JPS5923298B2 - 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, phenylbenzoate compounds containing cyano groups are excellent in colorlessness and chemical stability, and have large positive induced anisotropy due to the strong electron-withdrawing properties of cyano groups.
Although it is widely used as an FEM type display element, the phenylbenzoate compound that binds a perfluoro group according to the present invention is not known. The present invention has a strong electron-withdrawing group such as a cyano group, a trifluoromethyl group, or a nitro group,
Furthermore, by introducing a chemically stable perfluoroalkyl group, a new compound is provided, and when used as a component of a liquid crystal composition, it exhibits excellent effects in terms of stability and electrical properties. This work was completed after discovering that it can be achieved by the general formula: It represents an alkyl group or alkoxy group having 1 to 12 carbon atoms, a cyano group, a trifluoromethyl group, or a nitro group.

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

X has the same meaning as above. ] A compound represented by the general formula: [wherein Rf has the same meaning as above] in the presence or absence of an acid acceptor.

Z represents halogen. A method for producing a fluorine-containing phenyl benzoate compound (1) by reacting it with a compound represented by the general formula: [wherein X and Y have the same meanings as above.

] The compound shown in No. 1 is added in the presence of a dehydrating agent or
In the absence of the general formula: [wherein, Rf has the same meaning as ξ above.

A method for producing a fluorine-containing phenylbe]nozoate compound (1) by reacting it with a compound represented by ], p.
-Cyanophenol is represented by the general formula: [wherein Z' represents a hydroxy group or a halogen.

Rf has the same meaning as above. ] A fluorine-containing phenyl benzoate compound (1
), and a liquid crystal composition containing as a component one or more fluorine-containing phenyl benzoate compounds of general formula (1).

Representative examples of the fluorine-containing phenyl benzoate compounds of the present invention include those shown in Table 1 below.

The nitrogen-containing phenyl benzoate compound (1) of the present invention is produced by a general superstylation reaction, for example, by adding (1) p-cyanophenol or an alkali metal salt thereof in the presence of an acid acceptor. or by reacting (Ij) p-cyanophenol with substituted benzoyl halide in the presence or absence of a dehydrating agent.

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

These reactions (1) and (4) are usually carried out in an inert organic solvent (for example, ether, benzene carbon tetrachloride, etc.), and the reaction temperature is generally room temperature.
In order to complete the reaction more quickly, heating is also carried out as necessary. The fluorine-containing phenylbenzoate compound (1) of the present invention synthesized as described above belongs to smetatic liquid crystals and is useful as a component of a liquid crystal composition. By mixing with other liquid crystals, the stability and electrical properties 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 (g) of the present invention is
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 (1) Production of p-(3-trifluoromethylperfluorobutyl)benzoic acid: 200
3-trifluoromethyl perfluorobutyl iodide 19.5y (50 mmol), p-
12.4y (50 mmol) of iodobenzoic acid, 15.9y (250 mmol) of activated copper, and 100wL1 of dry dimethyl sulfoxide were added, and the mixture was heated and stirred at 130°C for 14.5 hours.

After cooling, the reaction mixture was added to 400 ml of water, and the precipitated solid was dried separately, extracted with 200 ml of ethanol, and concentrated to obtain 5.87 g of crude ρ-(3-trifluoromethylperfluorobutyl)benzoic acid. Ta. This crude product was recrystallized from ethanol and water. Melting point 189-1
Elemental analysis at 90°C, calculated value: C, 36.92%; H, l
．． 28%; F, 53.59%, actual value: C, 36.5O
%; H, l. 55%; F, 53.54% o The infrared absorption spectrum and mass spectrum were consistent with the predicted structural formula.

2) Production of p-(3-trifluoromethylperfluorobutyl)benzoyl chloride: 8.1 t (20 mmol) of benzoic acid obtained in (1) was heated under reflux with 35 ml of thionyl chloride for 3 hours, and then subjected to rectification. Yotsute p
-(3-trifluoromethylperfluorobutyl)benzoyl chloride 5.87 was obtained.

Boiling point: 79-81°C/0.8mmH70 Elemental analysis, calculated value: C, 35.25%; H, O. 98%, actual value: C, 3
5.50%; H, O. 80%.

The infrared absorption spectrum and mass spectrum were consistent with the predicted structural formula. (3) p/-cyanophenyl p-(3
-Production of trifluoromethylperfluorobutyl)benzoate: 4.86t (11.9 mmol) of p-(3-trifluoromethylperfluorobutyl)benzoyl chloride and 1.387t (11.6 mmol) of p-cyanophenol
mmol) to 20ml of anhydrous benzene11 anhydrous pyridine20
The reaction is allowed to proceed for 4 hours at room temperature in the presence of m1 under a stream of dry nitrogen.

The temperature is further increased to 50° C. and the reaction is continued for 4 hours. After cooling, the mixture was separated in a nitrogen stream, and the solution was dried to dryness under reduced pressure to obtain 5.5y of crude p'-cyanophenyl p-(3-trifluoromethylperfluorobutyl)benzoate.
This crude product was recrystallized from ethanol to obtain a purified product.
MR9O. O ~ 98.5℃ o elemental analysis, calculated value: C, 4
6.44%; H, l. 63%; N, 2.85%; F, 5
3,59%, actual value: C, 46.2O%; H, l. 38
%; N, 2.97%: F, 53.54% o The infrared absorption spectrum and mass spectrum were consistent with the predicted structural formula.

Example 2 (1) p-iodobenzoic acid 4.96f7
(20 mmol), Rf is (CF3)2CF(CF2C
F2)2 perfluoroalkyl iodide 9.92
y (20 mmol), copper 6.36V (50 mmol)
Example 1 using 40 ml of dimethyl sulfoxide and
Repeat the procedure of (1) to (CF3)2CF(CF2C
F2)2. C00H5.25f was obtained.

Melting point: 195-198°C.

Elemental analysis, calculated value: C, 34.36%; H, O. 82%
; F, 58. l6%, actual value: C, 34.53%; H
,O. 85%; F, 58. l5%.

(2) (CF3)2CF (CF2CF2) obtained in (1)
Repeating the procedure of Example 1(2) using 9.3y (19 mmol) of 2C00H and 55ml of thionyl chloride yielded (CF3)2CF(CF2CF2)2C0CI8.35
I got V.

Boiling point: 106°C/2nHV0 Elemental analysis, calculated value: C, 33. O4%; H, O. 79%
, Actual value: C, 32.89%; H, O. 59%.

(3) (CF3)2CF (CF2CF2) obtained in (2)
2- COCI2.54f7 (5 mmol), p-cyanophenol 0.6V (5 mmol), benzene 10
mI! and Example 1 (3) using 15 ml of pyridine.
Repeat the steps.

Obtained 2.50V.

MRIO9.6~121.3°C0 elemental analysis, calculated value:
C, 4O. 6l%; H, l. 35%: F, 2.37%,
Actual value: C, 42.63%; H, l. O8%; F,2
．． The infrared absorption spectra and mass spectra of the products of 54%o(1), (2), and (3) were consistent with the predicted structural formula.

Example 3 (1) p-iodobenzoic acid 2
4.8V (100 mmol), Rf is (CF3)2CF
(CF2CF2)3 perfluoroalkyl iodide 59.6y (100 mmol), copper 12.7y (2
04 mmol), and dimethyl sulfoxide 250 m
The procedure of Example 1 (1) was repeated using i to obtain v.

Melting point 196-198 by C0 elemental analysis, calculated value 2C,32
．． 54%; H, O. 85%, actual value: C, 32.49%
;H,O. 63%.

(2) (CF3)2CF (CF2CF2) obtained in (1)
Repeating the procedure of Example 1(2) using 6.0y (10 mmol) of 3C00H and 30ml of thionyl chloride yielded (CF3)2CF(CF2CF2)3C0CI2.17
I got V.

Boiling point: 92-103°C/2.0mmHy0 Elemental analysis, calculated value: C, 3l. 55%; H, O. 66%
, Actual value: C, 3l. 72%; H, O. 54%0(3)
(CF3)2CF(CF2CF2)3C0 obtained in (2)
CI 1.78y (1.9 mmol), p-cyanophenol 0.23V (1.9 mmol), benzene 10
The procedure of Example 1(3) was repeated using 10% of pyridine and 10% of pyridine. CNl. Obtained 5 Oy.

MRl3O. 7-140.7OC0 Elemental analysis, calculated value: C, 38.2l%; H, l. l6%
; N, 2. O3%, actual value: C, 39.9l%; H
,O. 85%; N, 2.25%.

The infrared absorption spectra and mass spectra of the products (1), (2), and (3) were consistent with the predicted structural formulas. Example 4 (1) p-iodobenzoic acid 24.8
Repeat the procedure of Example 1(1) using f7 (100 mmol), perfluoroalkyl iodide 52.2y (117 mmol) with Rf = C6Fl3, copper 31.8t (500 mmol) and dimethyl sulfoxide 250g. C6Fl3-COOH6.9f7 was obtained.

Melting point 196-198°C. Elemental analysis, calculated value: C, 37.
45%; H, l. l4%; F, 53. l4%, actual value: C, 37.35%; H, l. OO%; F, 53.4
The procedure of Example 1(2) was repeated using 6.4y (14.5 mmol) of C6Fl3-COOH obtained with O%o(l) and 50 ml of thionyl chloride to obtain C6Fl3CO
CI4. Obtained OV.

Boiling point: 75C/0.7mmH10 Elemental analysis, calculated value: C, 34. lO%; H, O. 87%
, Actual value: C, 3l. O2%; H, O. 90%o(3)
C6Fl3−《》→℃Cl3.48y(
7.6 mmol), p-soanophenol 0.9 V (7
．． 6 mmol), 20 ml of benzene and 20 ml of pyridine
Repeat the procedure of Example 1 (3) using m1 to obtain C3.
Obtained 9OV.

MR99.8-123.3℃ o elemental analysis, calculated value: C,
44.34%: H, l. 47%; N, 2.59%;
F, 45.66%, actual value: C, 44.36%; H,
l. l8%; N, 2.75%; F, 45.2O%o(
The infrared absorption spectra and mass spectra of the products 1), (2), and (3) were consistent with the predicted structural formulas.

Examples 5-6 (1) 18.71 (75 mmol) of p-iodobenzoic acid, 43.2 V (80 mmol) of perfluoroalkyl iodide whose Rf is C8Fl7, 1.9. IV (140 mmol) and dimethyl sulfoxide 120 mg by repeating the procedure of Example 1(1) to obtain C8F17-COOH16. Obtained OV.

Melting point 199-200'CO elemental analysis, calculated value: C, 3
3.33%; H, O. 93%, actual value: C, 33. O9
%; H, O. 73%. (2) COOH26. obtained in (1). The procedure of Example 1(2) was repeated using Oy (48.1 mmol) and thionyl chloride 120y to give 18.7y.

Boiling point 112-114.

C/ 1.0mmHy0 elemental analysis, calculated value 2C, 32.
29%; H, O. 72%, actual value: C, 32. l4%;
H.O. 7O%0 (3) In Example 5, C8 obtained in (2)
Fl7COCI3.45V (6.2 mmol), p-
Example 1 using cyanophenol 0.74y (6.2 mmol), benzene 20ml and pyridine 20ml
The procedure (3) was repeated to obtain C8F,7-CN3.7V.

MRll8~1457C0 Elemental analysis, calculated value: C, 4l. l9%; H, l. 25%
; N, 2. 18%, actual value: C, 4l. O2%; H
,O. 96%; N, 2.4O%o in Example 6 (2)
C8Fl7-COCI3. The procedure of Example 1(3) was repeated using 0.60V of CH3-0H (5.6 mmol), 20ml of benzene and 15ml of pyridine to obtain C8F,7-33.
I got 5y.

MRllll~112°C (monotropic).

Elemental analysis, calculated value: C, 4l. 90%; H, l. 75%
, Actual value: C, 4l. 86%; H, l. 44%o(1)
, (2), and (3), the infrared absorption spectra and mass spectra of all products were consistent with the predicted structural formula.

Examples 7 to 9 (1) p-iodobenzoic acid 12.4V (
50 mmol), Rf is (CF3)2CFCF2CF2
Perfluoroalkyl iodide 19.5y (50
Example 1 (1) using 15.9y (250 mmol) of copper and 100 ml of dimethyl sulfoxide
The procedure was repeated to obtain COOH5.8V.

Melting point: 189-190°C. Elemental analysis, calculated value: C, 36.
92%; H, 1.28%; F, 53.59%, actual value:
C, 36.5O%; H, l. 55%; F, 53.5
4%.

(2) (CF3)2CFCF2CF2. obtained in (1). C
00H8. IV (20 mmol) and thionyl chloride 3
5m1! , the procedure of Example 1 (2) was repeated to obtain (CF3)2CFCF2CF25.8t.

Boiling point 79-81°C/0.8 dew HyO elemental analysis, calculated value: C, 35.25%; H, O. 98%, actual value: C,
35.5O%: H, O. 8O%0(3) In Example 7 (
(CF3)2CFCF2CF2C0CII2 obtained in 2)
．． 86f7 (7 mmol), 0H1.19V (7 mmol) - 3.2V of C,Hll was obtained using 15ml of benzene and 5wj of pyridine.

MR57-58°C (monotropic).

Elemental analysis, calculated value: C, 5l. 49%; H, 3.54%
, Actual value: C, 5l. 4l%: H, 3.24% 0 Actual value 8 (CF,)2CFCF2CF2C0 obtained in (2)
CI3V (7.4 mmol), CF3OHl. 2V(
7.4 mmol), 10 benzene and 1 pyridine
The procedure of Example 1 (3) was repeated using CF
3) 2CFCF2CF2CF33.91V was obtained.

MR67.5-68.7°C (monotropic).

Elemental analysis, calculated value: C, 42.7O%; H, O. Ol%
, Actual value: C, 42.68%; H, O. Ol%. In Example 9, (CF3)2CFCF2CF2C0 obtained in (2)
CI1.85V (4.6 mmol), -0H0.6
4, (4.6 mmol), 10% benzene and 10% pyridine. Obtained O2V.

MR68.6-79.2°C. Elemental analysis, calculated value: C,
42.27%; H, O. O2%, actual value: C, 42. l
7%; H, O. The infrared absorption spectra and mass spectra of any of the products of O2%o(1), (2), and (3) were consistent with the predicted structure.

Example 10 C8Fl,-3.45y (6.2 mmol) obtained in Example 5 (2) and p-butoxyphenol 1.03V (6.2 mmol) were mixed with anhydrous benzene 2
0? 20ml of Ni and anhydrous pyridine! In the presence of 0C4H, 4.
I got 04v.

MR: 900C (Monotropic).

Elemental analysis, calculated value: C, 43.6O%; H, 2.47%
F, 46.95%, actual value: C, 43.4O%;
H, 2.5 l%: F, 46.92% o Example 11 (CF3)2CFCF2CF2-CO obtained in Example 1 (2)
CI4.86f7 (11.9 mmol) and p-pentyloxyphenol 2.14V (11.9 mmol) were reacted in the same manner as in Example 10 to give -0C,H,...
Obtained 6.24y.

MR: 70°C (monotropic).

Elemental analysis, calculated values: C, 5O. OO%; H, 3.44%
; F, 37.86%, actual value: C, 49.86%; H
, 3.62%; F, 3785%.

Example 12 In Example 11, p-hexyloxyphenol 2.31f7 (1
The same procedure was repeated except using 1.9 mmol) to obtain 0C6H136.26V.

MR: 65°C (monotropic).

Elemental analysis, calculated values: C, 5O. 88%; H, 3.7l%
F, 36.93%, actual value: C, 5O. 62%;
H, 3.62%; F, 36.90%.

Claims (1)

[Claims] 1 General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Rf is a perfluoroalkyl group having 1 to 12 carbon atoms; X is an alkyl group or alkoxy group having 1 to 12 carbon atoms. , represents a cyano group, a trifluoromethyl group or a nitro group. ] A fluorine-containing phenylbenzoate compound represented by: 2 General formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, Rf is a perfluoroalkyl group having 1 to 12 carbon atoms; Represents a methyl group or a nitro group. 1 of the fluorine-containing phenylbenzoate compound shown by
A liquid crystal composition comprising one or more species as components.