CN102617397A - Ortho-formyl aminobenzoyl hydrazide compound, preparation method thereof and application - Google Patents

Ortho-formyl aminobenzoyl hydrazide compound, preparation method thereof and application Download PDF

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CN102617397A
CN102617397A CN2012100363491A CN201210036349A CN102617397A CN 102617397 A CN102617397 A CN 102617397A CN 2012100363491 A CN2012100363491 A CN 2012100363491A CN 201210036349 A CN201210036349 A CN 201210036349A CN 102617397 A CN102617397 A CN 102617397A
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methyl
chloro
phenyl
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chlorine
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CN102617397B (en
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刘尚钟
欧俊军
朱笑坤
陈万义
刘峰
王磊
崔永亮
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China Agricultural University
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China Agricultural University
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Abstract

The invention discloses an ortho-formyl aminobenzoyl hydrazide compound, a preparation method thereof and application. The structural general formula of the compound is shown in a formula I. The preparation method of the compound includes the steps: placing a compound shown in a formula a and a compound shown in a formula b into organic solvents for ring-opening reaction, and obtaining the compound shown in the formula I after reaction. The insecticidal activity of the compound for plutella xylostella, aphis gossypii glover and carmine spider mite is higher than 90%, and the preparation method is simple and convenient in process, low in production cost and high in yield and has fine application prospect.

Description

Adjacent formamido group benzoyl hydrazine compound and preparation method thereof and application
Technical field
The invention belongs to ryania acceptor inhibitor field, be specifically related to adjacent formamido group benzoyl hydrazine compound and preparation method thereof and application.
Background technology
Ryania acceptor (Ryanodine Receptor; RyR) (Sarcoplasmic Reticulum is SR) on the calcium ion release channel of film, when the ryania acceptor inhibitor acts on the ryania acceptor to be positioned at the sarcoplasmic reticulum of carefully roaring; Can influence the insect Muscle contraction, make insect property of flaccid muscles paralysis.When lower concentration, on the calcium channel of the endoplasmic reticulum of carefully roaring and open passage, when high density, endoplasmic reticulum calcium channel inactivation.
Discovered in recent years a lot of ryania acceptor inhibitors, the researchist has successively found phthalic diamide, two types of high-activity compounds that act on the ryania acceptor of anthranilic diamides.The Tohnishi of Nihon Nihyaku Co., Ltd (Nihon Nohyaku Co.Ltd.) in 1998; M. wait the people in the process of research phthalyl aminated compounds; Having found has highly active compound---Flubendiamide (Flubendiamide to lepidoptera pest small cabbage moth (Plutella xylostella), prodenia litura (Spodoptera litura), Cnaphalocrocis medinali(rice leaf roller) (Cnaphalocrocis medinalis); NNI-001); Flubendiamide is a kind of to mammalian safe, efficient, low toxicity, wide spectrum, long environmentally friendly compound of the longevity of residure.This compound is developed by Nihon Nihyaku Co., Ltd and German Bayer AG jointly, is mainly used in the lepidoptera pest of control fruit, vegetables, cotton and paddy rice, in listing in 2007.Afterwards; E.I.Du Pont Company is the guide with the Flubendiamide; One of them carboxamido-group of phthalyl aminated compounds has been carried out location swap, and has carried out composition optimizes and found O-formammidotiazol-benzamide compounds later on---chlorine insect amide (Chlorantraniliprole), this compound not only with the flubendiamide structural similitude; And have identical mechanism of action, all to mammalian safe.Chlorantraniliprole still has goodish insecticidal activity under the inferior quality concentration very much; Like the LC50 to small cabbage moth is 0.01mg/L; And wide spectrum, the longevity of residure is long, toxicity is low and environmental friendliness, is effective sterilant of control lepidoptera pest, in listing in 2008.At present much to phthalic diamide, the research of anthranilic diamides two compounds; Group through to carboxy moiety and amino part changes, and has found in recent years much except the compound that insecticidal activity is arranged, to also have some to have the compound of sterilization and weeding activity.Like carboxy moiety is substituted benzene ring or naphthalene nucleus class (SELBY T P, SUN K M.hlsecdcidal 1,8-Naphnlalenedicar boxamides and Their Preparation; Use, and Compositions:WO, 2002032856); Carboxy moiety is phenyl pyrazoles (KOYANAGI T, YOKEDA T, HIGUCHI K; Et al.Preparation of Pyrazolyl Moiety-containing Anthranilamide COmpounds as Pest Control WO, 2006080311), carboxy moiety is compound (the KOYANAGI T that trifluoromethyl substituent is arranged on pyridylpyrazole-pyrazoles ring; MORITA M; NAKAMOTO K.Preparation of Anthranilamides as Pesticides:WO, 2005077934), on the pyrazoles ring halogen substituted compounds (HUGHES K A, LAHM G P are arranged; SELBY T P; Et al.Novel Pyrazole-based Anthranilamide Insecticides and Their Preparation Compositions, and Use:WO, 2004046129).
Summary of the invention
The purpose of this invention is to provide a kind of adjacent formamido group benzoyl hydrazine compound and preparation method thereof and application.
Adjacent formamido group benzoyl hydrazine compounds provided by the invention, its general structure is suc as formula shown in the I:
Figure BDA0000136374850000011
Formula I
Among the said formula I, X is at least a in hydrogen, the halogen; R 1At least a in hydrogen, the methyl; R 2For carbonatoms be 4-6 the aliphatics substituting group with contain at least a in the aliphatics substituting group that substituent carbonatoms is 4-6; R 3For carbonatoms is the 5-7 aromatic base, contains the aromatic base that substituent carbonatoms is 5-7.Preferably, said halogen is a chlorine or bromine; Said R 1Be hydrogen or methyl; Said R 2Be the tertiary butyl, the chloro tertiary butyl, tertiary amyl or cyclohexyl; R 3Be 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-p-methoxy-phenyl, 3-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2; 4-dichlorophenyl, 2; 3; 4; 5, at least a in 6-pentafluorophenyl group, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-chloro-5-pyridyl and the phenyl.
The method of adjacent formamido group benzoyl hydrazine compounds shown in the above-mentioned formula I of preparation provided by the invention; Comprise the steps: compound shown in compound shown in the formula a and the formula b is carried out ring-opening reaction in organic solvent, reaction finishes and obtains adjacent formamido group benzoyl hydrazine compounds shown in the said formula I;
Figure BDA0000136374850000021
Formula a formula b
Among said formula a and the formula b, R 1, R 2, R 3With the definition of X with aforementioned identical.
This reaction stream formula is as follows:
Figure BDA0000136374850000022
Midbody a2 is that raw material passes through method Tetrahedron Letters, 51 (10), 1383-1385 with a1; 2010 (Pingali et al.) halogenation makes.Midbody a3 prepares with reference to known method, for example makes with reference to CN101973956 (Puquan et al.) method.Midbody a prepares with reference to known method, Bioorganic & Medicinal Chemistry Letters for example, and 2005,4898-4906 (George P.Lahm et al.) acidylate makes.Midbody b with b1 be raw material with reference to Journal of Labelled Compounds and Radiopharmaceuticals, 1984 (10), 925-936 (Curt S.Cooper et al.) makes.
In the said ring-opening reaction step, temperature is 10～100 ℃, and preferred 20-30 ℃, the reaction times is 10-15 hour, and optimum condition is 14-30 hour.Said organic solvent is selected from least a in the alcohol that substituted fatty compounds that carbonatoms is 1-6, alicyclic compound that carbonatoms is 1-10, aromatic hydrocarbon that carbonatoms is 6-10, aromatic hydrocarbon halides that carbonatoms is 6-10, ether that carbonatoms is 2-6, ketone that carbonatoms is 2-6, acid amides that carbonatoms is 3-6, nitrile that carbonatoms is 2-6, sulfoxide class that carbonatoms is 2-4, ester class that carbonatoms is 3-8 and carbonatoms be 1-4; Preferred benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, normal hexane, methylene dichloride, trichloromethane, tetracol phenixin, 1; 2-ethylene dichloride, ether, dipropyl ether, THF, glycol dimethyl ether, ethylene glycol diethyl ether, acetone, butanone, mibk, acetonitrile, propionitrile, butyronitrile, N; At least a in dinethylformamide, DMAC N,N, N-methyl-formylaniline, N-Methyl pyrrolidone, HMPA, methyl acetate, ETHYLE ACETATE, DMSO 99.8MIN., methyl alcohol, ethanol, n-propyl alcohol, Virahol, terepthaloyl moietie, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and the diethylene glycol monoethyl ether.Compound shown in the said formula a is 1 with the mole dosage ratio that feeds intake of compound shown in the formula b: 1-1: 15, and preferred mole dosage ratio is 1: 12.
It is the medicine of activeconstituents that the application of said adjacent formamido group benzoyl hydrazine compounds shown in the formula I that the invention described above provides in the control of insect reaches with this neighbour's formamido group benzoyl hydrazine compounds, also belongs to protection scope of the present invention.Wherein, said insect is at least a in diamond-back moth section, Aphidiadae or the Tetranychidae, at least a in preferred small cabbage moth, melon aphid, cotten aphid and the carmine spider mite.
Formula I compound provided by the invention, under 600 μ g/mL concentration, the insecticidal activity of 30,131,280 pairs of small cabbage moths of compound is 100%, 217 pairs of small cabbage moth insecticidal activities of compound have surpassed 90%; The insecticidal activity of 32,234,301,309,372,402,403,404,451 pairs of melons of compound (cotton) aphid has all surpassed 90%; The insecticidal activity of 156,187,327 pairs of carmine spider mite of compound is 100%, and the insecticidal activity of 31,186 pairs of carmine spider mite of compound has all surpassed 90%.All above 90%, its preparation method technology is easy to the insecticidal activity of small cabbage moth, melon aphid, cotten aphid and carmine spider mite for this compounds, and production cost is low, and productive rate is high, has a good application prospect.
Embodiment
Below in conjunction with specific embodiment the present invention is done further elaboration, but the present invention is not limited to following examples.Said method is ordinary method if no special instructions.Said material all can get from open commercial sources if no special instructions.
Embodiment 1, compound 125:3-chloro-N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-2, the preparation of 2-dimethyl propylene acid amides
(formula is 1.0g a), is added in the 25mL reaction flask, adds the 10mL THF to take by weighing N-chloro pivaloyl group-3-methyl-5-chloro isatoic anhydride; Add 2-chlorine benzyl hydrazine (formula b) 0.57g then; Stirring at room ring-opening reaction 30 hours is filtered, and revolves to steam to remove to desolvate; The solid 1.18g of De Bai city behind the silicagel column purifying, productive rate 88.03%.
Wherein, (formula a) gets according to following method preparation reactant N-chloro pivaloyl group-3-methyl-5-chloro isatoic anhydride: 1.06g 3-methyl-5-chloro isatoic anhydride (formula a3) is placed the 50mL reaction flask, add 20mL anhydrous tetrahydro furan, 2.02g anhydrous triethylamine; Ice bath is cooled to below 5 ℃, and the 0.93g Chloropivaloyl chloride slowly is injected in the reaction flask with syringe, rises to stirring at room reaction 12 hours then; Revolve to steam and desolvate,, successively use saturated aqueous sodium carbonate and water washing with the methylene dichloride dissolving; Anhydrous sodium sulfate drying; Filter, remove the back De Bai solid 1.53g of city that desolvates, productive rate 93.2%.
The preparation (formula b) of reactant 2-chlorine benzyl hydrazine gets according to following method preparation: 85% Hydrazine Hydrate 80 50g is added in the 500mL reaction flask; Add ethanol 200mL, begin to be heated with stirring to backflow, take by weighing 2-chlorobenzyl chloride 16.0g then and slowly drop in the reaction flask; Dropwised the back stirring and refluxing 30 minutes; Revolve to steam to remove and desolvate and unnecessary Hydrazine Hydrate 80, get the yellowish liquid 10.2g of city, productive rate 65.3%.
In addition; Preparation N-chloro pivaloyl group-3-methyl-5-chloro isatoic anhydride (formula a) the reactant 3-methyl-5-chloro isatoic anhydride (formula a3) in the method according to following method preparation and get: 2-amino-3-methyl-5-chloro phenylformic acid (formula a2) 9.25g is placed the 250mL there-necked flask; Add 1; 4-dioxane 100mL, and be heated to backflow; Take by weighing TRIPHOSGENE 99.5 5.88g and be dissolved in 50mL 1, drop in the reaction flask behind the 4-dioxane, dropwised the back back flow reaction 6 hours, cooling after-filtration, petroleum ether, oven dry, the solid 10.30g of De Bai city, productive rate 97.6%;
Wherein, the 2-amino-3-methyl-5-chloro phenylformic acid (formula a2) as reactant gets according to following method preparation: 2-amino-3-tolyl acid 15.1g is placed the 250mL there-necked flask, add N; Dinethylformamide 100mL is heated to 70 ℃ under the mechanical stirring condition, add 14.52g N-chlorosuccinimide then in batches; Controlled temperature is lower than 80 ℃, and insulation reaction is 30 minutes behind reinforced the finishing, and stops heating; Under stirring reaction solution slowly is poured onto in the 500g ice, stirred 30 minutes, filter; The solid oven dry gets the grey solid 2-of city amino-3-methyl-5-chloro phenylformic acid (formula a2) 18.1g, productive rate 97.8%.
Embodiment 2, compound 125:3-chloro-N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-2, the preparation of 2-dimethyl propylene acid amides---reaction raw materials mol ratio is 1: 1.1
(formula is 1.0g a), is added in the 25mL reaction flask, adds the 10mL THF to take by weighing N-chloro pivaloyl group-3-methyl-5-chloro isatoic anhydride; Add 2-chlorine benzyl hydrazine (formula b) 0.52g then; Stirring at room ring-opening reaction 30 hours is filtered, and revolves to steam to remove to desolvate; The solid 0.91g of De Bai city behind the silicagel column purifying, productive rate 67.88%.
Embodiment 3, compound 125:3-chloro-N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-2, the preparation of 2-dimethyl propylene acid amides---reaction raw materials mol ratio is 1: 1.5
(formula is 1.0g a), is added in the 25mL reaction flask, adds the 10mL THF to take by weighing N-chloro pivaloyl group-3-methyl-5-chloro isatoic anhydride; Add 2-chlorine benzyl hydrazine (formula b) 0.65g then; Stirring at room ring-opening reaction 30 hours is filtered, and revolves to steam to remove to desolvate; The solid 1.02g of De Bai city behind the silicagel column purifying, productive rate 76.09%.
Embodiment 4, compound 125:3-chloro-N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-2,100 ℃ of the preparation of 2-dimethyl propylene acid amides---temperature of reaction
(formula is 1.0g a), is added in the 25mL reaction flask, adds the 10mL THF to take by weighing N-chloro pivaloyl group-3-methyl-5-chloro isatoic anhydride; Add 2-chlorine benzyl hydrazine (formula b) 0.57g then; Stirred ring-opening reaction 30 hours under 100 ℃ of conditions, filter, revolve to steam to remove and desolvate; The solid 0.12g of De Bai city behind the silicagel column purifying, productive rate 8.95%.
Embodiment 5, compound 125:3-chloro-N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-2, the 50 hours preparation of 2-dimethyl propylene acid amides---reaction times
(formula is 1.0g a), is added in the 25mL reaction flask, adds the 10mL THF to take by weighing N-chloro pivaloyl group-3-methyl-5-chloro isatoic anhydride; Add 2-chlorine benzyl hydrazine (formula b) 0.57g then; Stirring at room ring-opening reaction 50 hours is filtered, and revolves to steam to remove to desolvate; The solid 0.43g of De Bai city behind the silicagel column purifying, productive rate 32.08%.
The preparation of embodiment 6, compound 61:N-(4-chloro-2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl) phenyl) pivaloyl amine
(formula is 1.0g a), is added in the 25mL reaction flask, adds the 10mL THF with N-pivaloyl group-5-chloroisatoic anhydride; Add 2-chloro-5-hydrazine picoline (formula b) 0.67g then; Stirring at room ring-opening reaction 30 hours is filtered, and revolves to steam to remove to desolvate; The solid 1.25g of De Bai city behind the silicagel column purifying, productive rate 89.1%.
Wherein, (formula a) gets according to following method preparation N-pivaloyl group-5-chloroisatoic anhydride: 5-chloroisatoic anhydride 1.97g is placed the 50mL reaction flask, add 20mL anhydrous tetrahydro furan, 2.02g anhydrous triethylamine; Ice bath is cooled to below 5 ℃, and the 1.44g pivaloyl chloride slowly is injected in the reaction flask with syringe, rises to stirring at room reaction 12 hours then; Revolve to steam and desolvate,, successively use saturated aqueous sodium carbonate and water washing with the methylene dichloride dissolving; Anhydrous sodium sulfate drying; Filter, remove the back De Bai solid 2.65g of city that desolvates, productive rate 94.3%.
2-chloro-5-hydrazine picoline (formula b) gets according to following method preparation: 85% Hydrazine Hydrate 80 50g is added in the 500mL reaction flask; Adding ethanol 200mL begins to be heated with stirring to backflow, takes by weighing then slowly to drop in the reaction flask after 2-chloro-5-PMC 16.1g is dissolved in 50mL ethanol; Dropwised the back stirring and refluxing 30 minutes; Revolve to steam to remove and desolvate and unnecessary Hydrazine Hydrate 80, get the yellow oily matter 13.2g of city, productive rate 84.1%.
Embodiment 7, compound 327:N-(4-bromo-2-methyl-6-(2-(3-(trifluoromethyl) benzyl) hydrazine carbonyl) phenyl)-3, the preparation of 3-amide dimethyl butyrate
(formula is 1.0g a), is added in the 25mL reaction flask, adds the 10mL THF to take by weighing N-tertiary butyl ethanoyl-3-methyl-5-bromoisatin acid anhydrides; Add 3-trifluoromethyl benzyl hydrazine (formula b) 0.65g then; Stirring at room ring-opening reaction 30 hours is filtered, and revolves to steam to remove to desolvate; The solid 1.25g of De Bai city behind the silicagel column purifying, productive rate 88.4%.
Wherein, (formula a) gets according to following method preparation reactant N-tertiary butyl ethanoyl-3-methyl-5-bromoisatin acid anhydrides: 1.15 g3-methyl-5-bromoisatin acid anhydrides (formula a3) is placed the 50mL reaction flask, add 20mL anhydrous tetrahydro furan, 2.02g anhydrous triethylamine; Ice bath is cooled to below 5 ℃, and 0.81g tertiary butyl Acetyl Chloride 98Min. slowly is injected in the reaction flask with syringe, rises to stirring at room reaction 12 hours then; Revolve to steam and desolvate,, successively use saturated aqueous sodium carbonate and water washing with the methylene dichloride dissolving; Anhydrous sodium sulfate drying; Filter, remove the back De Bai solid 1.63g of city that desolvates, productive rate 92.3%.
3-trifluoromethyl benzyl hydrazine (formula b) gets according to following method preparation: 85% Hydrazine Hydrate 80 50g is added in the 500mL reaction flask; Add ethanol 200mL, begin to be heated with stirring to backflow, take by weighing 3-trifluoromethyl benzyl chloride 19.4g then and slowly drop in the reaction flask; Dropwised the back stirring and refluxing 30 minutes; Revolve to steam to remove and desolvate and unnecessary Hydrazine Hydrate 80, must not have the liquid 12.1g of city, productive rate 63.7%.
In addition; Preparation feedback thing N-tertiary butyl ethanoyl-3-methyl-5-bromoisatin acid anhydrides (formula a) in used reactant 3-methyl-5-bromoisatin acid anhydrides (formula a3) according to the preparation of following method and get: 2-amino-3-methyl-5-bromo-benzoic acid (formula a2) 11.45g is placed the 250mL there-necked flask; Add 1; 4-dioxane 100mL, and be heated to backflow; Take by weighing TRIPHOSGENE 99.5 5.88g and be dissolved in 50mL 1, drop in the reaction flask behind the 4-dioxane, dropwised the back back flow reaction 6 hours, cooling after-filtration, petroleum ether, oven dry, the solid 3-of De Bai city methyl-5-bromoisatin acid anhydrides (formula a3) 12.42g, productive rate 97.4%.
Reactant 2-amino-3-methyl-5-bromo-benzoic acid (formula a2) gets according to following method preparation: amino-3 tolyl acid 15.1g of 2-are placed the 250mL there-necked flask, add N, dinethylformamide 100mL; Be heated to 70 ℃ under the mechanical stirring condition, add 19.47g N-bromo-succinimide then in batches, controlled temperature is lower than 80 ℃; Insulation reaction is 30 minutes behind reinforced the finishing, and stops heating, stirs down reaction solution slowly is poured onto in the 500g ice; Stirred 30 minutes, and filtered, the solid oven dry; Get the brown solid 2-of city amino-3-methyl-5-bromo-benzoic acid (formula a2) 21.9g, productive rate 95.6%.
The preparation of embodiment 8, compound 496:N-(2-(2-benzyl hydrazine carbonyl)-6-aminomethyl phenyl) cyclohexanecarbonyl chloride
(formula is 1.0g a), is added in the 25mL reaction flask, adds the 10mL THF to take by weighing N-cyclohexyl formyl radical-3-methyl isatoic anhydride; Add benzyl hydrazine (formula b) 0.51g then, stirring at room reaction 30 hours is filtered; Revolve to steam to remove and desolvate the solid 1.17g of De Bai city behind the silicagel column purifying, productive rate 92.1%.
Wherein, (formula a) gets according to following method preparation reactant N-cyclohexyl formyl radical-3-methyl isatoic anhydride: 0.89g 3-methyl isatoic anhydride (formula a3) is placed the 50mL reaction flask, add 20mL anhydrous tetrahydro furan, 2.02g anhydrous triethylamine; Ice bath is cooled to below 5 ℃, and 0.88g cyclohexyl formyl chloride slowly is injected in the reaction flask with syringe, rises to stirring at room reaction 12 hours then; Revolve to steam and desolvate,, successively use saturated aqueous sodium carbonate and water washing with the methylene dichloride dissolving; Anhydrous sodium sulfate drying; Filter, remove the back De Bai solid 1.31g of city that desolvates, productive rate 91.6%.
Reactant benzyl hydrazine (formula b) gets according to following method preparation: 85% Hydrazine Hydrate 80 50g is added in the 500mL reaction flask; Add ethanol 200mL, begin to be heated with stirring to backflow, take by weighing benzyl chloride 12.6g then and slowly drop in the reaction flask; Dropwised the back stirring and refluxing 30 minutes; Revolve to steam to remove and desolvate and unnecessary Hydrazine Hydrate 80, get the yellowish liquid 5.93g of city, productive rate 48.6%.
Preparation feedback thing N-cyclohexyl formyl radical-3-methyl isatoic anhydride (formula a) in used reactant 3-methyl isatoic anhydride (formula a3) according to the preparation of following method and get: 2-amino-3-tolyl acid 7.55g is placed the 250mL there-necked flask; Add 1; 4-dioxane 100mL, and be heated to backflow; Take by weighing TRIPHOSGENE 99.5 5.88g and be dissolved in 50mL1, drop in the reaction flask behind the 4-dioxane, dropwised the back back flow reaction 6 hours, cooling after-filtration, petroleum ether, oven dry, the solid 8.41g of De Bai city, productive rate 95.1%.
According to last identical method, only the substituting group in the reactant is replaced, obtain the compound that is numbered 1-496 except that last 61,125,327 and 496 shown in the table 1.
Each substituting group tabulation in the compound shown in table 1, the formula I
Numbering X R 1 R 2 R 3
1 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2-chloro-phenyl-
2 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 3-chloro-phenyl-
3 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 4-chloro-phenyl-
4 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2-bromophenyl
5 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 3-bromophenyl
6 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 4-bromophenyl
7 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2-fluorophenyl
8 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 3-fluorophenyl
9 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 4-fluorophenyl
10 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2-aminomethyl phenyl
11 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 3-aminomethyl phenyl
12 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 4-aminomethyl phenyl
13 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2-p-methoxy-phenyl
14 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 3-p-methoxy-phenyl
15 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 4-p-methoxy-phenyl
16 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2-trifluoromethyl
17 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 3-trifluoromethyl
18 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 4-trifluoromethyl
19 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2-nitrophenyl
20 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 3-nitrophenyl
21 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 4-nitrophenyl
22 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2,4 dichloro benzene base
23 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base 2,3,4,5, the 6-pentafluorophenyl group
24 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2-cyano-phenyl
25 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 3-cyano-phenyl
26 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 4-cyano-phenyl
27 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 2-pyridyl
28 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 3-pyridyl
29 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base The 4-pyridyl
30 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base 2-chloro-5-pyridyl
31 Chlorine Hydrogen 1-chloro-2-methylpropane-2-base Phenyl
32 Chlorine Hydrogen The tertiary butyl The 2-chloro-phenyl-
33 Chlorine Hydrogen The tertiary butyl The 3-chloro-phenyl-
34 Chlorine Hydrogen The tertiary butyl The 4-chloro-phenyl-
35 Chlorine Hydrogen The tertiary butyl The 2-bromophenyl
36 Chlorine Hydrogen The tertiary butyl The 3-bromophenyl
37 Chlorine Hydrogen The tertiary butyl The 4-bromophenyl
38 Chlorine Hydrogen The tertiary butyl The 2-fluorophenyl
39 Chlorine Hydrogen The tertiary butyl The 3-fluorophenyl
40 Chlorine Hydrogen The tertiary butyl The 4-fluorophenyl
41 Chlorine Hydrogen The tertiary butyl The 2-aminomethyl phenyl
42 Chlorine Hydrogen The tertiary butyl The 3-aminomethyl phenyl
43 Chlorine Hydrogen The tertiary butyl The 4-aminomethyl phenyl
44 Chlorine Hydrogen The tertiary butyl The 2-p-methoxy-phenyl
45 Chlorine Hydrogen The tertiary butyl The 3-p-methoxy-phenyl
46 Chlorine Hydrogen The tertiary butyl The 4-p-methoxy-phenyl
47 Chlorine Hydrogen The tertiary butyl The 2-trifluoromethyl
48 Chlorine Hydrogen The tertiary butyl The 3-trifluoromethyl
49 Chlorine Hydrogen The tertiary butyl The 4-trifluoromethyl
50 Chlorine Hydrogen The tertiary butyl The 2-nitrophenyl
51 Chlorine Hydrogen The tertiary butyl The 3-nitrophenyl
52 Chlorine Hydrogen The tertiary butyl The 4-nitrophenyl
53 Chlorine Hydrogen The tertiary butyl The 2,4 dichloro benzene base
54 Chlorine Hydrogen The tertiary butyl 2,3,4,5, the 6-pentafluorophenyl group
55 Chlorine Hydrogen The tertiary butyl The 2-cyano-phenyl
56 Chlorine Hydrogen The tertiary butyl The 3-cyano-phenyl
57 Chlorine Hydrogen The tertiary butyl The 4-cyano-phenyl
58 Chlorine Hydrogen The tertiary butyl The 2-pyridyl
59 Chlorine Hydrogen The tertiary butyl The 3-pyridyl
60 Chlorine Hydrogen The tertiary butyl The 4-pyridyl
61 Chlorine Hydrogen The tertiary butyl 2-chloro-5-pyridyl
62 Chlorine Hydrogen The tertiary butyl Phenyl
63 Chlorine Hydrogen Neo-pentyl The 2-chloro-phenyl-
64 Chlorine Hydrogen Neo-pentyl The 3-chloro-phenyl-
65 Chlorine Hydrogen Neo-pentyl The 4-chloro-phenyl-
66 Chlorine Hydrogen Neo-pentyl The 2-bromophenyl
67 Chlorine Hydrogen Neo-pentyl The 3-bromophenyl
68 Chlorine Hydrogen Neo-pentyl The 4-bromophenyl
69 Chlorine Hydrogen Neo-pentyl The 2-fluorophenyl
70 Chlorine Hydrogen Neo-pentyl The 3-fluorophenyl
71 Chlorine Hydrogen Neo-pentyl The 4-fluorophenyl
72 Chlorine Hydrogen Neo-pentyl The 2-aminomethyl phenyl
73 Chlorine Hydrogen Neo-pentyl The 3-aminomethyl phenyl
74 Chlorine Hydrogen Neo-pentyl The 4-aminomethyl phenyl
75 Chlorine Hydrogen Neo-pentyl The 2-p-methoxy-phenyl
76 Chlorine Hydrogen Neo-pentyl The 3-p-methoxy-phenyl
77 Chlorine Hydrogen Neo-pentyl The 4-p-methoxy-phenyl
78 Chlorine Hydrogen Neo-pentyl The 2-trifluoromethyl
79 Chlorine Hydrogen Neo-pentyl The 3-trifluoromethyl
80 Chlorine Hydrogen Neo-pentyl The 4-trifluoromethyl
81 Chlorine Hydrogen Neo-pentyl The 2-nitrophenyl
82 Chlorine Hydrogen Neo-pentyl The 3-nitrophenyl
83 Chlorine Hydrogen Neo-pentyl The 4-nitrophenyl
84 Chlorine Hydrogen Neo-pentyl The 2,4 dichloro benzene base
85 Chlorine Hydrogen Neo-pentyl 2,3,4,5, the 6-pentafluorophenyl group
86 Chlorine Hydrogen Neo-pentyl The 2-cyano-phenyl
87 Chlorine Hydrogen Neo-pentyl The 3-cyano-phenyl
88 Chlorine Hydrogen Neo-pentyl The 4-cyano-phenyl
89 Chlorine Hydrogen Neo-pentyl The 2-pyridyl
90 Chlorine Hydrogen Neo-pentyl The 3-pyridyl
91 Chlorine Hydrogen Neo-pentyl The 4-pyridyl
92 Chlorine Hydrogen Neo-pentyl 2-chloro-5-pyridyl
93 Chlorine Hydrogen Neo-pentyl Phenyl
94 Chlorine Hydrogen Cyclohexyl The 2-chloro-phenyl-
95 Chlorine Hydrogen Cyclohexyl The 3-chloro-phenyl-
96 Chlorine Hydrogen Cyclohexyl The 4-chloro-phenyl-
97 Chlorine Hydrogen Cyclohexyl The 2-bromophenyl
98 Chlorine Hydrogen Cyclohexyl The 3-bromophenyl
99 Chlorine Hydrogen Cyclohexyl The 4-bromophenyl
100 Chlorine Hydrogen Cyclohexyl The 2-fluorophenyl
101 Chlorine Hydrogen Cyclohexyl The 3-fluorophenyl
102 Chlorine Hydrogen Cyclohexyl The 4-fluorophenyl
103 Chlorine Hydrogen Cyclohexyl The 2-aminomethyl phenyl
104 Chlorine Hydrogen Cyclohexyl The 3-aminomethyl phenyl
105 Chlorine Hydrogen Cyclohexyl The 4-aminomethyl phenyl
106 Chlorine Hydrogen Cyclohexyl The 2-p-methoxy-phenyl
107 Chlorine Hydrogen Cyclohexyl The 3-p-methoxy-phenyl
108 Chlorine Hydrogen Cyclohexyl The 4-p-methoxy-phenyl
109 Chlorine Hydrogen Cyclohexyl The 2-trifluoromethyl
110 Chlorine Hydrogen Cyclohexyl The 3-trifluoromethyl
111 Chlorine Hydrogen Cyclohexyl The 4-trifluoromethyl
112 Chlorine Hydrogen Cyclohexyl The 2-nitrophenyl
113 Chlorine Hydrogen Cyclohexyl The 3-nitrophenyl
114 Chlorine Hydrogen Cyclohexyl The 4-nitrophenyl
115 Chlorine Hydrogen Cyclohexyl The 2,4 dichloro benzene base
116 Chlorine Hydrogen Cyclohexyl 2,3,4,5, the 6-pentafluorophenyl group
117 Chlorine Hydrogen Cyclohexyl The 2-cyano-phenyl
118 Chlorine Hydrogen Cyclohexyl The 3-cyano-phenyl
119 Chlorine Hydrogen Cyclohexyl The 4-cyano-phenyl
120 Chlorine Hydrogen Cyclohexyl The 2-pyridyl
121 Chlorine Hydrogen Cyclohexyl The 3-pyridyl
122 Chlorine Hydrogen Cyclohexyl The 4-pyridyl
123 Chlorine Hydrogen Cyclohexyl 2-chloro-5-pyridyl
124 Chlorine Hydrogen Cyclohexyl Phenyl
125 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2-chloro-phenyl-
126 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 3-chloro-phenyl-
127 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 4-chloro-phenyl-
128 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2-bromophenyl
129 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 3-bromophenyl
130 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 4-bromophenyl
131 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2-fluorophenyl
132 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 3-fluorophenyl
133 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 4-fluorophenyl
134 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2-aminomethyl phenyl
135 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 3-aminomethyl phenyl
136 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 4-aminomethyl phenyl
137 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2-p-methoxy-phenyl
138 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 3-p-methoxy-phenyl
139 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 4-p-methoxy-phenyl
140 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2-trifluoromethyl
141 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 3-trifluoromethyl
142 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 4-trifluoromethyl
143 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2-nitrophenyl
144 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 3-nitrophenyl
145 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 4-nitrophenyl
146 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2,4 dichloro benzene base
147 Chlorine Methyl 1-chloro-2-methylpropane-2-base 2,3,4,5, the 6-pentafluorophenyl group
148 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2-cyano-phenyl
149 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 3-cyano-phenyl
150 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 4-cyano-phenyl
151 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 2-pyridyl
152 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 3-pyridyl
153 Chlorine Methyl 1-chloro-2-methylpropane-2-base The 4-pyridyl
154 Chlorine Methyl 1-chloro-2-methylpropane-2-base 2-chloro-5-pyridyl
155 Chlorine Methyl 1-chloro-2-methylpropane-2-base Phenyl
156 Chlorine Methyl The tertiary butyl The 2-chloro-phenyl-
157 Chlorine Methyl The tertiary butyl The 3-chloro-phenyl-
158 Chlorine Methyl The tertiary butyl The 4-chloro-phenyl-
159 Chlorine Methyl The tertiary butyl The 2-bromophenyl
160 Chlorine Methyl The tertiary butyl The 3-bromophenyl
161 Chlorine Methyl The tertiary butyl The 4-bromophenyl
162 Chlorine Methyl The tertiary butyl The 2-fluorophenyl
163 Chlorine Methyl The tertiary butyl The 3-fluorophenyl
164 Chlorine Methyl The tertiary butyl The 4-fluorophenyl
165 Chlorine Methyl The tertiary butyl The 2-aminomethyl phenyl
166 Chlorine Methyl The tertiary butyl The 3-aminomethyl phenyl
167 Chlorine Methyl The tertiary butyl The 4-aminomethyl phenyl
168 Chlorine Methyl The tertiary butyl The 2-p-methoxy-phenyl
169 Chlorine Methyl The tertiary butyl The 3-p-methoxy-phenyl
170 Chlorine Methyl The tertiary butyl The 4-p-methoxy-phenyl
171 Chlorine Methyl The tertiary butyl The 2-trifluoromethyl
172 Chlorine Methyl The tertiary butyl The 3-trifluoromethyl
173 Chlorine Methyl The tertiary butyl The 4-trifluoromethyl
174 Chlorine Methyl The tertiary butyl The 2-nitrophenyl
175 Chlorine Methyl The tertiary butyl The 3-nitrophenyl
176 Chlorine Methyl The tertiary butyl The 4-nitrophenyl
177 Chlorine Methyl The tertiary butyl The 2,4 dichloro benzene base
178 Chlorine Methyl The tertiary butyl 2,3,4,5, the 6-pentafluorophenyl group
179 Chlorine Methyl The tertiary butyl The 2-cyano-phenyl
180 Chlorine Methyl The tertiary butyl The 3-cyano-phenyl
181 Chlorine Methyl The tertiary butyl The 4-cyano-phenyl
182 Chlorine Methyl The tertiary butyl The 2-pyridyl
183 Chlorine Methyl The tertiary butyl The 3-pyridyl
184 Chlorine Methyl The tertiary butyl The 4-pyridyl
185 Chlorine Methyl The tertiary butyl 2-chloro-5-pyridyl
186 Chlorine Methyl The tertiary butyl Phenyl
187 Chlorine Methyl Neo-pentyl The 2-chloro-phenyl-
188 Chlorine Methyl Neo-pentyl The 3-chloro-phenyl-
189 Chlorine Methyl Neo-pentyl The 4-chloro-phenyl-
190 Chlorine Methyl Neo-pentyl The 2-bromophenyl
191 Chlorine Methyl Neo-pentyl The 3-bromophenyl
192 Chlorine Methyl Neo-pentyl The 4-bromophenyl
193 Chlorine Methyl Neo-pentyl The 2-fluorophenyl
194 Chlorine Methyl Neo-pentyl The 3-fluorophenyl
195 Chlorine Methyl Neo-pentyl The 4-fluorophenyl
196 Chlorine Methyl Neo-pentyl The 2-aminomethyl phenyl
197 Chlorine Methyl Neo-pentyl The 3-aminomethyl phenyl
198 Chlorine Methyl Neo-pentyl The 4-aminomethyl phenyl
199 Chlorine Methyl Neo-pentyl The 2-p-methoxy-phenyl
200 Chlorine Methyl Neo-pentyl The 3-p-methoxy-phenyl
201 Chlorine Methyl Neo-pentyl The 4-p-methoxy-phenyl
202 Chlorine Methyl Neo-pentyl The 2-trifluoromethyl
203 Chlorine Methyl Neo-pentyl The 3-trifluoromethyl
204 Chlorine Methyl Neo-pentyl The 4-trifluoromethyl
205 Chlorine Methyl Neo-pentyl The 2-nitrophenyl
206 Chlorine Methyl Neo-pentyl The 3-nitrophenyl
207 Chlorine Methyl Neo-pentyl The 4-nitrophenyl
208 Chlorine Methyl Neo-pentyl The 2,4 dichloro benzene base
209 Chlorine Methyl Neo-pentyl 2,3,4,5, the 6-pentafluorophenyl group
210 Chlorine Methyl Neo-pentyl The 2-cyano-phenyl
211 Chlorine Methyl Neo-pentyl The 3-cyano-phenyl
212 Chlorine Methyl Neo-pentyl The 4-cyano-phenyl
213 Chlorine Methyl Neo-pentyl The 2-pyridyl
214 Chlorine Methyl Neo-pentyl The 3-pyridyl
215 Chlorine Methyl Neo-pentyl The 4-pyridyl
216 Chlorine Methyl Neo-pentyl 2-chloro-5-pyridyl
217 Chlorine Methyl Neo-pentyl Phenyl
218 Chlorine Methyl Cyclohexyl The 2-chloro-phenyl-
219 Chlorine Methyl Cyclohexyl The 3-chloro-phenyl-
220 Chlorine Methyl Cyclohexyl The 4-chloro-phenyl-
221 Chlorine Methyl Cyclohexyl The 2-bromophenyl
222 Chlorine Methyl Cyclohexyl The 3-bromophenyl
223 Chlorine Methyl Cyclohexyl The 4-bromophenyl
224 Chlorine Methyl Cyclohexyl The 2-fluorophenyl
225 Chlorine Methyl Cyclohexyl The 3-fluorophenyl
226 Chlorine Methyl Cyclohexyl The 4-fluorophenyl
227 Chlorine Methyl Cyclohexyl The 2-aminomethyl phenyl
228 Chlorine Methyl Cyclohexyl The 3-aminomethyl phenyl
229 Chlorine Methyl Cyclohexyl The 4-aminomethyl phenyl
230 Chlorine Methyl Cyclohexyl The 2-p-methoxy-phenyl
231 Chlorine Methyl Cyclohexyl The 3-p-methoxy-phenyl
232 Chlorine Methyl Cyclohexyl The 4-p-methoxy-phenyl
233 Chlorine Methyl Cyclohexyl The 2-trifluoromethyl
234 Chlorine Methyl Cyclohexyl The 3-trifluoromethyl
235 Chlorine Methyl Cyclohexyl The 4-trifluoromethyl
236 Chlorine Methyl Cyclohexyl The 2-nitrophenyl
237 Chlorine Methyl Cyclohexyl The 3-nitrophenyl
238 Chlorine Methyl Cyclohexyl The 4-nitrophenyl
239 Chlorine Methyl Cyclohexyl The 2,4 dichloro benzene base
240 Chlorine Methyl Cyclohexyl 2,3,4,5, the 6-pentafluorophenyl group
241 Chlorine Methyl Cyclohexyl The 2-cyano-phenyl
242 Chlorine Methyl Cyclohexyl The 3-cyano-phenyl
243 Chlorine Methyl Cyclohexyl The 4-cyano-phenyl
244 Chlorine Methyl Cyclohexyl The 2-pyridyl
245 Chlorine Methyl Cyclohexyl The 3-pyridyl
246 Chlorine Methyl Cyclohexyl The 4-pyridyl
247 Chlorine Methyl Cyclohexyl 2-chloro-5-pyridyl
248 Chlorine Methyl Cyclohexyl Phenyl
249 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2-chloro-phenyl-
250 Bromine Methyl 1-chloro-2-methylpropane-2-base The 3-chloro-phenyl-
251 Bromine Methyl 1-chloro-2-methylpropane-2-base The 4-chloro-phenyl-
252 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2-bromophenyl
253 Bromine Methyl 1-chloro-2-methylpropane-2-base The 3-bromophenyl
254 Bromine Methyl 1-chloro-2-methylpropane-2-base The 4-bromophenyl
255 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2-fluorophenyl
256 Bromine Methyl 1-chloro-2-methylpropane-2-base The 3-fluorophenyl
257 Bromine Methyl 1-chloro-2-methylpropane-2-base The 4-fluorophenyl
258 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2-aminomethyl phenyl
259 Bromine Methyl 1-chloro-2-methylpropane-2-base The 3-aminomethyl phenyl
260 Bromine Methyl 1-chloro-2-methylpropane-2-base The 4-aminomethyl phenyl
261 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2-p-methoxy-phenyl
262 Bromine Methyl 1-chloro-2-methylpropane-2-base The 3-p-methoxy-phenyl
263 Bromine Methyl 1-chloro-2-methylpropane-2-base The 4-p-methoxy-phenyl
264 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2-trifluoromethyl
265 Bromine Methyl 1-chloro-2-methylpropane-2-base The 3-trifluoromethyl
266 Bromine Methyl 1-chloro-2-methylpropane-2-base The 4-trifluoromethyl
267 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2-nitrophenyl
268 Bromine Methyl 1-chloro-2-methylpropane-2-base The 3-nitrophenyl
269 Bromine Methyl 1-chloro-2-methylpropane-2-base The 4-nitrophenyl
270 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2,4 dichloro benzene base
271 Bromine Methyl 1-chloro-2-methylpropane-2-base 2,3,4,5, the 6-pentafluorophenyl group
272 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2-cyano-phenyl
273 Bromine Methyl 1-chloro-2-methylpropane-2-base The 3-cyano-phenyl
274 Bromine Methyl 1-chloro-2-methylpropane-2-base The 4-cyano-phenyl
275 Bromine Methyl 1-chloro-2-methylpropane-2-base The 2-pyridyl
276 Bromine Methyl 1-chloro-2-methylpropane-2-base The 3-pyridyl
277 Bromine Methyl 1-chloro-2-methylpropane-2-base The 4-pyridyl
278 Bromine Methyl 1-chloro-2-methylpropane-2-base 2-chloro-5-pyridyl
279 Bromine Methyl 1-chloro-2-methylpropane-2-base Phenyl
280 Bromine Methyl The tertiary butyl The 2-chloro-phenyl-
281 Bromine Methyl The tertiary butyl The 3-chloro-phenyl-
282 Bromine Methyl The tertiary butyl The 4-chloro-phenyl-
283 Bromine Methyl The tertiary butyl The 2-bromophenyl
284 Bromine Methyl The tertiary butyl The 3-bromophenyl
285 Bromine Methyl The tertiary butyl The 4-bromophenyl
286 Bromine Methyl The tertiary butyl The 2-fluorophenyl
287 Bromine Methyl The tertiary butyl The 3-fluorophenyl
288 Bromine Methyl The tertiary butyl The 4-fluorophenyl
289 Bromine Methyl The tertiary butyl The 2-aminomethyl phenyl
290 Bromine Methyl The tertiary butyl The 3-aminomethyl phenyl
291 Bromine Methyl The tertiary butyl The 4-aminomethyl phenyl
292 Bromine Methyl The tertiary butyl The 2-p-methoxy-phenyl
293 Bromine Methyl The tertiary butyl The 3-p-methoxy-phenyl
294 Bromine Methyl The tertiary butyl The 4-p-methoxy-phenyl
295 Bromine Methyl The tertiary butyl The 2-trifluoromethyl
296 Bromine Methyl The tertiary butyl The 3-trifluoromethyl
297 Bromine Methyl The tertiary butyl The 4-trifluoromethyl
298 Bromine Methyl The tertiary butyl The 2-nitrophenyl
299 Bromine Methyl The tertiary butyl The 3-nitrophenyl
300 Bromine Methyl The tertiary butyl The 4-nitrophenyl
301 Bromine Methyl The tertiary butyl The 2,4 dichloro benzene base
302 Bromine Methyl The tertiary butyl 2,3,4,5, the 6-pentafluorophenyl group
303 Bromine Methyl The tertiary butyl The 2-cyano-phenyl
304 Bromine Methyl The tertiary butyl The 3-cyano-phenyl
305 Bromine Methyl The tertiary butyl The 4-cyano-phenyl
306 Bromine Methyl The tertiary butyl The 2-pyridyl
307 Bromine Methyl The tertiary butyl The 3-pyridyl
308 Bromine Methyl The tertiary butyl The 4-pyridyl
309 Bromine Methyl The tertiary butyl 2-chloro-5-pyridyl
310 Bromine Methyl The tertiary butyl Phenyl
311 Bromine Methyl Neo-pentyl The 2-chloro-phenyl-
312 Bromine Methyl Neo-pentyl The 3-chloro-phenyl-
313 Bromine Methyl Neo-pentyl The 4-chloro-phenyl-
314 Bromine Methyl Neo-pentyl The 2-bromophenyl
315 Bromine Methyl Neo-pentyl The 3-bromophenyl
316 Bromine Methyl Neo-pentyl The 4-bromophenyl
317 Bromine Methyl Neo-pentyl The 2-fluorophenyl
318 Bromine Methyl Neo-pentyl The 3-fluorophenyl
319 Bromine Methyl Neo-pentyl The 4-fluorophenyl
320 Bromine Methyl Neo-pentyl The 2-aminomethyl phenyl
321 Bromine Methyl Neo-pentyl The 3-aminomethyl phenyl
322 Bromine Methyl Neo-pentyl The 4-aminomethyl phenyl
323 Bromine Methyl Neo-pentyl The 2-p-methoxy-phenyl
324 Bromine Methyl Neo-pentyl The 3-p-methoxy-phenyl
325 Bromine Methyl Neo-pentyl The 4-p-methoxy-phenyl
326 Bromine Methyl Neo-pentyl The 2-trifluoromethyl
327 Bromine Methyl Neo-pentyl The 3-trifluoromethyl
328 Bromine Methyl Neo-pentyl The 4-trifluoromethyl
329 Bromine Methyl Neo-pentyl The 2-nitrophenyl
330 Bromine Methyl Neo-pentyl The 3-nitrophenyl
331 Bromine Methyl Neo-pentyl The 4-nitrophenyl
332 Bromine Methyl Neo-pentyl The 2,4 dichloro benzene base
333 Bromine Methyl Neo-pentyl 2,3,4,5, the 6-pentafluorophenyl group
334 Bromine Methyl Neo-pentyl The 2-cyano-phenyl
335 Bromine Methyl Neo-pentyl The 3-cyano-phenyl
336 Bromine Methyl Neo-pentyl The 4-cyano-phenyl
337 Bromine Methyl Neo-pentyl The 2-pyridyl
338 Bromine Methyl Neo-pentyl The 3-pyridyl
339 Bromine Methyl Neo-pentyl The 4-pyridyl
340 Bromine Methyl Neo-pentyl 2-chloro-5-pyridyl
341 Bromine Methyl Neo-pentyl Phenyl
342 Bromine Methyl Cyclohexyl The 2-chloro-phenyl-
343 Bromine Methyl Cyclohexyl The 3-chloro-phenyl-
344 Bromine Methyl Cyclohexyl The 4-chloro-phenyl-
345 Bromine Methyl Cyclohexyl The 2-bromophenyl
346 Bromine Methyl Cyclohexyl The 3-bromophenyl
347 Bromine Methyl Cyclohexyl The 4-bromophenyl
348 Bromine Methyl Cyclohexyl The 2-fluorophenyl
349 Bromine Methyl Cyclohexyl The 3-fluorophenyl
350 Bromine Methyl Cyclohexyl The 4-fluorophenyl
351 Bromine Methyl Cyclohexyl The 2-aminomethyl phenyl
352 Bromine Methyl Cyclohexyl The 3-aminomethyl phenyl
353 Bromine Methyl Cyclohexyl The 4-aminomethyl phenyl
354 Bromine Methyl Cyclohexyl The 2-p-methoxy-phenyl
355 Bromine Methyl Cyclohexyl The 3-p-methoxy-phenyl
356 Bromine Methyl Cyclohexyl The 4-p-methoxy-phenyl
357 Bromine Methyl Cyclohexyl The 2-trifluoromethyl
358 Bromine Methyl Cyclohexyl The 3-trifluoromethyl
359 Bromine Methyl Cyclohexyl The 4-trifluoromethyl
360 Bromine Methyl Cyclohexyl The 2-nitrophenyl
361 Bromine Methyl Cyclohexyl The 3-nitrophenyl
362 Bromine Methyl Cyclohexyl The 4-nitrophenyl
363 Bromine Methyl Cyclohexyl The 2,4 dichloro benzene base
364 Bromine Methyl Cyclohexyl 2,3,4,5, the 6-pentafluorophenyl group
365 Bromine Methyl Cyclohexyl The 2-cyano-phenyl
366 Bromine Methyl Cyclohexyl The 3-cyano-phenyl
367 Bromine Methyl Cyclohexyl The 4-cyano-phenyl
368 Bromine Methyl Cyclohexyl The 2-pyridyl
369 Bromine Methyl Cyclohexyl The 3-pyridyl
370 Bromine Methyl Cyclohexyl The 4-pyridyl
371 Bromine Methyl Cyclohexyl 2-chloro-5-pyridyl
372 Bromine Methyl Cyclohexyl Phenyl
373 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2-chloro-phenyl-
374 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 3-chloro-phenyl-
375 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 4-chloro-phenyl-
376 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2-bromophenyl
377 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 3-bromophenyl
378 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 4-bromophenyl
379 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2-fluorophenyl
380 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 3-fluorophenyl
381 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 4-fluorophenyl
382 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2-aminomethyl phenyl
383 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 3-aminomethyl phenyl
384 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 4-aminomethyl phenyl
385 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2-p-methoxy-phenyl
386 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 3-p-methoxy-phenyl
387 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 4-p-methoxy-phenyl
388 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2-trifluoromethyl
389 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 3-trifluoromethyl
390 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 4-trifluoromethyl
391 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2-nitrophenyl
392 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 3-nitrophenyl
393 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 4-nitrophenyl
394 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2,4 dichloro benzene base
395 Hydrogen Methyl 1-chloro-2-methylpropane-2-base 2,3,4,5, the 6-pentafluorophenyl group
396 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2-cyano-phenyl
397 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 3-cyano-phenyl
398 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 4-cyano-phenyl
399 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 2-pyridyl
400 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 3-pyridyl
401 Hydrogen Methyl 1-chloro-2-methylpropane-2-base The 4-pyridyl
402 Hydrogen Methyl 1-chloro-2-methylpropane-2-base 2-chloro-5-pyridyl
403 Hydrogen Methyl 1-chloro-2-methylpropane-2-base Phenyl
404 Hydrogen Methyl The tertiary butyl The 2-chloro-phenyl-
405 Hydrogen Methyl The tertiary butyl The 3-chloro-phenyl-
406 Hydrogen Methyl The tertiary butyl The 4-chloro-phenyl-
407 Hydrogen Methyl The tertiary butyl The 2-bromophenyl
408 Hydrogen Methyl The tertiary butyl The 3-bromophenyl
409 Hydrogen Methyl The tertiary butyl The 4-bromophenyl
410 Hydrogen Methyl The tertiary butyl The 2-fluorophenyl
411 Hydrogen Methyl The tertiary butyl The 3-fluorophenyl
412 Hydrogen Methyl The tertiary butyl The 4-fluorophenyl
413 Hydrogen Methyl The tertiary butyl The 2-aminomethyl phenyl
414 Hydrogen Methyl The tertiary butyl The 3-aminomethyl phenyl
415 Hydrogen Methyl The tertiary butyl The 4-aminomethyl phenyl
416 Hydrogen Methyl The tertiary butyl The 2-p-methoxy-phenyl
417 Hydrogen Methyl The tertiary butyl The 3-p-methoxy-phenyl
418 Hydrogen Methyl The tertiary butyl The 4-p-methoxy-phenyl
419 Hydrogen Methyl The tertiary butyl The 2-trifluoromethyl
420 Hydrogen Methyl The tertiary butyl The 3-trifluoromethyl
421 Hydrogen Methyl The tertiary butyl The 4-trifluoromethyl
422 Hydrogen Methyl The tertiary butyl The 2-nitrophenyl
423 Hydrogen Methyl The tertiary butyl The 3-nitrophenyl
424 Hydrogen Methyl The tertiary butyl The 4-nitrophenyl
425 Hydrogen Methyl The tertiary butyl The 2,4 dichloro benzene base
426 Hydrogen Methyl The tertiary butyl 2,3,4,5, the 6-pentafluorophenyl group
427 Hydrogen Methyl The tertiary butyl The 2-cyano-phenyl
428 Hydrogen Methyl The tertiary butyl The 3-cyano-phenyl
429 Hydrogen Methyl The tertiary butyl The 4-cyano-phenyl
430 Hydrogen Methyl The tertiary butyl The 2-pyridyl
431 Hydrogen Methyl The tertiary butyl The 3-pyridyl
432 Hydrogen Methyl The tertiary butyl The 4-pyridyl
433 Hydrogen Methyl The tertiary butyl 2-chloro-5-pyridyl
434 Hydrogen Methyl The tertiary butyl Phenyl
435 Hydrogen Methyl Neo-pentyl The 2-chloro-phenyl-
436 Hydrogen Methyl Neo-pentyl The 3-chloro-phenyl-
437 Hydrogen Methyl Neo-pentyl The 4-chloro-phenyl-
438 Hydrogen Methyl Neo-pentyl The 2-bromophenyl
439 Hydrogen Methyl Neo-pentyl The 3-bromophenyl
440 Hydrogen Methyl Neo-pentyl The 4-bromophenyl
441 Hydrogen Methyl Neo-pentyl The 2-fluorophenyl
442 Hydrogen Methyl Neo-pentyl The 3-fluorophenyl
443 Hydrogen Methyl Neo-pentyl The 4-fluorophenyl
444 Hydrogen Methyl Neo-pentyl The 2-aminomethyl phenyl
445 Hydrogen Methyl Neo-pentyl The 3-aminomethyl phenyl
446 Hydrogen Methyl Neo-pentyl The 4-aminomethyl phenyl
447 Hydrogen Methyl Neo-pentyl The 2-p-methoxy-phenyl
448 Hydrogen Methyl Neo-pentyl The 3-p-methoxy-phenyl
449 Hydrogen Methyl Neo-pentyl The 4-p-methoxy-phenyl
450 Hydrogen Methyl Neo-pentyl The 2-trifluoromethyl
451 Hydrogen Methyl Neo-pentyl The 3-trifluoromethyl
452 Hydrogen Methyl Neo-pentyl The 4-trifluoromethyl
453 Hydrogen Methyl Neo-pentyl The 2-nitrophenyl
454 Hydrogen Methyl Neo-pentyl The 3-nitrophenyl
455 Hydrogen Methyl Neo-pentyl The 4-nitrophenyl
456 Hydrogen Methyl Neo-pentyl The 2,4 dichloro benzene base
457 Hydrogen Methyl Neo-pentyl 2,3,4,5, the 6-pentafluorophenyl group
458 Hydrogen Methyl Neo-pentyl The 2-cyano-phenyl
459 Hydrogen Methyl Neo-pentyl The 3-cyano-phenyl
460 Hydrogen Methyl Neo-pentyl The 4-cyano-phenyl
461 Hydrogen Methyl Neo-pentyl The 2-pyridyl
462 Hydrogen Methyl Neo-pentyl The 3-pyridyl
463 Hydrogen Methyl Neo-pentyl The 4-pyridyl
464 Hydrogen Methyl Neo-pentyl 2-chloro-5-pyridyl
465 Hydrogen Methyl Neo-pentyl Phenyl
466 Hydrogen Methyl Cyclohexyl The 2-chloro-phenyl-
467 Hydrogen Methyl Cyclohexyl The 3-chloro-phenyl-
468 Hydrogen Methyl Cyclohexyl The 4-chloro-phenyl-
469 Hydrogen Methyl Cyclohexyl The 2-bromophenyl
470 Hydrogen Methyl Cyclohexyl The 3-bromophenyl
471 Hydrogen Methyl Cyclohexyl The 4-bromophenyl
472 Hydrogen Methyl Cyclohexyl The 2-fluorophenyl
473 Hydrogen Methyl Cyclohexyl The 3-fluorophenyl
474 Hydrogen Methyl Cyclohexyl The 4-fluorophenyl
475 Hydrogen Methyl Cyclohexyl The 2-aminomethyl phenyl
476 Hydrogen Methyl Cyclohexyl The 3-aminomethyl phenyl
477 Hydrogen Methyl Cyclohexyl The 4-aminomethyl phenyl
478 Hydrogen Methyl Cyclohexyl The 2-p-methoxy-phenyl
479 Hydrogen Methyl Cyclohexyl The 3-p-methoxy-phenyl
480 Hydrogen Methyl Cyclohexyl The 4-p-methoxy-phenyl
481 Hydrogen Methyl Cyclohexyl The 2-trifluoromethyl
482 Hydrogen Methyl Cyclohexyl The 3-trifluoromethyl
483 Hydrogen Methyl Cyclohexyl The 4-trifluoromethyl
484 Hydrogen Methyl Cyclohexyl The 2-nitrophenyl
485 Hydrogen Methyl Cyclohexyl The 3-nitrophenyl
486 Hydrogen Methyl Cyclohexyl The 4-nitrophenyl
487 Hydrogen Methyl Cyclohexyl The 2,4 dichloro benzene base
488 Hydrogen Methyl Cyclohexyl 2,3,4,5, the 6-pentafluorophenyl group
489 Hydrogen Methyl Cyclohexyl The 2-cyano-phenyl
490 Hydrogen Methyl Cyclohexyl The 3-cyano-phenyl
491 Hydrogen Methyl Cyclohexyl The 4-cyano-phenyl
492 Hydrogen Methyl Cyclohexyl The 2-pyridyl
493 Hydrogen Methyl Cyclohexyl The 3-pyridyl
494 Hydrogen Methyl Cyclohexyl The 4-pyridyl
495 Hydrogen Methyl Cyclohexyl 2-chloro-5-pyridyl
496 Hydrogen Methyl Cyclohexyl Phenyl
The fusing point of above-mentioned part of compounds and nuclear-magnetism detected result are as follows:
Compound 1 3-chloro-N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl) phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 11.27 (s, 1H, NH), 10.35 (d, J=2.1Hz, 1H, NH), 8.45 (d; J=3.0Hz, 1H, ArH), 7.61 (d, J=0.8Hz, 1H, ArH), 7.47-7.51 (dd; JJ1=3.0Hz, J2=0.8Hz, 1H, ArH), 7.34-7.39 (m, 2H, ArH), 7.06-7.13 (m; 2H, ArH), 5.75 (s, 1H, NH), 4.07 (s, 2H, CH 2), 3.77 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.29 (s, 6H, CH 3) fusing point: 187.3-188.4 ℃.
Compound 73-chloro-N-(4-chloro-2-(2-(2-luorobenzyl) hydrazine carbonyl) phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.87 (d, J=2.0Hz, 1H, NH), 9.28 (s, 1H, NH), 8.08 (d, J=0.7Hz, 1H, ArH), 7.13-7.55 (m, 6H, ArH), 5.44 (d, J=2.0Hz, 1H, NH), 4.00 (d, J=2.0Hz, 2H, CH 2), 3.77 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 1.28 (s, 6H, CH 3) fusing point: 207.5-208.3 ℃.
Compound 9 3-chloro-N-(4-chloro-2-(2-(4-luorobenzyl) hydrazine carbonyl) phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.83 (d, J=2.0Hz, 1H, NH), 9.30 (s, 1H, NH), 7.12-7.58 (m, 6H, ArH), 5.42 (d, J=1.0Hz, 1H, NH), 3.94 (d, J=2.0Hz, 2H, CH 2), 3.80 (s, 2H, CH 2), 2.19 (s, 3H, CH 3), 1.30 (s, 6H, CH 3) fusing point: 195.6-195.8 ℃.
Compound 17 3-chloro-N-(4-chloro-2-(2-(3-trifluoromethyl benzyl) hydrazine carbonyl) phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 11.27 (s, 1H, NH), 10.36 (s, 1H, NH), 8.47 (d, J=3.0Hz, 1H, ArH), 7.75 (s, 1H, ArH), 7.49-7.68 (m, 5H, ArH), 5.93 (s, 1H, NH), 4.08 (s, 2H, CH 2), 3.73 (s, 2H, CH 2), 1.10 (s, 6H, CH 3) fusing point: 179.1-179.8 ℃.
Compound 30 3-chloro-N-(4-chloro-2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl) phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.77 (d, J=1.7Hz, 1H, NH), 9.25 (s, 1H, NH), 8.39 (d; J=0.6Hz, 1H, ArH), 7.84-7.88 (dd, J1=2.7Hz, J2=0.8Hz, 1H, ArH), 7.64 (d; J=2.7Hz, 1H, ArH), 7.46-7.49 (m, 2H, Ar), 7.17-7.21 (dd, J1=3.1Hz, J2=0.7Hz; 1H, ArH), 5.63 (m, 1H, NH), 3.96 (d, J=1Hz, 2H, CH 2), 3.78 (s, 2H, CH 2), 1.28 (s, 6H, CH 3) fusing point: 188.3-188.5 ℃.
Compound 31 N-(2-(2-benzyl hydrazine carbonyl)-4-chloro-phenyl-)-3-chloro-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.86 (d, J=2.0Hz, 1H, NH), 9.30 (s, 1H; NH), 7.85 (d, J=0.8Hz, 1H, ArH), 7.45-7.47 (dd, J1=0.8Hz; J2=0.2Hz, 1H, ArH), 7.22-7.36 (m, 5H, ArH), 5.34-5.39 (m; 1H, NH), 3.94 (d, J=1.6Hz, 2H, CH 2), 3.78 (s, 2H, CH 2), 1.29 (s, 6H, CH 3) fusing point: 190.4-190.9 ℃.
Compound 32 N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl) phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 11.27 (s, 1H, NH), 10.36 (d, J=2.1Hz, 1H, NH), 8.45 (d, J=3.0Hz; 1H, ArH), 7.61-7.64 (m, 1H, ArH), 7.40-7.43 (m, 1H, ArH), 7.19-7.35 (m; 5H, ArH), 5.47 (s, 1H, NH), 3.93 (d, J=1.7Hz, 2H, CH 2), 1.16 (s, 9H, CH 3) fusing point: 157.1-157.8 ℃.
Compound 40 N-(4-chloro-2-(2-(4-luorobenzyl) hydrazine carbonyl) phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 11.25 (s, 1H, NH), 10.33 (d, J=6.3Hz, 1H, NH), 8.42 (d, J=9.0Hz; 1H, ArH), 7.58 (d, J=2.4Hz, 1H, ArH), 7.47 (dd, J=9.0,2.4Hz, 1H; ArH), 7.35 (dd, J=8.4,5.8Hz, 2H, ArH), 7.07 (t, J=8.8Hz, 2H; ArH), 5.71 (q, J=5.6Hz, 1H, NH), 3.90 (d, J=5.1Hz, 2H, CH 2), 1.13 (s, 9H, CH 3) fusing point: 143.7-144.9 ℃.
Compound 48 N-(4-chloro-2-(2-(3-trifluoromethyl benzyl) hydrazine carbonyl) phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 11.29 (s, 1H, NH), 10.38 (s, 1H, NH), 8.58 (d, J=3.0Hz, 1H, ArH), 7.77 (s, 1H, ArH), 7.51-7.70 (m, 5H, ArH), 5.94 (s, 1H, NH), 4.10 (s, 2H, CH 2), 1.20 (s, 9H, CH 3) fusing point: 152.4-154.8 ℃.
Compound 61 N-(4-chloro-2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl) phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.72 (d, J=2.1Hz, 1H, NH), 9.07 (s, 1H, NH), 8.38 (d; J=0.7Hz, 1H, ArH), 8.16 (d, J=2.9Hz, 1H, ArH), 7.84 (d, J=0.7Hz; 1H, ArH), 7.43-7.47 (m, 2H, ArH), 7.17-7.20 (dd, J1=2.1, J2=0.8Hz, 1H; ArH), and 5.62-5.68 (m, 1H, NH), 3.94 (d, J=1.5Hz, 2H, CH 2), 1.17 (s, 9H, CH 3) fusing point: 150.2-150.8 ℃.
Compound 69 N-(4-chloro-2-(2-(2-luorobenzyl) hydrazine carbonyl) phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 10.74 (s, 1H, NH), 10.35 (d, J=1.4Hz, 1H, NH2); 8.34 (d, J=3.0Hz, 1H, ArH), 7.61 (d, J=0.8Hz, 1H; ArH), and 7.49-7.55 (m, 2H, ArH), 7.14-7.20 (m, 3H, ArH); 4.04 (d, J=1.4Hz, 1H, NH), 2.17 (s, 2H, CH 2), 1.02 (s, 9H, CH 3) fusing point: 147.9-149.1 ℃.
Compound 71 N-(4-chloro-2-(2-(4-luorobenzyl) hydrazine carbonyl) phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, CHLOROFORM) δ 8.22 (d, J=0.9Hz, 1H, NH), 7.61-7.70 (m, 2H, ArH), 7.36-7.42 (m, 2H, ArH), 7.03-7.11 (m, 2H, ArH), 5.61-5.66 (m, 1H, NH), 4.03 (s, 2H, CH 2), 2.30-3.40 (s, 2H, CH 2), 1.07 (s, 9H, CH 3) fusing point: 132.1-133.1 ℃.
Compound 92 N-(4-chloro-2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl) phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.72 (d, J=2.1Hz, 1H, NH), 9.07 (s, 1H, NH), 8.38 (d; J=0.7Hz, 1H, ArH), 8.16 (d, J=2.9Hz, 1H, ArH), 7.84 (d, J=0.7Hz; 1H, ArH), 7.43-7.47 (m, 2H, ArH), 7.17-7.20 (dd, J1=2.1, J2=0.8Hz; 1H, ArH), 5.62-5.68 (m, 1H, NH), 4.65 (s, 2H, CH 2), 1.99 (s, 2H, CH 2), 0.97 (s, 9H, CH 3) fusing point: 159.5-161.3 ℃.
Compound 93 N-(2-(2-benzyl hydrazine carbonyl)-4-chloro-phenyl-)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.85 (d, J=2.0Hz, 1H, NH), 9.29 (s, 1H; NH), 7.84 (d, J=0.8Hz, 1H, ArH), 7.44-7.46 (dd, J1=0.8Hz; J2=0.2Hz, 1H, ArH), 7.21-7.35 (m, 5H, ArH), 5.33-5.38 (m; 1H, NH), 3.93 (d, J=1.6Hz, 2H, CH 2), 1.71 (s, 2H, CH 2), 1.28 (s, 9H, CH 3) fusing point: 147.6-149.1 ℃.
Compound 124 N-(2-(2-benzyl hydrazine carbonyl)-4-chloro-phenyl-) cyclohexanecarbonyl chloride
1H NMR (300MHz, DMSO) δ 11.12 (s, 1H, NH), 1.35 (s, 1H, NH), 8.54 (d; J=3.0Hz, 1H, ArH), 7.92 (d, J=0.8Hz, 1H, ArH), 7.62-7.66 (dd; J1=3.0Hz, J2=0.9Hz, 1H, ArH), 7.46 (s, 1H, ArH), 7.30-7.39 (m; 4H, ArH), 5.69 (s, 1H, NH), 3.94 (s, 2H, CH 2), 2.30-2.32 (m, 1H, CH), 1.63-1.93 (m, 10H, CH 2) fusing point: 216.3-217.9 ℃.
Compound 125 3-chloro-N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.91 (s, 1H, NH), 9.29 (s, 1H, NH), 7.61 (dd, J=7.2,2.2Hz, 1H, ArH), 7.44 (m, 2H, ArH), 7.32 (m, 2H, ArH), 7.26 (m, 1H, ArH), 5.54 (s, 1H, NH), 4.07 (s, 2H, CH 2), 3.77 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.28 (s, 6H, CH 3) fusing point: 188.2-190.0 ℃.
Compound 131 3-chloro-N-(4-chloro-2-(2-(2-luorobenzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-2,2-dimethyl propylene acid amides 1H NMR (300MHz, DMSO) δ 9.87 (d, J=7.0Hz, 1H, NH), 9.28 (s, 1H, NH); 7.52 (m, 1H, ArH), 7.46 (dd, J=2.4,0.5Hz, 1H, ArH), 7.32 (m; 1H, ArH), 7.24 (d, J=2.4Hz, 1H, ArH), 7.16 (m, 2H; ArH), 5.44 (d, J=7.0Hz, 1H, NH), 4.00 (s, 2H, CH 2), 3.77 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 1.28 (s, 6H, CH 3) fusing point: 200.3-201.4 ℃.
Compound 133 3-chloro-N-(4-chloro-2-(2-(4-luorobenzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.81 (d, J=5.1Hz, 1H, NH), 9.28 (s, 1H, NH); 7.46 (d, J=2.5Hz, 1H, ArH), 7.40 (m, 2H, ArH), 7.22 (d; J=2.5Hz, 1H, ArH), 7.14 (m, 2H, ArH), 5.40 (d; J=4.8Hz, 1H, NH), 3.92 (d, J=3.8Hz, 2H, CH 2), 3.78 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.28 (s, 6H, CH 3) fusing point: 186.5-186.7 ℃.
Compound 141 3-chloro-N-(4-chloro-2-(2-(3-trifluoromethyl benzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.82 (d, J=6.3Hz, 1H, NH), 9.27 (s, 1H, NH), 7.74 (s; 1H, ArH), 7.68 (d, J=7.3Hz, 1H, ArH), 7.58 (m, 2H, ArH); 7.46 (dd, J=2.5,0.6Hz, 1H, ArH), 7.18 (dd, J=2.5,0.4Hz, 1H); 5.61 (dd, J=10.9,4.8Hz, 1H, NH), 4.03 (d, J=4.7Hz, 2H, CH 2), 3.78 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.28 (s, 6H, CH 3) fusing point: 192.4-192.9 ℃.
Compound 146 3-chloro-N-(4-chloro-2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-2,2-dimethyl propylene acid amides
1HNMR (300MHz, DMSO) δ 9.86 (d, J=6.0Hz, 1H, NH), 9.26 (s, 1H, NH), 7.65 (d; J=8.3Hz, 1H, ArH), 7.58 (d, J=2.1Hz, 1H, ArH), 7.46 (d, J=2.2Hz; 1H, ArH), 7.41 (dd, J=8.3,2.2Hz, 1H), 7.25 (d, J=2.5Hz, 1H); 5.59 (dd, J=5.0Hz, 5.0Hz, 1H, NH), 4.03 (t, J=3.9Hz, 2H, CH 2), 3.77 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.27 (s, 6H, CH 3) fusing point: 187.7-190.8 ℃.
Compound 154 3-chloro-N-(4-chloro-2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl)-6-aminomethyl phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.77 (d, J=5.1Hz, 1H, NH), 9.25 (s, 1H, NH), 8.39 (d, J=2.0Hz; 1H, ArH), 7.86 (dd, J=8.2,2.5Hz, 1H, ArH), 7.47 (dd, J=5.9,0.5Hz; 1H, ArH), 7.46 (s, 1H, ArH), 7.20 (d, J=2.3Hz, 1H, ArH); 5.63 (dd, J=10.2,4.8Hz, 1H, NH), 3.95 (d, J=2.8Hz, 2H, CH 2), 3.78 (s, 2H, CH 2CH 2), 2.17 (s, 3H, CH 3), 1.28 (s, 6H, CH 3) fusing point: 183.7-185.3 ℃.
Compound 155 N-(2-(2-benzyl hydrazine carbonyl)-4-chloro-6-aminomethyl phenyl)-3-chloro-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.85 (d, J=6.1Hz, 1H, NH), 9.30 (s, 1H, NH), 7.46 (dd; J=2.5,0.6Hz, 1H, ArH), 7.35 (m, 4H, ArH), 7.27 (m; 1H, ArH), 7.23 (dd, J=2.5,0.4Hz, 1H, ArH), 5.37 (dd; J=10.1,5.2Hz, 1H, NH), 3.94 (d, J=4.5Hz, 2H, CH 2), 3.78 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.29 (s, 6H, CH 3) fusing point: 170.1-171.3 ℃.
Compound 156 N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.87 (d, J=5.5Hz, 1H, NH), 9.14 (s, 1H, NH); 7.61 (dd, J=7.1,2.2Hz, 1H, ArH), 7.43 (m, 2H, ArH); 7.31 (m, 2H, ArH), 7.26 (d, J=2.4Hz, 1H, ArH), 5.58 (d; J=5.7Hz, 1H, NH), 4.07 (d, J=4.1Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.20 (d, J=4.1Hz, 9H, CH 3) fusing point: 198.3-199.3 ℃.
Compound 162 N-(4-chloro-2-(2-(2-luorobenzyl) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 1H NMR (300MHz, DMSO) δ 9.86 (d, J=5.3Hz, 1H, NH), 9.14 (s, 1H; NH), 7.53 (td, J=7.8,1.8Hz, 1H, ArH), 7.44 (d, J=2.4Hz; 1H, ArH), 7.29 (m, 2H, ArH), 7.15 (m, 2H, ArH); 5.49 (d, J=5.3Hz, 1H, NH), 4.02 (d, J=2.8Hz, 2H, CH 2), 2.14 (s, 3H, CH 3), 1.20 (d, J=4.3Hz, 9H, CH 3) fusing point: 150.2-151.2 ℃.
Compound 164 N-(4-chloro-2-(2-(4-luorobenzyl) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.78 (d, J=6.5Hz, 1H, NH), 9.12 (s, 1H, NH); 7.44 (d, J=2.4Hz, 1H, ArH), 7.39 (m, 2H, ArH), 7.22 (d; J=2.4Hz, 1H, ArH), 7.14 (m, 2H, ArH), 5.45 (q; J=5.2Hz, 1H, NH), 3.92 (d, J=5.0Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.20 (s, 9H, CH 3) fusing point: 196.0-196.2 ℃.
Compound 172 N-(4-chloro-2-(2-(3-trifluoromethyl) benzyl) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.72 (d, J=2.1,1H, NH), 9.17 (s, 1H, NH), 7.64 (s; 1H, ArH), 7.43-7.57 (m, 3H, ArH), 7.35 (m, 1H, ArH), 7.07-7.08 (m; 1H, ArH), 5.48-5.53 (m, 1H, NH), 3.93 (d, J=1.6Hz, 2H, CH 2), 2.06 (s, 3H, CH 3), 1.18 (s, 9H, CH 3) fusing point: 157.5-158.1 ℃.
Compound 177 N-(4-chloro-2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.83 (s, 1H, NH), 9.10 (s, 1H, NH), 7.65 (d; J=8.3Hz, 1H, ArH), 7.57 (d, J=2.1Hz, 1H, ArH), 7.44 (m; 1H, ArH), 7.40 (dd, J=8.3,2.2Hz, 1H, ArH), 7.25 (d; J=2.5Hz, 1H), 5.63 (s, 1H, NH), 4.04 (s, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.18 (s, 9H, CH 3) fusing point: 206.2-207.5
Compound 185 N-(4-chloro-2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.73 (d, J=6.3Hz, 1H, NH), 9.08 (s, 1H, NH), 8.39 (d, J=2.3Hz; 1H, ArH), 7.86 (dd, J=8.2,2.5Hz, 1H, ArH), 7.46 (d, J=8.2; 2H, ArH), 7.44 (s, 1H, ArH), 7.20 (d, J=2.5Hz, 1H, ArH); 5.66 (dd, J=10.9,4.6Hz, 1H, NH), 3.95 (d, J=4.5Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.19 (s, 9H, CH 3) fusing point: 191.4-192.8 ℃.
Compound 186 N-(2-(2-benzyl hydrazine carbonyl)-4-chloro-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.80 (d, J=3.7Hz, 1H, NH), 9.13 (s, 1H, NH), 7.44 (d, J=2.1Hz, 1H, ArH), 7.34 (m, 4H, ArH), 7.25 (m, 2H, ArH), 5.40 (d, J=4.9Hz, 1H, NH), 3.94 (s, 2H, CH 2CH 2), 2.13 (s, 3H, CH 3), 1.23 (s, 9H, CH 3) fusing point: 170.1-171.3 ℃.
Compound 187 N-(4-chloro-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.84 (s, 1H, NH), 9.28 (s, 1H, NH), 7.62 (dd, J=7.1,2.2Hz, 1H, ArH), 7.42 (m, 2H, ArH), 7.31 (m, 2H, ArH), 7.20 (d, J=2.5Hz, 1H, ArH), 5.47 (s, 1H, NH), 4.06 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 2.08 (s, 2H, CH 2), 1.00 (s, 9H, CH 3) fusing point: 152.9-153.7 ℃.
Compound 193 N-(4-chloro-2-(2-(2-luorobenzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.81 (s, 1H, NH), 9.27 (s, 1H, NH), 7.53 (m, 1H, ArH), 7.44 (d, J=2.5Hz, 1H, ArH), 7.32 (m, 1H, ArH), 7.16 (m, 3H, ArH), 5.36 (s, 1H, NH), 4.00 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 2.11 (s, 2H, CH 2), 1.01 (s, 9H, CH 3) fusing point: 196.8-198.3 ℃.
Compound 203 N-(4-chloro-2-(2-(3-trifluoromethyl benzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1HNMR (300MHz, DMSO) δ 9.30 (s, 1H, NH), 7.67 (m, 4H, ArH), 7.36 (d, J=2.4Hz, 1H, ArH), 7.26 (d, J=2.4Hz, 1H, ArH), 4.73 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 1.99 (s, 2H, CH 2), 0.97 (s, 9H, CH 3) fusing point: 165.6-165.7 ℃.
Compound 208 N-(4-chloro-2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.78 (s, 1H, NH), 9.25 (s, 1H, NH), 7.67 (d, J=8.3Hz; 1H, ArH), 7.57 (d, J=2.1Hz, 1H, ArH), 7.43 (d, J=2.4Hz, 1H; ArH), 7.40 (dd, J=8.3,2.2Hz, 1H, ArH), 7.19 (d, J=2.4Hz; 1H, ArH), 5.53 (s, 1H, NH), 4.03 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 2.04 (s, 2H, CH 2), 1.00 (s, 9H, CH 3) fusing point: 177.1-177.5 ℃.
Compound 217 N-(2-(2-benzyl hydrazine carbonyl)-4-chloro-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.77 (s, 1H, NH), 9.26 (s, 1H, NH), 7.43 (dd, J=2.5,0.5Hz; 1H, ArH), 7.34 (m, 4H, ArH), 7.26 (m, 1H, ArH), 7.16 (dd, J=2.5; 0.5Hz, 1H, ArH), 5.27 (s, 1H, NH), 3.94 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 2.12 (s, 2H, CH 2), 1.02 (s, 9H, CH 3) fusing point: 179.1-183.0 ℃.
Compound 234 N-(4-chloro-2-(2-(3-trifluoromethyl benzyl) hydrazine carbonyl)-6-aminomethyl phenyl) cyclohexanecarbonyl amine
1H NMR (300MHz, DMSO) δ 9.70 (d, J=6.2Hz, 1H, NH), 9.24 (s, 1H, NH), 7.74 (s; 1H, ArH), 7.68 (d, J=7.2Hz, 1H, ArH), 7.59 (m, 2H, ArH); 7.42 (d, J=2.4Hz, 1H, ArH), 7.13 (d, J=2.4Hz, 1H, ArH), 5.56 (dd; J=10.9,5.0Hz, 1H, NH), 4.03 (d, J=4.6Hz, 2H, CH 2), 2.28 (m, 1H, CH), 2.13 (s, 3H, CH 3), 1.77 (m, 4H, CH 2), 1.65 (s, 1H, CH 2), 1.27 (m, 5H, CH 2) fusing point: 174.3-175.8 ℃.
Compound 248 N-(2-(2-benzyl hydrazine carbonyl)-4-chloro-6-aminomethyl phenyl) cyclohexanecarbonyl amine
1H NMR (300MHz, DMSO) δ 9.73 (s, 1H, NH), 9.26 (s, 1H, NH), 7.43 (dd, J=2.5,0.6Hz; 1H, ArH), 7.35 (m, 4H, ArH), 7.26 (m, 2H, ArH), 7.17 (dd, J=2.5; 0.4Hz, 1H, ArH), 5.33 (s, 1H, NH), 3.93 (s, 2H, CH 2), 2.29 (m, 1H, CH), 2.12 (s, 3H, CH 3), 1.80 (m, 2H, CH 2), 1.73 (m, 2H, CH 2), 1.63 (m, 1H, CH 2), 1.28 (m, 5H, CH 2) fusing point: 182.6-183.8 ℃.
Compound 249 N-(4-bromo-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-3-chloro-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.91 (s, 1H, NH), 9.29 (s, 1H, NH), 7.58-7.63 (m, 2H, Ar), 7.38-7.43 (m, 2H, Ar), 7.26-7.36 (m, 2H, Ar), 5.53 (s, 1H, NH), 4.07 (s, 2H, CH 2), 3.77 (s, 2H, CH 2), 2.15 (s, 3H, CH 3), 1.28 (s, 6H, CH 3) fusing point: 178.8-179.5 ℃.
Compound 257 N-(4-bromo-2-(2-(4-luorobenzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3-chloro-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.83 (d, J=2.0Hz, 1H, NH), 9.30 (s, 1H, NH), 7.49-7.58 (m, 3H, ArH), 7.12-7.25 (m, 3H, ArH), 5.42 (d, J=1.0Hz, 1H, NH), 3.94 (d, J=2.0Hz, 2H, CH 2), 3.80 (s, 2H, CH 2), 2.19 (s, 3H, CH 3), 1.30 (s, 6H, CH 3) fusing point: 179.2-180.5 ℃.
Compound 265 N-(4-bromo-2-methyl-6-(2-(3-(trifluoromethyl) benzyl) hydrazine carbonyl) phenyl)-3-chloro-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.81 (d, J=1.9Hz, 1H, NH), 9.25 (s, 1H, NH), 7.73 (s, 1H, ArH), 7.52-7.69 (m, 4H, ArH), 7.30 (d, J=0.7Hz, 1H, ArH), 5.56-5.62 (m, 1H, NH), 4.03 (d, J=1.3Hz, 2H, CH 2), 3.78 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.27 (s, 6H, CH 3) fusing point: 181.8-183.3 ℃.
Compound 270 N-(4-bromo-2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3-chloro-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.88 (s, 1H, NH), 9.25 (s, 1H, NH), 7.62 (d, J=2.7Hz; 1H, ArH), 7.57 (d, J=0.2Hz, 1H, ArH), 7.54-7.57 (m, 1H, ArH); 7.34-7.40 (m, 2H, ArH), 5.55 (s, 1H, NH), 4.01 (s, 2H, CH 2), 3.74 (s, 2H, CH 2), 2.14 (s, 3H, CH 3), 1.24 (s, 6H, CH 3) fusing point: 186.1-186.4 ℃.
Compound 278 N-(4-bromo-2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3-chloro-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.77 (d, J=2.1Hz, 1H, NH), 9.25 (s, 1H, NH), 8.38 (d, J=0.6Hz; 1H, ArH), 7.83-7.88 (dd, J1=2.8Hz, J2=0.8Hz, 1H, ArH), 7.58 (d, J=0.7Hz; 1H, ArH), 7.45-7.49 (dd, J1=2.8Hz, J2=0.2Hz, 1H, ArH), 7.32 (d, J=0.7Hz; 1H, ArH), 5.59-5.65 (m, 1H, NH), 3.95 (d, J=1.5Hz, 2H, CH 2), 3.78 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.28 (s, 6H, CH 3) fusing point: 190.4-190.5 ℃.
Compound 279 N-(2-(2-benzyl hydrazine carbonyl)-4-bromo-6-aminomethyl phenyl)-3-chloro-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.85 (s, 1H, NH), 9.29 (s, 1H, NH), 7.59 (s, 1H, ArH), 7.22-7.58 (m, 6H, ArH), 5.35 (s, 1H, NH), 3.94 (s, 2H, CH 2), 3.78 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.28 (s, 6H, CH 3) fusing point: 207.1-207.9 ℃.
Compound 280 N-(4-bromo-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.85 (s, 1H, NH) 9.11 (s, 1H, NH), 7.56-7.62 (m, 2H, Ar), 7.40-7.43 (m, 2H, Ar), 7.25-7.38 (m, 2H, Ar), 5.56 (s, 1H, NH), 4.06 (s, 2H, CH 2), 2.12 (s, 3H, CH 3), 1.19 (s, 9H, CH 3) fusing point: 177.5-178.7 ℃.
Compound 296 N-(4-bromo-2-methyl-6-(2-(3-(trifluoromethyl) benzyl) hydrazine carbonyl) phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.77 (d, J=1.9Hz, 1H, NH), 9.08 (s, 1H, NH), 7.74 (s; 1H, ArH), 7.52-7.69 (m, 4H, ArH), 7.30 (d, J=0.8Hz, 1H, ArH); 5.63 (d, J=1.7Hz, 1H, NH), 4.04 (d, J=1.2Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.19 (s, 9H, CH 3) fusing point: 204.0-205.2 ℃.
Compound 301 N-(4-bromo-2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.82 (d, J=2.0Hz, 1H, NH), 9.09 (s, 1H, NH); 7.64 (d, J=2.8Hz, 1H, ArH), 7.56-7.58 (m, 2H, ArH), 7.42 (d; J=0.7Hz, 1H, ArH), 7.36-7.40 (m, 2H, ArH), 5.59-5.65 (dd, J1=3.6Hz; J2=1.6Hz, 1H, NH), 4.03 (d, J=1.5Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.79 (s, 9H, CH 3) fusing point: 210.7-212.6 ℃.
Compound 309 N-(4-bromo-2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.73 (d, J=2.1Hz, 1H, NH), 9.08 (s, 1H, NH), 8.39 (d; J=0.7Hz, 1H, ArH), 7.84-7.88 (dd, J1=2.9Hz, J2=0.9Hz, 1H, ArH), 7.57 (d; J=0.8Hz, 1H, ArH), 7.45 (d, J=2.8,1H, ArH), 7.32 (d, J=0.8Hz; 1H, ArH), 5.56-5.68 (m, 1H, NH), 3.94 (d, J=1.5Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.18 (s, 9H, CH 3) fusing point: 187.7-187.9 ℃.
Compound 310 N-(2-(2-benzyl hydrazine carbonyl)-4-bromo-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.80 (d, J=1.3Hz, 1H, NH), 9.13 (s, 1H, NH), 7.58 (s, 1H, ArH), 7.22-7.57 (m, 6H, ArH), 7.39 (d, J=1.5Hz, 1H, NH), 3.94 (d, J=0.5Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.20 (s, 9H, CH 3) fusing point: 168.3-169.6 ℃.
Compound 311 N-(4-bromo-2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.85 (s, 1H, NH), 9.27 (s, 1H, NH), 7.61-7.64 (dd; J1=2.4Hz, J2=0.6Hz, Ar), 7.55-7.56 (d, J=0.6Hz, 1H, Ar), 7.40-7.44 (m; 1H, Ar), 7.26-7.36 (m, 3H, Ar), 4.07 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 2.09 (s, 2H, CH 2), 1.00 (s, 9H, CH 3) fusing point: 181.4-181.7 ℃.
Compound 317 N-(4-bromo-2-(2-(2-luorobenzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.82 (s, 1H, NH), 9.28 (s, 1H, NH), 7.13-7.57 (m, 6H, ArH), 5.37 (s, 1H, NH), 4.01 (s, 2H, CH 2), 2.18 (s, 3H, CH 3), 2.12 (s, 2H, CH 2), 1.02 (s, 9H, CH 3) fusing point: 195.6-195.9 ℃.
Compound 327 N-(4-bromo-2-methyl-6-(2-(3-(trifluoromethyl) benzyl) hydrazine carbonyl) phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.73 (d, J=1.4Hz, 1H, NH), 9.24 (s, 1H, NH), 7.74 (s, 1H; ArH), and 7.62-7.70 (m, 1H, ArH), 7.52-7.60 (m, 3H, ArH), 7.24 (d, J=0.7Hz; 1H, ArH), 5.51 (d, J=1.3Hz, 1H, NH), 4.04 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 2.09 (s, 2H, CH 2), 1.01 (s, 9H, CH 3) fusing point: 200.9-202.1 ℃.
Compound 332 N-(4-bromo-2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.85 (d, J=2.0Hz, 1H, NH), 9.12 (s, 1H, NH), 7.59-7.69 (m, 3H, ArH), 7.39-7.45 (m, 2H, ArH), 5.62-5.67 (dd, J1=3.6Hz, J2=1.6Hz, 1H, NH), 4.06 (d, J=1.5Hz, 2H, CH 2), 2.15 (s, 3H, CH 3), 1.61 (s, 2H, CH 2), 1.21 (s, 9H, CH 3) fusing point: 188.8-189.4 ℃.
Compound 340 N-(4-bromo-2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.24 (s, 1H, NH), 8.41 (d, J=0.7,1H, ArH), 7.83-7.87 (dd, J1=2.7Hz, J2=0.8Hz, 1H, ArH), 7.47-7.87 (m, 2H, ArH), 7.38 (d, J=0.7,1H, ArH), 4.65 (s, 2H, CH 2), 2.16 (s, 3H, CH 3), 1.98 (s, 2H, CH 2), 0.97 (s, 3H, CH 3) fusing point: 178.9-180.1
Compound 341 N-(2-(2-benzyl hydrazine carbonyl)-4-bromo-6-aminomethyl phenyl)-3,3-amide dimethyl butyrate ℃.
1H?NMR(300MHz，DMSO)δ9.77(d，J＝1.5Hz，1H，NH)，9.26(s，1H，NH)，7.55-7.57(dd，J1＝0.8Hz，J2＝0.2Hz，1H，ArH)，7.23-7.39(m，6H，ArH)，5.26(d，J＝2.3Hz，1H，NH)，3.94(d，J＝1.2Hz，2H，CH 2)，2.17(s，3H，CH 3)，2.12(s，2H，CH 2)，1.01(s，9H，CH 3)
Fusing point: 211.9-212.9 ℃.
Compound 358 N-(4-bromo-2-methyl-6-(2-(3-(trifluoromethyl) benzyl) hydrazine carbonyl) phenyl) cyclohexanecarbonyl chloride
1H NMR (300MHz, DMSO) δ 9.70 (d, J=2.1Hz, 1H, NH), 9.23 (s, 1H, NH), 7.72 (s, 1H; ArH), and 7.61-7.71 (m, 1H, ArH), 7.53-7.59 (m, 3H, ArH), 7.25 (d, J=0.7Hz; 1H, ArH), 5.52-5.58 (m, 1H, NH), 4.02 (d, J=1.5Hz, 2H, CH 2), 2.24-2.30 (m, 1H, CH), 2.13 (s, 3H, CH 3), 1.12-1.82 (m, 10H, CH 2) fusing point: 173.4-173.7 ℃.
Compound 363 N-(4-bromo-2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl) cyclohexanecarbonyl chloride
1H NMR (300MHz, DMSO) δ 9.82 (d, J=2.0Hz, 1H, NH), 9.09 (s, 1H, NH), 7.56-7.66 (m, 3H, ArH), 7.36-7.42 (m, 2H, ArH), 5.59-5.65 (dd, J1=3.6Hz, J2=1.6Hz, 1H, NH), 4.03 (d, J=1.5Hz, 2H, CH 2), 2.28-2.30 (m, 1H, CH), 1.34-1.82 (m, 10H, CH 2) fusing point: 167.4-168.2
Compound 372 N-(2-(2-benzyl hydrazine carbonyl)-4-bromo-6-aminomethyl phenyl) cyclohexanecarbonyl chloride ℃.
1H NMR (300MHz, DMSO) δ 9.73 (s, 1H, NH), 9.25 (s, 1H, NH), 7.56 (d, J=0.7,1H, ArH), 7.23-7.38 (m, 6H, ArH), 5.34 (s, 1H, NH), 3.93 (s, 2H, CH 2), 2.26-2.34 (m, 1H, CH), 2.10 (s, 3H, CH 3), 1.20-1.83 (m, 10H, CH 2) fusing point: 175.7-177.1 ℃.
Compound 373 3-chloro-N-(2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl)-2,2-dimethyl propylene acid amides
1H?NMR(300MHz，DMSO)δ9.79(s，1H，NH)，9.32(s，1H，NH)，7.59-7.63(dd，J1＝0.6Hz，J2＝2.4Hz，1H，Ar)，7.38-7.44(m，1H，Ar)，7.30-7.36(m，3H，ArH)，7.17-7.29(m，2H，ArH)，4.08(s，2H，CH 2)，3.77(s，2H，CH 2)，2.16(s，3H，CH 3)，1.29(s，6H，CH 3)
Fusing point: 189.7-192.8 ℃.
Compound 394 3-chloro-N-(2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.74 (d, J=2.0Hz, 1H, NH), 9.17 (s, 1H, NH), 7.43-7.68 (m; 2H, ArH), 7.34-7.41 (m, 2H, ArH), 7.18-7.27 (m, 3H, ArH), 5.62-5.69 (dd; J1=3.6Hz, J2=1.7Hz, 1H, NH), 4.07 (d, J=1.6Hz, 2H, CH 2), 3.82 (s, 2H, CH 2), 2.15 (s, 3H, CH 3), 1.21 (s, 9H, CH 3) fusing point: 180.5-180.8 ℃.
Compound 402 3-chloro-N-(2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl)-6-aminomethyl phenyl)-2,2-dimethyl propylene acid amides ℃.
1H NMR (300MHz, DMSO) δ 9.58 (d, J=1.9Hz, 1H, NH), 9.26 (s, 1H, NH), 8.39 (d, J=0.8; 1H, ArH), 7.85-7.89 (dd, J1=2.7, J2=0.8,1H, ArH), 7.46 (d, J=2.7Hz; 1H, ArH), 7.29-7.33 (dd, J1=2.8, J2=0.8,1H, ArH), 7.13-7.20 (m, 2H; ArH), 5.59 (d, J=1.8,1H, NH), 3.96 (d, J=1.0Hz, 2H, CH 2), 3.80 (s, 2H, CH 2), 2.14 (s, 3H, CH 3), 1.31 (s, 6H, CH 3) fusing point: 195.7-196.2 ℃.
Compound 403 N-(2-(2-benzyl hydrazine carbonyl)-6-aminomethyl phenyl)-3-chloro-2,2-dimethyl propylene acid amides
1H NMR (300MHz, DMSO) δ 9.69 (d, J=2.0Hz, 1H, NH), 9.20 (s, 1H, NH), 7.15-7.39 (m, 8H, ArH), 5.36-5.43 (dd, J1=3.6Hz, J2=1.8Hz, 1H, NH), 3.95 (d, J=1.4Hz, 2H, CH 2), 3.56 (s, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.22 (s, 6H, CH 3) fusing point: 144.8-144.9 ℃.
Compound 404 N-(2-(2-(2-benzyl chloride base) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.74 (s, 1H, NH), 9.18 (s, 1H, NH), 7.59-7.62 (m, 1H, Ar), 7.37-7.43 (m, 1H, Ar), 7.27-7.32 (m, 3H, ArH), 7.16-7.26 (m, 2H, ArH), 4.08 (s, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.20 (s, 9H, CH 3) fusing point: 207.9-208.5 ℃.
Compound 420 N-(2-methyl-6-(2-(3-(trifluoromethyl) benzyl) hydrazine carbonyl) phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.66 (d, J=2.1Hz, 1H, NH), 9.14 (s, 1H, NH), 7.74 (s; 1H, ArH), 7.52-7.69 (m, 3H, ArH), 7.30-7.34 (m, 1H, ArH), 7.14-7.23 (m; 2H, ArH), 5.59-5.65 (m, 1H, NH), 4.05 (d, J=1.5Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.20 (s, 9H, CH 3) fusing point: 158.7-163.1 ℃.
Compound 425 N-(2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.72 (d, J=2.0Hz, 1H, NH), 9.15 (s, 1H, NH), 7.56-7.65 (m; 2H, ArH), 7.38-7.42 (dd, J1=2.9Hz, J2=0.7Hz, 1H, ArH), 7.31-7.35 (dd; J1=2.3Hz, J2=0.5Hz, 1H, ArH), 7.16-7.25 (m, 2H, ArH), 5.60-5.66 (dd; J1=3.7Hz, J2=1.7Hz, 1H, NH), 4.05 (d, J=1.6Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.11 (s, 9H, CH 3) fusing point: 179.8-185.7 ℃.
Compound 434 N-(2-(2-benzyl hydrazine carbonyl)-6-aminomethyl phenyl) pivaloyl amine
1H NMR (300MHz, DMSO) δ 9.69 (d, J=2.0Hz, 1H, NH), 9.19 (s, 1H, NH), 7.15-7.38 (m, 8H, ArH), 5.37-5.42 (dd, J1=3.6Hz, J2=1.8Hz, 1H, NH), 3.96 (d, J=1.6Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.22 (s, 9H, CH 3) fusing point: 157.0-158.1 ℃.
Compound 441 N-(2-(2-(2-luorobenzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.81 (s, 1H, NH), 9.27 (s, 1H, NH), 7.12-7.61 (m, 7H, ArH), 5.36 (s, 1H, NH), 4.00 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 2.11 (s, 2H, CH 2), 1.00 (s, 9H, CH 3) fusing point: 157.2-158.3 ℃.
Compound 451 3,3-dimethyl--N-(2-methyl-6-(2-(3-(trifluoromethyl) benzyl) hydrazine carbonyl) phenyl) yulocrotine
1H NMR (300MHz, DMSO) δ 9.63 (d, J=2.1Hz, 1H, NH), 9.21 (s, 1H, NH), 7.75 (s, 1H, ArH), 7.52-7.70 (m, 3H, ArH), 7.29-7.33 (m, 1H, ArH), 7.12-7.18 (m, 2H, ArH), 5.51 (s, 1H, NH), 4.05 (s, 2H, CH 2), 2.17 (s, 3H, CH 3), 2.08 (s, 2H, CH 2), 1.02 (s, 9H, CH 3) fusing point: 184.3-185.8 ℃.
Compound 456 N-(2-(2-(2, the 4-dichloro benzyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 9.72 (d, J=2.0Hz, 1H, NH), 9.16 (s, 1H, NH); 7.57-7.67 (m, 2H, ArH), 7.39-7.43 (dd, J1=2.8Hz, J2=0.7Hz, 1H, ArH); 7.33-7.36 (m, 1H, ArH), 7.16-7.26 (m, 2H, ArH), 5.61-5.67 (dd, J1=3.6Hz; J2=1.7Hz, 1H, NH), 4.05 (d, J=1.6Hz, 2H, CH 2), 2.13 (s, 3H, CH 3), 1.63 (s, 2H, CH 2), 1.20 (s, 9H, CH 3) fusing point: 180.7-181.5 ℃.
Compound 464 N-(2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl)-6-aminomethyl phenyl)-3, the 3-amide dimethyl butyrate
1H NMR (300MHz, DMSO) δ 8.38 (d, J=0.7,1H, ArH), 7.96-8.00 (m, 1H, ArH); 7.85-7.90 (dd, J1=2.8, J2=0.8Hz, 1H, ArH), 7.66 (m, 1H, ArH); 7.54 (d, J=2.8Hz, 1H, ArH), 7.39-7.41 (m, 1H, ArH), 6.79-6.83 (t; J=2.0Hz, 1H, NH), 4.16 (d, J=1.9Hz, 2H, CH 2), 2.81 (s, 2H, CH 2), 2.53 (s, 3H, CH 3), 1.03 (s, 9H, CH 3) fusing point: 135.1-136.0 ℃.
Compound 482 N-(2-methyl-6-(2-(3-(trifluoromethyl) benzyl) hydrazine carbonyl) phenyl) cyclohexanecarbonyl chloride
1H NMR (300MHz, DMSO) δ 9.64 (s, 1H, NH), 9.27 (s, 1H, NH), 7.57-7.80 (m, 4H, ArH), 7.32-7.39 (m, 1H, ArH), 7.18-7.25 (m, 2H, ArH), 5.60 (s, 1H, NH), 4.09 (s, 2H, CH 2), 2.32-2.35 (m, 1H, CH), 2.18 (s, 3H, CH 3), 1.67-1.88 (m, 5H, CH 2), 1.28-1.45 (m, 5H, CH 2) fusing point: 164.1-165.7 ℃.
Compound 495 N-(2-(2-((6-chloropyridine-3-yl) methyl) hydrazine carbonyl)-6-aminomethyl phenyl) cyclohexanecarbonyl chloride
1H NMR (300MHz, DMSO) δ 9.58 (d, J=1.9,1H, NH), 9.26 (s, 1H, NH), 8.39 (d, J=0.8Hz; 1H, ArH), 7.85-7.89 (dd, J1=2.7, J2=0.8Hz, 1H, ArH), 7.45 (d, J=2.7,1H; ArH), and 7.30-7.33 (m, 1H, ArH), 7.19-7.29 (m, 1H, ArH), 7.13-7.18 (m, 1H; ArH), 5.59 (d, J=1.8Hz, 1H, NH), 3.96 (d, J=1.0Hz, 2H, CH 2), 2.28 (m, 1H, CH), 2.13 (s, 3H, CH 3), 1.17-1.83 (m, 10H, CH 2) fusing point: 176.4-180.2 ℃.
Compound 496 N-(2-(2-benzyl hydrazine carbonyl)-6-aminomethyl phenyl) cyclohexanecarbonyl chloride
1H NMR (300MHz, DMSO) δ 9.69 (d, J=2.0Hz, 1H, NH), 9.20 (s, 1H, NH), 7.15-7.39 (m, 8H, ArH), 5.36-5.42 (dd, J1=3.6Hz, J2=1.8Hz, 1H, NH), 3.95 (d, J=1.6Hz, 2H, CH 2), 2.28-2.30 (m, 1H, CH), 2.13 (s, 3H, CH 3), 1.19-1.82 (m, 10H, CH 2); Fusing point: 148.5-149.5 ℃.
By on can know that the equal structure of gained compound is correct, be compound shown in the formula I.
Embodiment 1-496 prepares the biological activity test of compound (numbering is followed successively by 1-497) shown in the gained formula I:
Standard control medicament: the former medicine of 95% chlorine insect amide; The former medicine of 95% Provado; The former medicine of 97.1% pyridaben.
The test target: small cabbage moth (Plutella xylostella Linnaeus), picked up from vegetables field, Beijing, and raised in 2006 at indoor brassicaceous vegetable blade; The raising condition is a room temperature (27 ± 1) ℃; Humidity is 80%, and intensity of illumination is 2000lux, and light application time is 12h every day.Under the indoor feeding condition, with worm age, body weight and physiological situation consistent 2 age primary larva carry out the test of medicament screening active ingredients.
Melon (cotton) aphid (Aphis gossypii) is picked up from Haidian District, Beijing City rose of Sharon tree, selects 3 age in days nymphs and gets and carry out the test of medicament screening active ingredients indoor.
Carmine spider mite (Tetranychus cinnabarinus Boisduval) picks up from the field, Haidian District, Beijing City, is transferred to captive breeding on the Kidney bean of chamber planting, selects for use female one-tenth mite to carry out the test of medicament screening active ingredients.
Medicament preparation:, carry out the indoor general sieve activity test of compound with above-mentioned insect target with reference to " pesticide biological activity determination standard operation standard (SOP) " requirement.Take by weighing the 12mg compound sample with ten thousand/balance in the 20ml weighing bottle; Get 2ml acetone/methanol (1: 1) mixed solvent with 1～5ml liquid-transfering gun again and add weighing bottle; After treating that it fully dissolves; Add 18ml and contain the aqueous solution of 0.05% triton x-100, abundant mixing, the mensuration liquid of 600mg/L.
The compound method of contrast medicament is with last identical.
The test dose of contrast medicament is respectively: the former pharmaceutical quantities of 95% chlorine insect amide is: 0.2 μ g/mL; The former pharmaceutical quantities of 95% Provado is: 2 μ g/mL; The former pharmaceutical quantities of 97.1% pyridaben is: 50 μ g/mL.
In addition, the embodiment of the invention test dose for preparing the compound 1-496 of gained is 600 μ g/mL.
Melon (cotton) aphid: select tape aphid Leaf of Shrubalthea, stay 3 ages in days if aphid will be with the aphid blade in soup, to flood 5s, dry back record borer population and put into the petridish that is added with the filter paper of preserving moisture, put into (25 ± 1) ℃ illumination box after adding a cover.Each chemicals treatment is more than 30.Check result after 24 hours.
Small cabbage moth: rape leave is flooded 5s in soup, put into the petridish that is added with the filter paper of preserving moisture after drying, insert small cabbage moth 2 instar larvaes, put into (25 ± 1) ℃ illumination box after adding a cover.20 of each chemicals treatment.Check result after 3 days.
Carmine spider mite: the beans leaf of the carmine spider mite of will having transferred floods 5s in soup, dries back record borer population and puts into the petridish that is added with the filter paper of preserving moisture, and petiole is preserved moisture with the cotton of preserving moisture, and puts into (25 ± 1) ℃ illumination box after adding a cover.Each chemicals treatment is more than 20.Check result after 48 hours.
Dead judgement criteria is: touch polypide, the individuality of can not normally creeping is regarded as death.
Corrected mortality (%)=(sample mortality ratio-blank mortality ratio)/(1-blank mortality ratio) * 100, the blank mortality ratio needn't be proofreaied and correct less than 5%, is invalid test greater than 20%.
Table 2, part of compounds are to the insecticidal activity of small cabbage moth, melon (cotton) aphid, carmine spider mite
Figure BDA0000136374850000271
Figure BDA0000136374850000281
Under 600 μ g/mL concentration, the insecticidal activity of 30,131,280 pairs of small cabbage moths of compound is 100%, and 217 pairs of small cabbage moth insecticidal activities of compound have surpassed 90%; The insecticidal activity of 32,234,301,309,372,402,403,404,451 pairs of melons of compound (cotton) aphid has all surpassed 90%; The insecticidal activity of 156,187,327 pairs of carmine spider mite of compound is 100%, and the insecticidal activity of 31,186 pairs of carmine spider mite of compound has all surpassed 90%, explains that formula I compound provided by the invention has a good application prospect.

Claims (10)

1. adjacent formamido group benzoyl hydrazine compounds shown in the formula I:
Figure FDA0000136374840000011
Formula I
Among the said formula I, X is at least a in hydrogen, the halogen;
R 1At least a in hydrogen, the methyl;
R 2For carbonatoms be 4-6 the aliphatics substituting group with contain at least a in the aliphatics substituting group that substituent carbonatoms is 4-6;
R 3For carbonatoms is the 5-7 aromatic base, contains the aromatic base that substituent carbonatoms is 5-7.
2. compound according to claim 1 is characterized in that: among the said formula I, said halogen is a chlorine or bromine;
Said R 1Be hydrogen or methyl;
Said R 2Be the tertiary butyl, 1-chloro-2-methylpropane-2-base, tertiary amyl or cyclohexyl;
R 3Be phenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-p-methoxy-phenyl, 3-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2; 4-dichlorophenyl, 2; 3; 4; 5,6-pentafluorophenyl group, 2-cyano-phenyl, 3-cyano-phenyl, 4-cyano-phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-chloro-5-pyridyl.
3. method for preparing said adjacent formamido group benzoyl hydrazine compounds shown in claim 1 or the 2 arbitrary formula I; Comprise the steps: compound shown in compound shown in the formula a and the formula b is carried out ring-opening reaction in organic solvent, reaction finishes and obtains adjacent formamido group benzoyl hydrazine compounds shown in the said formula I;
Figure FDA0000136374840000012
Formula a formula b
Among said formula a and the formula b, R 1, R 2, R 3Identical with the definition of X with claim 1.
4. method according to claim 3 is characterized in that: in the said ring-opening reaction step, temperature is 10～100 ℃, and preferred 20-30 ℃, the reaction times is 10-50 hour, preferred 14-30.
5. according to claim 3 or 4 described methods; It is characterized in that: said organic solvent is selected from least a in the alcohol that substituted fatty compounds that carbonatoms is 1-6, alicyclic compound that carbonatoms is 1-10, aromatic hydrocarbon that carbonatoms is 6-10, aromatic hydrocarbon halides that carbonatoms is 6-10, ether that carbonatoms is 2-6, ketone that carbonatoms is 2-6, acid amides that carbonatoms is 3-6, nitrile that carbonatoms is 2-6, sulfoxide class that carbonatoms is 2-4, ester class that carbonatoms is 3-8 and carbonatoms be 1-4; Preferred benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, normal hexane, methylene dichloride, trichloromethane, tetracol phenixin, 1; 2-ethylene dichloride, ether, dipropyl ether, THF, glycol dimethyl ether, ethylene glycol diethyl ether, acetone, butanone, mibk, acetonitrile, propionitrile, butyronitrile, N; At least a in dinethylformamide, DMAC N,N, N-methyl-formylaniline, N-Methyl pyrrolidone, HMPA, methyl acetate, ETHYLE ACETATE, DMSO 99.8MIN., methyl alcohol, ethanol, n-propyl alcohol, Virahol, terepthaloyl moietie, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and the diethylene glycol monoethyl ether.
6. according to the arbitrary described method of claim 3-5, it is characterized in that:
Compound shown in the said formula a is 1 with the mole dosage ratio that feeds intake of compound shown in the formula b: 1-1: 1.5, and preferred mole dosage ratio is 1: 1.2.
7. the application of said adjacent formamido group benzoyl hydrazine compounds in the control of insect shown in claim 1 or the 2 arbitrary formula I.
8. the pest control medicine that is activeconstituents with said adjacent formamido group benzoyl hydrazine compounds shown in claim 11 or the 2 arbitrary formula I.
9. according to claim 7 or 8 described application, it is characterized in that: said insect is at least a in diamond-back moth section, Aphidiadae or the Tetranychidae.
10. application according to claim 9 is characterized in that: said insect is selected from least a in small cabbage moth, melon aphid, cotten aphid and the carmine spider mite.
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CN104557619A (en) * 2014-12-30 2015-04-29 中国农业大学 Methoxyimino phenylacetate compounds containing nitrohydrazinecarboximidamide structures as well as preparation method and application of methoxyimino phenylacetate compounds
CN104557620A (en) * 2014-12-30 2015-04-29 中国农业大学 Strobilurin compound containing nitrohydrazinecarboximidamide structure as well as preparation method and application of strobilurin compound

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CN101298451A (en) * 2007-04-30 2008-11-05 中国中化集团公司 Benzamide compounds and use thereof
CN102093335A (en) * 2010-11-26 2011-06-15 贵州大学 Acylhydrazone and hydrazide derivatives and application thereof

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CN101298451A (en) * 2007-04-30 2008-11-05 中国中化集团公司 Benzamide compounds and use thereof
CN102093335A (en) * 2010-11-26 2011-06-15 贵州大学 Acylhydrazone and hydrazide derivatives and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557619A (en) * 2014-12-30 2015-04-29 中国农业大学 Methoxyimino phenylacetate compounds containing nitrohydrazinecarboximidamide structures as well as preparation method and application of methoxyimino phenylacetate compounds
CN104557620A (en) * 2014-12-30 2015-04-29 中国农业大学 Strobilurin compound containing nitrohydrazinecarboximidamide structure as well as preparation method and application of strobilurin compound

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