Title of Invention

PREPARATION OF AN AMINOARYL-CONTAINING ORGANOSILICON COMPOUND AND METHODS OF PREPARING INTERMEDIATES USED IN ITS PREPARATION

Abstract A method of manufacturing an organosilicon compound of general formula (1): said method being characterized by causing a reaction between a compound of general formula (2): and an active metal or a metalloorganic compound of general formula (3): R11MX (3) thus preparing a Grignard compound of general formula (4): where R1, R2, R3, R4, R5,R6, R7, R8, R9, R10, R11, M, X, Y,m and n are as defined in the specification.
Full Text Technical Field
[0001]
The present invention relates to a novel method of manufacturing an aminoaryl-containing
organosilicon compound and to a method of manufacturing an intermediate product of the
aforementioned compound.
Background Art
[0002]
Organosilicon compounds having aminoaryl groups are know per se, and examples of several
methods suitable for synthesis of these compounds have been published. For example,
Journal of Organic Chemistry, No. 51, page 2434(1986) discloses a method of synthesis of a
p-dimethylmethoxysilylaniline or p-methylmethoxyphenylaniline by preparing a
Grignard reagent from an N,N-bis (trimethylsilyl)-p-bromoaniline and deprotecting [the
obtained product] with methanol after reaction with, a dimethyldichlorosilane or
diphenyldichlorosilane. In this example, however, a Grignard reagent is used also for
synthesis of the N,N-bis(trimethylsilyl)-p-bromoamline, and since the low-efficient Grignard
reaction has to be repeated twice, the aforementioned method is not suitable for commercial
use.
[0003]
On the other hand, practical examples of Japanese Patent Application Publication (hereinafter
Kokai) H8-99979 disclose a specific method of synthesis of N,N-bis (trimethylsilyl)
bromoaniline for use as a starting material. However, this method is based on the use of N-
trimethylsilyldiethylamine which is a readily available material. Alternatively, the method
requires specific synthesis of N-trimethylsilyl-p-bromoaniline which is not easy to perform.

[0004]
Furthermore, Synthetic Communication, No.16, p. 809 (1986) discloses a method of synthesis
of 4-dimethylmethoxysilyl-2,6-diethylaniline. This method, however, cannot be
implemented on an industrial scale since it utilizes an organic lithium agent that is even less
efficient than the Grignard reagent and therefore requires that the synthesis reaction be
conducted in two stages.
[0005]
Journal of Organic Chemistry, No. 66, p. 7449 (2001) discloses a coupling reaction that is
conducted between a p-iodoaniline and a trimethoxysilane in the presence of a catalyst. This
method is rather impractical for industrial application since it requires the use of a large
mount of an expensive palladium catalyst.
Disclosure of Invention
[0006]
Based on the above description of the state of the art, the present invention is aimed at
providing an efficient method for manufacturing an aminoaryl-containing organosilicon
compound without the use of an organic lithium agent having low efficiency or an expensive
palladium agent and at performing the aforementioned method in a single Grignard reaction.
It is another object to provide an intermediate product of the aforementioned organosilicon
compound.
[0007]
The inventors herein have conducted a profound study aimed at achieving the above objects.
Based on the results of this study, it has been found that an aminoaryl-containing
organosilicon compound can be synthesized by:

causing a reaction between a compound of general formula (2):

(where Rl, R2, R3, and R4 are independently alkyl groups with 1 to 4 carbon atoms, R5 is an
oxygen atom or an alkylene group with 1 to 6 carbon atoms, and R6, R7, R8, and R9
independently represent a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an
alkoxy group with 1 to 4 carbon atoms; and X is a halogen atom) and an active metal or a
metalloorganic compound of general formula (3):
R11MX (3)
(where R11 is a univalent hydrocarbon group, Mis a bivalent metal, X is a halogen atom),
thus preparing a Grignard compound of general formula (4):

(where R1, R2, R3, R4, R5,R6, R7, R8, R9, M, and X are the same as defined above);
causing a reaction between the obtained Grignard compound and an organosilicon
compound of general formula (5):
YnSiR104.-n (5)
(where Y, R10, and n are the same as defined above), thus obtaining an organosilicon
compound of general formula (1):


(where R1, R2, R3, R4, R5,R6, R7, R8, R9, R10, Y, n are the same as defined above, and m is an
integer between 1 and n);
deprotecting the obtained organosilicon compound; and then obtaining the target
compound of general formula (6):
[Sixth Chemical Formula]

(where R6, R7, R8, R9, R10, Y, n, and m are the same as defined above) in a single-stage
Grignard reaction. Thus the authors arrived at the present invention.
[0008]
The aforementioned compound of general formula (2) can be produced by causing a reactio:
between a compound represented by general formula (7):


(where Rl, R2, R3, and R4 are independently alkyl groups with 1 to 4 carbon atoms, R5 is an
oxygen atom or an alkylene group with 1 to 6 carbon atoms, and Z1 and Z2 independently
represent halogen atoms) and a compound represented by general formula (8):

(where R6, R7, R8, and R9 independently represent a hydrogen atom, an alkyl group with 1 to
4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms; and X is a halogen atom), the
reaction being carried out under basic conditions and in the absence of an organic metal
compound.
[0009]
[Effects of the Invention]
Arninoaryl-containing organosilicon compounds are suitable for use as a starting material for
polyimide resin, polyimide silicone resin, etc. Since such compounds have higher thermal
stability than conventional aminoalkyl-containing organosilicon compounds, they are suitable
for use as silane coupling agents for high-temperature applications. The effect of the
invention consists of providing such animoaryl-containing organosilicon compounds that can
be synthesized with high production efficiency.

Best Mode for Carrying Out the Invention
[0010]
The present invention allows synthesis of an aminoaryl-containning organosilicon compound
in the following three steps:
1. Synthesis of the compound of general formula (2);
2. Synthesis of an organosilicon compound of general formula (1) from a compound of
general formula (2) by a Grignard reaction; and
3. Deprotection of the organosilicon compound of general formula (1).
Each of these steps will now be considered separately.
[0011]

According to the invention, the silyl-protected haloaniline compound of general formula (2):

(where R1, R2, R3, and R4 independently represent alkyl groups with 1 to 4 carbon atoms;
R5 represents an oxygen atom or an alkylene group with 1 to 6 carbon atoms;
R6, R7, R8, and R9 independently represent a hydrogen atom, an alkyl group with 1 to 4
carbon atoms, or an alkoxy group with 1 to 4 carbon atoms; and X represents a halogen atom)
is used as an intermediate product for synthesis of the aminoaryl-containing organosilicon
compound of general formula (6).
[0012]
The alkyl groups with 1 to 4 carbon atoms may be represented by a methyl group, ethyl
group, propyl group, isopropyl group, butyl group, iso-butyl group, sec-butyl group, and tert-
butyl group. The methyl group is preferable.

[0013]
The alkoxy groups with 1 to 4 carbon atoms may be represented by a methoxy group, ethoxy
group, propoxy group, isopropoxy group, butoxy group, iso-butoxy group, sec-butoxy group,
and tert-butoxy group, of which the methoxy group or the ethoxy group is preferable.
[0014]
The alkylene group with 1 to 6 carbon atoms can be represented by a methylene group,
ethylene group, propylene group, isopropylene (-CH2 -CH (CH3) -) group, butylenes group,
iso-butylene (-CH2 -CH(CH3) -CH2 -) group, sec-butylene (CH(CH3) -CH2 - CH2-), and tert-
butylene (-CH2 -C(CH3)2 -). The methylene and ethylene groups are preferable. Most
preferable is the ethylene group.
[0015]
The halogen atom can be represented by a fluorine atom, chlorine atom, bromine atom, or
iodine atom, of which chlorine or bromine atom, and especially chlorine atom is preferable.
[0016]
The compound of general formula (2) can be easily synthesized by causing a reaction
between the compound of general formula (7):

(where R1, R2, R3, and R4 are independently alkyl groups with 1 to 4 carbon atoms, R5 is an
oxygen atom or an alkylene group with 1 to 6 carbon atoms, and Z1 and Z2 independently
represent halogen atoms) and a compound represented by general formula (8):


(where R6, R7, R8, and R9 independently represent a hydrogen atom, an alkyl group with 1 to
4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms; and .X is a halogen atom), the
reaction being carried out under basic conditions and without the presence of an organic
metal compound.
[00171
The compound of general formula (7) can be exemplified, e.g., by 1,3-dichloro-1, 1,3,3-
tetraisopropyldisiloxane, 1,2-bis (chlorodimethylsilyl) ethane, etc.
[0018]
The compound of general formula (8) can be represented by m-chloroaniline, p-chloroaniline,
m-bromoaniline, p-bromoaniline, 2,6-diethyl-4-bromoaniline, etc.
[0019]
The aforementioned basic conditions are achieved without an organic metal compound but
with the use of a sodium carbonate, or other inorganic basic compounds, or with the use of
amines, or other organic basic compounds. The use of organic basic compounds is preferable.
Examples of such organic basic compounds are the following: triethylamine, picoline, 1,8-
diazabicyclo[5.4.0] undeca-7-ene, or similar aliphatic amines, aromatic amines, or cyclic
amines. Triethylamine, or similar tertiary aliphatic amines are most preferable from the point
of view of reactivity with respect to the compound of general formula (7).
[0020]
The compound of general formula (7) is available on the market in the form of several
reagents, each of which can be used for the purposes of the invention. If necessary, however,
this compound can be synthesized by a known reaction between simple compounds. For

example, 1,2-bis (chlorodimethylsilyl) ethane can be easily synthesized by means of a
bydrosilation reaction between a chlorodimethylvinylsilane and chlorodimethylsilane.
[0021]
The compound of general formula (8) is readily available since it is commercially produced
in the form of several reagents.
[0022]
The reaction between the compounds of general formulae (7) and (8) can be easily
performed, e.g., by mixing these compounds in the presence of the aforementioned basic
compound, but to avoid intense reaction, it is recommended to add one of the compounds
dropwise to a system that contains the other compound. A reaction between both compounds
creates a salt of the aforementioned basic compound.
[0023]
The reaction can be carried out at a temperature within the range of 0 to 120°C, preferably
between room temperature and 80°C.
[0024]
A solvent is not an indispensable component of the aforementioned reaction, but for
improving stirring conditions during the reaction, a solvent that is inert with respect to the
compounds (7) and (8) can be used. Examples of such solvent are toluene, xylene, heptane,
etc.
[0025]
Upon completion of the reaction between compounds (7) and (8), compound of formula (2)
can be separated from the reaction product by filtering or washing out the basic compound
salt. The obtained compound of general formula (2) can be further subjected to purification
via distillation or another process for increasing the yield of the reaction that will be
described later.

[0026]

In the next step, the compound of general formula (2) is converted into a Grignard reagent.
The Grignard reagent of the compound of formula (2) can be easily synthesized by a
conventional Grignard preparation method. In accordance with the invention, the compound
of general formula (2) is caused to react with an active metal or an organic metal compound
. of general formula (3):
R11MX (3)
(where R11 is a univalent hydrocarbon group, M is a bivalent metal, and X is a halogen
atom), whereby a Grignard reagent of general formula (4) is produced:

(where Rl, R2, R3, R4, R5,R6, R7, R8, R9, M, and X are the same as defined above).
[0027]
The univalent hydrocarbon group can be represented by a univalent saturated hydrocarbon
group having 1 to 10, preferably 1 to 6, and even more preferably, 1 or 2 carbon atoms, or by
a univalent unsaturated hydrocarbon group having 2 to 10, preferably 2 to 8 or 2 to 6, and
even more preferably, 2 to 4 carbon atoms.
[0028]
The aforementioned univalent saturated hydrocarbon group having 1 to 10 carbon atoms
can be exemplified by a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl
group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl
group, octyl group, nonyl group, decyl group, or other alkyl groups.

[0029]
The aforementioned unsaturated hydrocarbon groups with 2 to 10 carbon atoms can be
divided into unsaturated aliphatic hydrocarbon groups with 2 to 10 carbon atoms and
aromatic hydrocarbon groups with 6 to 10 carbon atoms. The unsaturated aliphatic
hydrocarbon groups with 2 to 10 carbon atoms can be exemplified by a vinyl group, 1-
propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, or similar
alkenyl groups. The vinyl group is preferable from the point of view of cross-linking
reactivity of the polysiloxane. The aromatic hydrocarbon group with 6 to 10 carbon atoms
can be represented by a phenyl group, tolyi group, xylyl group, etc.
[0030]
Among all univalent hydrocarbon groups, most preferable is the alkyl group with 1 to 10
carbon atoms, especially, the methyl group.
[0031]
The bivalent metal atoms along with active metals can be represented by alkali earth metals
or zinc group metals, especially magnesium or zinc.
[0032]
It is recommended to carry out the reaction between the compound of general formula (2) and
the active metal or the organic metal compound of general formula (3) in the presence of an
ether-type solvent. For example, the Grignard reagent of general formula (4) can be easily
prepared by gradually adding an ether solution of the compound of formula (2) in a dropwise
manner to the organic metal compound of general formula (3) or the active metal in an ether
solvent.
[0033]
The aforementioned ether solvent may be exemplified by diethyl ether, tetrahydrofuran, bis
(2-methoxyethyl) ether, or other ether-type solvent normally used for synthesis of Grignard
reagents. Tetrahydrofuran is preferable in view of its high reactivity and low cost.

[0034]
The reaction can be carried out at a temperature within the range of 0°C to the boiling point
of the solvent, but preferably between 50°C and 80°C.
[0035]
The obtained Grignard reagent of general formula (4) is then caused to react with a silicon
compound of general formula (5):
YnSiR104.n (5)
(where Y is a hydrolysable group, R10 is a univalent hydrocarbon group, and n is an integer
between 1 and 4),
whereby an organosilicon compound of general formula (1);

(where,
R1, R2, R3, and R4 independently represent alkyl groups with 1 to 4 carbon atoms;
R5 represents an oxygen atom or an alkylene group with 1 to 6 carbon atoms;
R6, R7, R8, and R9 independently represent a hydrogen atom, an alkyl group with 1 to 4
carbon atoms, or an alkoxy group with 1 to 4 carbon atoms;
R10 represents a univalent hydrocarbon group;
Yrepresents ahydrolysable group;
n is an integer from 1 to 4; and
m is an integer between 1 and n) is synthesized. The organosilicon compound of general
formula (1) comprises a second intermediate product used in the synthesis of the aminoaryl-
containing organosilicon compound of general formula (6).

[0036]
The hydrolysable group can be exemplified by an arbitrary hydrolysable group, but
preferable are halogen atoms and alkoxy groups with 1 to 4 carbon atoms, especially,
chlorine atoms, methoxy groups, and ethoxy groups.
[0037]
The following are specific examples of silicon compounds of general formula (5):
chlorotrimethylsilane, dimehtyldichlorosilane, tetrachlorosilane, methoxytrimethylsilane,
dimethoxydimethylsilane, methyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, etc.
[0038]
Equivalent relationships in the reaction between the Grignard reagent of general formula (4)
and the silicon compound of formula (5) can be arbitrary, and the appropriate equivalent
quantities are selected with reference to the required values of "m" and "n". For example,
when it is necessary to obtain an organosilicon compound with n > 1 and m = 1, it is
recommended, for an increase in the product yield, to use the silicon compound of general
formula (5) in an excess of the Grignard reagent of general formula (4) by 2 to 5 equivalent
amounts. On the other hand, when it is necessary to obtain the organosilicon compound with
n = m, the Grignard reagent of general formula (4) should be used either in the same
equivalent amount as the silicon compound of general formula (5) or in a small excess over
the silicon compound.
[0039]
Normally, the aforementioned reaction is carried out either with dropwise addition of the
silicon compound of formula (5) to the Grignard reagent of formula (4), or, vice verse, with
dropwise addition of the Grignard reagent of formula (4) to the silicon compound of formula
(5).
[0040]
When in the above reaction the Grignard reagent of formula (4) is prepared with participation
of a solvent, this solvent can be used as a continuous reaction solvent. Furthermore, if

necessary, a solvent inert to the reagents, such as toluene, xylene, heptane, tetrahydrofuran,
etc., can be added to the reaction system.
[0041]
It is recommended to conduct the last mentioned reaction at a temperature within the range of
-20°C to 80°C, preferably at a temperature between 0°C and 20°C.
[0042]
Upon completion of the above reaction, the organosilicon compound of formula (1) is
separated by removing the salt formed in the reaction by filtering or washing, and, if
necessary, the solvent is removed by distillation. Alternatively, the reaction mixture can be
used for the next step as it is, i.e., without separation operations.
[0043]

The organosilicon compound of general formula (1) is subjected to a deprotection reaction
and is turned into an aminoaryl-containing organosilicon compound of general formula (6):

(where R6, R7, R8, and R9 independently represent a hydrogen atom, an alkyl group with 1 to
4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms;
R10 represents a univalent hydrocarbon group;
Y represents a hydrolysable group;
n is an integer from 1 to 4; and
m is an integer between 1 and n).

[0044]
The deprotection reaction is a reaction that is carried out, preferably in the presence of a
catalyst, between a compound having an active hydrogen atom and the organosilicon
compound of general formula (1).
[0045]
A catalyst suitable for the aforementioned reaction is a compound that can be used as an
acidic or a basic compound. The acidic compound may be represented by a mineral acid or its
salt, such as a hydrochloric acid, sulfuric acid, aminonium chloride, etc. The basic compound
can be exemplified by a metal hydroxide or alkoxide, such as sodium hydroxide, potassium
hydroxide, sodium methoxide, or the like. In some cases, when impurities or by-products
present in the reaction system may function as catalysts, the reaction may be carried out
without addition of a catalyst.
[0046]
From the view point of improved reactivity to the organosilicon compound of general
formula (1), it is recommended that the aforementioned compound with active hydrogen
comprises one with a hydroxyl group. Examples of such compounds are water, methanol,
ethanol, and the like.
[0047]
It is recommended that deprotection be carried out at a temperature close to room
temperature, but if necessary, the deprotection reaction can be carried out with heating. The
reaction may be carried out without the presence of a solvent in the reaction system. If
necessary, however, a solvent, neutral to the reagents of the reaction, such as toluene, xylene,
heptene, tetrahydrofuran, etc. can be present.
[0048]
Upon completion of the deprotection reaction, the aminoaryl-containing organosilicon
compound of general formula (6) can be purified to a sufficient purity by removing by-
products via stripping. If necessary, further purification can be conducted by distillation or
by other means.

[0049]
A product of hydrolyzation of the aminoaryl-containing organosilicon compound of general
formula (6) can be obtained by reacting the aminoaryl-containing organosilicon compound of
general formula (6) with water as a compound that contains active hydrogen. In case the
active-hydrogen containing compound is water, the deprotection reaction can be carried out
simultaneously with the hydrolyzation reaction, whereby synthesis of a product of hydrolysis
of the aminoaryl-containing organosilicon compound of general formula (6) can be
simplified.
[0050]
The following are examples of the aforementioned aminoaryl-containing organosilicon
compounds of general formula (6) and products of the hydrolyzation: p-aminophenyl-
trimethylsilane, bis (p-aminophenyl) dimethylsilane, p-aminophenyl-trimethoxysilane, bis (p-
aminophenyl) dimethoxysilane, p-aminophenyl-dimethylmethoxysilane, p-aminophenyl-
triethoxysilane, 1,3-bis (p-aminophenyl) 1,1,3,3-tetramethylsiloxane, m-
aminophenyltrimethylsilane, m-aminophenyltrimethoxysilane, o-aminophenyl-
trimethylsilane, o-arrdnophenyltrimethoxysilane, (4-amino-3,5-diethylphenyl)
trimethylsilane, etc.
[Practical Examples]
[0051]
The invention will be further described in more detail with reference to practical examples,
which, however, should not be construed as limiting the scope of application of the invention.
[0052]
[Practical Example 1]
A1-liter four-neck flask equipped with a thermometer, stirrer, and a refiuxing cooler was
loaded with 63.8 g (0.5 mole) of p-chloroaniline, 111.3 g (1.1 mole) of triethylamine, and
toluene (200 g). While the components were stirred, a solution of 107.6 g (0.5 mole) of 1,2-
bis (chlorodimethylsilyl) ethane in 60 g of toluene were added dropwise. The reaction heat
raised the temperature in the system from room temperature to 45°C. After the reaction
mixture was aged by hot refiuxing for 2 hours at 110°C, it was cooled to room temperature,

the salt was removed by filtering, and after the solvent was removed by distillation in
vacuum, a compound of general formula (I):

was produced with a yield of 89%.
[0053]
[Practical Example 2]
A 300-milliliter four-neck flask equipped with a thermometer, stirrer, and a refluxing cooler
was loaded with 5.35 g (0.22 mole) of magnesium and 54 g of tetrahydrofuran, and then the
content was activated by adding 1.85 g (0.02 mole) of t-butyl chloride, while the components
were stirred in a nitrogen flow.
[0054]
An appropriate Grignard reagent was prepared by adding a solution of 54;0 g (0.2 mole) of
the compound of the aforementioned formula obtained in Practical Example 1 in 54 g of
tetrahydrofuran. The solution was added dropwise at 55°C. The obtained Grignard reagent
solution was added dropwise to a solution of 21.7 g (0.2 mole) of chlorotrimethylsilane in 30
g of tetrahydrofuran. The salt formed in the reaction was removed by filtering, and a
deprotection reaction was carried out by adding 5 0 g of methanol. Sodium methoxide was
added until the liquid became neutral, the solvent was removed by distillation, and the
product was again distilled in vacuum to produce a p-aminophenyltrimethoxysilane with a
yield of 62%.
[0055]
[Practical Example 3]
A compound of formula (H):


was produced with a yield of 79% in the same manner as in Practical Example 1, except that
m-chloroaniline was used instead of the p-chloroaniline.
[0056]
[Practical Example 4]
A 300-milliliter four-neck flask equipped with a thermometer, stirrer, and a refluxing cooler
was loaded with 5.35 g (0.22 mole) of magnesium and 54 g of tetrahydrofuran, and then the
content was activated by adding 3.76 g (0.02 mole) of 1,2-dibromoethane, while the
components were stirred in a nitrogen flow.

[0057]
An appropriate Grignard reagent was prepared by adding a solution of 54.0 g (0.2 mole) of
the compound of the aforementioned formula obtained in Practical Example 3 in 54 g of
tetrahydrofuran. The solution was added dropwise at 55°C. The obtained Grignard reagent
solution was added dropwise to 91.3 g (0.6 mole) of tetramethoxysilane. The salt formed in
the reaction was removed by filtering, and after distillation in vacuum, a compound of
formula (ID):

was produced with a yield of 54%.
[0058]
[Practical Example 5]
A 100-milliliter three-neck flask equipped with a thermometer, stirrer, and a refluxing cooler
was loaded with 33.8 g (0.95 mole) of the compound of the aforementioned formula obtained


in Practical Example 4 and 35 g of tetrahydrofuran. Methanol (15 g) was then added
dropwise. The reaction heat raised the temperature of the system from room temperature to
48°C. After the solvent was removed by distillation, the product was distilled in vacuum to
produce m-aminophenyl trimethoxysilane with a yield of 96%.
[0059],
[Practical Example 6]
An appropriate Grignard reagent corresponding to the compound of formula (H) was
prepared by the same method as in Practical Example 4. The obtained Grignard reagent was
added dropwise to 72.1 g (0.6 mole) of a dimethoxydimethylsilane. The salt formed in the
process was removed by filtering, and the product was distilled in vacuum to produce a
compound of formula (IV):

with the yield of 58%.
[0060]
[Practical Example 7]
A 100-milliliter three-neck flask equipped with a thermometer, stirrer, and a refluxing cooler
was loaded with 40.7 g (0.126 mole) of the compound of aforementioned formula (IV).
Methanol (10 g) was then added dropwise. The reaction heat raised the temperature of the
system from room temperature to 65°C. After the residual methanol was removed by
distillation, the product was distilled in vacuum to produce m-aminophenyl
dimethylmethoxysilane with a yield of 96%. The obtained product was hydrolyzed,
whereby an oil having 1,3-bis (m-arninophenyl)-1.1.3.3-tetramethyldisiloxane as amain
component was obtained.

We Claim :
1. A method of manufacturing an organosilicon compound of general formula (1):

where,
R1, R2, R3, and R4 independently represent alkyl groups with 1 to 4 carbon atoms;
R5 represents an oxygen atom or an alkylene group with 1 to 6 carbon atoms;
R6, R7, R8, and R9 independently represent a hydrogen atom, an alkyl group with 1 to 4
carbon atoms, or an alkoxy group with 1 to 4 carbon atoms;
R10 represents a univalent hydrocarbon group;
7 represents a halogen atom or an alkoxy group with 1 to 4 carbon atoms;
n is an integer from 1 to 4; and
m is an integer between 1 and n,
said method being characterized by causing a reaction between a compound of
general formula (2):


where R1, R2, R3, R4, R5,R6, R7, R8, and R9 are the same as defined above, and X
designates a halogen atom) and an active metal or a metalloorganic compound of
general formula (3):
R11MX (3)
where R11 is a univalent hydrocarbon group, M is a bivalent metal, and X is a halogen
atom), thus preparing a Grignard compound of general formula (4):

where R1, R2, R3, R4, R5,R6, R7, R8, R9, M, and X are the same as defined above), and
then causing a reaction between the obtained Grignard compound and an organosilicon
compound of general formula (5):
YnSiR104-n (5)
where Y, R10, and n are the same as defined above.
2. The method as claimed in claim 1 optionally comprising subjecting said manufacturing


where R1 to R10, Y, n and m are as defined in Claim 1, to a deprotection reaction to give an
aminoaryl-containing organosilicon compound represented by general formula (6):

where R6, R7, R8, R9, R10, Y, n, and m are the same as defined above.
3. A compound of general formula (4):

where R1 to R9, M and X are the same as defined in claim 1.


ABSTRACT

PREPARATION OF AN AMINOARYL-CONTAINING ORGANOSILICON COMPOUND AND
METHODS OF PREPARING INTERMEDIATES USED IN ITS PREPARATION
A method of manufacturing an organosilicon compound of general formula (1):

said method being characterized by causing a reaction between a compound of general formula (2):

and an active metal or a metalloorganic compound of general formula (3):
R11MX (3)
thus preparing a Grignard compound of general formula (4):

where R1, R2, R3, R4, R5,R6, R7, R8, R9, R10, R11, M, X, Y,m and n are as defined in the specification.

Documents:

01277-kolnp-2007-abstract.pdf

01277-kolnp-2007-assignment.pdf

01277-kolnp-2007-claims1.0.pdf

01277-kolnp-2007-claims1.1.pdf

01277-kolnp-2007-correspondence others 1.1.pdf

01277-kolnp-2007-correspondence others.pdf

01277-kolnp-2007-description complete.pdf

01277-kolnp-2007-form 1.pdf

01277-kolnp-2007-form 3 1.1.pdf

01277-kolnp-2007-form 3.pdf

01277-kolnp-2007-form 5.pdf

01277-kolnp-2007-international publication.pdf

01277-kolnp-2007-international search report.pdf

01277-kolnp-2007-pct priority document notification.pdf

01277-kolnp-2007-priority document.pdf

1277-KOLNP-2007-(17-02-2012)-CORRESPONDENCE.pdf

1277-KOLNP-2007-ABSTRACT 1.1.pdf

1277-KOLNP-2007-ABSTRACT.pdf

1277-KOLNP-2007-ASSIGNMENT 1.1.pdf

1277-KOLNP-2007-ASSIGNMENT.pdf

1277-KOLNP-2007-CLAIMS 1.1.pdf

1277-KOLNP-2007-CLAIMS.pdf

1277-KOLNP-2007-CORRESPONDENCE 1.1.pdf

1277-KOLNP-2007-CORRESPONDENCE 1.2.pdf

1277-KOLNP-2007-CORRESPONDENCE.pdf

1277-KOLNP-2007-DESCRIPTION (COMPLETE) 1.1.pdf

1277-KOLNP-2007-DESCRIPTION (COMPLETE).pdf

1277-KOLNP-2007-EXAMINATION REPORT.pdf

1277-KOLNP-2007-FORM 1 1.1.pdf

1277-KOLNP-2007-FORM 1.pdf

1277-KOLNP-2007-FORM 13 1.1.pdf

1277-KOLNP-2007-FORM 13 1.2.pdf

1277-KOLNP-2007-FORM 18 1.1.pdf

1277-KOLNP-2007-FORM 18 1.2.pdf

1277-kolnp-2007-form 18.pdf

1277-KOLNP-2007-FORM 2 1.1.pdf

1277-KOLNP-2007-FORM 2.pdf

1277-KOLNP-2007-FORM 3 1.1.pdf

1277-KOLNP-2007-FORM 3 1.2.pdf

1277-KOLNP-2007-FORM 3.pdf

1277-KOLNP-2007-FORM 5 1.1.pdf

1277-KOLNP-2007-FORM 5.pdf

1277-KOLNP-2007-GPA 1.1.pdf

1277-KOLNP-2007-GPA.pdf

1277-KOLNP-2007-GRANTED-ABSTRACT.pdf

1277-KOLNP-2007-GRANTED-CLAIMS.pdf

1277-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

1277-KOLNP-2007-GRANTED-FORM 1.pdf

1277-KOLNP-2007-GRANTED-FORM 2.pdf

1277-KOLNP-2007-GRANTED-SPECIFICATION.pdf

1277-KOLNP-2007-OTHERS 1.1.pdf

1277-KOLNP-2007-OTHERS.pdf

1277-KOLNP-2007-REPLY TO EXAMINATION REPORT 1.1.pdf

1277-KOLNP-2007-REPLY TO EXAMINATION REPORT 1.2.pdf

1277-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

1277-KOLNP-2007-SPECIFICATION 1.1.pdf

1277-KOLNP-2007-SPECIFICATION.pdf

1277-KOLNP-2007-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf


Patent Number 254013
Indian Patent Application Number 1277/KOLNP/2007
PG Journal Number 37/2012
Publication Date 14-Sep-2012
Grant Date 12-Sep-2012
Date of Filing 11-Apr-2007
Name of Patentee DOW CORNING TORAY CO., LTD.
Applicant Address 1-3, MARUNOUCHI 1-CHOME, CHIYODA-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 WAKITA, KEIJI C/O DOW CORNING TORAY CO., LTD. 2-2, CHIGUSAKAIGAN, ICHIHARA-SHI, CHIBA, 2990108
2 SUGIURA, YASUSHI C/O DOW CORNING TORAY CO., LTD. 2-2, CHIGUSAKAIGAN, ICHIHARA-SHI, CHIBA, 2990108
PCT International Classification Number C07F 7/08
PCT International Application Number PCT/JP2005/018723
PCT International Filing date 2005-10-04
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2004-291548 2004-10-04 Japan