WO2007059663A1 - N-isoindol-dione-substituted phenylurea compounds having herbicidal activity - Google Patents

Abstract

The present invention discloses herbicidal N-isoindol-dione-substituted phenylurea compounds of formula (I),wherein X is hydrogen, halogen, cyano or methyl, wherin halogen is F or Cl, Y is hydrogen or halogen, wherin halogen is F or Cl, R1 is (C1-C6) linear or branched alkyl, (C1-C6) haloalkyl, mono- or multi-substituted phenyl, or mono- or multi-substituted benzoyl, and R2 is hydrogen, (C1-C4) linear or branched alkyl. When the compounds are applied in the soil treatment at preemergence or the setm and foliage treatment at postemergence at 75 g ai/ha, they show good herbicidal activity against dicotyledonous weeds such as Abutilon theophrasti, Chenopodium album, Amaranthus ascedense and the like that the control efficacy is more than 80%, and show certain control efficacy against some monocotyledonous weeds such as Digitaria sanguinalis, Echinochloa crus-galli and Setaria viridis and the like.

Description

 Herbicidally active N-isoindoledione substituted stupid urea compound

Technical field

 The present invention relates to a herbicidal N-isoindolindione substituted phenylurea compound and a process for the preparation thereof. Background technique

 So far, there have been many reports on protoporphyrinogen oxidase inhibitor herbicides and urea herbicides, such as: acesulfame, flufenacetate, oxazinone, chlorpyrifos, oxafluridone However, there are reports of N-isoindanedion-substituted phenylurea structural compounds. Moreover, new and improved herbicidal compounds and compositions are needed due to the disadvantages of herbicides having a single herbicidal spectrum or the use of weeds for a period of time.

Summary of the invention

 SUMMARY OF THE INVENTION An object of the present invention is to provide a herbicidal N-isoindanedione substituted phenylurea compound and a process for the preparation thereof.

 The invention is represented by the structural formula (I):

 (I)

 among them

 X is hydrogen, cyano, cyano, methyl, 3⁄4 means fluorine and chlorine;

 Y is hydrogen, halogen, halogen means fluorine and chlorine;

1 is (d-C ₆ ) linear or branched alkyl, (d-C ₆ )haloalkyl, monosubstituted or polysubstituted phenyl, monosubstituted or polysubstituted benzoyl;

R ² is hydrogen, (d-C ₄ ) a straight or branched fluorenyl group. The compound of the formula (I) in the present invention may be an intermediate of 2-(5-amino-2,4-disubstituted phenyl)-4,5,6,7-tetrahydro-2H-isoindole-1, 3 -Dione A is a starting compound for the synthesis of different substituents of urea compounds by two different routes:

(1) When R ² is a hydrogen atom, the preparation method of the formula (I) is: synthesizing a disubstituted urea by an isocyanate method, That is, a certain amount of alkyl isocyanate, substituted phenyl isocyanate or substituted benzoyl isocyanate is added to the solvent. The corresponding amount of the intermediate 2-(5-amino-2,4-disubstituted phenyl) is added dropwise under the protection of nitrogen. 4, 5, 6, 7-tetrahydro-2H-isoindole-1, 3-dione A, after completion of the dropwise addition, the reaction is carried out at a certain temperature for 1 to 12 hours to obtain the target compound (I). The preferred solvent for the above reaction is dichloroethane; a preferred molar ratio is A:B = 1: 1. 3; preferred reaction temperature is the reflux temperature of the selected solvent; a preferred reaction time is 5 hours. The specific synthetic route is represented by equation (1).

(2) When R ^{2 is} not a hydrogen atom, the general formula ( I ) is prepared by: one-pot synthesis of trisubstituted urea, that is, adding a certain amount of solid phosgene in a solvent, and then dropping it under nitrogen protection. The corresponding amount of the intermediate 2-(5-amino-2,4-dihalophenyl)-4,5,6,7-tetrahydro-2H-isoindole-1, 3-dione A and triethyl The amine is reacted at room temperature for half an hour, and the corresponding amount of the disubstituted amine C and triethylamine are added dropwise again, and the reaction is carried out at a certain temperature for 1 to 12 hours to obtain the target compound (I). The preferred solvent in the above reaction is dichloroethane; a preferred molar ratio is A: C (R'R ² NH) _: solid phosgene: triethylamine = 1: 1: 0: 35: 4; The reaction temperature is about 25 ;; the preferred reaction time is half an hour. The specific synthetic route is expressed by equation (2).

 The intermediate (A) was synthesized by the method described in the reference EP0786453.

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

Synthetic fractions The compounds of the formula (I) of the present invention are shown in Table 1. Table 1: Chemical structure and melting point of a part of the compound of the formula (I) of the present invention

No. YXR ¹ R ² m. p C)

01 C1 F 3 ^— CF3C6H4 H 215.3 217· 1

02 C1 F 4-0CF ₃ C ₆ 3⁄4 H

03 C1 F 4- CI C ₆ H 222.4 223· 3

 04 C1 F 2 - CI Ce H 194.5 196· 0

 05 C1 C1 3- CF3 Ce3⁄4 H 202.4-203.6

06 C1 F 2 - CH3. 6 H

07 C1 F 2-F, 6-FC ₆ H ₃ CO H 214.6 217· 7

08 FF 2-F, 6-FC ₆ H ₃ CO H 255· 5 257· 0

09 C1 H 2-F, 6-FC ₆ H ₃ CO H 279.6 9

10 C1 F 2- CI, 6-FC ₆ H ₃ CO H 275· 9 277· 5

11 C1 H 2-C1, 6-FC ₆ H ₃ CO H

12 C1 F 2-C1, 6- CI C ₆ H ₃ CO H 289.7 291· 5

13 C1 H 2-C1, 6- CI C ₆ 3⁄4 CO H 288.9 289· 7

14 C1 H 2- CI, 4-C1 C ₆ 3⁄4 CO H 24 CO6 cn.9 248· 3

15 C1 F 2-C1, -C1 C ₆ CO H 277.7 CO ι279· 1

 ι

16 C1 HC _e H ₅ CO H

 0

 C1 F ο

17 C ₆ H ₅ CO H cn

26 C1 F CH ₃ CH ₃ The invention (I) has the effect of eliminating cockroaches and weeding, and can have fiber 'J dicotyledonous weeds behind the seedling brain. detailed description

Example 1: 1-[2-Chloro-5-(1 3-dioxo-4 5 6,7-tetrahydro-1H-isoindole-2(3H)-yl)-4-fluorophenyl]- Preparation of 3-(3-trifluoromethylphenyl)urea (Compound 01 in Table 1). Add 30 mL of dichloroethane and 0.97 g (5.2 mmol) of trifluoromethylphenylisocyanate to a 100 mL three-necked flask equipped with a drying tube and a reflux condenser. Magnetically stir and add 1.17 g (4 mmol) under nitrogen. 2-(5-Amino-4-chloro-2-fluorophenyl)isoindole-1,3-dione, dropping at room temperature for 0.5, heating to reflux reaction 5, desolvation to give a pale yellow solid, column The target product was obtained 1.44 g, ie 1-[2-chloro-5-(1,3-di- 4,5,6,7-tetrahydro-1H-isoindole-2(3H)-yl)- 4-fluorophenyl]-3-(3-trifluoromethylphenyl)urea, 95%, mp 215.3~217·1°C, yield 85%.

'HNMR (CDC1 ₃ , ppm) δ: 1.88 (s, 4H, cyclohexene), 2.48 (s, 4H, cyclohexene), 7.11 (s, 1H, m_F ₃ C- Ph-N- H), 7.32~8.25 (m , 6H, Ar- H), 7.68 (s, 1H, NH). Example 2: 1-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-Iisoindole-2 (3τ3⁄4-yl)-4-fluorophenyl] Preparation of 3-(2,6-difluoro-benzoyl)urea (Compound 07 in Table 1).

 To a 100 mL three-necked flask equipped with a drying tube and a reflux condenser, 30 mL of dichloroethane and 0.42 g (2.3 mmol) of m-trifluoromethylbenzoyl isocyanate were added, magnetically stirred, and 0.57 g of nitrogen was added under nitrogen protection ( 1.9 mmol) 2-(5-Amino-4-chloro-2-fluorophenyl)isoindole-1,3-dione. After the dropwise addition, the reaction was carried out at room temperature for 0.5 h, then heated to reflux reaction 5, and the solution was decomposed to give a pale-yellow solid, which was obtained by column chromatography to give the desired product, which is 1-[2-chloro-5- (1, 3-dioxy- 4, 5, 6, 7-tetrahydro-isoindole-2(3yl)-4-fluorophenyl]-3-(2,6-difluoro-benzoyl)urea, content 95 ° /., Mp 214.6 to 217.7 ° C, yield 75%.

 'Η NR (CDC ppm) δ: 1.85 (s, 4H, cyclohexene), 2.45 (s, 4H, cyclohexene), 7.00~ 8.29 (m, 5H, ArH), 8.50 (s, 1H, Ar-NH), 11.00 (s, 1H, NH). Example 3: 3-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-isoindole-2(3-yl)-4-fluorophenyl]- 1, 1-Dipropylurea (Compound 19 in Table 1).

Add 80 mL of dichloroacetic acid and 0.44 g (1.48 mmol) of solid phosgene to a 250 mL three-necked flask equipped with a drying tube, stir and dissolve, and add 1.17 g (4 mmol) of 2-(5-amino-) under nitrogen protection. 40 mL of 4-chloro-2-fluorophenyl)isoindole-1,3-dione and 0.8 g (8 mmol) of triethylamine in dichloroacetic acid. After 30 min, drop at room temperature. Min, add 0.4 g (4 mmol) of dipropylamine and 0.8 g (8 mraol) of triethylamine in 40 mL of dichloroethane solution, and let it flow for 30 min at room temperature for 30 min. The reaction solution was washed with water (100 mL×3), and then evaporated. , ie 3-[2-chloro-5-(1,3-dioxo-4, 5, 6, 7-tetrahydro-1 006000690

Isophthalic acid 哚 -2(3^)-yl)- 4-fluorophenyl]- 1, 1-dipropylurea, content 90%, m. p. 97.5-99.3 °C, yield

55%.

3⁄4 NR (C paralysis DC1 ₃ , ppm) δ: 0.93~0.98 (m, 6H, CH ₃ ), 1.61~1.74 (m, 4H, CH ₂ ), 1.82 (s, 4H, cyclohexe藜ne) , 2.41 ( s, 4H, cyclohexene), 3.25~3.30 (m, 3H, NCH ₂ ), 6.94 (s, 1H, NH), 7·22~8·34 (m, 2H, Ar-H).

 Head M concave Application Example 1: Potted weeding test Tang Ma test

Accurately weigh the sample, dissolve it with a suitable solvent, add a small amount of emulsifier, add distilled water to a volume of 10 ml, spray with a suitable sprayer, and convert the unit area to 75 gai/ha. Set the dog tail in a plastic pot with a cross-sectional area of 64 cm ²

The amount of soil is filled, flattened, and water is immersed. Choosing the seeds with full grain size and uniform size is selected from Chenopodiunialbimi, ramie i Abut Hon theophrasti, iA aran castor ascedense, and monocotyledon. Taria sanguinalis) ^ Echinochloa criAS- a7J, Set aria viridis, singular, dicotyledonous tillers, each 1/3 of the area, covered with lcm thick fine soil and drenched, set Concave

Cultured in a greenhouse. When the monocotyledonous test material grows to 1 leaf 1 heart stage, the dicotyledon test material grows to 2 true leaf stage, the seedling stem and leaf spray treatment is carried out with the liquid medicine, and the seedling soil treatment is carried out the next day after the test material is planted. Then put back the greenhouse Matang. After 15 days, visually measure the growth of the ground, and calculate the growth inhibition rate according to the following formula:

 Valerian

 Growth inhibition rate (%) = 100* (control plant height - treated plant height) I control strain

 Tail grass dog Grading activity according to growth inhibition rate:

 ++ , > 80%; +, 80~ 50%; -, < 50%. Table 2: Results of potted weeding test Soil treatment (75 g ai/ha) Stem and leaf treatment (75 g ai/ha)

01 - -

02 - -

03 - - - - - - + + ++

 04 - - - - - - ++ + ++

 05 - - - - - - - - -

06 - - - - - - ++ + ++

 07 - - - - - - ++ ++ ++

 08 - - - - - - ++ ++ ++

09 1111 ++ ++ ++ ++ ++ ++

 ++ ++ ++

 ++ ++ ++

++ - ++

― - ― - ++ 一 ―

 One + - one ― - - ― -

++ ++ ++ - ― ― ++

++ ++ ++ ― a ― + + ++

 - ++ ++ + + ++ ++

 ― one - ― ― - ++ + ++

 ― - - + a ++ ++ ++

 + + ― one one ++ ++ ++

 + - + ++ ++ ++ Table 2 lists the N-isoindanedione-substituted phenylurea partial compounds represented by the general formula (I) of the present invention, and the pre-emergence soil treatment and post-emergence of potted plants The inhibitory effect of stem and leaf treatment. Some of the compounds of the present invention, such as compounds of 04, 06, 11, 13, 19, 21, 25, etc. in Table 2, at a dose of 75 g ai/ha, are treated with pre-emergence soil or post-emergence stems and leaves, for castor, Dicotyledonous weeds such as cockroaches and cockroaches showed good herbicidal activity and 80% control effect. They also had certain control effects on some monocotyledonous weeds such as crabgrass, valerian and foxtail.

Claims

Rights request  A N-isoindolinedion-substituted phenylurea compound characterized by having the structure represented by the formula (I):

among them  X is hydrogen, halogen, cyano, methyl, halogen means fluorine and chlorine;  Y is hydrogen, halogen, halogen means fluorine and chlorine; R ¹ is (d-C ₆ ) linear or branched alkyl, (C,-C _e )haloindenyl, monosubstituted or polysubstituted phenyl, monosubstituted or polysubstituted benzoyl; R ² is hydrogen, (dC straight or branched fluorenyl.  The N-isoindenyldione-substituted phenylurea compound according to claim 1, wherein the characteristic compound is: 1-[2-chloro-5-(1,3-dioxo-4, 5, 6 ,7-tetrahydro-1H-isoindole-2(3H)-yl)-4-fluorophenyl]-3-(3-trifluoromethylphenyl)urea  1-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindole-2(3H)-yl)-4-fluorophenyl]-3 - (4-trifluoromethoxyphenyl)urea  1-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindole-2(3H)-yl)-4-fluorophenyl]-3- (4-chlorophenyl) urea  1-[2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-111-iso-indole-2(311)-yl)-4-fluorophenyl]- 3-(2-chlorophenyl)urea  1-[2,4-Dichloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindole-2(3H)-yl)-4-fluorophenyl ]-3 - (3-trifluoromethylphenylurea)  1-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindole-2(3H)-yl)-4-fluorophenyl]-3 -0-toluene urea 1-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetraoxa-1 isoindole-2(3^)-yl)-4-fluorophenyl]-3 - (2, 6-difluoro-benzoyl)urea 1-[2,6-Difluorobenzoyl-3-(5-(1,3-dioxo-4, 5, 6, 7-tetrahydro-1 isoindole-2 (3-yl)) (2 ,4-difluorophenyl)urea  1-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1 1 fluorenyl-2(3-yl)-4-fluorophenyl]-3- ( 2-chloro-6-fluorobenzoyl)urea  1-[2-Chloro-5-(1,3-dioxy-4,5,6-7-tetrahydro-1isoindole-2(3-yl)phenyl]-3-(2,6- Difluoro -benzoyl)urea  1-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1 1isoindole-2(3^-yl)-4-fluorophenyl]-3- (2,6-dichloro-benzoyl)urea  1_[2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1^isoindole-2(3-yl)phenyl]-3-(2,6- Dichloro-benzoyl)urea  1_[2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-isoindole-2(3^-yl)phenyl]-3-(2, 4-di Chloro-benzoyl)urea  1-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1isoindole-2(3^-yl)-4-fluorophenyl]-3- ( 2, 4-dichloro-benzoyl)urea  1-benzoyl-3-(2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1-isoindole-2(3^-yl)-phenyl) Urea  1-Benzoyl-3-(2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1 1isoindole-2(3^-yl) 4-fluorobenzene Urea  3-(5-(1,3-Dioxy-4,5,6,7-tetrahydro-1/isoindole_2(3^)-yl)-2,4-difluorophenyl]-1 Dipropyl urea  3-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro- 1-isoindole-2(3-yl)-4-fluorophenyl]- 1, 1 -dipropylurea  3-(5-(1,3-Dioxy-4,5,6,7-tetrahydro-1^isoindole-2(3-yl)-2,4-difluorophenyl)-1,1 - Diisopropylurea  3-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-Iisoindole-2-yl)-4-fluorophenyl]- 1, 1 -di Isopropyl urea  3-[2-Chloro-5-(1,3-dioxo-4, 5, 6,7-tetrahydro-1 1isoindole-2(3^)-yl)-4-fluorophenyl]- 1 , 1-dibutylurea 3-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1^isoindole-2(3-yl)phenyl]-1, 1-dipropene Base urea 3-[2-Chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1 1isoindole-2(3^-yl)phenyl]-1, 1-dibutyl 5-urea. 3-[2-chloro-5-( 1, 3-dioxo-4, 5, 6, 7-tetrahydro-1 1isoindole-2(3^)-yl)-4-fluorophenyl ]-1, 1 -diethylurea  3-[2-Chloro-5-(1,3-dioxy-4,5,6,7-tetrahydro- 1 isoindole-2(3J3⁄4-yl)-4-fluorophenyl]- 1, 1 - Dimethylurea.  The method for producing an N-isoindanedion-substituted phenylurea compound according to claim 1 or 2, which is characterized in that: The compound of the formula (I) can be used as the intermediate 2-(5-amino-2,4-disubstituted phenyl)_4, 5, 6, 7-tetrahydro-2H-isoindole-1, 3-dione A For the starting materials, the urea compounds of different substituents are separately synthesized by two different routes - (1) When R ² is a hydrogen atom, the preparation method of the general formula (I) is: synthesizing the disubstituted urea by the isocyanate method, that is, Add a certain amount of mercapto isocyanate, substituted phenyl isocyanate or substituted benzoyl isocyanate B to the solvent, and add the corresponding amount of the intermediate 2-(5-amino-2,4-disubstituted phenyl)-4 under nitrogen protection. , 5, 6, 7-tetrahydro-2H-isoindole-1,3-dione A, after completion of the dropwise addition, the reaction is carried out at a certain temperature for 1 to 12 hours to obtain the target compound (I), preferably in the above reaction. The solvent is dichloroethane; the preferred molar ratio is A:B = 1: 1. 3 _{; the} preferred reaction temperature is the reflux temperature of the selected solvent; the preferred reaction time is 5 hours; the specific synthesis route uses the equation (1) indicates -

(2) When R ^{2 is} not a hydrogen atom, the general formula ( I ) is prepared by: one-pot synthesis of trisubstituted urea, that is, adding a certain amount of solid phosgene in a solvent, and then dropping it under nitrogen protection. The corresponding amount of the intermediate 2-(5-amino-2,4-dihalophenyl)-4,5,6,7-tetrahydro-2H-isoindole-1, 3-dione A and triethyl The amine is reacted at room temperature for half an hour, and the corresponding amount of the disubstituted amine C and triethylamine are added dropwise again, and the reaction is carried out at a certain temperature for 1 to 12 hours to obtain the target compound (I). The preferred solvent in the above reaction. Is a dichloroethane; a preferred molar ratio is A: C (R'R ² NH) _: solid phosgene: triethylamine = 1:1: 0. 35: 4; a preferred reaction temperature is about 25 ;; The preferred reaction time is half an hour; the specific synthetic route is expressed by equation (2):

The use of the N-isoindoledione substituted phenylurea compound according to claim 1 or 2, characterized in that, at a dose of 75 g ai/ha, for most broadleaf weeds and parts Monocotyledonous weeds have good herbicidal activity.