NO802356L - FUNCTIONALLY SUBSTITUTED PHENOXYLKYL ALCOXYSILANES AND PROCEDURES FOR THEIR PREPARATION - Google Patents

Description

The present invention relates to new compounds which are stated in claim 1.

The invention also provides a method for the preparation of these new compounds, and this method involves reacting a haloalkylsilane with the general formula

with an anhydrous alkali or alkaline earth metal phenoxide or thiophenoxide of the formula or an anhydrous alkali or alkaline earth metal salt of a hydroxy or mercaptopyridine of the formula

at a temperature between ambient temperature bg 200°C in an inert atmosphere and in the presence of a liquid reaction medium consisting mainly of at least one dipolar, aprotic liquid and optionally at least one liquid hydrocarbon boiling between 40 and 200°C at ambient pressure, to keep the resulting reaction mixture at a temperature between 40 and 200°C

for a sufficient period of time for the desired phenoxyalkyl or thiophenoxyalkyl alkoxysilane to form, and to isolate the silane from the resulting mixture. This method can also be used for the production of known silanes containing functional groups, including the aminophenoxypropyl silanes described in US-A 4 049 691, to which reference is hereby made.

The compounds according to the invention are functionally substituted phenoxy-, thiophenoxy-, pyridyloxy- and thiopyridyloxy-alkylsilanes with the general formula stated in claim 1. The functional substituents of the phenyl group, which are denoted by R<1> in the general formula, can be alkenyl with 2 -5 carbon-

atoms,

-SOR<8>and/or -NO2. The different substituents denoted by R1-R10 are further defined in the main claim. Amino groups are the preferred substituent due to the many useful applications of this class of compounds. The substituent can be in the ortho, meta or para position in relation to the oxygen or sulfur atom represented by Z in the general formula. The phenoxy, thiophenoxy, pyridyloxy or thiopyridyloxy group is connected to the silicon atom by means of an alkene group which can be methylene or a higher alkene group with 3-12 carbon atoms in either a straight or branched chain. Compounds where R5 is ethene 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 alkene group, the silicon atom is also bound to three alkoxide or aryloxide groups which are represented by OR<6> in the general formula, or two alkoxide or aryloxide groups and one hydrocarbyl or cyanoalkyl group. The term "hydrocarbyl" includes alkyl, cycloalkyl, aryl, alkaryl and aralkyl, as indicated in the definition of R<6> and R<7>.

The compounds according to the invention are suitably prepared by reacting an alkali metal or alkaline earth metal salt, preferably the sodium or potassium salt, of the desired phenol, thiophenol hydroxypyridine or thiopyridine with a haloalkylsilane of the general formula

This reaction is strongly exothermic and is preferably carried out under an inert atmosphere and in the absence of even trace amounts of water, as it is known that water readily reacts with silanes with 2 or 3 alkoxy or aryloxy groups bound to the silicon to give polymeric products. The reaction medium is a dipolar aprotic liquid such as dimethylsulfoxide, N,N-dimethylformamide, tetramethylurea, N-methylpyrrolidone or hexamethylmethylphosphoramide. The dipolar aprotic liquid makes up from 1 to approx. 100% by weight of the reaction medium, preferably 20-50% by weight. The possible remaining part of the reaction medium mainly consists of at least one liquid hydrocarbon which boils from 40 to approx. 200°C under atmospheric pressure. The purpose of the liquid hydrocarbon is to facilitate the removal of any water present in the reaction mixture by azeotrope distillation. The haloalkylsilane is preferably gradually added to a reaction mixture containing the alkali metal salt. When the addition is complete and any exothermic reaction has subsided, it is usually desirable to heat the reaction mixture to a temperature of 70-150°C for several hours to ensure substantially complete conversion of the reactant moieties to the desired functionally substituted phenoxyalkyl, thiophenoxyalkyl -, thiopyridyloxyalkyl- or pyridyloxyalkylsilane. The present compounds, many of which are colorless, high-boiling, viscous oils, are soluble in the reaction medium and can be easily isolated by removing the above-mentioned liquid hydrocarbon and the dipolar solvent. Some of the compounds may darken if exposed to light or air for long periods of time.

As previously mentioned, the method is applicable for the production of any phenoxyalkylsilane, some of which are known compounds.

The tri(hydrocarbyloxy)haloalkylsilanes or di(hydrocarbyloxy)haloalkylsilanes that are used as one of the reaction components in the preparation of the compounds according to the invention are either commercially available or can be easily produced by reacting the corresponding haloalkyltrihalosilane or a silane with the formula

where X<1> and X<2> are chlorine, bromine or iodine, with an alcohol R<6>OH containing 1-12 carbon atoms. Alternatively, the hydroxyl group can be attached to a carbocyclic or heterocyclic ring structure such as a cyclohexyl or phenyl group. The haloalkyltrihalosilane can be prepared by reacting a haloalkene such as allyl chloride or methallyl chloride with a trihalosilane HSiX<2>, at ambient temperature in the presence of a platinum catalyst. Methods for the production of silane intermediates are well known in the art. A detailed discussion of the reaction conditions is therefore not necessary here.

Examples of the preferred functionally substituted phenols and thiophenols which can be used in the preparation of the compounds according to the invention are aminophenols, aminothiophenols and aminochlorophenols where the amino group is in the ortho-, meta- or para-position in relation to the hydroxyl group, the isomeric hydroxybenzaldehydes and the isomeric esters of hydroxybenzoic acid and mercaptobenzoic acid where the alcohol residue in 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 which may be present on the phenyl group are described in the present preparation. In addition, the phenyl group may contain 1 or 2 alkyl, cycloalkyl or aryl groups.

Alternatively, the amino group of an aminophenol or aminothiophenol can first be reacted to form an amide, imide, carbamate, sulfonamide or other group before the phenol or thiophenol in the form of its alkali metal or alkaline earth metal salt is reacted with the haloalkyl alkoxysilane.

An anhydrous form of the alkali metal or alkaline earth metal salt of the phenol, thiophenol, hydroxypyridine or mercaptopyridine can be prepared using the free metal or a hydrogenide or an alkoxide of the metal, e.g. sodium hydrogenide or sodium methoxide. To any of these compounds is added a solution of the desired phenol, thiophenol or pyridine derivative in a dipolar aprotic liquid which may optionally contain a liquid hydrocarbon. The metal, metal hydrogenide or metal alkoxide is conveniently used as a dispersion or slurry in a liquid hydrocarbon. The temperature of the reaction medium is kept between ambient temperature and approx. 50°C to avoid an uncontrolled exothermic reaction.

The functionally substituted silanes according to the invention are useful as coupling agents for binding an organic polymer to an inorganic material such as glass fibers or metal, as flocculating agents for water purification, as a finish for glass fibers or textile fabrics, and as a component in polishing agents and waxes, especially for cars. The compound according to the invention can be reacted with liquid hydroxy- or alkoxy-terminated organopolysiloxanes together with optional fillers to form elastomeric products which are applicable as coating materials, sealing compounds and molding compounds. Compounds where R<1> in the general formula is amine or dialkylamine (-NH2 or -NR;}) give waxes and polishing agents resistance to detergents.

The following examples show preferred embodiments of the invention, without this being limited to the compounds in the examples. All shares and percentages are parts by weight or percentages by weight, unless otherwise stated.

Example 1

Preparation of m-aminophenoxypropylmethyldimethoxysilane

A reactor was charged with 60 g (0.55 mol) of p-aminophenol, 43.28 g of a 50% aqueous solution of sodium hydroxide

1 3

(0.54 mol NaOH), 112 cn<r>dimethylsulfoxide and 120 cm toluene. The resulting mixture was heated to the boiling point i

6 hours under a nitrogen atmosphere to remove all the water that was present by azeotropic distillation. The reaction mixture was then allowed to cool to approx. 75°C, after which 100.4 g (0.56 mol) of 3-chloropropyl-methyldimethoxysilane was added dropwise while the reactor mixture was stirred. After addition was complete, the reaction mixture was heated to 115 g for about 16 hours, after which the mixture was allowed to cool and was filtered to remove any solids. The solvents were then removed under a pressure of about 15 mm Hg at a temperature of about 60° C. The pressure was then reduced to 3-4 mm Hg, and the material boiling between 230 and 235° C was recovered. This fraction weighed 112 g, corresponding to a yield of 80% calculated on the starting materials .Analysis by vapor phase chromatography showed that the purity of the product was higher than 98%.The infrared and nuclear magnetic resonance spectra of the product were consistent with the proposed structure.

Example 2

Preparation of 3,5 bis(carbomethoxy)phenoxypropyltrimethoxysilane

Using the general procedure described in Example 1, a reactor was charged with 115.5 g (0.55 mol) of 3,5 bis(carbomethoxy)phenol, 43.28 g of a 50% aqueous solution of sodium hydroxide (equivalent to 0.54 mol NaOH), 112 cm 3 dimethylsulfoxide and 120 cm<3>toluene. The resulting mixture was heated to the boiling point under a nitrogen atmosphere for 6 hours to remove substantially all of the water present by azeotropic distillation. The reaction mixture was then allowed to cool to approx. 75°C, after which 109 g (0.55 mol) of chloropropyltrimethoxysilane was added dropwise to the reaction mixture. After the addition was complete, the temperature of the reaction mixture was increased to 115°C and held at this level for approx. 16 hours, after which the reaction mixture was allowed to cool to ambient temperature. The reaction mixture was then filtered, and the toluene, the dimethyl sulfoxide and the other volatile materials were removed under reduced pressure produced by a water suction pump. The liquid residue was then distilled under a pressure of 3-4 mm Hg, and the fraction boiling between 240 and 270°C was collected. Fractional distillation of this material, which weighed 95 g, gave 75 g of a viscous colorless oil, which was collected in the boiling point range of 250-252°C under a pressure of 3 mm Hg. The infrared and nuclear magnetic resonance spectra of the product were consistent with the proposed structure. The vapor phase chromatogram showed that the product was at least 98% pure. The product gradually solidified on standing.

Example 3

Preparation of o-propenylphenoxypropyl-trierethoxysilane

Using the general procedure described in Example 1, a reactor was charged with 73.7 g (0.55 mol) of o-allylphenol, 43.28 g of a 50% aqueous solution of sodium hydroxide (0.54 mol NaOH), 112 cm 3 dimethylsulfoxide and 120 cm 3 toluene. The resulting mixture was heated to the boiling point for 6 hours under a nitrogen atmosphere to remove any water present by azeotropic distillation. The reaction mixture was then allowed to cool to approx. 75°C, after which 109 g (0.56 mol) of 3-chloropropyltrimethoxysilane was added dropwise while the reaction mixture was stirred. After the addition was complete, the reaction mixture was heated to 115°C for approx. 16 hours, after which the mixture was allowed to cool and was filtered to remove any solids. The solvents were then removed under a pressure of approx. 15 mm Hg at a temperature of approx. 60°C. The pressure was then reduced to 2 mm Hg, and the material boiling at 146°C was collected. The weight of this fraction corresponded to a yield of 90% calculated on the starting materials. Analysis by steam chromatography showed that the purity of the product was higher than 98%. The infrared and nuclear magnetic resonance spectra of the product were consistent with the proposed structure.

Example 4

Preparation of m-aminophenoxy-2-methylpropyl-methyldimethoxysilane

Using the general procedure described in Example 1, a reactor was charged with 60 g (0.55 mol), p-aminophenol, 43.28 g of a 50% aqueous solution of sodium hydroxide (0.54 mol NaOH), 112 cm 3 dimethylsulfoxide and 120 cm 3 toluene. The resulting mixture was heated to the boiling point for 6 hours under a nitrogen atmosphere to remove any water present by azeotropic distillation. The reaction mixture was then allowed to cool to approx. 75°C, after which 117 g (0.56 mol) of 2-methylchloropropylmethyldimethoxysilane was added dropwise while the reaction mixture was stirred. After the addition was complete, the reaction mixture was heated to 115°C for approx. 16 hours, after which the mixture was allowed to cool and was filtered to remove any solids. The solvents were then removed with a pressure of approx. 15 mm Hg and a temperature of approx. 60°C. The pressure was then reduced to 2 mm Hg, and the material boiling at 165°C was collected. An analysis by vapor phase chromatography showed that the purity of the product, which was a pale yellow viscous liquid, was higher than 98%.

Example 5

Preparation of p-carbomethoxyphenoxypropyl-methyldimethoxysilane

Using the general procedure described in Example 1, a reactor was charged with 83.7 g (0.55 mol) of methyl p-hydroxybenzoate, 43.28 g of a 50% aqueous solution of sodium hydroxide (0 .54 mol NaOH), 112 cm<3>dimethyl sulfoxide and 120 cm 3 toluene. The resulting mixture was heated to the boiling point for 6 hours under a nitrogen atmosphere to remove any water present by azeotropic distillation. The reaction mixture was then allowed to cool to approx. 75°C, after which 109 g (0.56 mol) of 3-chloropropyltrimethoxysilane was added dropwise while the reaction mixture was stirred. After the addition was complete, the reaction mixture was heated to 115°C for approx. 16 hours, after which the mixture was allowed to cool and was filtered to remove any solids. The solvents were then removed under a pressure of approx. 15 mm Hg at a temperature of approx. 60°C. The pressure was then reduced to 2 mm Hg, and the material boiling between 230 and 235°C was collected. The weight of this fraction corresponded to a yield of 92% calculated on the starting materials. Analysis by vapor phase chromatography showed that the purity of the product was higher than 98%. The infrared and nuclear magnetic resonance spectra of the product were consistent with the proposed structure.

Example 6

Preparation of m-succinimidophenoxypropyltrimethoxysilane

A solution containing 200 g of succinic anhydride, 218 g of m-aminophenol and 1 L of glacial acetic acid was heated to the boiling point for 16 hours in a reactor equipped with a mechanically driven stirrer and a water-cooled reflux condenser. The reaction mixture solidified on cooling to ambient temperature. The solid was pulverized, washed with water to remove acetic acid and then dried. The resulting m-succinimidophenol (105.1 g, 0.55 mol) was placed in a reactor equipped with a nitrogen inlet, a water-cooled reflux condenser and a Dean-Stark trap. The resulting mixture was heated to the boiling point for 6 hours under a nitrogen atmosphere to remove any water present by azeotropic distillation. The reaction mixture was then allowed to cool to approx. 75°C, after which 109 g (0.56 mol) of 3-chloropropyltrimethoxysilane was added dropwise while the reaction mixture was stirred. After the addition was complete, the reaction mixture was heated to 115°C for approx. 16 hours, after which the mixture was allowed to cool and then filtered to remove any solids. The solvents were then removed at a pressure of approx. 15 mm Hg and a temperature of approx. 60°C. The pressure was then reduced to 0.5 mm Hg, and the material boiling at 228°C was collected. Analysis by vapor phase chromatography showed that the purity of the product, which was a white solid, was higher than 98%. The infrared and nuclear magnetic resonance spectra of the product were consistent with the proposed structure.

Claims (10)

1. Silane with the general formula whereR<1> is alkenyl with 2-5 carbon atoms, SO2R<6> , -SOR<8> or - NO2 ; R<2> is C 1-alkyl, alkoxy or thio-alkoxy and contains 1-12 carbon atoms; R3 is Cl, Br, I, COOR <8> , is alkyl of 1-12 carbon atoms, R<5> is methylene or alkene of 3-12 carbon atoms; R <6> and R <7> are selected separately from alkyl, cyanoalkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl, all alkyl groups present as whole or part of R <6> and R <7>, contains 1-12 carbon atoms; R<8> is selected from alkyl, cycloalkyl, aryl, alkaryl and aralkyl, all alkyl groups containing 1-12 carbon atoms; wherein R <1> 1 and R1<3> are each selected from hydrogen, chlorine, bromine, iodine and alkyl with 1-12 carbon atoms and R12 and Ru are selected - c each independently from hydrogen and alkyl of 1-12 carbon atoms; Z is oxygen, sulfur, or m is an integer from 1 to 5, including 1, 2 or 3; n is 0, 1 or 2; p is 2 or 3; q is 1, 2 or 3 and t is 0 or 1, with the following proviso, a) when m is 2, at least one of the R <*> groups is -NH2/ - NR <8> H, -NR8 , ;and the remaining R: group -CtJ, Cl, Br, I or IIO2 , b) when m is 3, one of the R <1-> groups is NH2 , -NR <8> H, ;or ;and the other two R <*-> groups chlorine, bromine or iodine^ c") when m is 4 or 5, R <1> is chlorine, bromine or iodine, d) n must be 1 or 2 when m is 1 and R1 is -NH2 or -N02r e) the sum of m and n is equal to or less than 5, and f) when p is 3, is or R <2> alkyl, R <6> and R<7> each selected from cyanoalkyl and alkenyl and Z-S- or 2. Silane as stated in claim 1, characterized in that R <1> is -NH2 , -NR| or - CEO. 3. Silane as stated in claim 1, characterized in that R <5> is propene. 4. Silane as stated in claim 1, characterized in that R<6> and R<7> are alkyl with 1-4 carbon atoms, preferably methyl. 5. Silane as stated in claim 1, characterized in that n is 1 and R<2> is methyl. 6. Silane as stated in claim 1, characterized in that R <1> is CH3 COO-, m is 2 and n is 0. 7. Method for producing a silane as stated in one of the preceding claims, characterized in that an anhydrous alkali metal or alkaline earth metal compound with the general formula or is reacted in a substantially equimolar amount with a haloalkylsilane of the formula where M means an alkali metal and X means chlorine, bromine or iodine, the reaction of the alkali metal compound and the silane being carried out under essentially anhydrous conditions at a temperature between ambient temperature and 200°C in a liquid reaction medium consisting at least in part of at least one dipolar aprotic liquid, while any remaining part of said liquid reaction medium mainly consists of a liquid hydrocarbon boiling between 40 and 200°C, that the resulting reaction medium is kept at a temperature of 40-200°C for a sufficient period of time so that the alkali metal compound and the silane are essentially completely converted into the desired functional phenoxyalkyl, thiophenoxyalkyl or pyridyloxyalkylsilane, and that the silane is isolated by filtering the reaction medium and evaporation of the solvent from the liquid phase. 8. Method as stated in claim 7, characterized in that the dipolar aprotic liquid is dimethylsulphoxide, N,N-dimethylformamide, tetramethylurea or hexamethylphosphoramide. 9. Method as stated in claim 7, characterized in that the reaction between the alkali metal compound and the silane is carried out in an inert atmosphere. 10. Method as stated in claim 7, characterized in that the dipolar aprotic liquid constitutes 1-100 percent by weight of the reaction medium.