JPS5910652B2 - Fluorine-containing phenylbenzoate compounds and their uses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluorine-containing phenylbenzoate compound, and more particularly to a novel fluorine-containing phenylbenzoate compound, its production method, and its use as a liquid crystal composition.

Since liquid crystal materials were used in display devices, a large number of liquid crystal compounds have been synthesized and used alone or in mixtures.

Among them, the general formula 2X'oharo□CN [wherein x' represents an alkyl group or an alkoxy group having 4 to 7 carbon atoms].

] The phenylbenzoate compound represented by is colorless and has excellent chemical stability, and also has large positive induced anisotropy due to the strong electron-withdrawing property of the cyano group, and is widely used as an FEM type display element. Due to the cyano group in the group, its stability is limited, and its electrical properties are still unsatisfactory, so it has been desired to improve these drawbacks.

The present inventors have discovered that each of the above-mentioned drawbacks can be improved by introducing a trifluoromethyl group in place of the cyano group in the conventional phenyl benzoate compound represented by the above general formula.

In other words, we have found that when certain new fluorine-containing phenyl benzoate compounds into which these trifluoromethyl groups have been introduced are used as components of liquid crystal compositions, their stability and electrical properties are significantly improved. It is. The gist of the present invention is the general formula: [wherein x represents an alkyl group or alkoxy group having 1 to 12 carbon atoms, or an acyloxy group having 2 to 13 carbon atoms.

A fluorine-containing phenyl benzoate compound represented by the general formula: [wherein Y represents hydrogen or an alkali metal.

] The compound represented by c in the presence or absence of an acid acceptor*
General formula below: [In the formula, X has the same meaning as above.

Z represents halogen. A fluorine-containing phenyl benzoate compound obtained by reacting with a compound represented by [
1], p-trifluoromethylphenol [
] in the presence or absence of a dehydrating agent, = general formula: [wherein, X has the same meaning as above.

] A method for producing a fluorine-containing phenyl benzoate compound [1], which comprises reacting with a compound represented by [1], and containing one or more of the fluorine-containing phenyl benzoate compounds [1] as a component. It exists in liquid crystal compositions.

Examples of the fluorine-containing phenyl benzoate compound [1] of the present invention include those shown in Table 1 below.

The fluorine-containing phenyl benzoate compound [1] of the present invention is produced by, for example, (1) p-trifluoromethylphenol or an alkali metal salt thereof [] in the presence or absence of an acid acceptor. or (4) reacting p-trifluoromethylphenol [] with substituted benzoyl acid [V] in the presence or absence of a dehydrating agent. manufactured by the method.

Examples of the acid acceptor include aliphatic tertiary amines such as soda carbonate, pyridine, and triethylamine, and examples of the dehydrating agent include phosphorus pentoxide, anhydrous zinc chloride, metaphosphoric acid, polyphosphoric acid, and aromatic tertiary amines. Examples include sulfonic acid.

These reactions (i) and (1) are usually carried out in an inert organic solvent (e.g. ether, benzene, carbon tetrachloride, etc.), and the reaction temperature is generally room temperature, but the reaction can be completed more quickly. In order to achieve this, heating is also performed as necessary. The fluorine-containing phenyl benzoate compound [1] of the present invention synthesized as described above belongs to the smectite liquid crystal and is useful as a component of a liquid crystal composition. By mixing with other liquid crystals through processing, the stability and electrical properties mentioned above can be significantly improved.

Furthermore, because of its stability, it is not affected by the conditions of the environment in which it is used, and can withstand long-term use. In addition, the fluorine-containing phenyl benzoate compound [1] of the present invention
In addition to being extremely useful as a component of the liquid crystal composition, it also has interesting uses as a physiologically active substance.

Next, examples will be shown to specifically explain the present invention.

Example 1 p-n-butylbenzoyl chloride 3.0
7 (15.3 mmol) and 2.48 mmol (15.3 mmol) of p-trifluoromethylphenol are reacted in 15 ml of anhydrous benzene in the presence of 5 ml of anhydrous pyridine for 3 hours at room temperature while flowing dry nitrogen.

The temperature is further increased to 50° C. and the reaction is continued for 4 hours. After cooling, the mixture was filtered under a nitrogen stream, and the filtrate was dried under reduced pressure to obtain 3.65y of crude p'-trifluoromethylphenyl p-n-butylbenzoate. This crude product was recrystallized from enool, dissolved in benzene, treated with activated alumina, and recrystallized twice from methanol to obtain a purified product.

Melting point: 67.8°C. Elemental analysis, calculated value: C, 67.08%
．． ; Hl5, 28%, actual value: Cl67. l3%; Hl
5. The O4%o infrared absorption spectrum and mass spectrum were consistent with the predicted structural formula.

Example 2 p-n-pentylbenzoyl chloride 12.77 (6
0.4 mmol) and 12.07 (74.1 mmol) of p-trifluoromethylphenol in 30 m of anhydrous benzene.
1, was reacted in the same manner as in Example 1 in the presence of 15 ml of anhydrous pyridine to obtain crude p''-trifluoromethylphenyl p-
12.8y of n-pentyl benzoate was obtained.

It was purified in the same manner as in Example 1.

Melting point of purified product: 66.8°C 0 Elemental analysis, calculated value: C, 67.86%; Hl 5.65%, actual value: Cl 67.77%; Hl 5.
5l% o Example 3 p-n-hexylbenzoyl chloride 13.97 (6
2 mmol) and p-trifluoromethylphenol 10
．． 0? (61.8 mmol) was reacted in 30 ml of anhydrous benzene in the presence of 10111 anhydrous pyridine in the same manner as in Example 1 to produce crude p'-trifluoromethylphenyl p-n.
-Hexylbenzoate 11.47 were obtained.

It was purified in the same manner as in Example 1.

Melting point of purified product: 58.8°C.

Elemental analysis, calculated values: C, 68.57%, Hl 5.28%, actual values: Cl 68.39%; Hl 5.
45% o Example 4 p-n-heptylbenzoyl chloride 11.67f (
48.9 mmol) and p-trifluoromethylphenol 7.457 (46.0 mmol) in anhydrous benzene 30
In the presence of 15 ml of anhydrous pyridine, crude p'-trifluoromethylphenyl p was reacted in the same manner as in Example 1.
-n-heptylbenzoate 11.39y was obtained.

It was purified in the same manner as in Example 1.

Melting point of purified product: 61.0°C.

Elemental analysis, calculated value: C, 69.23%; Hl 632%, actual value: C, 69. l3%; Hl6.2
3% o Example 5 p-n-octylbenzoyl chloride 12.547 (
49.7 mmol) and 8.03y (49.6 mmol) of p-trifluoromethylphenol were reacted in the same manner as in Example 4 to obtain crude p'-trifluoromethylphenyl p-n.
-octyl benzoate 13.267 was obtained.

It was purified in the same manner as in Example 1.

Melting point of purified product: 58.5°C.

Elemental analysis, calculated value: Cl69.84%; Hl, 6.6l%, actual value: Cl69.7O%; Hl6
,49%.

Example 6 p-n-octylbenzoic acid 4.68y (2
0 mmol) and p-trifluoromethylphenol3.
247 (20 mmol) in 50 ml of benzene, 5.0 phosphorus pentoxide? The mixture was reacted for 5 hours under reflux to obtain 6.0 grams of crude p'-trifluoromethylphenyl p-n-octylbenzoate.

Melting point 58.5℃ o Elemental analysis, calculated value: C, 69.84%
; Hl6.6l%, actual value: Cl69.73%; Hl6.
52% o Example 7 p-n-pentaoxybenzoyl chloride 10.27
(45 mmol) and 7.24 y (45 mmol) of p-trifluoromethylphenol were reacted in the same manner as in Example 4 to obtain 11.5 y of crude p'-trifluoromethylphenyl p-n-pentaoxybenzoate. .

It was purified in the same manner as in Example 1.

Melting point of purified product: 78.5°C o Elemental analysis, calculated value: C, 64.59%; Hl 5.38%, actual value: Cl 64.82%; Hl 5.
24% o Example 8 p-n-hexaoxybenzoyl chloride 14.97
(62 mmol) and 10.0y (61.8 mmol) of p-trifluoromethylphenol were reacted in the same manner as in Example 4 to produce crude p'-trifluoromethylphenyl p-n-.
16.2V of hexaoxybenzoate was obtained.

It was purified in the same manner as in Example 1.

MRl74.7~76.5℃o elemental analysis, calculated value: Cl
65.57%; H, 5.74%, actual value: Cl65.45%; H, 5.
59%.

Example 9 p-n-heptaoxybenzoyl chloride 11.59
y (45.6 mmol) and p-trifluoromethylphenol 7.387 (45.6 mmol) were reacted in the same manner as in Example 4 to obtain crude p'-trifluoromethylphenyl p.
-n-pentaoxibe, zoate 12.8V was obtained.

It was purified in the same manner as in Example 1.

MRl 62.9-74.3°C. Elemental analysis, calculated value: C,
66.32%; Hl6. O8%, actual value: Cl65.6O%; H15.
96%.

Example 10 p-n-octaoxybenzoyl chloride 15.04
7 (56.1 mmol) and p-trifluoromethylphenol 9.017 (55.7 mmol) were reacted in the same manner as in Example 4 to obtain crude p'-trifluoromethylphenyl p.
13.7 units of -n-octaoxybenzoate were obtained.

It was purified in the same manner as in Example 1.

MR, 62.5-72.5℃ o elemental analysis, calculated value: C,
67.01%; Hl6.35%, actual value: Cl66.89%; Hl6,
18% o Example 11 p-acetoxybenzoyl chloride 10.997 (5
5.4 mmol) and 8.977 (55.4 mmol) of p-trifluoromethylphenol were reacted in the same manner as in Example 4 to obtain 8.727 of crude p'-trifluoromethylphenyl p-acetoxybenzoate. .

It was purified in the same manner as in Example 1.

Melting point: 143°C. Elemental analysis, calculated value: Cl59.26%;
Hl3.4O%, actual value: Cl59. O4%; H13.
2l%.

Claims (1)

[Claims] 1 General formula: ▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X represents an alkyl group or alkoxy group having 1 to 12 carbon atoms, or an acyloxy group having 2 to 13 carbon atoms. [In the formula, X represents an alkyl group or alkoxy group having 1 to 12 carbon atoms, or an acyloxy group having 2 to 13 carbon atoms. A liquid crystal composition comprising one or more of the fluorine-containing phenylbenzoate compounds represented by the following as a component.