JPH0881475A - Cyclohexanecarbaldehyde compound and method for producing silacyclohexane type liquid crystal compound using the same - Google Patents

Abstract

(57) [Abstract] [Purpose] A cyclohexanecarbaldehyde compound and a silacyclohexane type liquid crystal compound are produced by deriving the compound. [Structure] A cyclohexanecarbaldehyde 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, and a branched alkyl group having 3 to 8 carbon atoms. Alternatively, it represents an alkoxyalkyl group having 2 to 7 carbon atoms.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclohexanecarbaldehyde 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 element utilizes optical anisotropy and dielectric anisotropy of a liquid crystal material, and depending on its display mode, TN type (twisted nematic type), STN type (super twisted nematic type). , SBE type (super birefringence type),
DS type (dynamic scattering type), guest-host type, DAP type (aligned phase deformation type), PD type (polymer dispersion type) and O
There are various types such as MI type (optical mode interference type).
The most common display device is based on the Schut-Helfrich effect and has a twisted nematic structure.

The properties required for the liquid crystal substances used for these liquid crystal displays are slightly different depending on the display system, but they are stable against a wide range of liquid crystal temperature, moisture, air, light, heat, electric field and the like. Things are commonly requested in any display method. Furthermore, it is desired that the liquid crystal material has a low viscosity and provides a short addressing time, a low threshold voltage and a high contrast in the cell.

[0004]

With the recent widespread use of liquid crystal displays, the properties required of liquid crystal materials are becoming more and more severe. In particular, it has been desired to further improve the characteristics of conventional liquid crystal substances, such as lowering of driving voltage, wide temperature range corresponding to vehicle needs, and improvement of low temperature performance.

From these viewpoints, the present inventors have developed a novel liquid crystal compound containing a silicon atom in the molecule for the purpose of improving a liquid crystal substance, and filed an application for it.

The object of the present invention is to provide a method for producing a cyclohexanecarbaldehyde 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. It is what

[0007]

[Means for Solving the Problems] That is, the present invention provides a compound represented by the general formula (II):

Embedded image (In the formula, R is a phenyl group, a tolyl group, a carbon number of 1
-10 straight-chain alkyl group, C1-C10 mono- or difluoroalkyl group, C3-C8 branched chain alkyl group or C2-C7 alkoxyalkyl group, X is R, OR group , CN, F, Cl, Br, CF ₃ , OCF ₃ ,
OCHF ₂ , OCHFCl, OCF ₂ Cl, CF ₂ Cl,
_{- (O) m -CY 1 =} CX 1 CX 2 (. M is 0 or 1, Y ₁ and X ₁ is H, F or Cl, X ₂ represents F or Cl) or -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,
X ₃ represents H, F or Cl. ), Y is a halogen (preferably F or Cl) or CH ₃ group, and i is an integer of 0 to 2. ) Silacyclohexane type liquid crystal compound represented by the formula, and the general formula (III)

[Chemical 17] (In the formula, Y and Z are each independently of each other halogen (preferably F or Cl) or CH ₃ , i and j.
Each independently represents an integer of 0 to 2. ) A useful intermediate for producing a silacyclohexane type liquid crystal compound represented by formula (I):

[Chemical 18] (In the formula, Ar is a phenyl group or a tolyl group, R is Ar, a linear alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms.
It represents a mono- or difluoroalkyl group having 10 carbon atoms, a branched chain alkyl group having 3 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 7 carbon atoms. ) Is a cyclohexanecarbaldehyde compound represented by.

The present invention also provides a cyclohexanecarbaldehyde compound represented by the general formula (I)

[Chemical 19] (In the formula, X is R, OR group, 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 CX
₂ (m is 0 or 1, Y ₁ and X ₁ are H, F or Cl, X ₂ is F or Cl) or —O— (CH ₂ ) _r — (C
F ₂ ) _s- X ₃ (r and s are 0, 1 or 2, and (r + s) is 2, 3 or 4, X ₃ represents H, F or Cl), and Y is halogen (preferably,). F or Cl) or C
H ₃ and i represent an integer of 0 to 2. ) Is reacted with an ylide compound represented by the general formula

Embedded image A compound of the general formula

[Chemical 21] After obtaining the compound represented by
By reduction, the general formula (II)

[Chemical formula 22] A method for producing a silacyclohexane type liquid crystal compound, which comprises obtaining a silacyclohexane type liquid crystal compound represented by:

The present invention also provides a cyclohexanecarbaldehyde compound represented by the general formula (I)

[Chemical formula 23] (In the formula, X is R, OR group, 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 CX
₂ (m is 0 or 1, Y ₁ and X ₁ are H, F or Cl, X ₂ is F or Cl) or —O— (CH ₂ ) _r — (C
F ₂ ) _s- X ₃ (r and s are 0, 1 or 2, and (r + s) is 2, 3 or 4, X ₃ represents H, F or Cl), and Y and Z are each other. Independently of each other, halogen (preferably F or Cl) or CH ₃ , i and j each independently represent an integer of 0 to 2. ) Is reacted with an ylide compound represented by the general formula

[Chemical formula 24] A compound of the general formula

[Chemical 25] After obtaining the compound represented by
By reduction, general formula (III)

[Chemical formula 26] A method for producing a silacyclohexane type liquid crystal compound, which comprises obtaining a silacyclohexane type liquid crystal compound represented by:

The present invention also provides a cyclohexanecarbaldehyde compound represented by the general formula (I)

[Chemical 27] (In the formula, X'is halogen, Y is halogen or C
H ₃ and i represent an integer of 0 to 2. ) Is reacted with an ylide compound represented by the general formula

[Chemical 28] A compound of the general formula

[Chemical 29] (In the formula, M represents MgU (U represents halogen), ZnU, TiU _k (OW) _3−k (W represents an alkyl group, and k represents an integer of 0 to 3) or B (OV) ₂ (V
Represents H or an alkyl group. ), Z is halogen or CH
₃ , j represents an integer of 0 to 2. ) Is reacted with an organometallic reagent represented by

[Chemical 30] A compound of the general formula

[Chemical 31] After obtaining the compound represented by
By reduction, general formula (III)

[Chemical 32] A method for producing a silacyclohexane type liquid crystal compound, which comprises obtaining a silacyclohexane type liquid crystal compound represented by:

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

The general formula (I) of the present invention

[Chemical 33] (In the formula, Ar is a phenyl group or a tolyl group, R is Ar, a linear alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms.
It represents a mono- or difluoroalkyl group having 10 carbon atoms, a branched chain alkyl group having 3 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 7 carbon atoms. The cyclohexanecarbaldehyde compound represented by the formula () is an application previously filed by the present inventors (Japanese Patent Application No. 6-
71825), and is easily manufactured from the cyclohexanone compound.

For example, as shown in the following reaction formula [Formula 34], an ylide compound and Wittig produced from an alkoxymethyltriphenylphosphonium salt by the action of a base.
The reaction is performed to obtain an alkyl enol ether compound, which is then synthesized by acid-catalyzed hydrolysis.

[0014]

Embedded image (In the formula, R ′ represents an alkyl group, specifically, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and Q represents halogen, preferably Cl, Br or I.)

As the alkoxymethyltriphenylphosphonium salt, methoxymethyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium iodide, ethoxymethyltriphenylphosphonium chloride, ethoxymethyltriphenylphosphonium bromide, ethoxymethyltriphenyl Phenylphosphonium iodide or the like can be used.

As the base used for the production of ylide, n
Examples include organic lithiums such as -butyllithium, s-butyllithium, t-butyllithium, methyllithium and phenyllithium, alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, and sodium dimcyl.

The reaction is carried out by using 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. In a solvent mixed with aprotic polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, etc., preferably 0 to the reflux temperature of the solvent, more preferably 10 to 40 ° C. Perform within the temperature range.

The cyclohexanone compound is added to the ylide compound produced in these solvents to advance the Wittig reaction to obtain an alkyl enol ether compound.

As the acid catalyst used for the hydrolysis of the alkyl enol ether compound, inorganic acids such as hydrochloric acid and sulfuric acid,
Organic acids such as acetic acid, oxalic acid, trifluoroacetic acid and chloroacetic acid can be mentioned. This hydrolysis is carried out at 0 to 80 ° C, preferably 10 to 40 ° C.

The cyclohexanecarbaldehyde compound thus obtained is used for the production of various silacyclohexane type liquid crystal compounds. Hereinafter, a method for producing the derivative of the cyclohexanecarbaldehyde compound will be described.

First, a phosphorus ylide compound, which is easily prepared from a corresponding phosphonium salt by the action of a base, is reacted with the above cyclohexane compound to obtain an olefin compound by the Wittig reaction.

[0022]

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

As the base used for the production of ylide, n
Examples include organic lithiums such as -butyllithium, s-butyllithium, t-butyllithium, methyllithium and phenyllithium, alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, and sodium dimcyl.

The reaction is carried out by using 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. Or an aprotic polar solvent such as N, N-dimethylformamide, dimethylsulfoxide, or hexamethylphosphoric triamide. The reaction is preferably carried out at 0 to reflux temperature, more preferably 10 to 40 ° C.

The ylide compounds formed in these solvents are
Add Witt with cyclohexanecarbaldehyde compound
The ig reaction proceeds to obtain an olefin compound.

Next, a double bond of the obtained olefin compound is obtained.
The mixture is hydrogenated by catalytic reduction to give a saturated compound. This
The reaction is preferably 0 to 150 ° C, more preferably 20 to 10 ° C.
The higher the pressure at 0 ° C, the higher the reaction rate.
Atmospheric pressure ~ 20kg / cm because there is about² A range of
Good

[0027]

Embedded image

Examples of the catalyst used for 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 give good results. Further, it is preferable to use a palladium type or nickel type.

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

[0030]

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

Examples of the electrophile include halogen, hydrogen halide, metal halide, sulfonic acid derivative, acid halide, alkyl halide and the like. 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 (ultraviolet ray, visible light) may be irradiated. The desilylation reaction is preferably 0-80.
C., more preferably 10 to 40.degree.

As a reagent used for reduction of the produced halosilacyclohexane compound, sodium hydride, calcium hydride, trialkylsilanes, boranes, metal hydrides such as dialkylaluminum, lithium aluminum hydride, sodium borohydride , Complex hydride compounds such as lithium borohydride, potassium borohydride, tributylammonium borohydride (Complex
hybrid) or a substituted hydride compound thereof, that is, lithium trialkoxy aluminum hydride, sodium di (methoxyethoxy) aluminum hydride,
Examples thereof include lithium triethylborohydride and sodium cyanoborohydride. Reduction reaction is 0 to 1
The temperature is preferably 50 ° C, and more preferably 20 to 120 ° C.

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

Among the products obtained by the reaction formula [Chem. 35], a general formula corresponding to n = 0

[Chemical 38] (Wherein X ′ represents halogen (preferably Cl, Br or I)), the compound represented by the general formula corresponding to n = 1

[Chemical Formula 39] It is also possible to lead to a compound represented by.

This reaction follows the equation:

[0036]

[Chemical 40] (In the formula, M represents MgU (U represents halogen (preferably Cl, Br or I)), ZnU, TiU.
_k (OW) _3-k (w is an alkyl group, preferably 1 to 1 carbon atoms
The alkyl group of 6 and k represent the integer of 0-3. ) Or B
(OV) ₂ (V represents H or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms)). )

This reaction is carried out in the presence of a transition catalyst. Palladium or nickel compounds are particularly preferable as the transition catalyst. 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).
Alternatively, a compound composed of a divalent palladium compound such as palladium acetate, palladium chloride, 1,1-bis (diphenylphosphino) ferrocene] palladium (II) chloride and a ligand, or a combination of these with a reducing agent is used. You can

As the nickel catalyst, for example, [1,3-
Bis (diphenylphosphino) propane] nickel (I
Divalent nickel compounds such as I) chloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) chloride, bis (triphenylphosphine) nickel (II) chloride, and tetrakis (triphenylphosphine) nickel Examples thereof include zero-valent nickel compounds such as (0).

When the organometallic reagent is a boric acid derivative,
That is, when M is B (OV) ₂ , the reaction is preferably performed in the presence of a base. As the base, for example, an inorganic base such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or the like, or an organic base such as triethylamine, tributylamine, dimethylaniline or the like can be used. These reaction temperatures are preferably 0 to 100 ° C., more preferably 20 to 7 ° C.
It may be carried out at 0 ° C.

The compound obtained by the reaction formula [Chemical formula 40] can be converted into a silacyclohexane type liquid crystal compound according to the reaction formulas [Chemical formula 36] and [Chemical formula 37].

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

[0042]

EXAMPLES The present invention will be described in more detail with reference to specific examples. Unless otherwise specified, the reaction was carried out at room temperature of 25 ° C.

Example 1 Preparation of 4- (4-phenyl-4-n-propyl-4-silacyclohexyl) cyclohexanecarbaldehyde methoxymethyltriphenylphosphonium chloride 3
In a mixture of 5.0 g and 300 ml of tetrahydrofuran,
11.3 g of potassium t-butoxide was added at 0 ° C. to prepare an ylide solution. To this ylide solution, 31.5 g of 4- (4-phenyl-4-n-propyl-4-silacyclohexyl) cyclohexanone was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water, extracted with ethyl acetate, and the ethyl acetate solution was washed with brine, dried and concentrated. N-Hexane was added to the residue, the resulting triphenylphosphine oxide was filtered off, and the filtrate was concentrated to obtain a methyl enol ether compound. 180 ml of methylene chloride on this
200 ml of 20% hydrochloric acid was added, and the mixture was stirred at room temperature for 18 hours. The methylene chloride solution is collected, washed, dried and concentrated, and then purified by column chromatography to obtain the desired product 31.
2 g (yield 95%) was obtained. IR (liquid film) νmax: 2920, 2860, 172
^{0,1440,1195,1110cm -1 1 H-NMR (CDCl} 3) δ: 0.50-2.52 (2
5H, m), 7.20-7.65 (5H, m), 9.5
0-9.76 (1H, d × 2 (2 corresponding to stereoisomers
1H signal for one doublet)) ppm

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

Example 2 Using 4- (4-phenyl-4-n-pentyl-4-silacyclohexyl) cyclohexanone, in the same manner as in Example 1, 4- (4-phenyl-4)
-N-pentyl-4-silacyclohexyl) cyclohexanecarbaldehyde was obtained. IR (liquid film) νmax: 2920, 2860, 172
^{0,1445,1190,1110cm -1 1 H-NMR (CDCl} 3) δ: 0.50-2.50 (2
9H, m), 7.20-7.65 (5H, m), 9.5.
0-9.76 (1H, d x 2) ppm

[Example 3] (4,4-diphenyl-4-
Silacyclohexyl) cyclohexanone was used in the same manner as in Example 1 to obtain 4- (4,4-diphenyl-4-silacyclohexyl) cyclohexanecarbaldehyde. Melting point: 107 ° C IR (KBr disc) νmax: 2920, 285
^{0,1715,1425,1115,1105cm -1 1 H-NMR (CDCl} 3) δ: 0.80-2.50 (1
9H, m), 7.20-7.75 (10H, m), 9.
50-9.70 (1H, m) ppm

Example 4 Trans-4- (trans-4- (2- (3,4-difluorophenyl) ethyl) cyclohexyl) -1-n-
Production of propyl-1-silacyclohexane To a mixture of 48.0 g of 3,4-difluorobenzyltriphenylphosphonium bromide and 400 ml of tetrahydrofuran, 12.0 g of potassium t-butoxide was added,
An ylide solution was prepared. In this ylide solution, 4- (4-
Phenyl-4-n-propyl-4-silacyclohexyl) cyclohexanecarbaldehyde (32.9 g) was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water, extracted with ethyl acetate, and the ethyl acetate solution was washed with brine.
Dried and concentrated. N-Hexane was added to the residue, the resulting triphenylphosphine oxide was filtered off, the filtrate was concentrated and then purified by column chromatography to give 4- (4
-(2- (3,4-Difluorophenyl) ethenyl) cyclohexyl) -1-phenyl-1-n-propyl-1
-39.9 g (yield 91%) of silacyclohexane was obtained. IR (liquid film) νmax: 2920, 2860, 151
5,1290,1110,960cm ^-1

Next, 38.0 g of this product was added to ethyl acetate 3
It was dissolved in 00 ml and catalytically reduced using 500 mg of palladium-carbon as a catalyst. After uptake of 1 equivalent of hydrogen, the catalyst is filtered off and the filtrate is concentrated to give 4- (4- (2- (3,4-
Difluorophenyl) ethyl) cyclohexyl) -1-
38.2 g (quantitative yield) of phenyl-1-n-propyl-1-silacyclohexane was obtained. IR (liquid film) νmax: 2920, 2860, 151
5,1280,1110 cm ^-1

Next, this product 30.0 g (68 mmo)
13.0 g of iodine monochloride was added dropwise to a mixture of 1) and 500 ml of carbon tetrachloride, and the mixture was stirred at room temperature for 30 minutes. The mixture was concentrated to give a crude product of 1-chloro-4- (2- (3,4-difluorophenyl) ethyl) cyclohexyl-1-phenyl-1-silacyclohexane. This product was dissolved in 30 ml of tetrahydrofuran, and 2.00 g of lithium aluminum hydride and 20 m of tetrahydrofuran.
It was added dropwise to the mixture of 1 and stirred at 40 ° C. for 12 hours. The reaction mixture was poured into diluted hydrochloric acid, extracted with ethyl acetate, the ethyl acetate solution was washed with brine, dried and concentrated, and then purified by column chromatography to obtain 12.8 g of the desired product (yield 5
2%) was obtained. IR (liquid film) νmax: 2920, 2852, 210
0,1520,1286,887,818 cm ^{-1 13} C-NMR (CDCl ₃ ) δ: 10.14 (s), 1
4.79 (s), 17.79 (s), 17.95
(S), 28.61 (s), 29.58 (s), 32.
54 (s), 33.54 (s), 37.46 (s), 3
9.08 (s), 44.16 (s), 45.96
(S), 116.66 (d), 116.92 (d), 1
23.93 (dd), 140.06 (dd), 147.
50 (dd), 151.12 (dd) ppm

The following compounds were obtained in the same manner as in Example 4.

Example 5 The same procedure as in Example 4 was carried out using 4-fluorobenzyltriphenylphosphonium bromide and 4- (4-phenyl-4-n-pentyl-4-silacyclohexyl) cyclohexanecarbaldehyde. To give trans-4- (trans-4- (2- (4-fluorophenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane. IR (KBr disc) νmax: 2918, 285
0,2100,1512,1232,887,823c
m ^{−1 13} C-NMR (CDCl ₃ ) δ: 10.12 (s), 1
4.79 (s), 17.80 (s), 17.94
(S), 28.60 (s), 29.60 (s), 32.
51 (s), 33.58 (s), 37.47 (s), 3
9.45 (s), 44.15 (s), 45.96
(S), 114.90 (d), 129.54 (d), 1
38.73 (d), 161.07 (d) ppm

Example 6 Using 4-fluorobenzyltriphenylphosphonium bromide, trans-4- (trans-4- (2- (4
-Fluorophenyl) ethyl) cyclohexyl) -1-
n-Pentyl-1-silacyclohexane was obtained. IR (KBr disc) νmax: 2918, 285
0,2100,1512,1230,887,823c
m ^{−1 13} C-NMR (CDCl ₃ ) δ: 10.11 (s), 1
2.19 (s), 14.00 (s), 22.36
(S), 24.12 (s), 28.60 (s), 29.
62 (s), 32.52 (s), 33.59 (s), 3
5.40 (s), 37.48 (s), 39.47
(S), 44.16 (s), 45.96 (s), 11
4.9 (d), 129.54 (d), 138.73
(D), 161.08 (d) ppm

[Example 7] 4- (4-phenyl-4-n)
-Pentyl-4-silacyclohexyl) cyclohexanecarbaldehyde in the same manner as in Example 4, trans-4- (trans-4- (2- (3,4-difluorophenyl) ethyl) cyclohexyl) -1-n. -Pentyl-1-silacyclohexane was obtained. IR (liquid film) νmax: 2920, 2852, 209
8, 1520, 1286, 1211, 1119, 88
7,816 cm ^{-1 13} C-NMR (CDCl ₃ ) δ: 10.10 (s), 1
0.46 (s), 12.19 (s), 13.99
(S), 22.36 (s), 24.11 (s), 28.
60 (s), 29.57 (s), 32.54 (s), 3
3.54 (s), 35.40 (s), 37.41
(S), 39.06 (s), 44.12 (s), 45.
94 (s), 116.71 (d), 116.95
(D), 123.96 (dd), 140.09 (d
d), 147.50 (dd), 151.13 (dd) p
pm

Example 8 Trans-4- (trans-) was carried out in the same manner as in Example 4 except that 4-trifluoromethoxybenzyltriphenylphosphonium bromide was used.
4- (2- (4-trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane was obtained. IR (KBr disc) νmax: 2918,284
8,2102,1510,1279,1211,119
8,1165,887,818 cm ^{-1 13} C-NMR (CDCl ₃ ) δ: 10.16 (s), 1
4.82 (s), 17.79 (s), 17.97
(S), 28.65 (s), 29.63 (s), 32.
73 (s), 33.60 (s), 37.60 (s), 3
9.29 (s), 44.21 (s), 46.02
(S), 120.58 (q), 120.81 (s), 1
29.45 (s), 141.92 (s), 147.22
(Q) ppm

Example 9 4-trifluoromethoxybenzyl triphenylphosphonium bromide and 4-
Using (4-phenyl-4-n-pentyl-4-silacyclohexyl) cyclohexanecarbaldehyde in the same manner as in Example 4, trans-4- (trans-4- (2
-(4-Trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-n-pentyl-1-silacyclohexane was obtained. IR (KBr disc) νmax: 2920, 285
0, 2102, 1510, 1223, 1198, 116
5,887,833,816 cm ^{-1 13} C-NMR (CDCl ₃ ) δ: 10.12 (s), 1
2.20 (s), 13.99 (s), 22.37
(S), 24.13 (s), 28.62 (s), 29.
62 (s), 32.70 (s), 33.58 (s), 3
5.41 (s), 37.56 (s), 39.28
(S), 44.17 (s), 45.99 (s), 12
0.56 (q), 120.81 (s), 129.46
(S), 141.92 (s), 147.19 (q) pp
m

Example 10 Using 4-chlorobenzyltriphenylphosphonium chloride, trans-4- (trans-4- (2- (4
-(4-Chlorophenyl) phenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane was obtained. IR (KBr disc) νmax: 2918,284
8,2100,1487,1095,1003,88
7,843,810 cm ^{-1 13} C-NMR (CDCl ₃ ) δ: 10.12 (s), 1
4.79 (s), 17.81 (s), 17.94
(S), 28.60 (s), 29.61 (s), 32.
97 (s), 33.60 (s), 37.58 (s), 3
9.31 (s), 44.16 (s), 45.96
(S), 126.80 (s), 128.17 (s), 1
28.81 (s), 128.86 (s), 132.98
(S), 137.20 (s), 139.60 (s), 1
42.80 (s) ppm

Example 11 Trans-4- (trans-) was carried out in the same manner as in Example 4 using 4-chloro-3-fluorobenzyltriphenylphosphonium bromide.
4- (2- (4- (4-chloro-3-fluorophenyl) phenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane was obtained. IR (KBr disc) νmax: 2920, 285
0,2096,1560,1481,1200,107
0,982,889,845,804 cm ^{-1 13} C-NMR (CDCl ₃ ) δ: 10.12 (s), 1
4.79 (s), 17.79 (s), 17.93
(S), 28.60 (s), 29.61 (s), 32.
98 (s), 33.60 (s), 37.56 (s), 3
9.26 (s), 44.15 (s), 45.95
(S), 114.88 (d), 119.45 (d), 1
23.14 (d), 126.76 (s), 128.98
(S), 130.69 (s), 136.17 (d), 1
41.83 (d), 143.46 (s), 158.29
(D) ppm

Example 12 trans-4- (trans-4- (2- (4- (4-fluorophenyl) phenyl) ethyl) cyclohexyl)
Production of -1-n-propyl-1-silacyclohexane 4- (4-phenyl-4-n) was prepared in the same manner as in Example 4.
-Propyl-4-silacyclohexyl) cyclohexanecarbadehyde 15.0 g of ylide and Wit prepared from 4-bromobenzyltriphenylphosphonium bromide
The tig reaction is carried out and 4- (4- (2- (4-bromophenyl) ethenyl) cyclohexyl-1-phenyl-1-
20.9 g (yield 50%) of n-propyl-1-silacyclohexane was obtained. IR (liquid film) νmax: 2920, 2850, 148
5,1115,1070,1010,965,800c
m ^-1

A mixture of 18.0 g of this product, 500 mg of tetrakis (triphenylphosphine) palladium (0) and 100 ml of tetrahydrofuran was added at room temperature to 1.0 M.
42 ml of a tetrahydrofuran solution of 4-fluorophenylzinc chloride was added dropwise and stirred for 19 hours. The reaction mixture was poured into an aqueous solution of ammonium chloride and extracted with ethyl acetate. The ethyl acetate solution was washed with brine, dried, concentrated, and purified by column chromatography to give 4-
(4- (2- (4- (4-fluorophenyl) phenyl) ethenyl) cyclohexyl) -1-n-propyl-
16.2 g of 1-silacyclohexane (yield 71%) was obtained. IR (liquid film) νmax: 2920, 2850, 160
0,1495,1235,1110,805 cm ^-1

15.0 g of this product was hydrogenated in the same manner as in Example 4 to give 4- (4- (2- (4- (4-fluorophenyl) phenyl) ethyl) cyclohexyl)-
1-n-propyl-1-silacyclohexane 14.8 g
(Yield 98%) was obtained. IR (KBr disc) νmax: 2920, 285
0, 1600, 1495, 1235, 1115, 815
cm ^-1

In the same manner as in Example 4, 10.0 g of this product was subjected to a desilylation reaction with iodine monochloride and then reduced with lithium aluminum hydride to obtain the desired product 5.
2 g (yield 61%) was obtained. IR (KBr disc) νmax: 2918, 285
2,2102,1498,1225,1221,116
1,889,843,820 cm ^{-1 13} C-NMR (CDCl ₃ ) δ: 10.12 (s), 1
4.79 (s), 17.80 (s), 17.94
(S), 28.60 (s), 29.62 (s), 32.
94 (s), 33.61 (s), 37.59 (s), 3
9.33 (s), 44.16 (s), 45.96
(S), 115.50 (d), 126.84 (s), 1
28.45 (d), 128.79 (s), 137.28
(D), 137.50 (s), 142.40 (s), 1
62.26 (d) ppm

The following compounds were obtained in the same manner as in Example 12.

[Example 13] Trans-4- (trans-4- (2- (4- (3,4-
Difluorophenyl) phenyl) ethyl) cyclohexyl) -1-n-propyl-1-silacyclohexane was obtained. IR (KBr disc) νmax: 2916,285
0, 2104, 1506, 1402, 1309, 127
9,1182,1065,982,889,843,8
10 cm ^{-1 13} C-NMR (CDCl ₃ ) δ: 10.13 (s), 1
4.79 (s), 17.80 (s), 17.94
(S), 28.60 (s), 28.61 (s), 32.
96 (s), 33.60 (s), 37.58 (s), 3
9.28 (s), 44.16 (s), 45.96
(S), 115.72 (d), 117.37 (d), 1
22.71 (dd), 126.76 (s), 128.9
1 (s), 136.38 (s), 138.30 (d
d), 143.05 (s), 148.25 (dd), 1
51.90 (dd) ppm

[0064]

INDUSTRIAL APPLICABILITY As described above, the cyclohexanecarbaldehyde compound of the present invention is a useful synthetic intermediate in the production of liquid crystal compounds, and various silacyclohexane type liquid crystal compounds can be obtained by deriving this compound. It can be manufactured.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09K 19/40 9279-4H G02F 1/13 500 // C07B 61/00 300 (72) Inventor Ogihara Work 1 28, Nishi-Fukushima, Chubiki-mura, Nakakubiki-gun, Niigata Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (72) Inventor Tatsushi Kaneko 1 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata 1 Shin-Etsu Chemical Co., Ltd. Company Synthetic Technology Laboratory (72) Inventor Mutsuo Nakajima 28, Nishi-Fukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture 1 Shin-Etsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. A cyclohexanecarbaldehyde 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, and a branched alkyl group having 3 to 8 carbon atoms. Alternatively, it represents an alkoxyalkyl group having 2 to 7 carbon atoms. 2. A cyclohexanecarbaldehyde compound represented by the general formula (I) according to claim 1, and a general formula: (In the formula, X is R, OR group, 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 CX
₂ (m is 0 or 1, Y ₁ and X ₁ are H, F or Cl, X ₂ is F or Cl) or —O— (CH ₂ ) _r — (C
F ₂ ) _s- X ₃ (r and s are 0, 1 or 2, and (r + s) is 2, 3 or 4, X ₃ represents H, F or Cl), Y is halogen or CH _3. , I represents an integer of 0 to 2. ) With an ylide compound represented by the formula: A compound represented by the following general formula: After obtaining the compound represented by
By reduction, the compound of the general formula (II): A method for producing a silacyclohexane type liquid crystal compound, comprising obtaining a silacyclohexane type liquid crystal compound represented by: 3. A cyclohexanecarbaldehyde compound represented by the general formula (I) according to claim 1, and a general formula: (In the formula, X is R, OR group, 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 CX
₂ (m is 0 or 1, Y ₁ and X ₁ are H, F or Cl, X ₂ is F or Cl) or —O— (CH ₂ ) _r — (C
F ₂ ) _s- X ₃ (r and s are 0, 1 or 2, and (r + s) is 2, 3 or 4, X ₃ represents H, F or Cl.), Y and Z are each other. Independently of halogen or CH ₃ , i and j are each independently 0 to 2
Represents the integer. ), And reacting with an ylide compound represented by the general formula: A compound represented by the following 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, comprising obtaining a silacyclohexane type liquid crystal compound represented by: 4. A cyclohexanecarbaldehyde compound represented by the general formula (I) according to claim 1, and a general formula: (In the formula, X'is halogen, Y is halogen or C
H ₃ and i represent an integer of 0 to 2. ) With an ylide compound represented by the formula: A compound of the general formula (In the formula, M represents MgU (U represents halogen), ZnU, TiU _k (OW) _3-k (w represents an alkyl group, and k represents an integer of 0 to 3) or B (OV) ₂ (V
Represents H or an alkyl group. ), Z is halogen or CH
₃ , j represents an integer of 0 to 2. ) Is reacted with an organometallic reagent represented by the formula (1) in the presence of a transition metal catalyst to give a compound of the general formula A compound represented by the following 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, comprising obtaining a silacyclohexane type liquid crystal compound represented by: