a11
JI!EG/Unit Processes Review
Friedel-Crafts Acylations b y K. LeRoi Nelson and Richard
THE
T. Hawkins, Brigham Young University, Prouo, Utah
b
Olefin acylations resulting in mixed products emphasize the need for better understanding of double-bond migrations
1
The Fries rearrangement has become a sophisticated reaction in its own right
tendency of Friedel-Crafts acylations to assume a routine status is frequently offset by the advent of novel reagents, unusual conditions, and unique applications. For example, a wide interest is foreseen in the use of perchloryl fluoride as an acylating agent as well as a fluorinating agcnt. T h e perchloryl aromatics, unaffected in acid or neutral media but hydrolyzed to phenols in strong alkali, are comparatively stable, although found to be sensitive to vigorous shock or high temperatures (56). Other nonroutine acylating reagents include benzoyloxytrichlorosilane (706), tris(bromomethy1)acetyl chloride ( G 7 ) , aryl- and alkylisocyanates (76) acetylsulfenyl chloride ( 7 4 , and [ p-(p-methoxyphenyl)ethylamino]acetonitrile hydrochloride and its propyl analog (77) T h e current interest in the chemistry of sandlvich-type compounds is reflected in the number of acylations of ferrocenes (45,4 3 , 76, 79, QO), of osmocene and ruthenocene (75) of cyclopentadienylmanganese tricarbonyl (30), and in the failure reported with mesitylenechromium tricarbonyl (69). The previously noted use of acylthiophenes in the syntheses of aliphatic compounds is becoming routine ( 9 7 ) . More complicated reactions are exemplified in the use of 4-methyl-3-mercaptoacetanilide to prepare 8-acetamido-5-methyl2,3-~yclopentanothiochromanone and related compounds (43), and diphenyl diselenomalonate to make 4-hydroxy-lselenocoumarin (709). The need for increased understanding of possible olefin double-bond migrations is emphasized by acylation reactions leading to a mixture of products (4: 7, 22, 72, 77). ~
10 1 8
(47) have been reported. A study of the preparation of 4-hydroxybenzophenone2’,3-dicarboxylic acid from phthalic anhydride and salicylic acid specifies optimum reaction conditions (78). Mixtures of NaCl and A1C13 ( 6 ) ; of NaC1, KC1: and A1C13 ( 3 6 ) ; or of NaBr, KC1, and AlC13 (89) have been claimed to provide higher reaction temperatures, higher purity products, and regulation of the reactivity of the AlC13 such as in the demethylation of methoxy compounds. T h e effects of various substrates, catalysts, and solvents upon the results of Fries rearrangements conducted at high temperatures with no solvent and also at low temperatures in solution have been explored (32). I n addition, a comparison of .41C13 and Tic14 as catalysts in the deep-seated rearrangement is required Fries rearrangement has been reported to explain the formation of l-methyl-3(37). (o - methylaminophenyl) - 2 - oxo - 1,2,3,Studies have appeared on the use of 4-tetrahydroquinoxaline from the 4-.VFeC13 with acyl halides ( 7 ) ; of Sic14 oxide of l-methyl-3-(iV-methylbenz- and A1C13 with carboxylic acids or amido) -2-oxo- Ii2,3,4-tetrahydroquinoxa- haloacyl halides (707); of PoC13, line ( 4 9 ) . H3P0,>and ZnClz with aryl carboxylic Historical interest in the Friedelacids (88); and of AlCl3 and ZnC12 with Crafts reactions was revived by Cadiot acyl halides (702, 703). Dolgov and and M‘illemart (27) in a discussion of Bnatov (40) have reported a catalyst preFriedel’s original laboratory notes on the pared by treating aluminum with hydrofirst Friedel-Crafts patent. gen chloride gas in benzene. T h e effects of solvents have been considered (70,87).
‘The rearrangement of 3-nitro-2to 4-nitro-2thienoylbenzoic acid thienoylbenzoic acid was confirmed by Newman and Ihrman (68); they also showed the production of the corresponding thiophanthraquinone. A 1,5aryl migration has been demonstrated by Lansbury and Letsingcr (GZ), in the conversion of 8-benzhydry-1-1-naphthoic acid to the hemiacetal of %[phenyl(hydrox);)methyl]-I-naphthophenone. A
Reaction Condi;ions T h e effects of temperature upon the cyclization of ðylenic carboxylic acids by polyphosphoric acid (80) and the effects of various reaction conditions upon the cyclization (Jvith simultaneous debenzylation as a competitive reaction) of p- (m-benzyloxyphenyl) propionic acid
INDUSTRIAL AND ENGINEERING CHEMISTRY
Kinetics and Mechanism Extensive studies have been reported, by Denney and Klemchuk (38, 3 9 ) , of the relative selectivity of replacement of hydrogen and deuterium in benzoylation by the thoughtful choice of 2deuterio-2’-carboxybiphenylas a n all-in-
a n ) m # f l Unit Processes Review
*
one-molecule reagent-substrate system. ditions. T h e reaction was concluded to (96); and comparative reactivities (97). The isotope effect varied from 1.15 to be intramolecular with acid anhydrides Orientation and isomer separations in 4.71 and depended on solvent, catalyst, and to involve an electrophilic substituacetylations of 2-methoxynaphthalene and homogeneity of the medium, being tion catalyzed by the diarylcadmium and its 6-alkyl homologs (79) as well as greater in better solvating and homoserving as a Lewis acid (35). phenanthrene ( 7 1 ) have been studied. Unsymmetrically substituted glutaric geneous media. Thesynthesis of diduryl ketone and isoVigorous studies of the kinetics of acids and anhydrides lead to the lessmeric by-products has received attention benzoylation have been continued by (46). The reaction between allylsuccinic hindered ketones (50, 54, 64). ConBrown and coworkers (75, 76, 57). figuration of the aryl-substituted acid anhydride and benzene has been exThe rates varied with the nature of the governs the structure of the cyclic ketone amined (73),as has the ring closure of the solvent. I n 1,2-dichoroethylene the reresulting from ring-closure acylation. acid chloride of @-(1-phenanthry1)proaction was first order for toluene and For example, the distribution between pionic acid ( 3 4 ,wherein the use of CS2 as first order for the 1 to 1 benzoyl chloride3-benzyl-2-phenylindanone and 2,3-disolvent prevented the formation of the AlCI8 complex. Benzoylation with benphenyltetralone depends upon the conby-product noted with nitrobenzene. zoyl bromide and AlBr3 was about 2070 figuration of the starting 2,3,4-triphenylAcylations with 3,4-dicarboxylic acid faster. Relative rates were reported for derivatives of substituted furans were butanoic acid (63, 64). The Dielsthe series of methylbenzenes. DiscrepAlder product from anthracene and mareported by Nightingale and Sukornick ancies with calculated rates were exleic anhydride will acylate another (70), and Rips and Buu-Hoi' have efplained by suggesting the formation of aromatic but cannot undergo ringfected mono- and diacylation of triternary nitrobenzene-AlC13-polymethyl- closure acylation (55). substituted pyrroles (87). Substituent benzene complexes. Several optically active acid chlorides effects and product isomer ratios in the T h e 1 to 1 mixture of acetyl chloride have been prepared and subjected to the cyclization of 3'-substituted 2-carboxy and AlC13 appears to be a pure liquid acylation reaction. When the active diphenyl ethers have been evaluated (47), complex. Thus, the infrared band for and the SnClz-catalyzed additions of a-carbon bears a hydrogen, the product the carbonyl absorption was found to be acyl chlorides to disubstituted cycloketone from anisole is inactive. Trishifted from 1807 to 1637 cm.-l Strong hexenes (28) have been reported. substituted acetyl chlorides without bulky bands a t 2203 and 2307 cm.-l were groups give active ketones. A highly attributed to the presence of the acetylhindered example gave some inactive Applications ium ion (29). Acetic anhydride reacts ketone as well as carbonyl loss with aniwith hydrogen chloride in acetic acid to Polystyrene has been converted to sole. All active acid chlorides gave ingive acetyl chloride and acetic acid. poly(pacety1styrene) in 92% yield using active products with benzene (73). T h e equilibrium constant for this reacacetyl chloride and AlC1,. T h e reaction The benzoylation of ethylene was shown tion was reported to be 5. T h e reaction to give the trans-bromovinyl phenyl failed with SnC14 and gave only a poor was shown to be rapid in the forward yield with acetic anhydride. Reactions ketone (3). direction by use of carbon-14 as a tracer. were successful with butyroyl chloride T h e reverse reaction was sdid to be slow. and stearoyl chloride but failed with Product Studies Mixtures of acetic anhydride and acetyl succinic or phthalic anhydrides (72). chloride with hydrogen chloride gave Acylations of azulenes have been exThe benzoylation of p-methoxy-tertrates of acetylation of @-naphthol in plored extensively, including formylabutylbenzene is ortho to the methoxy agreement with predicted rates (83). group. T h e tert-butyl blocking group tions with and without catalysts ( 9 5 ) ; Vilsmeyer formylation of acenaphthylcomparative formylations by means of can then be removed to give o-methoxyene occurs a t the 1-position to give a n dimethylformamide or N-methylformanibenzophenones. Several substituted unstable product rather than the 5lide with POC13, including diformylations benzoyl chlorides have been used (60). substituted product predicted by molecular-orbital theory (78). The successful Fries rearrangement of 1-naphthyl trimethylacetate was claimed to indicate that the trimethylacetylium ion is not an intermediate (770). This I conclusion, however, may not be fully I valid when compared to the studies of I Rothstein and coworkers (see previous I reviews) which indicated that direct I acylation with trimethylacetyl chloride I succeeded with active aromatic nuclei I (e.g., phenols and ethers), whereas carI bon monoxide was split out with less I AVAILABLE FOR ONE DOLLAR I active aromatics like benzene. Studies I of the steric and electronic nature of I hindering substituents have led to I the conclusion that complex formation at I the phenoxy1 oxygen atom is essential to I successful Fries rearrangements, while Complete bibliography and tables of reactions for the 1959 Unit Processes I the carbonyl oxygen atom does not have I Review of Friedel-Crafts Acylations. an important role in the reaction (82). I T h e reaction of m-anisylcadmium with acid chlorides to give p-anisyl ketones I was reported. I t was established that I no rearrangement of the organocadmium Use coupon on reverse side. I reagent occurred under the reaction conVOL. 52, NO. 12
0
DECEMBER 1960
1019
an 4-
Unit Processes Review
T h e preparation of 2-phenyl-3-pyrrocolinyl-1-glyoxylyl chloride utilized oxalyl chloride in benzene and ether (2). T h e synthesis of diphoschistesic acid involves the conversion of lecanoric acid (4-carboxy-3 -hydroxy-5 -methylphenyl2,4-dihydroxy-6-methylbenzoate) into its 3-formyl derivative (85). T h e ring-closure acylation leading to 2,3 - dihydro - 3,7,7- trioxo - 1H - pyrido[3,2,1-kl]phenothiazine provides a n interesting example of successful intramolecular acylation into a deactivated ring (53). Double-ring closures occur in the formation of 5,lO-dioxoindeno [2,1-a] indene (94) and 1H,1’H-2,2’,3,3’-tetra1,l’ - dioxospirobibenzonaphhydro thene (26). An AlCls-urea melt is the medium for giving a 9670 yield of bis(fi-acetamidopheny1)sulfoxide using thionyl chloride (8). I n CS2, 2,b-dialkylphenols are converted to triarylsulfonium chlorides (presumably via the sulfoxides) (44). Some highly hindered sulfones have been synthesized by direct sulfonylation (98). Several a- and/or p-hydroxyphenyl sulfones have been prepared from a Friestype rearrangement of the corresponding sulfonates ( 9 ) . A complex example of vinyl ketone deacylation occurs in 3’-acetyl-3-ethylidene - 2‘.4,6 - trimethyl - 2’ grisen - 4’one (37). Several fatty amides have been made by olefin acylations using carbamyl chloride (58). Acylation of acetylene followed by conjugate addition of methyl alcohol gives the ethyl ester of 8,8-dimethoxy-6-oxooctanoicacid (84). Formylation of 2-vinylselenophene provides the corresponding substituted acrolein in 5570 yield (708). Two recent theses have been devoted to studies of
acylation (51, 74). Two additional examples of ketones with carbon-14 labeling at the carbonyl group have been described (27,33), as have two additional examples of ketones labeled with deuterium (20, 705).
T h e attempted benzoylation of achloroacetanilide was unsuccessful. T h e pura isomer failed to react with acetyl chloride, benzoyl chloride, and with chloroacetyl chloride (65). Triphenylmethane was not benzoylated using SnC14 (62). Fluoranthene was not forUnexpected Results mylated ( I S ) . Several failures in atAcetylation of e-cresol a t 120’ C. tempts to close five-, six-: and sevengives 2-hydroxy-3-methylacetophenone, membered rings have been reported. as would be expected from a Fries reSuccessful reactions had been observed arrangement of the acetate (24). Acylain closely related systems (5, 23, 42,52). tion of resorcinol in ether solution gives An attempted Hoesch reaction bey- but not a- or @-substitution (86). tween resorcinol and ethyl a-phenylT h e principal product from succinoylacyanoacerate was unsuccessful (59). rion of p-diethylbenzene was 3-(4I t was reported that 2,4-dibromophenyl ethylbenzoy1)propanoic acid by acyl benzoate did not undergo the Fries rereplacement of a n ethyl group (17). arrangement, even though the acetate Several instances were noted wherein and szveral other esters reacted as exoxalyl chloride reacted Tvith loss of CO pected (25); 2-methoxyphenyl chloro(93, 100, 707). Xcenaphthene showed a acetate also failed to rearrange (99). significant fraction of benzyl hydrogen replacement to give 1- as well as 3Literature Cited propion) lacenaphthene (704). A small amount o l x , j - diacetyl - 2 - carboxy - 4’- (1) Ahmad, M . S., Baddeley. G.. Topping, R. M., Chem. €8 Znd. (London) 1958, pp. hydroxydiphenyl ether accompanied the 1.7_ 3 7_ 4 I. ring closure which gave 1-acetyl-2-hy(2) Ames, D. E., Grey, T. F.?Jones, W. ‘4,. droxyxanthone (67). J . Chem. Soc. 1959, pp. 620-2. -4cetylation of cycloalkenes gave satu(3) Rngclctti, E., Montanari, F., 0311. s ~ i . Jac. chim. ind. Bologna 16, 140-3 (1958). rated nonhalogen-bearing ketones, mix(4) Ansell, M. F., Brown, S. S.;J . Chem. tures of @-, y-, and 6-chloroketones in See. 1958, pp. 2955-61. addition to unsaturated ketones. T h e (5) Baddar, F. G., El-Assal, L. S., DOSS, proportion of chloroketones decreased N. -4.; ZEid.,1959, pp. 1027-32. (6) Baddar, F. G., Fleifel, 4.M., Sherif, S., with increasing ring size. Cyclopentene /bid.. 1959. DD. 1009-12. gave mostly y-chloroketone (szc), @(7) Baddele);, ’&., Wrench, E.; Zbid.: 19.59, chloroketone was the major product DD. 1324-7. from cyclohexene, while cycloheptene (8j ‘Badische Anilin- & Soda-Fabrik A.-G.: Ger. Patent 964,593 (May 23, 1957). and cyclo-octene gave predominantly (9) Baliah, V.: Uma, M., Rec. trau. chim. unsaturated ketones (66) Ethylene re77, 667-73 (1958). acted with maleic anhydride and also (10) Bassilios, H. F., Makar, S . M., with benzoyl chloride to give vinyl Salem, 4.Y . , Bull. SX. chim. Franc? 1958, pp. 1430-6. producm which would be expected from (11) Bergmann, E. D., Katz, D., J . Ciie:n. isobutylene (92). SOC.1958, pp. 3216-17. (12) Blanchette, J. A,, Cotman, J. D., Jr., J . Or?. Chem. 23, 1117-22(1958). (13) Bleazard. it7.% Rothstein, E.. J . Cbem. ‘ S o c . 1958, pp. 3789-94. (14) Bohme, H., Goubcaud. H. N‘., Chem. Ber. 92, 366-9 (1959). (15) Brown. H. C.. Bolto. B. A.. Jensen. ‘ F, R., J . ’Org, Cbdm. 23, 414-16’(1958). ’ (16) Zbid., pp. 417-19. (17) ,Buu-Hoi, N. P., Lavit, D., Bull. SOC. chim. France 1958, pp. 290-2. SEND ORDER COUPON TO: EDITOR, I/EC (18) ,Buu-Hoi: N. P., Lavit, D., Rec. trav. chim. 7 7 , 724-8 (1958). I (19) Buu-Hoi’, X . P., Lavit, D., Collard, J., 1 155 Sixteenth St., N.W. Croat. Chem. Acta 29, 291-5 (1957) I (20) Buu-Hoi. N. P., Xuong, N. D., Comfit. Washington 6, D. C. rend. 247, 654-6 (1958). (21) Cadiot, P., Willemart, A, Congr. intern. aluminium Paris 1, 63-7 (1955). (22) Chanp, -. C... Hua Hsiieh Hsiieh Pa0 24, 69 Complete manuscript: Nelson and Hawkins (1958). (23) Chatterjee, A., Clhatterjee, R. C., Bhattacharvva, B. K., J . Indian Chem. Enclosed: Ocash Ucheck Umoney order .Toe. 35, 39f-’8 ‘(1958). (24) Chhaya, G. S., Trivedi, P. L., Jadhav: G. V., J . Unil;. Bombay, Swt. A [N.S.] 26, (Make payable t o American Chemical Society) I Pt. 5, 22-7 (1958). I (25) Christian, C. M., Amin, G. C., J . I Indian Cizem. Sac. 36, 111-14 (1939). I (26) Clar, E., Kemp, W., Stewart, D. G . ; Nameandtitle................................... I Tetrahedron 3, 325-33 (1 958). I (27) Collins, C. J., Rainey, W. T.: others, J . ilm. Cbem. Soc. 81, 460-66 (1959). Address.................. I
-
-
~
i
.............. ....................................
1020
INDUSTRIAL AND ENGINEERING CHEMISTRY
I I I I I
’
a (28) Colonge, J., Bonnard, L., Bull. SOC. chim. France 1958, pp. 742-5. (29) Cook, D., Can. J . Chem. 37, 48-53 (1959). (30) Cotton, F. A,, Leto, J. R., Chem. @ Znd. (London) 1958, pp. 1368-9. (31) Cullinane, N. M., Edwards, B. F. R., J . Appl. Chem. (London) 9, 133-6 (1959). (32) Cullinane, N. M., Edwards, B. F. R., J . Chem. Soc. 1958, pp. 2926-9. (33) Curtin, D. Y., Flynn, E. W., Nystrom, R. F., J . Am. Chem. Soc. 80, 4599-601 (19581. (34) Dinnenberg, H., Kessler, H. J., Ann. 620, 32-46 (1959). (35) Dauben, W. G., Collette, J. W., J . Am. Chem. Sac. 81, 967-72 (1959). (36) Dayan, J. E., Roberts, S. M. (to General Aniline & Film Gorp.), U. S. Patent 2,853,522 (Sept. 23, 1958). (37). Dean, F. M., Francis, T., Manunapichu, K., J . Chem. SOL.1958,pp. 4551-8. (38) Denney, D. B., Klemchuk, P. P., J . Am. Chem. Soc. 80, 3285-8 (1958). (39) ICid., pp. 6014-16. (40) Dolgov, B. N., Bnatov, S. A., Nnuch. Doklady Vysshei Shkoly, Khim. i Khim. Tekhnol. 1959, No. 1, 127-8. (41) Donbrow, M., J . Chem. SOC.1959,pp. 1613-15. Evans, E. A., Ibid., 1958, pp. 3737-9. Farbenfabriken Baver A.-G..‘ Brit. Patent 805,870 (Dec. 17,1958). (44) Farbenfabriken Bayer A.-G., Ger. Patent 948,332 (Aug. 30, 1956). (45) Fischer, E. O., Pleszke, K., Clzem. Ber. 91. 2719-26 (1958). (46) Galinkamp, d.,Fiber, A. C., Rec. trav. chim. 77, 850-3 (1958). (47) Goldberg, A. A,, Wragg, A. H., J . Chem. Soc. 1958, pp. 4227-34. (48) Graham, P. J. (to E. I. du Pont de Nemours & Co., Inc.), U. S. Patent 2,849,469 (Aug. 26, 1958). (49) Habib, M. S., Rees, C. W., Chem. & Znd. (London), 1959, p. 367. (50) Hauser, C. R., Tetanbaum, M. T., J . o r g . Chem. 23, 1146-9 (1958). (51) Hendry, C. M., Univ. Microjilms (Ann Arbor, Mich.), L. C. Card No. Mic. 585147; Dissertatzon Abstr. 19, 2762-3 (1 959). (52) Hromatka, O., Preininger, E., Sauter, F., Monatsh. 89, 790-7 (1958). (53) Zbzd., pp. 817-23. (54) Huang, R. L.. Lee, K.-H., J . Chem. SOC.1959, p. 923-8. (55) Hurd, C. D., Tockman, A., J . Am. Chem. Sod. 81, 116-19 (1959). (56) Inman, C. E., Oesterling, R. E., Tyczkowski, E. A.. Ibid., 80, 5286-8 (1958). ~
(57) Jensen, F. R., Marino, G., Brown, H. C., Zbid., 81, 3303-7 (1959). (58) Kaufmann, H. P., Skiba, K. J., Fette, Seifen, Anstrichmittel 59, 340-4 (1957). (59) Kawase, Y., Bull. C h m . SOC.Jaban 31, 440-2 (1958). (60) Kulka, M. (to Dominion Rubber Go.. Ltd.). Can. Patent 560.324 (Julv 15, ’1958).’ (61) Lamb, F., Suschitzky, H., Tetrahedron 5, 1-9 (1959). (62) Lansbury, P. T., Letsinger, R. L., J . Am. Chem. SOC.81, 940-3 (1959). (63) Lednicer, D., Hauser, C. R., Zbid., 80, 3409-12 (1958). (64) Ibid., pp. 6364-7. (65) Mehta, V. K., Patel, S. R., J . Indian Chem. Soc. 36, 99-102 (1959). (66) Nenitzescu, C. D., Pogany, J., Mihai, G., Acad. rep. Popdare Romtne, Studii cercetari chim. 6, 375-89 (1958). (67) Nerdel, F., Heymons, A., Gansau, H., Chem. Ber. 91, 944-8 (1958). (68) Newman, M. S., Ihrman, K. G., J . Am. Chem. SOC.80, 3652 (1958). (69) Nicholls, B., Whiting, M. C., J . Chem. SOG.1959, pp. 551-6. (70) Nightingale, D. V., Sukornick, B., J . o r g . Chem. 24, 497-500 (1959). (71) N. V. Philips’ Gloeilampenfabrieken, Dutch Patent 86,359 (Oct. 15, 1957). (72) Pandit, A. L., Kulkarni, A. B., Current Sci. (India) 27, 254-5 (1958). (73) Phillips, D. D., Hill, T. B., J . Am. Chem. SOG. 80, 3663 (1958). (74) Prasad, R., Univ. Microfilms (Ann Arbor, Mich.), L. C. Card No. Mic 585171; Dissertation Absfr. 19, 2478 (1959). (75) Rausch, M. D., Fischer, E. O., Grubert, H., Chem. CY Ind. (London) 1958, pp. 756-7. (76) Rausch, M., Shaw, P., others, J . o r g . Chem. 23, 505-7 (1958). (77) Re, L., Schinz, H., Helv. Chim. Acta 41, 1695-1709 (1958). (78) Reichel, I., Valceanu, R., Acad. rep. populare Romtne, Baza cercatari ;tiin;. Timigoara, Studii cercetdri jtiinj., Ser. jtiinfe chim. 4, No. 3-4, 19-31 (1957). (79) Rinehart, K. L., Jr., Michejda, C. J., Kittle. P. A.. J . Am. Chem. Soc. 81. 3162-3 (i959j. (80) Riobt, O., Compt. rend. 247, 1016-18 (1958). ( S i Rips, R., Buu-HOT, N. P., J . Org. Ahem. 24, 551-4 (1959). (82) Saharia, G. S., Sharman, B. R., J . Sei. Ind. Research (India) 16B, 125-8 ( 1957). (83) Satchell, D. P. N., Chem. @ Tnd. (London) 1958,p. 1442. ~
’
\
,
n
r
d Unit Processes Review
(84) Schmidt, U., Grafen, P., C/&em.Ber. 92, 1177-84 (1959). (85) Seshardi, T. R., Venkatasubramanian, G. B., J . Chem. SOC.1959, . pp. __ 1658-9.(86) Shah, R. C., Sauger Univ. J . 1, Pt. 2, NO. 3, 21-5 (1953-54). (87) Sladkov, A. M., Zhur. Obshchri: Khim. 28, 1742-5 (1958). (88) Stanley, L. N. (to General Aniline & Film Coru.). U. S. Patent 2.854.485 , , (Sept. 30, i958). (89) Stanlev, L. N., Roberts, S. M. (to General Aniline & Film Gorp.), Itid., 2,861,105 (Nov. 18, 1958). (90) Sweeney, W. M. (to Texas Co.), Ibid., 2,852,542(Sept.16, 1958). (91) TaYts, S. Z.: Khim. Sera-Org. Soedinenil Soderzhashch. v. Neft, i Nefteprodukt., Akad. Nauk S.S.S.R., Bashkir. Filial., Materialy Vtor3i Sessii 1956, pp. 80-6. (92) Taylor, H. T., J . Chem. Soc. 1958,pp. 3922-4. (93) Thomas, F. D., 11, Shamma, M., 80, Fernelius, W. C., J . Am. Chem. SOC. 5864-7 (1958’). (94) Torf, S. F., Khromov-Borisov, N. V., Zhur. Obshcher Khim. 28, 2452 (1958). (95) Treibs, W., Natiirwissenschaften 45, 336 (1958). (96) Treibs, W., Neupert, H. J., Hiebsch, J., Chem. Ber. 92, 141-54 (1959). (97) Ibid., pp. 1216-23. (98) Truce, W. E.: Ray, W. J., Jr., others, J . Am. Chem. Sac. 80, 3625-9 (1958). (99) Tung, T.-S., Chung, T.-S., MinlonHuang, Yao Hsueh Hsueh Pa0 6, 164-8 (19%).
(103) Zbid.; 2,861,104 (Nov. 18, 1958). (104) Wade, D. A., Peters, A. T., J . Chem. SOL.1958. DU. 3504-6. (105) Wib&g;K. B., Slaugh, L. H., J . Am. Chem. Snc. 80, 3033-9 (1958). (106) Yur’ev, Y . K., Belyakova, Z . V., ZhIL7. ObshcheY Khim. 28. 1755-60 (19581. (107) Yur’ev, Y . K., Bdlyakova, Z. V., Volkov, V. P., Zbid., 28, 2372-6 (1958). (108) Yur’ev, Y. K., Mezentsova, N. M., Vas’iovskiY, V. E., Ibid., 28, 3262-5 (1958). --, (109) Ziegler. E., Nolken, E., Monatsh. 89, 737-40 (1958). (110) Zimmer, H., Eibeck, R. E., Naturwissenschaften 11, 263 (1958). \
VDL. 52, NO. 12
DECEMEER 1960
102 1
