JP2002069081A - Cyclohexanone compound and method for producing silacyclohexane type liquid crystal compound using the same - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing a cyclohexanone compound and a silacyclohexane type liquid crystal compound which is a derivative thereof. A cyclohexanone compound represented by the following general formula (I). However, Ar is a phenyl group or a tolyl group, R is Ar, a linear alkyl group having 1 to 10 carbon atoms, a mono- or difluoroalkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 8 carbon atoms. Or an alkoxyalkyl group having 2 to 7 carbon atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cyclohexanone compound and a method for producing a silacyclohexane type liquid crystal compound using the same.

[0002]

2. Description of the Related Art A liquid crystal display device utilizes an optical anisotropy and a dielectric heteroelectric property of a liquid crystal material. Depending on the display mode, a TN type (twisted nematic type) and an STN type (super twisted nematic type) are used. , SBE type (super birefringent type),
DS type (dynamic scattering type), guest-host type, DAP type (deformed type of aligned phase), PD type (polymer dispersed type) and O
There are various types such as MI type (optical mode interference type).
The most common display devices are based on the Schadt-Helfrich effect and have a twisted nematic structure.

The properties required of the liquid crystal material used in these liquid crystal displays slightly vary depending on the display system, but the liquid crystal temperature range is wide, and the liquid crystal material is stable against moisture, air, light, heat, an electric field, and the like. This is commonly required in any of the display methods. Further, it is desired that the liquid crystal material has a low viscosity and provides a short address time, a low threshold voltage and a high contrast in the cell.

[0004]

In recent years, as the applications of liquid crystal displays have expanded, the characteristics required for liquid crystal materials have become increasingly severe and strict. In particular, it has been desired to further improve the characteristics of conventional liquid crystal materials, such as lowering the driving voltage, widening the temperature range corresponding to the needs for vehicles, and improving low-temperature performance.

[0005] From such a viewpoint, the inventors have developed a novel liquid crystal compound containing a silicon atom in a molecule for the purpose of improving a liquid crystal material, and have previously filed an application.

An object of the present invention is to provide a method for producing a cyclohexanone compound which is a useful synthetic intermediate for producing these silacyclohexane type liquid crystal compounds and a silacyclohexane type liquid crystal compound which is a derivative thereof. Things.

[0007]

That is, the present invention provides a cyclohexanone compound represented by the following general formula (I).

Embedded image However, Ar is a phenyl group or a tolyl group, R is Ar, a linear alkyl group having 1 to 10 carbon atoms, a mono- or difluoroalkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 8 carbon atoms. Or an alkoxyalkyl group having 2 to 7 carbon atoms.

Further, the present invention provides a compound of the general formula

Embedded image(Where R¹ And R^TwoAre each having 1 to 4 carbon atoms
Alkyl group or R¹And R^TwoAnd-(CH_Two)
_Four-,-(CH_Two)_Five-And-(CH_Two)_TwoO (CH_Two)_Two−
Represents any of ) And enamine compounds represented by
Michael addition reaction with

Embedded image Is obtained by subjecting the Michael adduct to intramolecular aldol condensation as it is or hydrolyzing the Michael adduct to obtain the general formula

Embedded image By obtaining a ketoaldehyde compound represented by the following formula, and then subjecting the ketoaldehyde compound to intramolecular aldol condensation,

Embedded image (However,

Embedded image Is

Embedded image Or

Embedded image Represents ), And then hydrogenating the cyclohexenone compound to produce the cyclohexanone compound represented by the general formula (I). .

The present invention also relates to a cyclohexanone compound represented by the above general formula (I),

Embedded image (Wherein, M is MgU (U represents halogen), ZnU, TiU _k (OW) _3-k (W is an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, and k is 0 to 3)
Represents an integer. ) Or Li, X is CN, F, Cl, B
r, CF ₃ , OCF ₃ , OCHF ₂ , OCHFCl, OC
F ₂ Cl, CF ₂ Cl, (O) _m CY ₁ = CX ₁ X ₂ (m is 0
Or 1, Y ₁ and X ₁ represent H, F or Cl, and X ₂ is F
Or Cl. ), O (CH ₂ ) _r (CF ₂ ) _s X ₃ (r
And s is 0, 1 or 2 and (r + s) is 2, 3 or 4
And X ₃ represents H, F or Cl. ), R or OR group, Y represents halogen or CH ₃ , and i represents an integer of 0 to 2. ) With an organometallic reagent represented by the general formula

Embedded image By obtaining a compound represented by the following, then hydrogenation or hydrogenation after dehydration, by the general formula

Embedded image After obtaining the compound represented by
By reduction, the general formula (II)

Embedded image A method for producing a silacyclohexane-type liquid crystal compound characterized by obtaining a silacyclohexane-type liquid crystal compound represented by the formula:

The present invention also relates to a cyclohexanone compound represented by the above general formula (I),

Embedded image (In the formula, M represents MGu (U represents a _{halogen.), ZnU, TiU k (} OW) 3-k (W is preferably an alkyl group having 1 to 6 carbon atoms in the alkyl group, k is 0 to 3 integer representing the.) or Li, X 'is halogen, Y is halogen or _CH 3, i or display the integer from 0 to 2 Li, X is CN, F, Cl, Br, CF 3, OCF 3, OCHF 2 ,
OCHFCl, OCF ₂ Cl, CF ₂ Cl, (O) _m CY ₁
= CX ₁ X ₂ (m is 0 or 1, Y ₁ and X ₁ are H, F or C
and X ₂ represents F or Cl. ), O (CH ₂ ) _r
(CF ₂ ) _s X ₃ (r and s are 0, 1 or 2 and (r +
s) is a number satisfying 2, 3 or 4, and X ₃ is H, F or Cl
Represents ), R or OR groups, Y and Z each independently represent halogen (preferably F or Cl) or CH ₃ , i and j each independently represent an integer of 0 to 2. ) With an organometallic reagent represented by the general formula

Embedded image By obtaining a compound represented by the following, then hydrogenation or hydrogenation after dehydration, by the general formula

Embedded image After obtaining the compound represented by
By reduction, the compound represented by the general formula (III)

Embedded image A method for producing a silacyclohexane-type liquid crystal compound characterized by obtaining a silacyclohexane-type liquid crystal compound represented by the formula:

The present invention also relates to a cyclohexanone compound represented by the above general formula (I),

Embedded image (Wherein, M is MgU (U represents halogen), ZnU, TiU _k (OW) _3-k or Li, X ′ is halogen (preferably Cl, Br or I), and Y is halogen (preferably F or Cl) or CH ₃ , i is from 0 to 2
Represents an integer. ) With an organometallic reagent represented by the general formula

Embedded image By obtaining a compound represented by the following, then hydrogenation or hydrogenation after dehydration, by the general formula

Embedded image A compound represented by the formula:

Embedded image (Wherein M ′ is MgU (U represents halogen), ZnU, TiU _k (OW) _{3 -k} (W is an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, and k is 0 to 3) And B (OV) ₂ (V represents H or an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms)) and an organometallic reagent represented by a transition metal catalyst. In the presence of

Embedded image After obtaining the compound represented by
By reduction, the compound represented by the general formula (III)

Embedded image A method for producing a silacyclohexane-type liquid crystal compound characterized by obtaining a silacyclohexane-type liquid crystal compound represented by the formula:

Next, the present invention will be described in more detail.

The general formula (I) of the present invention

Embedded image (Wherein, Ar is a phenyl group or tolyl group, R is Ar, a linear alkyl group having 1 to 10 carbon atoms,
And represents a mono- or difluoroalkyl group of 10, a branched alkyl group having 3 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 7 carbon atoms. The cyclohexanone compound represented by the general formula

Embedded image(Where R¹ And R^TwoAre each having 1 to 4 carbon atoms
Alkyl group or R¹And R^TwoAnd-(CH_Two)
_Four-,-(CH_Two)_FiveAnd-(CH_Two)_TwoO (CH_Two)_Two-
Indicates one of them. ) Enamine compound and methyl
From vinyl ketone, Sto as described in detail below
rk method (G. Stork et al.,J. Amer. Chem.
Soc.,85, 207 (1963)).
You.

An enamine compound as a starting material can be easily synthesized from a silacyclohexaneacetaldehyde compound and a secondary amine. First, silacyclohexaneacetaldehyde was first filed by the present inventors (Japanese Patent Application No. 6-123).
208) Silacyclohexane carbaldehyde compound and silacyclohexane compound (Japanese Patent Application No. 6-78125)
, Can be easily manufactured, for example, as follows.

For example, as shown in the following reaction formula [Chemical Formula 47], an ylide compound produced from an alkoxymethyltriphenylphosphonium salt by the action of a base and Wittig
The reaction is performed to obtain an alkyl enol ether compound, which is then converted to a silacyclohexaneacetaldehyde compound by hydrolysis with an acid catalyst.

[0016]

Embedded image (Wherein, R ′ is an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
And Q is halogen, preferably Cl, Br or I. )

Examples of the alkoxymethyltriphenylphosphonium salts include methoxymethyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium iodide, ethoxymethyltriphenylphosphonium chloride, ethoxymethyltriphenylphosphonium bromide, and ethoxymethyltrioxide. Phenylphosphonium iodide and the like can be used.

The base used for the production of ylide is n
Organic lithiums such as -butyllithium, s-butyllithium, t-butyllithium, methyllithium and phenyllithium; alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; and dimsyl sodium.

The reaction is carried out by reacting ethers such as tetrahydrofuran, diethyl ether, di-n-butyl ether and 1,4-dioxane, and hydrocarbons such as n-hexane, n-heptane, isooctane, benzene, toluene, xylene and cumene. And an aprotic polar solvent such as N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide and the like. The temperature is adjusted appropriately, but preferably 0 to
It is good to carry out at the reflux temperature of the solvent, more preferably at 10-40 ° C. At the above temperature, the reaction completion time varies depending on the structure of the starting silacyclohexanecarbaldehyde or ylide compound and the reaction temperature, but the reaction is preferably carried out for 30 minutes to 5 hours.

A silacyclohexanecarbaldehyde compound is added to the ylide compound formed in these solvents, and
The tig reaction proceeds to obtain an alkyl enol ether compound.

The hydrolysis of the alkyl enol ether compound is preferably carried out at 0 to 80 ° C., more preferably at 10 to 4 ° C.
Perform at 0 ° C. Examples of the acid catalyst to be used include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as oxalic acid, trifluoroacetic acid and chloroacetic acid. The amount of the catalyst varies depending on the structure of the alkyl enol ether compound obtained by the reaction and the type of the acid catalyst, but is preferably 0.1 to 50% by weight.

Further, the following reaction formulas [Formula 48] and [Formula 5]
As shown in [1] and [Formula 54], it can be synthesized from a silacyclohexane compound.

The reaction of [formula 48] is as follows.

Embedded image

Here, A ¹ is CN or COA ² (A ² is O
R ³ (R ³ represents an alkyl group having 1 to 6 carbon atoms) or

Embedded image(R^FourAnd R^FiveIs an alkyl group having 1 to 6 carbon atoms,
(CH _Two)_Four-,-(CH _Two)_Five-Or-(CH _Two)_Two-O-
(CH _Two)_TwoRepresents-. ).

The above reaction will be described in more detail.

Of

Embedded image As triethyl phosphinoacetate (trie
thiophosphonoacetate, trimethylphosphonoacetate, methyldiethylphosphonoacetate, diethylcyanomethylphosphonate (diet)
hyl cyanomethylphosphonat
e), diisopropylcyanomethylphosphonate and the like. N-butyllithium, s
Organic lithiums such as -butyllithium, t-butyllithium, methyllithium and phenyllithium, alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, dimsyl sodium, sodium hydride, potassium hydride, hydrogen Lithium oxide and the like. Examples of the solvent include ethers such as tetrahydrofuran, diethyl ether, di-n-butyl ether and 1,4-dioxane, and n-hexane, n-hexane and the like.
Examples of the solvent include a mixture of hydrocarbons such as heptane, isooctane, benzene, toluene, xylene, and cumene, and aprotic polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, and hexamethylphosphoric triamide. The reaction conditions are preferably such that the temperature ranges from 0 to 70 ° C. and the time ranges from 30 minutes to 5 hours. As the conditions for hydrogenation, the pressure is from atmospheric pressure to 20
kg / cm ² and the temperature are preferably in the range of 0 to 150 ° C.
Examples of the catalyst include metals such as palladium, platinum, rhodium, nickel and ruthenium. Examples of the reducing agent include sodium hydride, calcium hydride, trialkylsilanes, borane, metal hydrides such as dialkylaluminum, lithium aluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, Complex hydride such as tributylammonium borohydride (Complex hydride)
e) and substituted hydride compounds thereof, that is, lithium trialkoxyaluminum hydride, sodium di (methoxyethoxy) aluminum hydride, lithium triethylborohydride, sodium cyanoborohydride and the like. The reduction reaction is preferably performed at -70 to 100C. Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; and hydrocarbons such as hexane and isooctane.

The reaction of [Formula 51] is as follows.

Embedded image

Here, A ³ is CN or COA ⁵ (A ⁵ is O
H, OR ⁶ (R ⁶ represents the same group as R ³ ) or

Embedded image (R ⁷ represents the same group as R ^4, and R ⁸ represents the same group as R ⁵ ). A ⁴ represents COOR ⁹ (R ⁹ represents the same group as R ³ ).

The above reaction will be described in more detail.

[0030]

Embedded image Examples thereof include methyl cyanoacetate, ethyl cyanoacetate, cyanoacetic acid, dimethyl malonate, diethyl malonate, and dimethylaminoethyl acetate. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and cumene, and hydrocarbons such as hexane and isooctane. Further, the reaction conditions are as follows: the temperature is 60 to 150 ° C., preferably 80 to 1 to remove azeotropically the water by-produced
Performed at 40 ° C. Examples of the base include secondary amines such as piperidine and pyrrolidine, ammonia and organic acid salts thereof. As the organic acid salts, carboxylic acids such as formic acid, acetic acid, propionic acid and benzoic acid, n-butyllithium,
Examples thereof include organic lithiums such as s-butyllithium, t-butyllithium, methyllithium, and phenyllithium, alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide, and dimsyl sodium. As the conditions for hydrogenation, the pressure is preferably in the range of atmospheric pressure to 20 kg / cm ² , and the temperature is preferably in the range of 0 to 150 ° C. Examples of the catalyst include metals such as palladium, platinum, rhodium, nickel and ruthenium. In the above reaction, an inorganic acid such as HCl or H ₂ SO ₄ , a salt of the inorganic acid with lithium, sodium or potassium, and one equivalent of water are used. As the solvent, toluene, xylene, cumene, diethylbenzene,
Examples include aromatic hydrocarbons such as phenetole, aromatic ethers, dimethylformamide, dimethylacetamide, dimethylimidazolidinone, dimethylurea, dimethylsulfoxide, and high boiling aprotic polar solvents such as hexamethylphosphoric triamide. The reaction temperature is preferably in the range of 100 to 200 ° C., and the reaction time is 2 hours.
A range of up to 12 hours is preferred. Examples of the reducing agent include sodium hydride, calcium hydride, trialkylsilanes, borane, metal hydrides such as dialkylaluminum, lithium aluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, Complex hydrides such as tributylammonium borohydride and the like, and substituted hydride compounds thereof, such as lithium trialkoxyaluminum hydride, sodium di (methoxyethoxy) aluminum hydride, lithium triethylborohydride, sodium cyanoborohydride and the like Is mentioned. The reduction reaction is preferably performed at -70 to 100C. Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; and hydrocarbons such as hexane and isooctane.

The reaction of [Formula 54] is as follows.

Embedded image

Here, R ¹⁰ is the same group as R ³ or — (C
H ₂ ) ₂ — or — (CH ₂ ) ₃ —, and R ¹¹ represents the same group as R ³ .

The above reaction will be described in more detail.

As R ¹⁰ OH, R ¹⁰ has 1 to 1 carbon atoms.
A monohydric alcohol such as an alkyl group of HO- (C
_{H 2) 2 -OH, HO- (} CH 2) 3 -OH,

Embedded image HO- (CH _{2) 2} dihydric alcohol, such as ₄ -OH and the like. Examples of the acid used for the dehydration reaction include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and perchloric acid and salts thereof, and organic acids such as p-toluenesulfonic acid, camphorsulfonic acid and trifluoroacetic acid. In order to promptly remove generated water, it is also useful to use hydrocarbons such as benzene, toluene, xylene, cumene, hexane, and isooctane as a solvent and accelerate the reaction by azeotropic distillation. The Lewis acid, AlX ⁴ ₃ (X ⁴ represents a _{^{halogen.), ZnX 4 2, MgX}} 4 2, FeX 4
₂ , BF _{3 and the} like. Reaction temperature is -50 to 100
° C, preferably -30 to 50 ° C. As the solvent,
Solvent-free or halogenated hydrocarbons such as methylene chloride and chloroform. of

Embedded image As for R ¹¹ , ethyl vinyl ether, butyl vinyl ether and the like can be mentioned. Is preferably performed at 0 to 80 ° C, more preferably at 10 to 40 ° C. As the acid catalyst to be used, hydrochloric acids, inorganic acids such as sulfuric acid,
Organic acids such as oxalic acid, trifluoroacetic acid, chloroacetic acid and the like can be mentioned. The amount of the catalyst varies depending on the structure of the alkyl enol ether compound obtained by the reaction and the type of the acid catalyst, but is preferably 0.1 to 50% by weight. The hydrogenation temperature varies depending on the structure of the silacyclohexanone, but is preferably 0 to 150 ° C., more preferably 20 to 100 ° C., and the higher the pressure, the higher the reaction rate. , The atmospheric pressure to 20
kg / cm ² is good. Examples of the catalyst used for hydrogenation include metals such as palladium, platinum, rhodium, nickel and ruthenium. In particular, palladium-
Good results are obtained using carbon, palladium-barium sulfate, palladium-diatomaceous earth, platinum oxide, platinum-carbon, rhodium-carbon, Raney nickel and the like. Alternatively, a catalyst such as trifluoroacetic acid or perchloric acid may be added to increase the reaction rate.

Next, the obtained silacyclohexaneacetaldehyde compound is subjected to a dehydration reaction with a secondary amine to obtain an enamine compound.

[0036]

Embedded image

In this dehydration reaction, water produced using a hydrocarbon solvent such as benzene, toluene, xylene, cumene, n-hexane and n-heptane is azeotropically distilled (Azetrop).
The reaction rate can be increased by removing e) from the system. At this time, the reaction temperature varies depending on the type of the solvent and the like, but is preferably carried out at a temperature of from 20 ° C. to the reflux temperature of the solvent. It may be added. Although it depends on the structure of the compound to be obtained and the type of catalyst, the amount of the catalyst is preferably 0.1 to 50% by weight. In addition, a method is also used in which anhydrous salts such as anhydrous potassium carbonate and neglected sodium carbonate are added to remove generated water. Preferred examples of the secondary amine include dimethylamine, diethylamine, di-n-propylamine, pyrrolidine, piperidine, and morpholine. The secondary amine is preferably added at a ratio of 1: 1 to 1: 3 (equivalent) to the acetaldehyde compound.

The enamine compound thus synthesized is subjected to a Michael addition reaction with methyl vinyl ketone.

[0039]

Embedded image

Using methyl vinyl ketone in an amount of 1 to 5 equivalents, preferably 1 to 1.5 equivalents to the enamine compound, in a solvent at 0 to 150 ° C. for several tens of minutes or less at 0 to 150 ° C. depending on the structure of the enamine Heat for several tens of hours. As a solvent, benzene, toluene, xylene, cumene, n-hexane, n
-Hydrocarbons such as heptane, isooctane, cyclohexane, tetrahydrofuran, diethyl ether, di-n
Ethers such as -butyl ether and 1,4-dioxane, alcohols such as methanol, ethanol, propanol and butanol, N, N-dimethylformamide,
Dimethyl sulfoxide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone,
Polar solvents such as N, N'-dimethylpropyleneurea are used alone or in combination. At this time, a protic solvent,
For example, when methanol, ethanol, or the like is included, proton transfer in the Michael reaction is accelerated, and the reaction time may be reduced in some cases.

The obtained Michael adduct is subjected to intramolecular aldol condensation as it is, or the Michael adduct is treated with an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as oxalic acid, trifluoroacetic acid or chloroacetic acid. General formula obtained by hydrolysis

Embedded image Is subjected to intramolecular aldol condensation to give a cyclohexenone compound as shown in the reaction formula [Formula 60].

[0042]

Embedded image

In this case,

Embedded image Is

Embedded image Or

Embedded image become.

This aldol condensation reaction is catalyzed by a base or an acid. The catalyst may be newly added, or since the secondary amine of enamine used for the Michael addition in the previous step has a catalytic action as it is, the aldol condensation reaction may proceed without adding another catalyst. This aldol condensation reaction varies depending on the structure of the solvent and the compound, but is preferably performed at room temperature to the reflux temperature of the solvent.

As the base catalyst, organic bases such as the above-mentioned secondary amine, triethylamine, tri-n-butylamine and dimethylaniline; inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate;
Or sodium methoxide, sodium ethoxide,
Alkoxides such as potassium t-butoxide can be mentioned. Inorganic acids such as hydrochloric acid and sulfuric acid as acid catalysts,
p-toluenesulfonic acid, benzenesulfonic acid, acetic acid,
Organic acids such as propionic acid, oxalic acid, trifluoroacetic acid and chloroacetic acid can be mentioned. These base catalysts and acid catalysts may be used alone or in a mixture of 0.1 to 50% by weight.
It is good to use under.

In the base-catalyzed aldol condensation reaction, the generated cyclohexenone compound further reacts with the catalyst amine to form a cyclohexenone enamine compound, for example, a compound of the general formula

Embedded image Or the aldol condensation reaction is a β-hydroxyketone compound, ie,
General formula

Embedded image In the case where the reaction is stopped at the stage of the compound represented by the formula, it can be led to the cyclohexenone compound by acid treatment.

Next, as shown in the reaction formula [Chemical Formula 66], the double bond of the obtained cyclohexenone compound is hydrogenated by catalytic reduction to give a cyclohexanone compound represented by the general formula (I) of the present invention. Get. The hydrogenation temperature depends on the structure of the silacyclohexanone, but is preferably 0.
To 150 DEG ° C., further preferably 20 to 100 ° C., but further pressure increases the higher the reaction rate, since there are restrictions of the apparatus such, may be the atmospheric pressure to 20 kg / cm ^2.

[0048]

Embedded image

Examples of the catalyst used for hydrogenation include metals such as palladium, platinum, rhodium, nickel and ruthenium. In particular, use of palladium-carbon, palladium-barium sulfate, palladium-diatomaceous earth, platinum oxide, platinum-carbon, rhodium-carbon, Raney nickel or the like gives good results. Alternatively, a catalyst such as trifluoroacetic acid or perchloric acid may be added to increase the reaction rate.

The cyclohexanone compound represented by the general formula (I) obtained as described above is used for producing various silacyclohexane type liquid crystal compounds. Hereinafter, a method for producing the derivative of the cyclohexanone compound will be described.

First, an organometallic reagent easily prepared from the corresponding halide is reacted with the above cyclohexanone compound to obtain an alcohol compound.

[0052]

Embedded image (In the formula, n represents 0 or 1.)

As the organometallic reagent, Grignard
Examples include reagents, organozinc reagents, organolithiums, organotitanium reagents, and the like, and in each case, the reaction proceeds at a high yield. This reaction depends on the type of ketone and the structure of the organic metal, but is preferably carried out at −70 to 150 ° C. for 3 hours.
It may be performed for 0 minutes to 5 hours. Specifically, Li-based
It is more preferable to perform the treatment at 70 to 0 ° C. and at room temperature to 150 ° C. for Mg, Ti, and Zn. Usually, this reaction is carried out with diethyl ether,
Ethers such as THF and dioxane, and tan, hydrogen such as benzene, toluene, xylene, mesitylene, hexane, heptane, and octane may be used alone or in combination.

Next, a cyclohexanone compound is obtained by subjecting the obtained alcohol compound to hydrogenolysis (hydrogenolysis) or by performing a dehydration reaction with an acid catalyst, and then hydrogenating the resulting double bond. The hydrogenation is preferably performed at 0 to 150 ° C., more preferably 20 to 100 ° C., under atmospheric pressure to 20 kg / cm ² .

[0055]

Embedded image

Examples of the catalyst used for hydrogenolysis and hydrogenation include metals such as palladium, platinum, rhodium, nickel and ruthenium. In particular, palladium-carbon, palladium-barium sulfate, palladium-diatomaceous earth, platinum oxide, platinum-carbon, rhodium-carbon, Raney nickel, palladium oxide, nickel-diatomaceous earth, and the like are preferably used. Gives better results.

Examples of the acid used for the dehydration reaction include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and perchloric acid and salts thereof, and organic acids such as p-toluenesulfonic acid, camphorsulfonic acid and trifluoroacetic acid. . In order to promptly remove generated water, it is also useful to use hydrocarbons such as benzene, toluene, xylene, cumene, hexane, and isooctane as a solvent and accelerate the reaction by azeotropic distillation.

Subsequently, a halosilacyclohexane compound is converted into a halosilacyclohexane compound by a desilylation reaction using an electrophile, and a reduction reaction is further performed.

[0059]

Embedded image (In the formula, EW represents an electrophile and W represents a halogen.)

Examples of the electrophilic reagent include halogen, hydrogen halide, metal halide, sulfonic acid derivative, acid halide, and alkyl halide. In particular, iodine, bromine, chlorine, iodine monochloride, hydrogen chloride, hydrogen bromide, hydrogen iodide, mercury (II) chloride, trimethylsilyl chlorosulfonate, acetyl chloride, acetyl bromide, benzoyl chloride, t-butyl chloride, etc. It can be preferably exemplified. In order to increase the reaction rate, Lewis acids such as aluminum chloride, zinc chloride, titanium tetrachloride, and boron trifluoride may be added or light (visible light, ultraviolet light) may be applied. The desilylation reaction is preferably from 0 to 80
C., more preferably 10 to 40.degree. The electrophile is preferably used in an amount of 1 to 5 equivalents, more preferably 1 to 2 equivalents, based on the silacyclohexane compound.

Reagents used for reducing the resulting halosilacyclohexane compound include metal hydrides such as sodium hydride, calcium hydride, trialkylsilanes, borane, dialkylaluminum, lithium aluminum hydride, sodium borohydride Complex hydride compounds such as lithium, lithium borohydride, potassium borohydride, tributylammonium borohydride (Complex
hydride) and their substituted hydride compounds, that is, lithium trialkoxyaluminum hydride, sodium di (methoxyethoxy) aluminum hydride, lithium triethylborohydride, sodium cyanoborohydride and the like. The reduction reaction is preferably performed at 0 to 150 ° C., more preferably 20 to 1 ° C.
It is good to carry out at 20 ° C.

As described above, it has become possible to synthesize a silacyclohexane type liquid crystal compound.

Further, among the products obtained by the reaction formula [Chemical Formula 68], a general formula corresponding to n = 0

Embedded image (X ′ represents a halogen), n
General formula corresponding to = 1

Embedded image It is also possible to lead to the compound represented by

This reaction follows the following equation.

[0065]

Embedded image (In the formula, M ′ is MgU (U represents halogen, preferably Cl, Br or I.), ZnU, TiU
_k (OW) _3-k or B (OV) ₂ (V represents H or an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms). )

This reaction is performed in the presence of a transition catalyst.
Palladium or nickel compounds are particularly preferred as transition catalysts.

Examples of the palladium catalyst include zero-valent palladium compounds such as tetrakis (triphenylphosphine) palladium (0) and di [1,2-bis (diphenylphosphino) ethane] palladium (0), and palladium acetate. A compound comprising a divalent palladium compound such as palladium chloride and [1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride and a ligand, or a combination of these with a reducing agent can be used.

Examples of the nickel catalyst include 1,3-bis (diphenylphosphino) propane nickel (II) chloride, 1,2-bis (diphenylphosphino) ethane nickel (II) chloride, bis (triphenylphosphine) nickel (II) A divalent nickel compound such as chloride and a zero-valent nickel compound such as tetrakis (triphenylphosphine) nickel (0) can be exemplified.

When the organometallic reagent is a boric acid derivative,
That is, when M ′ is B (OV) ₂ , the reaction is desirably performed in the presence of a base. As the base, for example, sodium carbonate, sodium hydrogen carbonate, potassium carbonate,
Inorganic bases such as sodium hydroxide and potassium hydroxide and organic bases such as triethylamine, tributylamine and dimethylaniline can be used.

The compound obtained by the reaction formula [Formula 72] can be converted to a silacyclohexane type liquid crystal compound according to the reaction formula [Formula 69]. At this time, the temperature is preferably 0 to
It is good to carry out at 150 ° C, more preferably at 20 to 120 ° C.

The compound produced as described above can be purified by a conventional method such as recrystallization or chromatography to obtain the desired trans- or trans-form silacyclohexane-type liquid crystal compound.

[0072]

The present invention will be described below in more detail with reference to specific examples.

Example 1 Production of 4- (4-phenyl-4-n-propyl-4-silacyclohexyl) cyclohexanone 246 g of 4-phenyl-4-n-propyl-4-silacyclohexanecarbaldehyde was added to methoxymethyl 800 ml of tetrahydrofuran from 350 g of triphenylphosphonium chloride and 130 g of potassium t-butoxide
Was dropped into the ylide solution prepared in the above. After stirring at room temperature for 2 hours, the reaction mixture was poured into water and extracted with ether.
The ether solution was washed with brine, dried and concentrated, and n-hexane was added to the residue. The generated triphenylphosphine oxide crystals were separated by filtration, and the filtrate was concentrated to obtain crude methyl ether. This was dissolved in methylene chloride, 20% hydrochloric acid was added, and the mixture was stirred at room temperature for 5 hours. The methylene chloride layer was washed with brine, dried and concentrated, and then purified by silica gel chromatography to obtain 4-phenyl-4-n-propyl-4-silacyclohexylacetaldehyde (255 g).
(98% yield). IR (liquid film) νmax: 2920, 1720, 110
5,695cm ^-1

This, 75 g of pyrrolidine and 8 benzene
The resulting water was removed while refluxing 00 ml of the mixture.
When the distillation of water stopped, a mixture of 80 g of methyl vinyl ketone and 200 ml of methanol was added, and the mixture was stirred at room temperature for 48 hours. 100 ml of acetic acid, 50 g of sodium acetate and 100 ml of water were added to the reaction mixture, and the mixture was stirred for 4 hours. The reaction mixture was extracted with benzene, washed with brine, dried, concentrated and purified by silica gel chromatography to give 4
164 g of-(4-phenyl-4-n-propyl-4-silacyclohexyl) -2-cyclohexenone (αβ-unsaturated ketone), 4- (4-phenyl-4-n-propyl-4-silacyclohexyl) -3-cyclohexenone 7
0 g (βγ-unsaturated ketone) 70 g (a total of 76
%). IR (liquid film) νmax (αβ-unsaturated ketone): 292
0,1675,1105,695 cm ^-1 IR (liquid film) νmax (βγ-unsaturated ketone): 292
0,1715,1105,700cm ^-1

The mixture of the unsaturated ketones was dissolved in 300 ml of ethanol, and hydrogenated under a pressure of 10 kg / cm ^{2 using} 2.0 g of palladium-carbon as a catalyst. When the theoretical amount of hydrogen was consumed, the catalyst was separated by filtration and concentrated under reduced pressure to obtain 234 g (yield: 99%) of the desired product. ¹ H-NMR (CDCl ₃ ) δ: 0.50-2.60 (2
5H, m), 7.25-7.65 (5H, m) ppm GS-MS (70 eV) (m / z) ⁺ : 105,12
3,208,236,271,314 IR (liquid film) νmax: 2920, 1710, 142
5,1105,700cm ^-1

The following compounds were obtained in the same manner as in Example 1.

Example 2 4- (4- (3-methylbutyl) -4-phenyl-4-
Silacyclohexyl) cyclohexanone Obtained from 4- (3-methylbutyl) -4-phenyl-4-silacyclohexanecarbaldehyde in the same manner as in Example 1.

Example 3 4- (4,4-diphenyl-4-silacyclohexyl)
Production of cyclohexanone From 4,0.0-diphenyl-4-silacyclohexanecarbaldehyde 30.0 g, 4,4-diphenyl-4-silacyclohexanecarbaldehyde was prepared in the same manner as in Example 1.
Diphenyl-4-silacyclohexylaldehyde 29.
4 g (93% yield) were obtained. IR (liquid film) νmax: 3060, 2920, 171
0,1425,1110,725,695cm ^-1

29.4 g of this and 8.6 g of piperidine
The resulting water was removed while refluxing a mixture of water and 100 ml of benzene. When distillation of water stopped, 7.5 g of methyl vinyl ketone and 100 ml of 1,4-dioxane were added, and 2
Stirred at 40 ° C. for hours. 20% hydrochloric acid 200 in the reaction mixture
After the mixture was refluxed for 2 hours, the organic layer was washed with brine, dried and concentrated to give α- (4,4-diphenyl-4).
-Silacyclohexyl) -α- (3-ketobutyl) acetaldehyde (32.4 g, yield 89%) was obtained. IR (liquid film) νmax: 3060, 2920, 171
5,145,1105,725,700 cm ^-1 GS-MS (70 eV) (m / z) ⁺ : 43,105,
183,199,287,307,364

32.4 g of this product was put in 100 m of ethanol.
and added 0.5 g of sodium ethoxide.
After refluxing for an hour, the mixture was poured into 20% hydrochloric acid and extracted with ethyl acetate. The ethyl acetate solution was washed with brine, dried and concentrated, and then purified by silica gel chromatography to obtain 4-ethyl acetate.
(4,4-diphenyl-4-silacyclohexyl) -2
18.0 g of cyclohexenone (αβ-unsaturated ketone)
And 4- (4,4-diphenyl-4-silacyclohexyl) -3-cyclohexenone (βγ-unsaturated ketone) 1
2.2 g (97% in total yield) was obtained. IR (liquid film) νmax (αβ-unsaturated ketone): 306
0,2920,1680,1415,1110,72
5,700 cm ^-1 IR (liquid film) νmax (βγ-unsaturated ketone): 306
0,2920,1705,1420,1105,72
5,700cm ^-1

This mixture of unsaturated ketones was hydrogenated in the same manner as in Example 1 to give 29.9 g of the desired product (yield 9%).
9%). ¹ H-NMR (CDCl ₃ ) δ: 0.80-2.50 (1
8H, m), 7.20-7.70 (10H, m) ppm IR (KBr disc) νmax: 3050, 292
0, 1710, 1415, 1110, 980, 705c
m ^-1 melting point: 92.1 ° C

The following compounds were obtained in the same manner as in Example 3.

Example 4 4- (4-n-pentyl-4-phenyl-4-silacyclohexyl) cyclohexanone As in Example 3, from 4-n-pentyl-4-phenyl-4-silacyclohexanecarbaldehyde Obtained. ¹ H-NMR (CDCl ₃ ) δ: 0.50-2.50 (2
9H, m), 7.20-7.65 (5H, m) ppm IR (liquid film) νmax: 2920, 1715, 141
5,1105,700cm ^-1

Example 5 4- (4- (4-pentenyl) -4-phenyl-4-silacyclohexyl) cyclohexanone From 4- (4-pentenyl) -4-phenyl-4-silacyclohexyl) cyclohexanecarbaldehyde Obtained in the same manner as in Example 3.

Example 6 Preparation of trans, trans-4- (4- (4-fluorophenyl) cyclohexyl) -1-n-propyl-1-silacyclohexane 1.0 M p-fluorophenylmagnesium chloride in tetrahydrofuran 4- (4-phenyl-4-n-propyl-4-silacyclohexyl) in 120 ml
31.5 g of cyclohexanone was added dropwise at 40 to 50 ° C. After stirring at 50 ° C. for 2 hours, the mixture was poured into a saturated aqueous solution of ammonium chloride and extracted with benzene. P in benzene solution
-Toluenesulfonic acid monohydrate (1.0 g) was added, and the generated water was distilled off under reflux. When the distillation of water stops, the benzene solution is washed with an aqueous solution of sodium hydrogen carbonate, dried and concentrated to give crude 4- (4- (4-fluorophenyl) -3.
-Cyclohexenyl) -1-phenyl-1-n-propyl-1-silacyclohexane was obtained. This was dissolved in 100 ml of ethanol, and palladium-carbon 1.0
g as a catalyst, and the catalyst was filtered off and concentrated.
4- (4- (4-fluorophenyl) cyclohexyl)
35.0 g (88% yield) of -1-phenyl-1-n-propyl-1-silacyclohexane was obtained. IR (liquid film) νmax: 2920, 2860, 151
0,1225,1110,825,695cm ^-1

100 g of 1.0 M iodine monochloride in carbon tetrachloride was added to 35 g of this at room temperature, stirred for 30 minutes and concentrated. Residue in tetrahydrofuran 100m
and at 0 ° C., lithium aluminum hydride 4.0
g and 50 ml of tetrahydrofuran.
The reaction mixture was stirred for 1 hour, poured into 200 ml of 5% hydrochloric acid, and extracted with ethyl acetate. After ordinary washing, drying and concentration, the residue was purified by silica gel chromatography to obtain 15.2 g (yield 54%) of the desired product. ¹³ C-NMR (CDCl ₃ ) δ: 10.14 (s), 1
4.78 (s), 17.81 (s), 17.95
(S), 28.63 (s), 29.95 (s), 34.
85 (s), 43.60 (s), 43.93 (s), 4
5.89 (s), 114.86 (d), 128.00
(D), 143.38 (s), 161.12 (d) pp
m IR (KBr disc) νmax: 2918,284
8, 2104, 1605, 1510, 1448, 122
7,1159,985,887cm ^-1

The following compounds were obtained in the same manner as in Example 6.

Example 7 Trans, trans-4- (4- (4 (4)-(4-phenyl-4-pentyl-4-silacyclohexyl) cyclohexanone and 4-chloro-3-fluorophenyl magnesium chloride were used. -Chloro-3-fluorophenyl) cyclohexyl-1-n-pentyl-1-silacyclohexane GS-MS (70 eV) (m / z) ⁺ : 71,99,1
43,187,269,309,345,380

Example 8 Trans, trans-4- was prepared using 4- (4-phenyl-4-pentyl-4-silacyclohexyl) cyclohexanone and p-fluorophenylmagnesium chloride.
(4- (4-fluorophenyl) cyclohexyl) -1
-N-pentyl-1-silacyclohexane was obtained. ¹³ C-NMR (CDCl ₃ ) δ: 10.12 (s), 1
2.19 (s), 14.01 (s), 22.37
(S), 24.13 (s), 28.63 (s), 29.
95 (s), 34.86 (s), 35.41 (s), 4
3.60 (s), 43.94 (s), 45.91
(S), 114.86 (d), 128.00 (d), 1
43.37 (d), 161.12 (d) ppm IR (KBr disc) νmax: 2918, 284
8,2100,1603,1510,1227,98
7,885 cm ^-1

Example 9 trans, trans-4- (4- (3- (3- (4-phenyl-3-n-propyl-4-silacyclohexyl) cyclohexanone) and 3,4-difluorophenylmagnesium bromide were used. , 4-Difluorophenyl) cyclohexyl) -1-n-propyl-1-silacyclohexane was obtained. ¹ H-NMR (CDCl ₃ ) δ: 0.38-0.62 (2
H, m), 0.84-1.43 (15H, m), 1.6.
6-1.76 (2H, m), 1.80-1.95 (4
H, m), 2.38 (1H, tt), 3.66-3.7
6 (1H, m), 6.83-7.09 (3H, m) pp
m IR (KBr disc) νmax: 2924,285
4,2100,1606,1518,1279,98
7,887 cm ^-1

Example 10 Using 4- (4-phenyl-4- (methylbutyl) -4-silacyclohexyl) cyclohexanone and 3,4-difluorophenylmagnesium bromide, trans, trans-4- (4- (3 , 4-Difluorophenyl) cyclohexyl) -1- (3-methylbutyl) -1-silacyclohexane was obtained. ¹³ C-NMR (CDCl ₃ ) δ: 9.70 (s), 1
0.01 (s), 22.12 (s), 28.60
(S), 29.80 (s), 30.70 (s), 33.
48 (s), 34.65 (s), 43.52 (s), 4
3.89 (s), 45.84 (s), 115.38
(D), 116.71 (d), 124.45 (dd),
144.79 (dd), 148.52 (dd), 15
0.16 (dd) ppm IR (liquid film) νmax: 2922, 2852, 210
0, 1608, 1518, 1279, 1207, 98
7,889 cm ^-1

Example 11 trans, trans-4- (4- (3- (3- (3-phenyl-4- (pentenyl) -4-silacyclohexyl) cyclohexanone) and 3,4-difluorophenyl magnesium bromide were used. , 4-Difluorophenyl) cyclohexyl) -1- (4-pentenyl) -1-silacyclohexane was obtained. ¹³ C-NMR (CDCl ₃ ) δ: 10.01 (s), 1
1.73 (s), 23.89 (s), 28.56
(S), 29.77 (s), 34.61 (s), 37.
16 (s), 43.50 (s), 43.83 (s), 4
5.80 (s), 114.54 (s), 115.30
(D), 116.66 (d), 122.39 (dd),
138.57 (s), 144.70 (dd), 148.
49 (dd), 150.13 (dd) ppm IR (liquid film) νmax: 2922, 2852, 210
0,1606,1518,1279,1117,88
7,818 cm ^-1

Example 12 Using 4- (4-phenyl-4- (pentenyl) -4-silacyclohexyl) cyclohexanone and 3,4-difluorophenylmagnesium bromide, trans, trans-4- (4- (3 , 4-Difluorophenyl) cyclohexyl) -1-n-pentyl-1-silacyclohexane was obtained. ¹³ C-NMR (CDCl 3): δ 10.11 (s), 1
2.17 (s), 13.99 (s), 22.38
(S), 24.14 (s), 28.62 (s), 29.
80 (s), 34.65 (s), 35.43 (s), 4
3.55 (s), 43.89 (s), 45.86
(S), 115.36 (d), 116.70 (d), 1
22.42 (s), 144.78 (s), 148.43
(Dd), 150.17 (dd) ppm IR (KBr disc) νmax: 2922,285
2,2100,1606,1518,1279,120
7,987,887cm ^-1

Example 13 4- (4-phenyl-4- (pentyl) -4-silacyclohexyl) silacyclohexanone and p-[(S) -2
-Methylbutyl] phenylmagnesium bromide was used to obtain trans, trans-4- (4-((S) -2-methylbutyl) phenyl) cyclohexyl) -1-n-pentyl-1-silacyclohexane.

Example 14 Using 4- (4-phenyl-4- (propyl) -4-silacyclohexyl) silacyclohexanone and trifluoromethoxyphenyl magnesium bromide,
Trans-4- (4- (4-trifluoromethoxyphenyl) cyclohexyl) -1-n-propyl-1-silacyclohexane was obtained. ¹³ C-NMR (CDCl ₃ ): δ 10.16 (s), 1
4.76 (s), 17.79 (s), 17.97
(S), 28.65 (s), 29.91 (s), 34.
70 (s), 43.60 (s), 44.10 (s), 4
5.91 (s), 120.57 (q), 120.76
(S), 127.96 (s), 146.45 (s), 1
47.28 (s) ppm IR (KBr disc) νmax: 2924,285
4,2108,1510,1263,1225,119
0,1161,985,887cm ^-1

Example 15 Trans, trans-4- (4- (4-tri-4-phenyl-4-n-pentyl-4-silacyclohexyl) cyclohexanone and trifluoromethoxyphenyl magnesium bromide were used. Fluoromethoxyphenyl) cyclohexyl) -1-n-pentyl-1-silacyclohexane was obtained. ¹³ C-NMR (CDCl ₃ ): δ 10.11 (s), 1
2.17 (s), 13.99 (s), 22.37
(S), 24.12 (s), 28.62 (s), 29.
90 (s), 34.68 (s), 35.40 (s), 4
3.57 (s), 44.08 (s), 45.88
(S), 120.55 (q), 120.76 (s), 1
27.96 (s), 146.46 (s), 147.26
(S) ppm IR (KBr disc) νmax: 2924,285
4,2102,1510,1267,1223,119
4,1159,987,887 cm ^-1

Example 16 Trans, trans-4- was prepared using 4- (4-phenyl-4-n-propyl-4-silacyclohexyl) cyclohexanone and chlorophenylmagnesium bromide.
(4- (4-chlorophenyl) cyclohexyl) -1-
There was obtained n-propyl-1-silacyclohexane.

Example 17 Preparation of trans, trans-4- (4-n-propyl-4-silacyclohexyl) cyclohexyl-4'-fluorobiphenyl In the same manner as in Example 6, 4- (4-phenyl -4-n
-Propyl-4-silacyclohexyl) cyclohexanone was reacted with 4- (4-fluorophenyl) phenylmagnesium bromide (25 g), and the resulting alcohol was dehydrated and catalytically reduced to give 4- (4-phenyl- 4-n-propyl-4-silacyclohexyl) cyclohexyl-4'-fluorobiphenyl was obtained, then reacted with iodine monochloride, and further reduced with lithium aluminum hydride to obtain 14.4 g of the desired product (yield 3).
6%). ¹³ C-NMR (CDCl ₃ ): δ 10.13 (s), 1
4.78 (s), 17.81 (s), 17.95
(S), 28.62 (s), 29.98 (s), 34.
66 (s), 43.61 (s), 44.32 (s), 4
5.91 (s), 115.49 (d), 126.86
(S), 127.28 (s), 128.46 (d), 1
37.29 (s), 137.75 (s), 146.99
(S), 162.27 (d) ppm IR (KBr disc) νmax: 2920, 209
8,1493,1236,984,847,845,8
18cm ^-1

The following compounds were obtained in the same manner as in Example 17.

Example 18 Trans, trans-4- (4) was prepared using 4- (4-phenyl-4-n-pentyl-4-silacyclohexyl) cyclohexanone and 4- (4-fluorophenyl) phenylmagnesium bromide. -N-pentyl-4-silacyclohexyl) cyclohexyl-4'-fluorobiphenyl was obtained. ¹³ C-NMR (CDCl ₃ ): δ 10.11 (s), 1
2.18 (s), 14.01 (s), 22.36
(S), 24.12 (s), 28.62 (s), 29.
98 (s), 34.66 (s), 35.40 (s), 4
3.62 (s), 44.32 (s), 45.91
(S), 115.49 (d), 126.85 (s), 1
27.27 (s), 128.45 (d), 137.29
(S), 137.73 (s), 146.98 (s) 16
2.27 (d) ppm IR (KBr disc) νmax: 2918, 209
8, 1493, 1448, 1236, 985, 847,
818 cm ^-1

Example 19 Production of trans, trans-4- (4-n-propyl-4-silacyclohexyl) cyclohexyl-3 ′, 4′-difluorobiphenyl trans, trans-4- (4- (4- (4- 4.11 g of chlorophenyl) cyclohexyl) -1-n-propyl-1-silacyclohexane, 200 m of 1,3-bis (diphenylphosphino) propane nickel (II) chloride
g and 50 ml of ether in 1.0M 3,4
12 ml of a tetrahydrofuran solution of -difluorophenylmagnesium bromide was added dropwise. After stirring at room temperature for 18 hours, the mixture was poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. After ordinary washing, drying and concentration, the residue is purified by silica gel chromatography to obtain 3.52 g of the desired product
(85% yield). ¹³ C-NMR (CDCl ₃ ) δ: 10.12 (s), 1
4.77 (s), 17.80 (s), 17.94
(S), 28.61 (s), 29.95 (s), 34.
63 (s), 43.60 (s), 44.33 (s), 4
5.89 (s), 115.75 (d), 117.39
(D), 122.75 (dd), 126.81 (s),
127.41 (s), 136.65 (s), 138.3
0 (dd), 147.64 (S), 149.71 (d
d), 150.47 (dd) ppm IR (KBr disc) νmax: 2916, 284
8,2104,1533,1506,1279,98
5,889,845,814cm ^-1

The following compounds were obtained in the same manner as in Example 19.

Example 20 trans, trans-4- (4- (4-chlorophenyl) cyclohexyl) -1-n-pentyl-1-silacyclohexanone was used for trans, trans-4- (4
-N-pentyl-4-silacyclohexyl) cyclohexyl-3 ', 4'-difluorobiphenyl was obtained. ¹³ C-NMR (CDCl ₃ ) δ: 10.10 (s), 1
2.16 (s), 14.00 (s), 22.36
(S), 24.11 (s), 28.61 (s), 29.
95 (s), 34.63 (s), 35.39 (s), 4
3.60 (s), 44.33 (s), 45.89
(S), 115.75 (d), 117.38 (d), 1
22.72 (dd), 126.80 (s), 127.4
0 (s), 136.64 (S), 138.29 (d
d), 147.63 (s), 148.27 (dd), 1
51.91 (dd) ppm IR (liquid film) νmax: 2918, 2106, 153
1,1506,1311,985,887,835,8
10cm ^-1

[0104]

As described above, the cyclohexanoone compound of the present invention is a useful synthetic intermediate for producing a liquid crystal compound, and various silacyclohexane type liquid crystal compounds can be obtained by deriving this compound. Can be manufactured.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tsutomu Ogihara 28, Nishifukushima, Okufukumura, Nakakubijo-gun, Niigata Pref. Shinetsu Chemical Industry Co., Ltd. Synthetic Technology Research Laboratories (72) Inventor Mutsuo Nakajima Nakatsugi-gun, Niigata (28) Inventor Tatsushi Kaneko, 28, Nishifukushima, Nakakushiro-gun, Niigata Prefecture, Japan Shin-Etsu Chemical Industry Co., Ltd. F term (reference) 4H027 BD02 BD04 DJ04 DJ05 4H049 VN01 VP01 VQ02 VQ07 VQ84 VR24 VS03 VS05 VS23 VS35 VU25 VW02 VW35 VW38

Claims (5)

[Claims] 1. A cyclohexanone compound represented by the following general formula (I). Embedded image However, Ar is a phenyl group or a tolyl group, R is Ar, a linear alkyl group having 1 to 10 carbon atoms, a mono- or difluoroalkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 8 carbon atoms. Or an alkoxyalkyl group having 2 to 7 carbon atoms. 2. A compound of the general formula(Where R¹ And R^TwoAre each having 1 to 4 carbon atoms
Alkyl group or R¹And R^TwoAnd-(CH_Two)
_Four-,-(CH_Two)_Five-And-(CH_Two)_TwoO (CH_Two)_Two−
Represents any of ) And enamine compounds represented by
Michael addition reaction with vinyl vinyl ketone gives the general formulaAnd obtains the Michael adduct represented by
Intramolecular aldol condensation or
By hydrolyzing the adduct, a compound of the general formulaThe ketoaldehyde compound represented by
By subjecting aldehyde compounds to intramolecular aldol condensation
And the general formula(However,IsOrRepresents ) To obtain a cyclohexenone compound represented by the following formula:
Hydrogenation of this cyclohexenone compound
Thus, the system represented by the general formula (I) described in claim 1
A method for producing a clohexanone compound.
A method for producing a rohexanone compound. 3. A cyclohexanone compound represented by the general formula (I) according to claim 1 and a compound represented by the general formula: (Wherein, M is MgU (U represents halogen), ZnU, TiU _k (OW) _{3 -k} (W is an alkyl group, k represents an integer of 0 to 3) or Li and X are C
N, F, Cl, Br, CF 3, OCF 3, OCHF 2, O
_{CHFCl, OCF 2 Cl, CF 2} Cl, (O) m CY 1 =
CX ₁ X ₂ (m is 0 or 1, Y ₁ and X ₁ are H, F or Cl
And X ₂ represents F or Cl. ), O (CH ₂ )
_r (CF ₂ ) _s X ₃ (r and s are 0, 1 or 2 and (r +
s) is a number satisfying 2, 3 or 4, and X ₃ is H, F or Cl
Represents ), R or OR groups, Y is halogen or CH ₃ ,
i represents an integer of 0 to 2. ) Is reacted with an organometallic reagent represented by the general formula: Is obtained by hydrogenation or dehydration followed by hydrogenation to give a compound of the general formula After obtaining the compound represented by
By reduction, the compound represented by the general formula (II) A method for producing a silacyclohexane type liquid crystal compound, characterized by obtaining a silacyclohexane type liquid crystal compound represented by the formula: 4. A cyclohexanone compound represented by the general formula (I) according to claim 1 and a compound represented by the general formula: (Wherein, M is MgU (U represents halogen), ZnU, TiU _k (OW) _{3 -k} (W is an alkyl group, k represents an integer of 0 to 3) or Li and X are C
N, F, Cl, Br, CF 3, OCF 3, OCHF 2, O
_{CHFCl, OCF 2 Cl, (O} ) m CY 1 = CX 1 X
₂ (m is 0 or 1, Y ₁ and X ₁ represent H, F or Cl, X ₂ represents F or Cl), O (CH ₂ ) _r (C
F ₂ ) _s X ₃ (r and s are 0, 1 or 2 and (r + s)
Is a number satisfying 2, 3 or 4, and X ₃ represents H, F or Cl. ), CF ₂ Cl, R or OR groups, Y and Z each independently represent halogen or CH ₃ , i and j each independently represent an integer of 0 to 2. Is reacted with an organometallic reagent represented by the general formula: Is obtained by hydrogenolysis or dehydration followed by hydrogenation to give a compound of the general formula After obtaining the compound represented by
By reduction, the compound of the general formula (III) A method for producing a silacyclohexane type liquid crystal compound, characterized by obtaining a silacyclohexane type liquid crystal compound represented by the formula: 5. A cyclohexanone compound represented by the general formula (I) according to claim 1 and a compound represented by the general formula: (Wherein, M is MgU (U represents halogen), ZnU, TiU _k (OW) _{3 -k} (W represents an alkyl group, k represents 0, 1, 2, or 3), or Li, X Is a halogen, Y is a halogen or CH ₃ , i is an integer of 0 to 2), and reacted with an organometallic reagent represented by the general formula: Is obtained by hydrogenolysis or dehydration followed by hydrogenation to give a compound of the general formula A compound of the formula (Wherein, M ′ is MgU (U represents halogen), ZnU, TiU _k (OW) _{3 -k} (W represents an alkyl group, k represents 0, 1, 2, or 3) or Li, X ′ is halogen, Y is halogen or CH ₃ , i is an integer of 0 to 2 or an organic metal reagent represented by B (OV) ₂ (V represents H or an alkyl group) Is reacted in the presence of a transition metal catalyst to give a compound of the general formula After obtaining the compound represented by
By reduction, the compound represented by the general formula (III) A method for producing a silacyclohexane type liquid crystal compound, characterized by obtaining a silacyclohexane type liquid crystal compound represented by the formula: