U.S. patent application number 09/879280 was filed with the patent office on 2001-12-13 for preparation of (polycyclic secondary-amino) dialkoxysilane.
This patent application is currently assigned to Ube Industries, Ltd.. Invention is credited to Ikeuchi, Hiroyuki, Oue, Masayoshi, Sakakibara, Yasuhisa.
Application Number | 20010051723 09/879280 |
Document ID | / |
Family ID | 26593717 |
Filed Date | 2001-12-13 |
United States Patent
Application |
20010051723 |
Kind Code |
A1 |
Ikeuchi, Hiroyuki ; et
al. |
December 13, 2001 |
Preparation of (polycyclic secondary-amino) dialkoxysilane
Abstract
A (polycyclic secondary-amino)dialkoxysilane favorably
employable as a catalyst for polymerization of .alpha.-olefin can
be prepared by reacting tetrachlorosilane or a mono
(C.sub.1-C.sub.8) alkyltrichlorosilane with a polycyclic
secondary-amine in a non-hydrous, non-alcoholic organic solvent in
the presence of a hydrogen chloride-trapping reagent, to produce a
(polycyclic secondary-amino) chlorosilane and reacting the
(polycyclic secondary-amino) chlorosilane with an alkali metal
alkoxide or an alkaline earth metal alkoxide in the presence of a
lower alcohol.
Inventors: |
Ikeuchi, Hiroyuki; (Chiba,
JP) ; Sakakibara, Yasuhisa; (Chiba, JP) ; Oue,
Masayoshi; (Yamaguchi, JP) |
Correspondence
Address: |
REED SMITH LLP
375 PARK AVENUE
NEW YORK
NY
10152
US
|
Assignee: |
Ube Industries, Ltd.
|
Family ID: |
26593717 |
Appl. No.: |
09/879280 |
Filed: |
June 12, 2001 |
Current U.S.
Class: |
546/14 ;
548/406 |
Current CPC
Class: |
C07F 7/188 20130101;
C07F 7/126 20130101; C07F 7/025 20130101 |
Class at
Publication: |
546/14 ;
548/406 |
International
Class: |
C07F 007/10 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 12, 2000 |
JP |
2000-174740 |
Feb 7, 2001 |
JP |
2001-030886 |
Claims
What is claimed is:
1. A process for preparing a (polycyclic
secondary-amino)dialkoxysilane which comprises the steps of:
reacting tetrachlorosilane or a
mono(C.sub.1-C.sub.8)alkyltrichlorosilane with a polycyclic
secondary-amine in an essentially non-hydrous, non-alcoholic
organic solvent in the presence of a hydrogen chloride-trapping
reagent, to produce a (polycyclic secondary-amino)chlorosilane; and
reacting the (polycyclic secondary-amino)chlorosilane with an
alkali metal alkoxide or an alkaline earth metal alkoxide in the
presence of a lower alcohol.
2. The process of claim 1, wherein the (polycyclic
secondary-amino)chloros- ilane produced in the non-alcoholic
organic solvent is caused to react with the reaction with an alkali
metal alkoxide or an alkaline earth metal alkoxide in the presence
of a lower alcohol, without isolation from the organic solvent.
3. The process of claim 2, wherein a salt which is formed by a
reaction between the hydrogen chloride-trapping reagent and
hydrogen chloride produced in the reaction between the
tetrachlorosilane or a mono(C.sub.1-C.sub.8)alkyltrichlorosilane
with a polycyclic secondary-amine is removed after the first step
is complete.
4. The process of claim 3, wherein the removal of the salt is
performed by filtration or a combination of dissolution of the salt
in an aqueous solvent and removal of the aqueous solvent containing
the salt.
5. The process of claim 1, wherein the non-alcoholic organic
solvent is an aliphatic hydrocarbon having 5 to 8 carbon atoms.
6. The process of claim 1, wherein the lower alcohol is methanol or
ethanol.
7. The process of claim 1, wherein the polycyclic secondary-amine
is perhydroisoquinoline or perhydroquinoline.
8. The process of claim 1, wherein the
mono(C.sub.1-C.sub.8)alkyltrichloro- silane is
methyltrichlorosilane or ethyltrichlorosilane.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a process for preparing
(polycyclic secondary amino)dialkoxysilanes.
BACKGROUND OF THE INVENTION
[0002] A great number of silane compounds have been proposed as
catalyst components for enhancing stereoregularity in the
polymerization of .alpha.-olefins. Particularly, (polycyclic
secondary-amino)dialkoxysilane- s have been known as good catalyst
components and paid attention.
[0003] U.S. Pat. No. 5,939,573 (issued Aug. 17, 1999) describes a
process for the preparation of di(polycyclic amino)dimethoxysilanes
utilizing Grignard reaction. The Grignard reaction requires a
specific reaction solvent such as a dialkyl ether or a cyclic
ether. Further, it is required to frequently treat byproduced
magnesium methoxyhalide with extraction in the course of the
reaction for recovering the target product.
[0004] Japanese Patent Provisional Publication No. 11-130785
discloses an alternative process in which tetrachlorosilane, a
polycyclic secondary amine, and an alcohol are reacted in the
presence of a hydrogen chloridetrapping reagent such as an amine
compound, to prepare a di(polycyclic amino)dialkoxysilane.
[0005] Japanese Patent Provisional Publication No. 11-158190
discloses another alternative process in which tetrachlorosilane, a
polycyclic secondary amine, and an alkali metal alkoxide or an
alkaline earth metal alkoxide are reacted in the presence of the
hydrogen chloridetrapping reagent, to prepare a di(polycyclic
amino)dialkoxysilane.
[0006] The latter two preparing processes utilizing no Grignard
reaction have disadvantageous features in that a relatively great
amount of impurities are produced and the yield of the target
compound is relatively low.
[0007] It is an object of the present invention to provide a
process for preparing (polycyclic secondary-amino)dialkoxysilanes
with a high purity and a high yield.
SUMMARY OF THE INVENTION
[0008] The present invention resides in a process for preparing a
(polycyclic secondary-amino)dialkoxysilane which comprises the
steps of:
[0009] reacting tetrachlorosilane or a
mono(C.sub.1-C.sub.8)alkyltrichloro- silane with a polycyclic
secondary-amine in an essentially non-hydrous, non-alcoholic
organic solvent in the presence of a hydrogen chloride-trapping
reagent, to produce a (polycyclic secondary-amino)chlorosilane;
and
[0010] reacting the (polycyclic secondary-amino)chlorosilane with
an alkali metal alkoxide or an alkaline earth metal alkoxide in the
presence of a lower alcohol.
[0011] The reactants and the products in the reaction adopted in
the reaction of the process of the invention can be stated by
chemical formulas as follows:
Tetrachlorosilane: SiCl.sub.4
Mono (C.sub.1-C.sub.8) alkyltrichlorosilane:
R.sup.1.sub.mSiCl.sub.3
(Polycyclic secondary-amino)chlorosilane:
R.sub.kR.sup.1.sub.mSiCl.sub.2
(Polycyclic secondary-amino)dialkoxysilane:
R.sub.kR.sup.1.sub.mSi(OR.sup.- 2).sub.2
[0012] In the above-mentioned formulas, R represents a polycyclic
secondary-amino group, each of R.sup.1 and R.sup.2 independently
represents a hydrocarbyl group having 1 to 8 carbon atoms, k is 1
or 2, and m is 0 or 1.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The steps of the process according to the invention are
further described below in more detail.
[0014] The first step are directed to the preparation of a
(polycyclic secondary-amino)chlorosilane by reacting
tetrachlorosilane or a mono(C.sub.1-C.sub.8)alkyltrichlorosilane
with a polycyclic secondary-amine in an essentially nonhydrous,
non-alcoholic organic solvent in the presence of a hydrogen
chloride-trapping reagent.
[0015] Representative polycyclic secondary amines are polycyclic
perhydro secondary amines. Their examples include amine compounds
having cyclohexyl ring such as perhydroindole, perhydroisoindole,
perhydroquinoline, perhydroisoquinoline, perhydrocarbazole,
perhydroiminostilbene, perhydroacridine, and
perhydrobenzo[f]quinoline, perhydrobenzo[g]quinoline,
perhydrobenzo[g]isoquinoline, and perhydrophenanthoridine. One or
more substituents such as alkyl, phenyl, and cycloalkyl can be
attached to the carbon atom(s) of the cyclohexyl ring.
[0016] Preferable polycyclic secondary amines are perhydroindole,
perhydroisoindole, perhydroquinoline, perhydroisoquinoline, and
their derivatives having one or more substituents. These polycyclic
secondary-amines can be in the cis form, in the trans form, and in
their mixture.
[0017] The mono(C.sub.1-C.sub.8)alkyltrichlorosilane preferably is
methyltrichlorosilane and ethyltrichlorosilane. Tetrachlorosilane
is also preferred.
[0018] The reaction solvent is a non-alcoholic organic solvent.
Their examples include inert hydrocarbon solvents such as pentane,
hexane, heptane, octane, cyclohexane, benzene, toluene and hexane
and non-alcoholic polar organic solvents having no active hydrogens
such as ethers, ketones, esters, and amines. The hydrocarbon
solvents are preferred so as to readily separate and recover a salt
of the hydrogen chloride-trapping reagent with by-produced hydrogen
chloride from the reaction mixture. Preferred are low boiling-point
solvents such as pentane, hexane, and heptane.
[0019] The non-alcoholic organic solvent to be employed in the
reaction should be essentially anhydrous. The term of "essentially
anhydrous" is used to mean the water content of not more than 1 wt.
%, specifically not more than 0.1 wt. %, more specifically not more
than 0.03 wt. %.
[0020] The hydrogen chloride-trapping reagent can be any basic
nitrogen containing compound or any phosphorus compound. Examples
are amines, amides, imines, nitrites, and oximes. Preferred
examples of the hydrogen chloridetrapping reagents include
trimethylamine, triethylamine, tripropylamine, tributylamine,
trihexylamine, dimethylphenylamine, triphenylamine,
N-methylpyrolidine, Nmethylpiperidine, and their derivatives.
Preferred examples also include aromatic heterocyclic compounds
such as pyridine, quinoline, isoquinoline, and their derivatives.
Most preferred is triethylamine.
[0021] Alternatively, the polycyclic secondary amine, which is one
of the starting compounds in the first step, can be employed in an
excessive amount so that the additional secondary amine can serve
as the hydrogen chloride-trapping reagent.
[0022] In performing the reaction of the first step,
tetrachlorosilane or monoalkyltrichlorosilane is preferably brought
into contact with a polycyclic secondary amine in the presence of a
hydrogen chloride-trapping reagent. For instance, it is preferred
that a mixture of a hydrogen chloride-trapping reagent and a
polycyclic secondary amine is dropwise added to a reaction solvent
containing the chlorosilane compound.
[0023] The reaction of the first step is ordinarily performed at a
temperature of -30 to 100.degree. C., preferably at -10 to
60.degree. C., ordinarily for a period of 1 to 1,000 minutes,
preferably for 5 to 500 minutes.
[0024] The (polycyclic secondary-amino)chlorosilane can be
represented by the formula of R.sub.kR.sup.1.sub.mSiCl.sub.2 (R is
a polycyclic secondary-amino group, R.sup.1 is a hydrocarbyl group
having 1 to 8 carbon atoms, k is 1 or 2, and m is 0 or 1). Examples
are bis(polycyclic secondary amino)dichlorosilanes and
alkyl(polycyclic secondary amino)dichlorosilanes.
[0025] Examples of the (polycyclic secondary-amino)chlorosilanes
include bis(perhydroindolino)dichlorosilane,
bis(perhydroisoindolino)dichlorosila- ne,
bis(perhydroquinolino)dichlorosilane,
bis(perhydroisoquinolino)dichlor- osilane,
methyl(perhydroindolino)dichlorosilane, methyl(perhydroisoindolin-
o)dichlorosilane, methyl(perhydroquinolino)dichlorosilane,
methyl(perhydroisoquinolino)dichlorosilane,
ethyl(perhydroindolino)dichlo- rosilane,
ethyl(perhydroisoindolino)dichlorosilane,
ethyl(perhydroquinolino)dichlorosilane,
ethyl(perhydroisoquinolino)dichlo- rosilane,
n-propyl(perhydroindolino)dichlorosilane,
n-propyl(perhydroisoindolino)dichlorosilane,
n-propyl(perhydroquinolino)d- ichlorosilane, n-propyl
(perhydroisoquinolino)dichlorosilane,
isopropyl(perhydroindolino)dichlorosilane,
isopropyl(perhydroisoindolino)- dichlorosilane,
isopropyl(perhydroquinolino)dichlorosilane,
isopropyl(perhydroisoquinolino)dichlorosilane,
n-butyl(perhydroindolino)d- ichlorosilane,
n-butyl(perhydroisoindolino)dichlorosilane,
n-butyl(perhydroquinolino)dichlorosilane,
n-butyl(perhydroisoquinolino)di- chlorosilane,
isobutyl(perhydroindolino)dichlorosilane,
isobutyl(perhydroisoindolino)dichlorosilane,
isobutyl(perhydroquinolino)d- ichlorosilane,
isobutyl(perhydroisoquinolino)dichlorosilane,
sec-butyl(perhydroindolino)dichlorosilane,
sec-butyl(perhydroisoindolino)- dichlorosilane,
sec-butyl(perhydroquinolino)dichlorosilane,
secbutyl(perhydroisoquinolino)dichlorosilane,
ter-butyl(perhydroindolino)- dichlorosilane,
ter-butyl(perhydroisoindolino)dichlorosilane,
ter-butyl(perhydroquinolino)dichlorosilane,
ter-butyl(perhydroisoquinolin- o)dichlorosilane,
cyclopentyl(perhydroindolino)dichlorosilane,
cyclopentyl(perhydroisoindolino)dichlorosilane,
cyclopentyl(perhydroquino- lino)dichlorosilane,
cyclopentyl(perhydroisoquinolino)dichlorosilane,
cyclohexyl(perhydroindolino)dichlorosilane,
cyclohexyl(perhydroisoindolin- o)dichlorosilane,
cyclohexyl(perhydroquinolino)dichlorosilane, and
cyclohexyl(perhydroisoquinolino)dichlorosilane.
[0026] In the course of the reaction of the first step, a salt of a
hydrogen chloride-trapping reagent and by-produced hydrogen
chloride is produced in the reaction mixture. The reaction mixture
containing the salt of hydrogen chloride-trapping reagent and
by-produced hydrogen chloride can be directly subjected to the
reaction of the second step. It is preferred, however, that the
salt is removed from the reaction mixture before the reaction
mixture is subjected to the reaction of the second step. The
removal of the salt from the reaction step can be performed by
filtration or a combination of extraction with an aqueous solvent
and separation of the aqueous extract.
[0027] In the second procedure, the reaction mixture of the first
step is mixed with water, so as to dissolve the salt in water, and
the water portion is separated. The remaining organic solution is
then dehydrated and subjected to the reaction of the second step.
The water to be mixed with the reaction mixture preferably is in
such amount that the water dissolve the whole amount of the
by-produced salt. The dehydration of the reaction mixture subjected
to the extraction with water can be carried out using a dehydrating
reagent such as molecular sieve. It is preferred that almost whole
water content is removed from the reaction mixture.
[0028] In the second step, the (polycyclic
secondary-amino)chlorosilane is caused to react with an alkali
metal alkoxide or an alkaline earth metal alkoxide in the presence
of a lower alcohol. Generally, the reaction mixture obtained in the
first step per se is, directly or after removal of the by-produced
salt, subjected to the second step. A portion of the solvent of the
reaction mixture can be removed, or an essentially non-hydrous
organic solvent can be added.
[0029] The alkali metal can be sodium or potassium. The alkaline
earth metal can be magnesium or calcium. The alkoxide can be
methoxide or ethoxide. Sodium methoxide is most preferred.
[0030] The lower alcohol employed in the second step preferably is
methanol, ethanol, or propanol. Methanol is most preferred.
[0031] The alkali metal alkoxide or alkaline earth metal alkoxide
is preferably employed in the form of an alcoholic solution,
particularly a homogeneous alcoholic solution. In the alcoholic
solution, the alkoxide is generally contained in an amount of 10
wt. % or more, preferably in an amount of 20 wt. % or more. Most
preferred is a concentration in the range of 20 to 40 wt. %.
[0032] It is preferred that a solution of sodium methoxide in
methanol is employed in the reaction of the second step.
[0033] The alcoholic solution of an alkali metal alkoxide or an
alkaline earth metal alkoxide can be produced by dissolving the
alkali metal alkoxide or alkaline earth metal alkoxide in a lower
alcohol. In place of the alkali metal alkoxide or alkaline earth
metal alkoxide, an alkali metal hydride, an alkaline earth metal
hydride, an organic alkali metal compound, or an organic alkaline
earth metal compound can be dissolved in a lower alcohol.
[0034] Examples of the alkali metal or alkaline earth metal
hydrides include lithium hydride, sodium hydride, and magnesium
hydride. Examples of the organic alkali metal compounds include
butyl lithium, phenyl lithium, and cyclopentadienyl sodium.
Examples of the organic alkaline earth metal compounds include
dialkylmagnesiums such as dibutylmagnesium, butylethylmagnesium,
and dihexylmagnesium, and Grignard compounds such as alkylmagnesium
chloride, alkylmagnesium bromide, and alkylmagnesium iodide. In the
Grignard compounds, the alkyl can be methyl, ethyl, propyl, butyl,
hexyl, or octyl.
[0035] The hydrogen chloride-trapping reagent, polycyclic secondary
amines, alkali metal or alkaline earth metal alkoxide, and reaction
solvents employed in the reactions of the invention are also
preferred to have a water content as small as possible.
[0036] The reaction of the second step is ordinarily carried out at
a temperature of -30 to 100.degree. C., preferably at -10 to
80.degree. C., more preferably 0 to 70.degree. C., ordinarily for a
period of 1 to 1,000 minutes, preferably for 3 to 500 minutes.
[0037] In the case that triethylamine is employed as the hydrogen
chloride-trapping agent, a molar ratio of the chlorosilane
compound/polycyclic secondary amine ordinarily is in the range of
0.3 to 1.3, preferably 0.4 to 1.2. The polycyclic secondary amine
can be employed singly or in combination of two amines. In the case
that two polycyclic secondary amines are employed in combination, a
molar ratio of the chlorosilane compound/one polycyclic secondary
amine ordinarily is in the range of 0.9 to 1.1, preferably 0.95 to
1.05. The polycyclic secondary amine can be employed singly or in
combination of two amines. In the case that the polycyclic
secondary amine is employed in excessive amount so that a portion
of the amine can serve as the hydrogen chloride-trapping reagent, a
molar ratio of the chlorosilane compound/polycyclic secondary amine
ordinarily is in the range of 0.1 to 0.6, preferably 0.15 to
0.55.
[0038] The hydrogen chloride-trapping reagent is employed at a
molar ratio of generally 0.3 to 1.5, preferably 0.4 to 1.35, in
terms of chlorosilane compound/hydrogen chloride-trapping reagent.
The alkali metal alkoxide or alkaline earth metal alkoxide is
employed at a molar ratio of generally 0.1 to 0.6, preferably 0.15
to 0.55, in terms of chlorosilane compound/alkoxide.
[0039] As describe hereinbefore, when the second step is started
after completion of the first step, the salt of a hydrogen
chloride-trapping reagent and by-produced hydrogen chloride formed
in the reaction of the first step can be separated. The separated
salt can be neutralized with an aqueous alkaline solution such as
an aqueous sodium hydroxide solution to recover the hydrogen
chloride-trapping reagent. The recovered reagent may be then
purified for the use as the hydrogen-trapping reagent.
[0040] According to the process of the invention, a bis(polycyclic
perhydroamino)dialkoxysilane is produced when tetrachlorosilane is
employed, while an alkyl(polycyclic perhydroamino)dialkoxysilane is
produced when a monoalkyltrichlorosilane is employed.
[0041] Representative bis(polycyclic perhydroamino)dialkoxysilanes
are bis(polycyclic perhydroamino)dimethoxysilanes such as
bis(perhydroisoquinolino)dimethoxysilane,
bis(perhydroquinolino)dimethoxy- silane,
bis(perhydroindolino)dimethoxysilane, and bis(perhydroisoindolino)-
dimethoxysilane.
[0042] The bis(polycyclic perhydroamino)dimethoxysilane can be
present in geometric isomers such as cis-form and trans-form.
Therefore, there are three geometric isomers such as
bis(cis-polycyclic perhydroamino)dimethoxysilane,
bis(trans-polycyclic perhydroamino)dimethoxysilane, and
(cis-polycyclic perhydroamino)(trans-polycyclic
perhydroamino)dimethoxysilane. In the case of
bis(perhydroisoquinolino)dimethoxysilane, there are three geometric
isomers, i.e., bis(cis-perhydroisoquinolino)dimethoxysilane,
bis(trans-perhydroisoquinolino)dimethoxysilane, and
(cisperhydroisoquinolino)(trans-perhydroisoquinolino)di
methoxysilane.
[0043] Representative examples of the alkyl(polycyclic
perhydroamino)dialkoxysilanes are alkyl(polycyclic
perhydroamino)dimethoxysilanes. Examples of the alkyl(polycyclic
perhydroamino)dimethoxysilanes include
methyl(perhydroindolino)dimethoxys- ilane,
methyl(perhydroisoindolino)dimethoxysilane,
methyl(perhydroquinolin- o)dimethoxysilane,
methyl(perhydroisoquinolino)dimethoxysilane,
ethyl(perhydroindolino)dimethoxysilane,
ethyl(perhydroisoindolino)dimetho- xysilane,
ethyl(perhydroquinolino)dimethoxysilane, ethyl(perhydroisoquinol-
ino)dimethoxysilane, n-propyl(perhydroindolino)dimethoxysilane,
n-propyl(perhydroisoindolino)dimethoxysilane,
n-propyl(perhydroquinolino)- dimethoxysilane,
n-propyl(perhydroisoquinolino)dimethoxysilane,
isopropyl(perhydroindolino)dimethoxysilane,
isopropyl(perhydroisoindolino- )dimethoxysilane,
isopropyl(perhydroquinolino)dimethoxysilane,
isopropyl(perhydroisoquinolino)dimethoxysilane,
n-butyl(perhydroindolino)- dimethoxysilane,
n-butyl(perhydroisoindolino)dimethoxysilane,
n-butyl(perhydroquinolino)dimethoxysilane,
n-butyl(perhydroisoquinolino)d- imethoxysilane,
isobutyl(perhydroindolino)dimethoxysilane,
isobutyl(perhydroisoindolino)dimethoxysilane,
isobutyl(perhydroquinolino)- dimethoxysilane,
isobutyl(perhydroisoquinolino)-dimethoxysilane,
sec-butyl(perhydroindolino)dimethoxysilane,
sec-butyl(perhydroisoindolino- )dimethoxysilane,
sec-butyl(perhydroquinolino)dimethoxysilane,
secbutyl(perhydroisoquinolino)dimethoxysilane,
ter-butyl(perhydroindolino- )dimethoxysilane,
ter-butyl(perhydroisoindolino)dimethoxysilane,
ter-butyl(perhydroquinolino)dimethoxysilane,
ter-butyl(perhydroisoquinoli- no)dimethoxysilane,
cyclopentyl(perhydroindolino)dimethoxysilane,
cyclopentyl(perhydroisoindolino)dimethoxysilane,
cyclopentyl(perhydroquin- olino)dimethoxysilane,
cyclopentyl(perhydroisoquinolino)dimethoxysilane,
cyclohexyl(perhydroindolino)dimethoxysilane,
cyclohexyl(perhydroisoindoli- no)dimethoxysilane,
cyclohexyl(perhydroquinolino)dimethoxysilane, and
cyclohexyl(perhydroisoquinolino)dimethoxysilane.
[0044] The present invention is further described by the following
examples.
[0045] In the following examples, the reaction products were gas
chromatographically analyzed using the apparatuses described
below.
[0046] GC-14A (Shimazu Seisakusho Co., Ltd.), FID detector, glass
capillary column: G-100 (20 m), column temperature: 100.degree. C.
to 260.degree. C., rate of temperature elevation: 20.degree.
C./min., detector temperature: 280.degree. C., injection
temperature: 280.degree. C., carrier gas: helium (flow rate: 50
mL/min.)
EXAMPLE 1
[0047] An inner space of a 500 mL-volume flask equipped with a
dropping funnel and a stirring fan is purged with nitrogen gas. In
the flask were then placed 240 mL of nheptane (distilled and
dehydrated) and 3.4 g (20 mmol.) of tetrachlorosilane. Through the
dropping funnel, a mixture of 20 mL of n-heptane (distilled and
dehydrated), 5.6 g (40 nmol.) of perhydroisoquinoline (mixture of
cisform (75 molar %) and trans-form (25 molar %)) and 4.6 g (45
mmol.) of triethylamine (hydrogen chloride-trapping reagent) was
dropwise placed into the flask under chilling with ice. The mixture
in the flask was stirred for 2 hours.
[0048] The reaction mixture was filtered on a glass filter (G4),
and the residue on the filter was washed three portions of
n-heptane (20 mL). The filtrate and washings were combined and
placed again in the same flask equipped with a dropping funnel and
a stirring fan.
[0049] Into the flask was dropwise placed through the dropping
funnel a methanol solution of sodium methoxide (28 wt. % solution),
until 40 mmol. of sodium methoxide was introduced into the flask.
The mixture was then stirred at 25.degree. C. for 8 hours. The
reaction mixture was concentrated and then placed under reduced
pressure to recover the reaction product by distillation.
[0050] There was obtained bis(perhydroisoquinolino)dimethoxysilane
(colorless clear liquid, b.p.: 180.degree. C./1 mmHg). Yield: 94.5%
(on the basis of Si content). Purity: 98.5% (determined gas
chromatographically).
[0051] The residue on the filter was triethylamine hydrochloride,
and triethylamine was recovered by decomposition using 10 mL of 5%
aqueous sodium hydroxide solution.
EXAMPLE 2
[0052] The procedures of Example 1 were repeated except that the
mixture produced by addition of the methanolic sodium methoxide
solution was stirred at 60.degree. C. for 3 hours, to obtain
bis(perhydroisoquinolino)- dimethoxysilane (colorless clear
liquid). Yield: 95.3% (on the basis of Si content). Purity: 99.5%
(determined gas chromatographically).
[0053] The residue on the filter was triethylamine hydrochloride,
and triethylamine was recovered by decomposition using 10 mL of 5%
aqueous sodium hydroxide solution.
EXAMPLE 3
[0054] The procedures of Example 1 were repeated except that
triethylamine (hydrogen chloride-trapping reagent) was not used
while perhydroisoquinoline was used in a double amount (11.2 g, 80
mmol.), to obtain bis(perhydroisoquinolino)dimethoxysilane
(colorless clear liquid). Yield: 92.1% (on the basis of Si
content). Purity: 97.7% (determined gas chromatographically).
[0055] The residue on the filter was triethylamine hydrochloride,
and triethylamine was recovered by decomposition using 10 mL of 5%
aqueous sodium hydroxide solution.
EXAMPLE 4
[0056] The procedures of Example 1 were repeated except for
replacing perhydroisoquinoline with perhydroquinoline (mixture of
cis-form (50 molar %) and trans-form (50 molar %)), to obtain
bis(perhydroquinolino)di- methoxysilane (colorless clear liquid,
b.p.: 189.5.degree. C./1 mmHg)). Yield: 90.1% (on the basis of Si
content). Purity: 97.9% (determined gas chromatographically).
[0057] The residue on the filter was triethylamine hydrochloride,
and triethylamine was recovered by decomposition using 10 mL of 5%
aqueous sodium hydroxide solution.
EXAMPLE 5
[0058] The procedures of Example 4 were repeated except for
replacing the filtration of the residue produced in the first
reaction with the below-mentioned separation procedure, to obtain
bis(perhydroquinolino)dim- ethoxysilane (colorless clear liquid).
Yield: 88.6% (on the basis of Si content). Purity: 98.0%
(determined gas chromatographically).
[0059] Separation procedure: Under chilling with ice, 150 mL of
distilled water is added to the reaction mixture, to dissolve
triethylamine hydrochloride in the water. The mixture separates
into an aqueous layer and a heptane layer. The heptane layer is
recovered using a separating funnel. The heptane layer is
immediately introduced into a flask containing 100 cc of a
synthetic zeolite adsorbent (Zeolam, ball, 3A). The content is
quickly stirred, and filtered.
EXAMPLE 6
[0060] An inner space of a 500 mL-volume flask equipped with a
dropping funnel and a stirring fan is purged with nitrogen gas. In
the flask were then placed 240 mL of nheptane (distilled and
dehydrated) and 6.8 g (40 mmol.) of tetrachlorosilane. Through the
dropping funnel, a mixture of 20 mL of n-heptane (distilled and
dehydrated), 11.2 g (80 mmol.) of perhydroquinoline (mixture of
cisform (50 molar %) and trans-form (50 molar %)) and 9.2 g (90
mmol.) of triethylamine (hydrogen chloride-trapping reagent) was
dropwise placed into the flask under chilling with ice. The mixture
in the flask was stirred for 2 hours.
[0061] Under chilling with ice, 150 mL of distilled water was added
to the reaction mixture, to dissolve triethylamine hydrochloride in
the water. The mixture separated into an aqueous layer and a
heptane layer. The heptane layer was recovered using a separating
funnel. The heptane layer was immediately introduced into a flask
containing 100 cc of a synthetic zeolite adsorbent (Zeolam, ball,
3A). The content was quickly stirred, and filtered. The filtrate
was placed again in the same flask equipped with a dropping funnel
and a stirring fan.
[0062] Into the flask was dropwise placed through the dropping
funnel a methanol solution of sodium methoxide (28 wt. % solution),
until 80 mmol. of sodium methoxide was introduced into the flask.
The mixture was then stirred at 25.degree. C. for 8 hours. The
reaction mixture was concentrated and then placed under reduced
pressure to recover the reaction product by distillation.
[0063] There was obtained bis(perhydroquinolino)dimethoxysilane
(colorless clear liquid). Yield: 89.9% (on the basis of Si
content). Purity: 98.8% (determined gas chromatographically).
EXAMPLE 7
[0064] The procedures of Example 1 were repeated except that
tetrachlorosilane was replaced with ethyltrichlorosilane (3.3 g, 20
mmol.), the distilled and dehydrated nheptane was added in an
amount of 10 mL, perhydroisoquinoline was employed in an mount of
2.8 g (20 mmol.) and triethylamine was added in an amount of 2.6 g
(25 mmol.), to obtain ethyl(perhydroisoquinolino)dimethoxysilane
(colorless clear liquid, b.p.: 120-125.degree. C./0.3 mmHg). Yield:
92.2% (on the basis of Si content). Purity: 98.9% (determined gas
chromatographically).
[0065] The residue on the filter was triethylamine hydrochloride,
and triethylamine was recovered by decomposition using 10 mL of 5%
aqueous sodium hydroxide solution.
COMPARISON EXAMPLE 1
[0066] The procedures of Example 1 were repeated except that a
mixture of 20 mL of n-heptane (distilled and dehydrated), 40 mL of
methanol, and 4.6 g (45 mmol.) of triethylamine was added to the
filtrate obtained in the first step, in place of the methanolic
sodium methoxide solution (28 wt. %), to obtain
bis(perhydroisoquinolino)dimethoxysilane (colorless clear liquid).
Yield: 77.7% (on the basis of Si content). Purity: 91.0%
(determined gas chromatographically).
COMPARISON EXAMPLE 2
[0067] The procedures of Example 1 were repeated except that 40 mL
of n-heptane slurry containing 20 mmol of sodium methoxide was
added to the filtrate obtained in the first step, in place of the
methanolic sodium methoxide solution (28 wt. %), to obtain
bis(perhydroisoquinolino)dimetho- xysilane (colorless clear
liquid). Yield: 81.1% (on the basis of Si content). Purity: 90.8%
(determined gas chromatographically).
* * * * *