FUNCTIONALLY SUBSTITUTED PHENOXYALKYL ALKOXYSILANES AND METHOD FOR PREPARING SAME

PHENOXYALKYL ALKOXYSILANES SUBSTITUES PAR DES FONCTIONS ET METHODE POUR LES PREPARER

English 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.

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
<IMG> or <IMG>
wherein R1 is -NH2, -NR8H, -NR82 , <IMG> , -CHO, -CN,
-COR8, -COOR8, C1, Br, I, <IMG> , <IMG> , <IMG> ,
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?, <IMG> or <IMG> ; 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;
14

R9 is <IMG> , -CH=CH-,<IMG> or <IMG> , 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 <IMG>, 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?,
<IMG> , <IMG> 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 <IMG> 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

<IMG> , -COOR8 , <IMG> , <IMG> or ; R2
is alkyl, R6 and R7 are individually selected from cyanoalkyl and
alkenyl and Z is
-?- or <IMG>.
2. A silane represented by the general formula
wherein R1 is -NH2, -NR8H, -NR?, <IMG> , CHO, -CN,
COR8, -COOR8, C1, Br, I,
<IMG> , <IMG> , <IMG>,
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
16

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 <IMG> ,-CH=CH-, <IMG> or <IMG> , 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 <IMG>, 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?,
<IMG> , <IMG> 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 <IMG> 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;
17

e) the sum of m and n is equal to or less than 5; and
f) when p is 3, R1 is
<IMG> , -COOR8 , <IMG> , <IMG> or <IMG>; R2
is alkyl, R6 and R7 are individually selected from cyanoalkyl and
alkenyl
and Z is <IMG> or <IMG>.
3. A silane represented by the general formula
<IMG>
R3 is Cl, Br, I, -COOR8,
-CN, -NH2, -NR8H, <IMG>, <IMG> or <IMG> ; 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.
18

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
<IMG> or <IMG>
wherein R1 is -NR8H, -NR?,<IMG> , -CHO, -CN,
-COR8, -COOR8, Cl, Br, I, <IMG>, <IMG>,<IMG> ,
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,
19

-CN, -NH2, -NR8H, <IMG>, <IMG> or <IMG> ; 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 <IMG> , -CH=CH-,<IMG> or <IMG> , 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, <IMG> or<IMG>, 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? ,

<IMG> , <IMG> or -COOR8 and any remaining R1
is -CN, Cl, Br, I or -NO2; b) when m is 3 one of R1 is -NR8H,
<IMG> or <IMG> 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
<IMG> , -COOR8, <IMG> , <IMG> or <IMG> ; R2
is alkyl, R6 and R7 are individually selected from cyanoalkyl and
alkenyl and Z is
<IMG> or <IMG>.
12. A silane represented by the general formula
<IMG>

wherein R is <IMG> 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
<IMG> or
<IMG> wherein R1 is -NH2, -NR8H, <IMG>,
<IMG> , -CHO, -CN, -COR8, -COOR8, Cl, Br, I,
<IMG> , <IMG> , <IMG> , 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?,
<IMG> or <IMG>; R4 is alkyl containing from 1 to 12
22

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
<IMG> , -CH=CH-, <IMG> or <IMG> , 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,
<IMG> or <IMG>, 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 ,
<IMG> , <IMG> , <IMG> , -COOR8 or
<IMG> and any remaining R1 is -CN, Cl, Br, I or -NO2,
b) when m is 3 one of R1 is -NH2,
23

-NR8H,NR? or <IMG> 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
<IMG> , -COOR8, <IMG> , <IMG> or <IMG> ; 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
<IMG> <IMG> with a haloalkylsilane of
the general formula
<IMG>
wherein M represents an alkali or alkaline earth metal and X is
chlorine, bromine or iodine, and wherein the reaction of said
24

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
<IMG>
wherein R1 is -NH2, -NR8H, -NR?, <IMG> , -CHO, -CN,
-COR8, -COOR8, Cl, Br, I,
<IMG> , <IMG> , <IMG> , 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
<IMG> , -CH=CH-, <IMG> or <IMG> , 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?,
<IMG> , <IMG> , <IMG> , -COOR8 or <IMG> and any
remaining R1 is -CN, Cl, Br, I or -NO2, b) when m is 3 one of R1
is -NH2, -NR8H, -NR? or
<IMG> 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;
26

e) the sum of m and n is equal to or less than 5, and f) when p is
3, R1 is
<IMG> , -COOR8 , <IMG> <IMG> or <IMG> ; 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
<IMG> with a haloalkylsilane of the general
formula <IMG> 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.
27

15. A method for preparing a silane represented by the
general formula
<IMG>
wherein R3 is Cl, Br, I, -COOR8, -CN, -NH2, -NR8H, -NR?,
<IMG> or <IMG> ; 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
<IMG> with a haloalkylsilane of the
general formula <IMG>
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
28

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.
29

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.

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
-- 2 --
~. .
.

~.~ 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
3-P
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-
- 5 -
-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
R7
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.
-- 6 --
_,
. .
: ., .. . , : . :

~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
-- 7 --
:,.

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
- 8 --
.
. ~ .
.:~ . . . . .
. .
.
- : : ~ -
,

~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.
EXAMPLE 2
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
EXAMPLE 3
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.
EXAMPLE 4
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
-- 10 --
;: ''`

` ~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.
EXAMPLE 5
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%.
EXAMPLE 6
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~
EXAMPLE 7
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 .
' : , : :: .
., , . : ~
. : - ~ : ; ; : ;: . :
:. .~
. : ' ~ . ~ ' :
:,; - . .