JPH03240755A - Novel fluorine compound, its intermediate, production of the intermediate and liquid crystal composition containing novel fluorine compound - Google Patents

Abstract

NEW MATERIAL:The novel fluorine compound expressed by formula I (R is 2-20C alkyl or alkoxy; T and X are H, F or methyl and are different from each other; p is oxycarbonyl or carbonyloxymethyl; b is carbonyloxy, oxycarbonyl or single bond; a and q are p-phenylene, group of formula II, formula III, cyclohexylene, etc.; n is 2-20; l is 1-2). EXAMPLE:4'-octyloxybiphenyl 2,11-difluoroundecanoate. USE:A material for a liquid crystal composition having high chemical stability, exhibiting chiral smectic C phase over a wide temperature range near room temperature and having high spontaneous polarization. PREPARATION:The objective compound of formula I can be produced by reacting a novel fluorine compound of formula IV (Z is hydroxymethyl or carboxyl) with a desired bivalent cyclic compound.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention can take a stable thermotropic liquid crystal state, and can be used, for example, in displays such as liquid crystal televisions, optical printer heads, optical Fourier transform elements, light valves, etc. The present invention relates to a novel fluoro compound used in a liquid crystal material useful as a material for optoelectronics-related elements, and a liquid crystal composition containing this compound.

The present invention also relates to an intermediate of the above-mentioned fluoro compound and a method for producing the same, particularly a method for producing an optically active form thereof, and such an intermediate can be used as an intermediate for compounds used in medicines, agricultural chemicals, etc. in addition to liquid crystal materials. can do.

(Prior Art) Currently, liquid crystal materials are used as various display elements for watches, calculators, small televisions, etc., but these are mainly nematic liquid crystal materials. This nematic liquid crystal utilizes operation based on the weak interaction (ΔεE2/2) between the dielectric anisotropy Δε and the electric field E, so the response time to the electric field is several orders of magnitude.
It is slow at 0 msec.

For this reason, there are limits to its use in fields that require high-speed response, and the display capacity is also reaching its limit.
This is one of the obstacles to achieving larger screens.

By the way, in 1975, 4-(4-n-decyloxybenzylideneamino)cinnamic acid-2-methylbutyl ester (DOB) was synthesized by R.B. Meyer et al.
With the emergence of ferroelectric liquid crystals, of which AMBC' is a typical example, and surface-stabilized ferroelectric liquid crystal (SSFLC) cells that utilize bistable states in thin cells proposed by N., A., and C1ark et al. , a liquid crystal cell with high-speed response on the μsec order and memory performance has become possible.

For this reason, many ferroelectric liquid crystal compounds have been synthesized to date.
Proposed.

(Problems to be Solved by the Invention) By the way, in order for the ferroelectric liquid crystal compounds that have been synthesized and proposed so far to be used as liquid crystal materials, they must exhibit a chiral smectic C phase in a wide temperature range at least near room temperature, and must exhibit a large spontaneous It needs to be polarized and chemically stable. However, it is difficult to obtain a single compound that satisfies these requirements, and, as in the case of conventional nematic liquid crystal materials, efforts have been made to address this by mixing several types of compounds. there were. Incidentally, a type of phenylpyrimidine compound has been proposed as this type of liquid crystal material (for example, Japanese Patent Application Laid-Open No. 63-235393).

However, there are still only a few types of such ferroelectric liquid crystal compounds, and it is currently impossible to provide a fully satisfactory ferroelectric liquid crystal composition.

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a novel fluoro compound that is chemically stable, exhibits a chiral smectic C phase in a wide temperature range near room temperature, and is useful as a material for a liquid crystal composition that has a large spontaneous polarization, an intermediate thereof, and a novel fluoro compound, an intermediate thereof, and an intermediate thereof. An object of the present invention is to provide a method for producing an intermediate and a liquid crystal composition containing a novel fluoro compound.

(Means for Solving the Problems) The present invention has the following general formula (I), R-(ab)7-Q-p-C-(CH2)++-F
(I) [wherein R is an alkyl group or an alkoxy group having 2 to 20 carbon atoms, T and X are a hydrogen atom, a fluorine atom or a methyl group, and are not the same as each other,
p is an oxycarbonyl group or a carbonyloxymethylene group, b is a carbonyloxy group, an oxycarbonyl group, or a single bond, a and q are the following formula, (wherein T and X are a hydrogen atom, a fluorine atom, or a methyl group, and each other The present invention relates to a novel fluoro compound represented by a hydroxymethyl group or a carboxyl group, and n is an integer of 2 to 20, which are different from each other, and a method for producing the same.

As a specific embodiment of the method for producing such an intermediate, ■ a divalent group selected from the group consisting of compounds represented by the following general formula, n
is 2-20. 1 represents an integer of 1 to 2] and a liquid crystal composition containing the same.

In the above formula (I), R and n are determined from a practical manufacturing standpoint.

The present invention also provides trimethylaluminum to act on a fluoroepoxide represented by the following general formula, z-C(Ct+z+F (n) (in the formula, n represents an integer of 2 to 20), which is an intermediate of the above-mentioned fluoro compound. The following general formula, F-fCtbhCH-C, is characterized by
A method for producing a fluoroalcohol represented by H20H(IV)CH3 (in the formula, n is the same as the above), ■ the following general formula, F-(CH2-hC-CH2(V) (in the formula, TI is a hydrogen atom or a methyl group, n is 2 to 20
The following general formula is characterized by reacting an amine-hydrogen fluoride complex with a fluoroepoxide represented by (indicating an integer of A method for producing a fluoroalcohol represented by the following general formula, F-+CH2-hC-CH20H (■) (where T and The general formula of the following formula, F(CHz+1C-CO□H(■)) (where T, X and n is the same as the above), and The following general formula, F-+CH2+i-C, characterized by reduction with lithium aluminum oxide
A method for producing a fluoroalcohol represented by H-CHs H (IX) (in the formula, n is the same as above) is mentioned.

In the method for producing the intermediate, the formula (III), (
It is preferable to use optically active compounds as the compounds represented by V) and (■).

In addition, as a method for synthesizing the compound represented by the above formula (IX),
Method of replacing chlorine in chloroalcohol with fluorine using KF [
Chem, Abs, 74.529805 (19
71)] and a method of fluorinating only the primary hydroxyl group of a diol [JP-A-61-205220], but the former has an insufficient yield, and the latter uses expensive tetrafluoride. There was a problem in that butylammonium or the like had to be used.

Examples of the fluoro compound represented by the above formula (It) of the present invention include 4-fluoro-2-methyl-1-butanol, 4-fluoro-2-methyl-1-butanol,
-Fluoro-2-methylbutanoic acid, 2,4-difluoro-1-butanol, 2,4-difluorobutanoic acid, 2.
4-difluoro-2-methyl-1-butanol, 2.4
Difluoro-2-methylbutanoic acid, 5-fluoro-2methyl-1-pentanol, 5-fluoro-2-methylpentanoic acid, 2,5-difluoro-1-pentanol, 2
．． 5-difluoropencunic acid, 2,5-difluoro-2
Methyl-1-pentanol, 2,5-difluoro-2-
Methylpentanoic acid, 6-fluoro-2-methyl-1-hexanol, 6-fluoro-2-methylhexanoic acid, 2
゜6-difluoro-■-hexanol, 2,6-difluorohexanoic acid, 2,6-difluoro-2-methylhexanoic acid, 7-fluoro-2-methyl-l-heptatool, 7fluoro-2-methylhebutanoic acid , 2,7-difluoro-1-heptatool, 2,7-difluorohebutanoic acid, 2,7-difluoro-2-methyl-1-heptatool, 2,7-difluoro-2-methylheptazoic acid, 8-fluoro- 2-methyl-■-octatool, 8-fluoro-
2-Methyloctanoic acid, 2,8-difluoro-1-octatool, 2,8-difluorooctanoic acid, 2,8-difluoro-2methyl-1-octatool, 2,8-difluoro-2-methyloctanoic acid , 9-fluoro-2-methyl-1-nonanol, 9-fluoro-2-methylnonanoic acid, 2,9-difluoro-1-nonanol, 2,9-
Difluorononanoic acid, 2,9-difluoro-2-methyl-1-nonanol, 2,9-difluoro-2-methylnonanoic acid, 10-fluoro-2-methyl-1-decanol, IO-fluoro-2-methyldecanoic acid, 2. IO-difluoro-1-decanol, 2. IO-difluorodecanoic acid, 2. IO-difluoro-2-methyl-1-decanol, 2,10-difluoro-2-methyldecanoic acid, 1
1-Fluoro-,2-methyl-1-undecanol, 11
-Fluoro-2-methylundecanoic acid, 2.11-difluoro-1-undecanol, 2.11-difluoroundecanoic acid, 2.11-difluoro-2-methyl-1-
undecanol, 2,11-difluoro-2-methylundecanoic acid, ■2-fluoro-2methyl-1-dodecanol, 12-fluoro-2-methyldodecanoic acid, 2,
Examples include 12-difluoro-1-dodecanol, 2,12-difluorododecanoic acid, 2,12-difluoro-2-methyl-1-dodecanol, and 2,12-difluoro-2-methyldodecanoic acid.

The physical and chemical properties of typical compounds of the above formula (I[) are shown below.

'H-NMR (CDCj23, 7MS standard, δ value pp
m): 0.91 (3H, d, 6.4Hz), 1
．． 29 (18H, m) 3.47 (2H, m),
4.43 (2H, dt, 47.9H2,6,OH
2) lO-fluoro-2-methyl-1-decanol'H
-NMR (in CDCj73, 7MS standard, δ value ppm)
:0.91 (3H, d, 6.4H2), 1.29
(16H, m) 3.47 (2H, m), 4.4
3 (2H, dt, 47.9H2,6,OH2)2.
11-difluoro-1-undecanol boiling point: 120
-130°C/2 mmHg (Kugeroll)'H
-NMR (in CDCA 3, 7MS standard, δ value ppm)
:1.33 (17H,m), 3.46
(IH, HCH20, d, JH)l=5.0Hz)
, 3.9 (2,5H,m, y2CHzO,ZC8
2F), 4.82 (1.5HL m, I/'2CLF
, ACHF), lO-fluoro-2-methyldecanoic acid MS (diazomethane treated product): 218 (M+
), 187 (M-OCH3), 2.11-difluoroundecanoic acid Melting point: 54-57°C 'H-NMR (in CDCj73, 7MS standard, δ value pp
m): 1.2-2.0 (m, 16H), 4
．． 40 (2H, dt, 48Hz, 6Hz).

4.93 (LH, dt, 49Hz, 6Hz
), 10.5 (IH, s).

IR (KBr, cm-1): 2900. 2850
．． 1710. 1465. 1260°Cαl) o
Knee 5.2° (cl, 0. CHC (13)) Next, the method for producing the compound of formula (n) above will be specifically explained.

Among the compounds of the above formula (II), first, the compound in which X and Y are a hydrogen atom and a methyl group, respectively, and Z is a hydroxymethyl group, that is, the compound of the above formula (IV), is represented by the above formula (III). It is obtained by reacting trimethylaluminum with fluoroepoxide. It is preferable to use 1 to 1.5 equivalents of trimethylaluminum based on the raw material, and the solvent may be a hydrocarbon solvent such as hexane or toluene, or a halogenated hydrocarbon solvent such as dichloromethane or chloroform. in particular,
It is preferable to use a 1N hexane solution of trimethylaluminum, while a high concentration such as a 2N solution or a 2N hexane solution is preferably used.
If the reaction is carried out for a long time by using more than an equivalent amount of trimethylaluminum, the terminal FCl2 groups will also be methylated, resulting in a compound represented by the following formula % (where n is an integer from 2 to 20). may be produced as a by-product.

Incidentally, the epoxide represented by the above formula (I[I) is
It can be produced by the method described in Japanese Patent No. 1-014798.

Next, among the compounds of the above formula (n), a compound in which X is a fluorine atom, Y is a hydrogen atom or a methyl group, and Z is a hydroxymethyl group, that is, a compound of the above formula (VI), It is obtained by reacting the fluoroepoxide represented by formula (V) with an amine-hydrogen fluoride complex, and the conditions described in Japanese Patent Application No. 1-056056 can be used as the reaction conditions.

Furthermore, among the compounds represented by the above formula (It), a compound in which Z is a carboxyl group, that is, a fluorocarboxylic acid represented by the above formula (■), is a compound represented by the above formula (n), in which Z is a carboxyl group. A compound that is a hydroxymethyl group,
That is, it can be obtained by oxidizing the fluoroalcohol represented by the above formula (■). The reaction conditions are:
The conditions described in Japanese Patent Application No. 1278471 can be used.

Finally, the fluoroalcohol represented by the above formula (IX) can be obtained by reducing the fluoroepoxide represented by the above formula (III) with lithium aluminum hydride. As for this reaction condition, JP-A-63-3167
The conditions described in Publication No. 49 can be used.

Next, the novel fluoro compound represented by the above formula (I), which is the final product, will be explained.

Representative examples of this compound and their physical and chemical properties are as follows.

IR (KBr, cm J:2920.2840
．． 1760. 1610. 1495°1225,
820' H-NMR (in CDCA's, 7MS standard, δ value ppm) Near, 6 (d.

2H), 7.5(d, 2H), 7.2(d
, 2H), 7,0. (d, 2H), 5
．． 2 (dt, 49.6Hz, IH), 4.
5 (dt, 49.6Hz, 2H), 4.
0(t, 2H), 2.3~1.0 (28
H), 0.9(t, 3H)Mass(M+):
502 υ IR (KBr, cm””): 2920. 2840
．． 1775. 1430. 1190゜'H-NM
R (in CDCA 3, 7MS standard, δ value ppm): 3
．． 6 (s.

2H), 8.5(d, 2H), 7.2(d
, 2H), 5.2 (dt, 48.6Hz.

IH), 4.4 (dt, 48.6Hz, 2
H), 2.6(t, 2H), 2.2-1.
2 (28H), 0.9 (t, 3H) Mass
(M''): 502 4-(2,11-difluoroundecyloxycarbonyl)IR (KBr, cm-'): 2920.28
30. 1720. 1600. 1270°1160
, 755'H-NMR (in CDC13, 7MS standard, δ value ppm
) :8.2(d.

4H), 7.4(d, 2H), 7.0(d
, 2H), 4.82(d, m, 50Hz
.

LH), 4.6-4.3 (4H), 4.0 (t,
2H), 1.9-1.2 (28H).

0.9 (t, 3H) Mass (M+): 560 Sewing machine IR (KBr, cm'): 2920. 284
0°1440, 1255°1760, 1605. 1580°'H-NMRCC II s, 7MS standard, δ value p
pm) :9.0(s.

2H), 8.4(d, 2H), 7.5(d
, 2H), 7.3(d, 2H), 7.
0(d, 2H), 5.2(dt, 49.6
Hz, IH), 4.4(dt, 50.6H
z.

2H), 4.0(t, 3H), 2.3-1.1(2
4H), 0.9(t, 3H)Mass(M”
): 552 Carboxylic acid IR (KBr, cm'): 2920. 2840
．． 1750. 1730. 1580°1500,
1280. 11B0. 1075. 820'H-N
MR (in CDC1a, 7MS standard, δ value ppm): 8
．． 2 (d.

2H), 7.7 (d, 2H), 7.6 (d,
2H), 7.3-6.9 (6H).

4.5 (dt, 49.6Hz, 2H).

2.7 (m, IH), 2.0-1.0 (31H)
, 0.9(t, 3f()Mass(M”):61
8 The fluoro compound of the present invention represented by the above general formula (I) can be synthesized by the following method.

In the above formula (I), when p is an oxycarbonyl group, optically active 2. ω-difluoroalkanoic acid or 2-methyl-ω-fluoroalkanoic acid with phenol and N,N-
It is obtained by dehydration condensation with dicyclohexylcarbodiimide (DCC) in the presence of dimethylaminopyridine.

Also, optically active 2. It can also be obtained by converting ω-difluoroalkanoic acid or 2methyl-ω-fluoroalkanoic acid into acid chloride with thionyl chloride, and then reacting it with phenols. In addition, when b is a carbonyloxy group, after reacting a phenol protected at the 4-position with the above carboxylic acid to form an oxycarboxy group, the protecting group is removed to form a hydroxyl group, and this is reacted with a benzoic acid. It's okay. In addition, when b is an oxycarbonyl group, after reacting the 4-position protected phenol with the above carboxylic acid to form an oxycarbonyl group, the previously protected 4-position is converted into a carboxyl group, and this is reacted with the phenol. It's okay.

In the above (I), when p is a carbonyloxymethylene group, optically active 2. It is obtained by dehydrating and condensing ω-difluoro-1-alkanol or 2-methyl-ω-fluoro-1-alkanol with DCC in the presence of carboxylic acids and N,N-dimethylaminopyridine. It can also be obtained by converting carboxylic acids into acid chlorides with thionyl chloride and then reacting them with the alkanols mentioned above.

In addition, when b is a carbonyloxy group, a benzoic acid protected at the 4-position is reacted with the above alkanol to form a carbonyloxymethylene group, the protecting group is removed to form a hydroxyl group, and the benzoic acid is reacted with this. You can let me. When b is an oxycarbonyl group, the benzoic acids protected at the 4-position are reacted with the above alkanols to form a carbonyloxymethylene group, and then the previously protected 4-position is converted into a carboxyl group, which is then combined with a phenol. You can also react.

Furthermore, by using an alcohol or carboxylic acid consisting of a pyrimidine ring, a pyridine ring, a halogen-substituted phenyl ring, or a cyclohexane ring as the phenols or benzoic acids or in place of them, the general formula (I
), a compound in which a and q are each a pyrimidine ring, a pyridine ring, a halogen-substituted phenyl ring, or a cyclohexane ring other than a phenyl ring can be synthesized.

(Example) Next, the present invention will be specifically explained using examples.

Kantoyotan 1 Preparation of bacterial suspension Nocardia corrina (Nocardia corrina)
allina) B-276 (FERM-P-4094)
3 platinum loops of
Add tap water to 10 g of glucose and 5 g of sodium chloride to make 1 liter, and adjust the pH to 7.5 with specified caustic soda aqueous solution.
5007 containing 100-
The mixture was inoculated into a Sakaro flask with a capacity of 1 1/2, and cultured with shaking at 30°C for 16 hours.

This culture solution was placed in a container 31 containing a liquid medium 21 similar to the above.
Inoculated into a jar fermenter with a capacity of 30℃ and aeration rate of 2.
Culture was carried out for 7 minutes at a stirring rotation speed of 1100 Orp for 48 hours.

The bacterial bodies produced by these cultures were 0. Olmol
A bacterial suspension was prepared by washing with /l phosphate buffer (PH8), then washing with the reaction medium shown below, and resuspending in the same reaction medium.

In addition, the bacterial concentration of the bacterial suspension is 30 g/l as a dry concentration.
I made it so that

Reaction medium KtHPOll, 74 g MgSO4・7Ht0 1.50 gFeS04
7H 200,05 g Glucose 32 g Water iz Epoxidation of olefins Bacterial suspension prepared according to the above procedure 750 d, n-
Put 1125ml of hexadecane and 1.11-fluoro-l-undecene ioog into two 51-volume jar fermenters, and heat at 30°C with air flow rate of 300 i/min.
The reaction was carried out for 136 hours at a stirring rotation speed of 11,000 rpm.

After oil and water separation, the oil phase was added to a freshly prepared similar suspension solution and reacted in the same manner for 114 hours. After that,
After oil and water separation again, 94 g (yield 43%) of (+)11-fluoro-1,2-epoxyundecane having the following physical and chemical properties was obtained by column chromatography rectification.

Boiling point near 6°C 10.6mmHg Specific gravity: 0.9297 (α) o: +9.11'(neat)'H-N
MR (in CDCIl 3, TMS standard, δ value 1) I)m
): 1.3216H, m), 2.46 (IH, dd,
5H2,3Hz), 2.75(1N, t.

5Hz), 2.90 (IH, m), 4.43 (2H
, dt, 47.4Hz.

Using 70 g of 10-fluoro-1-decene as a raw material and reacting it under the same conditions as those described in Reference Example 1, (+)10- having the following physical and chemical properties was obtained. 32 g (yield: 42%) of fluoro-1,2-functional poxydecane was obtained.

Boiling point: 84-86°C/2mmHg Specific gravity: 0.9371 [α) D: 49.42° (neat) Hexane solution of 1.0 mon # of Sanitoyo Onitrimethylaluminum 7.5 vtl (7.5 mmol) Then, 0.94 g (5,0 m mo j7 ) of (+)-11-fluoro-1,2-epoxyundecane was added at room temperature under a nitrogen stream.
was dripped. After stirring at room temperature for 1 hour and at 50° C. for 1 hour, the mixture was further refluxed for 2 hours.

The reaction mixture was then diluted with hexane and poured portionwise into 1N hydrochloric acid, and after drying the organic phase over magnesium sulfate,
The solvent was distilled off under reduced pressure, and 0.93 g of 11-fluoro-2-methyl-1-undecanol having the above-mentioned physical and chemical properties was obtained as a crude product (yield 59% in terms of gas chromatography purity).
) was obtained.

(+)- to 1007 nl (100 m mol!) of a 1.0 moA/n hexane solution of trimethylaluminum
11-fluoro1,2-epoxyundecane 8.28g
(44 mmol) was added dropwise, stirred overnight at room temperature, and then subjected to the same post-treatment as in Example 1 to obtain 2-methyl-1-dodecanol from which fluorine was eliminated.

Ooku type l Trimethylaluminum 1. Omol/II hexane solution 39m7! (39 mmol) under water cooling (+
)-10-fluoro D-1,2-epoxydecane 5.23
g (30 mmol Il) was added dropwise. Next, the temperature was gradually raised to room temperature, and after further stirring at room temperature for 5 hours, the same post-treatment as in Example 1 was performed to obtain a crude product of 10-fluoro-2-methyl-1-decanol.

Example 3 Pyridine-hydrogen fluoride complex (30
/70 w/w%) 3.95g and placed on the water bath (+)-
11-Fluo0-1.2-Epoxyundecane1.8
After dropping 8 g (lom mo (1) over 3 minutes,
Stirred for 0 minutes. Next, the reaction solution was poured into 30 ml of water, extracted with ether, and the ether phase was washed with a 5% aqueous sodium carbonate solution and water. Thereafter, it was dried over sodium sulfate, the solvent was distilled off, and the mixture was distilled under reduced pressure using Kugelol to obtain 0.43 g (yield: 21%) of 2,11-difluoro-1-undecanol having the above-mentioned physicochemical properties.

The above compound was analyzed by GC as MTPA (α-methoxy-α-trifluoromethylphenylacetic acid) ester using a conventional method (PEG 20M, 25m).

190°C), and its optical purity was 88%ee.

Example 4 2.7 g (i Pr)zNH4HF (1
1.88 g (+)-11-fluoro-1,2-epoxyundecane (10
m mon ) was added dropwise over 3 minutes, and the mixture was stirred on a water bath for 1 hour and at room temperature for 1 hour. Hereinafter, the same post-processing as in Example 3 was performed, and 2. (2) 0.34 g (yield 17%) of 1-difluoro-1-undecanol was obtained.

Example 5 10-Fluoro-2-methyldecanoic acid To the crude product obtained in Example 2, 3N sulfuric acid 80- and acetone 20- were added, and while keeping the temperature below 25°C by cooling with water, 9.5 g of potassium permanganate was added. (60m mo (1
) was added little by little. After further stirring at room temperature for 2 hours, sodium bisulfite was added to reduce excess oxidizing agent, acidified with hydrochloric acid, and extracted with ether.

Next, this extract was extracted with an aqueous sodium hydroxide solution, the aqueous phase was acidified with hydrochloric acid, re-extracted with ether, dried and concentrated to obtain IO-fluoro-2-methyldecanoic acid having the above-mentioned physicochemical properties. Obtained.

The structure of the product was confirmed as a methyl ester by treatment with diazomethane in a manner similar to that described above.

Example 6 2, If-difluoro-I-undecanol 0.34 g
(1.7 mmol), acetone 17 nl, concentrated sulfuric acid 0.6
0.54 g (3,4 m mo 1 ) of potassium permanganate at below 20 °C after adding 5 g and 4.5 g of water.
was added. Next, after stirring at 20° C. or lower for 7 hours, the mixture was poured into ice water, and sodium hydrogen sulfate was added to reduce excess potassium permanganate. After that, add hydrochloric acid to adjust the pH.
was reduced to 1 or less and extracted with ether, and the ether phase was further extracted with a 10% aqueous sodium hydroxide solution. Hydrochloric acid was added to the obtained sodium hydroxide aqueous solution phase to adjust the pH to 1 or less, and after extraction with chloroform, the chloroform phase was washed with water. This chloroform phase was dried with sodium sulfate,
After the solvent was distilled off, the residue was distilled under reduced pressure using Kugelrohr to obtain 0.15 g of 2,11-difluoroundecanoic acid (yield: 41%) having the above-mentioned physicochemical properties.

Example 7 Lithium aluminum hydride 0.04 g (l m mo
l) in ether 3-, and (+)-11
-Fluo C1-1,2-epoxyundecane 0.19g
(l m mal ) in ether (2-) was added dropwise under water cooling. After stirring at 0° C. for 1 hour, the mixture was diluted with ether, and a saturated aqueous solution of sodium sulfate was added dropwise to precipitate the salt. The supernatant was dried over magnesium sulfate, concentrated, and distilled to obtain 0.17 g (yield: 89%) of D)-11-fluoro-2-undecanol having the following physicochemical properties.

Boiling point: 160-180°C150mC15O Kugelol) [:α) o: +4.6° (c 1.1.
CHC#s)'H-NMR (in CDCa, TM
S standard, δ value ppm): 1.18 (3H, d, 6
．． 3Hz), 1.31 (18H, m), 3.80
(IH, m).

4.44 (2H, dt, 47.4H2, 6, 3H2)
.

In addition, when the above compound was subjected to F-NMR measurement using MTPA (α-methoxy-α-trifluoromethylphenylacetic acid) ester using a conventional method, its optical purity was 78.
%ee.

Lithium aluminum hydride 0.04g (1m mo
Using 0.17 g (1 mmoA) of (+)-10-fluoro-1,2-epoxydecane and (+)-10-fluoro-1,2-epoxydecane, the same procedure as in Example 7 was performed to obtain (+)-1 having the following physical and chemical properties.
0-fluoro-2-decanol 0.17 g (yield 9
4%).

Boiling point: 160-170°C150mC15O Kugelol) [(Zlo: +5.1' (C1,3,
CHCj23)' H-NMR (in CDC42s, TM
S standard, δ value ppm): 1.18 (3H, d,
6.3Hz), 1°34 (16H, m), 3.
80 (IH, m).

4.43 (2H, dt, 47.4Hz, 6.3
Hz).

Optical purity (MTPA method) = 82%ee 607 mg (2,73 m moi!) of 2,11-difluoroundecanoic acid chloride and 1.02 g (8,57 m mo!) of thionyl chloride were placed in a roundecanoate flask. 6
Heated at 0-70°C for 8 hours. After cooling, excess thionyl chloride was distilled off under reduced pressure to obtain 0.571 g of light brown liquid (yield: 8
7%).

4-(4'
-octyloxyphenyl)phenol 409 mg (
After dissolving 1,37 mmol) in 157 nl of dry 1,2-dichloroethane, approximately 1,6-
was added, and while stirring at room temperature, 300 μl of 2,11-difluorooctanoic acid chloride (
1,25 m moj2) was added. - After stirring day and night, the mixture was poured into 3N hydrochloric acid 3 (W). This was extracted with chloroform, the organic phases were combined, washed with a 10% aqueous solution of sodium chloride, and then dried over magnesium sulfate.

After filtering off the magnesium sulfate, it was concentrated and dried to obtain 0.79 g of pale brown crystals. This was isolated by silica gel column chromatography and further recrystallized from a mixed solution of ethanol and chloroform to obtain 0.51 g of white crystals having the above-mentioned physical and chemical properties.

Evaluation of liquid crystallinity The above compound was injected into a 2.8 μm thick cell made of glass with transparent electrodes coated with polyimide and subjected to rubbing treatment, and observed with a polarized light microscope while controlling the temperature on a hot stage. The temperature was changed at a rate of 2°C per minute.

As a result, during the cooling process, the isotropic liquid turned into crystals at 85.3°C. On the other hand, during the heating process, the crystal changed to an isotropic liquid at 95.1°C.

Nyloxy)phenyl)pyrimidine 218 mg (0,
981 mmob) and 2-(4-hydroxyphenyl)
-5-nonylpyrimidine 299 mg (1,00m
mor! ) (Journal Future Practice
Hemy (Journal fuel Praktisch)
e Chemie) Volume 323, No. 2, 199-206 (
(1981)) and 13 mg (0.11 m mol) of N,N-dimethylaminopyridine.
) in 7d of dry methylene chloride, dicyclohexylcarbodiimide 0.26g (1,26m mol
) was added. - After stirring overnight, the precipitated crystals were filtered, and the filtrate was concentrated and dried under reduced pressure to obtain a light brown oil. This was separated by silica gel column chromatography and recrystallized to give a white crystal with the above physical and chemical properties.
g (yield 24%) was obtained.

Evaluation of liquid crystallinity The above compound was injected into a 4 μm thick cell made of glass with a transparent electrode coated with polyimide and subjected to rubbing treatment, and observed with a polarized light microscope while controlling the temperature on a hot stage. The temperature change was the same as in Example 9.

As a result, during the cooling process, the isotropic liquid turned into a crystal at 36°C. On the other hand, during the heating process, the crystal changed to an isotropic liquid at 52°C.

After dissolving 9.79 g (46.1 m mo I!) of 4-benzyloxybenzaldehyde in 100% acetone, 16 g of potassium permanganate was added over about 6 hours, followed by stirring overnight. Then convert this to 3007
Add 50g of sodium hydrogen sulfite to the water.
was added, then concentrated hydrochloric acid was added to bring the pH to below 1. After that, the acetone was distilled off, the mixture was allowed to cool, and the precipitated crystals were collected by filtration and recrystallized from ethanol to give 7.95 g of white crystals.
(yield 76%).

4-benzyloxybenzoic acid obtained as described above.
50 g (2,19 m mo (1) and 29 mg N,N-dimethylaminopyridine (0,24 m mo
) and 2,11-difluoroundecanol 0.40
g (1,92 mmol) and dry methylene chloride 45
In addition to 7 rLl, 0.50 g (2.43 mmol) of dicyclohexylcarbodiimide was added while heating. ■ After stirring at night, the precipitated crystals were filtered, the filtrate was concentrated, and the white crystals obtained by drying under reduced pressure were purified by silica gel column chromatography, and 0.29 g of white crystals were obtained.
(yield 36%).

4-(2,11-difluoroundecyloxycarbonyl)phenylbenzyl ether obtained as described above
．． 27 g (0.65 m mo 1 ) was dissolved in 2,5-ethyl acetate, 33 μm of 5% palladium-carbon powder was added thereto, and the mixture was brought into contact with hydrogen gas at room temperature and pressure for 5 days. Thereafter, 5% palladium-carbon powder was filtered, the filtrate was concentrated, and the crystals obtained were purified by silica gel chromatography to obtain 0.19 g of white crystals (yield 91%) having the above-mentioned physical and chemical properties. ) was obtained.

Synthesis of the title compound 4-octyloxybenzoic acid 214 mg (0,83
m m01 ) and 4-(2,1
0.19 g (0.58 mmor!) of 1-difluoroundecyloxycarbonylphenol and N,N-
Dimethylaminopyridine 8 mg (0,065m m
ol) was added to dry methylene chloride 5-, stirred and dissolved, and then 166 mg of dicyclohexylcarbodiimide was added.
(0.81 m mon ) was added and stirred overnight. Thereafter, the precipitated crystals were filtered, the filtrate was concentrated, and the crystals obtained were purified by silica gel column chromatography and recrystallization to give 0.27 g of white crystals (yield: 84%).
) was obtained.

Evaluation of liquid crystallinity The liquid crystallinity of the above compound was evaluated in the same manner as in Example 9, except that the thickness of the cell was 3.9 μm.

During the cooling process, it changed from an isotropic liquid to a cholesteric phase at 51.8°C, to a smectic A phase at 46.8°C, and crystallized at 41°C. On the other hand, during the heating process, the crystal changed to an isotropic liquid at 61'C.

270 μ (1,12 mmol) of 2,11-difluoroundecanoic acid chloride synthesized by the method described in Example 9
), 2-(4-hexyloxyphenyl) 5- (
4-hydroxyphenyl)pyrimidine 392 mg (
1,13m mol)
Volume 323, Issue 2, 1
99-206 (1981)) containing dry 1,2-dichloroethane 10- and dry pyridine! , 61 rll of the mixed solution. - After stirring overnight, add 30% of this to a 10% aqueous sodium carbonate solution.
and extracted with chloroform. The organic phase was then washed with water and dried over magnesium sulfate. After that, the magnesium sulfate was filtered, and the filtrate was concentrated and dried to obtain light brown crystals.
．． 58g was obtained. This was purified by silica gel column chromatography and recrystallization to obtain 0.30 g (yield: 77%) of white crystals having the above-mentioned physical and chemical properties.

Evaluation of liquid crystallinity The liquid crystallinity of the above compound was evaluated in the same manner as in Example 9, except that the thickness of the cell was 3.2 μm.

In the temperature-lowering process, it changed from an isotropic liquid to a smectic A phase at 178°C, changed to a xyl smectic C phase at 147.7°C, and became a crystal at 96°C. On the other hand, in the heating process, 119
At ℃, the crystal changed to a chiral smectic C phase. Also,
When the spontaneous polarization was measured using the triangular wave method, it was 127.7°C.
, 48 nC/cm under the conditions of 100H2, 30Vpp
2 was shown.

On the other hand, the above-synthesized 2-(4-hexyloxyphenyl) 5-
When 3% of (4-(1,10-difluorodecylcarbonyloxy)phenyl)pyrimidine was added and liquid crystallinity was evaluated (cell thickness: 3.0 μm).

10V/μm) and exhibited a xylsmectic C phase at -11.0 to 58.9°C. Further, the spontaneous polarization at 25°C was 3.4 nC/cnI2, the tilt angle was 18.5°, and the response time was 77 μSeC.

Inujindan□ Carboxylic acid 11-fluoro-2-methylundecanoic acid 1.20g
(5,50 mmol), p-benzyloxyphenol 1.24 g, and N,N-dimethylaminopyridine 29
■(0.24 mmoi7) and dry methylene chloride 45-
After the mixture was homogenized, 0.50 g (2.43 mmol) of dicyclohexylcarbodiimide was further added, and the mixture was stirred overnight at room temperature. After that, filter the crystals,
The filtrate was concentrated and dried under reduced pressure to obtain 3.05 g of reddish brown oil. Next, this was purified by silica gel chromatography to obtain 2.00 g of white crystals (yield: 90%).

2.00 g (5,00 mmol) of 4-(10-fluoro-1-methyldecylcarbonyl ether) obtained as above was added to ethanol. After dissolving in a mixed solvent of 3- and ethyl acetate lO-,
Add 0.21 g of 50% palladium-carbon powder,
It was brought into contact with hydrogen gas for about 4 days at room temperature and pressure. After that, the palladium-carbon powder was filtered, the filtrate was concentrated, reduced pressure, and purified by silica gel column chromatography.
1.40 g (yield 90%) of a colorless transparent liquid was obtained.

Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid After dissolving 12.3 g of potassium hydroxide in 100% of water, 240% of ethanol and 10.1 g of 4'-hydroxybiphenyl-4-carboxylic acid (47.2 mmol ) was added, and after refluxing for 30 minutes, 1-bromooctane 2
7.0 g (140 mmon) was added and refluxed for 5 hours.

After distilling off the ethanol, the mixture was allowed to cool and poured into 3,007 liters of water, and then concentrated hydrochloric acid was added to adjust the pH to 1 liter or less. The precipitated crystals were collected by filtration and recrystallized twice from hydrous acetic acid to obtain 11.6 g of white crystals having the above physical and chemical properties (yield 75%).
I got it.

Synthesis of the title compound 4'-octyloxybiphenyl-4-carboxylic acid 0.
45g (1,38m mor!) and 4-(t
0.35 g (1,13 m moj7) of o-fluoro-1 methyldecylcarbonyloxy)phenol;
N,N-dimethylaminopyridine 17mg (0,14
m mon ) was suspended in 257 nl of dry methylene chloride. To this, dicyclohexylcarbodiimide 0.
31 g was added using dry methylene chloride 15-. - After stirring overnight, the crystals were filtered, the filtrate was concentrated, and the white crystals obtained were purified by silica gel column chromatography and recrystallized to give 0.53 g of white crystals (yield 76%). Obtained.

(Effects of the Invention) The fluoro compound of the present invention has extremely excellent effects as a material for optoelectronics-related elements, such as being able to take a stable thermotropic liquid crystal state and becoming a ferroelectric liquid crystal with large spontaneous polarization and fast response speed. It is something that plays.

Therefore, the present invention can be said to be a liquid crystal material that is useful as a material for optoelectronic-related elements that utilize liquid crystals and electrochemistry, such as displays such as liquid crystal televisions, printer heads, optical Fourier transform elements, and light valves.

Further, the intermediates of the fluoro compounds of the present invention, particularly the optically active forms thereof, are useful as liquid crystal compounds as well as functional materials for medicines, agricultural chemicals, and the like.

Claims (1)

[Claims] 1. The following general formula (I), ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R is an alkyl group or an alkoxy group having 2 to 20 carbon atoms, T and X are a hydrogen atom, a fluorine atom or a methyl group, which are not the same, p is an oxycarbonyl group or a carbonyloxymethylene group, is a carbonyloxy group, an oxycarbonyl group or a single bond, a and q are the following formula, ▲ Formula , chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ (Y is a halogen atom), ▲ There are mathematical formulas, chemical formulas, tables, etc. A divalent group selected from the group consisting of the compounds represented by ▼, n is an integer of 2 to 20, and l is an integer of 1 to 2. A novel fluoro compound represented by 2. The following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, T and A novel fluoro compound represented by a carboxyl group (n is an integer of 2 to 20). 3. The following general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, n represents an integer from 2 to 20) characterized by the action of trimethylaluminum on fluoroepoxide A method for producing a fluoroalcohol represented by the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼(IV) (In the formula, n indicates the same thing as above). 4.The following general formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, T^1 is a hydrogen atom or a methyl group, and n is 2 to 2
There are the following general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼(VI) (in the formula, T^ 1 and n are the same as above). 5.The following general formula, ▲Mathematical formula, chemical formula, table, etc.▼(VII) (In the formula, T and X are hydrogen atoms, fluorine atoms, or methyl groups, and are not the same as each other, and n is 2 to 20 The general formula of the following formula, which is characterized by oxidizing a fluoroalcohol represented by (indicating an integer of A method for producing a fluorocarboxylic acid represented by 6. It is characterized by reducing the fluoroepoxide represented by the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼(III) (in the formula, n represents an integer from 2 to 20) with lithium aluminum hydride. A method for producing a fluoroalcohol represented by the following general formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IX) (where n indicates the same as the above). 7. In claims (3) to (6), the above formula (III),
The method according to any one of claims (3) to (6), characterized in that optically active substances are used as the compounds represented by (V) and (VII). 8. A liquid crystal composition containing the novel fluoro compound according to claim 1.