CN100465160C - N-isoindoledione substituted phenylamides with herbicidal activity - Google Patents

Abstract

The invention discloses N-isoindoledione substituted phenylamide compounds represented by the general formula (I) with herbicidal activity. Where X is hydrogen, chlorine in halogen, fluorine; Y is hydrogen, halogen (fluorine, chlorine, bromine); R ¹ is (C ₁ -C ₆ ) haloalkyl, substituted phenyl; R _m is monosubstituted or multisubstituted , the same or different hydrogen, alkyl, nitro, amino, halogen; m represents the number of substituents optional 1,2,3,4; the present invention pre-emergence soil treatment or post-emergence under the dosage of 75g ai/ha When the stems and leaves are treated, it shows good herbicidal activity against dicotyledonous weeds such as velvetleum, quinoa, and amaranthus, and some monocotyledonous weeds such as crabgrass, barnyardgrass, and foxtail, with a control effect of ≥80%.

Description

N-isoindoledione substituted phenylamides with herbicidal activity

Technical field: The present invention relates to N-isoindoledione substituted phenylamide compounds with herbicidal activity and a preparation method thereof.

Background technique:

There are many reports about amides and their combination herbicides, but due to the large amount of use or use for a period of time, weeds develop resistance to it, so it is necessary to change or improve the structure of the compound in order to invent new herbicidal compounds. Patent EP0786453 reports that compounds with the following structure types have very good herbicidal activity, but the N-isoindoledione substituted phenylamides related to the present invention have not been reported in the literature.

SUMMARY OF THE INVENTION: The present invention provides a herbicidally active N-isoindoledione-substituted phenylamide compound and a preparation method thereof, which is represented by the general structural formula (I):

in

Het is

X is hydrogen, chlorine and fluorine in halogen;

Y is hydrogen, halogen (fluorine, chlorine, bromine);

R ¹ is (C ₁ -C ₆ ) haloalkyl, substituted phenyl;

R _m is one or more substitutions, the same or different hydrogen, alkyl, nitro, amino, halogen;

When Het in the general formula (I) of the present invention is

When, the preparation method of target compound _C1 is as follows:

Add the intermediate (A ₁ ) and haloalkyl acid chloride (B) into the solvent, heat the reaction for 1-12 hours to obtain the target compound (C ₁ ), the molar ratio of the feed is A:B=1:1.1; the selected solvent can be benzene Or dichloroethane, temperature of reaction is the reflux temperature of selected solvent; The reaction time is 4 hours;

The reaction equation is as follows:

When Het in the general formula (I) of the present invention is

, the preparation method of target compound _C2 is as follows:

Add a certain amount of intermediate (A ₂ ) and triethylamine to the solvent, add a corresponding amount of substituted benzoyl chloride (B) dropwise under ice water cooling, and react at a certain temperature for 1-12 hours after the dropwise addition to obtain the target Compound (C ₂ ), the feeding molar ratio is A:B:triethylamine=1:1:1.1; the selected solvent can be benzene or dichloroethane, the reaction temperature is 20-25°C; the reaction time is 2 hours;

The reaction equation is as follows:

Intermediates A ₁ and A ₂ can be synthesized by referring to the method described in document EP0786453.

The preparation and use of the active compounds according to the invention are exemplified by the following examples, but the technical content of these examples does not limit the scope of the invention.

The synthesized part of the compounds represented by the general formula (I) of the present invention is shown in Table 1.

Table 1: the chemical structure and fusing point of the compound shown in part general formula (I) of the present invention

The invention exhibits good herbicidal activity on dicotyledonous weeds such as velvetleaf, quinoa, and amaranthus, and some monocotyledonous weeds such as crabgrass, barnyardgrass, and green foxtail, and the control effect is more than 80%.

Detailed ways:

Example 1: 3-chloro-N-(2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)- Preparation of 4-fluorophenyl)-2,2-dimethylpropanamide (compound C ₁ -02 in Table 1).

In a 100 mL round bottom flask was added 0.96 g (3.3 mmol) of the intermediate 2-(5-amino-4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-isoindole- 1,3-diketone A ₁ , 30mL of benzene and 0.37g (3.6mmol) of 3-chloro-2,2-dimethyl-propionyl chloride B were magnetically stirred, heated to 100°C, and refluxed for 4 hours to stop the reaction. 150 mL of water was added to the reaction solution, and the organic layer was separated. The organic layer was washed with water, saturated aqueous sodium carbonate solution and saturated brine successively, dried over anhydrous magnesium sulfate, and precipitated under reduced pressure to obtain 1.22 g of white crystals, namely 3-chloro-N- (2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-4-fluorophenyl)-2,2 -Dimethylpropionamide (compound C ₁ -02), content 83%, yield 82%, mp 125.6-126.6°C.

¹ H NMR (CDCl ₃ , ppm) δ: 1.43 (s, 3H, CH ₃ ), 1.58 (s, 3H, CH ₃ ), 1.80-1.84 (m, 4H, 2CH ₂ ), 2.41-2.45 (m, 4H , 2CH ₂ ), 3.68(s, 2H, CH ₂ Cl), 7.26-7.31(t, 1H, Ar-H, J=6.9Hz), 8.03(s, 1H, HN), 8.43(d, 1H, Ar -H, J = 7.5 Hz).

Example 2: 4-chloro-N-(2-chloro-5-(1,3-dioxoisoindol-2-yl)-4-fluorophenyl)benzamide (compound C ₂ -02 in Table 1 ) preparation.

Add 1.16g (4.0mmol) intermediate 2-(5-amino-4-chloro-2-fluorophenyl)-2H-isoindole-1,3-dione A ₂ , 30mL di Chloroethane and 0.45g (4.4mmol) triethylamine, magnetically stirred, under ice-water cooling, slowly add 0.7g (4.0mmol) p-chlorobenzoyl chloride B dropwise, and react at room temperature for 2h after the dropwise addition. 100 mL of water was added to the reaction solution, and the organic layer was separated. The organic layer was washed with water and saturated brine successively, dried over anhydrous sodium sulfate, precipitated under reduced pressure, and subjected to silica gel column chromatography to obtain 1.54 g of white crystal 4-chloro-N- (2-Chloro-5-(1,3-dioxoisoindol-2-yl)-4-fluorophenyl)benzamide (Compound C ₂ -02). Content 95%, yield 85%, mp173.0～175.0℃.

¹ H NMR (CDCl ₃ , ppm) δ: 1.45 (s, 3H, CH ₃ ), 3.69 (s, 2H, CH ₂ Cl), 7.18-7.22 (m, 1H, Ar-H), 7.35-7.37 (t , 1H, Ar-H, J=6.9Hz), 7.51-7.54(m, 1H, Ar-H), 7.85-7.88(m, 1H, Ar-H), 8.05(s, 1H, CONH), 8.54( d, 1H, Ar-H, J = 7.5 Hz).

Example 3: N-(-5-(5-amino-1,3-dioxindol-2-yl)2-chloro-4-fluorophenyl)-3-chloro-,2-dimethyl Preparation of Propionamide (Compound _C2-06 in Table 1).

Add 2.68g (8.0mmol) intermediate 2-(5-amino-4-chloro-2-fluorophenyl)-5-nitroisoindole-1,3-dione A ₂ into a 100mL round bottom flask, 50mL dichloroethane and 0.89g (8.8mmol) triethylamine, magnetically stirred, under ice water cooling, slowly add 1.30g (8.0mmol) p-chlorobenzoyl chloride B dropwise, after the dropwise addition, react at room temperature for 2h. 100mL of water was added to the reaction solution, and the organic layer was separated. The organic layer was washed with water and saturated brine successively, dried over anhydrous sodium sulfate, and precipitated under reduced pressure to obtain a white solid (N-(-5-(5-nitro-1 , 3-dioxoisoindol-2-yl) 2-chloro-4-fluorophenyl)-3-chloro-, 2-dimethylpropanamide) 3.0 g, content 86%.

Add 3.0 g (5.7 mmol) of the above-mentioned intermediate into a 100 mL round bottom flask Base)-3-chloro-, 2-dimethylpropanamide, 30mL glacial acetic acid, magnetically stirred, heated to 60°C, added 1.6g (28.5mmol) of iron powder in batches, and kept warm for 30min after the addition was complete. After cooling, the reaction solution was poured into 100 mL of ice water, and 50 mL of ethyl acetate was added for extraction. The organic layer was washed with water and saturated brine successively, dried over anhydrous sodium sulfate, precipitated under reduced pressure, and chromatographed on a silica gel column to obtain 1.9 g of a light yellow solid 4 -Chloro-N-(2-chloro-5-(1,3-dioxoisoindol-2-yl)-4-fluorophenyl)benzamide (compound C ₂ -06) content 93%, yield 74 %, mp 145.6-147.2°C.

¹ H NMR (CDCl ₃ , ppm) δ: 1.43 (s, 6H, 2CH ₃ ), 3.69 (s, 2H, CH ₂ Cl), 4.45 (s, 2H, Ar-NH ₂ ), 6.88-6.94 (m, 1H, Ar-H), 7.35-7.38(t, 1H, Ar-H, J=6.9Hz), 7.43-7.45(m, 1H, Ar-H), 7.85-7.88(m, 1H, Ar-H) , 8.04 (s, 1H, CONH), 8.44 (d, 1H, Ar-H, J = 7.5 Hz).

Example 4: 3-chloro-N-(2-chloro-5-(5,6-dichloro-1,3-dioxoisoindol-2-yl)-4-fluorophenyl)2,2- Preparation of Dimethylpropanamide (Compound _C2-07 in Table 1).

Add 1.80 g (5.0 mmol) of intermediate 2-(5-amino-4-chloro-2-fluorophenyl) 5,6-dichloroisoindole-1,3-dione _A to a 100 mL round bottom flask , 35mL dichloroethane and 0.55g (5.5mmol) triethylamine, magnetically stirred, under ice water cooling, slowly add 0.77g (5.0mmol) p-chlorobenzoyl chloride B dropwise, after the dropwise addition, react at room temperature for 2h . 100 mL of water was added to the reaction solution, and the organic layer was separated. The organic layer was washed with water and saturated brine successively, dried over anhydrous sodium sulfate, precipitated under reduced pressure, and subjected to silica gel column chromatography to obtain 2.0 g of white crystal 3-chloro-N- (2-chloro-5-(5,6-dichloro-1,3-dioxoisoindol-2-yl)-4-fluorophenyl)2,2-dimethylpropanamide (compound C ₂ - 07). Content 92%, yield 81%.

¹ H NMR (CDCl ₃ , ppm) δ 1.44 (s, 6H, 2CH ₃ ), 3.69 (s, 2H, CH ₂ Cl), 7.33-7.36 (t, 1H, Ar-H, J=6.9Hz), 7.80 (s, 2H, Ar-H), 8.06 (s, 1H, CONH), 8.43 (d, 1H, Ar-H, J = 7.5 Hz).

Application Example 1: Potted Plant Weeding Test

Accurately weigh the sample, dissolve it with a suitable solvent, add a small amount of emulsifier, add distilled water to make it 10ml, and spray it with an appropriate sprayer, equivalent to 75gai/ha per unit area. Fill the plastic pots with a cross-sectional area of 64cm ² quantitatively, flatten them, and water them thoroughly. Select dicotyledonous leaves with plump grains and the same size and choose Chenopodium album, Abutilon theophrasti, and Amaranthusascedense. Monocotyledons (Digitaria sanguinalis), barnyardgrass (Echinochloacrus-galli), and foxtail (Setaria viridis) were used as monocotyledonous plants, and planted in separate pots, each accounting for 1/3 of the pot area, covered with 1cm thick fine soil and drenched water and cultivated in a greenhouse. When the monocotyledonous test material grows to the stage of 1 leaf and 1 heart, and the dicotyledonous test material grows to the stage of 2 true leaves, spray the stems and leaves after the emergence with the liquid medicine, and treat the soil before the seedling the next day after the test material is sown. Then return to the greenhouse. After 15 days, the growth situation of the upper part of the ground was visually measured, and the growth inhibition rate was calculated according to the following formula:

Growth inhibition rate (%)=100*(control plant height-treatment plant height)/control plant height

Grading of herbicidal activity based on growth inhibition rate:

++, >80%; +, 80-50%; -, <50%.

Table 2: Potted weeding test results

NT: Not tested.

Table 2 has listed some compounds of the present invention, such as C ₁ -02, C ₁ -03, C ₁ -04, C ₁ -06, C ₁ -07, C ₂ -04, etc. Inhibitory effects of soil treatments and post-emergence stem-leaf treatments. As shown in table 2, when the N-isoindole diketone substituted phenyl amides compound shown in general formula (I) of the present invention is under the dose of 75g ai/ha during pre-emergence soil treatment or post-emergence stem and leaf treatment, to Dicotyledonous weeds such as velvetleaf, quinoa, and amaranthus and some monocotyledonous weeds such as crabgrass, barnyardgrass, and foxtail showed good herbicidal activity, with a control effect of ≥80%.

Claims (4)

1.N-isoindole dione substituted phenyl amide compound, it is characterized in that the having general formula structure of (I):

Wherein

Het is

X is a hydrogen, the chlorine in the halogen, fluorine;

Y is a hydrogen, the fluorine in the halogen, chlorine, bromine;

R ¹Be (C ₁-C ₆) haloalkyl, halogenophenyl;

R _mBe hydrogen identical or inequality, (C ₁-C ₄) alkyl, amino, halogen; M represents substituent number, optional 1,2.

2. N-isoindole dione substituted phenyl amide compound according to claim 1, its characterization compound is:

3-chloro-N-(2-chloro-5-(1,3-dioxy-4,5,6,7-tetrahydrochysene-1H-isoindole-2 (3H)-yl)-4-fluorophenyl)-2,2-dimethyl propylene acid amides

4-chloro-N-(2-chloro-5-(1,3-dioxy isoindole-2-yl)-4-fluorophenyl) benzamide

N-(5-(5-amino-1,3-dioxy isoindole-2-yl) 2-chloro-4-fluorophenyl)-3-chloro-, 2-dimethyl propylene acid amides

3-chloro-N-(2-chloro-5-(5,6-two chloro-1,3-dioxy isoindole-2-yl)-4-fluorophenyl) 2,2-dimethyl propylene acid amides.

3. the preparation method of N-isoindole dione substituted phenyl amide compound according to claim 1 and 2 is characterized in that: the Het of compound is in general formula of the present invention (I)

The time, the preparation method of general formula (I) compound is as follows:

In solvent, add intermediate (A ₁) and haloalkyl acyl chlorides (B), obtaining target compound (I) in reacting by heating 1-12 hour, molar ratio is A ₁: B=1: 1.1; Selected solvent can be benzene or ethylene dichloride, and temperature of reaction is the reflux temperature of selected solvent; Reaction times is 4 hours;

Reaction equation is as follows:

When the Het of general formula of the present invention (I) compound is

The time, the preparation method of general formula (I) compound is as follows:

In solvent, add a certain amount of intermediate (A ₂) and triethylamine, the frozen water cooling drips the substituted benzoyl chloride (B) of respective amount down, dropwises to react at a certain temperature to obtain target compound (I) in 1-12 hour, and molar ratio is A ₂: B: triethylamine=1:1:1.1; Selected solvent can be benzene or ethylene dichloride, and temperature of reaction is 20-25 ℃; Reaction times is 2 hours;

Reaction equation is as follows:

4. the purposes of N-isoindole dione substituted phenyl amide compound according to claim 1 and 2 is characterized in that: most of broadleaf weedss and part monocotyledon weed are had good weeding activity.