JPH08225497A - Substituted phenyl carbonate derivative - Google Patents

Abstract

PURPOSE: To obtain a compound useful as a synthetic intermediate for an N- substituted phenyl-3,4,5,6-tetrahydrophthalimide derivative having excellent herbicidal activities. CONSTITUTION: This compound of formula I (R<1> is a 1-6C alkyl; X is a halogen; Y is H, nitro or amino), e.g. 2-chloro-4-fluorophenyl(isobutyl) carbonate. The compound of formula I is obtained by reacting 2-chloro-4-fluorophenol of formula II with an alkyl chloroformate (e.g. isobutyl chloroformate). A nitrobenzene derivative is further obtained by subsequently nitrating the resultant compound with fuming nitric acid, etc. The prepared nitrobenzene derivative is reduced in the presence of hydrogen by using a Pd/C catalyst to afford an aniline derivative. An N-substituted phenyl-3,4,5,6-tetrahydrophthalimide derivative has high herbicidal effects in a low dose and hardly causes the phytotoxicity to main crops.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a substituted phenyl carbonate derivative useful as an intermediate for the production of N-substituted phenyl-3,4,5,6-tetrahydrophthalimide derivative having excellent herbicidal activity.

[0002]

2. Description of the Related Art Conventionally, as an N-substituted phenyl-3,4,5,6-tetrahydrophthalimide derivative having herbicidal activity, for example, N- (2-fluoro-4-chloro-5-isopropoxyphenyl)- 3,4,5,6-Tetrahydrophthalimide (Japanese Patent Publication No. 63-20428) or N- (2-fluoro-4-chloro-5-alkyloxyphenyl) -3,4,5,6-tetrahydrophthalimide (Japanese Patent Publication No. 63-20428) KAISHO 58-72563) is known. Also, the phenyl ring on the nitrogen atom is 2,4-
Compounds substituted with a dihalo-5-cycloalkyloxy group are disclosed in JP-A-63-68562, 63-6.
It is described as an example in Japanese Patent Nos. 8563 and 63-280060.

Furthermore, the present inventors have introduced a cycloalkyloxy group, particularly a cyclopentyloxy group, as a substituent at the 5-position of a phenyl ring in an N-substituted phenyl-3,4,5,6-tetrahydrophthalimide derivative. It was found that the low herbicidal treatment of weeds has a high herbicidal effect, and the phytotoxicity to major crops is significantly reduced.

[0004]

The present invention is based on the above-mentioned N-
It is an object of the present invention to provide a substituted phenyl carbonate derivative which is useful as an intermediate for producing a substituted phenyl-3,4,5,6-tetrahydrophthalimide derivative.

[0005]

Means for Solving the Problems As a result of earnest research on a method for producing a tetrahydrophthalimide derivative, the present inventors have found that a substituted phenyl carbonate derivative is useful as an intermediate for the production, and arrived at the present invention. .

That is, the present invention provides the following general formula [I]

[0007]

Embedded image

(In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, X represents a halogen atom, and Y represents a hydrogen atom, a nitro group or an amino group.) I will provide a.

The substituted phenyl carbonate derivative of the present invention can be produced by the following synthetic route (see Examples).

[0010]

Embedded image

(In the formula, R ¹ and X have the same meanings as described above.)

That is, a carbonate derivative [Ia] is obtained by reacting 2-chloro-4-fluorophenol with an alkyl chloroformate such as isobutyl chloroformate. Nitrobenzene derivative [Ib] is obtained by nitrating this carbonate derivative [Ia] with fuming nitric acid.
And Then, the anibenzene derivative [Ic] can be obtained by reducing the nitrobenzene derivative [Ib] in the presence of hydrogen using a catalyst such as palladium / carbon. At this time, when R ¹ is an isobutyl group, it is particularly preferable in that the product of these steps is an oily substance or a low melting point solid.

Next, a method for producing an N-substituted phenyl-3,4,5,6-tetrahydrophthalimide derivative using the compound of the present invention as a raw material will be described.

The N-substituted phenyl-3,4,5,6-tetrahydrophthalimide derivative has the general formula [II]

[0015]

[Chemical 4]

(In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms, and X represents a halogen atom. The cycloalkyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.) An aniline derivative represented by and 3,4,5,6-
It can be easily produced by reacting with tetrahydrophthalic anhydride in an inert solvent. As the inert solvent, a solvent such as benzene, toluene, xylene, chlorobenzene, acetic acid, or a mixed solvent thereof can be used. The reaction temperature is selected from room temperature to 150 ° C, but it is preferably carried out at 50 to 120 ° C in terms of good yield. After the reaction, the desired product can be easily isolated by a usual post-treatment, and can be taken out as a pure product by recrystallization from an alcohol solvent such as methanol.

The aniline derivative represented by the general formula [II] as a raw material can be produced from the above-mentioned aniline derivative [Ic] which is a compound of the present invention by the following synthetic route.

[0018]

Embedded image

(In the formula, R and X have the same meanings as described above. R ² represents an alkyl group having 1 to 6 carbon atoms, an allyl group having 3 to 4 carbon atoms or an aralkyl group having 7 to 8 carbon atoms. Y represents a chlorine atom, a bromine atom, an iodine atom, a methylsulfonyloxy group or a p-toluenesulfonyloxy group.)

That is, the aniline derivative [Ic] of the present invention
In the presence of a base such as potassium carbonate, sodium carbonate or magnesium oxide, acetonitrile, acetone, N, N-
The carbamate derivative [III] is derived by reacting it with a chloroformate in a solvent such as dimethylformamide. Then, the carbamate derivative [III] is treated with a base such as sodium hydroxide or potassium carbonate in a protic solvent to selectively hydrolyze only the carbonate group to convert it into a phenol derivative [IV]. To be done. Obtained phenol derivative [IV]
A cycloalkyloxy group can be introduced at the 5-position of the phenyl ring by reacting the compound represented by the general formula RY [V] with a base such as potassium carbonate, sodium carbonate or magnesium oxide. The reaction is preferably carried out in a suitable solvent, and acetonitrile, acetone, methanol, ethanol, N, N-dimethylformamide or the like can be used. The carbamate derivative [VI] thus obtained is reacted in, for example, an aqueous sodium hydroxide solution to hydrolyze a carbamate, or when R ² in the general formula [VI] is, for example, a benzyl group. The aniline derivative represented by the general formula [II] can be obtained by hydrogenolysis using a catalytic reduction method using palladium carbon.

The aniline derivative represented by the general formula [Ic], which is a raw material, can be produced by the method shown in the following Reference Example. The compound represented by the general formula [V] is commercially available, or can be easily prepared from the commercially available compound.

Furthermore, N-substituted phenyl-3,4,5,6
-The tetrahydrophthalimide derivative has the general formula [VII]

[0023]

[Chemical 6]

It can also be produced by reacting a phenol derivative represented by the formula (wherein X has the same meaning as described above) with a compound represented by the general formula [V]. For the reaction, acetonitrile, N, N-dimethylformamide, acetone, in the presence of a base such as potassium carbonate, sodium carbonate, magnesium oxide or sodium methoxide,
It is preferably carried out in a solvent such as methanol.

The phenol derivative represented by the general formula [VII], which is a starting material for the reaction, is described in JP-A-58-83672.
Although it is a compound described in the publication, it can be produced by the synthetic route shown below.

[0026]

[Chemical 7]

(In the formula, X and R ¹ have the same meanings as described above.)

That is, by reacting the aniline derivative represented by the general formula [Ic] with 3,4,5,6-tetrahydrophthalic anhydride in an inert solvent such as benzene, toluene or acetic acid, The tetrahydrophthalimide derivative represented by the general formula [VIII] is introduced, and then, by selectively hydrolyzing the carbonate group at the 5-position of the phenyl ring in the presence of a base, the phenol represented by the general formula [VII] is obtained. Derivatives can be obtained. Examples of the base to be used include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide and the like, and the reaction is carried out at room temperature to about 100 ° C. in a protic solvent such as methanol, ethanol and water. It is preferable that the yield is good.

[0029]

The present invention will be described in more detail with reference to the following examples and reference examples, but the present invention is not limited to these examples.

Example 1

[0031]

Embedded image

In a 300 cc eggplant-shaped flask equipped with a dropping funnel, 2-chloro-4-fluorophenol (2
9.3 g, 0.20 mol) was added and 2N-N was added under ice cooling.
An aOH aqueous solution (100 ml) was added and the mixture was stirred for 30 minutes. Then, isobutyl chloroformate (30 ml, d = 1.05)
(3,31.6 g, 0.23 mol) was added dropwise, and the mixture was stirred for 2 hours while gradually raising the temperature to room temperature. After completion of the reaction, the mixture was extracted with methylene chloride (100 ml × 3 times) and dried over anhydrous magnesium sulfate. After removing the drying agent, the solvent and the like were distilled off under reduced pressure to give a colorless transparent oil of 2-chloro-4-fluorophenyl (isobutyl) carbonate (45.8 g, 0.186 mmol, yield 93.0%). ) Got.

¹ H-NMR (CDCl ₃ , TMS, ppm): δ1.00 (6
H, d, J = 6.9Hz), 2.05 (1H, t & sep, J = 6.3 and 6.9Hz), 4.0
5 (2H, d, J = 6.3Hz), 6.8 ~ 7.3 (3H, m).

Next, fuming nitric acid (100 ml, 98%, d = 1.52) was put in a 200 cc eggplant-shaped flask, and 2-chloro-4-fluorophenyl (isobutyl) carbonate (10 g, 40. 5 mmol) was added slowly. After stirring for 30 minutes as it was, the reaction mixture was poured onto ice. Precipitated 2-fluoro-4-chloro-5
-A light yellow solid of isobutyloxycarbonyloxynitrobenzene was filtered and washed with water. White crystals of the target compound (10.8g, 36.9mm) after sufficient drying
ol, yield 91.0%) was obtained.

Melting point: 38.0-40.0 ° C.¹ H-NMR (CDCl₃, TMS, ppm): δ1.00 (6H, d, J = 6.9H
z), 2.07 (1H, t & sep, J = 6.3 and 6.9Hz), 4.07 (2H, d, J =
6.3Hz), 7.42 (1H, d, J_HF= 10.2Hz), 8.02 (1H, d, J _HF= 6.9
Hz).

2-Fluoro-4 thus obtained
-Chloro-5-isobutyloxycarbonyloxynitrobenzene (10 g, 34.3 mmol), toluene as solvent (100 ml), and 10% Pd / as catalyst.
C (1.5 g) was charged into a 300 cc pressure-resistant glass autoclave. After thoroughly replacing the inside with hydrogen, stirring was started under a hydrogen pressure of 4 atm. As the reaction progresses, heat is generated (up to about 50 ° C), but stirring is continued,
Further, hydrogen was added as needed and stirred until the absorption of hydrogen stopped. After the reaction was completed, Pd / C was separated by filtration, and the released water was removed with a desiccant. By distilling off the solvent under reduced pressure, it is possible to obtain almost pure 2-fluoro-4-chloro-
5-isobutyloxycarbonyloxyaniline (9.
42 g) of a yellow oil was quantitatively obtained.

¹ H-NMR spectrum (CDCl ₃ , TMS, pp
m): δ1.00 (6H, d, J = 6.9Hz), 2.04 (1H, t & sep, J = 6.3 a
nd 6.9Hz), 4.04 (2H, d, J = 6.3Hz), 6.97 (1H, d, J _HF = 6.9
Hz), 7.24 (1H, d, J _HF = 9.0Hz).

Reference Example 1

[0039]

[Chemical 9]

2-fluoro-4-chloro-5-isobutyloxycarbonyloxyaniline (6 obtained in Example 1
5.0 g, 0.248 mol) and potassium carbonate (32
g, 0.232 mmol) in acetone (300 ml), methyl chloroformate (23.4 g, 0.248 mo)
1) was added, and the mixture was stirred under reflux for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 1N hydrochloric acid (300 ml) was added, and the precipitated solid was collected by filtration. This product was thoroughly washed with water and dried to give N- (2-fluoro-4-chloro-5
White crystals of methyl isobutyloxycarbonyloxyphenyl) carbamate (56.6 g, yield 71.4)
%) Was obtained.

Melting point: 72.2-78.8 ° C. ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ1.00 (6H, 6H,
d, J = 6.5Hz), 2.05 (1H, t & sep, J = 6.5Hz), 3.78 (3H, s), 4.03
(2H, d, J = 6.5Hz), 6.85 (1H, br s), 7.08 (1H, d, J _HF = 10.2H
z), 8.10 (1H, d, J _HF = 7.5Hz) .IR spectrum (KBr disk, cm ^-1 ): 1773,1733,1545,128
5,1235,1180.

The above-obtained N- (2-fluoro-4-
Methyl chloro-5-isobutyloxycarbonyloxyphenyl) carbamate (14.0 g, 43.8 mmo
l) was dissolved in methanol (100 ml), and then potassium carbonate (7.26 g, 52.3 mmol) was added to the mixture to give 50.
The reaction was carried out at 0 ° C for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and acetic acid (20 ml) was added to the obtained solid substance to dissolve it. The solid precipitated by pouring this into ice water was isolated by filtration. The crystals were thoroughly washed with water and dried to give white crystals of methyl N- (2-fluoro-4-chloro-5-hydroxyphenyl) carbamate (9.
60 g, 43.7 mmol, yield 99.8%) were obtained.

Melting point: 140.0-141.0 ° C. ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ1.57 (3H,
s), 3.78 (3H, s), 5.53 (1H, s), 6.75 (1H, br s), 7.05 (1H, d, J
_{. HF = 10.5Hz), 7.82 (} 1H, d, J HF = 7.5Hz) IR spectrum ^{(KBr disk, cm -1):} 3440,1717,1630,156
0,1430,1250.

The above-obtained N- (2-fluoro-4-
Methyl chloro-5-hydroxyphenyl) carbamate (5.0 g, 22.8 mmol) and potassium carbonate (3.
89 g, 28.1 mmol) of acetonitrile (50 m
l) The solution was stirred under reflux for 1 hour. Then, bromocyclopentane (4.07 g, 27.3 mmol) was added dropwise, and the mixture was further reacted for 3 hours. After completion of the reaction, the solvent was evaporated under reduced pressure, 1N hydrochloric acid (100 ml) was added to acidify the mixture, and the mixture was extracted with ethyl acetate (100 ml × 3 times). The organic layer was washed with water, dried, and the solvent was evaporated under reduced pressure to give N- (2-fluoro-4-chloro-5-
Methyl cyclopentyloxyphenyl) carbamate (5.56 g, 19.3 mmol, yield 84.7%) was obtained.

Melting point: 120.0-123.0 ° C. ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ 1.40-2.1
0 (8H, m), 3.77 (3H, s), 4.77 (1H, m), 6.82 (1H, br s), 7.07 (1
_{. H, d, J HF =} 10.5Hz), 7.83 (1H, d, J HF = 7.5Hz) IR spectrum ^{(KBr disk, cm -1):} 1714,1535,1500,141
5,1255,1190.

N- (2-fluoro-4) thus obtained
Ethyl alcohol (30 ml) and 2N aqueous sodium hydroxide solution (50 ml) were added to methyl -chloro-5-cyclopentyloxyphenyl) carbamate (5.75 g, 20.0 mmol), and the mixture was heated with stirring in an oil bath at 110 ° C for 4 hours. did. After completion of the reaction, the solvent was distilled off and ethyl acetate (10
It was extracted with 0 ml × 3 times). Wash the organic layer with saturated saline,
After drying, the solvent was distilled off under reduced pressure to give an oily 2-
Fluoro-4-chloro-5-cyclopentyloxyaniline (4.36 g, 19.0 mmol, yield 95.0%)
I got The spectrum data and the like are as shown in Reference Example 2.

Reference Example 2

[0048]

[Chemical 10]

2-Fluoro-4-chloro-5-methoxycarbonyloxyaniline (22.0 g, 100 mmo
l) and potassium carbonate (13.8 g, 100 mmol) in acetone (300 ml), ethyl chloroformate (1
6.3 g, 150 mmol) was added and the mixture was stirred at 60 ° C. for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and 1N hydrochloric acid (1
(00 ml) was added to acidify, and then ethyl acetate (100 ml x 3
Times). The organic layer was washed with water, dried, and the solvent was distilled off under reduced pressure to collect the precipitated solid by filtration. This product was recrystallized from chloroform-hexane to give N-
White crystals of ethyl (2-fluoro-4-chloro-5-methoxycarbonyloxyphenyl) carbamate (2
(3.3 g, yield 80.2%) was obtained.

Melting point: 143.8 to 147.2 ° C. ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ1.13 (3H, t, J
= 6.5Hz), 3.92 (3H, s), 4.23 (2H, q, J = 6.5Hz), 6.80 (1H, br
s), 7.15 (1H, d, J _HF = 10.5Hz), 8.12 (1H, d, J _HF = 8.0Hz) .IR spectrum (KBr disk, cm ^-1 ): 1770, 1730,1545,129
0,1235,1215.

The obtained ethyl N- (2-fluoro-4-chloro-5-methoxycarbonyloxyphenyl) carbamate (45.2 g, 155 mmol) was added to potassium carbonate (21.4 g, 155 mmol) and methanol (1).
(00 ml) was added, and the mixture was reacted under heating under reflux for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and 1N
Hydrochloric acid (300 ml) was added to acidify and ethyl acetate (10
It was extracted with 0 ml × 3 times). The organic layer was washed with water, dried and the solvent was distilled off under reduced pressure, and the precipitated solid was collected by filtration. This product was recrystallized from chloroform-hexane to give N-
White crystals (35.2 g, yield 97%) of ethyl (2-fluoro-4-chloro-5-hydroxyphenyl) carbamate were obtained.

Melting point: 151.5 to 154.2 ° C. ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ1.32 (3 H, t,
J = 7.2Hz), 4.23 (2H, q, J = 7.2Hz), 5.84 (1H, s), 6.80 (1H, br
s), 7.04 (1H, d, J _HF = 10.5Hz), 7.85 (1H, d, J _HF = 7.5Hz) .IR spectrum (KBr, cm ^-1 ): 3440,1710,1560,1430,125
0.

Then, the obtained N- (2-fluoro-4-
Ethyl chloro-5-hydroxyphenyl) carbamate (10.0 g, 42.8 mmol) and potassium carbonate (8.
87 g, 64.2 mmol) of acetonitrile (150
ml) solution was stirred at 80 ° C. for 1 hour. Next, cyclopentyl bromide (9.57 g, 84.2 mmol) was added dropwise, and the reaction was further performed for 7 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 1N hydrochloric acid (100 ml) was added to acidify the mixture, and the mixture was extracted with ethyl acetate (100 ml × 3 times).
The organic layer was washed with water, dried, and the solvent was evaporated under reduced pressure to give ethyl N- (2-fluoro-4-chloro-5-cyclopentyloxyphenyl) carbamate (1
2.7 g, yield 98%) was obtained.

Melting point: 92.8-97.8 ° C. ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ1.33 (3H,
t, J = 7.0Hz), 1.40 to 2.10 (8H, m), 4.32 (2H, q, J = 7.0Hz), 4.8
8 (1H, m), 6.87 (1H, br s), 7.15 (1H, d, J _HF = 10.5Hz), 7.92 (1
H, d, J _HF = 7.0Hz) .IR spectrum (KBr, cm ^-1 ): 1710,1535,1495,1415,125
Five.

In this reaction, the reaction proceeds similarly even if cyclopentyl p-toluene sulfonate is used instead of cyclopentyl bromide, and the desired N- (2-
Ethyl fluoro-4-chloro-5-cyclopentyloxyphenyl) carbamate could be obtained in a yield of 95%.

N- (2-fluoro-4-chloro-5-cyclopentyloxyphenyl) thus obtained
Ethyl alcohol (50 ml) and 2N aqueous sodium hydroxide solution (100 ml) were added to ethyl carbamate (12.7 g, 42.1 mmol), and the mixture was placed in an oil bath at 110 ° C. for 4 times.
The mixture was heated and stirred for an hour. After completion of the reaction, the solvent was distilled off, and the mixture was extracted with ethyl acetate (100 ml × 3 times). The organic layer was washed with saturated brine, dried and the solvent was evaporated under reduced pressure to give oily 2-fluoro-4-chloro-5-cyclopentyloxyaniline (9.36 g, 40.8 mmol, yield 97).
%) Was obtained.

¹ H-NMR spectrum (CDCl ₃ , TMS, pp
m): δ 1.40 to 2.07 (8H, m), 3.72 (2H, brs), 4.57 (1H, m), 6.
35 (1H, d, J _HF = 8.0Hz), 6.98 (1H, d, J _HF = 10.5Hz) .IR spectrum (KBr disk, cm ^-1 ): 2980,1635,1510,142
3,1250,1190.

Reference Example 3

[0059]

[Chemical 11]

N- produced by the method shown in Reference Example 2
Ethyl (2-fluoro-4-chloro-5-methoxycarbonyloxyphenyl) carbamate (1.45 g,
4.97 mmol) and potassium carbonate (1.03 g, 7.4
A solution of 6 mmol) in ethanol (5.0 ml) was stirred under reflux for 1 hour and then cyclopentyl bromide (1.
11 g, 7.46 mmol) was added and the mixture was further stirred for 2 hours. After completion of the reaction, the mixture was poured into 1N hydrochloric acid (50 ml) and extracted with ethyl acetate (50 ml × 3 times). The organic layer was dried and then concentrated under reduced pressure to give off-white crystals of ethyl N- (2-fluoro-4-chloro-5-cyclopentyloxyphenyl) carbamate (1.41 g, 4.6).
9 mmol, yield 94.4%) was obtained. The spectral data and the like are as shown in Reference Example 2.

Reference Example 4

[0062]

[Chemical 12]

2-Fluoro-4-chloro-5-cyclopentyloxyaniline (0.50 g, 2.18 mmo
1) and 3,4,5,6-tetrahydrophthalic anhydride (0.398 g, 2.61 mmol) in acetic acid (3.0
The solution was stirred under reflux for 3 hours. Water (20 ml) was added to the obtained reaction mixture, and ethyl acetate (20 ml x
3 times). After drying the organic layer, the solvent was distilled off under reduced pressure, and the resulting pale yellow oily substance was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 8 /
1) and N- (2-fluoro-4-chloro-5-
Cyclopentyloxyphenyl) -3,4,5,6-tetrahydrophthalimide colorless transparent oil (0.513
g, 1.41 mmol, yield 65%) were obtained. Ethanol (1.0 ml) was added to this product and recrystallized to obtain a white solid.

Melting point: 69.0-75.2 ° C. ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ 1.30-
2.10 (12H, m), 2.40 (4H, m), 4.68 (1H, m), 6.75 (1H, d, J _HF = 7.
0Hz), 7.20 (1H, d, J _HF = 9.0Hz) .IR spectrum (KBr disk, cm ^-1 ): 1725,1505,1430,138
5,1200.

Reference Example 5

[0066]

[Chemical 13]

N- produced by the method shown in Reference Example 1
Methyl (2-fluoro-4-chloro-5-isobutyloxycarbonyloxyphenyl) carbamate (5.3
7 g, 16.8 mmol) and 3-methylcyclopentyl p-toluenesulfonate (5.0 g, 20.2 mmo)
1) and potassium carbonate (2.32 g, 16.8 mmo)
A solution of 1) in methanol (50 ml) was stirred under reflux for 5 hours. After completion of the reaction, the reaction mixture was mixed with 1N hydrochloric acid (100 m
l), and extracted with ethyl acetate (50 ml x 3 times). After drying the organic layer, the solvent was evaporated under reduced pressure to give off-white crystals of methyl N- {2-fluoro-4-chloro-5- (3-methylcyclopentyl) oxyphenyl} carbamate (3.81 g). , 12.6 mmol, yield 75.2%) was obtained.

¹ H-NMR spectrum (CDCl ₃ , TMS, pp
m): δ 1.02 and 1.08 (total 3H, d, J = 6.0Hz), 1.25〜2.40
(7H, m), 3.77 (3H, s), 4.75 (1H, m), 6.68 (1H, br s), 7.05 (1
H, d, J _HF = 10.5Hz), 7.75 (1H, d, J _HF = 7.5Hz).

The resulting methyl N- {2-fluoro-4-chloro-5- (3-methylcyclopentyl) oxyphenyl} carbamate (3.45 g, 11.4 mmo)
Ethyl alcohol (20 ml) and 2N aqueous sodium hydroxide solution (30 ml) were added to l), and the mixture was stirred under reflux for 3 hours. After completion of the reaction, the reaction mixture was directly extracted with ethyl acetate (50 ml × 3 times). The organic layer was washed with saturated saline and dried, and then the solvent was distilled off under reduced pressure.
-Fluoro-4-chloro-5- (3-methylcyclopentyl) oxyaniline (1.77 g, 7.26 mmo
l, yield 63.6%) was obtained.

¹ H-NMR spectrum (CDCl ₃ , TMS, pp
m): δ1.02 and 1.10 (total 3H, d, J = 6.0Hz), 1.22〜2.58
(7H, m), 3.75 (2H, br s), 4.65 (1H, m), 6.33 (1H, d, J _HF = 8.0H
z), 6.98 (1H, d, J _HF = 10.0Hz).

Reference Example 6

[0072]

Embedded image

2-Fluoro-4-chloro-5- (3-methylcyclopentyl) oxyaniline (1.76 g,
A solution of 7.22 mmol) and 3,4,5,6-tetrahydrophthalic anhydride (1.32 g, 8.68 mmol) in acetic acid (15 ml) was stirred under reflux for 4 hours. The resulting reaction mixture was added to 1N hydrochloric acid (50 ml) and extracted with ether (50 ml × 3 times). After drying the organic layer, the solvent was evaporated under reduced pressure, and the obtained reddish brown oily substance was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 8/1). By recrystallizing the obtained colorless transparent oil of N- {2-fluoro-4-chloro-5- (3-methylcyclopentyl) oxyphenyl} -3,4,5,6-tetrahydrophthalimide from methanol, White solid (0.93g, 2.38mm
ol, yield 33.0%) was obtained. Melting point: 68.0 to 70.0 ° C ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ 1.01 a
nd 1.08 (total 3H, each d, J = 6.0Hz), 1.25〜2.20 (11H,
m), 2.49 (4H, m), 4.70 (1H, m), 6.72 (1H, d, J _HF = 6.0Hz), 7.20
(1H, d, J _HF = 9.0Hz) .IR spectrum (KBr disk, cm ^-1 ): 1720,1500,1430,137
5,1195.

Reference Example 7

[0075]

[Chemical 15]

2-Fluoro-4-chloro-5-methoxycarbonyloxyaniline (20.0 g, 91.1 mm
ol) and 3,4,5,6-tetrahydrophthalic anhydride (14.0 g, 92.0 mmol) in acetic acid (200 m
l) The solution was reacted under heating under reflux for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, water (200 ml) was added, and the mixture was extracted with ethyl acetate (100 ml × 3 times). The organic layer was washed with an aqueous sodium carbonate solution and water, dried and then
By refining the oily substance obtained by distilling off the solvent under reduced pressure by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/5),
N- (2-Fluoro-4-chloro-5-methoxycarbonyloxyphenyl) -3,4,5,6-tetrahydrophthalimide white solid (26.2 g, 72.1 mmo)
1, yield 79.2%) was obtained.

Melting point: 138.5-146.2 ° C. ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ1.82 (4H,
m), 2.42 (4H, m), 3.93 (3H, s), 7.21 (1H, d, J _HF = 6.5Hz), 7.33
(1H, d, J _HF = 9.0Hz). IR spectrum (KBr disk, cm ^-1 ): 1765,1725,1508,150
0,1440,1430,1260,1195.

The N- (2-fluoro-
4-chloro-5-methoxycarbonyloxyphenyl)
-3,4,5,6-tetrahydrophthalimide (11.
8 g, 33.4 mmol) of methanol (100 ml)
Potassium carbonate (4.6 g, 33.3 mmol) was added to the solution, and the mixture was stirred under reflux for 5 hours. After the reaction was completed, the mixture was poured into 1N hydrochloric acid (200 ml), and ethyl acetate (1
(00 ml × 3 times). The organic layer was washed with water, dried, and the solvent was evaporated under reduced pressure to give a crude product (9.4 g). This was recrystallized from ether / hexane to give N- (2-fluoro-4-chloro-5-hydroxyphenyl) -3,4,5,6-tetrahydrophthalimide as a white solid (6.7 g, 22.
7 mmol, yield 67.8%) was obtained.

Melting point: 145.5 to 156.4 ° C. ¹ H-NMR spectrum (CDCl ₃ , TMS, ppm): δ1.80 (4H,
m), 2.40 (4H, m), 6.00 (1H, br s), 6.85 (1H, d, J _HF = 6.5Hz),
7.17 (1H, d, J _HF = 9.0Hz) .IR spectrum (KBr, cm ^-1 ): 3440,1785,1720,1530,143
0,1395,1185.

Reference Example 8

[0081]

Embedded image

N- (2-fluoro-4-chloro-5-hydroxyphenyl) -3,4,5,6-tetrahydrophthalimide (2.0 g, 6.76 mmol) and potassium carbonate (0.60 g, 4.34 mmol). ) In acetonitrile (50 ml) in cyclopentyl bromide (1.
2 g, 8.1 mmol) was added, and the mixture was stirred under reflux for 2 hours. After the reaction was completed, 1N hydrochloric acid (20
ml) was added and the mixture was extracted with ethyl acetate (20 ml × 3 times).
The organic layer was washed with water, dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, ethanol (5 ml) was added to the obtained pale yellow oily substance, and precipitated N- (2-fluoro-4-chloro- 5-cyclopentyloxyphenyl)
White solid of -3,4,5,6-tetrahydrophthalimide (0.75 g, 2.06 mmol, yield 30.5%)
Was isolated by filtration. Spectral data etc. refer to Reference Example 4
As shown in.

Reference Example 9

[0084]

[Chemical 17]

N- (2-fluoro-4-chloro-5-hydroxyphenyl) -3,4,5,6-tetrahydrophthalimide (2.0 g, 6.76 g) and potassium carbonate (0.60 g, 4.34 mmol) ) In acetonitrile (50 ml) was added cyclopentyl p-toluenesulfonate (1.90 g, 8.11 mmol) to give 80
The mixture was stirred at ° C for 2 hours. After the reaction was completed, 1N hydrochloric acid (20 ml) was added to the obtained reaction mixture, and ethyl acetate (20 ml × 3
Times). The organic layer was washed with water, dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, ethanol (5 ml) was added to the obtained pale yellow oily substance, and precipitated N- (2-fluoro-4-chloro- 5-Cyclopentyloxyphenyl) -3,4,5,6-tetrohydrophthalimide white solid (0.77 g, 2.12 mmol,
Yield 31.4%) was isolated by filtration. The spectral data and the like are as shown in Reference Example 4.

Reference Example 10

[0087]

Embedded image

Cyclopentanol (50.0 g, 0.58
mol) and p-toluenesulfonyl chloride (120
g, 0.629 mol) was dissolved in pyridine (200 ml), poured into ice water (about 1 L), and stirred sufficiently.
The precipitated solid was filtered and dried to give a cyclopentyl p-toluenesulfonate white solid (94.9).
g, 0.390 mol, yield 68.1%) was obtained.

Melting point: 30 ° C. or lower ¹ H-NMR (CDCl ₃ , TMS, ppm): δ 1.23 to 2.07 (8 H,
m), 2.45 (3H, s), 4.98 (1H, m), 7.38 (2H, d, J = 9.0H
z), 7.85 (2H, d, J = 9.0Hz).

Reference Example 11

[0091]

[Chemical 19]

Cyclopentanol (10 g, 0.116 mol), p-toluenesulfonyl chloride (24.3 g, 0.128 mol) and ether (100 ml) were added and dissolved in a 200 cc eggplant-shaped flask. Then, powdery potassium hydroxide (32.5 g, 0.58 mol) was slowly added while cooling to 10 ° C. or lower in a water bath. After the addition, stirring was continued for 2 hours at the same temperature. After completion of the reaction, the mixture was poured into ice water (20 ml), and the organic layer and the aqueous layer were separated. The organic layer was dried and then concentrated under reduced pressure to obtain a pale yellow viscous liquid of cyclopentyl p-toluenesulfonate (22.0 g, yield 81.8%).

Reference Example 12

[0094]

Embedded image

By the same method as in Reference Example 10, 3-methylcyclopentanol (5.0 g, 49.9 mmol)
And p-toluenesulfonyl chloride (10.0 g, 5
2.5 mmol) was reacted with pyridine (50 ml) to give 3-methylcyclopentyl p-toluenesulfonate (11.7 g, 46.2 mmol, yield 92.5%).
I got

¹ H-NMR (CDCl ₃ , TMS, ppm): δ 0.93 a
nd 1.00 (total 3H, each d, J = 6.0Hz), 1.20 ~ 2.30 (7H, m),
2.48 (3H, s), 4.97 (1H, m), 7.38 (1H, d, J = 8.0Hz), 7.85 (1H,
d, J = 8.0Hz).

N-substituted phenyl-3,4, which can be produced by the method illustrated in the above Examples and Reference Examples
Table 1 shows representative examples of 5,6-tetrahydrophthalimide derivatives.

Table 1 N-Substituted Phenyl-3,4,5,6
-Tetrahydrophthalimide derivative

[0099]

[Chemical 21]

[0100]

[Table 1]

[0101]

[Table 2]

N-substituted phenyl-3 thus obtained,
The 4,5,6-tetrahydrophthalimide derivative has excellent performance as a herbicide as described above.

When this compound is used as a herbicide, it can be used as it is, but generally, one or several kinds of auxiliary agents can be mixed and used as a herbicide. Usually, as an auxiliary agent, various carriers, fillers, solvents, surfactants, stabilizers and the like are mixed and formulated into a form such as a wettable powder, an emulsion, a powder, a granule and a flowable agent by a conventional method. Preference is given to using.

The solvent which is one of the auxiliary agents in the herbicides containing the N-substituted phenyl-3,4,5,6-tetrahydrophthalimide derivative as an active ingredient is, for example, water, alcohols, ketones, ethers, Aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, acid amides, esters, nitriles and the like are suitable, and one kind or a mixture of two or more kinds thereof is used.

As the extender, clays such as kaolin and bentonite, talc, talc such as pyrophyllite, diatomaceous earth,
Mineral powders such as oxides of white carbon and soybean powders, plant powders such as CMC, etc. are used. Further, a surfactant may be used as a spreading agent, a dispersant, an emulsifier, and a penetrant. Examples of the surfactant include nonionic surfactants, cationic surfactants and amphoteric surfactants. These surfactants are utilized as one kind or a mixture of two or more kinds depending on the application.

Preferable use of the herbicide containing the compound of the present invention as an active ingredient includes soil treatment, water surface treatment, foliage treatment and the like, and a particularly excellent effect is obtained by applying the control weeds from before germination to during larvae. Can be mentioned.

In addition, N-substituted phenyl-3,4,5,6
-A herbicide containing a tetrahydrophthalimide derivative as an active ingredient may be combined with other active ingredients that do not inhibit the herbicidal activity of the present active ingredient, such as other herbicides, insecticides, fungicides, plant growth regulators, etc. It is also possible to use them in combination or in combination.

Next, N-substituted phenyl-3,4,5,6
-The present invention will be described in more detail with reference to formulation examples of a herbicide containing a tetrahydrophthalimide derivative as an active ingredient and examples in which the herbicidal effect of the herbicide was examined. The parts are parts by weight.

Formulation Example 1 (Emulsion) 20 parts of the compound 10 shown in Table 1, 35 parts of xylene, 40 parts of cyclohexanone, and 5 parts of Solbol 900A (manufactured by Toho Kagaku Co., Ltd.) were uniformly mixed to obtain an emulsion. Other compounds listed in Table 1 were processed in the same manner as above to obtain emulsions.

Formulation Example 2 (Wettable powder) A mixture of 50 parts of the compound 10 shown in Table 1, 50 parts of diatomaceous earth, 22 parts of clay and 3 parts of Lunox R100C (manufactured by Toho Kagaku Co., Ltd.) is uniformly mixed and ground to be hydrated. I got an agent.

Formulation Example 3 (Granule) 5 parts of Compound 10 shown in Table 1, 35 parts of bentonite,
A mixture of 55 parts of talc and 5 parts of sodium lignin sulfonate was uniformly mixed and pulverized, and then water was added to knead the mixture, which was granulated by an extrusion granulator, dried and sized to obtain a granule. Other compounds listed in Table 1 were treated in the same manner as above,
A granule was obtained.

Test Example 1 (Effect on paddy field weeds) Paddy soil was filled in a Wagner pot of 1 / 5,000 are, and seeds of millet, eel, firefly, and 2-3 were added to the pot.
Leaf-stage rice seedlings (variety: Nihonbare) were sown or transplanted and kept in a flooded state. After 5 days, the compound shown in Table 1 which was made into a wettable powder or an emulsion according to the formulation example was used at 5, 2.5, 1,
A predetermined amount of the diluted solution was surface-treated on the water so that the amount became 0.5 g.
On the 20th day after the treatment, the herbicidal effect on the test plant and the phytotoxicity against rice were investigated according to the following criteria, and the second
The results in the table were obtained.

[0113]

[Table 3]

Commercially available Lonstar (trade name) was used as the reference compound A, and the same formulation method and treatment method were used.
The herbicidal activity and phytotoxicity to crops were investigated by the same criteria, and the results are shown.

[0115]

[Chemical formula 22]

[0116]

[Table 4]

Test Example 2 (Effect of Treatment of Upland Soil) A vat having an area of 16 × 11 cm ² and a depth of 7 cm was filled with upland soil, and seeds of crabgrass, chrysalis, barnyard grass, soybean, and corn were sown. The top was covered with 1 cm of soil. The next day, the first was made into a wettable powder or emulsion according to the formulation example.
A predetermined amount of the diluting solution was uniformly sprayed onto the soil cover so that the compounds shown in the table were 20, 10, and 5 g per are. On the 20th day after the treatment, the herbicidal effect on the test weeds and the phytotoxicity against soybean and corn were examined in the same manner as in Test Example 1. The results are shown in Table 3.

[0118]

[Table 5]

Test Example 3 (Effect of foliage treatment) A vat having an area of 16 × 11 cm ² and a depth of 7 cm was filled with field soil, which was sowed with seeds of crabgrass, chrysalis, barnyard grass and soybean, and grown after 15 days. The foliar portion of the plant was spray-treated with a predetermined concentration of a wettable powder according to the formulation example or a diluted solution of the compound shown in Table 1 in the form of an emulsion at a water amount of 10 liters per are. On the 20th day after the treatment, the herbicidal effect on the test weeds and the phytotoxicity against soybean were examined in the same manner as in Test Example 1. Table 4 shows the results.

[0120]

[Table 6]

[0121]

INDUSTRIAL APPLICABILITY By using the compound of the present invention, especially isobutyl compound as an intermediate, N-substituted phenyl-3,
The 4,5,6-tetrahydrophthalimide derivative is conveniently prepared. The derivative is useful as a herbicide because it has a high herbicidal effect on weeds at a low dosage and has little chemical damage to main crops.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoko Tateno 2-32-40, Futamatagawa, Asahi-ku, Yokohama-shi, Kanagawa (72) Inventor Emiko Ejiri 5-3-5 Wakamatsu, Sagamihara-shi, Kanagawa House Azuma No. 202 (72) ) Inventor Kikuko Harasawa 4-17-11 Sanamihara City, Kanagawa Prefecture No. 302 Daio Building 302 (72) Inventor Yuichi Onji 3-27-2 Tatsumidai Higashi, Ichihara City, Chiba Koyo Dormitory No. 504 (72) Inventor Ukai Teiyuki 4-15-12 Minamisurugadai, Fujieda City, Shizuoka Rainbow Home B-202 (72) Inventor Matsuin Shoin 3-13-13-106, Kahama, Adachi-ku, Tokyo

Claims (2)

[Claims] 1. The following general formula: (In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, X represents a halogen atom, Y represents. A hydrogen atom, a nitro group or amino group) substituted phenyl carbonate derivative represented by the. 2. The substituted phenyl carbonate derivative according to claim 1, wherein R ¹ represents an isobutyl group.