CA1152511A

CA1152511A - Functionally substituted phenoxyalkyl alkoxysilanes and method for preparing same

Info

Publication number: CA1152511A
Application number: CA000355796A
Authority: CA
Inventors: Irwin B. Silverstein; Abe Berger
Original assignee: M&T Chemicals Inc
Current assignee: M&T Chemicals Inc
Priority date: 1979-08-08
Filing date: 1980-07-09
Publication date: 1983-08-23
Also published as: GB2055871A; KR850000912B1; NL8003863A; GB2055871B; IT8009514A0; IT1153845B; ES491385A0; KR830003504A; NO802356L; JPS5645491A; FR2463148B1; SE8004782L; BE884652R; FR2463148A1; ES8105009A2; JPS6352629B2; CH661928A5; DE3025034A1

Abstract

ABSTRACT OF THE DISCLOSURE
Novel functionally substituted phenoxyalkyl-, thiophenoxyalkyl-and pyridyloxyalkylsilanes are prepared by reacting substantially equimolar amounts of an alkali- or alkaline earth metal phenoxide, thiophenoxide or pyridyloxide with a haloalkylsilane under anhydrous conditions using a di-polar, aprotic solvent in combination with a liquid hydrocarbon. The func-tionally substituted silanes are useful as coupling agents, flocculating agents for water purification, as sizings for glass fibers or fabrics and as an ingredient in polishes and waxes, particularly for automobiles.

Description

~lS2Sl~

BACKGROU~D OF THE I~VE~IO~
This invention relates to a new class of organosilicon compounds.
More particularly, this invention relates to novel functionally substituted phenoxyalkyl-, thiophenoxyalkyl- and pyrid~loxyalkylsilanes and to a method for preparing these compounds.
The novel compounds of this in~ention exhibit the general formula ZR5Si ~ ( )p or 3~P

R55i ~ IP wherein R ig -NH2, -~R8H, -NR82, - ~ R9 , -CHO, -CN, -COR , -COOR , lo ,S02R ~CR8 IQCIOR8 Cl, , , ~R10 <~10 ' Clo , S02R8, ~oR8 snd -N02; R is alkyl, sIkoxy or thioalkoxy and contains from l to 12 carbon stoms; R3 is Cl, Br, I, -COOR , -CN, -~H2, -~R H, COOR OR~ :

-~R2 -~ < R10 or _~ f 10 ; R i9 alkyl containing from l to~
12 carbon atoms; R5 i9 methylene or alkylene containing from 3 to:l2 carbon atoms; R and R7 are indi~idually selected from the group consisting of slkyl~ cyanoalkyl, alkenyl, cycloalk~l, aryl, alkaryl and aralkyl, wherein any slkyl group present as all or part of R6 and R7 contsins from l to 12 8 ance ~
carbon atoms, R ~is selected from the group consisting of alkyl, cyclcaIkyl, ~ 5251~

aryl, aIkaryl and aralkyl wherein any alkyl group contains from 1 to 12 car-bon atoms; R9 is ~ CR=CR-, ~3 or ~ ~ wher~:in R and R 3 are individu~lly selected from the group consisting of hydrogen, chlorine, bro~ine, iodine and ~lkyl containing from 1 to 12 carbon atoms;
R and R are individually selected from the group consisting of hydrogen and alkyl containing from 1 to 12 carbon atoms; Z is oxygen, sulfur, -~- or !~ m is an integer from 1 to 5~ inclusi~e; n is 0, 1 or 2, p is 2 or 3, q is 1, 2 or 3 and t is O or 1, with the proviso that a) when m is 2, one or both of R are COR COOR
-NH2, -NR8H, -NR2, -N ~ , -N <

C ~ ~ 10 or -COOR8 and any remaining R
R

is -CN, Cl, ~r, I or -~02j`b) when m is 3 one of Rl is -NE2, NR H, R
-NR2, or N /R9 and the remaining two Rl groups are chlorine, bromine oR

~. .

.

~.~ 5Z~

or iodine; c~ when m is ~ or 5, Rl is chlorine, bromine or iodine; d) n is 1 or 2 when m is 1 and Rl is -~H2 or -N02; e~ t~e sum of m and n is equal to or less than 5, and f) ~'when p is 3, Rl i9 O O

_~ ~ R~ , -COOR , -N \ , -N \
o CoR3 or -N ; R2 is alkyl, R6 and R7 are individually selected \R10 O O
from cyanoaIkyl and alkenyl and Z is -~- or -~ :

This invention also provides a method for preparing the aforemen-tioned no~el compounds, said method consisting of reacting a haloalk~l-silane of the general formula ~ (OR )p XR5Si ~ with an anhydrous alkali- or alkaline earth metal phenoxide or thiophenoxide of the formula ZM
I

n ~ Rl or an anhydrous alkali- or alkaline earth metal salt of a hydroxy- or mercaptopyridine of the formula ",_~",ZH
Rt at a temperature of from ambient to 200 C under an ~ - 3 -:. ' . , ~

.
., :
,. : . :, .

5ZS~l inert atmosphere and in the presence of a liquid reaction medium consisting essentially of at least one dipolar, aprotic liquid, and optionally, at least one liquid hydrocarbon ~oiling from 40 to 200C under ambient pressure, m~intain-ing the resultant reaction mixture at a temperature of from 40 to 200C for a period of time sufficient to form the desired phenoxyalkyl- or thiophenoxyaIkyl alkoxysilane and isolating the silane from said resultant mixture. The present method is also applicable to the prep æ ation of kncwn silanes containing func-tional groups, including the aminophenoxypropyl silanes disclosed in United States Patent 4,049,691, issued Septemker 20, 1977.
m e present compounds are functionally substituted phenoxy-, thio-phenoxy, pyridyloxy and thiopyridyloxyalkylsilanes of the general formulae dis-closed in the preceding section of this specification. The functional substi-tuent on the phenyl group, represented by Rl in the general formula, 1l can be -NH2, -NR H, -NR2 , -N\ R , -CHO, -CN, -COR , -COOR , O
O O

~ SO2R /CR8 /COR8 SO R8 Cl, Br, I~ N\ R10 ~ N~ R10 ' \ Rl0 ' 2 -SOR8 and -N02. m e various substituents represented by Rl to R10 are defined in the preceding section of this specification. kmino groups are the preferred sub-stituent 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 or sulfur atom represented by Z in the foregoing formula. m e phenoxy, thiophenoxy, pyridyloxy or thiopyridyloxy group is Joined to the silicon atom by means of an alkylene group that can be methyl-ene or a higher alkylene group containing from 3 to 12 carbon atoms in either a liner or branched configuration. Compounds wherein R5 is ethylene have been found to be so unstable in the presence o~ even trace amounts of aque-ous 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 oR6 in the foregoing for-mula or to two alkoxide or aryloxide groups and one hydrocarbyl or cyano-alkyl group. The ter~ "hydrocarbyl" includes alkyl, cycloalkyl, aryl, alkaryl and aralkyl, as previously defined for R and R7.
The present compounds are conveniently prepared by reacting an alkali metal- or alkaline earth metal salt, preferably the sodiu~ or potas-sium salt, of the desired phenol, thiophenol, hydroxypyridine or thiopyrid-ine with a haloalkylsilane of the general formula (oR6)p XR5Si ~ . This reaction is highly exothermic and is preferably R3-p conducted under an inert atmosphere and in the absence of even trace amounts of water, since water is known to react readily with silanes containing 2 or 3 aIkoxy or aryloxy groups bonded to silicon to yield polymeric products.
The reaction medium is a dipolar, aprotic liquid such as dimethyl sulfoxide, ~ dimethylformamide, tetramethylurea, N-methyl pyrolidone or hexamethyl-phosphoramide. ~he dipolar, aprotic liquid constitutes from 1 to about 100 by weight of the reaction medium, preferably from 20 to 50~ by weight. Any remaining portion of the reaction medium consists essentially of at least one liquid hydrocarbon boiling from 40 to about 200C under atmospheric pressure. The purpose of the liquid hydrocarbon is to facilitate the re-moval by azeotropic distillation of any water present in the reaction mix--I , ~iS251~

ture. Preferably, the haloalkylsilane is gradually added to a reaction mix-ture 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 at from 70 to about 150 C for several hours to ensure sub-stantially complete conversion of the reactants 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 readily isolatable by removal of the aforementioned liquid hydrocarbon and dipolar 10 liquid. Some of the compounds may darken if exposed to light or air for ;~
extended periods of time.
As previously disclosed the present method is applicable to the preparation of any phenoxyalkylsilane, some of ~hich are known compounds.
~ he tri(hydrocarbyloxy)haloalkylsilanes or di(hydrocarbyloxy)-haloalkylsilanes 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 or a silane of the formula X~5Si , wherein Xl and X are chlorine, bromine or iodine, ~x2 ~

with an alcohol, R OH, that contains from 1 to 12 carbon atoms. Alternative-20 ly, the hydroxyl group can be bonded to a carbocyclic or heterocyclic ring -structure such as a cyclohexyl or phenyl group. The h~loalkyltrihalosilane can be prepared by re~ctine a haloalkene such as allyl chloride or methallyl chloride ~ith a trihalosilane, HSiX3, at ambient temperature in the presence of a platinum catalyst. Procedures for preparing the intermediate silanes are ~ell known in the art. A detailed discussion of reaction conditions is therefore not required in this specification.

_, . .

: ., .. . , : . :

~152Sl~

Illustrative of the preferred functionally substituted phenols and thioph~nols that can be employed to prepare the present compounds are amino-phenols, aminothiophenols and aminochlorophenols 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 mercaptobenzoic acids wherein the alcohol residue of the ester contains from 1 to 12 carbon atoms. If the alcohol contains a phenyl group, the num-ber of carbon atoms is from 7 to 18. Other functional substituents that can be present on the phenyl group are disclosed in the present specification and claims. In addition the phenyl group may contain 1 or 2 alkyl, cyclo-alkyl or aryl groups.
Alternatively, the amino group of an aminophenol or aminothio-phenol can be prereacted to form an amide, imide, carbamate, sulfonamide or other group prior to reaction o~ the phenol or thiophenol, in the form of its alkali metal or alkaline earth metal salt, with the haloalkylalkoxy-silane.
An anhydrous form of the alkali metal or alkaline earth metal salt of the phenol, thiophenol, hydroxypyridine or mercaptopyridine can be pre-pared by employing the free metal or a hydride or alkoxide of the metal, such as sodium hydride or methoxiae. Any of these compounds are added to a solu-tion of the desired phenol, thiophenol or pyridine deri~ative in a dipolar aprotic liquia which may optionally contain a liquid hydrocarbon. The metal, metal hydride or metPl alkoxide is conveniently employed as a dispersion or slurry in a liquid hydrocarbon. The temperature of the reaction medium is maintained between ambient and about 50 C to avoid _n uncontrollable exo-thermic reaction.
The functionally substituted silanes of this invention are useful as coupling agents for bonding an organic polymer to an inorganic material :,.

l~S25~1 such as glass fibers or metal, as flocculating agents for water purifica-tion, as sizings for glass fibers or ~abrics and as an ingredient in pol-ishes and waxes, particularly for automobiles. The present compounds can be reacted with liquid hydroxy- or alkoxy-terminated organopolysiloxanes to-gether with optional fillers to form elastomeric products that are useful as coating materials, sealants and molding compositions. Compounds wherein Rl of the foregoing formula is amino or dialkylamino (-~H2 or -~R2) impart detergent resistance to waxes and polishes.
The following examples disclose preferred embodiments of the pres-ent compounds and should not be interpreted as limiting the scope of the ac-companying claims. All parts and percentages are by weight unless otherwise specified.
EXq~IE 1 Preparation of 3(p-aminophenoxy)propyl Trimethoxysilane A glass reactor was charged with 60 g (0.55 mole) p-aminophenol, 43.28 g of à 50% aqueous solution of sodium hydroxide (0.54 mole NaOX)`, 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 trimethoxysilane was added dropwise while the reaction mixture was stirred. The temperature of the reaction mixture increased spontaneoualy 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 of 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 were then removed under a pressure Qf ab~ut 15 ~m o~ mercury at a temperature of about 6Q C. The .
. ~ .
.:~ . . . . .

. .
.
- : : ~ -, ~1525~1 pressure ~Tas then reduced to from 3 to 4 mm of mercury and the material boiling from 170 to 180 C was recovered. This fraction, which weighed 70 g, was distilled using a fractionating column and a 50 g portion boiling from 1~5 to 1~7 C under a pressure of 3 mm of mercury, was collected. The color-less liquid was found to contain 10.19% silicon and 5.20% nitrogen. The calculated values for 3(p-aminophenoxy)propyl trimethoxy silane are 10.33%
silicon and 5.1~% nitrogen. The infrared and nuclear magnetic resonance spectra of the product were in agreement with the proposed structure.

Preparation of m-aminophenoxy~ro~yl Methyldimethoxysilane Using the general procedure described in Example 1 ~ reactor was charged with 60 e (0.55 mole) of p-aminophenol, ~3.28 g of a 50% by weight aqueous solution of sodium hydroxide (0.54 mole NaOH), 112 cc dimethylsulfox-ide 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 100.~ g (o.56 mole) of 3-chloropropyl methyldimethoxysilane was added dropwise while the reaction mixture was stirred. Following completion of the addition the reaction mixture was heat-et at 115 C for about 16 hours, following which the mixture was allowed to cool and was filtered to remove any solid material. The solvents were 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 material boiling from 230 to 235 C was recovered. This fraction weighed 112 g, equivalent to a yield of 80% based on starting materials. Analysis by vapor phase chromatography indicated that the purity of the product was greater than 98%. The inI'rared and nuclear magnetic resonance spectra of the product were consistent ~ith the propQ~ed structure, _ g ~

~ .
,: :

5~1 Preparation of 3~5 Bis(carbomethoxy)phenoxy~rop2~_~rimethoxysilane Using the general procedure described in Example 1 a reactor was charged with 115.5 g (0.55 mole~ 3,5 bis(carbomethoxy)phenol, 43.28 g of a 50% by weight aqueous solution of sodiu~ hy~oxide (equivalent to o.54 mole NaOH), 112 cc dimethylsulfoxide and 1200 cc toluene. The resultant mixture uas heated at 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 about 75C, at which time 109 g (0.555 mole) of chloropropyl trimethoxysilane were adaed dropwise to the reaction mixture. Upon completion of this addition the temperature of the reaction mixture was increased to 115 C and maintained at this level for about 16 hours, at which time the reaction mixture was allowed to cool to ambient temperature. The reaction mixture was then filtered and the toluene, dimethylsulfoxide and other volatile materials were remo~ed under the re-duced pressure produced by a water aspirator. The liquid residue was then distilled under a pressure of from 3 to 4 mm of mercury and the fraction boiling from 240 to 270C was collected and weighed 95 g. Fractional dis-tillation of this material yielded 75 g of a viscous, colorless oil that was collected over the boiling range from 250 to 252 C under a pressure of 3 m~
of mercury. The infrared and nuclear magnetic resonance spectra of the product were consistent with the proposed structure. The vapor phase chrom-atogram indicated that the product was at least 98g pure. The product grad-ually solidified upon standing.

Preparation of o-pro~enylphenoxypropyl trimethoxysilane Using the general procedure described in Example 1 a reactor was charged with 73,7 g ~Q,55 ~ole~ of orallylphenol, 43,28 g of ~ 50~ by ~eight ;: ''`

` ~L1525~

aqueous solution of sodium hydroxide (0.54 mole ~aOH), 112 cc dimethylsul-foxide and 120 cc toluene. The resultant mixture was heated to the boiling point Por 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 (o.s6 mole) of 3-chloropropyl trimethoxysilane was added dropwise while the reaction mixture was stirred.
Following completion of the addition the reaction mixture was heated at 115C for about 16 hours, following which the mixture was allowed to cool ana was filtered to remove any solid material. The solvents were then re-movea under a pressure of about 15 mm of mercury at a temperature of about 60c. The pressure was then reduced to 2 mm of mercury and the material boiling at 146C Nas collected. The weight of this fraction was equivalent to a yield of 90% based on starting materials. Analysis by vapor phase chromatography indicated that the purity of the product was greater than 98~. The infrared and nuclear magnetic resonance spectra of the product were consistent with the proposed structure.

Preparation of m-aminophenoxy-2-methylpropyl Methyldimethoxysilane Using the general procedure described in Example 1 a reactor is charged with 60 g (0.55 mole) of p-aminophenol, 43.20 g of a 50~ by weight aqueous solution of sodium hydroxide (0.54 mole ~aO~, 112 cc dimethylsul-foxide and 120 cc toluene. ~he resultant mixture is 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 is then allowed to cool to about 75C, at which time 117 g (o.56 mole) of 2-methylchloro-propyl methyldimethoxysilane are added dropwise while the reaction mixture is stirred. Following completion of the addition the reaction ~ixture is heated at 115 C ~o~ about 16 h9ur~ follo~ng ~h~ck the m~xture is allo~ed , .
'' ' , ' .:
:. . .
, ~
.
.

` 1152511 to cool and is filtered to remove any solid material. The solvents are then removed under a pressure of about 15 mm o~ mercury at a temperature of about 60C. The pressure is then reduced to 2 mm of mercury and the ma-terial boiling at 165 C is collected. Analysis by vapor phase chromatog-raphy indicates that the purity of the product, a pale yellow ~iscous liq-uid, was greater than 98%.

Preparation of p-carbomethoxyphenoxypropyl Methyldimethoxysilane Using the general procedure described in Example 1 a reactor was charged with 83.7 g ~0.55 mole) of methyl-p-hydroxybenzoate, 43.28 e of a 50% by weight aqueous solution of sodium hydroxide (0.5~ mole ~aOH), 112 cc dimethylsulfoxide and 120 cc toluene. ~he 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 (0.56 mole) of 3-chloro-propyl trimethoxysilane were added dropwise while the reaction mixt~re was stirred. Following completion of the addition the reaction mixture was heated at 115 C for about 16 hours, following which the mixture was allowed to cool and was filtered to remove any solid material. The sol~ents were then removed under a pressure o~ about 15 mm of mercury at a temperature of about 60C. ~he pressure was then reduced to 2 mm of mercury and the mate-rial boiling from 230 to 235 C was collected. ~he weight o~ this faction was equivalent to a yield of 92% based on starting materials. Analysis by ~apor phase chromatography indicated that the purity of the product was greater than 9O%. ~he infrared and nuclear magnetic resonance spectra of the product were consistent with the proposed structure.

- 12 _ .
, - . :, - ~ : -: ~ . ~ . -: ; :
- ~ , . . .
:

- : ~ ~ . . . :

- 1152~

Preparation of m-Succinimidophenoxypropyl Trimethoxysilane A solution containing 200 g of succinic anhydride, 218 g m-amino-phenol and one liter of glacial acetic acid was heated at 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 upon cooling to ambient temperature. ~he solid was pulverized, washed with water to re-move the acetic acid, then dried. The resultant m~succinimidophenol (105.1 g, 0.55 mole) together with 43.28 g of a 50% by weight aqueous solution of sodium hydroxide, 112 cc dimethylsulfoxide and 120 cc toluene were placed in a reactor equipped with a nitrogen inlet, water-cooled reflux condenser and Dean-Stark trap. 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 75 C, at which time 109 e (o.56 mole) of 3-chloropropyl trimethoxy-silane was added dropwise while the reaction mixture was stirred. Follow-ing completion of the addition the reaction mixture was heated at 115C for about 16 hours, following which the mixture was allowed to cool and was fil-tered to remove any solid material. The solvents were then remo~ed under a pressure of about 15 mm of mercury at a temperature of about 60 C. The pressure was then reduced to 0.5 mm of mercury and the material boiling at 228C was collected. Analysis by vapor phase chromatography indicated that the purity of the product, a white solid, was greater than 98%. The infra~
red and nuclear magnetic resonance spectra of the product were consistent with the proposed structure.

- 13 .

' : , : :: .
., , . : ~
. : - ~ : ; ; : ;: . :
:. .~
. : ' ~ . ~ ' :
:,; - . .

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A silane represented by the general formula or wherein R1 is -NH2, -NR8H, -NR82 , , -CHO, -CN, -COR8, -COOR8, C1, Br, I, , , , SO2R8, -SOR8 -NO2 or C1-5 alkenyl; R2 is alkyl, alkoxy or thio-alkoxy and contains from 1 to 12 carbon atoms; R3 is C1, Br, I, -COOR8, -CN, -NH2, -NR8H, -NR?, or ; R4 is alkyl containing from 1 to 12 carbon atoms; R5 is methylene or alkylene containing from 3 to 12 carbon atoms; R6 and R7 are individually selected from the group consisting of alkyl, cyanoalkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl, wherein any alkyl group present as all or part of R6 and R7 contains from 1 to 12 carbon atoms; R8 and R10 are selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl wherein any alkyl group contains from 1 to 12 carbon atoms;

R9 is , -CH=CH-, or , wherein R11 and R13 are individually selected from the group consisting of hydrogen, chlorine, bromine, iodine and alkyl containing from 1 to 12 carbon atoms; R12 and R14 are individually selected from the group consisting of hydrogen and alkyl containing from 1 to 12 carbon atoms;
Z is oxygen, sulfur, -?- or , m is an integer from 1 to 5, inclusive; 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 proviso that a) when m is 2, one or both of R1 are -NH2, -NR8H, -NR?, , or -COOR8 and any remaining R1 is -CN, C1, Br, I or -NO2; b) when m is 3 one of R1 is NH2, -NR8H, <-NR? or and the remaining two R groups are chlorine, bromine or iodine; c) when m is 4 or 5, R1 is chlorine, bromine or iodine; d) n is 1 or 2 when m is 1 and R1 is -NH2 or -NO2; e) the sum of m and n is equal to or less than 5; and f) when p is 3, R1 is , -COOR8 , , or ; R2 is alkyl, R6 and R7 are individually selected from cyanoalkyl and alkenyl and Z is -?- or .

2. A silane represented by the general formula wherein R1 is -NH2, -NR8H, -NR?, , CHO, -CN, COR8, -COOR8, C1, Br, I, , , , SO2R8, -SOR8 -NO2 or C1-5 alkenyl; R2 is alkyl, alkoxy or thioalkoxy and contains from 1 to 12 carbon atoms; R5 is methylene or alkylene containing from 3 to 12 carbon atoms; R6 and R7 are individually selected from the group consisting of alkyl, cyano-alkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl, wherein any alkyl group present as all or part of R6 and R7 contains from 1 to 12 carbon atoms; R8 and R10 are selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl wherein any alkyl group contains from 1 to 12 carbon atoms;

R9 is ,-CH=CH-, or , wherein R11 and R13 are individually selected from the group consisting of hydrogen, chlorine, bromine, iodine and alkyl containing from 1 to 12 carbon atoms; R12 and R14 are individually selected from the group consisting of hydrogen and alkyl containing from 1 to 12 carbon atoms;

Z is oxygen, sulfur, -?- or , m is an integer from 1 to 5, inclusive; n is 0, 1 or 2; p is 2 or 3; with the proviso that a) when m is 2, one or both of R1 are -NH2, -NR8H, -NR?, , or -COOR8 and any remaining R1 is -CN, C1, Br, I or -NO2; b) when m is 3 one of R1 is NH2, -NR8H, -NR? or and the remaining two R1 groups are chlorine, bromine or iodine; c) when m is 4 or 5, R1 is chlorine, bromine or iodine; d) n is 1 or 2 when m is 1 and R1 is -NH2 or -NO2;

e) the sum of m and n is equal to or less than 5; and f) when p is 3, R1 is , -COOR8 , , or ; R2 is alkyl, R6 and R7 are individually selected from cyanoalkyl and alkenyl and Z is or .

3. A silane represented by the general formula R3 is Cl, Br, I, -COOR8, -CN, -NH2, -NR8H, , or ; R4 is alkyl containing from 1 to 12 carbon atoms; R5 is methylene or alkylene containing from 3 to 12 carbon atoms; R6 and R7 are individually selected from the group consisting of alkyl, cyanoalkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl, wherein any alkyl group present as all or part of R6 and R contains from 1 to 12 carbon atoms; q is 1, 2 or 3 and t is 0 or 1.

4. A silane according to claim 1 or 2 wherein R1 is -NH2, -NR? and -CHO.

5. A silane according to claim 1, 2 or 3 wherein R5 is propylene.

6. A silane according to claim 1, 2 or 3 wherein R6 and R7 are alkyl and contain from 1 to 4 carbon atoms.

7. A silane according to claim 1, 2 or 3 wherein R6 and R7 are methyl.

8. A silane according to claim 1 or 2 wherein n is 0 or 1.

9. A silane according to claim 1 or 2 wherein n is 1 and R2 is methyl.

10. A silane according to claim 1 or 2 wherein R1 is CH3COO-, m is 2 and n is 0.

11. A silane represented by the general formula or wherein R1 is -NR8H, -NR?, , -CHO, -CN, -COR8, -COOR8, Cl, Br, I, , , , SO2R8, -SOR8 or C1-5 alkenyl; R2 is alkyl, alkoxy or thioalkoxy and contains from 1 to 12 carbon atoms; R3 is Cl, Br, I, -COOR8, -CN, -NH2, -NR8H, , or ; R4 is alkyl containing from 1 to 12 carbon atoms; R5 is methylene or alkylene containing from 3 to 12 carbon atoms; R6 and R7 are individually selected from the group consisting of alkyl, cyanoalkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl, wherein any alkyl group present as all or part of R6 and R7 contains from 1 to 12 carbon atoms; R8 and R10 are selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl wherein any alkyl group contains from 1 to 12 carbon atoms;

R9 is , -CH=CH-, or , wherein R11 and R13 are individually selected from the group consisting of hydrogen, chlorine, bromine, iodine and alkyl containing from 1 to 12 carbon atoms; R12 and R14 are individually selected from the group consisting of hydrogen and alkyl containing from 1 to 12 carbon atoms;
Z is oxygen, sulfur, or, m is an integer from 1 to 5, inclusive; 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 proviso that a) when m is 2, one or both of R1 are -NR8H, _NR? , , or -COOR8 and any remaining R1 is -CN, Cl, Br, I or -NO2; b) when m is 3 one of R1 is -NR8H, or and the remaining two R1 groups are chlorine, bromine or iodine; c) when m is 4 or 5, R1 is chlorine, bromLne or iodine; e) the sum of m and n is equal to or less than 5; and f) when p is 3, R is , -COOR8, , or ; R2 is alkyl, R6 and R7 are individually selected from cyanoalkyl and alkenyl and Z is or .

12. A silane represented by the general formula wherein R is or -COOR8, R5 is methylene or propylene; R6 and R are methyl; R8 is alkyl, containing from 1 to 4 carbon atoms; m is an integer from 1 to 5, inclusive; and p is 2 or 3.

13. A method for preparing a silane represented by the general formula or wherein R1 is -NH2, -NR8H, , , -CHO, -CN, -COR8, -COOR8, Cl, Br, I, , , , SO2R8, -SOR8 -NO2 or C1-5 alkenyl; R2 is alkyl, alkoxy or thioalkoxy and contains from 1 to 12 carbon atoms; R3 is Cl, sr, I, -COOR8, -CN, -NH2, -NR8H, -NR?, or ; R4 is alkyl containing from 1 to 12 carbon atoms; R5 is methylene or alkylene containing from 3 to 12 carbon atoms, R6 and R7 are individually selected from the group consisting of alkyl, cyanoalkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl, wherein any alkyl group present as all or part of R6 and R7 contains from 1 to 12 carbon atoms; R8 and R10 are selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl wherein any alkyl group contains from 1 to 12 carbon atoms; R9 is , -CH=CH-, or , wherein R11 and R13 are individually selected from the group consisting of hydrogen, chlorine, bromine, iodine and alkyl containing from 1 to 12 carbon atoms, R12 and R14 are individually selected from the group con-sisting of hydrogen and alkyl containing from 1 to 12 carbon atoms;
Z is oxygen, sulfur, or , m is an integer from 1 to 5, inclusive; n is 0, 1 or 2, p is 1, 2 or 3, q is 1, 2 or 3 and t is 0 or 1, with the proviso that a) when m is 2, one or both of R1 are -NH2, NR8H, -NR2 , , , , -COOR8 or and any remaining R1 is -CN, Cl, Br, I or -NO2, b) when m is 3 one of R1 is -NH2, -NR8H,NR? or and the remaining two R1 groups are chlorine, bromine or iodine; c) when m is 4 or 5, R1 is chlorine, bromine or iodine; d) n is 1 or 2 when m is 1 and R1 is -NH2 or -NO2; e) the sum of m and n is equal to or less than 5, and f) when p is 3, R1 is , -COOR8, , or ; R2 is alkyl, R6 and R7 are individually selected from cyanoalkyl and alkenyl and Z is -?- -?- said method comprising reacting substantially equimolar amounts of an anhydrous alkali metal or alkaline earth metal compound of the general formula with a haloalkylsilane of the general formula wherein M represents an alkali or alkaline earth metal and X is chlorine, bromine or iodine, and wherein the reaction of said alkali metal- or alkaline earth 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 at least in part of at least one dipolar, aprotic liquid wherein any remaining portion of said liquid reaction medium comprising a liquid hydrocarbon boiling from 40 to 200°C, 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 functional phenoxyalkyl-, thiophenoxyalkyl- or pyridyloxyalkylsilane and recovering said silane from the liquid phase.

14. A method for preparing a silane represented by the general formula wherein R1 is -NH2, -NR8H, -NR?, , -CHO, -CN, -COR8, -COOR8, Cl, Br, I, , , , SO2R8 , -SOR8 -NO2 or C1-5 alkenyl; R2 is alkyl, alkoxy or thioalkoxy and contains from 1 to 12 carbon atoms; R5 is methylene or alkylene containing from 3 to 12 carbon atoms, R6 and R7 are individually selected from the group consisting of alkyl, cyanoalkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl, wherein any alkyl group present as all or part of R6 and R7 contains from 1 to 12 carbon atoms; R8 and R10 are selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, wherein any alkyl group contains from 1 to 12 carbon atoms; R9 is , -CH=CH-, or , wherein R11 and R13 are individually selected from the group consisting of hydrogen, chlorine, bromine, iodine and alkyl containing from 1 to 12 carbon atoms, R12 and R14 are individually selected from the group consisting of hydrogen and alkyl containing from 1 to 12 carbon atoms; Z is oxygen, sulfur, -?- or -?-, m is an integer from 1 to 5, inclusive; n is 0, 1 or 2, p is 1, 2 or 3, with the proviso that a) when m is 2, one or both of R1 are -NH2, -NR8H, -NR?, , , , -COOR8 or and any remaining R1 is -CN, Cl, Br, I or -NO2, b) when m is 3 one of R1 is -NH2, -NR8H, -NR? or and the remaining two R1 groups are chlorine, bromine or iodine; c) when m is 4 or 5, R1 is chlorine, bromine or iodine; d) n is 1 or 2 when m is 1 and R1 is -NH2 or -NO2;

e) the sum of m and n is equal to or less than 5, and f) when p is 3, R1 is , -COOR8 , or ; R2 is alkyl, R6 and R7 are individually selected from cyanoalkyl and alkenyl and Z is -?- or - -?- said method comprising reacting substantially equimolar amounts of an anhydrous alkali metal- or alkaline earth metal compound of the general formula with a haloalkylsilane of the general formula wherein M represents an alkali metal and X is chlorine, bromine, or iodine, and wherein the reaction of said alkali metal- or alkaline earth 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 at least in part of at least one dipolar, aprotic liquid wherein any remaining portion of said liquid reaction medium comprising a liquid hydrocarbon boiling from 40 to about 200°C, 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 functional phenoxyalkyl-, thiophenoxyalkyl- or pyridyloxy-alkylsilane and recovering said silane from the liquid phase.

15. A method for preparing a silane represented by the general formula wherein R3 is Cl, Br, I, -COOR8, -CN, -NH2, -NR8H, -NR?, or ; R4 is alkyl containing from 1 to 12 carbon atoms; R5 is methylene or alkylene containing from 3 to 12 carbon atoms, R6 and R7 are individually selected from the group consisting of alkyl, cyanoalkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl, wherein any alkyl group present as all or part of R6 and R7 contains from 1 to 12 carbon atoms; q is 1, 2 or 3 and t is 0 or 1, said method comprising reacting substantially equimolar amounts of an anhydrous alkali metal- or alkaline earth metal compound of the general formula with a haloalkylsilane of the general formula wherein M represents an alkali metal and X is chlorine, bromine or iodine, and wherein the reaction of said alkali metal- or alkaline earth metal compound and the silane is conducted under substan-tially anhydrous conditions at a temperature of from ambient to 200°C in a liquid reaction medium consisting at least in part of at least one dipolar, aprotic liquid wherein any remaining portion of said liquid reaction medium comprising a liquid hydrocarbon boiling from 40 to about 200°C, 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 functional phenoxyalkyl-, thiophenoxy-alkyl- or pyridyloxyalkylsilane and recovering said silane from the liquid phase.

16. A method according to claim 13 or 14 wherein R1 is -NH2, -NR? or -CHO.

17. A method according to claim 13, 14 or 15 wherein R5 is propylene.

18. A method according to claim 13, 14 or 15 wherein R6 and R are alkyl and contains from 1 to 4 carbon atoms.

19. A method according to claim 13, 14 or 15 wherein R6 and R7 are methyl.

20. A method according to claim 13, 14 or 15 wherein X is chlorine.

21. A method according to claim 13, 14 or 15 wherein M is sodium.

22. A method according to claim 13, 14 or 15 wherein said dipolar aprotic liquid is selected from the group consisting of dimethylsulfoxide, N, N-dimethylformamide, tetramethyl urea and hexamethylphosphoramide.

23. A method according to claim 13, 14 or 15 wherein the reaction between the alkali metal compound and the silane is conducted under an inert atmosphere.

24. A method according to claim 13, 14 or 15 wherein the dipolar, aprotic liquid constitutes from 1 to 100%, by weight, of said reaction medium.

25. A method according to claim 13 or 14 wherein R1 is CH3COO-, m is 2 and n is 0.