Process for the preparation of beta-alkenyltrimethylsilanes

Abstract: A process is claimed for making β-alkenyltrimethylsilanes and trimethylsilyl carboxylates. This process comprises contacting a mixture of hexamethyldisilane and an alkene carboxylate, having a β-unsaturated carbon atom, with novel organo-palladium or organo-nickel complexes as catalysts, at a temperature within a range of 100 to 250°C. Our process is especially useful for making allyltrimethylsilane and trimethylsilyl acetate.

Description: The present invention is a process for making β-alkenyltrimethylsilanes and trimethylsilyl carboxylates. This process comprises contacting a mixture of hexamethyldisilane and an alkene carboxylate, having a β-unsaturated carbon atom, with novel organo-palladium or organo-nickel complexes as catalysts, at a temperature within a range of 100°C. to 250°C. Our process is especially useful for making allyltrimethylsilane and trimethylsilyl acetate. β-alkenyltrimethylsilanes and trimethylsilyl carboxylates are useful intermediates for introducing organofunctional silicon functionalities into silicone and organic polymers. The present method provides a means for converting hexamethyldisilane to these intermediates in near quantitative yield. Urata et al., Bull. Chem. Soc. Jpn. 57:607-608 (1984) teach that allylic esters react with hexamethyldisilane in the presence of catalytic amounts of Pd(PPh 3 ) 4 , Pd{P(OPh) 3 } 4 or RhCl(PPh 3 ) 3 (where Ph=phenyl) to give the corresponding allylic silanes in good yield. Urata et al. reported that Pd{P(OPh) 3 } 4 effectively catalyzed the reaction of allyl acetate with hexamethyldisilane to give an excellent yield of β-alkenyltrimethylsiloxane. However, Pd(PPh 3 ) 4 and RhCl(PPh 3 ) 3 caused significant formation of propylene and (E) 1-propenyltrimethylsilane resulting from the double-bond migration of allyltrimethylsilane. We have discovered novel organo-palladium and organo- nickel complexes which serve as catalysts to effect the reaction between hexamethyldisilane and alkene acetates to form β-alkenyltrimethylsilanes and trimethylsilyl carboxylates, without experiencing the double-bond shift of Urata et al., supra. The present invention is a process for making β-alkenyltrimethylsilanes and trimethylsilyl carboxylates. The process comprises contacting a mixture of hexamethyldisilane and an alkene carboxylate described by formula R 1 2 C=C(R 1 )-CH 2 -0C(O)R 2 (1) with a catalyst described by formula (R 3 / 2PPh) 2 Pdx 2 (2) or (R 3 3 P) 2 NiX 2 (3) at a temperature within a range of 100°C. to 250°C.; where each R 1 is independently selected from a group consisting of hydrogen atom, saturated hydrocarbon radical comprising 1 to 18 carbon atoms, aralkyls and aryls; R 2 is selected from a group consisting of saturated hydrocarbon radicals comprising 1 to 18 carbon atoms, aralkyls and aryls; each R 3 is an independently selected alkyl comprising 1 to 8 carbon atoms; Ph is phenyl; and each X is an independently selected halogen atom selected from chlorine or bromine atoms. The present process is conducted as a batch, semi-continuous or continuous process. The process is also conducted in standard type reactors suitable for retaining the feed materials under pressure. The mixture of the present process comprises hexamethyldisilane. This hexamethyldisilane is made by any standard method known in the art. The hexamethyldisilane can also be a by-product of a process for making organohalosilanes where an organic halide is reacted with elemental silicon at an elevated temperature in the presence of a catalyst to form monosilanes. The hexamethyldisilane can further be part of a high-boiling mixture (>70°C.) resulting from the distillation of the product of the above process. The composition of such a high-boiling mixture is further described in U.S. Patent No. 5,430,168 and need not be further described herein. The mixture of the present process further comprises an alkene carboxylate as described by formula (1). Each R 1 is independently selected from a group consisting of hydrogen atom, saturated monovalent hydrocarbon radical comprising 1 to 18 carbon atoms, aralkyls and aryls. In addition to hydrogen atoms, R 1 is an alkyl such as methyl, ethyl, propyl, tert-butyl, decyl and octadecyl; a cycloalkyl such as cyclopentyl and cyclohexyl; aralkyls such as benzyl, beta-phenylethyl and beta-phenylpropyl; and aryls such as phenyl, tolyl and naphthyl. Preferred is when R1 is hydrogen. In formula (1), R 2 is selected from a group consisting of saturated monovalent hydrocarbon radicals comprising 1 to 18 carbon atoms, aralkyls and aryls. R 2 is any of those hydrocarbon radicals as described for R 1 . Preferred is when R 2 is a saturated monovalent hydrocarbon radical comprising 1 to 6 carbon atoms. Most preferred is when R 2 is methyl. The preferred alkene carboxylate in the present process is allyl acetate. The mole ratio of alkene carboxylate to hexamethyldisilane added to our process is within a range of 0.1:1 to 10:1. It is preferred that the alkene carboxylate be added to our process in a stoichiometric excess in relation to the amount of hexamethyldisilane added. Preferred is when the mole ratio of alkene carboxylate to hexamethyldisilane is within a range of 1:1 to 3:1. The mixture comprising the hexamethyldisilane and alkene carboxylate is contacted with a catalyst as described by formula (2) or (3). In formula (2) and (3), each substituent R 3 is an independently selected alkyl comprising 1 to 8 carbon atoms. R 3 is, for example, methyl, ethyl, propyl, tert-butyl, butyl, pentyl and octyl. Preferred is when R 3 is methyl or ethyl. In formulas (2) and (3), each substituent X is a halogen independently selected from bromine or chlorine atoms. Preferred is when X is chlorine. Preferred catalysts for use in the claimed process are described by formulas (Me 2 PPh) 2 PdCl 2 and (Et 3 P) 2 NiCl 2 , where Me is methyl, Et is ethyl and Ph is phenyl. This nomenclature will be used hereinafter in abbreviated form. The concentration of catalyst added to the present process is that amount providing 1 X 10 -2 g·atom to 1 X 10 -5 g·atom of palladium or nickel per mole of alkene carboxylate. Preferred is when the catalysts provides 5 X 10 -3 g·atom to 5 X 10 -4 g·atom of palladium or nickel. In the present process, the mixture comprising the hexamethyldisilane and alkene carboxylate is contacted with the catalyst at a temperature within a range of 100 to 250°C. A preferred temperature range is 150 to 225°C. The products of our process are β-alkenyltrimethylsilanes described by formula Me 3 Si-CH 2 -(R 1 )C=CR 1 2 and trimethylsilyl carboxylates described by formula Me 3 Si-OC(O)R 2 , where R 1 and R 2 are as previously described. A preferred product of the present process is β-allyltrimethylsilane. The following examples are provided to illustrate the present invention. These examples are not intended to limit the appended claims. The reactions reported in the examples were conducted in sealed Pyrex™ glass tubes. A reaction mixture as described in each example was placed in the glass tube and cooled in an isopropyl alcohol (IPA) and dry ice bath. The tube was then heat sealed and heated at the temperature and time described for each example. After the described reaction period, the contents of the tube were cooled and analyzed by gas chromatography using a flame ionization detector (GC-FID). The results are reported as the area percent (area %) under the GC-FID trace. In the formulas of the examples Me is methyl and Ph is phenyl. Example 1 The reaction mixture comprised 0.29 g (0.003 mole) of Me 3 SiSiMe 3 , 0.3 g (0.004 mole) of allyl acetate and 0.0036 g of (Me 2 PPh) 2 PdCl 2 . The mixture was heated at 150°C. for 21 hours, then cooled and analyzed by GC-FID. The analysis indicated the presence of no Me 3 SiSiMe 3 , 16.6 area % of allyl acetate, 47.0 area % of allylSiMe 3 and 34.0 area % of Me 3 SiOC(O)CH 3 . Example 2 The process described in Example 1 was repeated without the (Me 2 PPh) 2 PdCl 2 catalyst. No reaction occurred. Example 3 The reaction mixture comprised 0.29 g of Me 3 SiSiMe 3 , 0.3 g of allyl acetate and 0.004 g of (Et 3 P) 2 NiCl 2 . The mixture was heated at 150°C. for 21 hours, then cooled and analyzed by GC-FID. The analysis indicated the presence of 37.7 area % Me 3 SiSiMe 3 , 31.6 area % allyl acetate, 15.2 area % allylSiMe 3 and 14.3 area % Me 3 SiOC(O)CH 3 . Example 4 The reaction mixture comprised 0.29 g of Me 3 SiSiMe 3 , 0.3 g of allyl acetate and 0.004 g of (Et 3 P) 2 NiCl 2 . The mixture was heated at 200°C. for 21 hours, then cooled and analyzed by GC-FID. The analysis indicated the presence of 10 area % Me 3 SiSiMe 3 , 1.4 area % allyl acetate, 32.0 area % allylSiMe 3 and 47.5 area % Me 3 SiOC(O)CH 3 . Example 5 The process described in Example 4 was repeated without the (Et 3 P) 2 NiCl 2 catalyst. No reaction occurred.

Claims: A process for making β-alkenyltrimethylsilanes and trimethylsilyl carboxylates comprises contacting a mixture comprising hexamethyldisilane and an alkene carboxylate described by formula R 1 2 C=C(R 1 )-CH 2 -0C(O)R 2 with a catalyst described by formula (R 3 / 2PPh) 2 PdX 2 or (R 3 3 P) 2 NiX 2 , at a temperature within a range of 100 to 250°C.; where each R 1 is independently selected from a group consisting of hydrogen atom, saturated hydrocarbon radicals comprising 1 to 18 carbon atoms, aralkyls and aryls; R 2 is selected from a group consisting of saturated hydrocarbon radicals comprising 1 to 18 carbon atoms, aralkyls and aryls; each R 3 is an independently selected alkyl comprising 1 to 8 carbon atoms; Ph is phenyl; and each X is an independently selected halogen atom selected from bromine or chlorine atoms. A process according to claim 1 where the mixture comprises hexamethyldisilane present in a high-boiling mixture resulting from the distillation of a product of a process where an organic halide is reacted with elemental silicon at elevated temperatures to form monosilanes. A process according to claim 1 or claim 2 where the alkene carboxylate is allyl acetate. A process according to any of claims 1 to 3 where the mole ratio of alkene carboxylate to hexamethyldisilane in the mixture is within a range of 0.1:1 to 10:1. A process according to any of claims 1 to 4 where each R3 is independently selected from methyl or ethyl. A process according to any of claims 1 to 5 where the catalyst is selected from (Me 2 PPh) 2 PdCl 2 or (Et 3 P) 2 NiCl 2 where Me is methyl, Et is ethyl and Ph is phenyl. A process according to any of claims 1 to 6 where the mixture comprises 1 X 10 -2 g·atom to 1 x 10 -5 g·atom of palladium or nickel per mole of alkene carboxylate.

Inventors: BANK HOWARD MARVIN, NGUYEN BINH THANH, BANK, HOWARD MARVIN, NGUYEN, BINH THANH
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1997
Main classification: C07F7
IPC codes: C07F7, B01J31, C07B61