CN100465160C - N-isoindole dione substituted phenyl amide compound with herbicidal activity - Google Patents
N-isoindole dione substituted phenyl amide compound with herbicidal activity Download PDFInfo
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- CN100465160C CN100465160C CNB2005100324266A CN200510032426A CN100465160C CN 100465160 C CN100465160 C CN 100465160C CN B2005100324266 A CNB2005100324266 A CN B2005100324266A CN 200510032426 A CN200510032426 A CN 200510032426A CN 100465160 C CN100465160 C CN 100465160C
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- China
- Prior art keywords
- chloro
- isoindole
- compound
- substituted phenyl
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
Abstract
The invention discloses a substituted phenylamide compound of N-isoindole diketone with weed removal activity in the general formula (I), wherein Het is as (II), (III) on the right; X is hydrogen, halogen (F and Cl); Y is hydrogen and halogen (F, Cl and Br); R1 is (C1-C6) halogenated alkyl, substituted phenyl; Rm is monosubstituted or polysubstituted, the same or different hydrogen, alkyl, nitro, amino, halogen; the substitute number of m can be 1, 2, 3, 4. The invention possesses excellent weed removal activity for dicotyledon weed such as American jute, Chenopodiaceae and amaranth when 75g ai/ha compound is sprayed on the soil before pre-emergence cultivation or on the haulm after cultivation, which can avoid certain monocotyledon weed with prevention rate not less than 80%.
Description
Technical field: the present invention relates to N-isoindole dione substituted phenyl amide compound that has weeding activity and preparation method thereof.
Background technology:
Relevant amides and composition weedicide thereof have report more, but because usage quantity is big or after use for some time, weeds produce resistance to it, therefore need to change or improve the structure of compound, in the hope of inventing new herbicidal compound.Patent EP0786453 has reported that the compound of following structure type has extraordinary weeding activity, but bibliographical information is seen at the relevant N-isoindole dione substituted phenyl amide compound end that the present invention relates to.
Summary of the invention: the invention provides a kind of N-isoindole dione substituted phenyl amide compound with weeding activity and preparation method thereof, this compounds is represented with general structure (I):
Wherein
Het is
X is a hydrogen, the chlorine in the halogen, fluorine;
Y is a hydrogen, halogen (fluorine, chlorine, bromine);
R
1Be (C
1-C
6) haloalkyl, substituted-phenyl;
R
mBe a replacement or polysubstituted, an identical or different hydrogen, alkyl, nitro, amino, halogen; M represents substituent number optional 1,2,3,4.
Het is in general formula of the present invention (I)
The time, target compound C
1The preparation method as follows:
In solvent, add intermediate (A
1) and haloalkyl acyl chlorides (B), obtained target compound (C in reacting by heating 1-12 hour
1), molar ratio is A: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:
Het is in general formula of the present invention (I)
The time, target compound C
2The preparation method 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 (C in 1-12 hour
2), molar ratio is A: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:
Intermediate A
1And A
2But the method that reference EP0786453 describes is synthetic.
The preparation of active compound and using according to the present invention by following embodiment illustration, but the technology contents of these embodiment does not limit the scope of the invention.
Compound shown in the synthetic part general formula of the present invention (I) sees Table 1.
Table 1: the chemical structure and the fusing point of the compound shown in the part general formula of the present invention (I)
The present invention shows weeding activity preferably, preventive effect 〉=80% to part monocotyledon weeds such as broadleaf weeds such as piemarker, lamb's-quarters, recessed amaranth and lady's-grass, barnyard grass grass, Herba Setariae Viridis.
Embodiment:
Embodiment 1:3-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 (Compound C in the table 1
1-02) preparation.
In the 100mL round-bottomed flask, add 0.96g (3.3mmol) intermediate 2-(5-amino-4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydrochysene-2H-isoindole-1,3-diketone A
1, 30mL benzene and 0.37g (3.6mmol) 3-chloro-2,2-dimethyl-propionyl chloride B, magnetic agitation is heated to 100 ℃, stopped reaction behind the back flow reaction 4h.Add 150mL water in the reaction solution, tell organic layer, organic layer is water, saturated aqueous sodium carbonate and saturated brine washing successively, and through anhydrous magnesium sulfate drying, the decompression precipitation obtains the 1.22g white crystal, be 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 (Compound C
1-02), content 83%, yield 82%, m.p.125.6-126.6 ℃.
1H?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
2Cl)，7.26-7.31(t，1H，Ar-H，J＝6.9Hz)，8.03(s，1H，H-N)，8.43(d，1H，Ar-H，J＝7.5Hz)。
Embodiment 2:4-chloro-N-(2-chloro-5-(1,3-dioxy isoindole-2-yl)-4-fluorophenyl) benzamide (Compound C in the table 1
2-02) preparation.
In the 100mL round-bottomed flask, add 1.16g (4.0mmol) intermediate 2-(5-amino-4-chloro-2-fluorophenyl)-2H-isoindole-1, the 3-diketone A
2, 30mL ethylene dichloride and 0.45g (4.4mmol) triethylamine, magnetic agitation, the frozen water cooling slowly drips 0.7g (4.0mmol) parachlorobenzoyl chloride B down, dropwises and at room temperature reacts 2h.Add 100mL water in the reaction solution, tell organic layer, organic layer is water and saturated brine washing successively, anhydrous sodium sulfate drying is through decompression precipitation, silica gel column chromatography, obtain 1.54g white crystal 4-chloro-N-(2-chloro-5-(1,3-dioxy isoindole-2-yl)-4-fluorophenyl) benzamide (Compound C
2-02).Content 95%, yield 85%, m.p.173.0～175.0 ℃.
1H?NMR(CDCl
3，ppm)δ：1.45(s，3H，CH
3)，3.69(s，2H，CH
2Cl)，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＝7.5Hz)。
Embodiment 3:N-(5-(5-amino-1,3-dioxy isoindole-2-yl) 2-chloro-4-fluorophenyl)-3-chloro-, 2-dimethyl propylene acid amides (Compound C in the table 1
2-06) preparation.
In the 100mL round-bottomed flask, add 2.68g (8.0mmol) intermediate 2-(5-amino-4-chloro-2-fluorophenyl)-5-nitro isoindole-1, the 3-diketone A
2, 50mL ethylene dichloride and 0.89g (8.8mmol) triethylamine, magnetic agitation, the frozen water cooling slowly drips 1.30g (8.0mmol) parachlorobenzoyl chloride B down, dropwises and at room temperature reacts 2h.Add 100mL water in the reaction solution, tell organic layer, organic layer is water and saturated brine washing successively, anhydrous sodium sulfate drying, get white solid (N-(5-(5-nitro-1 through the decompression precipitation, 3-dioxy isoindole-2-yl) 2-chloro-4-fluorophenyl)-and the 3-chloro-, 2-dimethyl propylene acid amides) 3.0g, content 86%.
In the 100mL round-bottomed flask, add above-mentioned intermediate 3.0g (5.7mmol) N-(5-(5-nitro-1,3-dioxy isoindole-2-yl) 2-chloro-4-fluorophenyl)-the 3-chloro-, 2-dimethyl propylene acid amides, the 30mL glacial acetic acid, magnetic agitation, heat temperature raising to 60 ℃ adds iron powder 1.6g (28.5mmol) in batches, the reinforced insulation reaction 30min that finishes.Cooling, in the reaction solution impouring 100mL frozen water, add the 50mL ethyl acetate, extraction, organic layer is water and saturated brine washing successively, and anhydrous sodium sulfate drying is through the decompression precipitation, silica gel column chromatography gets 1.9g faint yellow solid 4-chloro-N-(2-chloro-5-(1,3-dioxy isoindole-2-yl)-4-fluorophenyl) benzamide (Compound C
2-06) content 93%, yield 74%, m.p.145.6-147.2 ℃.
1H?NMR(CDCl
3，ppm)δ：1.43(s，6H，2CH
3)，3.69(s，2H，CH
2Cl)，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＝7.5Hz)。
Embodiment 4:3-chloro-N-(2-chloro-5-(5,6-two chloro-1,3-dioxy isoindole-2-yl)-4-fluorophenyl) 2,2-dimethyl propylene acid amides (Compound C in the table 1
2-07) preparation.
In the 100mL round-bottomed flask, add 1.80g (5.0mmol) intermediate 2-(5-amino-4-chloro-2-fluorophenyl) 5,6-dichloro isoindole-1,3-diketone A
2, 35mL ethylene dichloride and 0.55g (5.5mmol) triethylamine, magnetic agitation, the frozen water cooling slowly drips 0.77g (5.0mmol) parachlorobenzoyl chloride B down, dropwises and at room temperature reacts 2h.Add 100mL water in the reaction solution, tell organic layer, organic layer is water and saturated brine washing successively, anhydrous sodium sulfate drying is through decompression precipitation, silica gel column chromatography, obtain 2.0g white crystal 3-chloro-N-(2-chloro-5-(5,6-two chloro-1,3-dioxy isoindole-2-yl)-the 4-fluorophenyl) 2,2-dimethyl propylene acid amides (Compound C
2-07).Content 92%, yield 81%.
1H?NMR(CDCl
3，ppm)δ?1.44(s，6H，2CH
3)，3.69(s，2H，CH
2Cl)，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＝7.5Hz)。
Application Example 1: potted plant weeding test
Accurately take by weighing sample, after the The suitable solvent dissolving, add small amounts of emulsifiers, adding distil water is settled to 10ml and adopts suitable spraying machine sprinkling again, and reduced unit's area dose is 75gai/ha.At sectional area 64cm
2The plastic tub alms bowl in quantitative dress soil, flatten, water permeable, choose full seed, dicotyledonous select for use lamb's-quarters (Chenopodium album), piemarker (Abutilon theophrasti), recessed amaranth (Amaranthusascedense) of the same size, unifacial leaf is selected lady's-grass (Digitaria sanguinalis), barnyard grass grass (Echinochloacrus-galli), Herba Setariae Viridis (Setaria viridis) for use, divide single, double cotyledon plant to divide the pot culture kind, respectively account for 1/3 of alms bowl area, cover thick fine earth of 1cm and trickle, place hot-house culture.Treat that unifacial leaf examination material grows to 1 heart stage of 1 leaf, dicotyledonous examination material grows to 2 leaf periods, carry out seedling with soup after the cauline leaf spraying handle, soil treatment before the seedling is carried out in the sowing of examination material next day.Put back to the greenhouse subsequently.Range estimation overground part growing state after 15 days, calculate growth inhibition ratio according to following formula:
Growth inhibition ratio (%)=100* (contrast plant height-processing plant height)/contrast plant height
Carry out the weeding activity classification according to growth inhibition ratio:
++，>80％；+，80～50％；-，<50％。
Table 2: potted plant weeding test-results
NT: not test.
Table 2 has been listed part of compounds of the present invention, as C
1-02, C
1-03, C
1-04, C
1-06, C
1-07, C
2-04, the inhibition effect that cauline leaf behind soil treatment and the bud before the potted plant examination material plant bud is handled such as.As shown in table 2, N-isoindole dione substituted phenyl amide compound shown in the general formula of the present invention (I) is when cauline leaf is handled behind soil treatment or the seedling before the seedling under the dosage of 75g ai/ha, part monocotyledon weeds such as broadleaf weeds such as piemarker, lamb's-quarters, recessed amaranth and lady's-grass, barnyard grass grass, Herba Setariae Viridis are shown weeding activity preferably, preventive effect 〉=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.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100324266A CN100465160C (en) | 2005-11-24 | 2005-11-24 | N-isoindole dione substituted phenyl amide compound with herbicidal activity |
| PCT/CN2006/000689 WO2007059662A1 (en) | 2005-11-24 | 2006-04-17 | N-isoindol-dione-substituted phenylamide compounds having herbicidal activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100324266A CN100465160C (en) | 2005-11-24 | 2005-11-24 | N-isoindole dione substituted phenyl amide compound with herbicidal activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1970540A CN1970540A (en) | 2007-05-30 |
| CN100465160C true CN100465160C (en) | 2009-03-04 |
Family
ID=38066900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100324266A Expired - Fee Related CN100465160C (en) | 2005-11-24 | 2005-11-24 | N-isoindole dione substituted phenyl amide compound with herbicidal activity |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100465160C (en) |
| WO (1) | WO2007059662A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953420A (en) * | 1972-01-29 | 1976-04-27 | Badische Anilin- & Soda-Fabrik Aktiengesellschaft | Azo pigments derived from 2-hydroxy-3-carboxynaphthalene containing a substituted or unsubstituted phthalimide |
| EP0077938A2 (en) * | 1981-10-23 | 1983-05-04 | Mitsubishi Kasei Corporation | N-(3-substituted aminophenyl) tetrahydrophthalimides and herbicidal composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439229A (en) * | 1981-06-29 | 1984-03-27 | Rohm And Haas Company | Substituted phthalimides herbicides |
| AU557324B2 (en) * | 1981-12-25 | 1986-12-18 | Sumitomo Chemical Company, Limited | Tetrahydro phthalimide compounds |
| CA2195831A1 (en) * | 1996-01-29 | 1997-07-30 | Bunji Natsume | Phthalimide compound and herbicide containing the same |
-
2005
- 2005-11-24 CN CNB2005100324266A patent/CN100465160C/en not_active Expired - Fee Related
-
2006
- 2006-04-17 WO PCT/CN2006/000689 patent/WO2007059662A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953420A (en) * | 1972-01-29 | 1976-04-27 | Badische Anilin- & Soda-Fabrik Aktiengesellschaft | Azo pigments derived from 2-hydroxy-3-carboxynaphthalene containing a substituted or unsubstituted phthalimide |
| EP0077938A2 (en) * | 1981-10-23 | 1983-05-04 | Mitsubishi Kasei Corporation | N-(3-substituted aminophenyl) tetrahydrophthalimides and herbicidal composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1970540A (en) | 2007-05-30 |
| WO2007059662A1 (en) | 2007-05-31 |
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