CN102070629A - Novel nicotine and clothianidin analogue pesticide and preparation method thereof - Google Patents
Novel nicotine and clothianidin analogue pesticide and preparation method thereof Download PDFInfo
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- CN102070629A CN102070629A CN2010106083071A CN201010608307A CN102070629A CN 102070629 A CN102070629 A CN 102070629A CN 2010106083071 A CN2010106083071 A CN 2010106083071A CN 201010608307 A CN201010608307 A CN 201010608307A CN 102070629 A CN102070629 A CN 102070629A
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Abstract
The invention belongs to a pesticide and particularly relates to a novel nicotine and clothianidin analogue pesticide chemically named 1-(2-chloro-5-thiazolmethyl)-3-methyl-5-acylamino-hexahydrotriazine-2-N-nitroimine and a preparation method thereof. There is no new effective pesticide for killing rice planthoppers with increased resistance in the prior art. In the method, ethanol is used as a solvent, carboxylic acid and thionyl chloride are used as raw materials, and a reaction is performed under heating reflux to form an ester; the ester and hydrazine hydrate are dissolved in ethanol, and heating reflux is performed to obtain a hydrazide compound (II); the hydrazide compound (II), clothianidin and paraformaldehyde are added into ethanol, and heating reflux is performed; the reaction solution is cooled and filtered; and filtrate is subjected to chromatographic column purification by using acetone and ethyl acetate, which are in a ratio of 2:1, as eluant, and thus, the white solid compound of a general formula (I) is obtained. The pesticide has the advantages that: the pesticidal effect is desirable, the toxicity to human and animals is low, and environment pollution is avoided; the using method is simple and convenient; and the preparation method is simple. R may be hydrocarbyl, heterocyclo, benzyl and substituted aromatic ring.
Description
Technical field
The invention belongs to agricultural chemical insecticide, specifically class neonicotine thiophene worm amine analogue sterilant and preparation method thereof.This neonicotine thiophene worm amine analogue sterilant chemical name is 1-(2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine.
Background technology
Anabasine insecticide (Neonicotinoid insecticides, NNS) be insect nAChR (nicotinic acetyrlcholine receptors, nAChRs) inhibitor, be after organic phosphates, amino formate, pyrethroid insecticides the 4th generation novelty sterilant, be the invention that the sterilant research field is significant.Such biocidal activity height, insecticidal spectrum is wide, to Mammals and hydrocoles safety, good system's rerum natura and environment friendly is arranged simultaneously, and does not have cross resistance between traditional agricultural chemicals, so be a most important class of the high malicious sterilant of current replacement.
Thiophene worm amine is the neonicotine sterilant of Beyer Co., Ltd in Application and Development in 1996.Its mechanism of action is similar to other anabasine insecticides, is mainly used in crops such as paddy rice, vegetables, fruit tree, control Hemiptera, Coleoptera, Diptera and some lepidoptera pest.In recent years, because anabasine insecticide is long-term, a large amount of and frequent the use, it is serious day by day to make that pest resistance strengthens problem.Particularly insect such as rice terrace planthopper produces resistance to anabasine insecticides such as thiophene worm amine in recent years, and killing rate reduces.Prior art does not still have and effectively kills resistance and strengthen the planthopper novel pesticide and come out.The present invention has prepared 1-(2-chloro-5-thiazole methyl)-5-amide group-Hexahydrotriazine-2-N-nitro-imine compound that serial domestic and foreign literature does not appear in the newspapers, and its preparation method is provided.
Summary of the invention
The purpose of this invention is to provide a class anabasine thiophene worm amine sterilant analogue: have the active 1-of efficient insecticide (2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine compounds.
Another object of the present invention provides the preparation method of such anabasine thiophene worm amine sterilant analogue 1-(2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine compounds.
One class neonicotine thiophene worm amine sterilant analogue, chemical name is 1-(2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine; Represent with general formula (I):
R is all kinds of alkyl, heterocyclic radical, benzyl, aromatic ring yl and replaces aromatic ring yl
Neonicotine thiophene worm amine sterilant method for preparing analogue is:
(1) preparation hydrazide compound: ethanolic soln is added in the reaction vessel, is that 1: 1.2 carboxylic acid, sulfur oxychloride is dissolved in the ethanolic soln with mol ratio, and heating reflux reaction generates ester;
With mol ratio is that 1: 1.6 ester and hydrazine hydrate is dissolved in reflux in the ethanol; After reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling; Again the solid of separating out is carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters and obtain hydrazide compound (II);
(2) neonicotine thiophene worm amine sterilant analogue 1-(2-chloro-5-the thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine of preparation general formula (I):
Ethanolic soln is added in the reaction vessel, hydrazide compound (II), thiophene worm amine, Paraformaldehyde 96 are joined reflux in the ethanol; Hydrazide compound (II) is 1: 1 with the mol ratio of thiophene worm amine; After reacting completely, cooling is filtered; Be eluent chromatography column purifying with filtrate with 2: 1 acetone-ethyl acetate again, make white solid compound 1-(2-chloro-5-the thiazole methyl)-3-methyl-5-acetamido-Hexahydrotriazine-2-N-nitro-imine of general formula for (I);
Reaction formula is: step 1:
Step 2:
R is all kinds of alkyl, heterocyclic radical, benzyl, aromatic ring yl and replaces aromatic ring yl
General formula (I) neonicotine thiophene worm amine sterilant analogue 1-(2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine compound can be made into the pesticide formulation such as emulsion, aqueous suspension and aqueous emulsion.
General formula (I) neonicotine thiophene worm amine sterilant analogue 1-(2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine compound has the efficient insecticide activity to mythimna separata, brown planthopper, aphis craccivora etc., to the person poultry safety.
Main points of the present invention are:
With ethanol is solvent, is raw material with carboxylic acid, sulfur oxychloride, and heating reflux reaction generates ester; Be dissolved in reflux in the ethanol with ester and hydrazine hydrate, make hydrazide compound (II).Hydrazide compound (II), thiophene worm amine, Paraformaldehyde 96 are joined reflux in the ethanol; Cooling is filtered; Is eluent chromatography column purifying with filtrate with 2: 1 acetone-ethyl acetate, makes the white solid compound of general formula for (I).
The present invention synthesizes first in the world and prepared chemical name is a class neonicotine thiophene worm amine analogue sterilant of 1-(2-chloro-5-thiazole methyl)-5-amide group-Hexahydrotriazine-2-N-nitro-imine compound.This compound can prepare multiple formulation agricultural chemical insecticides such as aqua, emulsion, suspension agent as the sterilant raw material, to multiple kinds of crops insect good disinsection effect, the person poultry toxicity is low, and is environmentally safe.
Advantage of the present invention is:
Advantage of the present invention is:
1, has efficient insecticide activity, good disinsection effect.
2, toxicity is low, the person poultry safety.
3, promote crop growth.
4, using method is easy.
5, the preparation method is simple.
6, the reaction times is short.
Embodiment:
Further set forth technical characterstic of the present invention below in conjunction with specific embodiment.
One class neonicotine thiophene worm amine analogue sterilant, chemical name is 1-(2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine compound, represents with general formula (I):
R is all kinds of alkyl, heterocyclic radical, benzyl, aromatic ring yl and replaces aromatic ring yl
1-(2-chloro-5-the thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine examples for compounds of the present invention's preparation is:
(is 1-(2-chloro-5-thiazole methyl)-3-methyl-5-acetamido-Hexahydrotriazine-2-N-nitro-imine a);
(b) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-nonanoyl amido-Hexahydrotriazine-2-N-nitro-imine;
(c) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(2-thenoyl amido)-Hexahydrotriazine-2-N-nitro-imine;
(d) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(2-furoyl amido)-Hexahydrotriazine-2-N-nitro-imine;
(e) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-phenylacetyl amido-Hexahydrotriazine-2-N-nitro-imine;
(f) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-benzoylamino-Hexahydrotriazine-2-N-nitro-imine;
(g) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(3 '-toluyl amido)-Hexahydrotriazine-2-N-nitro-imine;
(h) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(4 '-tert.-butylbenzene formamido-)-Hexahydrotriazine-2-N-nitro-imine;
(i) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(3 '-N, N-dimethylamino benzoylamino)-Hexahydrotriazine-2-N-nitro-imine;
(j) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(4 '-chloro-benzoyl amino)-Hexahydrotriazine-2-N-nitro-imine;
Embodiment 1:
Preparation (is 1-(2-chloro-5-thiazole methyl)-3-methyl-5-acetamido-Hexahydrotriazine-2-N-nitro-imine a):
In the there-necked flask of 100ml, 4.40g (0.05mo l) ethyl acetate, 4.71g (0.08mol, 85%) hydrazine hydrate are added in the ethanol of 50ml.The magnetic stirring heating refluxed 4 hours, and after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out was carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtained needle crystal (acethydrazide) 2.42g, yield 65.4% at last.
1.48g (0.02mol) acethydrazide, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 were joined in the ethanol of 30ml reflux 7 hours.After reacting completely, cooling is filtered.The chromatography column purifying that is eluent with 2: 1 acetone-ethyl acetate with filtrate again, obtain at last white solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-acetamido-Hexahydrotriazine-2-N-nitro-imine, 2.7g, yield 39.3%. fusing point: 117 ℃-118 ℃.
Ultimate analysis: measured value C% 35.63 H% 3.77 N% 27.45
Calculated value C% 34.54 H% 4.06 N% 28.19
IR (KBr compressing tablet cm
-1) 3134 (N-H), 1630 (C=N), 1100 (C-N);
1H?NMR(CDCl
3/400MHz)：9.721(s，1H，N-H)，7.651(s，1H，thiazole-H)，4.715(s，2H，thiazole-CH
2)，4.520-4.541(d，J＝8.4Hz，4H，triazine-H)，2.886(s，3H，N-CH
3)，2.503(s，3H，C-CH
3)。
Make compound with present embodiment, by the prior art method, make aqueous pesticide solution, field spray is to the aphis craccivora killing rate more than 95%.
Embodiment 2:
Preparation (b) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-nonanoyl amido-Hexahydrotriazine-2-N-nitro-imine:
In 250mL exsiccant three-necked bottle, add 50ml ethanol and 13.01g (0.1mol) acid, drip 14.28g (0.12mol) sulfur oxychloride under the magnetic agitation, reflux 5 hours, after question response finishes, underpressure distillation obtains light yellow oily liquid and appoints acetoacetic ester 12.61g, yield 79.7%.
In the there-necked flask of 100ml, appoint acetoacetic ester, 4.71g (0.08mol, 85%) hydrazine hydrate to be added in the ethanol of 30ml 7.91g (0.05mo l).The magnetic stirring heating refluxed 6 hours, and after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out was carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtained white solid (hydrazides) 4.44g, yield 61.7% at last.
Appoint hydrazides, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 to join in the ethanol of 30ml reflux 7 hours 2.88g (0.02mol).After reacting completely, cooling is filtered.The chromatography column purifying that is eluent with 2: 1 acetone-ethyl acetate with filtrate again, obtain to such an extent that white solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-appoints amide group-Hexahydrotriazine-2-N-nitro-imine at last, 3.68g, yield 41.2%. fusing point: 81 ℃-82 ℃.
Ultimate analysis: measured value C% 43.93 H% 6.75 N% 22.68
Calculated value C% 45.78 H% 6.33 N% 21.99
IR (KBr compressing tablet cm
-1) 3129 (N-H), 1615 (C=N), 1112 (C-N);
1H?NMR(CDCl
3/400MHz)：8.045(s，1H，N-H)，7.562(s，1H，thiazole-H)，4.851(s，2H，thiazole-CH
2)，4.5374.548(d，J＝4.4Hz，4H，triazine-H)，3.128(s，3H，N-CH
3)，2.0472.085(t，J＝4.4Hz，2H，CO-CH
2)，1.5521.586(s，2H，C
6H
13-CH
2)，1.2751.323(s，2H.)。
Make compound with present embodiment, by the prior art method, make aqueous pesticide solution, field spray is to aphis craccivora killing rate 100%.
Embodiment 3:
Preparation (c) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(2-thenoyl amido)-Hexahydrotriazine-2-N-nitro-imine:
In 250mL exsiccant three-necked bottle, add 50ml ethanol and 12.82g (0.1mol) thenoic acid, drip 14.28g (0.12mol) sulfur oxychloride under the magnetic agitation, reflux 4 hours, after question response finishes, underpressure distillation obtains light yellow oily liquid thenoic acid ethyl ester 11.29g, yield 72.3%.
In the there-necked flask of 100ml, 7.81g (0.05mol) thenoic acid ethyl ester, 4.71g (0.08mol, 85%) hydrazine hydrate are added in the ethanol of 30ml.The magnetic stirring heating refluxed 5 hours, and after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out was carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtained white solid (thiophene hydrazides) 4.19g, yield 58.9% at last.
2.84g (0.02mol) thiophene hydrazides, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 were joined in the ethanol of 30ml reflux 8 hours.After reacting completely, cooling is filtered.The chromatography column purifying that is eluent with 2: 1 acetone-ethyl acetate with filtrate again, obtain at last light yellow solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-thiophene-carboxamides base-Hexahydrotriazine-2-N-nitro-imine, 3.28g, yield 39.4%. fusing point: 84 ℃-85 ℃.
Ultimate analysis: measured value C% 40.03 H% 3.48 N% 22,19
Calculated value C% 37.57 H% 3.39 N% 23.58
IR (KBr compressing tablet cm
-1) 3210 (N-H), 1619 (C=N), 1122 (C-N);
1H?NMR(CDCl
3/400MHz)：9.188(s，1H，N-H)，7.458(s，1H，thiazole-H)，6.9006.949(m，3H，thiophene-H)，4.704(s，2H，thiazole-CH
2)，4.4844.494(d，J＝4Hz，4H，triazine-H)，2.985(s，3H，N-CH
3)。
Make compound with present embodiment, by the prior art method, make aqueous pesticide solution, field spray is to the aphid killing rate more than 90%.
Embodiment 4:
Preparation (d) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(2-furoyl amido)-Hexahydrotriazine-2-N-nitro-imine:
In 250mL exsiccant three-necked bottle, add 50ml ethanol and the acid of 11.00g (0.1mol) 2-furans, drip 14.28g (0.12mol) sulfur oxychloride under the magnetic agitation, reflux 4 hours, after question response finishes, underpressure distillation, obtain light yellow oily liquid thenoic acid ethyl ester 10.60g, yield 76.8%.
In the there-necked flask of 100ml, 6.90g (0.05mol) 2-furans acetoacetic ester, 4.71g (0.08mol, 85%) hydrazine hydrate are added in the ethanol of 30ml.The magnetic stirring heating refluxed 5 hours, and after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out was carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtained white solid (2-furans hydrazides) 4.33g, yield 68.7% at last.
2.52g (0.02mol) 2-furans hydrazides, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 were joined in the ethanol of 30ml reflux 7 hours.After reacting completely, cooling is filtered.Again with filtrate with the chromatography column purifying that 2: 1 acetone-ethyl acetate are eluent, obtain at last white solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(2-furans amide group)-Hexahydrotriazine-2-N-nitro-imine,
3.34g, yield 41.8%. fusing point: 97 ℃-98 ℃.
Ultimate analysis: measured value C% 41.11 H% 3.45 N% 23,91
Calculated value C% 39.05 H% 3.53 N% 24.52
IR (KBr compressing tablet cm
-1) 3158 (N-H), 1624 (C=N), 1108 (C-N);
1H?NMR(CDCl
3/400MHz)：8.987(s，1H，N-H)，7.516(s，1H，thiazole-H)，7.3357.346(m，1H，furan-H)，6.4136.422(m，2H，furan-H)，4.689(s，2H，thiazole-CH
2)，4.4734.481(d，J＝4Hz，4H，triazine-H)，3.013(s，3H，N-CH
3)。
Make compound with present embodiment, by the prior art method, make agricultural-chemical emulsion, field spray is to the rice flying lice killing rate more than 90%.
Embodiment 5:
Preparation (e) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-phenylacetyl amido-Hexahydrotriazine-2-N-nitro-imine:
In 250mL exsiccant three-necked bottle, add 50ml ethanol and 13.62g (0.1mol) toluylic acid, drip 14.28g (0.12mol) sulfur oxychloride under the magnetic agitation, reflux 6 hours, after question response finishes, underpressure distillation obtains colourless transparent liquid Phenylacetic acid ethylester 10.60g, yield 76.8%.
In the there-necked flask of 100ml, 8.21g (0.05mol) Phenylacetic acid ethylester, 4.71g (0.08mo l, 85%) hydrazine hydrate are added in the ethanol of 30ml.The magnetic stirring heating refluxed 5 hours, and after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out was carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtained white solid phenylacetyl hydrazine 4.69g, yield 62.4% at last.
3.00g (0.02mol) phenylacetyl hydrazine, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 were joined in the ethanol of 30ml reflux 7 hours.After reacting completely, cooling is filtered.The chromatography column purifying that is eluent with 2: 1 acetone-ethyl acetate with filtrate again, obtain at last faint yellow solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-phenylacetyl amido-Hexahydrotriazine-2-N-nitro-imine, 3.29g, yield 38.8%. fusing point: 78 ℃-79 ℃.
Ultimate analysis: measured value C% 41.11 H% 3.45 N% 23,91
Calculated value C% 39.05 H% 3.53 N% 24.52
IR (KBr compressing tablet cm
-1) 3206 (N-H), 1671 (C=N), 1135 (C-N);
1H?NMR(CDCl
3/400MHz)：8.058(s，1H，N-H)，7.335
-7.346(m，6H，Ph-H，thiazole-H)，4.645(s，2H，thiazole-CH
2)，4.4334.464(d，J＝12.4Hz，4H，triazine-H)，3.474(s，2H，Ph-CH
2)，3.029(s，3H，N-CH
3)。
Make compound with present embodiment, by the prior art method, make aqueous pesticide solution, field spray is to the rice flying lice killing rate more than 90%.
Embodiment 6:
Preparation (f) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-benzoylamino-Hexahydrotriazine-2-N-nitro-imine:
In the there-necked flask of 100ml, 7.50g (0.05mol) ethyl benzoate, 4.71g (0.08mol, 85%) hydrazine hydrate are added in the ethanol of 30ml.The magnetic stirring heating refluxed 5 hours, and after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out was carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtained transparent crystals benzoyl hydrazine 5.29g, yield 77.8% at last.
2.72g (0.02mol) benzoyl hydrazine, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 were joined in the ethanol of 30ml reflux 8 hours.After reacting completely, cooling is filtered.Again with filtrate with the chromatography column purifying that 2: 1 acetone-ethyl acetate are eluent, obtain at last white solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(2-furans amide group)-Hexahydrotriazine-2-N-nitro-imine,
4.57g, yield 55.9%. fusing point: 232 ℃-233 ℃.
Ultimate analysis: measured value C% 44.13 H% 3.71 N% 24.09
Calculated value C% 43.96 H% 3.93 N% 23.92
IR (KBr compressing tablet cm
-1) 3182 (N-H), 1645 (C=N), 1109 (C-N);
1H?NMR(CDCl
3/400MHz)：7.808(s，1H，N-H)，7.449
-7.611(m，5H，Ph-H)，7.421(s，1H，thiazole-H)，4.585(s，2H，thiazole-CH
2)，4.4494.504(d，J＝22Hz，4H，triazine-H)，2.949(s，3H，N-CH
3)。
Make compound with present embodiment, by the prior art method, make agricultural chemicals suspension agent, convert between the paddy field and spray, to the aphid killing rate more than 90%.
Embodiment 7:
Preparation (g) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(3 '-toluyl amido)-Hexahydrotriazine-2-N-nitro-imine:
In 250mL exsiccant three-necked bottle, add 50ml ethanol and 13.62g (0.1mol) m-methyl benzoic acid, drip 14.28g (0.12mol) sulfur oxychloride under the magnetic agitation, reflux 6 hours, after question response finishes, underpressure distillation, obtain colourless transparent liquid m-methyl benzoic acid ethyl ester 11.45g, yield 69.7%.
In the there-necked flask of 100ml, 8.21g (0.05mol) m-methyl benzoic acid ethyl ester, 4.71g (0.08mol, 85%) hydrazine hydrate are added in the ethanol of 30ml.The magnetic stirring heating refluxed 7 hours, and after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out was carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtained toluyl hydrazine 5.43g between transparent crystals, yield 72.4% at last.
Toluyl hydrazine, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 between 3.00g (0.02mol) were joined in the ethanol of 30ml reflux 8 hours.After reacting completely, cooling is filtered.The chromatography column purifying that is eluent with 2: 1 acetone-ethyl acetate with filtrate again, obtain at last white solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(2-toluyl amido)-Hexahydrotriazine-2-N-nitro-imine, 4.57g, yield 55.9%. fusing point: 166 ℃-167 ℃.
Ultimate analysis: measured value C% 44.13 H% 3.71 N% 24.09
Calculated value C% 43.34 H% 4.28 N% 23.13
IR (KBr compressing tablet cm
-1) 3138 (N-H), 1621 (C=N), 1113 (C-N);
1H?NMR(CDCl
3/400MHz)：8.229(s，1H，N-H)，7.544(s，1H，thiazole-H)，7.472(s，1H，Ph-H)，7.3297.435(m，3H，Ph-H)，4.845(s，2H，thiazole-CH2)，4.661(s，4H，triazine-H)，3.188(s，3H，N-CH
3)，2.426(s，3H，Ph-CH
3)。
Make compound with present embodiment, by the prior art method, make aqueous pesticide solution, field spray is to the aphid killing rate more than 90%.
Embodiment 8:
Preparation (h) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(4 '-tert.-butylbenzene formamido-)-Hexahydrotriazine-2-N-nitro-imine:
In 250mL exsiccant three-necked bottle, add 50ml ethanol and 17.80g (0.1mol) p-tert-butyl benzoic acid, drip 14.28g (0.12mol) sulfur oxychloride under the magnetic agitation, reflux 7 hours, after question response finishes, underpressure distillation, obtain colourless transparent liquid p-tert-butyl benzoic acid ethyl ester 13.76g, yield 66.8%.
In the there-necked flask of 100ml, 10.30g (0.05mo l) p-tert-butyl benzoic acid ethyl ester, 4.71g (0.08mol, 85%) hydrazine hydrate are added in the ethanol of 30ml.The magnetic stirring heating refluxed 8 hours, and after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out was carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtained white solid at last to tert.-butylbenzene formyl hydrazine 7.18g, yield 74.8%.
3.84g (0.02mol) is joined in the ethanol of 30ml reflux to tert.-butylbenzene formyl hydrazine, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 7 hours.After reacting completely, cooling is filtered.The chromatography column purifying that is eluent with 2: 1 acetone-ethyl acetate with filtrate again, obtain at last white solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(3-tert.-butylbenzene formamido-)-Hexahydrotriazine-2-N-nitro-imine, 4.81g, yield 51.7%. fusing point: 162 ℃-163 ℃.
Ultimate analysis: measured value C% 44.13 H% 3.71 N% 24.09
Calculated value C% 48.98 H% 5.19 N% 21.04
IR (KBr compressing tablet cm
-1) 3128 (N-H), 1645 (C=N), 1093 (C-N);
1H?NMR(CDCl
3/400MHz)：8.217(s，1H，N-H)，7.477
-7.628(m，5H，thiazole-H，Ph-H)，4.855(s，2H，thiazole-CH
2)，4.6534.667(d，J＝6Hz，4H，triazine-H)，3.146(s，3H，N-CH
3)，1.342(s，9H，C-CH
3)。
Make compound with present embodiment, by the prior art method, make agricultural-chemical emulsion, field spray is to the aphid killing rate more than 90%.
Embodiment 9:
Preparation (i) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(3 '-N, N-dimethylamino benzoylamino)-Hexahydrotriazine-2-N-nitro-imine:
In 250mL exsiccant three-necked bottle, add 50ml ethanol and 16.50g (0.1mol) m-dimethyl amino benzoic acid, drip 14.28g (0.12mol) sulfur oxychloride under the magnetic agitation, reflux 7 hours, after question response finishes, underpressure distillation, obtain colourless transparent liquid m-dimethyl amino benzoic acid ethyl ester 10.56g, yield 57.4%.
In the there-necked flask of 100ml, 9.65g (0.05mol) m-dimethyl amino benzoic acid ethyl ester, 4.71g (0.08mol, 85%) hydrazine hydrate are added in the ethanol of 30ml.The magnetic stirring heating refluxed 7 hours, after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out is carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtain white solid m-dimethyl amino benzoyl hydrazine 7.01g, yield 78.3% at last.
3.58g (0.02mol) m-dimethyl amino benzoyl hydrazine, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 were joined in the ethanol of 30ml reflux 9 hours.After reacting completely, cooling is filtered.The chromatography column purifying that is eluent with 2: 1 acetone-ethyl acetate with filtrate again, obtain at last white solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(2-dimethylamino benzoylamino)-Hexahydrotriazine-2-N-nitro-imine, 3.74g, yield 41.3%. fusing point: 141 ℃-142 ℃.
Ultimate analysis: measured value C% 46.38 H% 4.19 N% 24.31
Calculated value C% 45.08 H% 4.67 N% 24.74
IR (KBr compressing tablet cm
-1) 3122 (N-H), 1637 (C=N), 1098 (C-N);
1H?NMR(CDCl
3/400MHz)：8.322(s，1H，N-H)，7.544(s，1H，thiazole-H)，7.3037.323(d，J＝8Hz，1H，Ph-H)，7.107(s，1H，Ph-H)，6.9206.936(m，2H，Ph-H)，4.826(s，2H，thiazole-CH
2)，4.654(s，4H，triazine-H)，3.167(s，3H，triazine-CH
3)，3.025(s，6H)。
Make compound with present embodiment, by the prior art method, make agricultural-chemical emulsion, field spray is to mythimna separata killing rate 100%.
Embodiment 10:
Preparation (j) 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(4 '-chloro-benzoyl amino)-Hexahydrotriazine-2-N-nitro-imine:
In 250mL exsiccant three-necked bottle, add 50ml ethanol and 15.70g (0.1mol) Chlorodracylic acid, drip 14.28g (0.12mol) sulfur oxychloride under the magnetic agitation, reflux 8 hours, after question response finishes, underpressure distillation, obtain colourless transparent liquid m-dimethyl amino benzoic acid ethyl ester 10.56g, yield 57.4%.
In the there-necked flask of 100ml, 9.25g (0.05mol) Ethoforme, 4.71g (0.08mol, 85%) hydrazine hydrate are added in the ethanol of 30ml.The magnetic stirring heating refluxed 8 hours, and after reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling, again the solid of separating out was carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters to it and obtained white solid at last to chlorobenzoyl hydrazine 5.02g, yield 58.7%.
3.43g (0.02mol) is joined in the ethanol of 30ml reflux to chlorobenzoyl hydrazine, 4.98g (0.02mol) thiophene worm amine, 1.80g (0.06mol) Paraformaldehyde 96 12 hours.After reacting completely, cooling is filtered.The chromatography column purifying that is eluent with 2: 1 acetone-ethyl acetate with filtrate again, obtain at last white solid 1-(2-chloro-5-thiazole methyl)-3-methyl-5-(3-chloro-benzoyl amino)-Hexahydrotriazine-2-N-nitro-imine, 3.54g, yield 39.8%. fusing point: 145 ℃-146 ℃.
Ultimate analysis: measured value C% 41.76 H% 4.03 N% 20.59
Calculated value C% 40.55 H% 3.40 N% 22.07
IR (KBr compressing tablet cm
-1) 3127 (N-H), 1619 (C=N), 1114 (C-N);
1H?NMR(CDCl
3/400MHz)：8.405(s，1H，N-H)，7.430
-7.665(m，5H，thiazole-H，Ph-H)，4.841(s，2H，thiazole-CH
2)，4.666(s，4H，triazine-H)，3.185(s，3H，N-CH
3)。
Make compound with present embodiment, by the prior art method, make aqueous pesticide solution, field spray is to the aphid killing rate more than 90%.
The foregoing description is a preference of the present invention, does not represent the present invention.All all variations in the spirit and principles in the present invention are all within protection scope of the present invention.
Claims (4)
1. a class neonicotine thiophene worm amine sterilant analogue, chemical name is 1-(2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine; Represent with general formula (I):
R is all kinds of alkyl, heterocyclic radical, benzyl, aromatic ring yl and replaces aromatic ring yl
2. neonicotine thiophene worm amine sterilant method for preparing analogue is:
(1) preparation hydrazide compound: ethanolic soln is added in the reaction vessel, is that 1: 1.2 carboxylic acid, sulfur oxychloride is dissolved in the ethanolic soln with mol ratio, and heating reflux reaction generates ester;
With mol ratio is that 1: 1.6 ester and hydrazine hydrate is dissolved in reflux in the ethanol; After reacting completely, solvent is sloughed in decompression, and solid is separated out in cooling; Again the solid of separating out is carried out recrystallization with the mixed solvent of 10: 1 alcohol-waters and obtain hydrazide compound (II);
(2) neonicotine thiophene worm amine sterilant analogue 1-(2-chloro-5-the thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine of preparation general formula (I):
Ethanolic soln is added in the reaction vessel, hydrazides, thiophene worm amine, Paraformaldehyde 96 are joined reflux in the ethanol; Hydrazide compound (II) is 1: 1 with the mol ratio of thiophene worm amine; After reacting completely, cooling is filtered; Be eluent chromatography column purifying with filtrate with 2: 1 acetone-ethyl acetate again, make white solid compound 1-(2-chloro-5-the thiazole methyl)-3-methyl-5-acetamido-Hexahydrotriazine-2-N-nitro-imine of general formula for (I);
Reaction formula is: step 1:
Step 2:
R is all kinds of alkyl, heterocyclic radical, benzyl, aromatic ring yl and replaces aromatic ring yl
3. general formula (I) neonicotine thiophene worm amine sterilant analogue 1-(2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine compound can be made into the pesticide formulation such as emulsion, aqueous suspension and aqueous emulsion.
4. general formula (I) neonicotine thiophene worm amine sterilant analogue 1-(2-chloro-5-thiazole methyl)-3-methyl-5-amide group-Hexahydrotriazine-2-N-nitro-imine compound is to mythimna separata, brown planthopper, aphis craccivora etc. are had the efficient insecticide activity, to the person poultry safety.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267991A (en) * | 2010-12-28 | 2011-12-07 | 上海师范大学 | Neonicotinoid clothianidin compound, preparation method and application thereof |
| CN103238617A (en) * | 2012-07-04 | 2013-08-14 | 河北威远生物化工股份有限公司 | Clothianidin synergia solubility granula and preparation method thereof |
| CN109928868A (en) * | 2019-03-22 | 2019-06-25 | 河北科技大学 | The synthetic method and its application of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- |
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| JP2610988B2 (en) * | 1989-03-09 | 1997-05-14 | 日本バイエルアグロケム 株式会社 | New heterocyclic compounds and insecticides |
| AU628229B2 (en) * | 1989-11-10 | 1992-09-10 | Agro-Kanesho Co. Ltd. | Hexahydrotriazine compounds and insecticides |
| JP2001515066A (en) * | 1997-08-20 | 2001-09-18 | ノバルティス アクチエンゲゼルシャフト | Method for producing substituted 2-nitroguanidine derivative |
| CN101606522A (en) * | 2009-05-26 | 2009-12-23 | 上海师范大学 | N-aroyl tetrahydropyrimidineinsecticide insecticide and preparation method thereof |
| CN102070629A (en) * | 2010-12-28 | 2011-05-25 | 上海师范大学 | Novel nicotine and clothianidin analogue pesticide and preparation method thereof |
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2010
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Cited By (5)
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| CN102267991A (en) * | 2010-12-28 | 2011-12-07 | 上海师范大学 | Neonicotinoid clothianidin compound, preparation method and application thereof |
| CN102267991B (en) * | 2010-12-28 | 2014-04-02 | 上海师范大学 | Neonicotinoid clothianidin compound, preparation method and application thereof |
| CN103238617A (en) * | 2012-07-04 | 2013-08-14 | 河北威远生物化工股份有限公司 | Clothianidin synergia solubility granula and preparation method thereof |
| CN103238617B (en) * | 2012-07-04 | 2015-01-28 | 河北威远生化农药有限公司 | Clothianidin synergia solubility granula and preparation method thereof |
| CN109928868A (en) * | 2019-03-22 | 2019-06-25 | 河北科技大学 | The synthetic method and its application of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- |
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