JPH07233140A - Fluorine-containing benzene derivative - Google Patents

Abstract

(57) [Summary] [Structure] [Chemical Formula 1] (In the formula, X represents a nitro group or an amino group, and Y represents -S-.
Or -SO ₂ - indicates, Rf is -C _n F _{2n + 1} or -C _n
F _2n H, m is 1 to 8, and n is an integer of 1 to 18). The compound of the present invention is useful as a raw material for a dichroic dye.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel benzene derivative having a fluorine-containing hydrocarbon group in its side chain, which is useful as a synthetic intermediate for dyes, pharmaceuticals, agricultural chemicals, liquid crystals and the like.

[0002]

2. Description of the Related Art Compounds containing fluorine have a unique viscoelasticity,
Since it tends to exhibit stability, surface activity, physiological activity, etc., its application to dyes, pharmaceuticals, agricultural chemicals, surfactants, liquid crystals, etc. is being investigated.

[0003]

However, fluorine-containing compounds are generally difficult to synthesize, and therefore the development of their applications has been limited. Therefore, the present invention provides a fluorine-containing compound useful as a synthetic intermediate for dyes, pharmaceuticals and agricultural chemicals, surfactants, liquid crystals and the like.

[0004]

The compound of the present invention is represented by the following formula.

[0005]

[Chemical 2]

[0006] (wherein, X represents a nitro group or an amino group, Y is -S- or -SO ₂ - indicates, Rf is -C _n F
_{2n + 1} or indicates -C _n F _2n H, m is an integer of 1 to 8, n is an integer of 1~18) Rf- (CH _{2) m} of the compounds of the present invention - the carbon chain of the group The length of the is appropriately selected depending on the final product derived from the compound of the present invention. For example in the case of a dichroic dye for liquid crystals, Rf- (CH _{2) m} - number of carbon atoms of the groups generally 2-12
Is preferred. Further, in the case of the surfactant, those having a long carbon chain are generally preferable. The compounds of the present invention are
It can be produced from thiophenols by the following route.

[0007]

[Chemical 3]

These reactions can be carried out according to conventional methods. For example, the first stage alkylation reaction generally proceeds easily in a polar solvent at room temperature. Further, the reduction of the nitro form to the amino form may be carried out by dissolving the nitro form in a suitable solvent and reducing with hydrochloric acid / iron under heating, or by catalytic reduction with hydrogen using a noble metal catalyst or the like. Further, the oxidation of the thioether body to the sulfone body can be easily carried out by using potassium permanganate or hydrogen peroxide.

[0009]

EXAMPLES Next, the present invention will be specifically described by way of examples. Example 1 To 20 ml of dimethylformamide, 24 mmol of p-aminothiophenol was added, 30 mmol of sodium hydride was added with stirring, and the mixture was stirred at room temperature for 3 hours.
Then, 30 mmol of 2- (perfluorobutyl) ethyl iodide was added, and the mixture was stirred overnight at room temperature under a nitrogen atmosphere. The reaction mixture was discharged into 150 ml of water and extracted with ether. The ether layer was washed and dried, the solvent was distilled off, and the residue was purified by distillation to obtain the desired product having the following structure.

[0010]

[Chemical 4]

The physical properties of this compound were as follows. bp 114 ° C./130 Pa; ¹ H NMR (CDCl ₃ ) δ 2.31 (tt, J =
16.8 and 8.2Hz, 2H), 2.93 (t
t, J = 8.2 and 3.2 Hz, 2H), 3.7
5 (br s, 2H), 6.65 (d, J = 8.5H)
z, 2H), 7.26 (d, J = 8.5 Hz, 2H); EIMS (70 eV) m / z (rel intensi)
ty) 371 (M ⁺ , 100), 124 (88).

Example 2 The following object was obtained in exactly the same manner as in Example 1 except that 2- (perfluorohexyl) ethyl iodide was used instead of 2- (perfluorobutyl) ethyl iodide. .

[0013]

[Chemical 5]

The physical properties of this compound are as follows. bp 120 ° C./1.3 mmHg; ¹ H NMR (CDCl ₃ ) δ 2.32 (tt, J =
17.7 and 8.2Hz, 2H), 2.93 (t
t, J = 8.2 and 3.1 Hz, 2H), 3.7
2 (br s, 2H), 6.63 (d, J = 8.2H
z, 2H), 7.26 (d, J = 8.2 Hz, 2H); EIMS (70 eV) m / z (rel intensi)
ty) 471 (M ⁺ , 25), 124 (100).

Example 3 30 mmol of p-nitrothiophenol was added to 20 ml of dimethylformamide, 50 mmol of sodium hydride was added with stirring, and the mixture was stirred at room temperature for 3 hours. Then 2- (perfluorobutyl) ethyl iodide 3
5 mmol was added, and the mixture was stirred overnight at room temperature under a nitrogen atmosphere, the reaction mixture was discharged into 150 ml of water, and a yellow precipitate was collected by filtration. This was recrystallized from hexane to obtain the target product having the following structure.

[0016]

[Chemical 6]

The physical properties of this compound are as follows. bp 136 ° C./1.0 mmHg; ¹ H NMR (CDCl ₃ ) δ 2.50 (tt, J =
16.5 and 8.2 Hz, 2H), 3.29 (t
t, J = 8.2 and 2.4 Hz, 2H), 7.3
8 (d, J = 8.9 Hz, 2H), 8.18 (d, J =
8.9 Hz, 2 H); EIMS (70 eV) m / z (rel intensi)
ty) 401 (M ⁺ , 100), 371 (18), 16
8 (25).

Example 4 The following object was obtained in exactly the same manner as in Example 3 except that 2- (perfluorohexyl) ethyl iodide was used instead of 2- (perfluorobutyl) ethyl iodide. .

[0019]

[Chemical 7]

The physical properties of this compound are as follows. mp 40-41 ° C .; ¹ H NMR (CDCl ₃ ) δ 2.45 (tt, J =
16.5 and 8.1 Hz, 2H), 3.27 (t
t, J = 8.1 and 2.6 Hz, 2H), 7.3
7 (d, J = 9.0 Hz, 2H), 8.18 (d, J =
9.0 Hz, 2H); EIMS (70 eV) m / z (rel intensi)
ty) 501 (M ⁺ , 90), 170 (52), 109
(50), 77 (32).

Example 5 The following compound synthesized according to Example 3

[0022]

[Chemical 8]

4 mmol was added to 10 ml of acetic acid, and 75 ml of water containing 10 mmol of potassium permanganate was added at 40 ° C. with stirring. After 15 minutes, the reaction product was discharged into excess water containing sodium hydrosulfite, and a white precipitate was collected by filtration. This was recrystallized from hexane to obtain the following target product.

[0024]

[Chemical 9]

The physical properties of this compound were as follows. mp 121-123 ° C .; ¹ H NMR (CDCl ₃ ) δ 2.06 (tt, J =
17.1 and 8.2 Hz, 2H), 2.81 (t
t, J = 8.2 and 4.0 Hz, 2H), 7.5
9 (d, J = 8.5 Hz, 2H), 7.90 (d, J =
8.5 Hz, 2 H); EIMS (70 eV) m / z (rel intensi)
ty) 433 (M ⁺ , 6), 186 (100), 122
(74), 77 (38).

Example 6 Example 5 except that the compound synthesized according to Example 4 was used.
The following target was obtained in the same manner as in.

[0027]

[Chemical 10]

The physical properties of this compound were as follows. mp 122-123 ° C .; ¹ H NMR (CDCl ₃ ) δ 2.65 (tt, J =
16.0 and 8.2 Hz, 2H), 3.39 (t
t, J = 8.2 and 3.8 Hz, 2H), 8.1
7 (d, J = 8.9 Hz, 2H), 8.48 (d, J =
8.9 Hz, 2 H); EIMS (70 eV) m / z (rel intensi)
ty) 533 (M ⁺ , 5), 186 (100), 122
(72), 77 (70).

Example 7 The following compound synthesized according to Example 5

[0030]

[Chemical 11]

2 mmol and 12 mmol of concentrated hydrochloric acid were heated and refluxed with 25 ml of methanol, to which 12 m of iron powder was added.
Mol was gradually added and stirred. After confirming the disappearance of the raw material by thin layer chromatography, the reaction product was discharged into excess water containing caustic soda, and the precipitate was collected by filtration. It was then Soxhlet extracted with methanol. After concentrating this extract, column chromatography purification was performed using dichloromethane to obtain the following target product.

[0032]

[Chemical 12]

The physical properties of this compound are shown below. ¹ H NMR (CDCl ₃ ) δ 2.56 (tt, J =
17.7 and 8.4 Hz, 2H), 3.27 (t
t, J = 8.4 and 3.7 Hz, 2H), 4.3
0 (br s, 2H), 6.74 (d, J = 8.7H)
z, 2H), 7.68 (d, J = 8.7 Hz, 2H); EIMS (70 eV) m / z (rel intensi)
ty) 403 (M ⁺ , 64), 156 (100), 10
8 (69), 92 (79), 65 (59).

Example 8 The following target product was obtained in the same manner as in Example 7 except that the compound synthesized in Example 6 was used.

[0035]

[Chemical 13]

The physical properties of this compound were as follows. mp 164-165 ° C .; ¹ H NMR (CDCl ₃ ) δ 2.56 (tt, J =
17.0 and 8.4 Hz, 2H), 3.26 (t
t, J = 8.4 and 4.4 Hz, 2H), 4.2
8 (br s, 2H), 6.74 (d, J = 8.7H)
z, 2H), 7.67 (d, J = 8.7 Hz, 2H); EIMS (70 eV) m / z (rel intensi)
ty) 503 (M ⁺ , 32), 471 (51), 140
(100), 124 (69), 92 (52).

Application Example 1 Compound obtained in Example 7

[0038]

[Chemical 14]

Acetone containing 0.8 g (2 mmol)
Dimethylformamide mixed solution (mixing ratio 1: 1) 20 ml
0.5 ml of concentrated hydrochloric acid was added to and cooled to 0 ° C. To this was added 5 ml of an aqueous solution containing 0.14 g (2 mmol) of sodium nitrite. After 15 minutes, the following compound was added to this mixed solution.

[0040]

[Chemical 15]

Aqueous solution 1 containing 0.42 g (2 mmol)
0 ml was added at 0 ° C., and the mixture was stirred at the same temperature for 1 hr. Then, the reaction mixture was discharged into excess water, and the precipitate was collected by filtration. This was refluxed for 6 hours in an aqueous solution containing 4 g of sodium hydroxide. After cooling, it was extracted with dichloromethane. The extract was purified by column chromatography using a 4: 1 mixture of dichloromethane: acetone to obtain 0.5 g (yield 50%) of a monoazo compound having the following structure.

[0042]

[Chemical 16]

The physical properties of this compound were as follows. mp 197-198 ° C .; ¹ H NMR (CDCl ₃ ) δ 2.62 (tt, J =
18.0 and 8.2 Hz, 2H), 3.37 (t
t, J = 8.2 and 4.8 Hz, 2H), 4.2
2 (br s, 2H), 6.76 (d, J = 8.8H
z, 2H), 7.86 (d, J = 8.8Hz, 2H),
8.02 (d, J = 3.0 Hz, 4H); EIMS (70 eV) m / z (rel intensi)
ty) 507 (M ⁺ , 18), 120 (42), 92
(100); UV (EtOH) 424 nm (19800).

Acetone: dimethylformamide: water 2: 0.5: containing 0.5 g (1 mmol) of this compound.
To 25 ml of 0.5 mixture, add 0.25 ml of concentrated hydrochloric acid,
Cooled to ° C. Then sodium nitrite 0.07g (1
5 ml of an aqueous solution containing (mmol) was added. After 15 minutes, 5 ml of an acetone solution containing 0.3 g (2 mmol) of N, N-diethylaniline was added to this solution at 0 ° C. with stirring.
The temperature was maintained for 1 hour. The reaction mixture was discharged into excess water and the precipitate was collected by filtration. This was purified by column chromatography using dichloromethane to obtain a dye having the following structure.

[0045]

[Chemical 17]

The physical properties of this dye were as follows. λmax (EtOH): 505 nm ¹ H NMR (CDCl ₃ ) δ 1.26 (t, J =
7.0 Hz, 6H), 2.64 (tt, J = 18.0)
and 8.4 Hz, 2H), 3.39 (tt, J =
8.4 and 4.0 Hz, 2H), 3.49 (q,
J = 7.0 Hz, 4H), 6.75 (d, J = 9.2H)
z, 2H), 7.91 (d, J = 9.2Hz, 2H),
7.99 (d, J = 8.7 Hz, 2H), 8.10
(D, J = 8.7 Hz, 2H), 8.11 (s, 4
H); EIMS (70 eV) m / z (rel intensi)
ty) 667 (M ⁺ , 23), 148 (100);

This azo dye is called as ZLI-1565 under the trade name.
A red guest-host type liquid crystal composition was prepared by dissolving it at a concentration of 1 wt% in a phenylcyclohexane liquid crystal mixture commercially available as (E. MERCK). This was coated with a polyimide resin, cured, and rubbed to face a glass substrate with a transparent electrode, and the glass substrate was sealed in a cell having a gap of 9 μm configured so that liquid crystals were aligned in parallel.

The absorbance (A //) of linearly polarized light parallel to the orientation direction of this red-colored cell and the absorbance (A⊥) of linearly polarized light perpendicular to the orientation direction were measured, and the absorption peak (λmax: 512 nm) was measured. The order parameter (S) in S was 0.76 as a result of obtaining from the following formula S = (A // − A⊥) / (A / ++ 2A⊥).

The trade name Z is used in place of the above ZLI-1565.
Using a fluorine-based liquid crystal mixture commercially available as LI-4792 (manufactured by E. MERCK), the order parameter was determined in the same manner. As a result, S = 0.76 (λma)
x: 506 nm). From the above, this dye is useful as a dichroic dye.

Application Example 2 The following compound obtained in Example 1

[0051]

[Chemical 18]

To 10 ml of acetic acid solution containing 0.30 g (0.8 mmol), 0.12 of 4-nitrosonitrobenzene was added.
g (0.8 mmol) was added, and the mixture was stirred at room temperature overnight. The reaction product was collected by filtration, washed with water and dried to give 0.34 g of the following compound
(Yield 83%) was obtained.

[0053]

[Chemical 19]

The physical properties of this compound were as follows. mp 119-120 ° C .; ¹ H NMR (CDCl ₃ ) δ 2.49 (tt, J =
16.5 and 8.2 Hz, 2H), 3.26 (t
t, J = 8.2 and 3.2 Hz, 2H), 7.4
5 (q, J = 8.8 Hz, 2H), 7.96 (d, J =
8.8 Hz, 2 H), 8.03 (d, J = 9.1 Hz,
2H), 8.39 (d, J = 9.1 Hz, 2H); EIMS (70 eV) m / z (rel intensi)
ty) 505 (M ⁺ , 23), 355 (100), 12
2 (22).

0.25 g (0.5 mmol) of this compound
100 ml of 85% ethanol solution containing Na ₂ S (1
(5 mmol) aqueous solution (5 ml) was added and the mixture was refluxed for 1 hour. The reaction mixture was discharged into 30 ml of water, and the precipitate was collected by filtration. This was washed with water, dried and purified by column chromatography using dichloromethane to obtain 0.086 g (yield 34%) of a monoazo compound having the following structure.

[0056]

[Chemical 20]

The physical properties of this monoazo compound were as follows. mp 97-98 ° C .; ¹ H NMR (CDCl ₃ ) δ 2.44 (tt, J =
16.6 and 8.1 Hz, 2H), 3.19 (t
t, J = 8.1 and 2.9 Hz, 2H), 4.0
6 (br s, 2H), 6.74 (d, J = 8.9H)
z, 2H), 7.43 (d, J = 8.7Hz, 2H),
7.80 (d, J = 8.9 Hz, 2H), 7.82
(D, J = 8.7 Hz, 2H); EIMS (70 eV) m / z (rel intensi)
ty) 475 (M ⁺ , 60), 120 (40), 92
(100). In the same manner as in Application Example 1, this monoazo compound and N, N-
A dye having the following structure was obtained by reacting with diethylaniline.

[0058]

[Chemical 21]

The physical properties of this dye were as follows. λmax (hexane): 466 nm; mp 138-140 ° C .; ¹ H NMR (CDCl ₃ ) δ 1.25 (t, J =
7.0 Hz, 6 H), 2.47 (tt, J = 18.6)
and 8.2 Hz, 2H), 3.23 (tt, J =
8.2 and 2.9 Hz, 2H), 3.48 (q,
J = 7.0 Hz, 4H), 6.75 (d, J = 9.2H)
z, 2H), 7.45 (d, J = 8.4Hz, 2H),
7.90 (d, J = 9.2 Hz, 2H), 7.92
(D, J = 8.4 Hz, 2H), 7.97 (d, J =
8.8Hz, 2H), 8.03 (d, J = 8.8Hz,
2H); EIMS (70 eV) m / z (rel intensi)
ty) 635 (M ⁺ , 40), 620 (18), 176
(12), 148 (100). The order parameter of this dye in a liquid crystal mixture was found to be S = 0.77 (λm in ZLI-1565).
ax: 502 nm), S = 0.7 in ZLI-4792.
7 (λmax: 498 nm).

Claims (1)

[Claims] Claims: (In the formula, X represents a nitro group or an amino group, and Y represents -S-.
Or --SO _2- , and Rf is --C _n F _{2n + 1} or --C
_n F _2n H, m is an integer of 1 to 8, and n is 1 to 1.
A benzene derivative represented by (indicating an integer of 8).