JPH0453869B2 - - Google Patents

Description

[Detailed description of the invention]

DESCRIPTION OF RELATED APPLICATIONS This invention is related to U.S. Pat. No. 4,730,055, entitled "Process for Preparing Silylated Aromatic Imides." Background of the Invention Before this application, Tetrahedron Letters by Yamamoto et al.
1653 (1980), activated aromatic acyl halides, such as P-nitrobenzoyl chloride, can be prepared by decarbonylation using hexamethyldisilane as the silylation reactant, resulting in loss of carbon monoxide. , which could be converted to the corresponding aromatic silane. However, it was also found that aromatic silylation was only partially successful since the main product of Yamamoto et al.'s reaction was the corresponding aromatic silyl ketone. The present invention uses the formula (1) instead of hexamethyldisilane used in Yamamoto et al. A halogenated polysilane of formula (2) in the presence of an effective amount of a transition metal to be revealed later. is based on the discovery that when used in the reaction with an aromatic acyl halide, an organic silane of formula (3) R ¹ [-Si(R ² ) ₂ X] _n can be obtained in good yield. In the _formula , X is a _halogen group, R is R ¹ is a monovalent or polyvalent aromatic group of C _(6-20) selected from a hydrocarbon group and a substituted hydrocarbon group. It is an organic group, R ² is C _(1-20) selected from monovalent organic groups, n is an integer of 1 to 50, and m is an integer of 1 to 4. DESCRIPTION OF THE INVENTION According to the present invention, there is provided a step of: (A) carrying out a reaction between an aromatic acyl halide of formula (2) and a halogenated polysilane of formula (1) in the presence of an effective amount of a transition metal catalyst; , and (B) A method for producing an organic silane of formula (3) is provided, which comprises a step of recovering the organic silane of formula (3) from the mixture obtained in (A). Some examples of aromatic acyl halides included in formula (2) are benzoyl chloride, anhydrous trimellitic acid chloride, chlorobenzoyl chloride, anisoyl chloride, nitrobenzoyl chloride, toluoyl chloride, cyanobenzoyl chloride, bromobenzoyl chloride, and dimethylamino chloride. There are monofunctional aromatic acyl halides such as benzoyl and Nn-butyl trimellitimide acid chlorides. Examples of the polyfunctional aromatic polyacyl halide included in formula (2) include terephthaloyl chloride, phthaloyl chloride, isophthaloyl chloride, and the like. Some of the aromatic silas included in formula (3) are phenyldimethylchlorosilane, phenylmethyldichlorosilane, chlorophenyldimethylchlorosilane, anisyldimethylchlorosilane, nitrophenyldimethylchlorosilane, tolyldimethylchlorosilane, and cyanophenyldimethyl. Examples include chlorosilane, 4-dimethylchlorosilylphthalic anhydride, N-n-butyl-4-dimethylchlorosilylphthalimide, bromophenyldimethylchlorosilane, and the like. Among the polysilanes contained in formula (1), for example, chloropentamethyldisilane, 1,2-dichlorotetramethyldisilane, 1,1-dichlorotetramethyldisilane, 1,1,2-trimethyltrichlorodisilane, 1,1 , 2,2-tetrachlorodimethyldisilane, hexachlorodisilane, 1,2-
Dibromotetramethyldisilane, 1,2-difluorotetramethyldisilane, 1,1,2,2,
4,4,5,5-octamethyl-1,2,4,5
-Tetrasila-cyclohexasiloxane, 1-chlorononamethyltetrasyl-3-oxane, 1,
Examples include 2-dichloro-1,2-diphenyldimethyldisilane. The groups contained in R and R ² in formulas (1) and (3) are, for example,
C _(1-8) alkyl group (methyl, ethyl, propyl,
butyl, pentyl, etc.), chlorobutyltrifluoropropyl, cyanopropyl, and the same monovalent aryl groups and substituted 1 as defined below as R ¹
It is a valent aryl group. Monovalent aromatic groups and substituted aromatic groups contained in R ¹ in formulas (2) and (3) include phenyl, xylyl, tolyl, naphthyl, halogenated aromatic groups (chlorophenyl, dichlorophenyl, trichlorophenyl). fluorophenyl, difluorophenyl, bromophenyl, dibromophenyl, etc.), nitro and polynitro aromatic groups and aryl ether groups (eg anisoyl, ethoxyphenyl, propoxyphenyl, diphenyl ether). Furthermore, substituted aromatic groups included in R ¹ include, for example, cyanophenyl, polycyanophenyl, and phthalimide groups. An example of a preferable organic silane included in formula (3) is a halogenated sylarylene represented by the following formula. (Four) (In the formula, R ³ is a monovalent group or a substituted monovalent group defined as R and R ² above, which may be the same or different, and the group contained in R ⁴ is C _{(6-13 )} divalent aromatic groups and substituted C _(6-13) divalent aromatic groups, such as phenylene, xylylene, tolylene, naphthelene and their halogenated derivatives, where X is as previously defined) A particularly preferred sylarylene halide is sylphenylene chloride, ie 1,4-(bis-chlorodimethylsilyl)benzene. The synthesis of these silphenylene compounds is carried out from terephthaloyl chloride and 1,2-dichlorotetramethyldisilane as shown in the formula below. Transition metal catalysts used in the practice of this invention include bisbenzonitrilepalladium dichloride, bisacetonitrilepalladium dichloride, allylpalladium chloride dimer, bis(triphenylphosphine)palladium dibromide, bis(triphenylphosphine)palladium dibromide, and bis(triphenylphosphine)palladium dibromide. phosphine) palladium iodide, tetrakis(triphenylphosphine) palladium, palladium dichloride, bis(diphenylmethyl)phosphine palladium dichloride, palladium on carbon, palladium on silica. Furthermore, rhodium
Complexes of iridium, cobalt, platinum and other group metals are also used. A preferred transition metal catalyst is bisbenzonitrile palladium dichloride. Amine or phosphine cocatalysts such as trimethylamine, triethylamine, tributylamine, pyridine, N,N,N',N'-tetramethylethylenediamine, triphenylphosphine, tri-p
-Tolylphosphine, tri-o-anisylphosphine, trimethyl or tributylphosphine, tricyclohexylphosphine may be used to facilitate decarbonylation. The effective amount of the transition metal catalyst is 0.05% to 0.15% by weight based on the weight of the aromatic acyl halide of formula (2).
It is. The effective amount of cocatalyst is from 0.10% to 0.30% by weight based on the weight of the aromatic acyl halide. In the practice of this invention, a halogenated polysilane of formula (1) and a
A reaction is started between the organic acid halides in (2).
The reaction is carried out under various conditions. For example, the reactants may be combined in an inert atmosphere in the absence of a solvent or from about 100 to
Heat to the desired temperature while stirring in a non-reactive solvent with a boiling point above 300°C. For example, O-
Xylene, anisole, mesitylene, non-halogenated aromatic or aliphatic solvents can be used. It is also possible to carry out the reaction in the gas phase by passing the gaseous reactant over a layer containing a transition metal catalyst bound to a polymeric support material. Other operations used to carry out the reaction include fluid flow, in which the reactants are dissolved in a hot, non-reactive solvent, or, if the reactants are compatible, passed directly over the polymer-bound catalyst. It is a device. Depending on the value of m in formula (2), which is an organic acid halide, and whether the halogenated polysilane is a monofunctional halopolysilane or a polyfunctional halopolysilane, the halogenated polysilane and the organic acid halide The molar ratio of varies widely. It is necessary to use enough halogenated polysilane to provide at least 2 gram atoms of silicon in the halogenated polysilane per mole of organic acyl halide. The temperature used when carrying out the reaction between the halogenated polysilane and the organic acyl halide depends on the properties of the reactants and the conditions of use, such as whether an organic solvent is used or not, as mentioned above.
℃, preferably 135 to 145℃. The halogenated organosilanes produced by the practice of the present invention include sylarylene silane diols, sylarylene siloxane polymers obtained therefrom,
It can be hydrolyzed to a variety of useful intermediates such as bis(siloxane anhydrides), bis(siloxane imides), and the like. The following examples are presented to enable those skilled in the art to better practice the invention, and are given by way of illustration and not limitation. All parts are by weight. Example 1 20 g (9.5×10 ^-2 mol) of anhydrous trimellitic acid chloride
and 23 g (0.1 mol) of 1,1,2,2-tetrachlorodimethyldisilane are heated with stirring under an atmosphere of dry nitrogen until a homogeneous solution at a temperature of about 135 DEG C. is obtained. A cocatalyst mixture of 123 mg (0.5 mol %) of bis(benzonitrile)palladium chloride and 250 mg (1 mol %) of triphenylphosphine is then added, producing a red solution;
Carbon monoxide is generated from the reaction mixture. The reaction temperature is maintained at 140-150°C, and methyltrichlorosilane is continuously removed from the reaction solution. Methyltrichlorosilane (14.1 g) is obtained in quantitative yield after 2 hours. The reaction mixture was then distilled at 170-174°C.
10 g of 4-dichloromethylsilyl phthalic anhydride having a boiling point of 0.01 Torr are obtained, ie a yield of 41%. It is a clear viscous oil. Further product identification is carried out by NMR and IR spectra. Elemental analysis shows theoretically calculated value: C ₉ H ₆ O ₃ SiCl ₂ ; 259.9463, measured value: 259.9464. 2 g of 4-dichloromethylsilyl phthalic anhydride
Dissolve in 20 ml of methylene chloride and add the resulting solution to 20 ml of water. The resulting mixture is stirred rapidly for 2 hours. Collect the organic phase and from the resulting material
Evacuating the organic solvent for 30 min at 120 °C yields a clear glassy solid. Based on IR analysis, the product is a methylsiloxane resin in which phthalic anhydride groups are chemically bonded to silicon. Methylsiloxane resins are useful as coupling agents for making composite materials. Example 2 A mixture of 10 g (4.76 x 10 ^-2 mol) of anhydrous trimellitic acid chloride and 9 g (5 x 10 ^-2 mol) of 1,2-dichlorotetramethyldisilane is heated at about 135° C. until a homogeneous solution is obtained. Heat under a dry nitrogen atmosphere. 91 mg (0.5 mole %) of bis(benzonitrile) palladium chloride and 124 mg (1.0 mole %) of triphenylphosphine are then added. The resulting solution is clear red and carbon monoxide separates from the mixture upon addition of the catalyst. Dimethylchlorosilane having a boiling point of 70° C. is removed continuously until 5.8 g are collected. The product is obtained with a yield of 97%. Based on the method of production of the product, the product is dimethylchlorosilylphthalic anhydride. Furthermore, IR and
Identification is done by NMR spectrum. Add 50 ml of a tetrahydrofuran solution containing 0.43 ml of water to the dimethylchlorosilyl phthalic anhydride.
The resulting solution is stirred under reduced pressure for 3 hours at room temperature, removing HCl as it forms. Evaporate the tetrahydrofuran and replace with 100 ml of 1:1 toluene/nonane solution. Heating produces a crystalline solid. The resulting solution is decanted from the colored oil containing the catalyst. 134-135℃ by recrystallization
8.1 g of 1,3-bis(4-phthalic anhydride)-tetramethyldisiloxane are obtained as colorless needles with a melting point of , ie a yield of 80%. The resulting bis(siloxane anhydride) is an important intermediate in the production of silicone polyimide block polymers, which are useful insulating materials. According to the above procedure, 1500 grams (7.13 moles) of trimellitic anhydride acid chloride and 1490 grams (7.48 moles) of 1,2-dichlorotetramethyldisilane
The reaction mixture containing 145 ml was directly heated in a nitrogen atmosphere.
Stir at ℃. Once the mixture is homogeneous,
1.65 grams of bis(benzonitrile)palladium chloride (4.3 x 10 ^-3 mol, 600 ppm) and 2.24 grams of triphenylphosphine (8.54 x 10 ^-3 mol,
1200ppm). Violent evolution of carbon monoxide gas occurred, accompanied by fever. External heat was reduced to maintain a constant reaction temperature of 140-150°C. Dimethyldichlorosilane with a boiling point of 69-70°C was formed and simultaneously removed continuously from the reaction mixture. 145−150℃
After 15 hours, gas evolution ceased and gas chromatographic analysis showed 93% conversion to 4-chlorodimethylsilyl phthalic anhydride. The crude product also contains significant amounts of dimethyldichlorosilane, which is removed under reduced pressure and placed on dry ice/
Condensed in an acetone trap. When gas chromatographic analysis showed complete removal of volatile chlorosilanes, 2 liters of dry tetrahydrofuran were added to dissolve the oily product and 64.2 ml of water was added dropwise over 3 hours.
During that time, the solution was kept at 25°C. Gaseous HCl was removed from the system under reduced pressure. After stirring for 5 hours at room temperature, the product precipitated out of solution. The crude product was separated and the solvent was removed from the liquid in vacuo to give another portion of product. The two parts were combined and dissolved in hot toluene. When cooled, crystalline 1,3-bis(4
-phthalic anhydride)-tetramethyldisiloxane
gave 1185 grams (78% isolated yield). Example 3 Terephthaloyl chloride 1.0 g (4.9 mmol), 1,
2-dichlorotetramethyldisilane 3.7g (19.6
A mixture consisting of 187 mg (5 mol %) of bis-(benzonitrile)palladium dichloride and 256 mg (10 mol %) of triphenylphosphine is heated to 140 DEG C. under an atmosphere of dry nitrogen. The mixture, initially a yellow solution, turns deep red. After 4 hours of heating, 1,4
-bis(dimethylchlorosilyl)benzene is obtained in quantitative yield. 1,4-bis(dimethylchlorosilyl)benzene was identified as 1,4-bis(dimethylchlorosilyl) by the procedure of Corey et al., JACS, 85, 2430 (1963).
This is done by comparing with a standard sample obtained by chlorinating benzene with triphenylchloromethane. Example 4 10 g (6 x 10 ^-2 mol) of P-cyanobenzoyl chloride and 1,2-dichlorotetramethyldisilane
The reaction mixture containing 15 g (1.25 mol) is heated to 135° C. until the solution becomes homogeneous. Bis(benzonitrile)palladium dichloride 200 mg (1 mol%)
and triphenylphosphine 274 mg (2 mol%)
A cocatalyst mixture containing is then added. Carbon monoxide gas evolution begins immediately and the reaction is heated at 140° C. for 12 hours, during which dimethylcyclodyrane is continuously removed. bp93℃/ by vacuum distillation
7 g (60% isolated yield) of 4-chlorodimethylsilylbenzonitrile of 0.1 Torr, mp 40-43°C are obtained. The produced chlorodimethylsilylbenzonitrile in the form of a low-melting, moisture-sensitive solid can be replaced by the corresponding 1,3-bis(4-
benzonitrile)-tetramethyldisiloxane. Further identification of disiloxane
This is done using NMR and IR spectra. Example 5 A heated, stirred addition funnel containing a heated, supported catalyst bed containing 2.0 g of 10% palladium on activated carbon (total palladium number)
4.5%), a gravity flow continuous reaction vessel consisting of a vent, separate collection and storage vessels for carbon monoxide and volatile silane monomer, and a collector for silylated aromatics. Anhydrous trimellitic acid chloride (10g, 4.8x
10 ^-2 mol) and 1,2-dichlorotetramethyldisilane (13 g, 6.9 x 10 ^-2 mol) into the addition funnel, stir and heat to 140°C to homogenize the solution.
Then, the mixture was poured into a catalyst bed heated to 210°C with 1 ml/ml of it.
Add at a speed of 5 minutes. Generation of CO gas was observed,
3.5g dimethyldichlorosilane (57% theoretical yield)
is collected in a lateral reservoir. Analysis of the material collected in the bottom vessel revealed dimethyldichlorosilane,
It can be seen that it contains 77% of 4-chlorodimethylsilyl phthalic anhydride and 12% of unreacted anhydrous trimellitic acid chloride. The total conversion rate is 89%. Example 6 A mixture of 2.93 grams (2.1×10 ⁻² mol) of benzoyl chloride and 5 grams (2.2×10 ⁻² mol) of 1,2-dichlorotetramethyldisilane was heated directly to 140° C. in a dry nitrogen atmosphere. 8 milligrams of bis(benzonitrile)palladium chloride (2.08 x 10 ^-5 mol, 1270 ppm) and 11 milligrams of triphenylphosphine (4.2 x 10 ^-5 mol,
2500 ppm) of the catalyst mixture, gaseous carbon monoxide was generated. The reaction mixture was heated to 140 °C for 20
heated for an hour. The mixture was then distilled to give bp68
2.46 grams (91% yield) of dimethyldichlorosilane at -72°C and 3.12 grams (87% yield) of phenyldimethylchlorosilane at bp 85°C/20 Torr were obtained. Example 7 Following the procedure of Example 6, a series of additional silylated aromatic organic materials were prepared by decarbonylation of arylacyl chlorides, as shown by the following formulas. R ⁵ and a are defined below.

【table】

[Table] Example 8 Terephthaloyl chloride 100 grams (0.49 mol)
and sym-tetrachlorodimethyldisilane 116
(0.51 mol) of the mixture was heated to 145° C. in a dry nitrogen atmosphere. After the solution is homogeneous, add palladium (1% loading on 12-30 mesh carbon).
5.3 grams (0.1 mol%) was added to start generating carbon monoxide. The mixture was maintained at a temperature of 68-71°C to continuously remove methyltrichlorosilane.
After 24 hours at 145°C, add 5.3g of the second catalyst and
After a period of time, the catalyst was charged in the same manner. Mixture 1x5
Heated for an additional 72 hours at °C. Fractional distillation of the mixture yielded 62 grams of p-dichloromethylsilylbenzoyl chloride (50% isolated yield) at bp 126°C/3 Torr.
was obtained as a colorless liquid. Its identification was further confirmed by NMR
This was confirmed by IR spectrum. An ether solution containing 5 grams (1.97×10 ⁻² mol) of p-dichloromethylsilylbenzoyl chloride and 50 ml of solvent was stirred at room temperature, and 0.4 ml of water was added thereto. The resulting mixture was stirred at room temperature for 15 minutes. Removal of the solvent yielded 3.54 grams (92% isolated yield) of a silicone liquid containing benzoyl chloride and methyl groups in the side chains. The identity of the product was further confirmed by IR spectrum. Example 9 Terephthaloyl chloride 50 grams (0.25 mole)
A mixture of 116 grams (0.51 mol) of sym-tetrachlorodimethyldisilane and 116 grams (0.51 mole) of sym-tetrachlorodimethyldisilane was heated directly to 145° C. in a dry nitrogen atmosphere. Once the mixture was homogeneous, a steam activated 4-8 mesh was charged with 10.6 grams (1 mole percent) of 5% palladium on wood flour carbon to generate carbon monoxide. The formed methyltrichlorosilane of bp 68-71°C was continuously removed by distillation. Completion of the reaction was determined by gas chromatographic analysis. 1,4-bis-dichloromethylsilylbenzene was obtained by fractional distillation. Example 10 A reaction mixture containing 20 grams (7.43×10 ⁻² mol) of hexachlorodisilane and 15.7 grams (7.43×10 ⁻² mol) of trimellitic anhydride acid chloride was heated directly to 145° C. in a dry nitrogen atmosphere. Once the mixture was homogeneous, carbon monoxide was generated by placing 1.58 grams (1 mole percent) of 5% palladium on 4-8 mesh wood flour carbon activated with steam. Then the whole mixture
Heated to 145-150°C for 10 hours. After cooling, the catalyst was filtered off and the liquid was distilled to obtain a substantial yield of 4-trichlorosilylphthalic anhydride. The identity of this compound was further confirmed by IR spectrum and mass spectrum. Although the above examples relate to only a few of the numerous variations that may be used in the practice of the silylation process of the present invention, a wide variety of halogenated polysilanes of formula (1) of the present invention, It is clear that it concerns the use of organic acyl halides of formula (2) and the transition metal catalysts indicated in the preceding description of these examples.

Claims (1)

[Claims] 1 (A) In the presence of an effective amount of a transition metal catalyst, the formula Aromatic acyl halide and formula of the formula R ¹ [-Si(R ² _{) 2} A method of producing organic silane. (However, X is a halogen group, R is X, hydrogen, C _(1-13) 1
C-valent hydrocarbon group, substituted C _(1-13) selected from monovalent hydrocarbon groups, [formula] and divalent -O-, -S-, and mixtures thereof that can form a linking group of [formula]. , R ¹ is a C _(6-20) monovalent or polyvalent aromatic organic group selected from hydrocarbon groups and substituted hydrocarbon groups, and R ² is a C _(1-20) monovalent organic group. (where n is 1 and m is an integer from 1 to 4). 2. The method according to claim 1, wherein the halogenated polysilane is 1,1,2,2-tetrachlorodimethyldisilane. 3. The method according to claim 1, wherein the aromatic acyl halide is anhydrous trimellitic acid chloride. 4. The method according to claim 1, wherein the aromatic acyl halide is terephthaloyl chloride. 5. The method according to claim 1, wherein the halogenated polysilane is 1,2-dichlorotetramethyldisilane. 6. The method of claim 1, wherein the transition metal catalyst is a cocatalyst consisting of bis-(benzonitrile)palladium chloride and triphenylphosphine. 7. The method according to claim 1, which is carried out by a continuous method. 8. The method of claim 1, wherein the transition metal catalyst is palladium on carbon.