JP5519955B2 - Process for producing fluorine-containing compound and intermediate - Google Patents

Description

  The present invention relates to a simple and efficient method for producing a fluorine-containing compound useful as a liquid crystal compound and an intermediate used therefor.

Liquid crystal elements include mobile devices such as mobile phones and PDAs, display devices for office automation equipment such as copiers and personal computer monitors, display devices for home appliances such as liquid crystal televisions, clocks, calculators, measuring instruments, automotive meters, It is used for applications such as cameras, and various performances such as a wide operating temperature range, a low operating voltage, high-speed response, and chemical stability are required.
In such a liquid crystal element, a material exhibiting a liquid crystal phase is used, but there is no compound that satisfies all of the above characteristics alone, and a liquid crystal compound or a non-liquid crystal compound having excellent characteristics has not been present. By mixing a plurality of liquid crystal compositions, a liquid crystal composition satisfying the required performance was obtained.

In addition, in various properties required for the compound used in the liquid crystal composition as described above, it has excellent compatibility with other liquid crystal materials or non-liquid crystal materials, is chemically stable, and is used for a liquid crystal element. In this case, it is important to have a high speed response over a wide temperature range and a low voltage drive.
In this regard, Patent Document 1 describes a method for producing a difluoromethyl ether derivative having a specific structure, and Patent Document 2 describes a method for producing a difluoromethyleneoxy derivative having a specific structure. Yes. These documents describe that by using these production methods, a difluoromethyl ether derivative or a difluoromethyleneoxy derivative can be produced easily and safely in a high yield.

JP 2002-053513 A JP 2004-269432 A

  However, the above method has problems such as a long number of steps, use of a toxic or corrosive reagent, and difficulty in scaling up.

An object of the present invention is to solve the above problems.
That is, an object of the present invention is to provide a highly versatile production method capable of easily and efficiently obtaining a compound useful as a functional material such as a liquid crystal material.
Another object of the present invention is to provide an intermediate useful in such a production method.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a target compound in a high yield by a production method in which an alkenyl derivative is used as a starting material, dihalodifluoromethane is added, and etherification is performed. I found out that The present invention can provide such a manufacturing method.
Moreover, this invention can provide the specific intermediate body (the compound represented by Formula (3) mentioned later) in such a manufacturing method.

This invention provides the manufacturing method of the compound represented by the following Formula (5-1) which has the following 1st process and 2nd process.
First step: A step of producing a compound represented by the following formula (3-1) by adding a compound represented by the following formula (2) to the compound represented by the following formula (1-1).
Second step: The compound represented by the following formula (5-1) is reacted with the compound represented by the following formula (4-1) in the presence of a base to the compound represented by the following formula (3-1). Manufacturing process.
R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CH = CHR ⁴ 1)
CF ₂ Br ₂ ... Formula (2)
R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CHX ¹ -CHR ⁴ -CF ₂ X ² ..Formula (3-1)
HO-Ph ^1- (Z ⁵ -A ⁵ ) _e- (Z ⁶ -A ⁶ ) _f -R ² Formula (4)
R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CH = CR ⁴ -CF ₂ O-Ph ¹ -(Z ⁵ -A ⁵ ) _e- (Z ⁶ -A ⁶ ) _f -R ²
... Formula (5-1)
Symbols in formulas (1-1) to (5-1) have the following meanings.
R ¹ and R ² : each independently a linear alkyl group having 2 to 5 carbon atoms or a fluorine atom.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ : 1,4 substituted with trans-1,4-cyclohexylene group, 1,4-phenylene group and one or two fluorine atoms A phenylene group.
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ : single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —.
Ph ¹ : 1,4-phenylene group which is unsubstituted or substituted with a halogen atom.
a, b, c, d, e and f: 0 or 1 independently of each other. However, a + b + c + d is 2, and e = f = 0.
X ¹ and X ² : a bromine atom.
R ⁴ : hydrogen atom.

The present invention also provides a compound represented by the following formula (3-1).
^{R 1 - (A 1 -Z 1} ) a - (A 2 -Z 2) b - (A 3 -Z 3) c - (A 4 -Z 4) d -CHX 1 -CHR 4 -CF 2 X 2 · ..Formula (3-1)
(The symbols in the formula have the following meanings.
R ¹ : a linear alkyl group having 2 to 5 carbon atoms.
A ¹ , A ² , A ³ and A ⁴ : trans-1,4-cyclohexylene group.
Z ¹ , Z ² , Z ³ and Z ⁴ : single bond.
a, b, c and d: 0 or 1 independently of each other. However, a + b + c + d is 2.
X ¹ and X ² : a bromine atom.
R ⁴ : hydrogen atom. )

ADVANTAGE OF THE INVENTION According to this invention, the versatile manufacturing method which can obtain a compound useful as functional materials, such as a liquid crystal material, simply and efficiently can be provided. The compound represented by the formula (5) obtained by the production method of the present invention is excellent in compatibility with other liquid crystal materials or non-liquid crystal materials, is chemically stable, and is used for a liquid crystal electro-optical element. In this case, it has excellent high-speed response over a wide temperature range and can be driven at a low voltage. In addition, by appropriately selecting a ring group, a substituent and a linking group constituting the compound, various performances required for the liquid crystal element, specifically, for example, a wide operating temperature range, a low operating voltage, a high-speed response. Liquid crystal composition satisfying the properties and chemical stability can be prepared.
In addition, the present invention can provide an intermediate useful in such a production method.

The present invention will be described.
Hereinafter, the compound represented by the formula (1) may be referred to as “compound (1)”, and the other compounds represented by the formulas (2) to (5) may also be described in the same manner.

<R ¹ and R ² >
In the compounds (1), (3), (4) and (5), R ¹ and R ² have the same meaning as described above. Moreover, the substitution of a fluorine atom and the substitution of an etheric oxygen atom or a thioetheric sulfur atom may be performed simultaneously on the aliphatic hydrocarbon group. Moreover, as an aliphatic hydrocarbon group, an alkyl group and an alkenyl group are preferable.

Hereinafter, an alkyl group substituted with at least one of an etheric oxygen atom, a thioetheric sulfur atom and a fluorine atom is referred to as a “substituted alkyl group”.
An alkenyl group substituted with at least one of an etheric oxygen atom, a thioetheric sulfur atom and a fluorine atom is referred to as a “substituted alkenyl group”.

Examples of the substituted alkyl group include an alkoxy group, an alkoxyalkyl group, an alkylthio group, an alkylthioalkyl group, a fluoroalkyl group, and a fluoroalkoxy group.
In addition, examples of the substituted alkenyl group include an alkenyloxy group, an alkenylthio group, and a fluoroalkenyl group.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the alkoxyalkyl group include a methoxymethyl group and an ethoxymethyl group.
Examples of the alkylthio group include a methylthio group, an ethylthio group, and a propylthio group.
Examples of the alkylthioalkyl group include a methylthiomethyl group and an ethylthiomethyl group.
Further, examples of the fluoroalkyl group include a trifluoromethyl group and a pentafluoroethyl group.
Further, examples of the fluoroalkoxy group include a trifluoromethoxy group and a difluoromethoxy group.
Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, a 3-butenyl group, and a 3-pentenyl group.
Moreover, an allyloxy group is mentioned as an alkenyloxy group.
Moreover, an allylthio group is mentioned as an alkenylthio group.
Examples of the fluoroalkenyl group include a 1,2,2-trifluorovinyl group.

Each of R ¹ and R ² is preferably a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, a substituted alkyl group, or a substituted alkenyl group, and a linear alkyl having 2 to 5 carbon atoms More preferably, it is a group or a fluorine atom.

^{<A 1 ,A 2 ,A 3 ,A 4} ,A 5 OyobiA ^6>
In the compound (1), the compound (3), the compound (4) and the compound (5), A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ have the same meaning as described above.

  Here, substitution of a halogen atom, a cyano group or an alkyl group having 1 to 10 carbon atoms and substitution of a nitrogen atom or an oxygen atom may be performed simultaneously on the same group.

In addition, the group in which one or more hydrogen atoms in the groups of A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are substituted is 1 substituted with 1 or 2 fluorine atoms. , 4-phenylene group.

Examples of the group in which one or two ═CH— groups present in the 1,4-phenylene group are substituted with nitrogen atoms include 2,5-pyrimidinylene groups and 2,5-pyridinylene groups. It is done.
In addition, one or two —CH ₂ — groups present in the trans-1,4-cyclohexylene group are 1, 3 as a group substituted with an etheric oxygen atom or an etheric sulfur atom. -Dioxane-2,5-diyl group and 1,3-dithian-2,5-diyl group are mentioned.

Each of A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ is substituted with a trans-1,4-cyclohexylene group, a 1,4-phenylene group and one or two fluorine atoms. A 1,4-phenylene group is preferred.

Here, these cyclic groups have bonds at the 1-position and 4-position.
In the present specification, the right side of the cyclic group is the 1st position and the left side is the 4th position. For example, A ¹ in the compound (1) is the 1st position on the side bonded to Z ¹ and the 4th position on the side bonded to R ¹ .

<Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ >
In the compounds (1), (3), (4) and (5), Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ have the same meaning as described above.

Here, the substitution of a fluorine atom and the substitution of an etheric oxygen atom or a thioetheric sulfur atom may be performed simultaneously on the same group.
Further, the aliphatic hydrocarbon group is preferably an alkylene group, an alkenylene group or an alkynylene group.
Examples of the alkylene group include — (CH ₂ ) ₂ — and — (CH ₂ ) ₄ —.
Examples of the alkenylene group include —CH═CH—, — (CH ₂ ) ₂ —CH═CH—, —CH ₂ —CH═CH—CH ₂ —, —CH═CH— (CH ₂ ) ₂ —. It is done.
Examples of the alkynylene group include —C≡C— and — (CH ₂ ) ₂ —C≡C—.
Examples of the alkylene group in which one or more hydrogen atoms in the group are substituted with fluorine atoms include —CHF—CHF—, — (CF ₂ ) ₂ —, and — (CH ₂ ) ₃ —CF ₂ —. .
Examples of the alkylene group in which one or more —CH ₂ — in the group is substituted with an etheric oxygen atom or a thioetheric sulfur atom include —CH ₂ O—, —OCH ₂ —, —CH ₂ S— and — SCH ₂ — may be mentioned.

Each of Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ is preferably a single bond, — (CH ₂ ) — or — (CF ₂ ) ₂ —.

<Ph ¹ >
In the compounds (4) and (5), Ph ¹ has the same meaning as described above.
As Ph ¹ , a 1,4-phenylene group which is unsubstituted or substituted with a halogen atom is preferable, and a 1,4-phenylene group which is substituted with a fluorine atom is particularly preferable.

<A, b, c, d, e and f>
In the compounds (1), (3), (4) and (5), a, b, c, d, e and f have the same meaning as described above.
Here, it is preferable that a + b + c + d is 2, and it is preferable that e = f = 0.

<Other symbols>
In the compound (2), X ¹ and X ² have the same meaning as described above. X ¹ and X ² are preferably bromine atoms from the viewpoint of reactivity.
In the compounds (1), (3) and (5), n represents the same meaning as described above, and is preferably 0.
In the compounds (1), (3) and (5), Ak has the same meaning as described above.
In the compounds (1), (3) and (5), R ³ and R ⁴ have the same meaning as described above. When n is 0, R ⁴ is preferably a hydrogen atom.

In compound (1), compound (3) and compound (5), when n is 1, R ³ and R ⁴ together form a ring, and a “CHR ³ -Ak—CH═CR ⁴ ” moiety Preferably forms a 4-membered ring or a 6-membered ring, and more preferably forms a 6-membered ring.
When n is 1, it is preferable that R ³ and R ⁴ jointly form a single bond, —CH ₂ — or — (CH ₂ ) ₂ —. Moreover, Ak is preferably a single bond or —CH ₂ —. In particular, when R ³ and R ⁴ jointly form a single bond and Ak is also a single bond, or R ³ and R ⁴ jointly form — (CH ₂ ) ₂ — and Ak forms —CH ₂ —. Is preferred.

In the production method of the present invention, n in the compound (1), the compound (3) and the compound (5) is preferably 0.
That is, in the present invention, the compound represented by the formula (1) is a compound represented by the following formula (1-1), and the compound represented by the formula (3) is represented by the following formula (3-1): It is preferable that it is a manufacturing method which is a compound represented by these, and the compound represented by the said Formula (5) is a compound represented by the following Formula (5-1).

R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CH = CHR ⁴ 1)
R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CHX ¹ -CHR ⁴ -CF ₂ X ² ..Formula (3-1)
R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CH = CR ⁴ -CF ₂ O-Ph ¹ -(Z ⁵ -A ⁵ ) _e- (Z ⁶ -A ⁶ ) _f -R ² ... Formula (5-1)

  The symbols in Formula (1-1), Formula (3-1), and Formula (5-1) are common to the symbols in Formula (1) to Formula (5) described above, and the same symbols are the same. Means content.

Even when n is 1, it is preferable that the CHR ³ —Ak—CH═CR ⁴ moiety in the compounds (1), (3) and (5) has a structure in which a 6-membered ring is formed.
That is, in the present invention, the compound represented by the formula (1) is a compound represented by the following formula (1-2), and the compound represented by the formula (3) is represented by the following formula (3-2): It is more preferable that the compound represented by formula (5) is a production method in which the compound represented by the formula (5) is a compound represented by the following formula (5-2).

  The symbols in Formula (1-2), Formula (3-2), and Formula (5-2) are the same as those in Formulas (1) to (5) described above, and the same symbols are the same. Means content.

Next, a 1st process and a 2nd process provided with the manufacturing method of this invention are demonstrated.
In the following, N, N-dimethylformamide may be referred to as “DMF”, tetrahydrofuran as “THF”, and dimethyl sulfoxide as “DMSO”.

<First step>
In the production method of the present invention, the first step is a step of producing the compound (3) by adding the compound (2) to the compound (1).
Here, the starting compound (1) is also available as a commercial product. Moreover, it can obtain by the method described in the literature of organic synthesis, such as literatures, such as Unexamined-Japanese-Patent No. 08-170078, Unexamined-Japanese-Patent No. 10-114690, New Experimental Chemistry Course (Maruzen Co., Ltd. publication). it can.
Compound (2) is also commercially available from Sigma-Aldrich.

  The reaction conditions in the first step can be carried out by mixing the compound (1), the compound (2) and the radical initiator in the absence of solvent or in a solvent.

  As the solvent, water, aromatic compounds, aliphatic hydrocarbons, alicyclic hydrocarbons, aliphatic ether compounds, cyclic ether compounds, aprotic polar solvents, protic polar solvents, halogen atomized hydrocarbons may be used. desirable. For example, as the aromatic compound, benzene, toluene, chlorobenzene, and bromobenzene are preferable. As the aliphatic hydrocarbon, hexane and heptane are preferable. As the alicyclic hydrocarbon, cyclohexane is preferable. As the aliphatic ether compound, diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether are preferable. As the cyclic ether compound, THF and dioxane are preferable. As the aprotic polar solvent, DMF, DMSO, and acetonitrile are preferable. As the protic polar solvent, methyl alcohol, ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, and n-butyl alcohol are preferable. As the halogen atomized hydrocarbon, dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane are preferable. The reaction can also be carried out by mixing the solvent. More preferred reaction solvents are aromatic compounds, aliphatic hydrocarbons, alicyclic hydrocarbons, aliphatic ether compounds, and cyclic ether compounds that can be easily distilled off under reduced pressure.

About the usage-amount of a solvent, what is necessary is just the quantity which can implement reaction safely and stably. Preferably it is the range of 0-20 times amount by mass with respect to compound (1).
The reaction temperature should just be temperature which can stir favorably. Although it depends on the structure of the compound, the range of -40 ° C to 80 ° C is preferred. A more preferable reaction temperature is in the range of −40 ° C. to 80 ° C. which can suppress the decomposition of —CF ₂ — of the compound (1) as a raw material or the compound (3) as a product and can improve the conversion rate. is there.

  As for the usage-amount of a compound (2), an equivalent or more is preferable with respect to a compound (1), More preferably, it exists in the range of 1.05-6.5 equivalent.

As the radical initiator, azo compounds, borane compounds, and inorganic salts can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 4,4′-azobis (4-cyanopentanoic acid), triethylborane and sodium dithionite are preferred.
The amount of the azo compound added is preferably 0.01 equivalent or more with respect to the compound (1). More preferably, it is the range of 0.01-1.5 equivalent with respect to compound (1).

<Second step>
Next, the second step will be described.
In the production method of the present invention, the second step is a step of reacting compound (3) with compound (4) in the presence of a base to produce compound (5), that is, a step of etherification.

  Compound (4) used for the etherification reaction is commercially available from Sigma-Aldrich. In addition, R.A. L. Kidwell et al. (Org. Syn., Coll. Vol., 5,918 (1973)), methods described in JP-A-3-246244, JP-A-62-207229, and experimental chemistry course (Maruzen) The compound (4) can also be produced by referring to, for example, Publishing Co., Ltd.).

The etherification reaction of the second step can be carried out under generally known reaction conditions.
As the base that can be used in the etherification reaction, alkali metal hydroxides, alkali metal carbonates, metal alkoxides, alkali metal hydrides, metal oxides such as silver oxide, and amines are preferable. For example, the alkali metal hydroxide is preferably potassium hydroxide or sodium hydroxide. For example, as the alkali metal carbonate, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, and cesium carbonate are preferable. For example, as the metal alkoxide, sodium methoxide, sodium ethoxide, and potassium tert-butoxide are preferable. For example, sodium hydride is preferable as the alkali metal hydride. For example, diethylamine and triethylamine are preferable as the metal oxide. More preferred are alkali metal hydroxides and alkali metal carbonates that are easy to handle.

  Moreover, it is preferable that it is 2 equivalent or more about the usage-amount of a base, and it is more preferable that it is 2-5 equivalent with respect to a compound (3). There exists a tendency for the conversion of reaction to improve that it is 2 equivalents or more.

  As the reaction solvent, any ordinary solvent can be used as long as it does not react with any of the compound (3), the base, and the compound (4). For example, aromatic compounds, aliphatic hydrocarbons, alicyclic hydrocarbons, aliphatic ether compounds, cyclic ether compounds, aprotic polar solvents, and water can be used as preferred examples of the reaction solvent. Further, for example, as the aromatic compound, benzene and toluene are preferable. As the aliphatic hydrocarbon, hexane and heptane are preferable. As the alicyclic hydrocarbon, cyclohexane is preferable. As the aliphatic ether compound, diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether are preferable. As the cyclic ether compound, THF and dioxane are preferable. As the aprotic polar solvent, DMF, DMSO, acetonitrile, and 1-methyl-2-pyrrolidinone are preferable. The etherification reaction can also be carried out by mixing the solvent. More preferred reaction solvents are aromatic compounds, cyclic ether compounds, and aprotic polar solvents having a relatively high boiling point that can increase the reaction rate and complete the reaction in a short time.

  About the usage-amount of a solvent, what is necessary is just the quantity which can implement reaction safely and stably. Preferably it is the range of 5-20 times amount by mass with respect to compound (3).

The reaction temperature is preferably in the range of room temperature to 200 ° C. More preferably, it is in the range of 80 ° C. to 130 ° C. which can suppress the decomposition of the —CF ₂ — group of the compound (3) and the product compound (5) and can improve the conversion rate.

  The reaction time largely depends on the kind of the compound (3) and the reaction temperature, but is preferably 1 to 10 hours when carried out in the range of 80 to 130 ° C.

  In the etherification reaction in the second step, the reaction rate can be improved by adding a halide salt or a quaternary ammonium salt. As the halide salt, potassium bromide and potassium iodide are preferred. As the quaternary ammonium salt, a tetraalkyl group ammonium halide and a tetraalkyl group ammonium tetrafluoroborate are preferable. The amount of the halogenated salt or quaternary ammonium salt used is preferably 0.03 equivalent or more relative to the compound (3). More preferably, it is the range of 0.05-0.3 equivalent with respect to compound (3).

  Hereinafter, the present invention will be described more specifically with reference to examples. The following examples are intended to illustrate the present invention without limiting the present invention.

1- (2-trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1,1-difluoropropoxy) -3,4,5-trifluorobenzene was prepared. This compound is compound (5) in which a = b = 1, c = d = e = f = 0, R ¹ is an n-propyl group, A ¹ and A ² are all trans-1,4-cyclo This corresponds to a compound in which a xylene group, Z ¹ and Z ² are all single bonds, Ph ¹ is a 2,6-difluoro-1,4-phenylene group, and R ² is a fluorine atom.

[First step]
1- (2-trans-4- (trans-4-propylcyclohexyl) cyclohexyl) ethylene 23 g (98 mmol) synthesized by a known method, triethylborane (manufactured by Wako Pure Chemical Industries, Ltd.) 50 ml of a 1.0 mol / l THF solution, 34 g (162 mmol) of dibromodifluoromethane (Sigma Aldrich) was added, and oxygen was passed through the solution while cooling with ice. Then, 20 g (95 mmol) of difluorobromomethane was added every half day. This completed the reaction in 2 days.
Thereafter, 100 ml of water was added to stop the reaction, normal post-treatment was performed, and the extract was concentrated under reduced pressure to obtain 1,3-dibromo-1,1-difluoro-3- (trans-4- (trans-4- (4) 24 g of propylcyclohexyl) cyclohexyl) propane were obtained. The yield was 61%.

[Second step]
24 g (54.90 mmol) of 1,3-dibromo-1,1-difluoro-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propane obtained in the first step, potassium carbonate (manufactured by Nippon Soda Co., Ltd.) ) 22.76 g (164.71 g), 3,4,5-trifluorophenol (manufactured by Sigma-Aldrich) (8.94 g (60.39 mmol)) and 110 ml of DMF were stirred at 110 ° C. for 3 hours. After cooling, extraction was performed twice with 100 ml of hexane, and normal post-treatment was performed. As a result, 32 g of a crude product was obtained. By purifying this by silica gel column chromatography using a developing solvent hexane, 1- (2-trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1,1-difluoropropoxy) -3,4 Thus, 15 g (37.2 mmol) of 5-trifluorobenzene was obtained. The yield was 68%.

In addition, the measurement result of various spectrum data strongly supported the structure of the corresponding compound.
1H NMR (CDCl3, [delta]): 6.80 (m, 2H, Ar), 6.25 (m, 1H, vinyl), 5.52 (m, 1H, vinyl), 2.0-0.7 (br , 27H).
¹⁹ F NMR (CDCl ₃ , δ): −67.84 (d, 2F, CF ₂ O), −133.56 (m, 2F, Ar), −164.88 (m, 1F, Ar).

Claims (2)

The manufacturing method of the compound represented by the following Formula (5-1) which has the following 1st process and 2nd process.
First step: A step of producing a compound represented by the following formula (3-1) by adding a compound represented by the following formula (2) to the compound represented by the following formula (1-1).
Second step: The compound represented by the following formula (5-1) is reacted with the compound represented by the following formula (4-1) in the presence of a base to the compound represented by the following formula (3-1). Manufacturing process.
R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CH = CHR ⁴ 1)
CF ₂ Br ₂ ... Formula (2)
R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CHX ¹ -CHR ⁴ -CF ₂ X ² ..Formula (3-1)
HO-Ph ^1- (Z ⁵ -A ⁵ ) _e- (Z ⁶ -A ⁶ ) _f -R ² Formula (4)
R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CH = CR ⁴ -CF ₂ O-Ph ¹ -(Z ⁵ -A ⁵ ) _e- (Z ⁶ -A ⁶ ) _f -R ²
... Formula (5-1)
Symbols in formulas (1-1) to (5-1) have the following meanings.
R ¹ and R ² : each independently a linear alkyl group having 2 to 5 carbon atoms or a fluorine atom.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ : independently of each other, trans-1,4-cyclohexylene group, 1,4-phenylene group and one or two fluorine atoms A substituted 1,4-phenylene group;
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ : independently of each other, a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —.
Ph ¹ : 1,4-phenylene group which is unsubstituted or substituted with a halogen atom.
a, b, c, d, e and f: 0 or 1 independently of each other. However, a + b + c + d is 2, and e = f = 0.
X ¹ and X ² : a bromine atom.
R ⁴ : hydrogen atom. A compound represented by the following formula (3-1).
R ^1- (A ¹ -Z ¹ ) _a- (A ² -Z ² ) _b- (A ³ -Z ³ ) _c- (A ⁴ -Z ⁴ ) _d -CHX ¹ -CHR ⁴ -CF ₂ X ² ..Formula (3-1)
(The symbols in the formula have the following meanings.
R ^1: linear alkyl group having a carbon number of 2-5.
A ¹ , A ² , A ³ and A ⁴ : trans-1,4-cyclohexylene group.
Z ^1, Z ^2, Z ³ and Z ^4: single binding.
a , b, c and d: 0 or 1 independently of each other. However, a + b + c + d is 2.
X ¹ and X ² : a bromine atom.
R ⁴ : hydrogen atom. )