JPS58121252A - Aniline derivative - Google Patents

Abstract

NEW MATERIAL:An aniline derivative expressed by formulaI(X is O or S). EXAMPLE:p-(Bromodifluoromethylthio)nitrobenzene. USE:A synthetic intermediate for insecticides. For example, the compound expressed by formulaIis reacted with phosgene, etc. to convert the amino group into an isocyanate group, and the resultant compound expressed by formula IV is reacted with a phrazoline derivative of formula V to give a compound expressed by formula VI having the insecticidal activity. PROCESS:A nitrobenzene derivative expressed by formula II is reacted with dibromodifluoromethane in the presence of a base, e.g. an alkali metallic hydride, to give a p-substituted nitrobenzene expressed by formula III, which is then reduced to afford the aniline derivative expressed by formulaI. The reaction for obtaining the compound expressed by formula III is preferably carried cut in an aprotic solvent, e.g. THF, at room temperature. The reductive reaction is carried out by heating the p-substituted nitrobenzene expressed by formula III in the presence of an acid, e.g. hydrochloric acid, and iron powder under refuxing.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aniline derivative represented by the general formula (wherein X is an oxygen atom or a sulfur atom).

The aniline derivative represented by the general formula (1) is reacted with phosgene etc. to convert the amino group to incyanate group, and then
By reacting with pizzoline derivatives, compounds useful as insecticides can be obtained (see reference side below).

The Ayun9ne derivative represented by the general formula (1) of the present invention can be produced according to the following reaction formula.

(I) (wherein, By this, p-substituted nitrobenzene represented by the above general formula (2) is produced.

The nitrobenzene derivatives represented by the above-mentioned general formula values, which are raw materials, are p-nitrothiophenol and hypo-nitrophenol. These are industrially easily available compounds. Further, one of the raw materials, dibromodifluoromethane, is also a compound that is easily available as an industrial raw material.

It is essential that this step be carried out in the presence of a base. As the base, an alkali metal hydride such as sodium hydride or an organic lithium compound such as butyllithium can be used.

The amount of base used is usually LO to L5 relative to the nitrobenzene derivative as a raw material.

When this step is carried out, it is desirable to carry out it in an aprotic solvent such as N,N-dimethylformamide (hereinafter abbreviated as DMF), dimethoxyethane, tetrahydro7rane, dimethyl sulfoxide or the like.

In order to efficiently obtain p-substituted nitrobenzene, it is preferable to sufficiently contact the nitrobenzene derivative with a base in an aprotic solvent and then react with dibromodifluoromethane.

The reaction proceeds at 0° C. to room temperature, but it is preferable to carry out K at room temperature in order to efficiently obtain the target product.

[Second process]

In this step, the aniline derivative represented by the general formula (2) is produced by reducing the p-substituted nitrobenzene represented by the general formula (2) obtained in the first step.

Reduction methods include iron reduction under acidic conditions and tin reduction.
A reduction method using hydrochloric acid, a reduction method using zinc, and a water red reaction using a metal catalyst can be adopted. For example, in the reduction method using iron, the reaction proceeds quickly and the desired aniline derivative can be efficiently obtained by heating and refluxing iron powder in the presence of an acid such as acetic acid or hydrochloric acid in an organic solvent such as ethanol. It is.

Example 1 Sodium hydride (50-18 J) g, 167 in water bath
Kp-nitrothiophenol (25gs161
mmol) in dimethylformamide (200y) was added, and the mixture was stirred in a water bath for 60 minutes. Dibromodifluoromethane (50g,
A solution of 238 mmol) was added thereto, and the mixture was stirred in a water bath for 1 hour and then at room temperature for 5 hours.

Water was added, extracted with methylene chloride, and dried over anhydrous magnesium sulfate. The crude product obtained by concentration was purified by column chroma dog 2 filter to obtain 40Ag of p-(7'romodifluoromethylthio)nitrobenzene. Yield 88
%.

m-p・=72-76℃.

'H-NMR: J 7.93 (2H, d), 8J6 (
21-1,4)・”i'i-NMR:δ(OF3002
H) 53.8 (s) - Elemental analysis ■ Calculated value: 0.29jO, H, IJ2. N, 493
゜Actual value: 0.29A2. H, 1, 42, N, 4
86゜Example 2 Ethanol (300m) Kp-(7'romodifluoromefkf-o)nitrobenzene (32.4g), iron powder (
25g) and acetic acid (60*) were added, and the mixture was heated under reflux for 1 hour. After most of the solvent was removed under reduced pressure, water was added and the mixture was extracted with ether. The extract was washed with brine and then dried over anhydrous magnesium sulfate. After distilling off the solvent, it is purified by column chromatography! =15.5 g of p-(bromodifluoromethylthio)aniline as a colorless oil. Yield: 54 cm.

'H-NMR: δ! 1.90(2)Ls), 6-6
3 (2H, d).

7At(2H,d)-19F-NMR(OFjO02H): δ56.7(s
) Example 3 50% hydrogenated sodium A (5-Og, 104mmo
l ) was added to DMF (20 m/ ) and cooled in a water bath. To this was added p-nitrophenol (139 g, 100
A solution of mmof) in DMF (100y) was added dropwise. 10
After stirring for a minute, dibromodifluoromethane (25 g,
Add a solution of 119 mmol) in DMF (60 ml),
The mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water and extracted with ether. The ether layer was dried over anhydrous magnesium sulfate and the solvent was distilled off, followed by distillation to obtain p-nitro(bromodifluoromethoxy)benzene (13-4 g).

Yield 50-0 Boiling point near 4-77℃10. ITorr・'H-NMR
(ODO1s): J 7J O (d-J = 9H
z)-8-50 (d, J-9Hz).

'F-NMR(ODOI3):J(OF3CO2H):
61.9(s)-M8:m/e 269(9), 26
7(10), 189(11).

188 (100).

Example 4 xp, /-+ (100aj) medium iCp (7'romodifluorotetramethoxy)nitrobenzene (10.0g),
Iron powder (7-5 g) and acetic acid (ISg) were added, and the mixture was heated under reflux for 2 hours. Most of the ethanol is distilled off, water is added,
Extracted with ether. After washing with ether layered saline solution, it was dried over anhydrous magnesium sulfate. #! The medium was removed and the mixture was distilled to obtain 6.2 g of p-(bromodifluoromethoxy)aniline. Yield: 70 cm.

α1 Boiling point: 65-726'7orr-'H-NMR: δ353(2)Ls), 6J3(
21(,d).

7.0'5 (2H, d).

1? F-NMR: δ 65 (JCs>- Reference Example 1 41-hydroxy-2-phenylacetophenone 17 g
, 50 g of sodium hydroxide, 40 d of water, 5 d of dioxane
0 iu solution and heated to 70-80°C. Further, while continuing heating, 22 g of Freon 22 gas was blown into the reactor over 1 hour. Cooling drain water 150a (, nibble ether 15
0M1 was added and an extraction operation was performed to obtain an organic layer. After drying with 9 um of anhydrous sulfuric acid, the ether was distilled off to give 174 g of 4
Next, 17.5 g of the compound obtained here was added to 0.9 d of piperidine.
, 25at of acetic acid, 0-9dj7-formalin, and 180Il of methyl alcohol, and the mixture was reacted under reflux for 3 hours. After concentrating the reaction mixture under reduced pressure, 15% of water was added.
0MtS chlorinated form 200% was added and the layers were separated to obtain an organic layer. After drying over anhydrous sodium sulfate, chloroform was distilled off to give 18 J) g of eedifluoromethoxy-2-
Phenyl acrylophenone was obtained. Then this product 17
．． 5g and hydrazine hightray) 8d in 150#I1
A reflux reaction was carried out for 3 hours in 0% alcohol. After the reaction, the mixture was concentrated under a passing pressure, and then 80 d of water and 100 d of chloroform were added to obtain an organic layer. After drying with anhydrous sodium sulfate,
Chloroform was distilled off to obtain 175 g of 3-(4-difluoromethoxyphenyl)-4-phenyl-2-pyrazoline (melting point 65-75°C).

Reference Example 2 74 g of p-(p-tetramodifluoro p-methylthio)aniso was added to 4
Dissolved in 0ml of ethyl acetate. Add this solution to 40ml
was added dropwise to ethyl acetate while introducing phosge/. After the completion of the dropwise addition, phosgene was introduced for another 10 minutes. The reaction mixture was concentrated under reduced pressure to obtain 4 g of product (nn 1-5790).
. The product was immediately used as a raw material for Reference Example B without being purified.

Reference Example 6 9p-promodifluoromethylteotzenyl isocyanate 5-g obtained in Reference Example 2 and 3-(4-difluoromethoxycouphenyl)-4-phenyl-2-pyrazoline obtained in Reference Example 5.8 g was added to 150 d of dry ethyl ether and stirred at room temperature for 6 hours. The precipitated crystals were collected by filtration and washed with n-hexane. 5. %, this product was determined by nuclear magnetic resonance absorption spectroscopy to be 9l-(4
-dibromodifluorotetramethyldeophenylcarbamoyl)-3-(4-9fluoromethoxyphenyl)-4-phenyl-2-pyrazoline.

Melting point: 166-136'C.

Reference Example 4 1-(4-ProtemodifluoroIf-ruthiophenyl-carpamoyl)-5-(4-difluoromethoxyphenyl)-4-phenyl-2-pyrazoline 4 obtained in Reference Example 5
After dissolving g in 4O*O acetic acid, 80R1 of 30-
Hydrogen peroxide solution was added and heated to 60C. After 4 hours, the reaction solution was added to water and evaporated. Extraction was carried out twice with 50 ml of chloroform, and the chloroform layer was washed with 50 ml of sodium bicarbonate aqueous solution and then dried over anhydrous sodium sulfate.

The solvent was poured off under reduced pressure to obtain 3.8 g of crude product.

This was crystallized with 20y of n-hexane-ether (1:1) to obtain 2.2 g of product. This product was confirmed by nuclear magnetic resonance absorption spectroscopy to be 1-(4-bromodifluoromethylsulfonyyl-7-carbamoyl).
It was confirmed that it was -3-(4-difluoromethoxyphenyl)-4-phenyl-2-pyrazoline.

Melting point: 159-162°C.

Reference Example 5 Same as Reference Example 1. However, in place of 4-hydroxy-2-phenyl-acetra-1-non, C-2-(4
-Fluotetraphenylated, A/)-acetophenone (184 g) was used.

Edifluoromethoxy-2-(4-
Fluoro-phenyl)-acetophenone (melting point 50-5
6°C). Then, formalin was reacted to obtain 4'-difluoromethoxy-2-(4-fluorophenyl)acrylophenone (n%'1.5594). Next, this compound was reacted with hydrazine hydrate to produce 15.2
g of 6-(4-difluoromethoxyphenyl)-4-
(4-fluorophenyl)-2-virazoline was obtained.

This product was immediately used as a raw material for Reference Example 7 without being purified.

Reference Example 6 BrF200ONH2→BrFzO0ONOOp-4 g of (bromodifluoromethoxy)aniline was dissolved in 40 d of ethyl acetate. This solution was added dropwise to 40y of ethyl acetate while introducing phosgene. 10 more after the completion of dripping
Phosgene was introduced for minutes. The reaction mixture was concentrated under reduced pressure to obtain 4 g of product (n DI J 903). This product was immediately used as a raw material for Reference Example 7 without being purified.

Reference Example 7 6-(4-difluoromethoxyphenyl)-4-(4-fluorophenyl) p-promodifluoromethoxyphenyl obtained in Reference Example 2) 7.1g0l-(4
-Promodifluoromethoxyphenylcarbamo 4/I/
) -3-(4-difluoromethoxyphenyl)-4-
(4-fluorophenyl)-2-pyrazoline was obtained.

Melting point: 121-5 to 125.5°C.

The structure of this product was confirmed by nuclear magnetic resonance absorption spectroscopy.

Reference Example 8 Insecticidal test against Spodoptera japonica. 1-(4-dibromodifluoromethylthiophenylcarbamoyl)-3-(
4-difluoromethoxyphenyl)-4-phenyl-2
-pyrazoline, 1-(4-promodifluoromethylsulfonylphenylcarba) -3-(4-difluoromethoxyphenyl)-4-phenyl-2-pyrazoline and 1-(4-7'amodifluoromethoxyphenyl) Approximately 1 part of the leaves of Citrus trifolium were added to a water emulsion of 1.25 ppm concentration of
The larvae were immersed for 0 seconds, air-dried, and placed in a petri dish, into which 2nd instar larvae of Spodoptera were released, covered with a perforated lid, and housed in a thermostatic chamber at 25°C. Mortality rate was investigated after 48 hours.

Both compounds showed a mortality rate of 100%.

Incidentally, a similar test was carried out with 1-(4-chlorophenylka #, p
<Moyl)-3-(4-chlorophenyl)-4-phenyl-2-pyrazoline, the mortality rate was 70.

patent applicant Sagami Central Chemical Research Institute

Claims (1)

[Claims] (1) Aniline derivatives represented by the general formula (wherein, X is an oxygen atom or a sulfur atom).