KR850000912B1 - Process for the preparation of phenoxy-alkyl alkoxy silanes - Google Patents

Abstract

Silanes of formula (I) were prepd. by the reaction of II and III. In (1), R1=-NH2, -COOR8, C2-5 alkenyl; R5 lower alkenyl; R6,R7 = lower alkyl; R8=lower alkyl; m = 1 or 2; P = 2 or 3; M = alkali metal; X=halogen. Thus, 0.55 mol m-H2NC6H4OH and 0.54 mol NaOH were reacted with 112 cc dimethylsulfoxide and 120 cc toluene. The products were cooled to about 75≰C and added with 0.56 ml 3- chloropropylmethylmethoxysilane to give m- aminophenoxypropylmethyldimethoxysilane (80% yield).

Description

Process for preparing phenoxyalkyl alkoxysilane

The present invention relates to a new class of organosilicon compounds, and in particular, to the process for the preparation of substituted phenoxyalkyl-, thiophenoxyalkyl- and pyridyloxy alkylsilanes. Offenoxyalkyl- and pyridyloxyalsilanes are prepared by reacting the same molar ratio of alkali- or alkaline earth metal phenoxides and thiophene oxides with haloalkylsilanes under anhydrous conditions using a dipolar, neutral solvent combined with liquid hydrocarbons. .

The new compound of the present invention is represented by the following general formula.

-CHO, -CN, -COR⁸, -COOR⁸, Cl, Br, I, -

SO₂R⁸, -SOR⁸, -NO₂와 2-5개의 탄소원자를 함유하는 알켄일 이고 ; R²는 1-12개의 탄소원자를 함유하는 알킬, 알콕시 또는 티오알콕시이고 ; R³는 Cl, Br, I, -COOR⁸, -CN, -NH₂, -NR⁸H, -NR⁸ ₂, -

이며 ; R⁴는 1-12개의 탄소원자를 함유하는 알킬이고, R⁵는 메틸렌 또는 3-12개의 탄소원자를 함유하는 알킬렌이며 ; R⁶와 R⁷은 각기 알킬, 시아노알킬, 알켄일, 시클로알킬, 아릴, 알카릴로부터 선택한 것이고 여기서 알킬은 1-12개의 탄소원자를 함유한다. ; R⁹는

이고, 여기서 R¹¹와 R¹³은 각기 수소, 염소, 취소, 옥소와 1-12개의 탄소원자를 함유하는 알킬로부터 선택한 것이고, R¹²과 R¹⁴는 각기 수소와 1-12개의 탄소원자를 함유하는 알킬로부터 선택한 것이고 ; Z는 산소, 유황,

이고, m는 1-5의 정수이고, n은 0,1 또는 2이고, p는 2 또는 3이고 q는 1,2 또는 3이고, t는 0 또는 1이다.[Wherein R ¹ is -NH ₂ , -NR ⁸ ₂ ,-

-CHO, -CN, -COR ⁸ , -COOR ⁸ , Cl, Br, I,-

_{^{SO 2 R 8, -SOR 8,}} -NO ₂ and an alkenyl group containing from 2-5 carbon atoms; R ² is alkyl, alkoxy or thioalkoxy containing 1-12 carbon atoms; R ³ is Cl, Br, I, -COOR ⁸ , -CN, -NH ₂ , -NR ⁸ H, -NR ⁸ ₂ ,-

And; R ⁴ is alkyl containing 1-12 carbon atoms, R ⁵ is methylene or alkylene containing 3-12 carbon atoms; R ⁶ and R ⁷ are each selected from alkyl, cyanoalkyl, alkenyl, cycloalkyl, aryl, alkaryl, wherein alkyl contains 1-12 carbon atoms. ; R ⁹ is

Wherein R ¹¹ and R ¹³ are each selected from hydrogen, chlorine, cancellation, oxo and alkyl containing 1-12 carbon atoms, and R ¹² and R ¹⁴ are each from hydrogen and alkyl containing 1-12 carbon atoms Selected; Z is oxygen, sulfur,

M is an integer from 1-5, n is 0, 1 or 2, p is 2 or 3, q is 1,2 or 3, and t is 0 or 1.

또는 -COOR⁸이고 나머지 R¹은 -CN, Cl, Br, I 또는 -NO₂이고 ; b) m가 3이면 R¹중 하나는 -NH₂, -NR⁸H, -NR⁸ ₂또는

이고 나머지 두 R¹은 염소, 취소 또는 옥소이고 ; c) m가 4이 또는 5이면 R¹은 염소, 취소 또는 옥소이고 ; d) m가 1이면 n은 1 도는 2이고 R¹은 -NH₂, 또는 -NO₂이고 ; e) m와 n의 합은 5 또는 그 이하이다.]Where a) m is 2, then one or two of R ¹ is —NH ₂ , —NR ⁸ H, —NR ⁸ ₂ or

Or -COOR ⁸ and the remaining R ¹ is -CN, Cl, Br, I or -NO ₂ ; b) when m is 3 one of R ¹ is —NH ₂ , —NR ⁸ H, —NR ⁸ ₂ or

And the other two R ¹ are chlorine, cancel or oxo; c) when m is 4 or 5 R ¹ is chlorine, cancel or oxo; d) when m is 1 n is 1 degree 2 and R ¹ is -NH ₂ , or -NO ₂ ; e) the sum of m and n is 5 or less.]

의 할로알킬실란을 일반식

으로 표시되는 무수알카리-또는 알카리토류금속 펜옥사이드 또는 티오펜옥사이드나 히드록시 또는 일반식

으로 표시되는 메르카토피리딘의 무수알카리금속-또는 알카리토류금속염과 반응시키고, 생성된 반응혼합물을 40-200℃의 온도에서 충분한 시간동안 유지하여 원하는 펜옥시알킬-또는 티오펜옥시알킬 알콕시실란을 형성시키고 이 반응혼합물로부터 실란을 단리시켜서 제조한다. 본 방법은 미국 특허 4,049,691에 서술된 아미노펜옥시프로필실란을 포함한 관능기를 함유하는 실란을 제조함을 알 수 있다.The invention also relates to a process for the preparation of the new compounds described above, which method is in the presence of a liquid reaction medium consisting mainly of at least one dipolar neutral liquid and at least one liquid hydrocarbon having a boiling point of 40-20 ° C. under normal pressure. General formula at room temperature up to 200 ℃ under inert gas

Haloalkylsilane of the general formula

Anhydrous alkali- or alkaline earth metal phenoxide or thiophene oxide or hydroxy or general formula represented by

React with anhydrous alkali metal- or alkaline earth metal salt of merkatopyridine represented by < RTI ID = 0.0 > and < / RTI > It is prepared by isolating the silane from the reaction mixture. It can be seen that this method produces silanes containing functional groups including aminophenoxypropylsilanes described in US Pat. No. 4,049,691.

-CHO, -CN, -COR⁸, -COOR⁸, Cl, Br, I,

-SO₂R⁸, -SOR⁸, -NO₂와 2-5개의 탄소원자를 함유하는 알켄일이 있다. R¹에서부터 R¹⁰으로 표시되는 여러가지 치환분은 서술한 바와 같으며, 아미노기는 본 화합물의 증류를 여러가지로 유용하게 사용하기 때문에 바람직한 치환분이다. 치환분은 상기식에서 Z로 표시된 산소 또는 유황원자와 함께 오르토, 메타 또는 파라에 위치할 수 있다. 펜옥시, 티오펜옥시 또는 티오피리딜옥시기는 메틸렌 또는 선상 또는 분지쇄상의 3-12개의 탄소원자를 함유하는 더 높은 알킬렌기인 알킬렌기에 의하여 실리콘 원자에 결합된다. R⁵가 에틸렌인 화합물은 미량의 수성산 또는 염기의 존재하에서까지도 불안정하기 때문에 실제로 사용할 수 없다. 상술한 알킬렌기와 더불어 실리콘원자는 OR⁶로 표시되는 아릴옥사이드기 또는 세 알콕사이드에 결합되거나 또는두알콕사이드나 아릴옥사이드기와 한 하이드로카르빌 또는 시아노알킬기에 결합된다. "하이드로카르빌"이란 술어는 R⁶와 R⁷으로 전술한 바와 같이 알킬, 시클로알킬, 아릴, 알카릴과 알알킬을 표시한다.The compounds are organosubstituted, organosubstituted phenoxy-, thiophenoxy, pyridyloxy and thiopyridyloxy alkylsilanes as described above. The functional substituent represented by R ¹ in the general formula of the phenyl group is -NH ₂ , -NR ⁸ H, -NR ₂ ⁸ ,

-CHO, -CN, -COR ⁸ , -COOR ⁸ , Cl, Br, I,

-SO there is alkenyl containing from _{^{2 R 8, -SOR 8, -NO}} 2 , and 2-5 carbon atoms. The various substitutions represented by R ¹ to R ¹⁰ are as described above, and the amino group is a preferred substitution since the distillation of the present compound is usefully used in various ways. Substituents may be located in ortho, meta or para with oxygen or sulfur atoms represented by Z in the above formula. Phenoxy, thiophenoxy or thiopyridyloxy groups are bonded to silicon atoms by methylene or alkylene groups, which are higher alkylene groups containing 3-12 carbon atoms in linear or branched chain. Compounds in which R ⁵ is ethylene cannot be used in practice because they are unstable even in the presence of traces of aqueous acids or bases. In addition to the alkylene group described above, the silicon atom is bonded to the aryloxide group or the three alkoxides represented by OR ⁶ or to the two alkoxide or the aryloxide group and one hydrocarbyl or cyanoalkyl group. The term "hydrocarbyl" denotes alkyl, cycloalkyl, aryl, alkaryl and alalkyl as described above with R ⁶ and R ⁷ .

의 할로알킬실란과 반응시켜서 제조한다. 본 반응은 아주 높은 발열반응으로 불활성기체하에 무수상태에서 행하는 것이 바람직하데, 그 이유는 물이 실리콘에 결합된 2 또는 3알콕시 또는 아릴옥시를 함유하는 실란과 쉽게 반응하여 중합체를 생성하기 때문이다. 반응매체는 디메틸설폭사이드, N, N-디메틸포름아미드, 테트라메틸우레아, N-메틸피롤리돈 또는 헥사메틸포스포아미드와 같은 쌍극성, 중성액체이다. 쌍극성, 중성액체는 약 1-100중량%, 바람직하기는 20-50중량%의 반응매체로 이루어진다.The present compounds are generally formulated with alkali metal salts or alkaline earth metal salts of the desired phenol, thiophenol, hydropyridine or thiopyridine, preferably sodium or potassium salts.

It is prepared by reacting with haloalkylsilane. The reaction is preferably carried out in anhydrous state under an inert gas with a very high exothermic reaction, since water readily reacts with silanes containing 2 or 3 alkoxy or aryloxy bonded to silicon to form a polymer. The reaction medium is a dipolar, neutral liquid such as dimethyl sulfoxide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone or hexamethylphosphoamide. The bipolar, neutral liquid consists of about 1-100% by weight of the reaction medium, preferably 20-50% by weight.

The remainder of the reaction medium consists of at least one liquid hydrocarbon having a boiling point of about 20-200 ° C. under normal pressure. The use of liquid hydrocarbons is to remove water present in the reaction mixture by azeotropic distillation. Preferably haloalkylsilane is added in braille to the reaction mixture containing alkali metal salts.

After the addition, when the exothermic reaction is over, the reaction mixture is heated at about 70-150 ° C. for several hours to give the reactant the desired organosubstituted phenoxyalkyl-, thiophenoxyalkyl-, thiopyridyloxyalkyl-, or pyridyloxyalkyl Completely convert to silane. Colorless, high boiling point, viscous oils can be easily isolated by dissolving the compound in the reaction medium and removing the liquid hydrocarbons and bipolar liquids. Some compounds become black after prolonged exposure to light or air. As described above, it can be seen that the method relates to the preparation of phenoxyalkylsilanes, some of which are known compounds.

의 실란(여기서 X¹과 X²은 염소, 취소, 또는 옥소이다)을 1-12개의 탄소원자를 함유하는 알콜, R⁶OH와 반응시켜서 쉽게 얻을 수 있다. 또한 히드록실기는 시클로헥실 또는 페닐기와 같은 탄소환식환 또는 복소환식환에 결합될 수 있다.Tri (hydrocarbyloxy) haloalkylsilanes or di (hydrocarbyloxy) haloalkylsilanes used as one of the reagents for preparing the compounds are commercially available, but the corresponding haloalkyltrihalosilanes or general formula

Can be easily obtained by reacting a silane of X ¹ and X ² with chlorine, cancellation or oxo, with an alcohol containing 1-12 carbon atoms, R ⁶ OH. The hydroxyl group may also be bonded to a carbocyclic ring or heterocyclic ring such as a cyclohexyl or phenyl group.

Haloalkyltrihalosilanes can be prepared by reacting haloalkenes such as allyl chloride or metallyl chloride with trihalosilane, HSiX ² ₃ at room temperature under a platinum catalyst.

Methods of preparing intermediate silanes are known in the art and the description of reaction conditions has not been described in detail herein.

Sensory substituted phenols and thiophenols which can be used to prepare the present compounds are, for example, aminophenols, aminothiophenols and aminochlorophenols, wherein the amino groups are hydroxyl groups, isomeric hydroxybenzaldehydes, hydroxybenzoic acid and merkato It is in the ortho, meta or para position relative to the isoether of benzoic acid, wherein the alcohol residue of the ester contains 1-12 carbon atoms. If the alcohol contains a phenyl group, the number of carbon atoms is 7-18. Other functional substituents that may be present on the phenyl group are indicated in the present specification and claims. The phenyl group also contains 1 or 2 alkyl, cycloalkyl or allyl groups.

Amino groups of aminophenols or aminothiophenols may be reacted in advance to form amides, imides, carbamates, sulfonamides or other groups before reacting the phenols or thiophenols with haloalkylalkoxysilanes in the form of their alkali or alkaline earth metal salts. Can be.

Anhydrides of alkali or alkaline earth metals of phenol, thiophenol, hydroxypyridine or mercatypyridine can be prepared from bipolar neutral liquids using hydrides or alkoxides of free metals or metals such as sodium hydride or methoxide. To a solution of phenol or pyridine derivative. Metals, metal hydrides or metal alkoxides are generally used dispersed or mixed in liquid hydrocarbons.

The temperature of the reaction medium is maintained between room temperature and about 50 ° C. to avoid uncontrollable exothermic reaction.

The organoleptically substituted silanes of the present invention are useful as binders for bonding organic polymers to inorganic materials such as glass fibers or metals, as binders for water tablets, as sizing for glass fibers or textiles, and as components for abrasives and waxes for automobiles. The compounds can be reacted with liquid hydroxy- or alkoxy-terminated organopolysiloxanes with fillers to form elastomers useful as coatings, sealants, molding compositions. Wherein R ¹ is amino or dialkylamino (—NH ₂ or —NR ₂ ⁴ ), the compounds show washing resistance against wax and abrasive.

The following examples illustrate the invention by way of example and not by way of limitation in the appended claims, unless otherwise indicated, the weights are in parts and percentages.

Example 1

Preparation of m-aminophenoxypropyl methyldimethoxysilane

The reactor is charged with 60 (0.55 mole) aminophenol, 43.28 g of 50% aqueous sodium hydroxide solution (0.54 mol NaOH), 112 cc of dimethylsulfoxide and 120 cc of toluene. The reaction mixture is heated to boiling point under nitrogen gas for 6 hours and all water present in azeotropic distillation is removed. The reaction mixture is cooled to about 75 ° C. and then 100.4 g (0.56 mole) of 3-chloropropyl methyldimethoxysilane is added dropwise while stirring the reaction mixture. After the addition was completed, the reaction mixture was heated to 115 ° C. for about 16 hours, then the mixture was cooled and filtered to give a solid. The solvent is removed under the pressure of about 15 mm mercury at a temperature of about 60 ° C., then the pressure is reduced to 3-4 mm of mercury and the material with a boiling point of 230-235 ° C. is recovered.

This fraction is 80% yield based on the starting material by weight. Analysis of the product by vapor phase chromatography showed a purity of 98% or more. The product showed the expected structure with infrared and nuclear magnetic high-spectrum spectra.

Example 2

Preparation of 3,5 bis (carbomethoxy) phenoxypropyl trimethoxysilane

The reactor was charged with 115.5 g (0.55 mole) of 3,5 bis (carbomethoxy) phenol, 43.28 g of 50% by weight aqueous sodium hydroxide solution (0.54 mole NaOH), 112 cc of dimethylsulfoxide and 1200 cc of toluene, and the reaction mixture Is heated to boiling point under nitrogen gas for 6 hours and all water actually removed by azeotropic distillation is removed.

The reaction mixture is cooled to about 75 ° C. and then 109 g (0.555 mole) of chloropropyl trimethoxysilane is added dropwise to the reaction mixture. After this addition the temperature of the reaction mixture is raised to 115 ° C. and maintained at this level for about 16 hours, and the reaction mixture is cooled to room temperature. The reaction mixture is filtered and then toluene, dimethylsulfoxide and other volatiles are removed. Remove under reduced pressure caused by water aspirator. The residue was collected and sorted at a boiling point of 250-252 ° C. under a pressure of 3-4 mm mercury and 75 g of viscous, colorless oil. The product had the structure expected in the infrared and nuclear magnetic resonance spectra. It has been shown. The product solidifies gradually upon standing.

Example 3

Preparation of 0-propenpheneoxypropyl trimethoxysilane

The reactor is charged with 73.7 g (0.55 mole) of 0-arylphenol, 43.28 g of 5% aqueous sodium hydroxide solution (0.54 mole NaOH), 112 cc of dimethylsulfoxide and 120 cc of toluene. The reaction mixture is heated to boiling point under nitrogen gas for 6 hours and all water present is removed by azeotropic distillation. The reaction mixture is cooled to about 75 ° C. and then 109 g (0.56 mole) of 3-chloropropyl trimethoxysilane is added dropwise while stirring the reaction mixture. After the addition, the reaction mixture is heated at 115 ° C. for about 16 hours, and then the mixture is cooled and filtered to separate the solid material. The solvent is removed under the pressure of about 15 mm mercury at a temperature of about 60 ° C. and then the material is stirred at 146 ° C.

The weight of this fraction was equivalent to a yield of 90% based on the starting material. Purification by vapor phase chromatography showed that the product had a purity of at least 98% and the product showed the expected structure with infrared and nuclear magnetic resonance spectra.

Example 4

Preparation of m-aminophenoxy-2-methylpropyl methyldimethoxysilane

The reactor was charged with 60 g (0.55 mole) of p-aminophenol, 43.28 g of 50 wt% sodium hydroxide solution (0.54 mole NaOH), 112 cc of dimethylsulfoxide and 120 cc of toluene, and the reaction mixture was placed under nitrogen gas for 6 hours. Heat to boiling point and remove any water present by azeotropic distillation. The reaction mixture is cooled to about 75 ° C. and then 117 g (0.56 mole) of 2-methylchloropropyl methyldimethoxysilane is added dropwise while stirring the reaction mixture. After the addition, the reaction mixture was heated at 115 ° C. for about 16 hours, and then cooled and filtered to remove the solid material.

The solvent is removed under the pressure of about 15 mm mercury at a temperature of about 60 ° C., then the pressure is lowered to 2 mm of mercury and the material is agitated at 165 ° C. Analysis by vapor phase chromatography showed that the product was a pale yellow viscous liquid with a purity of at least 98%.

Example 5

The reactor was charged with 83.7 g (0.55 mole) of methyl-p-hydroxybenzoate, 43.28 g of 50% by weight aqueous sodium hydroxide solution (0.54 mole NaOH), 112 cc of dimethyl sulfoxide and 120 cc of toluene, and the reaction mixture was filled with nitrogen gas. Under boiling for 6 hours to remove all water present by azeotropic distillation. The reaction mixture is cooled to about 75 ° C. and then 109 g (0.56 mole) of 3-chloropropyl trimethoxysilane is added dropwise while stirring the reaction mixture. After the addition was completed, the reaction mixture was heated at 115 ° C. for about 16 hours, and then the mixture was cooled and filtered to remove the solid material. The solvent is removed under the pressure of about 15 mm mercury at a temperature of about 60 ° C., the pressure is reduced to 2 mm of mercury and the material collected at 230-235 ° C. is collected. The weight of this fraction was equivalent to a yield of 92% based on the starting material. Analysis of the product by vapor phase chromatography showed a purity of 98% or more. The product shows the expected structure with infrared and nuclear magnetic resonance spectra.

Example 6

Preparation of m-succinimidophenoxypropyl trimethoxysilane

A solution containing 200 g of succinic anhydride, 218 g of m-aminophenol and 1 liter of glacial acetic acid is heated to a boiling point for 16 hours in a reactor equipped with a mechanical stirrer and a water-cooled reflux condenser. The reaction mixture is cooled to room temperature to solidify, the solid is pulverized, washed with water to remove acetic acid and then dried.

M-succinimidophenol (105.1, 0.55 mol), 112 cc dimethylsulfoxide and 120 cc of toluene, together with 43.28 g of 50% by weight aqueous sodium hydroxide solution, were placed in a reactor equipped with a nitrogen inlet, a water reflux condenser and a Dean Stark trap. The reaction mixture is heated to boiling point under nitrogen gas for 6 hours and all water present is removed by azeotropic distillation. The reaction mixture is cooled to about 75 ° C. and then 109 g (0.56 mole) of 3-chloropropyl trimethoxysilane is added dropwise while stirring the reaction mixture. After the addition, the reaction mixture is heated to 115 ° C. for about 16 hours, the mixture is cooled, and then filtered to remove the solid material. The solvent is removed under the pressure of about 15 mm mercury at a temperature of about 60 ° C., then the pressure is reduced to 0.5 mm mercury and the material is agitated at 228 ° C. Purity of the product as a white solid was greater than 98% by analysis by vapor phase chromatography. The product showed the expected structure with infrared and nuclear magnetic resonance spectra.

Claims (1)

A process for producing a silane represented by the following general formula (I), wherein the compound of the following general formula (II) is reacted with a haloalkyl silane of the following general formula (III).

(Wherein R ¹ is —NH ₂ ,

Alkenyl containing -COOR ⁸ and 2-5 carbon atoms, R <^5> is lower alkenyl; R ⁶ and R ⁷ each represent lower alkyl; R ⁸ is lower alkyl, m is an integer of 1 or 2, p is an integer of 2 or 3; M is an alkali metal and X represents a halogen).