CN103694179B - A kind of bishydrazide compound and preparation method thereof - Google Patents

A kind of bishydrazide compound and preparation method thereof Download PDF

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CN103694179B
CN103694179B CN201310647650.0A CN201310647650A CN103694179B CN 103694179 B CN103694179 B CN 103694179B CN 201310647650 A CN201310647650 A CN 201310647650A CN 103694179 B CN103694179 B CN 103694179B
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chloro
bis
bishydrazide
preparation
hydrazine
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CN103694179A (en
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李洪森
张帅
王旭东
朱延亮
牛吉莹
宋文丰
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Shanghai University of Engineering Science
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/22—Nitrogen and oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/18—Sulfur atoms

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Abstract

The present invention relates to a kind of bishydrazide compound and preparation method thereof, this compound chemical structure formula is as follows: wherein, R 1for the alkoxyl group of the alkyl of 1-4 carbon atom, a 1-4 carbon atom, halogen or hydrogen; R 2for methylamino, dimethylin, isopropylamine base, Propylamino, butylamine base, morpholinyl, piperidyl or rosickyite base; R 3for chlorine or rosickyite base.Compared with prior art, present invention process flow process is simple, applied widely, being suitable for use in sanitary insect pest if fly, mosquito, flea etc. and Agricultural pests are as in the controls such as rice aqueous phase first, beet armyworm, small cabbage moth, mythimna separata, is the sterilant that a class has application prospect.

Description

A kind of bishydrazide compound and preparation method thereof
Technical field
The present invention relates to a kind of inhibitor and preparation method thereof, especially relate to a kind of bishydrazide compound and preparation method thereof.
Background technology
Bishydrazide compounds is widely used in the control of crop pests, obtained many commercial pesticide species, but in life-time service process, pest resistance to insecticide constantly strengthens.It is made to be restricted in application agriculturally.
Chinese patent CN101190905A discloses a kind of N-(2,3-dihydro-2, the 4-dimethyl benzofuran-5-acyl group) preparation of-N-tertiary butyl-N-(substituted benzoyl) hydrazine insecticides and the application of their Control pests.The compound of this invention is poor for the lethality rate of mythimna separata and wriggler.
Summary of the invention
Object of the present invention is exactly provide a kind of technical process simple to overcome defect that above-mentioned prior art exists, bishydrazide compound applied widely and preparation method thereof.
Object of the present invention can be achieved through the following technical solutions:
A kind of bishydrazide compound, this compound chemical structure formula is as follows:
Wherein, R 1for the alkoxyl group of the alkyl of 1-4 carbon atom, a 1-4 carbon atom, halogen or hydrogen; R 2for methylamino, dimethylin, isopropylamine base, Propylamino, butylamine base, morpholinyl, piperidyl or rosickyite base; R 3for chlorine or rosickyite base.
A preparation method for above-mentioned bishydrazide compound, comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone:
By mucochloric acid and hydrazonium sulfate, 4,5-bis-chloro-3 (2H) pyridazinone is synthesized in condensation under the katalysis of sodium-acetate;
(2) preparation of benzoyl hydrazine or substituted benzoyl hydrazides:
Ethyl benzoate or substituted ethyl benzoate and hydrazine hydrate are synthesized benzoyl hydrazine or substituted benzoyl hydrazides through reacting by heating in the first solvent;
(3) preparation of bishydrazide:
Benzoyl hydrazine obtained for step (2) or substituted benzoyl hydrazides and alpha-halogen acetyl halide are synthesized bishydrazide under the effect of the second solvent and basic catalyst;
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl }-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } synthesis of-substituted benzoyl hydrazides:
The bishydrazide and 4 obtained by step (3), 5-bis-chloro-3 (2H) pyridazinone is in the 3rd solvent, condensation synthesis N-{2-[4 under basic catalyst effect, chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl }-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl }-substituted benzoyl hydrazides;
(5) preparation of target compound:
The N-{2-[4 obtained by step (4); chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl-substituted benzoyl hydrazides in the 4th solvent with aminated compounds or mercaptan compound under the effect at basic catalyst through heating synthesising target compound.
In step (1), the mol ratio of mucochloric acid, hydrazonium sulfate and sodium-acetate is 1: (1-2): (1-2);
In step (1), the temperature of reaction of condensation synthesis 4,5-bis-chloro-3 (2H) pyridazinone is 50-100 DEG C, and the reaction times is 1-3 hour.
In step (2), the mol ratio of ethyl benzoate or substituted ethyl benzoate and hydrazine hydrate is 1: (1-2);
The first solvent described in step (2) is methyl alcohol or ethanol;
In step (2), the temperature of heating is 50-115 DEG C.
Substituted ethyl benzoate described in step (2) comprises ethyl p-methyl benzoate, Ethoforme or ethyl anisate; Corresponding described substituted benzoyl hydrazides comprises toluyl hydrazine, p-chloro benzoyl hydrazine or to methoxybenzoyl hydrazine.
In step (3), the mol ratio of benzoyl hydrazine or substituted benzoyl hydrazides and alpha-halogen acetyl halide is 1: (1-1.5);
Alpha-halogen acetyl halide described in step (3) is alpha-brominated acetyl bromide or alpha-chloro Acetyl Chloride 98Min.;
The second solvent described in step (3) is methyl alcohol, ethanol, tetrahydrofuran (THF) or trichloromethane;
In step (3), the temperature of synthesis bishydrazide is 50-100 DEG C.
In step (4), the mol ratio of bishydrazide and 4,5-bis-chloro-3 (2H) pyridazinone is (1-1.5): 1;
The 3rd solvent described in step (4) is methyl alcohol, ethanol, tetrahydrofuran (THF) or DMF.
N-{2-[4 in step (5), chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl }-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } mol ratio of-substituted benzoyl hydrazides and aminated compounds or mercaptan compound is (1-1.5): 1;
The add-on of step (5) neutral and alkali catalyzer and N-{2-[4; chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl }-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } mass ratio of-substituted benzoyl hydrazides is (1.5-2): 1.
The 4th solvent described in step (5) comprises chloroform, tetrahydrofuran (THF), DMF, ethylene dichloride, tetracol phenixin, 1,2-ethylene dichloride or ethanol;
Aminated compounds described in step (5) comprises methylamine, dimethylamine, Isopropylamine, propylamine, butylamine, morpholine or piperidines; Described mercaptan compound is propylmercaptan or isopropyl mercaptan;
In step (5), the temperature of heating synthesising target compound is 30-100 DEG C, and the time is 4-15 hour.
Step (3), step (4) and the basic catalyst described in step (5) comprise salt of wormwood, sodium carbonate, saleratus, sodium bicarbonate, potassium hydroxide, sodium hydroxide or triethylamine.
Compared with prior art, present invention process flow process is simple, applied widely, be suitable for use in sanitary insect pest if fly, mosquito, flea etc. and Agricultural pests are as in the controls such as rice aqueous phase first, beet armyworm, mythimna separata, can suppress the performance of insect particularly growth of mosqito larva, be the sterilant that a class has application prospect.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of bishydrazide compounds, this compound molecule formula is as follows:
Wherein, R 1for methyl, R 2for morpholinyl, R 3for chlorine, the synthetic method of this bishydrazide compounds comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone
In 250mL there-necked flask, add the rare aldehydic acid of 50g dichloro-fourth and a small amount of water, stir, make the aqueous solution, then add 39g hydrazonium sulfate, 38.2g sodium-acetate, is heated to 80-100 DEG C, reacts 2 hours.Cool after complete reaction, reaction solution is poured in cold water, occurs a large amount of pale yellow precipitate, suction filtration, dry.Products therefrom dehydrated alcohol carries out recrystallization, productive rate 89.5%.
(2) synthesis of 4-methyl-benzoyl hydrazine
In 250ml there-necked flask, add 4-methyl-benzoic acid ethyl ester (i.e. ethyl p-methyl benzoate) 70ml (0.485mol) and 51.5ml (0.485mol) hydrazine hydrate, add the mixing of 70ml dehydrated alcohol again, with mechanic whirl-nett reaction, be heated to 115 DEG C, condensing reflux reacts 8 hours.Solution is water white transparency.Cooling, reaction solution is poured in 200ml cold water, occurs a large amount of white solid, suction filtration, and dry, recrystallizing methanol obtains product (to toluyl hydrazine), and productive rate is 82.4%.
(3) preparation of bishydrazide
In the 250ml there-necked flask that dry and absorption unit are housed, add 0.147mol to toluyl hydrazine, 60ml trichloromethane, 0.162mol salt of wormwood stirred, and slowly drips 12ml (0.147mol) chloroacetyl chloride, 80 DEG C of reactions 8 hours.Poured into by reaction solution in 200ml frozen water, and constantly stir, after leaving standstill, filter out precipitation, dry, recrystallization, productive rate is 70.34%.
The physical properties of the bishydrazide that the present embodiment obtains is as follows:
Fusing point: 168.6-170.5 DEG C.
1HNMR(CDCl 3)：2.37(s，3H)，4.17(s，2H)，7.29(d，2H，J＝8.0Hz)，7.77(d，2H，J＝8.0Hz)，10.38(s，2H)。
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } preparation of-4-toluyl hydrazine
In the there-necked flask of 250ml, add bishydrazide 3.9g (0.017mol), 2.81g (0.017mol) 4,5-dichloro pyridazinone, 4g salt of wormwood, 30mlDMF, stirring reaction in oil bath pan, reflux 5 hours, elimination salt of wormwood after cooling, underpressure distillation is poured in 100ml frozen water after removing part DMF solvent and is stirred, and weigh to obtain after the drying of precipitation suction filtration 5.3g (0.015mol), and productive rate is 87.8%.
(5) N-{2-[the chloro-5-morpholinyl-3 of 4-(2H)-pyridazinone]-ethanoyl } preparation of-4-toluyl hydrazine
In the there-necked flask of 250ml; N-{2-[4; chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl }-4-toluyl hydrazine 4.0g (0.011mol); 1.48g (0.017mol) morpholine; 4g salt of wormwood; 40mlDMF; be heated to 80 DEG C; react 5 hours; elimination salt of wormwood after cooling; pour in 100ml frozen water and stir, 3.66g, product N-{2-[the chloro-5-morpholinyl-3 of 4-(2H)-pyridazinone]-ethanoyl of weighing to obtain after precipitation suction filtration drying the productive rate of-4-toluyl hydrazine is 82.2%.
The present embodiment obtains product N-{2-[4-chloro-5-morpholinyl-3 (2H)-pyridazinone]-ethanoyl } physical properties of-4-toluyl hydrazine is as follows:
Fusing point: 211.6-211.8 DEG C
1HNMR(DMSO)：2.29(s，3H)，3.41(t，4H)，3.72(t，4H)，4.63(s，1H)，5.03(s，1H)，7.05(d，1H，J＝8.0Hz7.13(d，1H，J＝8.0Hz)，7.67(d，1H，J＝8.0Hz)，7.78(d，1H，J＝8.0Hz)，7.92(s，1H)，9.28(s，1H)，10.06(s，1H)
IR(KBrcm-1)：3367，2995，2956，2854，1642，1591，1577，1555，1491，1448，1413，1255，1122，882。
Embodiment 2
A kind of bishydrazide compounds, this compound molecule formula is as follows:
Wherein, R 1for methyl, R 2for piperidyl, R 3for chlorine, the synthetic method of this bishydrazide compounds comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone
In 250mL there-necked flask, add the rare aldehydic acid of 50g dichloro-fourth and a small amount of water, stir, make the aqueous solution, then add 39g hydrazonium sulfate, 38.2g sodium-acetate, is heated to 80-100 DEG C, reacts 2 hours.Cool after complete reaction, reaction solution is poured in cold water, occurs a large amount of pale yellow precipitate, suction filtration, dry.Products therefrom dehydrated alcohol carries out recrystallization, productive rate 89.5%.
(2) synthesis of 4-methyl-benzoyl hydrazine
In 250ml there-necked flask, add 4-methyl-benzoic acid ethyl ester 70ml (0.485mol) and 51.5ml (0.485mol) hydrazine hydrate, then add the mixing of 70ml dehydrated alcohol, with mechanic whirl-nett reaction, be heated to 115 DEG C, condensing reflux reacts 8 hours.Solution is water white transparency.Cooling, reaction solution is poured in 200ml cold water, occurs a large amount of white solid, suction filtration, and dry, recrystallizing methanol obtains product, and productive rate is 82.4%.
(3) preparation of bishydrazide
In the 250ml there-necked flask that dry and absorption unit are housed, add 0.147mol to toluyl hydrazine, 60ml trichloromethane, 0.162mol salt of wormwood stirred, and slowly drips 12ml (0.147mol) chloroacetyl chloride, 80 DEG C of reactions 8 hours.Poured into by reaction solution in 200ml frozen water, and constantly stir, after leaving standstill, filter out precipitation, dry, recrystallization, the productive rate of bishydrazide is 70.34%.
The physico-chemical property of obtained bishydrazide is as follows:
Fusing point: 168.6-170.5 DEG C.
1HNMR(CDCl3)：2.37(s，3H)，4.17(s，2H)，7.29(d，2H，J＝8.0Hz)，7.77(d，2H，J＝8.0Hz)，10.38(s，2H)。
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } preparation of-4-toluyl hydrazine
In the there-necked flask of 250ml, add bishydrazide 3.9g (0.017mol), 2.81g (0.017mol) 4,5-dichloro pyridazinone, 4g salt of wormwood, 30mlDMF, stirring reaction in oil bath pan, reflux 5 hours, elimination salt of wormwood after cooling, underpressure distillation is poured in 100ml frozen water after removing part DMF solvent and is stirred, and weigh to obtain after the drying of precipitation suction filtration 5.3g (0.015mol), and productive rate is 87.8%.
(5) N-{2-[the chloro-5-piperidyl-3 of 4-(2H)-pyridazinone]-ethanoyl } preparation of-4-toluyl hydrazine
In the there-necked flask of 250ml; N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl }-4-toluyl hydrazine 4.0g (0.011mol), 1.45g (0.017mol) piperidines; 4g salt of wormwood; 40mlDMF, is heated to 80 DEG C, reacts 5 hours; elimination salt of wormwood after cooling; pour in 100ml frozen water and stir, weigh to obtain after the drying of precipitation suction filtration 3.24g, and productive rate is 73.1%.
Product N-{2-[4-chloro-5-piperidyl-3 (2H)-pyridazinone]-ethanoyl } physical properties of-4-toluyl hydrazine is as follows:
Fusing point: 196.3 ~ 197.8 DEG C.
1HNMR(DMSO)：1.62(s，6H)，2.37(s，3H)，3.38(s，4H)，4.78(s，2H)，7.28(t，2H，7.78(d，2H，J＝7.6Hz)，7.93(s，1H)，10.21(s，1H)，10.37(s，1H)。
IR(KBr，cm -1)：3196，2918，2852，1681，1650，1612，1514，1468，1358，1119，829。
Embodiment 3
A kind of bishydrazide compounds, this compound molecule formula is as follows:
Wherein, R 1for methyl, R 2for dimethylin, R 3for chlorine, the synthetic method of this bishydrazide compounds comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone
In 250mL there-necked flask, add the rare aldehydic acid of 50g dichloro-fourth and a small amount of water, stir, make the aqueous solution, then add 39g hydrazonium sulfate, 38.2g sodium-acetate, is heated to 80-100 DEG C, reacts 2 hours.Cool after complete reaction, reaction solution is poured in cold water, occurs a large amount of pale yellow precipitate, suction filtration, dry.Products therefrom dehydrated alcohol carries out recrystallization, productive rate 89.5%.
(2) synthesis of 4-methyl-benzoyl hydrazine
In 250ml there-necked flask, add 4-methyl-benzoic acid ethyl ester 70ml (0.485mol) and 51.5ml (0.485mol) hydrazine hydrate, then add the mixing of 70ml dehydrated alcohol, with mechanic whirl-nett reaction, be heated to 115 DEG C, condensing reflux reacts 8 hours.Solution is water white transparency.Cooling, reaction solution is poured in 200ml cold water, occurs a large amount of white solid, suction filtration, and dry, recrystallizing methanol obtains product, and productive rate is 82.4%.
(3) preparation of bishydrazide
In the 250ml there-necked flask that dry and absorption unit are housed, add 0.147mol to toluyl hydrazine, 60ml trichloromethane, 0.162mol salt of wormwood stirred, and slowly drips 12ml (0.147mol) chloroacetyl chloride, 80 DEG C of reactions 8 hours.Poured into by reaction solution in 200ml frozen water, and constantly stir, after leaving standstill, filter out precipitation, dry, recrystallization, productive rate is 70.34%.
The physical properties of bishydrazide is as follows:
Fusing point: 168.6-170.5 DEG C
1HNMR(CDCl3)：2.37(s，3H)，4.17(s，2H)，7.29(d，2H，J＝8.0Hz)，7.77(d，2H，J＝8.0Hz)，10.38(s，2H)。
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } preparation of-4-toluyl hydrazine
In the there-necked flask of 250ml, add bishydrazide 3.9g (0.017mol), 2.81g (0.017mol) 4,5-dichloro pyridazinone, 4g salt of wormwood, 30mlDMF, stirring reaction in oil bath pan, reflux 5 hours, elimination salt of wormwood after cooling, underpressure distillation is poured in 100ml frozen water after removing part DMF solvent and is stirred, and weigh to obtain after the drying of precipitation suction filtration 5.3g (0.015mol), and productive rate is 87.8%.
(5) N-{2-[the chloro-5-dimethylin-3 of 4-(2H)-pyridazinone]-ethanoyl } preparation of-4-toluyl hydrazine
In the there-necked flask of 250ml; N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl }-4-toluyl hydrazine 4.0g (0.011mol), 0.72g (0.016mol) dimethylamine; 4g salt of wormwood; 40mlDMF, is heated to 80 DEG C, reacts 5 hours; elimination salt of wormwood after cooling; pour in 100ml frozen water and stir, weigh to obtain after the drying of precipitation suction filtration product 3.11g, and productive rate is 78.1%.
Product N-{2-[4-chloro-5-dimethylin-3 (2H)-pyridazinone]-ethanoyl } physical properties of-4-toluyl hydrazine is as follows:
Fusing point: 287.1 ~ 287.3 DEG C.
1HNMR(DMSO)：2.37(s，3H)，3.10(s，6H)，4.76(s，2H)，7.30(d，2H，J＝8.0Hz)，7.78(d，2H，J＝8.0Hz)，7.90(s，1H)，10.19(s，1H)，10.34(s，1H)。
IR(KBr，cm -1)：3271，3035，2958，2917，1697，1669，1626，1606，1499，1443，1325，1164，882。
Embodiment 4
A kind of bishydrazide compounds, this compound molecule formula is as follows:
Wherein, R 1for methyl, R 2for rosickyite base, R 3for rosickyite base, the synthetic method of this bishydrazide compounds comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone
In 250mL there-necked flask, add the rare aldehydic acid of 50g dichloro-fourth and a small amount of water, stir, make the aqueous solution, then add 39g hydrazonium sulfate, 38.2g sodium-acetate, is heated to 80-100 DEG C, reacts 2 hours.Cool after complete reaction, reaction solution is poured in cold water, occurs a large amount of pale yellow precipitate, suction filtration, dry.Products therefrom dehydrated alcohol carries out recrystallization, productive rate 89.5%.
(2) synthesis of 4-methyl-benzoyl hydrazine
In 250ml there-necked flask, add 4-methyl-benzoic acid ethyl ester 70ml (0.485mol) and 51.5ml (0.485mol) hydrazine hydrate, then add the mixing of 70ml dehydrated alcohol, with mechanic whirl-nett reaction, be heated to 115 DEG C, condensing reflux reacts 8 hours.Solution is water white transparency.Cooling, reaction solution is poured in 200ml cold water, occurs a large amount of white solid, suction filtration, and dry, recrystallizing methanol obtains product, and productive rate is 82.4%.
(3) preparation of bishydrazide
In the 250ml there-necked flask that dry and absorption unit are housed, add 0.147mol to toluyl hydrazine, 60ml trichloromethane, 0.162mol salt of wormwood stirred, and slowly drips 12ml (0.147mol) chloroacetyl chloride, 80 DEG C of reactions 8 hours.Poured into by reaction solution in 200ml frozen water, and constantly stir, after leaving standstill, filter out precipitation, dry, recrystallization, productive rate is 70.34%.
The physical properties of bishydrazide is as follows:
Fusing point: 168.6-170.5 DEG C.
1HNMR(CDCl 3)：2.37(s，3H)，4.17(s，2H)，7.29(d，2H，J＝8.0Hz)，7.77(d，2H，J＝8.0Hz)，10.38(s，2H)。
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } preparation of-4-toluyl hydrazine
In the there-necked flask of 250ml, add bishydrazide 3.9g (0.017mol), 2.81g (0.017mol) 4,5-dichloro pyridazinone, 4g salt of wormwood, 30mlDMF, stirring reaction in oil bath pan, reflux 5 hours, elimination salt of wormwood after cooling, underpressure distillation is poured in 100ml frozen water after removing part DMF solvent and is stirred, and weigh to obtain after the drying of precipitation suction filtration 5.3g (0.015mol), and productive rate is 87.8%.
(5) N-{2-[4,5-dipropyl sulfenyl-3 (2H)-pyridazinone]-ethanoyl } preparation of-4-toluyl hydrazine
In the there-necked flask of 250ml; add N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl }-4-toluyl hydrazine 4.0g (0.011mol), 1.90g (0.025mol) propylmercaptan; 4g salt of wormwood; 40mlDMF, is heated to 80 DEG C, reacts 5 hours; elimination salt of wormwood after cooling; pour in 100ml frozen water and stir, weigh to obtain after the drying of precipitation suction filtration 3.84g, and productive rate is 80.4%.
Product N-{2-[4,5-dipropyl sulfenyl-3 (2H)-pyridazinone]-ethanoyl } physical properties of-4-toluyl hydrazine is as follows:
Fusing point: 237.1 ~ 238.3 DEG C.
1HNMR(DMSO)：1.04(t，3H)，1.13(t，3H)，1.62(m，2H)，1.76(m，2H)，2.98(t，2H)，3.28(t，2H)，4.78(s，2H)，7.29(d，2H，J＝8.0Hz)，7.76(d，2H，J＝8.0Hz)，7.93(s，1H)，9.98(s，1H)，10.37(s，1H)。
IR(KBr，cm -1)：3278，2958，2917，1697，1669，1626，1606，1499，1424，1222，1164，880。
Embodiment 1 ~ 4 adopts Toxicity Determination method to carry out performance test.
The experimental technique of Toxicity Determination is:
Medicament preparation and test method
First accurately take each medicament 20mg with electronic balance, dissolve with a small amount of DMF respectively, after sample dissolution, be diluted to 500mg/L with the aqueous solution of the tensio-active agent containing 0.05% stand-by.
Test method
Mythimna separata: adopt leaf of Semen Maydis leaching medicine method, maize leaf is flooded in liquid 5s and take out, after liquid dries naturally, clip leaf of Semen Maydis, 3 instar larvaes of feeding, often 4 repetitions are established in process, respectively at checking dead borer population after 48h and 72h, calculate mortality ratio.
Wriggler: adopt larva immersion method.With culex pipiens pollens 3 instar larvae, a certain amount of liquid and pure water are mixed with the liquid of 200mg/L, access wriggler, often process arranges 4 repetitions
Test-results is:
Sample is as shown in table 1 in the test result of 500mg/L to mythimna separata and wriggler,
Table 1 test-results
Sample number into spectrum Mythimna separata (lethality rate %) Wriggler (lethality rate %)
Embodiment 1 89.2 67.0
Embodiment 2 77.0 54.0
Embodiment 3 78.0 88.0
Embodiment 4 88.0 84.0
Embodiment 5
A kind of bishydrazide compound, this compound chemical structure formula is as follows:
Wherein, R 1for hydrogen; R 2for methylamino; R 3for chlorine.
The preparation method of above-mentioned bishydrazide compound, comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone:
Be 1: 1: 1 by the mol ratio of mucochloric acid, hydrazonium sulfate and sodium-acetate; By mucochloric acid and hydrazonium sulfate, 4,5-bis-chloro-3 (2H) pyridazinone is synthesized in condensation under the katalysis of sodium-acetate, and temperature of reaction is 50 DEG C, and the reaction times is 3 hours;
(2) preparation of benzoyl hydrazine:
The mol ratio of reacting by ethyl benzoate and hydrazine hydrate is 1: 1, and ethyl benzoate and hydrazine hydrate are synthesized benzoyl hydrazine through reacting by heating in the first solvent (methyl alcohol), and the temperature of heating is 50 DEG C;
(3) preparation of bishydrazide:
Be 1: 1 by the mol ratio of benzoyl hydrazine and alpha-halogen acetyl halide, benzoyl hydrazine obtained for step (2) and alpha-halogen acetyl halide (alpha-brominated acetyl bromide) are synthesized bishydrazide under the effect of the second solvent (methyl alcohol) and basic catalyst (sodium carbonate), and the temperature of synthesizing bishydrazide is 50 DEG C.
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } synthesis of-benzoyl hydrazine:
By bishydrazide and 4, the mol ratio of 5-bis-chloro-3 (2H) pyridazinone is 1: 1, the bishydrazide and 4 obtained by step (3), 5-bis-chloro-3 (2H) pyridazinone is in the 3rd solvent (methyl alcohol), condensation synthesis N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl under basic catalyst (sodium carbonate) effect }-benzoyl hydrazine;
(5) N-{2-[the chloro-5-3 of 4-(2H)-pyridazinone]-ethanoyl } preparation of-benzoyl hydrazine compound:
By N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } mol ratio of-benzoyl hydrazine and aminated compounds is 1: 1; The add-on of basic catalyst and N-{2-[4; chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl } mass ratio of-benzoyl hydrazine is 1.5: 1; N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl by obtained for step (4) }-benzoyl hydrazine in the 4th solvent (chloroform) with aminated compounds (methylamine) under the effect of basic catalyst (sodium carbonate) through heating synthesising target compound.The temperature of heating is 30 DEG C, and the time is 15 hours.
Embodiment 6
A kind of bishydrazide compound, this compound chemical structure formula is as follows:
Wherein, R 1for chlorine; R 2for isopropylamine base; R 3for chlorine.
The preparation method of above-mentioned bishydrazide compound, comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone:
Be 1: 1.5: 1.5 by the mol ratio of mucochloric acid, hydrazonium sulfate and sodium-acetate; By mucochloric acid and hydrazonium sulfate, 4,5-bis-chloro-3 (2H) pyridazinone is synthesized in condensation under the katalysis of sodium-acetate, and temperature of reaction is 70 DEG C, and the reaction times is 2 hours;
(2) preparation of substituted benzoyl hydrazides:
The mol ratio of reacting by substituted ethyl benzoate and hydrazine hydrate is 1: 1.5, by substituted ethyl benzoate and hydrazine hydrate in the first solvent (ethanol) through the synthesizing substituted formyl hydrazine of reacting by heating, the temperature of heating is 100 DEG C;
Wherein, substituted ethyl benzoate is Ethoforme; Corresponding substituted benzoyl hydrazides is p-chloro benzoyl hydrazine.
(3) preparation of bishydrazide:
Be 1: 1.3 by the mol ratio replacing benzoyl hydrazine and alpha-halogen acetyl halide, substituted benzoyl hydrazides obtained for step (2) and alpha-halogen acetyl halide (alpha-brominated acetyl bromide) are synthesized bishydrazide under the effect of the second solvent (ethanol) and basic catalyst (saleratus), and the temperature of synthesizing bishydrazide is 80 DEG C.
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } synthesis of-substituted benzoyl hydrazides:
By bishydrazide and 4, the mol ratio of 5-bis-chloro-3 (2H) pyridazinone is 1.2: 1, the bishydrazide and 4 obtained by step (3), 5-bis-chloro-3 (2H) pyridazinone is in the 3rd solvent (ethanol), condensation synthesis N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl under basic catalyst (saleratus) effect }-substituted benzoyl hydrazides;
(5) N-{2-[4-chloro-5 replace-3 (2H)-pyridazinones]-ethanoyl } preparation of-substituted benzoyl hydrazide compound:
By N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } mol ratio of-substituted benzoyl hydrazides and aminated compounds is 1.2: 1; The add-on of basic catalyst and N-{2-[4; chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl } mass ratio of-substituted benzoyl hydrazides is 1.8: 1; N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl by obtained for step (4) }-substituted benzoyl hydrazides in the 4th solvent (tetrahydrofuran (THF)) with aminated compounds (Isopropylamine) under the effect of basic catalyst (saleratus) through heating synthesising target compound.The temperature of heating is 70 DEG C, and the time is 8 hours.
Embodiment 7
A kind of bishydrazide compound, this compound chemical structure formula is as follows:
Wherein, R 1for methoxyl group; R 2for Propylamino; R 3for chlorine.
The preparation method of above-mentioned bishydrazide compound, comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone:
Be 1: 2: 2 by the mol ratio of mucochloric acid, hydrazonium sulfate and sodium-acetate; By mucochloric acid and hydrazonium sulfate, 4,5-bis-chloro-3 (2H) pyridazinone is synthesized in condensation under the katalysis of sodium-acetate, and temperature of reaction is 100 DEG C, and the reaction times is 1 hour;
(2) preparation of substituted benzoyl hydrazides:
The mol ratio of reacting by substituted ethyl benzoate and hydrazine hydrate is 1: 2, by substituted ethyl benzoate and hydrazine hydrate in the first solvent (methyl alcohol) through the synthesizing substituted formyl hydrazine of reacting by heating, the temperature of heating is 115 DEG C;
Wherein, substituted ethyl benzoate is ethyl anisate; Corresponding substituted benzoyl hydrazides is to methoxybenzoyl hydrazine.
(3) preparation of bishydrazide:
Be 1: 1.5 by the mol ratio replacing benzoyl hydrazine and alpha-halogen acetyl halide, substituted benzoyl hydrazides obtained for step (2) and alpha-halogen acetyl halide (alpha-chloro Acetyl Chloride 98Min.) are synthesized bishydrazide under the effect of the second solvent (tetrahydrofuran (THF)) and basic catalyst (potassium hydroxide), and the temperature of synthesizing bishydrazide is 100 DEG C.
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } synthesis of-substituted benzoyl hydrazides:
By bishydrazide and 4, the mol ratio of 5-bis-chloro-3 (2H) pyridazinone is 1.5: 1, the bishydrazide and 4 obtained by step (3), 5-bis-chloro-3 (2H) pyridazinone is in the 3rd solvent (tetrahydrofuran (THF)), condensation synthesis N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl under basic catalyst (potassium hydroxide) effect }-substituted benzoyl hydrazides;
(5) N-{2-[4-chloro-5 replace-3 (2H)-pyridazinones]-ethanoyl } preparation of-substituted benzoyl hydrazide compound:
By N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } mol ratio of-substituted benzoyl hydrazides and aminated compounds is 1.5: 1; The add-on of basic catalyst and N-{2-[4; chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl } mass ratio of-substituted benzoyl hydrazides is 2: 1; N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl by obtained for step (4) }-substituted benzoyl hydrazides in the 4th solvent (ethylene dichloride) with aminated compounds (propylamine) under the effect of basic catalyst (potassium hydroxide) through heating synthesising target compound.The temperature of heating is 100 DEG C, and the time is 4 hours.
Embodiment 8
A kind of bishydrazide compound, this compound chemical structure formula is as follows:
Wherein, R 1for chlorine; R 2for butylamine base; R 3for chlorine.
The preparation method of above-mentioned bishydrazide compound, comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone:
Be 1: 1.8: 1.8 by the mol ratio of mucochloric acid, hydrazonium sulfate and sodium-acetate; By mucochloric acid and hydrazonium sulfate, 4,5-bis-chloro-3 (2H) pyridazinone is synthesized in condensation under the katalysis of sodium-acetate, and temperature of reaction is 60 DEG C, and the reaction times is 2 hours;
(2) preparation of substituted benzoyl hydrazides:
The mol ratio of reacting by substituted ethyl benzoate and hydrazine hydrate is 1: 1.2, by substituted ethyl benzoate and hydrazine hydrate in the first solvent (methyl alcohol) through the synthesizing substituted formyl hydrazine of reacting by heating, the temperature of heating is 75 DEG C;
Wherein, substituted ethyl benzoate is Ethoforme; Corresponding substituted benzoyl hydrazides is p-chloro benzoyl hydrazine.
(3) preparation of bishydrazide:
Be 1: 1.2 by the mol ratio replacing benzoyl hydrazine and alpha-halogen acetyl halide, substituted benzoyl hydrazides obtained for step (2) and alpha-halogen acetyl halide (alpha-chloro Acetyl Chloride 98Min.) are synthesized bishydrazide under the effect of the second solvent (trichloromethane) and basic catalyst (triethylamine), and the temperature of synthesizing bishydrazide is 60 DEG C.
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } synthesis of-substituted benzoyl hydrazides:
Be 1.3: 1 by the mol ratio of bishydrazide and 4,5-bis-chloro-3 (2H) pyridazinone, by obtained for step (3) two
Hydrazides and 4,5-bis-chloro-3 (2H) pyridazinone is at the 3rd solvent (N, dinethylformamide) in, condensation synthesis N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl under basic catalyst (triethylamine) effect }-substituted benzoyl hydrazides;
(5) N-{2-[4-chloro-5 replace-3 (2H)-pyridazinones]-ethanoyl } preparation of-substituted benzoyl hydrazide compound:
By N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } mol ratio of-substituted benzoyl hydrazides and aminated compounds is 1.2: 1; The add-on of basic catalyst and N-{2-[4; chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl } mass ratio of-substituted benzoyl hydrazides is 1.8: 1; N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl by obtained for step (4) }-substituted benzoyl hydrazides in the 4th solvent (tetracol phenixin) with aminated compounds (butylamine) under the effect of basic catalyst (triethylamine) through heating synthesising target compound.The temperature of heating is 50 DEG C, and the time is 10 hours.

Claims (10)

1. a bishydrazide compound, is characterized in that, this compound chemical structure formula is as follows:
Wherein, R 1for the alkoxyl group of the alkyl of 1-4 carbon atom, a 1-4 carbon atom, halogen or hydrogen; R 2for methylamino, dimethylin, isopropylamine base, Propylamino, butylamine base, morpholinyl, piperidyl or rosickyite base; R 3for chlorine or rosickyite base.
2. a preparation method for bishydrazide compound as claimed in claim 1, is characterized in that, the method comprises the following steps:
The preparation of (1) 4,5-bis-chloro-3 (2H) pyridazinone:
By mucochloric acid and hydrazonium sulfate, 4,5-bis-chloro-3 (2H) pyridazinone is synthesized in condensation under the katalysis of sodium-acetate;
(2) preparation of benzoyl hydrazine or substituted benzoyl hydrazides:
Ethyl benzoate or substituted ethyl benzoate and hydrazine hydrate are synthesized benzoyl hydrazine or substituted benzoyl hydrazides through reacting by heating in the first solvent;
(3) preparation of bishydrazide:
Benzoyl hydrazine obtained for step (2) or substituted benzoyl hydrazides and alpha-halogen acetyl halide are synthesized bishydrazide under the effect of the second solvent and basic catalyst;
(4) N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl }-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } synthesis of-substituted benzoyl hydrazides:
The bishydrazide and 4 obtained by step (3), 5-bis-chloro-3 (2H) pyridazinone is in the 3rd solvent, condensation synthesis N-{2-[4 under basic catalyst effect, chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl }-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl }-substituted benzoyl hydrazides;
(5) preparation of target compound:
The N-{2-[4 obtained by step (4); chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl-substituted benzoyl hydrazides in the 4th solvent with aminated compounds or mercaptan compound under the effect at basic catalyst through heating synthesising target compound.
3. the preparation method of a kind of bishydrazide compound according to claim 2, is characterized in that, in step (1), the mol ratio of mucochloric acid, hydrazonium sulfate and sodium-acetate is 1:(1-2): (1-2);
In step (1), the temperature of reaction of condensation synthesis 4,5-bis-chloro-3 (2H) pyridazinone is 50-100 DEG C, and the reaction times is 1-3 hour.
4. the preparation method of a kind of bishydrazide compound according to claim 2, is characterized in that, in step (2), the mol ratio of ethyl benzoate or substituted ethyl benzoate and hydrazine hydrate is 1:(1-2);
The first solvent described in step (2) is methyl alcohol or ethanol;
In step (2), the temperature of heating is 50-115 DEG C.
5. the preparation method of a kind of bishydrazide compound according to claim 2, is characterized in that, the substituted ethyl benzoate described in step (2) comprises ethyl p-methyl benzoate, Ethoforme or ethyl anisate; Corresponding described substituted benzoyl hydrazides comprises toluyl hydrazine, p-chloro benzoyl hydrazine or to methoxybenzoyl hydrazine.
6. the preparation method of a kind of bishydrazide compound according to claim 2, is characterized in that, in step (3), the mol ratio of benzoyl hydrazine or substituted benzoyl hydrazides and alpha-halogen acetyl halide is 1:(1-1.5);
Alpha-halogen acetyl halide described in step (3) is alpha-brominated acetyl bromide or alpha-chloro Acetyl Chloride 98Min.;
The second solvent described in step (3) is methyl alcohol, ethanol, tetrahydrofuran (THF) or trichloromethane;
In step (3), the temperature of synthesis bishydrazide is 50-100 DEG C.
7. the preparation method of a kind of bishydrazide compound according to claim 2, is characterized in that, in step (4), the mol ratio of bishydrazide and 4,5-bis-chloro-3 (2H) pyridazinone is (1-1.5): 1;
The 3rd solvent described in step (4) is methyl alcohol, ethanol, tetrahydrofuran (THF) or DMF.
8. the preparation method of a kind of bishydrazide compound according to claim 2, it is characterized in that, N-{2-[4 in step (5), chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl }-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } mol ratio of-substituted benzoyl hydrazides and aminated compounds or mercaptan compound is (1-1.5): 1;
The add-on of step (5) neutral and alkali catalyzer and N-{2-[4; chloro-3 (the 2H)-pyridazinones of 5-bis-]-ethanoyl }-benzoyl hydrazine or N-{2-[chloro-3 (the 2H)-pyridazinones of 4,5-bis-]-ethanoyl } mass ratio of-substituted benzoyl hydrazides is (1.5-2): 1.
9. the preparation method of a kind of bishydrazide compound according to claim 2, it is characterized in that, the 4th solvent described in step (5) comprises chloroform, tetrahydrofuran (THF), DMF, ethylene dichloride, tetracol phenixin, 1,2-ethylene dichloride or ethanol;
Aminated compounds described in step (5) comprises methylamine, dimethylamine, Isopropylamine, propylamine, butylamine, morpholine or piperidines; Described mercaptan compound is propylmercaptan or isopropyl mercaptan;
In step (5), the temperature of heating synthesising target compound is 30-100 DEG C, and the time is 4-15 hour.
10. the preparation method of a kind of bishydrazide compound according to claim 2, is characterized in that,
Step (3), step (4) and the basic catalyst described in step (5) comprise salt of wormwood, sodium carbonate, saleratus, sodium bicarbonate, potassium hydroxide, sodium hydroxide or triethylamine.
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