JP2012236807A - Compound having fluorinated oxabicyclo nonane structure and liquid crystal composition thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composition and a display element having negative dielectric anisotropy (Δε) of a large absolute value and being excellent in chemical stability, and to provide a compound having negative Δε of a large absolute value and being excellent in chemical stability.SOLUTION: A fluorinated oxabicyclo nonane derivative represented by general formula (I), a liquid crystal composition including the derivative, and a display element using the liquid crystal composition are provided. The liquid crystal composition has the negative Δε of a large absolute value, and is excellently chemically stable, and the liquid crystal display element using the composition is useful for a VA mode, an IPS mode, a PSA mode and the like.

Description

  The present invention relates to a fluorinated oxabicyclononane derivative useful as an electro-optical liquid crystal display material, a liquid crystal composition containing the same, and a liquid crystal display device using the same.

  Liquid crystal display elements are currently widely used because of their excellent features such as low voltage operation and thin display. There are many display methods for liquid crystal display elements, but the VA method (Vertical Alignment) or IPS method (In-Plane-Switching) is used for large panels such as LCD TVs that require high-quality images. PSA method (Polymer-Sustained Alignment) has been put into practical use. A liquid crystal composition having a negative dielectric anisotropy (Δε) value is used for the VA method and the PSA method, and a liquid crystal composition having a positive or negative value for Δε is used for the IPS method. As described above, the VA method, IPS method, and PSA method, which are effective display methods for obtaining a high-quality image, require a liquid crystal compound and a liquid crystal composition having a negative Δε value, and are strongly demanded. ing.

  Conventionally, a compound having a 2,3-difluorophenylene group (see Patent Document 1) has been mainly used as a component of a liquid crystal composition having a negative Δε. However, a liquid crystal composition using this compound has a problem that the absolute value of Δε is not sufficiently large (see Patent Document 2).

  In addition, a compound having a 2,2-difluorobicyclo [2.2.2] octane-1,4-diyl group (see Patent Document 3), 2,2,3,3-tetrafluorobicyclo [2.2.2] octane- A compound having a 1,4-diyl group has also been developed (see Patent Document 4), but the absolute value of Δε is not sufficiently large, and in addition, 2,2-difluorobicyclo [2.2.2] octane-1,4- The compound having a diyl group has a problem in chemical stability.

  As described above, there has been a strong demand for a compound having a negative Δε, a sufficiently large absolute value, and excellent chemical stability.

JP-T-2-503441 JP-A-10-176167 JP 2010-202542 A JP 2010-215524 A

  Providing a compound having a negative Δε, a large absolute value, and excellent chemical stability, and a Δε containing the compound, a negative, a large absolute value, and a chemical stability. It is to provide an excellent liquid crystal composition and a display element.

  As a result of studying a fluorinated oxabicyclononane derivative, a nematic liquid crystal composition and a display element using the fluorinated oxabicyclononane derivative, the present inventor has completed the present invention.

  The present invention relates to the general formula (I)

(Wherein Z represents the general formula (II)

(In the formula, one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently substituted with —O— or —S—, and Two or more hydrogen atoms may be independently substituted with fluorine atoms).
R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. group (one -CH in each group ₂ - or not adjacent two or more -CH ₂ - -O is independently -, - S -, - CO -, - COO- or -OCO- in And may be substituted, and one —CH ₂ — or two or more hydrogen atoms that are not adjacent to each other may be independently substituted with a fluorine atom.
A ¹ and A ² are each independently trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5. -Diyl group, bicyclo [2.2.2] octane-1,4-diyl group, or 1,4-phenylene group (one or more hydrogen atoms in each group are independently substituted with fluorine atoms or chlorine atoms) Which may have been
X ¹ and X ² are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —C ₄ H ₈ —, —COO—, —OCO—, —CH═. CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, —SCH ₂ —, —CH ₂ S—, —CSO—, —OCS—, —CF ₂ S -, - SCF ₂ -, or represents -C≡C-,
m and n are each independently 0, 1, 2 or 3 (m + n is 0, ¹ , 2 or 3, and when there are a plurality of A ¹ , A ² , X ¹ and / or X ² , They may be the same or different. And a liquid crystal composition and a liquid crystal display device containing the same are also provided.

  The fluorinated oxabicyclononane derivative of the present invention has a negative Δε, a large absolute value, excellent chemical stability, and the composition of a liquid crystal composition used for VA mode, IPS mode, PSA mode, etc. It is useful as a member. In addition, the liquid crystal composition of the present invention has a negative Δε and a large absolute value, and is excellent in chemical stability, and a display element using this is a liquid crystal display element such as a VA mode, an IPS mode, and a PSA mode. Useful.

  In the general formula (I), the group represented by the general formula (II) is

In the case where importance is attached to the chemical stability and the absolute value of Δε, the group represented by the formula (II-1) is preferable, and in the case where importance is attached to the ease of production, the formula (II-1) or the formula The group represented by (II-3) is preferred.

R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. A group (one or more hydrogen atoms in each group may be independently substituted with fluorine atoms, and one —CH ₂ — or two or more —CH— _2- represents independently substituted with -O-, -S-, -CO-, -COO- or -OCO-, but represents an alkyl group having 1 to 7 carbon atoms, a carbon atom An alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms. An alkoxy group having 1 to 5 carbon atoms or charcoal More preferably alkenyloxy group having the number of atoms of 2 to 5, is preferably linear.

A ¹ and A ² are each independently trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5. -Diyl group, bicyclo [2.2.2] octane-1,4-diyl group or 1,4-phenylene group (one or more hydrogen atoms in each group are independently substituted with fluorine atoms) A trans-1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, or a 1,4-phenylene group (one or more in each group). Are preferably independently substituted with fluorine atoms.), Preferably a trans-1,4-cyclohexylene group or unsubstituted or one or more hydrogen atoms independently substituted with fluorine atoms 1,4-phenylene group More preferably, trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group or 2,3-difluoro-1, A 4-phenylene group is preferred.

X ¹ and X ² are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —C ₄ H ₈ —, —COO—, —OCO—, —CH═. CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, —SCH ₂ —, —CH ₂ S—, —CSO—, —OCS—, —CF ₂ S —, —SCF ₂ — or —C≡C—, but a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —CF ₂ O—, —OCF ₂ — or —CF ₂ CF ₂ - is preferable, a single _{bond, -OCH 2 -, - CH 2} O- or _-C 2 _{H 4} - is more preferable.

  In general formula (I), the heteroatoms are not directly bonded to each other.

  Specific examples of preferred compounds are shown below, but the present invention is not limited thereto.

(R ^a and R ^b are each independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms. Represents an oxy group.)
(Production Method 1) General formula (III) that can be synthesized according to the synthesis method described in Patent Document 3.

^{(Wherein, R 1, A 1, X} 1 and m each represent the same meaning as R ^1, A ^1, X ¹ and m in formula (I), Z ¹ is the general formula (IV)

(In the formula, for —CH ₂ — other than those adjacent to the carbonyl group, one —CH ₂ — or two or more —CH ₂ — not adjacent to each other is substituted with —O— or —S—. And one or more hydrogen atoms in the group may be each independently substituted with a fluorine atom. ) And a general formula (V)

(Wherein R ² , A ² , X ² and n each represent the same meaning as R ² , A ² , X ² and n in formula (I), Y represents a chlorine atom, bromine atom, iodine atom, A benzenesulfonyloxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a leaving group such as trifluoromethanesulfonyloxy group). (VI)

(In the formula, R ¹ , R ² , A ¹ , A ² , X ¹ , X ² , m and n are R ¹ , R ² , A ¹ , A ² , X ¹ , X ² in the general formula (I), respectively. , M and n have the same meaning, and Z ² represents the formula (VII)

(In the formula, for —CH ₂ — other than those adjacent to the carbonyl group, one —CH ₂ — or two or more —CH ₂ — not adjacent to each other is substituted with —O— or —S—. And one or more hydrogen atoms in the group may be independently substituted with fluorine atoms). Can be obtained.

  Preferred as bases are metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates and organic bases, among which alkali metal carbonates, alkali metal phosphates, alkali metal hydroxides and organic bases. Is preferred. As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are preferable, as the alkali metal carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate are preferable, and as the metal phosphate, sodium phosphate, Sodium hydrogen phosphate, potassium phosphate and potassium hydrogen phosphate are preferred, and organic bases include triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, pyridine, 2,3-lutidine 2,4-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 2,4,6-collidine, 3,5,6-collidine, 4-dimethylaminopyridine, 1,5 -Diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, N, N, N ', N', N ''-pentamethylguanidine, 1,5 , 7-G Azabicyclo [4.4.0] dec-5-ene, and the like. Among them, 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] undec-7-ene are preferable, and 1,8-diazabicyclo [5.4.0] undec-7 is particularly preferable. -En is more preferred. These organic bases can be used alone or in combination.

  Y is a leaving group, and examples thereof include a bromine atom, an iodine atom and a trifluoromethanesulfonyloxy group, and a bromine atom and a trifluoromethanesulfonyloxy group are more preferable.

  At this time, any solvent can be used as long as it allows the reaction to proceed appropriately. Ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used. As the ether solvent, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether and the like are preferable. As the chlorine solvent, dichloromethane, 1,2-dichloroethane, carbon tetrachloride and the like are used. Preferably, the hydrocarbon solvent is preferably pentane, hexane, cyclohexane, heptane and octane, the aromatic solvent is preferably benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, and the polar solvent is N, N -Dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and the like are preferable. Of these, polar solvents such as tetrahydrofuran and N, N-dimethylformamide and N, N-dimethylacetamide are more preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, but is preferably from -20 ° C to 120 ° C.

  The resulting ketone derivative represented by general formula (VI) is oxidized to give general formula (VIII)

(In the formula, R ¹ , R ² , A ¹ , A ² , X ¹ , X ² , m and n are R ¹ , R ² , A ¹ , A ² , X ¹ , X ² in the general formula (I), respectively. , M and n have the same meaning, and Z ³ represents the general formula (IX)

(In the formula, for —CH ₂ — other than those adjacent to the carbonyl group, one —CH ₂ — or two or more —CH ₂ — not adjacent to each other is substituted with —O— or —S—. And one or more hydrogen atoms in the group may be independently substituted with fluorine atoms). A lactone derivative represented by
As the oxidation method, a method using hydrogen peroxide, performic acid, peracetic acid, trifluoroperacetic acid, o-sulfoperbenzoic acid, perphthalic acid, m-chloroperbenzoic acid (mCPBA) or the like is preferable. Chloroperbenzoic acid (mCPBA) is particularly preferred.

  At this time, any solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents, chlorine solvents, hydrocarbon solvents, polar solvents, and the like can be preferably used. As the ether solvent, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether and the like are preferable. As the chlorine solvent, dichloromethane, 1,2-dichloroethane, carbon tetrachloride and the like are used. Preferred examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, heptane, and octane, and examples of the polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, and acetic acid. And water are preferred. Among these, polar solvents such as acetic acid are more preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, but is preferably from -20 ° C to 180 ° C.

  The resulting lactone derivative represented by the general formula (VIII) is enolated with a base and then alkylated to give the general formula (X)

(In the formula, R ¹ , R ² , A ¹ , A ² , X ¹ , X ² , m and n are R ¹ , R ² , A ¹ , A ² , X ¹ , X ² in the general formula (I), respectively. , M and n have the same meaning, and Z ⁴ represents the general formula (XI)

(Wherein R ³ represents an alkyl group having 1 to 5 carbon atoms, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O— or —S—. And at least one hydrogen atom in the group may be independently substituted with a fluorine atom.). Can be obtained.

  As the base, metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates and organic bases are preferred, among which alkali metal carbonates, alkali metal phosphates, alkali metal hydroxides and Organic bases are preferred. As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are preferable, as the alkali metal carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate are preferable, and as the metal phosphate, sodium phosphate, Sodium hydrogen phosphate, potassium phosphate and potassium hydrogen phosphate are preferred, and organic bases include triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, pyridine, 2,3-lutidine 2,4-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 2,4,6-collidine, 3,5,6-collidine, 4-dimethylaminopyridine, 1,5 -Diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, N, N, N ', N', N ''-pentamethylguanidine, 1,5 , 7-G Azabicyclo [4.4.0] dec-5-ene, and the like. Of these, metal hydrides are preferable, and sodium hydride is more preferable. These bases can be used alone or in combination. Alkylating agents include alkyl halides such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide and ethyl iodide, and dialkyl esters such as dimethyl sulfate, diethyl sulfate, dimethyl carbonate and diethyl carbonate. And the like. Among these, methyl iodide and dimethyl sulfate are preferable, and dimethyl sulfate is more preferable.

  At this time, any solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents, chlorine solvents, hydrocarbon solvents, polar solvents, and the like can be preferably used. As the ether solvent, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether and the like are preferable. As the chlorine solvent, dichloromethane, 1,2-dichloroethane, carbon tetrachloride and the like are used. Preferably, the hydrocarbon solvent is preferably pentane, hexane, cyclohexane, heptane, octane, etc., and the polar solvent is N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, etc. preferable. Among these, polar solvents such as N, N-dimethylformamide are more preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, but is preferably from -20 ° C to 120 ° C.

  By fluorinating the enol ether derivative represented by the general formula (X), the general formula (XII)

(In the formula, R ¹ , R ² , A ¹ , A ² , X ¹ , X ² , m and n are R ¹ , R ² , A ¹ , A ² , X ¹ , X ² in the general formula (I), respectively. , M and n have the same meaning, and Z ⁵ represents the general formula (XIII)

(In the formula, one —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently substituted with —O— or —S—, and one or more in the group The hydrogen atom of may be independently substituted with a fluorine atom. ) Can be obtained.

  Fluorinating agents include tetrafluoroboric acid N-fluoropyridinium salt, trifluoromethanesulfonic acid N-fluoropyridinium salt, tetrafluoroboric acid N-fluoro-2,6-dichloropyridinium salt, trifluoromethanesulfonic acid N- Fluoro-2,6-dichloropyridinium salt, tetrafluoroborate N-fluoro-2,4,6-trimethylpyridinium salt, trifluoromethanesulfonic acid N-fluoro-2,4,6-trimethylpyridinium salt, bis (four Fluoroboric acid) N, N'-difluoro-2,2'-bipyridinium salt, N-fluoro-4,6-dimethylpyridinium-2-sulfonate, N-fluoro-4-methylpyridinium-2-sulfonate, N- Fluoro-5-trifluoromethylpyridinium-2-sulfonato, N-fluoro-6-trifluoromethylpyridinium-2-sulfonato, N-fluoro-4,6-bis (trifluoromethyl) pyridinium-2-sulfate Fluoropyridinium salts such as rufonato, trifluorotetraalkylammonium salts such as bistetrafluoroboric acid 1-chloromethyl-4-fluoro-1,2-diazoniabicyclo [2.2.2] octane salt, N-fluorobenzenesulfonamide And the like.

  At this time, any solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents, chlorine solvents, hydrocarbon solvents, polar solvents, and the like can be preferably used. As the ether solvent, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether and the like are preferable. As the chlorine solvent, dichloromethane, 1,2-dichloroethane, carbon tetrachloride and the like are used. Preferred examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, heptane and octane, and examples of the polar solvent include acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane. Etc. are preferred. Of these, acetonitrile and 1,2-dichloroethane are preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  The reaction temperature can be within the range from the freezing point of the solvent to the reflux temperature.

  The fluorinated oxabicyclononane derivative represented by the general formula (I) can be obtained by further fluorinating the obtained difluorolactone derivative represented by the general formula (XII).

Fluorinating agents include fluorine gas (F ₂ ), sulfur tetrafluoride, diethylaminosulfur trifluoride (DAST), 2,2-difluoro-1,3-dimethylimidazolidine (DFI), bis (2-methoxyethyl) amino Sulfur trifluoride, iodine pentafluoride (IF ₅ ) and pyridinium poly (hydrogen fluoride) are preferred, but sulfur tetrafluoride and diethylaminosulfur trifluoride (DAST), bis (2-methoxyethyl) aminosulfur trifluoride Is particularly preferred.

  At this time, any solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents, chlorine solvents, hydrocarbon solvents, polar solvents, and the like can be preferably used. As the ether solvent, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether and the like are preferable. As the chlorine solvent, dichloromethane, 1,2-dichloroethane, carbon tetrachloride and the like are used. Preferred examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, heptane, and octane, and examples of the polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane. preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  The reaction temperature can be within the range from the freezing point of the solvent to the reflux temperature.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples.

  The phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC). The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), infrared resonance spectrum (IR), mass spectrum (MS) and the like.

In the following examples and comparative examples, “%” means “mass%”.
Example 1 5-Ethoxy-3,3,4,4-tetrafluoro-1- (4-propylphenyl) -2-oxa-bicyclo [3.2.2] nonane (Ia)

(1-1) While 1 and ethyl acrylate were dissolved in tetrahydrofuran at room temperature, a tetrahydrofuran solution of potassium t-butoxide was added dropwise, followed by stirring for 3 hours. After terminating the reaction with hydrochloric acid, the mixture was extracted with dichloromethane, washed with water and saturated brine, and the organic solvent was distilled off. The obtained yellow liquid was dissolved in a mixed solution of dimethyl sulfoxide and brine and stirred at 150 ° C. for 2 hours. After the heating was finished, extraction with toluene, washing with water and saturated brine, and the organic solvent was distilled off. Purification by column chromatography yielded 2.
(1-2) 2 and ethylene glycol and a catalytic amount of p-tosylic acid were dissolved in toluene and heated to reflux. After completion of the reaction, a sodium hydrogen carbonate solution was added, extracted with toluene, and washed with water and saturated brine. The organic solvent was distilled off and purified by column chromatography to give 3.
(1-3) Tetrahydrofuran solution of [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride in a tetrahydrofuran solution of propylzinc bromide 3 at a rate that keeps the temperature below 30 ° C Was added dropwise and stirred at room temperature for 5 hours. After confirming the completion of the reaction, filtration was performed, and saturated saline was added to the filtrate. The organic layers were separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 4.
(1-4) While a mixed solvent of methyllithium in diethoxyethane / tetrahydrofuran was cooled at −70 ° C., a tetrahydrofuran solution of 4 was added dropwise. After slowly raising the temperature to 0 ° C., 10% hydrochloric acid was added to make the reaction solution acidic. The reaction solution was raised to 60 ° C. and reacted for 3 hours. After confirming the completion of the reaction, the mixture was extracted with ethyl acetate and washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. The organic solvent was distilled off and purified by column chromatography to give 5.
MS m / z: 258 (M ⁺ , 100)
(1-5) While 5 and triethyl orthoformate and ethanol were being stirred under ice-cooling, hydrochloric acid gas was blown into the mixture, followed by heating under reflux for 30 minutes. After completion of the reaction, a sodium hydrogen carbonate solution was added, extracted with ethyl acetate, and washed with water and saturated brine. The organic solvent was distilled off and purified by column chromatography to obtain 6.
¹ H-NMR (400 MHz, CDCl ₃ ): 0.95 (t, J = 5.5Hz, 3H), 1.21 (t, J = 5.3Hz, 3H), 1.61-1.67 (m, 2H), 1.91-2.23 (m , 8H), 2.56 (t, J = 5.8Hz, 2H), 2.61 (s, 2H), 3.50 (dd, J = 10.5, 5.4Hz, 2H), 7.07-7.10 (m, 2H), 7.14-7.16 ( m, 2H).
MS m / z: 286 (M ⁺ , 100)
(1-6) While 6 was dissolved in dichloromethane, m-chloroperbenzoic acid was added little by little, the temperature was slowly raised, and the mixture was heated to reflux for 8 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 7.
MS m / z: 302 (M ⁺ , 100)
(1-7) While sodium hydride was suspended in N, N′-dimethylformamide, a solution of 7 in N, N′-dimethylformamide was added dropwise with ice cooling, followed by stirring for 1 hour. A solution of dimethyl sulfate in N, N'-dimethylformamide was added dropwise under ice-cooling, followed by reaction for 2 hours. The reaction solution was poured into ice and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 8.
(1-8) While 8 was dissolved in dichloromethane, trifluoromethanesulfonic acid N-fluoropyridinium salt was added little by little, the temperature was raised, and the mixture was heated to reflux for 10 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 9.
(1-9) After 9 is dissolved in dichloromethane in a Hastelloy autoclave, a small amount of water is added and cooled with liquid nitrogen. Sulfur tetrafluoride was introduced therein and reacted at 120 ° C. After cooling to room temperature, the product was washed with water and an aqueous sodium hydrogen carbonate solution, purified by ethanol recrystallization, and 5-ethoxy-3,3,4,4-tetrafluoro-1- (4-propylphenyl) -2- Oxa-bicyclo [3.2.2] nonane (Ia) was obtained.
¹ H-NMR (400 MHz, CDCl ₃ ): 0.96 (t, J = 6.7Hz, 3H), 1.25-1.68 (m, 13H), 2.44-2.57 (m, 2H), 3.43 (s, 2H), 7.05 -7.14 (m, 4H)
MS m / z: 360 (M ⁺ , 100)
Example 2 1- (4-Ethoxy-2,3-difluorophenyl) methoxy-2,2,3,3-tetrafluoro-5-propyl-4-oxa-bicyclo [3.2.2] nonane (IIa) Synthesis of

(2-1) While stirring 4-hydroxy-1-propyl-bicyclo [2.2.2] octan-2-one 10, potassium hydride and tetrahydrofuran, 4-bromomethyl-2,3-difluoro-1 -Ethoxybenzene was added dropwise, followed by stirring at 50 ° C for 12 hours. After completion of the reaction, the reaction solution is poured into ice and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethanol to obtain 11.
(2-2) While 11 was dissolved in dichloromethane, m-chloroperbenzoic acid was added little by little, the temperature was slowly raised, and the mixture was heated to reflux for 7 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 12.
(2-3) While sodium hydride was suspended in N, N′-dimethylformamide, a solution of 12 N, N′-dimethylformamide was added dropwise under ice cooling, followed by stirring for 1 hour. A solution of dimethyl sulfate in N, N'-dimethylformamide was added dropwise under ice-cooling, followed by reaction for 2 hours. The reaction solution was poured into ice and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 13.
(2-4) While 13 was dissolved in dichloromethane, trifluoromethanesulfonic acid N-fluoropyridinium salt was added little by little, the temperature was raised, and the mixture was heated to reflux for 10 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 14.
(2-4) After dissolving 14 in dichloromethane in a Hastelloy autoclave, add a small amount of water and cool with liquid nitrogen. Sulfur tetrafluoride was introduced therein and reacted at 120 ° C. After cooling to room temperature, it was washed with water and an aqueous sodium hydrogen carbonate solution, purified by ethanol recrystallization, and 1- (4-ethoxy-2,3-difluorophenyl) methoxy-2,2,3,3-tetrafluoro -5-Propyl-4-oxa-bicyclo [3.2.2] nonane (IIa) was obtained.
¹ H-NMR (400 MHz, CDCl ₃ ): 0.95 (t, J = 6.7Hz, 3H), 1.30-1.54 (m, 15H), 3.97 (dd, J = 6.5, 6.5 Hz, 2H), 4.65 (s , 2H), 6.42-6,46 (m, 1H), 6.81-6.84 (m, 1H).
MS m / z: 426 (M ⁺ , 100)
(Example 3) Preparation of liquid crystal composition (1)
Host liquid crystal composition comprising the following composition (H)

Was prepared. Here, the dielectric anisotropy (Δε) of the host liquid crystal composition (H) was 0.04.

  A liquid crystal composition (M-a) comprising 80% of the host liquid crystal (H) and 20% of the compound (IIa) obtained in Example 2 was prepared. The dielectric anisotropy (Δε) of this composition was -1.10.

  In the liquid crystal composition (M-a) containing the compound (IIa) of the present invention, the dielectric anisotropy (Δε) was greatly reduced to a negative value as compared with the base liquid crystal (H). This shows that the compound (IIa) of the present invention has a negative Δε and an extremely large absolute value.

Further, when (Ma) was heated at 150 ° C. for 1 hour in a nitrogen atmosphere and the voltage holding ratio was measured at 70 ° C., it was 99% higher than the voltage holding ratio of the host liquid crystal composition (H). Indicated. This shows that the compound (IIa) of the present invention can be sufficiently used as a liquid crystal display material from the viewpoint of stability. In addition, the liquid crystal composition (Ma) contains 20% of the compound (IIa), but since the liquid crystal composition showed a stable liquid crystal phase without causing precipitation, the compound of the present application was superior to other liquid crystal compositions. It has also been shown to be compatible and compatible.
Comparative Example 1 Preparation of liquid crystal composition (2)
Host liquid crystal (H) 80% and compound (IIb) described in JP2010-215524A (Patent Document 4)

A liquid crystal composition (M-b) comprising 20% was prepared. The dielectric anisotropy (Δε) of this composition was −0.85.

The liquid crystal composition (Mb) containing the compound (IIb) described in Patent Document 3 has a smaller absolute value of dielectric anisotropy (Δε) than the liquid crystal composition (Ma) described in Example 3. From this, it was found that when the compound (IIa) of the present invention was added to the liquid crystal composition, the absolute value of Δε could be improved as compared with the case where the compound (IIb) described in Patent Document 4 was added.
Example 4 Synthesis of 5-ethoxy-3,3,4,4-tetrafluoro-1- (trans-4-propylcyclohexyl) -2-oxa-bicyclo [3.2.2] nonane (IIIa)

(4-1) While stirring potassium cyanide and tetrahydrofuran under ice-cooling, a tetrahydrofuran solution of 1-bromomethyl-4-propylcyclohexane 15 was added, and the temperature was raised to room temperature. After terminating the reaction with hydrochloric acid, the mixture was extracted with ethyl acetate, washed with water and saturated brine, and the organic solvent was distilled off. Purification by column chromatography gave 16.
(4-2) A solution of potassium t-butoxide in tetrahydrofuran was added dropwise to a solution of 16 and ethyl acrylate dissolved in tetrahydrofuran at room temperature, and the mixture was stirred for 3 hours. After terminating the reaction with hydrochloric acid, the mixture was extracted with dichloromethane, washed with water and saturated brine, and the organic solvent was distilled off. The obtained yellow liquid was dissolved in a mixed solution of dimethyl sulfoxide and brine and stirred at 150 ° C. for 2 hours. After the heating was finished, extraction with toluene, washing with water and saturated brine, and the organic solvent was distilled off. Purification by column chromatography gave 17.
(4-3) 17 and ethylene glycol and a catalytic amount of p-tosylic acid were dissolved in toluene and heated to reflux. After completion of the reaction, a sodium hydrogen carbonate solution was added, extracted with toluene, and washed with water and saturated brine. The organic solvent was distilled off and purified by column chromatography to obtain 18.
(4-4) While the mixed solvent of methyllithium in diethoxyethane / tetrahydrofuran was cooled at −70 ° C., 18 tetrahydrofuran solution was added dropwise. After slowly raising the temperature to 0 ° C., 10% hydrochloric acid was added to make the reaction solution acidic. The reaction solution was raised to 60 ° C. and reacted for 3 hours. After confirming the completion of the reaction, the mixture was extracted with ethyl acetate and washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. The organic solvent was distilled off and purified by column chromatography to obtain 19.
MS m / z: 258 (M ⁺ , 100)
(4-5) While 19 and triethyl orthoformate and ethanol were being stirred under ice-cooling, hydrochloric acid gas was blown into the mixture, followed by heating under reflux for 30 minutes. After completion of the reaction, a sodium hydrogen carbonate solution was added, extracted with ethyl acetate, and washed with water and saturated brine. The organic solvent was distilled off and purified by column chromatography to obtain 20.
(4-6) While 20 was dissolved in dichloromethane, m-chloroperbenzoic acid was added little by little, the temperature was slowly raised, and the mixture was heated to reflux for 8 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 21.
MS m / z: 302 (M ⁺ , 100)
(4-7) While sodium hydride was suspended in N, N′-dimethylformamide, 21 N, N′-dimethylformamide solution was added dropwise under ice-cooling, followed by stirring for 1 hour. A solution of dimethyl sulfate in N, N'-dimethylformamide was added dropwise under ice-cooling, followed by reaction for 2 hours. The reaction solution was poured into ice and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 22.
(4-8) While 22 was dissolved in dichloromethane, trifluoromethanesulfonic acid N-fluoropyridinium salt was added little by little, the temperature was raised, and the mixture was heated to reflux for 10 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 23.
(4-9) After dissolving 23 in dichloromethane in a Hastelloy autoclave, add a small amount of water and cool with liquid nitrogen. Sulfur tetrafluoride was introduced therein and reacted at 120 ° C. After cooling to room temperature, it was washed with water and aqueous sodium hydrogen carbonate solution, recrystallized from ethanol and purified to give 5-ethoxy-3,3,4,4-tetrafluoro-1- (trans-4-propylcyclohexyl). ) -2-Oxa-bicyclo [3.2.2] nonane (IIIa) was obtained.
MS m / z: 366 (M ⁺ , 100)
Example 5 Synthesis of 3,3,4,4-tetrafluoro-1-propyl-5- (trans-4-propylcyclohexylmethoxy) -2-oxa-bicyclo [3.2.2] nonane (IVa)

(5-1) 4-hydroxy-1-propyl-bicyclo [2.2.2] octan-2-one 24, 1-bromomethyl-4-propylcyclohexane was added dropwise to potassium carbonate suspended in ethanol. And stirred at 70 ° C. for 22 hours. After completion of the reaction, the reaction solution was poured into ice and extracted with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethanol to obtain 25.
(5-2) While 25 was dissolved in dichloromethane, m-chloroperbenzoic acid was added little by little, the temperature was slowly raised, and the mixture was heated to reflux for 8 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 26.
(5-3) While sodium hydride was suspended in N, N′-dimethylformamide, a solution of 26 N, N′-dimethylformamide was added dropwise under ice cooling, followed by stirring for 1 hour. A solution of dimethyl sulfate in N, N'-dimethylformamide was added dropwise under ice-cooling, followed by reaction for 2 hours. The reaction solution was poured into ice and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 27.
(5-4) While 27 was dissolved in dichloromethane, trifluoromethanesulfonic acid N-fluoropyridinium salt was added little by little, the temperature was raised, and the mixture was heated to reflux for 10 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 28.
(5-5) After 28 is dissolved in dichloromethane in a Hastelloy autoclave, a small amount of water is added and cooled with liquid nitrogen. Sulfur tetrafluoride was introduced therein and reacted at 120 ° C. After cooling to room temperature, it was washed with water and an aqueous sodium hydrogen carbonate solution, and then purified by ethanol recrystallization to 3,3,4,4-tetrafluoro-1-propyl-5- (trans-4-propylcyclohexylmethoxy) 2-Oxa-bicyclo [3.2.2] nonane (IVa) was obtained.
MS m / z: 394 (M ⁺ , 100)
Example 6 5- {Difluoro- (4-propylphenyl) -methoxy} -3,3,4,4-tetrafluoro-1- (4-propylphenyl) -2-oxa-bicyclo [3.2.2] Synthesis of nonane (Va)

(6-1) While 5 was dissolved in tetrahydrofuran under ice-cooling, a tetrahydrofuran solution of potassium t-butoxide was added dropwise, followed by stirring for 3 hours. After terminating the reaction with hydrochloric acid, the mixture was extracted with ethyl acetate, washed with water and saturated brine, the organic solvent was distilled off, and the solvent was distilled off under reduced pressure. Recrystallization from ethanol gave 29.
(6-2) In a suspension of sodium hydride in tetrahydrofuran, a tetrahydrofuran solution of 29 was added dropwise under ice cooling, followed by stirring for 1 hour. Methoxymethylene chloride was added dropwise under ice cooling, followed by reaction for 2 hours. The reaction solution was poured into ice and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 30.
(6-3) While 30 was dissolved in dichloromethane, m-chloroperbenzoic acid was added little by little, the temperature was slowly raised, and the mixture was heated to reflux for 8 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 31.
(6-4) While sodium hydride was suspended in N, N′-dimethylformamide, a solution of 31 N, N′-dimethylformamide was added dropwise under ice cooling, followed by stirring for 1 hour. A solution of dimethyl sulfate in N, N'-dimethylformamide was added dropwise under ice-cooling, followed by reaction for 2 hours. The reaction solution was poured into ice and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 32.
(6-5) While 32 was dissolved in dichloromethane, trifluoromethanesulfonic acid N-fluoropyridinium salt was added little by little, the temperature was raised, and the mixture was heated to reflux for 10 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 33.
(6-5) Hydrochloric acid was added dropwise to a tetrahydrofuran solution of 33 under ice cooling. The temperature was slowly raised to room temperature and the reaction was carried out for 3 hours. After confirming the completion of the reaction, the mixture was extracted with ethyl acetate and washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. The organic solvent was distilled off and purified by column chromatography to obtain 34.
(6-6) 34 and 4-propylbenzoic acid chloride were reacted in dichloromethane. After washing with water and aqueous sodium hydrogen carbonate solution, purification was performed by column chromatography to obtain 35.
(6-7) After dissolving 35 in dichloromethane in a Hastelloy autoclave, add a small amount of water and cool with liquid nitrogen. Sulfur tetrafluoride was introduced therein and reacted at 120 ° C. After cooling to room temperature, it was washed with water and an aqueous sodium hydrogen carbonate solution, purified by recrystallization, and 5- {difluoro- (4-propylphenyl) -methoxy} -3,3,4,4-tetrafluoro-1 -(4-Propylphenyl) -2-oxa-bicyclo [3.2.2] nonane (Va) was obtained.
MS m / z: 500 (M ⁺ , 100)
Example 7 Synthesis of 1- (4-ethylphenyl) -3,3,4,4-tetrafluoro-5-propyl-2,7-dioxa-bicyclo [3.2.2] nonane (VIa)

(7-1) Butyllithium was added dropwise while 4-ethylbromobenzene was dissolved in tetrahydrofuran and cooled at -55 ° C. There, 36 is dripped at -55 degreeC, and reaction is performed for 1 hour. The reaction is terminated with an aqueous ammonium chloride solution, followed by extraction with ethyl acetate, washing with water and saturated brine, and the organic solvent is distilled off. To the concentrated solution, toluene and a catalytic amount of p-tosylic acid were added and heated to reflux. After completion of the reaction, a sodium hydrogen carbonate solution was added, extracted with toluene, and washed with water and saturated brine. The organic solvent was distilled off and purified by column chromatography to obtain 37.
(7-2) 37 was dropped into the formic acid prepared by a conventional method under ice cooling. After stirring at 50 ° C. for 9 hours, the mixture was cooled to room temperature, water was added, and extraction was performed with toluene. The organic solvent was distilled off by washing with water, saturated aqueous sodium hydrogensulfite solution, water and saturated brine in this order. The total amount of the obtained reaction mixture was suspended in ethanol with vigorous stirring at room temperature, 30% aqueous sodium hydroxide solution was added thereto, and the mixture was vigorously stirred for 2 hours. Then concentrated hydrochloric acid was added on an ice bath. The white precipitate was filtered off to obtain 38.
(7-3) Manganese dioxide was added to 38 dissolved in dichloromethane, and the mixture was stirred at 40 ° C. for 14 hours, cooled to room temperature, water added, and extracted with dichloromethane. The mixture was washed with water and saturated brine in that order, and the organic solvent was distilled off to obtain 39.
(7-4) 39, ethylene glycol, and a catalytic amount of p-tosylic acid were dissolved in toluene and heated to reflux. After completion of the reaction, a sodium hydrogen carbonate solution was added, extracted with toluene, and washed with water and saturated brine. The organic solvent was distilled off and purified by column chromatography to obtain 40.
(7-5) 40 and boron trifluoride / tetrahydrofuran were dissolved in tetrahydrofuran, and while stirring under ice cooling, sodium borohydride was added and the temperature was raised to room temperature. The mixture was reacted at room temperature for 3 hours, extracted with ethyl acetate, and washed with water and saturated brine. The organic solvent was distilled off and purified by column chromatography to obtain 41.
(7-6) While 41 is dissolved in tetrahydrofuran, 10% hydrochloric acid is added dropwise at room temperature. Then, reaction was performed at 50 degreeC for 4 hours. The aqueous layer was separated and washed with sodium hydrogen carbonate solution and saturated brine. The organic solvent was distilled off and purified by recrystallization to give 42.
(7-7) While 42 was dissolved in dichloromethane, m-chloroperbenzoic acid was added little by little, the temperature was slowly raised, and the mixture was heated to reflux for 8 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 43.
(7-8) While sodium hydride was suspended in N, N′-dimethylformamide, a solution of 43 N, N′-dimethylformamide was added dropwise under ice cooling, followed by stirring for 1 hour. A solution of dimethyl sulfate in N, N'-dimethylformamide was added dropwise under ice-cooling, followed by reaction for 2 hours. The reaction solution was poured into ice and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 44.
(7-9) While 44 was dissolved in dichloromethane, trifluoromethanesulfonic acid N-fluoropyridinium salt was added little by little, the temperature was raised, and the mixture was heated to reflux for 10 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 45.
(7-10) After dissolving 45 in dichloromethane in a Hastelloy autoclave, add a small amount of water and cool with liquid nitrogen. Sulfur tetrafluoride was introduced therein and reacted at 120 ° C. After cooling to room temperature, it was washed with water and an aqueous sodium hydrogen carbonate solution, and purified by recrystallization, and 1- (4-ethylphenyl) -3,3,4,4-tetrafluoro-5-propyl-2,7 -Dioxa-bicyclo [3.2.2] nonane (VIa) was obtained.
MS m / z: 346 (M ⁺ , 100)
Example 8 Synthesis of 5-butoxy-3,3,4,4-tetrafluoro-1-propyl-2-oxa-bicyclo [3.2.2] nonane (VIIa)

(8-1) 4-Hydroxy-1-propyl-bicyclo [2.2.2] octan-2-one 24, and potassium carbonate suspended in ethanol, bromobutane was added dropwise and stirred at 70 ° C. for 2 hours. did. After completion of the reaction, the reaction solution was poured into ice and extracted with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethanol to obtain 46.
(8-2) While 46 was dissolved in dichloromethane, m-chloroperbenzoic acid was added little by little, then the temperature was raised slowly, and the mixture was heated to reflux for 8 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 47.
(8-3) While sodium hydride was suspended in N, N′-dimethylformamide, 47 N, N′-dimethylformamide solution was added dropwise under ice-cooling, followed by stirring for 1 hour. A solution of dimethyl sulfate in N, N'-dimethylformamide was added dropwise under ice-cooling, followed by reaction for 2 hours. The reaction solution was poured into ice and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with water and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to give 48.
(8-4) While 48 was dissolved in dichloromethane, trifluoromethanesulfonic acid N-fluoropyridinium salt was added little by little, then the temperature was raised, and heating under reflux was performed for 10 hours. After confirming the completion of the reaction, water was added, the organic layer was separated, and the resulting organic layers were combined and washed with saturated brine. The organic solvent of the obtained solution was distilled off and purified by column chromatography to obtain 49.
(8-5) After dissolving 49 in dichloromethane in a Hastelloy autoclave, add a small amount of water and cool with liquid nitrogen. Sulfur tetrafluoride was introduced therein and reacted at 120 ° C. After cooling to room temperature, the mixture was washed with water and an aqueous sodium hydrogen carbonate solution, and purified by recrystallization, and 5-butoxy-3,3,4,4-tetrafluoro-1-propyl-2-oxa-bicyclo [3.2. 2] Nonane (VIIa) was obtained.
MS m / z: 312 (M ⁺ , 100)

Claims (10)

Formula (I)

(Wherein Z represents the general formula (II)

(In the formula, one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently substituted with —O— or —S—, and Two or more hydrogen atoms may be independently substituted with fluorine atoms).
R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. group (one -CH in each group ₂ - or not adjacent two or more -CH ₂ - -O is independently -, - S -, - CO -, - COO- or -OCO- in And may be substituted, and one —CH ₂ — or two or more hydrogen atoms that are not adjacent to each other may be independently substituted with a fluorine atom.
A ¹ and A ² are each independently trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5. -Diyl group, bicyclo [2.2.2] octane-1,4-diyl group, or 1,4-phenylene group (one or more hydrogen atoms in each group are independently substituted with fluorine atoms or chlorine atoms) Which may have been
X ¹ and X ² are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —C ₄ H ₈ —, —COO—, —OCO—, —CH═. CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, —SCH ₂ —, —CH ₂ S—, —CSO—, —OCS—, —CF ₂ S -, - SCF ₂ -, or represents -C≡C-,
m and n are each independently 0, 1, 2 or 3 (m + n is 0, ¹ , 2 or 3, and when there are a plurality of A ¹ , A ² , X ¹ and / or X ² , They may be the same or different. A fluorinated oxabicyclononane derivative represented by: In the general formula (I), R ¹ and R ² are each independently an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or a carbon atom. The compound according to claim 1, which is an alkenyloxy group having a number of 2 to 7. In general formula (I), A ¹ and A ² are each independently trans-1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, or 1,4-phenylene. The compound according to claim 1 or 2, which is a group (one or more hydrogen atoms in each group may be independently substituted with a fluorine atom). In the general formula (I), X ¹ and X ² are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —CF ₂ O—, —OCF ₂ — or The compound according to claim 1, which is —CF ₂ CF ₂ —. In the general formula (I), R ¹ and R ² are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon atom. An alkenyloxy group of 2 to 5, wherein A ¹ and A ² are each independently a trans-1,4-cyclohexylene group or unsubstituted or one or more hydrogen atoms are independently fluorine atoms 2. The 1,4-phenylene group substituted by X ¹ and X ² are each independently a single bond, —OCH ₂ —, —CH ₂ O— or —C ₂ H ₄ —. Compound. In general formula (I), m + n is 1 or 2. The compound of any one of Claims 1-5. A liquid crystal composition containing one or more compounds according to claim 1. A liquid crystal display device using the liquid crystal composition according to claim 7. 9. The liquid crystal display element according to claim 8, which is active matrix driven. The liquid crystal display element according to claim 8, which is displayed in a vertical alignment mode or a PSA mode.