CN103420884B - There is bisamide derivatives and the preparations and applicatio of optical activity and rotamerism - Google Patents
There is bisamide derivatives and the preparations and applicatio of optical activity and rotamerism Download PDFInfo
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- CN103420884B CN103420884B CN201310183112.0A CN201310183112A CN103420884B CN 103420884 B CN103420884 B CN 103420884B CN 201310183112 A CN201310183112 A CN 201310183112A CN 103420884 B CN103420884 B CN 103420884B
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- halogen
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- cycloalkyl
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- SKHCDRLTAOLKHQ-UHFFFAOYSA-N O=C(c1c2c(I)ccc1)OC2=O Chemical compound O=C(c1c2c(I)ccc1)OC2=O SKHCDRLTAOLKHQ-UHFFFAOYSA-N 0.000 description 1
- HNPVERUJGFNNRV-UHFFFAOYSA-N OC(c1cccc(I)c1C(O)=O)=O Chemical compound OC(c1cccc(I)c1C(O)=O)=O HNPVERUJGFNNRV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom not containing sulfur-to-oxygen bonds, e.g. polysulfides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/10—Compounds containing sulfur atoms doubly-bound to nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a kind of bisamide derivatives and the preparations and applicatio with optical activity and rotamerism, structure is as shown in general formula (I-1) and (I-2), and in formula, each substituted radical is defined in the specification.The compound of general formula (I-1) and (I-2) has excellent insecticidal activity.The present invention is that novel chiral bisamide analog derivative not only improves original compound resistance, and improves insecticidal activity and reduce production cost.
Description
Technical field
The present invention relates to a kind of bisamide derivatives and the preparations and applicatio with optical activity and rotamerism.
Background technology
In recent years, due to market continuous expansion and the resistance of insect, the work-ing life of medicine etc. problem and people to the pay attention to day by day of environment, need scientists constantly to study, endeavour to develop more effectively, insecticide variety that low cost, low toxicity, environmentally safe and novelty have unique mechanism of action.
Patent WO2006022225 openly has the chirality bisamide compounds of better insecticidal activity as follows.
For design and synthesis has the novel derivative of insecticidal bioactivity, and improve insecticide resistance and reduce production cost, the class novelty that design and synthesis has no bibliographical information has the bisamide analog derivative of optical activity and rotamerism, biological activity test shows, the insecticidal activity that the performance of this analog derivative is higher.
Summary of the invention
The object of the present invention is to provide a kind of bisamide derivatives and the preparations and applicatio with optical activity and rotamerism.This compound can improve original compound resistance and improve insecticidal activity.
The bisamide derivatives with optical activity and rotamerism provided by the invention has following general formula:
In formula:
X is H, halogen, SCN, cyano group, nitro, C
1-C
6alkyl, C
2-C
6thiazolinyl, C
2-C
6alkynyl, C
3-C
6cycloalkyl, C
1-C
6haloalkyl, C
1-C
4alkoxyalkyl, C
1-C
4hydroxyalkyl, C
1-C
4alkoxyl group, C
1-C
4halogenated alkoxy, C
1-C
4alkylthio, C
2-C
6alkoxy carbonyl, C
2-C
6alkyl-carbonyl, C
1-C
4alkyl sulphonyl, C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphinyl imido grpup, C
1-C
4alkylthio, C
1-C
4alkylamino, C
2-C
8dialkyl amido, C
3-C
6cycloalkyl amino, C
3-C
6trialkylsilkl, C
2-C
6alkyl amino-carbonyl, C
3-C
8dialkyl amino carbonyl, phenyl, phenoxy group, benzyl, five yuan of hetero-aromatic rings or optional being replaced by 1-3 substituting group of six-membered Hetero-aromatic, these substituting groups are independent of halogen separately, SCN, CN, nitro, hydroxyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
6haloalkyl, C
1-C
4halogenated alkoxy, C
1-C
4alkylthio, C
1-C
4hydroxyalkyl;
R
1h, C
1-C
6alkyl, C
2-C
6alkenyl, C
2-C
6alkynyl or C
3-C
6cycloalkyl;
R
2h, C
1-C
6alkyl, C
2-C
6alkenyl, C
2-C
6alkynyl or C
3-C
6cycloalkyl;
R
3halogen, H, C
1-C
6alkyl, C
2-C
6alkenyl, C
2-C
6alkenyloxy, C
2-C
6alkynyl, C
3-C
6cycloalkyl, C
4-C
7alkyl-cycloalkyl, C
1-C
6haloalkyl, C
1-C
6halogenated alkoxy, C
2-C
6halogen alkenyl, C
2-C
6alkynyl halide, C
3-C
6halogen cycloalkyl, C
4-C
7haloalkylcycloalkyl, C
2-C
6carbalkoxy, C
2-C
6haloalkoxycarbonyl;
R
4halogen, H, C
1-C
6alkyl, C
2-C
6alkenyl, C
2-C
6alkenyloxy, C
2-C
6alkynyl, C
3-C
6cycloalkyl, C
4-C
7alkyl-cycloalkyl, C
1-C
6haloalkyl, C
1-C
6halogenated alkoxy, C
2-C
6halogen alkenyl, C
2-C
6alkynyl halide, C
3-C
6halogen cycloalkyl, C
4-C
7haloalkylcycloalkyl, C
2-C
6carbalkoxy, C
2-C
6haloalkoxycarbonyl;
R
5h, halogen, C
1-C
6alkyl, C
2-C
6alkenyl, C
2-C
6alkenyloxy, C
2-C
6alkynyl, C
3-C
6cycloalkyl, C
4-C
7alkyl-cycloalkyl, C
1-C
6haloalkyl, C
1-C
6halogenated alkoxy, C
2-C
6halogen alkenyl, C
2-C
6alkynyl halide, C
3-C
6halogen cycloalkyl, C
4-C
7haloalkylcycloalkyl, C
2-C
6carbalkoxy, C
2-C
6haloalkoxycarbonyl;
A is C
0-C
6alkyl, C
2-C
6alkenyl, C
2-C
6alkenyloxy, C
3-C
6cycloalkyl, C
4-C
7alkyl-cycloalkyl, C
1-C
6haloalkyl, C
1-C
6halogenated alkoxy, C
2-C
6halogenated alkenyl, C
3-C
6halogenated cycloalkyl, C
4-C
7haloalkylcycloalkyl;
B is C
1-C
6alkyl, C
2-C
6thiazolinyl, C
3-C
6cycloalkyl, C
2-C
6haloalkyl, C
1-C
4alkoxyl group, C
1-C
4halogenated alkoxy, C
1-C
4alkoxyalkyl, C
1-C
4hydroxyalkyl, C
1-C
4alkylthio, C
1-C
4alkylamino, C
2-C
8dialkyl amido, C
3-C
6cycloalkyl amino, phenyl, five yuan of hetero-aromatic rings or optional being replaced by 1-3 substituting group of six-membered Hetero-aromatic, these substituting groups are independent of halogen separately, SCN, CN, nitro, hydroxyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4halogenated alkoxy, C
1-C
4alkylthio, C
1-C
4alkylamino, C
2-C
8dialkyl amido, C
3-C
6cycloalkyl amino, C
2-C
6alkyl-carbonyl, C
2-C
6carbalkoxy, C
2-C
6alkyl amino-carbonyl, C
3-C
8dialkyl amino carbonyl;
W is H, cyano group, nitro, halogen, hydroxyl, guanidine radicals, thiocyano, cyanic acid base, tetrazole Huan ， oxadiazole rings, optional being replaced by 1-3 substituting group of these heterocycles, and these substituting groups are independent of halogen separately, SCN, CN, nitro, hydroxyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4halogenated alkoxy, C
1-C
4haloalkyl;
M＝O，NR
6；
R
6h, halogen, cyano group, nitro, thiocyano, C
1-C
6alkyl, C
2-C
6alkenyl, C
2-C
6alkenyloxy, C
2-C
6alkynyl, C
3-C
6cycloalkyl, C
4-C
7alkyl-cycloalkyl, C
1-C
6haloalkyl, C
1-C
6halogenated alkoxy, C
2-C
6halogen alkenyl, C
2-C
6alkynyl halide, C
3-C
6halogen cycloalkyl, C
2-C
6alkyl-carbonyl, C
2-C
6carbalkoxy, C
2-C
6alkyl amino-carbonyl, phenyl, five yuan of hetero-aromatic rings or optional being replaced by 1-3 substituting group of six-membered Hetero-aromatic, these substituting groups are independent of halogen separately, SCN, CN, nitro, hydroxyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4halogenated alkoxy, C
1-C
6haloalkyl, C
1-C
6halogenated alkoxy;
K=O or S; N=0,1.
Y is phenyl, benzyl, phenoxy group; benzoyl, phenylamino, 5 or 6 yuan of heterocycle aromatic ring yls; 8 of naphthyl or aromatics; 9 or 10 yuan of assorted bicyclic systems condensed, each ring or ring system optional by 1-5 separately independently substituting group replace, these substituting groups separately independence from halogen; SCN; cyano group, nitro, C
1-C
6alkyl, C
2-C
6thiazolinyl, C
2-C
6alkynyl, C
3-C
6cycloalkyl, C
1-C
6haloalkyl, C
1-C
4alkoxyalkyl, C
1-C
4hydroxyalkyl, C
1-C
4alkoxyl group, C
1-C
4halogenated alkoxy, C
1-C
4alkylthio, C
2-C
6alkoxy carbonyl, C
2-C
6alkyl-carbonyl, C
1-C
4alkyl sulphonyl, C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphinyl imido grpup, C
1-C
4alkylthio, C
1-C
4alkylamino, C
2-C
8dialkyl amido, C
3-C
6cycloalkyl amino, C
3-C
6trialkylsilkl, C
2-C
6alkyl-carbonyl, C
2-C
6carbalkoxy, C
2-C
6alkyl amino-carbonyl, C
3-C
8dialkyl amino carbonyl;
In the definition of above-claimed cpd, no matter term used is used alone or is used in compound word, represent following substituting group:
Halogen: fluorine, chlorine, bromine or iodine;
Alkyl: straight or branched alkyl, such as methyl, ethyl, propyl group, sec.-propyl or the tertiary butyl;
Haloalkyl: straight chain or branched-chain alkyl, the hydrogen atom on these alkyl can some or all of replace by halogen atom, such as, haloalkyl is chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl or trifluoromethyl such as.
Thiazolinyl: straight or branched also can have double bond, such as vinyl or allyl group on any position;
Alkynyl: straight or branched also can have triple bond, such as ethynyl or propargyl on any position;
In five yuan or hexa-member heterocycle, heteroatoms is N, O or S;
Alternatively, X is H, halogen, thiocyano, cyano group, nitro, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl, trichloromethyl, chloromethyl, dichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, seven fluorine sec.-propyls, 1-hydroxyl hexafluoro isopropyl, methoxyl group, chlorine methoxyl group, dichloro methoxyl group, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, trichloromethoxy, oxyethyl group, pentafluoroethoxy, tetrafluoro oxyethyl group, 2, 2, 2-trifluoro ethoxy, 1, 2, 2-trifluoro ethoxy, 1, 1, 2-trifluoro ethoxy, positive propoxy, isopropoxy, amino, methylamino, ethylamino-, Tri N-Propyl Amine base, acetamido, formamido-, trifluoroacetyl amido, methylsulfonyl amido, methylthio group, methylsulfinyl imido grpup, carboxaldehyde radicals, ethanoyl, propionyl, C
1-C
6alkylaminocarbonyl or haloalkane amino-carbonyl, methylsulfonyl ester group,
R
1, R
2be H, methyl, allyl group;
R
3, R
4, R
5be H, halogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-hexyl, cyclohexyl, trifluoromethyl, trichloromethyl, chloromethyl, dichloromethyl, methyl fluoride, difluoromethyl, trifluoromethoxy, methoxyl group, chlorine methoxyl group, dichloro methoxyl group, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, trichloromethoxy, oxyethyl group, pentafluoroethoxy, positive propoxy, isopropoxy;
A is methyl, halogenated methyl, ethyl, propyl group, halogenated ethyl, vinyl halides base;
B is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl, methoxyl group, trifluoromethoxy, oxyethyl group, positive propoxy, isopropoxy, phenyl, benzyl, furans cyclic group, pyridine cyclic group, thiazole cyclic group, pyrroles's cyclic group, wherein aromatic nucleus can be replaced by 1-3 substituting group arbitrarily, these substituting groups are cyano group, nitro, halogen, methyl, ethyl, isobutyl-, trifluoromethoxy, trifluoromethyl, trichloromethoxy, trichloromethyl;
W is H, cyano group, nitro, halogen, hydroxyl, guanidine radicals, thiocyano, cyanic acid base, tetrazole ring, 3-Jia oxadiazole ring, 3-tri-Fu Jia oxadiazole ring;
M＝O，NR
6：
R
6h, halogen, cyano group, nitro, thiocyano, t-Butyldimethylsilyl, ethanoyl, trifluoroacetyl group, three fluorosulfonyls, phenyl, five yuan of hetero-aromatic rings or optional being replaced by 1-3 substituting group of six-membered Hetero-aromatic, these substituting groups are cyano group, nitro, halogen, methyl, ethyl, isobutyl-, trifluoromethoxy, trifluoromethyl, trichloromethoxy, trichloromethyl etc.;
K=O or S;
n＝0，1：
Y is phenyl, benzyl, phenoxy group, benzoyl, phenylamino, 5 or 6 yuan of heterocycle aromatic ring yls, 8 of naphthyl or aromatics, 9 or 10 yuan of assorted bicyclic systems condensed, each ring or ring system optional by 1-5 separately independently substituting group replace, these substituting groups are independent of halogen separately, SCN, cyano group, nitro, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl, trichloromethyl, chloromethyl, dichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, seven fluorine sec.-propyls, 1-hydroxyl hexafluoro isopropyl, methoxyl group, chlorine methoxyl group, dichloro methoxyl group, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, trichloromethoxy, oxyethyl group, pentafluoroethoxy, tetrafluoro oxyethyl group, 2, 2, 2-trifluoro ethoxy, 1, 2, 2-trifluoro ethoxy, 1, 1, 2-trifluoro ethoxy, positive propoxy, isopropoxy, amino, methylamino, ethylamino-, Tri N-Propyl Amine base, acetamido, formamido-, trifluoroacetyl amido, methylsulfonyl amido, methylthio group, methylsulfinyl imido grpup, carboxaldehyde radicals, ethanoyl, propionyl.
The step that the described preparation method with optically active bisamide derivatives and geometrical isomer thereof comprises:
There is bisamide derivatives (I-1) synthesis of optical activity and rotamerism:
Compounds of formula II and compound of formula III (mol ratio is 1: 1) are dissolved in organic solvent, then add appropriate acid or alkali, under temperature is for-10 DEG C to boiling point, react 0.5-48 hour obtained target compound IV; General formula compound IV is dissolved in the organic solvent of organic bases under condition of ice bath, then adds general formula compound V, reacts and obtain general formula compound I-1 in 3-24 hour under temperature is 0 DEG C to room temperature condition.
Described organic solvent is selected from methylene dichloride, chloroform, tetracol phenixin, benzene,toluene,xylene, hexanaphthene, normal hexane, ethyl acetate, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, DMF or dimethyl sulfoxide (DMSO).
Described acid (acid and Compounds of formula II mol ratio 0.001-0.1: 1) is selected from: methylsulphonic acid, Phenylsulfonic acid, p-methyl benzenesulfonic acid, acetic acid, phosphoric acid ester, or hydrochloric acid, sulfuric acid or phosphoric acid.
Described alkali is selected from organic bases (alkali and Compounds of formula II mol ratio 0.001-0.1): triethylamine, pyridine, 1,8-diaza-dicyclo (5,4, O) undecylene-7 or N, accelerine, or mineral alkali: sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium methylate, sodium tert-butoxide or potassium tert.-butoxide.
Described oxygenant has potassium permanganate, metachloroperbenzoic acid (mCPBA), NaIO
4/ RuO
2, H
2o
2, ozone.
Described organic solvent is selected from methylene dichloride, chloroform, tetracol phenixin, benzene,toluene,xylene, hexanaphthene, normal hexane, ethyl acetate, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, DMF or dimethyl sulfoxide (DMSO).
The preparation of general formula I-2 compound is as general formula I-1 compound.
Of the present invention have optically active bisamide derivatives and geometrical isomer thereof for the preparation of agricultural chemical insecticide.Especially for oriental armyworm, the control of the insect such as small cabbage moth and beet armyworm.
In optically active compound of the present invention, sulphur nitrogen double bond connects different substituting groups and there is non-corresponding isomer simultaneously, and the present invention also comprises their mixture of cis-trans-isomer, optical isomer, non-corresponding isomer, raceme or any ratio; Or their salt used in agricultural of correspondence.
Provided by the invention have optically active bisamide derivatives and geometrical isomer thereof and be equipped with the pesticide composition of agriculture acceptable auxiliary agent composition for preventing and treating the purposes of insect as activeconstituents.
Provided by the invention have optically active bisamide derivatives and the higher insecticidal activity of geometrical isomer performance thereof.Not only improve original compound resistance, also improve insecticidal activity and reduce production cost.
Embodiment
Further illustrate the present invention below in conjunction with embodiment, its objective is that can better understand content of the present invention is embody substantive distinguishing features of the present invention, therefore the cited case should not be considered as limiting the scope of the invention.
Embodiment 1
The synthesis of N-[1-(S-methyl-N-cyano group thiocarbonyl)-2-propyl group] the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide (derivative 83):
Steps A: preparation 3-iodo phthalic acid
By water (100mL), 3-nitrophthalic acid (21.10g) and, sodium hydroxide (9.2g), 2g Iron(III) chloride hexahydrate, 8g activated carbon and 80% hydrazine hydrate (12.5g) Hybrid Heating, obtained 3-aminophthalic acid.3-aminophthalic acid (18.1g) is dissolved in the vitriol oil and water mixed liquid, and keep low temperature, add Sodium Nitrite (10.4g), liquor kalii iodide (25g) successively, aftertreatment obtains solid 3-iodo phthalic acid.
Step B: preparation 3-iodo Tetra hydro Phthalic anhydride
3-iodo phthalic acid (29.2g) and diacetyl oxide (30mL) mix the micro-aftertreatment of boiling of post-heating and obtain solid 3-iodo Tetra hydro Phthalic anhydride.
Step C: preparation (S)-1-methylthio group-2-propylamine
(S)-1-methylthio group-2-propyl alcohol (7.51g) and chlorsulfonic acid (11.65g) are dissolved in glycol dimethyl ether, keep temperature lower than 50 DEG C.The mixing of the sulfuric ester of (the S)-1-methylthio group-2-propyl alcohol obtained, NaOH (4g) and sodium methyl mercaptide (70.09g) solution, heating obtains (S)-1-methylthio group-2-propylamine.
Step D: preparation (S)-2-iodo-6-carboxy-N-(1-methylthio group-2-propyl group) benzamide
Under room temperature, 3-iodo Tetra hydro Phthalic anhydride (2.74g), (S)-1-methylthio group-2-propylamine (1.05g) and triethylamine (1.00g) are mixed into dichloromethane solution, obtain the iodo-6-carboxy-N of solid 2--(1-methylthio group-2-propyl group) benzamide.
Step e: preparation N-(1-methylthio group-2-propyl group) the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide
The iodo-6-carboxy-N of 2--(1-methylthio group-2-propyl group) benzamide (1.90g) and triethylamine (0.50g) are dissolved in dichloromethane solvent, methylsulfonyl chloride (0.57g), 3-Aminotrifluorotoluene (0.806g) is added successively under keeping low temperature, aftertreatment obtains solid N-(1-methylthio group-2-propyl group) the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide.
Step F: the synthesis of preparation N-[1-(S-methyl-N-cyano group thiocarbonyl)-2-propyl group] the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide (derivative 78 and 360):
Keep below room temperature, N-(1-methylthio group-2-propyl group) the iodo-N ' of-3--(3-trifluoromethyl)-1, the mixing of 2-benzene first diamide (0.52g), single cyanogen ammonia (0.063g) and acetic acid phenyl-iodide (0.322g) is dissolved in 1, in 4-dioxane solvent, aftertreatment obtains solid N-[1-(S-methyl-N-cyano group thiocarbonyl)-2-propyl group] the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide.
Embodiment 2
The synthesis of N-[1-(S-methyl-N-TFA base thiocarbonyl)-2-propyl group] the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide (derivative 77):
Keep below room temperature; N-[1; 1-dimethyl-2-(S-methyl-N-cyano group thiocarbonyl) ethyl] the iodo-N ' of-3--(3-trifluoromethyl phenyl)-1; 2-benzene first diamide (0.56g) and trifluoroacetic anhydride (0.63g) are dissolved in methylene dichloride; obtain solid N-[1; 1-dimethyl-2-(S-methyl-N-TFA base thiocarbonyl) ethyl] the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide.
Embodiment 3
The synthesis of N-[1-(S-methyl-N-cyano group thiocarbonyl) sulfoxide group-2-propyl group] the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide (derivative 79):
Under ice bath, metachloroperbenzoic acid (0.26g), salt of wormwood (1.24g) aqueous solution and N-[1-(S-methyl-N-cyano group thiocarbonyl)-2-propyl group] the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide (0.56g) is dissolved in ethanolic soln, aftertreatment obtains solid N-[1-(S-methyl-N-cyano group thiocarbonyl) sulfoxide group-2-propyl group] the iodo-N ' of-3--(3-trifluoromethyl)-1,2-benzene first diamide.
Now according to the preparation method of above embodiment and the chirality bisamide class analog derivative adopting different raw materials to prepare: 01 ~ 562, partial derivatives
1hNMR (BrukerAV400spectrometerusingtetramethylsilaneastheintern alstandard) data list table 2 in.
Table 1a
Table 1b
Table 1c
Table 1d
Table 2
Embodiment 5
Utilize and provided by the inventionly there is optically active bisamide derivatives and geometrical isomer is tested, verify insect evaluated biological activity:
By provided by the invention any one there is optical siomerism and rotamerism bisamide analog derivative (01 ~ 562) is dissolved in solvent, water and tensio-active agent, be mixed into homogeneous aqueous phase, be diluted with water to any required concentration during use, tested object and testing method as follows:
1) to the evaluated biological activity of oriental armyworm: supply examination insect to be oriental armyworm (MythimnaseparataWalker), the normal population that indoor leaf of Semen Maydis is raised.Adopt leaf dipping method, dipping Maize Seedling leaf is in the solution configured, and put into diameter 7cm culture dish after drying, access 4 instar larvaes, each concentration repeats 3 times; Contrast acetone soln soaking maize leaf breeding grub; Viewing test result after 24 hours, 48 hours, 72 hours;
2) to the evaluated biological activity of small cabbage moth: supplying examination insect to be small cabbage moth 2 instar larvae (Plutellaxylostella (L.)), is the normal population that indoor are normally raised; Adopt leaf dipping method, with tweezers dipping cabbage leaves in the solution configured, time 2--3 second, get rid of remaining liquid; Each 1, totally 3, each sample; After liquid is dry, put into the long straight type of 10cm in vitro, access 2 age diamondback moth larvae, build the mouth of pipe with gauze; Test process is placed in standard treatment chamber, viewing test result after 24 hours, 48 hours, 72 hours;
3) to the evaluated biological activity of beet armyworm: supplying examination insect to be beet armyworm 3 instar larvae (LaphygmaexiguaHubner), is the normal population that indoor are normally raised; Adopt leaf dipping method, with tweezers dipping cabbage leaves in the solution configured, time 2--3 second, get rid of remaining liquid; Each 1, totally 3, each sample; After liquid is dry, put into diameter 7cm culture dish, access beet armyworm 3 instar larvae, is placed in test process in standard treatment chamber, viewing test result after 24 hours, 48 hours, 72 hours;
The partial test result of above-mentioned test is as shown in table 3.
Table 3
To two kinds of optical body R/S biological activity contrasts of part same structure formula, as shown in table 4:
Table 4
Mortality levels in table: A level is 100%-90%; B level is 90%-70%; C level is 70%-50%; D level is 50%-0%.
As shown in Table 6, the biological activity that chirality S body bisamide analog derivative is more excellent than the performance of R body bisamide analog derivative: beet armyworm (LaphygmaexiguaHubner) and small cabbage moth (Plutellaxylostella (L.)), both all show very excellent activity, for oriental armyworm (MythimnaseparataWalker), the biological activity of S body is better.
Claims (2)
1. a bisamide derivatives, has following structural formula:
Wherein, R
1=H, R
2=H, CH
3, A=CH
2, B=CH
3; N is 0,1; Q is CN, COCF3; X is 3-Cl, 3-Br, 3-I; Y is phenyl, and C is the 2-CH on phenyl
3-4-CF (CF
3)
2substituting group.
2. bisamide derivatives according to claim 1 is equipped with the pesticide composition of agriculture acceptable auxiliary agent composition as activeconstituents, for preventing and treating the purposes of insect.
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| CN201310183112.0A CN103420884B (en) | 2013-05-17 | 2013-05-17 | There is bisamide derivatives and the preparations and applicatio of optical activity and rotamerism |
| PCT/CN2013/087940 WO2014183415A1 (en) | 2013-05-17 | 2013-11-27 | Double-amide derivative with optical activity and geometrical isomerism, and preparation and application |
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| CN105315277A (en) * | 2014-08-04 | 2016-02-10 | 南开大学 | Chiral bisamide derivatives and preparation and application thereof |
| CN104402785A (en) * | 2014-09-26 | 2015-03-11 | 南开大学 | Novel bisamides derivative and preparation method and application thereof |
| US10743535B2 (en) | 2017-08-18 | 2020-08-18 | H&K Solutions Llc | Insecticide for flight-capable pests |
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| CN102503876A (en) * | 2011-09-28 | 2012-06-20 | 南开大学 | Bisamide derivative, preparation method for same and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015027951A (en) * | 2011-11-02 | 2015-02-12 | 日本農薬株式会社 | Phthalamide derivative, agricultural and horticultural pesticide containing said derivative, and method of utilizing the same |
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- 2013-11-27 WO PCT/CN2013/087940 patent/WO2014183415A1/en active Application Filing
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|---|---|---|---|---|
| CN1222506A (en) * | 1997-11-25 | 1999-07-14 | 日本农药株式会社 | Phthalic acid diamide derivatives, agricultural and horticultural insecticides, and method for application of insecticides |
| CN1255491A (en) * | 1998-11-30 | 2000-06-07 | 日本农药株式会社 | Butyl benzene orthobenzol diacid amide derivative or its salt, garderning pesticide and its application method |
| CN1692098A (en) * | 2002-08-26 | 2005-11-02 | 日本农药株式会社 | Sulfonamide derivatives, insecticides for agricultural and horticultural use, and usage thereof |
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| CN102503876A (en) * | 2011-09-28 | 2012-06-20 | 南开大学 | Bisamide derivative, preparation method for same and application thereof |
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| WO2014183415A1 (en) | 2014-11-20 |
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