CN1313276A - Diacyl hydrazide compounds as insecticide, intermediate for preparing said compounds and their preparing process - Google Patents
Diacyl hydrazide compounds as insecticide, intermediate for preparing said compounds and their preparing process Download PDFInfo
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- CN1313276A CN1313276A CN 01108161 CN01108161A CN1313276A CN 1313276 A CN1313276 A CN 1313276A CN 01108161 CN01108161 CN 01108161 CN 01108161 A CN01108161 A CN 01108161A CN 1313276 A CN1313276 A CN 1313276A
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Abstract
The present invention relates to an insecticide, N,N'-bisubstituted-N,N'-diaocylhydrazide compounds, the intermediate for synthesizing it and the process for preparing said compounds.
Description
The present invention relates to a kind of as sterilant the diacyl hydrazide compounds and prepare the intermediate of this kind compound and their preparation method.
Two hydrazide kind compounds have many patent reports abroad as the sterilant of lepidopterous insects, for example:
JP NO.8231528 has reported that the compound with following array structure has insecticidal activity
A is hydrogen atom, methyl, ethyl in the formula
R
5Be hydrogen atom, cyano group
R
6Be tertiary butyl
R
1Be methyl, ethyl
R
2, R
3, R
4Be hydrogen atom, methyl, halogen atom
JP NO.8231529 has reported that following structure two hydrazide kind compounds have high insecticidal activity to Cnaphalocrocis medinali(rice leaf roller), prodenia litura.
In the formula, A is a hydrogen atom, methyl
R
1, R
3Be hydrogen atom, methyl
R
3, R
4, R
5Be hydrogen, halogen atom, methyl
R
6Be hydrogen atom, cyano group
R
7Be hydrogen atom, tertiary butyl JP NO.6172342 has reported the insecticidal effect with compound of following array structure
In the formula, A is O-CH
2-O, CH=CH-O, CH
2CH
2CH
2O, O-CH
2-CH
2-O
R
6Be (C1-C3) alkyl, halogen atom
n=0,1
R=N (R
7) R
8, R
7, R
8=alkyl, CO
2R
9, R
9=(C1-C3) alkyl
R
5=the tertiary butyl ,-CH (CH
3)-Bu-t
R
2, R
3, R
4=hydrogen atom, halogen atom, methyl EP.NO.984009 has made report to the insecticidal activity of following structural compounds
In the formula, R
1, R
2Be hydrogen atom, halogen atom, methyl A is
(R=Cl,CH
3,Et,CH
3O)
Wherein some compound has super-active to the nicotine noctuid, 1.5ppm kill ratio 100%, at present, two hydrazide kind compounds are as sterilant, its industrialized kind is few, and wherein Mimic (rice mite) can be representative, and its insecticidal activity is not very high, and about the benzheterocycle carboxylic acid derivative of hydrazides class, patent report is not a lot.
The purpose of this invention is to provide a kind of new diacyl hydrazide insecticides, make it have higher inhibitory or killing effect the more general snout moth's larva of insect pest on fruit, vegetables, the isometric crop of corn, moth class etc.
The structural formula of the compound that relates among the present invention is as follows:
(compound 1)
The preparation method of chemical compounds I and intermediate thereof (compound ii) is provided below:
1, the preparation of chemical compounds I:, be dissolved in toluene with N-benzo oxygen heterocyclic ring acyl group-N '-replacement hydrazine (compound ii); Under the ice bath,, dropwise stirring at normal temperature a few hours to the toluene solution that wherein splashes into equivalent virtue formyl chloride simultaneously and the acid binding agent of equivalent, handle N-benzo oxygen heterocyclic ring acyl group-N '-replacement-N '-sweet-smelling formacyl hydrazine (chemical compounds I).
The reaction equation of this step:
2, the preparation of compound ii: with benzo oxygen heterocyclic ring carboxylic acid (compound III) with SOCl
2It is not refining standby to make the acyl chlorides precipitation;
Under the ice bath with toluene (or the CH of above-mentioned acyl chlorides
2Cl
2, CHCl
3) solution and equivalent acid binding agent be added drop-wise in N '-substituting group hydrazine aqueous solution simultaneously, dropwises stirring at normal temperature a few hours, handle N-benzo oxygen heterocyclic ring acyl group-N '-replacement hydrazine (compound ii).
The reaction equation of this step is:
The compound that is provided among the present invention finds that through the living body biological screening active ingredients compound that has has higher insecticidal activity to lepidoptera pests such as small cabbage moth, oblique mosquito noctuid, Pyrausta nubilalis (Hubern)., mythimna separata, cotton bollworm larvaes.
Preparation embodiment of the present invention is provided below
Embodiment one: N-(2,3-dihydro-2,7-dimethyl-cumarone-6-acyl group)-N '-tertiary butyl-N '-(3, the 5-dimethylbenzoyl) hydrazines (compound N o.1)
According to the following steps:
(1) with 11.0g (0.0574mol) 2,3-dihydro-2,7-dimethyl benzofuran-6-carboxylic acid [it is synthetic referring to document Gazzetta.chim.Italiana.1981. (111) 383-7] is dissolved in 50mlCHCl
3In, normal temperature adds SOCl down
213.0ml, refluxed 2 hours, boil off CHCl
3And excessive SOCl
2, and add 50ml toluene, not refining standby.
21.0 gram hydrochloric acid tertiary butyl hydrazine, be dissolved in the 20ml water, under 5 ℃, splash into 20% solution that contains 6.9gNaOH, in this mixed liquid, drip the toluene solution of above-mentioned acyl chlorides under 5 ℃ simultaneously and contain 20% solution of 2.3 gram NaOH, the control rate of addition adds simultaneously, reinforced time 1-2 hour, remove ice-water bath, 15-20 ℃ was stirred 2 hours, layering, water layer extracts with toluene 2 * 50ml.Merge organic layer, and with the 10%NaOH solution washing, washing, dry pressure reducing and steaming toluene gets yellow solid, is N-(2,3-dihydro-2,7-dimethyl-cumarone-6-acyl group)-N '-tertiary butyl hydrazine 11.4g, yield 76%.
(2) with 11.4gN-(2; 3-dihydro-2;-dimethyl-cumarone-6-acyl group)-N '-tertiary butyl hydrazine is dissolved in 50ml toluene; contain 7.35g3 to wherein dripping simultaneously under 10 ℃; the 50ml toluene solution of 5-dimethyl benzoyl chloride and contain 20% aqueous solution of 1.74gNaOH, the control rate of addition; add simultaneously; remove ice bath, stirring at room 2 hours is filtered; filter flask washs with 10%NaOH solution 2 * 20ml; 2 * 20ml washing, 2 * 20ml toluene wash, drying; weigh white solid N-(2; 3-dihydro-2,7-dimethyl benzofuran-6-acyl group)-N '-tertiary butyl-N '-(3, the 5-dimethylbenzoyl) 15.3g product; mp137.5-139.3 ℃, yield 89%.1HNMR(300MHz?DCCl
3)δ(ppm)：1.41-1.42(3H)；1.57(9H)；1.89-1.91(3H)；2.24(6H)；2.69-2.80(1H)；3.19-3.30(1H)；4.85-4.89(1H)；6.10-6.15(1H)；6.81-6.83(1H)；6.92-7.06(1H)；7.18(2H)；7.93(1H)。
Embodiment two: N-(2-methyl cumarone-5-acyl group)-N '-tertiary butyl-N '-(3, the 5-dimethylbenzoyl) hydrazines (compound N o.2)
According to the following steps:
(1) 4.0g2-methyl cumarone-5-carboxylic acid [it is synthetic referring to document J.C.S.Perkin.I.1976.1-5] is dissolved in 30mlCHCl
3In, normal temperature adds SOCl down
23.2ml, refluxed 2 hours, boil off CHCl
3And excessive SOCl
2, and add 20ml toluene, not refining standby.
11.3g hydrochloric acid tertiary butyl hydrazine, be dissolved in the 20ml water, under 5 ℃, splash into 20% solution that contains 3.6gNaOH, in this mixed liquid, drip the toluene solution of above-mentioned acyl chlorides under 5 ℃ simultaneously and contain 20% solution of 0.ggNaOH, the control rate of addition adds simultaneously, reinforced time 1-2 hour, remove ice-water bath, 15-20 ℃ was stirred 2 hours, layering, water layer extracts with toluene 2 * 50ml.Merge organic layer, and with the 10%NaOH solution washing, washing, dry pressure reducing and steaming toluene gets yellow solid, is N-(2-methyl cumarone-5-acyl group)-N '-tertiary butyl hydrazine 4.2g, yield 75%.
(2) 4.2gN-(2-methyl cumarone-5-acyl group)-N '-tertiary butyl hydrazine is dissolved in 30ml toluene; contain 2.9g3 to wherein dripping simultaneously under 5 ℃; the 20ml toluene solution of 5-dimethyl benzoyl chloride; with 20% aqueous solution that contains 0.68gNaOH, the control rate of addition adds simultaneously; remove ice bath; stirring at room 2 hours is filtered, and filter is washed with 10%NaOH solution 2 * 10ml; 2 * 20ml washing; 2 * 20ml toluene wash, drying, weigh white solid N-(2-methyl cumarone-5-acyl group)-N '-tertiary butyl-N '-(3; the 5-dimethylbenzoyl) hydrazine; 5.48g product, mp212.0-214.0 ℃, yield 85%.1HNMR(300MHz?DCCl
3)δ(ppm)：1.50-1.60(9H)；2.17(6H)；2.35(1H)；2.41(3H)6.20(1H)；6.85(1H)；7.06-7.09(2H)；7.24-7.26(1H)；7.38(1H)；8.38(1H)。
Table 1, by the compound and the physical parameter thereof of above-mentioned preparation example one, two methods preparation:
Test the one, two, three, the 4th below, the controlled trial that the activity test of pesticide compound of the present invention and present result of use are carried out with insecticides rice mite preferably.
The indoor virulence test of test one, small cabbage moth.
Testing method: soak the leaf feeding method.
(1) sample is prepared: sample concentration 50ppm, be about to 25mg sample+20g solvent (DMF)+emulsified water (emulsifier tween-80 accounts for 0.005%), and establish blank and the contrast of rice mite concentration simultaneously, its compound method and rice mite are together.
(2) punch on luxuriant dish blade with 2.5cm diameter punch tool, take out the leaf dish,, be put on the thieving paper after soaking and dry blade immersion liquid 10s in the solution that has prepared.
(3) the leaf dish of handling is put into the culture dish of the 6cm diameter of having got ready, and 3 in every ware is chosen into trying 10 of worms 3 ages again, builds the ware lid.
(4) examination worm contact medicament is checked dead borer population after 5 days, and test repeats 3 times, and the result gets its mean value calculation mortality ratio such as table 2.The virulence test of 1 pair of small cabbage moth of table 2 compound
| Test compound | Concentration PPM | Mortality ratio % |
| ????No.1 | ?????50 | ?????96.7 |
| ?????10 | ?????73.3 | |
| The rice mite | ?????50 | ?????96.7 |
| ?????10 | ?????46.7 |
The indoor test of test two, bollworm.
Testing method: soak the leaf feeding method.
(1) sample preparation: sample concentration and rice mite concentration are set as table, establish the blank contrast simultaneously, and (1) roughly the same in its compound method and the test one.
(2) punch on luxuriant dish blade with 2.5 cm diameter punch tool, take out the leaf dish, blade was soaked in the solution that has prepared 10 seconds, be put on the thieving paper after soaking and dry.
(3) the leaf dish of handling is put into the culture dish of 6 cm diameters of having got ready, and 3 in every ware is chosen into 5 of 3 instar larvaes again, builds the ware lid.
(4) examination worm contact medicament is checked dead borer population after 4 days, and test repeats 3 times, and the result gets its mean value calculation mortality ratio such as table 3.
Table 3 leaf dipping method is measured compound 1 and the virulence of rice mite to cotton bollworm larvae
| Test compound | Concentration ppm | Corrected mortality % |
| ????No.1 | ????1000 | ???????84.6 |
| ????500 | ???????70.1 | |
| ????200 | ???????68.5 | |
| The rice mite | ????1000 | ???????93.6 |
| ????500 | ???????92.3 | |
| ????200 | ???????76.3 |
The indoor test of test three, prodenia litura:
Testing method: soak the leaf feeding method.
(1) sample preparation: sample concentration and rice mite concentration are set as table, establish the blank contrast simultaneously, and (1) roughly the same in its compound method and the test one.
(2) the fresh corn blade is cut into about 2.5 centimetres wide, the maize leaf of 5 cm long, each blade soaked medicine about 10 seconds.
(3) after blade dried, each blade of handling was put into the culture dish of 6 cm diameters of having got ready, chose into 10 of examination worms again, built the ware lid.
(4) examination worm contact medicament is checked dead borer population after 5 days, and test repeats 3 times, and the result gets its mean value calculation mortality ratio such as table 4.
Table 4 leaf dipping method comparative compound 1 and rice mite are compared the virulence of prodenia litura 4 instar larvaes
| Test compound | Concentration ppm | Mortality ratio % |
| ????No.1 | ????200 | ?????100 |
| The rice mite | ????200 | ?????100 |
The indoor test of test four, Pyrausta nubilalis (Hubern)..
Purpose: the insecticidal activity of checking and 1 pair of Pyrausta nubilalis (Hubern). of mensuration compound.
Testing method: dip method.
(1) sample preparation: sample concentration and rice mite concentration are set as table, establish the blank contrast simultaneously, and (1) roughly the same in its compound method and the test one.
(2) 10 examination worms of the same size of picking have 10 centimetres of high glass of gauze to refer in the line pipe in one.
(3) end that tries worm will be housed and immerse soup 10 seconds, and take out the back and on thieving paper, be stained with the branch that anhydrates.
(4) will soak medicine examination worm and choose in 6 centimetres of culture dish, add artificial diet, build the ware lid.
(5) dip method is measured the virulence of 1 pair of corn borer larvae of compound, and the result is as shown in table 6.
(6) examination worm contact medicament is checked dead borer population after 7 days, and test repeats 3 times, and the result gets its mean value calculation mortality ratio as table.
Dip method is measured the virulence of 1 pair of Pyrausta nubilalis (Hubern). 5 instar larvae of compound, and the result is as shown in table 5.
Table 5 dip method is measured the virulence of 1 pair of Pyrausta nubilalis (Hubern). 5 instar larvae of compound
| Test compound | Concentration (ppm) | Corrected mortality % |
| ????No.1 | ?????200 | ??????95.70 |
| The rice mite | ?????200 | ??????65.20 |
Test five, the test of mythimna separata indoor virulence.
Purpose: checking and measure compound 1, rice mite insecticidal activity to armyworm larvae.
Testing method: soak the leaf feeding method.
The mythimna separata leaf dipping method
(1) sample preparation: sample concentration and the contrast of medicament rice mite, establish blank simultaneously, (1) roughly the same in its compound method and the test one.
(2) it is wide the fresh corn leaf to be cut into about 2.5cm, the maize leaf that 5cm is long, and each blade soaks the about 10s of medicine.
(3) after blade dried, each culture dish was chosen into the examination worm about 10, puts into and soaks 5 in medicine blade, built the ware lid.
(4) check: examination worm contact medicament is checked dead borer population after 4 days, test repeats 3 times, and the result gets its mean value calculation mortality ratio such as table 6.
Table 6 soaks the virulence that the leaf feeding method is measured 1 pair of mythimna separata 3 instar larvae of compound
| Test compound | Concentration ppm | Corrected mortality % |
| ????No.?1 | ????12.50 | ?????100 |
| ????6.25 | ??????90 | |
| ????3.125 | ?????88.60 | |
| The rice mite | ????12.50 | ?????100 |
| ????6.25 | ??????80 | |
| ????3.125 | ????76.70 |
Claims (4)
1, a kind of diacyl hydrazide compounds (chemical compounds I) as sterilant, its structural formula is as follows:
In the formula:
R
1Be 1-3 identical or different hydrogen atom, halogen atom, (C1-C3) alkyl, (C1-C3) alkoxyl group or nitro;
R
2Be aryl, substituted aryl;
R
3Be hydrogen atom, cyano group;
R
4Be hydrogen atom, tertiary butyl;
A is O-CH (CH
3)-CH
2, O-CH (CH
2CH
3)-CH
2, O-C (CH
3)
2-CH
2
O-CH (CH
3)-CH (CH
3), O-C (CH
3)=CH, O-CH
2-O-CH
2Deng.
2, a kind of synthetic intermediate (compound ii) that is used for the chemical compounds I of claim 1, its structural formula is as follows:
In the formula:
R
1Be 1-3 identical or different hydrogen atom, halogen atom, (C1-C3) alkyl, (C1-C3) alkoxyl group or nitro;
R
2Be aryl, substituted aryl;
R
3Be hydrogen atom, cyano group;
R
4Be hydrogen atom, tertiary butyl;
A is O-CH (CH
3)-CH
2, O-CH (CH
2CH
3)-CH
2, O-C (CH
3)
2-CH
2
O-CH (CH
3)-CH (CH
3), O-C (CH
3)=CH, O-CH
2-O-CH
2Deng.
3, a kind of synthetic intermediate (compound III) that is used for the compound ii of claim 2, its structural formula is as follows:
In the formula:
R
1Be 1-3 identical or different hydrogen atom, halogen atom, (C1-C3) alkyl, (C1-C3) alkoxyl group or nitro;
A is O-CH (CH
3)-CH
2, O-CH (CH
2CH
3)-CH
2, O-C (CH
3)
2-CH
2
O-CH (CH
3)-CH (CH
3), O-C (CH
3)=CH, O-CH
2-O-CH
2Deng.
4, a kind of preparation method who is used for the chemical compounds I of claim 1, this structural formula of compound is as follows:
R in the formula
1Be 1-3 identical or different hydrogen atom, halogen atom, (C1-C3) alkyl, (C1-C3) alkoxyl group or nitro; R
2Be aryl, substituted aryl; R
3Be hydrogen atom, cyano group; R
4Be hydrogen atom, tertiary butyl; A is O-CH (CH
3)-CH
2, O-CH (CH
2CH
3)-CH
2, O-C (CH
3)
2-CH
2, O-CH (CH
3)-CH (CH
3), O-C (CH
3)=CH, O-CH
2-O-CH
2Deng; Follow these steps to carry out:
A, benzo oxygen heterocyclic ring carboxylic acid (compound III) is made acyl chlorides by general method, acyl chlorides and the hydrazine aqueous solution under the condition that acid binding agent exists, are made N-benzo oxygen heterocyclic ring acyl group-N '-replacement hydrazine (compound ii);
B, with N-benzo oxygen heterocyclic ring acyl group-N '-replacement hydrazine (compound ii), under the condition that acid binding agent exists, carry out condensation with substituted benzoyl chloride, obtain N-benzo oxygen heterocyclic ring acyl group-N '-replacement-N '-substituted benzoyl hydrazine (chemical compounds I).
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|---|---|---|---|
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|---|---|---|---|
| CNB011081619A CN1161325C (en) | 2001-03-26 | 2001-03-26 | Diacyl hydrazide compounds as insecticide, intermediate for preparing said compounds and their preparing process |
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|---|---|
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| CN1161325C CN1161325C (en) | 2004-08-11 |
Family
ID=4657046
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|---|---|---|---|
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| US8828907B2 (en) | 2009-03-25 | 2014-09-09 | Bayer Cropscience Ag | Active ingredient combinations having insecticidal and acaricidal properties |
| CN102246762A (en) * | 2011-05-23 | 2011-11-23 | 陕西韦尔奇作物保护有限公司 | Insecticidal composition containing furan tebufenozide and amide compounds |
| CN104145971A (en) * | 2011-05-26 | 2014-11-19 | 陕西韦尔奇作物保护有限公司 | Insecticidal composition containing fufenozide and carbamates |
| CN103651474A (en) * | 2011-05-28 | 2014-03-26 | 陕西韦尔奇作物保护有限公司 | Insecticidal composition containing furan tebufenozide |
| WO2013156331A1 (en) | 2012-04-16 | 2013-10-24 | Basf Se | Synergistic compositions comprising pyraclostrobin and an insecticidal compound |
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| CN1161325C (en) | 2004-08-11 |
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