CN1321983C - Pyrazole-containing semicarbazide compound and its preparation method and use - Google Patents

Pyrazole-containing semicarbazide compound and its preparation method and use Download PDF

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CN1321983C
CN1321983C CNB2005100489358A CN200510048935A CN1321983C CN 1321983 C CN1321983 C CN 1321983C CN B2005100489358 A CNB2005100489358 A CN B2005100489358A CN 200510048935 A CN200510048935 A CN 200510048935A CN 1321983 C CN1321983 C CN 1321983C
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pyrazole
dimethyl
semicarbazide compound
methyl
ethyl
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CN1654457A (en
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谭成侠
沈德隆
翁建全
曹耀艳
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The present invention relates to a semicarbazide compound containing pyrazole, a preparation method thereof and an application thereof. The semicarbazide compound containing pyrazole is disclosed in the formula (I). The preparation method comprises the following steps: 1-methyl-3-ethyl-4-substituents-5-pyrazolyl formyl hydrazine takes an addition reaction with substituted phenyl isocyanate in an organic solvent at the temperature of 0 to 20DEGC, and a product is obtained by post processing. The semicarbazide compound containing pyrazole can be applied to a herbicide and an insectofungicide.

Description

A kind of pyrazole-containing semicarbazide compound, preparation method and application thereof
(1) technical field
The present invention relates to a kind of pyrazole-containing semicarbazide compound, preparation method and application thereof.
(2) background technology
Pyrazole compound is being played the part of important role in heterocyclic pesticide.Because that pyrazole compound shows is efficient, low toxicity and diversity structure, thereby has boundless research and development prospect.Before the present invention makes, still there is not the compound report of phenyl benzoyl-amido ureas structure abroad, domestic have the Li Laizhong of Shandong Normal University once to report phenyl benzoyl-amido ureas structure, and the compound of this structure has certain weeding activity.The present invention replaces the substituted pyrazolecarboxylic ring benzoyl group in the phenyl benzoyl-amido urea structure and forms the pyrazole-containing semicarbazide compounds.
(3) summary of the invention
Pyrazole-containing semicarbazide compounds that provides a kind of biologically active and preparation method thereof is provided the object of the invention.
Described pyrazole-containing semicarbazide compounds is suc as formula shown in (I):
Wherein X represents Cl or Br, R represent methylidene, nitro, chlorine atom, 2,4-dimethyl, 3,4-dimethyl, 2,4-difluoro, 2,6-dimethyl or hydrogen atom.
Formula (I) compound of following substituting group definition is the preferred of compound of the present invention:
X is Cl, and R is one of following: nitro, 2-methyl, 3,4-dimethyl, 2,4-difluoro, 2,6-dimethyl;
X is Cl, and R is 2-nitro or 2-methyl;
X is Br, and R is a 2-chlorine, 2,4-dimethyl or 3,4-dimethyl.
A kind of preparation method of above-mentioned pyrazole-containing semicarbazide compounds, comprise the steps: to carry out addition reaction suc as formula the substituted phenyl isocyanate shown in the 1-methyl shown in (II)-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine and the formula (III) at 0～20 ℃ in organic solvent, aftertreatment gets product;
Figure C20051004893500051
Wherein X and R definition is the same.
Based on the consideration of productive rate and cost, the described reaction times was good with 1～20 hour.
Described substituted phenyl isocyanate: the molar ratio of 1-methyl-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine is preferably 1～1.5: 1, and described consumption of organic solvent is preferably 20～60 times of 1-methyl-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine quality.
It is one of following that described organic solvent is preferably: tetrahydrofuran (THF), ethyl acetate, toluene, chlorobenzene.
Described aftertreatment can be: reaction finishes, and filters, and filter cake trichloromethane recrystallization gets described pyrazole-containing semicarbazide compounds.
The preparation method of described pyrazole-containing semicarbazide compounds recommends to be undertaken by following parameter:
Described substituted phenyl isocyanate: the molar ratio of 1-methyl-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine is 1～1.1: 1, and described consumption of organic solvent is 20 times of 1-methyl-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine quality; The addition reaction temperature is 0～20 ℃, and the reaction times is 1～5 hour.
Described 1-methyl-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine can adopt following method to make:
1-methyl-3-ethyl-4-replacement-5-pyrazole carboxylic acid ethyl ester and excess hydrazine hydrate are under agitation carried out back flow reaction, and reaction finishes the back concentrating under reduced pressure, uses ethyl alcohol recrystallization, gets white, needle-shaped crystals and is 1-methyl-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine.
With monocotyledon weed lady's-grass Digitaria sanguinalis, barnyard grass grass Echinochloa crus-galli, Herba Setariae Viridis Setaria viridis (or wild avena sativa Avena fatua), broadleaf weed piemarker Abutilontheophrasti (or chickweed Stelleria media or black nightshade Solanum nigrum), lamb's-quarters Chenopodiumalbum, weeds such as recessed amaranth Amaranthus ascedense or Amaranthus retroflexus Amaranthus retroflexus carry out the weeding activity test to institute's synthetic pyrazole-containing semicarbazide compounds and find, X=Br, R=2-Cl, 2,4-dimethyl or 3, the dimethylated formula of 4-(I) compound is to broadleaf weed piemarker Abutilontheophrasti (or chickweed Stelleria media or black nightshade Solanum nigrum), the inhibition activity of weeds such as lamb's-quarters Chenopodiumalbum reaches more than 90%.
Adopt the Potter spray method synthetic compound to be carried out the insecticidal activity assay of mythimna separata (Mythimna separata), adopt dipping plant method the synthetic compound to be carried out the insecticidal activity assay of green rice leafhopper (Nephotettix cincticeps), adopt leaf worm the synthetic compound to be carried out the insecticidal activity assay of black bean aphid (Aphis fabae), adopt leaf worm with soaking method has been carried out two-spotted spider mite (Tetranchus urticae) to the synthetic compound insecticidal activity assay with soaking method.The result shows that X=Cl is that formula (I) compound has certain insecticidal activity to mythimna separata, and the formula of X=Br (I) compound does not have insecticidal activity substantially.
Adopt toxic potato agar substratum (PDA) method that the synthetic compound has been carried out Pyricularia oryzae (Pyricularia oryzae), fusarium graminearum (Gibberella zeae), the fungicidal activity of Phytophthora capsici germ (Phytophthora capsici) and botrytis cinerea pers (Botrytis cinerea) is measured, adopt the toxic potato agar substratum of excised leaf (PDA) method that the fungicidal activity that the synthetic compound has carried out Rhizoctonia solani Kuhn (Rhizoctonia solani) is measured, adopt potted plant toxic potato agar substratum (PDA) method that the fungicidal activity that the synthetic compound has carried out Sclerotinia sclerotiorum (Sclerotonia sclerotiorum) is measured, adopt potted plant stem and leaf of Wheat to preserve the spore method fungicidal activity that the synthetic compound has carried out wheat powdery mildew (Blumeria graminis) is measured.The result shows that X is Cl, and R is that formula (I) compound of 2-nitro or 2-methyl has stronger fungicidal activity to wheat powdery mildew.
(4) embodiment
Below in conjunction with specific embodiment the present invention is further specified, but protection scope of the present invention is not limited to this.
Embodiment 1
4.05g (20mmol) 1-methyl-3-ethyl-4-chloro-5-pyrazoles formyl hydrazine is joined in the 40mL chlorobenzene, under stirring, ice bath drips 20mmol 3-aminomethyl phenyl isocyanic ester, 30min drips complete, react 5h then in about 5 ℃, reaction is finished, and filters, filter cake chloroform recrystallization, obtain white solid, fusing point 176-178 ℃, yield is 91%.
This compound 1H NMR and IR are as described below,
1H NMR(DMSO-D 6，δ/ppm)1.18(3H，t，J＝4.5Hz，CH 2 CH 3)，2.26(3H，s，Ph-CH 3)，2.57(2H，q， CH 2CH 3)，3.9(3H，s，NCH 3)，6.78-7.31(4H，m，Ph-H)，8.40(1H，s，PyCO NHNH)，8.80(1H，s，PyCONH NH)，10.19(1H，s，CO NH-Ph)IR(KBr，V CO/cm -1)1703，1652
Embodiment 2
4.05g (20mmol) 1-methyl-3-ethyl-4-chloro-5-pyrazoles formyl hydrazine is joined in the 70mL toluene, ice bath stirs and drips 22mmol 2-aminomethyl phenyl isocyanic ester down, 40min drips complete, in about 3 ℃, react 3h then, reaction is finished, and filters filter cake chloroform recrystallization, obtain white solid, fusing point 206-208 ℃.Yield is 93%.
This compound 1H NMR and IR are as described below,
1H NMR(DMSO-D 6，δ/ppm)1.18(3H，t，J＝4.75Hz，CH 2 CH 3)，2.22(3H，s，Ph-CH 3)，2.57(2H，q， CH 2CH 3)，3.88(3H，s，NCH 3)，6.96-7.67(4H，m，Ph-H)，8.06(1H，s，PyCO NHNH)，8.68(1H，s，PyCONH NH)，10.27(1H，s，CO NH-Ph)IR(KBr，V CO/cm -1)1704，1660
Embodiment 3
4.05g (20mmol) 1-methyl-3-ethyl-4-chloro-5-pyrazoles formyl hydrazine is joined in the 40mL ethyl acetate, under stirring, ice bath drips 21mmol 3-chloro-phenyl-isocyanic ester, 30min drips complete, in about 1 ℃, react 1h then, reaction is finished, and filters filter cake chloroform recrystallization, obtain white solid, fusing point 189-191 ℃.Yield is 90%.
This compound 1H NMR and IR are as described below,
1H NMR(DMSO-D 6，δ/ppm)1.18(3H，t，J＝4.75Hz，CH 2 CH 3)，2.57(2H，q， CH 2CH 3)，3.89(3H，s，NCH 3)，7.00-7.71(4H，m，Ph-H)，8.61(1H，s，PyCO NHNH)，9.14(1H，s，PyCONH NH)，10.21(1H，s，CO NH-Ph)IR(KBr，V CO/cm -1)1701，1672
Embodiment 4
4.94g (20mmol) 1-methyl-3-ethyl-4-bromo-5-pyrazoles formyl hydrazine is joined in the 30mL tetrahydrofuran (THF), under stirring, ice bath drips 20mmol 3-nitrophenyl isocyanic ester, 30min drips complete, in about 2 ℃, react 2h then, reaction is finished, and filters filter cake chloroform recrystallization, obtain white solid, fusing point 330-331 ℃.Yield is 91%.
This compound 1H NMR and IR are as described below,
1HNMR(DMSO-D 6，δ/ppm)1.18(3H，t，J＝4.75Hz，CH 2 CH 3)，2.57(2H，q， CH 2CH 3)，3.92(3H，s，NCH 3)，7.55-8.55(4H，m，Ph-H)，8.79(1H，s，PyCO NHNH)，9.47(1H，s，PyCONH NH)，10.28(1H，s，CO NH-Ph)IR(KBr，V CO/cm -1)1705，1685
Embodiment 5
4.05g (20mmol) 1-methyl-3-ethyl-4-chloro-5-pyrazoles formyl hydrazine is joined in the 81g trichloromethane, under stirring, ice bath drips 20mmol 3-aminomethyl phenyl isocyanic ester, 30min drips complete, react 5h then in about 18 ℃, reaction is finished, and filters, filter cake chloroform recrystallization, obtain white solid, fusing point 176-178 ℃, yield is 93%.
Embodiment 6
The chlorobenzene consumption changes 18.4ml (20.25g) into, and other is operated with embodiment 1.Yield is 90%.
Embodiment 7
Change organic solvent into the 80mL tetrahydrofuran (THF), other are operated with embodiment 1.Yield is 89%.
Embodiment 8～31
The substituted phenyl isocyanate that conversion is different, other reactant, consumption and processing parameter make respective compound respectively and see Table 1 all with embodiment 1.
Table 1
The embodiment title Formula (I) compound Molecular formula Yield (%) Fusing point (℃)
X R
1 Cl 3-CH 3 C 15H 18ClN 5O 2 92％ 201-203
8 Cl 4-Cl C 14H 15Cl 2N 5O 2 92％ 208-210
9 Cl H C 14H 16ClN 5O 2 90％ 178-180
10 Cl 2-NO 2 C 14H 15ClN 6O 4 91％ 227-229
11 Cl 4-NO 2 C 14H 15ClN 6O 4 82％ 184-186
12 Cl 3-NO 2 C 14H 15ClN 6O 4 90％ 227-229
2 Cl 2-CH 3 C 15H 18ClN 5O 2 93％ 206-208
13 Cl 4-CH 3 C 15H 18ClN 5O 2 92％ 184-186
14 Cl 2-Cl C 14H 15Cl 2N 5O 2 90％ 186-188
3 Cl 3-Cl C 14H 15Cl 2N 5O 2 90％ 189-191
15 Cl 2, the 4-dimethyl C 16H 20ClN 5O 2 90％ 215-217
16 Cl 3, the 4-dimethyl C 16H 20ClN 5O 2 91％ 192-194
17 Cl 2, the 4-difluoro C 14H 14ClF 2N 5O 2 83％ 181-183
18 Cl 2, the 6-dimethyl C 16H 20ClN 5O 2 92％ 244-246
19 Br 3-CH 3 C 15H 18BrN 5O 2 90％ 192-194
20 Br 4-Cl C 14H 15BrClN 5O 2 93％ 216-218
21 Br H C 14H 16BrN 5O 2 91％ 178-180
22 Br 2-NO 2 C 14H 15BrN 6O 4 92％ 188-189
23 Br 4-NO 2 C 14H 15BrN 6O 4 80％ 193-195
4 Br 3-NO 2 C 14H 15BrN 6O 4 91％ 330-331
24 Br 2-CH 3 C 15H 18BrN 5O 2 91％ 209-211
25 Br 4-CH 3 C 15H 18BrN 5O 2 92％ 201-203
26 Br 2-Cl C 14H 15BrClN 5O 2 90％ 203-205
27 Br 3-Cl C 14H 15BrClN 5O 2 91％ 195-197
28 Br 2, the 4-dimethyl C 16H 20BrN 5O 2 91％ 216-218
29 Br 3, the 4-dimethyl C 16H 20BrN 5O 2 91％ 216-218
30 Br 2, the 4-difluoro C 14H 14BrF 2N 5O 2 81％ 193-195
31 Br 2, the 6-dimethyl C 16H 20BrN 5O 2 92％ 248-250
The test of embodiment 32 weeding activity
1 specimen
Embodiment 23,25,26 makes the pyrazole-containing semicarbazide compounds.
2 screening methods
1.1 screening target: monocotyledon weed lady's-grass Digitaria sanguinalis, barnyard grass grass Echinochloacrus-galli, Herba Setariae Viridis Setaria viridis (or wild avena sativa Avena fatua), broadleaf weed piemarker Abutilon theophrasti (or chickweed Stelleria media or black nightshade Solanum nigrum), lamb's-quarters Chenopodium album, recessed amaranth Amaranthus ascedense or Amaranthus retroflexus Amaranthusretroflexus;
1.2 the cultivation of target: at sectional area 64cm 2The plastic tub alms bowl in quantitatively the dress soil pressure is flat, place Stainless steel basin, choose full seed, seed of the same size, divide single, double cotyledon plant to divide the alms bowl sowing, respectively account for 1/3 of alms bowl area, cover the thick fine earth of 1cm, add water to upper layer of soil from plastic tub alms bowl bottom and soak into, place hot-house culture, material to be tried grows to required leaf age to be handled;
1.3 treatment dosage: single dose, generally adopt 2250g a.i./ha or 75g a.i./ha, do suitably to adjust according to classes of compounds;
1.4 processing mode: before the seedling behind soil treatment and the seedling cauline leaf handle, soil treatment before the seedling is carried out in the sowing of examination material next day, unifacial leaf examination material grow to 1 heart stage of 1 leaf, dicotyledonous examination material grow to 2 leaf periods and carry out seedling after cauline leaf handle;
1.5 schedule of operation
1.5.1 accurately take by weighing sample, add a little emulsifying agent with suitable solvent dissolving back, add the distilled water of 10mL low-grade fever again;
1.5.2 get the hot-house culture material, respectively numbering;
1.5.3 pipette quantitatively by dosage is set that soup carries out cauline leaf spraying and the soil spraying is handled, be contrast with spray solvent and clear water respectively;
Place hot-house culture 1.5.4 handle the examination material;
1.5.5 investigation
Handle 15 back range estimation overground part growing states, calculate growth inhibition ratio (preventive effect);
1.5.6 result's statistics
According to investigation result, calculate the preventive effect of each compound as follows to weeds:
Preventive effect (%)=100 (contrast plant height-processing plant height)/contrast plant height
Gained the results are shown in Table 2.
Carry out the weeding activity classification according to preventive effect: A level preventive effect＞90%B level preventive effect 75～90%C level preventive effect 50～75%D level preventive effect 25～50% E level preventive effect＜25%
Table 2 pyrazole-containing semicarbazide compounds is to the restraining effect of grass
The embodiment title Formula (I) compound Handle Lady's-grass The dog tail Barnyard grass Piemarker Lamb's-quarters The thorn amaranth
X R
Embodiment 23 Br 2-Cl Cauline leaf 0 0 0 100 95 100
Soil 0 0 0 0 0 0
Embodiment 25 Br 2, the 4-dimethyl Cauline leaf 90 80 70 100 100 100
Soil 50 50 0 100 100 100
Embodiment 26 Br 3, the 4-dimethyl Cauline leaf 0 0 0 50 50 70
Soil 0 0 0 50 100 100
The general sieve of embodiment 33 insecticidal activities
1 for the examination target
Mythimna separata (Mythimna separata) is indoor with maize seedling raising sensitive strain for many years; Black bean aphid (Aphis fabae) is indoor sensitive strain of throughout the year raising with the broad bean seedling; Green rice leafhopper (Nephotettix cincticeps) is indoor with paddy rice seedling raising sensitive strain for many years; Two-spotted spider mite (Tetranychus urticae) is indoor sensitive strain of throughout the year raising with the broad bean seedling.Indoor conditions: 25 ± 5 ℃ of temperature, relative humidity 65 ± 5% and periodicity of illumination 12/12h (L/D).
2 reagent agents
Embodiment 10,11,12,2,16,17,18,19,31 makes the pyrazole-containing semicarbazide compounds.
3 test methods
The mythimna separata test method adopts Potter spray method (seeing the SCBZ/CH-HN-2000-001 bar), and concentration is 1000mg/L;
The black bean aphid test method adopts pickling process (seeing the SCBZ/CH-HN-2000-004 bar), and concentration is 500mg/L
The green rice leafhopper test method adopts the processing plant to connect worm method (seeing the SCBZ/CH-HN-2000-002 bar), and concentration is 500mg/L.
The two-spotted spider mite test method adopts pickling process (seeing the SCBZ/CH-HN-2000-003 bar), and concentration is 500mg/L;
Check result after 48 hours, as shown in table 3.
4 evaluated biological activity
Mortality ratio is being the A level more than 90%, is the B level between 70～90%, is the C level between 50～70%, is the D level between 0～50%.Activity enters primary dcreening operation for the compound of A level.
The test of table 3 pyrazole-containing semicarbazide compound desinsection living-article
Sequence number Formula (I) compound Mythimna separata Aphid Leafhopper Red spider
Mortality ratio (%) The virulence rank Mortality ratio (%) The virulence rank Mortality ratio (%) The virulence rank Mortality ratio (%) The virulence rank
X R
10 Cl 2-NO 2 33.33 D 0 0
11 Cl 4-NO 2 9.10 D 0 0
12 Cl 3-NO 2 5.30 D 0 0
2 Cl 2-CH 3 47.60 D 0 0
16 Cl 3, the 4-dimethyl 11.80 D 0 0
17 Cl 2, the 4-dimethyl 5.0 D 0 0
18 Cl 2, the 6-dimethyl 5.0 D 0 0
19 Br 3-CH 3 10.60 D 0 0
31 Br 2, the 6-dimethyl 0 0 3.66 D
The screening of embodiment 34 fungicidal activities
1. for the examination bacterial classification
Pyricularia oryzae (Pyricularia oryzae), Rhizoctonia solani Kuhn (Rhizoctonia solani), botrytis cinerea pers (Botrytis cinerea), Sclerotinia sclerotiorum (Sclerotonia sclerotiorum), fusarium graminearum (Gibberella zeae), Phytophthora capsici germ (phytophythora capsici).Above bacterial classification all is kept in the refrigerator (4-8 ℃), is inoculated in the culture dish from the test tube slant in 2-3 days before the test, cultivates to be for experiment under optimal temperature.Experiment is potato agar substratum (PDA) with substratum.Wheat powdery mildew is preserved spore with stem and leaf of Wheat and is for experiment.
2 measuring methods
Accurately take by weighing an amount of embodiment 1～4 and 8～31 and make compound, with suitable solvent dissolving and adding small amounts of emulsifiers, be diluted to finite concentration earlier with clear water.Concrete grammar is as follows:
Pyricularia oryzae, fusarium graminearum, Phytophthora capsici germ and botrytis cinerea pers: adopt toxic medium therapy, general sieve concentration is 25ppm.
Rhizoctonia solani Kuhn: adopt the excised leaf culture method, general sieve concentration is 500ppm.
Sclerotinia sclerotiorum and wheat powdery mildew: adopt pot-culture method, general sieve concentration is 500ppm.
3 fungicidal activity evaluations
Handle incidence and the mycelial growth situation of back routine observation record blade, plant,, calculate preventive effect and inhibiting rate according to disease index and hyphal diameter.The fungicidal activity grade standard is divided: A level-preventive effect (inhibiting rate) 〉=95%, B level-70%≤preventive effect (inhibiting rate)＜95%, C level-50%≤preventive effect (inhibiting rate)＜70%, D level-preventive effect (inhibiting rate)＜50%.
4 The selection result
As can be seen from Table 4, pyrazole-containing semicarbazide compound fungicidal activity of the present invention is more weak or do not have an activity.
The test of table 4 pyrazole-containing semicarbazide compound fungicidal activity
The embodiment title Formula (I) compound Gibberellic hypha The phytophthora root rot bacterium Pyricularia oryzae Ash arrhizus bacteria Sheath blight fungus The sclerotium germ The white powder germ
Inhibiting rate (%) The virulence rank Inhibiting rate (%) The virulence rank Inhibiting rate (%) The virulence rank Inhibiting rate (%) The virulence rank Preventive effect (%) The virulence rank Preventive effect (%) The virulence rank Preventive effect (%) The virulence rank
X R
1 Cl 3-CH 3 0 D 0 D 5.1 D 21.6 D 0 D 0 D 10.0 D
8 Cl 4-Cl 0 D 0 D 0 D 31.8 D 0 D 0 D 15.0 D
9 Cl H 24.0 D 14.9 D 51.3 C 70.1 B 0 D 0 D 20.0 D
10 Cl 2-NO 2 18.6 D 8.9 D 51.3 C 31.8 D 0 D 0 D 15.0 D
11 Cl 4-NO 2 12.7 D 6.3 D 27.4 D 30.2 D 0 D 0 D 14.3 D
12 Cl 3-NO 2 37.3 D 29.8 D 30.7 D 31.8 D 0 D 0 D 15.0 D
2 Cl 2-CH 3 0 D 0 D 0 D 12.7 D 0 D 0 D 10.0 D
13 Cl 4-CH 3 0 D 0 D 0 D 19.1 D 0 D 0 D 90.0 A
14 Cl 2-Cl 5.3 D 0 D 15.4 D 0 D 0 D 0 D 20.0 D
3 Cl 3-Cl 0 D 0 D 10.2 D 0 D 0 D 0 D 30.0 D
15 Cl 2, the 4-dimethyl 5.3 D 0 D 10.2 D 0 D 0 D 0 D 20.0 D
16 Cl 3, the 4-dimethyl 0 D 0 D 10.2 D 0 D 0 D 0 D 80.0 B
17 Cl 2, the 4-difluoro 24.0 D 0 D 20.5 D 0 D 0 D 0 D 20.0 D
18 Cl 2, the 6-dimethyl 0 D 0 D 10.2 D 25.5 D 0 D 0 D 20.0 D
19 Br 3-CH 3 0 D 0 D 28.1 D 7.3 D 0 D 0 D 0 D
20 Br 4-Cl 0 D 0 D 14.0 D 2.9 D 0 D 0 D 0 D
21 Br H 0 D 0 D 17.5 D 0 D 0 D 0 D 0 D
22 Br 2-NO 2 0 D 0 D 52.6 C 4.4 D 0 D 0 D 0 D
23 Br 4-NO 2 0 D 0 D 42.1 D 24.8 D 0 D 0 D 0 D
4 Br 3-NO 2 00 D 0 D 17.5 D 0 D 0 D 0 D 0 D
24 Br 2-CH 3 0 D 0 D 17.5 D 10.2 D 0 D 0 D 0 D
25 Br 4-CH 3 0 D 0 D 17.5 D 4.4 D 0 D 0 D 0 D
26 Br 2-Cl 0 D 0 D 24.6 D 0 D 0 D 0 D 0 D
27 Br 3-Cl 0 D 0 D 45.6 D 36.5 D 0 D 0 D 0 D
28 Br 2, the 4-dimethyl 0 D 0 D 45.6 D 29.2 D 0 D 0 D 0 D
29 Br 3, the 4-dimethyl 0 D 0 D 45.6 D 10.2 D 0 D 0 D 0 D
30 Br 2, the 4-difluoro 0 D 0 D 45.6 D 7.3 D 0 D 0 D 0 D
31 Br 2, the 6-dimethyl 0 D 0 D 28.1 D 7.3 D 0 D 0 D 0 D

Claims (10)

1, suc as formula the pyrazole-containing semicarbazide compound shown in (I),
Figure C2005100489350002C1
Wherein X represents Cl or Br, R represent methylidene, nitro, chlorine atom, 2,4-dimethyl, 3,4-dimethyl, 2,4-difluoro, 2,6-dimethyl or hydrogen atom.
2, pyrazole-containing semicarbazide compound as claimed in claim 1 is characterized in that described X is Cl, and R is one of following: nitro, 2-methyl, 3,4-dimethyl, 2,4-difluoro, 2,6-dimethyl.
3, pyrazole-containing semicarbazide compound as claimed in claim 2 is characterized in that described R is 2-nitro or 2-methyl.
4, pyrazole-containing semicarbazide compound as claimed in claim 1 is characterized in that described X is Br, and R is a 2-chlorine, 2,4-dimethyl or 3,4-dimethyl.
5, the preparation method of the described pyrazole-containing semicarbazide compound of a kind of claim 1, comprise the steps: to carry out addition reaction suc as formula the substituted phenyl isocyanate shown in the 1-methyl shown in (II)-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine and the formula (III) at 0～20 ℃ in organic solvent, aftertreatment gets product;
Wherein X represents Cl or Br, R represent methylidene, nitro, chlorine atom, 2,4-dimethyl, 3,4-dimethyl, 2,4-difluoro, 2,6-dimethyl or hydrogen atom.
6, the preparation method of pyrazole-containing semicarbazide compound as claimed in claim 5, it is characterized in that the described addition reaction time is 1～20 hour, substituted phenyl isocyanate: the molar ratio of 1-methyl-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine is 1.0～1.5: 1, and consumption of organic solvent is 20～60 times of 1-methyl-3-ethyl-4-replacement-5-1 pyrazoles formyl hydrazine quality.
7, the preparation method of pyrazole-containing semicarbazide compound as claimed in claim 5 is characterized in that described organic solvent is one of following: tetrahydrofuran (THF), ethyl acetate, toluene, chlorobenzene.
8, as the preparation method of the described pyrazole-containing semicarbazide compound of one of claim 5～7, it is characterized in that described substituted phenyl isocyanate: the molar ratio of 1-methyl-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine is 1.0～1.1: 1, and described consumption of organic solvent is 20 times of 1-methyl-3-ethyl-4-replacement-5-pyrazoles formyl hydrazine quality; The addition reaction time is 1～5 hour.
9, the described pyrazole-containing semicarbazide compound of claim 1 is as herbicide applications.
10, the described pyrazole-containing semicarbazide compound of claim 1 is as the application of insectofungicide.
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CN103242248A (en) * 2013-05-06 2013-08-14 浙江工业大学 Pyrazine semicarbazide compound as well as preparation method and application thereof
CN105777639A (en) * 2016-01-26 2016-07-20 浙江博仕达作物科技有限公司 Pyrazole hydrazide compound and use thereof
CN107954993A (en) * 2017-12-04 2018-04-24 杨子辉 A kind of preparation method of 5- pyrazoles hydrazide kind compound and application
CN117658918A (en) * 2021-01-05 2024-03-08 西北农林科技大学 Application of diphenylpyrazole compound

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CN1183409A (en) * 1995-09-08 1998-06-03 化学工业部沈阳化工研究院 Insecticidal acaricidal pyrazoles compounds and preparation thereof
CN1382127A (en) * 1999-12-09 2002-11-27 辛根塔参与股份公司 Pyrazolecarboxamide and pyrazolethioamide as fungioide

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CN1183409A (en) * 1995-09-08 1998-06-03 化学工业部沈阳化工研究院 Insecticidal acaricidal pyrazoles compounds and preparation thereof
CN1382127A (en) * 1999-12-09 2002-11-27 辛根塔参与股份公司 Pyrazolecarboxamide and pyrazolethioamide as fungioide

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