JPS5879959A - P-nitro(bromodifluoromethoxy)benzene and its production - Google Patents

Abstract

NEW MATERIAL:A compound of the formula. USE:Herbicide and a synthetic intermediate of p-trifluoromethoxyaniline, which is used as an insecticide. PREPARATION:The reaction of p-nitrophenol with dibromodifluoromethane is carried out in the presence of a base such as sodium hydroxide or butyl lithium, preferably in an aprotonic solvent such as dimethylformamide or tetrahydrofruan at -60 deg.C to room temperature, preferably at room temperature. The amount of the used base is 1.0-1.5 equivalent based on p-nitrophenol. The product can be led to a p-nitro(trifluoromethoxy)benzene derivative by its reaction with hydrogen fluoride.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides p-nitro(bromodifluoromethoxy) represented by the structural formula % (1)
Concerning benzene and its production method.

p-Nitro(bromodifluoromethoxy)benzene represented by the above-mentioned structural formula (1) of the present invention is a new compound.
(9fluoromethoxy)benzene (see reference side below). It is already known that p-nitro(trifluoromethoxy)benzene can be converted to p-trifluoromethoxylinline by subjecting it to a reduction reaction (see US Pat. No. 3,211,1124). p-
) Rifluoromethoxyaniline is useful as a synthetic intermediate for many herbicides and insecticides (for example, JP-A-53
-95961 and West German Patent Publication No. 2,801.31 (
(See S).

Conventionally, p-nitro(trifluoromethoxy)benzene is produced by reacting p-nitrophenol with carbonyl fluoride and then heating it with sulfur fuside. (U.S. Pat. No. 3,213,124)
), 2) Chlorination of p-methoxybenzoic acid chloride to produce p-
) A method in which the dichloromethoxy compound is converted into a p-trifluoromethoxy compound by halogen exchange, and this is made into an amide, which is then reacted with an odor under alkaline conditions (0, A,
51.15517 i) and 3) Method of heating p-aminophenol with carbon tetrachloride and fluoride water (J,
Org, Ohem, .

44.2907) is known. [7 or 1-These methods require reaction at high temperature in an autoclave, p-) under milder reaction conditions! It has been desired to develop a method for synthesizing J-fluoromethoxyaniline. The present inventor has discovered that p-nitro(bromodifluoromethoxy)benzene (1) is effective as a synthetic intermediate for obtaining p-trifluoromethoxyaniline under mild conditions, and has completed the present invention.

The production method of the present invention can be expressed by the reaction formula shown below.

(I) The production method of the present invention involves reacting p-nitrophenol and dibromodifluoromethane in the presence of a base to produce p-nitro(bromodifluoromethoxy)benzene.

The production method of the present invention requires that it be carried out in the presence of a base. Hydrogenated as a base) IJ
Aqueous alkali metal compounds such as aluminum and organic lithium compounds such as butyllithium can be used. The base used is usually 1.
Use 0 to 1.5 regular leaves.

When carrying out the production method of the present invention, it is desirable to carry out the process in an aprotic solvent such as N,N-dimethylformamide (hereinafter abbreviated as DMF), dimethoxyethane, tetrahydrofuran, dimethyl sulfoxide or the like.

p-nitro(bromodifluoromethoxy) of the present invention
To efficiently obtain p-
Preferably, the nitrophenol is sufficiently contacted with the base and then reacted with dibromodifluoromethane.

Although the reaction proceeds at 0° C. to room temperature, it is preferable to carry out the reaction at room temperature in order to obtain the desired product efficiently.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Reference Examples.

Example 50% sodium hydride (s, oy, 104 mmol)
was added to DMF (20 mg) and cooled in a water bath. To this, p-=to07z/-J (13,9Jir, 10C1m
A solution of mo 1 ) in DMF (100 m) was added dropwise. 1
After stirring for 0 minutes, dibromodifluoromethane (25g
, 119 mmol) of DMP ((5011/) was added and stirred at room temperature for 5 hours. The reaction solution was poured into water and extracted with ether. After the ether was loaded with anhydrous magnesium sulfate and the solvent was distilled off. was distilled to obtain p-nitro(bromodifluoromethoxy)benzene (13.4p). Yield: 50 yen.

Boiling point 74-77℃10. ITorr.

'HNMR (ODOIs) J 7.40 (d, J==
9Hz).

8.30 (d, J=91-Iz).

"F-NMfL (ODOI 6) δ (OF, 002H)
61.9 (S).

M8 m/e 2696) L 2'67 (10), 1
89(11).

188 (100).

Reference Example In a polyethylene container, p-nitro(bromodifluoromethoxy)benzey (19,1,!i', 71.6 mmo
l ) in isoprobyl ether (6OR1:), and to this was added a fluorohydrogen pyridine solution (70/30.40).
wt) was added and mixed. Approximately 100 ml of mercury oxide was added every 15 minutes. The reaction was completed in about 4 hours. The reaction solution was poured into water and extracted with ether. The ether layer was washed with sodium hydroxide solution, then with brine, and then dried over anhydrous magnesium sulfate. After removing the solvent, it is distilled and p
-Nitro(trifluoromethoxy)benzene (11,5
g) was obtained. Yield: 76 cm.

Boiling point 46-50°C 70.15 Torr.

'H-NMR (ODO1s) J 7.42 (d,
J==9Hz).

8.35 (d, J = 9Hz).

patent applicant Sumo Central Chemical Research Institute 71

Claims (1)

[Claims] (1) p-nitro(bromodifluoromethoxy)benzene. Q) P-nitrophenol and dibromodifluoromethane are reacted in the presence of a base.
- A method for producing nitro(bromodifluoromethoxy)benzene.