JP2003128596A - Method for producing phenylethane derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a phenylethane derivative with a simple method at a low cost. SOLUTION: The method for the production of a phenylethane derivative of formula (3) comprises the reaction of a compound of formula (1) with a compound of formula (2) in the presence of a copper salt catalyst. In the formulas, A<1> to A<4> are each 1,4-phenylene or 1,4-cyclohexylene; A<1> and A<2> may be single bond; Z<1> to Z<3> are each a single bond, CH2 CH2 , CH2 O, OCH2 , COO, OCO, CF2 O, OCF2 , CH=CH or C≡C; R<1> is H, F, an alkyl, 4,4-ethylenedioxycyclohexyl or 4,4-trimethylenedioxycyclohexyl; R<2> is H, a halogen atom, cyano, thiocyano or an alkyl; X is a halogen, an alkylsulfonyloxy or an arylsulfonyloxy; Y is MgBr, MgCl or Li; (n), (m) and (p) are each 0 or 1; and (q) is an integer of 0-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal compound and a method for producing a phenylethane derivative which is useful mainly as a raw material for synthesizing a liquid crystal compound in the presence of a copper salt.

[0002]

BACKGROUND ART A display element using a liquid crystal compound is a clock,
Widely used for displays such as calculators and word processors. These display elements have a refractive index anisotropy of a liquid crystal compound,
It utilizes the dielectric anisotropy. In the liquid crystal phase,
There are a nematic liquid crystal phase, a smectic liquid crystal phase, and a cholesteric liquid crystal phase, but those utilizing the nematic liquid crystal phase are most widely used. As a display method, dynamic scattering (DS) type, orientation phase deformation (DAP) type, guest / host (GH) type, twisted nematic (TN) type, super twisted nematic (STN) type, thin film transistor (TFT)
Type and in-plane switching (IPS) type.

In recent years, with the widespread use of liquid crystal display devices required for a wide operating temperature range, such as those for small video, mobile phones, in-vehicle panels, etc., characteristic elements capable of providing a display having a good low temperature compatibility of liquid crystal compositions. Has become. Considering that the conventional liquid crystal molecules have a wide liquid crystal temperature range, a large dielectric anisotropy, a large optical anisotropy, etc., a 6-membered ring structure is directly connected, A rigid straight line has been preferred. However, a liquid crystal composition containing these rigid liquid crystal molecules has a high crystallinity, or has a high rate of exhibiting a defect such as showing a smectic phase at a low temperature. Therefore, an ethylene bond (“ethylene bond” in the present invention is a carbon-carbon double bond in the present invention) in the liquid crystal molecular structure, which has a relatively good liquid crystal physical property and easily retains a nematic phase suitable for display at low temperature. However, a compound having an ethylene chain (—CH ₂ CH ₂ —) as a linking group has been attracting attention. The fact that the liquid crystal compound having an ethylene bond has the effect of expanding the nematic phase in the low temperature region is also described in the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, 2000, Maruzen Co., Ltd., page 318). It is a well-known fact. These liquid crystal compounds having an ethylene bond have a relatively low clearing point and high compatibility as compared with a liquid crystal compound having no ethylene bond, and the above-mentioned liquid crystal composition for a liquid crystal display panel which requires a wide operating temperature range. As a component of a product, its usage is increasing year by year.

However, such a liquid crystal molecule having an ethylene bond has a drawback that it is difficult to introduce it at a low cost because the introduction of the ethylene chain is not easy and the number of manufacturing steps increases. For example, the liquid crystal compound having the structure of the above formula (5) is superior in compatibility as compared with the conventionally used compound of the formula (4), but the compound of the formula (5) has an ethylene chain. Since it contains, the number of synthetic steps is long, and it is very expensive as compared with the compound of the formula (4).

For the compound of the formula (5), conventionally, a method involving a Friedel-Crafts reaction as shown in Scheme 1 has been widely used. (Scheme 1)

However, in the Friedel-Crafts reaction, a halogen-based solvent such as methylene chloride or dichloroethane is usually used. Since it has been found that most of halogen-based solvents have toxicity, mutagenicity, carcinogenicity, etc., recently, the method has changed to the method via the Grignard reaction as shown in Scheme 2. However, this method cannot be said to be a simple method due to the low cis-trans selectivity of the cyclohexene ring and the large number of steps, and therefore requires a high production cost. (Scheme 2)

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a simple and low cost method for producing a liquid crystal compound having a phenylethane structure or a synthetic intermediate thereof. To provide a method.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a copper salt is used as a catalyst in formula (1)
A method for synthesizing the phenylethane derivative represented by the formula (3) with high selectivity and in a high yield was established by reacting the compound represented by the formula (1) with the organometallic compound represented by the formula (2). That is, the present invention has the following configurations. (1) A method for producing a phenylethane derivative represented by formula (3), which comprises reacting the compound represented by formula (1) with the compound represented by formula (2) in the presence of a copper salt catalyst. (In these formulas, A ^{1 to} A ⁴ are each independently 1,4-H may be replaced with F 1,4-
Phenylene, one or two -CH = may be replaced by -N = 1,4-phenylene or one or not consecutive two -CH _2, - is -O- or -
1,4-cyclohexylene optionally substituted with S-, in which A ¹ and / or A ² may be a single bond; Z ^{1 to} Z ³ are each independently a single bond,
CH ₂ CH ₂ , CH ₂ O, OCH ₂ , COO, OCO,
CF ₂ O, OCF ₂ , CH = CH or C≡C;
R ¹ is H, F, 4,4-ethylenedioxycyclohexyl, or 4,4-trimethylenedioxycyclohexyl, R ² is H, a halogen atom, a cyano group, or a thiocyano group, and R ¹ and Each R ² may independently be an alkyl having 1 to 15 carbon atoms, and one or more —CH ₂ — in this alkyl is one of —O—, —S— and —CH═CH—. May be replaced with one or two kinds of groups, but the terminal —CH ₂ — is not replaced with —O— or —S—, and a plurality of —O— or —S— may be consecutive — O- and -S- are not continuous and one or more H in this alkyl may be replaced by F; X is halogen, one or more H is F.
Alkylsulfonyloxy, which may be replaced with or arylsulfonyloxy; Y is MgBr,
MgCl or Li; n, m and p are each independently 0 or 1, and q is an integer of 0-4. (2) The method for producing a phenylethane derivative according to the item (1), wherein the copper salt catalyst is a monovalent copper salt. (3) The method for producing a phenylethane derivative according to the item (1), wherein X is an iodine atom, a trifluoromethanesulfonyloxy group or a paratoluenesulfonyloxy group. (4) The method for producing a phenylethane derivative according to the item (1), wherein A ² is 1,4-cyclohexylene. (5) The method for producing a phenylethane derivative according to item (1), wherein A ² is 1,4-cyclohexylene and the copper salt catalyst is a monovalent copper salt. (6) Item (1) above, wherein A ² is 1,4-cyclohexylene, the copper salt catalyst is a monovalent copper salt, and X is iodine, a trifluoromethanesulfonyloxy group or a paratoluenesulfonyloxy group. The method for producing the phenylethane derivative according to 1. (7) Phenylethane according to any one of (2), (5) and (6) above, wherein the monovalent copper salt is copper cyanide, copper bromide, copper iodide or a mixture thereof. Method for producing derivative.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is represented by the formula (3), which comprises reacting the compound represented by the formula (1) with the compound represented by the formula (2) in the presence of a copper salt catalyst. It is a method for producing a phenylethane derivative.

R ¹ in equations (1) and (3) is
H, F, 4,4-ethylenedioxycyclohexyl,
It is 4,4-trimethylenedioxycyclohexyl or alkyl having 1 to 15 carbons. Then, -CH ₂ of 1 or more in the alkyl - is -O -, - S- and -
It may be replaced with one or two groups of CH = CH-, but it is not included when the terminal is -OH or -SH, and when a plurality of -O- or -S- are continuous. It does not include the case where -O- and -S- are consecutive. Also, one or more H in this alkyl may be replaced with F. Examples of the case where R ¹ is unsubstituted alkyl include:
Linear alkyl such as methyl, ethyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl and isobutyl, 2-methylbutyl, 2-octyl, 3, Examples thereof include branched alkyl such as 3-dimethylnonyl.

When R ¹ is alkyl in which one or more --CH ₂ --is replaced by --O--, examples include methoxy, ethoxy, propyloxy, butoxy, hexyloxy, heptyloxy, decyloxy and dodecyl. Linear alkoxy such as oxy, isopropyloxy, t-butyloxyoxy, branched alkoxy such as 2-octyloxy and 4-methylnonyloxy, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, propoxymethyl, Alkoxyalkyl such as hexyloxymethyl and pentyloxypropyl, alkoxyalkoxyalkyl such as methoxyethoxymethyl, ethoxypropoxymethyl, propoxypropoxyethyl and butoxymethoxymethyl, and methoxymethoxy, ether. Kishimetokishi, propoxy methoxy, alkoxyalkoxy such as methoxy butoxy and butoxy hexyloxy.

Examples of R ¹ being alkyl in which one or more --CH ₂ --is replaced by --S-- include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, nonylthio, decylthio and Examples thereof include alkylthio such as undecylthio, alkylthioalkyl such as methylthiomethyl, ethylthiomethyl, ethylthiopropyl and butylthiomethyl.

R ¹ is one or more -CH ₂ -is -CH = C
Examples of the alkyl which may be substituted with H- include vinyl, 1-propenyl, 1-butenyl,
3-butenyl, 1-pentenyl, 2-pentenyl, 3-
Linear alkenyl such as pentenyl, 1-hexenyl, 3-hexenyl, 1-heptenyl, 3-heptenyl, 5-heptenyl, 1-nonenyl, 3-nonenyl, 5-nonenyl, 3-dodecenyl and 7-dodecenyl, 1,3-
Linear dienyl such as butadienyl, 1,5-hexadienyl, 1,5-heptadienyl and 1,5-nonadienyl, and branched such as isopropenyl, 3-methyl-3-butenyl and 3-methyl-1-butenyl And alkenyl and the like.

Examples of R ¹ when _two —CH ₂ — are alkyl substituted with —CH═CH— and O include 2-propenyloxy, vinyloxymethyl, 2
-Alkenyloxy or alkenyloxyalkyl such as butenyloxy and 3-butenyloxymethyl.

Examples of R ¹ when one or more H is alkyl substituted by F include fluoromethyl, difluoromethyl, trifluoromethyl, 1,1,
2-trifluoroethyl, 2,2-difluoroethyl,
Fluoroalkyl such as pentafluoroethyl, 1,2,2-trifluoropropyl, 4,4,6,6-tetrafluorobutyl and 3,3,4,4,5,5,6,6-octafluorooctyl are Can be mentioned.

Examples of R ¹ in the case of an alkyl in which one or more H is replaced by F and at the same time one —CH ₂ — is replaced by —O— include trifluoromethoxy, 2,2 Included are fluoroalkoxys such as difluoroethoxy, pentafluoroethoxy, 2,2,3,3,3-pentafluoropropyloxy and perfluorohexyloxy.

Then, as an example of R ¹ in the case where alkyl is such that one or more H is replaced by F and at the same time one --CH ₂ --is replaced by --CHCH--,
2,2-difluorovinyl, 3,3-difluoro-2-
Included are fluoroalkenyls such as propenyl and 4,4-difluoro-3-butenyl.

R ² in equations (2) and (3) is
H, a halogen atom, a cyano group, a thiocyano group, or an alkyl having 1 to 15 carbon atoms. One or more -CH ₂ - in the alkyl may -O -, - S- and -CH = CH
-May be replaced by one or two groups, but is not included when the terminal is -OH or -SH,
When a plurality of -O- or -S- are continuous or -O- and-
The case where S- is continuous is not included. Also, one or more H in this alkyl may be replaced with F. And
Examples of the case where R ² is alkyl include the same groups as those mentioned above as the examples when R ¹ is alkyl.

A ^{1 to} A in the formulas (1) to (3)
^{And 4} , independently of each other, 1,4-phenylene in which one or more H may be replaced by F, or one or two -CH = may be replaced by -N = 1,4- Phenylene or one or two non-sequential -CH ₂
-May be replaced by -O- or -S- 1,
It is 4-cyclohexylene. As some of these specific examples, unsubstituted 1,4-phenylene, 2-fluoro-
1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6
-Difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, pyridine-2,5-diyl,
Pyrimidine-2,5-diyl, 1,4-cyclohexylene, 1,4-dioxane-2,5-diyl, 1,3-dioxane-2,5-diyl, thian-2,5-diyl,
1,3-dithian-2,5-diyl, 1,4-dithian-2,5-diyl and the like can be mentioned. In addition, A ¹ and / or A ² may be a single bond.
And, A ² is preferably 1,4-cyclohexylene.

Z ^{1 to} Z ³ in formulas (1) to (3) are each independently a single bond, CH ₂ CH ₂ , CH ₂ O,
OCH ₂ , COO, OCO, CF ₂ O, OCF ₂ , CH
= CH or C≡C.

X in the formula (1) is halogen, alkylsulfonyloxy in which one or more H may be replaced by F, or arylsulfonyloxy. Examples of alkylsulfonyloxy include methanesulfonyloxy, fluoromethanesulfonyloxy, difluoromethanesulfonyloxy, trifluoromethanesulfonyloxy, ethanesulfonyloxy, trifluoroethanesulfonyloxy and the like. In addition, examples of arylsulfonyloxy include benzenesulfonyloxy and paratoluenesulfonyloxy.

The compound represented by the formula (2) is an organometallic compound. That is, Y in the formula (2) is MgBr, MgCl.
Alternatively, it is Li. And n, m, and p in Formula (1) -Formula (3) are each independently 0 or 1, and q is an integer of 0-4. The compounds represented by the formulas (1) and (3) may include optical isomers.

The copper salt catalyst used in the present invention is preferably a monovalent or divalent copper salt. The monovalent copper salt is preferably copper (I) iodide, copper (I) bromide, copper (I) cyanide, copper (I) acetate, or copper (I) thiocyanide. As the divalent copper salt catalyst, copper (II) chloride, copper (II) fluoride, copper (II) bromide, and copper (II) acetate are preferable, and these divalent copper salts are lithium chloride and lithium bromide. You may mix and use it with lithium salts, such as. In this case, the addition amount of the lithium salt is selected in the range of 10 to 200 mol% with respect to the copper salt, but considering the reaction yield, it is preferably about equimolar to the copper salt. And, the preferred copper salt catalyst used in the present invention is a monovalent copper salt, and among them, copper cyanide, copper bromide, copper iodide or a mixture thereof is more preferable. The addition amount of the copper salt catalyst used in the present invention is selected in the range of 0.5 to 100 mol% with respect to the compound represented by the formula (1), preferably 5 to 50 mol%, more preferably 10 to 10. 30 mol%
Is.

The reaction solvent used in the reaction of the present invention may be any one as long as it does not inhibit the reaction itself, and can be selected from common solvents and used. That is, pentane, hexane, heptane, octane and other aliphatic hydrocarbons, toluene, benzene and other aromatic hydrocarbons, diethyl ether,
It is preferable to select from ether solvents such as tetrahydrofuran, dioxane, and tertiary butyl methyl ether, and amide solvents such as dimethylformamide and N-methylpyrrolidinone, and to use as a single solvent or a mixed solvent of a plurality of solvents.

The reaction of the present invention can be carried out between -70 ° C and 150 ° C. The reaction temperature range is preferably from -50 ° C to the boiling point of the solvent from the viewpoint of easy operation, and more preferably from -20 to 50 ° C from the viewpoint of good reaction yield.

In order to isolate the product from the reaction system after completion of the reaction, the methods used in ordinary chemical operations can be applied. For example, the product can be taken out from the reaction system by adding water to the reaction solution to deactivate the unreacted compound of formula (2) and then extracting with an organic solvent.
When the reaction product needs to be in a state of higher purity, purification operations such as recrystallization, distillation and silica gel chromatography may be carried out individually or in combination. Alternatively, the functional group may be converted without purification of the reaction product into a compound that is easier to purify, and then the above-mentioned purification operations may be carried out alone or in combination.

The compound of formula (1), which is the starting material of the present invention, is
It can be synthesized by a commonly known simple method. That is,
The compound when X is a halogen atom is synthesized by reacting an alcohol derivative in which X is OH in the formula (1) with a hydrohalic acid or a commonly used halogenating agent. Examples of commonly used halogenating agents include phosphine-halogen complexes and N-halogenated succinimides. The compound in which X is a sulfonyloxy group is obtained by converting an alcohol derivative in which X is OH in the formula (1) into a substituted sulfonyl chloride in the presence of a tertiary amine such as triethylamine or diethylamine, pyridine, or a base such as dimethylaminopyridine. Alternatively, it is synthesized in high yield by reacting with sulfonic anhydride.

The organometallic compound of the formula (2) which is the raw material of the present invention is prepared by reacting the compound of the formula (2) in which Y is halogen with metallic magnesium, metallic lithium or the like according to a general method. Is synthesized. Also,
The compound in which Y is Li can also be synthesized by treating this halide with a solution of alkyllithium. These organometallic compounds may not be isolated after the reaction. It is preferable to use the reaction solution as it is in the next reaction because the operation is simple. Therefore, the solvent in the synthesis reaction of the organometallic compound needs to be a solvent that does not inhibit the synthesis reaction of the phenylethane derivative, and the above-mentioned solvent that can be used in the synthesis reaction of the phenylethane derivative is used. Is preferred.

[0029]

The present invention will be further described in detail with reference to examples, but the present invention is not limited to these examples. Example 1 4- (2- (trans-4-pentylcyclohexyl)
Ethyl) phenyl t-butyl ether (a compound of the formula (3) in which R ¹ = pentyl, A ² = 1,4-cyclohexyl, R ² = t-butyloxy, n = m = p = q = 0) is sufficient. Copper (I) iodide 1.6 dried
6 g (8.72 mmol) and 2- (trans-4-pentylcyclohexyl) ethyl paratoluenesulfonate 15.6 g (44.3 mmol) in THF 150 m.
While stirring the solution suspended in 1 at room temperature, 36.5 ml (63.9 mmol) of 1.75 M 4-t-butyloxyphenylmagnesium chloride solution was slowly added dropwise thereto. After completion of the dropping, the reaction solution was stirred for another 4 hours. Then, the reaction solution was poured into 240 ml of 0.5N hydrochloric acid, and the precipitated crystals were separated by filtration. Then, the filtrate was extracted three times with 100 ml of toluene each. The organic layer was washed with water, saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give an orange oil (17.55 g). As a result of various analyses, it was confirmed that this was a mixture having a content rate of the title compound of 83%. GCMS (EI): 331 (M +), 107,315,
275, 274, 41, 29, 57 ¹ H-NMR (ppm, CDCl ₃ ) δ: 7.08 (2
H, d, J = 10.0 Hz), 6.88 (2H, d, J
= 10.0 Hz), 2.56 (2H, dd, J = 6.
3,9.8 Hz) 0.6 to 1.9 (22H, m)

Example 2 4- (2- (4,4-ethylenedioxycyclohexyl
Ru) ethyl) bromobenzene (in the formula (3), R¹
= 4,4-ethylenedioxycyclohexyl, A ^Two= Single
Bond, R^Two= Br, compound in which n = m = p = q = 0)
Synthesis of 1.00 g (5.25 m) of sufficiently dried copper (I) iodide
mol) and 2- (4,4-ethylenedioxycyclohexyl)
Xyl) ethyl paratoluenesulfonate 10.2 g
(30.0 mmol) suspended in THF (20 ml)
The solution was stirred at room temperature in 20 ml of THF.
1,4-Dibromobenzene 12.5 g (53.0 mmo
l) and magnesium 1.25 g (51.4 mmol)
4-bromophenyl magnesium bromide prepared from
The solution was slowly added dropwise. After completion of dropping, add 4 more reaction solutions.
Stir for hours, pour into 240 ml of 0.5N hydrochloric acid to precipitate
The separated crystals were filtered off. And the filtrate is 100 ml of toluene
Extraction was carried out three times using each. Wash the organic layer with water and add saturated sodium bicarbonate.
Wash with water, dry over anhydrous magnesium sulfate, then depressurize
Concentrate down to give 11.1 g of an orange oil. silica gel
Isolate and purify using column chromatography.
7.50 g of crystals (23.1 mmol, yield 77%) was obtained.
It was This product was confirmed to be the title compound as a result of various analyses.
Was confirmed. GCMS (EI): 325 (M +),¹ H-NMR (ppm, CDCl_Three) Δ: 7.39 (2
H, d, J = 8.3 Hz), 7.03 (2H, d, J =
8.3 Hz), 3.94 (4H, s), 2.57 (2
H, dd, J = 8.1, 9.8 Hz)

Example 3 4- (2- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) ethyl)-(2-octyl) oxybenzene (in the formula (3), R ¹ = pentyl, A ¹ = ^{1,4-cyclohexylene,} A 2 = ^1,
4-cyclohexylene, R ² = 2-octyloxy, n
= 1, m = p = q = 0) 140 mg (0.735) of sufficiently dried copper (I) iodide
mmol) and 2- (trans-4- (trans-4-
Pentylcyclohexyl) cyclohexylethyl p-toluenesulfonate 1.60 g (3.68 mmol)
Was suspended in 10 ml of THF while stirring at room temperature, and 10.0 ml of 4- (2-octyl) oxyphenylmagnesium bromide solution having a concentration of 1M was added thereto (10.
0 mmol) was slowly added dropwise. After completion of dropping, the reaction solution was further stirred for 4 hours, poured into 10 ml of 0.5N hydrochloric acid, and the precipitated crystals were separated by filtration. Then, the filtrate was extracted three times with 10 ml of toluene each time. The organic layer was washed with water, saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a yellow oil (3.00 g). Isolation and purification using silica gel column chromatography gave 1.60 g of colorless crystals. Further, recrystallization was carried out using 10 ml of ethanol to obtain 1.00 g of colorless crystals.
(2.13 mmol, yield 58%) was obtained. As a result of various analyses, this product was confirmed to be the title compound. GCMS (EI): 469 (M +), ¹ H-NMR (ppm, CDCl ₃ ) δ: 7.06 (2
H, d, J = 8.5), 6.79 (2H, d, J = 8.
5 Hz), 4.29 (1H, tdd, J = 6.1, 6.
1, 6.1 Hz), 2.54 (2H, m), 0.8-
1.83 (48H, m) crystal-smectic B phase transition point-5.0 ° C smectic B phase-isotropic phase transition point 128.3 ° C

Example 4 5- (2- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) ethyl) -1,2,3
-Trifluorobenzene (in the formula (3), R ¹ = ethyl, A ¹ = 1,4-cyclohexylene, A ² = 1,4
- ^{cyclohexylene, R 2 = F, n =} 1, q = 2 a is synthesized sufficiently dried iodide compounds) (I) 140mg (0.735
mmol) and 2- (trans-4- (trans-4-
Ethyl cyclohexyl) cyclohexyl ethyl paratoluene sulfonate 3.00 g (7.64 mmol)
While stirring the solution suspended in 20 ml of HF at room temperature, 20.0 ml (20.0 m) of 1,2,3-trifluorophenyl magnesium bromide solution having a concentration of 1M was added thereto.
(mol) was slowly added dropwise. After completion of the dropping, the reaction solution was stirred for another 5 hours and then poured into 20 ml of cold 0.5N hydrochloric acid, and the precipitated crystals were separated by filtration. The filtrate is 10 ml of toluene
Extraction was carried out three times using each. The organic layer was washed with water, saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a yellow oil (4.90 g). It was isolated and purified using silica gel column chromatography to obtain 3.60 g of colorless crystals. Further, it was recrystallized using 30 ml of ethanol to obtain 2.30 g (6.53 mmol, colorless crystals)
Yield 85%) was obtained. As a result of various analyses, this product was confirmed to be the title compound. GCMS (EI): 352 (M +), ¹ H-NMR (ppm, CDCl ₃ ) δ: 6.76 (2
H, m), 2.65 (2H, t, J = 7.5 Hz),
0.8-1.83 (278H, m) Crystal-nematic phase transition temperature 64.3 ° C Nematic phase-isotropic phase transition temperature 65.5 ° C

[0033]

According to the method of the present invention, a liquid crystal compound and a phenylethane derivative mainly useful as a raw material for synthesizing a liquid crystal compound can be easily produced at low cost.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C07B 61/00 300 C07B 61/00 300 C07M 9:00 C07M 9:00 F term (reference) 4C022 FA02 4H006 AA02 AC22 BA05 BA37 BB25 BC10 BC34 BE24 GP03 4H039 CA41 CD20

Claims (7)

[Claims] 1. A process for producing a phenylethane derivative represented by formula (3), which comprises reacting the compound represented by formula (1) with the compound represented by formula (2) in the presence of a copper salt catalyst. . (In these formulas, A ^{1 to} A ⁴ are each independently 1,4-H may be replaced with F 1,4-
Phenylene, one or two -CH = may be replaced by -N = 1,4-phenylene or one or not consecutive two -CH _2, - is -O- or -
1,4-cyclohexylene optionally substituted with S-, in which A ¹ and / or A ² may be a single bond; Z ^{1 to} Z ³ are each independently a single bond,
CH ₂ CH ₂ , CH ₂ O, OCH ₂ , COO, OCO,
CF ₂ O, OCF ₂ , CH = CH or C≡C;
R ¹ is H, F, 4,4-ethylenedioxycyclohexyl, or 4,4-trimethylenedioxycyclohexyl, R ² is H, a halogen atom, a cyano group, or a thiocyano group, and R ¹ and Each R ² may independently be an alkyl having 1 to 15 carbon atoms, and one or more —CH ₂ — in this alkyl is one of —O—, —S— and —CH═CH—. May be replaced with one or two kinds of groups, but the terminal —CH ₂ — is not replaced with —O— or —S—, and a plurality of —O— or —S— may be consecutive — O- and -S- are not continuous and one or more H in this alkyl may be replaced by F; X is halogen, one or more H is F.
Alkylsulfonyloxy, which may be replaced with or arylsulfonyloxy; Y is MgBr,
MgCl or Li; n, m and p are each independently 0 or 1, and q is an integer of 0-4. ) 2. The method for producing a phenylethane derivative according to claim 1, wherein the copper salt catalyst is a monovalent copper salt. 3. The method for producing a phenylethane derivative according to claim 1, wherein X is an iodine atom, a trifluoromethanesulfonyloxy group or a paratoluenesulfonyloxy group. 4. A ² is 1,4-cyclohexylene,
The method for producing the phenylethane derivative according to claim 1. 5. A ² is 1,4-cyclohexylene,
The method for producing a phenylethane derivative according to claim 1, wherein the copper salt catalyst is a monovalent copper salt. 6. A ² is 1,4-cyclohexylene,
The method for producing a phenylethane derivative according to claim 1, wherein the copper salt catalyst is a monovalent copper salt, and X is iodine, a trifluoromethanesulfonyloxy group or a paratoluenesulfonyloxy group. 7. The monovalent copper salt is copper cyanide, copper bromide, copper iodide or a mixture thereof,
A method for producing the phenylethane derivative according to any one of 1.