General Routes to Functional Organotin Trichlorides and Trialkoxides

General Routes to Functional Organotin Trichlorides and Trialkoxides Involving the Tricyclohexylstannyl Group. Bernard Jousseaume, Mohammed Lahcini, ...
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Organometallics 1995, 14, 685-689

685

General Routes to Functional Organotin Trichlorides and Trialkoxides Involving the Tricyclohexylstannyl Group Bernard Jousseaume,* Mohammed Lahcini, and Marie-Claude Rascle Laboratoire de Chimie Organique et Organomttallique, URA 35 CNRS, Universitt Bordeaux I, 351, cours de la Libtration, 33405 Talence Cedex, France

Francois Ribot and Clement Sanchez Laboratoire de Chimie de la Matikre Condenste, URA 1466 CNRS, Tour 54, 4, place Jussieu, 75252 Paris Cedex 05, France Received July 12, 1994@ New functional organotin trialkoxides have been prepared in two steps from the corresponding organotricyclohexyltins, which were obtained by coupling an organometal species with tricyclohexyltin chloride, by reaction of (tricyclohexylstanny1)lithium with a n organic halide, or by hydrostannation of alkenes. Treatment of organotricyclohexyltins with tin tetrachloride gave the corresponding organotin trichlorides which were further transformed into functional organotin trialkoxides.

Introduction

the three alkoxide groups would provide the inorganic network after hydrolysis and the organic moiety with a polymerizable function would be the precursor of the organic network.

The sol-gel process can be applied for the preparation of oxides of almost every metal, even if most of the studies have been devoted to silica, alumina, and titania.l However, the materials prepared in this way are subject t o extensive shrinking, cracking, and shattering. Their mechanical properties can be improved by the incorporation of an organic phase linked to the metal atoms, to form organic-inorganic composite materials with covalent bonding between the two phasese2 Most of the research on these hybrid organic-inorganic materials has been based on silicon derivative^,^ since with transition metals the much more ionic metalcarbon bonds are not stable enough toward hydrolysis. Tin shows a behavior intermediate between those of silicon and transition metals. It forms strong bonds with carbon4 and can easily expand its coordination sphere up to 8, which makes hydrolysis reactions of tin alkoxides very fast.5 Tin oxide is an n-type semiconductor with applications for sensors, nonlinear optical devices, catalysts, etc.6 For these reasons, tin was selected for the design and preparation of new hybrid organic-inorganic materials based on the combination of organic and inorganic networks homogeneously distributed in the material.' The aim of this work was thus to prepare functional organotin trialkoxides in which

Triorganotin alkoxides and diorganotin dialkoxides have been the subject of numerous studies,8 and many different preparations of these compounds have been proposed in the literature. Only a few simple organotin trialkoxides are known, however, and their preparations are more limited.g One method involves the alcoholysis of organotin triamides by alcohols.1° In a second method, the reaction between an organotin trihalide and an alkoxide is used. l1 Transalkoxylations, which are possible with triorganotin alkoxides and diorganotin dialkoxides,8 are also of interest with organotin trialkoxides. They can lead to symmetrical or mixed alkoxides.12 As the second method is a one-step procedure, it was preferred as an entry t o functional organotin trialkoxides. Organotin trihalides can only be prepared by a few methods,13 the main one involving the cleavage of tetraorganotins by hydrogen halides, halogens, or tin tetra halide^.'^ As other methods are less genera1,15-21

Abstract published in Advance ACS Abstracts, December 1, 1994. (1) Brinker, C. J.;Scherer, G. W. Sol-Gel Science; Academic Press: London, 1990. (2) Ning, Y. P.;Mark, J. E. Polym. Bull. 1984, 12, 137. Schmidt, M. J. Non-Cryst. Solids 1988,100,51. (3) Schmidt. H.: Scholze. H.: Kaiser. A. J. Non-Crvst. Solids 1984. 63,'l. Schmidt, H.;Seiferling,'B. Mater. Res. SOC.Simp. Proc. 1986; 73,739. Wilkes, G. L.; Orler, B.; Huang, H. Polym. Prepr. (Am. Chem. Soc., Diu. Polym. Chem.) 1986,26, 300. (4) Neumann, W. P. The Organic Chemistry of Tin;Wiley: London, 1967; p 155. Poller, R. C.The Chemistry of Organotin Compounds; Logos: London, 1970; p 69. (5) Bradley, D. C. Coord. Chem. Rev. 1967, 2, 299. Sanchez, C.; Ribot, F.; Doeuff, S. In Inorganic and Organometallic Polymers with Special Properties; Laine, R. M., Ed.; NATO AS1 Series 206; Kluwer Academic: Dordrecht, The Netherlands, 1992; p 267. Ribot, F.; Banse, F.; Sanchez, C. Mater. Res. SOC.Symp. Proc. 1992, 271, 45. (6)Harrison, P. G. In Chemistry of Tin; Harrison, P. G., Ed.; Blackie: Glasgow, Scotland, 1989; p 421.

(7) Sanchez, C.; Ribot, F. New J. Chem., in press. (8) Bloodworth, A. J.; Davies, A. G. In Organotin Compounds; Sawyer, A. K., Ed.; Dekker: New York, 1972; Vol. 1, p 153. Wardell, J. L. In Chemistry of Tin; Harrison, P. G., Ed.; Blackie: Glasgow, Scotland, 1989; p 145. (9) Schumann, H.; Schumann, I. In Gmelin Handbook oflnorganic Chemistry; Kriierke, U., Ed.; Springer-Verlag: Berlin, 1989; Organotin Compounds, Vol. 17, p 12. (10) Lorberth, J.;Kula, M. R. Chem. Ber. 1964,97,3444. Thomas, M. Can. J. Chem. 1961,39,1386. (11) Davies, A. G.;Smith, L.; Smith, P. J. J.Organomet. Chem. 1972, 39, 279. Gaur, D. P.; Srivastrava, G.; Mehrotra, R. C. J. Organomet. Schroder, D. J. Organomet. Chem. Chem. 1973,63, 221. Reuter, H.; 1981, 455, 83. (12) Gupta, V. D.;Narula, C. IC Synth. React. Irwrg. Met.-Org.Chem. 1981, 11, 133. (13) Schumann, H.; Schumann, I. In Gmelin Handbook oflnorganic Chemistry; Bitterer, H., Ed.; Springer-Verlag:Berlin, 1979; Organotin Compounds, Vol. 6, p 210.

@

Results and Discussion

Q276-7333/95/2314-Q685$Q9.QQlQ0 1995 American Chemical Society

Jousseaume et al.

686 Organometallics, Vol. 14, No. 2, 1995 this one was chosen to prepare the desired functional organotin trihalides. Treatment of tetrakis(4-vinylphenyl)tin2, or tetrakis(3-buteny1)tin with 3 equiv of tin tetrachloride or hydrogen chloride was initially attempted, but it did not lead to the corresponding organotin trichlorides. Next, (4-vinylpheny1)tricyclohexyltin was chosen as the starting material. After reaction with tin tetrachloride, repeated crystallizations only gave impure product. However, (4-vinylpheny1)tin trichloride and tricyclohexyltin chloride could finally be separated by liquid-liquid extraction, as their solubilities are very different in polar and nonpolar solvents. When a mixture of (4-vinylpheny1)tin trichloride and tricyclohexyltin chloride, obtained aRer treatment of (4vinylpheny1)tricyclohexyltin with 1 equiv of tin tetrachloride in pentane, was extracted with acetonitrile, the trichloride migrated into the acetonitrile phase, along with only a small amount of tricyclohexyltin chloride. (4-Vinylpheny1)tricyclohexyltinwas purified by distillation and obtained in 77% yield. The cleavage of organotricyclohexyltinsby tin tetrachloride had already been mentioned in the preparation of tricyclohexyltin chloride.23 The reaction was extended to (3-butenylland (4-penteny1)tricyclohexyltin. Starting materials were prepared by the coupling of (3-buteny1)-or (4-pentenyllmagnesium bromide with tricyclohexyltin chloCH2=CHC1ride. (4-Chloropent-4-enyl~tricyclohexyltin, (CH2)3SnCy3, could also be prepared in this way. Cy,SnR

+ SnC1, - RSnCl, + Cy,SnCI

R = 4-(CH,=CH)C6H,, yield 73% R = CH,=CH(CH,),, yield 92%

R = CH,=CH(CH,),, yield 87% In these procedures, the coupling of Grignard or lithium reagents was successfully used to prepare organotricyclohexyltins. However, two other routes to tetraorganotins, the coupling of stannylmetals with (14) Davies, A. G.; Smith, P. J. In Comprehensiue Organometallic Chemistry; Wilkinson, G., Stone, F. G. A,, Abel, E. W., Eds.; Pergamon Press: Oxford, U.K., 1982; Vol. 2, p 591. (15)Bulten, E. J. J. Organomet. Chem. 1975, 97, 167. Bulten, E. J.; Gruter, H. F. M.; Martens, H. F. J. Organomet. Chem. 1976,117, 329. Murphy, J.;Poller, R. C. J.Organomet. Chem. Libr. 1979,9,189. (16) Meyer, A. Ber. Dtsch. Chem. a s . 1885,16, 1442. Tchakirian, A.; Lesbre, M.; Lewinsohn, M. Bull. SOC.Chim. Fr. 1936, 138. Druce, J. G. F. J. Chem. SOC.1922, 1859. Pope, W. J.; Peachy, S. J. Chem. SOC.1903, 7. (17) Corey, E. J.; Eckrich, T. M. Tetrahedron Lett. 1983,24, 163. (18) Burley, J. W.; Hutton, R. E.; Oake, V. J. Chem. SOC.,Chem. Commun. 1976,803. Hutton, R. E.; Burley, J. W. J. Organomet. Chem. 1978, 156, 369. Burley, J. W.; Hope, P.; Mack, A. G. J. Organomet. Chem. 1984,277, 737. Harrison, P. G.; King, T. J.; Healy, M. A. J. Organomet. Chem. 1979,182,17. Bulten, E. J.; van den Hurk, J. W. G. J. Organomet. Chem. 1978, 162, 161. Howie, R. A.; Paterson, E. S.; Wardell, J. L.; Burley, J. W. J. Orgummet. Chem. 1983,259, 71. (19)Ryu, I.; Suzuki, H.; Murai, S.; Sonoda, N. Organometallics 1987, 6, 212. (20) Nakahira, H.; Ryu, I.; Ikebe, M.; Oku, Y.; Ogawa, A.; Kambe, N.; Sonoda, N.; Murai, S. J. Org. Chem. 1992,57, 17. Ryu, I.; Murai, S.; Sonoda, N. J. Org. Chem. 1986, 51, 2389. (21)Nakahira, H.; Ryu, I.; Ogawa, A.; Kambe, N.; Sonoda, N. Organometallics 1990, 9, 277. Nakamura, E.; Shimada, J. I.; Kuwajima, I. Organometallics 1985, 4, 641. Nakamura, E.; Kawajima, I. Chem. Lett. 1983, 59. (22) Schuman, H.; Rodewald, G.; Rodewald, U. J. Organomet. Chem. 1978,187,305. (23) Kushlefsky, B. G.; Reifenberg, G. H.; Hirshman, J. L.; Considine, W. J. Ger. Offen. 1955463; Chem. Abstr. 1970, 73, 15000. Reifenberg, G. H.; Gitlitz, M. H. S. African Patent 7202018; Chem. Abstr. 1973, 79, 18853. We are indebted to Professor D. Seyferth for bringing these patents to our attention.

organic halides or t o ~ y l a t e and s ~ ~the addition of orgaare, in notin hydrides to unsaturated principle, applicable. To our knowledge, neither a (tricyclohexylstanny1)metalnor the addition of tricyclohexyltin hydride to an alkene has been reported. Tri~ , ~not ' to cyclohexyltin hydride adds to a l k y n e ~ ~but alkenes, even under high pressure.28 The first of these routes has been tested with (tricyclohexylstanny1)lithium, prepared from the corresponding tin hydride The required tricyclousing the procedure of hexyltin hydride was obtained by reduction of tricyclohexyltin hydroxide, a commercial starting material, with an excess of lithium aluminum hydride, thus avoiding the use30 of tricyclohexyltin chloride. Reaction of (tricyclohexylstanny1)lithium with 1-chloropropane gave the coupling compound in only low yield, but with 1-bromopropane and methyl iodide, the reaction was preparatively useful. The coupling was successfully extended to 6-bromo-l,3-hexadiene, to give (3,5-hexadieny1)tricyclohexyltin in 67%yield. i-Pr,NLi

Rx

Cy3SnH -i-przNK Cy,SnLi

Cy,SnR

RX = MeI, yield 63% RX = n-PrBr, yield 72% RX = CH,=CHCH=CH(CH,),Br, yield 67% RX = n-PrC1, yield 20% In the second approach, hydrostannation of unactivated alkenes such as allyl alcohol, 5-(benzyloxy)-l-pentene, and 3-butenyl acetate with tricyclohexyltin hydride in benzene under U V irradiation, or a t reflux with azobis(isobutyronitrile) (AIBN) as initiator, failed. However, under more drastic conditions, without solvent at 110 "C and with portionwise addition of AIBN, using a small excess of alkene to avoid extensive formation of hexacyclohexyltin, addition products were recovered in good yield. The reaction was successfully extended to other alcohols (3-butenol, 4-pentenol, and 5-hexenol) and esters (2-propenyl and 4-pentenyl acetates). It was regiospecific, and the adducts were easily purified by column chromatography. Cy,SnH

+ H,C=CHR

AIBN

Cy,SnCH,CH,R

R (% yield): CH,OH (88), (CH,),OH (601, (CH),OH (79), (CHJ4OH (651, (CH,),OCH,Ph (68), CH,OCOCH, (78), (CH,),0COCH3 (72), (CH,),OCOCH, (71) As in the previous case, these organotricyclohexyltins (24) See, for example: Lee, IC-W.; San Filippo, J. Organometallics 1982,1,1496. San Filippo, J.; Silbermann, J. J.Am. Chem. SOC.1982, 104, 2831. Smith, G. F.; Kuivila, H. G.; Simon, R.; Sultan, L. J.Am. Chem. SOC.1981,103,833. Kuivila, H. G. Adu. Chem. Ser. 1976, No. 157, 41. (25) van der Kerk, G. J. M.; Luijten, J. G. A.; Noltes, J. G. Chem. Ind. 1966, 352. van der Kerk, G. J . M.; Noltes, J. G. J.Appl. Chem. 1959,9,106. Neumann, W. P. Angew. Chem. 1964, 76,849. (26) Corey, E. J.; Ulrich, P.; Fitzpatrick, J. M. J. Am. Chem. SOC. 1976, 98, 222. (27) Rahm, A.; Grimau, J. J. Organomet. Chem. 1986,286, 297. (28) Rahm, A.; Ferkous, F.; Degueil-Castaing, M.; Jurczak, J.; Golebiowski. A. Synth. Inorg. Met.-Org. Chem. 1987, 17, 937. (29) Still. W. C. J.Am. Chem. SOC.1978. 100. 1481. (30)N e u " , W. P.; Schneider, B.; Son&er, k.Justus Liebigs Ann. Chem. 1966,692, 1.

Organotin Trichlorides and Trialkoxides

Organometallics, Vol. 14, No. 2, 1995 687

Table 1. Yields and Selected l19Sn NMR Data for Functional Organotin Trichlorides yield compd

wSnC$

(%)

lI9Sn chem shift (ppm)

lJsn-~ (Hz)

92

-5

672

87

-1

664

0

663

SnCI3

~

S

~

C

I83

~

CI

73

-68

1140

85

-112

845

74

- 147

848

HO-SnCI3

63

-80

894

HoS -nC13

90

-95

807

AcO-SnCI3

90

-38

746

89

-47

724

AcO-SnCI3

67

-67

735

PhCH20-SnCI3

75

-1

665

HO-SnCI3

Ho-~n~~3

AcO-

SnC13

Chart 1

c1 I ,c1

R'-Sn,

t R~OH were treated by tin tetrachloride in order to prepare the corresponding functional organotin trichlorides. With (3,5-hexadienyl)tricyclohexyltin,the reaction failed. Only intractable mixtures were obtained, extensive polymerization occurring during the cleavage. With functional propyl-, butyl-, pentyl-, and hexyltricyclohexyltins, the reactions worked well, leading to the corresponding trichlorides in good yield (see Table 1). l19Sn NMR spectroscopy resonances showed an upfield shift, with respect to nonfunctional alkyltin trichlorides, in trihalostannyl alcohols and esters; the effect was stronger with alcohols. In the alcohols, this could be indicative of pentacoordination of the metal (Chart 11, as has been established by X-ray and l19Sn NMR spectroscopy for P- and y-trichlorostannyl carbonyl compound^.^^^^^ To check this hypothesis, trichlorobutyltin was mixed with 1 equiv of methanol. The chemical shift of the metal was a t -181 ppm, in the same range as in the prepared trichlorostannyl alcohols, which confirmed the proposed pentacoordination. In esters, intermediate values may suggest an equilibrium between tetra- and pentacoordinated species, or a weak coordination. The variations of tin-carbon coupling constants, lJsn-c, are indicative of changes in coordination a t tin, within the same class of ~rganotins.,~ P-Trichlorostannyl ketones, where the metal is pentacoordinated, show lJsn-c higher than 810 Hz,,, whereas lJsn-c for butyltin trichloride, where the metal is tetracoordinated, was 648 Hz in deuteriochloroform and 939 Hz with 1 equiv of methanol. In (31)Omae, I. J . Organomet. Chem. Libr. 1986,18. Wrackmeyer, B. Annu. Rep. NMR Spectrosc. 1985,16, 73.

trichlorostannyl alcohols, these values were in the range of 850-900 Hz, thus indicative of pentacoordination of the tin. In trichlorostannyl esters and ethers, they were intermediate between the values for tetracoordinated and pentacoordinated species. That confirmed the deductions based on l19Sn NMR chemical shift studies. Three organotin trialkoxides were prepared from functional organotin trichlorides, (3-butenyl)-, (Cpenteny1)- and (6vinylphenyl)tin tri-t-amyloxide. The tamyloxy group was chosen because RSn(OCMe2Et)s compounds are liquids which can be purified by distillation. (3-Butenyll-and (Cpentenylltin tri-t-amyloxides were prepared by the reaction of the corresponding trichloride with t-amyl alcohol, in the presence of diethylamine and 1 equiv of sodium t-amyloxide t o complete the reaction.34 With (6vinylphenyl)tin trichloride, this method failed, the presence of a strong base leading to extensive polymerization. A procedure described for the preparation of tin tetraalk~xides,,~ using only diethylamine and t-amyl alcohol, was then successfully applied and gave the desired products in high yield. RSnC1,

+ 3(t-amyl)OH Et,NH

RSn(0-t-amyl),

R (% yield): CH,=CH(CH,), (70), CHZ=CH(CH,), (751, 4-(CH,=CH)C,jH4 (72) The synthesis and the properties of the new hybrid organic-inorganic materials, obtained after hydrolysis and polymerization of the organic function, will be published elsewhere. Experimental Section All reactions were carried out under a nitrogen atmosphere. Pentane, THF, and diethyl ether were distilled from sodium benzophenone ketyl prior use. F'yridine and diisopropylamine were distilled on KOH. Acetonitrile was distilled on CaH2. Methanol, ethanol, and t-amyl alcohol were distilled from magnesium. Acetyl chloride and tin tetrachloride were distilled before use. lH NMR spectra were recorded on a PerkinElmer-Hitachi R 24A or a Bruker AC-250 spectrometer (solvent CDC13, internal reference Mersi), 13C NMR spectra were taken on a Bruker AC-250 spectrometer (solvent CDCl3, internal reference Mersi), l19Sn NMR spectra were recorded on a Bruker AC-200 spectrometer (solvent C&, internal reference Me&%). For NMR data, the multiplicity, coupling constants in Hz, and integration are given in parentheses. Tin-hydrogen and tin-carbon coupling constants (Hz) are given in brackets. Preparation of 5-brom0-2-chloro-l-pentene.~~ In a three-necked flask was placed anhydrous potassium carbonate (34.3 g, 250 mmol), ethyl 3-oxobutanoate (28.3 g, 240 mmol), 2,3-dichloropropene (25 g, 220 mmol), and 132 mL of absolute ethanol. The mixture was heated at reflux for 16 h, and (32)Mitchell, T. J . Orgunomet. Chem. 1973,59,189.Harris, R.K.; Kennedy, J. D.; McFarlane, W. In NMR and the Periodic Table;Harris, R. K., Mann, B. E., Eds.; Academic Press: London, 1978; p 342. Jousseaume, B.; Noiret, N.; Pereyre, M.; Frances, J. M.; Petraud, M. Organometallics 1992,11,3910. Jousseaume, B.;Gouron, V.; Noiret, N.; Pereyre, M.; Frances, J. M. J . Orgunomet. Chem. 1993,450,97. (33)Nakahira, H.; Ryu, I.; Ikebe, M.; Oku, Y.; Ogawa, A.; Kambe, N.; Sonoda, N.; Murai, S. J . Org. Chem. 1992,57, 17. (34)Greco, C. C. Eur. Pat. Appl. EP0252543. (35)Thomas, I. M.; US.Patent 3,946,056.Chandler, C. D.; Fallon, G. D.; Koplick, A. J.; West, B. 0. Aust. J . Chem. 1987,40, 1427. Hampden-Smith, M. J.; Wark, T. A.; Rheingold, A.; Hoffmann, J. C. Can. J . Chem. 1991,69,121. (36)Drouin, J. Ph.D. Thesis, Universite de Paris Sud, 1976.

Jousseaume et al.

688 Organometallics, Vol. 14, No. 2, 1995 ethanol was distilled off. A 300 mL amount of water was added at 0 "C, and the mixture was extracted with diethyl ether (3 x 80 mL). After drying and removal of the solvent, a mixture of ethyl and methyl 4-chloro-4-pentenoates and 5-chloro-5-hexen-2-one was distilled (bp 72 (0.1 mm), 15 g). Ethyl 4-chloro-4-pentenoate: lH NMR 6 1.24 (t,8,3H), 2.422.58 (m, 4H), 4.04 (9, 8, 2H), 5.10 (t, 2, 2H). To a solution of the mixture (40 g) in 360 mL of THF at 0 "C was added 620 mL of aqueous NaOH (1N). The solution was stirred for 4 h at room temperature. It was then extracted three times with diethyl ether (120, 50, and 30 mL). Diethyl ether (120 mL) and a solution of 18 mL of 36 N HzS04 in 120 mL of water were successively added to the aqueous phase, which was subsequently extracted with diethyl ether (2 x 100 mL). After drying, evaporation, and recrystallization in petroleum ether, 20 g of 4-chloro-4-pentenoic acid was recovered (mp 41 "C): lH NMR 6 2.6 (bs, 4H), 5.15 (bs, 2H), 12 (bs, 1H); 13CNMR 6 32, 34, 113.3,140.5, 178.7. To a mixture of lithium aluminum hydride (25 g, 400 mmol) in 500 mL of diethyl ether was added 4-chloro-4-pentenoic acid (28 g, 210 mmol) in 100 mL of ether. After 3 h, the mixture was hydrolyzed at 0 "C. The usual workup gave 4-chloro-1-pentenol (22 g, 86%; bp 100°C (40 mm)): 'H NMR 6 1.72-1.78 (m, 2H), 2.35 (t, 6, 2H), 3.25 (bs, 1 H), 3.55 (t, 6, 2H), 5.11 (bs, 2H); 13C NMR 6 30, 35.5, 61.1, 112.4, 142.3. To a solution of 4-chloro-1-pentenol (2 g, 16 mmol) and 0.5 mL of pyridine in 10 mL of diethyl ether was added a solution of phosphorus tribromide (2 g, 7 mmol) in 5 mL of diethyl ether, at -30 "C under nitrogen. The mixture was stirred at -30 "C for 1.5 h and warmed to room temperature for 1 h. The solution was then washed with a saturated NaCl solution and dried, and the solvent was evaporated, Purification by chromatography on silica gel gave 5-bromo-2-chloro-1-pentene (1g, 35%): 'H NMR 6 2.09 (tt, 7, 7, 2H), 2.43 (t, 7, 2H), 3.36 (t, 7, 2H), 5.19 (bs, 2H); 13CNMR 6 29.8, 32.2, 37.3, 113.6, 140.8. Coupling of Grignard Reagents with Tricyclohexyltin Chloride. In a three-necked flask under nitrogen was prepared a Grignard reagent from 250 mmol of the organic halide and 6.3 g of magnesium (260 mmol) in 150 mL of diethyl ether (THF with 4-chlorostyrene). The mixture was heated at reflux for 30 min and then was added slowly via cannula to a solution of tricyclohexyltin chloride3' (60 g, 150 mmol) in 250 mL of diethyl ether. The resulting mixture was heated at reflux for 4 h. After hydrolysis with a saturated solution of NH4C1,the usual workup followed by recrystallization from absolute ethanol gave the tetraorganotin species. (4-Vinylpheny1)tricyclohexyltin: yield 75%; mp 109°C. Anal. Calcd for C26H4oSn: C, 66.26; H, 8.55. Found: C, 66.61; H, 8.74. 'H NMR: 6 1.21-1.77 (m, 33H), 5.32 (d, 10, lH), 5.83 (d, 18, lH), 6.71 (dd, 10, 18, lH), 7.38-7.50 (m, 4H). 13C NMR: 6 27.1 [343], 27.2,29.4 [56], 32.4 [16], 113.5, 125.7 [371, 137.1,137.2, 137.7 [25], 141.1 [302]. l19Sn NMR: 6 -100. (3-Buteny1)tricyclohexyltin: yield 78%; mp 110 "C. Anal. Calcd for CzzH40Sn: C, 62.43; H, 9.53. Found: C, 62.11; H, 9.28. lH NMR: 6 0.75-0.82 (m, [61], 2H), 1.2-1.77 (m, 33 H), 2.22 (m, [57], 2H), 4.80 (dd, 11, 1.7, lH), 4.91 (dd, 17, 1.7, lH), 5.85 (ddt, 11, 17, 6, 1H). 13C NMR: 6 5.8 [2561, 26.1 [3241, 27.3, 29.3 [531, 29.8 [161, 32.5 [231, 112.4, 142.7 [531. l19Sn NMR 6 -64. (4-Penteny1)tricyclohexyltin: yield 81%; mp 108 "C. Anal. Calcd for C23H4~Sn:C, 63.18; H, 9.68. Found: C, 62.85; H, 9.38. lH NMR: 6 0.67-0.75 (m, [601, 2H), 1.20-1.80 (m, 35 H), 2.05-2.15 (m, 2H), 4.77 (d, 10, lH), 4.94 (d, 17, lH), 5.81 (ddt, 17, 10,6, 1H). 13CNMR 6 6.4 [2541,25.9 [3131,26.9 [17], 27.3, 29.3 [541, 32.5 [23], 39.2 [531, 114.4, 139.1. l19Sn yield 74%; NMR 6 -65. (4-Chloropent-4-eny1)tricyclohexyltin: mp 78 "C. Anal. Calcd for C~3&1ClSn: C, 58.56; H, 8.76. Found: C, 58.42; H, 8.94. lH NMR: 6 0.85-0.95 (m, 2H), 1.23-2.21 (m, 35H), 2.37 (t,7,2H), 5.01 (bs, lH), 5.17 (bs, 1H). 13C NMR: 6 5.4 [2591, 25.1 [191, 25.9 [3241, 26.5, 29.2 [531, 32.5 [16], 44.1 [54], 119.0, 142.7; l19Sn NMR: 6 -65.4.

Preparation of TricyclohexyltinHydride. To a suspension of tricyclohexyltin hydroxide (30 g, 78 mmol) in 100 mL of diethyl ether was slowly added 7.6 g (200 mmol) of lithium aluminum hydride under nitrogen. The mixture was refluxed for 3 h. After hydrolysis and the usual workup, the pure tin hydride was isolated by distillation in a Kugelrohr apmm) (lit.30bp 147 "C paratus: yield 92%; bp 140 "C mm)). Preparation of (E)-6-Bromo-1,3-hesadiene. 3,5-Hexadieno13*(10 g, 100 mmol) in 10 mL of diethyl ether was slowly added to a solution of tetrabromomethane (60 g, 180 mmol) and triphenylphosphine (47 g, 180 mmol) in 120 mL of diethyl ether. The mixture was heated at reflux for 1 h. After addition of 300 mL of pentane, the mixture was filtered. After evaporation of the solvents, the bromide was recovered by distillation: yield 75%; bp 52 "C (2 mm); 'H NMR 6 2.62 (dt, 8, 7, 2H), 3.37 (t,7,2H), 4.98 (d, 10, lH), 5.11 (d, 16, lH), 5.75 (dt, 15, 8, lH), 6.12 (dd, 15, 10, lH), 6.31 (dt, 16, 10 1H); 13C NMR 6 32.2, 35.9, 116.7, 130.9, 133.6, 136.7. Coupling of (Tricyclohexylstanny1)lithium with Organic Halides. In a Schlenk tube at 0 "C, 20 mL of n-butyllithium (2.5 M) in hexane was added to diisopropylamine (4.8 g, 50 mmol) in 40 mL of THF. After 15 min at this temperature, tricyclohexyltin hydride (17 g, 46 mmol) was added slowly and the mixture was stirred for 15 min. At -40 "C, 55 mmol of the organic halide in 50 mL of THF was added. The mixture was warmed t o room temperature and stirred for 16 h. After hydrolysis with a saturated solution of NHdCl at 0 "C and the usual workup, the tetraorganotins were recovered by column chromatography on silica gel (eluent petroleum ether). Methyltricyclohexyltin:39yield 63%. Propyltricyclohe~yltin:3~ yield 72%. (E)-(3,5-Hexadienyl)tricyclohexyltin: yield 67%. Anal. Calcd for C~4H42Sn: C, 64.16; H, 9.42. Found: C, 64.55; H, 9.86. lH NMR 6 0.68-0.77 (m, [571,2H), 1.2-2.2 (m, 33H), 2.24-2.36 (m, [531, 2H), 5.05 (d, 10, lH), 5.15 (d, 17, lH), 5.75 (dt, 16, 10, lH), 6.08 (dd, 16, 10, lH), 6.55 (dt, 17, 10, 1H). l19Sn NMR: 6 -65. Hydrostannation Reactions. In a Schlenk tube under nitrogen, a mixture of the alkene (75 mmol), tricyclohexyltin hydride (22.5 g, 60 mmol), and AIBN (200 mg) was heated to 110 "C under nitrogen for 8 h. AIBN (200 mg) was added and the mixture heated for 8 h. The product was purified by chromatography on silica gel (petroleum ethedethyl acetate 90/10). (3-Hydroxypropyl)tricyclohexyltin: yield 88%; mp 129 "C. Anal. Calcd for CzlH4oSnO: C, 59.04; H, 9.44. Found: C, 58.63; H, 9.17. 'H NMR: 6 0.60-0.68 (m, [641,2H), 1.191.79 (m, 35H), 3.50 (t, 6, 2H), 4.2 (bs, 1H). 13C NMR: 6 1.8 [2411,27.2 [314], 28.9,29.7 [541, 32.3 [161,32.5 [161,66.8 [601. l19Sn NMR: 6 -63.2. (4-Hydroxybutyl)tricyclohexyltin: yield 60%; mp 131 "C. Anal. Calcd for CzzH4~0Sn: C, 59.88; H, 9.59. Found: C, 60.14; H, 9.48. lH NMR: 6 0.70-0.78 (m, [61], 2H), 1.19-1.78 (m, 37H), 3.59 (t, 6, 2H), 5.14 (bs, 1H). 13C NMR: 6 6.6 [2551, 23.5 [161, 25.9 [3331, 27.3, 29.3 [MI, 32.4 [18], 38.1 [561, 62.6. '19Sn NMR 6 -65. (5-Hydroxypenty1)tricyclohexyltin: yield 79%; mp 110 "C. Anal. Calcd for C23H4OSn: C, 60.68; H, 9.74. Found: C, 60.92; H, 9.54. lH NMR: 6 0.64-0.73 (m [61], 2H), 1.10-1.78 (m, 39H), 2.36 (9, lH), 3.54 (t, 7, 2H). 13C NMR: 6 6.7 [2671, 25.9 [3331, 26.7 [MI, 27.1,29.8 [52], 32.3 [53], 32.4,32.5 [161,62.8. 119SnNMR 6 -65. (6-Hydroxyhexyl)tricyclohexyltin:yield 65%. Anal. Calcd for C24H460Sn: C, 61.42; H, 9.88. Found: C, 61.89; H, 10.15. lH NMR: 6 0.72-0.81 (m [621,2H), 1.11-1.84 (m, 41H), 3.63 (t, 7,2H), 4.25 (bs, 1H). 13CNMR: 6 6.7 [2661, 25.3 [161, 25.3 [3171,27.3,27.4,28.9 [52], 32.5 [161,32.6,34.7 [511,63.1. l19Sn NMR 6 -64.8. (5-(Benzyloxy)pentyl~tricyclohexyltin: yield 68%. Anal. Calcd for CsoHaoOSn: C, 66.06; H, 9.24. Found: C,66.28;H,9.42. lHNMR60.77-0.87(m,2H), 1.011.94 (m, 39H), 4.57 (t, 7, 2H), 6.43 (s, 2H), 7.39 (s, 5H). 13C

(37) Pommier, J. C.; Pereyre, M.; Valade, J. C . R.Acad. Sci. 1966, 260,6397.

(39)Gielen, M.; De Clercq, M.; De Poorter, B. J.Organomet. Chem. 1972,34, 305.

(38) Martin, S. F.; Tu, C.; Chou, T. J.Am. Chem. SOC.1980,102, 6274. __ .

Organometallics, Vol. 14,No. 2, 1995 689

Organotin Trichlorides a n d Trialkoxides NMR: 6 9.0 [251], 26.1 [302], 27.3,27.4, 29.1, [571,32.3,32.5, 32.6, 70.6, 72.9, 127.5, 128.3. I19Sn NMR: 6 -64.4. (3(Acety1oxy)propyl)tricyclohexyltin: yield 78%; mp 47 "C. Anal. Calcd for C23H4202Sn: C, 58.87; H, 9.02. Found: C, 58.95; H, 8.89. IH NMR: 6 0.67-0.78 (m [651,2H), 1.12-1.84 (m, 35H), 2.04 (9, 3H), 3.96 (t, 7, 2H). 13C NMR: 6 2.1 [2471, 21.1, 26.1 [312], 26.4 [16], 27.3, 29.4 [53], 32.5 [161, 68.1 [541, 171.3. '19Sn NMR: 6 -64.0. (4-(Acetyloxy)butyl)tricyclohexyltin:yield 72%. Anal. Calcd for C24HM02Sn: C, 59.64; H, 9.18. Found: C, 59.97; H, 9.41. IH NMR: 6 0.58-0.67 (m [651, 2H), 1.121.80 (m, 37H), 2.02 (s, 3H), 3.93 (t, 7, 2H). 13C NMR: 6 6.6 [247], 21.1,25.5 [312], 26.8 [161,27.3,29.3 [531,32.5 [161,38.2 6 -64.3. [54], 67.9, 171.3. l19Sn NMR (5-(Acetyloxy)pentyl)tricyclohexyltin:yield 71%. Anal. Calcd for C25H4602Sn: C, 60.38; H, 9.32. Found: C, 60.12; H, 9.57. 'H NMR: 6 0.64-0.73 (m [60], 2H), 1.12-1.84 (m, 39H), 2.08 (s,3H), 4.02 (t,7,2H). 13CNMR: 6 6.6 [2581,20.1,25.9 [3121, 27.0 [16], 27.2,29.3 [55], 31.2 [58], 32.2,32.3 [161,64.7, 171.1. I19Sn NMR: 6 -65.0. Preparation of Functional OrganotinTrichlorides. To a solution of organotricyclohexyltin (50 mmol) in 100 mL of pentane was added slowly tin tetrachloride (50 mmol, 13.1g) under nitrogen. After 3 h, 200 mL of acetonitrile and 200 mL of pentane were added and the mixture was stirred for 18 h. The mixture was decanted, and the acetonitrile solution was extracted with pentane (3 x 50 mL). Evaporation of acetonitrile gave the trichlorides, which were distilled in a Kugelrohr apparatus. Hydroxy-substituted organotrichlorotin decomposed during the distillation. Trichloro(4-vinylpheny1)tinwas diluted with dry mineral oil (10% solution), and a few crystals of di-tert-butylcatechol were added before distillation: yield 73%; bp 100 "C mm). Anal. Calcd for CsH7C13Sn: C, 29.28; H, 2.15. Found: C, 28.96; H, 2.07. IH NMR: 6 5.29 (d, 10, lH), 5.68 (d, 20, lH), 6.70 (dd, 10,20, lH), 7.47 (s, 4H). NMR 6 117.8, 127.9 [129], 134.2 [801, 134.9 [11401, 135.5 [19], 142.3 1261. (3-Buteny1)tin trichloride: yield 92%; bp 85 "C mm). Anal. Calcd for C4H,SnC13: C, 17.15; H, 2.52. Found: C, 17.34; H, 2.79. IH NMR: 6 2.61 (t, 8 [891, 2H), 2.78 (dt, 7, 8 [236], 2H), 5.17 (dd, 10, 1, lH), 5.27 (dd, 17, 1, lH), 5.95 (ddt, 10,17,7,1H). 13CNMR 6 28.6 [581,33.6 [6721, 118.4, 136.0 [98]. (4-Penteny1)tin trichloride: yield 87%; bp 90 "C (10-3 mm). Anal. Calcd for C5HgC13Sn: C, 20.41; H, 3.08. Found: C, 20.87; H, 3.35. 'H NMR (60 MHz): 6 2.22.6 (m, 6H), 5.0-5.15 (m, 2H), 5.6-6.3 (m, 1H). 13CNMR: 6 23.9 [601, 33.4 [664], 34.9 [2281, 118.3, 135.9. (4-Chloro-4penteny1)tin trichloride: yield 83%;bp 95 "C mm). Anal. Calcd for C5HsC14Sn: C, 18.27; H, 2.45. Found C, 18.65; H, 2.62. IH NMR (C3D60): 6 1.24 (t, 8 [851, 2H), 2.48 (m, [1661, 2H), 2.91 (t, 8, 2H), 4.81 (s, lH), 5.02 (s, 1H). 13C NMR (C3D&): 6 22.2 [60], 30.4 [6641, 40.4 [2281, 114.5, 140.2. (3Hydroxypropy1)tin trichloride: yield 85%. Anal. Calcd for C3H,0C13Sn: C, 12.68; H, 2.48. Found: C, 13.11; H, 2.62. IH NMR: 6 2.02 (t, 5 [99], 2H), 2.32 (m [2591,2H), 3.71 (t, 5,2H), NMR: 6 25.2 [661, 26.7 [8451, 61.1 [931. (45.03 (bs, 1H). Hydroxybuty1)tin trichloride: yield 74%. Anal. Calcd for C4HgOC13Sn: C, 16.11; H, 3.04. Found: C, 15.84; H, 2.79. 'H NMR: 6 1.75-1.83 (m, 2H), 2.14-2.27 (m, 2H), 2.41-2.49(m, 2H), 4.05 (t,6, 2H), 4.49 (bs, 1H). 13CNMR: 6 25.5 [771, 30.4 [32], 39.3 [848]. (5-Hydroxypenty1)tintrichloride: yield 63%. Anal. Calcd for C6H110C13Sn: C, 19.24; H, 3.55. Found: C, 19.04; H, 3.41. IH NMR: 6 1.45-1.55 (m [3361, 2H), 1.571.63 (m, 2H), 1.80-1.88 (m, 2H), 2.14-2.18 (m [log], 2H), 3.94 (t, 6,2H), 5.82 (bs, 1H). 13C NMR: 6 25.8 [651, 29.7 [361,31.1, 38.9 [894], 63.9. (6-Hydroxyhexy1)tintrichloride: yield 90%.

Anal. Calcd for CsH130C13Sn: C, 22.09; H, 4.02. Found: C, 22.42; H, 3.85. lH NMR 6 1.40 (t, 5 [961, 2H), 1.62-1.64 (m, 2H), 1.78-1.83 (m, 2H), 2.27-2.34 (m, 2H), 3.79 (t, 6, 2H), 5.18 (bs, 1H). 13C NMR 6 24.6 [601, 30.9, 31.0, 31.7, 33.1 [807],63.5. (3-(Acetyloxy)propyl)tintrichloride: yield 90%; mp 78 "C. Anal. Calcd for CsH902C13Sn: C, 18.41; H, 2.78. Found: C, 18.84; H, 3.15. lH NMR: 6 2.08 (s,3H), 2.24-2.28 (m [96, 2561, 4H), 4.13 (t, 7, 2H). 13CNMR: 6 21.4, 23.9 [631, 29.9 [746], 64.9 [631, 171.9 (4-(Acetyloxy)butyl)tintrichloride: yield 89%; mp 86 "C. Anal. Calcd for CsH1102C13Sn: C, 21.18; H, 3.25. Found: C, 21.42; H, 3.53. 'H NMR: 6 1.67-1.73 (m, 2H), 1.92-1.96 (m, 2H), 2.02 (s, 3H), 2.29 (t, 6 [921, 2H), 4.09 (t, 6, 2H). 13C NMR: 6 21.1, 21.6 [571, 30.9 [1201, 32.9 [843], 63.5, 171.1. (5-(Acetyloxy)pentyl)tintrichloride: yield 67%. Anal. Calcd for C7H1302C13Sn: C, 23.74; H, 3.70. Found: C, 23.96; H, 3.44. lH NMR: 6 1.41-1.59 (m, 2H), 1.68-1.74(m, 2H), 1.82-1.88 (m, 2H), 2.15 (s, 3H), 2.38 (t [961, 2H), 4.10 (t,2H). 13CNMR 6 21.3,24.6 [611,27.7,28.5 [1281, 35.5 [735], 65.1, 173.7. (5-(Benzyloxy)pentyl)tintrichloride: yield 75%. Anal. Calcd for C1zH170Cl3Sn: C, 35.83; H, 4.26. Found: C, 35.47; H, 4.51. 'H NMR: 6 1.32-1.37 (m, 2H), 1.60-1.64 (m, 2H), 1.79-1.91 (m, 2H), 2.33 (t, 7 [871,2H), 3.52 (t, 7, 2H), 4.53 (s, 2H), 7.31 (5, 5H). 13C NMR: 6 24.7 [691, 28.1, 28.5 [116], 34.2 [6651, 70.0, 73.0, 128.3, 128.6, 128.9, 137.1. Preparation of Functional Organotin Tri-tert-amyloxides). In a three-necked flask, equipped with a mechanical stirrer, dropping funnel, and condenser, was placed the organotin trichloride (20 mmol) and 44 mL of dry pentane, under nitrogen. Diethylamine (4.5 g, 61 mmol) in 25 mL of pentane was added slowly at 0 "C. After the mixture was stirred for 3 h a t room temperature, tert-amyl alcohol (6 g, 69 mmol) was added dropwise at 0 "C. The mixture was then stirred for 18 h at room temperature. It was filtered, and the solvents were evaporated. The products (diluted in dry mineral oil in the case of (4-vinylpheny1)tintri-iert-amyloxide) were distilled in a Kugelrohr apparatus. (4-vinylpheny1)tin tri-tert-amyloxide: yield 70%; bp 110 "C (0.001 mm). Anal. Calcd for C23H4003Sn:C, 57.16; H, 8.34. Found: C, 56.84; H, 8.62. lH NMR: 6 0.95 (t, 7,9H), 1.32 (s, 18H), 1.63 (q, 7, 6H), 5.36 (dd, 11,0.7, lH), 5.85 (dd, 18, 0.7, lH), 6.65 (dd, 18, 11, 1H), 7.42-7.69 (m, 4H). 13CNMR: 6 9.3, 31.2 [181, 38.5 [281, 75.3 [39], 115.5, 126.8 [961,135.7 [571, 136.4 [ill, 139.6,139.9 [19]. l19Sn NMR: 6 -257. (3-Buteny1)tin tri-tert-amyloxide: yield 70%; bp 87 "C (0.001 mm). Anal. Calcd for C19H4003Sn: C, 52.44; H, 9.26. Found: C, 52.89; H, 9.51. 'H NMR: 6 0.95 (t, 7, 9H), 1.27 (9, 18H), 1.43 (t, 7 [156], 2H), 1.59 (q, 7, 6H), 2.54 (dt, 7,7 [105], 2H), 5.03 (d, 10, lH), 5.24 (d, 17, lH), 5.91 (ddt, 17, 10, 7, 1H). 13C NMR 6 9.1, 23.5 [7611, 28.7 [401, 31.1 [16], 38.3 [126], 74.6 [381, 114.9, 139.3 [1121. l19Sn NMR: 6 -194. (4-Penteny1)tin tri-tert-amyloxide: yield 75%; bp 90 "C (0.001 mm). Anal. Calcd for C20H4203Sn: C, 53.47; H, 9.42. Found: C, 53.12; H, 9.29. IH NMR: 6 0.93 (t, 7, 9 H), 1.19 (s, 18 H), 1.42 (t, 6, 2H), 1.45 (9, 7, 6H), 1.74-1.78 (m, 2 H), 2.14 (dt, 7, 7, 2H), 4.97 (d, 10, lH), 5.65 (d, 17, lH), 5.75 (ddt, 17, 10, 7, 1H). 13C NMR: 6 9.2, 23.9 [7581, 24.1 [40], 31.0, 36.9 [1201, 38.5 [30], 74.7 [40], 115.5, 137.5. I19Sn NMR: 6 -193.

Acknowledgment. We are indebted t o SipcamPhyteurop and to Schering-France for generous gifts of chemicals. OM940551W