JPH0753738B2 - Bis (1,2-bissilylethylene) derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to bis (1,2-diamine) useful as a synthetic intermediate for fine chemicals such as pharmaceuticals and agricultural chemicals.
And a method for producing the same.

[0002]

2. Description of the Related Art Hitherto, a bis (1,2-bissilylethylene) derivative and a method for producing it have not been known.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a method for industrially producing a bis (1,2-bissilylethylene) derivative under mild conditions using readily available raw materials, and particularly a novel compound. It was made for the purpose of providing.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that 1,2-bis (dimethylsilyl) benzene and a specific bis (acetylene) derivative are platinum compounds. Based on this finding, the present invention has been completed based on the finding that it rapidly reacts under mild conditions in the presence of bis (1,2-bissilylethylene) to give a bis (1,2-bissilylethylene) derivative.

That is, according to the present invention, 1,2-bis (dimethylsilyl) benzene and general formula (I) R ¹ -C≡C-A-C≡C-R ¹ [wherein R ¹ is an alkyl group, aryl group or an aralkyl group, A is an alkylene group, an arylene group, aralkylene group, Origoshiraniren _{group, -R 2 Si-O-SiR} 2 -
(Wherein R is an alkyl group), —C ₆ H ₄ —O—C ₆
H ₄ −, a ferrocenylene group, a furylene group, a thienylene group, or a pyridylene group] is reacted with a bis (acetylene) derivative in the presence of a platinum compound, the general formula (II):

[Chemical 3] (Wherein, Me is a methyl group, R ¹ and A have the same meanings as described above), and a method for producing a bis (1,2-bissilylethylene) derivative represented by the formula The present invention provides a novel compound represented by II).

In the method of the present invention, R ^{1 in} the bis (acetylene) derivative of the general formula (I) used as one of the reaction components is methyl, ethyl, propyl, isopropyl, butyl or hexyl. An alkyl group such as a dodecanyl group, a phenyl group, a tolyl group, a 1-naphthyl group,
An aryl group such as a 2-naphthyl group or an aralkyl group such as a benzyl group or a phenethyl group, and A represents an alkylene group, an arylene group, an aralkylene group, an oligosilanylene group, -R ₂ Si-O-SiR _2- , -C ₆ H ₄ -O-C
₆ H ₄ -, 1'ferrocenylene ferrocenylene group, such group, furylene group, such as 2,5-furylene group, 3,4-thienylene group, thienylene group or 2,6-pyridylene group, such as 2,5-thienylene And pyridylene groups.

Examples of such bis (acetylene) derivative are 1,4-bis (2-phenylethynyl) benzene, 1,4-bis (1-octynyl) benzene, 1,
1'-bis (2-phenylethynyl) ferrocene, bis {4- (2-phenylethynyl) phenyl} ether,
2,2-bis {4- (2-phenylethynyl) phenyl} propane, bis (2-phenylethynyl) dimethylsilane, 1,3-bis (2-phenylethynyl) -1,
1,3,3-Tetramethylsiloxane, 1,2-bis {4- (2-phenylethynyl) phenyl} -1,2-
Dimethyldisilane, 1,2-bis (2-phenylethynyl) -1,2-diisopropyl-1,2-dimethyldisilane, 2,5-bis (2-phenylethynyl) thiophene, 1,3-bis (2-phenyl Ethynyl) benzene,
2,5-bis (2-phenylethynyl) furan, 2,6
-Bis (2-phenylethynyl) pyridine, 1,4-bis (3-phenyl-1,1-dimethyl-2-propynyl) benzene, 1,6-bis (2-naphthylethynyl)
-1,1,2,2,3,3,4,4,5,5,6,6-
Examples include dodecamethylhexasilane.

In the method of the present invention, the reaction is considered to proceed according to the following equation.

[Chemical 4] (In the formula, Me, R ¹ and A have the same meanings as described above.)

In the method of the present invention, 1,2-
Bis (dimethylsilyl) benzene and bis (acetylene)
The ratio of the derivative used is usually 1:50 to 10 in molar ratio.
It is selected in the range of 0: 1, preferably 2: 5 to 5: 1.

In the method of the present invention, the platinum compound acts as a catalyst and various conventionally known compounds can be used, but it is preferable in terms of reaction rate to use a compound which is at least partially soluble in the reaction system. . A complex containing an organic ligand is particularly preferably used as these compounds. Examples of the ligand used in the present invention include phosphine, phosphonite, phosphinite, phosphite, olefin, acetylene, β-diketonato ligand, conjugated ketone,
Examples include amines and carbon monoxide. Specific examples thereof include trimethylphosphine, tributylphosphine, triethylphosphine, tricyclohexylphosphine, triphenylphosphine and tri (p-tolyl).
Chain phosphines such as phosphine, tri (p-anisyl) phosphine, diphenylmethylphosphine and phenyldimethylphosphine, p-methylphosphorene, p-methylphosphole, 9-methyl-9-phosphabicyclo [4.
2.1] Cyclic phosphines such as 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) -o-xylene, 1,2-bis (dimethylphosphino) benzene and other bisphosphines, dimethyl methylphosphonite, dimethyl phenylphosphonite and other phosphonites, methyl dimethylphosphinite , Phenyldiphenylphosphinite and other phosphinites, and triethylphosphite, triphenylphosphite, 1-phospha-
2,6,7-trioxa-4-ethylbicyclo [2,2
2,2] octane and other phosphites, ethylene, propene, cyclooctene, maleic anhydride, 1,5-hexadiene, 1,5-cyclooctadiene, 1,3-cyclopentadiene, 2,5-norbornadiene, 1, 3,
Olefins such as 5,7-cyclooctatetraene and dienes, β-diketonato ligands such as acetylacetonato, conjugated ketones such as dibenzylideneacetone, amines such as ethylenediamine and 2,2′-bipyridyl, and carbon monoxide Is mentioned. Therefore, specific examples of the platinum compound used in this reaction include (η-ethylene) bis (triphenylphosphine) platinum, tetrakis (diphenylmethylphosphine) platinum, dichlorobis (phenyldimethylphosphine) platinum and chlorohydridobis (tributylphosphine). ) Platinum, dichloro (tetramethylethylenediamine) platinum, dibromobis (triethylphosphite)
Platinum, bis (η-1,5-cyclooctadiene) platinum,
Dichloro (η-1,5-cyclooctadiene) platinum, dicarbonylbis (tributylphosphine) platinum, carbonatobis (tricyclohexylphosphine) platinum, bis (dibenzylideneacetone) bis (triphenylphosphine) platinum, bis (dibenzylideneacetone) ) Platinum and the like can be mentioned, but the invention is not limited thereto.

In addition, these platinum compounds are not used alone, but 2
It may be carried out in the presence of one or more species, and it is also included in the advantageous embodiment of the present invention that the addition of an organic ligand which is the same as or different from that contained in the platinum compound together with the platinum compound is carried out. .

The amount of these platinum compounds used may be a so-called catalytic amount, and 1,2-bis (dimethylsilyl) benzene 1
It is used in the range of 0.00001 to 0.5 mol per mol, and the ligand is used in the range of 1 to 20 mol, preferably 1 to 4 mol per mol of the platinum atom.

The reaction of the present invention can be easily carried out without using a solvent by using a mixture of 1,2-bis (dimethylsilyl) benzene and a bis (acetylene) derivative to be subjected to the reaction. However, the use of a solvent does not hinder the occurrence of this reaction, and is carried out in a solvent if necessary. These solvents are selected in consideration of the reactivity and boiling point of 1,2-bis (dimethylsilyl) benzene to be reacted, the boiling point of the bis (acetylene) derivative, etc., and a commonly used solvent such as a hydrocarbon-based solvent. Alternatively, it is preferable to select from ether solvents.

In the method of the present invention, the reaction proceeds even at 0 ° C. or lower, but heating to a temperature of up to 250 ° C. is also possible in order to reach a preferable rate. Although it depends on the structure of the raw material, a generally preferable temperature range is 0 to 150 ° C.

Separation of the product after the reaction is easily carried out by a commonly used means of organic chemistry such as ordinary distillation, recrystallization, chromatography, extraction with a solvent, or reprecipitation.

[0016]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ (where Ph is a phenyl group) is 0.005 mmol and 1,2-bis (dimethylsilyl) benzene is 0.25 mmol. And 1,4
4 ml of a benzene solution containing 0.125 mmol of -bis (1-octynyl) benzene was reacted at 30 ° C for 12 hours. After concentration, purification by preparative thin layer chromatography (silica gel, hexane-benzene = 3: 1) revealed that 1,4-bis {2- (5-benzo-1,1,4,4
-Tetramethyl-3-hexyl-1,4-disilacyclohexa-2,5-dienyl)} benzene was obtained with a yield of 78%. The compound could be crystallized from ethanol. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0018]

[Chemical 5] Melting point: 130-132 ° C. ¹ H-NMR (CDCl ₃ ): δ 7.65-7.55
(M, 4H), 7.4-7.35 (m, 4H), 6.9
0 (s, 4H), 2.18 (t, J = 7Hz, 4H),
1.4-1.1 (br, 16H), 0.83 (t, J =
7Hz, 6H), 0.41 (s, 12H), 0.18
(S, 12H) IR (KBr): 1258, 1241 cm ⁻¹ Elemental analysis C ₄₂ H ₆₂ Si ₄ (theoretical value) C 74.26%; H 9.20%: (actual value) C 73.94%; H 9.59%

Example 2 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 mmol and 1,2-bis (dimethylsilyl) benzene was added in an amount of 0.2.
Benzene solution 4 containing 5 mmol and 0.125 mmol of 1,1'-bis (2-phenylethynyl) ferrocene 4
ml was reacted at 30 ° C. for 18 hours. After concentration, purification by preparative thin layer chromatography (silica gel, hexane-benzene = 3: 1) revealed that 1,1'-bis {2- (5-benzo-1,1,4,4-tetramethyl -
3-phenyl-1,4-disilacyclohexa-2,5-
Dienyl)} ferrocene was obtained with a yield of 83%. The compound could be crystallized from ethanol. This compound is a new compound not listed in the literature, and its physical properties are
The spectral data were as follows.

[0020]

[Chemical 6] Melting point: 229-230.5 ° C ¹ H-NMR (CDCl ₃ ): δ 7.7-7.15
(M, 14H), 7.0-6.81 (m, 4H), 3.
89 (br s, 4H), 3.70 (br s, 4)
H), 0.5 (s, 12H), 0.12 (s, 12H) IR (KBr): 1245 cm ^-1 Elemental analysis C ₄₆ H ₅₀ Si ₄ Fe (theoretical value) C 71.65%; H 6. 54% (actual value) C 71.99%; H 6.89%

Example 3 Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 mmol and 1,2-bis (dimethylsilyl) benzene was added in an amount of 0.2.
5 mmol and 2,6-bis (2-phenylethynyl)
4 ml of benzene solution containing 0.125 mmol of pyridine
Was reacted at 30 ° C. for 18 hours. After concentration, purification by preparative thin layer chromatography (silica gel, hexane-benzene = 2: 1) revealed that 2,6-bis {2-
(5-benzo-1,1,4,4-tetramethyl-3-phenyl-1,4-disilacyclohexa-2,5-dienyl)} pyridine was obtained with a yield of 76%. The compound could be crystallized from ethanol. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0022]

[Chemical 7] Melting point: 230-232 ° C. ¹ H-NMR (CDCl ₃ ): δ 7.67-7.62
(M, 4H), 7.47-7.39 (m, 5H), 7.
15-7.00 (m, 6H), 6.87-6.79
(M, 4H), 6.21 (d, J = 7.7Hz, 2
H), 0.34 (s, 12H), 0.31 (s, 12)
H) IR (KBr): 1253, 1235 cm ^-1 Elemental analysis C ₄₁ H ₄₅ NSi ₄ (theoretical value) C 74.14%; H 6.83%; N 2.11%: (actual value) C 73.91 %; H 6.82%; N 2.08%

Example 4 Pt (CH ₂ = CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 mmol and 1,2-bis (dimethylsilyl) benzene was added in an amount of 0.2.
5 mmol and 2,5-bis (2-phenylethynyl)
4 ml of benzene solution containing 0.125 mmol of thiophene
Was reacted at 30 ° C. for 18 hours. After concentration, the product was purified by preparative thin layer chromatography (silica gel, hexane-benzene = 10: 1) to give 2,5-bis {2
-(5-benzo-1,1,4,4-tetramethyl-3-
Phenyl-1,4-disilacyclohexa-2,5-dienyl)} thiophene was obtained with a yield of 78%. The compound could be crystallized from ethanol. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0024]

[Chemical 8] Melting point: 158-160 ° C ¹ H-NMR (CDCl ₃ ): δ 7.61-7.54
(M, 4H), 7.42-7.35 (m, 4H), 7.
22-7.00 (m, 6H), 6.86-6.80
(M, 4H), 6.15 (s, 2H), 0.24 (s,
12H), 0.18 (s, 12H) IR (KBr): 1247 cm ⁻¹ Elemental analysis C ₄₀ H ₄₄ SSi ₄ (theoretical value) C 71.79%; H 6.62%; S 4.79%: ( Found: C 71.81%; H 6.61%; S 4.76%.

Example 5 Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ was added in an amount of 0.005 mmol and 1,2-bis (dimethylsilyl) benzene was added in an amount of 0.2.
5 mmol and 1,1,3,3-tetramethyl-1,3
-Bis (1-propynyl) -disiloxane 0.125
4 ml of a benzene solution containing mmol of water was reacted at 50 ° C. for 18 hours. After concentration, purification by preparative thin layer chromatography (silica gel, hexane-benzene = 4: 1) revealed that 1,1,3,3-tetramethyl-1,3-
Bis {2- (5-benzo-1,1,4,4-tetramethyl-3-methyl-1,4-disilacyclohexa-2,5
-Dienyl)} disiloxane was obtained with a yield of 75%.
The compound could be crystallized from ethanol. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0026]

[Chemical 9] Melting point: 76 ° C. ¹ H-NMR (CDCl ₃ ): δ 7.55-7.45
(M, 4H), 7.40-7.30 (m, 4H), 2.
23 (s, 6H), 0.35 (s, 24H), 0.28
(S, 12H) IR (KBr): 1254 cm ⁻¹ Elemental analysis C ₃₀ H ₅₀ OSi ₆ (theoretical value) C 60.53%; H 8.46%: (Actual value) C 60.66%; H 8. 50%

[0027]

According to the present invention, a bis (1,2-bissilylethylene) derivative can be obtained from a readily available 1,2-bis (dimethylsilyl) benzene and a bis (acetylene) derivative by a one-step reaction, The separation and purification are also easy. The resulting bis (1,2-bissilylethylene) derivative is a novel compound and is useful as a synthetic intermediate for fine chemicals such as pharmaceuticals and agricultural chemicals.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (2)

[Claims] 1. A general formula: [In the formula, Me is a methyl group, R ¹ is an alkyl group, an aryl group or an aralkyl group, A is an alkylene group, an arylene group, an aralkylene group, an oligosilanylene group, —R ₂ Si
-O-SiR ₂ - (wherein R is an alkyl group), -
C ₆ H ₄ —O—C ₆ H ₄ —, a ferrocenylene group, a furylene group, a thienylene group or a pyridylene group]. 2. 1,2-bis (dimethylsilyl) benzene and the general formula R ¹ -C≡C-A-C≡C-R ¹ [wherein R ¹ is an alkyl group, an aryl group or an aralkyl group, A alkylene group, an arylene group, aralkylene group, Origoshiraniren _{group, -R 2 Si-O-SiR} 2 -
(Wherein R is an alkyl group), —C ₆ H ₄ —O—C ₆
H ₄ -, ferrocenylene group, furylene group, a bis (acetylene) derivative represented by a thienylene group or a pyridylene group], which comprises reacting in the presence of a platinum compound, general formula 2] (In the formula, Me is a methyl group, and R ¹ and A have the same meanings as described above.) A method for producing a bis (1,2-bissilylethylene) derivative.