JPH11263793A - Cyclic silicon compound having functional group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a raw material monomer for a heat resistant material by reacting a cyclic silicon compound with a diazoester compound. SOLUTION: A compound of formula I [R<1> and R<2> are each an aliphatic, an aromatic or the like; R<3> to R<6> are each H, an aliphatic or an aromatic; R<7> is H, an aliphatic, an alkoxycarbonyl or the like; R<8> is an aliphatic, an aromatic, an amine or the like; (m)=1-3; (n)=0-4], e.g. 4- ethoxycarbonylmethyl-1,1,2,2-tetramethyl-1,2-disilacyclopentane. The compound of formula I is obtained by reacting a cyclic silicon compound of formula II (e.g. 1,1-dimethylsilacyclohexane) with a diazo compound of formula III (e.g. ethyl diazoacetate) in the presence of a catalyst consisting of a metal complex of rhodium such as rhodium acetate dimer in a solvent of dichloromethane or the like at a temperature from -50 deg.C to 100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a cyclic silicon compound having a functional group at the β-position of a silicon atom.

[0002]

2. Description of the Related Art Cyclic silicon compounds are useful as raw material monomers for heat-resistant polymer materials (Chem.
r., Vol. 5, pp. 260-279, 1993) Furthermore, cyclic silicon compounds having a functional group are widely used as synthetic intermediates for pharmaceuticals and agrochemicals (Journal of the Society of Synthetic Organic Chemistry, 54, 28).
9-302, 1996). As a conventional method for producing a cyclic silicon compound, a method based on a ring closure reaction using an alkyl halide having a chlorosilyl group at a terminal and magnesium metal is known (Comprehensive Organometallic).
Chemistry, Volume 2, pp. 226-296, Pergamon Press,
Oxford, 1982). However, in this method, since active magnesium is used, it was difficult to synthesize a cyclic silicon compound having a reactive functional group such as a carbonyl group. Therefore, the structure of the cyclic silicon compound obtained by this method is largely limited, and cannot be said to be a general synthesis method.

[0003]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a cyclic silicon compound having various functional groups at the β-position of a silicon atom.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by reacting a cyclic silicon compound with a diazoester compound in the presence of a rhodium catalyst, the conversion of silicon atoms The inventors have found that a cyclic silicon compound having a functional group at the β-position can be obtained regioselectively, and have completed the present invention. That is, the present invention provides a cyclic silicon compound represented by the following general formula (1):

[0005]

Embedded image

(Wherein R ¹ and R ² each independently represent an aliphatic group, an aromatic group, an alkoxyl group or a halogen atom, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen. R ⁷ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, or an acyl group, and R ⁸ represents an aliphatic group, an aromatic group, an alkoxyl group, or an amino group. M represents an integer of 1 to 3, n represents an integer of 0 to 4, provided that m is 1
Except when n is 0 or 1. When m is 2 or more,
Two or more R ¹ may be different from each other. Also,
When n is 2 or more, two or more R ⁵ may be different from each other. Further, when n is 1 or more, R ⁵
And R ⁴ may combine with each other to form a ring. ).

[0007]

DETAILED DESCRIPTION OF THE INVENTION The above general formula (2) used as a reaction raw material in the present invention

Embedded image Various cyclic silicon compounds represented by the formula are industrially easily available, and can be easily synthesized by utilizing a ring-closing reaction between an alkyl halide having a chlorosilyl group at a terminal and magnesium metal (Comprehensive).
Organometallic Chemistry, Volume 2, pp. 226-296, Pe
rgamon Press, Oxford, 1982). R ¹ and R ² in the general formula (2) represent an aliphatic group, an aromatic group, an alkoxyl group, an aryloxy group or a halogen atom, and R ³ ,
R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, an aliphatic group or an aromatic group. The aliphatic group at this time is usually an alkyl group, preferably a lower alkyl group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Any of a ring shape may be sufficient. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a cyclohexyl group, and the like.

The alkoxyl group preferably has 1 to 1 carbon atoms.
It has 0, more preferably 1 to 6 carbon atoms, and may be linear, branched or cyclic, and is preferably a lower alkoxyl group having 1 to 5 carbon atoms. The aryloxy group preferably has 6 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, and is preferably a phenoxy group. Specific examples include a methoxy group, an ethoxy group, a phenoxy group, and a t-butoxy group. The aromatic group is an aryl group, and preferably has 6 to 16 carbon atoms, and more preferably has 6 to 14 carbon atoms.
And a substituted or unsubstituted phenyl group is particularly preferred. As the substituent, an aliphatic group as described above or an alkoxyl group as described above is preferable. Specific examples include, for example, a phenyl group, a tolyl group, and a methoxyphenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. In the general formula (2), m is an integer of 1 to 3, and is preferably 1 or 2. n is an integer of 0 to 4, preferably 0, 1
Or 2. When m is 2 or more, two or more R ¹ may be different from each other. n is the same for R ⁵ when 2 or more. When n is 1 or more, R ⁴ and R ⁵ may be bonded to each other to form a preferably 5- to 7-membered condensed ring.

Specific examples of the cyclic silicon compound represented by the general formula (2) are as follows. 1,
1-dimethylsilacyclohexane, 1- (4-methoxyphenyl) -1-methylsilacyclohexane, 1-methoxy-1-methylsilacyclohexane, 1,1-dimethylsilacyclopentane, 1-methoxy-1-methylsilacyclopentane , 1,1-dimethylsilacyclobutane,
1,1-diphenylsilacyclobutane, 1,1-dichlorosilacyclobutane, 1,1-dimethoxysilacyclobutane, 1,1-diethylsilacyclobutane, 1,1-dipropylsilacyclobutane, 1-phenoxy-1-methylsilacyclobutane , 1- (4-methylphenyl) -1
-Methylsilacyclobutane, 1-methyl-1-phenylsilacyclobutane, 1-t-butoxy-1-phenylsilacyclobutane, 1-methoxy-1-methylsilacyclobutane, 1-chloro-1-methylsilacyclobutane, 1
-Bromo-1-methylsilacyclobutane, 1-fluoro-1-methylsilacyclobutane, 1-methyl-1-phenylsilacyclobutane, 2-methyl-1,1-dimethylsilacyclopentane, 2-phenyl-1,1- Dimethylsilacyclobutane, 1,1,2,2-tetramethyl-
1,2-disilacyclopentane, 1,1,2-trimethyl-2-phenyl-1,2-disilacyclopentane,
2,3-dihydro-1,1-dimethyl-1H-1-silylenedene, 1,2,3,4-tetrahydro-1,1-dimethyl-1-silanaphthalene, 1,1-dimethyl-1-
Silaperhydronaphthalene and the like.

The general formula (3) used in the present invention

Embedded image Is a compound easily synthesized from various industrially available raw materials including tosyl azide (Chem. Rev., Vol. 94, pp. 1091-1160, 1994). In the general formula (3), R ⁷ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group,
Or an acyl group. R ⁸ represents an aliphatic group, an aromatic group, an alkoxyl group, or an amino group, and a lower alkoxyl group is particularly preferred.

The preferred carbon numbers and specific examples of the aliphatic group, the aromatic group and the alkoxyl group in this case are the same as those described for the general formula (2). The alkoxycarbonyl group preferably has 2 to 11 carbon atoms, more preferably 2 to 9 carbon atoms, and specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a t-butyloxycarbonyl group. The amino group may have a substituent, and a dialkylamino group is particularly preferable. This substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and may be either aliphatic or aromatic. Specific examples include a dimethylamino group, a diethylamino group,
Examples thereof include a diphenylamino group and a dibenzylamino group. The acyl group preferably has 2 to 11 carbon atoms, more preferably 2 to 7 carbon atoms, and may be any of aliphatic and aromatic. Specifically, for example, an acetyl group, a propanoyl group,
And a benzoyl group.

Specific examples of the diazo compound represented by the general formula (3) are as follows. Ethyl diazoacetate, methyl diazoacetate, t-butyl diazoacetate, dimethyl diazomalonate, diethyl diazomalonate, di-t-butyl diazomalonate, ethyl diazoacetoacetate, diazo-N, N-dimethylacetamide, diazo-N, N-diethylacetamide , Diazo-N, N-diphenylacetamide, ethyl 2-diazobutanoate, ethyl 2-diazopropanoate, ethyl diazobenzoyl acetate and the like.

As the catalyst comprising a rhodium metal complex or a rhodium metal salt used in the present invention, various types are easily available industrially, and specific examples are as follows. Rhodium acetate dimer, rhodium trifluoroacetate dimer, rhodium octanoate dimer, rhodium benzoate dimer, rhodium pentafluorobenzoate dimer, rhodium heptafluoropropanoate dimer, rhodium chloride,
Rhodium acetoacetonate and the like.

The reaction of the present invention is preferably carried out in a solvent from the viewpoint of reaction efficiency. Examples of the solvent that can be used in the present invention include halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, and tetrachloroethylene; aromatic hydrocarbon solvents such as toluene and benzene; and aliphatic hydrocarbon solvents such as pentane, hexane, and decane. Hydrogen solvents and the like can be mentioned. The reaction can be carried out at a temperature in the range of −50 to 100 ° C., but is desirably carried out at room temperature to 100 ° C. in view of the efficiency of the reaction. The amount of the catalyst used is 0.00001 to 0.1 per mole of the compound represented by the general formula (2).
Mole, preferably 0.001 to 0.05 mole. The reaction time is usually 1 to 10 hours. Separation of the product after the reaction is easily carried out by ordinary purification and isolation methods such as distillation and recrystallization.

According to the present invention, a cyclic silicon compound having a functional group at the β-position of a silicon atom represented by the general formula (1) is obtained. R ^{1 to} R ⁸ , m and n in the general formula (1) are the same as those shown in the general formulas (2) and (3).

Specific examples of the cyclic silicon compound having a functional group represented by the general formula (1) are as follows. 4-methoxycarbonylmethyl-1,1,2,2
2-tetramethyl-1,2-disilacyclopentane, 4
-Ethoxycarbonylmethyl-1,1,2,2-tetramethyl-1,2-disilacyclopentane, 4-t-butoxycarbonylmethyl-1,1,2,2-tetramethyl-1,2-disila Cyclopentane, 4-ethoxycarbonylmethyl-1,1,2-trimethyl-2-phenyl-
1,2-disilacyclopentane, 3-methoxycarbonylmethyl-1,1-dimethyl-1-silacyclohexane, 3-ethoxycarbonylmethyl-1,1-dimethyl-1-silacyclohexane, 3-t-butoxycarbonylmethyl -1,1-dimethyl-1-silacyclohexane, 3- (diethoxycarbonylmethyl) -1,1-dimethyl-1-silacyclohexane, 3- (dimethoxycarbonylmethyl) -1,1-dimethyl-1-silacyclohexane , 3-t-butoxycarbonylmethyl-1-methyl-1-methoxy-1-silacyclohexane, 3-methoxycarbonylmethyl-1,1-dimethyl-1-silacyclopentane, 3-ethoxycarbonylmethyl-1,
1-dimethyl-1-silacyclopentane, 3-t-butoxycarbonylmethyl-1,1-dimethyl-1-silacyclopentane, 3-t-butoxycarbonylmethyl-
1,1-dimethyl-1-silacyclobutane, 3-ethoxycarbonylmethyl-1,1-dimethyl-2-methyl-
1-silacyclobutane, 3-t-butoxycarbonylmethyl-1-methyl-1-methoxy-1-silacyclohexane, 3-ethoxycarbonylmethyl-1,1-dimethyl-2-ethyl-1-silacyclobutane, 3-ethoxy Carbonylmethyl-1,1-dimethyl-1-silacyclobutane, 3-t-butoxycarbonylmethyl-1,1-
Dimethyl-1-silacyclobutane, 3- (dimethoxycarbonylmethyl) -1,1-dimethyl-1-silacyclobutane, 3- (diethoxycarbonylmethyl) -1,1
-Dimethyl-1-silacyclobutane, 3-acetonyl-
1,1-dimethyl-1-silacyclobutane, 3- (2-
(Oxobutyl) -1,1-dimethyl-1-silacyclobutane, 3-phenacyl-1,1-dimethyl-1-silacyclobutane, N, N-dimethyl- [3- (1,1-dimethylsilacyclobutyl)] acetamide , N, N-diethyl- [3- (1,1-dimethylsilacyclobutyl)]
Acetamide, N, N-diphenyl- [3- (1,1
-Dimethylsilacyclobutyl)] acetamide, 2-
Ethyl [3- (1,1-dimethylsilacyclobutyl)] propanoate, ethyl 2- [3- (1,1-dimethylsilacyclobutyl)] butanoate, 3-methoxycarbonylmethyl-1-methyl-1- Methoxysilacyclobutane, 3
-Methoxycarbonylmethyl-1-methyl-1-chlorosilacyclobutane, 3-methoxycarbonylmethyl-
1,1-dimethoxysilacyclobutane, 3-methoxycarbonylmethyl-1,1-dichlorosilacyclobutane,
3-ethoxycarbonylmethyl-2,3-dihydro-
1,1-dimethyl-1H-1-silynedene, 3-ethoxycarbonylmethyl-1,2,3,4-tetrahydro-1,1-dimethyl-1-silanaphthalene, 3-ethoxycarbonylmethyl-1,1-dimethyl -1-Silaperhydronaphthalene and the like.

[0017]

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

Example 1 1,2 in a dichloromethane solvent (0.5 ml) in the presence of rhodium acetate (2.3 mg, 0.005 mmol).
Ethyl diazoacetate (45.6 mg, 0.40 mmol) was added to 1,2,2-tetramethyl-1,2-disilacyclopentane (31.6 mg, 0.20 mmol) at room temperature.
It was dropped over time. After completion of the dropwise addition, the solvent was distilled off under reduced pressure, and the mixture was subjected to thin layer chromatography (developing solvent, ethyl acetate:
Separation and purification with hexane (1:10) gave 4-ethoxycarbonylmethyl-1,1,2,2-tetramethyl-1,2-disilacyclopentane (43.9 mg,
0.18 mmol, 91%) as a colorless transparent liquid. The reaction of this example is represented by the following formula.

[0019]

Embedded image

¹ H-NMR (300 MHz, C ₆ D ₆ ):
δ0.03-0.25 (m, 2H, CH ₂ ), 0.09 (d, J = 1.9 Hz, 12H, CH ₃ ),
0.99-1.07 (m, 2H, CH ₂ ), 1.00
(T, J = 7.1 Hz, 3H, CH ₃ ), 2.05-2.
20 (m, 1H, CH), 2.33 (d, J = 7.0H
z, 2H, CH ₂ ), 4.01 (q, J = 7.1 Hz,
_{2H, CH 2) IR (neat} ): 2958,2912,2858,1
731, 1369, 1251, 1170, 1129, 8
39,803 cm ^-1

Example 2 1,2 in a dichloromethane solvent (0.5 ml) in the presence of rhodium acetate (2.3 mg, 0.005 mmol).
Ethyl diazoacetate (45.6 mg, 0.40 mmol) was added dropwise to 1,2-trimethyl-2-phenyl-1,2-disilacyclopentane (46.7 mg, 0.21 mmol) at room temperature over 4 hours. After completion of the dropwise addition, the solvent was distilled off under reduced pressure, and the residue was separated and purified by thin-layer chromatography (developing solvent, ethyl acetate: hexane 1:10) to give 4-ethoxycarbonylmethyl-1,1,2-trimethyl-2. -Phenyl-1,2-disilacyclopentane (40.0 mg, 0.13 mmol, 62%) was obtained as a colorless transparent liquid. The reaction of this example is represented by the following formula.

[0022]

Embedded image

¹ H-NMR (300 MHz, C ₆ D ₆ ):
δ0.03-0.62 (m, 9H), 1.12-1.2
6 (m, 4H), 1.26 (t, J = 7.1 Hz, 3
H), 2.13 (m, 1H,), 2.42 (m, 2H)
, 4.13 (q, J = 7.1 Hz), 7.51-7.
50 (m, 5H) IR (neat): 3071, 2958, 2912, 2
858, 1734, 1429, 1251, 1191, 1
122,839,781,731,700 cm ^-1

Reference Example 1 1.1 in the presence of rhodium acetate (2.2 mg, 0.005 mmol) in dichloromethane solvent (0.5 ml).
-Dimethyl-1-silacyclobutane (22.0 mg,
0.22 mmol) in t-butyl diazoacetate (57.6).
mg, 0.41 mmol) at room temperature over 4 hours. After completion of the dropwise addition, the solvent was distilled off under reduced pressure, and the mixture was subjected to thin layer chromatography (developing solvent, ethyl acetate: hexane 1: 1).
As a result of separation and purification according to 8), 3-t-butoxycarbonylmethyl-1,1-dimethyl-1-silacyclobutane (30.1 mg, 0.14 mmol, 68%) was obtained as a colorless transparent liquid. The reaction of this example is represented by the following formula.

[0025]

Embedded image

¹ H-NMR (300 MHz, C ₆ D ₆ ):
δ 0.21 (d, J = 3.9 Hz, 6H, CH ₃ ), 0.2.
63 (m, 2H, CH ₂ ), 1.15 (m, 2H, CH
₂ ), 1.38 (s, 9H, CH ₃ ), 2.25 (d, J
_{= 7. 4Hz, 2H, CH 2} ), 2. 53 (m, 1H,
CH) IR (neat): 2966, 1731, 1369, 1
251, 1162, 1096, 806 cm ^-1

Reference Example 2 1.1 in the presence of rhodium acetate (3.5 mg, 0.008 mmol) in a dichloromethane solvent (0.5 ml).
-Dimethyl-1-silacyclopentane (35.7 mg,
0.31 mmol) to t-butyl diazoacetate (176.
7 mg, 1.24 mmol) was added dropwise at room temperature over 18 hours. After completion of the dropwise addition, the solvent was distilled off under reduced pressure, and the residue was separated and purified by thin-layer chromatography (developing solvent, chloroform: hexane 1: 6) to give 3-t-butoxycarbonylmethyl-1,1-dimethyl-1-. Silacyclopentane (42.8 mg, 0.19 mmol, 60%)
Was obtained as a colorless transparent liquid. The reaction of this example is represented by the following formula.

[0028]

Embedded image

¹ H-NMR (300 MHz, C ₆ D ₆ ):
δ 0.01 (d, J = 2.2 Hz, 6H, CH ₃ ), 0.1.
12 (m, 1H, CH ₂ ), 0.43 (m, 1H, CH
₂ ), 0.68 (m, 1H, CH ₂ ), 0.91 (m, 1
_{H, CH 2), 0.} 96- 1.10 (m, 1H, C
H ₂ ), 1.42 (s, 9H, CH ₃ ), 1.89-1.
_{99 (m, 1H, CH 2} ), 2. 06- 2. 15 (m,
_{2H, CH 2) IR (neat} ): 2932,1731,1369,1
251, 1160, 843, 803 cm ^-1

Example 4 1,1-Dimethyl-1-silacyclohexane (40.5 mg, 0.5 ml) in the presence of rhodium acetate (3.3 mg, 7.5 μmol) in dichloromethane solvent (0.5 ml).
32 mmol) and t-butyl diazoacetate (132.6 m
g, 0.93 mmol) was added dropwise at room temperature over 18 hours. After completion of the dropwise addition, the solvent was distilled off under reduced pressure, and the mixture was subjected to thin layer chromatography (developing solvent, ethyl acetate: hexane 1: 1).
Separation and purification by 9) gave 3-t-butoxycarbonylmethyl-1,1-dimethyl-1-silacyclohexane (48.5 mg, 0.20 mmol, 63%) as a colorless transparent liquid. The reaction of this example is represented by the following formula.

[0031]

Embedded image

[0032]¹H-NMR (300 MHz, C₆D₆):
δ-0.02 (d, J = 28.2 Hz, 6H, C
H₃), 0.15 (m, 1H, CH₂), 0.29 (m,
1H, CH₂), 0.53-0.67 (m, 1H, CH
₂), 0.73-0.86 (m, 2H, CH₂), 1.3
0-1.46 (m, 1H, CH₂), 1.40 (s, 9
H, CH ₃), 1.62-2.72 (m, 1H, C
H₂), 1.87-1.97 (m, 1H, CH₂), 1.
97- 2.94 (m, 1H, CH), 2.14 (m, 2
H, CH₂) IR (neat): 2966, 1731, 1369, 1
251, 1162, 1096, 806cm^-1

[0033]

The cyclic silicon compound represented by the general formula (1) of the present invention has various functional groups at the β-position of the silicon atom. This compound is regioselectively obtained by reacting the compound of the general formula (2) with the diazo compound of the general formula (3) in the presence of a rhodium catalyst. The thus-obtained cyclic silicon compound of the present invention can be used as a heat-resistant material, an organic synthesis reactant, a synthetic intermediate for medical and agricultural chemicals, and has a high industrial value.

Claims (1)

[Claims] 1. A cyclic silicon compound represented by the following general formula (1). Embedded image (Wherein, R ¹ and R ² represent each independently an aliphatic group, an aromatic group, an alkoxyl group or a halogen atom, R ³
, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an aliphatic group, or an aromatic group. R ⁷ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group or an acyl group. R ⁸ represents an aliphatic group, an aromatic group, an alkoxyl group or an amino group. m represents an integer of 1 to 3;
Represents an integer of 0 to 4. However, this excludes the case where m is 1 and n is 0 or 1. When m is 2 or more, two or more R
¹ may be different from each other. Further, when n is 2 or more, two or more R ⁵ may be different from each other. When n is 1 or more, R ⁵ and R ⁴ may be bonded to each other to form a ring. )