Preparation of (polycyclic secondary-amino)dialkoxysilane

Details Preparation of (polycyclic secondary-amino)dialkoxysilane Preparation of (polycyclic secondary-amino)dialkoxysilane

2001-06-12

2002-01-08

Shaver, Paul F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Silicon containing

C556S413000

Reexamination Certificate

active

06337416

ABSTRACT:

CROSS-REFERENCES TO RELATED APPLICATIONS
This application claims Paris Convention priority of Japanese Application Nos. 2000-174740 filed Jun. 12, 2000 and 2001-030886 filed Feb. 7, 2001, the complete disclosure of which are hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to a process for preparing (polycyclic secondary amino)dialkoxysilanes.
BACKGROUND OF THE INVENTION
A great number of silane compounds have been proposed as catalyst components for enhancing stereoregularity in the polymerization of &agr;-olefins. Particularly, (polycyclic secondary-amino)dialkoxysilanes have been known as good catalyst components and paid attention.
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 by-produced magnesium methoxyhalide with extraction in the course of the reaction for recovering the target product.
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 chloride-trapping reagent such as an amine compound, to prepare a di(polycyclic amino)dialkoxysilane.
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 chloride-trapping reagent, to prepare a di(polycyclic amino)dialkoxysilane.
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.
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.
SUMMERY OF THE INVENTION
The present invention resides in a process for preparing a (polycyclic secondary-amino)dialkoxysilane which comprises the steps of:
reacting tetrachlorosilane or a mono(C
1
-C
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.
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
4
Mono(C
1
-C
8
)alkyltrichlorosilane: R
1
m
SiCl
3
(Polycyclic secondary-amino)chlorosilane: R
k
R
1
m
SiCl
2
(Polycyclic secondary-amino)dialkoxysilane: R
k
R
1
m
Si(OR
2
)
2
In the above-mentioned formulas, R represents a polycyclic secondary-amino group, each of R
1
and R
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
The steps of the process according to the invention are further described below in more detail.
The first step are directed to the preparation of a (polycyclic secondary-amino)chlorosilane by reacting tetrachlorosilane or a mono(C
1
-C
8
)alkyltrichlorosilane with a polycyclic secondary-amine in an essentially nonhydrous, non-alcoholic organic solvent in the presence of a hydrogen chloride-trapping reagent.
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.
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.
The mono(C
1
-C
8
)alkyltrichlorosilane preferably is methyltrichlorosilane and ethyltrichlorosilane. Tetrachlorosilane is also preferred.
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.
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. %.
The hydrogen chloride-trapping reagent can be any basic nitrogen containing compound or any phosphorus compound. Examples are amines, amides, imines, nitriles, and oximes. Preferred examples of the hydrogen chloride-trapping reagents include trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, dimethylphenylamine, triphenylamine, N-methylpyrolidine, N-methylpiperidine, and their derivatives. Preferred examples also include aromatic heterocyclic compounds such as pyridine, quinoline, isoquinoline, and their derivatives. Most preferred is triethylamine.
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.
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.
The reaction of the first step is ordinarily performed at a temperature of −30 to 100° C., preferably at −10 to 60° C., ordinarily for a period of 1 to 1,000 minutes, preferably for 5 to 500 minutes.
The (polycyclic secondary-amino)chlorosilane can be represented by the formula of R
k
R
1
m
SiCl
2
(R is a polycyclic secondary-amino group, R
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.
Examples of the (polycyclic secondary-amino)chlorosilanes include bis(perhydroindolino)dichlorosilane, bis(perhydroisoindolino)dichlorosilane, bis(perhydroquinolino)dichlorosilane, bis(perhydroisoquinolino)dichlorosilane, methyl(perhydroindolino)dichlorosilane, methyl(perhydroisoindolino)dichlorosilane, methyl(perhydroquinolino)dichlorosilane, methyl(perhydroisoquinolino)dichlorosilane, ethyl(perhydroindolino)dichlorosilane, ethyl(perhydroisoindolino)dichlorosilane, ethyl(perhydroquinolino)dichlorosilane, ethyl(perhydroisoquinolino)dichlorosilane, n-propyl(perhydroindolino)dichlorosilane, n-propyl(perhydroisoindolino)dichlorosilane, n-propyl(perhydroquinolino)dichlorosilane, n-propyl(perhydroisoquinolino)dichlorosilane, isopropyl(perhydroindolino)dichlorosilane, isopropyl(perhydroisoindolino)

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