JPH09241272A - 2-stanylvinylborane compound and production of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound simultaneously having a vinylstannane structure and a vinylborane structure useful for the production of a medicine, an agrochemical, etc., and useful as a reactant with various compounds. SOLUTION: This 2-stannylvinylborane compound is represented by formula I [R<1> , R<2> are each H, an aliphatic (oxycarbonyl) group, an aromatic (oxycarbonyl) group or a (substituted) silyl; R<3> to R<5> are each an aliphatic group or an aromatic group; R<6> , R<7> are each a halogen or amino, and R<6> and R<7> may bind to form a ring in the case that R<6> and R<7> are both amino], for example, 1,3-dimethyl-2-[(Z)-2-phenyl-2-(trimethylstannyl)ethenyl]-1,-3-diaza-2- boracyclopentane. The compound of the formula I is obtained by reacting a compound of the formula: R<1> -C≡C-R<2> with a compound of formula II in the presence of a catalyst consisting of a metal complex or a metal salt of a group X metal.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a 2-stannylvinylborane compound and a method for producing the same. This 2-stannyl vinyl borane compound has a vinyl stannane structure and a vinyl borane structure, which are useful in the production of medicines, agricultural chemicals, etc., in the same molecule, and is used as a synthetic reaction agent for various compounds. (For example, J. Org. Chem, Vol. 59, 47.
38-4742, 1994, Angew. Chem. Int. Ed. Engl, 2
Volume 5, Pages 508-524, 1986, and Chem. Rev, 95.
Volume, 2457-2483, 1995).

[0002]

2. Description of the Related Art As a conventional method for producing a 2-stannylvinylborane compound, a method utilizing an intramolecular alkyl substitution reaction from a trialkylhalostannane and a lithium salt of 1-alkynyltrialkylborate is known. (For example, Tetrahedron Lett, 805-808, 1976, and J. Org. Chem, 51, 767-768, 1986).
However, in this method, since an active alkynyllithium reagent is used, it is difficult to synthesize a 2-stannylvinylborane compound having a reactive functional group such as a carbonyl group or a halogen. Therefore, the structure of the 2-stannylvinylborane compound obtained by this method is greatly limited, and it cannot be said to be a general synthetic method. In addition, there was a big problem in terms of process, because more than the equivalent amount of salt was by-produced, the stirring efficiency was lowered, and complicated filtration treatment was involved.

[0003]

In view of the above circumstances, it is an object of the present invention to provide a 2-stannylvinylborane compound having various substituents and an advantageous method for producing the same.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by reacting an alkyne compound with a stannylborane compound in the presence of a Group 10 transition metal catalyst, The inventors have found that a -stannyl vinyl borane compound can be obtained regioselectively and stereoselectively, and have completed the present invention. That is, according to the present invention, the general formula

Embedded image (In the formula, R ¹ and R ² are hydrogen, an aliphatic group, an aromatic group,
An aliphatic oxycarbonyl group, an aromatic oxycarbonyl group or a substituted or unsubstituted silyl group, R ³ and R ⁴
And R ⁵ represents an aliphatic group or an aromatic group, R ⁶ and R ⁷ represent a halogen or an amino group, and R ⁶ and R
^{When 7} represents an amino group, R ⁶ and R ⁷ may combine to form a ring) to provide a 2-stannylvinylborane compound. Further, according to the present invention, the general formula

Embedded image (In the formula, R ¹ and R ² are hydrogen, an aliphatic group, an aromatic group,
An aliphatic oxycarbonyl group, an aromatic oxycarbonyl group or a substituted or unsubstituted silyl group, R ³ and R ⁴
And R ⁵ represents an aliphatic group or an aromatic group, R ⁸ represents an aliphatic group or an aromatic group, and two R ^{8 s} may combine to form a ring. Nylvinylborane compounds are provided. Furthermore, according to the present invention, in order to produce the 2-stannylvinylborane compound (1),

Embedded image (Wherein R ¹ and R ² have the same meanings as described above), and an alkyne compound represented by the general formula

Embedded image (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meanings as described above).
A method of reacting in the presence of a catalyst consisting of a metal complex of a Group 0 metal or a metal salt is provided. Furthermore, according to the present invention, in order to produce a 2-stannylvinylborane compound of the general formula (2), an aliphatic hydroxy compound or an aromatic compound is added to the 2-stannylvinylborane compound of the general formula (1). A method of reacting a hydroxy compound is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The alkyne compound used as a reaction raw material in the present invention is represented by the above general formula (3). In the general formula (3), R ¹ and R ² represent hydrogen, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group or a substituted or unsubstituted silyl group. The aliphatic group includes a chain or cyclic alkyl group or alkenyl group. The number of carbon atoms in the aliphatic group is 1.
-18, preferably 1-12. Moreover, this aliphatic group may have various substituents. Such substituents include various ones containing a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, for example, a hydroxy group, a carboxyl group, an aliphatic oxy group, an aromatic oxy group, an aliphatic group. Oxycarbonyl group, aromatic oxycarbonyl group, acyl group, amino group, nitro group, cyano group,
Examples thereof include thiol group, mercapto group, silyl group and halogen. Specific examples of the aliphatic group include, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, cyclohexyl group, 3-methyl-3-butenyl group, 3-octynyl group, trimethylsiloxyhexyl group. , 2-chloroethyl group, dimethylaminomethyl group and the like.

The aromatic group includes both an aromatic group consisting of a carbocycle and an aromatic group consisting of a heterocycle. In this case, examples of the carbocycle include a condensed ring such as a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring, in addition to a benzene ring, a biphenyl ring, and a bis (phenyl) alkane. On the other hand, as the heterocyclic ring, a five-membered ring such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazyl; a six-membered ring such as pyran, pyrone, pyridine, pyridazine, pyrimidine and pyrazine; indole, carbazole, coumarin, benzopyrone Condensed rings such as quinoline, isoquinoline, acridine, phthalazine, quinazirine, and quinolixane. Further, this aromatic ring may have various substituents. Examples of such a substituent include hydrocarbon groups such as an alkyl group and an alkenyl group, as well as various substituents shown for the aliphatic group. Specific examples of the aromatic group include a phenyl group, a tolyl group, a naphthyl group, an aminophenyl group, a pyridyl group, a thienyl group, and a furyl group.

Examples of the aliphatic oxycarbonyl group and the aromatic oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group and a 1-butoxyloxycarbonyl group. These aliphatic oxycarbonyl group and aromatic oxycarbonyl group can have various substituents shown for the aliphatic group.

The silyl group includes substituted and unsubstituted silyl groups. Further, the substituted silyl group includes a silyl group substituted with an aliphatic group or an aromatic group. Examples of the aliphatic group and aromatic group in this case include the above-mentioned various groups. Specific examples of the substituted silyl group include a trimethylsilyl group, a monomethylsilyl group, a triethylsilyl group, a triphenylsilyl group and a tribenzylsilyl group.

Specific examples of the alkyne compound represented by the general formula (3) are as follows. Acetylene, 1-octyne, 4-octyne, 1-propynylbenzene, 2,2-dimethyl-3-hexyne, 1,5-decadiyne, 5-methyl-4-hexene-1-yne, phenylacetylene, diphenylacetylene, 3 -Ethynylaniline, 2-ethynylpyridine, trimethylsilylacetylene, 4-chloro-1-butyne, 5-trimethylsiloxy-1-octyne, propynoic acid methyl ester, acetylenedicarboxylic acid di-t-butyl ester, 2-ethynylfuran, 6 -Dimethylamino-1-hexyne, 3
-Ethynylthiophene, 2-ethynyltoluene, 1-ethynylnaphthalene and the like.

In the above general formula (4) showing the stannyl borane compound used as a reaction raw material in the present invention, R ³ and R ⁴
And R ⁵ represents an aliphatic group or an aromatic group, and R ⁶ and R ⁷ represent a halogen or an amino group. The stannyl borane compound shown here is a compound that is easily obtained by reacting a stannyl lithium compound with a haloborane compound (for example, J. Org. Chem. Magazine, vol. 52, p. 297-306, 1973, Chem. Ber. 114, 3056-3062, 1
981). Examples of the aliphatic group and aromatic group in this case include those described above for the alkyne compound. Further, examples of the halogen include chlorine, bromine, iodine and the like. The amino group includes substituted and unsubstituted amino groups. The substituted amino group includes an amino group substituted with an aliphatic group or an aromatic group. Examples of the aliphatic group and aromatic group in this case include the above-mentioned various groups. Specific examples of the amino group include a dimethylamino group, a diethylamino group, a diphenylamino group and a dibenzylamino group. When R ⁶ and R ⁷ represent an amino group, R ⁶ and R ⁷ can combine to form a ring. The ring in this case is a ring containing boron and nitrogen. The amino group forming such a ring includes aliphatic and aromatic divalent amino groups. Specific examples thereof include an N, N-dimethyldimethylene diamino group,
In addition to alkylenediamino groups such as N, N-dimethyltrimethylenediamino group and cyclohexylenediamino group, phenylenediamino group and phenylenedimethyldiamino group can be mentioned.

Specific examples of the stannyl borane compound represented by the general formula (4) are as follows. Chloro (dimethylamino) (trimethylstannyl) borane, Bromo (dimethylamino) (trimethylstannyl) borane, Iodo (dimethylamino) (trimethylstannyl)
Borane, bis (dimethylamino) (tributylstannyl) borane, bis (diethylamino) (trimethylstannyl) borane, 1,3-dimethyl-2- (trimethylstannyl) -1,3-diaza-2-boracyclopentane ,
1,3-dimethyl-2- (triphenylstannyl)-
1,3-diaza-2-boracyclohexane and the like. In addition, the stannylborane compound used in the present invention can be used as it is without purification after synthesis.

The catalyst comprising a metal complex or metal salt of a Group 10 metal used in the present invention includes a metal complex and a metal salt of nickel, a metal complex and a metal salt of palladium, a metal complex and a metal salt of platinum. It A specific example is as follows. Tetracarbonylnickel, dicarbonylbis (triphenylphosphine) nickel, bis (1,5-cyclooctadiene) nickel,
(Η ² -Ethylene) bis (triethylphosphine) nickel, tetrakis (tricyclohexylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, chloro (η-cyclopentadienyl) (triphenylphosphine) nickel, palladium acetate.

Dichlorobis (benzonitrile) palladium, dichloro (1,5-cyclooctadiene) palladium, dibromobis (dimethylphenylphosphine) palladium, dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium, diiodo [1 , 4-bis (dimethylphosphino) butane], di-μ-chloro-
Dichlorobis (isocyanide) dipalladium, di-μ-
Chloro-dichlorobis (triphenylphosphine)) dipalladium, dichloro-μ-bis [bis (diphenylphosphino) methane] dipalladium, tetrakis (triphenylphosphine) palladium, tris (triethylphosphine) palladium, bis (tricyclohexylphosphine) Palladium, tetrakis (triethylphosphite) palladium, tetrakis (triphenylacin) palladium, carbonyltris (triphenylphosphine)
Palladium, (μ2-ethylene) bis (triphenylphosphine) palladium, (μ2-maleic anhydride)
[1,2-bis (diphenylphosphino) ethane] palladium, bis (cycloocta-1,5-diene) palladium, bis (dibenzylideneacetone) palladium, chloro (methyl) (1,5-cyclooctadiene) palladium, Dimethyl [1,2-bis (dimethylphosphino)]
Ethane] palladium, dimethyl [1,3-bis (dimethylphosphino) propane] palladium, dimethyl [1,
2-bis (dimethylamino) ethane] palladium, dimethylbis (1-phospha-2,6,7-oxobicyclo [2,2,2] octane) palladium, diphenylbis (methyldiphenylphosphinite) palladium, dibenzylbis (trimethyl) Phosphine) palladium, diethynylbis (triethylphosphine) palladium, dineopentyl (2,2'-bipyridyl) palladium, bromo (methyl) bis (triethylphosphine) palladium,
Benzoyl (chloro) bis (trimethylphosphine) palladium, cyclopentadienyl (phenyl) (triethylphosphine) palladium, η-allyl (pentamethylcyclopentadienyl) palladium, η-allyl (1,5-cyclooctadiene) palladium Tetrafluoroborate, bis (η-allyl) palladium, bis (acetylacetonato) palladium, dichloroethylenediaminepalladium, palladium chloride.

Dichlorobis (acetonitrile) platinum, bis (1,5-cyclooctadiene) platinum, bis (dibenzylideneacetone) platinum and the like. These Group 10 metal catalysts also include complexes solvated with general-purpose solvents such as tetrahydrofuran and benzene. As these catalysts, those synthesized in the reaction system may be used as they are without purification. Also,
These catalysts can be used as a mixed system catalyst of two or more kinds or as a mixed system catalyst with the ligand used in the complex.

To produce the 2-stannylvinylborane compound of the general formula (1) according to the present invention, the alkyne compound of the general formula (3) and the stannylborane compound of the general formula (4) are added in the presence of the catalyst. React with. The reaction temperature is -50 to 250 ° C, preferably 0 to 150 ° C. The amount ratio of the alkyne compound and the stannylborane compound is not particularly limited, but the stannylborane compound is 0.5 to 1.5 mol, preferably 0.8 to 1.5 mol, per 1 mol of the alkyne compound.
A ratio of 1.2 mol is preferable. The amount of the catalyst used is 0.00001 to 0.
The amount is 1 mol, preferably 0.001 to 0.05 mol. When carrying out the above reaction, a reaction solvent is not always necessary, but when a solvent is used, toluene,
Aromatic hydrocarbons such as benzene, ethers such as diethyl ether, dibutyl ether and tetrahydrofuran,
Examples thereof include saturated saturated hydrocarbons such as pentane, hexane, and decane. Separation of the product after the reaction is easily carried out by a usual purification and isolation method such as distillation and recrystallization.

The 2-stannylvinylborane compound represented by the general formula (2) is obtained by reacting the 2-stannylvinylborane compound represented by the general formula (1) with an aliphatic hydroxy compound or an aromatic hydroxy compound. Can be manufactured. The reaction in this case is
For example, it is expressed by the following equation.

Embedded image The reaction temperature in this case is −50 to 200 ° C., preferably 0.
１００100 ° C. Aliphatic hydroxy compounds and aromatic hydroxy compounds include monohydroxy compounds and dihydroxy compounds. Examples of such organic hydroxy compounds include aliphatic and aromatic monohydroxy compounds such as methanol, ethanol, propanol, butanol, cyclohexyl alcohol, benzyl alcohol and phenol; ethylene glycol, propylene glycol, butylene glycol, pinacol and the like. Examples thereof include alkylene glycol and aliphatic and aromatic dihydroxy compounds such as catechol. In the case of a monohydroxy compound, the use ratio is 2 to 2.5 mol per 1 mol of the stannyl borane compound, and in the case of a dihydroxy compound, the ratio is 1 to 1.3 mol per 1 mol of the stannyl borane compound. When a dihydroxy compound is used, two R ^8's are bonded to each other to obtain a compound having a structure in which oxygen and boron form a service ring.

According to the method of the present invention, the above general formula (1)
A 2-stannylvinylborane compound represented by and (2) is obtained. Specific examples of the 2-stannylvinylborane compounds represented by the general formulas (1) and (2) are as follows. 1,3-dimethyl-2-
[(Z) -2- (trimethylstannyl) ethenyl]-
1,3-diaza-2-boracyclopentane, 1,3-dimethyl-2-[(Z) -2-trimethylstannyl-1-
Octenyl] -1,3-diaza-2-boracyclopentane, (Z) -bis (diethylamino) boryl-2- (trimethylstannyl) -1-octene, 1,3-dimethyl-2-[(E)- 1,2-Dipropyl-2- (trimethylstannyl) ethenyl] -1,3-diaza-2-boracyclopentane, 1,3-dimethyl-2-[(E) -1-
Methyl-2-phenyl-2- (trimethylstannyl) ethenyl] -1,3-diaza-2-boracyclopentane,
2,2-Dimethyl-trimethylstann-4-dimethylaminoiodoboryl-3-hexene, 1,3-dimethyl-2-[(Z) -2-trimethylstannyl-5-octyne-1-enyl] -1 , 3-diaza-2-boracyclopentane, bromo (dimethylamino) [(Z) -5-methyl-2-trimethylstannyl-1,4-heptadienyl] borane, 1,3-dimethyl-2-[(Z ) -2-Phenyl-2- (trimethylstannyl)]-1,3-diaza-2-boracyclopentane, (Z) -1-bis (diethylamino) boryl-2-phenyl-2- (trimethylstannyl) Ethene, (E) -bis (diethylamino) boryl-1,2-diphenyl-2-trimethylstannyl-
1-ethene, 3-[(Z) -2-chloro (dimethylamino) boryl-1- (trimethylstannyl) ethenyl] aniline, 2-[(Z) -2-bis (dimethylamino) boryl-1- ( Tributylstannyl) ethenyl] pyridine, 1,3-dimethyl-2-[(Z) -2-trimethylsilyl-2- (trimethylstannyl) ethenyl] -1,
3-diaza-2-boracyclopentane, 2-[(Z)-
4-chloro-2- (triphenylstannyl) butenyl]
-1,3-Dimethyl-1,3-diaza-2-boracyclohexane, 1- [bis (diethylamino) boryl] -2
-(Trimethylstannyl) maleic acid di-t-butyl ester (Z) -1-bis (dimethylamino) boryl-2-tributylstannyl-3-dimethylaminopropene 3-[(Z) -2-diethoxyboryl-1 -(Triphenylstannyl) ethenyl] thiophene, 2-[(Z)-
2-Tolyl-2- (tributylstannyl) ethenyl]-
1,3-dioxa-2-boracyclopentane, 2-
[(Z) -2-naphthyl-2- (tributylstannyl)
Ethenyl] -1,3-dioxa-2-boracyclopentane, 2-[(Z) -2- (trimethylstannyl) ethenyl] -1,3-dioxa-2-boracyclopentane,
4,4,5,5-tetramethyl-2-[(Z) -2-
Trimethylstannyl-1-octenyl] -1,3-dioxa-2-boracyclopentane, 2-[(Z) -2-trimethylstannyl-1-octenyl] -1,3-dioxa-2-bora-4. , 5-benzocyclopentane, 4,
4,5,5-Tetramethyl-2-[(E) -1,2-
Dipropyl-2- (trimethylstannyl) ethenyl]-
1,3-dioxa-2-boracyclopentane, 2-
[(E) -1-Methyl-2-phenyl-2- (trimethylstannyl) ethenyl] -1,3-dioxa-4,5-
Benzo-2-boracyclopentane, (E) -2,2-dimethyl-3-trimethylstannyl-4-diphenoxyboryl-3-hexene 4,4,5,5-tetramethyl-2-[(Z) -2-Trimethylstannyl-5-octyne-1-enyl] -1,
3-dioxa-2-boracyclopentane, dibutoxy [(Z) -5-methyl-2-trimethylstannyl-1,
4-heptadienyl] borane, 2-[(Z) -2-phenyl-2- (trimethylstannyl) ethenyl] -1,3
-Dioxa-4,5-benzo-2-boracyclopentane, (E) -1-diethoxyboryl-1,2-diphenyl-2- (trimethylstannyl) ethene, 3-[(Z)
-2-diethoxyboryl-1- (trimethylstannyl)
Ethenyl] aniline, 2-[(Z) -2-diethoxyboryl-1- (tributylstannyl) ethenyl] pyridine, 4,4,5,5-tetramethyl-2-[(Z) -2
-Trimethylsilyl-2- (trimethylstannyl) ethenyl] -1,3-dioxa-2-boracyclopentane,
2-[(Z) -4-chloro-2- (triphenylstannyl) butenyl] -1,3-dimethyl-1,3-dioxa-2-boracyclopentane, 4,4,5,5-tetramethyl -2-[(Z) -3-Bromo-2- (trimethylstannyl) propenyl] -1,3-dioxa-2-boracyclopentane, (Z) -1-diethoxyboryl-2-
Trimethylstannyl-3-trimethylsiloxy-1-octene, (Z) -2-diethoxyboryl-1- (tributylstannyl) ethenylacetic acid methyl ester, diethoxyboryl-2- (trimethylstannyl) maleic acid di-
t-butyl ester, 2-[(Z) -2-furanyl-2
-(Tributylstannyl) ethenyl] -1,3-dioxa-4,5-benzo-2-boracyclopentane, (Z)
-1-diethoxyboryl-2-tributylstannyl-3
-Dimethylaminopropene and the like.

[0018]

Next, the present invention will be described more specifically with reference to examples.

Example 1 Tetrakis (triphenylphosphine) palladium (0.
(01 mmol) in benzene (1 ml) at room temperature under a nitrogen atmosphere with phenylacetylene (1 mmol) and 1,3-dimethyl-2- (trimethylstannyl) -1,3-diaza-
2-Boracyclopentane (1 mmol) was added and the reaction was carried out at room temperature for 5 hours, then 1,3-dimethyl-2-[(Z) -2-phenyl-2- (trimethylstannyl) represented by the following formula was obtained. Ethenyl] -1,3-diaza-2-boracyclopentane (Compound A) was obtained quantitatively.

[Chemical 6]

The spectrum of compound A is shown below. ¹ H-NMR (C ₆ D ₆ ): δ 0.23 (s, 9H, SnMe ₃ ), 2.59 (s, 6H, N
Me), 2.99 (s, 4H, NCH ₂ ), 6.69 (s, 1H, CH), 7.05-7.
30 (m, 5H, Ph); ¹³ C-NMR (C ₆ D ₆ ) -7.78, 34.49,51.60,
126.31, 126.61, 128.53, 140.33, 149.57, 160.60.

Example 2 When 1-octyne was used in place of phenylacetylene in Example 1 to carry out a similar reaction, 1,3-dimethyl-2-[(Z) -2-trimethyl represented by the following formula: Stannyl-1-octenyl] -1,3-diaza-2-boracyclopentane (Compound B) was quantitatively obtained.

Embedded image

Next, the spectrum of compound B is shown. ¹ H-NMR (C ₆ D ₆ ): δ 0.24 (s, 9H, SnMe ₃ ), 0.90 (t, 3H, J
= 6.7 Hz, ¹³ CH ₃ (CH ₂ ) ₄ CH ₂ ), 1.27-1.53 (m, 8H, CH ₃ (CH
₂ ) 4CH ₂ ), 2.48 (t, 2H, J = 7.3 Hz, CH ₃ (CH ₂ ) ₄ CH ₂ ), 2.5
9 (s, 6H, NMe), 2.90 (s, 4H, NCH ₂ ), 6.39 (s, 1H, C
H); ¹³ C-NMR (C ₆ D ₆ ) -8.55, 14.31, 23.08, 29.20, 30.3
0, 32.12, 34.53, 45.45, 51.56, 136.79, 160.82.

Example 3 Instead of 1,3-dimethyl-2- (trimethylstannyl) -1,3-diaza-2-boracyclopentane of Example 1, bis (diethylamino) (trimethylstannyl)
When the same reaction was performed using borane, (Z) -bis (diethylamino) boryl-2-phenyl-2- (trimethylstannyl) ethene (compound C) represented by the following formula was quantitatively obtained.

Embedded image

Next, the spectrum of compound C is shown. ¹ H-NMR (C ₆ D ₆ ): δ 0.25 (s, 9H, SnMe
₃ ), 1.00 (t, 12H, J = 7.0H
z, CH ₃ CH ₂ N), 3.02 (broad,
8H, CH ₃ CH ₂ N), 6.91 (s, 1
H, CH), 7.03-7.25 (m, 5H,
Ph); ¹³ C-NMR (C ₆ D ₆ ) -7.6.
15.7, 42.6, 125.9, 126.
5, 128.5, 149.3, 150.0, 1
53.7.

Example 4 When 1-octyne was used in place of phenylacetylene in Example 3 and a similar reaction was performed, (Z) -bis (diethylamino) boryl-2-trimethylstannyl-1-octene compound D was obtained. Obtained quantitatively.

Embedded image

Next, the spectrum of compound D is shown. ¹ H-NMR (C ₆ D ₆ ): δ 0.28 (s, 9H, SnMe ₃ ),
0.90 (t, 3H, J = 6.8 Hz, CH ₃ (CH ₂ ) ₄ CH ₂ ), 1.01 (t, 12
H, CH ₃ CH ₂ N), 1.30-1.52 (m, 8H, CH ₃ (CH ₂ ) ₄ CH ₂ ), 2.45
(t, 2H, J = 6.9 Hz, CH ₃ (CH ₂ ) ₄ CH ₂ ), 2.94-3.09 (broad,
8H, CH ₃ CH ₂ N), 6.61 (s, 1H, CH); ¹³ C-NMR (C ₆ D ₆ ) -8.
31, 14.31, 15.75, 23.14, 29.33, 30.37, 32.17, 42.7
3,45.08, 145.16, 153.86.

Example 5 When tolan was used instead of phenylacetylene of Example 3 to carry out the reaction at 80 ° C., the following formula (E) was obtained.
-Bis (diethylamino) boryl-1,2-diphenyl-2- (trimethylstannyl) ethene (Compound E) was obtained quantitatively.

Embedded image

Next, the spectrum of compound E is shown. ¹ H-NMR (C ₆ D ₆ ): δ 0.27 (s, 9H, SnMe ₃ ), 0.98 (t, 12H,
J = 7.0 Hz, CH ₃ CH ₂ N), 3.16 (q, 8H, J = 7.0 Hz, CH ₃ CH
₂ N), 6.84-7.43 (m, 10H, Ph).

Example 6 When acetylenedicarboxylic acid di-t-butyl ester was used in place of phenylacetylene in Example 3 and a similar reaction was carried out, bis (diethylamino) boryl-2- (trimethyl) represented by the following formula was obtained. Stannyl) maleic acid di
t-Butyl ester (Compound F) was obtained quantitatively.

Embedded image

Next, the spectrum of compound F is shown. ¹ H-NMR (C ₆ D ₆ ): δ 0.33 (s, 9H, SnMe ₃ ), 0.96 (t, 12H,
J = 7.0 Hz, CH ₃ CH ₂ N), 1.46 (s, 9H, tBu), 1.49 (s, 9
H, tBu), 2.99 (q, 8H, J = 7.0 Hz, CH ₃ CH ₂ N).

Example 7 In place of the tetrakis (triphenylphosphine) palladium of Example 1, dimethyl (1,2-dimethylphosphinoethane) palladium was used to carry out a similar reaction to obtain 1,3-dimethyl-2. -[(Z) -2-phenyl-
2- (Trimethylstannyl) ethenyl] -1,3-diaza-2-boracyclopentane was obtained quantitatively. The spectrum of the compound obtained was in agreement with that obtained in Example 1.

Example 8 Bis (dibenzylideneacetone) palladium (0.05 mmo
Triphenylphosphine (0.1 mmol) was added to a solution of l) in benzene (1 ml) under a nitrogen atmosphere, and the mixture was stirred at room temperature for several minutes and then phenylacetylene (1 mmol) and 1,3-dimethyl-2- (trimethylstannyl). -1,3-diaza-
2-Boracyclopentane (1 mmol) was added and the reaction was carried out at room temperature for 5 hours to give 1,3-dimethyl-2-[(Z)-
2-Phenyl-2- (trimethylstannyl) ethenyl]
-1,3-diaza-2-boracyclopentane was obtained quantitatively. The spectrum of the compound obtained was in agreement with that obtained in Example 1.

Example 9 A solution of palladium chloride (0.05 mmol) in benzene (1 ml) was charged with tetramethylethylenediamine (0.05 ml) under a nitrogen atmosphere.
mmol) and heat and stir to dissolve the precipitate completely. After cooling the reaction mixture to room temperature, phenylacetylene (1 mm
ol) and 1,3-dimethyl-2- (trimethylstannyl) -1,3-diaza-2-boracyclopentane (1 mm
ol) was added and the reaction was carried out at room temperature for 5 hours to give 1,3-dimethyl-2-[(Z) -2-phenyl-2- (trimethylstannyl) ethenyl] -1,3-diaza-2-bora. Cyclopentane was obtained quantitatively. The spectrum of the compound obtained was in agreement with that obtained in Example 1.

Example 10 Tetrakis (triphenylphosphine) palladium (0.
01 mmol) in benzene (1 ml) at room temperature under nitrogen atmosphere with 1-octyne (1 mmol) and 1,3-dimethyl-
2- (Trimethylstannyl) -1,3-diaza-2-boracyclopentane (1 mmol) was added, the reaction was carried out at room temperature for 5 hours and then treated with pinacol (1 mmol).
4,4,5,5-tetramethyl-2 represented by the following formula
-[(Z) -2-Trimethylstannyl-1-octenyl] -1,3-dioxa-2-boracyclopentane (Compound G) was quantitatively obtained.

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The spectrum of Compound G is shown below. ¹ H-NMR (C ₆ D ₆ ): δ 0.32 (s, 9H, SnMe ₃ ), 0.83 (t, 3H, J
= 6.8 Hz, CH ₃ (CH ₂ ) ₄ CH ₂ ), 1.03 (s, 12H, CMe), 1.16-1.
40 (m, 8H, CH ₃ (CH ₂ ) ₄ CH ₂ ), 2.39 (t, 2H, J = 7.5Hz, CH
₃ (CH ₂ ) ₄ CH ₂ , 6.39 (s, 1H, CH); ¹³ C-NMR (C ₆ D ₆ ) -6.39,
14.23, 22.90, 24.79, 29.31, 29.91, 32.08, 45.40, 1
31.42, 177.34.

Example 11 When catechol was used in place of pinacol in Example 10 to carry out the same reaction, 2-[(Z) represented by the following formula:
2-Trimethylstannyl-1-octenyl] -1,3
-Dioxa-2-bora-4,5-benzocyclopentane was obtained quantitatively.

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[0037]

According to the method of the present invention, 2-stannyl having a vinylstannane structure and a vinylborane structure in a molecule is formed from an alkyne compound and a stannyborane compound in the presence of a catalyst composed of a metal complex or a metal salt of a Group 10 metal. The vinyl borane compound can be produced in high yield and high selectivity under mild conditions. Further, by reacting the 2-stannylvinylborane compound thus obtained with an organic hydroxy compound, a 2-stannylvinylborane compound having an organic oxy group bonded to a boron atom can be easily obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masato Tanaka 1-1 Higashi, Tsukuba-shi, Ibaraki Institute of Industrial Science and Technology

Claims (4)

[Claims] 1. A compound of the general formula (In the formula, R ¹ and R ² are hydrogen, an aliphatic group, an aromatic group,
An aliphatic oxycarbonyl group, an aromatic oxycarbonyl group or a substituted or unsubstituted silyl group, R ³ and R ⁴
And R ⁵ represents an aliphatic group or an aromatic group, R ⁶ and R ⁷ represent a halogen or an amino group, and R ⁶ and R
^{When 7} represents an amino group, R ⁶ and R ⁷ may combine with each other to form a ring). 2. A compound of the general formula (In the formula, R ¹ and R ² are hydrogen, an aliphatic group, an aromatic group,
An aliphatic oxycarbonyl group, an aromatic oxycarbonyl group or a substituted or unsubstituted silyl group, R ³ and R ⁴
And R ⁵ represents an aliphatic group or an aromatic group, R ⁸ represents an aliphatic group or an aromatic group, and two R ^{8 s} may combine to form a ring. Nyl vinyl borane compound. 3. A general formula: (In the formula, R ¹ and R ² are hydrogen, an aliphatic group, an aromatic group,
An aliphatic oxycarbonyl group, an aromatic oxycarbonyl group or a substituted or unsubstituted silyl group, R ³ and R ⁴
And R ⁵ represents an aliphatic group or an aromatic group, R ⁶ and R ⁷ represent a halogen or an amino group, and R ⁶ and R
^{When 7} represents an amino group, R ⁶ and R ⁷ may combine with each other to form a ring), and in the method for producing a 2-stannylvinylborane compound represented by the general formula: (Wherein R ¹ and R ² have the same meanings as described above), and an alkyne compound represented by the general formula: (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meanings as described above).
The above method, wherein the reaction is carried out in the presence of a catalyst composed of a metal complex of a Group 0 metal or a metal salt. 4. A compound of the general formula (In the formula, R ¹ and R ² represent hydrogen, an aliphatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group or a substituted or unsubstituted silyl group, and R ³ , R ⁴ and R ⁵
Represents an aliphatic group or an aromatic group, R ⁸ represents an aliphatic group or an aromatic group, and two R ⁸ may combine with each other to form a ring) 2-stannylvinylborane In the method of producing a compound, a compound of the general formula: (In the formula, R ⁶ and R ⁷ represent halogen or an amino group, and when R ⁶ and R ⁷ represent an amino group, R ⁶ and R ^7
May combine with each other to form a ring, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as defined above.
The above method, characterized in that the stannyl vinyl borane compound is reacted with an aliphatic hydroxy compound or an aromatic hydroxy compound.