CN102260219A - 1-(1,2,4-triazolyl)ketoxime ether-acylamide and application thereof - Google Patents
1-(1,2,4-triazolyl)ketoxime ether-acylamide and application thereof Download PDFInfo
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Abstract
The invention discloses 1-(1,2,4-triazolyl)ketoxime ether-acylamide disclosed as a chemical structural formula I, wherein R is selected from hydrogen, C1-C2 alkyl group, and C3-C4 straight-chain or branched alkyl group; R1 is selected from hydrogen, C1-C2 alkyl group, and C3-C4 straight-chain or branched alkyl group; and Y is selected from aromatic group or benzyl group. The 1-(1,2,4-triazolyl)ketoxime ether-acylamide disclosed as the chemical structural formula I can be used for preparing bactericide or weedicide for killing Sclerotinia scleotiorum.
Description
Technical field
The present invention relates to new compound of a class and its production and application, specifically be 1-(1,2, the 4-triazolyl) ketoxime ether acid amides and preparation method thereof with its as preparation sterilant or herbicide applications.
Background technology
Wang Sheng must wait [Journal of Natural Science of Hunan Normal University, 2005,28 (1): 57-59] describe a series of 4-chloro-acetophenone class oxime ether amide compounds, measured sterilization, weeding and the insecticidal activity of new compound, filter out activity preferably compound carry out general sieve, general sieve the results are shown in Table 1.
Table 1 4-chloro-acetophenone class oxime ether amide compound is antibacterial, weeding and insecticidal activity
[chemistry circular such as Cheng Hua, 2006,69 (8): 635-638] novel pesticide efficient in order to seek, low toxicity, a series of oxime ether amidess have been described, and estimated the compound of describing to the inhibition activity of Pyricularia oryzae, gibberella saubinetii, Phytophthora capsici, botrytis cinerea pers and wheat powdery mildew, when general sieve concentration was 500mg/L, part of compounds reached more than 80% the potted plant activity of wheat powdery mildew, and active result lists table 2 in.This compounds does not have tangible desinsection and weeding activity.
Table 2 substituted benzoyl aldehydes oxime ether amide compound bacteriostatic activity (wheat powdery mildew, 500mg/L)
Yuan Liping etc. [ZL 02112336.5.2007-04-04] have described a series of 2,4-dichloroacetophenone amide oxime, and 100mg/L, 50mg/L, 25mg/L ..., the 1mg/L isoconcentration down test 2,4 dichloro benzene ethyl ketone amide oxime to the stripped fungicidal activity of bacterial leaf spot, rice blast, banded sclerotial blight, corn stigma, head blight, anthrax, gray mold, sclerotium disease.The result shows, when test concentrations is 100mg/L, and the stripped fungicidal activity that the oxime ether amide compound that contains triazole ring is done well to bacterial leaf spot and anthrax.In addition, the test target compound 1000mg/L, 500mg/L, 250mg/L ..., when 25mg/L, 10mg/L to the inhibition activity of rice blast, banded sclerotial blight, melon anthrax, melon Powdery Mildew, sclerotium disease.Test concentrations is 100 or during 1000mg/L, the active result who contains the oxime ether acid amides of triazole ring lists table 3 in.
Table 3 contains the 2,4 dichloro benzene second ketoxime ether acid amides bacteriostatic activity of triazole ring
The test of a isolated activity, the potted plant active testing of b
Yuan Liping etc. [the 5th national pharmaceutical toxicology academic discussion collection of thesis. Shanghai: Chinese insectology meeting, 1999,12-15] be parent with oxime ether aromatic amine, described a series of new compounds that contain the tertiary butyl and triazole ring, its result to the indoor bacteriostatic activity of cucumber white powder, cucumber anthrax, gray mold, the red enzymophathy of wheat class, cotton withered, rhizoctonia rot of cotton etc. lists table 4 in.This compounds is not seen weeding and insecticidal activity report.
Table 4 contains the indoor bacteriostatic activity of oxime ether amides of the tertiary butyl and triazole ring
The present invention is intended to utilize principle of hybridization that the active group oxime ether of agricultural chemicals is incorporated into 1; 2; in the 4-triazole class compounds; adopt the Willianmson etherification method: with 3,3-dimethyl-1-(1,2; the 4-triazolyl) Diacetylmonoxime and acylting agent react 3; 3-dimethyl-1-(1,2, the 4-triazolyl) Diacetylmonoxime ether acid amides.
Summary of the invention
The purpose of this invention is to provide the 1-shown in the chemical structural formula I (1,2, the 4-triazolyl) ketoxime ether acid amides:
Wherein, R is selected from hydrogen, C
1～C
2Alkyl, C
3～C
4The straight or branched alkyl; R
1Be selected from: hydrogen, C
1～C
2Alkyl, C
3～C
4The straight or branched alkyl; Y is selected from: Ar or ArCH
2: the Ar=phenyl, the 2-fluorophenyl, the 2-chloro-phenyl-, the 2-bromophenyl, the 2-iodophenyl, 2-(trifluoromethyl) phenyl, the 3-aminomethyl phenyl, the 3-fluorophenyl, the 3-chloro-phenyl-, the 3-bromophenyl, the 3-iodophenyl, 3-(trifluoromethyl) phenyl, the 3-p-methoxy-phenyl, the 4-fluorophenyl, the 4-bromophenyl, the 4-iodophenyl, 4-(trifluoromethyl) phenyl, the 4-p-methoxy-phenyl, 2, the 3-3,5-dimethylphenyl, 2, the 4-3,5-dimethylphenyl, 3, the 4-3,5-dimethylphenyl, 3, the 5-3,5-dimethylphenyl, 2, the 6-3,5-dimethylphenyl, 2, the 3-dichlorophenyl, 3, the 4-dichlorophenyl, 3, the 5-dichlorophenyl, 2, the 6-dichlorophenyl.
The purpose of this invention is to provide the preparation method of the 1-shown in the chemical structural formula I (1,2, the 4-triazolyl) ketoxime ether acid amides, undertaken by following chemical equation:
R is selected from hydrogen, C in the reaction formula
1～C
2Alkyl, C
3～C
4The straight or branched alkyl; R
1Be selected from: hydrogen, C
1～C
2Alkyl, C
3～C
4The straight or branched alkyl; Y is selected from: Ar or ArCH
2: the Ar=phenyl, the 2-fluorophenyl, the 2-chloro-phenyl-, the 2-bromophenyl, the 2-iodophenyl, 2-(trifluoromethyl) phenyl, the 3-aminomethyl phenyl, the 3-fluorophenyl, the 3-chloro-phenyl-, the 3-bromophenyl, the 3-iodophenyl, 3-(trifluoromethyl) phenyl, the 3-p-methoxy-phenyl, the 4-fluorophenyl, the 4-bromophenyl, the 4-iodophenyl, 4-(trifluoromethyl) phenyl, the 4-p-methoxy-phenyl, 2, the 3-3,5-dimethylphenyl, 2, the 4-3,5-dimethylphenyl, 3, the 4-3,5-dimethylphenyl, 3, the 5-3,5-dimethylphenyl, 2, the 6-3,5-dimethylphenyl, 2, the 3-dichlorophenyl, 3, the 4-dichlorophenyl, 3, the 5-dichlorophenyl, 2, the 6-dichlorophenyl.
The purpose of this invention is to provide the 1-shown in the chemical structural formula I (1,2, the 4-triazolyl) ketoxime ether acid amides and kill the sterilant of Sclerotinia sclerotiorum or the application in the weedicide in preparation.
The purpose of this invention is to provide the 1-(1 shown in the chemical structural formula I, 2, the 4-triazolyl) the ketoxime ether acid amides is N-rubigan-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] propionic acid amide or N-(3, the 4-dichlorophenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] propionic acid amide kills the application of the sterilant of Sclerotinia sclerotiorum in preparation.
The purpose of this invention is to provide the 1-(1 shown in the chemical structural formula I, 2,4-triazolyl) the ketoxime ether acid amides is N-(3-methylbenzene)-2-[3,3-dimethyl-1-(1,2,4-triazol-1-yl) butyl-2-methylene azyloxy] ethanamide removes the herbicide applications of piemarker, thorn amaranth or lamb's-quarters in preparation.
The purpose of this invention is to provide the 1-(1 shown in the chemical structural formula I, 2, the 4-triazolyl) the ketoxime ether acid amides is N-(3, the 4-3,5-dimethylphenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] ethanamide, N-(4-p-methoxy-phenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] ethanamide, N-benzyl-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] propionic acid amide or N-(3-aminomethyl phenyl) 2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] propionic acid amide removes the herbicide applications of thorn amaranth or lamb's-quarters in preparation.
The present invention compared with prior art has following advantage:
Documents [the 5th national pharmaceutical toxicology academic discussion collection of thesis. Shanghai: Chinese insectology meeting, 1999,12-15; ZL 02112336.5.2007-04-04; Chemistry circular, 2006,69 (8): 635-638] the oxime ether Propionamides compound of describing does not have the active report of Sclerotinia sclerotiorum extremely, does not have the report of weeding activity yet; The invention provides the 1-shown in the chemical structural formula I (1,2, the 4-triazolyl) ketoxime ether acid amides and have the activity of Sclerotinia sclerotiorum extremely; Or has a weeding activity.1-(1,2, the 4-triazolyl) ketoxime ether acid amides kills the sterilant of Sclerotinia sclerotiorum or the application in the weedicide in preparation.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1 N-benzyl-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of ethanamide (4a)
2.16g (20.2mmol) benzylamine, 1.95g (14.1mmol) salt of wormwood, 1.73g (2.88mmol) PEG600,20mL methylene dichloride, N
2Protection slowly drips 3.02g (27.0mmol) chloroacetyl chloride under the condition of ice bath, 30min dropwises, and TLC follows the tracks of reaction 6.9h.Revolve steaming, washing, drying, ethyl alcohol recrystallization gets 2.67g white solid 3a, yield 71.9%, m.p.88～90 ℃.
0.92g (5.0mmol) compound 2,0.86g (4.96mmol) N-benzyl-2-chlor(o)acetamide, 0.15g (0.5mmol) Tetrabutyl amonium bromide (TBAB), 0.08g (0.05mmol) KI, 15mL toluene.Slowly drip 1.98g20% sodium hydroxide (9.9mmol) solution, drip in the 10min, slowly be warming up to 60 ℃, TLC follows the tracks of reaction 8.3h afterreaction and finishes.Cooling, separatory, washing, anhydrous sodium sulfate drying spends the night.Filter, revolve steaming, the dehydrated alcohol recrystallization gets 0.59g white solid 4a, yield 36.2%, m.p.128～130 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.06(s，9H，3×CH
3)，4.52(d，J＝5.2Hz，2H，CH
2)，4.68(s，2H，CH
2)，4.98(s，2H，NOCH
2)，7.14～7.31(m，5H，C
6H
5)，8.07(s，2H，C
2H
2N
3H)。
Embodiment 2 N-(3-aminomethyl phenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of ethanamide (4b)
Press embodiment 1 operation preparation 3b, reaction 3.9h, behind the ethyl alcohol recrystallization the 2.32g white solid, yield 62.7%, m.p.86～87 ℃; Press embodiment 1 operation preparation compound 4b, reaction 2.8h, yield 24.2%, m.p.101～102 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，2.37(s，3H，CH
3)，2.27(s，3H，CH
3)，4.73(s，2H，CH
2)，5.09(s，2H，NOCH
2)，6.97(d，J＝7.6Hz，1H，C
6H
44-H)，7.25(t，J＝8.4Hz，1H，C
6H
45-H)，7.37(d，J＝8.4Hz，1H，C
6H
46-H)，7.47(s，1H，C
6H
42-H)，7.94(s，1H，C
2H
2N
33-H)，8.23(s，1H，C
2H
2N
3?5-H)，9.19(s，1H，CONH)。
Embodiment 3 N-(3, the 4-3,5-dimethylphenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of ethanamide (4c)
Press embodiment 1 operation preparation 3c, reaction 1.5h, behind the ethyl alcohol recrystallization the 2.75g pale solid, yield 69.2%, m.p.94～96 ℃; Press embodiment 1 operation preparation compound 4c, reaction 1.4h, yield 49.5%, m.p.121～123 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，2.24(s，3H，CH
3)，2.27(s，3H，CH
3)，4.73(s，2H，CH
2)，5.09(s，2H，NOCH
2)，7.11(d，J＝7.6Hz，1H，C
6H
35-H)，7.30(dd，J
1＝8.0Hz，J
2＝2.4Hz，1H，C
6H
36-H)，7.40(s，1H，C
6H
32-H)，7.93(s，1H，C
2H
2N
33-H)，8.20(s，1H，C
2H
2N
35-H)，9.15(s，1H，CONH)。
Embodiment 4 N-(2, the 6-3,5-dimethylphenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of ethanamide (4d)
Press embodiment 1 operation preparation 3d, reaction 5.1h, behind the ethyl alcohol recrystallization the 1.96g white solid, yield 49.2%, m.p.141～143 ℃; Press embodiment 1 operation preparation compound 4d, reaction 9.1h, yield 21.8%, m.p.155～157 ℃.
1H?NMR(DMSO-d
6，400Hz)δ：1.11(s，9H，3×CH
3)，2.13(s，2H，CH
2)，5.22(s，2H，NOCH
2)，7.10(m，3H，C
6H
3)，7.79(s，1H，C
2H
2N
33-H)，8.66(s，1H，C
2H
2N
35-H)，9.24(s，1H，CONH)。
Embodiment 5 N-(2-bromophenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of ethanamide (4e)
Press embodiment 1 operation preparation 3e, reaction 4.0h, ethyl alcohol recrystallization gets the 1.44g white solid, yield 28.6%, m.p.70～72 ℃; Press embodiment 1 operation preparation compound 4e, reaction 9.0h, yield 49.2%, m.p.138～141 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.20(s，9H，3×CH
3)，4.75(s，2H，CH
2)，5.12(s，2H，NOCH
2)，7.03(dt，J
1＝7.8Hz，J
2＝1.4Hz，1H，C
6H
44-H)，7.34(dt，J
1＝7.8Hz，J
2＝1.2Hz，1H，C
6H
45-H)，7.55(dd，J
1＝8.2Hz，J
2＝1.4Hz，1H，C
6H
4?3-H)，7.87(s，1H，C
6H
4?6-H)，8.23(s，1H，C
2H
2N
3?3-H)，8.30(s，1H，C
2H
2N
3?5-H)，8.63(s，1H，CONH)。
Embodiment 6 N-(2-chloro-phenyl-)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of ethanamide (4f)
Press embodiment 1 operation preparation 4f.
Embodiment 7 N-(3-trifluoromethyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of ethanamide (4g)
Press embodiment 1 operation preparation 3g, reaction 7.5h, ethyl alcohol recrystallization gets the 1.73g white solid, yield 36.1%, m.p.73～75 ℃; Press embodiment 1 operation preparation compound 4g, reaction 6.2h, yield 55.3%, colourless oil liquid.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，4.76(s，2H，CH
2)，5.11(s，2H，CH
2)，7.41(d，J＝7.6Hz，1H，C
6H
4?4-H)，7.49(t，J＝8.0Hz，1H，C
6H
4?5-H)，7.87(s，1H，C
6H
4?2-H)，7.92(d，J＝8.4Hz，1H，C
6H
4?6-H)，7.94(s，1H，C
2H
2N
33-H)，8.23(s，1H，C
2H
2N
35-H)，9.46(s，1H，CONH)。
Embodiment 8 N-(4-p-methoxy-phenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of ethanamide (4h)
Press embodiment 1 operation preparation 3h, reaction 2.6h, behind the ethyl alcohol recrystallization 2.56g purple solid, yield 63.7%, m.p.116～118 ℃; Press embodiment 1 operation preparation compound 4h, reaction 7.5h, yield 58.1%, m.p.126～128 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，3.81(s，3H，NOCH
3)，4.73(s，2H，CH
2)，5.09(s，2H，NOCH
2)，6.90(d，J＝9.2Hz，2H，C
6H
43，5-H)，7.48(d，J＝9.2Hz，2H，C
6H
4?2，6-H)，7.89(s，1H，C
2H
2N
3?3-H)，8.21(s，1H，C
2H
2N
3?5-H)，9.16(s，1H，CONH)。
Embodiment 9 N-(3, the 4-dichlorophenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of ethanamide (4i)
Press embodiment 1 operation preparation 3i, reaction 3.3h, ethyl alcohol recrystallization gets the 3.87g brown solid, yield 80.9%, m.p.102～103 ℃; Press embodiment 1 operation preparation compound 4i, reaction 3.5h, yield 8.0%, m.p.130～131 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，4.73(s，2H，CH
2)，5.10(s，2H，NOCH
2)，7.41(d，J＝6.8Hz，C
6H
3?5-H)，7.52(dd，J
1＝8.8Hz，J
2＝2.4Hz，1H，C
6H
3?6-H)，7.84(d，J＝2.4Hz，1H，C
6H
3?2-H)，7.95(s，1H，C
2H
2N
33-H)，8.21(s，1H，C
2H
2N
3?5-H)，9.38(s，1H，CONH)。
Embodiment 10 N-benzyl-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of propionic acid amide (4j)
2.16g (20.2mmol) benzylamine, 1.95g (14.1mmol) salt of wormwood, 1.73g (2.88mmol) PEG600,20mL methylene dichloride, N
2Protection slowly drips 3.40g (27.0mmol) α-chlorpromazine chloride under the condition of ice bath, 30min dropwises, and TLC follows the tracks of reaction 1.5h.Revolve steaming, washing, drying, ethyl alcohol recrystallization gets 3.91g pale solid 3j, yield 98.0%, m.p.63～65 ℃.
Press embodiment 1 operation preparation compound 4j, reaction 10.8h, white solid 0.28g, yield 16.3%, m.p.87～90 ℃.
1H?NMR(CDCl
3+D
2O，400Hz)δ：1.07(s，9H，3×CH
3)，1.50(d，J＝7.2Hz，3H，CH
3)，4.41(dd，J
1＝14.8Hz，J
2＝5.4Hz，1H，NCH
2)，4.56(dd，J
1＝14.8Hz，J
2＝6.4Hz，1H，NCH
2)，4.69(d，J＝13.6Hz，1H，CH
2)，4.78(q，J＝7.2Hz，1H，CH)，5.26(d，J＝13.6Hz，1H，CH
2)，7.23～7.29(m，5H，C
6H
5)，7.56(d，J＝8.8Hz，2H，C
6H
43，5-H)，7.83(s，1H，C
2H
2N
3?3-H)，8.06(s，1H，C
2H
2N
3?5-H)。
Embodiment 11 N-(3-aminomethyl phenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of propionic acid amide (4k)
Press embodiment 10 operation preparation 3k, reaction 2.3h, ethyl alcohol recrystallization gets the 3.69g brown solid, yield 92.6%, m.p.57～60 ℃; Press embodiment 1 operation preparation compound 4k, reaction 6.9h, yield 43.3%, m.p.128～130 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，1.53(d，J＝7.2Hz，3H，CH
3)，2.36(s，3H，CH
3)，4.81(q，J＝7.2Hz，1H，CH)，4.82(d，J＝13.6Hz，1H，CH
2)，5.36(d，J＝13.6Hz，1H，CH
2)，6.96(d，J＝7.6Hz，1H，C
6H
4?4-H)，7.24(q，J＝7.6Hz，1H，C
6H
4?5-H)，7.35(d，J＝8.0Hz，1H，C
6H
4?6-H)，7.49(s，1H，C
6H
4?2-H)，7.95(s，1H，C
2H
2N
3?3-H)，8.21(s，1H，C
2H
2N
3?5-H)，9.00(s，1H，CONH)。
Embodiment 12 N-(2, the 6-3,5-dimethylphenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of propionic acid amide (4l)
Press embodiment 10 operation preparation 3l, reaction 12.3h, ethyl alcohol recrystallization gets the 3.00g white solid, yield 70.5%, m.p.135～137 ℃; Press embodiment 1 operation preparation compound 4l, reaction 4.0h, yield 35.5%, m.p.154～156 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，1.59(d，J＝7.2Hz，3H，CH
3)，2.19(s，6H，2×CH
3)，4.78(d，J＝13.6Hz，1H，CH
2)，4.87(q，J＝7.2Hz，1H，CH)，5.38(d，J＝13.6Hz，1H，CH
2)，7.06～7.11(m，3H，C
6H
3)，7.55(s，1H，C
2H
2N
3?3-H)，8.17(s，1H，C
2H
2N
3?5-H)，8.76(s，1H，CONH)。
Embodiment 13 N-(2-bromophenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of propionic acid amide (4m)
Press embodiment 10 operation preparation 3m, reaction 5.8h, ethyl alcohol recrystallization gets the 4.02g faint yellow solid, yield 76.2%, m.p.82～83 ℃; Press embodiment 1 operation preparation compound 4m, reaction 10.7h, yield 61.3%, m.p.66～68 ℃.
1H?NMR(CDCl
3+D
2O，400Hz)δ：1.19(s，9H，3×CH
3)，1.56(d，J＝6.8Hz，3H，CH
3)，4.77～5.11(m，3H，CH，CH
2)，7.01(dt，J
1＝8.0Hz，J
2＝1.6Hz，1H，C
6H
4?4-H)，7.33(dt，J
1＝8.0Hz，J
2＝1.6Hz，1H，C
6H
4?5-H)，7.53(dd，J
1＝8.0Hz，J
2＝1.2Hz，1H，C
6H
4?3-H)，7.88(s，1H，C
6H
4?6-H)，8.22(s，1H，C
2H
2N
3?3-H)，8.28(dd，J
1＝8.0Hz，J
2＝1.2Hz，1H，C
2H
2N
35-H)。
Embodiment 14 N-(4-chloro-phenyl-)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of propionic acid amide (4n)
Press embodiment 10 operation preparation 3n, reaction 4.2h, ethyl alcohol recrystallization gets the 1.50g faint yellow solid, yield 34.2%, m.p.106～108 ℃; Press embodiment 1 operation preparation compound 4n, reaction 6.3h, yield 76.4%, m.p.127～129 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，1.52(d，J＝7.2Hz，3H，CH
3)，2.27(s，3H，CH
3)，4.82(d，J＝13.6Hz，1H，CH
2)，4.82(q，J＝6.8Hz，1H，CH)，5.37(d，J＝13.6Hz，1H，CH
2)，7.31(dd，J
1＝6.4Hz，J
2＝2.0Hz，2H，C
6H
4?3，5-H)，7.56(dd，J
1＝6.8Hz，J
2＝2.0Hz，2H，C
6H
4?2，6-H)，7.93(s，1H，C
2H
2N
3?3-H)，8.24(s，1H，C
2H
2N
3?5-H)，9.17(s，1H，CONH)。
Embodiment 15 N-(3, the 4-dichlorophenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of propionic acid amide (4o)
Press embodiment 10 operation preparation 3o, reaction 3.7h, ethyl alcohol recrystallization gets the 2.78g brown solid, yield 54.9%, m.p.124～126 ℃; Press embodiment 1 operation preparation compound 4o, reaction 3.7h, yield 27.1%, m.p.141～143 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.13(s，9H，3×CH
3)，1.52(d，J＝7.2Hz，3H，CH
3)，4.82(q，J＝7.8Hz，1H，CH)，4.83(d，J＝13.2Hz，1H，CH
2)，5.38(d，J＝13.2Hz，1H，CH
2)，7.40(d，J＝2.4Hz，1H，C
6H
35-H)，7.51(dd，J
1＝8.8Hz，J
2＝2.4Hz，1H，C
6H
3?6-H)，7.86(d，J＝8.8Hz，1H，C
6H
3?2-H)，7.98(s，1H，C
2H
2N
3?3-H)，8.30(s，1H，C
2H
2N
3?5-H)，9.28(s，1H，CONH)。
Embodiment 16 N-(3, the 4-3,5-dimethylphenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of propionic acid amide (4p)
Press embodiment 10 operation preparation 3p, reaction 1.7h, ethyl alcohol recrystallization gets the 2.81g white solid, yield 66.0%, m.p.133～135 ℃; Press embodiment 1 operation preparation compound 4p, reaction 5.1h, yield 45.9%, m.p.137～139 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，1.52(d，J＝7.2Hz，3H，CH
3)，2.23，2.26(2×s，6H，C
6H
33，4-CH
3)，4.79(q，J＝7.2Hz，1H，CH
2)，4.82(d，J＝14.0Hz，1H，CH
2)，5.34(d，J＝14.0Hz，1H，CH
2)，7.09(d，J＝8.0Hz，1H，C
6H
3?5-H)，7.29(d，J
1＝8.0Hz，1H，C
6H
3?6-H)，7.41(s，1H，C
6H
3?2-H)，7.93(s，1H，C
2H
2N
3?3-H)，8.19(s，1H，C
2H
2N
3?5-H)，8.88(s，1H，CONH)。
Embodiment 17 N-(3-trifluoromethyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] preparation of propionic acid amide (4q)
Press embodiment 10 operation preparation 3q, reaction 3.8h, ethyl alcohol recrystallization gets the 3.46g white solid, yield 68.2%, m.p.63～66 ℃; Press embodiment 1 operation preparation compound 4q, reaction 4.4h, yield 33.0%, m.p.103～104 ℃.
1H?NMR(CDCl
3，400Hz)δ：1.14(s，9H，3×CH
3)，1.55(d，J＝6.8Hz，3H，CH
3)，4.82(d，J＝13.2Hz，1H，CH
2)，4.85(q，J＝6.8Hz，1H，CH)，5.40(d，J＝13.2Hz，1H，CH
2)，7.39(d，J＝8.0Hz，1H，C
6H
4?4-H)，7.47(t，J＝8.0Hz，C
6H
4?5-H)，7.91，7.89(2×s，2H，C
6H
4?2，6-H)，7.95(s，1H，C
2H
2N
3?3-H)，8.21(s，1H，C
2H
2N
3?5-H)，9.33(s，1H，CONH)。
Embodiment 18 1-(1,2, the 4-triazolyl) ketoxime ether acid amides or its salt fungicidal activity are measured
1. for examination bacterial classification Pyricularia oryzae (Pyricularia oryzae), Rhizoctonia solani Kuhn (Rhizoctonia solani), botrytis cinerea pers (Botrytis cinerea), Sclerotinia sclerotiorum (Sclerotonia sclerotiorum), fusarium graminearum (Gibberella zeae), Phytophthora capsici germ (phytophythora capsici).Above bacterial classification all is kept in the refrigerator (4～8 ℃), tests to be inoculated in the culture dish from the test tube slant in preceding 2～3 days, cultivates to be for experiment under optimal temperature.Experiment is potato agar substratum (PDA) with substratum.Wheat powdery mildew is preserved spore with stem and leaf of Wheat and is for experiment.
2. measuring method accurately takes by weighing an amount of new compound to be measured, with suitable solvent dissolving and adding small amounts of emulsifiers, is diluted to finite concentration with clear water earlier.Concrete grammar is as follows:
Pyricularia oryzae, fusarium graminearum, Phytophthora capsici germ, botrytis cinerea pers and Sclerotinia sclerotiorum: adopt toxic medium therapy, general sieve concentration is 25mg/L.
Rhizoctonia solani Kuhn: adopt the excised leaf culture method, general sieve concentration is 500mg/L.
Wheat powdery mildew: adopt pot-culture method, general sieve concentration is 500mg/L.
3 fungicidal activity evaluations
Handle incidence and the mycelial growth situation of back routine observation record blade, plant,, calculate preventive effect and inhibiting rate according to disease index and hyphal diameter.
Rhizoctonia solani Kuhn: look blank incidence survey record scab diameter, calculate prevention effect (%).
In the formula: P represents prevention effect, D
0Expression blank scab diameter, D
1The scab diameter is handled in expression.
1-(1,2, the 4-triazolyl) ketoxime ether acid amides or the general sieve result of its salt fungicidal activity, compound 4n and 4o show higher bacteriostatic activity, when general sieve concentration is 25mg/L, the inhibiting rate of Sclerotinia sclerotiorum are respectively 71.0% and 52.3%.
1-(1,2, the 4-triazolyl) ketoxime ether or its salt have good Sclerotinia sclerotiorum activity extremely, can be used for preparing the sterilant of Sclerotinia sclerotiorum extremely.
The weeding activity of embodiment 191-(1,2, the 4-triazolyl) ketoxime ether acid amides is measured
1 test objective
In indoor general sieve new compound virulence to piemarker, thorn amaranth, lamb's-quarters, lady's-grass and dog tail under confession examination concentration, estimate its weeding activity.
2 test conditionss
2.1 for the examination target
Target is piemarker (Abutilon theophrasti), thorn amaranth (Amaranthus spinosus L), lamb's-quarters (Chenopodium album), lady's-grass (Digitaria sanguinalis), barnyard grass (Echinochloa crus-galli) and dog tail (Setaria viridis);
2.2 culture condition
Culture condition for examination target and test back target is 20 ± 5 ℃ of temperature, relative humidity 65 ± 5%.
2.3 plant and instrument
Electronic balance (sensibility reciprocal ten thousand/), 100ml beaker, graduated cylinder, crop spraying machine etc.
3 test design
3.1 test medicine 1-(1,2, the 4-triazolyl) ketoxime ether acid amides.
3.2 the general sieve of experimental concentration is established single dose 2250g ai/ha.
3.3 medicament preparation
Take by weighing 1-(1,2, the 4-triazolyl) ketoxime ether acid amides aequum with ten thousand/electronic balance; Solvent: N, dinethylformamide (DMF), 0.2%; Emulsifying agent: Tween80,0.1%; Add clear water and be diluted to desired concn.
4 test methods
With reference to " pesticide bioactivity is estimated SOP ".Cauline leaf is handled and the preceding soil treatment of seedling treatment dosage 2250g ai/ha after adopting NY/T 1155.4-2006 and NY/T 1155.3-2006 standard to carry out seedling.Quantitatively the dress soil pressure is flat in the plastic tub alms bowl of sectional area 64cm2, place Stainless steel basin, choose full seed, seed of the same size, divide single, double cotyledon plant to divide the alms bowl sowing, respectively account for 1/3 of alms bowl area, cover the thick fine earth of 1cm, add water to upper layer of soil from plastic tub alms bowl bottom and soak into, place hot-house culture, treat unifacial leaf examination material grow to 1 heart stage of 1 leaf, dicotyledonous examination material grow to 2 leaf periods and carry out seedling after cauline leaf handle; The examination material is sowed and is carried out the preceding soil treatment of seedling next day.Observe target after 15 days and germinate and growing state, the range estimation growth inhibition ratio.Clear water contrast and solvent control are established in test, and every processing repeats for three times.
5 investigation methods and evaluated biological activity method
Observe target after 15 days and germinate and growing state, the range estimation growth inhibition ratio.
6 general sieve results
By the general sieve of weeding activity to 1-(1,2, the 4-triazolyl) ketoxime ether acid amides.Carry out cauline leaf and handle under 2250g ai/ha concentration, compound 4b is respectively 70%, 90% and 80% to the weeding activity of piemarker (Abutilon theophrasti), thorn amaranth (Amaranthus spinosus L) and lamb's-quarters (Chenopodium album).Soil treatment before under 2250g ai/ha concentration, carrying out seedling, compound 4b is 90% to the weeding activity of thorn amaranth (Amaranthus spinosus L) and lamb's-quarters (Chenopodium album); Carry out cauline leaf and handle under 2250g ai/ha concentration, compound 4c and 4j are respectively 60% and 70% to the weeding activity of thorn amaranth (Amaranthus spinosus L) and lamb's-quarters (Chenopodium album); Compound 4h and 4k are 70% to the weeding activity of thorn amaranth (Amaranthus spinosus L) and lamb's-quarters (Chenopodium album).
1-(1,2, the 4-triazolyl) ketoxime ether acid amides has weeding activity preferably, can be used as the preparation herbicide applications.
Claims (6)
1. the 1-shown in the chemical structural formula (I) (1,2, the 4-triazolyl) ketoxime ether acid amides:
Wherein, R is selected from hydrogen, C
1～C
2Alkyl, C
3～C
4The straight or branched alkyl; R
1Be selected from: hydrogen, C
1～C
2Alkyl, C
3～C
4The straight or branched alkyl; Y is selected from: Ar or ArCH
2: the Ar=phenyl, the 2-fluorophenyl, the 2-chloro-phenyl-, the 2-bromophenyl, the 2-iodophenyl, 2-(trifluoromethyl) phenyl, the 3-aminomethyl phenyl, the 3-fluorophenyl, the 3-chloro-phenyl-, the 3-bromophenyl, the 3-iodophenyl, 3-(trifluoromethyl) phenyl, the 3-p-methoxy-phenyl, the 4-fluorophenyl, the 4-bromophenyl, the 4-iodophenyl, 4-(trifluoromethyl) phenyl, the 4-p-methoxy-phenyl, 2, the 3-3,5-dimethylphenyl, 2, the 4-3,5-dimethylphenyl, 3, the 4-3,5-dimethylphenyl, 3, the 5-3,5-dimethylphenyl, 2, the 6-3,5-dimethylphenyl, 2, the 3-dichlorophenyl, 3, the 4-dichlorophenyl, 3, the 5-dichlorophenyl, 2, the 6-dichlorophenyl.
2. the preparation method of the described 1-of claim 1 (1,2, the 4-triazolyl) ketoxime ether acid amides is characterized in that being undertaken by following chemical equation:
R, R in the reaction formula
1With the definition of Y according to claim 1.
3. the described 1-of claim 1 (1,2, the 4-triazolyl) ketoxime ether acid amides kills the sterilant of Sclerotinia sclerotiorum or the application in the weedicide in preparation.
4. the described 1-(1 of claim 1,2, the 4-triazolyl) the ketoxime ether acid amides is N-rubigan-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] propionic acid amide or N-(3, the 4-dichlorophenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] propionic acid amide kills the application of the sterilant of Sclerotinia sclerotiorum in preparation:
5. described 1-(1,2, the 4-triazolyl) the ketoxime ether acid amides of claim 1 is N-(3-methylbenzene)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] ethanamide removes the herbicide applications of piemarker, thorn amaranth or lamb's-quarters in preparation:
6. the described 1-(1 of claim 1,2, the 4-triazolyl) the ketoxime ether acid amides is N-(3, the 4-3,5-dimethylphenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] ethanamide, N-(4-p-methoxy-phenyl)-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] ethanamide, N-benzyl-2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] propionic acid amide or N-(3-aminomethyl phenyl) 2-[3,3-dimethyl-1-(1,2, the 4-triazol-1-yl) butyl-2-methylene azyloxy] propionic acid amide removes the herbicide applications of thorn amaranth or lamb's-quarters in preparation:
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| CN103130773A (en) * | 2013-03-13 | 2013-06-05 | 湖南大学 | N'-pyridyl methylene acethydrazide and preparation method and application thereof |
| CN104327056A (en) * | 2014-10-09 | 2015-02-04 | 湖南大学 | Preparation method for 1-(benzofuran-5-yl)-2-(1, 2, 4-triazole-1-yl)ketoxime ether and application thereof |
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| CN103130773A (en) * | 2013-03-13 | 2013-06-05 | 湖南大学 | N'-pyridyl methylene acethydrazide and preparation method and application thereof |
| CN103130773B (en) * | 2013-03-13 | 2014-05-07 | 湖南大学 | N'-pyridyl methylene acethydrazide and preparation method and application thereof |
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