FR2569701A1 - Silylation process - Google Patents

Abstract

Process for the silylation of organic substrates by use of a halogenated polysilane such as 1,1,2,2-(tetrachloro)dimethylsilane and an organic acyl halide such as the acid chloride of trimellitic anhydride in the presence of a catalyst containing a transition metal. Application to the manufacture of organic silanes.

Description

 Prior to the present invention, as shown by Yamamoto et al. In Tetrahydron Letters, 1653 (1980), it was known that an activated aromatic acyl halide such as p-nitrobenzoyl chloride could be converted to the corresponding aromatic silane with starting of carbon monoxide resulting from a decarbonylation reaction using hexamethyldisilane as a silylating agent. However, it has also been found that the silylation of the aromatic nucleus is not a total success, since Yamamoto et al., The corresponding aromatic silylketone, was obtained mainly as product.

en réaction avec un halogénure d'acyle aromatique répondant à la formule

en présence d'une quantité efficace d'un catalyseur contenant un métal de transition, tel qu'on le définira ci-après, on obtient, en un rendement quantitatif, un silane organique répondant à la formule
(3) Rl[-SitR2)2X]m sachant que, dans les formules, X représente un radical halogène, R est choisi parmi X, l'hydrogène, des radicaux hydrocarbonés monovalents en C(1 13)' des radicaux hydrocarbonés monovalents en C(1-13) substitués, et des radicaux -O-, -S-divalents et leurs mélanges, qui peuvent former des groupes de liaison -SiOsI- et=-SiSSi--
R1 représente un radical organique aromatique monovalent ou polyvalent en C(620) choisi dans le groupe constitué par des radicaux hydrocarbonés et des radicaux hydrocarbonés substitués, R2 est choisi parmi des radicaux organiques monovalents en C(120) > n représente un nombre entier compris entre 1 et 50 inclus, et m représente un nombre entier compris entre 1 et 4 inclus.The present invention is based on the discovery that if instead of hexamethyldisilane employed by Yamamoto et al, a halogenated polysilane of the formula is used,

in reaction with an aromatic acyl halide having the formula

in the presence of an effective amount of a transition metal-containing catalyst, as will be defined hereinafter, an organic silane having the formula is obtained in quantitative yield
(3) Rl [-SitR2) 2X] m knowing that, in the formulas, X represents a halogen radical, R is chosen from X, hydrogen, monovalent hydrocarbon radicals of C (1 13) 'monovalent hydrocarbon radicals in C (1-13) substituted, and -O-, -S-divalent radicals and mixtures thereof which can form linking groups -SiOsI- and = -SiSSi--
R1 represents a monovalent or polyvalent C (620) aromatic organic radical selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R2 is chosen from C (120) monovalent organic radicals> n represents an integer between 1 and 50 inclusive, and m represents an integer between 1 and 4 inclusive.

The present invention provides a process for preparing organic silanes of formula (3) which comprises
(A) reacting an aromatic acyl halide of formula (2) and a halogenated polysilane of formula (1) in the presence of an effective amount of a metal-containing catalyst; transition and
(B) the subsequent recovery of the organic silane having formula (3) of the resulting mixture of (A).

 For example, among certain aromatic acyl halides of formula (2), there may be mentioned a monofunctional aromatic acyl halide such as benzoyl chloride, trimellitic anhydride acid chloride, chlorobenzoyl, anisoylbenzoyl chloride, nitrobenzoyl chloride, toluoyl chloride, cyanobenzoyl chloride, bromobenzoyl chloride, dimethylazinobenzoyl chloride, N-butyl trimellitic imide acid chloride, and the like.

 Examples of polyfunctional aromatic acyl polyhalides having the formula (-2) include terephthaloyl chloride, phthaloyl chloride, isophthaloyl chloride, and the like.

 There may be mentioned, for example, among certain aromatic silanes which correspond to formula (3), phenyldimethylchlorosilane, phenylmethyldichlorosilane, chlorophenyldimethylchlorosilane, anisyldimethylchlorosilane, nitrophenyldimethylchlorosilane, tolyl dimethylchlorosilane, cyanophenyldimethylchlorosilane, dimethylchlorosilyl anhydride. Phthalic acid, N, n-butyl dimethylchlorosyl-4-phthalimide, bromophenyldimethylchlorosilane, etc.

 For example, among the polysilanes of formula (i) are chloropentamethyldisilane, dichloro-1,2-tetramethyldisilane, dichloro-1,1-tetramethyldisilane, trimethyl-1,1,2-trichlorodisilane, tetrachlorobenzene, 1,1,2,2-dimethyldisilane, hexachlorodisilane, 1,2-dibromethyltetrasethyldisilane, 1,2-difluoro-tetramethyldisilane, 1-octamethyl, 1,2,2,4,4,5,5 tetrasila -1,2, 4,5-cyclohexasiloxane, chloro-1 nonamethyltetrasiloxa-3 ane, 1,2-dichloro-diphenyldimethyldisilane 1,2, etc.

 For example, radicals which can represent R and R2 in the formulas (1) and (3) include C (1 g) alkyl radicals, and for example methyl, ethyl, propyl or butyl radicals. , pentyl, etc.

chlorobutyl, trifluoropropyl, cyanopropyl as well as monovalent aryl radicals and substituted monovalent aryl radicals such as those defined for R 1 below.

 There may be mentioned, for example, among certain monovalent aromatic radicals and substituted aromatic radicals that can represent R 1 in the formulas (2) and (3), phenyl, xylyl, tolyl, naphthyl radicals, halogenated aromatic radicals such as radicals chlorophenyl, dichlorophenyl, trichlorophenyl, etc., fluorophenyl, difluorophenyl, etc., bromophenyl, dibromophenyl, etc. ; aromatic nitro and polynitro radicals as well as alkyl oxide radicals and, for example, anisoyl, ethoxyphenyl, propoxyphenyl and diphenyl ether radicals.

There may also be mentioned, for example, among the substituted aromatic radicals that may represent R 1, cyanophenyl, polycyanophenyl and phthalimido radicals.

dans laquelle R3 peut représenter des radicaux monovalents et des radicaux monovalents substitués identiques ou différents, choisis parmi ceux que peuvent représenter R et R plus haut, et R4 peut représenter des radicaux choisis parmi des radicaux aromatiques divalents en C(6 13) et des radicaux aromatiques divalents en C(613) substitués, comme les radicaux phénylène, xylylène, tolylène, naphtylène et leurs dérivés halogénés et X est tel qu'on l'a défini précédemment. On recommande particulièrement parmi les halogénures de silarylène, un chlorure de silphénylène ou le bis (chlorodiméthylsilyl)-1,4 benzène.On peut synthétiser ce composé de silphénylène à partir de chlorure de téréphtaloyle et de dichloro-1,2 tétraméthyldisilane, comme le montre l'équation suivante

Some of the recommended organic silanes of formula (3) are silarylene halides of the following formula,

in which R 3 may represent monovalent radicals and identical or different substituted monovalent radicals selected from those which may be R and R above, and R 4 may represent radicals selected from divalent C (6-13) aromatic radicals and radicals. Substituted C (613) divalent aromatics, such as phenylene, xylylene, tolylene, naphthylene and their halogenated derivatives and X is as previously defined. Particularly preferred among the silarylene halides, a silphenylene chloride or bis (chlorodimethylsilyl) -1,4 benzene. This silphenylene compound can be synthesized from terephthaloyl chloride and 1,2-dichlorotetramethyldisilane, as shown in FIG. the following equation

 Among the transition metal-containing catalysts which can be used in the practice of the present invention are bisbenzonitrilepalladium dichloride, bisacetonitrilepalladium dichloride, allylpalladium chloride dimer, bis (dibromide), triphenylphosphine) palladium, bis (triphenylphosphine) palladium iodide, tetrakis (triphenylphosphine) palladium, palladium dichloride, bis (diphenylmethyl) phosphine palladium dichloride, palladium on carbon, palladium on silica. Other metal complexes such as rhodium, iridium, cobalt, platinum and other Group VI II complexes can also be used. Among catalysts containing transition metals, bisbenzonitrile palladium dichloride is recommended.

 It is possible to use a cocatalyst containing an amine or a phosphine such as trimethylamine, triethylamine, tributylamine, pyridine, tetramethyl-N, N, N ', N'-ethylenediamine, triphenylphosphine, tri-p-tolylphosphine, tri-o-anisylphosphine ,. trimethyl or tributylphosphine, tricyclohexylphosphine to facilitate decarbonylation.

 An effective amount of a transition metal-containing catalyst of from 0.05 wt.% To 0.15 wt.%, Based on the weight of the aromatic acyl halide of formula (2), will be used.

An effective amount of cocatalyst of between 0.10% and 0.30% by weight, based on the weight of the aromatic acyl halide, will be used.

 In the practice of the present invention, the reaction is initiated between the halogenated polysilane of formula (1) and the organic acid halide of formula (2) in the presence of an effective amount of catalyst containing a transition metal. The reaction can be carried out under a wide variety of conditions. For example, the reactants can be heated to the desired temperature in the absence of a solvent by stirring them in an inert atmosphere or in the presence of a non-reactive solvent having a low temperature. boiling point greater than about 100 to 300 ° C. For example, o-xylene, anisole, mesitylene, or non-halogenated aliphatic or aromatic solvents may be used. It may also be possible to carry out the gas phase reaction by passing the reactants over a bed containing the transition metal-containing catalyst bound to a polymer support material.

It is also possible to use, for carrying out the reaction, a liquid flow system in which the reactants are dissolved in a hot non-reactive solvent or if the reactants are compatible, they can be passed over a polymer-bound catalyst. .

 According to the value of m in the formula (2) of the organic acyl halide and depending on whether the halogenated polysilane is a monofunctional or polyfunctional halopolysilane, the molar proportions of the halogenated polysilane and the organic acid halide can vary widely. .

 It is necessary to use sufficient halogenated polysilane to have at least two gram atoms of silicon of the halogenated polysilane per mole of the organic acyl halide.

 To carry out the reaction between the halogenated poly silane and the organic acyl halide, it is possible to use, for example, temperatures of 110 to 300 ° C., and preferably of 135 to 145 ° C. depending on the nature of the reactants and the conditions used, such as the presence or absence of an organic solvent, etc. as we said before.

 The halogenated organic silanes prepared in accordance with the practice of the present invention can be hydrolyzed to various useful intermediates such as silarylene silane diols and silarylene siloxane polymers obtained therefrom, siloxane-derived bisanhydrides, bisimides derived therefrom. siloxanes, etc.

 In order for those skilled in the art to be better able to practice the present invention, the following examples are given in order to illustrate the invention and not to limit it. All parts are by weight.

Example 1

 A mixture of 20 grams (9.5-102 moles) of acid chloride of trimetellic anhydride and 23 grams (0.1 mole) of 1,1,2,2-tetrachloro dimethyldisilane was heated with stirring under stirring. a dry nitrogen atmosphere until a homogeneous solution was obtained which was at a temperature of about 135oC. A mixture of cocatalysts composed of 123 milligrams (0.5 mole percent) of bis (benzonitrile) palladium chloride and 250 milligrams (1 mole percent) of triphenylphosphine was then introduced, resulting in the formation of a red solution and the production of carbon monoxide which was allowed to escape from the reaction mixture. The reaction temperature was maintained between 140-150 ° C. and the methyltrichlorosilane was continuously removed from the reaction. After 2 hours, methyltrichlorosilane was obtained in quantitative yield (14.1 grams). The reaction mixture was then distilled and 10 grams of dichloromethylsilyl-4-phthalic anhydride (41% yield) was obtained having a boiling point of 170 ° -174 ° C., at 1.33 Pa.

 It was a viscous transparent oil. The identity of the product was further confirmed by its IR and NMR spectra.

Elemental Analysis: Calculated: C9H36SiCl2 259.9463, Found: 259.9464.

 2 grams of dichloromethylsilyl phthalic anhydride were dissolved in 20 ml of methylene chloride and the resulting solution was added to 20 ml of water. The resulting mixture was stirred rapidly for 2 hours. A clear glassy solid was obtained after collecting the organic phase and removing the organic solvent from the resulting material for 30 minutes at 1200C. The resulting product was a methylsiloxane resin bearing chemically bonded phthalic anhydride groups bound to silicon, according to IR analysis. Methylsiloxane resin is useful as a coupling agent for the manufacture of composites.

Example 2

 A mixture of 10 grams (4.76 x 10 -2 moles) of trimellitic anhydride acid chloride and 9 grams (5 x 102 moles) of 1,2-dichloro-tetramethyldisilane was heated under an atmosphere of dry nitrogen until a homogeneous solution is obtained at about 135 ° C. A cocatalyst consisting of 91 milligrams (0.5 mole percent) of bis (benzonitrile) palladium chloride and 124 milligrams (1 The resulting solution was bright red and carbon monoxide separated from the mixture when the catalyst was added.) Dimethyldichlorosilane having a boiling point of 70 ° C. was continuously removed. C until 5.8 grams have been collected. A product yield of 97% was obtained. According to this method of preparation, the product was dimethylchlorosilylphthalic anhydride. Its identity was further confirmed by its IR and NMR spectra.

 50 ml of tetrahydrofuran solution containing 0.43 ml of water was added to dimethylchlorosilylphthalic anhydride. The resulting solution was stirred at room temperature for 3 hours under reduced pressure to remove HC1 as it was formed. The tetrahydrofuran was evaporated and replaced with 100 ml of a 1: 1 toluene / nonane solution. During heating, a crystalline solid was formed. The resulting solution was separated by decantation from the colored oily material which contained the catalyst. 8.1 grams, a yield of 80% bis (dicarboxy-1 ', 2'-phenyl-4') dianhydride, was obtained by recrystallization. 1,3-tetramethyldisiloxane as colorless needles having a melting point of 134-135 ° C. The resulting siloxane-derived bisanhydride is an interesting intermediate for the production of silicone-polyimide block polymers which constitute interesting insulating and dielectric materials .

 According to the process described above, a reaction mixture containing 1500 g (7.13 moles) of trimellitic anhydride acid chloride and 1490 g (7.48 g) was stirred in the absence of water. moles) of 1,2-dichlorotetramethyldisilane at 1450 under a nitrogen atmosphere. When the mixture became homogeneous, 1.65 g (4.3 x moles, 600 ppm) of bis (benzonitrile) palladium chloride and 2.24 g (8.54 x 10 3 moles, 1200 ppm) of triphenylphosphine. This resulted in a large release of carbon monoxide accompanied by an exothermic reaction. External heat was reduced to maintain a constant reaction temperature of 10-1500C. Dimethyldichlorosilane having a boiling point of 60-70 ° C. was continuously removed from the mixture as it was formed.

After 15 hours at 145-150 ° C, gas evolution ceased and gas chromatographic analysis showed a conversion of 93% dimethyldichlorosilyl-4-phthalic anhydride. of dimethyldichlorosilane which was lifted under reduced pressure and condensed in a dry ice / acetone trap.

 When gas chromatographic analysis indicated the complete disappearance of the volatile chlorosilanes, 2 liters of dry tetrahydrofuran were added to dissolve the oily product and then 64.2 ml of water were dripped for 3 hours. while the solution was maintained at 25 C. Gaseous HC1 system was removed under reduced pressure. After stirring at room temperature for 5 hours, the resulting product was precipitated. The crude product was filtered and the filter solution was removed in vacuo to give a second product fraction. The two parts were combined and dissolved in hot toluene. Cooling yielded 1185 g (78% yield of isolated product) of crystalline bis (crystalline phthalic anhydride) 1,3-tetramethyldisiloxane.

Example 3
A mixture of 1.0 gram (4.9 millimoles) of terephthaloyl chloride, 3.7 grams (19.6 millimoles) of 1,2-dichloro tetramethyldisilane, 187 milligrams (5 mole percent) of sodium dichloride, was added. bis (benzonitrile) palladium and 256 milligrams (10 mole percent) of triphenylphosphine at 1400C under a dry nitrogen atmosphere. The mixture that was initially a yellow solution became dark red. After heating for 4 hours, 1,4-bis (dimethylchlorosilyl) benzene was obtained in quantitative yield, as shown by gas chromatographic analysis. The identity of 1,4-bis (dimethylchlorosilyl) benzene was verified by comparison with an authentic sample prepared by chlorinating 1,4-bis (dimethylsilyl) benzene with triphenylchloromethane according to the method of Corey et al., JACS, 85. , 2430 (1963).

Example 4
A reaction mixture containing 10 grams (6x10 mole) of p-cyanobenzoyl chloride and 15 grams (1.25 mole equivalent) of 1,2-dichloro-tetramethyldisilane was heated to 1350 ° C and during this time the solution became homogeneous. . A mixture of cocatalysts containing 200 mg of bis (benzonitrile) palladium dichloride (1 mole percent) and 274 mg of triphenylphosphine 2 mole percent was then introduced. The gaseous release of carbon monoxide was immediately started and the reaction mixture was heated at 1400C for 12 hours with continuous removal of dimethyldichlorosilane. Vacuum distillation of 7 grams (60% isolated product yield) was obtained. 4-chlorodimethylsilyl benzonitrile, having a boiling point of 93 ° C at 13.3 Pa and a melting point of 40 ° -43 ° C. The resulting chlorodimethylsilylbenzonitrile was hydrolyzed as a highly sensitive solid. Moisture content, low melting point, to obtain bis (cyano-4'-phenyl) -1,3-tetramethyldisiloxane in the form of a colorless liquid The identity of the disiloxane was further confirmed by its IR spectra and NMR.

Example 5
A gravity continuous flow reactor, consisting of a heated introduction flask, whose contents were agitated, a catalyst bed on a heated support, containing 2 grams of a palladium catalyst over activated carbon (4), was used. , 5% of total palladium), an open end, and a reservoir for respectively collecting carbon monoxide and volatile monomeric silanes and a container for collecting the silylated aromatic material. 10 grams (4.8 x 102 moles) of acid chloride of trimetellic anhydride and 13 grams (6.9 x 10 -2 moles) of 1,2-dichlorotetramethyldisilane were placed in the introduction funnel of which the contents were stirred and heated to 140 ° C, during which time the solution became homogeneous. The mixture was then introduced into the catalyst bed, which was heated to 210 ° C, at room temperature. 1 ml / 5 min., evolution of gaseous CO was observed and 3.5 g (ie 57% of the theoretical yield) of dimethyldichlorosilane were collected in the side tank Analysis of the material collected in the bottom container found to contain dimethyldichlorosilane, 77% 4-chlorodimethylsilyl phthalic anhydride, and 12% acid chloride of unreacted trimetellic anhydride, resulting in a total conversion of 89%.

Example 6
A mixture of 2.93 g (2.1 x 10 -2 moles) of benzoyl chloride and 5 g (2.2 x 10 -2 moles) of 1,2-dichlorotetramethyldisilane was heated under a dry nitrogen atmosphere. at 140 ° C. A catalyst mixture containing 8 mg (2.08 × 10 5 mol, 1270 ppm) of bis (benzonitrile) palladium chloride and 11 mg (4.2 × 10 5, 250 ppm) of triphenylphosphine was introduced resulting in the release of carbon monoxide The reaction mixture was heated at 1400C for 20 hours The mixture was then distilled to yield 2.46 g (91% yield) of dimethyldichlorosilane having a boiling point of 68-720C and 3.12 g (87% yield) of phenyldimethyl chlorosilane having a boiling point of 850C at 2.66 kPa.

dans laquelle R5 et a sont définis ci-dessous
R5 a Taux de rendement en
conversion produit isolé 8
H 1 85 89 o-CH3 1 17 13 m-CH3 1 100 47 p-CH3 1 100 58 o-Cl 1 50 25 m-Cl 1 83 73 p-Cl 1 75 86 o-OMe 1 100 32 m-OMe 1 87 71 p-OMe 1 61 52
1 (1 eq.) 44 19 m-COCl 1 (1 eq.) 86 61
1 t1 eq.) 91 83 o-COCl 1 (2 eq.) ND ND m-COCl 1 (2 eq.) b 66 p-COCl 1 (2 eq.) b 63
m-NO2 1 100 74
P-NO2 1 100 72
p-CN 1 87 77 3,4 acide anhydride
(trimellitique) 1 100 83
R5 a Taux de rendement en
conversion produit isolé % 3,4 acide anhydride
N-butylimide (trimellitimide) 1 100 81* b essai jusqu'à conversion complète * rendement déterminé par chromatographie en phase gazeuse.Example 7
Following the procedure of Example 6, several additional silylated aromatic organic materials from the decarbonylation of arylacyl chloride were prepared as shown by the following equation

in which R5 and a are defined below
R5 a Rate of return in
isolated product conversion 8
## STR5 ## 87 71 p-OMe 1 61 52
1 (1 eq.) 44 19 m-COCl 1 (1 eq.) 86 61
1 t1 eq.) 91 83 o-COCl 1 (2 eq.) ND ND m-COCl 1 (2 eq.) B 66 p-COCl 1 (2 eq.) B 63
m-NO2 1 100 74
P-NO2 1 100 72
p-CN 1 87 77 3,4 anhydrous acid
(trimellitic) 1 100 83
R5 a Rate of return in
conversion product isolated 3.4% anhydride
N-butylimide (trimellitimide) 1,100 81 * b test until complete conversion * yield determined by gas chromatography.

Example 8
A mixture of 100 g (0.49 moles) of terephthaloyl chloride and 116 g (0.51 moles) of symmetrical tetrachlorodimethyldisilane was heated to 1450C under a dry nitrogen atmosphere. After the solution had become homogeneous, 5.3 g (0.1 mole percent) of palladium (12-30 mesh carbon grains, 1% of the filler percentage) which resulted in a release of carbon.

Methyltrichlorosilane was continuously removed while maintaining the mixture at 68-7 ° C. After 24 hours at 1450C a second amount of catalyst equal to 5.3 g followed by a similar charge after 48 hours was introduced. The mixture was then heated for 72 hours at 1450C. Fractional distillation of the mixture afforded 62 g (50% isolated product yield) of p-di chloromethylsilylbenzoyl chloride having a boiling point of 126 ° C as a colorless liquid. confirmed by its IR and NMR spectra.

 A solution in ether containing 5 g (1.97 x 10 -2 mol) of p-dichloromethylbenzoyl chloride and 50 ml of solvent to which 0.4 ml of water was added was stirred at room temperature. The mixture was stirred for 15 minutes at room temperature. Removal of the solvent provided 3.54 g (92% isolated product yield) of a silicone fluid containing incomplete benzoyl chloride and methyl groups. The identity of the product was then confirmed by its infrared spectrum.

Example 9
A mixture of 50 g (0.25 moles) of terephthaloyl chloride and 116 g (0.51 moles) of tetrachlorodimethyldisilane was heated at 1450C under a dry nitrogen atmosphere. After homogenization of the mixture, 10.6 g (1 mole percent) of palladium on steam-activated charcoal (4-8 mesh, 5% filler) was charged causing carbon monoxide evolution. Methyltrichlorosilane having a boiling point of 68-71 ° C was formed which was removed continuously by distillation. The end of the reaction was determined by gas chromatography analysis.

Fractional distillation provided 1,4-bis-dichloromethylsilylbenzene.

Example 10
A reaction mixture containing 20 g (7.43 x 10 mol) of the hexachlorodisilane and 15.7 g (7.43 x 10 -2 mol) of the acid chloride of the trimetellic anhydride was heated to 145 ° C. under When the mixture became homogeneous, 1.58 g (1 mole percent) of palladium on steam-activated charcoal (4-8 mesh grains, 5% charge) was introduced, causing a clearing. The total mixture was then heated to 145-150 ° C. for 10 hours.

 After cooling, the catalyst was removed by filtration and distillation of the filtrate gave a significant amount of 4-trichlorosilyl phthalic anhydride.

The identity of the compound was subsequently confirmed by its IR and mass spectra.

 Although the above examples relate to only a few of the many variations that can be used in practicing the silylation process of the present invention, it is to be understood that the present invention relates to the use of a much greater diversity of halogenated polysilanes of formula (1), organic acyl halides of formula (2) and transition metal-containing catalysts as shown in the description above.

Claims (9)

 A process for the preparation of organic silanes having the formula R 1 [Si (R 2) 2 x] m, characterized in that it comprises:  (A) reacting an organic acyl halide having the formula,

 and a halogenated polysilane having the formula

 in the presence of an effective amount of a transition metal-containing catalyst and  (B) the subsequent recovery of the organic silane from the mixture resulting from (A), given that, in the formulas, X represents a halogen radical, R is chosen from X, hydrogen, monovalent hydrocarbon radicals of C (1 13) substituted monovalent C (III) hydrocarbon radicals, and -O-, -Sivalent radicals and mixtures thereof which can form -SiOsI- and -SiSSi-linking groups, R1 represents a monovalent or polyvalent organic C (1-20) radical chosen from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals, R is chosen from monovalent radicals that R may represent, n represents an integer between 1 and 50 inclusive, and m represents an integer between 1 and 4 inclusive.  2. Method according to claim 1, characterized in that the halogenated polysilane is 1,1,2,2-tetrachloro dimethyldisilane.  3. Process according to claim 1, characterized in that the organic acyl halide is the acid chloride of trimetellic anhydride.  4. Process according to claim 1, characterized in that the organic acyl halide is terephthaloyl chloride.  5. Method according to claim 1, characterized in that the halogenated polysilane is 1,2-dichloro-tetramethyldisilane  6. Process according to claim 1, characterized in that the transition metal-containing catalyst is a cocatalyst composed of bis (benzonitrile) palladium chloride and triphenylphosphine.  7. Process according to claim 1, characterized in that it is carried out continuously.  8. Process according to claim 1, characterized in that the catalyst containing a transition metal is a palladium on carbon catalyst.  9. Organic silane chosen from the class consisting of 4-chlorodimethylsilyl phthalic anhydride, 4-dichloromethylsilyl phthalic anhydride, 4-trichlorosilyl phthalic anhydride, 4-butyl chlorodimethylsilyl phthalimide, 4-N-butyl dichlorodimethylsilyl phthalimide, N-butyl-4-trichlorosilyl phthalimide, 2-chlorodimethylsilyl benzoyl chloride, 2-dichloromethylsilyl benzoyl chloride, 2-trichlorosilyl benzoyl chloride, 3-chlorodimethylsilyl benzoyl chloride, 3-dichloromethylsilyl benzoyl chloride , 3-trichlorosilyl benzoyl chloride, 4-dichloromethylsilyl benzoyl chloride, 4-trichlorosilyl benzoyl chloride.