JPH04283589A - Production of vinyl silane compounds - Google Patents

Abstract

PURPOSE:To effectively produce the subject compound substantially without producing any homo disproportionation product by reacting a vinyl silane compound with a mono substituted olefin compound in the presence of a new catalyst. CONSTITUTION:(A) A vinyl silane compound of formula: CH2=CHSiR1R2R3 (R1 is lower alkyl, lower alkoxy; R2, R3 are lower alkyl) is reacted with (B) a mono substituted olefin compound of formula: CH2=CHR4 (R4 is lower alkyl, aryl, etc.,) in the presence of a compound of formula I or II or a mixture thereof to produce the objective compound of formula: R4CH=CHSiR1R2R3. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas in a sealed tube at a temperature of >=120 deg.C for 5-40hr. The objective compounds wherein R1, R2 are methyl; R3 is ethoxy; and R4 is n-butoxycarbonyl, etc., are new compounds useful as intermediates for drugs, starting material for organic synthesis, etc. The catalyst of formula II is a new compound.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to a method for producing vinylsilanes using a ruthenium catalyst, a new ruthenium silyl complex and a method for producing the same, and a method for producing vinylsilanes using the ruthenium silyl complex.

0002

[Prior Art] Conventionally, a ruthenium catalyst Ru3(CO)12 was used for the disproportionation catalytic reaction between vinylsilanes and monosubstituted olefins, and CH2=CHSi(OE
t)3 and CH2=CH(CH2)n CH3 in combination with (EtO)3SiCH=CH(CH2)n CH
3 (B. Marciniec, et
al. J. Mol. Catal. , 46,
(1988) 329), Me3SiCH=C in the combination of CH2=CHSiMe3 and CH2=CHC6H5
Method for producing HC6H5 (Y. Seki, et a
l. J. Organomet. Chem. , 3
69, (1988) 117) is known. However, in these reactions, the homodisproportionation products (EtO)3SiCH=CHSi(OEt)3 and
There was a problem that Me3SiCH=CHSiMe3 and the like were produced as by-products.

0003

Problems to be Solved by the Invention and Means for Solving the Problems As a result of intensive research into the disproportionation reaction of vinylsilanes, the present inventors discovered that the ruthenium catalyst Ru(
The present inventors have discovered that when Cl)(CO)H(PPh3)3 is used as a catalyst, the olefin disproportionation reaction proceeds with almost no homodisproportionation products produced, and the present invention has been completed.

That is, the present invention provides the general formula CH2=CH
A vinyl silane compound represented by SiR1R2R3 (wherein R1 represents a lower alkyl group or a lower alkoxy group,
R2 and R3 independently represent a lower alkyl group), and a monosubstituted olefin compound represented by the general formula CH2=CHR4 (wherein R4 is a lower alkyl group, a lower alkoxy group,
Lower alkoxycarbonyl group, aryl group, or Si
R5R6R7 (in the formula, R5 represents a lower alkyl group or a lower alkoxy group, and R6 and R7 independently represent a lower alkyl group)), Ru(Cl)(CO)H(PP
h3)3 or RuCl(CO)(PPh3)2(S
iR1R2R3) (wherein R1 represents a lower alkyl group or a lower alkoxy group, and R2 and R3 independently represent a lower alkyl group) or a mixture thereof, with the general formula R4CH= CHSiR1
A vinyl silane compound represented by R2R3 (wherein R1,
R2, R3, and R4 are the same as defined above) The present invention also provides the following formula: RuCl(CO)(PP
h3)2(SiR1R2R3) (wherein, R1, R2,
and R3 are the same as defined above), a novel ruthenium silyl complex represented by the general formula CH2=CHSiR1R2
A vinyl silane compound represented by R3 (in the formula, R1, R2
, and R3 are the same as defined above) and Ru(Cl)
A method for producing the ruthenium silyl complex, characterized by reacting (CO)H(PPh3)3, and a monosubstituted olefin compound represented by the general formula CH2=CHR4 (wherein R4 is the same as defined above). with the general formula R4CH=CHSiR1
A vinyl silane compound represented by R2R3 (wherein R1,
R2, R3, and R4 are the same as defined above).

The vinyl silane compound used as a reaction raw material in the method of the present invention has the general formula CH2=CHSiR.
It is represented by 1R2R3, where R1 represents a lower alkyl group or a lower alkoxy group, and R2 and R3 independently represent a lower alkyl group. In this specification, lower alkyl group refers to an alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s
Examples include ec-butyl group or tert-butyl group, and lower alkoxy group represents an alkoxy group having 1 to 6 carbon atoms, such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group. , sec
-butoxy group or tert-butoxy group. All of these vinylsilane compounds are known compounds, and commercially available products or those produced by methods described in literature can be used.

The monosubstituted olefin compound used as a reaction raw material in the method of the present invention has the general formula CH2=CH
It is represented by R4, where R4 is a lower alkyl group, a lower alkoxy group, a lower alkoxycarbonyl group, an aryl group,
or SiR5R6R7 (in the formula, R5 represents a lower alkyl group or a lower alkoxy group, and R6 and R7 independently represent a lower alkyl group). In this specification, a lower alkoxycarbonyl group refers to a carbonyl group substituted with an alkoxy group having 1 to 6 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, and a n-butoxycarbonyl group. Examples of the aryl group include a phenyl group, a substituted phenyl group, a pyridyl group, and the like. All of these monosubstituted olefin compounds are known compounds, and commercially available products or those produced by methods described in literature can be used.

The ruthenium catalyst Ru(Cl)(CO)H(PPh3)3 used in the process of the invention is a known complex, described by Inorg. Syn. , 15, 48 (
1974). Also,
The formula used in the present invention is RuCl(CO)(PPh
3) The ruthenium silyl complex represented by 2(SiR1R2R3) (wherein R1, R2, and R3 are as described above) is a new complex, and has the general formula CH2=CHSiR
A vinyl silane compound represented by 1R2R3 (wherein R1
, R2, and R3 are as described above) and Ru(Cl
)(CO)H(PPh3)3. One example of reaction conditions is Ru(Cl)(C
O)H(PPh3)3, excess amount of CH2=C
A vinyl silane compound represented by HSiR1R2R3,
For example, in a solvent such as tetrahydrofuran in a sealed tube,
Examples include a method of reacting at ~70°C for 15 to 18 hours and, if necessary, producing the product by column chromatography or the like. In the IR spectrum of the complex, two CO absorption lines are observed using the KBr method (1900 and 1920 cm for a compound in which R1, R2, and R3 are all methyl groups; R1 is an ethoxy group and R2 and R3 are methyl groups). 190 in compound
5, 1923 cm-1), and one in methylene chloride solution (for example, 1916 cm-1 in a compound where R1, R2, and R3 are all methyl groups; 1922 cm-1 in a compound where R1 is an ethoxy group and R2 and R3 are methyl groups) 1) It has been found that there are two types of crystalline states in the solid state. In the method of the present invention, these complexes can be used alone or as a mixture as reaction catalysts. Ru(Cl)(CO)H(PP
When using h3)3, the formula RuCl(CO)(PPh3)2(SiR1R
2R3) (wherein R1, R2, and R3 are as described above) is partially produced,
Such a mixed catalyst state is also included in the method of the present invention.

[0008] When reacting a vinyl silane compound and a monosubstituted olefin compound by the method of the present invention, the above-mentioned ruthenium catalyst is added to the raw material vinyl silane compound at a rate of 0.
．． 005 to 0.05 mol, and as a solvent, for example, tetrahydrofuran, methylene chloride, toluene,
1 to 10% of benzene etc. to the raw material vinyl silane compound
It may be used at a ratio of 0 times the volume. The reaction is preferably carried out in a sealed tube, and the reaction may be carried out for 5 to 40 hours at a reaction temperature of 70° C. or higher, preferably 120° C. or higher, in an inert gas atmosphere such as nitrogen or argon. Furthermore, the amount of the vinylsilane compound used relative to the monosubstituted olefin compound is 0.5 to 10 equivalents, preferably 2 equivalents or more, thereby suppressing the formation of homodisproportionated products.

By carrying out the disproportionation reaction under such reaction conditions, a vinylsilane compound represented by the general formula R4CH=CHSiR1R2R3 (wherein R1, R2, R3,
and R4 are the same as defined above) can be efficiently produced. Among these compounds, R1, R2, and R3 are methyl groups, and R4 is a methoxycarbonyl group; R1, R2, and R3 are methyl groups,
A compound in which R4 is an n-butoxycarbonyl group; R1 and R2 are a methyl group, R3 is an ethoxy group, and R
A compound where 4 is a phenyl group; a compound where R1 and R2 are a methyl group, R3 is an ethoxy group, and R4 is a methoxycarbonyl group; and a compound where R1 and R2 are a methyl group and R3 is an ethoxy group; Compounds in which R4 is an n-butoxycarbonyl group are new compounds, and all are useful compounds as pharmaceuticals, raw materials for organic synthesis, etc.

[0010] Formula RuCl(CO)(PPh3)2(Si
R1R2R3) (wherein R1, R2, and R3 are as described above) and ethylene, or a monosubstituted olefin compound represented by the general formula CH2=CHR4 (wherein R4 is a lower alkyl group, Lower alkoxy group, lower alkoxycarbonyl group, aryl group, or S
R4CH
A vinylsilane having the formula =CHSiR1R2R3 (wherein R1, R2, R3, and R4 are as described above) is produced. The reaction is usually carried out in a sealed tube, e.g. toluene,
40 to 160°C, preferably 70 to 120°C using a solvent such as benzene, tetrahydrofuran, or ethylene chloride.
It will be held in When the olefin is a gas such as ethylene or propylene, the reaction may be carried out in an autoclave under pressure of 1 atmosphere or more.

[0011]

[Effects of the Invention] Vinylsilane compounds can be efficiently produced by the method of the present invention. In particular, according to the method of the invention,
It is extremely useful because it allows olefins to be disproportioned without producing homodisproportionate by-products. Furthermore, the ruthenium silyl complex provided by the present invention is useful because it can efficiently silylate monosubstituted olefin compounds.

0012

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In the following examples all reactions and work-up of products were carried out under an atmosphere of inert gas (nitrogen or argon). The solvent used was a commercially available special grade reagent deoxygenated by bubbling with argon gas. Tetrahydrofuran was used by drying it with sodium and benzophenone and then distilling it. Degassed silica gel (manufactured by Wako Pure Chemical Industries, Ltd.) was used for column chromatography. The product was identified using IR (Shimadzu, IR-27G), NMR.
(JEOL, GSX-500, GSX-400, GS
X-100), CH elemental analysis (RIKEN Microanalysis Laboratory), GLC (HP-5890A, capillary column J
&W DB1 30m).

Example 1 20 mg of Ru(Cl)(CO)H(PPh3)3(0
．． 021 mmol), 0.2 ml CH2=CHSiR
1R2R3 (1.30 mmol of a compound where R1, R2, and R3 are all methyl groups, or 1.21 mmol of a compound where R1 is an ethoxy group and R2 and R3 are methyl groups), 0.4
ml of CH2=CHR4(R4=SiMe3 compound 2.60 mmol, R4=SiMe2(OEt) compound 2.42 mmol, R4=COOMe compound 4
．． 44 mmol, 3.49 mm of compound with R4=C6H5
ol, or 3.09 mmo of a compound where R4=O-n-Bu
1), and 2 ml of tetrahydrofuran in a sealed tube,
Heated at 0°C for 14 hours. After adding a predetermined amount of internal standard (C n H2n+2) to the reaction solution, the yield was determined by GLC. The calibration curve was created as follows. The product (50 mg) isolated by distillation was taken into a sample tube, and a solution prepared so that the standard substance (C n H2n + 2) containing half the number of moles of the product in tetrahydrofuran was added 1, 2,
3 or 4 ml was added. A calibration curve was created by analyzing it by GLC. When the plot did not fall on the line, it was plotted again using a different ratio. The product was isolated by distillation using a reaction solution that was reacted on a scale of 5 to 10 times the above amount, and subjected to NMR, IR, and elemental analysis.

The above results are shown in Table 1 below.
Table 1


CH2=CHSiR1R2R3C
H2=CHR4 R4CH=C
HSiR1R2R3 R1
R2 R3 R4
Yield (%) 1) trans/cis tur
over Me Me Me2)
SiMe3 37.6
44/56 34 Me
Me Me Me
74.3 76/24
92 Me Me Me
Ph 66.0
99/ 1 41 M
e Me Me COOMe
59.4 93/7
37 Me Me
Me On-Bu 74.
5 78/22 4
6 OEt Me Me2) Si
Me2OEt 49.1 67
/33 42 OEt Me
Me Ph
72.2 99/ 1
42 OEt Me Me
COOMe 69.7
83/17 40 OEt
Me Me O-n-Bu
83.8 84/16
48 1) CH2=CHSiMe
2R1 Standard 2) CH2=CHSiR1R2R3 0
．． 6ml

Example 2 Effect of temperature on the process of the invention 20 mg of Ru(Cl)(CO)H(PPh3)3(0
．． 021 mmol), 0.2 ml CH2=CHSiM
e3 (1.30 mmol), 0.4 ml CH2=C
HC6H5 (3.49 mmol) and 4 ml of tetrahydrofuran were sealed in a tube and heated at 70°C, 100°C, 120°C.
°C, and heated at 140 °C for 14 hours. As a result, the yield at each temperature was 24.2% (70°C) and 49.7% (
100℃), 69.4% (120℃), and 66.0%
(140°C).

Example 3 Effect of the amount of solvent in the process of the invention 100 mg of Ru(Cl)(CO)H(PPh3)3
(0.11 mmol) and 2 ml of CH2=CHSiM
Propylene (CH2=CHCH3) was added to e3 (13.3 mmol) at a reaction temperature of 70°C at a pressure of 4.5 Kg/cm2, and the mixture was reacted in an autoclave in the presence of each volume of toluene. The results are shown in Table 2 below.

[0017]
Table 2


Ru(Cl)(CO)H(PPh3)
3 Toluene Reaction time Product distribution (
GLC analysis%)

A B C
100mg 5ml
13 hours 82.1 3.4
14.5 100 20
15 64.1
6.4 29.1 100
5 24
74.2 5.0 20.8
100 10
21 68.9 5.3
25.8 A: CH2=CHSiMe3
B: cis-CH3CH=CHSiMe
3C: trans-CH3CH=CHS
iMe3 The physicochemical properties of the vinylsilane compound obtained in each example are as shown below.

[0018]

[Chemical formula 1]

[0019]

[Case 2]

[0020]

[Chemical formula 3]

[0021]

[C4]

[0022]

[Table 1]

[0023]

[Table 2]

Example 4-A Ruthenium silyl complex R
Production of uCl(CO)(PPh3)2(SiMe3) 2
00mg RuCl(CO)H(PPh3)3(0.2
1 mmol), 38 ml of tetrahydrofuran, and 0
．． 5 ml CH2=CHSiMe3 (3.24 mmo
1) was sealed and heated at 70°C for 18 hours. After evaporating the solvent under reduced pressure and dissolving in the minimum amount of methylene chloride, the residue was subjected to silica gel column chromatography and a yellow band was eluted with benzene/hexane (3/1). After distilling off the solvent under reduced pressure, orange crystals were obtained by recrystallizing from methylene chloride/hexane. Yield 101 mg (yield 63%) Decomposition point 159-161°C IR (KBr, cm-1): 1900, 1920 (CO
), 845 (Si-C) IR (CH2Cl2, cm-1) 1916 (CO)1
H-NMR (C6D6) SiMe3 0.6
2 ppm31P-NMR (CDCl3) PPh
3 35.15

Example 4-B Ruthenium silyl complex RuCl(CO)(PPh3)2
Preparation of SiMe2(OEt) 200 mg RuCl
(CO)H(PPh3)3 (0.21 mmol), 10
ml of tetrahydrofuran and 1 ml of CH2=CH
SiMe2(OEt) (6.05 mmol) was sealed in a tube and 6
Heated at 0°C for 15 hours. After distilling off the solvent under reduced pressure, yellow crystals were obtained by recrystallizing from benzene/hexane. Yield 99mg (yield 60%) Decomposition point 176
~178°C IR (KBr, cm-1): 1905, 1923 (CO
)IR(CH2Cl2, cm-1) 1922(CO)
1H-NMR (CDCl3) SiMe3
0.25 ppmCH3(EtO) 0.76
(t, J=7Hz) CH2(EtO) 3.27
(q, J=7Hz)

Example 5 Preparation of vinylsilane compound using ruthenium silyl complex 100 mg of Ru(Cl)(CO)(PPh3)2(
SiMe3) (0.11 mmol), 2 ml CH2
=CHSiMe3 (13.3 mmol) and 20 m
1 of toluene was charged into a 50 ml autoclave, and propylene (CH2=CHCH3) was added thereto at 4.5K.
It was added at a pressure of g/cm2 and stirred for 30 minutes while connected to the bomb. Thereafter, the autoclave was removed from the cylinder and heated in an oil bath at 140° C. for 14 hours. The reaction solution was prepared in Example 1.
Analyzed in the same way. For the calibration curve, CH2=CHSiMe3
A calibration curve was used. As a result, CH3CH=CHSiMe3 with a trans/cis isomer ratio of 76/24 was obtained in a yield of 74%.

Claims (6)

[Claims] [Claim 1] General formula CH2=CHSiR1R2R
3 (wherein R1 represents a lower alkyl group or a lower alkoxy group, and R2 and R3 independently represent a lower alkyl group), and a vinylsilane compound represented by the general formula CH2=C
A monosubstituted olefin compound represented by HR4 (wherein R4
is a lower alkyl group, a lower alkoxy group, a lower alkoxycarbonyl group, an aryl group, or a SiR5R6R7 (
In the formula, R5 represents a lower alkyl group or a lower alkoxy group, and R6 and R7 independently represent a lower alkyl group), and Ru(Cl)(CO)H(PPh3)3 or RuCl(CO) (PPh3)2(SiR1R2R3
) (wherein R1 represents a lower alkyl group or a lower alkoxy group, R2 and R3 independently represent a lower alkyl group) or a mixture thereof, with the general formula R4CH=CHSiR1R2R3 A method for producing a vinylsilane compound represented by (wherein R1, R2, R3, and R4 are the same as defined above). Claim 2: The following formula: RuCl(CO)(PPh
3) A novel ruthenium silyl complex represented by 2(SiR1R2R3) (wherein R1 represents a lower alkyl group or a lower alkoxy group, and R2 and R3 independently represent a lower alkyl group). [Claim 3] General formula CH2=CHSiR1R2R
3 (in the formula, R1 represents a lower alkyl group or a lower alkoxy group, and R2 and R3 independently represent a lower alkyl group) and Ru(Cl)(CO
)H(PPh3)3, R
uCl(CO)(PPh3)2(SiR1R2R3)
(wherein R1, R2, and R3 are as described above). 4. Formula RuCl(CO)(PPh3)2(
SiR1R2R3) (wherein, R1 represents a lower alkyl group or a lower alkoxy group, and R2 and R3 independently represent a lower alkyl group) and a monosubstituted olefin compound represented by the general formula CH2=CHR4 ( In the formula, R4 is a lower alkyl group, a lower alkoxy group, a lower alkoxycarbonyl group, an aryl group, or a SiR5R6R7 (wherein, R5 represents a lower alkyl group or a lower alkoxy group, and R6 and R7 are independently lower alkyl groups. ),
R4CH=CHSiR1R2R3 (wherein, R1, R2,
R3 and R4 are as described above). 5. A silylating agent comprising the ruthenium silyl complex according to claim 2. 6. The silylating agent according to claim 5 for silylating monosubstituted olefins.