CN102002018B - (2-oxo-benzothiazole)-3-diacetyl hydrazone compound as well as preparation method and application thereof - Google Patents
(2-oxo-benzothiazole)-3-diacetyl hydrazone compound as well as preparation method and application thereof Download PDFInfo
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- CN102002018B CN102002018B CN 201010536723 CN201010536723A CN102002018B CN 102002018 B CN102002018 B CN 102002018B CN 201010536723 CN201010536723 CN 201010536723 CN 201010536723 A CN201010536723 A CN 201010536723A CN 102002018 B CN102002018 B CN 102002018B
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- oxo
- phenyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 150000002576 ketones Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000004809 thin layer chromatography Methods 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 39
- -1 substituted-phenyl Chemical group 0.000 claims description 28
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 17
- 238000001953 recrystallisation Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 241000223195 Fusarium graminearum Species 0.000 claims description 11
- 241000813090 Rhizoctonia solani Species 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 241001425390 Aphis fabae Species 0.000 claims description 9
- 241001454293 Tetranychus urticae Species 0.000 claims description 9
- 239000000645 desinfectant Substances 0.000 claims description 8
- 241000221696 Sclerotinia sclerotiorum Species 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 5
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000000749 insecticidal effect Effects 0.000 abstract description 10
- 230000003385 bacteriostatic effect Effects 0.000 abstract description 2
- 239000003899 bactericide agent Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002917 insecticide Substances 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 15
- 239000012065 filter cake Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000003814 drug Substances 0.000 description 12
- 230000001954 sterilising effect Effects 0.000 description 11
- 150000007857 hydrazones Chemical class 0.000 description 9
- 238000011160 research Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 240000006677 Vicia faba Species 0.000 description 7
- 235000010749 Vicia faba Nutrition 0.000 description 7
- 235000002098 Vicia faba var. major Nutrition 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 231100000225 lethality Toxicity 0.000 description 4
- 235000010603 pastilles Nutrition 0.000 description 4
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- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
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- 230000000855 fungicidal effect Effects 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
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- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 2
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- UUWJBXKHMMQDED-UHFFFAOYSA-N 1-(3-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(Cl)=C1 UUWJBXKHMMQDED-UHFFFAOYSA-N 0.000 description 1
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 1
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 description 1
- LAOOXBLMIJHMFO-UHFFFAOYSA-N 1-[2-(diethylamino)ethylamino]-4-methylthioxanthen-9-one;hydron;chloride Chemical compound Cl.S1C2=CC=CC=C2C(=O)C2=C1C(C)=CC=C2NCCN(CC)CC LAOOXBLMIJHMFO-UHFFFAOYSA-N 0.000 description 1
- YRNDGUSDBCARGC-UHFFFAOYSA-N 2-methoxyacetophenone Chemical compound COCC(=O)C1=CC=CC=C1 YRNDGUSDBCARGC-UHFFFAOYSA-N 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000123650 Botrytis cinerea Species 0.000 description 1
- 241000272639 Brachycaudus mimeuri Species 0.000 description 1
- AZORMKLCFWUMBF-UHFFFAOYSA-N C/C(/c1cccc(Cl)c1)=N\[N]C(CN(c1ccccc1S1)C1=O)=O Chemical compound C/C(/c1cccc(Cl)c1)=N\[N]C(CN(c1ccccc1S1)C1=O)=O AZORMKLCFWUMBF-UHFFFAOYSA-N 0.000 description 1
- HZOQHIMPULCTBL-UHFFFAOYSA-N C/C(/c1ccccc1)=N\[N]C(CN(c1ccccc1S1)C1=O)=O Chemical compound C/C(/c1ccccc1)=N\[N]C(CN(c1ccccc1S1)C1=O)=O HZOQHIMPULCTBL-UHFFFAOYSA-N 0.000 description 1
- 241001330975 Magnaporthe oryzae Species 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 241000244206 Nematoda Species 0.000 description 1
- 239000005822 Propiconazole Substances 0.000 description 1
- 241001558929 Sclerotium <basidiomycota> Species 0.000 description 1
- 241000256247 Spodoptera exigua Species 0.000 description 1
- 241000985245 Spodoptera litura Species 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 239000000417 fungicide Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
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- 230000001843 schistosomicidal effect Effects 0.000 description 1
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- 238000004659 sterilization and disinfection Methods 0.000 description 1
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- 239000004308 thiabendazole Substances 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 229960004546 thiabendazole Drugs 0.000 description 1
- 235000010296 thiabendazole Nutrition 0.000 description 1
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- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention discloses a (2-oxo-benzothiazole)-3-diacetyl hydrazone compound as shown in formula (I) as well as a preparation method and application thereof. The preparation method comprises the following steps: adding (2-oxo-benzothiazole)-3-acethydrazide as shown in formula (II) and ketone as shown in formula (III) in an absolute ethyl alcohol solvent, stirring and heating to 78 DEG C, performing refluxing reaction for 1-5h, tracking the reaction by a thin layer chromatography, postprocessing the reaction solution after the reaction is finished to obtain the compound as shown in formula (I), wherein the compound has good insecticidal and bacteriostatic activity, and can be utilized as an insecticide and a bactericidal agent.
Description
(1) technical field
The present invention relates to a kind of (2-oxo-benzothiazole)-3-acetyl hydrazone compounds and preparation method thereof and application.
(2) background technology
Because of life-time service sterilant and disinfectant, cause disease and pest to produce resistance in recent years, so use existing sterilant and disinfectant to prevent and treat the difficulty that becomes.Therefore, the sterilant of research and development novel texture and disinfectant or primer become very urgent.
Because heterogeneous ring compound (especially fused heterocyclic compound) has biological activity widely, its low toxicity, the characteristics such as efficient, environmentally friendly have in addition become the focus of current pesticide developing.As the important member in fused heterocyclic compound, benzothiazole and derivative thereof have pesticide bioactivity widely, also receive very big concern in the initiative of novel pesticide and disinfectant.For example, WO 9406783 has disclosed a class 2-(2-fluorine ethylmercapto group)-4,5,6, and 7-four substituted benzothiazole derivatives have certain pesticide and miticide actility, and two-spotted spider mite, black peach aphid, housefly, beet armyworm etc. are all had insecticidal activity preferably; 2003; (the Pest Manag such as Sawada; 2003; 59 (1): 25-35) reported a kind of N '-benzothiazole ring carbonyl acyl group-N-tertiary butyl-3; 5-dimethyl benzene formyl hydrazine compound; the biological activity test result shows that this compound has good prevention effect to the larva of prodenia litura, and the lethality rate when concentration is 50mg/L reaches 100%.
Nineteen sixty-eight, (US 3017415, are 1962-01-16) a kind of systemic fungicides, and is with the dosage of 200～400ga.i./ha, effective to the fungal disease of multiple kinds of crops for the thiabendazole that Merck Chemical Co. promotes.EP 0590610 has disclosed benzothiazole derivatives, and detected result shows, under the concentration of 1.0mmol/L, compound all has good inhibiting rate to Pyricularia oryzae, wheat leaf rust germ, rhizoctonia solani, botrytis cinerea pers etc.
As for the hydrazone compounds that contains the benzothiazole structure, report is arranged also in document.For example, (Pharmazie, 2003,58 (8): 527-530) synthesized a class N '-thiazole imino--N-benzothiazole hydrazone compounds such as Mahran, sterilization and parasitocidal activity test result show, it all has certain prevention effect to nematode and schistosomicide.(the Il Farmaco such as Bilge C., 1999,54:842-845) reported a class (2-oxo-benzothiazole)-3-acetyl hydrazone compounds and as the application of spasmolytic, not identical with (2-oxo-benzothiazole)-3-acetyl hydrazone compounds provided by the invention.
(2-oxo-benzothiazole)-3-acetyl hydrazone compounds that the present invention designs and synthesizes, its structure, preparation method and be not reported as the research of sterilant and disinfectant.
(3) summary of the invention
The object of the invention is to provide a kind of (2-oxo-benzothiazole)-3-acetyl hydrazone compounds and preparation method thereof and application is particularly as the application of sterilant and disinfectant.
The technical solution used in the present invention is as follows:
A kind of suc as formula (2-the oxo-benzothiazole)-3-acetyl hydrazone compounds shown in (I):
In formula (I), R
1, R
2Independent separately is C
1～C
4Alkyl, phenyl or substituted-phenyl, the substituting group of described substituted-phenyl is one or more substituting group on phenyl ring, described substituting group is C
1～C
3Alkyl, halogen, nitro or methoxyl group.
R in described compound (I)
1Be preferably methyl; Work as R
1During for methyl, preferred R
2For one of following: methyl, ethyl, sec.-propyl, phenyl, 4-aminomethyl phenyl, 4-chloro-phenyl-, 3-chloro-phenyl-, 4-fluorophenyl, 4-bromophenyl, 4-nitrophenyl, 2,6-difluorophenyl, 2-p-methoxy-phenyl or 4-p-methoxy-phenyl.
R in described compound (I)
1Be methyl, R
2More preferably one of following: methyl, ethyl, sec.-propyl, 3-chloro-phenyl-, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-nitrophenyl or 2,6-difluorophenyl.
the preparation method of described (2-oxo-benzothiazole)-3-acetyl hydrazone compounds is: will add in anhydrous ethanol solvent suc as formula the ketone shown in (2-the oxo-benzothiazole)-3-acethydrazide shown in (II) and formula (III), stir and be heated to 78 ℃, back flow reaction 1～5h, thin-layer chromatography is followed the tracks of reaction, reaction finishes, the reaction solution aftertreatment is made (2-the oxo-benzothiazole)-3-acetyl hydrazone compounds shown in formula (I), the ratio of the amount of substance that feeds intake of the ketone shown in (2-the oxo-benzothiazole)-3-acethydrazide shown in described formula (II) and formula (III) is 1: 1.0～1.5, the volumetric usage of dehydrated alcohol is counted 2～5mL/mmol with the amount of substance of (2-oxo-benzothiazole)-3-acethydrazide,
In formula (III), R
1, R
2Independent separately is C
1～C
4Alkyl, phenyl or substituted-phenyl, the substituting group of described substituted-phenyl is one or more substituting group on phenyl ring, described substituting group is C
1～C
3Alkyl, halogen, nitro or methoxyl group.
The ratio of the amount of substance that feeds intake of the ketone shown in (2-the oxo-benzothiazole)-3-acethydrazide shown in described formula (II) and formula (III) is preferably 1: 1.0～and 1.1.
Described aftertreatment is: after reaction finished, reaction solution was cooling, filter to get solid crude product, made suc as formula (2-the oxo-benzothiazole)-3-acetyl hydrazone compounds shown in (I) with the recrystallization solvent recrystallization.
Described recrystallization solvent is the mixed solution of following one or more arbitrary proportions: sherwood oil, ethyl acetate, normal hexane or dehydrated alcohol.
Described thin-layer chromatography is followed the tracks of reaction, adopts sherwood oil and ethyl acetate mixture (V
Sherwood oil: V
Ethyl acetate=3: 1) be developping agent, the ultraviolet colour developing is followed the tracks of and is reacted to the completely dissolve of raw material (II) point, and namely raw material (II) reacts completely and is reaction end.
The invention still further relates to described (2-oxo-benzothiazole)-3-acetyl hydrazone compounds as the application of sterilant.Adopt pickling process synthetic compound to be carried out the insecticidal activity assay of black bean aphid (Aphis fabae) and two-spotted spider mite (Tetranchus urticae), general sieve concentration is 500mg/L.Result shows, the compound shown in formula (I) all has certain insecticidal activity to bean aphid, and the compound shown in segment bounds (I) has certain insecticidal activity to two-spotted spider mite.
The invention still further relates to described (2-oxo-benzothiazole)-3-acetyl hydrazone compounds as the application of disinfectant.Adopt pastille potato agar substratum (PDA) method that the fungicidal activity that synthetic compound has carried out Sclerotinia sclerotiorum (Sclerotonia sclerotiorum) and fusarium graminearum (Gibberella zeae) is measured, general sieve concentration is 25mg/L; Adopt the Broad Bean Leaves method that the fungicidal activity that synthetic compound has carried out Rhizoctonia solani Kuhn (Rhizoctonia solani) is measured, general sieve concentration is 500mg/L.Result shows, the compound shown in segment bounds (I) shows certain sterilizing activity to Sclerotinia sclerotiorum and fusarium graminearum, and the compound shown in most of formula (I) shows good sterilizing activity to Rhizoctonia solani Kuhn.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: the invention provides a kind of novel (2-oxo-benzothiazole)-3-acetyl hydrazone compounds, this compounds preparation is simple, shows good desinsection and sterilizing activity.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Thin-layer chromatography in all embodiment of the present invention is followed the tracks of reaction, adopts sherwood oil and ethyl acetate mixture (V
Sherwood oil: V
Ethyl acetate=3: 1) be developping agent, the ultraviolet colour developing is followed the tracks of and is reacted to the completely dissolve of raw material (II) point, and namely raw material (II) reacts completely and is reaction end.
Embodiment 1 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-1 (R
1=methyl, R
2Synthesizing=methyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 0.58g (10mmol) acetone are dissolved in the 20mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 1 hour.Thin-layer chromatography is followed the tracks of, and reaction finishes, reaction solution is cooling, filtration, and filter cake 15mL re-crystallizing in ethyl acetate makes white crystal 2.39g, i.e. Compound I-1.243～245 ℃ of fusing points, yield (in (2-oxo-benzothiazole)-3-acethydrazide, lower same) is 90.7%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(CDCl
3)δ：1.83(s，3H，-CCH
3 CH 3 )，2.04(s，3H，-C
CH 3 CH
3)，5.06(s，2H，-CH
2-)，6.91～7.44(m，4H，-Ph)，8.83(s，1H，-NH-)；
IR?v(cm
-1)：3453，3191，3041，1679，1596，1550，1476，1412，1332，1306，1276，1223，1187，1039，1022，988，750，735。
Embodiment 2 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-2 (R
1=methyl, R
2Synthesizing=ethyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 1.08g (15mmol) butanone are dissolved in the 30mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 1.5 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake makes white crystal 2.42g, i.e. Compound I-2 with 15mL sherwood oil recrystallization.170～172 ℃ of fusing points, yield are 87.3%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(CDCl
3)δ：1.14(t，3H，J＝7.5Hz，-CH
2 CH 3 )，1.83(s，3H，＝C
CH 3 C
2H
5)，2.32～2.36(q，2H，＝CCH
3 CH 2 CH
3)，5.08(s，2H，-CH
2-)，6.92～7.47(m，4H，-Ph)，8.52(s，1H，-NH-)；
IR?v(cm
-1)：3454，3203，3042，2939，1695，1670，1555，1476，1415，1374，1266，1224，1189，1042，986，748。
Embodiment 3 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-3 (R
1=methyl, R
2Synthesizing=phenyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 1.32g (11mmol) methyl phenyl ketone are dissolved in the 40mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 2.5 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake makes white crystal 2.80g, i.e. Compound I-3 with 20mL normal hexane recrystallization.244～245 ℃ of fusing points, yield are 86.0%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(CDCl
3)δ：2.20(s，3H，＝CPh
CH 3 )，5.23(s，2H，-CH
2-)，6.94～7.77(m，9H，-Ph)，9.12(s，1H，-NH-)；
IR?v(cm
-1)：3451，3192，3036，1694，1663，1556，1474，1420，1366，1333，1265，1235，1178，1103，992，763。
Embodiment 4 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-4 (R
1=methyl, R
2Synthesizing=2,6-difluorophenyl)
With 2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 1.56g (10mmol) 2, the 6-difluoro acetophenone is dissolved in the 50mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 3 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake obtains white crystal, i.e. Compound I-4 with 20mL dehydrated alcohol recrystallization 2.98g.247～249 ℃ of fusing points, yield are 82.6%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(d
6-DMSO)δ：2.26(s，3H，＝CPh
CH 3 )，5.00(s，2H，-CH
2-)，7.18～7.69(m，7H，-Ph)，11.27(s，1H，-NH-)；
IR?v(cm
-1)：3449，3201，3054，1698，1665，1474，1465，1369，1333，1236，1178，1110，1025，990，788，769。
Embodiment 5 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-5 (R
1=methyl, R
2Synthesizing=4-chloro-phenyl-)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 2.16g (14mmol) 4-chloro-acetophenone are dissolved in the 30mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 4 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake 20mL re-crystallizing in ethyl acetate obtains white crystal 3.13g, i.e. Compound I-5.241～243 ℃ of fusing points, yield are 87.0%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(d
6-DMSO)δ：2.29(s，3H，＝CPh
CH 3 )，5.21(s，2H，-CH
2-)，7.19～7.91(m，8H，-Ph)，11.10(s，1H，-NH-)；
IR?v(cm
-1)：3455，3216，3073，1704，1656，1479，1459，1373，1340，1257，1187，1008，991，827，746。
Embodiment 6 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-6 (R
1=methyl, R
2Synthesizing=4-aminomethyl phenyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 1.61g (12mmol) 4-methyl acetophenone are dissolved in the 25mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 5 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake obtains white crystal 3.02g, i.e. Compound I-6 with 15mL normal hexane recrystallization.246～248 ℃ of fusing points, yield are 89.0%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(CDCl
3)δ：2.20(s，3H，＝CPh
CH 3 )，2.39(s，3H，-Ph
CH 3 )，5.22(s，2H，-CH
2-)，6.94～7.67(m，8H，-Ph)，9.15(s，1H，-NH-)；
IR?v(cm
-1)：3447，3194，3110，1679，1475，1406，1329，1265，1183，1125，986，843，814，763。
Embodiment 7 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-7 (R
1=methyl, R
2Synthesizing=4-nitrophenyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 2.15g (13mmol) 4-nitro-acetophenone are dissolved in the 30mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 2.5 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake obtains light yellow crystal 2.99g, i.e. Compound I-7 with 15mL sherwood oil recrystallization.301～302 ℃ of fusing points, yield are 80.7%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(d
6-DMSO)δ：2.36(s，3H，＝CPh
CH 3 )，5.26(s，2H，-CH
2-)，7.20～8.27(m，8H，-Ph)，11.32(s，1H，-NH-)；
IR?v(cm
-1)：3456，3212，2958，1708，1652，1588，1515，1476，1459，1403，1384，1341，1154，1183，1131，1116，852，787。
Embodiment 8 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-8 (R
1=methyl, R
2Synthesizing=4-fluorophenyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 1.52g (11mmol) 4-fluoro acetophenone are dissolved in the 30mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 1.0 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake 20mL re-crystallizing in ethyl acetate obtains clear crystal 2.80g, i.e. Compound I-8.247～248 ℃ of fusing points, yield are 81.5%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(CDCl
3)δ：2.22(s，3H，＝CPh
CH 3 )，5.21(s，2H，-CH
2-)，6.94～7.78(m，8H，-Ph)，9.08(s，1H，-NH-)；
IR?v(cm
-1)：3358，3195，3073，2951，1679，1619，1596，1509，1475，1329，1222，1184，1161，1107，1011，988，871，768。
Embodiment 9 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-9 (R
1=methyl, R
2Synthesizing=3-chloro-phenyl-)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 1.55g (10mmol) 3-chloro-acetophenone are dissolved in the 45mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 2.0 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake obtains clear crystal 3.01g, i.e. Compound I-9 with 15mL dehydrated alcohol recrystallization.226～228 ℃ of fusing points, yield are 83.8%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(d
6-DMSO)δ：2.30(s，3H，＝CPh
CH 3 )，5.23(s，2H，-CH
2-)，7.20～7.91(m，8H，-Ph)，11.41(s，1H，-NH-)；
IR?v(cm
-1)：3453，3189，3078，1672，1589，1560，1474，1411，1326，1309，1276，1178，1142，886，815，794。
Embodiment 10 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-10 (R
1=methyl, R
2Synthesizing=2-p-methoxy-phenyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 1.80g (12mmol) 2-methoxyacetophenone are dissolved in the 40mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 3.5 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake 20mL re-crystallizing in ethyl acetate obtains clear crystal 2.83g, i.e. Compound I-10.217～219 ℃ of fusing points, yield are 79.6%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(CDCl
3)δ：2.21(s，3H，＝CPh
CH 3 )，3.88(s，3H，-OCH
3)，5.14(s，2H，-CH
2-)，6.92～7.44(m，8H，-Ph)，8.76(s，1H，-NH-)；
IR?v(cm
-1)：3453，3176，3033，1652，1594，1556，1475，1432，1330，1305，1270，1182，1126，987，865，746。
Embodiment 11 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-11 (R
1=methyl, R
2Synthesizing=4-p-methoxy-phenyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 1.80g (11mmol) 4-methoxyacetophenone are dissolved in the 50mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 5.0 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake obtains clear crystal 2.95g, i.e. Compound I-11 with 20mL normal hexane recrystallization.218～220 ℃ of fusing points, yield are 83.0%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(CDCl
3)δ：2.16(s，3H，＝CPh
CH 3 )，3.86(s，3H，-OCH
3)，5.21(s，2H，-CH
2-)，6.92～7.73(m，8H，-Ph)，9.07(s，1H，-NH-)；
IR?v(cm
-1)：3461，3218，3073，1656，1600，1513，1475，1407，1371，1303，1251，1178，1031，985，827，740。
Embodiment 12 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-12 (R
1=methyl, R
2Synthesizing=4-bromophenyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 2.09g (10.5mmol) 4-bromoacetophenone are dissolved in the 25mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 3.0 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake 15mL re-crystallizing in ethyl acetate obtains clear crystal 3.77g, i.e. Compound I-12.266～268 ℃ of fusing points, yield are 93.2%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(d
6-DMSO)δ：2.29(s，3H，＝CPh
CH 3 )，5.21(s，2H，-CH
2-)，7.19～7.84(m，8H，-Ph)，11.13(s，1H，-NH-)；
IR?v(cm
-1)：3455，3218，2989，2954，1706，1656，1478，1391，1340，1257，1128，1024，1004，991，846，789。
Embodiment 13 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-13 (R
1=methyl, R
2Synthesizing=sec.-propyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 0.95g (11mmol) 3-methyl-2-butanone are dissolved in the 45mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 5.0 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake obtains clear crystal 2.37g, i.e. Compound I-13 with the mixed solution recrystallization of 10mL ethyl acetate and 10mL sherwood oil.179～181 ℃ of fusing points, yield are 81.4%.
1H NMR, IR atlas analysis are as follows:
1H?NMR(CDCl
3)δ：1.13(d，6H，J＝7Hz，-CH
CH 3 CH 3 )，1.77(s，3H，＝CCH
3)，2.50～2.56(m，1H，-CH-)，5.07(s，2H，-CH
2-)，6.92～7.45(m，4H，-Ph)；8.70(s，1H，-NH-)；
IR?v(cm
-1)：3454，3183，3036，2955，2868，1692，1654，1587，1543，1423，1366，1180，983，864，716。
Embodiment 14 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-2 (R
1=methyl, R
2Synthesizing=ethyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 0.72g (10mmol) butanone are dissolved in the 35mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 1.5 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake obtains white crystal 2.35g, i.e. Compound I-2 with the mixed solution recrystallization of 10mL dehydrated alcohol and 5mL normal hexane.170～172 ℃ of fusing points, yield are 85.0%.
Embodiment 15 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-6 (R
1=methyl, R
2Synthesizing=4-aminomethyl phenyl)
2.25g (10mmol) (2-oxo-benzothiazole)-3-acethydrazide and 2.01g (15mmol) 4-methyl acetophenone are dissolved in the 50mL dehydrated alcohol, and stirring and dissolving is heated to 78 ℃, back flow reaction 5 hours.Reaction finishes, reaction solution is cooling, filtration, and filter cake obtains white crystal 3.06g, i.e. Compound I-6 with the mixed solution recrystallization of 5mL ethyl acetate, 5mL sherwood oil and 5mL normal hexane.246～248 ℃ of fusing points, yield are 90.2%.
Embodiment 16 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds desinsection and bacteriostatic activity test
(1) (2-oxo-benzothiazole)-3-acetyl hydrazone compounds insecticidal activity test
For trying target: black bean aphid (Aphis fabae, living survey section of Hunan Chemical Research Institute preserves) and two-spotted spider mite (Tetranchus urticae, living survey section of Hunan Chemical Research Institute preserves), if test is that 3 age in days aphids, two-spotted spider mite are healthy one-tenth mite with black bean aphid, is all indoor with broad bean seedling raising sensitive strain for many years.
The recovery room culture condition: the culture temperature for target after examination target and application of sample is 25 ± 5 ℃, and relative humidity is 65 ± 5%, and periodicity of illumination is 12/12h (L/D).
Medicament preparation: accurately take the prepared Compound I of 0.0050g embodiment 1～13-1～I-13 (content is in 100%) with ten thousand/electronic balance, use 0.2mLN, dinethylformamide (DMF) dissolving, add the clear water 9.8mL that contains 0.1% tween 80, stir, with the clear water dilution, be mixed with the medicament of 500mg/L, standby.
The preparation of blank sample: former medicine replaces with water, and other are prepared with medicament.
Concrete testing method is with reference to " pesticide bioactivity is estimated SOP ".
1) mensuration of (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-1～I-13 to the black bean aphid insecticidal activity:
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 medicament that is preparing and blank liquid respectively, was inserted on the sponge that suctions water, cover the lampshade that starts, be placed in the recovery indoor cultivation, regularly observe, check and put down in writing death condition after 72h, calculate mortality ratio.The experiment replicate(determination) is got average 2 times, the results are shown in Table 1.
2) mensuration of (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-1～I-13 to the two-spotted spider mite insecticidal activity:
Cut become the broad bean seedling of the two-spotted spider mite of mite with unsoundness, soak in the medicament for preparing and blank liquid and took out afterwards in 10 seconds, suck unnecessary liquid around plant and mite body with filter paper, be inserted on dress water and the beaker with para film (Shanghai is along thing Science and Technology Ltd. of Johnson ﹠ Johnson) sealing, and beaker is placed in the recovery indoor cultivation, regularly observe, check and put down in writing death condition after 72h, calculate mortality ratio.The experiment replicate(determination) is got average 2 times, the results are shown in Table 1.
(2) (2-oxo-benzothiazole)-3-acetyl hydrazone compounds sterilizing activity test
For trying target: fusarium graminearum (Gibberella zeae, the preservation of living survey section of Hunan Chemical Research Institute), Sclerotinia sclerotiorum (Sclerotonia sclerotiorum, the preservation of living survey section of Hunan Chemical Research Institute), Rhizoctonia solani Kuhn (Rhizoctonia solani, living survey section of Hunan Chemical Research Institute preserves), above-mentioned bacterial classification is stored in 4～8 ℃ of refrigerators, test front 2～3d and be inoculated in culture dish from the test tube slant, cultivate under optimal temperature, standby.
The recovery room culture condition: the culture temperature for target after examination target and application of sample is 25 ± 5 ℃, and relative humidity is 65 ± 5%.
Medicament preparation: accurately take 0.0050g Compound I-1～I-13 (content is in 100%) with ten thousand/electronic balance, with the 0.2mLDMF dissolving, add the sterilized water 9.8mL that contains 0.1% tween 80, stir, with the sterilized water dilution, be mixed with the medicament of 500mg/L, standby.
The preparation of control sample: replace Compound I-1～I-13 with Wocosin 50TK (propiconazole, Hunan Chemical Research Institute's pesticide formulation and applied system research provide), preparation respective concentration control sample, standby; Former medicine replaces with sterilized water, and other are prepared with medicament, makes blank.
With reference to farm-chemical indoor determination test rule NY/T1156.2-2006: adopt pastille potato agar substratum (PDA) method prepared (2-the oxo-benzothiazole)-3-acetyl hydrazone compounds I-1～I-13 of embodiment 1～13 to be carried out the sterilizing activity mensuration of fusarium graminearum (Gibberella zeae) and Sclerotinia sclerotiorum (Sclerotonia sclerotiorum), general sieve concentration is 25mg/L; Adopt the Broad Bean Leaves method that the sterilizing activity that embodiment 1～13 preparation compound carries out Rhizoctonia solani Kuhn (Rhizoctoniasolani) is measured, general sieve concentration is 500mg/L.
Concrete testing method is with reference to " pesticide bioactivity is estimated SOP ".
1) fusarium graminearum and Sclerotinia sclerotiorum sterilizing activity are measured: respectively get 500mg/L medicament and contrast liquid 2mL, add in the 38mLPDA substratum that is cooled to 45 ℃, making final concentration is the pastille culture medium flat plate of 25mg/L.Then from the cultured mycelia piece of testing germ colony edge picking diameter 6.5mm, move on the pastille substratum, be placed in the constant temperature biochemical cultivation case (SPX-150BY-II, upper oceanic rise open up plant and instrument company limited) of 28 ℃ and cultivate, measure colony diameter after 4 days, calculate growth inhibition ratio.Test parallel 4 times and get average, the results are shown in Table 1.
2) the Rhizoctonia solani Kuhn sterilizing activity is measured: Broad Bean Leaves is fully infiltrated 5s in medicament and contrast liquid, drain unnecessary liquid, after natural air drying, press the marks for treatment moisturizing and cultivate.There is the one side of mycelia to be inoculated in the processing blade diameter 5mm bacterium cake with inoculator central, each sample inoculation 30 blade, inoculation is placed on the constant temperature biochemical cultivation case (SPX-150BY-II of 28 ℃, upper oceanic rise is opened up plant and instrument company limited) in cultivate after 3 days, depending on the contrast incidence, measure colony diameter, calculate growth inhibition ratio, the results are shown in Table 1:
Desinsection and the sterilizing activity of table 1 (2-oxo-benzothiazole)-3-acetyl hydrazone compounds I-1～I-13
As can be seen from Table 1, the prepared compound of embodiment 1～13 all has certain insecticidal activity to bean aphid, Compound I-1 (R
1=methyl, R
2=methyl), Compound I-2 (R
1=methyl, R
2=ethyl) lethality rate is more than 70%, Compound I-4 (R
1=methyl, R
2=2,6-difluorophenyl) and Compound I-10 (R
1=methyl, R
2=2-p-methoxy-phenyl) lethality rate is more than 50%; Compound shown in segment bounds (I) has certain insecticidal activity to two-spotted spider mite, wherein Compound I-2 (R
1=methyl, R
2=ethyl) to its lethality rate more than 60%.
Compound shown in segment bounds (I) shows certain sterilizing activity to Sclerotinia sclerotiorum and fusarium graminearum, as Compound I-5 (R
1=methyl, R
2=4-chloro-phenyl-), I-12 (R
1=methyl, R
2=4-bromophenyl) to the inhibiting rate of sclerotium germ all more than 50%, I-11 (R
1=methyl, R
2=4-p-methoxy-phenyl) be 52.7% to the inhibiting rate of fusarium graminearum; Compound shown in most of formula (I) shows good inhibition activity, wherein Compound I-4 (R to Rhizoctonia solani Kuhn
1=methyl, R
2=2,6-difluorophenyl), I-6 (R
1=methyl, R
2=4-aminomethyl phenyl), I-7 (R
1=methyl, R
2=4-nitrophenyl), I-9 (R
1=methyl, R
2=3-chloro-phenyl-), I-11 (R
1=methyl, R
2=4-p-methoxy-phenyl), I-13 (R
1=methyl, R
2=sec.-propyl) to its inhibiting rate all more than 90%.
Claims (10)
1. (2-oxo-benzothiazole)-3-acetyl hydrazone compounds as shown in the formula (I):
In formula (I), R
1, R
2Independent separately is C
1~ C
4Alkyl, phenyl or substituted-phenyl, one or more substituting group is arranged on the phenyl ring of described substituted-phenyl, described substituting group is C
1~ C
3Alkyl, halogen, nitro or methoxyl group.
2. (2-oxo-benzothiazole)-3-acetyl hydrazone compounds as claimed in claim 1, is characterized in that R in described compound (I)
1Be methyl.
3. (2-oxo-benzothiazole)-3-acetyl hydrazone compounds as claimed in claim 1, is characterized in that in described compound (I) R
1During for methyl, R
2For one of following: methyl, ethyl, sec.-propyl, phenyl, 4-aminomethyl phenyl, 4-chloro-phenyl-, 3-chloro-phenyl-, 4-fluorophenyl, 4-bromophenyl, 4-nitrophenyl, 2,6-difluorophenyl, 2-p-methoxy-phenyl or 4-p-methoxy-phenyl.
4. method for preparing (2-oxo-benzothiazole)-3-acetyl hydrazone compounds as claimed in claim 1, it is characterized in that described method is: (2-oxo-benzothiazole)-3-acethydrazide that will be as shown in the formula (II) and the ketone shown in formula (III) add in anhydrous ethanol solvent, stir and be heated to 78 ℃, back flow reaction 1 ~ 5h, thin-layer chromatography is followed the tracks of reaction, reaction finishes, the reaction solution aftertreatment is made (2-the oxo-benzothiazole)-3-acetyl hydrazone compounds shown in formula (I), the ratio of the amount of substance that feeds intake of the ketone shown in (2-the oxo-benzothiazole)-3-acethydrazide shown in described formula (II) and formula (III) is 1:1.0 ~ 1.5,
In formula (III), R
1, R
2Independent separately is C
1~ C
4Alkyl, phenyl or substituted-phenyl, one or more substituting group is arranged on the phenyl ring of described substituted-phenyl, described substituting group is C
1~ C
3Alkyl, halogen, nitro or methoxyl group.
5. (2-oxo-benzothiazole)-3-acetyl hydrazone compounds preparation method as claimed in claim 4, the volumetric usage of described dehydrated alcohol is counted 2 ~ 5 mL/mmol with the amount of substance of (2-oxo-benzothiazole)-3-acethydrazide.
6. (2-oxo-benzothiazole)-3-acetyl hydrazone compounds preparation method as claimed in claim 4, is characterized in that the ratio of the amount of substance that feeds intake of the ketone shown in (2-the oxo-benzothiazole)-3-acethydrazide shown in described formula (II) and formula (III) is 1:1.0 ~ 1.1.
7. (2-oxo-benzothiazole)-3-acetyl hydrazone compounds preparation method as claimed in claim 4, it is characterized in that described aftertreatment is: after reaction finishes, reaction solution is cooling, filter to get solid crude product, makes as shown in the formula (I) (2-oxo-benzothiazole)-3-acetyl hydrazone compounds with the recrystallization solvent recrystallization.
8. (2-oxo-benzothiazole)-3-acetyl hydrazone compounds preparation method as claimed in claim 7, is characterized in that described recrystallization solvent is the mixed solution of following one or more arbitrary proportions: sherwood oil, ethyl acetate, normal hexane or dehydrated alcohol.
9. (2-oxo-benzothiazole)-3-acetyl hydrazone compounds as claimed in claim 1 is as the application of black bean aphid or two-spotted spider mite sterilant.
10. (2-oxo-benzothiazole)-3-acetyl hydrazone compounds as claimed in claim 1 is as the application of fusarium graminearum, Sclerotinia sclerotiorum or Rhizoctonia solani Kuhn disinfectant.
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|---|---|---|---|---|
| WO1994006783A1 (en) * | 1992-09-16 | 1994-03-31 | Zeneca Limited | Benzoxazole and benzothiazole derivatives |
| CN101805330A (en) * | 2010-04-23 | 2010-08-18 | 浙江理工大学 | 2-alkyl-benzimidazole-1-acetyl hydrazone and synthesis method and application thereof |
| CN101874496A (en) * | 2010-06-30 | 2010-11-03 | 浙江工业大学 | Application of acyl hydrazone derivative as fungicide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994006783A1 (en) * | 1992-09-16 | 1994-03-31 | Zeneca Limited | Benzoxazole and benzothiazole derivatives |
| CN101805330A (en) * | 2010-04-23 | 2010-08-18 | 浙江理工大学 | 2-alkyl-benzimidazole-1-acetyl hydrazone and synthesis method and application thereof |
| CN101874496A (en) * | 2010-06-30 | 2010-11-03 | 浙江工业大学 | Application of acyl hydrazone derivative as fungicide |
Non-Patent Citations (1)
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| Bilge Çakir,et al..Synthesis and anticonvulsant activity of some (2:4-substituted)benzaldehyde (2-oxobenzothiazolin-3-yl)acetohydrazones.《Il Farmaco》.1999,第54卷(第11-12期),第842-845页. * |
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