JPH08119887A - Production of trans-difluoroethylene derivative - Google Patents

Abstract

PURPOSE: To readily and economically obtain a trans-difluoroethylene derivative useful as a liquid crystal compound in high yield and by a short process by reacting a specific trifluoroethylene compound with a Li compound. CONSTITUTION: This compound of formula III is obtained by reacting (A) a compound of formula I [R<2> is an (F-substituted) 1-10C alkyl, a halogen or CN; A<4> is a (CN-substituted) 1,4-disubstituted cyclohexylene or a 1,4-disubstituted cyclohexenylene; Y<2> is COO, C≡C or CH2 CH2 ; A<3> is a (CN-substituted) 1,4- disubstituted cyclohexenylene or 1,4-disubstituted phenylene; (n) is 0 or 1] with a compound of formula II [R<1> is R<2> ; A<1> is A<4> ; Y<1> is Y<2> ; A<2> is a (CN-substituted) trans-1,4-disubstituted cyclohexylene; (m) is (n)].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing a trans-difluoroethylene derivative useful as a liquid crystal compound.

[0002]

2. Description of the Related Art As a method for producing a trans-difluoroethylene compound, there is a method described in JP-A-06-40967 by the present inventors.

[0003]

[Problems to be Solved by the Invention] However, JP-A-06-409
The method of No. 67 had a drawback in that the number of steps was long.

[0004]

SUMMARY OF THE INVENTION The present invention provides a short process,
And, a method for efficiently producing a trans-difluoroethylene compound is provided.

That is, according to the present invention, a trans-difluoroethylene derivative represented by the formula (1) is characterized in that a compound represented by the formula (6) is reacted with a compound represented by the formula (8). A method for manufacturing the same is provided.

R ^2- (A ⁴ ) _n -Y ² -A ³ -CF = CF ₂ (6) R ^1- (A ¹ ) _m -Y ¹ -A ² -Li (8) R ^1- (A ¹ ) _m -Y ¹ -A ² -CF = CF-A ³ -Y ^2- (A ⁴ ) _n -R ² (1)

However, in the formulas (6), (8), (1), A ¹ , A ² , A ³ , A ⁴ , R ¹ , R ² , Y ¹ , Y ² ,
n and m have the following meanings.

A ¹ and A ⁴ , which may be the same or different, are trans-1,4-di-substituted cyclohexylene group, 1,4-di-substituted cyclohexenylene group, or 1,4-
A di-substituted phenylene group is shown. Each of these groups is
It may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent.
Further, one or more CH in these groups may be substituted with a nitrogen atom. One or more CH ₂ of the trans-1,4-di-substituted cyclohexylene group or the 1,4-di-substituted cyclohexenylene group may be substituted with an oxygen atom or a sulfur atom.

A ^{2 represents a} trans-1,4-di-substituted cyclohexylene group. Each of the groups may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. Further, one or two or more CH in the group may be substituted by a nitrogen atom, one or two or more CH ₂ may be substituted with an oxygen atom or a sulfur atom.

A ³ : 1,4-disubstituted cyclohexenylene group,
Alternatively, it represents a 1,4-disubstituted phenylene group. These groups are
Each of them may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. In addition, 1 or 2 or more CH in the group is
It may be substituted with a nitrogen atom, and one or more CH ₂ may be substituted with an oxygen atom or a sulfur atom.

R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a hydrogen atom, a hydroxyl group or a hydroxyl group to which a protective group is bonded. Show. In the case of an alkyl group, carbon between carbon-carbon bonds or between an alkyl group and a ring group-
An oxygen atom may be inserted between the carbon bonds, a part of the carbon-carbon bond of the alkyl group may be a double bond or a triple bond, and —CH ₂ — of the alkyl group is a carbonyl group. May be substituted with. Further, some or all of the hydrogen atoms of the alkyl group may be replaced with fluorine atoms. Y ¹ and Y ² , which may be the same or different, are -COO-, -OCO-, -C≡C-, -CH ₂ CH _2- , -CH = CH-,-.
Indicates OCH _2- , -CH ₂ O-, or a single bond. n and m: 0 or 1 is shown, respectively.

The compound of the present invention represented by the formula (6) [hereinafter referred to as the compound (6). The same applies to other compounds. ] With the compound (8) can be represented by the following formula. According to this reaction, in the introduction of the substituent at the carbon atom of the terminal olefin of the compound (6), selective introduction into the trans moiety is possible.

[0013]

Embedded image

In the above reaction, the amount of the compound (8) is preferably about 1 to 10 mol, particularly preferably 1 to 2 mol, per 1 mol of the compound (6). The reaction temperature is preferably about -80 to 25 ° C, particularly -80 to -5.
0 ° C is preferred.

A solvent may be present in the reaction between the compound (6) and the compound (8). As the solvent, a hydrocarbon solvent, an ether solvent, an amine solvent, or
A mixed solvent composed of two or more of these is preferable. Petroleum ether, n-pentane, and n-hexane are preferable as the hydrocarbon solvent. As the ether solvent, diethyl ether, tetrahydrofuran (THF) and dimethoxyethane (DME) are preferable. As the amine solvent, triethylamine, N, N, N ', N'-tetramethylethylenediamine (TMEDA), hexamethylphosphoramide (H
MPA) is preferred. The amount of the solvent is preferably about 2 to 50 parts by weight, especially 5 to 1 part by weight of the compound (6).
10 parts by weight is preferred.

When it is desired to obtain a compound (1) in which R ¹ and R ² are cyano groups, a compound in which R ¹ and R ² are bromine atom or iodine atom is reacted with CuCN. Good. Further, R ^1, R ² is one of -CH ₂ in the alkyl group - is when it is desired to obtain those substituted carbonyl group, the compound R ^1, R ² is a hydrogen atom and (1) Friedel-Crafts reaction with an acyl halide is sufficient. Also, if it is desired to obtain one R ^1, R ² is a hydroxyl group, is to convert compounds R ^1, R ² is a hydroxyl group with a protecting group (1) to a hydroxyl group in the usual deprotection methods preferable.

When it is desired to obtain a compound (1) in which Y ¹ is a vinylidene group (-C = C-), a compound in which R ¹ and R ² are chlorine atom, bromine atom or iodine atom The coupling reaction between (1) and the alkenyl grinder compound may be performed. To obtain the compound (1) in which Y ¹ is an ethylidene group (-C≡C-), R ¹ , R ²
The compound (1) having a bromine atom or an iodine atom may be subjected to a coupling reaction with the alkynyllithium compound.

On the other hand, the compound (8) can be obtained by reacting the compound (7) with lithium metal. The reaction can be represented by the following chemical formula. Compound (7)
Can be easily obtained by halogenating a commercially available compound (7) in which X ³ is a hydroxyl group by a conventional method.

[0019]

Embedded image

However, compound (7) and compound (8)
In, A ¹ , A ² , R ¹ , Y ¹ , and m have the same meanings as described above. Further, X ³ represents a chlorine atom, a bromine atom, or an iodine atom.

In the reaction of reacting the compound (7) with lithium metal to form the compound (8), the amount of lithium metal is preferably about 1 to 10 mol, and more preferably 1 to 10 mol, relative to 1 mol of the compound (7). 2 mol is preferred.

A solvent may be present also in the reaction of the compound (7) with lithium metal. The solvent is preferably a hydrocarbon solvent or an ether solvent, particularly n-
Hexane, diethyl ether, THF, or a mixed solvent of two or more thereof is preferable. The amount of the solvent is preferably about 2 to 50 parts by weight, and particularly preferably 5 to 30 parts by weight, relative to 1 part by weight of the compound (7). The reaction temperature between the compound (7) and lithium metal is preferably about -80 to 25 ° C, and particularly preferably -80 to -50 ° C.

In the reaction of the compound (7) with lithium metal, it is preferable that an electron transfer agent is present. The presence of the electron transfer agent has the advantages that the lithium compound is easily produced and the yield is high.

As the electron transfer agent, an anion and an organic lithio compound (compound (8)) are generated from an organic halogen atom compound (compound (7)) through electron transfer from lithium metal, and an aromatic hydrocarbon. Are preferred, and aromatic hydrocarbons having two or more rings or aromatic hydrocarbons having a condensed ring are particularly preferred. Of these, naphthalene, biphenyl, 2,6-di-t-butylnaphthalene,
2,7-di-t-butylnaphthalene, 4,4'-di-t-butylbiphenyl, anthracene and the like are preferable, and naphthalene, biphenyl and 4,4'-di-t-butylbiphenyl are particularly preferable. The amount of the electron transfer agent is preferably about 0.01 to 3 times mol, and particularly preferably 0.1 to 2 mol, relative to 1 mol of the compound (7).
Molar is preferred.

The compound (8) obtained by reacting the compound (7) with lithium metal can be used for the reaction with the compound (6) without isolation and purification. Since the compound (8) produced in the reaction is much more stable when the A ² moiety is in the trans form, the compound (7) in which the A ² part is a mixture of cis form / trans form was used. However, most of the produced compound (8) has an advantage that the A ² portion is in the trans form.

On the other hand, the compound (6) is reacted with chlorotrifluoroethylene (2) and alkyllithium to give the compound (3), and the compound (3) is reacted with bromine or iodine to obtain the compound (4). Then, it can be synthesized by reacting the compound (4) with the compound (5).

CF ₂ = CFCl (2) CF ₂ = CFLi (3) CF ₂ = CFX ¹ (4) R ^2- (A ⁴ ) _n -Y ² -A ³ -X ² (5) R ^2- (A ⁴ ) _n -Y ² -A ³ -CF = CF ₂ (6) However, in the formulas (2), (3), (4), (5), and (6), A ³ , A ⁴ , R ² , Y ² , and n
Has the same meaning as described above, and X ¹ and X ² may be the same or different and each represent a bromine atom or an iodine atom.

The route for synthesizing compound (6) from chlorotrifluoroethylene (2) can be represented by the following chemical formula.

[0029]

Embedded image

First, compound (2) is reacted with alkyllithium to give compound (3). As the alkyllithium, a known or well-known compound used in the lithiation reaction can be used, and n-butyllithium (n-BuLi) is particularly preferable. The amount of alkyllithium is preferably about 1 to 3 mol, and particularly preferably 1 to 1.5 mol, per 1 mol of compound (1). The reaction between the compound (2) and alkyllithium is preferably carried out under low temperature conditions, usually about -120 to -30 ° C.

Next, the compound (3) is converted to the compound (4) by reacting with bromine or iodine. Bromine or iodine is 1 mol per 1 mol of the compound (3).
It is preferably about 4 to 4 mol, and particularly preferably 1 to 2 mol.
The reaction temperature of the compound (3) with bromine or iodine is -1.
20 to -30 degreeC is preferable. Obtained compound (4)
May be isolated and purified, but may be directly used in the next reaction.

A solvent may be present in the reaction of reacting the compound (3) with bromine or iodine. The solvent is preferably a hydrocarbon solvent or an ether solvent,
Especially n-hexane, diethyl ether, THF, or
These mixed solvents are preferable. The amount of the solvent is preferably about 2 to 50 parts by weight, and particularly preferably 5 to 30 parts by weight, relative to 1 part by weight of the compound (2). The reaction temperature is preferably about -120 to 25 ° C, particularly -90 ° C to
25 ° C is preferred. Chlorotrifluoroethylene (2)
In the usual case, the operation for synthesizing compound (4) from is preferably carried out continuously.

Next, the compound (4) is reacted with the compound (5) to give the compound (6). Compound (5) is
It is a commercially available compound and is easily available. Compound (4)
The reaction of the compound (5) with the compound (5) is preferably carried out in the presence of zinc and palladium catalysts according to the method reported by Burton et al. [J. Org. Chem., 53, 2714 (1988)].
This method is a preferred method suitable for the production of asymmetric difluoroethylene compounds.

The amount of zinc is preferably about 0.5 to 1.5 equivalents relative to 1 equivalent of the compound (4). Further, zinc is preferably used after being subjected to activation treatment. As the activation treatment method, a known treatment method used for activation of the zinc catalyst can be adopted. For example, a method of washing with dilute hydrochloric acid, ethanol, and ether in this order and drying well may be used.

As the palladium catalyst, (tetra (triphenylphospho)) palladium [Pd (PPh ₃ ) ₄ ] is preferable. The amount of the palladium catalyst is preferably about 0.01 to 0.03 mol with respect to 1 mol of the compound (4).

The reaction between the compound (4) and the compound (5) is
It is preferably carried out in the presence of a solvent. As the solvent,
Dimethylformamide (DMF) and THF are preferred.
The reaction temperature is preferably about 60 to 80 ° C, and the reaction time is preferably about 1 to 10 hours. The reaction pressure is not particularly limited, and it is usually preferable to carry out the reaction under normal pressure.

As another method for obtaining the compound (6), a method [J.Org.Chem., 21,400 (1956)] in which the compound (5) is lithiated and reacted with CF ₂ = CF ₂ is adopted. May be. However, in this method, the compound in which the substituents are introduced into both carbons of CF ₂ = CF ₂ is the main product, and the yield of the compound (6) is low, which is not preferable.

Since the method of synthesizing the compound (1) from chlorotrifluoroethylene (2) is a reaction with a smaller number of steps as compared with the conventional method and is a method with a high yield,
A very efficient and excellent method. In addition, since the starting material chlorotrifluoroethylene (2) is easily available, this method is also a highly useful method.

Further, in the compound (1), the stereo structure of the cyclohexane portion of A ² is trans. Further, in compound (8), when A ² is in the trans form,
It is more stable than the cis form. Therefore, compound (7)
When compound (8) is synthesized using A ² of cis / trans mixture, compound (8) is mostly converted to a stable trans form, and compound (8) is a compound (8) in which A ² is a trans form. ). Furthermore, the reaction between the compound (6) and the compound (8) is a reaction that can be carried out while maintaining the stereochemistry of the A ² portion. Therefore, in the reaction of the present invention, there is an advantage that the steric structure of the cyclohexane moiety of A ² of the compound (7) can be a cis / trans mixture.

The object compound (1) of the present invention is described below. The compound (1) is a compound represented by the following formula. However, in the formula (1), A ¹ , A ² , A
³ , A ⁴ , R ¹ , R ² , Y ¹ , Y ² , n, and m are
Indicates the above meaning. R ^1- (A ¹ ) _m -Y ¹ -A ² -CF = CF-A ³ -Y ^2- (A ⁴ ) _n -R ² (1)

[0041]

[Chemical 4]

Among them, A ¹ and A ⁴ are an unsubstituted trans-1,4-disubstituted cyclohexylene group, an unsubstituted
1,4-disubstituted cyclohexenylene group or unsubstituted 1,4-
A di-substituted phenylene group is preferred. A ² is preferably an unsubstituted trans-1,4-di-substituted cyclohexylene group or a trans-1,4-di-substituted cyclohexylene group in which one or more hydrogen atoms are replaced with halogen atoms. A ³
Is preferably an unsubstituted 1,4-di-substituted cyclohexenylene group or an unsubstituted 1,4-di-substituted phenylene group. Y ¹ ,
Y ² is preferably a single bond.

R ¹ is preferably an alkyl group having 1 to 10 carbon atoms or a halogen atom, and particularly preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a fluorine atom or a chlorine atom. . R ² is preferably an alkyl group having 1 to 10 carbon atoms, a halogen atom, or a hydroxyl group having a protective group, or a hydroxyl group, particularly a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group. A group, a fluorine atom, a chlorine atom and a hydroxyl group are preferred.

When R ¹ and / or R ² is a hydroxyl group with a protecting group, the protecting group includes a methyl group, a methoxymethyl group, a tetrahydropyran-2-yl group, an allyl group and a benzyl group. , Trimethylsilyl group, t-
A butyldimethylsilyl group and the like are preferable, and a tetrahydropyranin-2-yl group and a benzyl group are particularly preferable.

In the compound (1), the compound containing two ring structures is preferably the compound (9) in which m and n are 0 and Y ¹ and Y ² are single bonds. R ¹ -A ² -CF = CF-A ³ -R ² (9) However, A ² , A ³ , R ¹ and R ^{2 of the} compound (9)
Has the same meaning as above.

Specific preferred examples of the compound (9) include:
The following compounds may be mentioned. In the following description, not only the compound (9) but also “-Ph-” represents a 1,4-di-substituted phenylene group, and “-Cy-” represents a trans-1,4-di-substituted cyclohexylene group. And "-Ch-" represents a 1,4-di-substituted cyclohexenylene group, preferably a 1,4-di-substituted cyclohexenylene group having a double bond between the 3rd and 4th positions. R ¹ -Cy-CF = CF-Ph-R ² (9A)

[0047]

Embedded image

The following compounds may be mentioned as compounds obtained by substituting the 1,4-di-substituted phenylene group of the compound (9A) with the 1,4-di-substituted cyclohexenylene group. R ¹ -Cy-CF = CF-Ch-R ² (9B) The preferred structure of (9B) is as shown in the following formula (9B ').

[0049]

[Chemical 6]

Further, the following compounds are mentioned as a compound in which the 1,4-di-substituted phenylene group of the compound (9A) is a phenylene group "-PhF-" in which one or more hydrogen atoms are replaced by fluorine atoms. To be However, i is an integer of 1 to 4. R ¹ -Cy-CF = CF-PhF-R ² (9C)

[0051]

[Chemical 7]

In the compound (1), the ring structure is 3
As the compound containing a compound, one of m and n is 0,
Compound (10) and compound (11) in which the other is 1 and Y ¹ and Y ² are single bonds are preferable. R ¹ -A ¹ -Cy-CF = CF-A ³ -R ² (10) R ¹ -Cy-CF = CF-A ³ -A ⁴ -R ² (11) provided that compound (10) and compound ( 11) A
¹ , A ³ , A ⁴ , R ¹ , and R ² have the same meanings as described above.

Specific examples of the compound (10) and the compound (11) include the following compounds.

R ¹ -Ph-Cy-CF = CF-Ph-R ² (10A) R ¹ -Ph-Cy-CF = CF-Ch-R ² (10B) R ¹ -Cy-Cy-CF = CF- Ph-R ² (10C) R ¹ -Cy-Cy-CF = CF-Ch-R ² (10D) R ¹ -Ch-Cy-CF = CF-Ph-R ² (10E) R ¹ -Ch-Cy- CF = CF-Ch-R ² (10F) R ¹ -PhF-Cy-CF = CF-Ph-R ² (10G) R ¹ -PhF-Cy-CF = CF-Ch-R ² (10H) R ^1- Ph-Cy-CF = CF-PhF-R ² (10I) R ¹ -Cy-Cy-CF = CF-PhF-R ² (10J)

R ¹ -Ch-Cy-CF = CF-PhF-R ² (10K) R ¹ -Cy-CF = CF-Ph-Ph-R ² (11A) R ¹ -Cy-CF = CF-Ph- Cy-R ² (11B) R ¹ -Cy-CF = CF-Ph-Ch-R ² (11C) R ¹ -Cy-CF = CF-Ch-Ph-R ² (11D) R ¹ -Cy-CF = CF-Ch-Cy-R ² (11E) R ¹ -Cy-CF = CF-Ch-Ch-R ² (11F) R ¹ -Cy-CF = CF-PhF-Ph-R ² (11G) R ^1- Cy-CF = CF-PhF-Cy-R ² (11H) R ¹ -Cy-CF = CF-PhF-Ch-R ² (11I)

In the compound (1), the ring structure is 3
The following compounds are preferable as the compound in the case where Y ¹ and / or Y ² is other than a single bond.

R ¹ -Ph-C ≡ C-Ph-CF = CF-Cy-R ² (12A) R ¹ -Ph-CH ₂ CH ₂ -Ph-CF = CF-Cy-R ² (12B) R ¹ -Ph-OCH ₂ -Ph-CF = CF-Cy-R ² (12C) R ¹ -Ph-CH ₂ O-Ph-CF = CF-Cy-R ² (12D) R ¹ -Ph-COO-Ph- CF = CF-Cy-R ² (12E) R ¹ -Ph-OCO-Ph-CF = CF-Cy-R ² (12F) R ¹ -Ph-C ≡C-Cy-CF = CF-Ph-R ² (12G) R ¹ -Ph-CH ₂ CH ₂ -Cy-CF = CF-Ph-R ² (12H) R ¹ -Ph-OCH ₂ -Cy-CF = CF-Ph-R ² (12I) R ^1- Ph-CH ₂ O-Cy-CF = CF-Ph-R ² (12J)

R ¹ -Ph-COO-Cy-CF = CF-Ph-R ² (12K) R ¹ -Ph-OCO-Cy-CF = CF-Ph-R ² (12L) R ¹ -Ph-C ≡ C-Cy-CF = CF-Ch-R ² (12M) R ¹ -Ph-CH ₂ CH ₂ -Cy-CF = CF-Ch-R ² (12N) R ¹ -Ph-OCH ₂ -Cy-CF = CF-Ch-R ² (12O) R ¹ -Ph-CH ₂ O-Cy-CF = CF-Ch-R ² (12P) R ¹ -Ph-COO-Cy-CF = CF-Ch-R ² (12Q ) R ¹ -Ph-OCO-Cy-CF = CF-Ch-R ² (12R)

In the compound (1), the ring structure is 4
The compound (13) in the case where m and n are 1 is preferable as the compound containing a compound. R ¹ -A ¹ -Cy-CF = CF-A ³ -A ⁴ -R ² (13)

Specific examples of the compound (13) include the following compounds.

R ¹ -Ph-Cy-CF = CF-Ph-Ph-R ² (13A) R ¹ -Ph-Cy-CF = CF-Ch-Ch-R ² (13B) R ¹ -Ph-Cy- CF = CF-Ph-Cy-R ² (13C) R ¹ -Ph-Cy-CF = CF-Ph-Ch-R ² (13D) R ¹ -Ph-Cy-CF = CF-Ch-Ph-R ² (13E) R ¹ -Ph-Cy-CF = CF-Ch-Cy-R ² (13F) R ¹ -Cy-Cy-CF = CF-Ch-Ch-R ² (13G) R ¹ -Cy-Cy- CF = CF-Ph-Cy-R ² (13H) R ¹ -Cy-Cy-CF = CF-Ph-Ch-R ² (13I) R ¹ -Cy-Cy-CF = CF-Ch-Ph-R ² (13J)

R ¹ -Cy-Cy-CF = CF-Ch-Cy-R ² (13K) R ¹ -Ch-Cy-CF = CF-Ch-Ch-R ² (13L) R ¹ -Ch-Cy- CF = CF-Ph-Cy-R ² (13M) R ¹ -Ch-Cy-CF = CF-Ph-Ch-R ² (13N) R ¹ -Ch-Cy-CF = CF-Ch-Ph-R ² (13O) R ¹ -Ch-Cy-CF = CF-Ch-Cy-R ² (13P) R ¹ -Ph-Cy-CF = CF-PhF-Ph-R ² (13Q) R ¹ -Ph-Cy- CF = CF-PhF-Cy-R ² (13R) R ¹ -Ph-Cy-CF = CF-PhF-Ch-R ² (13S) R ¹ -Cy-Cy-CF = CF-PhF-Ph-R ² (13T)

R ¹ -Cy-Cy-CF = CF-PhF-Cy-R ² (13U) R ¹ -Cy-Cy-CF = CF-PhF-Ch-R ² (13V) R ¹ -Ch-Cy- CF = CF-PhF-Ph-R ² (13W) R ¹ -Ch-Cy-CF = CF-PhF-Cy-R ² (13X) R ¹ -Ch-Cy-CF = CF-PhF-Ch-R ² (13Y)

In the compound (1), the ring structure is 4
The following compounds are preferable as the compound in the case where Y ¹ and / or Y ² is other than a single bond.

R ¹ -Ph-C ≡ C-Cy-CF = CF-Ph-Ph-R ² (14A) R ¹ -Ph-CH ₂ CH ₂ -Cy-CF = CF-Ph-Ph-R ² ( 14B) R ¹ -Ph-OCH ₂ -Cy-CF = CF-Ph-Ph-R ² (14C) R ¹ -Ph-CH ₂ O-Cy-CF = CF-Ph-Ph-R ² (14D) R ¹ -Ph-COO-Cy-CF = CF-Ph-Ph-R ² (14E) R ¹ -Ph-OCO-Cy-CF = CF-Ph-Ph-R ² (14F) R ¹ -Ph-C ≡ C-Cy-CF = CF-Ph-Cy-R ² (14G) R ¹ -Ph-CH ₂ CH ₂ -Cy-CF = CF-Ph-Cy-R ² (14H) R ¹ -Ph-OCH _2- Cy-CF = CF-Ph-Cy-R ² (14I) R ¹ -Ph-CH ₂ O-Cy-CF = CF-Ph-Cy-R ² (14J)

R ¹ -Ph-COO-Cy-CF = CF-Ph-Cy-R ² (14K) R ¹ -Ph-OCO-Cy-CF = CF-Ph-Cy-R ² (14L) R ^1- Ph-C ≡ C-Cy-CF = CF-Ph-Ch-R ² (14M) R ¹ -Ph-CH ₂ CH ₂ -Cy-CF = CF-Ph-Ch-R ² (14N) R ¹ -Ph -OCH ₂ -Cy-CF = CF-Ph-Ch-R ² (14O) R ¹ -Ph-CH ₂ O-Cy-CF = CF-Ph-Ch-R ² (14P) R ¹ -Ph-COO- Cy-CF = CF-Ph-Ch-R ² (14Q) R ¹ -Ph-OCO-Cy-CF = CF-Ph-Ch-R ² (14R)

Further, A ¹ , A ³ , and A ⁴ of the compound (13) are groups in which a part of hydrogen atoms are replaced by halogen atoms or cyano groups, groups in which a part of CH groups are replaced by nitrogen atoms,
Alternatively, examples of the case where some of the CH ₂ groups are substituted with oxygen atoms or sulfur atoms include the following compounds.

[0068]

Embedded image

The above compound (1) obtained by the production method of the present invention is a compound useful as a liquid crystal compound. The compound (1) is usually used as a liquid crystal composition together with other liquid crystal material or non-liquid crystal material.
When used together with other materials, the liquid crystal composition can have a low viscosity and can be used as a liquid crystal display device having a high-speed response.

[0070]

EXAMPLES Examples of the present invention will be specifically described in the following examples, but the present invention is not limited thereto.

Example 1 Synthesis of iodotrifluoroethylene (4): A 300 ml four-necked flask was charged with 40 ml of diethyl ether and 40 ml of THF and cooled to -90 ° C.
To this, 10.0 g (85.8 mmol) of chlorotrifluoroethylene was blown. Then, n-BuLi in n-hexane (1.63 mol
/ l) was added dropwise in the amount of 58 ml (94.5 mmol) over 30 minutes. Furthermore-
After stirring at 90 ° C for 1 hour, 24.0 g (94.5 mmol) of I ₂ was added to THF60.
What was melt | dissolved in ml was dripped over 30 minutes. After further warming to room temperature and stirring for 30 minutes, the product was subjected to simple distillation with a solvent (bp 58 to 64 ° C). As a result of ¹⁹ F-NMR internal standard analysis of the fraction (p-chlorobenzotrifluoride was used as a standard substance), the desired iodotrifluoroethylene yield was 74%.
Got with.

[Example 2] 2- (4-n-propylphenyl) -1,
Synthesis of 1,2-trifluoroethylene (6): 180 g of the solution of iodotrifluoroethylene (4) obtained in Example 1 in a 300 ml three-necked flask equipped with a cooling tube (CF ₂ = 63.5 mmo as CFI)
l) and cooled to -10 ℃, followed by 5.4g of active zinc (82.6mm
ol) I put it in. Then, 4-n-propyl iodobenzene 12.0 g
(48.8 mmol) and Pd (PPh _{3) 4} was added 0.85 g, was reacted for 1 hour at 60 ° C.. After cooling, excess zinc was filtered, 100 ml of dilute hydrochloric acid was added to the filtrate, the mixture was extracted with methylene chloride, washed with water and dried, and then the solvent was distilled off under atmospheric pressure. The obtained liquid was purified by silica gel column chromatography and further distilled under reduced pressure to give 2- (4-n-propylphenyl) -1,1,2-
7.3 g (yield 75%) of trifluoroethylene was obtained. nC ₃ H ₇ -Ph-CF = CF ₂

¹⁹ F-NMR (CDCl ₃ ) δppm from CFCl ₃ : -101.6p
pm (d, d, J _FF = 33.1Hz, J _FF = 76.2Hz),-116.4ppm (d, d, J _FF
= 76.2Hz, J _FF = 109.3Hz),-177.0ppm (d, d, J _FF = 33.1Hz, J
_FF = 109.3Hz). MS m / e: 200 (M ⁺ ).

Example 3 Preparation of trans-4-n-propylcyclohexyllithium (8): In a 100 ml four-necked flask, 3.81 g (14.3 mmol) of 4,4'-di-t-butylbiphenyl and dry THF were added. 50 ml was put and it cooled at 0 degreeC. Under an argon gas atmosphere, 0.20 g (28.8 mmol) of lithium metal and 50 μl of bromine were added, and the mixture was stirred at the same temperature for 3 hours. Then, after confirming that the reaction liquid was deep blue, it was cooled to -70 ° C, and 1.15 g (7.17 mmol) of 1-chloro-4-n-propylcyclohexane (7) (cis / trans = 2/1) ) Was added dropwise with stirring at -50 ° C or lower. The mixture was further stirred at -70 ° C for 30 minutes.

Example 4 (E) -1- (4-n-propylphenyl)
-2- (trans-4-n-propylcyclohexyl) -1,2-
Synthesis of difluoroethylene (1): trans-4-n of Example 3
2- (4-n-propylphenyl) -1,1,2-trifluoroethylene (6) 1.19 g (5. 5) synthesized in Example 2 in a THF solution of -propylcyclohexyllithium (8) at -50 ° C or lower.
A mixed solution of 95 mmol) and 10 ml of dry THF was added dropwise over 5 minutes. Furthermore, after reacting at −78 ° C. for 30 minutes, −
The temperature was raised to 10 ° C., 50 ml of 1N hydrochloric acid was added, and the organic layer was separated. The aqueous layer was extracted with n-hexane, and the organic layer was washed with water and dried, the solvent was distilled off, the crude liquid obtained was purified by silica gel column chromatography, and the obtained solid was re-purified from methanol. Crystallize to give 1.06 g of (E) -1- (4-n-propylphenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene (1) (yield
58%) obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-C ₃ H ₇ (n)

[0076]

[Chemical 9]

The analysis results of this compound are shown below. ¹⁹ F-NMR (CDCl ₃ ) δppm from CFCl ₃ : -157.0ppm (d, d, J _FF =
122.5Hz, J _FH = 29.8Hz),-161.1ppm (d, d, J _FF = 122.5Hz, J
_FH = 6.6Hz) .MS m / e: 306 (M ⁺ ).

[Example 4A] CH ₃ -Cy-Cl was prepared in the same manner as in Example 3.
CH ₃ -Cy-Li was synthesized by lithiation of nC ₃ H ₇ obtained in Example 2.
CH ₃ -Cy-CF = CF-Ph-C ₃ H ₇ (n) was synthesized by reacting with -Ph-CF = CF ₂ . [Example 4B] C ₂ H ₅ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize C ₂ H ₅ -Cy-Li, and nC ₃ H ₇ -Ph-CF = CF obtained in Example 2 was synthesized. _By reacting with ₂ , C ₂ H ₅ -Cy-CF = CF-Ph-C ₃ H ₇ (n) was synthesized. [Example 4C] In the same manner as in Example 3, nC ₄ H ₉ -Cy-Cl was lithiated to synthesize C ₄ H ₉ -Cy-Li, and nC ₃ H ₇ -Ph-CF = CF obtained in Example 2 was synthesized. ₂
Was reacted with to synthesize nC ₄ H ₉ -Cy-CF = CF-Ph-C ₃ H ₇ (n).

[Example 4D] CF ₃ -Cy-Cl was prepared in the same manner as in Example 3.
Was synthesized to synthesize CF ₃ -Cy-Li, and nC ₃ H ₇ obtained in Example 2 was synthesized.
-Ph-CF = reacted with CF _2, were synthesized _{CF 3 -Cy-CF = CF-} Ph-C 3 H 7 (n).

[Example 4E] In the same manner as in Example 3, nC ₃ H ₇ O-Cy was used.
The -Cl and lithiated synthesized _{nC 3 H 7 O-Cy-} Li, is reacted with _{nC 3 H 7 -Ph-CF =} CF 2 obtained in Example _{2, nC 3 H 7 O-} Cy-CF = CF-P
hC ₃ H ₇ (n) was synthesized.

[Example 4F] CH ₂ = CHCH ₂ -in the same manner as in Example 3.
Example 2 was used to synthesize CH ₂ = CHCH ₂ -Cy-Li by lithiation of Cy-Cl.
CH ₂ = CHCH ₂ -Cy-C by reacting with nC ₃ H ₇ -Ph-CF = CF ₂ obtained in
F = CF-Ph-C ₃ H ₇ (n) was synthesized.

Example 5 (E) -1- (4-fluorophenyl) -2
Synthesis of-(trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: 2- (4-n-propylphenyl) -1,1,2-trifluoroethylene instead of 2- ( Four-
Fluorophenyl) -1,1,2-trifluoroethylene 1.
Reaction was carried out in the same manner as in Example 3 except that 05 g (5.97 mmol) was used.
Add (E) -1- (4-fluorophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene to 0.
89 g (yield 53%) was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-F

[0083]

[Chemical 10]

Example 6 (E) -1- (4-chlorophenyl) -2-
Synthesis of (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: In place of 2- (4-n-propylphenyl) -1,1,2-trifluoroethylene of Example 4, 4-tri A similar reaction was carried out using 15.3 g (59.5 mmol) of fluorovinylphenyl tetrahydropyranyl ether on a 10-fold scale of Example 4, and finally by treatment with acid,
(E) -1- (4-Hydroxyphenyl) -2- (trans-4-n-
Propylcyclohexyl) -1,2-difluoroethylene
8.33 g (yield 50%) was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-OH

Example 7 (E) -1- (4-chlorophenyl) -2-
Synthesis of (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: (E) -1- (4-hydroxyphenyl) -2- (trans obtained in Example 6 in a 50 ml four-necked flask. 1.54 g (5.50 mmol) of 4-n-propylcyclohexyl) -1,2-difluoroethylene and 30 ml of chloroform were charged, and the mixture was cooled to 0 ° C.

0.83 g (6.0 mmol) of K ₂ CO ₃ and PCl ₅ are added here.
Was added and the mixture was stirred at the same temperature for 1 hour. After warming to room temperature, it was neutralized with an aqueous NaHCO ₃ solution and the organic layer was separated. The aqueous layer was extracted with methylene chloride, washed with the organic layer together with water, dried and the solvent was distilled off.The obtained crude liquid was purified by silica gel column chromatography. Crystallize to (E) -1- (4-chlorophenyl) -2- (trans-4-n-propylcyclohexyl) -1,
1.26 g (yield 77%) of 2-difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-Cl

[0087]

[Chemical 11]

Example 8 (E) -1- (4-bromophenyl) -2-
Synthesis of (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Example 6 in a 200 ml four-necked flask.
3.70 g (13.2 mmol) of (E) -1- (4-hydroxyphenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene obtained in 1. and 100 ml of methylene chloride
Charged and cooled to 0 ° C. PPh ₃ 4.14g (15.8mmmo)
l3) and Br ₂ (2.53 g, 15.8 mmol) were added, the temperature was raised to room temperature, the mixture was stirred for 1 hour, an aqueous NaHCO ₃ solution was added, and the organic layer was separated. The aqueous layer was extracted with methylene chloride, combined with the organic layer, washed with water and dried, then the solvent was evaporated and the resulting crude liquid was purified by silica gel column chromatography to obtain (E) -1- (4-bromo Phenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene 3.32 g (yield 80%)
Obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-Br

[0089]

[Chemical 12]

[Example 8A] CH ₃ -Cy-Cl was prepared in the same manner as in Example 3.
CH ₃ -Cy-Li was synthesized by lithiation of the compound and Pr-O-Ph-CF = CF ₂ (where Pr is tetrahydropyran 2- was obtained from I-Ph-O-Pr in the same manner as in Example 2). The same applies to the following), to synthesize CH ₃ -Cy-CF = CF-Ph-O-Pr, which is treated with an acid and then chlorinated to produce CH ₃ -Cy-CF = CF-Ph. -Cl was synthesized.

[Example 8B] C ₂ H ₅ -Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize C ₂ H ₅ -Cy-Li and reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give C ₂
H ₅ was synthesized -Cy-CF = CF-Ph- O-Pr, and after chlorination and treatment with acid, was synthesized _{C 2 H 5 -Cy-CF =} CF-Ph-Cl.

[Example 8C] nC ₄ H ₉ -Cy- was prepared in the same manner as in Example 3.
Cl was lithiated to synthesize nC ₄ H ₉ -Cy-Li and reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give nC ₄ H ₉ -Cy-Li. the _{4 H 9 -Cy-CF = CF} -Ph-O-Pr synthesized, and after chlorination and treatment with acid, was synthesized _{nC 4 H 9 -Cy-CF =} CF-Ph-Cl.

[Example 8D] CF ₃ -Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize CF ₃ -Cy-Li and reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give CF.
₃ was synthesized -Cy-CF = CF-Ph- O-Pr, and after chlorination and treatment with acid, to synthesize _{CF 3 -Cy-CF = CF-} Ph-Cl.

[Example 8E] nC ₃ H ₇ O-Cy was prepared in the same manner as in Example 3.
-Cl was lithiated to synthesize nC ₃ H ₇ O-Cy-Li, and I-Ph-OP
nC ₃ H ₇ O-Cy-CF = CF-Ph-O-Pr was synthesized by reacting it with Pr-O-Ph-CF = CF ₂ obtained from r in the same manner as in Example 2 and treated with an acid. and the after chlorination, was synthesized _{nC 3 H 7 O-Cy-} CF = CF-Ph-Cl.

[Example 8F] CH ₂ = CHCH ₂ -in the same manner as in Example 3.
Cy-Cl was lithiated to synthesize CH ₂ = CHCH ₂ -Cy-Li, and I-Ph
CH ₂ = CHCH ₂ -Cy-CF = CF-Ph-O-Pr was synthesized by reacting Pr-O-Ph-CF = CF ₂ obtained from -O-Pr in the same manner as in Example 2, After treatment with acid, chlorination was performed to synthesize CH ₂ = CHCH ₂ -Cy-CF = CF-Ph-Cl.

Example 8G CH ₃ C≡C-Cy was prepared in the same manner as in Example 3.
-Cl is lithiated to synthesize CH ₃ C≡C-Cy-Li, and I-Ph-OP
CH ₃ C≡C-Cy-CF = CF-Ph-O-Pr was synthesized by reacting with Pr-O-Ph-CF = CF ₂ obtained from r in the same manner as in Example 2 and treated with an acid. Then, it was chlorinated to synthesize CH ₃ C≡C-Cy-CF = CF-Ph-Cl.

[Example 8H] nC ₃ H ₇ -Cy- was prepared in the same manner as in Example 3.
Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li and reacted with Pr-O-PhF-CF = CF ₂ obtained from I-PhF-O-Pr in the same manner as in Example 2 to give nC ₃ H ₇ -Cy-Li. the _{3 H 7 -Cy-CF = CF} -PhF-O-Pr synthesized, and after chlorination and treatment with acid, was synthesized _{nC 3 H 7 -Cy-CF =} CF-PhF-Cl.

[Example 8I] CH ₃ -Cy-Cl was prepared in the same manner as in Example 3.
CH ₃ -Cy-Li was synthesized by lithiation of the compound and reacted with F-Ph-CF = CF ₂ obtained from I-Ph-F in the same manner as in Example 2 to produce CH ₃ -Cy-C.
F = CF-Ph-F was synthesized.

[Example 8J] CH ₃ -Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize CH ₃ -Cy-Li and reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give CH
₃ was synthesized -Cy-CF = CF-Ph- O-Pr, and after bromination and treatment with acid, was synthesized _{CH 3 -Cy-CF = CF-} Ph-Br.

[Example 8K] nC ₃ H ₇ O-Cy was prepared in the same manner as in Example 3.
-Cl 2 was lithiated to synthesize nC ₃ H ₇ O-Cy-Li, which was reacted with F-Ph-CF = CF ₂ obtained from I-Ph-F in the same manner as in Example 2,
The _{nC 3 H 7 O-Cy-} CF = CF-Ph-F were synthesized.

[Example 8L] nC ₃ H ₇ O-Cy was prepared in the same manner as in Example 3.
-Cl was lithiated to synthesize nC ₃ H ₇ O-Cy-Li, and I-Ph-OP
nC ₃ H ₇ O-Cy-CF = CF-Ph-O-Pr was synthesized by reacting it with Pr-O-Ph-CF = CF ₂ obtained from r in the same manner as in Example 2 and treated with an acid. After that, bromination was performed to synthesize nC ₃ H ₇ O-Cy-CF = CF-Ph-Br.

Example 9 Synthesis of (E) -1- (4-trifluoromethoxyphenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: 2- (of Example 4 4-n-
2- (4-trifluoromethoxyphenyl) -1,1,2-instead of propylphenyl) -1,1,2-trifluoroethylene
The reaction was performed in the same manner as in Example 4 except that 1.44 g (5.95 mmol) of trifluoroethylene was used, and (E) -1- (4-trifluoromethoxyphenyl) -2- (trans-4-n-propylcyclohexyl)- 1,2-difluoroethylene 1.14 g (yield 55
%)Obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-OCF ₃

[0103]

[Chemical 13]

Example 10 (E) -1- (4-ethoxyphenyl)
-2- (trans-4-n-propylcyclohexyl) -1,2-
Synthesis of difluoroethylene: 2- (4-n-propylphenyl) -1,1,2-trifluoroethylene instead of 2-of Example 4
The reaction was performed in the same manner as in Example 4 except that 1.20 g (5.94 mmol) of (4-ethoxyphenyl) -1,1,2-trifluoroethylene was used, and (E) -1- (4-ethoxyphenyl) -2- (Trans-4-n
-Propylcyclohexyl) -1,2-difluoroethylene (1.10 g, yield 60%) was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-OC ₂ H ₅

[0105]

Embedded image

[Example 10A] In the same manner as in Example 3, CH ₃ -Cy-Cl was lithiated to synthesize CH ₃ -Cy-Li, and I-Ph-OC ₂ H _{5 was used} to give Example 2.
Was reacted with C ₂ H ₅ O-Ph-CF = CF ₂ obtained in a similar manner to
₃ -Cy-CF = CF-Ph-OC ₂ H ₅ was synthesized.

[Example 10B] In the same manner as in Example 3, C ₂ H ₅ -Cy-Cl was lithiated to synthesize C ₂ H ₅ -Cy-Li, and I-Ph-OC ₂ H _{5 was used} to give Example 2.
And reacted with _{C 2 H 5 O-Ph-} CF = CF 2 was obtained in the same manner, C ₂
H ₅ -Cy-CF = was synthesized _{CF-Ph-OC 2 H 5} .

[Example 10C] In the same manner as in Example 3, CF ₃ -Cy-Cl was lithiated to synthesize CF ₃ -Cy-Li, and I-Ph-OC ₂ H _{5 was used} to give Example 2.
Was reacted with C ₂ H ₅ O-Ph-CF = CF ₂ obtained in a similar manner to
₃ -Cy-CF = CF-Ph-OC ₂ H ₅ was synthesized.

[Example 10D] As in Example 3, nC ₃ H ₇ O-Cy-C
I-Ph-OC ₂ H ₅ was synthesized by lithiation of l to synthesize nC ₃ H ₇ O-Cy-Li.
Was reacted with C ₂ H ₅ O-Ph-CF = CF ₂ obtained in the same manner as in Example 2 to synthesize nC ₃ H ₇ O-Cy-CF = CF-Ph-OC ₂ H ₅ .

[Example 10E] Similar to Example 3, CH ₃ -Cy-Cl was lithiated to synthesize CH ₃ -Cy-Li, and I-Ph-OCF _{3 was used} to prepare Example 2
Was reacted in the same manner as in CF ₃ O-Ph-CF = CF ₂ to give CH _3-
Cy-CF = CF-Ph-OCF ₃ was synthesized.

Example 11 Synthesis of (E) -1- [4- (2-Methyl-1-propenyl) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Under an argon atmosphere, put 0.02 g (0.8 mmol) of magnesium and 10 ml of dry THF in a 100 ml three-necked flask equipped with a reflux tube,
Then 0.11 g (0.8 mmo of 2-methyl-1-propenyl bromide
l) Dropped. After the dropwise addition was completed, the mixture was refluxed for another hour and then allowed to cool to room temperature.

Separately, in an argon atmosphere, 50 with a reflux tube
(E) -1- (4-bromophenyl) -2- (trans-4-n-propylcyclohexyl) obtained in Example 8 in a ml three-necked flask.
-1,2-difluoroethylene 0.24 g (0.71 mmol) and 1,3-
20 ml of a dry THF solution containing 0.05 g of bis (diphenylphosphino) propanedichloronickel [NiCl ₂ (dppp)] was placed, and the above solution was added dropwise thereto using a dropping funnel.

After the dropping, the mixture was further stirred at room temperature for 24 hours,
20 ml of water was added. Further, 20 ml of 20% hydrochloric acid was added to separate the organic layer, which was washed with water and dried, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain (E) -1- [4- (2-methyl-1-propenyl) phenyl] -2-
0.15 g (yield 68%) of (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-CH = C (CH ₃ ) ₂

[0114]

[Chemical 15]

Example 12 Synthesis of (E) -1- [4- (Propyl-1-yne) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: 100 ml Four
30 ml of dry THF was added to the two-necked flask and cooled to -70 ° C. Next, 0.5 g (12.5 mmol) of propyne was blown in, and 0.88 ml (1.41 M) of n-BuLi n-hexane solution (1.61M) was added at the same temperature.
mmol) was added dropwise. After further stirring for 30 minutes, 0.19 g (1.4 mmol) of ZnCl ₂ dissolved in dry THF was added, and the temperature was raised to room temperature,
It was stirred for 30 minutes.

Then, after cooling to -20 ° C., obtained in Example 8
0.24 g of (E) -1- (4-bromophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene
(0.71 mmol) and 0.01 g of Pd (PPh ₃ ) ₄ were added.

After the addition, the temperature was raised to room temperature, and after stirring for 2 hours,
20 ml of 1N hydrochloric acid was added, the organic layer was separated, washed with water and dried, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain (E) -1- [4- (propyl-1
-In) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene 0.13 g (yield
61%) got. nC ₃ H ₇ -Cy-CF = CF-Ph-C≡C-CH ₃

[0118]

Embedded image

[Example 12A] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and Pr-O obtained from I-Ph-O-Pr by the method of Example 2 was used. CH ₃ -Cy-CF = CF by reacting with -Ph-CF = CF _2.
-Ph-O-Pr was synthesized, treated with acid and then brominated to give CH _3-
Synthesizing Cy-CF = CF-Ph-Br and finally alkenylating it to CH
_{3 -Cy-CF = CF-Ph} -CH = C (CH 3) 2 was synthesized.

[Example 12B] C ₂ H ₅ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize C ₂ H ₅ -Cy-Li, and the same method as in Example 2 was performed using I-Ph-O-Pr. in reacted with Pr-O-Ph-CF = CF 2 was obtained, C ₂ H ₅ -C
y-CF = CF-Ph-O-Pr was synthesized, treated with acid and then brominated to synthesize C ₂ H ₅ -Cy-CF = CF-Ph-Br, and finally alkenylated to C ₂ the _{H 5 -Cy-CF = CF-} Ph-CH = C (CH 3) 2 was synthesized.

[Example 12C] nC ₃ H ₇ O-Cy-Cl was used in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li and reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give nC ₃ H ₇ O-Cy-Li. ₃ H ₇ O-Cy-CF = CF-Ph-O-Pr was synthesized, treated with acid and then brominated to synthesize nC ₃ H ₇ O-Cy-CF = CF-Ph-Br, and finally Alkenylated to nC ₃ H ₇ O-Cy-CF = CF-Ph-CH = C (C
H ₃ ) ₂ was synthesized.

[Example 12D] In the same manner as in Example 3, CH ₃ -Cy-Cl was lithiated to synthesize CH ₃ -Cy-Li, and Pr obtained from I-Ph-O-Pr in the same manner as in Example 2 was used. -O-Ph-CF = CF ₂ to react with CH ₃ -Cy
It was synthesized -CF = CF-Ph-O- Pr, and after bromination and treatment with acid, to synthesize _{CH 3 -Cy-CF = CF-} Ph-Br, finally alkynylation, CH ₃ -Cy- CF = CF-Ph-C≡C-CH ₃ was synthesized.

[Example 12E] Similar to Example 3, CF ₃ -Cy-Cl was lithiated to synthesize CF ₃ -Cy-Li, and I-Ph-O-Pr was used for Example 2.
Was reacted with Pr-O-Ph-CF = CF ₂ obtained in a similar manner to CF _3-
Was synthesized Cy-CF = CF-Ph- O-Pr, and after bromination and treatment with acid, to synthesize _{CF 3 -Cy-CF = CF-} Ph-Br, finally alkynylation, CF ₃ -Cy -CF = CF-Ph-C≡C-CH ₃ was synthesized.

[Example 12F] nC ₃ H ₇ O-Cy-Cl was used in the same manner as in Example 3.
The was lithiated to synthesize _{nC 3 H 7 O-Cy-} Li, are reacted with Pr-O-Ph-CF = CF 2 was obtained in the I-Ph-O-Pr from example 2 method, nC ₃
H ₇ O-Cy-CF = CF-Ph-O-Pr was synthesized, treated with acid and then brominated to synthesize nC ₃ H ₇ O-Cy-CF = CF-Ph-Br, and finally alkenyl Then, nC ₃ H ₇ O-Cy-CF = CF-Ph-C≡C-CH ₃ was synthesized.

Example 13 (E) -1- (4-cyanophenyl)
Synthesis of -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: CuCN 0.07 g (0.8 mmol) and anhydrous dimethyl sulfoxide (DMSO) 30 ml are put into a 100 ml three-necked flask equipped with a cooling tube. , Heated to 90 ° C to dissolve. Then, with stirring, 0.24 g (0.71 mmol) of (E) -1- (4-bromophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene obtained in Example 8 was obtained. Was added. After that, the mixture was further stirred at 150 ° C for 1 hour and cooled to room temperature.

20 ml of water was poured, the mixture was extracted with methylene chloride, the organic layer was washed with saturated saline and dried over CaCl ₂ . After filtration, the solvent was evaporated, the obtained solid was purified by silica gel column chromatography, and (E) -1- (4-cyanophenyl) -2- (trans-4-n-propylcyclohexyl)-
0.17 g (yield 83%) of 1,2-difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-CN

[0127]

[Chemical 17]

[Example 13A] In the same manner as in Example 3, CH ₃ -Cy-Cl was lithiated to synthesize CH ₃ -Cy-Li, and Pr obtained from I-Ph-O-Pr in the same manner as in Example 2 was used. -O-Ph-CF = CF ₂ to react with CH ₃ -Cy
It was synthesized -CF = CF-Ph-O- Pr, and after bromination and treatment with acid, to synthesize _{CH 3 -Cy-CF = CF-} Ph-Br, and finally reacted with CuCN, CH ₃ - Cy-CF = CF-Ph-CN was synthesized.

[Example 13B] nC ₃ H ₇ O-Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li and reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give nC ₃ H ₇ O-Cy-Li. ₃ H ₇ O-Cy-CF = CF-Ph-O-Pr was synthesized, treated with acid and then brominated to synthesize nC ₃ H ₇ O-Cy-CF = CF-Ph-Br, and finally is reacted with CuCN, it was synthesized _{nC 3 H 7 O-Cy-} CF = CF-Ph-CN.

[Example 13C] CH ₂ = CHCH ₂ -Cy-C as in Example 3.
l was lithiated to synthesize CH ₂ = CHCH ₂ -Cy-Li, and I-Ph-OP
CH ₂ = CHCH ₂ -Cy-CF = CF-Ph-O-Pr was prepared by reacting with Pr-O-Ph-CF = CF ₂ obtained from r in the same manner as in Example 2 and treated with an acid. Then brominated to synthesize CH ₂ = CHCH ₂ -Cy-CF = CF-Ph-Br, and finally reacted with CuCN, CH ₂ = CHCH ₂ -Cy-CF = CF-Ph-
CN was synthesized.

Example 14 Synthesis of (E) -1- [4- (2,2-difluorovinyl) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Example 2 of 4
Instead of (4-n-propylphenyl) -1,1,2-trifluoroethylene, 2- (4-dimethoxymethylphenyl) -1,
The reaction was carried out in the same manner as in Example 4 using 1.38 g (5.95 mmol) of 1,2-trifluoroethylene, and finally treated with an acid to give (E) -1- (4-formylphenyl) -2- ( Transformer-4
0.96 g (yield 55%) of -n-propylcyclohexyl) -1,2-difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-CHO

In a 50 ml four-necked flask equipped with a cooling tube and a gas blowing tube, 20 ml of triglyme dehydrated with CaH ₂ was added.
Add, cool to 0 ° C, dibromodifluoromethane CF ₂ Br ₂
Was blown in at 1.38 g (6.58 mmol). Then, at 0 ° C, 2.15 g of trisdimethylaminophosphine (Me ₂ N) ₃ P (13.2 mmo
l) and 5 ml of triglyme solution were added dropwise over 5 minutes. After the dropping, the mixture was stirred at room temperature for 15 minutes, and was obtained in advance (E) -1-
(4-Formylphenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene 0.96 g (3.29
mmol) and 5 ml of triglyme solution were added dropwise at room temperature and further reacted at 85 ° C. for 2 hours.

After cooling to 0 ° C., 20 ml of water was added, the mixture was extracted with n-hexane, washed with water and dried, the solvent was distilled off, and the obtained solid was purified by silica gel column chromatography.
0.89 g (yield 83%) of (E) -1- [4- (2,2-difluorovinyl) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene was obtained. . nC ₃ H ₇ -Cy-CF = CF-Ph-CH = CF ₂

[0134]

Embedded image

Example 15 (E) -1- [4-[(E) -1,2-Difluoro-2-trifluoromethylvinyl] phenyl] -2- (trans-4-n-propylcyclohexyl)- Synthesis of 1,2-difluoroethylene: 2- (4-n-propylphenyl) of Example 4
Use 1.71 g (5.94 mmol) of (E) -1- (trifluoromethyl) -2- (4-trifluorovinylphenyl) -1,2-difluoroethylene instead of -1,1,2-trifluoroethylene The reaction was carried out in the same manner as in Example 4 except for (E) -1- [4-[(E) -1,
2-Difluoro-2-trifluoromethylvinyl] phenyl] -2- (trans-4-n-propylcyclohexyl) -1,
1.40 g of 2-difluoroethylene (yield 60%) was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-CF = CF-CF ₃

[0136]

[Chemical 19]

Example 16 of (E) -1- [4- (2,2,2-trifluoroethoxy) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene Synthesis (E) -1-
[4- (2,2-difluorovinyloxy) phenyl] -2-
Synthesis of (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Example 6 in a 100 ml four-necked flask.
1.49 g (5.32 mmol) of (E) -1- (4-hydroxyphenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene and 1,3-dimethyl- 30 ml of 2-imidazolidinone (DMEU) was charged and heated to 120 ° C.

0.1 ml of 2,2,2-trifluoroethylmethyl sulfonate was added dropwise thereto, the solution was stirred at 120 ° C. for 6 hours, 50 ml of ice water was added, and the organic layer was separated. The aqueous layer was extracted with methylene chloride, washed with water together with the organic layer, dried, the solvent was distilled off, and the resulting crude liquid was purified by silica gel column chromatography to obtain (E) -1- [4- 1.69 g (yield 88%) of (2,2,2-trifluoroethoxy) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-OCH ₂ CF ₃

Example 17 Synthesis of (E) -1- [4- (2,2-difluorovinyloxy) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: In a 50 ml three-necked flask equipped with a cooling tube, 0.52 g (5.14 mmol) of diisopropylamine and 10 ml of anhydrous THF were placed,
Cooled to 20 ° C. Then, n-BuLi n-hexane solution (1.7
3.0 ml (5.14 ml) of (0 mol / l) was added dropwise. Further, the mixture was stirred at -20 ° C for 15 minutes, and then at (-70 ° C) (E) -1- [4-
A mixture of 1.69 g (4.67 mmol) of (2,2,2-trifluoroethoxy) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene and 10 ml of anhydrous THF was added dropwise. Then, after stirring at −70 ° C. for 30 minutes, room temperature 3
Stirred for hours.

20 ml of water was poured, the mixture was extracted with methylene chloride, washed with water together with the organic layer, dried, the solvent was distilled off, and the resulting crude liquid was purified by silica gel column chromatography to obtain (E)- 1- [4- (2,2-difluorovinyloxy) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2
-1.17 g (yield 73%) of difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-OCH = CF ₂

[0141]

Embedded image

[0142] Example 17A] Example 3 and similarly CH ₃ -Cy-Cl by lithiation to synthesize CH ₃ -Cy-Li, at _{I-Ph-CH (OCH 3} ) the same method from ₂ to Example 2 The obtained (CH ₃ O) ₂ CH-Ph-CF = CF ₂ was reacted to synthesize CH ₃ -Cy-CF = CF-Ph-CH (OCH ₃ ) _2, which was treated with an acid and then subjected to Wittig reaction. CH ₃ -Cy-CF = CF-Ph-CH = C
F ₂ was synthesized.

[Example 17B] In the same manner as in Example 3, C ₂ H ₅ -Cy-Cl was lithiated to synthesize C ₂ H ₅ -Cy-Li, and I-Ph-CH (OCH ₃ ) _{2 was changed} to Example 2. A similar method was used to react with (CH ₃ O) ₂ CH-Ph-CF = CF ₂ to synthesize C ₂ H ₅ -Cy-CF = CF-Ph-CH (OCH ₃ ) ₂ with acid. After the treatment, Wittig reaction is performed and C ₂ H ₅ -Cy-CF = CF-Ph-CH =
CF ₂ was synthesized.

[Example 17C] nC ₃ H ₇ O-Cy-Cl was used in the same manner as in Example 3.
Of nC ₃ H ₇ O-Cy-Li by lithiation of I-Ph-CH (OC
(CH ₃ O) ₂ CH-Ph-CF = CF ₂ obtained from H ₃ ) _{2 in} the same manner as in Example _2.
It is reacted _{with, nC 3 H 7 O-Cy} -CF = CF-Ph-CH (OCH 3) 2 was synthesized, by after Wittig reaction was treated with an acid, nC ₃ H ₇
O-Cy-CF = CF-Ph-CH = CF ₂ was synthesized.

[Example 17D] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and I-Ph-CF = CF
From CF ₃ was obtained in the same manner as Example 2 _CF 3 CF = CF-
It is reacted with _{Ph-CF = CF 2, CH} 3 -Cy-CF = CF-Ph-CF
= CFCF ₃ was synthesized.

[Example 17E] nC ₃ H ₇ O-Cy-Cl was prepared in the same manner as in Example 3.
Was synthesized to synthesize nC ₃ H ₇ O-Cy-Li, and I-Ph-CF = CFCF
₃ is reacted with _{CF 3 CF = CF-Ph-} CF = CF 2 was obtained in the same manner as Example 2, it was synthesized _{nC 3 H 7 O-Cy-} CF = CF-Ph-CF = CFCF 3.

[Example 17F] In the same manner as in Example 3, CH ₃ -Cy-Cl was lithiated to synthesize CH ₃ -Cy-Li, and Pr obtained from I-Ph-O-Pr in the same manner as in Example 2 was used. CH ₂ = CH by reacting with -O-Ph-CF = CF _2.
CH ₂ -Cy-CF = CF-Ph-O-Pr was synthesized, treated with acid, then 2,2,
2-trifluoroethyl etherification, deHF removal, CH ₃ -Cy
-CF = CF-Ph-OCH = CF ₂ was synthesized.

Example 18 (E) -1- [4- (trans-4-n-propylcyclohexyl) phenyl] -2- (trans-4-n
-Propylcyclohexyl) -1,2-difluoroethylene: 2- [4- (trans-4-, instead of 2- (4-n-propylphenyl) -1,1,2-trifluoroethylene of Example 4 n-
Propylcyclohexyl) phenyl] -1,1,2-trifluoroethylene was used in the same manner as in Example 4 except that 1.68 g (5.96 mmol) was used, and (E) -1- [4- (trans-4-n- Propylcyclohexyl) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene 1.29
g (yield 56%) was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-Cy-C ₃ H ₇ (n)

[0149]

[Chemical 21]

[Example 18A] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and I-Ph-Cy-C ₃ H ₇ (n) was used in the same manner as in Example 2. CH ₃ -Cy-CF = CF-Ph-Cy-C ₃ H ₇ (n) was synthesized by reacting with nC ₃ H ₇ -Cy-Ph-CF = CF ₂ obtained by the above method.

[Example 18B] nC ₃ H ₇ O-Cy-Cl was used in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li and I-Ph-Cy-C ₃ H ₇
nC ₃ H ₇ -Cy-Ph-CF = CF ₂ obtained in the same manner as in Example 2 from (n)
Was reacted with to synthesize nC ₃ H ₇ O-Cy-CF = CF-Ph-Cy-C ₃ H ₇ (n).

[Example 18C] F-Cy-Cl was lithiated in the same manner as in Example 3 to synthesize F-Cy-Li, and I-Ph-Cy-C ₃ H ₇ (n) was used to give Example 2
And it is reacted with _{nC 3 H 7 -Cy-Ph-} CF = CF 2 was obtained in the same manner, was synthesized F-Cy-CF = CF- Ph-Cy-C 3 H 7 (n).

[Example 18D] In the same manner as in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-Cy-C ₂ H _{5 was changed} to Example 2. It is reacted with _{C 2 H 5 -Cy-Ph-} CF = CF 2 was obtained in the same manner, was synthesized _{nC 3 H 7 -Cy-CF =} CF-Ph-Cy-C 2 H 5.

Example 19 (E) -1- (4-n-propylbiphenyl) -2- (trans-4-n-propylcyclohexyl)-
Synthesis of 1,2-difluoroethylene: 2- (4-n-propylbiphenyl) -1,1, instead of 2- (4-n-propylphenyl) -1,1,2-trifluoroethylene in Example 4 Reaction was performed in the same manner as in Example 4 except that 1.64 g (5.94 mmol) of 2-trifluoroethylene was used, and (E) -1- (4-n-propylbiphenyl) -2-
1.34 g (yield 59%) of (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-Ph-C ₃ H ₇ (n)

[0155]

[Chemical formula 22]

[Example 19A] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and I-Ph-Ph-C ₃ H ₇ (n) was used in the same manner as in Example 2. is reacted with _{nC 3 H 7 -Ph-Ph-} CF = CF 2 was obtained in the manner, it was synthesized _{CH 3 -Cy-CF = CF-} Ph-Ph-C 3 H 7 (n).

[Example 19B] nC ₃ H ₇ O-Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li, and I-Ph-Ph-C ₃ H ₇
nC ₃ H ₇ -Ph-Ph-CF = CF ₂ obtained from (n) in the same manner as in Example _2.
Was reacted with to synthesize nC ₃ H ₇ O-Cy-CF = CF-Ph-Ph-C ₃ H ₇ (n).

[Example 19C] F-Cy-Cl was lithiated in the same manner as in Example 3 to synthesize F-Cy-Li, and I-Ph-Ph-C ₃ H ₇ (n) was used to give Example 2.
And it is reacted with _{nC 3 H 7 -Ph-Ph-} CF = CF 2 was obtained in the same manner, was synthesized F-Cy-CF = CF- Ph-Ph-C 3 H 7 (n).

[Example 19D] As in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-Ph-C ₂ H _{5 was used} to give Example 2. It is reacted with _{C 2 H 5 -Ph-Ph-} CF = CF 2 was obtained in the same manner, was synthesized _{nC 3 H 7 -Cy-CF =} CF-Ph-Ph-C 2 H 5.

[Example 19E] In the same manner as in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-Ph-F was used in the same manner as in Example 2. N- by reacting with F-Ph-Ph-CF = CF ₂ obtained in
The _{C 3 H 7 -Cy-CF =} CF-Ph-Ph-F were synthesized.

Example 20 Synthesis of (E) -1- [4- (4-methylphenethyl) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Under Argon Atmosphere In a 100 ml three-necked flask equipped with a reflux tube, 0.015 g (0.6 mmol) of magnesium and 10 ml of dry THF were placed. Then, 1 drop of 1-bromopropane was added, and a solution of 0.12 g (0.6 mmol) of 4-methylphenethyl bromide dissolved in 5 ml of THF was added dropwise. After the dropwise addition was completed, the mixture was refluxed for another hour and then allowed to cool to room temperature.

Separately, under argon atmosphere, with a reflux tube
(E) -1-obtained in Example 6 in a 00 ml three-necked flask.
(4-Bromophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene 0.2g (0.58mmo
l) and 0.01 g of 1,3-bis (diphenylphosphino) propanedichloronickel [NiCl ₂ (dppp)]
5 ml of the F solution was added, and the above solution was added dropwise thereto using a dropping funnel.

After the dropping, the mixture was further stirred at room temperature for 24 hours,
20 ml of water was added. Further, 20 ml of 20% hydrochloric acid was added to separate the organic layer, which was washed with water and dried, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain (E) -1- [4- (4-methylphenethyl) phenyl] -2-
0.14 g (yield 61%) of (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-CH ₂ CH ₂ -Ph-CH ₃

[0164]

[Chemical formula 23]

Example 21 Synthesis of (E) -1- [4- (2-p-methylphenylethenyl) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene : Example 20
1-bromo-2 instead of 4-methylphenethyl bromide
Reaction was performed in the same manner as in Example 20 except that 0.12 g (0.6 mmol) of-(4-methylphenyl) ethene was used, and (E) -1- [4- (2-p-methylphenylethenyl) phenyl]- Add 2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene to 0.
12 g (yield 55%) was obtained.

NC ₃ H ₇ -Cy-CF = CF-Ph-CH = CH-Ph-CH ₃

[0167]

[Chemical formula 24]

[Example 21A] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and Pr obtained from I-Ph-O-Pr in the same manner as in Example 2 was used. CH _3- by reacting with -O-Ph-CF = CF _2.
Cy-CF = synthesizes CF-Ph-O-Pr, and after bromination and treatment with _{acid, CH 3 -Cy-CF = CF} -Ph-Br was synthesized and finally Br-CH ₂ CH ₂ -Ph
Is reacted with -CH _3, was synthesized _{CH 3 -Cy-CF = CF-} Ph-CH 2 CH 2 -Ph-CH 3.

[Example 21B] nC ₃ H ₇ O-Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li, which was reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give nC ₃ H ₇ O-Cy-Li. ₃ H ₇ O-Cy-CF = CF-Ph-O-Pr was synthesized, treated with acid and then brominated to synthesize nC ₃ H ₇ O-Cy-CF = CF-Ph-Br, and finally Br-CH ₂ CH ₂ -Ph-CH ₃ reacted with nC ₃ H ₇ O-Cy-CF = CF
The _{-Ph-CH 2 CH 2 -Ph-} CH 3 were synthesized.

[Example 21C] As in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-O-Pr was used in the same manner as in Example 2. N-reacted with Pr-O-Ph-CF = CF ₂ obtained in
C ₃ H ₇ -Cy-CF = CF-Ph-O-Pr was synthesized, treated with acid and then brominated to synthesize nC ₃ H ₇ -Cy-CF = CF-Ph-Br, and finally Br.
Reaction with -CH ₂ CH ₂ -Ph-OC ₃ H ₇ (n), nC ₃ H ₇ -Cy-CF = CF-
It was synthesized _{Ph-CH 2 CH 2 -Ph-} OC 3 H 7 (n).

[Example 21D] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and Pr obtained from I-Ph-O-Pr in the same manner as in Example 2 was used. -O-Ph-CF = CF ₂ to react with CH ₃ -Cy
Was synthesized -CF = CF-Ph-O- Pr, and after bromination and treatment with acid, to synthesize _{CH 3 -Cy-CF = CF-} Ph-Br, finally Br-CH = CH-Ph-
Is reacted with CH _3, it was synthesized _{CH 3 -Cy-CF = CF-} Ph-CH = CH-Ph-CH 3.

[Example 21E] nC ₃ H ₇ O-Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li and reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give nC ₃ H ₇ O-Cy-Li. ₃ H ₇ O-Cy-CF = CF-Ph-O-Pr was synthesized, treated with acid and then brominated to synthesize nC ₃ H ₇ O-Cy-CF = CF-Ph-Br, and finally Br-CH = CH-Ph-CH ₃ was reacted with nC ₃ H ₇ O-Cy-CF = CF.
The -Ph-CH = CH-Ph- CH 3 were synthesized.

[Example 21F] In the same manner as in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-O-Pr was used in the same manner as in Example 2. N-reacted with Pr-O-Ph-CF = CF ₂ obtained in
C ₃ H ₇ -Cy-CF = CF-Ph-O-Pr was synthesized, treated with acid and then brominated to synthesize nC ₃ H ₇ -Cy-CF = CF-Ph-Br, and finally Br.
Reaction with -CH = CH-Ph-OC ₃ H ₇ (n), nC ₃ H ₇ -Cy-CF = CF-Ph
It was synthesized _{-CH = CH-Ph-OC 3} H 7 (n).

Example 22 Synthesis of (E) -1- [4- (2-p-toluylethynyl) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Example 2 of 4
1.62 g of 2- [4- (2-p-toluylethynyl) phenyl] -1,1,2-trifluoroethylene instead of (4-n-propylphenyl) -1,1,2-trifluoroethylene 5.96mmmol)
The reaction was performed in the same manner as in Example 4 except that the (E) -1- [4- (2-
p-toluylethynyl) phenyl] -2- (trans-4-n-
Propylcyclohexyl) -1,2-difluoroethylene
1.19 g (yield 53%) was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-C≡C-Ph-CH ₃

[0175]

[Chemical 25]

[Example 22A] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and I-Ph-C≡C-Ph-CH ₃ was used in the same manner as in Example 2. CH ₃ -Ph-C≡C-Ph-CF = CF ₂ obtained by the method was reacted to synthesize CH ₃ -Cy-CF = CF-Ph-C ≡C-Ph-CH ₃ .

[Example 22B] nC ₃ H ₇ O-Cy-Cl was used in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li, and I-Ph-C≡C-Ph
CH ₃ -Ph-C≡C-Ph-CF = CF obtained from -CH _{3 in} the same manner as in Example 2
₂ and reacted to synthesize _{nC 3 H 7 O-Cy-} CF = CF-Ph-C≡C-Ph-CH 3.

[Example 22C] As in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-C≡C-Ph-OC ₂
C ₂ H ₅ O-Ph-C≡C-Ph-CF = CF obtained from H _{5 in} the same manner as in Example 2
₂ and _{reacted, nC 3 H 7 -Cy-CF} = CF-Ph-C≡C-Ph-OC 2 H 5
Was synthesized.

Example 23 Synthesis of (E) -1- [4- (4-methylbenzyloxy) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Example 6 0.30 g (1.07 mmol) of (E) -1- (4-hydroxyphenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene obtained in 1., 0.15 g of potassium carbonate and acetone Was added, and 0.20 g of α-bromo-p-xylene was added at room temperature. Reflux for 4 hours, then cool,
After filtration, the solvent was distilled off, and the obtained crude crystals were purified by silica gel column chromatography to obtain (E) -1- [4- (4- (4-
Methylbenzyloxy) phenyl] -2- (trans-4-n
0.40 g (yield 90%) of (-propylcyclohexyl) -1,2-difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ph-OCH ₂ -Ph-CH ₃

[0180]

[Chemical formula 26]

Example 24 Synthesis of (E) -1- [4- (4-methylbenzoyloxy) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Example 6
Dissolve 0.30 g (1.07 mmol) of (E) -1- (4-hydroxyphenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene obtained in 10 ml in methylene chloride Then, 0.09 g of pyridine was added at room temperature, and after cooling to 0 ° C., 0.17 g of p-toluic acid chloride was further added.

The mixture was stirred at room temperature for 1 hour, cooled, diluted hydrochloric acid was added, the mixture was filtered, and the solvent was distilled off. The crude crystals obtained were purified by silica gel column chromatography to give (E) -1-
0.34 g (yield 80%) of [4- (4-methylbenzoyloxy) phenyl] -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene was obtained.

NC ₃ H ₇ -Cy-CF = CF-Ph-OCO-Ph-CH ₃

[0184]

[Chemical 27]

Example 24A Pr prepared in the same manner as in Example 2 from I-Ph-O-Pr by lithiation of CH ₃ -Cy-Cl to synthesize CH ₃ -Cy-Li in the same manner as in Example 3. -O-Ph-CF = CF ₂ to react with CH ₃ -Cy
-CF = CF-Ph-O-Pr was synthesized and treated with acid, then Br-CH ₂ -P
is reacted with h-CH _3, it was synthesized _{CH 3 -Cy-CF = CF-} Ph-OCH 2 -Ph-CH 3.

[Example 24B] nC ₃ H ₇ O-Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li and reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give nC ₃ H ₇ O-Cy-Li. ₃ H ₇ O-Cy-CF = CF-Ph-O-Pr was synthesized, treated with an acid, and then reacted with Br-CH ₂ -Ph-CH ₃ , resulting in nC ₃ H ₇ O-Cy-CF = CF
The -Ph-OCH ₂ -Ph-CH ₃ were synthesized.

[Example 24C] Similar to Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-O-Pr was used in the same manner as in Example 2. N-reacted with Pr-O-Ph-CF = CF ₂ obtained in
After synthesizing C ₃ H ₇ -Cy-CF = CF-Ph-O-Pr and treating with acid,
Reacted with Br-CH ₂ -Ph-OCH ₃ , nC ₃ H ₇ -Cy-CF = CF-Ph-OCH
The ₂ -Ph-OCH ₃ were synthesized.

[Example 24D] In the same manner as in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-O-Pr was used in the same manner as in Example 2. N-reacted with Pr-O-Ph-CF = CF ₂ obtained in
After synthesizing C ₃ H ₇ -Cy-CF = CF-Ph-O-Pr and treating with acid,
Reaction with Br-CH ₂ -Ph-F, nC ₃ H ₇ -Cy-CF = CF-Ph-OCH _2-
Ph-F was synthesized.

[Example 24E] In the same manner as in Example 3, CH ₃ -Cy-Cl was lithiated to synthesize CH ₃ -Cy-Li, and Pr obtained from I-Ph-O-Pr in the same manner as in Example 2 was used. -O-Ph-CF = CF ₂ to react with CH ₃ -Cy
-CF = CF-Ph-O-Pr was synthesized and treated with acid, then ClCO-Ph-
Is reacted with CH _3, it was synthesized _{CH 3 -Cy-CF = CF-} Ph-OCO-Ph-CH 3.

[Example 24F] nC ₃ H ₇ O-Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li and reacted with Pr-O-Ph-CF = CF ₂ obtained from I-Ph-O-Pr in the same manner as in Example 2 to give nC ₃ H ₇ O-Cy-Li. ₃ H ₇ O-Cy-CF = CF-Ph-O-Pr was synthesized, treated with acid, and then reacted with ClCO-Ph-CH ₃ , resulting in nC ₃ H ₇ O-Cy-CF = CF-P.
It was synthesized _{h-OCO-Ph-CH 3} .

[Example 24G] In the same manner as in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-O-Pr was used in the same manner as in Example 2. N-reacted with Pr-O-Ph-CF = CF ₂ obtained in
After synthesizing C ₃ H ₇ -Cy-CF = CF-Ph-O-Pr and treating with acid,
Reacted with ClCO-Ph-OCH ₃ , nC ₃ H ₇ -Cy-CF = CF-Ph-OCO-P
h-OCH ₃ was synthesized.

[Example 24H] In the same manner as in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ph-O-Pr was used in the same manner as in Example 2. N-reacted with Pr-O-Ph-CF = CF ₂ obtained in
After synthesizing C ₃ H ₇ -Cy-CF = CF-Ph-O-Pr and treating with acid,
It is reacted with _{ClCO-Ph-F, nC 3} H 7 -Cy-CF = CF-Ph-OCO-Ph-
F was synthesized.

Example 25 Synthesis of (E) -1- (4-n-propyl-1-cyclohexen-1-yl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene : Example 4
1.22 g of 2- (4-n-propyl-1-cyclohexene) -1,1,2-trifluoroethylene instead of 2- (4-n-propylphenyl) -1,1,2-trifluoroethylene (5.98mmmol)
The reaction was carried out in the same manner as in Example 4 except that it was used, and (E) -1- (4-n-propyl-1-cyclohexen-1-yl) -2- (trans-4
1.09 g (yield 59%) of -n-propylcyclohexyl) -1,2-difluoroethylene was obtained. nC ₃ H ₇ -Cy-CF = CF-Ch-C ₃ H ₇ (n)

[0194]

[Chemical 28]

[Example 25A] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and I-Ch-C ₃ H ₇ (n) was used to prepare Example 2
Was reacted with nC ₃ H ₇ -Ch-CF = CF ₂ obtained in a similar manner to
₃ -Cy-CF = was synthesized _{CF-Ch-C 3 H 7} (n).

[Example 25B] In the same manner as in Example 3, C ₂ H ₅ -Cy-Cl was lithiated to synthesize C ₂ H ₅ -Cy-Li, and I-Ch-C ₃ H ₇ (n) was used to give Example 2.
It is reacted with _{nC 3 H 7 -Ch-CF =} CF 2 was obtained in the same manner as, C ₂
H ₅ -Cy-CF = was synthesized _{CF-Ch-C 3 H 7} (n).

[Example 25C] Lithiation of CF ₃ -Cy-Cl was performed in the same manner as in Example 3 to synthesize CF ₃ -Cy-Li, and I-Ch-C ₃ H ₇ (n) was used to prepare Example 2
Was reacted with nC ₃ H ₇ -Ch-CF = CF ₂ obtained in the same manner as in
₃ -Cy-CF = was synthesized _{CF-Ch-C 3 H 7} (n).

[Example 25D] nC ₃ H ₇ O-Cy-Cl was prepared in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li, and I-Ch-C ₃ H ₇ (n)
After reacted with _{nC 3 H 7 -Ch-CF =} CF 2 was obtained in the same manner as Example 2, it was synthesized _{nC 3 H 7 O-Cy-} CF = CF-Ch-C 3 H 7 (n) .

[Example 25E] In the same manner as in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ch-CH _{3 was used} to give Example 2.
It is reacted with CH ₃ -Ch-CF = CF ₂ was obtained in the same manner as, nC ₃
The _{H 7 -Cy-CF = CF-} Ch-CH 3 were synthesized.

[Example 25F] Similar to Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Ch-C ₄ H ₉ (n) was used to prepare Example 2 By reacting with nC ₄ H ₉ -Ch-CF = CF ₂ obtained in the same manner as described above, nC ₃ H ₇ -Cy-CF = CF-Ch-C ₄ H ₉ (n) was synthesized.

Example 26 Synthesis of (E) -1- (5-n-propylpyrimidin-2-yl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Example 4 2- (4-
Example 4 except that 1.20 g (5.94 mmol) of 2- (5-n-propylpyrimidine) -1,1,2-trifluoroethylene was used instead of n-propylphenyl) -1,1,2-trifluoroethylene. The reaction is performed in the same manner as in (E) -1- (5-n-propylpyrimidine-2
-Yl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene (1.27 g, yield 55%) was obtained. In addition, "-Py-" represents a pyrimidine-2,5-diyl group. nC ₃ H ₇ -Cy-CF = CF-Py-C ₃ H ₇ (n)

[0202]

[Chemical 29]

[Example 26A] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and I-Py-C ₃ H ₇ (n) was used to prepare Example 2
Was reacted with nC ₃ H ₇ -Py-CF = CF ₂ obtained in a similar manner to
₃ -Cy-CF = was synthesized _{CF-Py-C 3 H 7} (n).

[Example 26B] C ₂ H ₅ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize C ₂ H ₅ -Cy-Li, and I-Py-C ₃ H ₇ (n) was used to prepare Example 2
It is reacted with _{nC 3 H 7 -Py-CF =} CF 2 was obtained in the same manner as, C ₂
H ₅ -Cy-CF = was synthesized _{CF-Py-C 3 H 7} (n).

[Example 26C] CF ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CF ₃ -Cy-Li, and I-Py-C ₃ H ₇ (n) was used to give Example 2
Was reacted with nC ₃ H ₇ -Py-CF = CF ₂ obtained in a similar manner to
₃ -Cy-CF = was synthesized _{CF-Py-C 3 H 7} (n).

[Example 26D] nC ₃ H ₇ O-Cy-Cl was used in the same manner as in Example 3.
Was lithiated to synthesize nC ₃ H ₇ O-Cy-Li, and I-Py-C ₃ H ₇ (n)
From nC ₃ H ₇ -Py-CF = CF ₂ obtained in the same manner as in Example 2 to synthesize nC ₃ H ₇ O-Cy-CF = CF-Py-C ₃ H ₇ (n). .

[Example 26E] In the same manner as in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Py-CH _{3 was used} to give Example 2
Was reacted in the same manner as in CH ₃ -Py-CF = CF ₂ to give nC ₃
The _{H 7 -Cy-CF = CF-} Py-CH 3 were synthesized.

[Example 26F] Similar to Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Py-C ₄ H ₉ (n) was used to prepare Example 2 By reacting with nC ₄ H ₉ -Py-CF = CF ₂ obtained by the same method as described above, nC ₃ H ₇ -Cy-CF = CF-Py-C ₄ H ₉ (n) was synthesized.

Example 27 Synthesis of (E) -1- (5-n-propyldioxan-2-yl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene: Example 4 2- (4-
Example 4 except that 1.25 g (5.95 mmol) of 2- (5-n-propyldioxane) -1,1,2-trifluoroethylene was used instead of n-propylphenyl) -1,1,2-trifluoroethylene. The reaction is performed in the same manner as in (E) -1- (5-n-propyldioxane-2
-Yl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene (1.11 g, yield 59%) was obtained. In addition, "-Do-" represents a dioxane-2,5-diyl group. nC ₃ H ₇ -Cy-CF = CF-Do-C ₃ H ₇ (n)

[0210]

Embedded image

[Example 27A] CH ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CH ₃ -Cy-Li, and I-Do-C ₃ H ₇ (n) was used to prepare Example 2
Was reacted with nC ₃ H ₇ -Do-CF = CF ₂ obtained in the same manner as in
₃ -Cy-CF = CF-Do-C ₃ H ₇ (n) was synthesized.

[Example 27B] C ₂ H ₅ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize C ₂ H ₅ -Cy-Li, and I-Do-C ₃ H ₇ (n) was used to give Example 2
By reacting with nC ₃ H ₇ -Do-CF = CF ₂ obtained in the same manner as
C ₂ H ₅ -Cy-CF = CF-Do-C ₃ H ₇ (n) was synthesized.

[Example 27C] CF ₃ -Cy-Cl was lithiated in the same manner as in Example 3 to synthesize CF ₃ -Cy-Li, and I-Do-C ₃ H ₇ (n) was used to give Example 2
Was reacted with nC ₃ H ₇ -Do-CF = CF ₂ obtained in the same manner as in
₃ -Cy-CF = was synthesized _{CF-Py-C 3 H 7} (n).

[Example 27D] nC ₃ H ₇ O-Cy-Cl was prepared in the same manner as in Example 3.
Is synthesized to synthesize nC ₃ H ₇ O-Cy-Li, and I-Do-C ₃ H ₇ (n) is synthesized.
After reacted with _{nC 3 H 7 -Do-CF =} CF 2 was obtained in the same manner as Example 2, it was synthesized _{nC 3 H 7 O-Cy-} CF = CF-Do-C 3 H 7 (n) .

[Example 27E] In the same manner as in Example 3, nC ₃ H ₇ -Cy-Cl was lithiated to synthesize nC ₃ H ₇ -Cy-Li, and I-Do-CH _{3 was used} to give Example 2.
It is reacted with CH ₃ -Do-CF = CF ₂ was obtained in the same manner as, nC ₃
The _{H 7 -Cy-CF = CF-} Do-CH 3 were synthesized.

[Example 27F] nC ₃ H ₇ -Cy-Cl was prepared in the same manner as in Example 93.
Was reacted with nC ₄ H ₉ -Do-CF = CF ₂ obtained from I-Do-C ₄ H ₉ (n) in the same manner as in Example 2 by lithiation of nC ₃ H ₇ -Cy-Li. Then, nC ₃ H ₇ -Cy-CF = CF-Do-C ₄ H ₉ (n) was synthesized.

[0219]

Although all the reactions of the present invention are not always clear, they can be represented by the following formula.

[0218]

[Chemical 31]

According to this method, chlorotrifluoroethylene (1) which is easily available is used. The target compound (1) can be synthesized in a high yield in a short step. In addition, since the raw material chlorotrifluoroethylene (1) is an inexpensive compound,
It is also an economical method.

In the reaction between the compound (4) and the compound (5), substitution of the halogen moiety X ³ of the compound (4) occurs. In the reaction, compound (5) is lithiated to CF ₂ = CF ₂
As compared with the conventional method of reacting with, the halogen moiety is preferentially substituted, so that an asymmetric compound with respect to the double bond can be obtained in a high yield. Also, the method is an easy reaction and efficient.

Further, since the trans isomer of compound (8) is more stable than the cis isomer, the compound (8) obtained can be obtained regardless of whether the A ² portion of compound (7) is the cis isomer or the trans isomer. The main product of which is the trans isomer in the A ² portion. Therefore, there is also an advantage that an inexpensive mixture of cis and trans isomers can be used as the compound (7).

The present invention can be applied in various ways within the range of not impairing the effects of the present invention. Further, according to the production method of the present invention, there is an advantage that another compound can be produced by further subjecting the obtained compound to another reaction.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 39/42 43/192 43/225 C 7419-4H 69/62 9546-4H 69/66 9546- 4H 69/75 A 9546-4H C 9546-4H D 9546-4H 69/753 9546-4H 69/76 A 9546-4H Z 9546-4H 69/773 69/86 9546-4H 69/92 9546-4H 255 / 50 C07D 211/14 211/18 211/38 211/40 239/26 239/34 319/06 C09K 19/16 9279-4H 19/18 19/20 19/30 19/34 G02F 1/13 500

Claims (7)

[Claims] 1. A process for producing a trans-difluoroethylene derivative represented by the formula (1), which comprises reacting a compound represented by the formula (6) with a compound represented by the formula (8). R ^2- (A ⁴ ) _n -Y ² -A ³ -CF = CF ₂ (6) R ^1- (A ¹ ) _m -Y ¹ -A ² -Li (8) R ^1- (A ¹ ) _m- Y ¹ -A ² -CF = CF-A ³ -Y ^2- (A ⁴ ) _n -R ² (1) However, in the formulas (6), (8) and (1), A ¹ and A
² , A ³ , A ⁴ , R ¹ , R ² , Y ¹ , Y ² , n, and m have the following meanings. A ¹ and A ⁴ may be the same or different, and are trans-1,4-di-substituted cyclohexylene group and 1,4-
A di-substituted cyclohexenylene group or a 1,4-di-substituted phenylene group is shown. Each of these groups may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. Further, one or more CH in these groups may be substituted with a nitrogen atom. In addition, one of trans-1,4-di-substituted cyclohexylene group or 1,4-di-substituted cyclohexenylene group
Alternatively, two or more CH ₂ may be substituted with an oxygen atom or a sulfur atom. A ² : represents a trans-1,4-di-substituted cyclohexylene group. Each of the groups may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. Further, 1 or 2 or more CH in the group may be substituted with a nitrogen atom, and 1 or 2
One or more CH ₂ may be substituted with an oxygen atom or a sulfur atom. A ³ : represents a 1,4-di-substituted cyclohexenylene group or a 1,4-di-substituted phenylene group. Each of these groups may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. Further, one or two or more CH in the group may be substituted by a nitrogen atom, one or two or more CH ₂ may be substituted with an oxygen atom or a sulfur atom. R ¹ and R ² , which may be the same or different, each represents an alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a hydrogen atom, a hydroxyl group, or a hydroxyl group to which a protective group is bonded. In the case of an alkyl group, between carbon-carbon bonds,
Or between the carbon-carbon bond between the alkyl group and the ring group,
An oxygen atom may be inserted, part of the carbon-carbon bond of the alkyl group may be a double bond or a triple bond, and —CH ₂ — of the alkyl group may be substituted with a carbonyl group. Good. Further, some or all of the hydrogen atoms of the alkyl group may be replaced with fluorine atoms. Y ¹ and Y ² , which may be the same or different, are -COO-, -OCO-, -C≡C-, -CH ₂ CH _2- , -CH = CH-,-.
Indicates OCH _2- , -CH ₂ O-, or a single bond. n and m: 0 or 1 is shown, respectively. 2. A method for producing a compound represented by formula (8), which comprises reacting the compound represented by formula (7) with lithium metal. R ^1- (A ¹ ) _m -Y ¹ -A ² -X ³ (7) R ^1- (A ¹ ) _m -Y ¹ -A ² -Li (8) However, in the formulas (7) and (8) A ¹ , A ² , R ¹ ,
Y ¹ , X ³ and m have the following meanings. A ¹ : trans-1,4-di-substituted cyclohexylene group, 1,4-
A di-substituted cyclohexenylene group or a 1,4-di-substituted phenylene group is shown. Each of these groups may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. Further, one or more CH in these groups may be substituted with a nitrogen atom. In addition, one of trans-1,4-di-substituted cyclohexylene group or 1,4-di-substituted cyclohexenylene group
Alternatively, two or more CH ₂ may be substituted with an oxygen atom or a sulfur atom. A ² : represents a trans-1,4-di-substituted cyclohexylene group. Each of the groups may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. Further, 1 or 2 or more CH in the group may be substituted with a nitrogen atom, and 1 or 2
One or more CH ₂ may be substituted with an oxygen atom or a sulfur atom. R ¹ represents a C 1-10 alkyl group, a halogen atom, a cyano group, a hydrogen atom, a hydroxyl group, or a hydroxyl group to which a protective group is bonded. In the case of an alkyl group, an oxygen atom may be inserted between the carbon-carbon bond or between the carbon-carbon bond between the alkyl group and the ring group.
May have some of the carbon bond is a double bond or triple bond, also, -CH ₂ alkyl group - may be replaced by a carbonyl group. Further, some or all of the hydrogen atoms of the alkyl group may be replaced with fluorine atoms. Y ¹ : -COO-, -OCO-, -C≡C-, -CH ₂ CH _2- , -CH = CH-,
-OCH _2- , -CH ₂ O-, or a single bond is shown. X ^3: a chlorine atom, an iodine atom or a bromine atom. m: 0 or 1 is shown. 3. The method according to claim 2, wherein the reaction is carried out in the presence of an electron transfer agent. 4. The method according to claim 3, wherein the electron transfer agent is an aromatic hydrocarbon having two or more rings or an aromatic hydrocarbon having a condensed ring. 5. The electron transfer agent is naphthalene, biphenyl,
The production method according to claim 4, which is 2,6-di-t-butylnaphthalene, 2,7-di-t-butylnaphthalene, 4,4′-di-t-butylbiphenyl, or anthracene. 6. A compound represented by formula (3) is obtained by reacting chlorotrifluoroethylene (2) with alkyllithium, and the compound represented by formula (3) is reacted with bromine or iodine. And a compound represented by formula (4), and a compound represented by formula (4) is reacted with a compound represented by formula (5) to form a compound represented by formula (6). Wherein the compound represented by the formula (6) is reacted with a compound represented by the formula (8).
A method for producing a trans-difluoroethylene derivative represented by: CF ₂ = CFCl (2) CF ₂ = CFLi (3) CF ₂ = CFX ¹ (4) R ^2- (A ⁴ ) _n -Y ² -A ³ -X ² (5) R ^2- (A ⁴ ) _n -Y ² -A ³ -CF = CF ₂ (6) R ^1- (A ¹ ) _m -Y ¹ -A ² -Li (8) R ^1- (A ¹ ) _m -Y ¹ -A ² -CF = CF-A ³ -Y ^2- (A ⁴ ) _n -R ² (1) However, formulas (3), (4), (5), (6), (8),
And in (1), A ¹ , A ² , A ³ , A ⁴ , R
¹ , R ² , Y ¹ , Y ² , X ¹ , X ² , n, and m are
It has the following meanings. A ¹ and A ⁴ may be the same or different, and are trans-1,4-di-substituted cyclohexylene group and 1,4-
A di-substituted cyclohexenylene group or a 1,4-di-substituted phenylene group is shown. Each of these groups may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. Further, one or more CH in these groups may be substituted with a nitrogen atom. In addition, one of trans-1,4-di-substituted cyclohexylene group or 1,4-di-substituted cyclohexenylene group
Alternatively, two or more CH ₂ may be substituted with an oxygen atom or a sulfur atom. A ² : represents a trans-1,4-di-substituted cyclohexylene group. Each of the groups may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. Further, 1 or 2 or more CH in the group may be substituted with a nitrogen atom, and 1 or 2
One or more CH ₂ may be substituted with an oxygen atom or a sulfur atom. A ³ : represents a 1,4-di-substituted cyclohexenylene group or a 1,4-di-substituted phenylene group. Each of these groups may be unsubstituted or may have one or more halogen atoms or cyano groups as a substituent. Further, one or two or more CH in the group may be substituted by a nitrogen atom, one or two or more CH ₂ may be substituted with an oxygen atom or a sulfur atom. R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a hydrogen atom, a hydroxyl group, or a hydroxyl group to which a protective group is bonded. In the case of an alkyl group, an oxygen atom may be inserted between the carbon-carbon bond or between the carbon-carbon bond between the alkyl group and the ring group.
May have some of the carbon bond is a double bond or triple bond, also, -CH ₂ alkyl group - may be replaced by a carbonyl group. Further, some or all of the hydrogen atoms of the alkyl group may be replaced with fluorine atoms. Y ¹ and Y ² , which may be the same or different, are -COO-, -OCO-, -C≡C-, -CH ₂ CH _2- , -CH = CH-,-.
Indicates OCH _2- , -CH ₂ O-, or a single bond. X ¹ and X ² : may be the same or different and each represents a bromine atom or an iodine atom. n and m: 0 or 1 is shown, respectively. 7. The process according to claim 6, wherein a zinc and palladium catalyst are present in the reaction between the compound represented by formula (4) and the compound represented by formula (5).