Textiles: spinning – twisting – and twining
Reexamination Certificate
2000-04-05
2001-06-26
Shaver, Paul F. (Department: 1621)
Textiles: spinning, twisting, and twining
Reexamination Certificate
active
06251057
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to processes for making the compounds of formula I which comprise a dehydrohalogenative coupling of hydrochlorosilanes of formula II with organic halides of formula III in the presence of Lewis base catalyst.
R
3
CH
2
SiR
1
Cl
2
(I)
HSiR
1
Cl
2
(II)
R
2
CH
2
X (III)
In formulas I and II, R
1
represents a hydrogen, chloro, or methyl; in formula III, X represents a chloro or bromo; in formula III, R
2
can be selected from the group consisting of a C
1-17
alkyl, a C
1-10
fluorinated alkyl with partial or full fluorination, a C
1-5
alkenyl groups, a silyl group containing alkyls, (CH
2
)
n
SiMe
3-m
Cl
m
wherein n is 0 to 2 and m is 0 to 3, aromatic groups, Ar(R′)
q
wherein Ar is C
6-14
aromatic hydrocarbon, R′ is a C
1-4
alkyl, halogen, alkoxy, or vinyl, and q is 0 to 5, a haloalkyl group, (CH
2
)
p
X wherein p is 1 to 9 and X is a chloro or bromo; or an aromatic hydrocarbon ArCH
2
X wherein Ar is C
6-14
aromatic hydrocarbon and X is a chloro or bromo. in formula I, R
3
is the same as R
2
in formula III and further, R
3
can also be (CH
2
)
p
SiR
1
Cl
2
or ArCH
2
SiR
1
Cl
2
when R
2
in formula III is (CH
2
)
p
X or ArCH
2
X, because of the coupling reaction of X with the compound of formula II.
2. Description of the Prior Art
In 1968, Benkeser and Smith reported the reduction of carbon tetrachloride to chloroform by using a 1:1 mixture of trichlorosilane and tertiary amine as reducing agents (Benkeser, R. A.; Smith, W. E.
J. Am. Chem. Soc.
1968, 90, 5307). They proposed that the amine-catalyzed reduction of carbon tetrachloride to chloroform proceeded via the formation of (trichloromethyl)trichlorosilane by the dehydrochlorinative coupling reaction between the carbon tetrachloride and trichlorosilane, and subsequent cleavage of the carbon-silicon bonded species by ammonium chloride to give chloroform and tetrachlorosilane. In 1969, Benkeser and co-workers also reported that benzyl chloride and benzyl chlorides could be silylated with trichlorosilane-tertiary amine 1:1 mixture to give the corresponding trichlorosilyl substituted products by the dehydrochlorinative coupling reaction (Benkeser, R. A., Gaul, J. M.; Smith, W. E.
J. Am. Chem. Soc.
1969, 91, 3666).
In 1975, Furuya and Sukawa reported allytrichlorosilane could be prepared in high yield by a coupling reaction of allyl chloride with a 1:1 mixture of trichlorosilane and tertiary amine in the presence of copper chloride as a catalyst (Furuya, N.; Sukawa, T. J.
Organometal. Chem.
1975, 96, C1).
Recently, Corriu and co-workers reported that the reaction of chloroform with trichlorosilane in the presence of excess tributylamine gave bis(trichlorosily)methane and tris(trichlorosilyl)methane (Corriu, R. J. P.; Granier, M.: Lanneau, G. F.
J. Organometal. Chem.
1998, 562, 79). These reports suggest that a chloroalkyl group containing organic compounds and organosilanes having Si-H bonds could undergo the dehydrochlorinative coupling reaction with trichlorosilane in the presence of an organic base.
The dehydrochlorinative coupling reaction is a novel method of forming silicon-carbon bonds useful for the synthesis of organosilicon compounds. Although the dehydrochlorinative coupling reaction of activated alkyl chlorides such as benzyl chloride or allyl chloride have been reported, the coupling reaction of unactivated alkyl chlorides with trichlorosilane has never been reported. In the previously reports, tertiary amine was used in excess, more than the stoichiometric amount respect to alkyl chloride. The tertiary amine used is a hydrogen chloride scavenger rather than a catalyst. Since the ammonium salt obtained from the tertiary amine and hydrogen chloride have to be neutralized to recycle the amine, it would be too costly to be utilized on an industry scale. It is necessary to find a way to reduce the usage of the amine or find another effective catalyst to apply the coupling reaction for industrial purposes.
The present inventors have discovered that a coupling reaction of alkyl halides and hydrochlorosilanes in the presence of various tertiary amines or tertiary phosphines as a catalyst proceeded to give the corresponding coupled products by liberating hydrogen halide as a gas. The dehydrohalogenative coupling reaction can be applied to not only the activated alkyl halides such as benzyl chloride or allyl chloride, but also to the unactivated alkyl halides such as n-alkylhexyl chloride or haloalkyl substituted organosilicon compound. Suitable amine catalysts include, but are not limited to triethylamine, tri-n-propylamine, tri-n-butylamine, N,N,N′,N′-tetramethylethylenediamine, pyridine, N,N-dimethyltoluidine, N-alkylpyrrolidine. Suitable phosphine catalysts include, but are not limited to tributylphosphine, triethylphosphine, tricyclohexylphosphine, triphenylphosphine, bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, and phosphine coordinated transition metallic compounds such as tetrakis(triphenylphosphine)palladium, tris(triphenylphosphine)rhodium chloride, or tetrakis(triphenylphosphine)platinum.
SUMMARY OF THE INVENTION
The present invention relates to processes for making compounds of formula I which comprises a dehydrohalogenative coupling between hydrochlorosilanes of formula II and organic halides of formula III in the presence of a Lewis base catalyst.
The reaction can be illustrated as follows:
In formulas I and II, R
1
represents a hydrogen, chloro, or methyl; in formula III, X represents a chloro or bromo; in formula III, R
2
can be selected from the group consisting of a C
1-17
alkyl, a C
1-10
fluorinated alkyl with partial or full fluorination, a C
1-5
alkenyl groups, a silyl group containing alkyls, (CH
2
)
n
SiMe
3-m
Cl
m
wherein n is 0 to 2 and m is 0 to 3, aromatic groups, Ar(R′)
q
wherein Ar is C
6-14
aromatic hydrocarbon, R′ is a C
1-4
alkyl, halogen, alkoxy, or vinyl, and q is 0 to 5, a haloalkyl group, (CH
2
)
p
X wherein p is 1 to 9 and X is a chloro or bromo; or an aromatic hydrocarbon, Ar CH
2
X wherein Ar is C
6-14
aromatic hydrocarbon and X is a chloro or bromo. in formula I, R
3
is the same as R
2
in formula III and further, R
3
can also be (CH
2
)
p
SiR
1
Cl
2
or ArCH
2
SiR
1
Cl
2
when R
2
in formula III is (CH
2
)
p
X or ArCH
2
X, because of the coupling reaction of X with the compound of formula II.
DETAILED DESCRIPTION OF THE INVENTION
In a sealed stainless steel tube, hydrochlorosilane represented by formula II, organic halide of formula III, solvent, and catalyst are placed all together under inert atmosphere. The amount of hydrochlorosilane of formula II used is two times or more, preferably 2 to 5 folds, relative to the amount of the compounds of formula III. Lewis bases of tertiary amine or tertiary phosphine are used as a catalyst in an amount sufficient to catalyze the reaction, generally, about 0.01 to 0.4 moles of the catalyst per mole of the organic halide of formula III. The catalysts can be represented by the following formula IV:
ZR″
3
(IV)
wherein, Z is a nitrogen or phosphorus, each R″ is independently selected from a C
1-12
alkyl, C
1-6
alkyl substituted aromatic, or phenyl group and two R″ can be covalently bonded to each other to form a cyclic compound.
The catalyst can also be a transition metal compound having one or more ZR″
3
group wherein Z and R″ are as defined above.
It is also possible to use the catalyst having the following formula V:
R″
2
Z(CH
2
)
y
ZR″
2
(V)
wherein, Z and R″ are defined as above.
The catalyst can also be an aromatic amine such as pyridine, having 1 to 12 carbon atoms and 1 to 3 nitrogen atoms.
The above catalysts can be used in an immobilized form on a silicon resin, silica, inorganic supporter or organic polymer.
In the reaction, a co-catalyst such as CuCl or Cu can be used in addition to the above mentioned catalysts. The reaction can be carried out in most organi
Cho Yeon Seok
Han Joon Soo
Jung Il Nam
Kang Seung-Hyun
Yoo Bok Ryul
Korea Institute of Science and Technology
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Shaver Paul F.
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