JPH09194485A - Production of alkynylsilanes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply and efficiently produce alkynylsilanes having wide uses as an organic synthetic reactant, etc., such as a protecting group or an alkynylating agent in high yield by reacting a specific halosilane with an alkynylcopper. SOLUTION: A halosilane represented by formula I [R<1> is H, an alkyl, an aryl, an alkenyl or an alkynyl having no acetylenic hydrogen; X is a halogen; (n) is an integer of 0-3] (e.g. chlorotrimethylsilane) is reacted with an alkynylcopper represented by formula II (R<2> is an alkyl, a cycloalkyl, an aryl, an alkenyl, an alkynyl having no acetylenic hydrogen, an alkoxy, silyl or an acyl) (e.g. phenylethynylcopper) to thereby simply and efficiently afford the objective alkynylsilane represented by formula III and having wide uses as an organic synthetic reactant, etc., such as a protecting group or an alkynylating agent [e.g. trimethyl(phenylethynyl)silane].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 1-alkynylsilanes using alkynylcopper.

[0002]

2. Description of the Related Art 1-Alkynylsilanes are protective groups for terminal alkynes ["Silicon Reagents in Organic Synthesis",
p.45, Academic Press, New York (1988)] and regioselective alkynylating agents for carbonyl compounds [Synthesis,
761 (1979); ibid. 991 (1984)] and other widely used reagents in organic synthesis [J. Org.
anomet. Chem., 422, 62 (1992); ibid. 416, 63 (199
1); ibid. 374, 106 (1989); ibid. 360, 113 (1989);
ibid. 337, 273 (1987)], its simple and efficient synthetic method is important.

As a conventional method for synthesizing 1-alkynylsilanes, a method of treating 1-alkyne with butyllithium or an ethyl Grignard reaction agent to form an alkynyl metal, and then silylating this with halosilane [J. Organomet.
Chem., 422, 62 (1992); ibid. 416, 63 (1991); ibid.
374, 106 (1989); ibid. 360, 113 (1989); ibid. 33
7, 273 (1987)] is generally widely used.

However, alkynyl lithium and alkynyl magnesium are highly reactive and easily react with various functional groups. Therefore, the conventional method has many problems as a general-purpose synthetic method of alkynylsilane having various functional groups.

The present inventors have recently used 1-metal zinc.
A simple method for producing alkynylsilanes was found [Tetra
hedron Lett. 36, 2769 (1995)]. However, while this method surpasses the conventional methods in terms of both simplicity and economy, it is not always satisfactory in that it requires a high reaction temperature and that 1-alkyne reduction often occurs as a side reaction. There wasn't.

[0006]

The object of the present invention is to provide an efficient method for producing 1-alkynylsilanes, which does not have such drawbacks.

[0007]

Means for Solving the Problems As a result of investigations on an efficient and industrially applicable production method of 1-alkynylsilanes, the present inventors have found that alkynylcopper is treated with halosilanes such as chlorotrimethylsilane. It was found that 1-alkynylsilanes can be obtained with high efficiency and high yield by heating and stirring, and the present invention has been completed.

That is, the present invention has the following general formula [I]

[0009]

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(Wherein R ¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or an alkynyl group having no acetylene hydrogen, X represents a halogen atom, and n represents an integer of 0 to 3). However, when n is 2 or more, two or more R ^1's may be different from each other.) The halosilane represented by the following general formula [II]

[0011]

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(Wherein R ² represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkenyl group having no acetylene hydrogen, an alkoxy group, a silyl group or an acyl group). The following general formula [III] consisting of reacting with alkynyl copper

[0013]

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(Wherein R ¹ , R ² and n have the same meanings as described above) and a process for producing an alkynylsilane.

The present invention also has the following general formula [IV]

[0016]

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(In the formula, R ¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or an alkynyl group having no acetylene hydrogen, provided that R ^1's may be different from each other. X is a halogen. And a halosilane represented by the following general formula [V]

[0018]

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## STR1 ## wherein R ³ represents a single bond or a divalent organic group, and alkynyl copper represented by the formula is reacted.

[0020]

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(Wherein R ¹ and R ³ have the same meanings as described above) and a process for producing an alkynylsilane.

Furthermore, the present invention provides the following general formula [VII]

[0023]

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(In the formula, R ¹ and R ⁴ represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or an alkynyl group having no acetylene hydrogen. R ⁵ represents a single bond or a divalent linking group. X represents a halogen atom, m and k each independently represent an integer from 0 to 2, provided that R ¹ and R ⁴ may be different from each other. General formula [II]

[0025]

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(In the formula, R ² is an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group having no acetylene hydrogen, an alkoxy group, a silyl group or an acyl group). The following general formula [VIII] is characterized in that alkynyl copper is reacted.

[0027]

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(Wherein R ¹ , R ² , R ⁴ , R ⁵ , m and k
Represents the same meaning as described above. ) Represented by the formula (1).

The features of the present invention are that the reaction efficiently proceeds at a lower reaction temperature and that the progress of side reactions can be suppressed.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Various halosilanes represented by the above general formula [I], [IV] or [VII] used in the present invention are industrially easily available. R ¹ and R ⁴ in the formulas of these general formulas have 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group and a hexyl group. 6 lower alkyl group, ethenyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group,
1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 1-hexenyl group, 3-hexenyl group, lower alkenyl group having 2 to 6 carbon atoms such as 5-hexenyl group, 1-propynyl group, 1-butynyl group , 2-butynyl group, 2-pentynyl group, 3-hexynyl group and the like, acetylene hydrogen-free lower alkynyl group having 3 to 6 carbon atoms, phenyl group, naphthyl group, furyl group, pyridyl group, thienyl group and the like Group can be exemplified. R ⁵ is a single bond or a divalent linking group, and the latter is, for example, a lower alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, a pentamethylene group or a hexamethylene group, or a vinylene group. Examples thereof include divalent unsaturated hydrocarbon groups such as ethynylene group and aryl groups such as phenylene group and naphthylene group. Further, a divalent linking group such as an oxygen atom, a carbonyl group or a group represented by —NR ⁶ — (wherein R ⁶ represents a lower alkyl group or an aryl group) can be exemplified.

Examples of the halosilane represented by the general formula [I] include dichlorosilane, trichlorosilane,
Chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, tetrachlorosilane, chlorotriethylsilane, dichlorodiethylsilane, trichloroethylsilane, chlorotripropylsilane, dichlorodipropylsilane, trichloropropylsilane, tributylchlorosilane, dibutyldichlorosilane, butyltri Chlorosilane, (t-butyl) dimethylchlorosilane,
Chlorotriphenylsilane, dichlorodiphenylsilane, trichlorophenylsilane, (chloro) (phenyl) dimethylsilane, (chloro) (phenyl) methylsilane, (dichloro) (phenyl) methylsilane, chloro (pyridyl) dimethylsilane, (dichloro) diethenylsilane, Chlorotri (phenylethynyl) silane, bromotrimethylsilane, iodotrimethylsilane, diio-
Examples include dodimethylsilane and the like.

As the halosilane represented by the general formula [IV], chlorotrimethylsilane, chlorotriethylsilane, chlorotripropylsilane, tributylchlorosilane, (chloro) (phenyl) dimethylsilane,
(Chloro) (phenyl) methylsilane, chlorotriphenylsilane, (t-butyl) dimethylchlorosilane, chloro (pyridyl) dimethylsilane, chlorotriethenylsilane, chlorotri (phenylethynyl) silane, bromotrimethylsilane, iodotrimethylsilane, etc. Can be illustrated.

Further, as the halosilane represented by the general formula [VII], 1,2-dichloro-1,1,2,2-tetramethyldisilane, 1,2-dichloro-1,2-dimethyl-1, 2-diphenyldisilane, 1,2-dichloro-1,
2-dimethyldisilane, 1,2-dichloro-1,1,2,2
-Tetra (phenylethynyl) disilane, 1,2-dichloro-1,1,2-trimethyl-2-ethenyldisilane,
1,2-dibromo-1,1,2,2-tetraphenyldisilane, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane, 1,3-dichloro-1,1,3,3 -Tetraisopropyldisiloxane, 1,3-dichloro-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-dichlorotetraphenyldisiloxane, 1,3-dibromo-1,
1,3,3-tetramethyldisiloxane, bis (chlorodimethylsilyl) methane, 1,3-bis (bromodimethylsilyl) propane, 1,3-bis (chlorodimethylsilyl) benzene, 2,6-bis (chloro Dimethylsilyl)
Naphthalene etc. can be illustrated.

The other raw material, the alkynyl copper represented by the above general formula [II], is a compound that can be easily synthesized and is industrially easily available [RD Stephens and CE Cast.
ro, J. Org. Chem., 28, 3313 (1963); CE Castro,
EJ Gauhan, and DC Owsley, J. Org. Chem., 31,
4071 (1966)]. R ² in the formula of the general formula is an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkenyl group having no acetylene hydrogen, an alkoxy group,
A silyl group or an acyl group can be used. Examples of the alkyl group include long-chain alkyl groups such as an octyl group, a decyl group, and a tridecyl group in addition to the above lower alkyl group, and these may be branched. Also,
Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group,
As the aryl group, those mentioned above can be mentioned.
As the alkenyl group, in addition to the above lower alkenyl group,
Examples thereof include long-chain alkenyl groups such as octenyl group, decenyl group and tridecenyl group, which may be branched. Examples of the alkynyl group having no acetylene hydrogen include the above-mentioned lower alkynyl group having no acetylene hydrogen, and long-chain alkenyl groups such as 1-octynyl group, 2-decynyl group and 5-tridecynyl group. ,
These may be branched. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, a heptyloxy group, and the like, which may be branched. Examples of the silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, (t-butyl) dimethylsilyl group, triphenylsilyl group, phenylmethylsilyl group, tri (phenylethynyl) silyl group, (phenyl Examples thereof include a dimethylsilyl group, a (pyridyl) dimethylsilyl group, and a triethenylsilyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butanoyl group, a hexanoyl group, a decanoyl group, a benzoyl group, a naphthoyl group and a furoyl group. Further, these groups may be further substituted with a halogen atom, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, an acyl group, an amino group, an alkenyl group, an aryl group, an acyl group, an alkoxy group, a silyl group or the like. . Specifically, for example, phenylethyne, trimethylsilylethyne, 2-propyne-1-ol, 3-butyne-1-ol, 4-pentyn-1-ol, 4-pentynic acid, 4-pentyne. Methyl acid 1,4-pentadecenoic acid, 1-decine, 1-hexyne, 1-pentyne, 1-octyne, 1-chloro-4-pentyne, 1-amino-4-pentyne, 3,3-dimethyl-1- Butyne, ethyl ethynyl ether, ethynyl cyclohexane, 1-ethynyl cyclohexene, 3-butynyl methyl ether, 1-amino-2-propyne, 1-dimethylamino-2-propyne, ethynyl methyl ketone,
Alkynyl copper obtained from ethynyl ethyl ketone, 1-ethynylbenzene, 1-ethynyl-4-chlorobenzene, 1-ethynyl-3-methylbenzene and the like can be used.

R ³ in the general formula [V] is a single bond or a divalent organic group, and examples of the latter include methylene group, ethylene group, propylene group, phenylene group, naphthylene group, ethynylene group and phenylene group. Methylene phenylene group, phenylene (2,2-propylidene) phenylene group, phenylene (bistrifluoromethylmethylene)
In addition to divalent hydrocarbon groups such as phenylene group, biphenylene group, anthracene-diyl group, phenyleneoxyphenylene group, phenylenecarbonylphenylene group, phenylenesulfonylphenylene group, phenylenefurfinylphenylene group, phenylene (dimethylsilylene) phenylene group , A phenylene (diphenylsilylene) phenylene group, a divalent group containing a hetero atom such as a pyridine-diyl group, and the like. Specifically, 1,3-butadiyne, 1,4-pentadiyne, 1,5-hexadiyne, 1,
6-heptadiyne, 1,2-diethynylbenzene, 1,3
-Diethynylbenzene, 1,4-diethynylbenzene,
Alkynyl derived from 1,4-diethynylnaphthalene, 1,5-diethynylnaphthalene, 1,6-diethynylnaphthalene, 4,4'-diethenylbiphenyl, hexatriyne, di (4-ethenylphenyl) sulfide, etc. Copper is mentioned.

From the viewpoint of reaction efficiency, it is desirable to carry out the method of the present invention in a solvent. For example, N, N-dimethylformamide, formamide, dimethylsulfoxide, hexamethylphosphoric triamide, tetrahydrofuran, dioxane, acetonitrile, diethyl ether, benzene,
Toluene and the like can be used alone or in combination. The reaction can be carried out in the range of 0 to 200 ° C, but it is preferable to carry out the reaction at room temperature to 150 ° C from the viewpoint of reaction efficiency.

From the viewpoint of reaction efficiency, it is desirable that the method of the present invention is carried out by coexisting zinc salt, metallic zinc, tertiary amines or phosphines in an equimolar amount or more with respect to alkynyl copper. As the zinc salt, for example, zinc chloride, zinc bromide, zinc iodide, or the like can be used. The metallic zinc may be in any form such as powder, sponge, granules and pellets, but it is preferable to use powder (zinc powder) in terms of reaction efficiency. As the tertiary amines, for example, pyridine, triethylamine, triisopropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, etc. can be used.
Examples of the phosphines that can be used include trimethylphosphine, triethylphosphine, triisopropylphosphine, triisobutylphosphine, triphenylphosphine, tricyclohexylphosphine, and the like. It is desirable that these coexisting compounds or metals be used in equimolar amounts or more with respect to alkynyl copper, and liquid compounds can also be used as a solvent.

[0038]

EXAMPLES The present invention will be described in more detail with reference to Examples and Reference Examples. However, the present invention is not limited to them.

Embodiment 1

[0040]

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Phenylethynyl copper (82 mg, 0.50
mmol) and chlorotrimethylsilane (217 m
g, 2.0 mmol) in acetonitrile (2.0 m
l, distilled from calcium hydride, the same below) N,
N, N ', N'-tetramethylethylenediamine (11
6 mg, 1.0 mmol) in a threaded test tube,
The mixture was stirred at 80 ° C for 5 hours. The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane) to obtain 56 mg of trimethyl (phenylethynyl) silane (0.32 mm
ol, yield 64%).

¹ H-NMR (CDCl ₃ ): δ0.26
(S, 9H), 7.26-7.49 (m, 5H) IR (neat): 2950, 2150, 1485, 1
250,860,840,755,685cm ^-1

Example 2

[0044]

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Octynyl copper (86 mg, 0.50 mmo
1) and chlorotrimethylsilane (217 mg, 2.
0 mmol) in acetonitrile (2.0 ml) with triphenylphosphine (263 mg, 1.0 mmol).
Was added and the mixture was stirred at 100 ° C. for 7 hours in a test tube with a screw. The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane) to give (1-octynyl) trimethylsilane 66.
mg was obtained (0.36 mmol, yield 73%).

¹ H-NMR (CDCl ₃ ): δ0.15
(S, 9H), 0.89 (t, J = 6.6Hz, 3
H), 1.26-1.57 (m, 12H), 2.21.
(T, J = 7.0 Hz, 2H) IR (neat): 2950, 2925, 2850, 2
170, 1250, 840, 755 cm ^-1

Example 3

[0048]

[Chemical 21]

5-chloro-pentynylcopper (83 mg,
0.50 mmol) and chlorotrimethylsilane (2
Zinc powder (260 mg, 4.0 mmo) in an acetonitrile solution (2.0 ml) of 17 mg, 2.0 mmol).
1) was added, and the mixture was stirred at 100 ° C. for 11 hours in a test tube with a screw. The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane) to give 5-chloro-1-trimethylsilyl-1-pentyne 50 mg (0.29 mmol ,
Yield 57%).

¹ H-NMR (CDCl ₃ ): δ0.15
(S, 9H), 1.97 (m, 2H), 2.41 (t,
J = 6.8Hz, 2H), 3.65 (t, J = 6.4H
z, 2H) IR (neat): 2950, 2170, 2124, 8
40,755 cm ^-1

Example 4

[0052]

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5-hydroxypentynyl copper (80 mg,
0.50 mmol) and chlorotrimethylsilane (4
Zinc powder (261 mg, 4.0 mmo) in an acetonitrile solution (2.0 ml) of 34 mg, 4.0 mmol).
1) was added, and the mixture was stirred at 100 ° C. for 12 hours in a test tube with a screw. The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane: ethyl acetate = 3: 1) to give 5- (trimethylsilyl) -4-pentyne-1-. All 63 mg was obtained (0.37 mmol, yield 74%).

¹ H-NMR (CDCl ₃ ): δ0.15
(S, 9H), 1.57 (s, 1H), 1.77 (m,
2H), 2.36 (t, J = 6.9Hz, 2H), 3.
74 (t, J = 6.0 Hz, 2H) IR (neat): 3350, 2950, 2170, 1
245, 1065, 840, 760cm ^-1

Example 5

[0056]

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Phenylethynyl copper (51 mg, 0.50
mmol) and chloro (dimethyl) (phenyl) silane (171 mg, 1.0 mmol) in acetonitrile solution (2.0 ml), N, N, N ′, N′-tetramethylethylenediamine (116 mg, 1.0 mmol) was added, Stirred in a threaded test tube at 100 ° C. for 12 hours. The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane) to give 1- [dimethyl (phenyl) silyl] -2.
-109 mg of phenylethyne were obtained (0.46 mmo
1, yield 92%).

¹ H-NMR (CDCl ₃ ): δ0.49
(S, 6H), 7.32-7.52 (m, 10H) IR (neat): 2970, 2170, 1495, 1
435, 1260, 1125, 840, 800, 710
cm ^-1

Example 6

[0060]

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Phenylethynyl copper (247 mg, 1.5
mmol) and dichlorodimethylsilane (108 m
g, 0.5 mmol) in acetonitrile (2.0 m
N) N, N ', N'-tetramethylethylenediamine (348 mg, 3.0 mmol) was added to 1), and the mixture was stirred at 100 ° C. for 12 hours in a test tube with a screw. The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane) to obtain 127 mg of dimethyldi (phenylethynyl) silane (0.49 mmol, yield 98%). ).

¹ H-NMR (CDCl ₃ ): δ0.48
(S, 6H), 7.22-7.46 (m, 10H) ¹³ C-NMR (CDCl ₃ , CHCl ₃ ): δ 0.5,9
0.5, 105.9, 122.7, 128.2, 12
8.8, 132.1 IR (neat): 2950, 2150, 1485, 1
250,845,750,685cm ^-1

Example 7

[0064]

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Phenylethynyl copper (247 mg, 1.5
mmol) and 1,2-dichloro-1,1,2,2-
N, N, N ', N was added to an acetonitrile solution (2.0 ml) of tetramethyldisilane (94 mg, 0.5 mmol).
′ -Tetramethylethylenediamine (348 mg, 3.
0 mmol) and at 100 ° C. in a threaded test tube,
It was stirred for 12 hours. After filtering the insoluble matter, the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to column chromatography.
After purification with (hexane), 91 mg of 1,2-bis (trimethylsilylethynyl) -1,1,2,2-tetramethyldisilane was obtained (0.28 mmol, yield 57).
%).

¹ H-NMR (CDCl ₃ ): δ0.39
(S, 12H), 7.26-7.48 (m, 10H) IR (neat): 2950, 2150, 1485, 1
240,840,790,750,685cm ^-1

Example 8

[0068]

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Phenylethynyl copper (204 mg, 2.0
mmol) and 1,3-dichloro-1,1,3,3-
Tetramethyldisiloxane (102 mg, 0.5 mmo
l) acetonitrile solution (2.0 ml) in N, N, N
′, N′-Tetramethylethylenediamine (348m
g, 3.0 mmol), and in a test tube with a screw, 10
The mixture was stirred at 0 ° C for 12 hours. The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane) to give 1,3-bis (trimethylsilylethynyl) -1,1,3,3-tetrahydrofuran. 56 mg of methyldisiloxane was obtained (0.17 mmol,
Yield 34%).

¹ H-NMR (CDCl ₃ ): δ0.39
(S, 12H), 7.26-7.49 (m, 10H) IR (neat): 2,975, 2,170, 1495,
1260, 1050, 855, 800, 760, 695
cm ^-1

Example 9

[0072]

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Phenylethynyl copper (82 mg, 0.50
mmol) and chlorotrimethylsilane (217 m
g, 2.0 mmol) in acetonitrile (2.0 m
Zinc chloride (136 mg, 1.0 mmol) was added to l), and the mixture was stirred at 100 ° C. for 5 hours in a test tube with a screw.
The insoluble material was filtered off, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by column chromatography (hexane) to give 75 m of trimethyl (phenylethynyl) silane.
g was obtained (0.43 mmol, yield 86%). The spectrum of this product coincided with that obtained in Example 1.

Example 10

[0075]

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Phenylethynyl copper (82 mg, 0.50
mmol) and chlorotrimethylsilane (217 m
g, 2.0 mmol) in acetonitrile (2.0 m
Zinc powder (260 mg, 4.0 mmol) was added to l), and the mixture was stirred at 100 ° C. for 5 hours in a test tube with a screw.
The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane). Trimethyl (phenylethynyl) silane 85 m
g was obtained (0.49 mmol, yield 98%). The spectrum of this product coincided with that obtained in Example 1. Example 11

[0077]

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Phenylethynyl copper (82 mg, 0.50
mmol) and chlorotrimethylsilane (217 m
g, 2.0 mmol) in pyridine (2.0 ml) was stirred in a test tube with a screw at 100 ° C. for 11 hours. The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane). Trimethyl (phenylethynyl) silane 62 mg
Was obtained (0.36 mmol, yield 72%). The spectrum of this product coincided with that obtained in Example 1.

Example 12

[0080]

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Copper complex of 1,7-octadiyne (116 m
g, 0.5 mmol) and chlorotrimethylsilane (434 mg, 4.0 mmol) in acetonitrile (2.0 ml) were added N, N, N ', N'-tetramethylethylenediamine (232 mg, 2.0 mmol), and screwed. Stirred at 100 ° C. for 15 hours in an attached test tube. The insoluble material was filtered off, the solvent was evaporated under reduced pressure, and the obtained crude product was purified by column chromatography (hexane) to give 1,8-bis (trimethylsilyl) -1,
69 mg of 7-octadiyne was obtained (0.28 mmol,
Yield 55%).

¹ H-NMR (CDCl ₃ ): δ0.15
(S, 12H), 1.63 (m, 4H), 2.25
(M, 4H) ¹³ C-NMR (CDCl ₃ , CHCl ₃ ): δ0.1,1
9.4, 27.6, 84.6, 107.0 IR (neat): 2970, 2190, 1435, 1
255,850,765,645cm ^-1

Comparative Example 1

[0084]

Embedded image

Phenylethyne (51 mg, 0.50 mm
ol) and chlorotrimethylsilane (217 mg,
2.0 mmol) in acetonitrile (2.0 ml)
Zinc powder (261 mg, 4.0 mmol) was added to and the mixture was stirred at 80 ° C. for 5 hours in a test tube with a screw. The desired product, trimethyl (phenylethynyl) silane, was not obtained at all.

Comparative Example 2

[0087]

Embedded image

Phenylethyne (51 mg, 0.50 mm
ol) and chlorotrimethylsilane (217 mg,
2.0 mmol) in acetonitrile (2.0 ml)
Zinc powder (261 mg, 4.0 mmol) and lead chloride (5.6 mg, 0.02 mmol) were added to and the mixture was stirred at 80 ° C. for 5 hours in a test tube with a screw. The desired product, trimethyl (phenylethynyl) silane, was not obtained at all.

[0089]

INDUSTRIAL APPLICABILITY According to the method of the present invention, 1-alkynylsilanes can be produced in a single step and in good yield under relatively mild conditions. In this method, side reactions such as reduction of 1-alkyne can be suppressed. Therefore, the method of the present invention is useful as a method for introducing a protective group into 1-alkyne, and the obtained 1-alkynylsilanes are useful as organic synthetic reaction agents such as alkynylating agents.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B01J 27/138 B01J 27/138 X 31/02 102 31/02 102X 31/24 31/24 X / / C07B 61/00 300 C07B 61/00 300

Claims (4)

[Claims] [Claim 1] The following general formula [I] (In the formula, R ¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an alkynyl group having no acetylene hydrogen. X represents a halogen atom. N represents an integer of 0 to 3. However, when n is 2 or more, two or more R ^1's may be different from each other.) And a halosilane represented by the following general formula [II] (In the formula, R ² is an alkyl group, a cycloalkyl group or an aryl group.
Represents an alkyl group, an alkenyl group, an alkynyl group having no acetylene hydrogen, an alkoxy group, a silyl group or an acyl group. ) Alkynylcopper represented by the following general formula [III] (In the formula, R ¹ , R ² and n have the same meanings as described above.) A method for producing an alkynylsilane. 2. The following general formula [IV]: (In the formula, R ¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or an alkynyl group having no acetylene hydrogen. However, R ¹ may be different from each other.
X represents a halogen atom. ) Represented by halosilane,
The following general formula [V] (Wherein R ³ represents a single bond or a divalent organic group), and is reacted with an alkynyl copper represented by the following:
The following general formula [VI] (In the formula, R ¹ and R ³ have the same meaning as described above.) A method for producing an alkynylsilane. 3. The following general formula [VII]: (In the formula, R ¹ and R ⁴ are a hydrogen atom, an alkyl group, and an aryl group.
Represents an alkyl group, an alkenyl group or an alkynyl group having no acetylene hydrogen. R ⁵ represents a single bond or a divalent linking group. X represents a halogen atom. X represents a halogen atom. m and k independently represent an integer of 0 to 2. However, R ¹ and R ⁴ may be different from each other. ) And a halosilane represented by the following general formula [II] (In the formula, R ² is an alkyl group, a cycloalkyl group or an aryl group.
Group, alkenyl group, alkenyl group having no acetylene hydrogen, alkoxy group, silyl group or acyl group. ) Alkynylcopper represented by the formula: (In the formula, R ¹ , R ² , R ⁴ , R ⁵ , m and k have the same meanings as described above.) A process for producing an alkynylsilane. 4. The reaction according to claim 1, wherein the reaction is carried out in the presence of one or more compounds or metals selected from zinc salts, metallic zinc, tertiary amines, and phosphines. Alternatively, the method for producing an alkynylsilane according to the item 3.