JP2768929B2 - 3- (1H-pyrrol-1-yl) benzenesulfonamide derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an N-substituted-3-substituted compound.
3- (1H-pyrrol-1-yl) useful as an intermediate for producing a (nitrogen-containing 5-membered) benzenesulfonamide derivative
It relates to a benzenesulfonamide derivative.

[0002]

2. Description of the Related Art Conventionally, many compounds have been proposed as herbicides, and many types of N-substituted benzenesulfonamide derivatives have been reported as herbicides.
As an N-substituted benzenesulfonamide in which a 5-membered ring is bonded to a benzene ring and a pyrimidine ring or 1,3,5-triazine ring is bonded to a nitrogen atom, for example, JP-A-58-123283 and 58-1319
No. 84 discloses a compound represented by the following general formula.

[0003]

Embedded image (Wherein Q represents a 5-membered ring, R ³ is H, F, Cl,
Represents Br, CH ₃ , CF ₃ or OCH ₃ , and R ⁴ is H
Or CH ₃ , W represents O or S, and A represents

Embedded image (Where X represents CH ₃ , OCH ₃ or Cl, and Y represents CH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , OCH ₃ , OC ₂
H ₅ etc., and Z represents CH or N) etc.)

In DE 1,938,904, 3- (2,
Although 5-dimethyl-1H-pyrrol-1-yl) benzenesulfonamide and its use as a medicinal component are described, nothing is described about the use of a herbicidal compound as an intermediate zone.

[0005]

By the way, heretofore, a herbicide exhibiting a certain herbicidal effect at a low dose so as to have an advantage of reducing its abundance in the environment, and crops and weeds regardless of changes in environmental conditions. There is a high demand for herbicides that exhibit excellent herbicidal effects, such as herbicides that exhibit intermittent selectivity and herbicides that do not cause phytotoxicity to subsequent crops in two crops. The present invention has been made to solve the above-described conventional needs.
That is, an object of the present invention is to provide an N-
An object of the present invention is to provide a novel intermediate for producing a substituted-3- (nitrogen-containing 5-membered ring) benzenesulfonamide derivative.

[0006]

Means for Solving the Problems The present inventors have disclosed in Japanese Patent Application Laid-Open Nos. 58-112283 and 58-131984.
The compound disclosed in the above publication has a 5-membered ring at the 2-position of benzenesulfonamide, whereas an unreported compound represented by the following general formula (II) having a 5-membered ring at the 3-position is excellent. It has been found that the present invention has an effective herbicidal effect, and the present invention has been completed with respect to an intermediate thereof.

[0007]

Embedded image (Wherein R ¹ is Cl, CH ₃ , COOCH ₃ or CO
OC ₂ H ₅ , R ² represents H or CH ₃ ,
Represents CH or N, and X ¹ represents CH ₃ , OCH ₃ or C
and X ² represents CH ₃ or OCH ₃ )

The present invention relates to the above N-substituted-3- (nitrogen-containing 5
The present invention relates to a 3- (1H-pyrrol-1-yl) benzenesulfonamide derivative which is an intermediate for producing a (membered ring) benzenesulfonamide derivative, and has the following general formula (I)
Indicated by

Embedded image (Wherein R ¹ is Cl, CH ₃ , COOCH ₃ or COO
Represents C ₂ H ₅ and R ² represents H or CH ₃ )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Specific examples of the 3- (1H-pyrrol-1-yl) benzenesulfonamide derivative represented by the above general formula (I) of the present invention include those shown in Table 1 below.

[0010]

[Table 1]

The compound of the present invention represented by the general formula (I)
The (1H-pyrrol-1-yl) benzenesulfonamide derivative can be synthesized according to the following reaction formula, using a known 3-aminobenzenesulfonamide derivative represented by the following general formula (IV) as a starting material.

Embedded image (Wherein R ¹ and R ² each have the same meaning as described above)

Specifically, a compound represented by the general formula (IV) and 2,5-dialkoxytetrahydrofuran or acetonylacetone are added to acetic acid or propionic acid, or
The mixture is stirred in dioxane containing a catalytic amount of 5% hydrochloric acid or 95% sulfuric acid at 50 to 120 ° C. for 0.5 to 10 hours. After completion of the reaction, the solvent was sufficiently distilled off, and the residue was washed with water.
Filter off. Next, the compound represented by the general formula (I) can be obtained with high purity by purifying by column chromatography. The compound represented by the general formula (IV) used in the above reaction scheme can be obtained from a nitrobenzene derivative, for example, as described in Bull. Chem. Soc. Jpn. , 55 , 382
4 (1982), or from a 3-nitroaniline derivative, for example, Chem. Ber. , 90 ,
841 (1957) and J.M. Macromol. Sc
i. , Chwm. , 1969 , 941 to synthesize a 3-nitrobenzenesulfonamide derivative, and then reduce the nitro group to an amino group using SnCl ₂ in methanol or ethanol containing 35% hydrochloric acid. it can.

The compound of the present invention represented by the general formula (I)
The (1H-pyrrol-1-yl) benzenesulfonamide derivative is an intermediate for producing an N-substituted-3- (nitrogen-containing 5-membered ring) benzenesulfonamide derivative represented by the general formula (II), which is useful as a herbicide. Used as That is, 3- (1H-) represented by the general formula (I) of the present invention.
Pyrrol-1-yl) benzenesulfonamide derivative and a phenylcarbamate represented by the following general formula (III)
With an N-substituted derivative represented by the general formula (II) by reacting
A 3- (nitrogen-containing 5-membered ring) benzenesulfonamide derivative can be obtained. The reaction formula is as follows.

[0014]

Embedded image (Wherein, R ¹ , R ² , Z, X ¹ and X ² each have the same meaning as described above)

In the above reaction, the organic solvent includes
Dimethylacetamide, N-methylpyrrolidone, acetonitrile and the like can be used. Further, as the base, diazabicyclooctane, diazabicyclononene,
Diazabicycloundecene and the like can be used. The reaction is carried out at a reaction temperature in the range of -20C to 100C, preferably 0C to 50C, for a reaction time in the range of 0.5 to 24 hours. After the reaction is completed, the reaction mixture is added to a dilute aqueous hydrochloric acid solution, the resulting precipitate is collected by filtration, air-dried, and the product is purified by a reprecipitation method, a purification method by column chromatography, or a washing method, and the purity is high. N-substituted-3- (nitrogen-containing 5-membered ring) benzenesulfonamide derivative represented by the above general formula (II) can be obtained. In addition,
The compound represented by the general formula (III) can be prepared from phenyl chloroformate and 2-amino-4,6-disubstituted pyrimidine (or 1,3,5-triazine), for example, as described in EP-A-238,070. Can be obtained.

N-substituted-3 represented by the above general formula (II)
-(Nitrogen-containing 5-membered ring) benzenesulfonamide derivative is
It shows a certain herbicidal effect at low dose and shows selectivity between crops and weeds. Therefore, herbicides containing this compound as an active ingredient, for example, before or after germination of dicotyledonous or monocotyledonous weeds in important crops such as wheat, rice, corn, soybean, cotton, sugar beet, potato, tomato, etc. Suitable for controlling. Examples of dicotyledonous weeds that can be controlled with a herbicide comprising an N-substituted-3- (nitrogen-containing 5-membered ring) benzenesulfonamide derivative represented by the above general formula (II) include Amarant
hus), genus Bidens, genus Stellaria, genus Solanum,
Abutilon, Convolvulus, Maurice (Matri)
caria), Gallium, Azechia (Lindernia) and the like. Also, as monocotyledon weeds, millet (Echinochlo)
a), genus Setaria, genus Digitaria, oat genus (Aven)
a), genus Cyperus, genus Alisma, genus Monocho (Monocho)
ria) and the like.

[0017]

The present invention will be described below by way of examples. Example 1 2- (aminosulfonyl) -4- (1H-pyrrole-1
-Yl) benzoic acid methyl ester (Compound No. I-5)
Synthesis of 4-amino-2- (aminosulfonyl) benzoic acid methyl ester (300 mg, 1.3 mmol) and 2,5-dimethoxytetrahydrofuran (0.23 ml) were dissolved in acetic acid (3 ml) and stirred at 110 ° C. for 1.5 hours. Then, acetic acid was distilled off, 30 ml of ice water was added, and the mixture was stirred for 20 hours. The precipitate was collected by filtration and air-dried. The resulting brown solid was purified by column chromatography using silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries, Ltd.) and dichloromethane. White solid, yield 175.7 mg,
Yield 48%. The physicochemical properties are shown in Table 2.

Examples 2 to 8 Other compounds shown in Table 2 were synthesized in the same manner as in Example 1. Table 2 shows the yield and physicochemical properties of each compound.

[Table 2]

Reference Example Synthesis of 2-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonylaminosulfonyl] -4- (1H-pyrrol-1-yl) benzoic acid methyl ester 2- (aminosulfonyl)- 4- (1H-pyrrole-1
-Yl) benzoic acid methyl ester 141.5 mg (0.
5 mmol) and (4,6-dimethoxypyrimidine-2-
Il) Carbamic acid phenyl ester 137.5 mg
(0.5 mmol) was dissolved in 1.5 ml of N, N-dimethylacetamide at room temperature. Then, 1,8-diazabicyclo [5.4.0] undec-7-ene82.
1 mg was added, and the mixture was stirred for 5 minutes, and then allowed to stand for 15 hours. Thereafter, 0.2 ml of 35% hydrochloric acid was added to 20 ml of ice water, and the reaction mixture was added in an amount of 0.2 ml with stirring.
After stirring for 20 minutes, the precipitate was collected by filtration and air-dried. The crude product was purified by reprecipitation using dichloromethane and petroleum ether. White solid, mp 158-162 [deg.] C, 196 mg obtained, 85% yield.

[0020]

According to the present invention, the compound represented by the general formula (I) 3
The-(1H-pyrrol-1-yl) benzenesulfonamide derivative is a compound represented by the general formula (II)
It is useful as an intermediate for producing a substituted 3- (nitrogen-containing 5-membered ring) benzenesulfonamide derivative. The N-substituted-3- (nitrogen-containing 5-membered ring) benzenesulfonamide derivative represented by the above general formula (II) exhibits a reliable herbicidal effect at a low dose, and can be selected between crops and weeds. Shows sex.
Therefore, herbicides containing this compound as an active ingredient include, for example, wheat, rice, corn, soybean,
It is particularly suitable for controlling dicotyledonous weeds and monocotyledonous weeds in important crops such as cotton, sugar beet, potatoes and tomatoes before or after germination, and in addition to agricultural land such as fields, paddy fields, orchards, It can also be used to control weeds on non-agricultural lands such as grounds and factory sites.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (I):
-Pyrrole-1-yl) benzenesulfonamide derivatives. Embedded image (Wherein R ¹ is Cl, CH ₃ , COOCH ₃ or COO
Represents C ₂ H ₅ and R ² represents H or CH ₃ )