JPH07173144A - Production of diphenyl ether derivative - Google Patents

Abstract

PURPOSE:To obtain a diphenyl ether derivative useful as an intermediate for producing a urea derivative useful as a herbicide by reacting a specific phenol derivative with a halonitrobenzene. CONSTITUTION:(A) A phenol derivative of formula I [Ar is an aryl of formula II to formula VI (R<1> to R<14> each is H, a lower alkyl or a lower alkoxy) is reacted with (B) a halonitrobenzene substituted at the ortho position or the para position in the presence of (C) an alkali metal hydroxide, carbonate or hydrogencarbonate and preferably N,N-dimethylformamide under reduced pressure continuously or while removing water or especially dimethylamine to give a diphenyl ether derivative of formula VII (ArO is in the ortho position or the para position) [e.g. 4-(3,4-dihydro-2-methoxy-2,4,4-trimethyl-2H-1- benzopyranyl-7-oxy)nitrobenzene, etc.].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a diphenyl ether derivative. This diphenyl ether derivative is useful as an intermediate for the production of a urea derivative useful as a herbicide (see Japanese Patent Publication No. 3-60829).

[0002]

2. Description of the Related Art When a phenol derivative and an ortho-position-substituted or para-position-substituted halonitrobenzene are used to produce a diphenyl ether derivative, water in the reaction system is usually removed. For example, in JP-A-63-192768, a base of general formula (VI
I)

[0003]

[Chemical 4]

[Wherein Ar is the following formulas (II), (III), (I
V), (V) or (VI)

[0005]

[Chemical 5]

(In the formula, R ¹ to R ¹⁴ represent a hydrogen atom, a lower alkyl group or a lower alkoxyl group, and these may be the same or different) and represent an aryl group. ] The water is removed using a Dean-Stark tube when synthesizing the compound represented by However, in all of these methods, water is removed at normal pressure, and when the reaction scale is increased, it becomes difficult to remove water smoothly, resulting in lower yield and longer reaction time. cause. Further, in particular, when N, N-dimethylformamide is used as a solvent, there is a drawback that a by-product N, N-dimethylaminonitrobenzene is produced by a reaction between dimethylamine and halonitrobenzene produced by hydrolysis of the solvent. It was

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it suppresses the production of by-products which become impurities, while keeping the yield of diphenyl ether derivative high in a short time. The purpose is to develop an industrial manufacturing method that can be obtained at a rate.

[0008]

The present invention provides a compound represented by the general formula (I): ArOH (I) [wherein Ar represents the following formula (II), (III), (IV), (V) or (VI).

[0009]

[Chemical 6]

(Wherein R ¹ to R ¹⁴ represent a hydrogen atom, a lower alkyl group or a lower alkoxyl group, which may be the same or different) and represent an aryl group. ] Ortho-position or para-position-substituted halonitrobenzene represented by the formula [1] is continuously treated with water under reduced pressure in the presence of an alkali metal hydroxide or carbonate or hydrogen carbonate and a suitable reaction solvent. Or, particularly when N, N-dimethylformamide is used as a reaction solvent, the reaction is carried out while removing water and dimethylamine formed.

[0011]

[Chemical 7]

(In the formula, Ar has the same meaning as above, and ArO
The substitution position of is the ortho position or the para position. ) Is a method for producing a diphenyl ether derivative. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The phenol derivative represented by the general formula (I) used as a raw material in the present invention can be synthesized by the method described in Japanese Patent Publication No. 3-60829. Further, among the phenol derivatives represented by the general formula (I), compounds in which Ar is an aryl group represented by the formula (II) are disclosed in
It can also be synthesized by the method described in 61-76475.

In the compound represented by the general formula (I), the lower alkyl group represented by R ¹ to R ¹⁴ means an alkyl group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, Examples thereof include n-propyl group, isopropyl group, n-butyl group, sec-butyl group, etc. The lower alkoxyl group means an alkoxyl group having 1 to 6 carbon atoms, for example, methoxy group, ethoxy group, n- Propoxy group,
Examples thereof include isopropoxy group, n-butoxy group, sec-butoxy group and the like.

Specific examples of the ortho-substituted or para-substituted halonitrobenzene include ortho-fluoronitrobenzene, ortho-chloronitrobenzene, ortho-bromonitrobenzene, ortho-iodonitrobenzene, para-fluoronitrobenzene, para-chloronitrobenzene and para-chloronitrobenzene. -Bromo nitrobenzene and para-iodo nitrobenzene are mentioned. The amount of such halonitrobenzene used is usually 0. 1 mol of the compound of the general formula (I).
It is 5 to 2.0 mol, preferably 0.9 to 1.3 mol.

Specific examples of the alkali metal hydroxide, carbonate or hydrogen carbonate include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate, preferably carbonic acid. Examples include potassium. The amount of the alkali metal hydroxide, carbonate or hydrogen carbonate used is usually 0.5 to 2.0 mol, preferably 0.9 to 1.3 mol, relative to 1 mol of the compound of the formula (I).

As the reaction solvent, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone, methanol, ethanol, n-propanol, isopropanol, n-butanol , Alcohol solvents such as t-butanol, ether solvents such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and hydrocarbons such as n-hexane and n-heptane. Two or more kinds of solvents may be mixed and used. The amount of these solvents used is the amount of the compound 1 of the general formula (I).
Usually 0 to 100 parts by weight, preferably 0.
5 to 10 parts by weight.

The temperature in the reaction is usually 0 to 200.
℃, preferably 100 to 160 ℃, the time is usually
It is 0.1 to 10 hours, preferably 0.5 to 8 hours. The pressure in the reaction is usually 200 to 755 mmHg, preferably 550 to 755 mmHg. Furthermore, as described above, after the completion of the reaction, the desired product (VII) can be obtained by employing a commonly used and easy separation method such as solvent extraction and crystallization. Further, the product (VII) of higher purity can be obtained by recrystallization and purification if necessary.

[0018]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. However, the technical scope of the present invention is not limited by these examples. (Comparative Example 1) 4- (3,4-dihydro-2-methoxy-2,4,4-trimethyl-2H-
Production of 1-benzopyranyl-7-oxy) nitrobenzene In a 200 mL round bottom flask equipped with a condenser, Dean-Stark tube and thermometer, the following formula (VIII)

[0019]

[Chemical 8]

3,4-dihydro-2-methoxy-2, represented by
4,4-Trimethyl-2H-1-benzopyran-7-ol 6.5 g
(29.2 mmole) and the following formula (IX)

[0021]

[Chemical 9]

2,4,4-trimethyl-4H-1-benzopyran-7-ol represented by 6.2 g (32.5 mmole), para-chloronitrobenzene 10.7 g (67.9 mmole), anhydrous potassium carbonate
8.5 g (61.7 mmole), 6.6 g of ethylbenzene, and 14.2 g of N, N-dimethylformamide were added, and the mixture was heated to 150 ° C. with stirring, and at the same time, water was taken out of the system and reacted for 5 hours. After cooling, the reaction solution added with 6.6 g of ethylbenzene was washed with 60.0 g of water, and methanol 79.1 was added to the separated oil layer.
g and 0.7 g of sulfuric acid were added, and the mixture was stirred under reflux conditions for 2 hours. The crystals formed were filtered and the following formula (X)

[0023]

[Chemical 10]

As a result, 18.0 g of pale yellow crystals of the target substance shown in (1) were obtained (yield: 85%, containing 232 ppm of para-N, N-dimethylaminonitrobenzene as an impurity). (Comparative Example 2) (4-fold scale reaction of Comparative Example 1) 4- (3,4-dihydro-2-methoxy-2,4,4-trimethyl-2H-
Production of 1-benzopyranyl-7-oxy) nitrobenzene 3,4-dihydro-2-methoxy-2,4,4-trimethyl-2H-1 in a 500 mL round bottom flask equipped with a condenser, Dean-Stark tube and thermometer. -Benzopyran-7-ol (VIII) 25.9 g (116.8
mmole) and 2,4,4-trimethyl-4H-1-benzopyran-7-
All (IX) 24.8 g (130.4 mmole), para-chloronitrobenzene 42.8 g (271.7 mmole), anhydrous potassium carbonate 3
4.0 g (246.4 mmole), 26.4 g of ethylbenzene and 56.8 g of N, N-dimethylformamide were added, and the mixture was stirred at 150 ° C.
The mixture was heated to 0.degree. C., and at the same time, water was taken out of the system and reacted for 10 hours. After cooling, the reaction solution containing 26.4 g of ethylbenzene was washed with 240.0 g of water, and 31 g of methanol was added to the separated oil layer.
6.4 g and 2.7 g of sulfuric acid were added, and the mixture was stirred for 2 hours under reflux conditions. The generated crystals were filtered to obtain 57.5 g of pale yellow crystals of the target product (X) (yield 68%, para-N, N- as impurities).
Containing 8241 ppm of dimethylaminonitrobenzene).

Example 1 4- (3,4-dihydro-2-methoxy-2,4,4-trimethyl-2H-
Production of 1-benzopyranyl-7-oxy) nitrobenzene 3,4-dihydro in a 500 mL round bottom flask equipped with a condenser with a vacuum pump connected to the top, a Dean-Stark tube, and a thermometer.
-2-Methoxy-2,4,4-trimethyl-2H-1-benzopyran-7
-Ol (VIII) 25.9 g (116.8 mmole) and 2,4,4-trimethyl-4H-1-benzopyran-7-ol (IX) 24.8 g (130.
4 mmole), para-chloronitrobenzene 42.8 g (271.7
mmole), 34.0 g (246.4 mmole) of anhydrous potassium carbonate, 26.4 g of ethylbenzene and 56.8 g of N, N-dimethylformamide are added and heated to 150 ° C. with stirring, while simultaneously extracting water and the produced dimethylamine from the system , 660-720
The reaction was carried out for 5 hours under a reduced pressure of mmHg. After cooling, the reaction solution was washed with 240.0 g of water and methanol 316.
4 g and 2.7 g of sulfuric acid were added, and the mixture was stirred for 2 hours under reflux conditions. The generated crystals were filtered to obtain 72.9 g of pale yellow crystals of the desired product (X) (yield 86%, containing no impurity para-N, N-dimethylaminonitrobenzene).

(Examples 2 to 4) The same procedure as in Example 1 was repeated except that the aromatic hydrocarbon solvent, the kind of base and the reaction pressure were as shown in Table 1. The results are shown in Table 1.

[0027]

[Table 1]

Reference Example 1 3,4-Dihydro-2-methoxy-2,4,4-trimethyl-2H-1-benzopyran-7-ol (VIII) and 2,4,4-trimethyl-4H-
Production of 1-benzopyran-7-ol (IX) resorcin 66.0 g (600 mmole), acetone 139.0 g (240
0 mmole), 96.0 g (3000 mmole) of methanol, toluene
264.0 g and 48.0 g of Amberlyst as an acid catalyst were reacted at 110 ° C. for 4 hours using an autoclave. The acid catalyst was removed by filtration, the solvent was evaporated, and the residue was purified by distillation under a reduced pressure of 10 mmHg to give 3,4-dihydro-2-methoxy-2,4,4-trimethyl-2H-1-benzopyran. -7-all (V
III) 37.0 g (yield 28%) and distillate 87.0 g containing 2,4,4-trimethyl-4H-1-benzopyran-7-ol (IX) 34.6 g (yield 30%) were obtained. Since this distillate contained 6.2 g of resorcin as an impurity, it was used after being extracted and removed using an aqueous sodium hydrogen carbonate solution.

[0029]

According to the present invention, the diphenyl ether derivative can be obtained in a short time in a high yield and a high purity even when the reaction is carried out on an enlarged scale.

Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location C07D 311/58 311/70 311/72 102 (72) Inventor Hiroaki Tan 6-Waki, Waki-cho, Kaku-gun, Yamaguchi Prefecture No. 1 and 2 Mitsui Petrochemical Industry Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the general formula (I): ArOH (I), wherein Ar is a compound represented by the following formula (II), (III), (IV), (V) or (VI): (Wherein R ¹ to R ¹⁴ represent a hydrogen atom, a lower alkyl group or a lower alkoxyl group, and these may be the same or different). ] And the ortho-position or para-position-substituted halonitrobenzene are reacted in the presence of an alkali metal hydroxide or carbonate or hydrogen carbonate while continuously removing water under reduced pressure conditions. The general formula (VII) is characterized in that (In the formula, Ar has the same meaning as described above, and the substitution position of ArO is the ortho position or the para position.). 2. A phenol derivative represented by the general formula (I) ArOH (I) (wherein Ar has the same meaning as described above) and an ortho-position or para-position-substituted halonitrobenzene, and an alkali metal water. In the presence of an oxide or a carbonate or a hydrogen carbonate and N, N-dimethylformamide, the reaction is continuously performed under reduced pressure while removing water and the dimethylamine formed, and the reaction is carried out by the general formula (V
II) [Chemical 3] (In the formula, Ar has the same meaning as described above, and the substitution position of ArO is the ortho position or the para position.).