JP3506180B2 - Cyclic organosilicon compound and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclic organosilicon compound, which has never been used before, and is useful as a raw material for heat resistant and flammable materials, and a process for producing the same.

[0002]

2. Description of the Related Art This compound could not be produced because of no known effective synthetic means.

[0003]

SUMMARY OF THE INVENTION The present invention aims at synthesizing a novel cyclic organosilicon compound.

[0004]

The cyclic organosilicon compound of the present invention has the chemical formula (1)

[0005]

[Chemical 6] (In the above formula, m is an integer of 2 to 20, R¹ , R² Has 1 carbon
-10 alkyl group, alkenyl group or lower alkyl
Group, lower alkenyl group, lower alkoxy group or halo
It is a phenyl group which may be substituted with gen. R¹ ，
R² Is for example -CH ₃ , -C₂H_Five, -C₃H₇, -CH (CH₃)₂,-
C_FourH₉, -CH = CH₂ , -CH₂ -CH = CH₂ , -C₆H₁₃ , -C₈
H₁₇ , -C_TenH_{twenty one}, -C₆H_Five, -C₆H_Four(CH₃), −C₆H_Four(CH =
CH₂), −C₆H_Four(OCH₃), −C₆H_FourBr and so on. ) Indicated by
It

The cyclic organosilicon compound of the present invention has the chemical formula (2)

[0007]

[Chemical 7] (In the above formula, n is an integer of 2 to 20, R¹ , R² Has 1 carbon
-10 alkyl group, alkenyl group or lower alkyl
Group, lower alkenyl group, lower alkoxy group or halo
It is a phenyl group which may be substituted with gen. R¹ ，
R² Is for example -CH ₃ , -C₂H_Five, -C₃H₇, -CH (CH₃)₂,-
C_FourH₉, -CH = CH₂ , -CH₂ -CH = CH₂ , -C₆H₁₃ , -C₈
H₁₇ , -C_TenH_{twenty one}, -C₆H_Five, -C₆H_Four(CH₃), −C₆H_Four(CH =
CH₂), −C₆H_Four(OCH₃), −C₆H_FourBr and so on. ) Indicated by
It

The present invention also provides a compound of formula (2) and a compound of formula (3)

[0009]

[Chemical 8] (In the above formula, R ² is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen.) Bis (fluorosilyl) ) A method of producing a compound of formula (1) by reacting with an acetylene compound in the presence of a catalyst, and a method of producing a compound of formula (2) by reducing a compound of formula (1) with a metal hydride. is there. The respective reaction formulas are shown below (reaction formulas (a) and (b)).

[0010]

[Chemical 9]

[0011]

[Chemical 10] The present inventors have separately filed a patent for the compound represented by the chemical formula (2) (where n is 1) necessary for producing the compound of the chemical formula (1) in which m is 2. The compounds of the chemical formulas (1) and (2) in which m and n are 2 to 20 can be produced by alternately and sequentially repeating the reactions according to the reaction formulas (a) and (b).

Used in the production of compounds of formula (1)
The catalyst is either platinum, palladium or ruthenium
It is a complex. As a specific example, as a Pt catalyst, Pt (dba)₂
(Dba: dibenzylideneacetone), Pt (CH₂= CH₂) (P
Ph₃)₂ ， PtCl₂(PPh₃)₂， PtCl ₂(PO₃C₆H₁₁)₂， Pt (PPh₃)
_Four ， Pt (PO₃C₆H₁₁)_Four ， Pt (CO)₂Pt (PPh₃)₂, Pt (PhCCPh) (P
Ph₃)₂ ， Pt (C₈H₁₂)₂， H₂PtCl₆ , Pd as a catalyst, Pd (db
a)₂， Pd (CH₂= CH₂) (PPh₃) ₂ ， Pd (PO₃C₆H₁₁)₂ ， Pd (CH₂
= CH₂) (PO₃C₆H₁₁)₂ ， Pd (PPh₃)_Four ， Pd (PO₃C₆H₁₁)_Four， PdC
l₂ ， Pd (CH₃(COO)₂ ， RuCl as a Ru catalyst₂(PPh₃)₃， RuC
l₂(PO₃C₆H₁₁)₃， RuCl₂(CO)₃， Ru₃(CO)₁₂ Etc.
Be done. Particularly preferably, Pt (dba)₂， Pt (CH₂= CH₂) (PPh₃)
₂ Is. In addition, these catalysts can be used as co-catalysts
10 equivalent NEt₃, PPh₃Ligands such as may be added. An example
PtCl₂(PPh₃)₂To NEt₃Is used by adding 2 equivalents of
Pt (dba)₂To PPh₃Is used by adding 2 equivalents thereof.

Specific examples of the metal hydride used for producing the compound of the chemical formula (2) include alkali metal hydrides such as LiH, NaH, KH, RbH and CsH.
As alkaline earth metal hydride, MgH ₂ , CaH
₂ , SrH ₂ , BaH _{2 and the} like, BH ₃ complex, AlH ₃ complex and the like as group 13 metal hydride, and LiAlH ₄ , NaAlH ₄ , KAlH ₄ and LiB as complex metal hydride.
_{H 4, NaBH 4, KBH 4} , Mg (BH 4) 2, Ca
(BH ₄ ) ₂ , Ba (BH ₄ ) ₂ , Sr (BH ₄ ) ₂ ,
Examples thereof include Al (BH ₄ ) ₃ .

The manufacturing method will be described. In the method for producing the compound represented by the chemical formula (1), a cyclic compound represented by the chemical formula (2), an acetylene compound represented by the chemical formula (3), and a catalyst are charged in a reaction vessel. A solvent is also added if necessary. The order of charging these reaction vessels is not particularly limited. These may be mixed simultaneously, or one or both of the raw materials may be continuously or intermittently fed into the reaction vessel during the reaction. High-purity nitrogen before the reaction in the reaction vessel,
It is preferable to replace with an inert gas such as high-purity argon. The reaction is performed for a predetermined time while stirring while controlling the reaction container to a predetermined reaction temperature. The desired compound can be easily separated and purified from the reaction solution by a usual method such as decantation, filtration, extraction with a solvent, distillation and chromatography.

The amount of the catalyst for the cyclic compound represented by the chemical formula (2) is 0.0001 to 0.5 mo / mol of the compound.
1, more preferably 0.001 to 0.1 mol.

As the solvent, aromatic solvents such as benzene and toluene and saturated hydrocarbon solvents such as cyclohexane and normal heptane are effectively used. The amount of the solvent for the cyclic compound of the chemical formula (2) is 0.2 per 1 mmol of the compound.
〜200 ml, more preferably 2-20 ml is suitable.

The amount of the acetylene compound used in the reaction is 0.02 to 20 with respect to 1 mol of the cyclic compound of the chemical formula (2).
0 mol, more preferably 0.2 to 20 mol, still more preferably 2 to 4 mol is suitable.

The reaction temperature is 0 ° C to 200 ° C, more preferably 20 to 150 ° C, still more preferably 60 to 100 ° C.

The reaction time is 1 to 100 hours, preferably 5 to 50 hours, although it depends on the amount of the compound and the catalyst charged. A compound having a larger n in the chemical formula (2) as a raw material tends to have a longer reaction time.

In the method for producing the cyclic compound represented by the chemical formula (2), first, the compound represented by the chemical formula (1), a metal hydride and a solvent are charged into a reaction vessel. The order of charging these reaction vessels is not particularly limited. These may be mixed simultaneously, or one or both of the raw materials may be continuously or intermittently fed into the reaction vessel during the reaction. The reaction is performed by stirring for a predetermined time while controlling the reaction container to a predetermined reaction temperature. The desired compound can be easily separated and purified from the reaction solution by a usual method such as decantation, filtration, extraction with a solvent, distillation and chromatography.

The amount of metal hydride is 0.2 to 200 mol, more preferably 1.0 to 20 mol, still more preferably 2 to 20 mol, based on 1 mol of the compound of the chemical formula (1).
Is.

As the solvent, ether solvents such as diethyl ether and THF, aromatic solvents such as benzene and toluene, saturated hydrocarbon solvents such as cyclohexane and normal heptane, and mixed solvents thereof are effectively used. The amount of the solvent is 1 to 500 with respect to 1 mmol of the compound of the chemical formula (1).
ml, more preferably 5 to 100 ml.

The reaction temperature is -30 ° C to 200 ° C, more preferably 0 to 100 ° C, still more preferably 20 to 60 ° C.

The reaction time depends on the reaction temperature and the amount of the raw material compound, but is 10 minutes to 40 hours, more preferably 1 hour to
20 hours is appropriate.

[0025]

EXAMPLES Examples will be described below. Example 1 In the chemical formula (1), R ¹ = CH ₃ , R ² = CH ₃ , m =
The production method of the polycyclic organosilicon compound of No. 2 is shown.

A condenser and a dropping funnel are attached to the upper part of the reaction vessel, and a magnetic stirring bar is installed inside a 500 ml glass reaction vessel. The inside of the reaction vessel was replaced with high-purity nitrogen gas. Then, in the reaction formula, R in the chemical formula (2)
Compound 7.00 in which ¹ = CH ₃ , R ² = CH ₃ , and n = 1
g (11.8 mmol) and bis (dibenzylideneacetone) platinum (O) catalyst 0.392 g (0.59 mmol)
Then, 200 ml of tetralin solvent was charged. Bis (dimethylfluorosilyl) acetylene 6.50 was added to the dropping funnel.
g (36.4 mmol) was charged.

The reaction vessel was immersed in an oil bath controlled at 100 ° C., and bis (dimethylfluorosilyl) acetylene was dropped from the dropping funnel over 10 minutes while stirring with a magnetic stirrer. The mixture was stirred for 50 hours while maintaining the reaction temperature at 100 ° C.

After confirming almost disappearance of the compound of the chemical formula (2) as a raw material by liquid chromatography, the reaction vessel was returned to room temperature and the reaction solution was taken out. The reaction liquid was supported on a silica gel separation column, eluted with a mixed solvent of benzene and hexane, and then precipitated with ethanol to give the target polycyclic organosilicon compound in a yield of 0.85 g (0.90 mmo).
l) was obtained. The yield from the bishydrosilyl compound is 7.
It was 6%.

The form is colorless crystals and the sublimation temperature is 345 to 345.
It was 360 ° C.

The measured value of elemental analysis is as follows: carbon 48.06%
(Theoretical value 48.35%), hydrogen 7.86% (theoretical value 7.
90%) and fluorine 7.68% (theoretical value 8.05%), and the measured values are in good agreement with the theoretical values within the range of measurement error.

From the mass spectrum (FD-MS), M ⁺ was 942. This is in agreement with the theoretical value.

The infrared absorption spectrum was measured by the KBr tablet method. The main absorption peak wave number (unit: cm ^-1 ) is 29
50, 2900, 1400, 1250, 1140, 10
It was 90.

¹ H-NMR was measured with a heavy chloroform solution. The chemical shift (δ value) is 0.
30 ppm to 0.46 ppm (72H, multiplet), 7.
It was 81 ppm (2H, singlet). 0.30 ppm
From 0.46 ppm to a total of 72 hydrogens, a total of 72 hydrogens of 24 methyl groups on silicon is 7.81 pp.
The two hydrogens of m can be identified as the two hydrogens on the benzene ring, which is in agreement with the theoretical value.

¹³ C-NMR was measured with a heavy chloroform solution. The chemical shift (δ value) is 0.
67 ppm, 1.32 ppm, 1.59 ppm (J _CF
= 16 Hz), 136.34 ppm, 144.88 pp
m, 177.42 ppm, 185.10 ppm, 18
The values were 8.98 ppm and 194.38 ppm.

[0035]²⁹Si-NMR measurement with deuterated chloroform solution
Decided Chemical shift (δ value) is based on TMS,
28.10ppm, -1.22ppm, 17.3ppm
(J _Si-F= 278 Hz). Example 2 R in the chemical formula (2)¹= CH₃ , R²= CH₃ , N =
The production method of the polycyclic organosilicon compound of No. 2 is shown. First 5
Attach a condenser to a 0 ml glass reaction vessel and react
Install a magnetic stir bar inside the container. High purity inside the reaction vessel
The atmosphere was replaced with nitrogen gas. Then in Example 1 in a reaction vessel
0.15 g (0.15 g) of the compound of formula (1) synthesized
9 mmol) and LiAlH_Four 0.045g (1.19m
(mol) and 10 ml of tetrahydrofuran were charged. Warm
Immerse the reaction vessel in an oil bath set to 40 ° C and magnetically stir
The mixture was reacted for 5 hours with stirring. Liquid chromatograph
After confirming that the raw materials have almost disappeared with a fee, remove the reaction vessel from the oil bath.
Remove and add 10 ml of saturated ammonium chloride solution to the reaction mixture.
Unreacted LiAlH_Four Disassemble and use a separating funnel.
The tetrahydrofuran layer and the aqueous layer were separated. Water layer benz
It was extracted with 100 ml of water. Separate the benzene layer with a separating funnel.
Released. Tetrahydrofuran layer and benzene layer are anhydrous sulfuric acid
Dry with sodium. Combine this organic layer into a rotary
ー Concentrate with evaporator and use for liquid chromatography
Then, the desired product was obtained. Yield 0.01
0 g (0.0115 mmol), the yield was 7.2%
It was

The compound form is colorless crystals.

From the mass spectrum (FD-MS), M ⁺ was 870. This is in agreement with the theoretical value.

The infrared absorption spectrum was measured by the KBr tablet method. The main absorption peak wave number (unit: cm ^-1 ) is 29
50, 2900, 2150, 1400, 1245, 11
It was 40,1120,1090. 2150 is SiH
Shows absorption of binding.

¹ H-NMR was measured with a heavy chloroform solution. The chemical shift (δ value) is 0.
25ppm (24H, doublet), 0.34ppm (24
H, singlet), 0.42 ppm (24H, singlet),
4.46 ppm (2H, multiplet) 7.81 ppm (2
H, singlet). 0.25ppm to 0.42p
The total 72 hydrogen of pm is 72 hydrogen of 24 methyl groups on silicon, the total hydrogen of 4.46 ppm is the hydrogen of SiH, and the total hydrogen of 7.81 ppm is 2 hydrogen. , Can be identified as a hydrogen on the benzene ring.

¹³ C-NMR was measured with a heavy chloroform solution. Chemical shift (δ value) is based on TMS,
1.60ppm, 0.75ppm, 2.54ppm, 1
36.4ppm, 144.9ppm, 181.0pp
m was 189.7 ppm and 191.0 ppm.

²⁹ Si-NMR was measured with a heavy chloroform solution. Chemical shift (δ value) is based on TMS,
It was 28.2 ppm, -18.4 ppm, and -5.1 ppm.

[0042]

The present invention provides a new cyclic organosilicon compound. This compound can be used as a constituent component of a heat resistant and flame resistant material.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuyoshi Utsumi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Koji Inoue 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Incorporated (72) Inventor Masato Tanaka, 1-1, Higashi, Tsukuba, Ibaraki, Institute of Industrial Science and Technology, Institute of Materials Engineering (72) Inventor, Yuko Uchimaru, 1-1, Higashi, Tsukuba, Ibaraki (56) References JP-A-5-310752 (JP, A) JP-A-6-247986 (JP, A) JP-A-6-247983 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A chemical formula (1): (In the above formula, m is an integer of 2 to 20, R ¹ and R ² are carbon atoms 1
-10 is an alkyl group, an alkenyl group or a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen. ) A cyclic organosilicon compound represented by 2. A chemical formula (2): (In the above formula, n is an integer of 2 to 20, R ¹ and R ² are carbon atoms 1
-10 is an alkyl group, an alkenyl group or a lower alkyl group, a lower alkenyl group, a lower alkoxy group or a phenyl group which may be substituted with halogen. ) A cyclic organosilicon compound represented by 3. A chemical formula (2): (In the above formula, n represents an integer of 1 to 19, and R ¹ and R ² are
It has the same meaning as in claim 2. ) And a cyclic organosilicon compound represented by the chemical formula (3): The cyclic organosilicon according to claim 1, wherein the bis (fluorosilyl) acetylene compound represented by the formula (wherein R ² has the same meaning as in claim 2) is reacted in the presence of a catalyst. Method for producing compound. 4. The method according to claim 3, wherein the catalyst is a complex of platinum, palladium or ruthenium. 5. The chemical formula (1): (In the above formula, m, R ¹ and R ² have the same meaning as in claim 1.) The compound represented by the formula (1) is reacted with a metal hydride. Method for producing compound.