CN102942536A - 4-tertiary butyl-5-(1-aryl-2-ethyl nitrate)-2-amido-thiazole with insecticidal activity and preparation method thereof - Google Patents

4-tertiary butyl-5-(1-aryl-2-ethyl nitrate)-2-amido-thiazole with insecticidal activity and preparation method thereof Download PDF

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CN102942536A
CN102942536A CN2012105092890A CN201210509289A CN102942536A CN 102942536 A CN102942536 A CN 102942536A CN 2012105092890 A CN2012105092890 A CN 2012105092890A CN 201210509289 A CN201210509289 A CN 201210509289A CN 102942536 A CN102942536 A CN 102942536A
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tertiary butyl
ethyl
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nitre
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胡艾希
彭俊梅
申坤
欧晓明
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Hunan University
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    • C07—ORGANIC CHEMISTRY
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    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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Abstract

The invention relates to 4-tertiary butyl-5-(1-aryl-2-ethyl nitrate)-2-amido-thiazole with a chemical structural formula I in the specification and a salt thereof, wherein Y1, Y2, Y3 and Y4 are selected from H, methyl, ethyl, hydroxyl, methoxyl, ethyoxyl, fluorine, chlorine, bromine, nitryl, trifluoromethyl and trifluoro-methoxy; Z is one of C1-C2 alkyl, C3-C4 linear chain or branch chain alkyl, chloric C1-C2 alkyl, chloric C3-C4 linear chain or branch chain alkyl, and aryl; and the salt is one of chloride, hydrobromide, sulfate, phosphate, mesylate, benzene sulfonate and tosilate. 4-tertiary butyl-5-(1-aryl-2-ethyl nitrate)-2-aminothiazole is acylated to prepare 4-tertiary butyl-5-(1-aryl-2-ethyl nitrate)-2-amido-thiazole. The 4-tertiary butyl-5-(1-aryl-2-ethyl nitrate)-2-amido-thiazole and salt thereof are applied in insecticide preparation.

Description

Have the 4-tertiary butyl-5-(1-aryl-2-nitre ethyl) of insecticidal activity-2-acylaminothiazole and preparation method
Technical field
The present invention relates to preparation method and the application of new compound, specifically the 4-tertiary butyl-5-(1-aryl-2-nitre ethyl)-the synthetic application with as sterilant of 2-acylaminothiazole.
Background technology
5-(4-the chlorophenylmethyl)-4-tertiary butyl-thiazolamine hydrobromate is that important medicine intermediate: 5-(4-the chlorophenylmethyl)-4-tertiary butyl-thiazolamine hydrobromate is through neutralization, the compound that obtains with the aromatic aldehyde reaction has biological activity, in pharmacy, use [Hunan University's journal natural science edition as cox 2 inhibitor, 2009,36(2), 70-74; Chinese invention patent, CN 101492426].Chinese invention patent (CN102070556A, 2011.5.25 is open; CN102067845A, 2011.5.25 is open) prepared 5-benzyl-4-alkyl-2-virtue aminothiazole hydrobromate.
Summary of the invention
The object of the present invention is to provide the 4-tertiary butyl shown in the chemical structural formula I-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole and salt thereof:
Figure BDA0000251560411
Y in the formula 1Be selected from: H, methyl, ethyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; Y 2, Y 4Be selected from: H, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; Y 3Be selected from: H, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; Z is selected from: C 1~ C 2Alkyl, C 3~ C 4Straight or branched alkyl, chloride C 1~ C 2Alkyl, chloride C 3~ C 4The straight or branched alkyl or the aryl shown in the formula II:
Figure BDA0000251560412
R in the formula II 1, R 5Be selected from: H, methyl, ethyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; R 2, R 4Be selected from: H, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; R 3Be selected from: H, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy.Salt is selected from: hydrochloride, hydrobromate, vitriol, phosphoric acid salt, mesylate, benzene sulfonate, tosilate.
The 4-tertiary butyl-the 5-[1-that the object of the present invention is to provide (4-chloro-phenyl-)-2-nitre ethyl]-2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt.
The 4-tertiary butyl-the 5-[1-that the object of the present invention is to provide (2,4 dichloro benzene base)-2-nitre ethyl]-2-(2,6-difluorobenzene formamido group) thiazole hydrobromide salt.
Figure BDA0000251560414
The 4-tertiary butyl-the 5-[1-that the object of the present invention is to provide (2,4 dichloro benzene base)-2-nitre ethyl]-2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt.
Figure BDA0000251560415
The object of the present invention is to provide the 4-tertiary butyl-5-(1-aryl-2-nitre ethyl)-preparation method of 2-acylaminothiazole and salt thereof, it is characterized in that its preparation feedback is as follows:
Figure BDA0000251560416
Or
Figure BDA0000251560417
The object of the present invention is to provide the 4-tertiary butyl-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole and the application of salt in the preparation sterilant thereof.
The present invention compared with prior art has following advantage:
The present invention has prepared the 4-tertiary butyl-5-(1-aryl-2-nitre ethyl first)-2-acylaminothiazole and salt thereof.Find the 4-tertiary butyl-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole and salt thereof has insecticidal activity.
Figure BDA0000251560418
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of thiazolamine hydrobromate
(1) 5-(4-chloro-phenyl-)-2, the preparation of 2-dimethyl-6-nitro-3-hexanone
0.12 mol 4,4-dimethyl-1-(4-chloro-phenyl-)-1-thiazolinyl-propione, 150 mL methyl alcohol, 0.60 mol Nitromethane 99Min. and 0.30 mol diethylamine, reflux 19.5 h.Revolve the steaming solvent, rare HCl transfers pH to neutral, the dilution of 300 mL methylene dichloride, washing, saturated nacl aqueous solution is washed, anhydrous magnesium sulfate drying, leave standstill, filter, revolve the steaming methylene dichloride, get crude product, a small amount of sherwood oil/alcohol mixed solvent washing, drying, get the 5-(4-chloro-phenyl-)-2,2-dimethyl-6-nitro-3-hexanone, yield 54.9 %, m.p.68～70 ℃. 1H?NMR(CDCl 3，400MHz)?δ：1.08(s，9H，3×CH 3)，2.89(dd，J=17.6?Hz，J=7.2?Hz，1H，CH 2)，2.98(dd，J=17.6?Hz，?J=7.2?Hz，1H，CH 2)，4.02～4.05?(m，H，CH)，4.60(dd，J=12.0?Hz，J=7.2?Hz，1H，O 2NCH 2)，4.68(dd，J=12.0?Hz，J=7.2?Hz，1H，O 2NCH 2)，7.17(d，J=8.0?Hz，2H，C 6H 4?2，6-H)，7.30(d，J=8.0?Hz，2H，C 6H 4?3，5-H)。
(2) 4-bromo-5-(4-chloro-phenyl-)-2, the preparation of 2-dimethyl-6-nitro-3-hexanone
0.01 mol 5-(4-chloro-phenyl-)-2,2-dimethyl-6-nitro-3-hexanone, 15 mL trichloromethanes and 3 acetone, stopped heating after the reflux drips the bromine that 0.012mol is dissolved in 5 mL trichloromethanes, keeps reaction solution to be blush, reacts 1.0 h.Cooling, revolve the steaming solvent, ethyl alcohol recrystallization gets 4-bromo-5-(4-chloro-phenyl-)-2,2-dimethyl-6-nitro-3-hexanone, yield 86.3%, m.p.117～119 ℃. 1H?NMR(CDCl 3，400MHz)，δ：0.94(s，9H，3×CH 3)，4.22～4.29(m，1H，CH)，?4.76～4.89(m，2H，CH 2NO 2)，5.22(dd，J=13.6?Hz，J=4.8?Hz，1H，CHBr)，7.15(d，J=8.4?Hz，2H，C 6H 4?2，6-H)，7.29(d，J=8.4?Hz，2H，C 6H 4?3，5-H)。
(3) the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of thiazolamine hydrobromate
5.0 mmol 4-bromo-5-(4-chloro-phenyl-)-2,2-dimethyl-6-nitro-3-hexanone, 5.0 mmol thiocarbamides and 50 mL ethanol, stirring and refluxing 19.5 h are cooled to room temperature, revolve the steaming solvent, white solid is separated out in cooling, filters a small amount of washing with alcohol of filter cake, dry, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-the thiazolamine hydrobromate, yield 82.3 %, 179 ~ 182 ℃ of m.p.. 1H?NMR(DMSO-d 6，400MHz)，δ：1.37(s，9H，3×CH 3)，5.21~5.24(m，1H，CH)，5.40~5.48?(m，2H，CH 2)，7.49(s，4H，C 6H 4)，8.64(br，2H，NH 2）。
Embodiment 2
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-kharophen thiazole and hydrobromate thereof
0.8 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 3 mL diacetyl oxides, stirring and dissolving, 60 ℃ of reactions, TLC monitoring reaction.After reaction is finished, under stirring, reaction solution is poured in the frozen water, separated out white solid, filter, drying gets the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-kharophen thiazole hydrobromide salt, yield 53.5 %, 192 ~ 194 ℃ of m.p.. 1H?NMR(DMSO-d 6，400MHz)，δ：1.35(s，9H，3×CH 3)，2.09(s，3H，COCH 3)，5.09(dd，J?=?14.0?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.36(dd，J?=?14.0?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.53(t，J?=?8.0?Hz，1H，CH)，7.43(s，4H，?C 6H 4Cl)，11.96(br，1H，NHCO）。
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-kharophen thiazole hydrobromide salt makes the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl through ammonia treatment]-2-kharophen thiazole.
Embodiment 3
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-propionamido thiazole and hydrobromate thereof
0.8 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 3 mL propionic anhydrides, stirring and dissolving, 60 ℃ of reactions, TLC monitoring reaction.After reaction is finished, add 30 mL water, 2 * 30 mL dichloromethane extractions merge organic phase, anhydrous sodium sulfate drying, leave standstill, filter, revolve the steaming solvent, cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-propionamido thiazole hydrobromide salt, yield 35.5 %, 146 ~ 148 ℃ of m.p.. 1H?NMR?(CDCl 3，400MHz)，δ：1.25(t，J?=?7.2?Hz，3H，CH 3)，1.38(s，9H，3×CH 3)，2.46(q，J?=?7.2?Hz，2H，CH 2)，4.80(dd，J?=?13.6?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.93(dd，J?=?13.6?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.61(t，J?=?8.0?Hz，1H，CH)，7.27(d，J?=?8.8?Hz，2H，C 6H 4Cl?2,6-H)，7.32(d，J?=?8.8?Hz，2H，C 6H 4Cl?3,5-H)，8.78(br，1H，NHCO）。
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-propionamido thiazole hydrobromide salt processes through pyridine and makes the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-propionamido thiazole.
Embodiment 4
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-chloro acetylamino thiazole
1.2 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 20 mL tetrahydrofuran (THF)s, stirring and dissolving, add 0.4 mL pyridine, drip the chloroacetyl chloride that 0.4 mL is dissolved in 10 mL tetrahydrofuran (THF)s under the ice bath, approximately 30 min drip off, transfer room temperature reaction to, the TLC monitoring reaction.After reaction is finished, separate out white solid, filter, washing, drying gets the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-chloro acetylamino thiazole, yield 19.8 %, 145 ~ 147 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.40(s，9H，3×CH 3)，4.25(s，2H，CH 2)，4.81(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.94(dd，J?=?13.6?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.63(t，J?=?8.0?Hz，1H，CH)，7.27(d，J?=?8.8?Hz，2H，C 6H 4Cl?2,6-H)，7.32(d，J?=?8.8?Hz，2H，C 6H 4Cl?3,5-H)，9.45(br，1H，NHCO）。
Embodiment 5
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(3,5-dinitrobenzene formamido group) thiazole and hydrobromate thereof
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol 3,5-dinitrobenzoic acid and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt, yield 30.2 %, 160 ~ 163 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.50(s，9H，3×CH 3)，4.88(dd，J?=?13.6?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.98(dd，J?=?13.6?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.60(t，J?=?8.0?Hz，1H，CH)，7.30(d，J?=?8.4?Hz，2H，C 6H 4?2,6-H)，7.38(d，J?=?8.4?Hz，2H，C 6H 4?3,5-H)，9.22(s，1H，C 6H 3?4-H)，9.29(s，2H，C 6H 3?2,6-H）。
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt is processed through sodium carbonate solution and is made the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(3,5-dinitrobenzene formamido group) thiazole.
Embodiment 6
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(3,5-, two trifluoromethyl benzamidos) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol 3,5-two trifluoromethylbenzoic acids and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(3,5-, two trifluoromethyl benzamidos) thiazole hydrobromide salt, yield 18.7 %, 94 ~ 97 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.45(s，9H，3×CH 3)，4.86(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.98(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.64(t，J?=?8.0?Hz，1H，CH)，7.30(d，J?=?8.8?Hz，2H，C 6H 4?2,6-H)，7.36(d，J?=?8.8?Hz，2H，C 6H 4?3,5-H)，8.10(s，1H，C 6H 3?4-H)，8.46(s，2H，C 6H 3?2,6-H）。
Embodiment 7
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(2-trifluoromethyl benzamido) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol o-trifluoromethyl phenylformic acid and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, the TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(2-trifluoromethyl benzamido) thiazole hydrobromide salt, yield 20.1 %, 105 ~ 108 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.32(s，9H，3×CH 3)，4.97(dd，J?=?13.6?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.22(dd，J?=?13.6?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.64(t，J?=?8.0?Hz，1H，CH)，7.40~7.45(m，5H，C 6H 4Cl，C 6H 4CF 3?5-H)，7.55~7.62(m，3H，C 6H 4CF 3?3,4,6-H）。
Embodiment 8
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(2,6-difluorobenzene formamido group) thiazole and hydrobromate thereof
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol 2,6-difluoro-benzoic acid and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(2,6-difluorobenzene formamido group) thiazole hydrobromide salt, yield 39.7 %, 185 ~ 188 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.40(s，9H，3×CH 3)，4.83(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.97(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.64(t，J?=?8.0?Hz，1H，CH)，7.04(t，J?=?8.4?Hz，2H，C 6H 3?3,5-H)，7.30(d，J?=?8.8?Hz，2H，C 6H 4?2,6-H)，7.34(d，J?=?8.8?Hz，2H，C 6H 4?3,5-H)，7.48~7.54(m，1H，C 6H 3?4-H）。
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(2,6-difluorobenzene formamido group) thiazole hydrobromide salt obtains the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl through ammonia treatment]-2-(2,6-difluorobenzene formamido group) thiazole.
Embodiment 9
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(4-dinitrobenzene formamido group) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol p-nitrobenzoic acids and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, the TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(4-dinitrobenzene formamido group) thiazole hydrobromide salt, yield 37.0 %, 131 ~ 133 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.44(s，9H，3×CH 3)，4.86(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.98(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.65(t，J?=?8.0?Hz，1H，CH)，7.30(d，J?=?8.8?Hz，2H，C 6H 4Cl?2,6-H)，7.35(d，J?=?8.8?Hz，2H，C 6H 4Cl?3,5-H)，8.16(d，J?=?8.8?Hz，2H，C 6H 4NO 2?2,6-H)，8.39(d，J?=?8.8?Hz，2H，C 6H 4NO 2?3,5-H）。
Embodiment 10
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(2-methyl-3-nitro benzamido) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol 2-methyl 3-nitrobenzoic acids and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, the TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(2-methyl-3-nitro benzamido) thiazole hydrobromide salt, yield 25.4 %, 84 ~ 87 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.42(s，9H，3×CH 3)，2.61(s，3H，CH 3)，4.85(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.98(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.66(t，J?=?8.0?Hz，1H，CH)，7.31(d，J?=?8.8?Hz，2H，C 6H 4?2,6-H)，7.36(d，J?=?8.8?Hz，2H，C 6H 4?3,5-H)，7.47(t，J?=?8.0?Hz，1H，C 6H 3?5-H)，7.74(d，J?=?8.0?Hz，1H，C 6H 3?6-H)，7.95(d，J?=?8.0?Hz，1H，C 6H 3?4-H)，9.11(br，1H，NHCO）。
Embodiment 11
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(2-methoxybenzoyl amino) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol o-methoxybenzoic acids and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, the TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(the 2-methoxybenzoyl is amino) thiazole hydrobromide salt, yield 17.3 %, 73 ~ 76 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.43(s，9H，3×CH 3)，4.11(s，3H，OCH 3)，4.84(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.97(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.63(t，J?=?8.0?Hz，1H，CH)，7.06(d，J?=?8.0?Hz，1H，C 6H 4OCH 3?3-H)，7.13(t，J?=?8.0?Hz，1H，C 6H 4OCH 3?5-H)，7.32(s，4H，C 6H 4Cl)，7.56(t，J?=?8.0?Hz，1H，C 6H 4OCH 3?4-H)，8.26(d，J?=?8.0?Hz，1H，C 6H 4OCH 3?6-H)，10.91(br，1H，NHCO）。
Embodiment 12
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(4-chlorobenzoyl amino) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol Chlorodracylic acids and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, the TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(the 4-chlorobenzoyl is amino) thiazole hydrobromide salt, yield 15.2 %, 115 ~ 119 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.44(s，9H，3×CH 3)，4.85(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.97(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.65(t，J?=?8.0?Hz，1H，CH)，7.29?(d，J?=?8.4?Hz，2H，C 6H 4Cl?2,6-H)，7.34(d，J?=?8.4?Hz，2H，C 6H 4Cl?3,5-H)，7.50(d，J?=?8.0?Hz，2H，NHCOC 6H 4Cl?3,5-H)，7.94(d，J?=?8.0?Hz，2H，NHCOC 6H 4Cl?2,6-H）。
Embodiment 13
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(2,6-dichloro-benzoyl amino) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol 2,6-dichlorobenzoic acid and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(2,6-dichloro-benzoyl is amino) thiazole hydrobromide salt, yield 41.5 %, 101 ~ 104 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.41(s，9H，3×CH 3)，4.84(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.99(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.64(t，J?=?8.0?Hz，1H，CH)，7.26~7.38?(m，7H，C 6H 4，C 6H 3)，9.06(br，1H，NHCO）。
Embodiment 14
The 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-preparation of 2-(2-chlorobenzoyl amino) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol 0-chloro-benzoic acids and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, the TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(the 2-chlorobenzoyl is amino) thiazole hydrobromide salt, yield 22.1 %, 95 ~ 98 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.40(s，9H，3×CH 3)，4.84(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，4.97(dd，J?=?13.2?Hz，J?=?8.0?Hz，1H，CH 2NO 2)，5.64(t，J?=?8.0?Hz，1H，CH)，7.30~7.35(m，4H，C 6H 4Cl)，7.40~7.42(m，1H，NHCOC 6H 4Cl?6-H)，7.47~7.49(m，2H，NHCOC 6H 4Cl?4,5-H)，7.82(d，J?=?7.6?Hz，1H，NHCOC 6H 4Cl?3-H)，9.51(br，1H，NHCO）。
Embodiment 15
The 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-preparation of thiazolamine hydrobromate
(1) 5-(2, the 4-dichlorophenyl)-2, the preparation of 2-dimethyl-6-nitro-3-hexanone
0.01 mol 4,4-dimethyl-1-(2,4-dichlorophenyl)-1-thiazolinyl-propione and 20 mL ethanol, stir lower add 0.05 mol Nitromethane 99Min. and 0.001 mol salt of wormwood, reflux 4.5 h.Cooling, 20 mL water place refrigerator to place and spend the night, and separate out white solid, filter, drying gets 5-(2, the 4-dichlorophenyl)-2,2-dimethyl-6-nitro-3-hexanone, yield 88.1%, 84 ~ 86 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.12(s，9H，3×CH 3)，3.03～3.06(m，2H，CH 2)，4.42～4.43(m，1H，CH)，4.75(d，J=6.0?Hz，2H，CH 2NO 2)，7.15(d，J=8.4?Hz，1H，C 6H 3?6-H)，7.22?(dd，J=8.4?Hz，J=2.0?Hz，1H，C 6H 3?5-H)，7.42(d，J=2.0?Hz，1H，C 6H 3?3-H)。
(2) 4-bromo-5-(2, the 4-dichlorophenyl)-2, the preparation of 2-dimethyl-6-nitro-3-hexanone
0.01 mol 5-(2, the 4-dichlorophenyl)-2,2-dimethyl-6-nitro-3-hexanone, 15 mL trichloromethanes and 3 acetone, stopped heating after the reflux, drip the bromine that 0.012mol is dissolved in 5 mL trichloromethanes, keep reaction solution to be blush, stopped reaction behind 1.0 h.The steaming solvent is revolved in cooling, crosses post, gets 4-bromo-5-(2, the 4-dichlorophenyl)-2,2-dimethyl-6-nitro-3-hexanone. 1H?NMR(CDCl 3，400MHz)，δ：1.11(s，9H，3×CH 3)，4.53～4.58(m，1H，CH)，5.11～5.16(m，2H，CH 2)，5.30(dd，J=13.6?Hz，J=4.4?Hz，1H，CHBr)，7.23～7.26(m，2H，C 6H 3?5，6-H)，7.41(s，1H，C 6H 3?3-H)。
(3) the 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-preparation of thiazolamine hydrobromate
10.0 mmol 4-bromo-5-(2, the 4-dichlorophenyl)-2,2-dimethyl-6-nitro-3-hexanone, 11.0 mmol thiocarbamides and 50 mL ethanol stir reflux, react 19 h, be cooled to room temperature, revolve the steaming solvent, cross post and get the 4-tertiary butyl-5-[1-(2, the 4-dichlorophenyl)-2-nitre ethyl]-the thiazolamine hydrobromate, yield 25.1 %. 1H?NMR(CDCl 3，400MHz)，δ：1.29(s，9H，3×CH 3)，4.55(dd，J?=?13.6?Hz，J?=?9.6?Hz，1H，CH 2NO 2)，4.86(dd，J?=?13.6?Hz，J?=?9.6?Hz，1H，CH 2NO 2)，5.13(br，2H，NH 2)，5.88(t，J?=?9.6?Hz，1H，CH)，7.25?(dd，J?=?8.4?Hz，J?=?2.0?Hz，1H，C 6H 3?5-H)，7.34(d，J?=?8.4?Hz，1H，C 6H 3?6-H)，7.45(d，J?=?2.0?Hz，1H，C 6H 3?3-H）。
Embodiment 16
The 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-preparation of 2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(2, the 4-dichlorophenyl)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol 3,5-dinitrobenzoic acid and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h adds 1.0 mmol N, N '-dicyclohexylcarbodiimide, the TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt, yield 14.2 %, 138 ~ 140 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.42(s，9H，3×CH 3)，4.78(dd，J?=?14.0?Hz，J?=?10.0?Hz，1H，CH 2NO 2)，4.93(dd，J?=?14.0?Hz，J?=?6.0?Hz，1H，CH 2NO 2)，5.60(q，J?=?10.0?Hz，J?=?6.0?Hz，1H，CH)，7.29(dd，J?=?8.4?Hz，J?=?2.4?Hz，1H，C 6H 3?5-H)，7.38(d，J?=?8.4?Hz，1H，C 6H 3?6-H)，7.50(d，J?=?2.4?Hz，1H，C 6H 3?3-H)，9.21(t，J?=?2.4?Hz，1H，?NHCOC 6H 3?4-H)，9.27(d，J?=?2.4?Hz，2H，NHCOC 6H 3?2，6-H）。
Embodiment 17
The 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-preparation of 2-(2-trifluoromethyl benzamido) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(2, the 4-dichlorophenyl)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol o-trifluoromethyl phenylformic acid and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-2-(2-trifluoromethyl benzamido) thiazole hydrobromide salt, yield 8.9 %, 91 ~ 93 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.36(s，9H，3×CH 3)，4.75(dd，J?=?14.0?Hz，J?=?9.2?Hz，1H，CH 2NO 2)，4.94(dd，J?=?14.0?Hz，J?=?6.4?Hz，1H，CH 2NO 2)，5.60(q，J?=?9.2?Hz，J?=?6.4?Hz，1H，CH)，7.29(dd，J?=?8.4?Hz，J?=?2.0?Hz，1H，C 6H 3?5-H)，7.39(d，J?=?8.4?Hz，1H，C 6H 3?6-H)，7.48(d，J?=?2.0?Hz，1H，C 6H 3?3-H)，7.65～7.70(m，4H，C 6H 4）。
Embodiment 18
The 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-preparation of 2-(2,6-difluorobenzene formamido group) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(2, the 4-dichlorophenyl)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol 2,6-difluoro-benzoic acid and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h adds 1.0 mmol N, N '-dicyclohexylcarbodiimide, the TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-2-(2,6-difluorobenzene formamido group) thiazole hydrobromide salt, yield 10.1 %, 92 ~ 94 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.34(s，9H，3×CH3)，4.74(dd，J?=?14.0?Hz，J?=?9.2?Hz，1H，CH 2NO 2)，4.93(dd，J?=?14.0?Hz，J?=?6.4?Hz，?1H，CH 2NO 2)，5.64(q，J?=?9.2?Hz，J?=?6.4?Hz，?1H，CH)，7.25～7.28(m，1H，C 6H 3?5-H)，7.38(d，J?=?8.8?Hz，1H，C 6H 3?6-H)，7.46(d，J?=?2.0?Hz，1H，C 6H 3?3-H)，7.03～7.07?(m，2H，NHCOC 6H 3?3，5-H)，7.49～7.53?(m，1H，NHCOC 6H 3?4-H)，9.33(br，1H，NHCO）。
Embodiment 19
The 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-preparation of 2-(4-nitrobenzoyl amido) thiazole hydrobromide salt
0.75 the mmol 4-tertiary butyl-5-[1-(2, the 4-dichlorophenyl)-2-nitre ethyl]-thiazolamine hydrobromate, 1.0 mmol p-nitrobenzoic acids and 40 mL methylene dichloride, stirring at room, add 0.125 mmol DMAP, stirring reaction 0.5 h, add 1.0 mmol N, N '-dicyclohexylcarbodiimide, TLC monitoring reaction.After reaction is finished, remove by filter the part dicyclohexylurea (DCU), cross post, get the 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-2-(4-nitrobenzoyl amido) thiazole hydrobromide salt, yield 5.9 %, 141 ~ 143 ℃ of m.p.. 1H?NMR(CDCl 3，400MHz)，δ：1.35(s，9H，3×CH 3)，4.75(dd，J?=?13.6?Hz，J?=?9.6?Hz，1H，CH 2NO 2)，4.94(dd，J?=?13.6?Hz，J?=?6.0?Hz，1H，CH 2NO 2)，6.02(q，J?=?9.6?Hz，J?=?6.0?Hz，1H，CH)，7.26(dd，J?=?8.8?Hz，J?=?2.0?Hz，1H，C 6H 3?5-H)，7.36(d，J?=?8.8?Hz，1H，C 6H 3?6-H)，7.48(d，J?=?2.0?Hz，1H，C 6H 3?3-H)，8.15(d，J?=?8.4?Hz，2H，C 6H 4?2,6-H)，8.38(d，J?=?8.4?Hz，2H，C 6H 4?3,5-H)，9.84(br，1H，NHCO）。
Embodiment 20
The 4-tertiary butyl-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole and salt pair mythimna separata, black bean aphid and two-spotted spider mite cytotoxicity mensuration
1 for the examination target
Mythimna separata (Mythimna sepatara) is with fresh corn leaf raising sensitive strain for many years; Test is 3 instar larvaes with worm; Black bean aphid (Aphis fabae) is indoor with broad bean seedling raising sensitive strain for many years, if test is 3 age in days aphids with worm; Two-spotted spider mite (Tetranychus urticae) is indoor with broad bean seedling raising sensitive strain for many years.Test is healthy one-tenth mite with worm.
2 culture condition
Culture condition for target after examination target and the test is 25 ± 5 ℃ of temperature, relative humidity 65 ± 5%, periodicity of illumination 12/12h(L/D).
3 test medicines (former medicine): the 4-tertiary butyl-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole and salt thereof.
4 medicaments are prepared former medicine: take by weighing aequum with ten thousand/electronic balance; Solvent: DMF (DMF), 0.2%; Emulsifying agent: Tween 80,0.2%; Add clear water and be diluted to desired concn.
5 test methods are with reference to " pesticide bioactivity is estimated SOP ".
The general sieve of mythimna separata: adopt spray method.In being lined with the culture dish of filter paper (Ф 90mm), put into the basically identical leaf of Semen Maydis section of size, access again 10 of third-instar larvaes, be put under the Potter spray tower and spray.Spray amount 1ml/10 head, 2 repetitions.Be disposed, be put into the observation indoor cultivation.Regularly observe.Check behind the 72h and the record death condition, calculate mortality ratio.
The general sieve of black bean aphid adopts pickling process.If will cut with the broad bean seedling of 3 age in days broad bean aphids, dipping took out in 10 seconds afterwards in the liquid for preparing, and was inserted on the sponge that suctions water, covered the lampshade that starts, and every processing repeats for 2 times.Be disposed, be put into the observation indoor cultivation, regularly observe, check behind the 72h and the record death condition, calculate mortality ratio.
Two-spotted spider mite is adopted pickling process.To cut with the broad bean seedling of red spider, and soak taking-up in 10 seconds in the liquid for preparing, and suck unnecessary liquid around plant and the mite body with filter paper, and be inserted on the beaker that dress water sealed, every processing repeats for 2 times.Be disposed, be put into the observation indoor cultivation, regularly observe, check behind the 72h and the record death condition, calculate mortality ratio.
6 cytotoxicities
The cytotoxicity of preferred compound: when effective constituent concentration is 500mg/L, behind the dispenser 72h, the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-mortality ratio of 2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt pair mythimna separata is 75.00%; When effective constituent concentration is 500mg/L, behind the processing 72h, the 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-2-(2,6-difluorobenzene formamido group) thiazole hydrobromide salt pair black bean aphid mortality ratio is 97.22%.When effective constituent concentration is 500mg/L, behind the processing 72h, the 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt pair two-spotted spider mite mortality ratio is 54.51%.
The 4-tertiary butyl-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole and salt thereof has good insecticidal activity, can be used as the preparation sterilant and use in agricultural.

Claims (6)

1. the tertiary butyl of the 4-shown in the chemical structural formula I-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole or its salt:
Figure FDA0000251560401
Y in the formula 1Be selected from: H, methyl, ethyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; Y 2, Y 4Be selected from: H, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; Y 3Be selected from: H, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; Z is selected from: C 1~ C 2Alkyl, C 3~ C 4Straight or branched alkyl, chloride C 1~ C 2Alkyl, chloride C 3~ C 4The straight or branched alkyl or the aryl shown in the formula II:
R in the formula II 1, R 5Be selected from: H, methyl, ethyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; R 2, R 4Be selected from: H, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; R 3Be selected from: H, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine, nitro, trifluoromethyl or trifluoromethoxy; Salt is selected from: hydrochloride, hydrobromate, vitriol, phosphoric acid salt, mesylate, benzene sulfonate, tosilate.
2. the described 4-tertiary butyl of claim 1-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole salt is the 4-tertiary butyl-5-[1-(4-chloro-phenyl-)-2-nitre ethyl]-2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt.
3. the described 4-tertiary butyl of claim 1-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole salt is the 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-2-(2,6-difluorobenzene formamido group) thiazole hydrobromide salt.
4. the described 4-tertiary butyl of claim 1-5-(1-aryl-2-nitre ethyl)-2-acylaminothiazole salt is the 4-tertiary butyl-5-[1-(2,4 dichloro benzene base)-2-nitre ethyl]-2-(3,5-dinitrobenzene formamido group) thiazole hydrobromide salt.
5. each described 4-tertiary butyl-5-(1-aryl-2-nitre ethyl in the claim 1 ~ 4)-and the preparation method of 2-acylaminothiazole or its salt, it is characterized in that its preparation feedback is as follows:
Figure FDA0000251560403
Figure FDA0000251560404
Or
Figure FDA0000251560405
Y in the formula 1, Y 2, Y 3, Y 4, Z definition as claimed in claim 1.
6. each described 4-tertiary butyl-5-(1-aryl-2-nitre ethyl in the claim 1 ~ 4)-2-acylaminothiazole or the application of its salt in the preparation sterilant.
CN2012105092890A 2012-12-03 2012-12-03 4-tertiary butyl-5-(1-aryl-2-ethyl nitrate)-2-amido-thiazole with insecticidal activity and preparation method thereof Pending CN102942536A (en)

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Cited By (3)

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CN103570643A (en) * 2012-12-03 2014-02-12 湖南大学 N-[4-tertbutyl-5-(2-nitroethyl)thiazole-2-yl]benzamide, preparation method and application
CN104530036A (en) * 2015-01-07 2015-04-22 湖南大学 5-piperonyl-4-alkyl-2-benzyliminothiazole and preparing method and application thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105585563B (en) * 2014-10-24 2018-09-21 湖南大学 1- (benzofuran -5- bases) -3- phenyl -2- (1,2,4- triazol-1-yls) propenyls and its application
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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5210205A (en) * 1989-12-21 1993-05-11 Ciba-Geigy Corporation Pesticidal compositions
ES2443690T3 (en) * 2005-09-02 2014-02-20 Nissan Chemical Industries, Ltd. Isoxazoline-substituted benzamide compound and harmful agent controlling agent
EP2319830B1 (en) * 2008-08-13 2016-11-02 Mitsui Chemicals Agro, Inc. Amide derivative, pest control agent containing the amide derivative, and use of the pest control agent
CN101845026B (en) * 2009-12-30 2011-10-19 湖南大学 5-(4-chlorophenylmethyl)-4-tertiary butyl thiazole derivatives and preparation method and application thereof
CN101781269B (en) * 2010-02-08 2011-10-19 湖南大学 4-tertiary butyl-2-(nitrobenzyl imino) thiazole derivative as well as preparation method and application thereof
CN102319244A (en) * 2011-07-22 2012-01-18 湖南大学 Application of 5-benzyl-4-alkyl-2-aryl aminothiazole serving as anti-cervical cancer medicaments
CN102942536A (en) * 2012-12-03 2013-02-27 湖南大学 4-tertiary butyl-5-(1-aryl-2-ethyl nitrate)-2-amido-thiazole with insecticidal activity and preparation method thereof

Cited By (3)

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CN103570643A (en) * 2012-12-03 2014-02-12 湖南大学 N-[4-tertbutyl-5-(2-nitroethyl)thiazole-2-yl]benzamide, preparation method and application
CN104530036A (en) * 2015-01-07 2015-04-22 湖南大学 5-piperonyl-4-alkyl-2-benzyliminothiazole and preparing method and application thereof
CN105078977A (en) * 2015-08-31 2015-11-25 南华大学 Application of 5-(2-nitro ethyl) thiazole derivatives as anticancer drug

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