CN102860305A - Application of 2, 4-dichlorobenzene oxygen acetyl-containing diacylhydrazine compound used as bactericide - Google Patents
Application of 2, 4-dichlorobenzene oxygen acetyl-containing diacylhydrazine compound used as bactericide Download PDFInfo
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Abstract
The invention discloses an application of diacylhydrazine compound used as bactericide. The diacylhydrazine compound provided by the invention is simple in preparation method, has excellent bactericidal activity and can be used as a type of bactericide for killing scab of cucumber, powdery mildew of cucumber, nuclear mildew of cucumber, cucumber leaf spot or cucumber anthracnose.
Description
Technical field
The present invention relates to a kind of bishydrazide compounds as the application of bactericide.
Background technology
Bishydrazide compounds has had the application in a lot of years in agricultural chemicals, especially as insect growth regulator, IGR.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.
Summary of the invention
The object of the present invention is to provide a kind of bishydrazide compounds, the present invention has the effect of bactericide.
The invention provides suc as formula the application of the bishydrazide compounds shown in the II as bactericide:
Among the formula II; R is phenyl, furyl, pyridine radicals, isoxazolyl, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, the alkyl of C1 ~ C5, thiazolinyl, 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, 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-fluorophenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-iodophenyl, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, methyl, propyl group, isopropyl, butyl, furyl, nicotinoyl base, different nicotinoyl base, cyclopropyl, sorb acidic group.
Describedly can use as bactericide suc as formula the bishydrazide compounds shown in the II, comparatively concrete, the described bactericide that can use, Cucumber Target Leaf Spot sick as scab of cucumber, powdery mildew of cucumber, cucumber pyrenomycetes or cucumber anthracnose suc as formula the bishydrazide compounds shown in the II.
More specifically, among the described formula II, R is phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-fluorophenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-iodophenyl, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, methyl, propyl group, isopropyl, butyl, furyl, nicotinoyl base, different nicotinoyl base, cyclopropyl, sorb acidic group, the described bactericide that can be used as scab of cucumber suc as formula the bishydrazide compounds shown in the II; Among the preferred formula II, R is 2-fluorophenyl, isopropyl, furyl, and is described suc as formula the bactericide of the bishydrazide compounds shown in the II as scab of cucumber.
More specifically, among the described formula II, R is phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-fluorophenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-iodophenyl, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, methyl, propyl group, isopropyl, butyl, furyl, nicotinoyl base, different nicotinoyl base, cyclopropyl, sorb acidic group, the described bactericide that can be used as Cucumber Target Leaf Spot suc as formula the bishydrazide compounds shown in the II; Among the preferred formula II, R is propyl group, isopropyl, sorb acidic group, 3-pyridine radicals, and is described suc as formula the bactericide of the bishydrazide compounds shown in the II as Cucumber Target Leaf Spot.
More specifically, among the described formula II, R is phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-fluorophenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-iodophenyl, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, methyl, propyl group, isopropyl, butyl, furyl, nicotinoyl base, different nicotinoyl base, cyclopropyl, sorb acidic group, the described bactericide that can be used as powdery mildew of cucumber suc as formula the bishydrazide compounds shown in the II; Among the preferred formula II, R is cyclopropyl, phenyl, 3-aminomethyl phenyl, 2-fluorophenyl, 4-methoxyphenyl, 4-iodophenyl, isoxazolyl, propyl group, and is described suc as formula the bactericide of the bishydrazide compounds shown in the II as powdery mildew of cucumber.
More specifically, among the described formula II, R is phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-fluorophenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-iodophenyl, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, methyl, propyl group, isopropyl, butyl, furyl, nicotinoyl base, different nicotinoyl base, cyclopropyl, sorb acidic group, the described bactericide that can be used as stem rot of cucumber suc as formula the bishydrazide compounds shown in the II; More preferably among the formula II, R is 3-aminomethyl phenyl, isoxazolyl, and is described suc as formula the bactericide of the bishydrazide compounds shown in the II as stem rot of cucumber.
More specifically, among the described formula II, R is phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-fluorophenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-iodophenyl, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, methyl, propyl group, isopropyl, butyl, furyl, nicotinoyl base, different nicotinoyl base, cyclopropyl, sorb acidic group, the described bactericide that can be used as cucumber anthracnose suc as formula the bishydrazide compounds shown in the II; More preferably among the formula II, R is cyclopropyl, phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-chlorphenyl, 2-methoxyphenyl, 4-iodophenyl, 1-cyano group-1-cyclopropyl, isopropyl, butyl, furyl, 4-pyridine radicals, and is described suc as formula the bactericide of the bishydrazide compounds shown in the II as cucumber anthracnose.
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 acethydrazide 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 acethydrazide, RCOCl, the ratio of the amount of substance of triethylamine is 1:1 ~ 1.1:1;
Among the RCOCl, R is phenyl, furyl, pyridine radicals, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, the alkyl of C1 ~ C5, cyclopropyl, 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 acethydrazide, preferred 3mL/mmol.
Shown in the described formula I 2,4-Dichlorophenoxy acethydrazide can make by the following method: 2,4-dichlorphenoxyacetic acid and SOCl
2Press amount of substance 1:1.5 and mix, in ethanolic solution, back flow reaction 5 hours, after reaction finished, the decompression distillation desolventizing made 2,4-dichlorphenoxyacetic acid ester; 2,4-dichlorphenoxyacetic acid ester mixes by amount of substance 1:1.1 with 80% hydrazine hydrate, 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 acethydrazide.
Described preparation method well known to a person skilled in the art the preparation method.
Bishydrazide compounds shown in the formula II provided by the invention has excellent bactericidal activity, embodiment shows the bactericide that can be used as scab of cucumber, powdery mildew of cucumber, cucumber pyrenomycetes disease, Cucumber Target Leaf Spot or cucumber anthracnose, the soil-borne disease that can prevent and treat economic crops.
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-dichlorphenoxyacetic acid ester: 10 mmol2,4-dichlorphenoxyacetic acid are dissolved in the ethanolic solution of 100 mL, then drip 15 mmol SOCl
2, after dropwising, refluxing 5 hours at 78 degree, reaction is revolved desolventizing after finishing, and gets 2.5g 2,4-dichlorphenoxyacetic acid ester, productive rate 95%.
In the round-bottomed flask of 100mL, 2,4-dichlorphenoxyacetic acid ester (10 mmol) and 80% hydrazine hydrate (11mmol) were refluxed 5 hours in ethanolic solution (100mL), after reaction finishes, cooling, then suction filtration, obtain white 2,4-Dichlorophenoxy acethydrazide solid (counting 10mmol).
In the 100mL round-bottomed bottle with 2; 4-Dichlorophenoxy acethydrazide (10 mmol), 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 acethydrazide is designated as Va.
Embodiment 2 ~ 24
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 1 | Va | Cyclopropyl |
| Embodiment 2 | Vb | Phenyl |
| Embodiment 3 | Vc | The 4-nitrobenzophenone |
| Embodiment 4 | Vd | The 4-chlorphenyl |
| Embodiment 5 | Ve | The 4-fluorophenyl |
| Embodiment 6 | Vf | The 3-aminomethyl phenyl |
| Embodiment 7 | Vg | The 3-chlorphenyl |
| Embodiment 8 | Vh | The 2-fluorophenyl |
| Embodiment 9 | Vi | The 2-chlorphenyl |
| Embodiment 10 | Vj | 2,4-dichlorophenyl |
| Embodiment 11 | Vk | The 2-methoxyphenyl |
| Embodiment 12 | Vl | The 4-methoxyphenyl |
| Embodiment 13 | Vm | The 4-iodophenyl |
| Embodiment 14 | Vn | 5-methyl-4-isoxazolyl |
| Embodiment 15 | Vo | 1-cyano group-1-cyclopropyl |
| Embodiment 16 | Vp | Methyl |
| Embodiment 17 | Vq | Propyl group |
| Embodiment 18 | Vr | Isopropyl |
| Embodiment 19 | Vs | Butyl |
| Embodiment 20 | Vt | Furyl |
| Embodiment 21 | Vu | The sorb acidic group |
| Embodiment 22 | Vv | The 3-pyridine radicals |
| Embodiment 23 | Vw | The 4-pyridine radicals |
It is as follows that product detects data:
V a:?White?solid,?yield?79?%,m.p.199-200?℃;?
1H?NMR?(DMSO-
d 6)?δ:?0.58-0.78(m,?4H,?cyclopropane),?1.55-1.67(m,?1H,?cyclopropane),?4.70(s,?2H,?CH
2O),?7.06(d,?
J=8.8Hz,?1H,?Ph),?7.35(d,?
J=8.9Hz,?1H,?Ph),?7.57(s,?1H,?Ph),?10.11(s,?2H,?NH);?ESI-MS:?302.55?[M-H]
-;?Elemental?analysis?for?C
12H
12Cl
2N
2O
3:?found?C?47.45,?H?4.08,?N?9.31;?calcu.?C?47.54,?H?3.99,?N?9.24.
V b:?White?solid,?yield?90?%,m.p.?148-150?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.80(s,?2H,?CH
2O),?7.35-7.59(m,?5H,?Ph),?7.84-7.92(m,?3H,?Ph),?10.22(s,?1H,NH),?10.47(s,?1H,NH);?ESI-MS:?338.54?[M-H]
-;?Elemental?analysis?for?C
15H
12Cl
2N
2O
3:?found?C?52.95,?H?3.46,?N?8.54;?calcu.?C?53.12,?H?3.57,?N?8.26.
V c:?White?solid,?yield?91?%,m.p.?209-211?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.82(s,?2H,?CH
2O),?7.13(d,?
J=9.9Hz,?1H,?Ph),?7.36-7.40(m,?1H,?Ph),?7.59(s,?1H,?Ph),?8.00(d,?
J=8.3Hz,?1H,?Ph),?8.34(d,?
J=8.3Hz,?1H,?Ph),?10.39(s,?1H,?NH),?10.85(s,?1H,?NH);?ESI-MS:?383.13?[M-H]
-;?Elemental?analysis?for?C
15H
11Cl
2N
3O
5:?found?C?47.02,?H?3.11,?N?11.12;?calcu.?C?46.90,?H?2.89,?N?10.94.
V d:?White?solid,?yield?88?%,m.p.?199-201?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.79(s,?2H,?CH
2O),?7.14(d,?
J=8.9Hz,?1H,?Ph),?7.38(d,?
J=8.9Hz,?1H,?Ph),?7.55-7.61(s,?3H,?Ph),?7.86(d,?
J=8.6Hz,?1H,?Ph),?10.27(s,?1H,?NH),?10.57(s,?1H,?NH);?ESI-MS:?371.93?[M-H]
-;?Elemental?analysis?for?C
15H
11Cl
3N
2O
3:?found?C?48.12,?H?3.11,?N?7.88;?calcu.?C?48.22,?H?2.97,?N?7.50.
V e:?White?solid,?yield?85?%,m.p.?173-175?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.79(s,?2H,?CH
2O),?7.14(d,?
J=8.9Hz,?1H,?Ph),?7.29-7.39(m,?3H,?ph),?7.59(d,?
J=6.5Hz,?1H,?Ph),?7.90-7.94(m,?2H,?ph),?10.39(s,?2H,?NH)?;?ESI-MS:?356.12?[M-H]
-;?Elemental?analysis?for?C
15H
11Cl
2FN
2O
3:?found?C?50.23,?H?3.08,?N?8.02;?calcu.?C?50.44,?H?3.10,?N?7.84.
V f:?White?solid,?yield?82?%,m.p.?160-162?℃;?
1H?NMR?(DMSO-
d 6)?δ:?2.33(s,?3H,?CH
3),?4.75(s,?2H,?CH
2O),?7.14(d,?
J=8.9Hz,?1H,?Ph),?7.32-7.37(m,?3H,?ph),?7.32-7.37(m,?3H,?ph),?7.54-7.62(m,?2H,?ph),?7.66(s,?1H,?Ph),?10.34(s,?2H,?NH)?;?ESI-MS:?352.65?[M-H]
-;?Elemental?analysis?for?C
16H
14Cl
2N
2O
3:?found?C?54.78,?H?4.22,?N?8.00;?calcu.?C?54.41,?H?4.00,?N?7.93.
V g:?White?solid,?yield?84?%,m.p.?170-172?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.76(s,?2H,?CH
2O),?7.11(d,?
J=8.9Hz,?1H,?Ph),?7.?37(d,?
J=8.9Hz,?1H,?Ph),?7.40-7.59(m,?3H,?ph),?7.80(d,?
J=8.9Hz,?1H,?Ph),?7.87(s,?1H,?Ph),?10.46(s,?2H,?NH);?ESI-MS:?371.64?[M-H]
-;?Elemental?analysis?for?C
15H
11Cl
3N
2O
3:?found?C?48.45,?H?2.78,?N?7.33;?calcu.?C?48.22,?H?2.97,?N?7.50.
V h:?White?solid,?yield?81?%,m.p.?148-150?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.79(s,?2H,?CH
2O),?7.12(d,?
J=8.9Hz,?1H,?Ph),?7.?27-7.38(m,?3H,?Ph),?7.53-7.61(m,?3H,?ph),?10.33(s,?2H,?NH)?;?ESI-MS:?356.44?[M-H]
-;?Elemental?analysis?for?C
15H
11Cl
2FN
2O
3:?found?C?50.56,?H?3.33,?N?8.02;?calcu.?C?50.44,?H?3.10,?N?7.84.
V i:?White?solid,?yield?90?%,m.p.?186-188?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.79(s,?2H,?CH
2O),?7.13(d,?
J=8.9Hz,?1H,?Ph),?7.?36(d,?
J=8.9Hz,?1H,?Ph),?7.41-7.50(m,?4H,?ph),?7.59(d,?
J=2.6Hz,?1H,?Ph),?10.40(s,?2H,?NH);?ESI-MS:?371.23?[M-H]
-;?Elemental?analysis?for?C
15H
11Cl
3N
2O
3:?found?C?48.44,?H?3.12,?N?7.78;?calcu.?C?48.22,?H?2.97,?N?7.50.
V j:?White?solid,?yield?91?%,m.p.?169-171?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.77(s,?2H,?CH
2O),?7.13(d,?
J=6.8Hz,?1H,?Ph),?7.34-7.39(dd,?
J=2.6Hz,?
J=2.6Hz,?1H,?Ph),?7.43-7.54(m,?2H,?ph),?7.59(d,?
J=2.6Hz,?1H,?Ph),?7.71(s,?1H,?Ph),?10.48(bs,?2H,NH)?;?ESI-MS:?405.88?[M-H]
-;?Elemental?analysis?for?C
15H
10Cl
4N
2O
3:?found?C?44.33,?H?2.44,?N?7.09;?calcu.?C?44.15,?H?2.47,?N?6.86.
V k:?White?solid,?yield?99?%,m.p.?175-177?℃;?
1H?NMR?(DMSO-
d 6)?δ:?3.86(s,?3H,?OCH
3),?4.76(s,?2H,?CH
2O),?7.03(t,?
J=7.4Hz,?1H,?Ph),?7.14(d,?
J=7.8Hz,?2H,?Ph),?7.32-7.37(m,?1H,?Ph),?7.47-7.51(m,?1H,?Ph),?7.55-7.58(m,?1H,?Ph),?7.71(d,?
J=7.6Hz,?1H,?Ph),?10.26(bs,?2H,NH);?ESI-MS:?368.13?[M-H]
-;?Elemental?analysis?for?C
16H
14Cl
2N
2O
4:?found?C?51.95,?H?4.08,?N?7.89;?calcu.?C?52.05,?H?3.82,?N?7.59.
V l:?White?solid,?yield?79?%,m.p.?174-175?℃;?
1H?NMR?(DMSO-
d 6)?δ:?3.80(s,?3H,?OCH
3),?4.78(s,?2H,?CH
2O),?7.00(d,?
J=8.8Hz,?2H,?Ph),?7.14(d,?
J=8.9Hz,?1H,?Ph),?7.35(d,?
J=8.9Hz,?1H,?Ph),?7.58(s,?1H,?Ph),?7.83(d,?
J=8.8Hz,?2H,?Ph),?10.26(s,?2H,?NH)?;?ESI-MS:?368.45?[M-H]
-;?Elemental?analysis?for?C
16H
14Cl
2N
2O
4:?found?C?52.11,?H?4.02,?N?7.87;?calcu.?C?52.05,?H?3.82,?N?7.59.
V m:?White?solid,?yield?88?%,m.p.?230-231?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.79(s,?2H,?CH
2O),?7.12(d,
?J=8.6Hz,?1H,?Ph),?7.35-7.39(m,?1H,?Ph),?7.59(d,
?J=8.9Hz,?2H,?Ph),?7.63(s,?1H,?Ph),?7.87(d,
?J=8.9Hz,?2H,?Ph),?10.26(s,?1H,?NH),?10.56(s,?1H,?NH);?ESI-MS:?463.88?[M-H]
-;?Elemental?analysis?for?C
15H
11Cl
2IN
2O
3:?found?C?38.98,?H?2.54,?N?6.23;?calcu.?C?38.74,?H?2.38,?N?6.02.
Vn ?:White?solid,?yield?99?%,m.p.?118-120?℃;?
1H?NMR?(DMSO-
d 6)?δ:?2.62(s,?3H,?Het-CH
3),?4.79(s,?2H,?CH
2O),?7.10(d,
?J=8.9Hz,?1H,?Ph),?7.37(d,
?J=8.9Hz,?1H,?Ph),?7.58(s,?1H,?Ph),?8.90(s,?1H,?Het-CH),?10.27(s,?1H,?NH),?10.37(s,?1H,?NH);?ESI-MS:?343.15?[M-H]
-;?Elemental?analysis?for?C
13H
11Cl
2N
3O
4:?found?C?45.66,?H?3.56,?N?12.31;?calcu.?C?45.37,?H?3.22,?N?12.21.
V o:?White?solid,?yield?98%,m.p.?188-190?℃;?
1H?NMR?(DMSO-
d 6)?δ:?1.51-1.64(m,?4H,?cyclopropane),?4.75(s,?2H,?CH
2O),?7.00(d,
?J=6.0Hz,?1H,?Ph),?7.33(d,
?J=6.1Hz,?1H,?Ph),?7.57(s,?1H,?Ph),?10.31(s,?2H,?NH);?ESI-MS:?327.66?[M-H]
-;?Elemental?analysis?for?C
13H
11Cl
2N
3O
3:?found?C?47.45,?H?3.43,?N?12.98;?calcu.?C?47.58,?H?3.38,?N?12.81.
V p:?White?solid,?yield?92?%,m.p.?172-173?℃;?
1H?NMR?(DMSO-
d 6)?δ:?2.48(s,?3H,?CH
3),?4.71(s,?2H,?CH
2O),?7.10(d,
?J=8.9Hz,?1H,?Ph),?7.33(d,
?J=8.9Hz,?1H,?Ph),?7.58(s,?1H,?Ph),?9.91(s,?2H,?NH);?ESI-MS:?276.12?[M-H]
-;?Elemental?analysis?for?C
10H
10Cl
2N
2O
3:?found?C?43.65,?H?3.78,?N?9.99;?calcu.?C?43.34,?H?3.64,?N?10.11.
Vq :?White?solid,?yield?96?%,m.p.?162-164?℃;?
1H?NMR?(DMSO-
d 6)?δ:?0.84(t,?
J=7.3Hz,?3H,?CH
3),?1.54(q,?
J=7.3Hz,?2H,?CH
2),?2.00(t,?
J=7.2Hz,?2H,?CH
2),?4.57(s,?2H,?CH
2O),?7.05(d,
?J=8.9Hz,?1H,?Ph),?7.34(d,
?J=8.9Hz,?1H,?Ph),?7.56(s,?1H,?Ph),?9.23(s,?1H,?NH),?9.95(s,?1H,?NH);?ESI-MS:?304.12?[M-H]
-;?Elemental?analysis?for?C
12H
14Cl
2N
2O
3:?found?C?47.44,?H?4.78,?N?9.23;?calcu.?C?47.23,?H?4.62,?N?9.18.
Vr :White?solid,?yield?92?%,m.p.?174-176?℃;?
1H?NMR?(DMSO-
d 6)?δ:?0.82(d,?
J=6.5Hz,?6H,?CH
3),?1.99-2.11(m,?1H,?CH),?4.70(s,?2H,?CH
2O),?7.01(d,
?J=9.0Hz,?1H,?Ph),?7.33(d,
?J=6.6Hz,?1H,?Ph),?7.56(s,?1H,?Ph),?9.97(s,?2H,?NH);?ESI-MS:?304.95?[M-H]
-;?Elemental?analysis?for?C
12H
14Cl
2N
2O
3:?found?C?47.11,?H?4.44,?N?10.36;?calcu.?C,?47.23;?H,?4.62;?N,?9.18.
Ｖs :?White?solid,?yield?93?%,m.p.?196-198?℃;?
1H?NMR?(DMSO-
d 6)?δ:?0.85(m,?3H,?CH
3),?1.48(m,?4H,CH
2),?2.08(t,?2H,CH
2),?4.81(m,?2H,?CH
2O),?7.01(d,?1H,?ph),?7.12(d,?1H,?ph),?7.58(d,?1H,?ph),?9.38(s,?2H,?NH)?;?ESI-MS:?318.15?[M-H]
-;?Elemental?analysis?for?C
13H
16Cl
2N
2O
3:?found?C?49.21,?H?5.22,?N?9.01;?calcu.?C?48.92,?H?5.05,?N?8.78.
Vt :?White?solid,?yield?92?%,m.p.?128-130?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.72(s,?2H,?CH
2O),?6.61(s,?1H,?Furan),?7.11-7.14(m,?2H,?Ph),?7.35(m,?
J=8.8Hz,?1H,?Furan),?7.57(s,?1H,?Furan),?7.82(s,?1H,?Ph),?10.31(s,?2H,NH);?ESI-MS:?328.00?[M-H]
-;?Elemental?analysis?for?C
13H
10Cl
2N
2O
4:?found?C?44.54,?H?3.29,?N?8.24;?calcu.?C?44.74,?H?3.06,?N?8.51.
Vu:? White?solid,?yield?98?%,m.p.?132-134?℃;?
1H?NMR?(DMSO-
d 6)?δ:?1.79(d,?
J=6.2Hz,?3H,?CH
3),?4.73(s,?2H,?CH
2O),?5.91(d,?
J=15.1Hz,?1H,?CH),?6.11-6.28(m,?2H,?CH),?7.03-7.14(m,?2H,?Ph),?7.35(d,
?J=8.9Hz,?1H,?Ph),?7.57(s,?1H,?Ph),?10.24(s,?2H,NH)?;?ESI-MS:?328.15?[M-H]
-;?Elemental?analysis?for?C
14H
14Cl
2N
2O
3:?found?C?50.95,?H?4.44,?N?8.88;?calcu.?C?51.08,?H?4.29,?N?8.51.
Vv:? White?solid,?yield?88?%,m.p.?197-199?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.81(s,?2H,?CH
2O),?7.14(d,
?J=8.9Hz,?1H,?Ph),?7.51-7.54(m,?1H,?Py),?7.58(s,?1H,?Ph),?8.19(d,
?J=8.0Hz,?1H,?Py),?8.74(d,
?J=3.2Hz,?1H,?Py),?9.00(s,?1H,?Py),?10.32(s,?1H,?NH),?10.69(s,?1H,?NH);?ESI-MS:?339.56?[M-H]
-;?Elemental?analysis?for?C
14H
11Cl
2N
3O
3:?found?C?49.65,?H?3.43,?N?12.31;?calcu.?C?49.43,?H?3.26,?N?12.35.
Vw: White?solid,?yield?92?%,m.p.?103-105?℃;?
1H?NMR?(DMSO-
d 6)?δ:?4.80(s,?2H,?CH
2O),?7.15(d,
?J=8.9Hz,?1H,?Ph),?7.38(d,
?J=8.9Hz,?1H,?Ph),?7.52(s,?1H,?Ph),?7.74(d,
?J=5.9Hz,?2H,?Py),?8.75(d,
?J=5.9Hz,?2H,?Py),?10.35(s,?1H,?NH),?10.78(s,?1H,?NH);?ESI-MS:?339.15?[M-H]
-;?Elemental?analysis?for?C
14H
11Cl
2N
3O
3:?found?C?49.19,?H?3.32,?N?12.53;?calcu.?C?49.43,?H?3.26,?N?12.35.
Embodiment 24 measures the bactericidal activity of compound
1. experimental condition
1.1 crop and target
For studying thing: cucumber (
Cucumis sativusL
.), kind is: the close thorn in Xintai City.
Subjects: scab of cucumber (
Cladosporium cucumerinum) spore suspension, Cucumber Target Leaf Spot (
Corynespora cassiicola) spore suspension, stem rot of cucumber (
Sclerotinia sclerotiorum(Lib.) de Bary) contain toxic medium method, powdery mildew of cucumber (
Erysiphe cichoracearum) spore suspension, cucumber anthracnose (
Colletotrichum orbiculare(Berk aLMont) Arx.).
1.2 environmental condition
2 cotyledon periods of cucumber seedling.
2. experimental scheme and arrangement
2.1 test medicine
2.1.1 test medicine and treatment dosage
Client provides 21 test samples, and each sample is all established an experimental concentration 500mg/L, take dimethyl formamide (DMF) as solvent.
2.1.2 contrast medicament
If solvent dimethylformamide contrast.
2.1.3 strains tested
Dosporium cucumerinumand its: HX; Cucumber Target Leaf Spot bacterium: SDHGHB060509; Cucumber sclerotiorum: XHL041203; The powdery mildew of cucumber bacterium; Cucumber anthracnose: 050910, preserve by Chinese Academy of Agricultural Sciences's vegetable or flower.
2.2 arrange the residential quarter
3 repetitions are established in all processing respectively, repeat 10 young plants at every turn, adopt randomized arrangement in the greenhouse.
2.3 test disposition
2.3.1 dispenser, vaccination ways
The fine morning reagent agent and contrast medicament are prepared by experimental concentration respectively, the vaccination ways of dosporium cucumerinumand its, Cucumber Target Leaf Spot bacterium, Powdery Mildew, anthrax bacteria adopts the spore suspension spray inoculation, the vaccination ways of cucumber sclerotiorum adopts mycelium inoculation, and moisturizing is cultivated after the inoculation.
2.3.2 meteorological data
Duration of test is take fine as main, and temperature of shed is minimum to be 18 ℃, is up to 30 ℃, and mean temperature is 24 ℃, and relative moisture remains on more than 80%.
2.3.3 soil information
Soil types: the peat composed of rotten mosses, vermiculite, chicken manure are than being 25:12:1.
Investigation
Wait to contrast abundant morbidity " Invest, Then Investigate " disease index.
Disease index carries out statistical computation according to formula well known in the art, and the severity of will falling ill is divided into 0 ~ 9 grade, adds up the sick numbers of sheets at different levels, calculates according to following formula.
Disease index=
* 100%
Relative control effect=
* 100%
The results are shown in following table 2.
Impact on crop
Administered compound is prevented and treated after scab of cucumber, brown spot, stalk break, powdery mildew, the anthracnose cucumber seedling safety, compares without the poisoning situation with blank to occur.
The bactericidal activity data of table 2 compound (relative control effect, %)
| No. | Cucumber Target Leaf Spot | Scab of cucumber | Powdery mildew of cucumber | Stem rot of cucumber | Cucumber anthracnose |
| Va | 10.00 | 10.00 | 59.09 | 13.82 | 89.79 |
| Vb | 49.00 | 20.00 | 100.00 | 15.55 | 72.52 |
| Vc | 37.00 | 37.00 | 34.54 | nd | 72.77 |
| Vd | 39.00 | 59.00 | 18.18 | 49.49 | 98.75 |
| Ve | 42.00 | 4.00 | 42.70 | 42.23 | 68.70 |
| Vf | 38.00 | nd | 77.60 | 51.17 | 46.48 |
| Vg | 38.00 | 19.00 | 35.71 | 31.85 | 66.94 |
| Vh | 38.00 | 71.00 | 67.27 | 16.14 | 19.87 |
| Vi | nd | nd | nd | -4.24 | 25.85 |
| Vj | 42.00 | 7.00 | 12.34 | 13.97 | 43.18 |
| Vk | 41.00 | 49.00 | 30.30 | 31.06 | 63.46 |
| Vl | 35.00 | 13.00 | 82.85 | 6.51 | 51.21 |
| Vm | 38.00 | 4.00 | 88.31 | 22.18 | 64.47 |
| Vn | 27.00 | 6.00 | 57.14 | 55.13 | 23.92 |
| Vo | 25.00 | 6.00 | 38.22 | 33.34 | 50.82 |
| Vp | 36.00 | 17.00 | 23.38 | 5.12 | 46.10 |
| Vq | 85.00 | 1.00 | 62.60 | 16.51 | 39.28 |
| Vr | 87.00 | 53.00 | -5.19 | 25.19 | 93.11 |
| Vs | 25.00 | 5.00 | 15.58 | 7.66 | 71.91 |
| Vt | 10.00 | 55.00 | 41.23 | 28.12 | 67.45 |
| Vu | 64.00 | 15.00 | 6.49 | 1.60 | 24.88 |
| Vv | 61.00 | 24.00 | 47.06 | 23.33 | 44.92 |
| Vw | 48.00 | 47.00 | 8.16 | 29.45 | 63.76 |
| chlorothalonil | 69.93 | 56.27 | 12.12 | 53.40 | 39.41 |
Claims (8)
1. suc as formula the application of the bishydrazide compounds shown in the II as bactericide:
II
Among the formula II; R is phenyl, furyl, pyridine radicals, isoxazolyl, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, the alkyl of C1 ~ C5, thiazolinyl, 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.
2. application as claimed in claim 1; it is characterized in that described R is phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-aminomethyl phenyl, 3-chlorphenyl, 2-fluorophenyl, 2-chlorphenyl, 2,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-iodophenyl, 5-methyl-4-isoxazolyl, 1-cyano group-1-cyclopropane base, methyl, propyl group, isopropyl, butyl, furyl, nicotinoyl base, different nicotinoyl base, cyclopropyl, sorb acidic group.
3. application as claimed in claim 1 is characterized in that described suc as formula the application of the bishydrazide compounds shown in the II as the bactericide of scab of cucumber, powdery mildew of cucumber, cucumber pyrenomycetes disease, Cucumber Target Leaf Spot or cucumber anthracnose.
4. application as claimed in claim 1 is characterized in that among the described formula II that R is 2-fluorophenyl, isopropyl, furyl, and is described suc as formula the application of the bishydrazide compounds shown in the II as the bactericide of scab of cucumber.
5. application as claimed in claim 1 is characterized in that among the described formula II, and R is propyl group, isopropyl, sorb acidic group, 3-pyridine radicals, and is described suc as formula the application of the bishydrazide compounds shown in the II as the bactericide of Cucumber Target Leaf Spot.
6. application as claimed in claim 1, it is characterized in that among the described formula II, R is cyclopropyl, phenyl, 3-aminomethyl phenyl, 2-fluorophenyl, 4-methoxyphenyl, 4-iodophenyl, isoxazolyl, propyl group, and is described suc as formula the application of the bishydrazide compounds shown in the II as the bactericide of powdery mildew of cucumber.
7. application as claimed in claim 1 is characterized in that among the described formula II, and R is 3-aminomethyl phenyl, isoxazolyl, and is described suc as formula the application of the bishydrazide compounds shown in the II as the bactericide of stem rot of cucumber.
8. application as claimed in claim 1, it is characterized in that among the described formula II, R is cyclopropyl, phenyl, 4-nitrobenzophenone, 4-chlorphenyl, 4-fluorophenyl, 3-chlorphenyl, 2-methoxyphenyl, 4-iodophenyl, 1-cyano group-1-cyclopropyl, isopropyl, butyl, furyl, 4-pyridine radicals, and is described suc as formula the application of the bishydrazide compounds shown in the II as the bactericide of cucumber anthracnose.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744358A (en) * | 2014-07-24 | 2015-07-01 | 浙江工业大学 | Pyridine formylhydrazine compounds with insecticidal activity and preparation method and application thereof |
| CN107266380A (en) * | 2016-04-06 | 2017-10-20 | 南开大学 | Application containing bishydrazide structure triazone derivatives and preparation method thereof and in terms of desinsection, sterilization |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101874485A (en) * | 2010-06-30 | 2010-11-03 | 浙江工业大学 | Use of diacylhydrazine compounds as bactericides |
-
2012
- 2012-09-14 CN CN2012103405848A patent/CN102860305A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101874485A (en) * | 2010-06-30 | 2010-11-03 | 浙江工业大学 | Use of diacylhydrazine compounds as bactericides |
Non-Patent Citations (2)
| Title |
|---|
| CHETAN S.SHRIPANAVAR ET AL: "synthesis and insecticidal activity of some nicotinic acid derivatives", 《J.CHEM.PHARM.RES.》 * |
| 柯少勇等: "具有生物活性的酰肼衍生物的研究进展", 《有机化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744358A (en) * | 2014-07-24 | 2015-07-01 | 浙江工业大学 | Pyridine formylhydrazine compounds with insecticidal activity and preparation method and application thereof |
| CN107266380A (en) * | 2016-04-06 | 2017-10-20 | 南开大学 | Application containing bishydrazide structure triazone derivatives and preparation method thereof and in terms of desinsection, sterilization |
| CN107266380B (en) * | 2016-04-06 | 2020-08-28 | 南开大学 | Bishydrazide structure-containing triazone derivative, preparation method thereof and application thereof in insecticidal and bactericidal aspects |
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