CN109169693A - A kind of novel amides compound containing pyrazole ring is preparing the application in herbicide - Google Patents

A kind of novel amides compound containing pyrazole ring is preparing the application in herbicide Download PDF

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CN109169693A
CN109169693A CN201810996538.0A CN201810996538A CN109169693A CN 109169693 A CN109169693 A CN 109169693A CN 201810996538 A CN201810996538 A CN 201810996538A CN 109169693 A CN109169693 A CN 109169693A
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phenyl
dimethyl
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ethyl
urea groups
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CN109169693B (en
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王翰
金涛
谭成侠
翁建全
武宏科
刘幸海
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Zhejiang University of Technology ZJUT
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a kind of novel amides compounds containing pyrazole ring to prepare the application in herbicide.It is using the seed of romaine lettuce (Lettuce) and bent grass (Agrostis) as subjects, before bioassay, the surface sterilizing that seed uses the Chlorox solution of 5-10% to carry out 10 minutes, cleaning down then is carried out with the deionized water of Millipore system, is then air-dried in gnotobasis.Sample treatment: all samples use acetone as solvent, and configuration concentration is the solution of 1 mM；Bioassay is carried out again, is measured the compound of the present invention with activity of weeding, especially there is preferable inhibition to romaine lettuce and bent grass, provided the foundation for the research and development of novel pesticide.

Description

A kind of novel amides compound containing pyrazole ring is preparing the application in herbicide
Technical field
The present invention relates to a kind of novel amides compound containing pyrazole ring, that is, 1,3- dimethyl-N-(2- (3- phenylcarbamido) Ethyl) -1H- pyrazole-4-carboxamide derivatives are preparing the application in herbicide.
Background technique
In recent decades, pesticide industry enters the epoch of rapid development, and a feature the most outstanding is exactly jeterocyclic chemistry Close object extensive application so that pesticide is big from toxicity, side effect is high, high residue old times turns to development for ultra high efficiency, without public affairs In harmful, environmental-friendly pesticides application new era, heterocyclic compound species are extensive, a variety of systems including nitrogenous, oxygen, sulphur etc. Column, but wherein also belong to nitrogen-containing heterocycle class using weight is higher in pesticide.Make a general survey of last century end so far, the jeterocyclic chemistry of new listing It closes object and contains nitrogen, such as sulfonylurea herbicide tribenuron-methyl (Tribenuron methyl), azoles fungicide triazolone (Triadimefon), Acaricide Fenpyroximate (Fenpyroximate), anabasine insecticide Diacloden (Thiamethoxam) Deng, it can be seen that, no matter heterocycle compound in weeding, sterilization or in desinsection, mite killing all has very good effect, wherein again Number nitrogen-containing hetero cyclics are the most prominent.
Instantly the exploitation of heterocycle noval chemical compound is the emphasis of noval chemical compound research, and pyrazole derivatives are as heterocyclic compound In an important class in new drug development field be even more that there is critical role.Due to pyrazole compound show it is efficient, low Poison and the characteristics of structure diversity, the pesticide species of many novel, efficient, environment amenable pyrazole derivatives also meet the tendency of and It is raw, but being widely used with such medicament, since action site is single, resistance problem is also increasingly prominent, and germ insect pest is Gradually these drugs are produced with different degrees of resistance, therefore the pyrazoles pesticide species for developing novel structure increasingly show One of its necessity and urgency, and the hot spot studied at present.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of novel amides containing pyrazole ring Class compound, that is, 1,3- dimethyl-N-(2- (3- phenylcarbamido) ethyl) -1H- pyrazole-4-carboxamide derivatives are preparing herbicide In application, some in these compounds explore method and technology of preparing with good herbicidal activity, for the synthesis of novel pesticide.
The novel amides compound containing pyrazole ring of one kind is preparing the application in herbicide, it is characterised in that its Shown in structural formula such as formula (I):
In formula (I): R is phenyl or substituted-phenyl, and the substituent group of the substituted-phenyl is halogen, 2- perfluoro propyl, ethoxy Base, trifluoromethyl, trifluoromethoxy, trimethyl urea groups, methyl, methoxyl group.
The novel amides compound containing pyrazole ring of one kind is in the herbicide that preparation prevents and treats romaine lettuce, bent grass Using, it is characterised in that shown in its structural formula such as formula (I):
In formula (I): R is phenyl or substituted-phenyl, and the substituent group of the substituted-phenyl is halogen, 2- perfluoro propyl, ethoxy Base, trifluoromethyl, trifluoromethoxy, trimethyl urea groups, methyl, methoxyl group.
The application, it is characterised in that R is one of following in formula (I): phenyl, 4- (2- perfluoro propyl) phenyl, 4- benzene Itrile group, 4- ethoxyl phenenyl, 2- trifluoromethyl, 3- fluorophenyl, trimethyl urea groups, 3,5 3,5-dimethylphenyls, 2- methoxybenzene Base, 2- chlorphenyl.
Compared with prior art, the beneficial effects are mainly reflected as follows: a series of new provided by the invention to contain pyrrole The amides compound of azoles ring has activity of weeding, especially has preferable inhibition to romaine lettuce and bent grass, is novel pesticide Research and development provide the foundation.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in This:
The preparation of 1 1,3- dimethyl-N-of embodiment (2- (3- phenylcarbamido) ethyl) -1H- pyrazole-4-carboxamide
(1) synthesis of (2- (1,3- dimethyl -1H- pyrazoles -4- formamido group) ethyl) t-butyl carbamate (II):
1,3- dimethyl -1H- pyrazoles -4- acyl chlorides (1.06g, 5mmol) is added in (20ml) methylene chloride, stirring is simultaneously N-Boc- ethylenediamine (0.88g, 5.5mmol) is slowly added dropwise, triethylamine (2.02g, 20mmol) then is added dropwise, 2h is stirred at room temperature, TLC (EA/PE=2/1 (V)) tracking, after complete reaction, uses DCM/H2O=1/1 (V) system extracts three times, and vacuum distillation is gone Except solvent, (2- (1,3- dimethyl -1H- pyrazoles -4- formamido group) ethyl) t-butyl carbamate shown in formula (II) is obtained.
(2) synthesis of N- (2- amino-ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide (III):
By (2- (1,3- dimethyl -1H- pyrazoles -4- formamido group) ethyl) t-butyl carbamate shown in formula (II) (1.68g, 5mmol) is added in (20ml) methylene chloride, is added trifluoroacetic acid (1.71g, 15mmol), 2h is stirred at room temperature, to anti- When system being answered to release (not bubbling) without gas, continue to stir 1h, reaction terminates, and vacuum distillation removes solvent and extra trifluoro second Acid obtains N- shown in formula (III) (2- amino-ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide.
(3) 1,3- dimethyl-N-(2- ((1- (methylamino) vinyl) amino) ethyl) -1H- pyrazole-4-carboxamide spreads out The synthesis of biological formula:
N- shown in formula (III) (2- amino-ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide is added in methylene chloride, It is fed intake, is stirred at room temperature, reaction overnight with molar ratio 1:1.1 with phenyl isocyanate, TLC (EA/PE=2/1 (V)) tracking, to anti- Removal solvent, petroleum ether elution should be evaporated under reduced pressure afterwards completely, 75% ethyl alcohol recrystallization crosses column purification, target compounds of formula is made 1,3- dimethyl-N-shown in (I -1) (2- (3- phenyl urea groups) ethyl) -1H- pyrazole-4-carboxamide, yield 20%, m.p.177- 178 DEG C, -1H- pyrazole-4-carboxamide structural formula is such as 1,3- dimethyl-N-shown in formula (I -1) (2- (3- phenyl urea groups) ethyl) Under:
1,3- dimethyl-N-(2- (3- phenyl urea groups) ethyl) -1H- pyrazole-4-carboxamide:1H NMR(500MHz, CDCl3)δ:2.46(s,3H,CH3),3.47(s,4H,2CH2),3.73(s,3H,CH3),5.93(s,1H,NH),7.01(s,1H, ), NH 7.04~7.07 (m, 1H, Ph), 7.26~7.32 (m, 4H, Ph), 7.36 (s, 1H, NH), 7.72 (s, 1H, CH)
2 1,3- dimethyl-N-of embodiment (2- (3- (4- (2- perfluoropropane) phenyl) urea groups) ethyl) -1H- pyrazoles -4- The preparation of formamide
(1) synthesis of (2- (1,3- dimethyl -1H- pyrazoles -4- formamido group) ethyl) t-butyl carbamate (II):
1,3- dimethyl -1H- pyrazoles -4- acyl chlorides (1.06g, 5mmol) is added in (20ml) methylene chloride, stirring is simultaneously N-Boc- ethylenediamine (0.88g, 5.5mmol) is slowly added dropwise, triethylamine (2.02g, 20mmol) then is added dropwise, 2h is stirred at room temperature, TLC (EA/PE=2/1 (V)) tracking, after complete reaction, uses DCM/H2O=1/1 (V) system extracts three times, and vacuum distillation is gone Except solvent, (2- (1,3- dimethyl -1H- pyrazoles -4- formamido group) ethyl) t-butyl carbamate shown in formula (II) is obtained.
(2) synthesis of N- (2- amino-ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide (III):
By (2- (1,3- dimethyl -1H- pyrazoles -4- formamido group) ethyl) t-butyl carbamate shown in formula (II) (1.68g, 5mmol) is added in (20ml) methylene chloride, is added trifluoroacetic acid (1.71g, 15mmol), 2h is stirred at room temperature, to anti- When system being answered to release (not bubbling) without gas, continue to stir 1h, reaction terminates, and vacuum distillation removes solvent and extra trifluoro second Acid obtains N- shown in formula (III) (2- amino-ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide.
(3) 1,3- dimethyl-N-(2- ((1- (methylamino) vinyl) amino) ethyl) -1H- pyrazole-4-carboxamide spreads out The synthesis of biological formula:
N- shown in formula (III) (2- amino-ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide is added in methylene chloride, It is fed intake, is stirred at room temperature, reaction overnight, TLC (EA/PE=2/ with molar ratio 1:1.1 with 4- (2- perfluoro propyl) phenyl isocyanate 1 (V)) tracking, vacuum distillation removal solvent, petroleum ether elution, 75% ethyl alcohol recrystallization cross column purification, system after complete reaction Obtain 1,3- dimethyl-N-(2- (3- (4- (perfluoro propyl -2- base) phenyl) urea groups) ethyl)-shown in target compounds of formula (I -2) 1H- pyrazole-4-carboxamide, yield 35.5%, m.p.165-167 DEG C, 1,3- dimethyl-N-(2- (3- (4- shown in formula (I -2) (2- perfluoro propyl) phenyl) urea groups) ethyl) -1H- pyrazole-4-carboxamide structural formula is as follows:
1,3- dimethyl-N-(2- (3- (4- (2- perfluoropropane) phenyl) urea groups) ethyl) -1H- pyrazole-4-carboxamide:1HNMR(500MHz,CDCl3)δ:2.45(s,3H,CH3),3.49(s,4H,2CH2),3.71(s,3H,CH3),6.28(s,1H, ), NH 6.91 (s, 1H, NH), 7.46 (d, J=8.5Hz, 2H, Ph), 7.50 (d, J=8.5Hz, 1H, NH), 7.72 (s, 1H, CH),8.17(s,1H,NH).
The system of 3 N- of embodiment (2- (3- (4- cyanophenyl base) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide It is standby
Phenyl isocyanate in 1 step of embodiment (3) is substituted for 4- cyanophenyl isocyanates, other operations are the same as real Example 1 is applied, N- (2- (3- (4- cyanophenyl base) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide, yield are obtained 21.2%, m.p.213-215 DEG C, N- shown in formula (I -3) (2- (3- (4- cyanophenyl base) urea groups) ethyl) -1,3- dimethyl -1H- pyrrole Azoles -4- formamide structural formula is as follows:
N- (2- (3- (4- cyanophenyl base) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide:1H NMR (500MHz,CDCl3)δ:2.46(s,3H,CH3),3.80(s,3H,CH3), 3.81~3.83 (m, 2H, CH2), 4.49~4.51 (m,2H,CH2), 7.02 (d, J=7.5Hz, 1H, NH), 7.20~7.22 (m, 1H, Ph), 7.29 (t, J=5.0Hz, 1H, NH), 7.49~7.53 (m, 1H, Ph), 7.64 (s, 1H, CH), 7.69~7.71 (m, 1H, Ph)13C NMR(151MHz,DMSO-d)δ: 163.52,150.70,148.52,137.60,133.18,132.14,126.57,122.44,115.49,115.30,40.73, 38.89,36.78,13.50.
4 N- of embodiment (2- (3- (4- ethoxyl phenenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide Preparation
Phenyl isocyanate in 1 step of embodiment (3) is substituted for 4- ethoxyphenyl isocyanate, other operations are same Embodiment 1 obtains N- (2- (3- (4- ethoxyl phenenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide, yield 34.3%, m.p.255-256 DEG C, N- shown in formula (I -3) (2- (3- (4- ethoxyl phenenyl) urea groups) ethyl) -1,3- dimethyl - 1H- pyrazole-4-carboxamide structural formula is as follows:
N- (2- (3- (4- ethoxyl phenenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide:1H NMR (500MHz,CDCl3) δ: 1.41 (t, J=7.0Hz, 3H, CH3),2.42(s,3H,CH3),3.45(s,4H,2CH2),3.78(s, 3H,CH3), 3.98~4.03 (m, 2H, CH2), 5.47 (s, 1H, NH), 6.72 (s, 1H, NH), 6.84 (d, J=9.0Hz, 2H, ), Ph 7.04 (s, 1H, NH), 7.16 (d, J=9.0Hz, 2H, Ph), 7.71 (s, 1H, CH)13C NMR(151MHz,DMSO-d) δ:164.72,158.09,156.11,149.15,131.91,130.83,123.96,115.21,115.10,114.91, 63.75,41.54,39.58,38.81,14.82,13.42.
5 N- of embodiment (2- (3- (2- trifluoromethyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazoles -4- formyl The preparation of amine
Phenyl isocyanate in 1 step of embodiment (3) is substituted for 2- trifluoromethylbenzene based isocyanate, other operations With embodiment 1, N- (2- (3- (2- trifluoromethyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide is obtained, Yield 67.6%, m.p.159-160 DEG C, N- shown in formula (I -5) (2- (3- (2- trifluoromethyl) urea groups) ethyl) -1,3- bis- Methyl-1 H- pyrazole-4-carboxamide structural formula is as follows:
N- (2- (3- (2- trifluoromethyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide:1H NMR (500MHz,CDCl3)δ:2.31(s,3H,CH3), 3.22~3.27 (m, 4H, 2CH2),3.76(s,3H,CH3), 7.11 (t, J= 5.0Hz, 1H, NH), 7.19 (t, J=7.5Hz, 1H, Ph), 7.57 (t, J=7.5Hz, 1H, Ph), 7.62 (d, J=8.0Hz, 1H, Ph), 7.82 (s, 1H, CH), 7.89 (t, J=5.0Hz, 1H, NH), 7.94 (d, J=8.0Hz, 1H, Ph), 8.03 (s, 1H, NH).
The system of 6 N- of embodiment (2- (3- (3- fluorophenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide It is standby
Phenyl isocyanate in 1 step of embodiment (3) is substituted for 3- fluorophenylisocyanate, other operations are the same as implementation Example 1, acquisition N- (2- (3- (3- fluorophenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide, yield 15%, m.p.207-208℃。
N- (2- (3- (3- fluorophenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide:1H NMR (500MHz,CDCl3)δ:2.30(s,3H,CH3), 3.20~3.23 (m, 2H, CH2), 3.24~3.27 (m, 2H, CH2),3.76 (s,3H,CH3), 6.38 (t, J=6.0Hz, 1H, NH), 6.67~6.71 (m, 1H, Ph), 7.03 (d, J=8.0Hz, 1H, Ph), 7.21~7.26 (m, 1H, Ph), 7.45~7.48 (m, 1H, Ph), 7.90 (t, J=5.5Hz, 1H, NH), 8.03 (s, 1H, CH), 8.87(s,1H,NH).
7 N- of embodiment (2- (trimethyl urea groups) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide preparation
Phenyl isocyanate in 1 step of embodiment (3) is substituted for trimethyl-urea, other operations are obtained with embodiment 1 Formula N- (2- (trimethyl urea groups) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide, yield 81.8%, m.p.163- 165℃。
N- (2- (trimethyl urea groups) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide:1H NMR (500MHz,CDCl3)δ:2.19(s,6H,CH3),2.29(s,3H,CH3),2.49(s,3H,CH3),3.42(s,4H,2CH2), 3.84(s,3H,CH3),5.79(s,1H,NH),6.93(s,2H,Ph),7.18(s,1H,NH),7.71(s,1H,CH).13C NMR (151MHz,DMSO-d)δ:168.16,164.13,158.60,149.19,136.99,131.68,131.27,129.57, 115.51,45.60,42.11,39.45,38.87,20.95,18.06,13.41.
Embodiment 8N- (2- (3- (3,5 3,5-dimethylphenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide Preparation
Phenyl isocyanate in 1 step of embodiment (3) is substituted for 3,5 dimethylphenyl isocyanates, other operations With embodiment 1, the N- as shown in formula (I -9) (2- (3- (3,5 3,5-dimethylphenyl) urea groups) ethyl) -1,3- dimethyl is obtained) - 1H- pyrazole-4-carboxamide, yield 45.5%, m.p.192-193 DEG C.
N- (2- (3- (3,5 3,5-dimethylphenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide:1H NMR (500MHz,CDCl3)δ:2.25(s,6H,2CH3),2.46(s,3H,CH3),3.47(s,4H,2CH2),3.73(s,3H,CH3), 5.91(s,1H,NH),6.71(s,1H,NH),6.91(s,2H,Ph),7.11(s,1H,NH),7.17(s,1H,NH),7.73(s, 1H,CH).13C NMR(151MHz,DMSO-d)δ:163.62,155.85,148.68,140.79,137.94,132.19, 123.15,116.30,115.94,115.10,40.52,39.54,39.45,38.91,21.62,13.57.
9 N- of embodiment (2- (3- (2- methoxyphenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide Preparation
Phenyl isocyanate in 1 step of embodiment (3) is substituted for 2- methoxyphenyl isocyanate, other operations are same Embodiment 1 obtains the N- as shown in formula (I -10) (2- (3- (2- methoxyphenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrrole Azoles -4- formamide, yield 75.8%, m.p.166-167 DEG C.
N- (2- (3- (2- methoxyphenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide:1H NMR (500MHz,CDCl3)δ:2.47(s,3H,CH3),3.51(s,4H,2CH2),3.75(s,3H,CH3),3.80(s,3H,CH3), 5.70 (s, 1H, NH), 6.84~6.86 (m, 1H, Ph), 6.92~6.96 (m, 2H, Ph+NH), 6.99~7.02 (m, 1H, Ph), 7.05 (s, 1H, NH), 7.70 (s, 1H, CH), 7.98~8.00 (m, 1H, Ph)13CNMR(151MHz,DMSO-d)δ:148.17, 133.77,128.12,123.12,122.89,121.22,120.98,119.85,119.66,110.30,110.13,55.68, 45.61,41.28,39.81,29.71.
The system of 10 N- of embodiment (2- (3- (2- chlorphenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide It is standby
Phenyl isocyanate in 1 step of embodiment (3) is substituted for 2- chlorophenyl isocyanate, other operations are the same as implementation Example 1 obtains the N- as shown in formula (I -11) (2- (3- (2- chlorphenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazoles -4- first Amide, yield 23.5%, m.p.145-146 DEG C.
N- (2- (3- (2- chlorphenyl) urea groups) ethyl) -1,3- dimethyl -1H- pyrazole-4-carboxamide:1H NMR (500MHz,CDCl3)δ:2.48(s,3H,CH3), 3.51~3.54 (m, 2HCH2), 3.56~3.59 (m, 2H, CH2),3.80 (s,3H,CH3), 5.67 (t, J=5.0Hz, 1H, NH), 6.60 (s, 1H, NH), 6.88 (s, 1H, NH), 7.00 (t, J= 6.5Hz, 1H, Ph), 7.25 (t, J=7.0Hz, 1H, Ph), 7.34~7.36 (m, 1H, Ph), 7.69 (s, 1H, CH), 8.03 (d, J=8.5Hz, 1H, Ph)13C NMR(151MHz,DMSO-d)δ:163.58,155.42,148.71,137.16,132.19, 129.54,127.90,122.91,121.63,121.26,115.10,40.52,39.35,38.93,13.59.
The test of 11 activity of weeding of embodiment
Subjects: the seed of romaine lettuce (Lettuce), bent grass (Agrostis).
Test process: seed treatment: before bioassay, seed uses the Chlorox solution of 5-10% to carry out 10 The surface sterilizing of minute then carries out cleaning down with the deionized water of Millipore system, then in gnotobasis apoplexy It is dry.Sample treatment: all samples use acetone as solvent, and configuration concentration is the solution of 1mM, place stand-by.
Bioassay: all bioassay are divided into duplicate measurement, thin in sterile 24 hole of apyrogeneity polystyrene It is carried out in born of the same parents' culture plate (CoStar 3524, Corning Incorporated).By a filter paper disk (Whatman Grade It 1,1.5cm) is placed in each hole ready for use.There are 200 μ L water in all control wells, contains 180 μ L in control+solvent hole Water and 20 μ L solvents, and have 180 μ L water and the suitably diluted sample of 20 μ L in all sample wells.Before sample is added, It first will be in 180 μ L water inlet holes.All plates are both placed in sterile environment, and reduce the machine of pollution as far as possible Meeting.5 seeds are put into all Kong Zhongjun, are sealed with lid.Plate is placed in the incubator of CU-36L5, temperature is 26 DEG C, Intensity of illumination is 120.1umol s-1m-2Under conditions of be incubated for, plate is at least incubated for 7 days, relatively subjective rows of plants is obtained Name.Ranking is divided into 5 grades: 0-5.Grade be 0 expression do not have apparent inhibiting effect (sample well plant with compare+it is molten Plant is identical in agent hole), class 5 is expressed as completely inhibiting, i.e., seed all in hole absolutely not germinates.
Activity of weeding test result is as shown in table 1.
The activity of weeding of each compound under 1 1mm of table
Obtained from table 1, preferable inhibition shown to romaine lettuce under compound 1mm of the present invention, especially (2), (8), (9), (10) compound；Preferable inhibition is shown to bent grass, especially (2) compound.

Claims (3)

1. a kind of novel amides compound containing pyrazole ring is preparing the application in herbicide, it is characterised in that its structural formula is such as Shown in formula (I):
(I)
In formula (I): R is phenyl or substituted-phenyl, and the substituent group of the substituted-phenyl is halogen, 2- perfluoro propyl, ethyoxyl, three Methyl fluoride, trifluoromethoxy, trimethyl urea groups, methyl, methoxyl group.
2. a kind of application of novel amides compound containing pyrazole ring in the herbicide that preparation prevents and treats romaine lettuce, bent grass, It is characterized in that shown in its structural formula such as formula (I):
(I)
In formula (I): R is phenyl or substituted-phenyl, and the substituent group of the substituted-phenyl is halogen, 2- perfluoro propyl, ethyoxyl, three Methyl fluoride, trifluoromethoxy, trimethyl urea groups, methyl, methoxyl group.
3. application according to claim 1 or 2, it is characterised in that R is one of following in formula (I): phenyl, 4-(2- perfluor Propyl) phenyl, 4- cyanophenyl base, 4- ethoxyl phenenyl, 2- trifluoromethyl, 3- fluorophenyl, trimethyl urea groups, 3,5 dimethyl Phenyl, 2- methoxyphenyl, 2- chlorphenyl.
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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1104636A (en) * 1992-06-11 1995-07-05 罗纳-普朗克农业有限公司 New compositions of matter
WO2004035545A2 (en) * 2002-10-18 2004-04-29 E.I. Du Pont De Nemours And Company Azolecarboxamide herbicides
WO2005070889A1 (en) * 2004-01-23 2005-08-04 E.I. Dupont De Nemours And Company Herbicidal amides
CN101360730A (en) * 2006-02-01 2009-02-04 拜尔农科股份有限公司 Fungicide N-cycloalkyl-benzyl-amide derivatives
WO2009024342A2 (en) * 2007-08-23 2009-02-26 Syngenta Participations Ag Novel microbiocides
CN103524417A (en) * 2013-10-31 2014-01-22 青岛农业大学 3-methyl-4-formyl pyrazol compounds
CN105418505A (en) * 2015-12-21 2016-03-23 浙江树人大学 Pyrazole amides compound, preparation method therefor and application thereof
CN106632044A (en) * 2016-12-30 2017-05-10 浙江工业大学 Amide compound containing methylpyrazole and preparation method the application thereof
CN106831587A (en) * 2017-01-22 2017-06-13 中国农业大学 Pyrazol acid amide compounds and preparation method and application
CN108084092A (en) * 2017-12-01 2018-05-29 浙江工业大学 A kind of new amide derivatives containing pyrazole ring and preparation method and application
CN108117520A (en) * 2017-12-01 2018-06-05 浙江工业大学 A kind of 1,3- dimethyl -1H- pyrazoles -4- amide derivatives and preparation method and application
CN108117519A (en) * 2017-12-01 2018-06-05 浙江工业大学 A kind of new amides compound containing pyrazole ring and preparation method and application
CN108383790A (en) * 2017-12-01 2018-08-10 浙江工业大学 A kind of amides compound and the preparation method and application thereof containing pyrazole ring

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1104636A (en) * 1992-06-11 1995-07-05 罗纳-普朗克农业有限公司 New compositions of matter
WO2004035545A2 (en) * 2002-10-18 2004-04-29 E.I. Du Pont De Nemours And Company Azolecarboxamide herbicides
WO2005070889A1 (en) * 2004-01-23 2005-08-04 E.I. Dupont De Nemours And Company Herbicidal amides
CN101360730A (en) * 2006-02-01 2009-02-04 拜尔农科股份有限公司 Fungicide N-cycloalkyl-benzyl-amide derivatives
WO2009024342A2 (en) * 2007-08-23 2009-02-26 Syngenta Participations Ag Novel microbiocides
CN103524417A (en) * 2013-10-31 2014-01-22 青岛农业大学 3-methyl-4-formyl pyrazol compounds
CN105418505A (en) * 2015-12-21 2016-03-23 浙江树人大学 Pyrazole amides compound, preparation method therefor and application thereof
CN106632044A (en) * 2016-12-30 2017-05-10 浙江工业大学 Amide compound containing methylpyrazole and preparation method the application thereof
CN106831587A (en) * 2017-01-22 2017-06-13 中国农业大学 Pyrazol acid amide compounds and preparation method and application
CN108084092A (en) * 2017-12-01 2018-05-29 浙江工业大学 A kind of new amide derivatives containing pyrazole ring and preparation method and application
CN108117520A (en) * 2017-12-01 2018-06-05 浙江工业大学 A kind of 1,3- dimethyl -1H- pyrazoles -4- amide derivatives and preparation method and application
CN108117519A (en) * 2017-12-01 2018-06-05 浙江工业大学 A kind of new amides compound containing pyrazole ring and preparation method and application
CN108383790A (en) * 2017-12-01 2018-08-10 浙江工业大学 A kind of amides compound and the preparation method and application thereof containing pyrazole ring

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
谭成侠等: "具有除草活性的吡唑类化合物的研究进展", 《现代农药》 *

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