JPH03258787A - 1,2-bissilylethylene derivative, 1,2-bissilylethane derivative and 1,1-bissilylethane derivative and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject compounds useful as a synthetic intermediate for medicines, agricultural chemicals, etc., under mild conditions using inexpensive raw materials available in a large amount by reacting specific hydrosilanes with acetylenes in the presence of a transition metal complex catalyst. CONSTITUTION:Hydrosilanes expressed by formula I (Y is bifunctional organic group, O, etc.; R<1> to R<4> are monofunctional organic group, halogen, etc.) [e.g. o-bis(dimethylsilyl)benzene] are reacted with acetylenes expressed by the formula R<5>CidenticalCR<6> (R<5> and R<6> are R<1>) in the presence of a transition metal complex catalyst [preferably tetrakis(diphenylmethylphosphine)platinum, etc.] selected from platinum, Pd, Ni, Ru, iron, Ir, Rh and Co, preferably at 0-150 deg.C to afford the objective compounds expressed by formulas II, III and/or IV. Furthermore, the compound expressed by formula IV (R<7> to R<16> are 1-15C organic group, H, etc.) in the objective compounds is a new compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to the production of 1,2-bissilylethylene derivatives and/or 1,2-bissilylethane derivatives and/or 1,2-bissilylethane derivatives by reacting hydrosilanes with acetylenes. ,1
- A method for producing a bissilylethane derivative. 1,2-bissilylethane derivatives, 1,2-bissilylethane derivatives, and 1,1-bissilylethane derivatives are useful as synthetic intermediates for fine chemicals such as medicines and agricultural chemicals.

[Conventional technique #! ] General formula R1R"5i-RsC=CR"-5iR'R'-
Y (wherein, R1, R'', R3, R', R',
1, R' and Y are each represented by (as described above);
2-bissilylethylene derivative and/or inside, R''*R'', R3t R', R', R' and Y
are as described above) and/or a 1,2-bissilylethane derivative represented by the general formula R1R25i-R'C(CH2R'')-5iR3
R'-Y (wherein, R1, R'', R', R',
The reaction of cyclic disilane and acetylene (double silylation reaction) is generally known as a method for producing 1,1-bissilylethane derivatives (R', R'' and Y are as described above). 1 Synthesis example of cyclic disilanes is limited, and it is generally expensive, so it is not considered to be an industrially advantageous method.Another method is the reaction of silylene and acetylene. -Disilar The production of 2,5-cyclohexadiene derivatives is also known, but the production of silylene generally requires harsh conditions such as irradiation with ultraviolet light or high temperatures around 300'C, and the by-product silacyclopentane is produced. This is not an industrially satisfactory method as it often produces Zhen.Another method is an intramolecular hydrosilylation reaction of silylacetylene having an organic group containing a silicon atom having a 5i-H bond as a substituent on silicon. Although it is also known (Topi
cs of Current Chemistry.

50 (1974) 44), the process for producing the above-mentioned silylacetylene, which is a raw material, is complicated and is not a satisfactory method.

[Problems to be Solved by the Invention] The present invention is directed to producing 1,2-bissilylethylene derivatives and/or 1,2-bissilylethane derivatives and/or 1,2-bissilylethane derivatives under mild conditions using raw materials that are inexpensive and available in large quantities. or 1,1
The object of the present invention is to provide a method for producing -bissilylethane derivatives industrially and advantageously.

Another object of the present invention is to provide novel 1,2-bissilylethane derivatives, 1,2-bissilylethane derivatives, and 1,1-bissilylethane derivatives obtained thereby.

[Means for Solving the Problems] As a result of intensive research by the present inventors to solve the above problems, (a) General formula HRlR"5i-Y-5iR3R'H (
However, in the formula, R1, R2, R3, R4 and Y are each as described above) and (b) hydrosilanes represented by the general formula RsC:CR'' (However, in the formula, Rs and R' are each as described above). (e) Platinum, palladium, nickel, ruthenium, iron,
It reacts rapidly under mild conditions in the presence of a transition metal complex selected from iridium, rhodium, and cobalt.
We have discovered a novel fact that provides a 2-bissilylethane derivative and/or a 1,2-bissilylethane derivative and/or a 1,1-bissilylethane derivative, and have completed the present invention based on this discovery.

That is, according to the present invention, the general formula R"R"5i-R"C=CR'-5iR3R'
-Y (wherein, R1, R", R3, R', R'
, R" and Y are respectively as described above) 1
, 2-bissilyl ethylene derivative and/or 1,2-bissilylethane represented by (wherein R1, R'', R', R', R', R' and Y are each as described above) Derivatives and/or 1 represented by (wherein R1, R2, R2, R4, RK, RK and Y are each as described above),
A method for producing a 1-bissilylethane derivative is provided.

The method of the present invention proceeds by a reaction represented by a linear equation.

HRlR"5i-Y-5iR3R'H+ R'CECR
'→)IRlR"5i-Y-5iR3R'H+R'
CECR' → 1 (RLR2Si-Y-SiR'R')
l + R'"CmiCR'→R1R"5i-RsC
(CH,R')-5iR'R'-Y (wherein R1
, R'', R', R', R'', R' and HY are each as described above) The hydrosilane (a) used in the present invention has the general formula HR
lR"5i-Y-5iR3R' H (wherein, R"
, R", R3, R' and Y are each represented by Examples include (hydrocarbyl) amino group, halogen atom, hydrogen atom, etc., which may be the same or different from each other. In the general formula, Y is 2
A valent organic group, an oxygen atom, a nitrogen atom, a sulfur atom, and 2
Specifically, as a valent organic group, (A) a divalent organic group having an aromatic ring structure (T3) an alkylene group (C) a divalent organic group containing a typical element as a hetero atom (D) as a hetero atom Examples include divalent organic groups containing transition metals.

As (A), for example.

etc.5 (B) is, for example, -CH,-, -CH2CH,-, -CH2CH,CH,
-, -HC=CH-.

etc. are listed.

(C) is, for example, -0-CI(,-, -CH2-0-CH2-, -CH,
-N(CL)-CB,-.

etc. are mentioned, As (D), for example, etc. can be mentioned.

Moreover, various substituents can be included as substituents on the carbon atoms of the divalent organic group. Specific examples of such substituents include alkoxy groups, aryloxy groups, acyloxy groups, alkoxycarbonyl groups, acyl groups, bis(hydrocarbyl)amino groups, halogen atoms, and hydrogen atoms.

More specific examples of hydrosilanes used in the present invention include 0-bis(dimethylsilyl)benzene, 0-bis(
Diphenylsilyl)benzene, 0-bis(dimethoxysilyl)benzene, 0-bis(diphenoxysilyl)benzene, 0-(bis(dimethylamino)silyl)(dimethylsilyl)zc Efuden, 0-bis(dichlorosilyl) ) Benzene, 3.
4-bis(dimethylsilyl)pyridine, 2゜3-bis(
dimethylsilyl)thiophene, 2,3-bis(dimethylsilyl)furan, 1,2-bis(dimethylsilyl)naphthalene, 1,2-bis(dimethylsilyl)anthracene, 1,2-bis(dimethylsilyl)-4- Methoxybenzene, 3゜4-bis(dimethylsilyl)phenylethyl ether, 1,2-bis(dimethylsilyl)-4-chlorobenzene, 1,2-bis(dimethylsilyl)ethane,
1,1,3.3-tetramethyldisiloxane, l,1,
3,3-tetramethyldisilazane, bis-η1-((dimethylsilyl)cyclopentagenyl)iron, bis-η5
-((dimethylsilyl)cyclopentagenyl)ruthenium and the like.

The acetylenes (b) used in the present invention have the general formula R''C
E CR' (wherein R5 and R1 are each as described above). Rs and R@ are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group,
Examples include an alkoxycarbonyl group, an alkoxymethyl group, an aryloxymethyl group, a bis(hydrocarbyl)amino group, a halogen atom, and a hydrogen atom.

More specific examples of acetylenes used in the present invention include unsubstituted acetylene, 1-propyne, 1-butyne, 2-
Butyne, 1-pentyne, 2-pentyne, 3-hexyne,
1-decyne, 4-decyne, cyclononine, cyclododecyne, phenylacetylene, o-1m-1 or p-tolylacetylene, 0-1m-1 or p-chlorophenylacetylene, 1-phenyl-1-propyne, 1-phenyl-2 -Propyne, 4-phenyl-1-butyne, diphenylacetylene, 1-phenyl-2-cyclohexylacetylene, ethyl ethynyl ether, phenylethynyl ether, methyl propiolate, ethynyl acetate, propynyl benzoate, chloroacetylene, 1,4-diacetoxy -2-butyne, 2-acetoxy-2-methyl-3-
Examples include butyne, 1-, ψα=1r-x-2-propyne, dimethyl acetylene dicarboxylate, and the like.

The molar ratio of hydrosilanes and acetylenes is usually in the range of 1/100 to 100, preferably in the range of 1/10 to 10. When a gaseous raw material is used, there is no problem in using the gaseous raw material beyond this range, and a method of bubbling the gaseous raw material into the reaction system should also be considered as an advantageous embodiment of the present invention.

According to the present invention, a novel 1.2-
Bissilylethylene derivative (1) and/or 1,2-
A bissilylethane derivative (n) and/or a 1,1-bissilylethane derivative (III) is provided.

(Su(II) (Ill) kuI-醊I Formula, R', R", R', Rlo, R"
and R'' is an alkyl group, an aryl group, or an alkoxy group.

Indicates an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, a bis(hydrocarbyl)amino group, a halogen atom, a hydrogen atom, etc. R11R”, R” and R
14 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a bis(hydrocarbyl)amino group, a halogen atom, a hydrogen atom, etc. The alkyl group, alkoxy group, and acyl group have a carbon number of 1.
-10 lower alkyl groups, alkoxy groups, and acyl groups, examples of aryl groups and aryloxy groups include acyloxy groups and alkoxycarbonyl groups having 6 to 15 carbon atoms, such as phenyl groups, tolyl groups, phenoxy groups, etc. , as the bis(hydrocarbyl)amino group, an acyloxy group having 1 to 10 carbon atoms.

Examples include an alkoxycarbonyl group and a bis(hydrocarbyl)amino group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

The transition metal complex catalyst (C) used in the present invention includes ((-- uN7. Its transition metal components include platinum, ruthenium, rhodium, palladium, nickel, iron, cobalt, and iridium, but especially platinum). ,ruthenium,
The use of rhodium and palladium is preferred. Various conventionally known transition metal complexes can be used, but from the viewpoint of reaction rate it is preferable to use compounds that are at least partially soluble in the reaction system. Complexes containing carbon monoxide or carbon monoxide are particularly preferably used. Here are some specific examples of these.

(η-ethylene)bis(triphenylphosphine)platinum, tetrakis(diphenylmethylphosphine)platinum, dichlorobis(phenyldimethylphosphine)platinum, chlorohydridobis(tributylphosphine)platinum, dichloro(tetramethylethylenediamine)platinum, dibromobis(triethyl) phosphite) platinum, dichlorobis(benzonitrile)platinum, bis(η-1,5-cyclooctadiene)platinum, dichloro(η-1,5-cyclooctadiene)platinum, dicarbonylbis(tributylphosph, W
Platinum, carbonatobis(tricyclohexylphosphine)platinum, bis(dibenzylideneacetone)bis(triphenylphosphine)platinum, (η-ethylene)bis(triphenylphosphine)palladium, tetrakis(diphenylmethylphosphine)palladium, dichlorobis(phenyldimethyl) phosphine)palladium, tris(dibenzylideneacetone)nipalladium, dichloro(η-1
,5-cyclooctadiene)palladium, bis(η-allyl)palladium, (η-ethylene)bis(triphenylphosphine)nickel, tricarbonyl(diphenylmethylphosphine)nickel, dibromobis(triethylphosphine)nickel, tetrakis(phenyl) dimethylphosphine) nickel, bromotris(tributylphosphine) nickel, bis(η5-cyclopentagenyl) nickel, bis(acetylacetonato) nickel.

Chlorotris (triphenylphosphine) rhodium, chloro(carbonyl) tris (tributylphosphine) rhodium, dodecacarbonyl four-mouth dirhodium, bis(
η-ethylene) (η-cyclopentagenyl) rhodium, chlorotris(triphenylphosphine)iridium, chloro(carbonyl)tris(tributylphosphine)iridium, chlorotris(triphenylphosphine)cobalt, chloro(carbonyl)tris(tributylphosphine) Cobalt, dodecacarbonyltriruthenium, (η-1,5-cyclooctadiene)(η-cyclooctatriene)ruthenium, tricarbonylbis(tributylphosphine)iron, tetracarbonyl(diphenylmethylphosphine)iron, pentacarbonyliron, etc. However, the present invention is not limited to these, and these transition metal compounds may be used not only alone, but also in combination of two or more, and those included in the transition metal compound together with the transition metal compound. An advantageous embodiment of the present invention also includes the addition of an organic ligand that is the same as or different from the above. Examples of such organic ligands include phosphine, phosphonite, phosketone, amine, and nitrile. Examples of these chains include trimethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(p-tolyl)phosphine, tri(p-anisyl)phosphine, diphenylmethylphosphine, phenyldimethylphosphine, etc. phosphine, p-methylphosphole, p-methylphosphole, 9-methyl-
Cyclic phosphines such as 9-phosphabicyclo[4,2,11 nonane, 1゜2-bis(dimethylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, 1,
4-bis(dimethylphosphino)butane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1' -bis(dimethylphosphino)ferrocene, 1゜1'-bis(diphenylphosphino)ferrocene, α,α'-bis(dimethylphosphino)-〇-xylene, 1,2-bis(dimethylphosphino)benzene, etc. bisphosphine, phosphonites such as dimethylmethylphosphonite and dimethylphenylphosphonite, phosphinites such as methyldimethylphosphinite and diphenylphosphinite, and phosphites such as triethylphosphite, triphenylphosphite and trimethylolpropane phosphite. ,ethylene,
Propene, cyclooctene, 1,5-hexadiene, 1
, 5-cyclooctadiene, 1,3-cyclopentadiene.

Examples include olefins such as norbornadiene, l,3,5.7-cyclooctatetraene, β-diketones such as acetylacetone, amines such as ethylenediamine and 2,2'-bipyridyl, and nitrites such as benzonitrile.

The amount of transition metal complex catalyst used may be a so-called catalytic amount, and the molar ratio to hydrosilane is 0.00001 to 0.5.
used within the range.

The reaction of the present invention can be easily carried out without using any particular solvent by using a mixture of hydrosilanes and acetylenes to be subjected to the reaction. It is not a hindrance to the process and can be carried out in a solvent if necessary.

These solvents are preferably selected from commonly used solvents, such as hydrocarbon-based or ether-based solvents, taking into consideration the reactivity and boiling point of the hydrosilanes to be reacted, the boiling point of the acetylenes, etc.

Although the reaction of the present invention will proceed below 0°C, it can be heated to temperatures up to 250°C to achieve preferred rates. Although it depends on the structure of the raw material, the preferred temperature range for boat fishing is 0 to 150°C.

Separation of the product after the reaction is easily carried out by separating unreacted raw materials by distillation or the like, and then subjecting the product to rectification, recrystallization, chromatography, or the like.

[Effects of the Invention] According to the present invention, 1,2-bissilylethylene derivatives and/or 1,2-bissilylethylene derivatives can be easily obtained from hydrosilanes and acetylenes.
．． 2-bissilylethane derivative and formula ζ・Umyo 1,1-e
ゎ1,7゜engineering 5. □Oka, urare, and their industrial significance are enormous.

[Example] Next, the present invention will be explained in more detail by way of examples.

Example I Pt(CH2=CHi)(PPhz)a, 0.005
mmol and 0-bis(dimethylsilyl)benzene.
2 m Q of benzene solution containing 25 mmol at 30°C.
2 mQ of a benzene solution containing 0.25 mmol of phenylacetylene was added, and the mixture was stirred at 30°C to perform one reaction. 1
After reacting for 9 hours, it was concentrated and distilled to give 1°1.4,4
-Tetramethyl-2-phenyl-1゜4-penzodisilar 2,5-cyclohexadiene and 1,1,3,3-tetramethyl-2-benzyl-1,3-penzodisilar 4
- a mixture of cyclopentenes with yields of 68% and 1, respectively
Obtained at 0%. The production ratio was determined by gas chromatography. All of the present compounds are new compounds that have not been described in any literature, and their physical property values and spectral data were as follows.

1.1,4.4-tetramethyl-2-phenyl-1,4
-penzodisilar 2,5-cyclohexadiene boiling point = 1
10℃/1mmHg (Kugerrohr) 1H-NMR (
CDCI, ): δ 7.65-7.58 (4H,
m).

7.45-7.20 (7H, m), 6.85 (
LH,s).

0.37 (6H, s), 0.36 (6H, s
) GC-MS (EI, 70eV); 294
(M”, 47), 279 (100) IR (Figure 1) Elemental analysis values: Actual value C73,86%, H7,63% Theoretical value C73,40%, H7,53% 1,1,3,3 -tetramethyl-2-benzyl-1,3
-Penzodisilar 4-cyclopentene 1H-NMR (C
DCl2): δ 7.6-7.2 (9H, m).

2.93 (2H, d J =8.5Hz)tO,
74 (LH,t, J = 8.5Hz).

0.21 (6H,s), 0.15 (6H,s)
GC-MS: 296 (M”, 2), 281
(100) Examples 2 to 7 Table 1 shows the results of a reaction conducted in the same manner as in Example 1 at 80° C. for 7 hours with different catalysts.

Table 1 P t (CHa ”CH2) (P P hi )
2Ru, (co)zz PtCjz(PPhWz RhC1(PPh3).

Pd(DBA)+2PPh.

PdCgz (PPhi)2 50 14 20 20 23 6 0 1 0 H 1,4.4-tetramethyl-2-phenyl-1゜4
-penzodisilar 2,5-cyclohexadiene, B is 1
,1,3.3-tetramethyl-2-benzyl-1゜3-
Shows penzodisilar 4-cyclopentene.

Moreover, the yield is a value analyzed by gas chromatography.

Examples 8 to 11 Table 2 shows the results of reactions carried out in the same manner as in Example 1 while changing acetylene, reaction temperature, and reaction time.

All of the following products are new compounds that have not been described in the literature.

Example 12 pt (CH,=CH,) (pph, )2 to 0.0
4 ml of a benzene solution containing 0.25 mmol of 0.05 mmol and 0.25 mmol of 0-bis(dimethylsilyl)benzene was stirred at 30° C. under an acetylene gas atmosphere (using a balloon) and reacted for 19 hours. When concentrated and distilled, a mixture of 1,1,4,4-tetramethyl-1,4-penfudisilar 2,5-cyclohexadiene and 1,1,4,4-tetramethyl-1,4-penfudisilar 5-cyclohexene is obtained, respectively. Yields of 46% and 23% were obtained, and the production ratios were determined by gas chromatography.

All of these compounds are new compounds that have not been described in the literature.
The spectral data were as follows.

1.1,4,4-tetramethyl-1,4-penzodisila-2,5-cyclohexadiene Boiling point: 95°C/20mmHg (Kugerrohr) 1H
-NMR, δ 7.7-7.2 (4H, m).

7.1 (2H,s), 0.29 (12H,s)
GC-MS; 21g (M”, 46), 203
(100) IR (Figure 6) 1.1,4.4-tetramethyl-1,4-penfudisilar 5-cyclohexene 1H-NMR: δ 7.7-7.2 (4H, m)
.

1.02 (4H,sL O,23(12H,s)G
C-MS: 220 (M”, 22), 205
(100) Example 13 Pt (CH2=CH2) (PPh, )z is 0.0
To 2 m Q of a benzene solution containing 0.5 mmol of 0.05 mmol and 0.25 mmol of 1゜2-bis(dimethylsilyl)ethane, 4-
Benzene solution containing 0.25 mmol of octyne 2 m Q
was added dropwise at 80°C, and the reaction was carried out at 80°C for 24 hours.

After concentration, distillation is performed to obtain 1,1,4,4-tetramethyl-2,3
-Dipropyl-1,4-disilar 2-cyclohexene was obtained with a yield of 60%.

1H-NMR (CDC13): δ 2.1-1.9
(4H, m).

1.4-11 (4H, m), 0.86 (6H, t
, J=7Hz).

0.71 (4H, s), 0.02 (12H, s)
.

GC-MS; 254 (M", 24), 5
9 (100) IR (Figure 8) Example 14 1, instead of 1,2-bis(dimethylsilyl)ethane
A reaction was carried out for 2 hours in the same manner as in Example 13 using 0.25 mmol of 3-bis(dimethylsilyl)propane and 0.25 mmol of 4-octyne. After the reaction, the mixture was concentrated and distilled.
1,1,4,4-tetramethyl-2,3-dipropyl-
1,4-disilated 2-cyclopentene was obtained with a yield of 11%.

1. Add 0.125 4-octyne to 2 mfl of benzene solution containing 0.5 mmol of 3,3-tetramethyldisiloxane.
2m+2 of a benzene solution containing mmol was added dropwise and the reaction was carried out at 70°C for 7 hours. After concentration, distillation was performed to obtain 2,2,5,5-tetramethyl-3,4-dipropyl with a yield based on 4-octyne. -1-oxa-2,5-disilar-3-cyclopentene was obtained in a yield of 8%.

At the same time, 1,1,3,3-tetramethyl-1-(1-propyl-1-pentenyl)-1,3-disiloxane
% GC-S; 268 (M”, 20), 22
5 (52), 59 (100) Example 15 and 1,3-bis((1-propyl-1-pentenyl)
18% of dimethyl)-1,3-disiloxane was obtained.

These production ratios were determined by analysis using gas chromatography.

2.2,5.5-tetramethyl-3,4-dipropyl-
1-Oxa-2,5-disylar 3-cyclopentene GC
-MS; 242 (M”, 19), 227 (1
00), 171 (12).

157 (15), 133 (86), 119 (
35).

117 (24), 73 (33) 1.1,3,3-tetramethyl-1(1-propyl-1
-pentenyl)-1,3-disiloxane Boiling point: 110°C 150mmHg (Kugerrohr) 1
H-NMR (CDC13): 65.9-5.7 (
IH, m).

4.8-4.7 (LH, m), 2.05 (4H,
q, J=7Hz) tl, 7-1.2 (4H, m),
0.9 (6H, t, J=7Hz).

0.1 (12H,S) GC-MS; 244 (M”, 2), 229
(3), 133 (100) 1,3-bis((1-propyl-1-pentenyl)dimethyl)-1,3-disiloxane"H-NMR (cocn, ): δ 5.8 (2H
, t, J=7Hz).

2.05 (8H, q, J=7Hz), 1.6-1.
1 (8H, m).

0.9 (12H, t, J==7Hz), 0.1 (
12H,s) GC-MS; 354 (M”, 4)
, 339 (11), 242 (33).

133 (100) IR (Figure 8)

[Brief explanation of drawings]

Figure 1 shows 1°1.4,
The infrared absorption spectrum of 4-tetramethyl-2-phenyl-1゜4-penzodisilar 2,5-cyclohexadiene was measured using the liquid film method, where the vertical axis is the transmittance (%) and the horizontal axis is the transmittance (%). (all-1). Figure 2 shows 1°1.4,
The infrared absorption spectrum of 4-tetramethyl-2,3-diphenyl-1,4-penzodisilar 2,5-cyclohexadiene was measured by the Nujol method, where the vertical axis is the transmittance (%) and the horizontal axis is the transmittance (%). The axis is (aa-1). Figure 3 shows the 1°1.4,
The infrared absorption spectrum of 4-tetramethyl-2,3-dipropyl-1,4-penzodisilar 2,5-cyclohexadiene was measured using the liquid film method, and the vertical axis is the transmittance (%).
), and the horizontal axis is (low 1). FIG. 4 shows the 1°1.4,
The infrared absorption spectrum of 4-tetramethyl-2-hexyl-1゜4-penzodisilar 2,5-cyclohexadiene was measured using the liquid film method, and the vertical axis is the transmittance (%) and the horizontal axis is the transmittance (%). The axis is (c++-1). FIG. 5 shows the 1°1.4,
The infrared absorption spectrum of 4-tetramethyl-2,3-bis(methoxycarbonyl)-1,4-penzodisila-2°5-cyclohexadiene was measured using a liquid film method.
The vertical axis is transmittance (%), and the horizontal axis is (portion ``1''). FIG. 6 shows the 1°1.4,
4-Tetramethyl-1,4-penzodisilar 2,5-cyclohexadiene and 1.1,4゜4-tetramethyl-1
The infrared absorption spectrum of a mixture of , 4-penfudisilar and 5-cyclohexene was measured by a liquid film method, where the vertical axis is transmittance (%) and the horizontal axis is (e11''1). FIG. 7 shows the 1°1.4,
The infrared absorption spectrum of 4-tetramethyl-2,3-diprobyl-1,4-disilar-2-cyclohexene was measured by the liquid film method, where the vertical axis is transmittance (%) and the horizontal axis is ( al-1). FIG. 8 shows the 1°1.3,
The infrared absorption spectrum of 3-tetramethyl-1-(1-propyl-1-pentenyl)-1,3-disiloxane is
It was measured using the liquid film method, and the vertical axis is transmittance (%).
The horizontal axis is (cm-1). Figure 9 shows 1゜3-bis((1-propyl-1-pentenyl)dimethyl))-1 synthesized according to an example of the present invention.
, 3-disiloxane, measured using the liquid film method, the vertical axis is transmittance (%), and the horizontal axis is (
am'''1) Tehe Mitsuru'P Fu Seisho (spontaneous) 1. Description of the case 1990 Patent Application No. 57273 2, Title of the invention 1. 2-Bissilylethylene derivative, l, 2- Process for producing bissilylethane derivatives and l,1-bissilylethane derivatives, and 1.2-bissilylethane derivatives (name after amendment) 3. Relationship with the case of the person making the amendment Patent applicant address Chiyohi-ku, Tokyo Kasumigaseki 1-3-1 Name (1
14) Director of the Agency of Industrial Science and Technology Ken Sugiura 4, “Title of the invention” column, “Claims J” column, “Detailed explanation of the invention” column, “Brief explanation of the drawings” in the designated representative specification Add the column and drawings. "Boiling point 90℃/2mmHg (Kugerrohr) H
-NMR (CDCIm): δ 2.20-2.00
(4H, a+). 1.41-1.15 (6H, m) 0.97-0.77 (IOH, m). 0.06 (12H,s) J(6
) Next to the second line from the bottom of the same page in the same book, enter rIR (10th line).
Figure)” is added. (7) On page 29 of the same book, line 11, add the following statement on a new line. "Boiling point 100℃/30mmHg (Kugerrohr)'H-NMR (CDC1,): δ 2.2 (4
H, m). 1.35 (4H, sextet, J=7.5Hz). 0.9 (6H, t, J=7.5Hz). 0.2 (12H,s) J(8)
After the 9th line from the bottom of the same page in the same book, start a new line and use rIR (liquid film method)
Add 1248 cm-' J. (9) Add the following statement on a new line after the 9th line of page 30 of the same book. 7. Contents of amendment (1) "l,2-bissilylethane derivatives, 1,2-bissilylethane derivatives, and 1,1-bissilylethane derivatives and their manufacturing method" on page 1, lines 3 to S of the specification " has been amended to "1,2-bissilylethane derivative, l,2-bissilylethane derivative, method for producing l,1-bissilylethane derivative, and 1,2-bissilylethane derivative." (2) Amend the "Claims" of the same book as shown in the attached sheet. (3) "And 1.2-...1" on page 6, lines 5-6 of the same book.
．． 1-bissilylethane derivative" is deleted. (4) Add the following statement on a new line after line 6 on page 27 of the same book. "Elemental analysis value: Actual value C66, 10%, 811.94
% theoretical value C66,06%, H11,H%” (5) Next to the 14th line of the same page in the same book, enter the following and write the following example 16 Pt(CHa=C)lx) (PPhx) z is 0. 0
0.5 mmol of benzene solution containing 0.25 mmol of 1.2-bis(dimethylsilyl)ethane and 2 ml of a benzene solution containing 0.25 mmol of diphenylacetylene.
1 was added dropwise at 80°C, and the reaction was carried out at 80'C for 1 hour. After concentration and distillation, 1,1,4.4-tetramethyl-2
, 3-diphenyl-1,4-disylar-2-cyclohexene was obtained in a yield of 83%. Boiling point 115℃/25+nmHg (Kugerrohr) Melting point 114-115℃ 'H-NMR (CDCM: δ 7.2-6.7 (
108, n+). 1.04 (4, s), 0.07 (12H, s
) GC-MS: 322(M", 100)', 3
07 (62) IR Figure 11 Elemental analysis values: Actual values C74,64%, H8,13% Theoretical values C66,06%, H8,12%” (10) Circular page 31 (Table 2) All pages Correct as follows. (11) Add the following statement on page 34, line 14 of the same book, on a new line. "Figure 10 shows examples of the present invention = 1, 1, synthesized from
4.4-tetramethyl-2,3-dipropyl-1,4-
The infrared absorption spectrum of disylar 2-cyclopentene was measured by the liquid film method, where the vertical axis is transmittance (%) and the horizontal axis (wave number (cm-')). 1, l, 4 synthesized according to the example of
．． The infrared absorption spectrum of 4-tetramethyl-2,3-diphenyl-1,4-disilar-2-cyclohexene was measured by the Nujol method, and the vertical axis is the transmittance (%).
, and the horizontal axis is [± wave number (cm-').'' (12) Figures 10 and 11 are added as attached drawings. (above) Claim (1) (a) - Formula HR'R"5i-Y"SiR'R
'H (wherein, Y represents a divalent organic group, an oxygen atom, a nitrogen atom, a sulfur atom, R'', R'', R' and R4
represents a monovalent organic group, a halogen atom, or a hydrogen atom) and (b) - formula R'C=CR" (wherein aM and R1 are the same or different 1 (represents a valent organic group, hydrogen atom, and halogen atom)
(c) Platinum, palladium, nickel, ruthenium, iron,
It is characterized by carrying out the reaction in the presence of a transition metal complex selected from iridium, rhodium, and cobalt. General formula R1R"5i-R"C=CR"-5iR3R'-
1, 2 bissilyl ethylene derivatives represented by Y (wherein R1, R'', R3, R4, R$R' and Y are each as described above) and/or (wherein R'' R2, R3 , R4, RSR6 and Y
are as described above) and/or R'', R13, R14, R'' and R'' have 1 to 1 carbon atoms.
1,2-bissilylethylene derivative (I) represented by 15 organic groups, hydrogen atoms, and halogen atoms. (However, in the formula, R', R', R3, R', RsR' and Y
are as described above). (2) General formula ()

Claims (2)

[Claims] (1) (a) General formula HR^1R^2Si-Y-SiR^
3R^4H (wherein, Y is a divalent organic group, an oxygen atom,
Hydrosilanes represented by a nitrogen atom, a sulfur atom, and R^1, R^2, R^3, and R^4 represent a monovalent organic group, a halogen atom, or a hydrogen atom; and (b) Acetylenes represented by the general formula R^5C≡CR^6 (wherein R^5 and R^6 represent the same or different monovalent organic groups, hydrogen atoms, and halogen atoms) , (c) platinum, palladium, nickel, ruthenium, iron,
General formula R^1R^2Si-R^5C=CR^6-SiR, characterized by reacting in the presence of a transition metal complex selected from iridium, rhodium, and cobalt.
^3R^4-Y (However, in the formula, R^1, R^2, R^3,
R^4, R^5, R^6 and Y are each as described above) 1,2-bissilylethylene derivative and/
Or general formula R^1R^2Si-R^5CH-CHR^6-S
iR^3R^4-Y (however, in the formula, R^1, R^2, R^
3, R^4, R^5, R^6 and Y are each as described above) and/or a 1,2-bissilylethane derivative represented by the general formula R^1R^2Si-R^5C (CH_2R^ 6)
-SiR^3R^4-Y (wherein, R^1, R^2,
R^3, R^4, R^5, R^6 and Y are each as described above). (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (II) (III) (However, in the formula, R ^7, R^8, R^9, R^1^0, R
^1^1, R^1^2, R^1^3, R^1^4, R^
1^5 and R^1^6 can be selected from organic groups having 1 to 15 carbon atoms, hydrogen atoms, and halogen atoms) and 1,2-bissilylethylene derivatives (I) and 1 , 2-bissilylethane derivative (II) and 1,1-bissilylethane derivative (III).