CN101889577B - Use of bishydrazide compounds as herbicide - Google Patents
Use of bishydrazide compounds as herbicide Download PDFInfo
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- CN101889577B CN101889577B CN 201010213077 CN201010213077A CN101889577B CN 101889577 B CN101889577 B CN 101889577B CN 201010213077 CN201010213077 CN 201010213077 CN 201010213077 A CN201010213077 A CN 201010213077A CN 101889577 B CN101889577 B CN 101889577B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 239000004009 herbicide Substances 0.000 title claims abstract description 10
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 6
- 244000237956 Amaranthus retroflexus Species 0.000 claims abstract description 9
- 241000196324 Embryophyta Species 0.000 claims abstract description 8
- 235000013479 Amaranthus retroflexus Nutrition 0.000 claims abstract description 7
- -1 pyridine radicals Chemical group 0.000 claims description 66
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 8
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 8
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 7
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 claims description 7
- 241000192043 Echinochloa Species 0.000 claims description 7
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 5
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 239000002689 soil Substances 0.000 abstract description 4
- 240000003176 Digitaria ciliaris Species 0.000 abstract description 2
- 235000017898 Digitaria ciliaris Nutrition 0.000 abstract description 2
- 244000058871 Echinochloa crus-galli Species 0.000 abstract description 2
- 235000001602 Digitaria X umfolozi Nutrition 0.000 abstract 1
- 235000005476 Digitaria cruciata Nutrition 0.000 abstract 1
- 235000006830 Digitaria didactyla Nutrition 0.000 abstract 1
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 abstract 1
- 235000010823 Digitaria sanguinalis Nutrition 0.000 abstract 1
- 235000014716 Eleusine indica Nutrition 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 23
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 21
- 238000000921 elemental analysis Methods 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- STHOVXWVIWPPHA-UHFFFAOYSA-N CCC(N(N)OC(C=CC(Cl)=C1)=C1Cl)=O Chemical compound CCC(N(N)OC(C=CC(Cl)=C1)=C1Cl)=O STHOVXWVIWPPHA-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001263 acyl chlorides Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- DXGIRFAFSFKYCF-UHFFFAOYSA-N propanehydrazide Chemical compound CCC(=O)NN DXGIRFAFSFKYCF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000009333 weeding Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- HVZWVEKIQMJYIK-UHFFFAOYSA-N nitryl chloride Chemical compound [O-][N+](Cl)=O HVZWVEKIQMJYIK-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
- MZHCENGPTKEIGP-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(Cl)C=C1Cl MZHCENGPTKEIGP-UHFFFAOYSA-N 0.000 description 1
- 241000426497 Chilo suppressalis Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- 235000011999 Panicum crusgalli Nutrition 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 241000256247 Spodoptera exigua Species 0.000 description 1
- 241000985245 Spodoptera litura Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses the use of bishydrazide compounds as a herbicide. The invention provides the bishydrazide compounds which have the advantages of: simple preparation method, good inhibition effect on dicotyledonous weeds such as rapes and amaranthus retroflexus, and a certain inhibition effect on barnyard grass and crabgrass of part of the compounds under the condition of processing stems, leaves and soil.
Description
(1) technical field
The present invention relates to a kind of bishydrazide compounds as the application of weed killer herbicide.
(2) background technology
Bishydrazide compounds has much been reported as insecticide is existing.U.S. Rhom and Hass finds and has reported the compound 1 of following bishydrazide structure first, is a kind of insect growth regulator, IGR.Nankai University has reported compound 2, has good sterilization and antioxidation activity.China Agricultural University has reported an other class bishydrazide compound 3, and this compounds has excellent active anticancer.
And disclosed compound 1 is mainly used in preventing and treating lepidoptera pest in these patents, such as diamond-back moth, and beet armyworm, striped rice borer, prodenia lituras etc. also can prevent and treat the insects such as coleoptera simultaneously.
(3) summary of the invention
The object of the present invention is to provide a kind of bishydrazide compounds, the present invention has excellent activity of weeding.
The invention provides suc as formula the application of the bishydrazide compounds shown in the II as weed killer herbicide:
Among the formula II; R is phenyl, benzyl, furyl, pyridine radicals, isoxazolyl, 5-methyl-4-isoxazolyl, 2; 4-Dichlorophenoxy methyl, 2; 4-Dichlorophenoxy propyl group, 1-cyano group-1-cyclopropane base, the alkyl of C1～C5, cyclopropyl, nicotinoyl base; different nicotinoyl base, substituted-phenyl; described substituted-phenyl is that 1 or plural substituent phenyl are arranged on the phenyl, and the substituting group of described substituted-phenyl is nitro, chlorine, fluorine, methyl, methoxyl group or iodine.
Comparatively preferred; described R is phenyl; the 4-nitrobenzophenone; the 4-chlorphenyl; the 4-fluorophenyl; the 3-aminomethyl phenyl; the 3-chlorphenyl; the 2-fluorophenyl; the 2-chlorphenyl; 2; the 4-dichlorophenyl; the 2-methoxyphenyl; 4-methoxyphenyl isoxazolyl; the 4-iodophenyl; 5-methyl-4-isoxazolyl; 1-cyano group-1-cyclopropane base; methyl; ethyl; propyl group; isopropyl; butyl; benzyl; 2; 4-Dichlorophenoxy methyl; furyl; the nicotinoyl base; different nicotinoyl base; cyclopropyl; 2; 4-Dichlorophenoxy methyl; 2,4-Dichlorophenoxy propyl group; 3-pyridine radicals or 4-pyridine radicals.
Comparatively concrete, describedly can be applicable to management of weeds rape, Amaranthus retroflexus, barnyard grass or lady's-grass suc as formula the bishydrazide compounds shown in the II.
Comparatively preferred, among the described formula II, R is phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 3-aminomethyl phenyl, cyclopropyl or 4-pyridine radicals, describedly is applied to the management of weeds barnyard grass suc as formula the bishydrazide compounds shown in the II.
Comparatively preferred, among the described formula II, R is 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2,4-dichlorophenyl, 4-methoxyphenyl, isoxazolyl, 1-cyano group-1-cyclopropyl, ethyl, isopropyl, benzyl, cyclopropyl, 3-pyridine radicals or 4-pyridine radicals describedly are applied to the management of weeds rape suc as formula the bishydrazide compounds shown in the II.
Comparatively preferred, among the described formula II, R is 3-chlorphenyl, 4-methoxyphenyl, 1-cyano group-1-cyclopropyl, ethyl, 4-iodophenyl or 3-pyridine radicals, describedly is applied to the management of weeds lady's-grass suc as formula the bishydrazide compounds shown in the II.
Comparatively preferred, among the described formula II, R is 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, isoxazolyl, 1-cyano group-1-cyclopropyl, ethyl, isopropyl, benzyl, cyclopropyl, 4-iodophenyl, 3-pyridine radicals or 4-pyridine radicals describedly are applied to the management of weeds Amaranthus retroflexus suc as formula the bishydrazide compounds shown in the II.
The method of application of the present invention is: the usage amount suc as formula the bishydrazide compounds shown in the II is 100g～200g/ mu.
Of the present inventionly can prepare in accordance with the following methods suc as formula the bishydrazide compounds shown in the II: 2 shown in the formula I, 4-Dichlorophenoxy propionyl hydrazine and acyl chloride compound R COCl are in the presence of the acid binding agent triethylamine, in the polar non-solute oxolane, be heated to reflux temperature, reacted 2～5 hours, reaction finishes rear suction filtration of afterreaction liquid cooling, get filtrate decompression distillation desolventizing, make suc as formula the bishydrazide compounds shown in the II with ethyl alcohol recrystallization after the remaining solid washing, shown in the described formula I 2,4-Dichlorophenoxy propionyl hydrazine, RCOCl, the ratio of the amount of substance of triethylamine is 1: 1～1.1: 1;
Among the RCOCl; R is phenyl, benzyl, furyl, pyridine radicals, isoxazolyl, 5-methyl-4-isoxazolyl, 2; 4-Dichlorophenoxy methyl, 2; 4-Dichlorophenoxy propyl group, 1-cyano group-1-cyclopropane base, the alkyl of C1～C5, cyclopropyl, nicotinoyl base; different nicotinoyl base, substituted-phenyl; described substituted-phenyl is that 1 or plural substituent phenyl are arranged on the phenyl, and the substituting group of described substituted-phenyl is nitro, chlorine, fluorine, methyl, methoxyl group or iodine.
The consumption of described oxolane is counted 2～4mL/mmol with the amount of substance of 2,4-Dichlorophenoxy propionyl hydrazine, preferred 3mL/mmol.
Shown in the described formula I 2,4-Dichlorophenoxy propionyl hydrazine can make by the following method: 2,4-Dichlorophenoxy propionic acid and SOCl
2Press amount of substance and mix at 1: 1.5, in ethanolic solution, back flow reaction 5 hours, after reaction finished, the decompression distillation desolventizing made 2,4-Dichlorophenoxy propionic ester; 2,4-Dichlorophenoxy propionic ester mixes by amount of substance with 80% hydrazine hydrate at 1: 1.1, and back flow reaction is 5 hours in ethanolic solution, after reaction finishes, and cooling, then suction filtration is got filter cake and is namely obtained 2,4-Dichlorophenoxy propionyl hydrazine.
Described preparation method is the known preparation methods of those skilled in the art.
Bishydrazide compounds shown in the formula II provided by the invention has preferably preventive effect to rape, Amaranthus retroflexus, barnyard grass or lady's-grass, from embodiment, all synthetic compounds are under the using dosage of 100g/ mu, to broadleaf weed such as rape, Amaranthus retroflexus has good inhibition, under the condition of cauline leaf and soil treatment, part of compounds also has certain inhibition to barnyard grass and lady's-grass.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1:N-encircles propiono-2, the preparation of 4-Dichlorophenoxy propionyl hydrazine
The preparation of 2,4-Dichlorophenoxy propionic ester: 10mmol2,4-Dichlorophenoxy propionic acid is dissolved in the ethanolic solution of 100mL, then drips 15mmol SOCl
2, after dropwising, refluxing 5 hours at 78 degree, reaction is revolved desolventizing after finishing, and gets 2.5g 2,4-Dichlorophenoxy propionic ester, productive rate 95%.
In the round-bottomed flask of 100mL, with 2,4-Dichlorophenoxy propionic ester (10mmol) refluxed 5 hours in ethanolic solution (100mL) with 80% hydrazine hydrate (11mmol), after reaction finishes, cooling, then suction filtration obtains white 2,4-Dichlorophenoxy propionyl hydrazine solid (counting 10mmol).
In the 100mL round-bottomed bottle with 2; 4-Dichlorophenoxy propionyl hydrazine (10mmol), triethylamine (10mmol) is dissolved in the oxolane of 30mL, under agitation drips cyclopropyl acyl chlorides (11mmol) (R among the acyl chloride compound R COCl is cyclopropyl); then back flow reaction 5 hours under 60 degree; cooling, suction filtration is got filtrate decompression distillation desolventizing; use the 20mL ethyl alcohol recrystallization after the remaining solid washing; make N-ring propiono-2,4-Dichlorophenoxy propionyl hydrazine is designated as Vp.
Embodiment 2～21
Reaction condition and operation are with embodiment 1, and difference is, change the acyl chloride compound, the R among the RCOCl such as following table 1, and the Product Labeling that obtains such as following table 1:
| The product numbering | R among the acyl chloride compound R COCl | |
| Embodiment 2 | Va | Phenyl |
| Embodiment 3 | Vb | The 4-nitrobenzophenone |
| Embodiment 4 | Vc | The 4-chlorphenyl |
| Embodiment 5 | Vd | The 4-fluorophenyl |
| Embodiment 6 | Ve | The 3-aminomethyl phenyl |
| Embodiment 7 | Vf | The 3-chlorphenyl |
| Embodiment 8 | Vg | The 2-chlorphenyl |
| Embodiment 9 | Vh | 2,4-dichlorophenyl |
| Embodiment 10 | Vi | The 2-methoxyphenyl |
| Embodiment 11 | Vj | The 4-methoxyphenyl |
| Embodiment 12 | Vk | Isoxazolyl |
| Embodiment 13 | Vl | 1-cyano group-1-cyclopropyl |
| Embodiment 14 | Vm | Ethyl |
| Embodiment 15 | Vn | Isopropyl |
| Embodiment 16 | Vo | Benzyl |
| Embodiment 1 | Vp | Cyclopropyl |
| Embodiment 17 | Vq | 2,4-Dichlorophenoxy methyl |
| Embodiment 18 | Vr | 2,4-Dichlorophenoxy propyl group |
| Embodiment 19 | Vs | The 4-iodophenyl |
| Embodiment 20 | Vt | The 3-pyridine radicals |
| Embodiment 21 | Vu | The 4-pyridine radicals |
It is as follows that product detects data:
Data for V a：White solid，yield 77.3％，m.p.148-149℃；
1H NMR(DMSO-d
6)δ：1.57(d，J＝6.56Hz，3H，Me)，4.91(q，J＝6.63Hz，1H，CHO)，7.18(d，1H，ph)，7.36-7.41(d，1H，ph)，7.43-7.61(m，4H，ph)，7.87(d，J＝6.97Hz，2H，ph)，10.40(bs，2H，NH)；ESI-MS：352[M-H]
-；Elemental analysis for C
16H
14Cl
2N
2O
3：found C 54.34，H 4.18，N 8.11；calcu.C 54.41，H 4.00，N7.93.
Data for V b：White solid，yield 99％，m.p.213-214℃；
1H NMR(DMSO-d
6)δ：1.57(d，J＝6.35Hz，3H，Me)，4.91(q，J＝6.78Hz，1H，CHO)，7.10-7.64(m，4H，ph)，8.07-8.44(m，3H，ph)，10.80(bs，2H，NH)；；ESI-MS：397[M-H]
-；Elemental analysis for C
16H
13Cl
2N
3O
5：foundC 48.33，H 3.46，N 10.54；calcu.C 48.26，H 3.29，N 10.55.
Data for V c：White solid，yield 96.92％，m.p.204-205℃；
1H NMR(DMSO-d
6)δ：1.51(d，J＝6.50Hz，3H，Me)，4.91(q，J＝6.72Hz，1H，CHO)，7.12(d，1H，ph)，7.33-7.36(d，1H，ph)，7.46-7.51(m，2H，ph)，7.57(d，1H，ph)，7.83-7.88(m，2H，ph)，10.43(bs，2H，NH)；ESI-MS：386[M-H]
-；Elemental analysis for C
16H
13Cl
3N
2O
3：found C 49.66，H 3.11，N 7.45；calcu.C49.57，H 3.38，N 7.23.
Data for V d：White solid，yield 89.19％，m.p.167-168℃；
1H NMR(DMSO-d
6)δ：1.53(d，J＝6.52Hz，3H，Me)，4.91(q，J＝6.59Hz，1H，CHO)，7.13(d，1H，ph)，7.24-7.29(m，2H，ph)，7.33-7.36(m，2H，ph)，7.56-7.57(m，1H，ph)，7.89-7.92(m，2H，ph)，10.40(bs，2H，NH)；ESI-MS：370[M-H]
-；Elemental analysis for C
16H
13Cl
2FN
2O
3：found C 51.58，H 3.46，N 7.65；calcu.C 51.77，H 3.53，N 7.55.
Data for V e：White solid，yield 87.0％，m.p.173-175℃；
1H NMR(DMSO-d
6)δ：1.54(d，J＝6.58Hz，3H，Me)，2.33(s，3H，Me)，4.88(q，J＝6.55Hz，1H，CHO)，7.14(d，1H，ph)，7.34-7.37(m，3H，ph)，7.57-7.67(m，3H，ph)，10.34(bs，2H，NH)；ESI-MS：356.12[M-H]
-；Elemental analysis for C
17H
16Cl
2N
2O
3：found C 55.45，H 4.44，N 7.87；calcu.C 55.60，H 4.39，N 7.63.
Data for V f：White solid，yield 81.02％，m.p.148-149℃；
1H NMR(DMSO-d
6)δ：1.53(d，J＝6.56Hz，3H，Me)，4.88(q，J＝6.56Hz，1H，CHO)，7.11(d，1H，ph)，7.28-7.36(m，3H，ph)，7.54-7.60(m，3H，ph)，10.35(bs，2H，NH)；；ESI-MS：386[M-H]
-；Elemental analysis forC
16H
13C
l3N
2O
3：found C 49.78，H 3.22，N 7.00；calcu.C 49.57，H 3.38，N 7.23.
Data for V g：White solid，yield 79.78％，m.p.178-180℃；
1H NMR(DMSO-d
6)δ：1.52(d，J＝6.45Hz，3H，Me)，4.89(q，J＝6.64Hz，1H，CHO)，7.01-7.07(m，1H，ph)，7.13(d，2H，ph)，7.33-7.36(m，1H，ph)，7.47-7.52(m，1H，ph)，7.57-7.58(m，1H，ph)，7.69-7.72(m，1H，ph)，10.43(bs，2H，NH)；ESI-MS：386[M-H]
-；Elemental analysis for C
16H
13C
l3N
2O
3：found C49.56，H 3.12，N 7.54；calcu.C 49.57，H 3.38，N 7.23.
Data for V h：White solid，yield 95.16％，m.p.207-209℃；
1H NMR(DMSO-d
6)δ：1.53(d，J＝6.48Hz，3H，Me)，4.89(q，J＝6.60Hz，1H，CHO)，7.08-7.10(m，1H，ph)，7.32-7.35(m，1H，ph)，7.44-7.58(m，3H，ph)，7.71(s，1H，ph)，10.47(bs，2H，NH)；ESI-MS：420[M-H]
-；Elemental analysis for C
16H
12Cl
4N
2O
3：found C 45.56，H 2.44，N 6.54；calcu.C 45.53，H 2.87，N 6.64.
Data for V i：White solid，yield 91.17％，m.p.151-153℃；
1H NMR(DMSO-d
6)δ：1.53(d，J＝6.48Hz，3H，Me)，3.86(s，3H，OMe)，4.89(q，J＝6.60Hz，1H，CHO)，7.08-7.10(m，1H，ph)，7.32-7.35(m，1H，ph)，7.44-7.58(m，3H，ph)，7.71(s，1H，ph)，10.47(bs，2H，NH)；ESI-MS：382[M-H]
-；Elemental analysis for C
17H
16Cl
2N
2O
4：found C 53.44，H 4.43，N 7.09；calcu.C53.28，H 4.21，N 7.31.
Data for V j：m.p.183-185℃；
1H NMR(DMSO-d
6)δ：1.54(d，J＝6.50Hz，3H，Me)，3.79(s，3H，OMe)，4.88(q，J＝6.41Hz，1H，CHO)，6.99(d，J＝8.67Hz，2H，ph)，7.13(d，1H，ph)，7.34-7.37(m，1H，ph)，7.57-7.58(m，1H，ph)，7.83(d，J＝8.55Hz，2H，ph)，10.31(bs，2H，NH)；ESI-MS：382[M-H]
-；Elemental analysis for C
17H
16Cl
2N
2O
4：found C 53.13，H 4.03，N 7.31；calcu.C 53.28，H 4.21，N 7.31.
Data for V k：White solid，yield 85.69％，m.p.221-222℃；
1H NMR(DMSO-d
6)δ：1.52(d，J＝6.53Hz，3H，Me)，2.62(s，3H，Het-Me)，4.89(q，J＝6.63Hz，1H，CHO)，7.08-7.11(m，1H，ph)，7.29-7.36(m，1H，ph)，7.53-7.59(m，1H，ph)，8.88(s，1H，Het-H)，10.35(bs，2H，NH)；ESI-MS：357[M-H]
-；Elemental analysis for C
14H
13Cl
2N
3O
4：found C 47.22，H 3.54，N 11.98；calcu.C46.95，H 3.66，N 11.73.
Data for V l：White solid，yield 98.99％，m.p.218-220℃；
1H NMR(DMSO-d
6)δ：0.78-0.96(m，4H，Cyclopropane-CH
2)，1.47(d，J＝6.56Hz，3H，CH
3)，4.80(q，J＝6.63Hz，1H，CHO)，7.04(d，J＝8.93Hz，1H，ph)，7.31(d，J＝6.32Hz，1H，ph)，7.56(s，1H，ph)，10.10(s，1H，NH)，10.13(s，1H，NH)；ESI-MS：341[M-H]
-；Elemental analysis for C
14H
13Cl
2N
3O
3：found C 45.66，H 3.56，N 12.31；calcu.C 45.37，H 3.22，N 12.21.
DataforV m：White solid，yield 91.52％，m.p.183-184℃；
1H NMR(DMSO-d
6)δ：1.40-1.42(m，6H，Me)，2.05(q，J＝2.63Hz，2H，CH
2)，4.81(q，J＝6.59Hz，1H，CHO)，6.97(d，J＝8.87Hz，1H，ph)，7.31(d，J＝8.93Hz，1H，ph)，7.56(s，1H，ph)，9.33(s，2H，NH)；ESI-MS：304[M-H]
-；Elemental analysis for C
12H
14Cl
2N
2O
3：found C 47.45，H 4.78，N 9.23；calcu.C47.23，H 4.62，N 9.18.
Data for V n：White solid，yield 83.45％，m.p.177-178℃；
1H NMR(DMSO-d
6)δ：0.92-1.00(m，6H，Me)，1.41-1.47(m，3H，CH
3)，4.74-4.82(m，1H，CHO)，6.97-7.10(m，1H，ph)，7.24-7.32(m，1H，ph)，7.54(s，1H，ph)，9.40(s，2H，NH)；ESI-MS：318[M-H]
-；Elementalanalysis for C
13H
16Cl
2N
2O
3：found C 49.10，H 4.88，N 8.97；calcu.C 48.92，H 5.05，N 8.78.
Data for V o：White solid，yield 98.99％，m.p.164-168℃；
1H NMR(DMSO-d
6)δ：0.82(t，J＝7.42Hz，3H，CH
3)，1.22(m，2H，CH
2)，1.41(m，2H，CH
2)，1.46(d，J＝6.63Hz，3H，CH
3)，2.08(t，J＝7.34Hz，2H，CH
2)，4.82(q，J＝6.62Hz，1H，CHO)，7.08(d，J＝8.91Hz，1H，ph)，7.30(d，J＝6.34Hz，1H，ph)，7.55(s，1H，ph)，9.96(bs，2H，NH)；ESI-MS：332[M-H]
-；Elementalanalysis for C
14H
18Cl
2N
2O
3：found C 50.44，H 5.78，N 8.23；calcu.C 50.46，H 5.44，N 8.41.
Data for V p：White solid，yield 90.81％，m.p.227-228℃；
1H NMR(DMSO-d
6)δ：0.67-0.72(m，4H，Cyclopropane-CH
2)，1.47(d，J＝6.58Hz，3H，CH
3)，1.53-1.60(m，1H，Cyclopropane-CH)，4.80(q，J＝6.63Hz，1H，CHO)，7.04(d，J＝8.93Hz，1H，ph)，7.31(d，J＝6.32Hz，1H，ph)，7.56(s，1H，ph)，10.10(s，1H，NH)，10.13(s，1H，NH)；ESI-MS：316[M-H]
-；Elemental analysis for C
13H
14Cl
2N
2O
3：found C 49.21，H 4.22，N 9.01；calcu.C 49.23，H4.45，N 8.83.
Data for V q：White solid，yield 93.23％，m.p.200-201℃；
1H NMR(DMSO-d
6)δ：1.50(d，J＝6.53Hz，3H，CH
3)，4.72(s，2H，CH
2)，4.83(q，J＝6.59Hz，1H，CHO)，7.05(t，2H，ph)，7.31-7.36(m，2H，ph)，7.57(d，2H，ph)，10.28(bs，2H，NH)；ESI-MS：451[M-H]
-；sElementalanalysis for C
17H
14Cl
4N
2O
4：found C 45.11，H 3.08，N 6.53；calcu.C 45.16，H 3.12，N 6.20.
Data for V r：White solid，yield 96.15％，m.p.245-246℃；
1H NMR(DMSO-d
6)δ：1.46(d，J＝6.52Hz，6H，CH
3)，4.80(q，J＝6.54Hz，2H，CHO)，7.05(d，J＝8.83Hz，2H，ph)，7.29-7.32(m，2H，ph)，7.55(s，2H，ph)，10.30(bs，2H，NH)；ESI-MS：465[M-H]
-；Elemental analysis forC
18H
16Cl
4N
2O
4：found C 46.12，H 3.23，N 6.23；calcu.C 46.38，H 3.46，N 6.01.
Data for V s：White solid，yield 77.68％，m.p.210-212℃；
1H NMR(DMSO-d
6)δ：1.52(d，J＝5.95Hz，3H，Me)，4.88(q，J＝6.51Hz，1H，CHO)，7.12(d，J＝9.98Hz，2H，ph)，7.31-7.37(m，2H，ph)，7.55-7.64(m，2H，ph)，7.83-7.86(m，2H，ph)，7.83(d，J＝8.55Hz，2H，ph)，10.43(bs，2H，NH)；ESI-MS：478[M-H]
-；Elemental analysis for C
16H
13Cl
2IN
2O
3：fuund C 39.95，H2.98，N 6.04；calcu.C 40.11，H 2.73，N 5.85.
Data for V t：White solid，yield 89.14％，m.p.166-167℃；
1H NMR(DMSO-d
6)δ：1.57(d，J＝6.51Hz，3H，CH
3)，4.93(q，J＝6.75Hz，1H，CHO)，7.15(d，J＝9.13Hz，1H，ph)，7.37-7.41(m，1H，ph)，7.53-7.62(m，2H，ph and py)，8.20-8.23(m，1H，py)，8.75-.877(m，1H，py)，9.02(s，1H，py)，10.42(s，1H，NH)，10.72(s，1H，NH)；ESI-MS：353[M-H]
-；Elemental analysis forC
15H
13Cl
2N
3O
3：found C 50.65，H 3.43，N 12.01；calcu.C 50.87，H 3.70，N 11.86.
Data for V u：White solid，yield 90.07％，m.p.173-175℃；
1H NMR(DMSO-d
6)δ：1.57(d，J＝6.53Hz，3H，CH
3)，4.93(q，J＝6.63Hz，1H，CHO)，7.15(d，J＝8.86Hz，1H，ph)，7.33-7.41(m，1H，ph)，7.61(s，1H，ph)，7.79(d，J＝5.63Hz，2H，py)，8.75(d，J＝5.65Hz，2H，py)，10.61(bs，2H，NH)；ESI-MS：353[M-H]
-；Elemental analysis for C
15H
13Cl
2N
3O
3：found C 50.66，H 3.83，N11.99；calcu.C 50.87，H 3.70，N11.86.
Pot-culture method is measured the activity of weeding of compound
In the plastics cuvette of diameter 8cm, put into a certain amount of soil, add a certain amount of water, after planting cover certain thickness soil, in greenhouse, cultivate, cover with plastics before coming up.Every day in addition quantitative clear water to keep normal growth.
Test material: barnyard grass (Echinochloa crusgalli (L.) Beauv.), lady's-grass (Digitariaadscendens), rape (Brassiaca napus) and Amaranthus retroflexus (Amaranthus retroflexus).Process 19 days " Invest, Then Investigate " results, leaf is subtracted weigh after lower, drug concentration is 100g/ mu, and dual mode adds medicine before minute seedling and behind the seedling, and with commercially available agricultural chemical 2,4-D tests by same method, as a comparative example.
Measure the overground part fresh weight, suppress percentage with fresh weight and represent drug effect.Active graded index: A level: 〉=80%; B level: 60～79%; C level: 40～59%; D level :≤39%.The activity data of the compound of surveying sees Table 2.
The activity of weeding result of table 2 compound
Claims (8)
1. suc as formula the application of the bishydrazide compounds shown in the II as weed killer herbicide:
Among the formula II, R is phenyl, pyridine radicals, isoxazolyl, 2,4-Dichlorophenoxy methyl, substituted-phenyl, described substituted-phenyl is 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-fluorophenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-iodophenyl or 2,4-Dichlorophenoxy methyl.
2. application as claimed in claim 1 is characterized in that described R is 3-pyridine radicals or 4-pyridine radicals.
3. application as claimed in claim 1 is characterized in that describedly being applied to management of weeds rape, Amaranthus retroflexus, barnyard grass or lady's-grass suc as formula the bishydrazide compounds shown in the II.
4. application as claimed in claim 1 is characterized in that among the described formula II, and R is phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 3-aminomethyl phenyl or 4-pyridine radicals, describedly is applied to the management of weeds barnyard grass suc as formula the bishydrazide compounds shown in the II.
5. application as claimed in claim 1, it is characterized in that among the described formula II, R is 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2,4-dichlorophenyl, 4-methoxyphenyl, isoxazolyl, 3-pyridine radicals or 4-pyridine radicals describedly are applied to the management of weeds rape suc as formula the bishydrazide compounds shown in the II.
6. application as claimed in claim 1 is characterized in that among the described formula II, and R is 3-chlorphenyl, 4-methoxyphenyl, 4-iodophenyl or 3-pyridine radicals, describedly is applied to the management of weeds lady's-grass suc as formula the bishydrazide compounds shown in the II.
7. application as claimed in claim 1, it is characterized in that among the described formula II, R is 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, isoxazolyl, 4-iodophenyl, 3-pyridine radicals or 4-pyridine radicals describedly are applied to the management of weeds Amaranthus retroflexus suc as formula the bishydrazide compounds shown in the II.
8. application as claimed in claim 3 is characterized in that the method for described application is: the usage amount suc as formula the bishydrazide compounds shown in the II is 100～200g/ mu.
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| CN102835393A (en) * | 2012-09-14 | 2012-12-26 | 浙江工业大学 | Application of 2, 4-dichlorbenzoxy acetyl contained diacylhydrazine compound as plant growth regulator |
| CN102835394A (en) * | 2012-09-14 | 2012-12-26 | 浙江工业大学 | Application of 2, 4-dichlorphenoxy acetyl-containing dihydrazide compound as herbicide |
| CN104628645B (en) * | 2014-12-23 | 2017-01-25 | 浙江工业大学 | Pyrazole-containing bishydrazide compound and preparation method and application thereof |
| CN107216291A (en) * | 2017-06-05 | 2017-09-29 | 杨子辉 | Fragrant phenoxy group propionic acid compounds containing bishydrazide and preparation method and application |
| CN108863935B (en) * | 2018-08-29 | 2020-07-14 | 浙江工业大学 | Application of amide compound containing pyrazole ring in preparation of herbicide |
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| EP0519083A1 (en) * | 1990-12-27 | 1992-12-23 | IHARA CHEMICAL INDUSTRY Co., Ltd. | Process for producing hexahydropyridazine-1,2-dicarboxylic acid derivative |
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| EP0519083A1 (en) * | 1990-12-27 | 1992-12-23 | IHARA CHEMICAL INDUSTRY Co., Ltd. | Process for producing hexahydropyridazine-1,2-dicarboxylic acid derivative |
| CN101234999A (en) * | 2008-02-28 | 2008-08-06 | 上海师范大学 | N-substituted formacyl glycyl hydrazine derivatives, preparation method and application thereof |
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