O
1
127
131
the metal enters the very activated 4 position. 387 Considerably more work has been done on the mixed nitrogen-sulfur heterocycles. In all of the single ring compounds, the metal enters adjacent to the sulfur. Isothiazole (128), for example, is metalated in the 5 position, adjacent t o the sul-
examined, metalation always occurred adjacent to the nitrogen and preferably on the naphthalene ring. 393--396 These results indicate that the sulfur over nitrogen preference in the reactivity relationship may not be correct. However, more work is necessary before definite conclusions can be made.
F. M E T A L A T I O N OF G R O U P IVA C O M P O U N D S 128
fur.= The ortho effect of both sulfur and nitrogen direct t o the same position in the thiazole nucleus, 389 and metalation occurs only at this 2 position. Even 4-methylthiazole is metalated at the 2 position.3g0In fact, the preference for this position is so dominant that 2,5-dimethylthiazole (129) is metalated on the 2-methyl group. 391
The preparations and reactions of many of the group IVA 397 organometallic compounds have been reviewed. le, The organic derivatives of the group IVAelements aremetalated very similarly to their more usual carbon analogs.398For example, triphenylbenzylsilane (132) is metalated adjacent to 49
BuLi
Ph3SiCHzPh+Ph,Si-CHPh I
ii
132 the silyl atom and undergoes the normal derivatization reactions. 399 Organogermyl compounds (133) are also smoothly BuLi
129
PhrGeH +Ph3GeLi 133
When the nitrogen and sulfur are in different rings, as in
N-benzylthieno[3,2-b]pyrrole (130) and the nitrogen is substituted by a benzylic carbon, metalation still occurs ortho t o the sulfur. Metalation of N-methylphenothiazine also produces an ortho sulfur derivative. 3 9 2
CH,
o I -
130
The above reactions indicate the following order of decreasing reactivity: SO2 > 0 > S > N. While this order is undoubtedly empirically correct for the compounds listed, it is unfortunate that in all of the nitrogen metalations, the nitrogen must be further substituted to prevent salt formation. This obviously does not allow for direct comparisons between groups to be made. In an attempt t o resolve this problem and to bring the nitrogen more clearly in line with the other relative metalation reactions, Shirley has studied the metalation of fused ring phenothiazines (131). These compounds are sufficiently sterically hindered that salt formation does not occur at the nitrogen.393 He found that in every fused-ring phenothiazine (387) C. V. Greco, M. Pesce, and J. M. Franco, J . Heterocyclic Chem., 3,391 (1966). (388) M. P. L. Caton, D. H. Jones, R. Slack, and K. R. H. Wooldridge, J. Chem. SOC.,446 (1964). (389) J. Metzger and B. Koether, Bull. Soc. Chim. France, 708 (1953). (390) R. Breslow and E. McNelis, J . Am. Chem. Soc., 81, 3080 (1959). (391) J. Beraud and J. Metzger, Bull. SOC.Chim. France, 2072 (1962). (392) D. A. Shirley and J. C. Goan, J. Organornetal. Chem., 2, 304 (1964). (393) D. A. Shirley and J. C. Liu, J . Org. Chem., 25, 1189 (1960).
metalated t o produce organogermyllithium derivatives. 4008 401 These derivatives can then be reacted further with a wide variety of derivatizing agents t o produce germyl-substituted compounds. 4°1-403 Many of these organometallic reagents have been used as metalating agents for other compounds and also to establish their relative metalating ability. 271,404-407 It has been suggested that the group IVA organolithium compounds exist as an equilibrium mixture with the diphenylPhaM-Li M
*PhzM + PhLi =
Sn or Pb
metallic compound and p h e n y l l i t h i ~ m .It~ ~was ~ further suggested that the actual metalating agent in this case was phenyllithium and not the group IVA organometallic compound. Gilman271*407 has shown that carbonation of the group IVA organometallic compound does not produce any benzoic acid, which surely would be formed if the above equilibrium existed to any extent. (394) D. A. Shirley and J. C. Gilmer, ibid., 27, 4421 (1962). (395) D. A. Shirley and T. G. Jackson, J . Organometal. Chem., 2. 188 (1964). (396) D. A. Shirley and W. E. Tatum, J. Org. Chem.. 25, 2238 (1960). (397) H. Schumann and M. Schmidt, Angew. Chem. Intern. Ed, Engl., 4, 1007 (1965). (398) V. G. Greber and A. Balciunas, Macromol. Chem., 71, 62 (1964). (399) H. Gilman and H. Hartzfeld, J . Am. Chem. Soc., 73, 5878 (1951). (400) H. Gilman and C. W. Gerow, ibid., 78, 5435 (1956). (401) D. A. Nicholson and A. L. Allred, Znorg. Chem., 4, 1747 (1965). (402) H. Gilrnan and C. W. Gerow, J . Am. Chem. Soc., 79,342 (1957). (403) D. A. Nicholson and A. L. Allred, Znorg. Chem., 4, 1751 (1965). (404) J. d’Ans, H. Zimrner, E. Endmlat, and K. Lubke, Nafurwissenschafren, 39, 450 (1952). (405) A. G. Brook and H. Gilman, J . Am. Chem. Soc., 76,2338 (1954). (406) H. Gilrnan and F. K. Cartledge, J. Organometal. Chem., 3, 255 (1965). (407) H. Gilman and C. W. Gerow, J. Org. Chem., 23, 1582 (1958).
712
J. M. Mallan and R. 1. Bebb
Most of the group IVA organometallic compounds prepared so far have contained phenyl groups. Gilman has recently reported the preparation of a branched aliphatic chain silyllithium compound. 408
bromolithium compounds have been prepared, but these are much less stable than the corresponding chloro compounds. An interesting practical application of a carbenoid reaction is illustrated by the reaction between butyllithium and a-chloropropylene oxide. (136). At low temperatures in T H F only
G. METALATION OF HALOORGANIC COMPOUNDS One of the standard methods of preparing organolithium com-
CI-CH,-CH-CH,
BuLi
THF 3
CI
'
/H
'C-C
H
\CH,OH 137
the trans isomer 137 is formed, but if the solvent is changed or the temperature raised, a mixture of cis and trans isomers is obtained. 153 Both carbenoids and b e n ~ y n e s 'can ~ be considered as special cases of halohydrocarbon metalations. However, some aromatic halogen compounds can also be metalated in the normal sense of the term. G i l m a ~ first ~ ' ~ demonstrated ~ that
135
dichloroethylene (134)has been metalated and, after carbonation, produced a 99 % yield of truns-2,3-dichloroacrylicacid (135).192,193 These haloorganolithium compounds are stable at low temperatures and undergo all of the normal organometallic reactions. Kobrich has applied the generic term "carbenoid" to these compounds. A wide variety of carbenoid compounds has been prefor example, dichloromethyllithium186~194* ~ Q S tri. ~ chloromethyllithium,186* I g 4 ,1 9 5 , 2 4 0 and mono-, di-, and trichlorovinyllithium. m These syntheses have also been extended to the aromatic systems, where such compounds as a-chlorobenzyllithium * 4,186 have been synthesized. The successful synthesis of carbenoids is dependent upon reaction conditions which are both conducive to the synthesis and in which the carbenoids are relatively stable. T H F accelerates their formation, and most of the carbenoids, except for trichlorovinyllithium, are stable in THF. The "Trapp" mixture (THF, ether, and hexane in a 4 :1 :1 ratio) has also been wed. The advantages of T H F have been demonstrated by other workers also. ls4 Most of these preparations are successful only at low (- 80 to - 100') temperatures. The carbenoids have been employed in carbene-type syntheses237-239,241,26'. 410-413 and various other syntheses.414-4l6 Use has also been made of the tendency for carbenoids to eliminate lithium halide at higher temperatures. Ig7,417 The following order of relative stability has been established for the carbenoids: Ph2C==C(Li)Cl = CH,O < CH3 < H < C1 and ortho < para for substituents on the phenyl ring;201 rruns-CHC14C1Li > CH,--CClLi > CC12=CCILi > cisC H C l d C I L i . lgZ The reactivity decreases in the following order: PhCCI2Li CC13Li >> PhtCClLi CChHLi. ls6Some
+
136
pounds is via halogen-metal exchange. Normally these compounds are prepared in ethereal or hydrocarbon solvents at room temperature. 409 Recently, Kobrich and his coworkers187 demonstrated that, using different conditions, compounds containing halogens (chlorine and bromine) can be metalated to yield haloorganolithium compounds. For example, trans-l,2-
134
/O\
L BuLi (-60") 2. eo,, H,O+
a I O O H
138
o-bromofluorobenzene (138) could undergo metal-halogen exchange at very low temperatures without benzyne formation. Since then, many fluorinated compounds have been successfullymetalated. For example, pentafluorobenzene (139) ~
~
F
B
F
F
192*193n
-
-
(408) H. Gilman, J. M. Holmes, and C. L. Smith, Chem.Ind. (London), 848 (1965). (409) G. F. Wright in,"Steric Effects in Organic Chemistry," M. S. Newman, Ed., John Wiley and Sons, New York, N. Y., 1956, p 394. (410) H. Gilman and D. Aoki, J. Organometal. Chem., 1, 449 (1964). (41 1) H. Gilman and D. Aoki, ibid., 2,44 (1964). (412) H. Gilman and D. Aoki, ibid., 2, 89 (1964). (413) M. Schlosser and V. Ladenberger, Angew. Chem. Intern. Ed. Engf., 5 , 519 (1966). (414) D. Y. Curtin and W. H. Richardson, J. A m . Chem. SOC.,81, 4719 ~- 11959). \----*(415) M. Lipp and D. Bernstein. Naturwissenschaften, 42, 578 (1955); Chem. Abstr., 51, 11293 (1957). (416) J. Normant, Bull. SOC.Chim. France, 1876 (1963). (417) K. Griesbaum, Angew. Chem. Intern. Ed. Engl., 5, 933 (1966).
T
F$cooH
139
F
F
has been metalated and carbonated to produce pentafluorobenzoic acid in good 419 Pentachlorobenzoic acid has been prepared similarly. 138,420 Tamborski has demonstrated that even 1,3-difluorobenzene (140)can be successfully metalated. This compound is relatively stable at low temperatures, but upon warming it quickly decomposes to benzyne. 421 Fluoroolefins are not nor-
F
140
mally metalated, but instead react with organometallic comp o ~ n d s . 4 1d z~a ~The chemistry of organofluorine compounds, including the organometallic reactions, has been reviewed. 424 (418 R. J. Harper, Jr., E. J. Soloski, and C. Tamborski, J. Org. Chem., 29, 3385 (1964). (419) C. Tamborski and E. J. Soloski, ibid.. 31, 743 (1966). (420) C. Tamborski, E. J. Soloski, and C. E. Dills, Chem. Ind. (London), 2067 (1965). (421) C. Tamborski and E. J. Soloski, J. Org. Chem., 31. 746 (1966). (422) P. Tarrant, P. Johncock, and J. Savory, ibid., 28, 839 (1963). (423) P. Tarrant, J. Savory, and E. S. Iglehart, ibid., 29, 2009 (1964). (424) H. Heaney, Organometal. Chem. Rev.. 1, 27 (1966).
Metalations by Organolithium Compounds
713
H. METALATION OF METALLOCENES Since their initial discovery, the metallocenes, more specifically ferrocene, have provoked wide interest among chemists. There are numerous review articles covering the preparations, reactions, and metalations of these compounds. 44,426-428 The first metalation of ferrocene was reported by two independent groups. Benkeser 429 found that butyllithium metal-
141
ates ferrocene (141) to give a mixture of mono- and dilithiated ferrocenes. Similar results have also been reported by Nesr n e y a n o ~ . 'The ~ ~ hydrogens in ferrocene are evidently more acidic than in benzene, since the latter is not metalated appreciably by butyllithium. 4 2 9 , 4 3 1 Indeed, even in the metalation of phenyl-substituted ferrocenes, which can be considered to be an intramolecular competition reaction, there is no evidence of phenyl metalation. 3 0 8 The metalation procedures and yields have been improved by other workers. 432-4 The overall >ield of metalated product can be increased by using the mixed solvent system THF-ether. 158 One of the biggest difficulties in the metalation of ferrocene has been to control the reaction to obtain either mono- or dilithiated compounds. The ortho lithiation reaction, discovered by H a u ~ e r , ~ ~is* presently ~19 the most efficient method to obJi
Metalation reactions have also been accomplished with substituted ferrocenes. Both i~opropylferrocene~~1 and diphenylf e r r o c e n y l ~ a r b i n o lhave ~ ~ ~ been successfully metalated. Ferrocenylmethyllithium has been prepared cia an ether cleavage reaction. 440 Treatment of lithiated ferrocenes with the appropriate reagents leads to substituted ferrocenes. For example, ferrocene derivatives containing silicon,441b ~ r ~ n azo , groups,446 ~ ~ ~ - ~ ~ ~ methyl groups,447and amino groups448*449 have been prepared. Lithiated cyclopentadienyl compounds react with ferrous chloride to produce ferrocenes. 4 4 7 , 4 3 0 , 4 5 1 This procedure has provided another route to ferrocenes of known structure. Metallocenes other than ferrocene have been successfully metalated by organolithium compounds. 4 5 2 , 46a The general order of reactivity toward metalation decreases in the order ferrocene > ruthenocene > osmocene. Ditolylchromium has also been dimetalated by butyllithium, and carbonation yields a dicarboxylic acid. 4 5 4
I. METALATION OF PHOSPHORUS COMPOUNDS Metalation of the simple phosphines produces a-lithiophosphines. For example, diphenylphosphine is metalated to produce diphenylphosphinyllithium. If an aliphaticmoiety is present, the first metalation usually occurs on the alkyl group,455-4s but dimetalation is less discriminant. 456 Phenyldimethylphosphine (143) is monometalated in only the methyl g r 0 u p , ~ ~ 6 ,CHJ CH,Li
Ph-P,
/
t.BuLi
Ph-P.
/
\ CHJ
143
142
tain a monolithiated ferrocene. Lithiation of these aminomethylated ferrocenes (142) is considerably faster than lithiation of unsubstituted ferrocenes.4s This reaction has been extended by other workers to produce 2-substituted derivatives of aminomethylated ferrocenes. (425) A. N. Nesmeyanov, Bull. SOC.Chim. France, 1229 (1965). (426) M. D. Rausch, Can. J . Chem., 41, 1289 (1963). (427) M. D. Rausch, Advances in Chemistry Series, No. 37, American Chemical Society, Washington, D. C., 1963, p 56. (428) M . D. Rausch, M. Vogel, and H. Rosenberg, J . Org. Chem., 2 2 , 900 (1957). (429) R. A. Benkeser, D. Goggin, and G. Schroll, J . Am. Chem. SOC.. 76, 4025 (1954). (430) A. N. Nesmeyanov, E. G . Perevalova, R. V. Golovnya, and 0. A. Nesmeyanova, Dokl. Akad. Nauk SSSR,97, 459 (1954); Chem. Absrr., 49, 9633 (1955). (431) R. A. Benkeser and J. L. Bach, J . Am. Chem. Soc., 86, 890 (1964). (432) S. I. Goldberg, L. H. Keith, and T. S . Prokopov, J. Org. Chem., 28, 850 (1963). (433) S. I. Goldberg, I). W. Mayo, M. Vogel, H. Rosenberg, and IM.D. Rausch, ibid., 24, 824 (1959). (434) G. R. Knox and P. L. Pauson, J . Chem. Soc., 4610 (1961). (435) A. N. Nesmeyanov, E. G . Perevalova, and Z. A. Beinoravichute, Dokl. Akad. Nauk SSSR, 112, 439 (1957); Chem. Abstr., 51, 13855 (1957). (436) A. N. Nesmeyanov, E. G. Perevalova, L. P. Yur'eva, and L. I. Denisovich, I Z D .Akad. Nauk SSSR, Otd. Khim. Nauk, 2241 (1962); Chem. Abstr., 58, 12597 (1963). (437) P. L. Pauson, J . Am. Chem. SOC.,76. 2187 (1954). (438) D. W. Slocum, E. W. Rock*tt, and C. R. Hauser, Chem. Itfd. (London), 1831 (1964). (439) D. W. Slocum, B. W. Rockett, and C. R. Hauser, J. Am. Chem. Soc., 87 ,1241 (1965). >
I
whereas the second lithium enters either the methyl or phenyl position. Phosphorus shows a similar ortho erect to the oxygen, sulfur, nitrogen heteroatoms in that the metal usually enters adjacent to the phosphorus. This is true even in addition reacactions; the addition of butyllithiurn to disubstituted vinyl(440) A. N. Nesmeyanov, E. G. Perevalova, and Yu. A. Ustynyuk, Proc. Acud. Sci. U S S R , 133, 921 (1960). (441) R. L. Schaaf, P. T. Kan, C. T. Lenk, and E. P. Deck, J. Org. Chem., 25, 1986 (1960). (442) A. N. Nesmeyanov, V. A. Sazonova, and V. N. Drosd, Proc. Acad. Sci. U S S R , 126, 437 (1959). (443) A. N. Nesmeyanov, V. A. Sazonova, and V. N. Drosd, Chem. Ber., 93, 2717 (1960); Chem. Abstr., 55, 4462 (1961). (444) A. N. Nesmeyanov, V. A. Sazonova, and A. V. Gerasimenko, Proc. Acad. Sci. U S S R . 147. 1027 (19621. (445) H. Shechter and.J. F. Helling, J: Org. Chem., 26, 1034 (1961). (446) A. N. Nesmeyanov, E. G. Perevalova, and T. V. Nikitina, Proc. Acad. Sci. USSR,138, 584 (1961). (447) A. N. Nesmeyanov, E. G. Perevalova, Z. A. Beinoravichute, and I. L. Malygina, Dokl. Akad. Nauk SSSR, 120, 1263 (1958); Chem. Abstr., 53, 1293 (1959). (448) G. R. Knox and P. L. Pauson, J . Chem. SOC.,4615 (1961). (449) A. N. Nesmeyanov, E. G . Perevalova, R. V. Golovnya, and L. S . Shilovtseva, Dokl. Akud. Nauk SSSR, 102, 535 (1955); Chem. Abstr., 50, 491,s (1956). (450) H. B. Sokolova, M. P. Shebanova, and H.-C. Chou, J . Gen. Chem. USSR, 33, 210 (1963). (451) L. Summers, R. H.Uloth, and A. Holmes, J . Am. Chem. SOC., 77. 3604 (19551. (452) G. R. Knox, J. D. Munro, P. L. Pauson, G. H. Smith, and W. E. Watts, J . Chem. SOC.,4619 (1961). (453) M. D. Rausch, E. 0. Fischer, and H. Grubert, J . Am. Chem. SOC.,82, 76 (1960). (454) H. P. Fritz and E. 0. Fischer, Z . Nuturforsch., 12B, 67 (1957). (455) A. M. Aguiar, J. Giacin, and A. Mills, J. Org. Chem., 27, 674 (1962). (456) D. J. Peterson and J. H. Collins, ibid., 31, 2373 (1966). (457) D. J. Peterson and H. R. Hays, ibid., 30, 1939 (1965). (458) J. J. Richard and C. V. Banks, ibid., 28. 123 (1963).
J. M. Mallan and R. L Bebb
714
RaPCH=CHz 144
+ BuLi +R~P-CH-CHZ-BU I
Li
phosphine (144) results in the lithium adding adjacent to the phosphorus. 469 It is interesting to contrast the behavior of diphenylmethylamine with diphenylmethylphosphine toward metalation. As discussed previously, the amine gives only meta ring metalation,346 but the phosphine is metalated only on the methyl group. 467 Seyferth has shown that triphenylphosphine oxide (145) Ph3P0 CH3Li+PhrP(0)CHa PhLi 145 Ph2P(0)CHs PhLi ----f Ph2P(O)CHzLi PhH
+
+
+
146
+
reacts with organolithium reagents through a combination of transmetalation and metalation reactions which over-all lead to a lithiated phosphine (146).460,461 A similar reaction occurs with triphenylphosphine sulfide. These same workers have also studied the reactions of phosphine-methylene compounds with organolithium reagents. 463-466
148
occurs only in the carboranyl moiety. There is no evidence of metalation in the phenyl ring. The metalation of carboranes has been used to prepare a wide variety of derivatives after treatment with the appropriate reagents. In this way carboxylic a ~ i d s , ~ silane ~ ~ o ~ ~ ~ - ~ ~ derivative^,'^^. 47g phosphine derivatives,46galcohol^,^^^-^^^ and mercury derivatives,'? have all been prepared. The preparation of carboranes and their derivatives has been the subject of several United States patents. 488,476,4i8, Metalation reactions have also been described for neocarboranes, which are isomers of the carboranes. 484 Organoboron compounds other than the ~arboranes48~-~~7 can also be metalated. For example, metalation of dihydroborated terminal acetylenes (149) followed by carbonation is reported to yield substituted malonic acids. 485 However, this IICECH
%
J. METALATION OF ORGANOBORON COMPOUNDS The metalation reactions of carboranes, which are known in
R-CH-CH(BR2)-
___c ?RULl
149
CO'
COOH
RCH:-CH
the Russian literature as barenes, were described along with the first preparation of these new compounds. 467 For example, the parent carborane (147) compound has been metalated by
I I COOH
work has been questioned by others487who claim that there is
no evidence for a 1,l-dilithiated compound. In the years covered by this review, the first metalation of an aromatic selenium compound (150) has been reported. As
butyllithium t o yield a monolithium derivative which undergoes the normal organometallic derivatization reactions. The metalation reaction can be controlled to produce either monoor dilithiated c a r b ~ r a n e s , ~ ~ ~with , * ~ a- 'variety ~~ of organometallic compounds. 472--(74 It is interesting to note that phenylcarborane (148) is similar to the ferrocenes in that metalation ~~~
~
(459) D. J. Peterson, J . Org. Chem., 31, 950 (1966). (460) D. Seyferth, D. E. Welch, and J. K. Heeren, J . Am. Chem. Soc., 85, 642 (1963). (461) D. Seyferth, D. E. Welch, and J. K. Heeren, ibid., 86, 1100 (1964). (462) D. Seyferth and D. E. Welch, J. OrganometaL Chem., 2, 1 (1964). (463) D. Seyferth, J. Fogel, and J. K. Heeren, J . Am. Chem. Soc., 88, 2207 (1966). (464) D. Seyferth, J. K. Heeren, G. Singh, and, in part, S. 0. Grim and W. B. Hughes, J. Organometal. Chem., 5,267 (1966). (465 D. Seyferth, W. B. Hughes, and J. K. Heeren, J. Am. Chem. Soc., 87, 2847 (1965). (466) D. Seyferth, W. B. Hughes, and J. K. Heeren, ibid., 87, 3467 (1965). (467) L. I. Zakharkin, V. I. Stanko, V. A. Brattsev, Yu. A. Chapovskii,
A. I. Klimova, 0. Yu. Oxlobystin, and A. A. Ponomarenko, h o c . Acad. Sci. USSR, 155, 371 (1964). (468) J. W. Ager, Jr., and T. L. Heying, U. S. Patent 3,148,219; Chem. Abstr., 61, 14710 (1964). (469) R. P. Alexander and H. Schroeder, Inorg. Chem., 2, 1107 (1963). (470) T. L. Heying, J. W. Ager, Jr., S. L. Clark, R. P. Alexander, S. Papetti, J. A. Reid, and S . I. Trotz, ibid., 2, 1097 (1963). (471) L. I. Zakharkin, V. I. Stanko, A. I. Klimova, and Yu. A. Chapovskii, Izv. Akad. Nauk S S S R , Ser. Khim.,2236 (1963); Chem. Absfr., 60,9301 (1964). (472) D. Grafstein, J. Bobinski, J. Dvorak, H. F. Smith, N. Schwartz, M. S. Cohen, and M. M. Fein, Inorg. Chem., 2 , 1120 (1963). (473) L. I. Zakharkin, V. I. Bregadze, and 0. Yu. Okhlobystin, J . Organomefal. Chem., 4,211 (1965). (474) L. 1. Zakharkin and A. V. Kazantsev, J . Gen. Chem. USSR,36, 1301 (1966).
150
I
COOH
expected, the metal enters the position peri to the heteroatom.
V I . Summary and General Trends in Organolithium Research Recent developments in the metalation reactions of organolithium compounds have been reviewed through 1966. Metal(475) T. L. Heying, U. S. Patent 3,092,659; Chem. Abstr., 59, 11556 (1963). (476) L. I. Zakharkin, V. N. Kalinin, and A. I. L'vov, Izu. Akad. Nauk SSSR, Ser. Khim., 1091 (1966); Chem. Abstr., 65, 10604 (1966). (477) L. I. Zakharkin and A. I. L'vov, J. Organomefal. Chem., 5 , 313 (1966). (478) S. Papetti, U. S. Patent 3,137,719; Chem. Abstr., 61, 5692 (1964). (479) S. Papetti and T. L. Heying, Inorg. Chern., 2, 1105 (1963). (480) T. L. Heying, U. S. Patent 3,167,590; Chem. Absfr., 62, 9173 (1965). (481)-T. L. Heying and R. P. Alexander, U. S. Patent 3,117,164; Chem. Absrr., 60, 6866 (1964). (482) L. I. Zakharkin and A. V. Kazantsev, J. Gen. Chem. USSR,36, 958 (1966). (483) L. I. Zakharkin and A. V. Kazantsev, ibid., 36,960 (1966). (484) D. Grafstein and J. Dvorak, Inorg. Chem., 2, 1128 (1963). (485) G. Cainelli, G. Dal Bello, and G. Zubiani, Tetrahedron Lerfers, 3429 (1965). (486) G. Cainelli, G. Dal Bello, and G. Zubiani, ibid., 4315 (1966). (487) G. Zweifel and H. Arzoumanian, ibid., 2535 (1966). (488) W. J. Burlant and E. S. Gould, J . Am. Chem. Soc., 76, 5775 (1954).
715
Metalations by Organolithium Compounds
ations have been demonstrated in almost every class of compounds which contain a replaceable, acidic hydrogen. The position of metalation has been generally established as occurring at the most acidic hydrogen in the compound, and ortho, or a,to a heteroatom, if one is present. Recent developments with the organolithium-amine complexes show that much interesting synthetic chemistry is still t o be explored through the use of these relatively new compounds. The present trend in organolithium research is concerned with mechanism, kinetic, and structural studies. These three previously neglected areas in organolithium chemistry are badly in need of much more intensive study. This work has been hampered in the past by the difficulties encountered in handling these very reactive materials. However, as more of these mechanical problems are solved, many interesting studies should be conducted in these areas.
V I / . Glossary and Tables The following abbreviations are used. BuLi n-butyllithium EGDE ethylene glycol dimethyl ether Ether diethyl ether G D M E glycol dimethyl ether i-PrLi isopropyllithium MeLi methyllithium PhLi phenyllithium THF tetrahydrofuran THP tetrahydropyran Tables 111-VI which follow give a summary of new organolithium compounds, relative activity of organolithium compounds, color of some organolithium compounds, and metalations by organolithium compounds, respectively.
Table III
New compound CF-CFLi CH2=CHLi
Summary of Some New Organolithium Compounds Final Method of state preparation" A A A A
C A
CHz=CHCHzLi trans-CHaCH=CHLi cis-CHsCH=CHLi CH2=C(CHs)Li CH2=C(CHa)CH2Li CH2-CHLi
\/
CHz trans-PhCH=CHLi CHaLi pTolyllithium o-Tolyllithium m-Tolyllithium 1-Naphthyllithium PhCH2Li Fluorenyllithium PhCH=CHLi CzHsLi PhLi PhCHzLi p-Xylyllithium
C B D A A A A A A A A A
B A A A A A
E E B E E E E
Ethyl ether Pentane Ethyl ether Solid Solid Ethyl ether Solid Ethyl ether THF Ethyl ether Solid Ethyl ether Ethyl ether Ethyl ether Ethyl ether Pentane Solid Ethyl ether Solid Solid Solid Solid Solid Solid Solid Solid Benzene Hydrocarbon Hydrocarbon Hydrocarbon Solid
? yield
Ref
64b 51b 50-75b
C
55
f f f
90 55 65 7ob 79 61b 4gb 14b 53b 7gb 66b 86b 72-82 62 48 56
C
d, e e
8
h i, j
i, i 212 212 212 i, i
k
k I 77, m n n n n 0
100 70-85 92b 93 100 75
P P Q, r 41 41, 42 41, 42
a A, transmetalation; B, lithium-metal exchange; C, transmetalation by lithium metal; D, ether cleavage; E, metalation. b Yield based on derivative formation. D. Seyferth, D. E. Welch, and G. Raab, J. Am. Chem. Soc., 84, 4266 (1962). D. Seyferth and M. A. Weiner, Chem. Ind. (London), 402 (1959). D. Seyferth and M. A. Weiner, J. Am. Chem. SOC.,83, 3583 (1961). f E. C. Juenge and D. Seyferth, J. Org. Chem., 26, 563 (1961). 0 R. West and W. H. Glaze, ibid., 26, 2096 (1961). Ir J. J. Eisch and A. M. Jacobs, ibid., 28, 2145 (1963). D. Seyferth and M. A. Weiner, ibid., 24,1395 (1959). i D. Seyferth and M. A. Weiner, ibid., 26,4797 (1961). D. Seyferth and H. M. Cohen, Inorg. Chem., 2, 625 (1963). D. Seyferth, L. G. Vaughan, and R. Suzuki, J . Organometal. Chem., 1, 437 (1964). T. V. Talalaeva and K. A. Kocheshkov, J. Gen. Chem. USSR, 23, 392 (1953); Chem. Abstr., 48, 3245 (1954). T. V. Talalaeva and K. A. Kocheshkov, Izu. Akad. Nauk SSSR, Old. Khim. Nauk, 126 (1953); Chem. Absrr., 48, 3285 (1954). T. V. Talalaeva and K. A. Kocheshkov, Izv. Akad. Nauk SSSR,Ord. Khim. mauk, 290 (1953); Chem. Abstr., 48,6389 (1954). p T. V. Talalaeva and K. A. Kocheshkov, Izu. Akad. Nauk SSSR, Ord. Khim. Nauk, 392 (1953); Chem. Abstr., 48, 6389 (1954). T. V. Talalaeva and K. A. Kocheshkov, Izu. Akad. Nauk SSSR, Ser. Khim., 855 (1964); Chem. Abstr., 61, 5675 (1964). T. V. Talalaeva, A. N. Rodionov, and K. A. Kocheshkov, Proc. Acad. Sei. USSR, Chem. Sect., 152, 703 (1963). 1
J. M. Mallan and R. 1. Bebb
716
Table I V Relative Activity of Organolithium Compounds Ref A. In competitive reactions toward the same substrate PhJSiLi > PhsGeLi > PhsSnLi > PhsPbLi B. Order of reactivity based on the ability to initiate polymerization Bu > benzyl > allyl > vinyl > phenyl C . Half-lives in diethyl ether at room temperature Butyllithium, 153 hr Cyclopropyllithium, 138 hr Ethyllithium, 54 hr Propyllithium, 30 hr Cyclohexyllithium, 0.5 hr D. Decomposition of butyllithium in various solvents THF, 2 hr Et20-THF, 24 hr Et20-THP, 1 week E. Relative stability of organolithiums GS. their metalating ability Stability ,a Zihr -0.44 -1.41 -2.14 -3.3 a
16 215
140
135
Metalatim ability,b " RLi PhCHtLi MeLi PhCH(CHa)Li PhLi
7 i 21 29.2 38.8 55.3
C
Stability measured as the rate of disappearance per hour. b Metalating ability toward dibenzofuran. c H. Gilman and H. A. McNinch,
J. Org. Chem., 27, 1889 (1962).
Table V Color of Some Organolithium Compounds Parent compound Chloroform Carbon tetrachloride Tris(triffuorovinyl)phenyltin Tetravinyltin Commercial preparation Propyne Allyl phenyl ether Tetraallyltin Pyrimidine Butyne Butyne Butyne Commercial preparation Commercial preparation Commercial preparation Commercial preparation 1-Methylpyrazob 2-Methoxythiophene 2-Methoxythiophene 2-Methylthiophene Hexachlorobenzene Hexachlorobenzene Bromobenzene Bromobenzene Fluorobenzene Commercial preparation o-Nitro bromobenzene o-Phenylenemercury 5-Methylpyridotetrazole 2-Methylpyridine 2-Methylpyridine
Metalatitzg agent BuLi BuLi PhLi BuLi 4BuLi Li metal BuLi BuLi BuLi 2BuLi 3BuLi
3BuLi BuLi PhLi PhLi BuLi BuLi BuLi Li metal Li metal Li metal PhLi Li metal BuLi PhLi PhLi
Solveitt THF THF Ether Hexane THF Benzene THF Hexane THF Hexane THF Hexane Hexane Hexane Hexane THF Heptane THF Hexane THF Ether THF Ether Ether Ether Ether THF Ether THF GDME THF Ether THF Ether Ether Ether Ether
Metalated compoutid Trichloromethyllithium Trichloromethyllithium Perfl uorovinyllithiurn Vinyllithium Ethyllithium Tetralithioprop yne Allyllithium Allyllithium Pyrimidinyllithium Butynyllithium 3-Methylpropynylenedilithium 3-Methylprop ynylenedilithium-
BuLi adduct Ii-Butyllithium sec-Butyllithium t-Butyllithium Methallyllithium I-Methyl-5-lithiopyrazole 2-Methoxy-5-lithiothiophene 2-Methoxy-5-lithiothiopheiie 5-Methyl-2-thienyllithium
Pentachlorophen yllithium Pentachlorophenyllithium
Phenyllithium Phenyllithium Phenyllithium Phenyllithium o-Nitrophenyllithium o-Dilithiobenzene 5-a-Lithiomethylpyridotetrazole
2-Pyridylmethyllithium 2-Pyridylmethyllithium
Color Purple-green Pale pink Brown Light yellow Pale straw Red-brown Red Yellow Orange Yellow Yellow Orange Pale straw Yellow Orange-yellow Green-yellow Yellow Yellow Green-yellow Green Light orangebrown Light yellow Deep red Deep green Red Pink-yellow Dark red Deep red Deep purple orange-brown Dark red
Ref 186 186 a
21 6 21 6 264 b
216 C
265 265
265 216 216 216 216 356 d 320
e 138 138
133 407
f
216 189
g
360 I2 347
Metalations by Organolithium Compounds
717
Table V (Continued) Metalating agent
Solcent
2,CDichlorobenzyl chloride
BuLi
THF
2,4-Dichloro-a-chlorobenzyllithium
o-Chlorobenzyl chloride Benzal chloride Benzal chloride 2-( 1-Propynyl)thiophene
BuLi BuLi BuLi BuLi
THF THF (-100') THF (-60") Ether
Benzyl chloride Toluene Tribenzyltin chloride Triphenylbenzpltin Tribenzyltin chloride Methylphenyl sulfide Lutidine Bis(a-methylbenzyl) ether a-Methy lbenzyltriphenyltin o-Methylbenzyl chloride
Li metal DABCO-BuLi PhLi PhLi MeLi DABCO-BuLi PhLi Li metal PhLi BuLi
Dioxane Hexane Ether Ether Ether THF Ether THF Ether THF
o-Chloro-a-chlorobenzyllithium a,a-Dichlorobenzyllithium a,a-Dichlorobenzyllithium 5-Lithio-2-(1-propynyl)thiophene Benzyllithium Benzyllithium Benzyllithium Benzyllithium Benzyllithium Phenylthiomethyllithium Lutidinyllithium a-Methylbenzyllithium a-Methylbenzyllithium o-Methyl-a-chlorobenzyllithium
p-Methylbenzyl chloride N-Methylbenzamide 2-Methyl-2-(2-thienyI)-J,3dioxolane
BuLi BuLi BuLi
THF THF Ether
p-Methyl-a-chlorobenzyllithium o-Lithio-N-methylbenzamide 2-Methyl-2-(2-thieny1-5-lithio)-
frans-8-Styryltrimethyltin
Styrene 1-Methylbenzimidazole
MeLi BuLi BuLi
Ether Ether
1,3-dioxolane truirs-8-Styryllithium Styryllithium 1-Methyl-2-lithiobenzimidazole
Phenylacetonitrile Indene Indene 1Phenylpyrazole 1-Phenylpyrazole
BuLi BuLi PhaSiLi BuLi 2BuLi
THF Ether THF Ether Ether
N-Methylindole Allylbenzene
BuLi BuLi
Ether Ether
Allylbenzene N-Methyl-o-toluamide
BuLi BuLi
THF THF
Benzyldimethylamine Benzyldimethylamine Benzyldimet hylamine
PhLi BuNa PhNa
Ether Octane Octane
Benzyldimethylamine 1-Fluoronaphthalene Ferrocene Ferrocenylmethyl methyl ether 1 -Methoxynaphthalene-8-d
PhK Li metal BuLi BuLi BuLi
Heptane THF Ether THF Ether
N,N-Dimeth yl-cu-phenylpropylamine Diazocyclopentadiene
BuLi
Ether
PhLi
Ether
Di benzofuran
Li metal
Dioxane
Dibenzofuran
Li metal
THF
Dibenzothiophene 5-oxide
BuLi
Ether
Thianthrene 5-oxide Diphenyl sulfone
BuLi BuLi
Ether Ether
Diphenyl sulfone Phenoxathiin ]&dioxide
2BuLi BuLi
Ether Ether
Parent compound
Metaluted compound
a-Lithiophenylacetonitrile 1 -1ndenyllithium 1-Indenyllithium 5-Lithio-1-phenylpyrazole l-(o-Lithiophenyl)-5-lithio-
pyrazole 1-Methyl-2-lithioindole 1-Phenylallyllithium I-Phenylallyllithium o-Lithiomethyl-N-methylbenzamide o-Lithiobenzyldimethylamine o-Sodiobenzyldimethylamine o-Sodiobenzyldimethylamine
Color
Ref'
Deep redpurple Pale rose Lavender Deep red Red
95
Lemon yellow Yellow Yellow Bright yellow Bright yellow Pale yellow Orange-red Cherry red Brown-yellow Pale yelloworange Pale orange Dark red Deep brown
38 50 216
Red Deep red Red liquid, green-yellow solid Yellow RWt Brown-yellow Dark red Bright yellow Green Green-redorange Red Dark red Brown Orange-red Red suspension Light red Green Orange Dark red Red-orange
o-Potassiobenzyldirnethylamine 1-Naphthyllithium Ferrocen yllithi um Ferrocenylmethyllithium Lithio-l-methoxynaphthalene8-d o-Lithio-N,N-dimethyl-y-phe- Red nylpropylamine PhenylazocyclopentadienylScarlet lithium Lithium 2-(2-lithiophenyl)phenBrick red oxide Lithium 2-(2-lithiophenyl)phenBlue-green to brown oxide 4Lithiodibenzothiophene 5Dark orange oxide 4,6-Dilithiothianthrene 5-oxide Orange o-Lithiodiphenyl sulfone Yellow-orange Yellow o,o'-Dilithiodiphenyl sulfone Orange-red 1,9-Dilithiophenoxathiin Yellow-orange 10-dioxide
95 186 186 1v
1
40 330 350 36 216 185 185 378 302 498 273 359 369 276 27 1 356 356 355 j
216 382 373 373 373 373
f k
440 293 379 448 288 1
323 328 324 341 324 384-
J. M. Mallan and R. 1. Bebb
718 Table V (Continued) Parent compound
Metalating agent
Solvent
Dibenzothiophene 5-dioxide
BuLi
Ether
Diphenyl ether Diphenyl phosphine N,N-Dimethyl(@-phenylisobuty1)amine Fluorene Fluorene Fluorene Fluorene Fluorene Fluorene
BuLi BuLi BuLi
THF THF Ether
N-Methylcarbazole Xanthene Diphenylmethane Diphenylmethane Triphenylphosphine oxide
PhLi EtLi BuLi BuLi BuLi Triphenylleadlithium Triphenyltinlithium BuLi Php-SiLi Ph,-Li adduct PhsSiLi MeLi
Ether THF THF THF Ether
Triphenylphosphine oxide
MeLi
Ether
Triphenylphosphine sulfide
MeLi
Triphenylphosphine sulfide
EtLi
2-Bromo-l , 1-diphenylethylene
BuLi
Ether
10-Methylacridan 10-Ethy lphenothiazine Phenyl (3-chloro-CN,N-dirnethylaminophenyl) sulfone
BuLi Ph8SiLi BuLi
Ether THF Ether
a-Methyl-a '-(phenethy1)-pyridine N-Phenylindole 2,2-Diphenyl-l-chloropropane Pyrene 12H-Benzo[a]phenothiazine
PhLi
Ether
BuLi Li meta BuLi BuLi
Ether Ether Ether Ether
12H-Benzo[b]phenothiazine
BuLi
Ether
Diphenylacetylene
EtLi
Ether
1,I-Diphenylethylene Diphenylacetylene
Allyllith i m BuLi
THF Ether
1,l-Diphenylethylene 1,l-Diphen ylethylene 1,l-Diphenylethylene Triphenylgermane Triphenylgermane %Phenylfluorene Tritylmethyl ether Triphenylmethane Triphenylmethane Triphenylmethane Triphenylmethane Triphenylmethyl chloride 14H-Dibenzo[u,c]phenothiazine
BuLi BuLi BuLi PhLi BuLi BuLi BuLi n-PrLi BuLi BuLi Ph2-Li adduct Li metal BuLi
THF
Benzene Ether THF Ether Ether Ether Ether Hexane THF THF Hexane
BuLi
Hexane
BuLi
Hexane
Fluorene
Metalated compound
4,6-Dilithiodibenzothiophene 5-dioxide 2,2'-Dilithiodiphenyl ether Diphenylphosphenyllithium
Color
Ref
Deep red
324
Dark green Orange-red Red
158 143 379
Ether Benzene Benzene Hexane Hexane-THF THF
o-Lithio-N,N-dimethyl(@-phenylisobuty1)arnine 9-Fluorenyllithium 9-Fluorenyllithium 9-Fluorenyllithium 9-Fluorenyllithium 9-Fluorenyllithium 9-Fluorenyllithium
Orange Orange Orange Yellow Orange-brown Brown
274 271
THF
9-Fluorenyllithium
Red
271
1-Lithio-N-methylcarbazole
Dark red Dark red Red Red Deep red
345 271 P 271
Orange-red
460
Red
462
Red
462
Yellow
4
Bright red Light green Yellow
271 342
Orange-red
350
9-Xanthyllithium Diphenylmethyllithium Diphenylmethyllithium a-Lithiomethyldiphenylphosphine oxide a-lit hiomethyldiphenylphosphine oxide a-lithiomethyldiphenylphosphine sulfide a-Lithioethyldiphenylphosphine sulfide l,l-Diphenyl-2-bromo-2-lithioethylene 9-Lithio-10-methylacridan CLithio- 10-ethylphenothiazine Phenyl (2-lithio-3-chloro-4-
m
n 253 0
461
r
N,N-dimethylaminophenyl) sulfone 2-Phenyl-1-(5-methyl-2-pyridy1)ethyllithium l-(o-Lithiopheny1)-2-lithioindole 2,ZDiphenyl-1-lithiopropane Pyrenyllithium 1-Lithio-12H-benzoIa1phenothiazine ll-Lithio-l2H-benzo[b]phenothiazine l-Phenyl-2-(o-lithiophenyl>llithio-1-butene l,l-Diphenyl-3-butenyllithium 1-Pheny1-2-(o-lithiophenyl)-llithio-1-hexene 1,l-Diphenyl-n-hexyllithium 1,l-Diphenyl-n-hexyllithium 1,l-Diphenyl-n-hexyllithium Triphenylgermyllithium Triphenylgermyllithiurn 9-Phenyl-9-fluorenyllithium 9-Phenyl-9-fluorenyllithium
Triphenylmethyllithium Triphenylmethyllithiurn Triphenylmethyllithium Triphenylmethyllithium Triphenylmethyllithium
l-Lithio-l4H-dibenzo[a,c]phenothiazine 1-Lithio- 14H-dibenzo[a,h]phenothiazine 6-Lithio-7H-dibenzo[c,h]phenothiazine
Orange Clear red Deep red Bright red
355 S
280 393
Deep orange
395
Green to bright yellow Deep red Red
268
Deep red Deep red Cherry red Yellow Pale green Orange Scarlet Red Red Red Deep red Brilliant red Red
216 268 216 61 250,251
400 401 298 298 205 405 274 t
216 394
Dark red
394
Red
394
Metalations by Organolithium Compounds
719
Table V (Continued) Metalat ing agent
Parent compound
Solvent
Metalated compound
Color
Ref
~
Purple to light 238 3-Lithio-3-(triphenylsilyl)-2chloropropene orange Dark red U Ether 9-Cinnamylidene-9-fluorenylPhLi lithium 2-LithioferrocenyldiphenylDark yellow 303 BuLi Ether Diphenylferrocenylcarbinol carbinol TriphenylmethylcyclopentadiYellow U Ether TriphenylmethylcyclopentaPhLi diene enyllithium (0-Lithiopheny1)triphenylphosBrown-deep 466 MeLi THF ether Tetraphenylphosphonium bromide phonium bromide red D. Seyferth, D. E. Welch, and G. Raab, J. Am. Chem. Soc., 84, 4266 (1962). J. J Eisch and A. M. Jacobs, J Org. Chem., 28,2145 (1963). 0 T. L. V. Ulbricht, Tetrahedron, 6,225 (1959) W. R. Biggerstaff and K. L. Stevens, J. Org. Chem., 28, 733 (1963). e R. D. Schuetz, D. D. Taft, J. P. O'Brien, J. L. Shea, and H. M. Mork, ibid., 28, 1420 (1963). f H. Gilman and T. S . Soddy, ibid., 22, 1121 (1957). 0 H. J. S. Winkler and G. Wittig, ibid., 28, 1733 (1963). h N. J. Leonard and A. S . Hay, J. Am. Chem. SOC.,78, 1984 (1956). * H. Gilman and S. D. Rosenberg, J. Org. Chem., 24,2063 (1959). H. F. Herbrandson and D. S . Mooney, J. Am. Chem. Soc., 79, 5809 (1957). H. Watanabe, I. Motoyama, and K. Hata, Bull. Chem. SOC.Japan, 39, 784 (1966). 2 H. Gilman and J. J. Dietrich, J. Org. Chem., 22,851 (1957). J. A. Gautier, M. Miocque, and H. Moskowitz, J. Organometal. Chem., 1,212 (1964). n T. V. Talalaeva and K. A. Kocheshkov, Izv. Akad. Nauk SSSR, Old. Khim. Nauk, 392 (1953); Chem. Abstr., 48,6389 (1954). W. S. Murphey and C. R. Hauser, J. Org. Chem., 31, 85 (1966). p J. J. Eisch and W. C. Kaska, ibid., 27, 3745 (1962). q D. Y . Curtin and E. W. Flynn, J. Am. Chem. Soc., 81, 4714 (1959). H. Gilman and G. Lichtenwalter, J. Org. Chem., 23, 1586 (1958). * H. E. Zimmerman and A. Zweig, J. Am. Chem. Soc., 83, 1196 (1961). J. J. Eisch and W. C. Kaska, Chern. Znd. (London), 470 (1961). E. D. Bergmann and Z . Pelchowicz, Bull. Soc. Chim. France, 809 (1953). W. F. Little and R. C. Koestler, J. Org. Chem., 26, 3247 (1961). L. Skatteboel, Acta Chem. Scand., 13, 1460 (1959). THF
PhsSiLi
3-(Triphenylsilyl)-2-~hloropropene Cinnamy lidenefluorene
0
f
Table VI Metalations by Organolithium Compounds Compound metalated
CHCIa
Chloroform
RLi
BuLi BuLi BuLi
CHIC12
Methylene chloride
MeLi BuLi
Sol cent
THF Ether Pet. ether THF Hexane THF Ether Pet. ether Ether THF Ether Pet. ether
BuLi MeLi BuLi MeLi BuLi BuLi
Ether THF Hexane Ether THF Ether Pet. ether
BuLi BuLi
CHIN
Diazomet hane
CJICI:
Trichloroethylene
MeLi MeLi MeLi MeLi MeLi MeLi BuLi BuLi BuLi
Hexane THF Ether Ether Ether Ether Ether Ether THF Ether Pet. ether THF Ether THF Ether Pet. ether
Reactant
%
Final product
yield
Benzophenone
Trichloromethyldip henylcarbinol
84
195
Carbon dioxide
Trichloroacetic acid
50
186
Mercuric chloride
Bis(trich1oromethyl)mercury
91-96
195
Benzene Benzophenone
Methyltropilidene Dichloromethyldiphenylcarbinol
30 80
241 202
trans-2-butene
40
237
t-Butylbenzene Carbon dioxide
l-Chloro-2,3-rrans-dimethylcyclopropane Methyl-t-butyltropilidene Dichloroacetic acid
25 60
241 186
Cumene Cyclohexene 2,2 '-Dichlorobenzophenone
Methylisopropyltropilidene 7-Chlorobicyclo[4.1 .O]heptane Dichloromethylbis(2-chloropheny1)carbinol
20 31
241 237 202
2,3-Dimethyl2-butene Mercuric chloride
l-Chlor0-2,2,3,3-tetramethylcyclopropane Bis(dichloromethy1)mercury
61
237
Toluene pXylene Benzonitrile Benzoyl bromide Fluorenone Bromine
Dimethyltropilidene Trimethyltropilidene 3- (or 5-) Phenyl-l,2,4-triazole 2-Phenyl-l,3,4-oxadiazole 9-Fluoreneimine Diazometh yllithium Bromotrichloroethylene
Capraldehyde
3-Hydroxy-1-chloro- 1-octyne
Carbon dioxide
Trichloroacrylic acid
82-97 40 10 42 35 41 50
36
Ref
194, 198 202 241 241 364 364 364 363 193 416
81
192, 193
720
J. M. Mallan and R. 1. Sebb Table VI (Continued) Compound metalated
RLi
Solvent
Reactant
PhLi
Ether
Cyclohexanone
Acetylene
PhLi
THF
trans-1,2Dichloroethylene
BuLi
Final product
%
yield
Ref
82
Triphenylchlorosilane Bromine
I-Hydroxycyclohexylethynyl chloride Bis(triphenylsi1yl)acetylene tram- 1 ,2-Dichlorobromoethylene
26
193
Carbon dioxide
trans-2,3-Dichloroacrylicacid
99
192, 193
Carbon dioxide
2-Chloroacrylic acid
99-10
192, 193
Carbon dioxide
Trifluoromethylsulfonylacetic acid
51
333
(@-Phenyl-8-hydrosyethyl) methyl sulfone (fl,p-Diphenyl-@-hydroxyethyl) methyl sulfone 1,2-Bis(a-hydroxyethyl)carborane 1,2-Di(l-hydroxy-l-ethyl)carborane
85
331
46
33 1
31
470 481
23
479
416 254
Vinyl chloride
BuLi
Methyl trifluoromethyl sulfone Dimethyl sulfone
BuLi
THF Ether Pet. ether THF Ether Pet. ether THF Ether Pet. ether Ether
BuLi
Benzene
Benzaldehyde
BuLi
Benzene
Benzophenone
BuLi BuLi
Ether Ether
Acetaldehyde Acetic acid
BuLi
Ether
1,2-Bis(chlorodimethylsily1)carborane
BuLi
Ether
Dimeric phenylphospha(II1)carborane
20
469
BuLi
Ether
1,2-Bis(chlorophenylphosphinokarborane 1,2-Bis(trichlorosily1)carborane
(CI2Si--C--C-)r
52
479
PhLi BuLi MeLi BuLi BuLi
Ether Ether Ether
3-Bromopropene n-Butyl bromide Carbon dioxide Carbon dioxide Carbon dioxide
1-Allylcarborane
70 69 24
470 470 468 471 472
1,2-Carboranedicarboxylic acid Di butylcarboranylenetin
87 66
470 473
1,2-Bis(chlorodirnethylsily1)carborane Dimethylchlorosilylcarborane
88
479
BuLi
Carborane
0 BioHio
BuLi
THF Heptane Ether Benzene Ether Ether
MeLi
Ether
MeLi
Ether
BuLi
Ether
BuLi
Ether
BuLi
Ether
BuLi
Ether
BuLi BuLi PhLi BuLi BuLi
Benzene Ether Ether Ether Ether
BuLi 2R Li
Carbon dioxide Di butyltin dichloride Dichlorodimethylsilane Dichlorodimethylsilane Dichlorodimethylsilane Dichlorodimethylsilane Dimethyldichloromethylsilane Dichlorodiphenylsilane Diphenylchlorophosphine Ethylene oxide Ethylene oxide Ethylene oxide Iodine Mercuric chloride
n-Butylcarborane Carboranecarboxylic acid Carboranecarboxylic acid 1,2-Carboranedicarboxylicacid
478
Dimethyldicarboranylsilane
478
Dimethyldicarboran-1-ylsilane
470
1,242’,2 ’-Dimethyl-2’-silapropy1ene)carborane I ,2-Bis(chlorodiphenylsilyl> carborane 1,2-Bis(diphenylphosphino)carborane 2-(Carboranyl)ethanol 1,2-Bis(j3-hydroxyethyl)carborane 1,2-Bis(hydroxyethyl)arborane 1-Iodocarborane Dicarboranylmercury
470 23
479
59
469
48
474 470 472 472 473
35 64 53
721
Metalations by Organolithium Compounds
Table VI (Continued) Compound metalated
RLi
R Li
Ether
BuLi
Ether
BuLi
Ether
BuLi
Ether
BuLi
BuLi BuLi
Benzene Ether Benzene Ether Ether Ether
MeLi
Ether
BuLi
Ether
MeLi
Ether
BuLi
Ether
2RLi RLi
Benzene Ether Ether
BuLi
4-Bromoisothiazole CChloroisothiazole CIodoisothiazole Isothiazole
Thiazole
Propyne
Reactant
Methylmercuric chloride Methyltrichlorosilane Phenyldichlorophosphine Phosphorus trichloride Propylene oxide
Final product
%
yield
Ref
Methylcarboranylmercury
51
473
1,2-Bis(dichloromethyIsilyl)carborane 1,2-Bis(chlorophenylphosphino)carborane Dimeric chlorophospha(II1)carborane
70
419
58
469
44
469
1-(Carboranyl)-2-propanol
50
474
Propylene oxide
1,2-Bis(j3-hydroxypropyl)carborane
80
474
1,2-Bis(trichlorosilyl)carborane Trimethyl(carb0ran-1-ylmethy1)silane Trimethylsilylcarborane
Ether
Tetrachlorosilane Trimethylchloromethylsilane Trimethylchlorosilane Trimethylchlorosilane Triphenylchlorosilane Triphenylchlorosilane Tri-n-prop yltin chloride Tri-n-propyltin chloride Carbon dioxide
BuLi BuLi
Ether Benzene
Methyl iodide Paraformaldehyde
BuLi
THF
Carbon dioxide
BuLi
THF
BuLi
THF
Dimethylformamide Carbon dioxide
BuLi
THF
BuLi
THF
BuLi BuLi BuLi
THF THF THF
BuLi BuLi BuLi BuLi PhLi BuLi BuLi BuLi
THF Ether Ether Ether Ether Ether Ether Ether
BuLi BuLi
Ether Hexane
2BuLi
Neocar borane
Solcent
MeLi MeLi MeLi
Ether THF Ether THF Ether THF
Dimethylformamide Dimethylformamide Bromine Carbon dioxide Dimethylformamide Methyl iodide Acetaldehyde Benzophenone Butyraldehyde Carbon dioxide Ethylene oxide Heptaldehyde Isobutyraldehyde Propionalde hyde Trimethylchlorosilane Bromotrifluoroethylene Chlorotrifluoroethylene 1,l-Dichlorodifluoroethylene
60
479 470, 478 478
1-Trimethylsilylcarborane
470
Triphenylsilylcarborane
478
1-Triphenylsilylcarborane
470
Carboranylenebis(tri-n-propyltin)
30
413
Tri-n-propylcarboranyltin
35
473
C,C '-Neocarboranedicarboxylic acid C-Methylneocarborane C,C '-Bis(hydroxymethy1)neocarborane 4-Bromo-5-isothiazolecarboxylic acid 4-Bromo-5-formylisothiazole
78
484
39 24
484 484
70
388
73
388
4-Chloro-5-isothiazolecarboxylic acid
68
388
4-Chloro-5-formylisothiazole
65
388
4-Iodo-5-formylisothiazole
33
388
5-Bromoisothiazole Isothiazole-5-carboxylicacid 5-Formylisothiazole
34 48 75
388 388 388
5-Methylisothiazole 241-Hydroxyethyl)thiazole Diphenyl-2-thiazolylcarbinol 2 4 1-Hydroxybuty1)thiazole 2-Thiazolecarboxylic acid 2-(2-Hydroxyethyl)thiazole 24 1-Hydroxyhepty1)thiazole 24 1-Hydroxy-2methylpropyl)thiazole 24 I-Hydroxypropy1)thiazole
40 30 22 90 40 30 90 90
388 391 391 391 389 391 391 391
50 50
391 264
1,3,3-Tris(trimethylsilyl)propyne
+
1,1,3,34etra(trimethylsily1)allene 1-Bromo-1,2-difluoropent-l-en-3yne l-Chloro-l,2-difluoropent-l-en-3yne 1,l-Dichloro-2-fluoropent-l-en-3yne
25 56
423
73
423
51
423
J. M. Mallan and R. L Bebb
122 Table VI (Continued) Compound metalated
Rci
Solvent
MeLi
2BuLi 2PhLi MeLi
Ether THF Ether THF Ether THF Ether Ether Ether
MeLi
Ether
BuLi
Hexafluoropropene Tetrduoroethylene 1,1,2-Trifluoro1,3-butadiene Carbon dioxide Carbon dioxide Chloromethyldimethylgermyl chloride Chloromethylgermy1 dichloride Trimethylgermyl chloride Carbon dioxide
BuLi
Benzaldehyde
MeLi MeLi Pyrazole Chloromethyldimethylsilanol
MeLi Carboranecarboxylic acid 1-Methylcarborane
Ether
Carbon dioxide
BuLi
Benzene Ether
Epichlorohydrin
RLi RLi BuLi
Ethyl benzoate Ethylene oxide Mercuric chloride Methyl benzoate Propylene oxide
yield
Ref
17
423
35
423
64
423
3-Pyrazolecarboxylicacid 9 7 3-Pyrazolecarboxylicacid (CHZC~)(CH~)~S~OG~(CH~)~74 (CHZCI)
U
(CH~C1)(CHs)2SiOGeOSi(CH1)2
68
b
CHzCl (CHS) CH2CI ( C H Z C I ) ( C H ~ ) ~ S ~ O G ~ M ~ ~ 80
b
Carboranedicarboxylic acid
471
1-(Methylcarborany1)benzyl 70 alcohol 1-Methyl-2-carboranylcarboxylic 20 acid 1,3-Bis(methylcarboranyl)-2-propanol 1,2-Epoxy-3-rnethylcarboranyl30 propane Methylcarboranylphenylcarbinol 72 1-(1-Methyl-2-carborany1)ethanol 65-90
C
/\
U
b
\
Bis(rnethylcarborany1)mercury 1-Methyl-2-benzoylcarborane 1-(l-Methyl-2-carboranyl)-2propanol 2-( l-Methyl-2-carboranyl)-lphenylethanol C-Methyl-C’-neocarboranylcarboxylic acid 3,5-Dibromo-2-carboxythiophene
484,471
474 483 474
72 61 72
473 483 474
62
474
19
484
36
d
34
d
Styrene oxide
BuLi BuLi
Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
PhLi
Ether
Carbon dioxide
BuLi
Ether
Deuterium oxide
BuLi BuLi
Ether Ether Hexane Ether
Tritium oxide Carbon dioxide
3-Thiophenecarboxylicacid 2,3-dicarboxythiophene 3-Bromo-2-thiophenecarboxylic acid 3-Bromo-2-thiophenecarboxylic acid 3-Deuteriothiophene 2,3dideuteriothiophene Thiophene-2-t thiophene-3-t 2-Carboxythiophene
Carbon dioxide
2-Thiophenecarboxylic acid
87
227, 228
Ether
Carbon dioxide
2-Thiophenecarboxylicacid
95
227
THF
Benzyl bromide
5-Benzyl-dbromo-3-methylisothiazole 4-bromo-3-methyl5 4 1,24iphenylethyl)isothiazole 4-Bromo-3-methyl-5-isothiazolecarboxylic acid 4-Bromo-5-formyl-3-methylisothiazole
13
388
2-d
Thiophene2-t Thiophene3-t 4Bromo-3methylisothiazole
Benzene Ether Ether
%
Final product
Benzene Ether Benzene Ether Ether
BuLi
Thiophene-
Ether
BuLi
RLi BuLi
C-Methylneocarborane 2,CDibromothiophene 3,CDibromothiophene 3-Bromothiophene
Reactant
BuLi 1:l BuLi 1:l BuLi
Carbon dioxide
BuLi
THF
Carbon dioxide
BuLi
THF
Dimethylformamide
+
225 36
231, d
72
231
+
225
+
+
225 228
10
56
388
51
388
723
Metalations by Organolithium Compounds
Table VI (Continued) Compound metalated
RLi
Solvent
BuLi
THF
Reactant Ethyl halide
Final product
TJ
yield
Ref
34
388
40 28
388 388
75
388
47
388
58
388
68
388
96 98 89 98 77 77 95 94 44 93 88
285 285 285 285 285 285 285 285 285 285 285
Lithium 2-furansulfinate 2-(Ethylthio)furan
55
53
208 e
Triphenyl-2-furyltin
44
f
73 54 62 31 22 47 76
211 211 319 319
4-Bromo-5-ethyl-3-methyliso-
thiazole 4-Bromo-3,5-dimethylisothiazole 4-Bromo-3-methyl-5-n-propylisothiazole 4-Chloro-3-methyl-5-isothiazolecarboxylic acid 4-Chloro-5-formyl-3-methylisothiazole 4-Iodo-3-methyl-5-isothiazolecarboxylic acid 4-Iodo-5-formyl-3-methylisothiazole Methylphenyl-2-fur ylcarbinol Phenyl-2-furylcarbinol
BuLi BuLi
THF THF
Methyl iodide n-Propyl halide
BuLi
THF
Carbon dioxide
BuLi
THF
4-bdo-3methylisothiazole
BuLi
THF
Dimethylformamide Carbon dioxide
BuLi
THF
Furan
BuLi BuLi BuLi BuLi BuLi BuLi BuLi BuLi BuLi BuLi BuLi
Ether Ether Ether Ether THF Ether Ether Ether Ether Ether Ether
BuLi BuLi
Ether Ether
BuLi
Ether
BuLi BuLi BuLi BuLi
Ether Ether Ether THF
Dimethylformamide Acetophenone Benzaldehyde Benzonitrile Benzophenone n-Butyl bromide Carbon dioxide Cyclohexanone Ethyl acetate Ethyl benzoate Isobutyraldehyde Methyl ethyl ketone Sulfur dioxide Sulfur, ethyl iodide Triphenyltin chloride Acetaldehyde Benzaldehyde Benzyl bromide Bromobenzene
BuLi BuLi N-Methyl-2lithiopyrrole 2,4,6Triphenylphenyllithium Poly-p-styryllithium BuLi BuLi
Ether Ether Ether
n-Butyl bromide Butyraldehyde Carbon dioxide
1-(2-Thienyl)ethanol 2-Thienylphenylcarbinol 2-Benzylthiophene 2-Phenylthiophene 2,5diphenylthiophene 2-n-Butylthiophene 1-(2-Thienyl)butanol Thiophene-2-carboxylic acid
Carbon dioxide
Thiophene-2-carboxylic acid
46
172
Ether
Carbon dioxide
Thiophene-2-carboxylic acid
43
&?
Ether Ether
2,2’-Bithienyl
64 64
314 21 1
PhLi
Ether
cis-4-Dimethylaminodi(2-thieny1)cyclohexylcarbinol
66
h
PhLi
Ether
trans-4Dimethylaminodi(2-thieny1)cyclohexylcarbinol
88
h
BuLi
Ether
BuLi BuLi BuLi
Ether Ether Ether
Cupric chloride 3-Cyclohexenylcarboxaldehyde cis-4-Dimethylaminocyclohexyl 2-thienyl ketone trana4Dimethylaminocyclohexyl 2-thienyl ketone N,N-Dimethylcarbamoyl chloride Dimethyl sulfate Ethyl bromide 2-Ethylbutyraldehyde
4-Chloro-3methylisothiazole
Thiophene
2-benzoyl furan
Diphenyl-2-furylcarbinol 2-n-But ylfuran
2-Furoic acid l-(2-Furyl)cyclohexanol Di(2-fury1)methylcarbinol Di(2-fury1)phenylcarbinol Isopropyl-2-furylcarbinol Methylethyl-2-furylcrbinol
+
2-Thieny l-3-cyclohexeny lcarbinol
Bis(a-thienyl) ketone 2-Methylthiophene 2-Ethylthiophene 1-(2-Thieny1)-2-ethyl1-butanol
319 21 1 392
207 65 61 72
319 319 211
J. M. Mallan and R. 1. Bebb
724
Tabte VI (Continued) Compound rnetalated
Pyrrole 3-Methylisothiazole
4Methylisothiazole CMethylthiazole
1-Butyne
1,l-Dimethyl2,2-dibromoethylene 1,2-Dichloroethylthioethyiene N-Methylimidazole
1-Methylpyrazole
Ethoxyacetylene
RLi
Solvent
Reactant
PhLi
Ether
PhLi
Ether
BuLi
Ether
BuLi PhLi
Ether Ether
BuLi BuLi BuLi BuLi BuLi BuLi BuLi BuLi
Ether Ether Ether Ether Ether Ether Ether THF
cis-Ethyl 4-dimethylaminocyclohexylcarboxylate trans-Ethyl 4-dirnethylaminocyclohexylcarboxylate ZEthylhexaldehyde n-Hexaldehyde 1-Methyl4 piperidone n-Octyl bromide Perchloryl fluoride Phenyl thiocyanate Propionalde hyde Sulfur dioxide Tritium oxide Carbon dioxide Carbon dioxide
BuLi
THF
BuLi BuLi
THF THF
BuLi
THF
BuLi BuLi
Final product
x
yield
Ref
cis-4-Dimethylaminodi(2-thienyl)cyclohexylcarbino1
86
h
trans-4-Dimethylaminodi(2-thieny1)cyclohexylcarbinol
68
h
15
21 1
63 34
21 1
1-(2-Thienyl)hexanol 4-(2-Thienyl)-l-methyl-4hydroxypiperidine 2-n-Octylthiophene 2-Fluorothiophene 2-Thienyl phenyl sulfide 1-(2-Thienyl)propanol Lithium 2-thiophenesulfinate 2-T-Thiophene Pyrrole-1-carboxylicacid 3-Met hylisothiazole-5-carboxylic acid 5-Formyl-3-met hylisothiazole
46 49 59 68
i
319
i
50
313 211 208 228 354 388
50
388
3,5-Dimethylisothiazole 4-Methylisothiazole-5-carboxylic acid
28 40
388 388
5-Formyl-4-meth ylisothiazole
55
388
Ether
Dimethylformamide Acetaldehyde
2-(a-Hydroxyethyl)-4-methylthiazole
48
390
Ether
Butyraldehyde
4-Methyl-2-thiazolylpropyl-
93
391
42
391
26 51
391 391
39
265
Dimethylformamide Methyl iodide Carbon dioxide
BuLi
Ether
Ethylene oxide
BuLi BuLi
Ether Ether
Methyl iodide Propylene oxide
BuLi BuLi
Hexane Hexane
Carbon dioxide Trimethylchlorosilane
carbinol (Hydroxy-2-ethyl)-2-methyl-4thiazole 2,4-Dimethylthiazole 2-(2-Hydroxypropyl)-4-methylthiazole 2-Methylglutaric acid 1,1,3-Tris(trimethylsilyl)-l,2butadiene 1,3,3-tris(trimethylsily1)-1-butyne 2-Bromo-3,3-dimethylacrylic acid
51
34
+
264 94
188
63
416
BuLi
THF
Carbon dioxide
BuLi
Ether
Acetone
l-Thioethyl-3-methyl-3-hydroxybutyne
BuLi BuLi
Ether Ether
Benzophenone Carbon dioxide
BuLi
Ether
BuLi
Ether
1-Naphthyl isocyanate Benzophenone
BuLi
Ether
Carbon dioxide
PhLi
Ether
Carbon dioxide
BuLi PhLi PhLi PhLi PhLi
Ether Ether Ether Ether Ether
Dimethyl sulfate Acetaldehyde Benzaldehyde Heptaldehyde Propionaldehyde
(2-1midazolyl)diphenylcar bin01 86 1-Methyl-2-imidazolecarboxylic 32 acid 1-methyl-5-imidazole1.5 carboxylic acid N-a-Naphthyl-1-methyl-2-imid- 66 azolecarboxamide 87 Diphenyl(1-methyl-5-pyrazoly1)carbinol 54-66 1-Methyl-5-pyrazolecarboxy'ic acid 39 1-Methyl-5-pyrazolecarboxylic acid 15 1,5-Dimethylpyrazole 42 1-Ethoxybut-1-yn-3-01 72 1-Ethoxy-3-phenylprop-1-yn-3-01 50 1-Ethoxvnon-1-vn-3-01 1-Ethoxypent-1-yn-3-01 41
+
358 358 358 a U
a a k k k k
Metalations by Organolithium Compounds
725 Table VI (Continued)
Compound metalated
Ethylthioacetylene 1,3-Dithiane
Ethyl ether Tetramethylammonium bromide
1-Vinylcarborane
RLi
3-Methylisot hiazole-4carboxylic acid Cyclopentadiene
s
Ref
Final product
yield
Ethylthiopropynoic acid (isolated as S-benzylthiuronium salt) Ethyl ethylthiopropynoate
63
I
56
I
2-(Hydroxyphenylmethyl)-1,3dithiane 2-(Dihydroxyphenylmethyl)-1,3dithiane 2-(Acetaldehyde diethyl acetal)1,3-dithiane
91
343
80
343
77
343
2-( 1-Hydroxycyclohexyl)-1,3dithiane 24 l-Hydroxycyclopentyl)-1,3dithiane lI3-Di(2-thiany1)propane
85
343
70
343
66
344
84
344
80
343 343
Ether
Carbon dioxide
MeLi
Ether
BuLi
Hexane
Ethyl chlorocarbonate Benzaldehyde
BuLi
Hexane
Benzophenone
BuLi
Hexane
BuLi
Hexane
8-Bromoacetaldehyde diethyl acetal Cyclohexanone
BuLi
Hexane
Cyclopentanone
BuLi
Hexane
BuLi
Hexane
BuLi BuLi Cyclohexyllithium PhLi
Hexane Hexane Ether
1,3-Dibromopropane 1,CDibromobutane Isopropyl iodide Propionaldehyde Carbon dioxide
Ether
Benzaldehyde
Trimethyl(2-phenyl-2-hydroxyethy1)ammonium bromide
58
m
PhLi
Ether
Benzophenone
21
1)1
PhLi
Ether
Fluorenone
Trimethyl-(2,2-diphenyl-2hydroxyethy1)ammonium bromide Trimet hyl(9-hydroxy-9-fluorenylmethy1)ammonium bromide 1-Vinyl-2-carboxycarborane 2 4 I-Vinyl-2-carborany1)ethanol
60
m
72
471 474
Bis(viny1carboranyl)mercury Methyl(vinylcarboranyl)mercury
51 51
473 473
1-( l-Vinyl-2-carboranyl)-2-pro-
72
474
4
308
80
308
68
308
28
360
34
i
52
388
37
n
BuLi BuLi
BuLi
Pyridotetrazole Pyridine
Reactant
PhLi
RLi RLi
2-Cyanothiophene 3-Cyanothiophene
Soluent
BuLi
Benzene Ether Ether Benzene Ether Benzene Ether Ether
Carbon dioxide Ethylene oxide Mercuric chloride Methylmercuric chloride Propylene oxide Carbon dioxide
3-Thienyllithium BuLi
Ether
Carbon dioxide
Ether
Carbon dioxide
PhLi
Ether
Carbon dioxide
PhLi
Ether
BuLi
THF Hexane
l-Methyl-4piperidone Bromine
PhLi
Ether
Benzoyl chloride
BuLi PhLi
Ether Ether
PhLi
Ether
BuLi
Ether
BuLi
Ether
Carbon dioxide o-Chlorobenzoyl chloride pChlorobenzoy1 chloride Chlorodiethylsilane 1,5-Dichlorohexamethyltrisiloxane
2-Isopropyl-l,3-dithiane 2-( 1-Hydroxypropyl)-1,3-dithiane 3-Cyclohexylpropionic acid
panol 5-Cyano-2-thiophenecarboxylic acid 3-Cyano-2-thiophenecarboxylic acid 3-Cyano-2-thiophenecarboxylic acid 5,8-Pyridotetrazoledicarboxylic acid 4-(2-Pyridyl)-l-methyl-4-liydroxypiperidine 5-Bromo-3-methylisothiazole-4carboxylic acid l-Benzoyl-6-hydroxy-&phenylfulvene Cyclopentadienecarboxylic acid l-(~-Chlorobenzoyl)-6-hydroxyB(o-chlorop heny1)fulvene 1-(p-Chlorobenzoy1)-&hydroxy&(p-chlorophenyl)fulvene Diet hylcyclopentadienylsilane
144
72
0
26
n
50
n
15
P
1-Cyclopentadienyl-5-chlorohexa- 40 methyltrisiloxane
441
J. M. Malian and R. L Bebb
726
Table VI (Continued) Compound metalated
2-Methylfuran
2-Methoxythiophene
3-Methoxythiophene Methyl 3-thienyl sulfone
Solvent
Reactant
Final oroduct
weld
BuLi
Ether
1,3-Dichlorotetramethyldisiloxane Dimethyldichlorosilane 2,3-Diphenylindone p-Methylbenzoyl chloride Methyltrichlorosilane p-Nitrobenzoyl chloride Phenylazocyclopentadienyllithium, FeCla Titanium tetrachloride pToluenesulfony1 azide Sulfur, n-butyl bromide Sulfur, ethyl iodide Sulfur, isobutyl bromide Acetophenone
I-Cyclopentadien yl-3-chlorotetra-
57
441
Cyclopentadienyldimethylchlorosilane 2,3-Diphenyl-3-(2,4-cqclopentadieny1)-I-indanone 1-(p-Toluoyl)-6-h)droxq-6-(ptoluoy1)fulvene Cyclopentadien>Iniethyldichlorosilane l-(p-Nitrobenzoyl)-6-hydroxy-6(p-nitropheny1)fulvene Phenylazoferrocene
69
441
27
4
44
n
55
441
39
n
6
448
Dicyclopentadienyltitanium dichloride Diazocyclopentadjene
74
451
35
r
66
e
77
e
59
e
11
S
17
S
69
S
72
S
61 67
320 320
5-Methoxy-2-methylthiophene 2-(5-Methoxy-2-thienyl)ethanol 5-(9-Fluorenylidene)-2(5H)-thiophenone
40 50
320
58
S
3-Methoxy-2-thiophenecarboxylic acid 24 3-Thienylsu1fonyl)acetic acid
86
304
60
305
5-Methyl-2-thiophenecarboxylic acid 2-Fluoro-5-methylthiophene (5-Methyl-2-thieny1thio)acetic acid 3-Methyl-5-thiophenecarboxylic acid 3-Methylthiophene-5-carboxylic acid 3-methylthiophene-2carboxylic acid 3-Methylthiophene-Scar boxylic acid 3-methylthiophene-2carboxylic acid
84
311
44
j
BuLi
Ether
BuLi
Ether
PhLi
Ether
BuLi
Ether
PhLi
Ether
PhLi
Ether
BuLi
Xylene
PhLi
Ether
BuLi
Ether
BuLi
Ether
BuLi
Ether
PhLi
Ether
Ref
methyldisiloxane
5 4 1-Phenyl-l-ethylidene)-2(5H)-
thiophene PhLi PhLi BuLi
Ether Ether Hexane
Allyl chloride Benzaldehyde Benzophenone
PhLi
Ether
Benzophenone
PhLi PhLi
Ether Ether
PhLi PhLi BuLi BuLi
Ether Ether Ether Hexane Ether
Carbon dioxide N,N '-Dimethylformamide Dimethyl sulfate Ethylene oxide 9-Fluorenone
BuLi
Ether
BuLi
3-Methylthiophene
?
RLi
Carbon dioxide Carbon dioxide Carbon dioxide
BuLi BuLi
Ether Ether
BuLi
Ether
Perchloryl fluoride Sulfur, ethyl 8bromoacetate Carbon dioxide
BuLi
Ether
Carbon dioxide
PhLi
Ether
Carbon dioxide
BuLi
Ether
BuLi
Ether
N,N-Dimethylformamide N,N-Dimethylformamide
5-Methoxy-2-allylthiophene J-Benzylidene-2(5H)-thiophene 5-Diphenylmethylene-2(SH)-thiophenone 5-Diphenylmethylene-2(5H)-thiophenone 5-Methoxy-2-thenoic acid 2-Methoxy-2-thenaldehyde
320
t
U
68
231
+
61 19
319
+
68 19
319
83 17 61
316
+
3-Methyl-Sthiophenaldehyde 3-methyl-2-thiophenealdehyde
3-Methyl-5-thenaldehyde
318
Metalations by Organolithium Compounds
721
Table VI (Continued)
Compound metalated
RLi
Solvent
Methyl 2-thienyl sulfide
BuLi
Ether
Carbon dioxide
BuLi
Ether
BuLi
Ether
Sulfur, methyl iodide Carbon dioxide
BuLi
Ether
Carbon dioxide
3BuLi
Ether
Carbon dioxide
BuLi
Ether
Acetaldehyde
BuLi
Ether
Butyraldehyde
PhLi
Ether
Carbon dioxide
BuLi BuLi
Hexane Hexane
Benzonitrile Benzophenone
BuLi BuLi
Hexane Hexane
BuLi
Hexane
Benzyl bromide Benzylideneaniline Cyclohexanone
BuLi
Hexane
BuLi
Hexane
BuLi
Hexane
BuLi
Hexane
BuLi
Hexane
BuLi
Hexane
Ethyl chloroformate Ethyl cyclohexanecarbox ylat e Ethyl formate
BuLi
Hexane
Isopropyl iodide
Methyl 3-thienyl sulfide N-Methylpyrrole N-Methylpyrrole 2,4-Dimethylthiazole
1,5-Dimethylpyrazole 2-Methyl-1,3dithiane
Isopropylcarborane Pentachlorobenzene Pentafluorobenzene 1,2,4,5-Tetrachlorobenzene 1,2,4,5-Tetrafluorobenzene
yield
Ref
5-Methylthio-2-thiophenecarboxylic acid 2,5-Bis(methylthio)thiophene
87
U
57
U
3-Methyl-2-thiophenecarboxylic 60-70 acid 42 N-Methylpyrrole-2-carboxylic acid N-Methylpyrrole-2,5-dicarboxylic 58 acid 57 2,4-Dimethyl-5-( 1-hydroxyethy1)thiazole 72 2,4-Dirnethyl-5-(1-hydroxybutyl)thiazole 34 1,3-Dimethyl-5-pyrazolecarboxylic acid 80 2-Methyl-2-benzoyl-l,3-dithiane 2-Methyl-2-(diphenylhydroxy83 methyl)-l,3-dithiane 2-Benzyl-2-methyl-l,3-dithiane 90 2-Methyl-2(a-anilinobenzyl)-1,370 dithiane 2-Methyl-1-(l-hydroxycyclo80 hexyl)-l,3-dithiane 89 1,4-Di(2-methyl-2-thianyl)butane
306
N,N-Diethyl-2-methyl-1,3-dithiane-Zacetamide
50
343
2,2 '-(a-Hydroxybenzy1idene)bis(2-methyl-l,3-dithiane) 2-Methyl-l,3-dithiane-2-carboxylic acid ethyl ester 2-Methyl-2-cyclohexanoyl-1,3dithiane a-Oxopropionaldehyde dithioketal
95
344
60
344
60
344
50
344
2-Methyl-2-isopropyl-l,3-
84
343
394 354 39 1 391 a
344 343 343 343 343 344
70
343
90
487
3-Heptanol
55
487
79
470
59
C
Carbon dioxide Carbon dioxide
Isopropenylcar boranecarboxylic acid Methylisopropen ylcarborane a-(1sopropylcarboranyl)benzyl alcohol 1-Isopropyl-2-carboxycarborane Pentachlorobenzoic acid
91
471 420
Carbon dioxide
Pentafluorobenzoic acid
82
418
BuLi
Hexane THF Ether
Carbon dioxide
2,3,5,6-Tetrachlorobenzoicacid
420
2BuLi
THF
Carbon dioxide
BuLi
Hexane THF
Carbon dioxide
48 27 30 42 3 67
BuLi
Hexane Ether
Carbon dioxide
85
419
Hexane
Styrene oxide
BuLi
Ether
Ethyl bromide (NaOH, H20d Ethyl bromide (NaOH, H20d Carbon dioxide
PhLi BuLi
Ether
MeLi BuLi
1-Isopropenylcarborane
1,4-Dibromobutane N,N-Diethyl-2chloroacetamide Ethyl benzoate
?
Final product
dithiane 2-Methyl-2-(2-hydroxy-Z-phenylethyl)-l,3-dithiane 3-Heptanol
BuLi 1,l-Diboropentane
Reactant
BuLi BuLi BuLi
THF
Methyl iodide Benzaldehyde
+ tetrachloroterephthalic acid 2,3,5,6-Tetrachlorobenzoicacid + tetrachloroterephthalic acid 2,3,5,6-Tetrafluorobenzoicacid + 2,3,5,6-tetrafluorotere-
470
420 418,419
phthalic acid 2,3,5,6-Tetrafluorobenzoic acid
J. M. Mallan and R L Bebb
728
Table VI (Continued) Compound metalated
1,2,3,4Tetrafluorobenzene 2,3,5,dTetrafluorophenol 2,3,5,6-Tetrafluorothiophenol 2,3,5,dTetrafluoroaniline m-Difluorobenzene Fluorobenzene Phenyllithium 2-Methoxythiophene 2-Methylthiophene 5-Methylpyridotetrazole CMethylpyridotetrazole 8-Methylpyridotet razole 2- Methylpyridine
?
Ref
yield
Solvent
BuLi
Hexane THF
Carbon dioxide
2,3,4,5-Tetrafluorobenzoicacid
BuLi
THF Hexane
Carbon dioxide
4-Hydroxy-2,3,5,6-tetrafluorobenzoic acid
83
421
BuLi
Ether Hexane
Carbon dioxide
4-Thiol-2,3,5,6-tetrafluorobenzoic 77 acid
421
BuLi
THF Hexane
Carbon dioxide
4-Amino-2,3,5,6-tetrafluorobe.nzoic acid
45
421
BuLi
THF Hexane THF
Carbon dioxide
2,dDifiuorobenzoic acid
88
421
Carbon dioxide
0-Fluorobenzoic acid
60
183
Carbon dioxide
21
78
316
BuLi
Ether
Methyl ptoluenesulfonate Dimethyl sulfide
Terephthalic acid (2) Isophthalic acid (1) 5-Methoxy-2-methylthiophene
5
BuLi
Pentanebenzene Ether
5-Methy lthio-2methylthiophene
75
316
PhLi
Ether
Carbon dioxide
5-Pyridotetrazoylacetic acid
42
360
PhLi
Ether
Carbon dioxide
dMethylpyridotetrazole-5,8dicarboxylic acid
11
360
PhLi
Ether
Carbon dioxide
5-Carboxy-8-methylpyridotetrazole
18
360
PhLi
Ether
347
Ether
(o-Aminopheny1)-(pmethoxyphenol)(2-pyridylmethyl)carbinol 2-Phenethylpyridine dibenzyl2-pyridylmethane 4-(2-Pyridyl)butanal diethyl acetal Di(2-pyridy1)methane tri(2pyridy1)methane 2-Amylpyridine C(2-Pyridy1)butanal diethyl acetal C&NCH,( CH2)n-H 3-(2-Pyridyl)propanal diethyl acetal 1,5-Diphenyl-6-(2-pyridyl)l,3hexadien-5-01 l@-(a-Picoly1)quinolizidine
78
PhLi
2-Amino-Cmethoxybenzophenone Benzyl chloride
38
V
BuLi BuLi
PhLi
Ether
PhLi
Ether
PhLi PhLi
Ether Ether
PhLi PhLi
Ether Ether
PhLi PhLi
Ether
PhLi PhLi PhLi
Ether Ether
PhLi PhLi PhLi PhLi PhLi PhLi
Ether Ether Ether Ether Ether Ether
PhLi PhLi
Ether Ether
Reactant
Final product
RLi
3-Bromopropanal diethyl acetal 2-Bromopyridine n-Butyl bromide 3-Chloropropanal diethyl acetal Cl(CH&mH 2-Chloroethanal diethyl acetal Cinnamylideneacetophenone AS( 10)-Dehydroquinolizidinium perchlorate Ethyl benzoate Ethyl bromide Isobutyl borate Isopropyl bromide Methyl acetate Methyl benzoate Methyl furoate Methyl iodide Methyl isobutyrate Methyl isovalerate Methyl propionate
+
+
418
52
37
W
30 25 79 60
0 0 W
40-65
X
38-49
W
Y 65
z
Phenyl tpicolyl ketone 2-Propylpyridine Lithium triisobutoxy-2-picolylborate
80 92 97
aa
2-Methyl-disobut ylpyridine
93 36 82 58 73 61
Acetyl 2-picolyl ketone Phenyl 2-picolyl ketone Fury1 2-picolyl ketone 2-Ethylpyridine Isobutyryl2-picolyl ketone Isovaleryl 2-picolyl ketone Propionyl2-picolyl ketone
67 50
V
348 V
aa
aa aa V
aa aa aa
729
Metalations by Organolithium Compounds
Table VI (Continued) Compound metalated
CMethylpyridine
Methylcyclopentadiene 2-Ethylfuran 2-(Ethy1thio)furan 2-Methoxy5-methylthiophene 2,fDirnethylthiophene 3,CDimethylthiophene 3,5-Dimethylthiophene Ethyl 2-thienyl sulfide Methyl 5methyl-2thienyl sulfide 5-Methyl-4ethylthiazole 1-Hexyne 1,2-Bis(ethylt hio)ethylene
2-Carboranylethyl acetate 1-Butylcarborane Bis(1-arboranylmethyl) ether
Solvent
Reactant
PhLi
Ether
PhLi
Ether
PhLi
Ether
PhLi PhLi PhLi
Ether Ether Ether
Methyl 2-thiophenecarboxylate Phenyl di(isobuty1)borate 5-Phenyl-2,Cpentadien- 1-a1 Propionaldehyde n-Propyl bromide Acetyl bromide
MeLi
Ether
Benzyl chloride
PhLi
Ether
MeLi PhLi
Ether Ether
MeLi MeLi PhLi MeLi BuLi
Ether Ether Ether Ether Ether
2-Bromoethanal diethyl acetal n-Butyl bromide Carbon dioxide, ethanol Ethyl bromide Isopropyl bromide n-Propyl bromide n-Propyl bromide Ferric chloride
BuLi
Ether
BuLi
Ether
BuLi
Ether
Sulfur, ethyl iodide Sulfur, ethyl iodide Carbon dioxide
BuLi
Ether
Carbon dioxide
4,5-Dirnethyl-2-thenoic acid
318
BuLi
Ether
Carbon dioxide
3,4-Dimethyl-2-thenoic acid
318
BuLi
Ether
BuLi
Ether
N,N-Dimethylformamide Carbon dioxide
BuLi
Ether
Carbon dioxide
BuLi
Ether
Propylene oxide
RLi BuLi
Ether Ether
Paraformaldehyde Acetone
BuLi
Ether
Benzaldehyde
BuLi
Ether
Cyclohexanone
BuLi
Ether Heptane
Carbon dioxide
BuLi
Final product
?
RLi
74
aa
Lithium diisobutoxy-2-picolylphenylborate l-Phenyl-6-(2-pyridyl)-I,3,5-hexatriene 2-(~-Hydroxybutyl)pyridine 2-Butylpyridine 1-(CPyridyl)-2-propanone
37
348
15
bb
L'
CPhenethylpyridine dibenzylCpyridylmethane 3-(4Pyridyl)propanal diethyl acetal
43 47 39
u
4-n-amyl pyridine
74 34
u
Ethyl p-(Cpyridyl)acetate 4-n-Propy lpyridine CIsobutylpyridine
74 82
u
Cn-butyl pyridine
60
Cn-Butylpyridine 1,l '-Dimethylferrocene
69
+
2-Methoxy-5-1nethyl-3-thenoic acid
BuLi
Ether
Ethylene oxide
BuLi
Ether
Paraformaldehyde
352
352 352
v 353 u
447 76
e
77
e
50
320
69
318
77
U
27
U
5-Methyl-Cethyl-2-(2-hydroxypropy1)thiazole
76
391
Hept-2-yn-1-01 l-Ethylthio-3-hydroxy-3-methyl1-butyne l-Ethylthio-3-hydroxy-3-phenyl1-propyne 1-(Ethylthioethynyl)-1-hydroxycyclohexane 2-(2-Hydroxyethyl)carboranecarboxylic acid
80 70
209 147
56
147
55
147
5-Ethylthio-2-thiophenecarboxylic acid 2-Methylthio-5-methy1-3-thiophenecarboxylic acid
Bis(2-carboxy- l-carboranylmethyl) ether Bis(2-~-hydroxyethyl-l-carboranylmethyl) ether Bis(2-hydroxymethyl-1-carboranylmethyl) ether
Carbon dioxide
cc
74 34
1-Butyl-2-carboxycarborane
THF
Ref
2-Thienyl 2-picolyl ketone
Carbon dioxide
BuLi
yield
475 471 50-9 1
dd
86
dd
50
dd
J. M. Mallan and R. 1. Bebb
730
Table VI (Continued) Compound metalated 2,3,5,6Heptafluorotoluene 2,3,5,6-Tetrafluorobenzoic acid
RLi
Benzal chloride
p-Bromoanisole o-Fluorotoluene pFluorotoluene pIodoanisole Norbornadiene Toluene
Phenyl methyl ether rn- Methoxyphenol
Final product
BuLi
Hexane THF
Carbon dioxide
BuLi
Hexane THF Hexane Ether Hexane THF Hexane Ether
Carbon dioxide
Tetrafluoroterephthalic acid
Chlorine
4-Chloro-2,3,5,6-tetrafluorobenzoic acid 4-Thiol-2,3,5,6-tetrafluorobenzoic acid
BuLi
Ether
BuLi
Ether
BuLi
BuLi
THF Hexane THF Hexane Ether
N,N-Dimethylcarbamoyl chloride Triphenylsilyl bromide Carbon dioxide
BuLi
Ether
Poly-p-styryllithium 2,4,6PhrPhLi BuLi
Ether
BuLi
BuLi
BuLi 2-(Propynyl)thiophene
Reactant
4-Trifluoromethyl-2,3,5,6-tetrafluorobenzoic acid
BuLi 2,3,5,6-Tetrafluorotoluene Benzothiazole
Solvent
Sulfur Carbon dioxide
4-Methyl-2,3,5,6-tetrafluoro-
? yield
Ref
77
42 1
94
419 419
69
419
88
421
benzoic
Tetramethylethylene Carbon dioxide
207
Bis(2-benzothiazolyl)ketone 2-Triphenylsilylbenzothiazole Phenylglyoxylic acid
19 42-61
ee 186, 195
48
186
37
tft
21
Ilt
34
g
25
172
N,N-Dimethylformamide Carbon dioxide
1-Chloro-1-phenyltetramethylcyclopropane 5-(Propynyl)thiophene-S-carboxylic acid 5 4 I-Propynyl)-2-formylthiophene 5-Bromo-2-methoxybenzoic acid
Carbon dioxide
5-Bromo-2-methoxybenzoic acid
THF
Carbon dioxide
2-Fluoro-3-methylbenzoicacid
3
183
BuLi
THF
Carbon dioxide
2-Fluoro-5-methylbenzoic acid
58
183
Poly-p-styryllithium BuLi
Ether
Carbon dioxide
5-Iodo-2-methoxybenzoicacid
22
g
Ether
Carbon dioxide
15
267
Hexane
Benzophenone
endo-2-Norcamphanecarboxylic acid Benzyldiphenylcarbinol
85
50
Carbon dioxide
Phenylacetic acid
24
170
BuLi
Ether THF Ether
Carbon dioxide
2-Methoxybenzoic acid
10
ff
BuLi
Ether
Carbon dioxide
2-Methoxy-6-hydroxy benzoic acid 2-methoxy-4-hydroxybenzoic acid 2-Methoxy-3-hydroxybenzoic acid 2-hydroxy-3-methoxybenzoic acid 3-Formyl-2-thiophenecarboxylic acid
13
300
BuLiDABCO BuLi
o-Methoxyphenol
BuLi
Ether
Carbon dioxide
3-Thiophenecarboxaldehyde ethylene acetal Phenyl methyl sulfide Thioanisole
BuLi
Ether
Carbon dioxide
BuLi
Ether
Tetraethoxysilane
BuLiDABCO BuLiDABCO BuLiDABCO BuLiDABCO
Hexane
Acetone
THF
Benzophenone
Hexane Hexane
+
5
2 2
300
78
312
Tetra(benzenethiomethy1)silane
42
gg
77
330
93
330
Deuterium oxide
1-Phenylmercapto-2-hydroxy2-methylpropane Phenyl (2J-diphenyl-2-hydroxy)ethyl sulfide Thioanisole-a-D
99
330
Isopropyl iodide
Phenyl isobutyryl sulfide
55
330
-+
731
Metalations by Organolithium Compounds
Table VI (Continued) Compound metalated 2-Ethylpyridine CEthylpyridine 2,CDimethylpyridine
RLi
Solvent
Reactant
Final product
x
weld
Ref
PhLi PhLi PhLi
Ether Ether Ether
Ethyl bromide Methyl iodide n-Butyl bromide
2-see-Butylpyridine 2-Isopropylpyridine 2-(4 '-Pyridy1)hexane
91 63 30
v
PhLi
Ether
Benzaldehyde
CMethyl-2-picolylphenylcarbinol
86
349
PhLi
Ether
Benzonitrile
28
350
2PhLi PhLi 2PhLi
Ether Ether Ether
Benzonitrile Benzyl chloride Benzyl chloride
30 20 25
350 350 350
PhLi
Ether
15
350
PhLi
Ether
67
hh
BuLi
Ether
1-Chloro-l,2diphenylethane Methyl benzoate, benzoyl chloride Carbon dioxide
BuLi
Ether
Deuterium oxide
BuLi
Ether
Methyl iodide
2,5-DimethylCethylthiazole
BuLi
Ether
Acetaldehyde
BuLi
Ether
Butyraldehyde
2-Isopropyl1,3-dithiane
BuLi
Hexane
Benzophenone
BuLi BuLi
Hexane Ether Heptane
Isopropyl iodide Ethylene oxide
Poly-p-styryllithium PhrSiLi PhLi
Et her
Carbon dioxide
THF Ether
BuLi
Ether
BuLi
Hexane Ether THF
Carbon dioxide N,N-Dimethylcarbamoyl chloride Triphenylchlorosilane Carbon dioxide
Tricyclo[4.1.0.02,7]heptane
3-Carboranylpropyl acetate Phenylacetylene
3-Phenylsydnone Benzofuran
Phenoxy-l,2dichloroethylene Thiaindene Thianaphthene
Poly-p-styryllithium BuLi
Ether
Carbon dioxide
a-Methyl-a '-phenacylpyridine 2-Methyl-5-phenethylpyridine 2-Methyl-6-(dibenzyImethyl)pyridine 1,2-Diphenyl-3-(a-picolyl-a ')propane 2-Phenacyl-6methylpyridine l-Carboxytricyclo[4.1.O.O2,7]heptane l-Deuteriotricyclo[4.1.0.02J]heptane l-MethyItricyclo[4.1.0.02J]Octane 5-Methyl-Cethyl-2(2-hydroxypropy1)thiazole 5-Methyl-Cethyl-2-(3-hydroxypenty1)thiazole 2-Isopropyl-2-(diphenylhydroxymethyl)-l,3-dithiane 2,2-Diisopropyl-l,3-dithiane 1,2-Bis-2,2'-h ydroxyethylcarborane
v
353
266 266 266
60
391
60
391
52
343
70
343 480
Phenylpropynoic acid
65
g
Phenylpropynoic acid N,N-Dimethylpropiolamide
40
271 207
Triphenylphenylethynylsilane
72
171
3-Phenylsydnone-4-carboxylic acid Benzofuran-Z-carboxylic acid
60
387
15
g
BuLi
Ether
N,N-Dimethylcarbamoyl chloride Cyclohexanone
BuLi BuLi
Ether Ether
Diethyl sulfate Acetaldehyde
2-Ethylthiaindene Methyl-2-thianaphthenylcarbinol
81-91 72
ii-kk
BuLi BuLi BuLi BuLi
Ether Ether Ether Ether
Phenyl-2-thianaphthenylcarbinol 2-Bromothianaphthene 2-Thianaphthenecarboxylic acid
70 39 82 68
325 325 231 325
BuLi
Ether
47
325
BuLi
Ether
BuLi BuLi
Ether Ether
Benzaldehyde Bromine Carbon dioxide pchlorobenzaldehyde pDimethylaminobenzaldehyde N,N-Dimethylcarbamoyl chloride Fluorobenzene Formaldehyde
Bis(2-benzofuranyl) ketone
1-(Phenoxyethyny1)cyclohexanol
60
416
pChloropheny1-2-thianaph-
thenylcarbinol p-Dimethylaminophenyl-2-naphthenylcarbinol Bis(2-thianaphthenyl) ketone 2-Phenylthianaphthene 2-Thianaphthenylmethanol
207
325
207 55
48
II mm
J. M. Mallan and I?.1. Bebb
132
Table VI (Cotitimed) Cornpowid metalated
CJIa2
W$Z CJI7N CJf7N
2,2'-Bithienyl 2,3'-Bithienyl
Indole Phenylacetonitrile
RLi
Solvent
Reactant
BuLi
Ether
BuLi BuLi
Ether Ether
Methyl o-toluenesulfonate Perchloryl fluoride Phenyl isocyanate
BuLi
Ether
o-Tolyl isocyanate
BuLi
Ether
PhLi PhLi
Ether Ether
Triphenylchlorosilane Carbon dioxide Carbon dioxide
Ref
43
325
BuLi BuLi BuLi BuLi
Ether Ether THF THF
Carbon dioxide Benzophenone n-Butyl bromide rr-Butyl bromide
BuLi
THF
Carbon dioxide
Ether Ether Ether
Carbon dioxide Carbon dioxide Carbon dioxide
Phenylcyanoacetic acid Phenylcyanoacetic acid Pheny lcyanoacetic acid
38-47 38-47 38-40
Carbon dioxide Carbon dioxide Deuterium oxide
Phenylcyanoacetic acid Phenylcyanoacetic acid a,a'-Dideuteriophenylnitrile
38-47 38-47 89
Ethylene chloride
1-Phenyl-1-cyanocyclopropane
69
155
BuLi
Ether Ether THF Hexane THF Hexane Ether
42-55
178
BuLi
Ether
38
181
BuLi
Dioxane
Benzalacet ophenone Benzophenone
28
179
BuLi
Ether
Benzophenone
BuLi
Ether
BuLi BuLi
Ether Ether
BuLi
Ether
BuLi
Ether
sec-BuLi
Ether
Benzyl styryl ketone Carbon dioxide p-chlorobenzalacetophenone p-Methoxybenzalacetophenone p- Methoxystyryl benzyl ketone Benzophenone
r-BuLi
Ether
Benzophenone
Cyclohexyllithium 3,5-MezPhLi
Ether
Benzophenone
Ether
Benzophenone
EtLi
Ether
Benzophenone
i-AmLi
Ether
Benzophenone
i-PrLi
Ether
Benzophenone
p-MeOPhLi
Ether
MeLi
Ether
p-Methoxybenzyl ketone Benzophenone
2,4-Diphenyl-3-butyl-3-hydroxybutanoic acid 2,3-Diphenyl-4-benzoylbutyric acid 2,3,3-Triphenyl-3-hydroxypropionic acid 2,3,3-Triphenyl-3-hydroxypropionic acid CBenzoyl-2,3-diphenylbutyric acid Phenylmalonic acid I-Phenyl-2-(p-chlorophenyl)-4benzoylbutyric acid l-Phenyl-2-(pmethoxyphenyl)-4benzoylbutyric acid 4-Benzoyl-3-(pmethoxyphenyl)2-phenylbutyric acid 2,3,3-Triphenyl-3-hydroxypropionic acid 2,3,3-Triphenyl-3-hydroxypropionic acid 2,3,3-Triphenyl-3-hydroxypropionic acid 2,3,3-Triphenyl-3-hydroxypropionic acid 2,3,3-Triphenyl-3-hydroxypropionic acid 2,3,3-Triphenyl-3-hydroxypropionic acid 2,3,3-Triphenyl-3-hydroxypropionic acid 2,4-Diphenyl-3-(p-methoxyphenyl)-3-hydroxybutyric acid 2,3,3-Triphenyl-3-hydroxypropionic acid
BuLi Sodium phenyl acetate
2-Methylthianaphthene
?
yield
2-Fluorothianaph thene 70 N-Phenylthianaphthene-281 car boxamide N-o-Tolylthianaphthene-241 carboxamide 2-Triphenylsilyldibenzothio90 phene 5-(2'-Thienyl)-2-thenoic acid 74 2,3 '-Bithienyl-5'-carboxylicacid (38) 2,3 '-bithienyl-2 '-carboxylic 75 acid (52) 1-Indolecarboxylic acid 61 2,3,3-Triphenylacrylonitrile 30 Phenyl-n-butylacetonitrile 73 a,a '-Di-n-butylphenylaceto69 nitrile Phenylcyanoacetic acid 38-47
MeLi o-MePhLi a-Naphth yllithium PhLi PrLi BuLi
GH702Na
Firral product
+
4652
j
325 325 ee 321 321 355 180, 182 155 155 180, 182, 369 180, 182 180, 182 182
180, 182 180, 182 155
179, 182
38
182
30 51
179, 182 181
29
181
29
182
18
179, 182
12-14
179, 182
20
179, 182
72
182
18-21
179, 182
35
179, 182
23-25
179, 182
38 3
182 179, 182
133
Metalations by Organolithiurn Compounds ~~
~
Table VI (Continued) Compound metalated
RLi
Solvent
Reactant
m-MePhLi
Ether
m-Tolyl benzyl ketone Benzophenone
o-MePhLi
Ether
o-MePhLi o-MePhLi
Ether Ether
o-MePhLi
Ether
o-MePhLi
Ether
o-MePhLi
Ether
o-MePhLi
Ether
pMePhLi
Ether
a-Naphthy l(CdWLi a-CloHGi
Ether Ether
a-CloH7Li
Ether
a-CloHiLi
Ether
a-CloHiLi
Ether
a-CIoHiLi cu-CloHiLi a-CloHiLi
Ether Ether Ether
PhLi
Ether
PhLi PhLi
Ether Ether
PrLi
Ether
PrLi RLi
Ether Ether
RLi
Ether
RLi
Ether
o-CH~ C&Li 0-cH3C&Li
Ether
Carbon dioxide o-Chlorobenzyl chloride p-Chlorobenzyl chloride m-Cyanobenzyl chloride Diethyl adipate
Ether
Diethyl malonate
o-ma-
Ether
Ethyl acetate
o-CHSCsHLi
Ethdr
Ethyl benzoate
eCH3CeHaLi o-CH~C&Li o-CH~C6H4Li
Ether
Ethyl cinnamate
Ether Ether
Ethyl plienylacetate Ethyl sebacate
Ether Ether
Carbon dioxide Carbon dioxide
Benzyl chloride o-Chlorobenzyl chloride pChlorobenzy1 chloride p-Chlorostyryl benzyl ketone pcyanobenzy 1 chloride Styryl ketone p-Tolyl benzyl ketone Benzalaniline Benzal-pmethoxyaniline Benzal-p-methylaniline Benzal-P-naphthylamine Benzophenone Carbon dioxide Iodine a-Naphthyl benzyl ketone Benzophenone Carbon dioxide Phenyl benzyl ketone Benzophenone
CsHLi
Cas CSHsNa
Styrene 1-Methylbenzimidazole
BuLi BuLi
F
Find product
yield
2,4-Diphenyl-3(m-tolyl)-340-43 hydroxybutyric acid 2,3,3-Triphenyl-3-hydroxypro64-67 pionic acid 2,3-Diphenylpropionic acid 75-17 71-74 3-Phenyl-2-(o-chlorophenyl)propionic acid 3-Phenyl-2-(pchlorophenyl)70-72 propionic acid 51 4-Benzoyl-3-(p-chlorophenyl)2-phenylbutyric acid 3-Phenyl-2-(pcyanophenyl)80-85 propionic acid 45 2,3,7-Tripheny l-5-oxo-6heptenoic acid 45 2,CDipheny1-3-(ptolyl)-3hydroxybutyric acid 74 2,3-Diphenyl-3-aminophenylpropionic acid 78 2,3-Diphenyl-3-amino(p methoxypheny1)propionicacid 2,3-Diphenyl-3-amino(ptolyl)60 propionic acid 2,3-Diphenyl-3-amino(p-naph70 thy1)propionic acid 65-70 2,3,3-Triphenyl-3-hydroxypropionic acid 42 Phenylmalonic acid 53 2,3-Diphenylsuccinic acid 28 2,4-Diphenyl-3-(a-naphthyl)3-hydroxybutyric acid 2,3,3-Triphenyl-3-hydroxypropionic acid 42 Phenylmalonic acid 2,3,4-Triphenyl-3-hydroxybutyric 39-41 acid 42-48 2,3,3-Triphenyl-3-hydroxypropionic acid 25 Phenylmalonic acid 73 2-Phenyl-3-(o-chlorophenyl)propionic acid 70 2-Phenyl-3-(pchlorophenyl)propionic acid 82 2-Phenyl-3-(m-cyanophenyl)propionic acid 16 1,6-Diphenyl-2,5-hexadione 33 7-phenyl-6-oxoheptanoic acid 6 1,S-Diphenyl-2,4-hexadione ethyl 4-phenyl-3-oxobutyrate 12 Benzyl methyl ketone (66%) 2,4-diphenyl-3-methy1-3hydroxyglutaric acid (9 %) 5 2,3,4-Triphenyl-3-hydroxy41 glutaric acid benzyl phenyl ketone 48 2,3,6-Triphenyl-5-oxo-hexanoic 10 acid benzyl styryl ketone 2,4-Diphenyl-3-benzyI-3-hydroxy- 2 glutaric acid benzyl ketone 40 11-Phenyl-10-oxoundecanoic 64 31 acid 1,12-diphenyl-2,11decadione Trace 2-Phenylheptanoic acid
+ + +
+
+
+
+
I-Methyl-2-benzimidazolecar-
boxylic acid
45
Ref 182 182 182, nn 182 182 182 182 181,182 182 182 182 182 182 182 182 182 182 177 177 182 179, 182 182 182 182 182 173 173 173 173 173 173 173 273 359
J. M. Mallan and R L Bebb
734 Table VI (Continued) .
1.
CaHsS
cabs. WoNO CtHoON
Compound metaIated
5-Methyl-4Hcyclopenta[blthiophene 5-MethyldHcyclopenta[blthiophene Phenylacetamide N-Methylbenzamide
Mi
BuLi
BuLi
Ether
Carbon dioxide
CCarboxy indene
00
BuLi
THF Hexane Hexane THF Hexane THF Hexane THF Hexane THF Hexane THF
n-Butyl bromide
Phenyl-n-butylacetamide
87
371
Acetophenone
o-( 1-Hydroxy-1-phenylethy1)-Nmethylbenzamide 3-Phenylphthalide
43
378
49
378
o-Benzimidoyl-N-methylbenzamide a,a'-Diphenyl-a-hydroxy-Nmethyl-o-toluamide
53
378
81
318
a-(4-Chlorophenyl)-a-hydroxya-phen yl-N-methyl-o-toluamide Spiro[cyclohexane-1 ,1 '-phthalanl3'-one
51
378
21
318
1,2,3,4,4a,lOb-Hexahydro-6Hdibenzo[b,cfjpyran-done Spiro[fluorene-9,1'-phthalanl3'-one 1,l '-Di-t-butylferrocene 1,l '-Bis(a,a '-dimethylbenzyl)ferrocene 1,l '-Di(a,a '-dimethylbenzylcyclopentadieny1)nickel Nona-2,Lt-diyn-l-ol Triphenylbenzylsilane
11
378
58
318
94 73-90
434
63
452
71 15
209 39
5
294
16
294
2.5BuLi
WlOOt WlOOS
pChlorobenzophenone
Ether
3,8-Octadiyne Benzyl methyl ether '.o-Methylanisole
RLi 2Li
Ether THF
BuLi
Ether
pMethylanisole Hydroquinone dimethyl ether Resorcinol dimethyl ether Resorcinol dimethyl ether 2-Methyl-2(2-thienyl)1,3-dioxolane
BuLi
Ether
Carbon dioxide
acid 2-Methoxy-lmethylbenzoic acid
Poly-pstyryllithium
Ether
Carbon dioxide
2,5-Dimethoxybenzoicacid
6
Carbon dioxide
2,6-Dimethoxybenzoicacid
35
172
Dimethylfulvene
Mesityllithium
Cyclohexene oxide Fluorenone Ferric chloride Ferric chloride Tetrapyridinenickel chloride Paraformaldehyde Triphenylchlorosilane Carbon dioxide
o-Methoxyphenylaceticacid
+
434
g
Poly-p-st yryllithium
Ether
Carbon dioxide
2,dDimethoxybenzoic acid
48
g
BuLi
Hexane Ether Hexane Ether Hexane Ether Hexane Ether Hexane Ether
Benzaldehyde
Phenyl-Zthienyl(Sacetylethyleneketa1)carbinol 2-Acetyl-5-benzoylthiophene
60
302
66
302
2-Acetyl-5-thiophenecarboxylic acid 2-Methyl-2-(2-thienyl-5-trimethylsilyl)-l,3-dioxolane Phenyl(2-acetylethylene ketal)+ thiophenecarboxylic acid amide Triphenyl(ptoluenesulfony1methy1)silane
70
302
96
302
65
302
31
gg
BuLi
BuLi BuLi Methyl ptolyl sulfone
Cyclohexanone
2-methox y-3-methylbenzoic
BuLi
CSHlOO$
Benzophenone
PhLi
2.5BuLi
WioOr
Benzonitrile
MeLi PhLi
2.5BuLi
WlOOi
Benzaldehyde
Hexane THF Hexane THF Hexane THF Ether Ether
2.5BuLi
WlOO
Ref 00
2.5BuLi
C,HlOO
yield
4-Carboxyindene
2.5BuLi
Wl 0 0
?
Final product
Carbon dioxide
2.5BuLi
ca10
Reactant
Ether
2.5BuLi
Cd-IlO
Solvent
BuLi
Ether
Benzonitrile Carbon dioxide Chlorotrimethylsilane Phenyl isocyanate Triphenylchlorosilane
735
Metalations by Organolithiurn Compounds
Table VI (Continued) Compound metalated Methyl p-tolyl sulfide
a-(Dimethylamino)fulvene Dimethylaniline
RLi
Solvent
x
Reactant
Final product
yield
Tetra(ptoluenethiomethy1)silane Trimethyl(ptoluenethiomethy1)silane Triphenyl(ptoluenethiomethy1)silane 1,l '-Bis(1-dimethylaminoethyl)ferrocene
53
gg
78
gg
67
gg
71
452
25
372
56 21
372 372
2-(0-Dimethylaminophenyl>2butanol 1-(0-Dimethylaminopheny1)cyclohexanol 2-(o-Dimethylarninophenyl)cyclohexanol l-(edimethylaminopheny1)cyclohexene 0-(Dimethylaminophenylbistrifluoromethy1)carbinol m-(dimethylaminophenylbistrifluoromethy1)carbinol 2-(4,6-Dimethylpicolyl)phenylcarbinol
20
372
31
372
14 7
372
71
372
64
349
Carboxymethylmethylphenylphosphine sulfide Methylphenyl(trimethylsily1methy1)phosphine sulfide bis(trimethylsilylmethy1)phenylphosphine sulfide 1,2-Dimethyltricyclo[4.1.O.O. nonane
36
457
BuLi
Ether
Tetraethoxysilane
BuLi
Ether
BuLi
Ether
MeLi
Ether
Trimethylchlorosilane Triphenylchlorosilane Ferrous chloride
BuLi
Hexane
Acetophenone
BuLi BuLi
Hexane Hexane
BuLi
Hexane
Benzophenone 4,4-Bis(dimethylamino)benzophenone 2-Butanone
BuLi
Hexane
Cyclohexanone
BuLi
Hexane
Cyclohexene oxide
BuLi
Hexane
Hexafluoroacetone
1-(0-Dimethylaminopheny1)-1phenylethanol 0-(N,N-Dimethy1amino)tritanol o,p ',p ' '-Tris(N,N-dimethylamino)tritanol
+
+
Ref
19
2,4,6-Trimethylpyridine Dimethylphenylphosphine
PhLi
Ether
Benzaldehyde
t-BuLi
Pentane
r-BuLi
Pentane
Carbon dioxide, sulfur Chlorotrimethylsilane, sulfur
1-Methyltricyclo[4.1.O.O.'3'1heptane Oct-l-yn-3ene 3-t-Butoxythiophene &Butyl 2-thienyl sulfone 2-t-Butylthiophene Ethyl 5-ethyl2-thienyl sulfide Tetravinyltin
BuLi
Ether
Methyl iodide
RLi
Ether
Paraformaldehyde
Non-Cen-2-yn-1-01
75
209
BuLi
Ether
Carbon dioxide
62
307
BuLi
Ether THF
N,N-Dimethylformamide
3-r-Butoxy-2-thiophenecar boxylic acid 3-t-ButyIsulfonyl-2,4-thiophenedicarboxaldehyde
38
340
BuLi
Ether
Carbon dioxide
68
396''.
BuLi
Ether
Carbon dioxide
2-r-Butyl-5-thiophenecarboxylic acid 2-Ethylthio-5-ethyl-3-thiophenecarboxylic acid
7
U
PhLi PhLi PhLi PhLi
Et her Ether Ether Ether
Dimethylvinylcarbinol Trivinylarsine Acrylic acid Tri-n-butylvinyltin
75 51 18 74
44 44 44 44
PhLi
Ether
Triphenylvinylsilane
60
44
BuLi
Benzenepet. ether Benzene Ether Benzene Ether
Acetone Arsenic trichloride Carbon dioxide Tri-n-butyltin chloride Triphenylsilicon fluoride Ferric chloride
1 ,1-Bis(trimethylsily1)ferrocene
50
433
Antimony trichloride Arsenic trichloride
Tris(phenylcarborany1)antimony
57
473
Tris(phenylcarborany1)arsine
55
473
Trimethylsilylcyclopentadiene Phenylcarborane
RLi RLi
456
+
266
zr7J-
J.
736
M. Malian and R. 1. Bebb
Table VI (Continued) Compound metalated
RLi
Solvent
Benzaldehyde
BuLi BuLi RLi RLi RLi BuLi
Benzene Ether Ether Benzene Ether Benzene Ether
RLi RLi BuLi RLi RLi RLi RLi
Benzene
BuLi
Benzene
RLi RLi
Benzene
RLi
Benzene Ether Benzene Ether Benzene Ether Benzene
RLi
Benzene
RLi RLi
Benzene Ether Benzene
RLi
Benzene
BuLi
Hexane
BuLi
Ether
BuLi
Ether
PhrSiLi BuLi
THF Pentanexylene Pentanexylene Ether
BuLi RLi
Cs"& CDH,
2-cButyl-1,3dithiane Indene
Benzene Ether Benzene Ether Ether
2RLi
RLi
2BuLi BuLi
PhLi
Pentanexylene Ether
PhLi BuLi
Ether Ether
BuLi
Reactant
Carbon dioxide Cyanogen chloride Diethyl phthalate Di-n-hexylchlorophosphine Epichlorohydrin Ethyl benzoate Ethyl pchlorobenzoate Ethylene oxide
x
Final oroduct
Ref
weld
a-(Phenylcarborany1)benzy1 alcohol Phenylcarboranecarboxylic acid
31
c
92
471,476
+
1-Phenyl-2-cyanocarborane 1-phenyl-2-chlorocarborane Phenylcarboranylphthalide Di-n-hexyl(phenylcarborany1)phosphine 1-(l-Phenyl-2-carborany1)-3chloro-Zpropanol Pheny lcarboranylphenylcarbinol Phenylcarboranyl-pchlorophenylcarbinol 2-( 1-Phenyl-2-carboranyl)ethanol
rr
63 52
483 473 474
74 12
483 483
92
474
59
473
10
62 72
473 483 483
86
482
62
413
73 94
483 482
52
473
12
474
64
473
25 37
473
95
482
61
473
61
473
84
473
2-t-Butyl-2-isopropy1-1,3-dithiane
45
343
@-Bromoethyl propionate Carbon dioxide
8-1- (or 3-) Indenyl propionate
14
276
1-1ndenecarboxylic acid
93
Carbon dioxide Dirnethyldichlorosilthe Dimethyldichlorosilane 2,3-Diphenylindone Methyltrichlorosilane Nitrous oxide, carbon dioxide Oxygen Tetraphenylcyclopentadienone
1-Indenecarboxylicacid 1-(Dimethylchlorosilyl) 1-indene
57
216, 278, 279,oo 271
64
ss
24
ss
Germanium tetrachloride Mercuric chloride Methyl benzoate Methyl pbromobenzoate Methyl cinnamate
Bis(phenylcarborany1)germanium dichloride Bis(pheny1carborane)mercuy 1-Phenyl-2-benzoylcarborane
Methylmercuric bromide Methyl ptoluate Phenyl styryl ketone Phosphorus trichloride Propylene oxide
Methyl(phenylcarborany1)mercury 1-Phenyl-2-ptoluoylcarborane
Silicon tetrachloride Stannic chloride Styryl r-butyl ketone Tin tetrabromide Trimethylchlorosilane Triphenyltin chloride Isopropyl iodide
1-Phenyl-2-p-bromobenoyl-
carborane 2-(2-Phenyl-l-carboranyl)-2phenyl ethyl ketone
2-(2-Phenyl-l-carboranyl) 2-phenyl ketone Bis(phenylcarborany1)chlorophosphine 1-(1-Phenyl-2-carboranyl) 2-propanol Bis(pheny1carboranyl)dichlorosilane Tris(phenylcarborany1)tin chloride bis(phenylcarborany1)tin dichloride 2-(2-Phenyl-1arboranyl) 2-r-butyl ketone Bis(phenylcarborany1)tin dibromide Trimethyl(phenylcarborany1)silane Triphenyl(phenylcarborany1)tin
+
-
1-(1-1ndenyl)dimethylsilyl-1
indene 2,3-Diphenyl-3-(l-indenyl)indanone 1-(Methyldichlorosily1)-1-indene
57
g
14
ss
Indene-1-carboxylic acid
62
277
Indene hydroperoxide 2,3,4,5-Tetraphenyl-3-(1-indenyl)4-cyclopenten-1-one
35
g
tt
Metalations by Organolithium Compounds
131
Table VI (Continued) Compound metalated
RLi
Solvent
Reactant
BuLi
n-PrLi
Pentanexylene Pentanexylene Pentanexylene Pentanexylene Ether
BuLi
Ether
Triethylchlorosilane Triethylchlorosilane Trimethylchlorosilane Trimethylchlorosilane Triphenylchlorosilane Benzophenone
BuLi
Ether
Carbon dioxide
3BuLi
Ether
Carbon dioxide
2BuLi BuLi 2BuLi
N-Phenylimidazole
ss
1,l-Bis(triethylsily1)-1-indene
28
ss
1-(Trimethylsilyl) 1-indene
59
ss
1,l-Bis(trirnethylsily1)-1-indene
15
ss
13 8 76
171, uu 358
60
358
5
358
5
358
20
358
1-Phenyl-1H-imidazole-2-carbox39 ylic acid anilide 39 1-Phenyl-5-pyrazolecarboxylic acid 1-(acarboxypheny1)10 pyrazole 4Oxopyrazolo[ 1,5-~]indolene 8 8( ?)-carboxy4oxopyazole26 [1,5-a]indolene 3-Methylthianaphthene-2-carbox- 65 ylic acid 53 1-Methyl-2-indolyldiphenylcarbinol 1-Methyl-2-indolecarboxylicacid 78 l-Methyl-2-indolyl-(loro50 pheny1)carbinol I-Methyl-2-indolyl butyl ketone
358
1,2-Dimethylindole
45
355
N-a-Naphthyl-1 -1nethyl-2-indolecarboxamide N-Phenyl-1-methyl-2-indolecarboxamide l-Methyl-2-(2 '-quinoly1)indole N-(o-Tolyl)-1-methyl-2-indolecarboxamide 1,1,4-Triphenyl-3-buten-l-01 Cinnamic acid (68) 2-Phenyl-2-butenoic acid (32) Allylbenzene (54) Propenylbenzene (46) 3,5-Dimethyl-2,4-diphenylnonanoic acid 3-methyl2-phenylheptanoic acid 2-Methyl-7-carboxy-2,3-dihydrobenzofuran
52
355
42
355
54
355 355
66
ww
Benzaldehyde
2-(P-Phenyl-fl-hydroxy)ethyl-Nmethylbenzamide
51
382
Benzophenone
2-(&3-Diphenyl-fl-hydroxy)-
93
382
+
Triphenyl-1-indenylsilane 1,l-bis(triphenylsily1)idene 1,a,a-Triphenyl- 1H-imidazole2-methanol N-Phenyl-2-imidazolecarboxylic acid H O
I
BuLi
Ether
BuLi
Ether
BuLi
Ether
Ethyl chloroformate Ethyl chloroformate, hydrazine Phenyl isocyanate
BuLi
Ether
Carbon dioxide
2BuLi
Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
BuLi
Ether
Benzophenone
BuLi BuLi
Ether Ether
BuLi
Ether
BuLi
Ether
BuLi
Ether
BuLi
Ether
Carbon dioxide pChlorobenzaldehyde N,N-Dimethylcarbamoyl chloride Methyl ptoluenesulfonate Naphthyl isocyanate Phenyl isocyanate
BuLi BuLi
Ether Ether
Quinoline o-Tolyl isocyanate
BuLi BuLi
Ether Ether
Benzophenone Carbon dioxide
BuLi
Ether
Propenylbenzene
BuLi
Et'isr
2-Methyldihydrobenzofuran N-Methyl-otoluamide
BuLi
AUylbenzene
BuLi
r
tt1ti
Hexme
Carbon dioxide Carbon dioxide
THF
BuLi
Hexane THF
Ref
50
CH-CK
3-Methylthianaphthene 1-Methylindole
yield
1-(Triethylsily1)-1-indene
N-C-c
1-Phenylpyrazole
?
Final product
I II
Pa
I-Phenyl- 1H-imidazole-2-carboxylic acid ethyl ester 1-Phenyl-1H-imidazole-2carboxylic acid hydrazide
+
+
+
ethyl-N-methylbenzamide
63
356 356 326 355 355 355 207
41 57
vu
84
vu
10
vu
VU
5
J. M. Mallan and R. L. Bebb
738
Table VI (Continued) Compound metalated
RLi
Solvent
BuLi
Hexane THF Hexane THF Hexane THF
Ref
Benzaldehyde Ether
Carbon dioxide
2-Methoxy-3-ethylbenzoic acid
294
Ether
Acetone
314
Benzaldehyde
PhLi
Ether Hexane Ether Hexane Ether Hexane Ether
BuLi
Ether
BuLi
Ether Hexane Ether Ether Hexane Ether Hexane
2-(Dimethylaminomethyl)phenyl- 40-46 dimethylcarbinol 2-(Dimethylaminomethyl)benz18 hydrol 24Dimethylaminomethy1)benzo63 phenone 2-(Dimethylaminomethyl)tri84 phenylcarbinol 2-(Dimethylaminomethyl)tri21 phenylcarbinol 2-(Dimethylaminomethyl)-2'80 chlorobenzhydrol 2-(Hydroxycyclohexyl)benzyldi36 methylamine Benzyldimethylamine-2-d o-Bromobenzyldimethylamine 69
BuLi N-AcetylbenBuLi zylamine 0-EthylBuLi anisole EknzyldiBuLi methylamine BuLi BuLi BuLi
BuLi BuLi BuLi BuLi BuLi BuLi
Ether Hexane Ether
Cyclohexanone
K yield
Finat product 1-Hydr oxycyclohexy1)-Nmethyl-o-toluamide a-(1-Hy droxycyclopenty I)-Nmethyl-o-toluamide a-(9-Hydroxy-9-fluorenyl)-Nmethyl-o-toluamide PhCHOHCHzCONHCHzPh
BuLi
Cyclopentanone Fluorenone
Benzonitrile Benzophenone Benzophenone 2-Chlorobenzaldehyde Cyclohexene oxide Deuterium oxide 2,3-Dibromo-2,3dimethylbutane 2-(Dimethylaminomethyl)benzophenone Hexachloroethane
65
382
41
382
50
382 311
314, xx 314 314 313 314 314 315 316
59
314
o-Chlorobenzyldimethylamine
63
316
4Methoxy benzaldehyde Methyl benzoate
2-(Dimethylaminomethyl)-4 'methoxybenzhydrol 2,2 '-Bisdimethylaminomethyltriphenylcarbinol
I8
314
59
374
Methylene iodide
o-Iodobenzyldimethylamine
64
316
Phenyl isocyanate
24dimethy laminomethyl)-Nphenylbenzamide 24Dimethylaminomethyl)3',4',5'-trimethoxybenzhydrol 2-(Dimethylaminomethyl)diphenyl-n-butylcarbinol 2,2-Di-n-amyl-l,3-dithiane 2-n-Amyl-2-(diphenylhydroxymethyl)-l,3-dithiane 2-n-Amyl-2-geranyl-1,3-dithiane
65
314
56
314
82 18
343 343
80
2-n-Amyl-2-isopropyl-1,3-
85
343 343
dithiane 1-Fluoro-2-naphthalenecarboxylic acid
30
183
9 9 66 59
151
BuLi BuLi
Ether
n-Valerophenone
BuLi BuLi
Hexane Hexane
n-Amyl bromide Benzophenone
BuLi BuLi
Hexane Hexane
Geranyl bromide Isopropyl bromide
BuLi
CY-(
2,2 '-Bisdimethylaminomethyltriphenylcarbinol
Ether Hexane Ether Hexane Ether Hexane Ether
BuLi
2-n-Amyl-1,3dithiane
Reactant
3,4,5-Trimethoxybenzaldehyde
1-Fluoronaphthalene Naphthalene
BuLi
THF
Carbon dioxide
BuLi
Carbon dioxide
1-Methylisoquinoline
BuLi BuLi
THF Ether Ether Ether
BuLi BuLi BuLi
Ether Ether Ether
BuLi BuLi
Ether Ether
Allyl bromide Benzalacetophenone Benzophenone Ethyl acetate Ethyl (bromomethy1)malonate Ethyl isobutyrate Ethyl methylenemalonate
+
Naphthalene-1-carboxylic acid naphthalene-2-carboxylic acid 1-(3-Buteny1)isoquinoline @-Phenyl-y-(1-isoquinoly1)butyrophenone hydrochloride Diphenylisoquinaldylcarbinol Methyl isoquinaldyl ketone j3-( 1-1soquinolyl)ethyl malonic ester Isopropyl isoquinaldyl ketone @-(I-1soquinolyl)ethyl malonic ester
314
YY
YY
100 35 16
YY YY YY
33 14
YY YY
Metalations by Organolithium Compounds
739
Table VI (Continued) Compound metalated
?
RLi
Soluent
Reactant
BuLi BuLi
Ether Ether
Isopropyl iodide Methallyl chloride
N-Phenylpyrrole
BuLi
Ether
Carbon dioxide
Quinaldine
PhLi
Ether
Ferrocene
BuLi
Ether
5-Phenyl-2,4-penta- l-Phenyl-6-(2-quinolyl)-5hydroxy-2,4-hexadiene dien-1-a1 Bis(diphenylhydroxymethy1)Benzophenone ferrocene Ferrocenylamine N-Benzylhydroxylamine Butyl borate Ferrocenylboronic acid 1,l'ferrocenylenediboronic acid Carbon dioxide Ferrocenemonocarboxylic acid ferrocenedicarboxylic acid
Final product
yield
I-Isobutylisoquinoline 1-(3-Methyl-3-butenyl)isoquinoline N-Phenylpyrrole-2-carboxylic acid
Ref
40 64
YY YY
20
354
Trace
BuLi BuLi
+
BuLi
THF Ether Ether
BuLi
Ether
Carbon dioxide, diazomethane
BuLi
THF
Chloroethylmethylsilane
BuLi BuLi BuLi BuLi BuLi
Ether THF Ether Ether Ether THF Ether
+
Chlorodiethylsilane Cobalt chloride Cobalt chloride, butyl bromide Diferrocenyl ketone
20
bb
435 25 26-44 13-18 26-78
+
Carboxymethylferrocene (59) 1,l '-dicarbomethoxyferrocene (41) (Ethylniethy1silyl)ferrocene
+
449 442,443 431, 432, 433, 159, 430, 453, 428 43 1
P
1,1'-bis(ethylmethylsily1)-
ferrocene Diethylsilylferrocene I ,1'bis(diethy1silyl)ferrocene Biferrocenyl Triferrocenyl quaterferrocenyl Triferrocenylcarbinol
+
P zz
+
ZZ
60-77
436, aaa
N,N-Dimethyl-2-ferrocenylethylamine Ferrocenechlorohydrin
13
zz, ccc,
Ferrocenecar bonitrile Ferrocenecarboxaldehyde Nitrous oxide
Diferrocenyl ketone
80
436
Diferrocenylcarbinol
62
aaa
Azoferrocene
25
446
Pyridine
a-Pyridylferrocene $- 1,l '-bis(a-pyridy1)ferrocene Triethylsilylferrocene I ,1 'bistriethylsilylferrocene Tri-n-hexylsilylferrocene di(tri-n-hexylsi1yl)ferrocene Trimethylsilylferrone 1,l'bis(trimethylsily1)ferrocene Triphenylsilylferrocene
24 3
444
2-dimethy lamino-
ethyl chloride Epichlorohydrin
BuLi
Ether
BuLi
Ether
BuLi
BuLi
Ether THF Ether THF Ether
BuLi
Ether
Triethylsilane
BuLi BuLi
Ether THF Ether
BuLi
Ether
BuLi
Ether
Tri-n-hexylbromosilane Trimethylchlorosilane Triphenylchlorosilane Carbon dioxide
BuLi PhLi
Ether Ether
Quinoline Carbon dioxide
BuLi
Ether
Carbon dioxide
3
bbb
ddd
BuLi
N-Benzylimidazole
G oHi ON* CioHioNa CioHioOs
1-Benzylpyrazole 3-Methyll-phenylpyrazole Osmocene
+
+ +
1-Benzyl-2-imidazolecarboxylic acid 2-Quinolyl-I-benzylimidazole 1-Benzyl-5-pyrazolecarboxylic acid 3-Methyl-l-phenylpyrazole-5-
P
32 35 19-57 27-43 49
433
67
358
29 57
a
428,431 429
358 357
carboxylic acid BuLi
Ether THF
Carbon dioxide
Osrnocenemonocarboxylic acid (42) osmocenedicarboxylic acid ( 5 8 )
+
453
J. M. Yallan and R. 1. Bebb
740
Table VI (Continued) Compound
metalated
RLi
Sohent
Ruthenocene
BuLi
Ether
Carbon dioxide
5-Methyl2,2'-dithienylmethane
BuLi
Ether
Carbon dioxide
BuLi
Ether
Ethylene oxide
BuLi
Ether
BuLi
Ether
N-Formaldimethylamine Carbon dioxide
BuLi
Ether
BuLi
5,5'-Dimethyl-3,3'bithienyl 24pchlorophenoxy) tetrahydropyran a-Dimethylaminophenylacetonitrile 2-Phenoxytetrahydropyran 2-Phenyl-l,3dithiane N,N-Dimethyl(&phenylisobutyl) amine f-Butyl phenyl sulfone
? yield
Ref
48-87
453
55
eee
75
eee
Carbon dioxide
2-Hydroxy-5-chlorobenzoicacid
25
ff
Ether
Ethyl bromide
Propiophenone
42
370
BuLi
Ether
Carbon dioxide
2-Hydroxybenzoic acid
60
ff
BuLi
Hexane
Isopropyl bromide
90
343
BuLi
Ether
Benzophenone
17
379
40-45
338
+
o-(a-Dimethylaminomethyliso-
eee 45-60
309,310
propy1)triphenylcarbinol
BuLi 2BuLi
N,N-Dimeth- BuLi yl-fJ-phenylethylamine BuLi
Ether THF Ether THF Ether THF Ether Ether
BuLi t-BuLi
Pentane
BuLi
t-BuLi
PhLi BuLi
Carbon dioxide
2-(t-Butylsulfonyl)bnzoic acid
Carbon dioxide
2-Butylisophthalic acid
44
338
Carbon dioxide
2-Ethylisophthalic acid
42
338
Benzaldehyde
0-( N,N-Dimethylamino-@-ethyl)-
380
diphenylcarbinol Hexane Ether Hexane Ether Hexane Ether Ether
BuLi
BuLi
Phenylmethyl-n-propylphosphine Phenylmethyl-n-propylphosphine sulfide Camphor Phenyl 2-thienyl sulfone I-Methoxynaphthalene-8-d 1-Methoxynaphthalene
Final product
Ruthenocenemonocarboxylic acid ruthenocenedicarboxylic acid 5 '-Methyl-Z,Z '-dithienylmethaneStarboxylic acid 5-@-Hydroxyethyl)-5 '-methyl2,2 '-dithienylmethane 5 '-Methyl-2,2 '4thienylmethane5-carboxaldehyde 2,2 '-Dicarboxy-5,5 '-dimethyl3,3 '-bithienyl
2BuLi
2-Methylbenzyldimethylamine
Reactant
Ether
Benzophenone Acetone Benzaldehyde Benzophenone Deuterium oxide Carbon dioxide, sulfur
380
0-( N,N-Dimethylamino-j3-ethyl)
triphenylcarbinol 2-[a-(Dimethylamino)o-tolyl]1,I-dimethylethanol 2-[a-(Dimethy1amino)o-tolyl]1-phenylethanol 2-[a-(Dimethylamino)o-tolyl]1,I-diphenylethanol 2-Methyl-dl-benzyldimethylamine Phenyl n-propylcarboxymethylphosphine sulfide
Carbon dioxide
Phenyl n-propylcarboxymethylphosphine sulfide
Carbon dioxide Carbon dioxide
Camphocarbonic acid 2-Benzenesulfonyl- S-thiophene-
46
381
77
381
80
381 375
fff fJf
60
415 332
carboxylic acid BuLi
Ether
Carbon dioxide
I-Methoxy-2-naphthoic acid-8-d
32
293
BuLi BuLi
Ether Ether Hexane
Carbon dioxide Carbon dioxide, diazomethane
1-Methoxy-8-naphthoic acid Methyl I-methoxy-2-naphthoate (83) 31 methyl 8-methoxy-1-naphthoate (1 7)
222 293
+
Metalations by Organolithium Compounds
741
Table VI (Continued) Compound metalated
lUi
Solvent
Reactant
Carbon dioxide, diazoniethane
Methyl 1-methoxy-2-naphtlioate (86) methyl 8-methoxy-1-naphthoate (14) Carbon dioxide, Methyl 1-methoxy-2-naphthoate (78) diazomethane methyl 8-methoxy-1-naphthoate (11) Benzophenone (2-Methoxy-3-naphthy1)diphenylcarbinol Carbon dioxide 2-Methoxy-3-naphthalenecarboxylic acid 2-Methoxy-3methylnaphthalene Methyl iodide Methyl 2-meTri(2-methoxy-3-naphthyl)thoxy-3-naphthyl- carbinol carboxylate 2-Ethoxy-3-quinolin~arboxyl~c Carbon dioxide acid Carbon dioxide $ 5 '-Dimethyl-Z,Z'-dithienylmethane-3- (or 4)carboxylic acid
BuLi LiBr
Ether Hexane
BuLi LiOEt
Ether Hexane
BuLi
Ether
BuLi
Ether
BuLi BuLi
Ether Ether
BuLi 2-Ethoxyquinoline BuLi 5,s '-Dimethyl-2,2'-dithienylmethane PhLi Pentamethylenefulvene BuLi Acetomesitylene 2,2-Dimethyl- BuLi chroman BuLi 5-Methoxy1~3~4tetrahydronaphthalene BuLi Phenol-2tetrahydroPyranYl ether 2-Ben~yl-l,3- BuLi dithiane BuLi 1&Dimethoxy-2,3,5trimethylbenzene BuLi n-Butyl ptolyl BuLi sulfone
Ether
BuLi
Ether
BuLi
Hexane Ether
Acetone
BuLi
Hexane Ether
Benzophenone
BuLi
Ether
Deuterium oxide
2-Methoxynaphthalene
a,a-Dimethylbenzyldimethylamine 2,3-Dimethylbenzyldimethylamine
N,N-Dimethyl-3-phenylpropylamine 2,2',3,3',5,5',6,6'-Octafluorobiphenyl
Ether
+
+
x
yield
Ref
22
293
25
293
50
ggL?
54
ggg
45 42
ggg ggg
1
hhit
51
eee
96
434
60
155
Ether
Ferrous chloride
THF
Deuterium oxide
1,l '-Di(1-phenylcyclohexy1)ferrocene Dideuterioacetomesitylene
Hexane Ether
Carbon dioxide
2,2-Dimethyl-8-chrotnancar box-
31
296
Ether
Carbon dioxide
ylic acid 5-Methoxy-l,2,3,4-tetrahydronaphthalenecarboxylic acid
6
242
EthW
Ethylene oxide
o-Phenoxy-6-phenylethanol
89
301
Hexane
Ethyl 2-benzyl-241,3-dithianyl)formate 1,4-Dimethoxy-2,5-dthyl-38-hydroxypropylbenzene
18
344
Ether
Ethyl chloroformate Acetaldehyde
Ether
Carbon dioxide
18
336
Ether
pToluenesulfony1 fluoride Benzophenone
2-(pToluenesulfonyl)pentanoic acid 1,l-Bislptoluenesulfony1)butane
60
336
2-(N,N-a,a'-Tetramethylamine methy1)benzhydrol
57
374
2-(2-Dimethylarninomethyl-6methylpheny1)-1.1-dimethylethanol 2-(2-Dimethylaminomethyl-6methylpheny1)-1,l-diphenylethanol
61
38 I
80
38 1
Benzophenone
BuLi
Hexane Ether Ether
Deuterium oxide
BuLi
THF
Carbon dioxide
BuLi
Final prodiict
Hexane
295
315
2-Methyl-d1-3-metliylbenzyldi-
methylamine 4-Dimethylaminel ,1,2-triphenyl-1-butanol N,N-Dimethyl-3-phenylpropylamine-a-dl 2,2',3,3 ',5,5',6,6'-0ctafluorobiphenyL4,4'-dicarboxylic acid
57
379 375
97
42 1
742
J. M. Malian and R. 1. Bebb Table VI (Continued) Compound metalated
Biphenylene
Phenothiazine
RLi
BuLi
Ether
BuLi
Ether
BuLi BuLi BuLi
Ether Ether
BuLi 2BuLi BuLi lBuLi 2BuLi 2BuLi 2BuLi Dibenzofuran
Dibenzothiophene 5oxide Phenoxathiin
Thianthrene 5-oxide
Solvent
Ether Ether Ether Ether Ether Ether
Li Dioxane Li Ether C6H6CH2Li THF Ca6CH2Li THP n-Butyl BuLi Ether BuLi Ether BuLi THF Ether BuLi THF BuLi Petroleum Ether MeLi Ether MeLi Ether THF MeLi THF a-Me(CHgTHF CeHa)Li PhLi Ether PhLi THF Ether PhLi THF Ether Poly-p-styryllithium 2,4,6-Ph*PhLi BuLi Ether BuLi
Ether
BuLi
Ether
BuLi
Reactant
Carbon dioxide, diazomethane N,N-Dimethylformamide Oxygen Acetyl chloride Benzophenone
1-Methoxycarbonylbiphenylene
49
Biphenylene-1-carboxaldehyde
Ref iii iii
Butyl acetate Carbon dioxide Dimethyl sulfate Ethylene oxide Lithium acetate Lithium benzoate Lithium propionate Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide
53 94-99 83-92 40 42 33
o-Hydroxybiphenyl 3,CBenzocoumarin Dibenzofuran4carboxylic acid Dibenzofuran-4-carboxylic acid Dibenzofuran-4-carboxylic acid
80 64 35 8 76
Carbon dioxide Carbon dioxide
Dibenzofuran-4-carboxylic acid Dibenzofuran-4carboxylic acid
5-56 69-86
Carbon dioxide Carbon dioxide
Dibenzofuran-4-carboxylicacid Dibenzofuran-4-carboxylicacid
75 1
157 156
Carbon dioxide Carbon dioxide
Dibenzofuran-4-carboxylic acid Dibenzofuran4carboxylic acid
2 12
157 157
Carbon dioxide Carbon dioxide
Dibenzofuran-4carboxylic acid Dibenzofuran-4-carboxylic acid
29 39
157 mmm
Carbon dioxide Carbon dioxide
Dibenzofuran-karboxylic acid Dibenzofuran-4-carboxylicacid
8 44
157 157
Carbon dioxide Carbon dioxide
Dibenzofuran4carboxylic acid Dibenzofuran-4carboxylic acid
55 21
g
Carbon dioxide
Dibenzofuran-4-carboxylicacid
4
N,N-Dimethylcarbamoyl chloride Triphenylchlorosilane Carbon dioxide
Bis(4dibenzofuranyl) ketone
Carbon dioxide Ether
Carbon dioxide
2MeLi BuLi 2BuLi
Ether Ether Ether
Carbon dioxide Carbon dioxide Carbon dioxide
Ether
yield
1-Hydroxybiphenylene 10-Acet ylphenothiazine 1-(Diphenylhydroxymethy1)phenothiazine 1-Acetylphenothiazine Phenothiazine-1-carboxylic acid 10-Methylphenothiazine 10-B-Hydroxyethylphenothiazine 10-Acetylphenothiazine 10-Benzoylphenothiazine 10-Propionylphenothiazine
2BuLi
3BuLi
?
Final product
Carbon dioxide
3BuLi
Ether
Carbon dioxide
MeLi
Ether
Carbon dioxide
18 40-88 70
iii
hy kkk 111 Jyj jjj jjj iJj jjy
jjj
288 288 mmm mmm 156 156, 157 156, 157
157 172 207
1-Triphenylsilyldibenzofuran
69
Dibenzothiophene-Ccarboxylic acid
36-55
323, 327
37
383. 384
4-Phenoxathiincarboxylic acid
+
1,6-phenoxathiindicarboxylic acid 4,6-Dicarboxyphenoxathiin 1,6-dicarboxyphenoxathiin 4-Phenoxathiincarboxylicacid Dibenzothiophene Dibenzothiophene Thianthrene Thianthrene- 1-carboxylic acid Dibenzothiophene Thianthrene o-Carboxyphenyl sulfide Dibenzothiophene Thianthrene 1-Thianthrenecarboxylic acid
+
ee
1
35 9 12 46 10 13 13 55 3
383, 384 384 nnn
327 327
3
53 8
nnn
1
nnn
743
Metalations by Organolithium Compounds
Table VI (Continued) Compound metalated
Dibenzothiophene 5 3 dioxide
Phenoxathiin 10-oxide
Thianthrene 5-dioxide
Phenoxathiin 10,IO-dioxide
Thianthrene 5,5,10-trioxide Dibenzothiophene
RLi
Solvent
Reactant
3MeLi
Ether
Carbon dioxide
lBuLi
Ether
Carbon dioxide
2BuLi
Ether
Carbon dioxide
3BuLi
Ether
Carbon dioxide
BuLi 2BuLi
Ether Ether
Carbon dioxide Carbon dioxide
3BuLi
Ether
Carbon dioxide
BuLi BuLi
Ether Ether
Carbon dioxide Carbon dioxide
PhLi
Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
2BuLi
Ether
Carbon dioxide
MeLi
Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
Li
Dioxane
Carbon dioxide
BuLi
Ether
Carbon dioxide
2BuLi BuLi
Carbon dioxide Carbon dioxide
BuLi
Ether Ether THF THF
Carbon dioxide
MeLi
Ether
Carbon dioxide
MeLi
THF
Carbon dioxide
MeLi
THF Ether THF
Carbon dioxide
Ether THF Ether
Carbon dioxide
PhLi PhLi PhLi BuLi
Ether
Carbon dioxide
Carbon dioxide N,N-Dimeth ylcarbamoyl chloride
x
Final product
yield
Thianthrene 1-Thianthrenecarboxylic acid Dibenzothiophene-4-carboxylic acid 5,5-dioxide Dibenzothiophene-4carboxylic acid 5,5-dioxide Dibenzothiophene-4,6-dicarboxylic acid 5,5-dioxide Dibenzothiophene-4,6-dicarboxylic acid 5,Sdioxide Thianthrene-1-carboxylicacid Phenoxathiin Diphenyl ether 1-Carboxyphenoxathiin Diphenyl ether Phenoxathiin Di(o-carboxyphenyl) ether o-Carboxyphenyl phenyl ether I-Carboxyphenoxathiin Butyl mercaptan 4Carboxythianthrene 5-dioxide 4,6-Dicarboxythianthrene5dioxide 4,6-Dicarboxythianthrene5dioxide 1,6-Dicarboxyphenoxathiin 10,lO-dioxide Phenoxathiin-1-carboxylicacid 10,lO-dioxide 1,9-Dicarboxyphenoxathiin 10,lO-dioxide I-Carboxyphenoxathiin 10,lOdioxide 1,9-Dicarboxyphenoxathiin 10,10-dioxide I-Carboxyphenoxathiin 10,lOdioxide 1,9-Dicarboxyphenoxathiin 10,lO-dioxide 2,2-Dicarboxyphenyl phenyl sulfone
60
Biphenyl o-Thiobiphenyl 4Dibenzothiophenecarboxylic acid Butyl Cdibenzothienyl ketone Dibenzothiophene-4-carboxylic acid Dibenzothiophene4carboxylic acid Dibenzothiophene-4carboxylic acid Dibenzothiophene4carboxylic acid Di benzothiophene-4-carboxylic acid Dibenzothiophene-4-carboxylic acid Dibenzothiophene-4-carboxylic acid Dibenzothiophene4carboxylic
acid Bis(Cdibenzothiopheny1)ketone
Ref
22
nnn 324
20
324
1
4 10
324
20 14 42 16 14 25
385 386
386
17
12 6
7 41 12
328 328
54
328
8
384
46
385
48
383, 384
15 93
384
18 3
384
17
328
21 18 25-35
288 157, 384
5
322
60
157
41
157
Trace
157
12
157
5
157
47
157
12
157
Trace
157 207
744
J.
M. Malian and R. L Bebb
Table VI (Continued) Compound metalated
CinHsSt
Thianthrene
CllHsSe
Dibenzoselenophene CllH9BrOtS m-Bromophenyl phenyl sulfone ClzH9Br0& p-Bromophenyl phenyl sulfone CltHsCIO 4Chlorophenyl phenyl ether CiaHgN a-Naphthylacetonitrile
RLi
Phenoxazine Sodium anaphthylacetate
CTriphenylsilyldibenzothiophene
42
ee
1-Thianthrenecarboxylic acid 1-Aminothianthrene 1-Thianthreneboronic acid 1-Thianthrenyltriphenylsilane
28 55 23 10
328 328 328 328
Dibenzoselenophene-1-carboxylic acid 1-Methyldibenzoselenophene 3-Bromo-2-carboxyphenyl phenyl sulfone
96
488
80 54
488 332
52
332
7
291
17
291
21
175, 182
55 24 41 50 38 69 41
175, 182 175, 182 175,182 175, 182 175, 182 284 182, ooo
10
182, ooo
16
182,000
57
182
45
182, ooo
7
182, ooo
Ref
BuLi BuLi BuLi BuLi
Ether Ether Ether Ether
BuLi
Ether
BuLi BuLi
Ether Ether
Dimethyl sulfate Carbon dioxide
BuLi
Ether
Carbon dioxide
4-Bromo-2-carboxyphenyl phenyl sulfone
BuLi
Ether
BuLi
Ether
PhLi
Ether
Diphenyldichlorosilane Triphenylchlorosilane Benzophenone
BuLi o-MePhLi a-ClaHiLi
Ether Ether Ether Ether Ether Ether Pentane Dioxane Pentane Dioxane Pentane Dioxane Ether
Carbon dioxide
Bis(2-phenoxy-5-chlorophenyl)diphenylsilane 2-Phenoxy-5-chlorophenyltriphenylsilane 3,3-Diphenyl-3-hydroxy-2-(anaphthy1)propionitrile 2-Naphthyl-2-carboxyacetonitrile 2-Naphthyl-2-carboxyacetonitrile 2-Naphthyl-2-carboxyacetonitrile 2-Naphthyl-2-carboxyacetonitrile 2-Naphthyl-2-carboxyacetonitrile Phenoxazine4carboxylic acid 3,3-Diphenyl-3-hydroxy-2-(anaphthy1)propionic acid 3,3-Diphenyl-3-hydroxy-2-(anaphthy1)propionic acid 3,3-Diphenyl-3-hydroxy-2-(anaphthy1)propionic acid 3,3-Diphenyl-3(hydroxy)-2-(anaphthy1)propionic acid 3,3-Diphenyl-3-hydroxy-2-(anaphthy1)propionic acid a-Naphthylmalonic acid
Carbon dioxide
a-Naphthylmalonic acid
29
174, 182
Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Iodine Benzophenone
a-Naphthylmalonic acid a-Naphthylmalonic acid a-Naphthylmalonic acid a-Naphthylmalonic acid a-Naphthylmalonic acid 2,3-Di(a-naphthyl)succinicacid 3,3-Dipheny1-3-hydroxy-2-(& naphthy1)propionic acid
35 42 20 37 38 30 32
174, 182 174, 182 174, 182 174, 182 174, 182 182, PPP 182, ooo
Benzophenone
3,3-Diphenyl-3-hydroxy-2-(8-
28
182, ooo
8
182, ooo
in-MePhLi
Ether Ether Ether Ether Ether Ether Pentane Dioxane Pentane Dioxane Pentane Dioxane Ether
17
176, 182
o-MePhLi
Ether
Benzophenone
18
176, 182
21
176, 182
37
182, ooo
19
176
PrLi BuLi BuLi i-AinLi
Pr Li B LLLi p-(IMe)?N-
naphthylacetate
? yield
Triphenylchlorosilane Carbon dioxide Methoxylamine Tri-n-butyl borate Triphenylchlorosilane Carbon dioxide
PhLi
Sodium 8-
Final product
Ether
i-PrLi
ClaHpOINa
Reactant
BuLi
l’h Li
CI2H8NO ClzHg4Na
Solvent
PhLi nz-MePhLi o-MePhLi pMePhLi a-CloHvLi PhLi PhLi BuLi i-AmLi i-PrLi
Pentane Dioxane Ether Dioxane Ether
Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Benzophenone Benzophenone Benzophenone Benzophenone Benzophenone
Benzophenone Benzophenone
PhLi
Ether
Benzophenone
PrLi
Pentane Dioxane Ether
Benzophenone Carbon dioxide
naphthy1)propionic acid 3,3-Diphenyl-3-hydroxy-2(8naphthy1)propionic acid 3,3-Diphenyl-3-hydroxy-2-(j3naphthy1)propionic acid 3,3-Diphenyl-3-hydroxy-2(B-
naphthy1)propionic acid 3,3-Dipheny1-3-hydroxy-2-@naphthy1)propionic acid 3,3-Diphenyl-3-hydroxy-2-(& naphthy1)propionic acid p-Naphthylmalonic acid
Metalations by Organolithium Compounds
745
Table V I (Corrtinued) Cobnipowid metalatvd
Dihydro-asindacene Diphenyl ether
RLi
m-MePhLi o-MePhLi p-MePhLi a-CloH,Li PhLi PhLi BuLi
BuLi
Ether Ether Ether Ether Ether Ether Hexanedimethoxyethane Ether
BuLi
Ether
BuLi t-BuLi Ph.,SiLi BuLi
Ether Pet. ether THF Ether
BuLi
Ether
BuLi
Ether
BuLi
Ether THF Ether
BuLi
2-Benzylpyridine I .7-Dimet hoxynaphthalene
2-(Ferroceny1)ethylamine rn-Methoxyphenyl 2letrahydropyranyl ether
Final product
Reactant
x
yield
Ref
176 176 176 176 176, 182 182
Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Iodine Ferroiis chloride
8-Naphthylmalonic acid j3-Naphthylrnalonic acid j3-Naphthylmalonic acid j3-Naphthylmalonic acid j3-Naphthylmalonic acid 2,3-Di(j3-naphthyl)succinic acid Bis(as-indacenyliron)
20 48 22 26 18-20 28 10
w9
Boron trifluoride etherate n-Butyl metaborate Carbon dioxide Carbon dioxide
10-Hydroxy-9-oxa-10-boraanthracene 10-Hydroxy-9-oxa-10-boraanthracene Di(2-carboxyphenyl) ether 2-Phenoxybenzoic acid
23
rrr
42
rrr
23-60 14
386, 292 134
Carboii dioxide Dibenzyldichlorosilane Di-12-dodecyldichlorosilane Diniet hyldichlorosilane Diphenylsilane
Di(Zcarboxypheny1) ether 10,lO-Dibenzylphenoxasilin
Trace 52
sss
Di-n-dodecylbis(o-phenoxypheny1)silane
17-29
289
10,10-Dimethylphenoxasilin
25-5 1
158, 292
10,lO-Diphenylphen~uasiln
20
Diphenyldichlorosilane Phenylsilane
Bis(2-phenoxyphen y I )di p henylsilane IO-Phenylphenoxasilin
34-40 26
290
Phenyltrichlorosilane Silicon tetrachloride Silicon tetrachloride Trimethylchlorosilane Triphenylchlorosilane Carbon dioxide Carbon dioxide
Tris(2-phenoxypheny1)pheny 1 silane 10,10’-Spirobiphenoxa,silin
14
291
25
292
Tetrakis(2-phenoxypheny1)silane
12
29 1
(Oxy-di-o-phenylene)bis(trimet hy Mane) 2-Phenox yphen y ltriphenyhilane
60
289
67
291
2-Carboxyphenyl phenyl sulfone
42-80 26
BuLi
Ether THF Ether
2BuLi
Ether
BuLi
Ether
BuLi
Ether
BuLi
Ether
BuLi 4BuLi
Ether Ether
BuLi
Ether
BuLi
Ether
PhLi
Ether
BuLi
Ether
Dimethyldichlorosilane Diphenyldichlorosilane 8-Dimethylaminoethyl chloride Carbon dioxide
BuLi
Ether
Dimethyl sulfate
BuLi
Ether
BuLi
Ether
N-Methylformanilide Ethyl formate
BuLi
Ether
Carbon dioxide
BuLi
Diphenyl sulfone
SOlLl~ilt
Di(o-carboxyphen yl)
sulfone 10,lO-Dimethylphenothiasilin 5,5-dioxide 10,10-Diphenylphenothiasilin 5,5-dioxide l-(Z-Pyridyl)-l-phenyl-3dimethylaminopropane 1,7-Dimethoxy-6-carboxynaphthalene 1,7-Diinethoxy-6-rnethyInaphthalene 1,7-Dimethoxy-6-naphthaldehyde
289
290 291, 292
332, 335 324
24
341
8
341
79
uuu
72
242
75
242
a4
242
N-Formyl-2-(ferrocenyl)ethylamine
86
uuu
2-Methor y-Bhydroxybenzoic
26
300
acid
J. M. Mallan and R. 1. Bebb
746 Table VI (Continued)
Compound metalated
Ci2HioN
ClaHz&3n C12H&
CisHio
2,4,6-Trimethylbenzyldimethylamine Tetraallyltin 1,3,3-Tris(trimethylsily1)propyne Fluorene
RLi
BuLi
Solvent
Hexane Ether
Reactant
Benzaldehyde
? Final product yield 2-[2-(Dimethylaminomethyl)-3,5- 81 dimethyIphenyl1-1-phenyl-
Ref
381
ethanol 36
rrrr
BuLi BuLi
Pentane Hexane
Carbon dioxide Trimethylchlorosilane
Vinylacetic acid
BuLi
79
www
9-Benzylfluorene
www www
9-(pChloro benzy1)fluorene
58 80 68
4
BuLi
Ether
Benzhydryl chloride Benzyl chloride n-Butyl bromide p-Chloro benzyl chloride pChlorophenyl styryl ketone 9-Diazofluorene 2-Benzyl chloride Benzyl chloride, formaldehyde 3-Bromo-1-propyne Carbon dioxide Carbon dioxide
9-Benzhydr ylfluorene
BuLi BuLi BuLi
Hexane Ether Hexane Hexane Ether
1-(p-Chlorophenyl)-3-phenyl-4-
90
4
biphenylene- 1-but anone Fluorenone azine 9,9-Dibenzylfluorene 9-Benzyl-9-fluorene methanol
65 90
xxx YYY YYY
3-(9-Fluorenyl)-l-propyne
40
zzz
Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid
61 54
406 172
Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide
Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid
42 78 25 58 76
406 172 407 406 g
Carbon dioxide
Fluorene-9-carboxylic acid
85
172
THF THF EGDE THF
Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide Carbon dioxide
Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid
66 50 69 0.5 22 65
27 1 406 407 271 404 172
BuLi
THF THF Ether Benzene Ether
Fluorene-9-carboxylic acid Fluorene-9-carboxylic acid (p,p’-Dichlorobenzhydry1idene)fluorene Fluorene-9-(N,N-dimethylcarboxamide
PhLi
Ether
PhLi
Ether
PhLi
Ether
BuLi
Ether
PhLi PhLi PhLi
Ether Ether Ether
BuLi PhLi PhLi
Ether Ether Ether
BuLi
Ether
Carbon dioxide Carbon dioxide 4,4’-Dichlorobenzophenone N,N-Dimethylcarbamoyl chloride 3,3-Diphenyl-1bromopropane 1,3-Diphenyl-lchloropropane Diphenyldichlorosilane 2,3-Diphenylindone 6-Iodo-1-hexyne 5-Iodo-1-pentyne 11-Iodo-1undecyne Nitrous oxide Nitrous oxide Phenyltrichlorsilane Tetraphenylcyclopentadienone
BuLi 2PhLi PhLi
Ether Ether Ether
PhLi
Ether
PhlMeSiLi Mesityllithium Ph5SizLi PhLi PhLi PhMerSiLi Polystyryllithium o-CHsCsH4Li Ph3GeLi PhrGeLi PhaGeLi PhsPbLi PhlPbLi 2,4,6PhoPhLi PhaSiLi Ph3SnLi BuLi
THF THF EGDE THF Ether
264
1,1,3,3-Tetra(trimethylsilyl)allene
9-n-But ylfluorene
1-Biphenylene-4,4-diphenyl-113butadiene l-BiphenyIene-2,4-diphenylbutane Diphenylbis(9-fluoreny1)silane
41-69 17-31
211, 406 271, 404 aaaa,
bbbb 207 cccc cccc
11
dddd
83
Q
62 68 62
zzz zzz
Fluorenone azine Fluorenone azine Phenyltris(9-fluoreny1)silane
28
xxx
47
277 dddd
2,3,4,5-Tetraphenyl-3-(9-fluoreny1)-4cyclopenten-1-one
72
4
2,3-Diphenyl-3-(9-fluorenyl)indanone 6-(9-Fluorenyl)-l-hexyne 5-(9-Fluorenyl)-l-pentyne 11-(9-Fluorenyl)-l-undecyne
zzz
Metalations by Organolithium Compounds
747
Table VI (Continued) Compound metalated
RLi BuLi
BuLi
THF Hexane TE.IF Hexane Ether
n-PrLi
Ether
PhLi
Ether
2BuLi
1-Phenylbenzimidazole Xanthene
Sotvent
Reactant Trimethylchlorosilane 2-Trimethylchlorosilane Trimethylene oxide Triphenylchlorosilane Carbon dioxide
BuLi PhaSiLi PhsSiLi
THF
BuLi
Ether
Ether THF
Carbon dioxide Carbon dioxide Chlorotriphenylsilane N,N-Dimethylcarbamoyl chloride N,N-Dimethylcarbamoyl chloride Carbon dioxide
BuLi
Ether
5-Methylcarbazole N -Benzy1thieno[3,2b]pyrrole
BuLi
Ether
BuLi
Ether Hexane Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
BuLi
Ether
Carbon dioxide
BuLi BuLi
Ether Ether
Dimethyl sulfate Ethylene oxide
BuLi
Ether
Formaldehyde
BuLi
Ether
BuLi BuLi
Ether Ether
N-Formyl-Nmethylaniline Lithium acetate Lithium benzoate
BuLi
Ether
Li-naphthalene PhaSiLi n-PrLi
THF THF Ether
Phenyl benzyl sulfide Phenyl benzyl sulfone p-Tolyl phenyl sulfone
BuLi
Bis(phenylthio)methane
Diphenylmethane
? weld
Ref
9-Trimethylsilylfluorene
74
274
9,9-Di(trimethylsilyI)fluorene
84
274
3-(9-Fluorenyl)-propanol1
44
210
9-(Triphenylsilyl)fluorene
70
171
I-Phenylbenzimidazole-2-car box-
25
eeee
51
fff
ylic acid
Thioxanthene
10-Methylphenothiazine
Final Rroduct
Excess BuLi
Carbon dioxide, diazomethane
Lithium propionate Carbon dioxide
Xanthene-9-carboxylic acid Xanthene-9-carboxylic acid 9-Triphenylsil y lxanthene
31 14
Xanthene-9-bis(N,N-dimethyl-
27 1 27 1
207
carboxamide)
Thioxanthene-9-bis(N,N-dimethylcarboxamide N-Methylcarbazole- 1-carboxylic acid 2-Carboxy-4-benzylthieno[3,244pyrrole 4-(a-Carbomethoxybenzyl)-2,5dicarbomethoxyt hieno[3,2-b]pyrrole 10-Methyl-I-phenothiazinecar10-methyl-4boxylic acid phenothiazinecarboxylic acid 4-(or 2-) 10-Methylphenothiazinecarboxylic acid 4,lO-Dimethylphenothiazine 4-B-Hydroxyethyl-1O-methylphenothiazine CHydroxymethyl-1O-methylphenothiazine 4-Formyl-1 O-methylphenothiazine CAcetyl-10-methylphenothiazine CBenzoyl-10-methylphenothiazine 4-Propionyl-1 O-methylphenothiazine Diphenylacetic acid
207 12
345
87
gggg
68
ggsg
iii
+
43
392
25 10
iii hi
10
iij
10
iii
23 21
iij
17
iii
70
272
iii
Diphenylacetic acid Benzhydryltriphenylsilane
57 66
27 1 171
Ether
Carbon dioxide Triphenylch lorosilane Carbon dioxide
2-Phenyl-2-(phenylthio)acetic acid
75
329
BuLi
Ether
Carbon dioxide
65
329
BuLi
Ether
Carbon dioxide
BuLi
THF
Benzaldehyde
BuLi
THF
Benzophenone
BuLi BuLi
THF THF
n-Butyl bromide Cyclohexanone
2-Phenyl-2-(phenylsuIfonyl)acetic acid 2-Carboxy-4-methylphenyl phenyl sulfone (41) 2-Carboxy-4'-methylphenyl phenyl sulfone (59) a-Phenyl-a-hy droxyacetaldehyde diphenyl thioacetal a,a-Dip henyl-a-hydroxyacetaldehyde diphenyl thioacetal Pentanal diphenyl thioacetal a-Hydroxycyclohexanecarboxaldehyde diphenyl thioacetal
334
87
330
80
330
96 92
330 330
na
J. M. Malian and R. 1. Bebb
Table VI (Continued) Compound metalated
ClrH1,N ClaH1:N ClpHl,OP
CiiHirP
N-Methyldiphenylamine 10-Methylacridan Diphenylmethylphosphine oxide Methyldiphenylphosphine
RLi
6
C,&hFeN
78 14
330 330 345
BuLi
Ether
Chlorotriphenylsilane Benzaldehyde
10-Methyl-9-(triphenyIsilyl>
81
tftr
31
458
81
458
21
457
25
458
25
458
BuLi BuLi BuLi BuLi
Dimethylaminomethylferrocene
BuLi
Hexane Ether Hexane Ether Ether Hexane Ether Hexane Ether Hexane Ether Ether Ether
Benzophenone Carbon dioxide, sulfur Di-n-oct ylphosphinyl chloride Diphenylphosphinyl chloride 3-Pentanone Ferrous chloride Trimethylchlorosilane
Ether Hexane Ether Hexane THF
Acetone
Ether Hexane Ether Hexane THF
Benzophenone
Hexachloroethane
BuLi
Ether Hexane Ether Hexane Hexane
BuLi
Ether
BuLi
Hexane Ether Hexane Ether Hexane Ether Hexane Ether Hexane Ether Hexane Ether Hexane Ether Hexane Ether Hexane Ether
BuLi BuLi BuLi BuLi BuLi BuLi BuLi
Benzonitrile Benzophenone
Deuterium oxide
acridan (2-Hydroxy-2-phenylethy1)diphenyl phosphine oxide (2-Hydroxy-2,2-diphenylethyl)diphenylphosphine oxide Carboxymethyldiphenylphosphine sulfide [(Di-n-octylphosphinyl)(diphenylphosphinyI)]methane Bis(diphenylphosphiny1)methane
67
(2-Ethyl-2-hydroxybutyl)6L diphenylphosphine oxide Di(3-butylindeny1)iron 20 3-Isopropyl-1-trimethylsilylferrocene (30) 1 '-Isopropyl-1-trimethylsilylferrocene (70) 2-(a,a-Dimethylhydroxymethyl)14 dimethylaminomethylferrocene 2-(Dimethylaminomet hy1)ferro58 cenylphenone 2,l '-Di(apdipheny1hydroxy45 methyl)dimethylaminomethylferrocene 2-(a,a-Diphenylhydroxymethyl)- 7'1-75 dimethylaminomethylferrocene Dimethylaminomethylferrocene72
458 450 43 1
439 439 439 438, 439 439
2-d
Deuterium oxide
Phenyl isocyanate Trioxymethylene
Dirnethylaminomethylferrocene2,l '-d 2-Chlorodimethylaminomethylferrocene 2-(Dimethylaminomethyl)-Nphenylferrocenecarboxamide 1-Hydroxymethyl-2-dimethylaminomethylferrocene 2-n-Amyl-l,3,5-trimethylbenzene
84
439
60
376
31
439 hhhh
67
bbb
44
458
SI
458
50
458
49
458
33
458
67
458
35
458
30
458
33
458
'XNM%
Ha
C1:H*,OP
Ref
Bis(pheny1thio)methane-a-d Acetaldehyde diphenyl thioacetal N-Methyl-N-phenplanthranilic acid
BuLi BuLi
CHf$L8
yield
Deuterium oxide Methyl iodide Carbon dioxide
3-Butylindene Isopropylferrocene
QaH2oN
?
Final product
THF THF Ether
BuLi
CIrHl7Fe
Reactant
BuLi BuLi BuLi
BuLi
cla1
Solvent
Di-n-hexylmethylphosphine oxide
BuLi BuLi BuLi BuLi BuLi BuLi BuLi BuLi
Acetaldehyde Acetophenone Benzaldehyde Benzophenone Butyraldehyde Carbon dioxide Di-n-hexylphosphinyl chloride Ethyl acetate Ethyl benzoate
Di-n-hexyl-(2-hydroxy-n-propyl)phosphine oxide Di-n-hexyl-(2-hydroxy-2-phenylpropy1)phosphine oxide Di-n-hexyl(2-hydroxyp henylethy1)phosphine oxide Di-n-hexyl-(2-hydroxy-2,2-dipheny1ethyl)phosphine oxide Di-n-hexy 1-(Zhydroxy-+penty1)phosphine oxide Carboxymethyl-di-n-hexylphosphine oxide Bis(di-n-hexylphosphinyl> methane Acetonyldi-n- hexylphosphine oxide Di-n-hexylphenacylp hosphine oxide
Metalations by Organolithium Compounds
749 ~
~
TabIe VI (Continued) Compound metaIated
RLi
BuLi Di-n-hexylmethylphosphine 3-chloro-4dimethyl-
Solvent
Reactant
3-Pentanone
yield
(2-Ethyl-2-hydroxybutyl)-di-nhexylphosphine oxide Carboxymethyl di-n-hexylphosphine sulfide
46
458
46
457
Ref
r-BuLi
Hexane Ether Pentane
BuLi
Ether
Carbon dioxide
3-Chloro-4dimethylaminophenyl phenyl sulfone 2-carboxylic acid
83
342
BuLi
THF Ether Hexane
Carbon dioxide
3,3-Di(khlorop henyl)-2thloroacrylic acid
88
203
EtLi
Ether
Carbon dioxide
+
12-15 12-15
125,268
BuLi
Ether
Carbon dioxide
2-Phenyl-3-(o-carboxyphenyl)Zpentenoic acid 2-phenyl3-ethylindone 2-Phenyl-3-(o-carboxyp heny1)2-heptenoic acid 2-phenyl-
+
14-15 1S-28
125,268
BuLi
THF Ether Hexane
Carbon dioxide
3-Phenyl-3-pchlorop henyl-2chloroacrylic acid
87
203
BuLi
THF Ether Pet. ether
Carbon dioxide
3,3-Bis(o-chlorop henyQ-2-chloroacrylic acid
76
201
BuLi
THF Ether Pet. ether
Carbon dioxide
3,3-Bis(pchlorophenyl)-2-chloroacrylic acid
86
201
BuLi
THF Ether Hexane Ether THF THF Ether Hexane THF Hexane Ether
Bromine
l,l-Diphenyl-2-chloro-2-brmoethylene
94
200
Carbon dioxide
3,3-Diphenyl-2-chloroacrylicacid
85-94
Iodine
1,l-Diphenyl-2-chloro-2-iodoethylene
98
199-201, 203 200
Mercuric chloride
18
200
THF Ether Hexane THF Ether Pet. ether THF Ether Pet. ether Ether
Methyl iodide
(l-Chloro-2,2-diphenylvinyl> mercuric chloride bis( 1chloro-2,2-diphenylvinyl)mercury 1,l-Diphenyl-2-chIoro-I-propene
Silver chloride
1-Chloro-2,2-diphenylvinylsilver
Silver chloride, bromine
2,2-Diphenyl-l-chloro- 1-bromoethylene
77
196
Carbon dioxide
1-(o-CarboxyphenyI)-24ndolecarboxylic acid 9,10-Dihydroanthracene- 10carboxylic acid 9,lO-Dihydroanthracene- 10carboxylic acid
15
355
38
R
72
271
Carbon dioxide, sulfur
aminophenyl phenyl sulfone l,l-Di(4chlorophenyl)chloroethylene Diphenylacetylene
?
Final product
3-but ylindone
1-Phenyl-lpchlorophenylchloroethylene 2,2-Bis(0-
chloroPhenyl)-
chloroethylene 2,2-Bis(p chlorophenyl> chloroethylene 2,2-DiphenyE chloroethylene
BuLi BuLi BuLi
BuLi BuLi BuLi I-Phmylindole 9,lO-Dihydroanthracene
BuLi Poly-pstyryllithium PhrSiLi
Ether
Carbon dioxide
THF
Carbon dioxide
+
69
86
200 196
J. M. Mallan and R. L Bebb
750
Table VI (Continued) Compound metalated
RLi BuLi
10-Ethylphenothiazine
Solvent Ether
BuLi BuLi
Ether
Reactant N,N-Dimethylcarbamoyl chloride Benzophenone Carbon dioxide
PhsSiLi
THF
Carbon dioxide
BuLi BuLi BuLi
Ether Ether Ether
Lithium acetate Lithium benzoate Carbon dioxide
BuLi
Carbon dioxide
BuLi
Ether THF THF
PhLi
THF
Carbon dioxide
BuLi
Ether
PhLi 2-Methyldstyrylpyridine 10-Ethylphen- BuLi oxazine MeLi
Ether
Triphenylsilyl bromide Propionaldehyde
9-Ethylcarbazole
10-Ethylphenothiazine 5-oxide Diphenylvinylphosphine Ditoluenechromium Ethylene glycol diphenyl ether pTolyl sulfone Acetaldehyde diphenyl thioacetal 2-Methyl-5phenethylpyridine b-Ionylidenebromomethane 3-Phenylindene Dibenzyl methylamine 4Trimethylsilylphenyl phenyl ether Allyltri-nbutyltin Pyrene
Carbon dioxide
Final product
? yield
9,lO-Di hydroxyanthracenebis(N,N-dimethylcarboxamide)
Ref 207
4(Diphenylhydroxymethyl)-lOethylphenothiazine
55
kkk
1O-Ethylphenothiazine- 1-carbox-
13 14
jjj, iiii
+
ylic acid IO-ethylphenothiazine-4-carboxylic acid 10-Ethylphenothiazine4carboxylic acid CAcetyI-IO-ethylphenothiazine 4Benzoyl- 1O-ethylphenothiazine 9-Ethylcarbazole-1-carboxylic acid 9-Ethylcarbazole-1-carboxylic acid 9-Ethylcarbazole-1-carboxylic acid 9-Ethylcarbazole-1-carboxylic acid 1-Triphenylsilyl-9-ethylcarbazole
2
271
13 17 2
jii
21
157
1
157
10
157
12
ee
Z-Methyl-&(a-benzhydryl-,%
iii
157
cc
hydroxybuty1)pyridine Ether
Carbon dioxide
10-Ethylphenoxazine-4-carboxylic acid
66
284
Ether
Carbon dioxide
15
284
BuLi
Ether
Carbon dioxide
BuLi
Ether
Iodine
10-Ethylphenoxazine-4carboxylic acid 4Carbomethoxy- 1O-ethylphenothiazine 4Iodo-10-ethylphenothiazine
BuLi
Ether Hexane
Carbon dioxide, sulfur
(a-Carboxy-whexy1)diphenylphosphine sulfide
Carbon dioxide
Dilithium-chromium ditoluate Ethylene glycol phenyl o-carboxyphenyl ether Ethylene glycol phenyl o-triphenylsilylphenyl ether 2-Carboxy-4,4’-dimethylphenyl phenyl sulfone a,a-Diphenyl-a-hydroxyacetone diphenyl thioketal
14
29 1
7
291
53
335
74
330
2-MethyI-6-(dibenzylmethyl)Dyridine
25
350
24
188
BuLi
ijjj
23
iiii
45
459 454
BuLi
Ether
Carbon dioxide
BuLi
Ether
BuLi
Ether
Triphenylchlorosilane Carbon dioxide
BuLi DABCO
THF
Benzophenone
PhLi
Ether
Benzyl chloride
BuLi
THF
Carbon dioxide
BuLi
Ether
Ferrous chloride
Di(3-phenylindeny1)iron
18
450
BuLi
Ether
Benzaldehyde
56
374
BuLi BuLi
Ether THF
Deuterium oxide Dichlorodiphenylsilane
2-(Benzylmethylaminomethyl)benzhydrol Dibenzylmethylamine-2d 2-Trimethylsilyl-10,lO-diphenylphenoxasilin
17
375 290
PhLi
Ether
4,6-DimethyI-l-hepten-Col
70
kkkk
BuLi
Ether
4Methyl-2pentanone Carbon dioxide
Pyrene-1,2- and -3-carboxylic acid
85
280
751
Metalations by Organolithium Compounds
Table VI (Continued) Compound metalated
RLi
12H-Benzo[alphenothiazine 12H-Benzo[blphenothiazine 7H-Benzo[c]phenothiazine 3-Benzylindene 1,I-Bis-(pmethoxyphenyl)2,2-dibromoethylene 2,Z-Dibenzyl1chloroethylene 2,2-Bis(p-tolyl)chloroethylene 2,2-Bk(0-tolyl)chloroethylene 2,2-Bis(omethoxyphenyl)chloroethylene 2,2-Bis(pmethoxypheny1)chloroethylene a-Ferrocenylfulvene 9-Trimethylsilylfluorene
BuLi
2-Phenyl-2p-tolylpropane Ct-Butylphenyl phenyl sulfone 2-Methylbenzyldimethylaniline Hydroquinonebis(Ztetrahydropyrwl) ether Methallyltriphenyltin IO-Phenylphenoxazine
Solvent Ether
Reactant Carbon dioxide
Final product 12H-benzo[a]phenothiazine-1-
? yield
Ref
94
393
carboxylic acid BuLi
Ether Hexane
Carbon dioxide
12H-benzo[b]phenothiazine-l1carboxylic acid
82
395
BuLi
Ether
Carbon dioxide
7H-benzo[c]phenothiazine-6carboxylic acid
41
396
BuLi
Ether
Ferrous chloride
Di( 3-benzylindeny1)iron
10
450
BuLi
THF
Carbon dioxide
a-Bromo-#l-bis(p-methoxypheny1)acrylic acid
69
188
BuLi
THF Ether Pet. ether THF Ether Pet. ether
Carbon dioxide
3,3-Dibenzyl-2-chloroacrylic acid
92-93
190,191
Carbon dioxide
3,3-Bis(p-tolyl>2-chloroacrylic acid
78
199, 201, 203
BuLi
THF Ether Pet. ether
Carbon dioxide
3,3-Bis(o-tolyl)-2-chloroacrylic acid
45
201
BuLi
THF Ether Pet. ether
Carbon dioxide
3,3-Bk(emethoxyphenyl)-2chloroacrylic acid
8
201,203
BuLi
THF
Carbon dioxide
3,3-Bis(p-methoxyp heny1)-2chloroacrylic acid
61
199, 201, 203
Ferrous chloride
1,l ’-Di(a-ferrocenylbenzy1)-
21
452
ferrocene 9-Methyl-9-(trimethylsilyl)fluorene 9,9-Di(trimethylsilyl)fluorene
31
Ill1
17
Ill1
BuLi
Ether Pet. ether PhLi
Ether
BuLi
Ether
Methyl iodide
BuLi
Ether
BuLi
Ether
Trimethylchlorosilane Carbon dioxide
BuLi
Ether
Carbon dioxide
BuLi
Benzonitrile
BuLi
Hexane Ether Hexane Ether Ether
PhLi
p-(a,a-Dimethy1benzyl)p henylacetic acid
mmmm
337
68
381
88
381
Carbon dioxide
2-Carboxy-4’-t-butylphenyl phenyl sulfone (69) 2carboxy-4-t-but ylphenyl phenyl sulfone (31) 24Dimethylaminomethy1)benzyl phenyl ketone 2-[a-(Dimethylamino)-o-tolyl]1,1,2-triphenylethanol 2,5-Dihydroxybenzoic acid
65
301
Ether
Acetaldehyde
2-Methyl-1-penten-4-01
59
495
BuLi
Ether
Carbon dioxide
Trace
284
MeLi
Ether
Carbon dioxide
10-Phenylphenoxazine-Ccarboxylic acid 10-Phenylphenoxazine-&arboxylic acid
Trace
284
BuLi
Benzophenone
+
J. M. Mallan and R. 1. Bebb
752
Table VI (Continued) Compound metalated
RLi
Solvent
Reactant
Final product
x
yield
Ref
EtLi
Ether
Benzophenone
84
46 1
MeLi EtLi
Ether Ether
Benzophenone Carbon dioxide
74 50
461 460,461
MeLi MeLi
Ether Ether
47 25
460, 461 461
EtLi MeLi MeLi
Ether Ether Ether
78 76 65
461 461 461
BuLi
Ether
EtLi
Ether
MeLi
Ether
Triphenylphosphine sulfide
MeLi
Triphenylgermane
BuLi BuLi
THF Ether Ether THF Ether Ether
Carbon dioxide Diphenylchlorophosphine, sulfur Hydrobromic acid Hydrobromic acid Triphenylchlorosilane Triphenyltin chloride Triphenyltin chloride Triphenyltin chloride Carbon dioxide Triphenyltin chloride Acetone Acetophenone
BuLi
THF
Acetyl chloride
BuLi
THF
Acetyl chloride
BuLi
Ether
Benzophenone
BuLi
THF
Benzoyl chloride
BuLi BULi
THF THF
BuLi BuLi MeLi PhLi BuLi BuLi
Ether Ether Ether Ether Ether THF
BuLi
Ether
Benzoyl chloride Benzoyltriphenylgermane 2-Butanone Carbon dioxide Carbon dioxide Carbon dioxide Di-n-propyl ketone pFluorobenzoyl chloride Isobutyrophenone
BuLi
THF
BuLi BuLi
Ether THF
BuLi
Ether
PhSiLi
BuLi
Ether Benzene EGDE Ether Ether
BuLi BuLi
Triphenylphosphine oxide
Triphenylsilane
MeLi
PhrSiLi Duryl &tolyl ketone Dirnesityl sulfone Diphenyln-hexylphosphine sulfide
Ethyl diphenylphosphine oxide Methyl diphenylphosphine oxide (Diphenylphosphinylrnethy1)-
triphenylsilane 69 (C,H,)zP(o)CH[sn(C8H,)sjCHzCHzCHa ( C & , ) Z P ( ~ ) C H ( C H ~ ) ~ ~ ( C & ~81 )~
461 460, 461
(Diphenylphosphinylmethy1)trip henyltin Carboxymethyldiphenylphosphine sulfide Triphenylstannylmethyldiphenylphosphine sulfide 2-Triphenylgermyl-2-propanol 1-Triphenylgermyl-l-phenyl-lethanol 1,l -Bis(triphenylgermyl)-1ethanol 1,1-Bis(triphenylgerrny1)-1ethanol Triphenylgermyldiphenylcarbinol Bis(triphenylgermy1)phenylcarbinol Benzoyltriphenylgerrnane 1,l-Bis(tripheny1gerrnyl)phenylcarbinol 2-Triphenylgermyl-2- butanol Triphenylgermanecarboxylicacid Triphenylgermanecarboxylicacid Triphenylgermanecarboxylicacid 4-Triphenylgermyl-4-heptanol Bis(triphenylgermy1)-pfluorophenylcarbinol 1-Triphenylgermyl- 1-phenyl-2methyl-1-propanol pMethoxybenzoyltripheny1germane 3-Triphenylgermyl-3-pentanol 1,l-Bis(triphenylgermy1)-1propanol p-Trifluoromethylbenzoyltriphenylgermane
76
460,461
39
460, 462
74
460
46 68
403 403
85
401
67
401
81
403
49
401
80 57
401
37 97 77 83 48 60
403 400 400 400 403 401
84
403
84
401
70 37
403 401
44
401
22 46 14
405, ntinn
Carbon dioxide
Triphenylacetic acid, triphenylsilanol Hexaphenyldisilane, tetrap henylsilane o-Duroylphenylacetic acid
17
270
Ether
Carbon dioxide
Monocarboxydimesityl sulfone
25
334
Ether Hexane
Carbon dioxide
(a-Carboxy-n-hexy1)diphenylphosphine sulfide
12
459
p-Methoxybenzoyl chloride 3-Pentanone Propionyl chloride pTrifluoromethy1benzoyl chloride Carbon dioxide Carbon dioxide
401
405, nnnn
11
Metalations by Olrganolithium Compounds
753
Table VI (Continued) Compound metalated
RLi
Solvent
Reactant
Final product
yield ?
Ref
9-Phen ylfluorene-9-car boxylic
80 80
298 172
Carbon dioxide
acid Phenyl-o-xenylacetic acid
25
0000
Ether
Carbon dioxide
Phenyl-p-xenylacetic acid
41
0000
Ether
Carbon dioxide
kiphenylacetic acid
71
405,
9-Phenylfluorene
BuLi PhLi
Ether
2-Benzylbiphenyl 4-Benzylbiphenyl Triphenylmethane
BuLi
Ether
BuLi BuLi
Carbon dioxide Carbon dioxide
9-Phenylfluorene-9-carboxylic acid
nwm, 0000
BuLi Excess PhLi +CHr C&Li PhaSiLi BuLi
Diphenylbenzylphosphine oxide
Carbon dioxide
Triphenylacetic acid
87
170
Ether
Carbon dioxide Carbon dioxide
Triphenylacetic acid Triphenylacetic acid
6 8
172 172
EGDE Ether
Triphenylacetic acid
37
405, nnnn 207
Triphenylmethyltriphenylsilane
34
205
Trimethyl(triphenylrnethy1)silane
70
gg
Diphenyl(1,2-diphenyl-Zhydroxy-2-ethy1)phosphine oxide Diphenyl(a-carboxybenzy1)phosphine oxide Lactam of 1-carboxy-14Hdibenzo[a,c]phenothiazine
90
PPPPl 9444
65
PPPP
85
394
n-PrLi
Ether
n-PrLi
Ether
PhLi
Ether
Carbon dioxide N,N-Dimethylcarbamoyl chloride Triphenylchlorosilane Trimethylchlorosilane Benzaldehyde
PhLi
Ether
Carbon dioxide
Hexane Ether
Carbon dioxide
Hexane
Carbon dioxide
l-Carboxy-l4H-dibenzo[a,h]phenothiazine
80
394
Hexane Ether
Carbon dioxide
dCarboxy-7H-dibenzo[c,h]phenothiazine
77
394
Ether
Dibromomethane
9-Bromomethyl-9-benzylfluorene
61
YYY
THF
Deuterium oxide
Phenyl (2,2-diphenyl)vinyl-1-d sulfide
87
330
Ether Ether
Carbon dioxide Carbon dioxide
18 13-57
Ether Ether THF THF
Water Water Triphenylsilane Chlor otriphenylsilane
3,3-Diphenylphthalide 9-PhenyMuorene-9carboxyiic acid %Phenylfluorene PPhenyMuorene 1,3-Bis(triphenylsilyl)propyne Tris(triphenylsily1)propadiene
5
41 1
PhrSiLi
Ether Ether Ether
l,ZBis(trip henylsily1)propene Tris(triphenylsily1)propadiene 1-Octene Vinylacetic acid 4,6Dimethyl-l-hepten-4-01
18 32 52
411
PhLi PhLi PhLi
25
65
kkkk kkkk,
PhLi
Ether
Allyltri-n-butyltin
69
rrrr rrrr
PhLi
Ether
Allyltriphenylgermane
54
rrrr
PhLi
Ether
Chlorotriphenylsilane Chlorot riphenylsilane n-Amyl iodide Carbon dioxide 4-Methyl-2pentanone Tri-ti-butyltin chloride Triphenyl germanium bromide Triphenylchlorosilane
I, 3-Bis(triphenylsily1)propyne 1,3-Bis(triphenylsilyI)propyne
13
Ether THF THF
Allyltriphenylsilane
74
kkkk,
14H-Dibenzo- BuLi [~I~henothiazine 14H-Dibenzo- BuLi [a,h]phenothiazine 7H-DibenzoBuLi [o,h]phenothiazine PhLi PBenzylfluorene BuLi Phenyl (2,2dipheny1)vinyl sulfide Tr iphenylBuLi PhLi methyl methyl BuLi ether PhLi E -(Triphe& PhLi PhLi sily1)proPYne PhaSiLi
AUyltriphenyltin
THF
Ether
Triphenyl-N,N-dimethylacetamide
20 71 32 23
172, 298 172, 298 298 298 41 1 411
rrrr
rrrr
J. M. Mallan and
754
R. 1. Bebb
Table VI (Continued) Compound metalated
RLi
Solvent
Final product
Reactant
x
yield
Ref
PhLi PhLi
Ether Ether
Triphenylsilane Water
PhLi
THF
Triphenylsilane
PhLi
Ether
Acetaldehyde
2-Methylpent-1-en-4-01
53
rrrr
PhLi
Ether
Triethylmethallylsilane
68
rrrr
Diphenylferrocenylcarbinol
BuLi
Ether
Triethylbromosilane Carbon dioxide
73
303
BuLi
Ether
Methyl iodide
69
303
Triphenylmethylcyclopentadiene Triphenylbenzylsilane Triphenylbenzyltin Triphenyl(phenethyny1)silane Dibenzhydryl ether 2-(cu,cu-Diphenylhydroxymethyl) dimethylaminomethylferrocene 1&Diphenylenebutane 1,l-Di(cyc1ohexylborony1)hexane
PhLi
Ether THF
Ferric chloride
2-Carboxydiphenylferrocenylcarbinol 2-Methyldip henylferrocenylcarbinol 1,l '-Bis(triphenylmethy1)ferrocene
18
PP
BuLi
Ether
Carbon dioxide
Phenylacetic acid
43
399
PhLi
Ether
Carbon dioxide
Phenylacetic acid
39
ssss
BuLi
Ether
Carbon dioxide
Phenylpropiolic acid
19
399
BuLi
Carbon dioxide
Di(ocarboxy)benzhydryl ether
LOW
299
BuLi
Benzene Ether THF
Benzophenone
2,l '-Di(cu,u-diphenylhydroxymethy1)dimethylaminomethylferrocene
71
439
PhLi
Ether
Benzyl chloride
65
YYY
BuLi BuLi BuLi
Benzaldehyde Benzophenone Carbon dioxide
45-50 45-50 65-70
486 486 485
20-25 20-25 30-35 25
486 486 486 257
58
257
PhoSiLi
THF THF THF Heptane THF THF THF Ether THF Ether THF THF
1,4-Dibenzyl-l,4-dibiphenylenebutane 1-Phenylhept- 1-ene 1,l-Diphenylhept-1-ene 2-Pentylmalonic acid
51
411
PhLi PhLi
THF THF
14
41 1 411
PhLi
THF
88
411
67
41 1
9-Cinnamylidenefluorene 1-(Triphenylsilyl)-lbutyne Methallyltriphenyltin
Triphenyl(diphenylmethyl). silane 1,3-Bis(trip henylsilylpropwe Tris(triphenylsily1)propadiene
BuLi BuLi BuLi BuLi BuLi
Cholestanone Cyclohexanone Di-n-amyl ketone Benzyl chloride Dimethyl sulfate Chlorotriphenylsilane Methyl iodide Chlorotriphenylsilane Deuterium oxide
Allyltriphenylsilane l,l-Biphenylene-4,4-diphenyl2-butene
60
rrrr cccc
41 1
3-n-Hexylidene-5-cu-cholestane n-Hexylidenecyclohexane 6-n- Amylundec-dene
Triphenyl(1,1,2-triphenylethyl)silane Triphenyl(1,l-diphenylethy1)silane Tris(triphenylsily1)propadiene l13-Bis(triphenylsilyl)-1-butyne Tetrakis(triphenylsily1)propadiene Tris(triphenylsily1)propadiene1-d
PhLi
THF
Methyl iodide
1,I ,3-Tris(triphenylsily1)-1,2butadiene
M. Wieber and C. D. Frohning, Angew. Chem., Intern. Ed. Engl., 5, 966 (1966). a R. Huttel and M. E. Schon, Ann., 625, 55 (1959). V. I. Stank0 and A. I. Klimova, J. Gen. Chem. USSR, 35, 1142 (1965). d P. Moses and S . Gronowitz, Arkiv Kemi, 18, 119 (1961); Chem. Absrr., 56,10173 (1962). e Ya. L. Gol'dfarb, Ya. L. Danyushevskii, and M. A. Vinogradova, Proc. Acad. Sci. USSR, 151,539 (1963). f H. Gilman and T. N. Goreau, J. Org. Chem., 17, 1470 (1952). D. Braun and E. Seelig, Chem. Ber., 97, 3098 (1964). * F. J. Villani and C. A. Ellis, J. Org. Chem., 29, 2585 (1964). i S. Oshiro, J. Pharm. SOC.Japan, 75, 658 (1955); Chem. Absrr., 50, 3436 (1956). i R. D. Schuetz, D. D. Taft, J. P. O'Brien, J. L. Shea, and H. M. Mork, J. Org. Chem., 28,1420 (1963). I: J. C. W. Postrna and J. F. Arens, Rec. Trav. Chim., 75, 1408 (1956). J. F. Arens, H. C. Volger, T. Doornbos, J. Bonnema, J. W. Greidanus, and J. H. van der Hende, ibid., 75, 1459 (1956). 0
J
755
Metalations by Organolithium Compounds
m G. Wittig and R. Polster, Ann., 599, 1 (1956). W. J. Linn and W. H. Sharkey, J. Am. Chem. SOC.,79, 4970 (1957). D. N. Kursanov, N. K. Baranetskaya, and V. N. Setkina, Dokl. Akad. Nauk, SSSR, 113, 116 (1957); Chem. Abstr., 51, 14711 (1957). p H. S. Nametkin, T. I. Chernysheva, and L. V. BabarB, J. Gen. Chem. USSR, 34,2270 (1964); Chem. Abstr., 61,9525 (1964). q E. D. Bergmann, G. Berthier, D. Ginsburg, Y. Hirshberg, D. Lavie, S. Pinchas, B. Pullman, and A. Pullman, Bull. SOC.Chim. France, 661 (1951). W. von E. Doering and C. H. DePuy, J. Am. Chem. SOC.,75, 5955 (1953). * W. R. Biggerstaff and K. L. Stevens, J. Org. Chem., 28, 733 (1963). W. Herz and L. Tsai, J. Am. Chem. SOC.,77, 3529 (1955). Ya. L. Gol'dfarb, M. A. Kalik, and M. L. Kirmalova, J. Gen. Chem. USSR, 29, 3592 (1959). p C . Osuch and R. Levine, J. Am. Chem. SOC.,78,1723 (1956). wG.Jones and H. D. Law, J. Chem. SOC.,3631 (1958). J. A. Gautier, I. Marszak, and M. Miocque, Bull. SOC.Chim. France, 415 (1958). Y B. M. Mikhailov, G . S. Ter-Sarkisyan, and F. B. Tutorskaya, Izu. Akad. Nauk SSSR, Otd. Khim. Nauk, 831 (1959); Chem. Abstr., 54, 1416 (1960). * N. J. Leonard and A. S. Hay, J. Am. Chem. SOC.,78, 1984 (1956). aa N. N. Goldberg, L. B. Barkley, and R. Levine, ibid., 73,4301 (1951). bb B. M. Mikhailov and G. S. Ter-Sarkisyan, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, 1267 (1960); Chem. Abstr., 55, 542 (1961). cc V. Hnevsova and I. Ernst, Collect. Czech. Chem. Commun., 25, 1468 (1960); Chem. Abstr., 54, 17393 (1960). D. Grafstein, J. Bobinski, J. Dvorak, J. E. Paustian, H. F. Smith, S. Karlan, C. Vogel, and M. M. Fein, Inorg. Chem., 2, 1125 (1963). R. H. Meen and H. Gilman, J. Org. Chenr., 20, 73 (1955).I' L. Santucci, L. Tavoletti, and D. Montalbano, Ric. Sci. Rend., A2, 46 (1962); Chem. Abstr., 58, 4460 (1963). 00 H. Gilman, L. F. Cason, and H. G. Brooks, J. Am. Chem. SOC.,75, 3760 (1953). N. N. Goldberg and R. Levine, ibid., 77, 4926 (1955). ii E. N. Karaulova. D. Sh. Meilanova, and G. D. Gal'pern, Dokl. Akad. Nauk SSSR, 123,99 (1958); Chem. Abstr., 53,5229 (1959). ij E. N. Karaulova, D. Sh. Meilanova, and G. D. Gal'pern, J. Gen. Chem. USSR, 30, 3262 (1960); Chem. Abstr., 55, 19892 (1961). kk E. N. Karaulova, D. Sh. Meilanova, and G. D. Gal'pern, Khim. Sera-i Azotorgan. Soedin., Soderzhashch. v Neft. i Nefteprod., Akad. Nauk SSSR, Bashkirsh. Filial, 3, 25 (1960); Chem. Abstr., 59, 1568 (1963). J. E. Banfield, W. Davies, N. W. Gamble, and S. Middleton, J. Chem. SOC.,4791 (1956). mm R. Gaertner, J. Am. Chem. SOC.,74, 766 (1952). nn G. Vasilev, Compt. Rend. Acad. Bulgare Sci., 10, 125 (1957); Chem. Abstr., 52, 5352 (3958). oo 0. Meth-Cohn and S. Gronowitz, Acta Chem. Scand., 20, 1733 (1966). p p W. F. Little and R. C. Koestler,J. Org. Chem., 26, 3247 (1961). 0'1 D. Seyferth and M. A. Weiner, Chem. Ind. (London), 402 (1959). L. I. Zakharkin and A. I. L'vov, J. Gen. Chem. USSR, 36, 777 (1966); Chem. Abstr., 65, 8939 (1966). L. H. Sommer and N. S. Marans, J. Am. Chem. SOC.,73, 5135 (1951). H. Hock and F. Ernst, Chem. Ber., 92, 2716 (1959). uu L. S. Miller, Iowa State Coll. J. Sci., 26, 249 (1952); Chem. Abstr., 48, 143 (1954). 0" H. F. Herbrandson and D. S. Mooney, J . Am. Chem. SOC., 79, 5809 (1957). J. G. Traynham, J. Sci. Lab., Denison Uniu., 42, Art. 415, 60 (1951); in Denison Uniu. Bull., 51, No. 1 (1951). 22 F. N. Jones and C. R. Hauser, J. Org. Chem., 27, 701 (1962). J. G. Cannon and G. L. Webster, J . Am. Pharm. Assoc., 46, 416 (1957). H. Watanabe, I. Motoyama, and K. Hata, Bull. Chem. SOC.Japan, 39, 784 (1966). aaa A. N. Nesmeyanov, E. G. Perevalova, L. I. Leont'eva, and Yu. A., Ustynyuk, Izv. Akad. Nauk SSSR, Ser. Khim., 556 (1966); Chem. Abstr., 65, 7214 (1966). m C. R. Hauser, J. K. Lindsay, and D. Lednicer, J. Org. Chem., 23, 358 (1958). cCC K. Hata, I. Motoyama, and H. Watanabe, Bull. Chem. SOC. Japan, 36, 1698 (1963); Chem. Abstr., 60, 6865 (1964). ddd K. Hata, I. Motoyama, and H. Watanabe, Bull. Chem. SOC.Japan, 37, 1719 (1964); Chem. Abstr., 62, 4051 (1965). E6a Ya. L. Gol'dfarb and M.L. Kirmalova, J. Gen. Chem. USSR, 29, 881 (1959).''1 L. Horner, W. D. Balzer, and D. J. Pzterson, Tetrahedron Letters, 3315 (1966). o m R. Huisgen and H. Rist, Ann., 594, 137 (1955). hhh H. Gilman and J. A. Beel, J. Am. Chem. SOC.,73, 774 (1951). i i i W. Baker, A. J. Boulton, C. R. Harrison, and J. F. W. McOmie, Proc. Chem. SOC., 414 (1964). j j i G. Cauquil, A. Casadevall, and E. Casadevall, Bull. SOC. Chim. France, 1049 (1960). kkk R. D. Nelson, Iowa State CON. J. Sci., 27, 229 (1953); Chem. Abstr., 48, 2069 (1954). l L L G. Cauquil, E. Casadevall, and A. Casadevall, Compt. Rend., 243, 159 (1956). n m m H. Gilman and H. A. McNinch, J. Org. Chem., 27, 1889 (1962). nnn H. Gilman and D. R. Swayampati, ibid., 21,1278 (1956). 000 I. M. Panaiotov and G. Borisov, Compt. Rend. Acad. Bulgare Sci., 9,27 (1956); Chem. Abstr., 52,7189 (1958). p p p I. M. Panaiotov, Compt. Rend. Acad. Bulgare Sci., 9, 25 (1956); Chem. Abstr., 52, 1974 (1958). 999 T. L. Katz and J. Schulman, J . Am. Chem. SOC.,86, 3169 (1964). r7r J. M. Davidson and C. M. French, J. Chem. SOC., 191 (1960). '** D. Wittenberg, D. Aoki, and H. Gilman, J. Am. Chem. SOC.,80, 5933 (1958). L. Skatteboel, Acta Chem. Scand., 13, 1460 (1959). uuu S. Raynolds and R. Levine, J. Am. Chem. W. S. Murphey and C. R. Hauser, SOC., 82, 1152 (1960). u u y J. M. Osgerby and P. L. Pauson, J. Chem. SOC., 4600 (1961). J. Org. Chem., 31, 85 (1966). Dzz F. M. Beringer, J. A. Farr, Jr., and S. Sands, J. Am. Chem. SOC.,75, 3984 (1953). vw G. Wittig, P. Davis, and G. Koenig, Chem. Ber., 84,627 (1951). J. A. Gautier, M. Miocque, and H. Moskowitz, J . Organmetal. Chem., 1,212 (1964). aaaa E. D. Bergmann, E. Fischer, Y. Hirshberg, and D. Lavie, Bull. SOC.Chim. France, 709 (1952). bm E. D. Bergmann, Y. Hirshberg, D. Lavie, Y. Sprinzak, and J. Szmuszkovicz, ibid., 703 (1952). cccc E. D. Bergmann and Z. Pelchowicz, ibid., 809 (1953). d d d d H. Gilman and J. Goodman, J. Org. Chem., 22, 45 (1957). de8e B. A. Tertov, N. A. Ivankova, and A. M. Simonov, J. Gen. Chem. USSR. 32, 2939 (1962). 'f" R. Nakai, E. T. Holmes and H. R. Snyder, J. M. Sugii, and H. Tomono, J. Pharm. SOC.Japan, 75, 1014 (1955); Chem. Abstr., 50, 4930 (1956). G. Cauquil, A. Casadevall, and E. Org. Chem., 29, 2155 (1964). J. Tirodlet and C. Moise, Compt. Rend., Ser. C, 262, 1889 (1966). Casadevall, ibid., 243, 590 (1956). jjjj H. Gilman, R. K. Ingham, J. F. Champaigne, Jr., J. W. Diehl, and R. 0. Ranck, J. Org. Chem., 19, 560 (1954). U k k D. Seyferth and M. A. Weiner, ibid., 24,1395 (1959). l l l L C. Eaborn and R. A. Shaw, J . Chem. SOC.,1420 (1955). m m m m H. E. Zimmerman and A. Zweig, J . Am. Chem. SOC.,83, 1196 (1961). nnnn A. G. Brook and H. Gilman, ibid., 76, 2333 (1954). OoD0 P. T. Lansbury and R. Thedford, J. Org. Chem., 27, 2383 (1962). p p p p L. Horner, H. Hoffmann, H. Wippel, and G. Klahre, Chem. Ber., 92, 2499 (1959). qq*g L. Horner and W. Klink, Tetrahedron Letters, 2467 (1964). rrrr D. Seyferth and M. A. Weiner, J . Org. Chem., 26, 4797 (1961). (a*' H. Gilman and S. D. Rosenberg, ibid., 24, 2063 (1959). L L t t H. Gilman and G. Lichtenwalter, ibid., 23, 1586 (1958). '1
QW
