CA1327044C - Silylation method - Google Patents
Silylation methodInfo
- Publication number
- CA1327044C CA1327044C CA000570203A CA570203A CA1327044C CA 1327044 C CA1327044 C CA 1327044C CA 000570203 A CA000570203 A CA 000570203A CA 570203 A CA570203 A CA 570203A CA 1327044 C CA1327044 C CA 1327044C
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- Prior art keywords
- accordance
- aromatic
- acylhalide
- chloride
- silica
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
Abstract
SILYLATION METHOD
ABSTRACT OF THE DISCLOSURE
A method is provided for silylating aromatic acylhalide by effecting reaction between an aromatic acylhalide and halogenated polysilane in the presence of an effective amount of a silicon supported transition methal catalyst. These supported transition metal complexes have been found to be recyclable and regenerable at the termination of the reaction.
ABSTRACT OF THE DISCLOSURE
A method is provided for silylating aromatic acylhalide by effecting reaction between an aromatic acylhalide and halogenated polysilane in the presence of an effective amount of a silicon supported transition methal catalyst. These supported transition metal complexes have been found to be recyclable and regenerable at the termination of the reaction.
Description
1 327 0~
RD-17,758 RD-17,758 sI~yLaTIo~ NETHOD
BACXGRO~ND OF ~ INVEN~IO~
In United States Patent Number 4,709,050, issued Novemher 24, 1987, SILYLATION METHOD AND ORGANIC
SILANES MADE THEREFROM, there is described a method for silylating aromatic acylhalide with halogenated polysilane in the presence of an effective amount of a transition metal catalyst. As shown by Yamamoto et al., Tetrahedron Letters, 1653 (1980) activated aromatic acylhalide, such as para-nitrobenzoylchloride, can be converted to the corresponding aromatic silane with a loss of carbon monoxide as a result of a decarbonylation reaction utilizing hexamethyldisilane as the silylating reactant.
It was found, however, that the silylation o~ the aromatic nucleus using hexamethyl disilane, resulted in only a minor amount of the desired aromatic silane, such as a paranitrophenyltrim~thylsilane, whll~ the major product was : the corresponding aromatic silylketnne.
In my U.S. Patent No. 4,709,054, issued November 24, 1987, and assigned to General Electric Company, there is taught that i~ halogenated polysilane of the formula, R(~i )n~i-X , ( 1 ) -`` 1 3~70~
RD-17,758 is reacted with aromatic acylhalide of the formula, O
Rl[CX]m , (2) in the presence of an ef~ective amount of a transition metal catalyst, a wide variety of aromatic silylation reaction products can be obtained at high yields resulting in the production of nuclear-bound carbon-silicon bonds, where X is a halogen radical, R is selected from X, hydrogen, C(1-13) monovalent hydrocarbon radicals, substituted C(1-13) monovalent hydrocarbon radicals, and divalent -0-, S- radicals and mixtures thereof which can form 9siosi- and -sissia connecting groups, R1 is a C(6_20) monovalent or polyvalent aromatic organic radical, n is an integer equal to 1 to 50 incl~sive, and m is an integer equal to 1 to 4 inclusive.
Although the method o~ U.S. Patent No.
4,709,0~4 provides for the production of organic silanes : ~ and silarylenes at high yields, it has been found difficult to recycle, regeneratP or salvage transition metal catalyst ; values from thP reaction mixture.
In addition, in instances where halogenated ;20 polysilane of the formula is used as a reactant, ~X ) 2 ~ A1 n l `` 1 3270l~
RD-17,758 where R, X and n are as previously defined, reaction can occur between the halogenated polysilane and the transition metal catalyst if a phosphine cocatalyst is used, resulting in reduced yield of nuclear-bound carbon-silicon bonds.
The present invention is based on my discovery that a wide variety of silylated aromatic reaction products having one or more nuclear-bound silicon atoms joined to an aromatic nucleus by carbon-silicon bonds can be made by effecting reaction betwe~n halogenated polysilane of formula (1~ and aromatic acylhalide of formula (2) in the presence of an effective amount of a supported transition metal complex having chemically combined groups of the formula, h ~ ~S i R2 \ /~MX ( 4 ) 5~ ~ 0 4-y U~
where R2 is a divalent C(2-14) organic radical~ Q is a nitrogen or phosphorous radical, R3 and R4 are monovalent C(1-14) alkyl or aryl radicals, M is a transition metal : selected ~rom palladium, platinum, rhodium or nickel, X is previously defined, y is an integer equal to 1 to 3 inclusi~e and pre~erably 2. Surprisingly, the supported transition metal complexes having chsmically combined groups of formula (4), which are preferably ~ilicon supported, have been found to ~e recyclable and regenerable at the termination of the reaction.
~RIEF DESCRIPTION OF THE DRAWTNG
FIGURE 1 compares the reaction mixtures catalyzed by the "Rich" silica~supported palladium catalyst and the "commeriçal" carbon-supported palladium catalyst.
STATEME~T OF~ T~E INVENTIQN
There is provided by the present invention, a method for making silylated aromatic organic materials 1 3~704~
RD-17,758 having at least one nuclear-bound silicon atom attached to an aromatic organic group by a carbon-silicon linkage comprising, (A) effecting reaction between a halogenated polysilane of formula (1) and aromatic acylhalide of formula (2) in the presence of an effective amount of a supported transition metal complex having chemically combined groups of formula (4), and (B) recovering silylated aromatic organic material from the mixture of (A).
Some of the supported transition metal complexes which can be used in the practice of the present invention are shown by A.G. Allum et al., "Supported Transition Metal Complexes II Silica as the Support", Journal or Or~anometallic Chemistry 87 (1975~, pp. 203-216, and M. Capka et al., Hydrosilylation Catalyzed by Transition Metal Complexes Coordinately Bound to Inorganic Supports" , Collection Czechoslov. Chem. Commun ., Vol . 39 , pp. 154 (1974). Additional supported transition metal catalysts which can be used are shown by U.S. Patent 4~083~803/ Oswald et al., U.S. 3,487,112, U.S. 3,726,809 and U.S. 3,832,4040 There are includes for example, in addition to silica, alumina and zeolites. The silica 5 substrate can be in the form o~ silica extrudate.
Among the halogenated polysilanes which axe included within formula (1) there are, ~or example, chloropentamethyldisilane, 1,2-dichlorotetramethyldisilane, 1,1-dichlorotetramPthyldisilane, 1,1,2-trimethyltrichloro~
disilane, 1,1,2,2-tetrachlorodimethyldisilane, hexachlorodisilane, 1,2-dibromotetramethyldisilane, 1,2-difluorotetramethyldisilane, 1,1,2,2,4,4,5,5,-octamethy -1,2,4,5-tetrasilacyclohexasiloxane, l-chlorononamethyltetrasil-3~oxane, 1,2-dichloro-1,2-diphenyldimethyldisilans, etc.
"` 1 3~70~'~
RD-17,758 Some of tha aromatic acyl halides which are included within formula (2) are, for example, monofunctional aromatic acyl halide such as benzoyl chloride, trimellitic anhydride acid chloride, chlorobenzoyl chloride, anisoyl 1 3270'-~
RD-17,758 chloride, nitrobenzoyl chloride, toluoyl chloride, cyanobenzoyl chloride, bromobenzoyl chloride, dimethylamino-benzoyl chloride, N-n-butyl trimellitic imide acid chloride, etc.
Polyfunctional aromatic polyacyl halides which are included within formula (2~ are, for example, terephthaloyl chloride, phthaloyl chloride, isophthaloyl chloride, etc.
There are included among organic silanes which can be made in accordance wi~h the practice of the method of the present invention compounds suoh as phenyldimethylchloro-silane, phenylmethyldichlorosilane, chlorophenyldimethyl-chlorosilane, anisyldimethylchlorosilane, nitrophenyl-dimethylchlorosilane, tolyldimethylchlorosilane, cyanophenyldimethylchlorosilane, 4-dimethylchlorosilyl-phthalic anhydride, N-n-butyl-4-dimethylchlorosilyl phthalimide, bromophenyldimethylchlorosilane, etc.
Radical~ which are included within R of formula ~1) are, for example, C(l 8) alkyl radicals, for example methyl, ethyl, propyl, butyl, pentyl, etc., chlorobutyl, trifluoropropyl, cyanopropyl; aryl radicals, for example phenyl, xylyl, tolyl, naphthyl, halogenated aryl radicals such as chlorophenyl, dichlorophenyl, trichlorophenyl, fluorophenyl, difluorophenyl, bromophenyl; nitro and pslynitro aromatic radicals as well a~ arylether radicals, for example, anisole, ethoxyphenyl, propoxyphenyl, diphenylether, cyanophenyl, etc.
Some of the monovalent aromatir radicals and substituted aromatic radicals which can be included within Rl of formula (2) ar2, for example, phenyl, xylyl, tolyl, naphthyl; halogenated aromatic radicals such as chlorophenyl, dichlorophenyl, trichlorophenyl, etc., fluorophenyl, difluorophenyl, etc., bromophenyl, dibrsmophenyl, etc.; nitro and polynitro axomatic radicals 1 3270~4 RD-17,758 as well as aryl ether radicals for example, anisoyl, ethoxyphenyl, propoxyphenyl, diphenylether. Additional substituted aromatic radicals which can be included within R1 are for example, cyanophenyl, polycyanophenyl, as well as phthalimido radicals.
Typical of the chemically combined groups of formula (4) are, for example, where R2 is selected from ethylene, propylene, butylene, octylene, tetradecylene, phenethyl, propylphenyl, butylphenyl and hexylphenyl; R3 and R4 are selected from methyl, ethyl, propyl, butyl, and isomers thereof, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, mesityl and anisyl; and X is selected from Cl, Br, I.
Further examples of the catalyst are, \ /
CH2) O PdC1 S -~}-Sl-tCH2) / r\
\ /
~i~CH2~-- - - r ~PdC12 .
28 / \
There are alss included among the aromatic silylation reaction products silarylene halidest such as 1,4-~bis-chlorodimethylsilyl)benzene. The synthesis of such RD-17,758 silphenylene compounds can be made from terephthaloyl chloride and 1,2~dichlorotetramethyldisilane.
An effective amount of silica-supported transition metal catalyst is an amount of silica-supported transition metal catalyst which is sufficient to provide from 0.005% by weight to 20% by weight of transition metal based on the weight of aromatic acyl halide.
In the practice of the present invention, reaction is initiated between the halogenated polysilane of formula (l) and the aromatic acylhalide of formula (2) in the presence of an effective amount o the silica~supported transition metal catalyst. Reaction can be carried out under a variety of conditions. For example, the reactants can be heated to the desired ~emperature in the absence of solvent, while being stirred under an inert atmosphere or in the presence of a nonreactive solvent with a boiling point greater than about 100C to 300C. Nonreactive solvents which can be used are, for example, o-xylene, anisole, mesitylene, or nor~alogenated aromatic or aliphatic solvents.
Depending upon the value of m in formula (2~ for the aromatic acylhalide, and whether the halogenated polysilane is a monofunctional or polyfunctional halopolysilane, mslar proportions of the halogenated polysilane and ~he aromatic acylhalide can vary widely.
There should be used sufficient halogenated polysilane to prcvide at least 2 gram atoms of 5ilicon of the halogenated polysilane, per mole of the aromatic acylhalide.
Temperatures which can be utilized in effecting reaction between the halogenated polysilane and the aromatic acylhalide are, for exampl~, 110C and preferably 135-145C
depending upon the nature of the reactants and conditions - 1 3270~
RD-17,75 utilized, such as with or without organic solvent, as previously discussed.
Organic silanes made in accordance with the practice of the present invention can be hydrolyzed to a variety of valuable intermediates, such as silarylenesilane diols, bis(siloxaneanhydrides), bis(siloxaneimides), etc.
In order that those skilled in the art will be better able to practice the present invention, the following examples are qiven by way of illustration and not by way of limitation. All parts are by weight.
EXAfflPLE 1 There was added 17.67 grams ~0.10 moles) of palladium dichloride to a mixture of 75 grams (0.20 moles) of diphenylphosphinoethyltriethoxysilane dissolved in 200 ml of dry dichloroethane. The diphenylphosphinoethyltriethoxy-silane was pr~pared in accordance with the method of A.G.
Allum et al., Journal Organomet.Chem. 87, 203 (1975). The mixture of palladium dichloride and the triphenylphosphino-ethyltriethoxysilane was heated to reflux until all of the suspended palladium dichloride was consumed. The resulting orange solution was alluted with 100 ml hexane. Upon cooling there was ~ormed 89.9 grams ~97%) of bis(diphenyl-phosphinoethyltriethoxysilyl)palladium dichloride as yellow crystal There was addad 585 grams of 1~8 in. diameter ~ilica extrudates to 60.7 grams of bis(diphenylphosphinoethyltriethoxysilyl)palladium dichloride di solved in 500 ml of methylene chloride. The color of the resulting solution changed and the extrudates were yellow orange. The catalyst was filtered and washed with methylene chloride and air-dried at 125C for two hours. Extrudates were then added to 700 ml of 5% aqueous --e,--1 3270~'~
RD-17,758 HCl and allowed to stand for 12 hours followed by filtration, washing with water and subse~ently acetone, ether and pentane. The resulting catalyst was then air-dried at 125C for eight hours. The catalyst was then immersed in an excess of hexamethyldisilazane for two hours at room temperature, followed by filtration, washing with methylene chloride and pentane and drying under vacuum at 80C for 15 hours. There was obtained a silica-supported palladium silylation catalyst having a plurality of chemically combined groups of the formula, Si--CH2CH2 P~ ~Cl ~ ~ 0 / Pd w ~ ----O--Si--CH2CH2 ~ P ~ ~Cl Chemical analysis showed that ~he catalyst contained 2.02%
by weiyht of palladium.
There was heated neat to 145C, a mixture of 562 gr~ms (2.67 moles) trimellitic anhydride acid chloride, 700 1~ grams (2.67 moles3 of 1,2-dichlorotetramethyldisilane and 40 grams (0.3 mole %) of the above silylatio~ catalyst having 2.02% by weight of palladium. Rapid outqassing of carbon monoxide occurred from the catalyst surface and dimethyldichlorosilane formed during reaction was continuously removed by distillation. After heating the mixture for 12 hours at 145C, gas chromatography indicated complete reaction of the trimellitic anhydride acid chloride. The resulting mixture was then decanted. Vacuum distillation resulted in ~he production of 169 grams (73%
1 32704~
RD-17,75B
yield) of 4-chlorodimethylsilylphthalic anhydride as a clear liquid, b.P. 141C/0.1 torr.
The procedure of Example 1 was repeated for making the silica-supported palladium catalyst except that there was used 89.9 grams (0.16 mole) of bis(diphenylphosphino~
ethyl)triethoxysilane and 1,064 grams of 200-300 mesh silica. Based on method of preparation and chemical analysis, there was obtained a silica-supported palladium catalyst having about 1% by weight of palladium.
A reaction mixture containing 203 grams (1.0 mole) of terephthaloylchloride and 187 grams (1.0 mole) of 1,2-dichlorotetramethyldisilane was stirred and heated neat to 245C until a homogeneous mixture was obtained. There was added to the mixture, 32 grams of the silica-suppor~ed 1% palladium catalyst. Rapid evolution of carbon monoxide gas occurred and dimethyldichlorosilane was remov~d continuously as it formed. After 12 hours at 145C NMR
analysis showed complete reaction of the terephthaloyl-~hloride. The reaction mixture was cooled to roomtemperature and filtered under nitrogen to remove the catalyst. Distillation of th~ mixture provided 174 grams (75%~ yield of 4~chlorodimethylsilylbenzoylchloride as a clear liquid, boiling point 97C/0.1 torr.
The procedure of Example 2 was repeated utilizing 10 grams (4.93 x 10 2 moles3 of terephthaloylchloride, 9.~
grams (4.93 x 10 2 moles) of 1,2-dichlorotetramethyldisilane and 3 grams of the 1% palladium (II) on silica ~rom Example 2. The mixture was heated to 145C neat. There was also utilized in the mixture, an unreactive GC internal standard, RD-17,~58 tetradecane (3.16 grams, l.~3 x 10 2 moles). After three hours, the reaction was stopped and the progress of the reaction was monitored by gas chromatography. The same procedure was repeated except that in place of the 3 grams of reused silica-supported 1% palladium prepared in Example 2, there was used 3 grams of a 1% commercially available palladium on carbon, Johnson-Mathey Corporation TS2276. An additional reaction was also run employing 3 grams of a commercially-available silica-supported 1% palladium catalyst from Engelhardt Company. It was determined that the latter- commercially available silica-supported palladium catalyst had the palladium absorbed onto the surface of the silica instead of being chemically combined, as shown in Examples 1 and 2.
lS The various mixtures were heated continuously for 3 hours under neat conditions and the progress of the respective reactions was monitored by gas chromatography.
The catalysts were then filtered, washed with methylene chloride, dried under nitrogen and reintroduced into fr sh aiiquots of the respective reaction mixtures. It was found that the reaction mixture containing the commercially available silica-supported palladium catalyst which was absorbed onto the surface of the silica, could not be satisfactorily monitored, as little or no reaction had 2S occurred. However, the re~ults of five runs were monitored, as shown in the drawing, comparing the reaction mixture catalyzed by the silica-support~d palladium catalyst having palladium chemically combined to silica through connecting groups of formula (4~ Xich" and the reaction mixture containing the "Gommercial" palladium catalyst using carbon as a support. After three runs, the respective catalysts ware removed from the mixtures, slurried in carbon tetrachloride, and gaseous chlorine was introduced. The ~ 3 2 1 0 '~ ~ ~D-17,758 Rich catalyst of the present invention turned yellow-orange in color and the rate of color change could be increased by mildly heating the carbon tetrachloride following filtration and washing with methylenechloride. After the catalysts were dry, they were reintroduced in fresh aliguots of starting materials. It was found that the "reactivated"
catalyst of the present invention "Rich" showed 85% of its initial activity from the first run, while no change was noted in the commercially available catalyst.
After several runs, the silica-supported catalyst of Example 1, a batch of 2% palladium on 1/8" silica extrudates, had been completely reduced to palladium black and was no longer active in the silylation process. The spent silica-supported palladium catalyst was then slurred in a 5% aqueous solution of copper chloride for 10 minutes and oxygen wa~ then bubbled through the mixture. An exothermic reaction occurred and the silica-supported palladium catalyst turned from black to yellow-oran~e in color. The mixture was then filtered and the silica-supported palladium catalyst was then analyzed.
Elemental analysis showed that the spent catalyst had 1.3%
palladium while the original wa~ 2.02% palladium. After the spent catalyst was reoxidized, the reactivated catalyst contained 0.7% pall~dium and 1% copper.
A reaction mixture containing 4.93 x 10 2 moles of trimellitic anhydride acid chloride and 4.93 x 10 3 moles o 1,2-dichlorotetramethyldisilane was heated to 145~ in the presence of 3 grams of the above-described silica-supported reactivated catalyst. After 3 hours at 145C, ~9 chromatography indicated complete reaction of the trimellitic anhydride acid chloride. The resulting mixture 1 327 0 ~ 4 RD-17,758 was then decanted and vacuum distilled to provide 7.23 grams or a 61% yield of 4-chlorodimethylsilylphthalic a~lydride.
The procedure o Example 2 was repeated for makin~
the 1% by weight of palladium catalyst.
A reaction mixture containing 3 gram (2.13 x 10 2 mole) of benzoyl chloride and 4.85 grams (2.13 mole3 or sym-tetrachlorodimethyl disilane was ~tirred and heated to 130-135~C neat until a homogeneous mixture was formed.
There was added to the mixture 2.2 g of 1% palladium on 200-300 mesh silica. Rapid evolution of carbon monoxide occurred and trichloromethylsilane was removed continuously as it formed. After 15 hours at 130C, NMR analysis showed complete reaction of benzoyl chloride.
The above reaction was repeated with other substrates, as shown by the followin~ equation and Table, where Ar is phenyl, or substituted phenyl:
R ( C133) Si(CH3)C12 ' + C~3SiC13 + C0 1327Q~
RD~7,7S8 TABLE
Substrate Mole % Mole %
where R = ArSiCH3C12 ArCl .~
P-Cl 8g 11 P-COCl 8~ 1~
3,4 N-CH3 36 7 o o 3,4 ~ O 95 5 ~ C
o The above results show that the silica supported catalyst of the present invention having chemically combined groups of formula (4~, has superior selectivity when used to make polyfunctional aryl silanes from aryl substrates substituted with a variety of activating groups employin~
polysilanes having silicon atoms wi~h at least two halogen radicals per silicon.
In contrast, a similar silylation reaction was conducted with the same substrates using the 1% commercially 1 32704~ RD-17,75~
available palladium on carbon catalyst of Example 3. It was found that a wide variation resulted in selectivity in accordance with the substituent R on the phenyl ring. For example, when R was hydrogen, only a trace of the desired phenyl silane was obtained while a 78% yield was obtained with chloroacylphthalicanhydride. A 67% yield was obtained with terephthaloyl chloride.
Although the bove examples are directed to only a few of the very many variables which can be utilized in the practice of the method of the present invention, it should be understood that the present invention is directed to a much broader variety of silica-supported palladium catalyst, halogenated polysilane and aromatic acylhalide shown in the description precesding these examples.
RD-17,758 RD-17,758 sI~yLaTIo~ NETHOD
BACXGRO~ND OF ~ INVEN~IO~
In United States Patent Number 4,709,050, issued Novemher 24, 1987, SILYLATION METHOD AND ORGANIC
SILANES MADE THEREFROM, there is described a method for silylating aromatic acylhalide with halogenated polysilane in the presence of an effective amount of a transition metal catalyst. As shown by Yamamoto et al., Tetrahedron Letters, 1653 (1980) activated aromatic acylhalide, such as para-nitrobenzoylchloride, can be converted to the corresponding aromatic silane with a loss of carbon monoxide as a result of a decarbonylation reaction utilizing hexamethyldisilane as the silylating reactant.
It was found, however, that the silylation o~ the aromatic nucleus using hexamethyl disilane, resulted in only a minor amount of the desired aromatic silane, such as a paranitrophenyltrim~thylsilane, whll~ the major product was : the corresponding aromatic silylketnne.
In my U.S. Patent No. 4,709,054, issued November 24, 1987, and assigned to General Electric Company, there is taught that i~ halogenated polysilane of the formula, R(~i )n~i-X , ( 1 ) -`` 1 3~70~
RD-17,758 is reacted with aromatic acylhalide of the formula, O
Rl[CX]m , (2) in the presence of an ef~ective amount of a transition metal catalyst, a wide variety of aromatic silylation reaction products can be obtained at high yields resulting in the production of nuclear-bound carbon-silicon bonds, where X is a halogen radical, R is selected from X, hydrogen, C(1-13) monovalent hydrocarbon radicals, substituted C(1-13) monovalent hydrocarbon radicals, and divalent -0-, S- radicals and mixtures thereof which can form 9siosi- and -sissia connecting groups, R1 is a C(6_20) monovalent or polyvalent aromatic organic radical, n is an integer equal to 1 to 50 incl~sive, and m is an integer equal to 1 to 4 inclusive.
Although the method o~ U.S. Patent No.
4,709,0~4 provides for the production of organic silanes : ~ and silarylenes at high yields, it has been found difficult to recycle, regeneratP or salvage transition metal catalyst ; values from thP reaction mixture.
In addition, in instances where halogenated ;20 polysilane of the formula is used as a reactant, ~X ) 2 ~ A1 n l `` 1 3270l~
RD-17,758 where R, X and n are as previously defined, reaction can occur between the halogenated polysilane and the transition metal catalyst if a phosphine cocatalyst is used, resulting in reduced yield of nuclear-bound carbon-silicon bonds.
The present invention is based on my discovery that a wide variety of silylated aromatic reaction products having one or more nuclear-bound silicon atoms joined to an aromatic nucleus by carbon-silicon bonds can be made by effecting reaction betwe~n halogenated polysilane of formula (1~ and aromatic acylhalide of formula (2) in the presence of an effective amount of a supported transition metal complex having chemically combined groups of the formula, h ~ ~S i R2 \ /~MX ( 4 ) 5~ ~ 0 4-y U~
where R2 is a divalent C(2-14) organic radical~ Q is a nitrogen or phosphorous radical, R3 and R4 are monovalent C(1-14) alkyl or aryl radicals, M is a transition metal : selected ~rom palladium, platinum, rhodium or nickel, X is previously defined, y is an integer equal to 1 to 3 inclusi~e and pre~erably 2. Surprisingly, the supported transition metal complexes having chsmically combined groups of formula (4), which are preferably ~ilicon supported, have been found to ~e recyclable and regenerable at the termination of the reaction.
~RIEF DESCRIPTION OF THE DRAWTNG
FIGURE 1 compares the reaction mixtures catalyzed by the "Rich" silica~supported palladium catalyst and the "commeriçal" carbon-supported palladium catalyst.
STATEME~T OF~ T~E INVENTIQN
There is provided by the present invention, a method for making silylated aromatic organic materials 1 3~704~
RD-17,758 having at least one nuclear-bound silicon atom attached to an aromatic organic group by a carbon-silicon linkage comprising, (A) effecting reaction between a halogenated polysilane of formula (1) and aromatic acylhalide of formula (2) in the presence of an effective amount of a supported transition metal complex having chemically combined groups of formula (4), and (B) recovering silylated aromatic organic material from the mixture of (A).
Some of the supported transition metal complexes which can be used in the practice of the present invention are shown by A.G. Allum et al., "Supported Transition Metal Complexes II Silica as the Support", Journal or Or~anometallic Chemistry 87 (1975~, pp. 203-216, and M. Capka et al., Hydrosilylation Catalyzed by Transition Metal Complexes Coordinately Bound to Inorganic Supports" , Collection Czechoslov. Chem. Commun ., Vol . 39 , pp. 154 (1974). Additional supported transition metal catalysts which can be used are shown by U.S. Patent 4~083~803/ Oswald et al., U.S. 3,487,112, U.S. 3,726,809 and U.S. 3,832,4040 There are includes for example, in addition to silica, alumina and zeolites. The silica 5 substrate can be in the form o~ silica extrudate.
Among the halogenated polysilanes which axe included within formula (1) there are, ~or example, chloropentamethyldisilane, 1,2-dichlorotetramethyldisilane, 1,1-dichlorotetramPthyldisilane, 1,1,2-trimethyltrichloro~
disilane, 1,1,2,2-tetrachlorodimethyldisilane, hexachlorodisilane, 1,2-dibromotetramethyldisilane, 1,2-difluorotetramethyldisilane, 1,1,2,2,4,4,5,5,-octamethy -1,2,4,5-tetrasilacyclohexasiloxane, l-chlorononamethyltetrasil-3~oxane, 1,2-dichloro-1,2-diphenyldimethyldisilans, etc.
"` 1 3~70~'~
RD-17,758 Some of tha aromatic acyl halides which are included within formula (2) are, for example, monofunctional aromatic acyl halide such as benzoyl chloride, trimellitic anhydride acid chloride, chlorobenzoyl chloride, anisoyl 1 3270'-~
RD-17,758 chloride, nitrobenzoyl chloride, toluoyl chloride, cyanobenzoyl chloride, bromobenzoyl chloride, dimethylamino-benzoyl chloride, N-n-butyl trimellitic imide acid chloride, etc.
Polyfunctional aromatic polyacyl halides which are included within formula (2~ are, for example, terephthaloyl chloride, phthaloyl chloride, isophthaloyl chloride, etc.
There are included among organic silanes which can be made in accordance wi~h the practice of the method of the present invention compounds suoh as phenyldimethylchloro-silane, phenylmethyldichlorosilane, chlorophenyldimethyl-chlorosilane, anisyldimethylchlorosilane, nitrophenyl-dimethylchlorosilane, tolyldimethylchlorosilane, cyanophenyldimethylchlorosilane, 4-dimethylchlorosilyl-phthalic anhydride, N-n-butyl-4-dimethylchlorosilyl phthalimide, bromophenyldimethylchlorosilane, etc.
Radical~ which are included within R of formula ~1) are, for example, C(l 8) alkyl radicals, for example methyl, ethyl, propyl, butyl, pentyl, etc., chlorobutyl, trifluoropropyl, cyanopropyl; aryl radicals, for example phenyl, xylyl, tolyl, naphthyl, halogenated aryl radicals such as chlorophenyl, dichlorophenyl, trichlorophenyl, fluorophenyl, difluorophenyl, bromophenyl; nitro and pslynitro aromatic radicals as well a~ arylether radicals, for example, anisole, ethoxyphenyl, propoxyphenyl, diphenylether, cyanophenyl, etc.
Some of the monovalent aromatir radicals and substituted aromatic radicals which can be included within Rl of formula (2) ar2, for example, phenyl, xylyl, tolyl, naphthyl; halogenated aromatic radicals such as chlorophenyl, dichlorophenyl, trichlorophenyl, etc., fluorophenyl, difluorophenyl, etc., bromophenyl, dibrsmophenyl, etc.; nitro and polynitro axomatic radicals 1 3270~4 RD-17,758 as well as aryl ether radicals for example, anisoyl, ethoxyphenyl, propoxyphenyl, diphenylether. Additional substituted aromatic radicals which can be included within R1 are for example, cyanophenyl, polycyanophenyl, as well as phthalimido radicals.
Typical of the chemically combined groups of formula (4) are, for example, where R2 is selected from ethylene, propylene, butylene, octylene, tetradecylene, phenethyl, propylphenyl, butylphenyl and hexylphenyl; R3 and R4 are selected from methyl, ethyl, propyl, butyl, and isomers thereof, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, mesityl and anisyl; and X is selected from Cl, Br, I.
Further examples of the catalyst are, \ /
CH2) O PdC1 S -~}-Sl-tCH2) / r\
\ /
~i~CH2~-- - - r ~PdC12 .
28 / \
There are alss included among the aromatic silylation reaction products silarylene halidest such as 1,4-~bis-chlorodimethylsilyl)benzene. The synthesis of such RD-17,758 silphenylene compounds can be made from terephthaloyl chloride and 1,2~dichlorotetramethyldisilane.
An effective amount of silica-supported transition metal catalyst is an amount of silica-supported transition metal catalyst which is sufficient to provide from 0.005% by weight to 20% by weight of transition metal based on the weight of aromatic acyl halide.
In the practice of the present invention, reaction is initiated between the halogenated polysilane of formula (l) and the aromatic acylhalide of formula (2) in the presence of an effective amount o the silica~supported transition metal catalyst. Reaction can be carried out under a variety of conditions. For example, the reactants can be heated to the desired ~emperature in the absence of solvent, while being stirred under an inert atmosphere or in the presence of a nonreactive solvent with a boiling point greater than about 100C to 300C. Nonreactive solvents which can be used are, for example, o-xylene, anisole, mesitylene, or nor~alogenated aromatic or aliphatic solvents.
Depending upon the value of m in formula (2~ for the aromatic acylhalide, and whether the halogenated polysilane is a monofunctional or polyfunctional halopolysilane, mslar proportions of the halogenated polysilane and ~he aromatic acylhalide can vary widely.
There should be used sufficient halogenated polysilane to prcvide at least 2 gram atoms of 5ilicon of the halogenated polysilane, per mole of the aromatic acylhalide.
Temperatures which can be utilized in effecting reaction between the halogenated polysilane and the aromatic acylhalide are, for exampl~, 110C and preferably 135-145C
depending upon the nature of the reactants and conditions - 1 3270~
RD-17,75 utilized, such as with or without organic solvent, as previously discussed.
Organic silanes made in accordance with the practice of the present invention can be hydrolyzed to a variety of valuable intermediates, such as silarylenesilane diols, bis(siloxaneanhydrides), bis(siloxaneimides), etc.
In order that those skilled in the art will be better able to practice the present invention, the following examples are qiven by way of illustration and not by way of limitation. All parts are by weight.
EXAfflPLE 1 There was added 17.67 grams ~0.10 moles) of palladium dichloride to a mixture of 75 grams (0.20 moles) of diphenylphosphinoethyltriethoxysilane dissolved in 200 ml of dry dichloroethane. The diphenylphosphinoethyltriethoxy-silane was pr~pared in accordance with the method of A.G.
Allum et al., Journal Organomet.Chem. 87, 203 (1975). The mixture of palladium dichloride and the triphenylphosphino-ethyltriethoxysilane was heated to reflux until all of the suspended palladium dichloride was consumed. The resulting orange solution was alluted with 100 ml hexane. Upon cooling there was ~ormed 89.9 grams ~97%) of bis(diphenyl-phosphinoethyltriethoxysilyl)palladium dichloride as yellow crystal There was addad 585 grams of 1~8 in. diameter ~ilica extrudates to 60.7 grams of bis(diphenylphosphinoethyltriethoxysilyl)palladium dichloride di solved in 500 ml of methylene chloride. The color of the resulting solution changed and the extrudates were yellow orange. The catalyst was filtered and washed with methylene chloride and air-dried at 125C for two hours. Extrudates were then added to 700 ml of 5% aqueous --e,--1 3270~'~
RD-17,758 HCl and allowed to stand for 12 hours followed by filtration, washing with water and subse~ently acetone, ether and pentane. The resulting catalyst was then air-dried at 125C for eight hours. The catalyst was then immersed in an excess of hexamethyldisilazane for two hours at room temperature, followed by filtration, washing with methylene chloride and pentane and drying under vacuum at 80C for 15 hours. There was obtained a silica-supported palladium silylation catalyst having a plurality of chemically combined groups of the formula, Si--CH2CH2 P~ ~Cl ~ ~ 0 / Pd w ~ ----O--Si--CH2CH2 ~ P ~ ~Cl Chemical analysis showed that ~he catalyst contained 2.02%
by weiyht of palladium.
There was heated neat to 145C, a mixture of 562 gr~ms (2.67 moles) trimellitic anhydride acid chloride, 700 1~ grams (2.67 moles3 of 1,2-dichlorotetramethyldisilane and 40 grams (0.3 mole %) of the above silylatio~ catalyst having 2.02% by weight of palladium. Rapid outqassing of carbon monoxide occurred from the catalyst surface and dimethyldichlorosilane formed during reaction was continuously removed by distillation. After heating the mixture for 12 hours at 145C, gas chromatography indicated complete reaction of the trimellitic anhydride acid chloride. The resulting mixture was then decanted. Vacuum distillation resulted in ~he production of 169 grams (73%
1 32704~
RD-17,75B
yield) of 4-chlorodimethylsilylphthalic anhydride as a clear liquid, b.P. 141C/0.1 torr.
The procedure of Example 1 was repeated for making the silica-supported palladium catalyst except that there was used 89.9 grams (0.16 mole) of bis(diphenylphosphino~
ethyl)triethoxysilane and 1,064 grams of 200-300 mesh silica. Based on method of preparation and chemical analysis, there was obtained a silica-supported palladium catalyst having about 1% by weight of palladium.
A reaction mixture containing 203 grams (1.0 mole) of terephthaloylchloride and 187 grams (1.0 mole) of 1,2-dichlorotetramethyldisilane was stirred and heated neat to 245C until a homogeneous mixture was obtained. There was added to the mixture, 32 grams of the silica-suppor~ed 1% palladium catalyst. Rapid evolution of carbon monoxide gas occurred and dimethyldichlorosilane was remov~d continuously as it formed. After 12 hours at 145C NMR
analysis showed complete reaction of the terephthaloyl-~hloride. The reaction mixture was cooled to roomtemperature and filtered under nitrogen to remove the catalyst. Distillation of th~ mixture provided 174 grams (75%~ yield of 4~chlorodimethylsilylbenzoylchloride as a clear liquid, boiling point 97C/0.1 torr.
The procedure of Example 2 was repeated utilizing 10 grams (4.93 x 10 2 moles3 of terephthaloylchloride, 9.~
grams (4.93 x 10 2 moles) of 1,2-dichlorotetramethyldisilane and 3 grams of the 1% palladium (II) on silica ~rom Example 2. The mixture was heated to 145C neat. There was also utilized in the mixture, an unreactive GC internal standard, RD-17,~58 tetradecane (3.16 grams, l.~3 x 10 2 moles). After three hours, the reaction was stopped and the progress of the reaction was monitored by gas chromatography. The same procedure was repeated except that in place of the 3 grams of reused silica-supported 1% palladium prepared in Example 2, there was used 3 grams of a 1% commercially available palladium on carbon, Johnson-Mathey Corporation TS2276. An additional reaction was also run employing 3 grams of a commercially-available silica-supported 1% palladium catalyst from Engelhardt Company. It was determined that the latter- commercially available silica-supported palladium catalyst had the palladium absorbed onto the surface of the silica instead of being chemically combined, as shown in Examples 1 and 2.
lS The various mixtures were heated continuously for 3 hours under neat conditions and the progress of the respective reactions was monitored by gas chromatography.
The catalysts were then filtered, washed with methylene chloride, dried under nitrogen and reintroduced into fr sh aiiquots of the respective reaction mixtures. It was found that the reaction mixture containing the commercially available silica-supported palladium catalyst which was absorbed onto the surface of the silica, could not be satisfactorily monitored, as little or no reaction had 2S occurred. However, the re~ults of five runs were monitored, as shown in the drawing, comparing the reaction mixture catalyzed by the silica-support~d palladium catalyst having palladium chemically combined to silica through connecting groups of formula (4~ Xich" and the reaction mixture containing the "Gommercial" palladium catalyst using carbon as a support. After three runs, the respective catalysts ware removed from the mixtures, slurried in carbon tetrachloride, and gaseous chlorine was introduced. The ~ 3 2 1 0 '~ ~ ~D-17,758 Rich catalyst of the present invention turned yellow-orange in color and the rate of color change could be increased by mildly heating the carbon tetrachloride following filtration and washing with methylenechloride. After the catalysts were dry, they were reintroduced in fresh aliguots of starting materials. It was found that the "reactivated"
catalyst of the present invention "Rich" showed 85% of its initial activity from the first run, while no change was noted in the commercially available catalyst.
After several runs, the silica-supported catalyst of Example 1, a batch of 2% palladium on 1/8" silica extrudates, had been completely reduced to palladium black and was no longer active in the silylation process. The spent silica-supported palladium catalyst was then slurred in a 5% aqueous solution of copper chloride for 10 minutes and oxygen wa~ then bubbled through the mixture. An exothermic reaction occurred and the silica-supported palladium catalyst turned from black to yellow-oran~e in color. The mixture was then filtered and the silica-supported palladium catalyst was then analyzed.
Elemental analysis showed that the spent catalyst had 1.3%
palladium while the original wa~ 2.02% palladium. After the spent catalyst was reoxidized, the reactivated catalyst contained 0.7% pall~dium and 1% copper.
A reaction mixture containing 4.93 x 10 2 moles of trimellitic anhydride acid chloride and 4.93 x 10 3 moles o 1,2-dichlorotetramethyldisilane was heated to 145~ in the presence of 3 grams of the above-described silica-supported reactivated catalyst. After 3 hours at 145C, ~9 chromatography indicated complete reaction of the trimellitic anhydride acid chloride. The resulting mixture 1 327 0 ~ 4 RD-17,758 was then decanted and vacuum distilled to provide 7.23 grams or a 61% yield of 4-chlorodimethylsilylphthalic a~lydride.
The procedure o Example 2 was repeated for makin~
the 1% by weight of palladium catalyst.
A reaction mixture containing 3 gram (2.13 x 10 2 mole) of benzoyl chloride and 4.85 grams (2.13 mole3 or sym-tetrachlorodimethyl disilane was ~tirred and heated to 130-135~C neat until a homogeneous mixture was formed.
There was added to the mixture 2.2 g of 1% palladium on 200-300 mesh silica. Rapid evolution of carbon monoxide occurred and trichloromethylsilane was removed continuously as it formed. After 15 hours at 130C, NMR analysis showed complete reaction of benzoyl chloride.
The above reaction was repeated with other substrates, as shown by the followin~ equation and Table, where Ar is phenyl, or substituted phenyl:
R ( C133) Si(CH3)C12 ' + C~3SiC13 + C0 1327Q~
RD~7,7S8 TABLE
Substrate Mole % Mole %
where R = ArSiCH3C12 ArCl .~
P-Cl 8g 11 P-COCl 8~ 1~
3,4 N-CH3 36 7 o o 3,4 ~ O 95 5 ~ C
o The above results show that the silica supported catalyst of the present invention having chemically combined groups of formula (4~, has superior selectivity when used to make polyfunctional aryl silanes from aryl substrates substituted with a variety of activating groups employin~
polysilanes having silicon atoms wi~h at least two halogen radicals per silicon.
In contrast, a similar silylation reaction was conducted with the same substrates using the 1% commercially 1 32704~ RD-17,75~
available palladium on carbon catalyst of Example 3. It was found that a wide variation resulted in selectivity in accordance with the substituent R on the phenyl ring. For example, when R was hydrogen, only a trace of the desired phenyl silane was obtained while a 78% yield was obtained with chloroacylphthalicanhydride. A 67% yield was obtained with terephthaloyl chloride.
Although the bove examples are directed to only a few of the very many variables which can be utilized in the practice of the method of the present invention, it should be understood that the present invention is directed to a much broader variety of silica-supported palladium catalyst, halogenated polysilane and aromatic acylhalide shown in the description precesding these examples.
Claims (18)
1. A method for making silylated aromatic organic material having at least one nuclear-bound silicon atom attached to an aromatic group by a carbon-silicon linkage comprising, (A) effecting reaction between a halogenated polysilane of the formula, , and aromatic acylhalide of the formula, in the presence of an effective amount of a silica-supported transition metal catalyst complex having chemically combined groups of the formula, and (B) recovering the silylated aromatic organic material from the mixture of (A), where X is halogen, M is a transition metal selected from palladium, platinum, or nickel, Q is a nitrogen or phosphorous radical, y is an integer having a value of from 1 to 3 inclusive, R is selected from X, hydrogen, C(1-13) monovalent hydrocarbon radicals, substituted C(1-13) monovalent hydrocarbon radicals, and divalent -O-, -S- radicals and mixtures thereof which can form ?SiOSi? and ?SiSSi?- connecting groups, R1 is a C(6-20) monovalent or polyvalent aromatic organic radical, R2 is a divalent C(2-14) organic radical, R3 and R4 are monovalent C(1-14) alkyl or aryl radicals, n is an integer equal to 1 to 50 inclusive, and m is an integer equal to 1 to 4 inclusive.
2. A method in accordance with claim 1, where the halogenated polysilane is 1,1,2,2-tetrachloro-dimethyldisilane.
3. A method in accordance with claim 1, where the aromatic acylhalide is trimellitic anhydride acid chloride.
4. A method in accordance with claim 1, where the aromatic acylhalide is terephthaloylchloride.
5. A method in accordance with claim 1, where the aromatic acylhalide is isophthaloyl chloride.
6. A method in accordance with claim 1, where the halogenated polysilane is 1,2-dichlorotetramethyl-disilane.
7. A method in accordance with claim 1, conducted in a continuous manner.
8. A method in accordance with claim 1, where the silyated aromatic organic material is organic silane.
9. A method in accordance with claim 1, where the silyated aromatic organic material is a silarylene.
10. A method in accordance with claim 8, where the organic silane is 4-chlorodimethylsilylphthalic anhydride.
11. A method in accordance with claim 8, where the organic silane is 4-chlorodimethylsilylbenzoyl chloride.
12. A method in accordance with claim 8, where the organic silane is N-butyl-4-chlorodimethylsilyl-phthalimide.
13. A method in accordance with claim 9, where the silarylene is 1,4-dichlorosilylphenylene.
14. A method in accordance with claim 1, where the aromatic acylhalide is 3-nitrobenzoyl chloride.
15. A method in accordance with claim 1, where the aromatic acylhalide is 4-nitrobenzoyl chloride.
16. A method in accordance with claim 1, where the aromatic acylhalide is benzoyl chloride.
17. A silica-supported transition metal catalyst complex made in accordance with claim 1.
18. A method in accordance with claim 1, where the catalyst is chemically reactivated with C12 or CuIIC12/O2.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08512737A GB2164040B (en) | 1984-09-04 | 1985-05-20 | Method for silylating aromatic imides and imides made therefrom |
| FR8512626A FR2569700A1 (en) | 1984-09-04 | 1985-08-22 | SILYLATION PROCESS OF AROMATIC IMIDES AND PRODUCTS OBTAINED |
| JP60193272A JPS6183191A (en) | 1984-09-04 | 1985-09-03 | Silylation of aromatic imide and imide manufactured therefrom |
| DE19853531466 DE3531466A1 (en) | 1984-09-04 | 1985-09-03 | SILYL-AROMATIC IMIDES AND METHOD FOR THE PRODUCTION THEREOF |
| US06/902,813 US4730055A (en) | 1984-09-04 | 1986-09-02 | Method for silylating aromatic imides and silylimides made therefrom |
| GB08715691A GB2196968A (en) | 1986-09-02 | 1987-07-03 | Method for silylating aromatic imides and silylimides made therefrom |
| DE3728575A DE3728575C2 (en) | 1986-09-02 | 1987-08-27 | Silyl aromatic imides and imide disiloxanes |
| FR878712142A FR2603285B1 (en) | 1986-09-02 | 1987-09-01 | PROCESS FOR THE SILYLATION OF AROMATIC IMIDES AND SILYLIMIDES THUS PREPARED |
| JP62218106A JPS63107943A (en) | 1986-09-02 | 1987-09-02 | Silylation of aromatic imide and produced silylimide |
| CA000570203A CA1327044C (en) | 1984-09-04 | 1988-06-23 | Silylation method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64730184A | 1984-09-04 | 1984-09-04 | |
| CA000570203A CA1327044C (en) | 1984-09-04 | 1988-06-23 | Silylation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1327044C true CA1327044C (en) | 1994-02-15 |
Family
ID=25671959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000570203A Expired - Fee Related CA1327044C (en) | 1984-09-04 | 1988-06-23 | Silylation method |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6183191A (en) |
| CA (1) | CA1327044C (en) |
| DE (1) | DE3531466A1 (en) |
| FR (1) | FR2569700A1 (en) |
| GB (1) | GB2164040B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4730055A (en) * | 1984-09-04 | 1988-03-08 | General Electric Company | Method for silylating aromatic imides and silylimides made therefrom |
| DE3715313A1 (en) * | 1986-09-02 | 1988-03-10 | Gen Electric | IMIDOPOLYSILOXANES AND METHOD FOR THEIR PRODUCTION |
| EP0292260B1 (en) * | 1987-05-19 | 1994-04-13 | Hitachi Chemical Co., Ltd. | Process for producing 1,3-bis(dicarboxyphenyl)-disiloxane derivative or dianhydride thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE792713A (en) * | 1971-12-15 | 1973-06-14 | Dow Corning | CATALYTIC PROCESS FOR THE TRANSFORMATION OF DISILANES INTO SILANES |
-
1985
- 1985-05-20 GB GB08512737A patent/GB2164040B/en not_active Expired
- 1985-08-22 FR FR8512626A patent/FR2569700A1/en not_active Withdrawn
- 1985-09-03 JP JP60193272A patent/JPS6183191A/en active Granted
- 1985-09-03 DE DE19853531466 patent/DE3531466A1/en not_active Withdrawn
-
1988
- 1988-06-23 CA CA000570203A patent/CA1327044C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| FR2569700A1 (en) | 1986-03-07 |
| GB8512737D0 (en) | 1985-06-26 |
| GB2164040A (en) | 1986-03-12 |
| JPS6183191A (en) | 1986-04-26 |
| JPH0547549B2 (en) | 1993-07-19 |
| DE3531466A1 (en) | 1986-03-13 |
| GB2164040B (en) | 1988-10-05 |
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