CA1109889A - Phenoxyalkyl trialkoxysilanes and method for preparing same - Google Patents
Phenoxyalkyl trialkoxysilanes and method for preparing sameInfo
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- CA1109889A CA1109889A CA326,358A CA326358A CA1109889A CA 1109889 A CA1109889 A CA 1109889A CA 326358 A CA326358 A CA 326358A CA 1109889 A CA1109889 A CA 1109889A
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- silane
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/54—Silicon-containing compounds
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/302—Water
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2125/00—Compositions for processes using internal mould release agents
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- C08L75/04—Polyurethanes
Abstract
Abstract of the Disclosure Novel phenoxyalkyll-, thiophenoxyalkyl- and pyridyloxyalkylsilanes are prepared by reacting substantially equimolar amounts of an alkali metal phenoxide, thiophenoxide or pyridyloxide with a haloalkyl- silane under anhydrous conditions using a dipolar, aprotic solvent in combination with a liquid hydrocarbon. She novel compounda are useful as coupling agents for glass fiber reinforced composites, flocculating agents for water purification and as sizings for glass fibers or fabrics.
Description
1~09889 This invention relates to a new class of organosilicon compounds. More particularly, this invention relates to novel phenoxyalkyl-, thio- phenoxyalkyl- and pyridyloxyalkyl-silanes and to a method for preparing these compounds.
According to the present invention, there is provided a silane represented by the general formula Rl ~OR Si (0R ) 3 wherein R is -CHO, -CN, -COR, -S02R, -SOR, or -SR
R is methylene or alkylene containing from 3 to 12 carbon atoms, R3 is alkyl, cycloalkyl or aryl and R4 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl wherein any alkyl group present in R3 and R4 contains from 1 to 12 carbon atoms.
The invention also provides a method for preparing a silane represented by the general formula Rl -h ~ OR Si (OR ) 3 wherein R is -CHO, -CN, -COR, -SO2R, -SOR, SR, -NH2, -NR H, or -N ( R4 ) 2~ R is methylene or alkylene containing from 3 to 12 carbon atoms, R3 is alkyl cycloalkyl or aryl and R4 is individually selected from the group consisting of alkyl, cycloal~yl, aryl, alkaryl and aralkyl wherein any alkyl group ~resent in R3 or R4 contains from 1 to 12 carbon atoms, said method consisting essentially of reacting substantially equimolar amounts of an Rl ,~
~10~3 with a haloalkylsilane of the general formula XR2Si(oR3)3 wherein M represents an alkali metal and x is chlorine, bromine or iodine, and wherein the reaction of said alkali metal compound and the silane is conducted under substantially anhydrous conditions at a temperature of from ambient to 200C in a liquid reaction medium consisting essentially of a liquid hydrocarbon boiling from 40 to 200C and a dipolar, aprotic liquid, maintaining the resultant reaction medium at a temperature of from 40 to 200C
for a period of time sufficient to substantially completely con-vert said alkali metal compound and said silane to the desiredphenoxyalkylsilane, and isolating said silane by filtering the reaction medium and evaporating the solvent from the liquid phase.
- la -~io9~9 Thc present compounds are functionally substituted phcnoxyalkyl-, thiophenoxyalkyl- or pyridyloxyalkylsilanes of the general formulae disclosed in the prec~ding section of this specification. ~he substituent on the phenyl group, represented by Rl in ~he aforementioned formula, can be ' ~rnn i c~fba~ Y 4 -MH2, dialkylamino, alkylamino, fcrm~ ~ar ~ }~ -COOR ), O
cyano ~-CN), -~R~, a halogen ~chlorine, bromine or iodine), -So2R4, -SoR4, nitro ~-N02), -SR4 or -oR4. Amino groups are preferred because of the many useful applications of this class of compounds. The substituent can be located ortho, meta or para with respect to the oxygen atom. The phenoxy, thiophenoxy or pyridyloxy group is joined to the silicon atom by means of an alkylene group that can be methylene or a higher alkylene group containing from 3 to 12 carbon atoms i~ either a linear or branched configuration.
Compounds wherein R2 is ethylene have been found to be so unstable in the presence of even trace amounts of aqueous acids or bases as to be useless for all practical purposes.
In addition to the aforementioned alkylene group the silicon atom is also bonded to three alkoxide or aryloxide groups represented by oR3 in the foregoing formula.
The presen~ compounds are conveniently prepared by reacting an alkali metal salt, preferably the sodium salt, of the desired phenol, thiophenol or hydroxypyridine with a haloalkylsilane of the general formula XR2Si~oR3)3. This reaction is highly exothermic and is preferably conducted under an inert atmosphere and in the absence of even trace amounts of water, since water is known to react readily ,~ _ ~ 11~9889 with trialkoxy- and triaryloxysilanes to yield polymeric products The reaction medium is a mixture of at least one liquid hydrocarbon bciling from ~lO to about ~00C and a di-polar, aprotic liquid such as dimethyl sulfoxide, N,N-dimethyl-formamide, tetramethyl urea or hexamethylphosphoramide.
Preferably, the trialkoxyhaloalkylsilane is gradually added to a reaction medium containing the alkali metal salt. ~en the addition is complete and any exothermic reaction has subsided, it is usually desirable to heat the reaction mixture at from 70 to about 150C for several hours to ensure sub-stantially complete conversion of the reactants to the desired phenoxyalkyl-, thiophenoxyalkyl~ or pyridyloxyalkyl tri-hydrocarbyloxysilane. The present compounds, many of which are colorless, high-boiling, viscous oils, are soluble in the reaction medium and readily isolatable by removal of the aforementioned liquid hydrocarbon and dipolar solvent.
Some of the compounds may darken if exposed to light or air for extended periods of time.
The trihydrocarbyloxyhaloalkylsilanes employed as one of the reagents for preparing the present compounds are either commercially available or can readily be obtained by reacting the corresponding haloalkyltrihalosilane, X'R2SiX2 wherein Xl and x2 are chlorine, bromine or iodine, with an alcohol, R30H, that contains from l to 12 carbon atoms. Alternatively, the hydroxyl group can be bonded to a carbocyclic or heterocyclic ring structure such as a cyclohexyl, pyridyl or phenyl group. The hydrocarbyloxy ~9 3 ~y trihalosilane can be prepared by reacting a haloalkene such as allyl chloride with a trihalosilane, HSiX2, at ambient temperature in the presence of a platinum catalyst. Pro-~ cedures for preparing the intermediate silanes are well : 5 known in the art. A detailed discussion of reaction conditions i~ therefore not required in this specification.
Illustrative of the phenols and thiophenols that can be employed to prepare the present compounds are aminophenols and aminothiophenols wherein the amino group is located in the ortho, meta or para position relative to the hydroxyl group, the isomeric hydroxybenzaldehydes ~,~ and the isomeric esters of hydroxybenzoic and mercapto-' benzoic acids wherein the alcohol residue of the ester contains from 1 to 12 carbon atoms. If the alcohol contains a phenyl group, the number of carbon atoms is from 7 to 18.
~ Other substituents that can be present on the phenyl group ;~ ~ ~are disclQsed in the pres,ent s,pecification and claims.
The functionally substituted silanes of this invention are useful as coupling agents for glass fiber-reinforced composites, flocculating agents for water ,~ purification and as sizings for glass fibers or fabrics.
'~ The present compounds can be reacted with liquid hydroxy-or a~koxy-terminated organopolysiloxanes together with , optlonal fillers to form elastomeric products that are useful as coating materials, sealants and molding compositions.
~ Compounds erein Kl of the ~regoing formula is amino or ~' ~ ~
11C~9~89 diallcylamino (-NH2 or -NR4) impart detergent resistance to waxes and polishes.
The following examples disclose preferred embodiments of the present compounds and should not be interpreted as limiting the scope of the accompanying claims. All parts and percentages are by weight unless otherwise specified.
.
Preparation of 3(p-aminophenoxy)propyl Trimethoxysilane A glass reactor was charged with 60 g (0.55 mole) p-aminophenol, 43.28 g of a 50% aqueous solution of sodium hydroxide (0.54 mole NaOH), 112 cc dimethylsulfoxide and 120 cc toluene. The resultant mixture was heated to the boiling point for six hours under a nitrogen atmosphere to remove all of the water present by azeotropic distillation.
The reaction mixture was then allowed to cool to about 75C, at which time 109 g (0.55 mole) of 3-chloropropyl trimethoxy-silane was added dropwise while the reaction mixture was stirred. The temperature of the reaction mixture increased ~0 spontaneously to 85C during this addition. The temperature of the reaction mixture was maintained at from 75 to 85C
by heating and control of the addition rate. Following completion o~ the addition, the reaction mixture was heated at 115C for 16 hours, following which the mixture was allowed to cool, and was filtered to remove any solid material.
The solvents weré then removed under a pressure of about 15 mm of mercury at a temperature of about 60C. The pressure was then reduced to from 3 to 4 mm of mercury and the mater~al bo ing from 170 to 180~C was recovsred. Thls ,.~ ' ll~g889 fraction, which weighed 70 g, was distilled using a fractionating column and a 50 g portion boillng from 175 to 177C under a pressure of 3 mm of mercury,was collected.
The colorle~s liquid was found to contain 10.19% silicon and 5.20% nitrogen. The calculated values for 3(p-amino-phenoxy) propyl trimethoxy silane are 10.33% silicon and 5.17% nitrogen. The infrared and nuclear magnetic resonance spectra o~ the product were in agreement with the proposed structure.
.~
llOg889 Preparation of 3(m-aminophenoxy)propyl Trimethoxysilane Using the general procedure described in the precedin.g Example 1, ~ ~eactor was charged wit'~ 300 g (2.75 .,.Gle) m-aminophenol~ 560 cc dimethylsulfoxide, 600 cc toluene and 216 cc of a 50% aqueous solution of sodium hydroxide (2.70 moles NaOH). The water present in the reactor was removed by azeotropic distillation under a nitrogen atmosphere at a temperature of 120C. The temperature of the reaction mixture was then lowered to 90C and maintained at about this value during the gradual addition of 545 g (2.75 mole) of 3-chloropropyl trimethoxysilane. Following completion of the addition, which required 2 hours, the reaction mixture was heated at the boiling point for 16 hours. The product was recovered and fractionally distilled as described in the preceding example. The fraction boiling from 178 to 180C at a pressure of 3 mm of mercury was collected and weighed 630 g (85% yield). The infrared and nuclear magnetic resonance spectra of the recovered product confirm the proposed structure - OCH2CH2CH2Si(OCH3) 3 A vapor phase chromatogram of the product indicated a purity of greater than 98%.
110~889 Preparation of 3(p-formylphenoxy)propyl Trimethoxysilane Using the general procedure described in the preceding Example l, a reactor was charged with 62.2 g (0.55 mole) p-hydroxybenzaldehyde, 112 cc dimethylsulfoxide, 120 cc toluene and 43.2 g of a 50% aqueous sodium hydroxide solution containing 0.54 mole NaOH. All of the water present was removed by azeotropic distillation at a temperature o~ about 110 to 115C. The reaction mixture was heated to, the boiling point during the gradual addition o~ 109 g (0.55 mole) of 3-chloropropyl trimethoxysilane. The product, 3(p-formylphenoxy)propyl trimethoxysilane, was isolated by filtration and removal of the solvents from the recovered liquid phase under reduced pressure followed,by fractional distillation of the residue. The fraction boiling at 208C
at a pressure of 3 mm of mercury was collected (85% yield, based on silane). The infrared and nuclear magnetic resonance spectra of the recovered product confirm the ~ proposed structuPe OCH - ~ - OCH 2 CH 2 CH 2 Si ( OCH 3 ) 3 The vapor phase chromatogram of the product indicated a purity of greater than 98%.
~Y
~ 9889 Preparation of 3(m-diethylaminophenoxy)propyl Trimethoxysilane Using the general procedure described in the l nreceding ~xa~ple 1, a reac~,or was charged with 90.75 g (0.55 mole) m-diethylaminopllenol, 112 cc dimethylsulfoxide, 120 cc toluene and 43.28 g of a 50% aqueous sodium hydroxide solution. All of the water present in the reactor was removed by azeotropic distillation. The reaction mixture was allowed to cool to 80C, at which time 109 g (0.55 mole) of chloropropyl trimethoxysilane were gradually added over a period of 2 hours. The temperature of the reaction mixture increased to 88C during the addition. Following completion of the addition, external heating was applied to maintain the temperature of the reaction mixture at 80C for 16 hours.
The reaction mixture was then allowed to cool and was filtered.
The liquid phase was recovered and evaporated under a pressure of 5 mm of mercury to remove the toluene and di-methylsulfoxide. The pressure inside the reactor was reduced to 2 mm and the product, 3(m-diethylaminophenoxy)propyl trimethoxysilane, collected at a temperature of 185-187C.
Analysis by vapor phase chromatography demonstrated that the product was 97% pure.
~' ,l,~q-'i~988~
Preparation of 3(3-pyridyloxy)propyl Trimethoxysilane Using the general procedure described in Example 1, a reactor was charged with 52.3 g (0.55 mole) 3-hydroxy-pyridine, 112 cc dimethylsulfoxide, 120 cc toluene and 43.2 g of a 50% aqueous sodium hydroxide solution. The water present in the reactor was removed by azeotropic distillation over a period of 64 hours. The temperature of the reaction mixture was maintained at from 85 to 105C during this time period. A 109 g portion of 3-chloropropyl trimethoxysilane was gradually added while the temperature of the reaction mixture was maintained at 95C. This temperature was maintained for 7 hours, at which time a vaporphase chromato-gram of the reaction mixture indicated that the reaction was su~stantially complete. The reaction mixture was then filtered and the diluents (toluene and dimethylsulfoxide) evaporated under a pressure of 5 mm of mercury. The product, 3(3-pyridyloxy)propyl trimethoxysilane, was collected at a temperature of 142C under a pressure of 1 mm of mercury.
A vapor phase chromatogram demonstrated that the product was 97% pure.
According to the present invention, there is provided a silane represented by the general formula Rl ~OR Si (0R ) 3 wherein R is -CHO, -CN, -COR, -S02R, -SOR, or -SR
R is methylene or alkylene containing from 3 to 12 carbon atoms, R3 is alkyl, cycloalkyl or aryl and R4 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl wherein any alkyl group present in R3 and R4 contains from 1 to 12 carbon atoms.
The invention also provides a method for preparing a silane represented by the general formula Rl -h ~ OR Si (OR ) 3 wherein R is -CHO, -CN, -COR, -SO2R, -SOR, SR, -NH2, -NR H, or -N ( R4 ) 2~ R is methylene or alkylene containing from 3 to 12 carbon atoms, R3 is alkyl cycloalkyl or aryl and R4 is individually selected from the group consisting of alkyl, cycloal~yl, aryl, alkaryl and aralkyl wherein any alkyl group ~resent in R3 or R4 contains from 1 to 12 carbon atoms, said method consisting essentially of reacting substantially equimolar amounts of an Rl ,~
~10~3 with a haloalkylsilane of the general formula XR2Si(oR3)3 wherein M represents an alkali metal and x is chlorine, bromine or iodine, and wherein the reaction of said alkali metal compound and the silane is conducted under substantially anhydrous conditions at a temperature of from ambient to 200C in a liquid reaction medium consisting essentially of a liquid hydrocarbon boiling from 40 to 200C and a dipolar, aprotic liquid, maintaining the resultant reaction medium at a temperature of from 40 to 200C
for a period of time sufficient to substantially completely con-vert said alkali metal compound and said silane to the desiredphenoxyalkylsilane, and isolating said silane by filtering the reaction medium and evaporating the solvent from the liquid phase.
- la -~io9~9 Thc present compounds are functionally substituted phcnoxyalkyl-, thiophenoxyalkyl- or pyridyloxyalkylsilanes of the general formulae disclosed in the prec~ding section of this specification. ~he substituent on the phenyl group, represented by Rl in ~he aforementioned formula, can be ' ~rnn i c~fba~ Y 4 -MH2, dialkylamino, alkylamino, fcrm~ ~ar ~ }~ -COOR ), O
cyano ~-CN), -~R~, a halogen ~chlorine, bromine or iodine), -So2R4, -SoR4, nitro ~-N02), -SR4 or -oR4. Amino groups are preferred because of the many useful applications of this class of compounds. The substituent can be located ortho, meta or para with respect to the oxygen atom. The phenoxy, thiophenoxy or pyridyloxy group is joined to the silicon atom by means of an alkylene group that can be methylene or a higher alkylene group containing from 3 to 12 carbon atoms i~ either a linear or branched configuration.
Compounds wherein R2 is ethylene have been found to be so unstable in the presence of even trace amounts of aqueous acids or bases as to be useless for all practical purposes.
In addition to the aforementioned alkylene group the silicon atom is also bonded to three alkoxide or aryloxide groups represented by oR3 in the foregoing formula.
The presen~ compounds are conveniently prepared by reacting an alkali metal salt, preferably the sodium salt, of the desired phenol, thiophenol or hydroxypyridine with a haloalkylsilane of the general formula XR2Si~oR3)3. This reaction is highly exothermic and is preferably conducted under an inert atmosphere and in the absence of even trace amounts of water, since water is known to react readily ,~ _ ~ 11~9889 with trialkoxy- and triaryloxysilanes to yield polymeric products The reaction medium is a mixture of at least one liquid hydrocarbon bciling from ~lO to about ~00C and a di-polar, aprotic liquid such as dimethyl sulfoxide, N,N-dimethyl-formamide, tetramethyl urea or hexamethylphosphoramide.
Preferably, the trialkoxyhaloalkylsilane is gradually added to a reaction medium containing the alkali metal salt. ~en the addition is complete and any exothermic reaction has subsided, it is usually desirable to heat the reaction mixture at from 70 to about 150C for several hours to ensure sub-stantially complete conversion of the reactants to the desired phenoxyalkyl-, thiophenoxyalkyl~ or pyridyloxyalkyl tri-hydrocarbyloxysilane. The present compounds, many of which are colorless, high-boiling, viscous oils, are soluble in the reaction medium and readily isolatable by removal of the aforementioned liquid hydrocarbon and dipolar solvent.
Some of the compounds may darken if exposed to light or air for extended periods of time.
The trihydrocarbyloxyhaloalkylsilanes employed as one of the reagents for preparing the present compounds are either commercially available or can readily be obtained by reacting the corresponding haloalkyltrihalosilane, X'R2SiX2 wherein Xl and x2 are chlorine, bromine or iodine, with an alcohol, R30H, that contains from l to 12 carbon atoms. Alternatively, the hydroxyl group can be bonded to a carbocyclic or heterocyclic ring structure such as a cyclohexyl, pyridyl or phenyl group. The hydrocarbyloxy ~9 3 ~y trihalosilane can be prepared by reacting a haloalkene such as allyl chloride with a trihalosilane, HSiX2, at ambient temperature in the presence of a platinum catalyst. Pro-~ cedures for preparing the intermediate silanes are well : 5 known in the art. A detailed discussion of reaction conditions i~ therefore not required in this specification.
Illustrative of the phenols and thiophenols that can be employed to prepare the present compounds are aminophenols and aminothiophenols wherein the amino group is located in the ortho, meta or para position relative to the hydroxyl group, the isomeric hydroxybenzaldehydes ~,~ and the isomeric esters of hydroxybenzoic and mercapto-' benzoic acids wherein the alcohol residue of the ester contains from 1 to 12 carbon atoms. If the alcohol contains a phenyl group, the number of carbon atoms is from 7 to 18.
~ Other substituents that can be present on the phenyl group ;~ ~ ~are disclQsed in the pres,ent s,pecification and claims.
The functionally substituted silanes of this invention are useful as coupling agents for glass fiber-reinforced composites, flocculating agents for water ,~ purification and as sizings for glass fibers or fabrics.
'~ The present compounds can be reacted with liquid hydroxy-or a~koxy-terminated organopolysiloxanes together with , optlonal fillers to form elastomeric products that are useful as coating materials, sealants and molding compositions.
~ Compounds erein Kl of the ~regoing formula is amino or ~' ~ ~
11C~9~89 diallcylamino (-NH2 or -NR4) impart detergent resistance to waxes and polishes.
The following examples disclose preferred embodiments of the present compounds and should not be interpreted as limiting the scope of the accompanying claims. All parts and percentages are by weight unless otherwise specified.
.
Preparation of 3(p-aminophenoxy)propyl Trimethoxysilane A glass reactor was charged with 60 g (0.55 mole) p-aminophenol, 43.28 g of a 50% aqueous solution of sodium hydroxide (0.54 mole NaOH), 112 cc dimethylsulfoxide and 120 cc toluene. The resultant mixture was heated to the boiling point for six hours under a nitrogen atmosphere to remove all of the water present by azeotropic distillation.
The reaction mixture was then allowed to cool to about 75C, at which time 109 g (0.55 mole) of 3-chloropropyl trimethoxy-silane was added dropwise while the reaction mixture was stirred. The temperature of the reaction mixture increased ~0 spontaneously to 85C during this addition. The temperature of the reaction mixture was maintained at from 75 to 85C
by heating and control of the addition rate. Following completion o~ the addition, the reaction mixture was heated at 115C for 16 hours, following which the mixture was allowed to cool, and was filtered to remove any solid material.
The solvents weré then removed under a pressure of about 15 mm of mercury at a temperature of about 60C. The pressure was then reduced to from 3 to 4 mm of mercury and the mater~al bo ing from 170 to 180~C was recovsred. Thls ,.~ ' ll~g889 fraction, which weighed 70 g, was distilled using a fractionating column and a 50 g portion boillng from 175 to 177C under a pressure of 3 mm of mercury,was collected.
The colorle~s liquid was found to contain 10.19% silicon and 5.20% nitrogen. The calculated values for 3(p-amino-phenoxy) propyl trimethoxy silane are 10.33% silicon and 5.17% nitrogen. The infrared and nuclear magnetic resonance spectra o~ the product were in agreement with the proposed structure.
.~
llOg889 Preparation of 3(m-aminophenoxy)propyl Trimethoxysilane Using the general procedure described in the precedin.g Example 1, ~ ~eactor was charged wit'~ 300 g (2.75 .,.Gle) m-aminophenol~ 560 cc dimethylsulfoxide, 600 cc toluene and 216 cc of a 50% aqueous solution of sodium hydroxide (2.70 moles NaOH). The water present in the reactor was removed by azeotropic distillation under a nitrogen atmosphere at a temperature of 120C. The temperature of the reaction mixture was then lowered to 90C and maintained at about this value during the gradual addition of 545 g (2.75 mole) of 3-chloropropyl trimethoxysilane. Following completion of the addition, which required 2 hours, the reaction mixture was heated at the boiling point for 16 hours. The product was recovered and fractionally distilled as described in the preceding example. The fraction boiling from 178 to 180C at a pressure of 3 mm of mercury was collected and weighed 630 g (85% yield). The infrared and nuclear magnetic resonance spectra of the recovered product confirm the proposed structure - OCH2CH2CH2Si(OCH3) 3 A vapor phase chromatogram of the product indicated a purity of greater than 98%.
110~889 Preparation of 3(p-formylphenoxy)propyl Trimethoxysilane Using the general procedure described in the preceding Example l, a reactor was charged with 62.2 g (0.55 mole) p-hydroxybenzaldehyde, 112 cc dimethylsulfoxide, 120 cc toluene and 43.2 g of a 50% aqueous sodium hydroxide solution containing 0.54 mole NaOH. All of the water present was removed by azeotropic distillation at a temperature o~ about 110 to 115C. The reaction mixture was heated to, the boiling point during the gradual addition o~ 109 g (0.55 mole) of 3-chloropropyl trimethoxysilane. The product, 3(p-formylphenoxy)propyl trimethoxysilane, was isolated by filtration and removal of the solvents from the recovered liquid phase under reduced pressure followed,by fractional distillation of the residue. The fraction boiling at 208C
at a pressure of 3 mm of mercury was collected (85% yield, based on silane). The infrared and nuclear magnetic resonance spectra of the recovered product confirm the ~ proposed structuPe OCH - ~ - OCH 2 CH 2 CH 2 Si ( OCH 3 ) 3 The vapor phase chromatogram of the product indicated a purity of greater than 98%.
~Y
~ 9889 Preparation of 3(m-diethylaminophenoxy)propyl Trimethoxysilane Using the general procedure described in the l nreceding ~xa~ple 1, a reac~,or was charged with 90.75 g (0.55 mole) m-diethylaminopllenol, 112 cc dimethylsulfoxide, 120 cc toluene and 43.28 g of a 50% aqueous sodium hydroxide solution. All of the water present in the reactor was removed by azeotropic distillation. The reaction mixture was allowed to cool to 80C, at which time 109 g (0.55 mole) of chloropropyl trimethoxysilane were gradually added over a period of 2 hours. The temperature of the reaction mixture increased to 88C during the addition. Following completion of the addition, external heating was applied to maintain the temperature of the reaction mixture at 80C for 16 hours.
The reaction mixture was then allowed to cool and was filtered.
The liquid phase was recovered and evaporated under a pressure of 5 mm of mercury to remove the toluene and di-methylsulfoxide. The pressure inside the reactor was reduced to 2 mm and the product, 3(m-diethylaminophenoxy)propyl trimethoxysilane, collected at a temperature of 185-187C.
Analysis by vapor phase chromatography demonstrated that the product was 97% pure.
~' ,l,~q-'i~988~
Preparation of 3(3-pyridyloxy)propyl Trimethoxysilane Using the general procedure described in Example 1, a reactor was charged with 52.3 g (0.55 mole) 3-hydroxy-pyridine, 112 cc dimethylsulfoxide, 120 cc toluene and 43.2 g of a 50% aqueous sodium hydroxide solution. The water present in the reactor was removed by azeotropic distillation over a period of 64 hours. The temperature of the reaction mixture was maintained at from 85 to 105C during this time period. A 109 g portion of 3-chloropropyl trimethoxysilane was gradually added while the temperature of the reaction mixture was maintained at 95C. This temperature was maintained for 7 hours, at which time a vaporphase chromato-gram of the reaction mixture indicated that the reaction was su~stantially complete. The reaction mixture was then filtered and the diluents (toluene and dimethylsulfoxide) evaporated under a pressure of 5 mm of mercury. The product, 3(3-pyridyloxy)propyl trimethoxysilane, was collected at a temperature of 142C under a pressure of 1 mm of mercury.
A vapor phase chromatogram demonstrated that the product was 97% pure.
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A silane represented by the general formula wherein R is -CHO, -CN, -COR4 , -S02R4 , -SOR4, or -SR4, R is methylene or alkylene containing from 3 to 12 carbon atoms, R3 is alkyl, cycloalkyl or aryl and R4 is selected from the group con-sisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl wherein any alkyl group present in R3 and R4 contains from 1 to 12 carbon atoms.
2. A silane according to claim 1 wherein R is -CHO.
3. A silane according to claim 1 wherein R is -(CH2)3-.
4. A silane according to claim 1 wherein R3 is alkyl and contains from 1 to 4 carbon atoms.
5. A silane according to claim 4 wherein R3 is methyl.
6. A method for preparing a silane represented by the general formula wherein R1 is -CHO, CN, -COR4, -S02R4, -S0R4, SR4, -NH2, -NR4M, or -N(R4) 2' R2 is methylene or alkylene containing from 3 to 12 carbon atoms, R3 is alkyl cycloalkyl or aryl and R4 is individually selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl wherein any alkyl group present in R3 or R4 contains from 1 to 12 carbon atoms, said method consisting essent-ially of reacting substantially equimolar amounts of an alkali metal compound of the general formula with a haloalkylsilane of the general formula XR2Si(OR3)3 wherein M
represents an alkali metal and X is chlorine, bromine or iodine, and wherein the reaction of said alkali metal compound and the silane is conducted under substantially anhydrous conditions at a temperature of from ambient to 200°C in a liquid reaction medium consisting essentially of a liquid hydrocarbon boiling from 40 to 200°C and a dipolar, aprotic liquid, maintaining the resultant reaction medium at a temperature of from 40 to 200°C for a period of time sufficient to substantially completely convert said alkali metal compound and said silane to the desired phenoxyalkylsilane, and isolating said silane by filtering the reaction medium and evaporating the solvent from the liquid phase.
represents an alkali metal and X is chlorine, bromine or iodine, and wherein the reaction of said alkali metal compound and the silane is conducted under substantially anhydrous conditions at a temperature of from ambient to 200°C in a liquid reaction medium consisting essentially of a liquid hydrocarbon boiling from 40 to 200°C and a dipolar, aprotic liquid, maintaining the resultant reaction medium at a temperature of from 40 to 200°C for a period of time sufficient to substantially completely convert said alkali metal compound and said silane to the desired phenoxyalkylsilane, and isolating said silane by filtering the reaction medium and evaporating the solvent from the liquid phase.
7. A method according to claim 6 wherein R1 is -CHO.
8. A method according to claim 6 wherein R2 is -(CH2)3-.
9. A method according to claim 6 wherein R3 is alkyl and contains from 1 to 4 carbon atoms.
10. A method according to claim 9 wherein R3 is methyl.
11. A method according to claim 6 wherein X is chlorine.
12. A method according to claim 6 wherein M is sodium.
13. A method according to claim 6 wherein said dipolar aprotic solvent is selected from the group consisting of dimethyl sulfoxide, N,N-dimethyl-formamide, tetramethyl urea and hexamethylphosphoramide.
_
_
14. A method according to claim 6 wherein the reaction between the alkali. metal compound and the silane is conducted under an inert atmosphere.
15. A method according to claim 6 wherein R2 is propylene - CH(CH3)-CH2-.
16. 3(p-formylphenoxy)propyl trimethoxysilane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90019778A | 1978-04-26 | 1978-04-26 | |
| US900,197 | 1978-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109889A true CA1109889A (en) | 1981-09-29 |
Family
ID=25412119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA326,358A Expired CA1109889A (en) | 1978-04-26 | 1979-04-25 | Phenoxyalkyl trialkoxysilanes and method for preparing same |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS54144344A (en) |
| KR (1) | KR850000074B1 (en) |
| BE (1) | BE875801A (en) |
| CA (1) | CA1109889A (en) |
| CH (1) | CH639392A5 (en) |
| DE (1) | DE2915072A1 (en) |
| DK (1) | DK148710C (en) |
| ES (1) | ES479900A1 (en) |
| FR (1) | FR2424281B1 (en) |
| GB (1) | GB2019862B (en) |
| IT (1) | IT1165955B (en) |
| MX (1) | MX149694A (en) |
| NL (1) | NL7903128A (en) |
| NO (2) | NO156610C (en) |
| SE (1) | SE7903595L (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES8105009A2 (en) * | 1979-08-08 | 1981-05-16 | M & T Chemicals Inc | Functionally Substituted Phenoxyalkyl Thiophenoxyalkyl Thiopyridyloxyalkyl and Pyridyloxyalkyl Silanes and Method for Preparing Same |
| CA1152512A (en) * | 1979-08-31 | 1983-08-23 | Abe Berger | Method for preparing aryloxyalkylsilanes |
| JP2630596B2 (en) * | 1987-07-27 | 1997-07-16 | 株式会社ブリヂストン | Silane coupling agent |
| DE3935638A1 (en) * | 1989-10-26 | 1991-05-02 | Consortium Elektrochem Ind | ORGANOSILYL ALKYL FLAVORS |
| JP5245076B2 (en) * | 2008-09-30 | 2013-07-24 | 大同化学工業株式会社 | Waste liquid treatment method |
| JP5360814B2 (en) * | 2009-03-12 | 2013-12-04 | 独立行政法人産業技術総合研究所 | Method for producing organic-inorganic composite material |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1054041A (en) * | 1900-01-01 | |||
| GB1062418A (en) * | 1964-01-27 | 1967-03-22 | Ici Ltd | New nitrogen-containing siloxanes |
| US3355425A (en) * | 1964-08-06 | 1967-11-28 | Dow Corning | Organopolysiloxanes |
| DE2215629A1 (en) * | 1972-03-30 | 1973-10-04 | Dynamit Nobel Ag | CORE SUBSTITUTED ARALKYL SILANES |
| FR2226407B1 (en) * | 1973-04-17 | 1978-05-26 | Rhone Progil | |
| US3926911A (en) * | 1973-06-07 | 1975-12-16 | Ciba Geigy Corp | Crosslinked polymers containing siloxane groups |
| FR2245663A1 (en) * | 1973-08-17 | 1975-04-25 | Rhone Progil | Aminophenoxy alkyl silanes and dimers, polymers - by catalytic hydrogenation of corresponding nitrophenols |
| FR2243022B1 (en) * | 1973-09-10 | 1977-09-23 | Rhone Progil |
-
1979
- 1979-04-03 GB GB7911609A patent/GB2019862B/en not_active Expired
- 1979-04-06 KR KR7901084A patent/KR850000074B1/en active
- 1979-04-12 DE DE19792915072 patent/DE2915072A1/en active Granted
- 1979-04-13 JP JP4430979A patent/JPS54144344A/en active Pending
- 1979-04-19 FR FR7909922A patent/FR2424281B1/en not_active Expired
- 1979-04-20 NL NL7903128A patent/NL7903128A/en not_active Application Discontinuation
- 1979-04-23 CH CH378979A patent/CH639392A5/en not_active IP Right Cessation
- 1979-04-23 NO NO791349A patent/NO156610C/en unknown
- 1979-04-23 BE BE0/194795A patent/BE875801A/en not_active IP Right Cessation
- 1979-04-24 IT IT09404/79A patent/IT1165955B/en active
- 1979-04-24 SE SE7903595A patent/SE7903595L/en not_active Application Discontinuation
- 1979-04-24 MX MX177424A patent/MX149694A/en unknown
- 1979-04-25 CA CA326,358A patent/CA1109889A/en not_active Expired
- 1979-04-25 ES ES479900A patent/ES479900A1/en not_active Expired
- 1979-04-25 DK DK170779A patent/DK148710C/en active IP Right Grant
-
1985
- 1985-04-30 NO NO851716A patent/NO851716L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2915072A1 (en) | 1979-11-08 |
| MX149694A (en) | 1983-12-13 |
| FR2424281A1 (en) | 1979-11-23 |
| SE7903595L (en) | 1979-10-27 |
| NO156610C (en) | 1987-10-21 |
| JPS54144344A (en) | 1979-11-10 |
| KR830001963A (en) | 1983-05-21 |
| NO851716L (en) | 1979-10-29 |
| CH639392A5 (en) | 1983-11-15 |
| IT7909404A0 (en) | 1979-04-24 |
| NL7903128A (en) | 1979-10-30 |
| FR2424281B1 (en) | 1985-06-28 |
| DE2915072C2 (en) | 1989-08-10 |
| NO156610B (en) | 1987-07-13 |
| NO791349L (en) | 1979-10-29 |
| GB2019862A (en) | 1979-11-07 |
| KR850000074B1 (en) | 1985-02-18 |
| GB2019862B (en) | 1982-05-19 |
| ES479900A1 (en) | 1979-11-16 |
| BE875801A (en) | 1979-08-16 |
| DK148710C (en) | 1986-01-27 |
| DK148710B (en) | 1985-09-09 |
| IT1165955B (en) | 1987-04-29 |
| DK170779A (en) | 1979-10-27 |
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