CN104529900A - Bactericidal activity of 1-substituted-N-substituted phenyl-5-amidogen-1H-pyrazole-4-formamide compound - Google Patents
Bactericidal activity of 1-substituted-N-substituted phenyl-5-amidogen-1H-pyrazole-4-formamide compound Download PDFInfo
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- CN104529900A CN104529900A CN201410852814.8A CN201410852814A CN104529900A CN 104529900 A CN104529900 A CN 104529900A CN 201410852814 A CN201410852814 A CN 201410852814A CN 104529900 A CN104529900 A CN 104529900A
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- substituted
- oxygen base
- phenyl
- pyrazole
- alkyl
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- 0 *c(c(*)c1)cc(NC(c2c(N)[n](*)nc2)=O)c1F Chemical compound *c(c(*)c1)cc(NC(c2c(N)[n](*)nc2)=O)c1F 0.000 description 6
Classifications
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- 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
- C07D231/38—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The invention relates to bactericidal activity of a 1-substituted-N-substituted phenyl-5-amidogen-1H-pyrazole-4-formamide compound, wherein R1 represents alkyl, substituted phenyl and the like, X1 represents halogen, X2 represents an alkoxy group, an ene oxygen group, an alkyne oxygen group, a halogenated ene oxygen group and the like, and X1 and X2 can form a benzo 6-element heterocyclic ring with a benzene ring. The 1-substituted-N-substituted phenyl-5-amidogen-1H-pyrazole-4-formamide compound shows the bactericidal activity at the testing concentrate.
Description
[technical field]: the present invention relates to the fungicidal activity that 1-replaces-N-substituted-phenyl-5-amino-1H-pyrazole-4-carboxamide compounds.
[background technology]: pyrazolecarboxamide compounds contains pyrazoles and acid amides two kinds of high reactivity building stones, has biological activity widely.Since the forties in 20th century, constantly there is in pesticide developing field bibliographical information to have bioactive pyrazolecarboxamide analog derivative, comprised sterilant, miticide, sterilant and weedicide etc.
The furametpyr (A) of SUMITOMO CHEMICAL chemical company exploitation in 1996, has special efficacy to most germs such as rice sheath blight disease, multiple paddy rice sclerotium disease, the white beautiful disease etc. of Basidiomycetes.
In Britain's plant protection meeting of 2003, Mitsui KCC describes new acid amide fungicides pyrrole metsulfovax (B), and its fungicidal spectrum is wide, demonstrates excellent activity to rust, sclerotium disease.
US 6054473 discloses the Compound C that a class has fungicidal activity, at 250g/hm
2time to barley white powder, 125g/hm
2time to barley sclerotium preventive effect 100%, 100g/hm
2time to the black star preventive effect 91% of apple, at 100g/hm
2time to cucumber powdery mildew fungus inhibiting rate 100%.
Compound D disclosed in JP 2004189738 under 500mg/L concentration to the killing rate of cabbage small cabbage moth more than 90%.
Compd E disclosed in WO 03010149 when 250mg/L to barley caryosphere bacterium, 100g/hm
2time 100% is reached to the preventive effect of apple powder mildew.
Disclosed in WO 03070705, a compounds F is at 100g/hm
2time can suppress apple powder mould, cucumber white powder, the black star of apple and tomato black spot completely, can be used for the control of the multiple diseases such as Powdery Mildew, rust, oidium, especially have well treatment and protected effect to net blotch of barley, apple mildew.
[summary of the invention]: the object of this invention is to provide a kind of 1-with fungicidal activity and replace-N-substituted-phenyl-5-amino-1H-pyrazole-4-carboxamide compounds.This compounds is different from the compound reported, novel structure.
The general formula of the compounds of this invention is (I):
In formula,
R
1for alkyl, substituted-phenyl etc.;
X
1for halogen;
X
2for alkoxyl group, alkene oxygen base, alkynyloxy group, haloalkene oxygen base etc.;
X
1and X
2also can form benzo 6-unit heterocycle with phenyl ring, its general formula is (II);
Wherein,
R is alkyl, thiazolinyl, alkynyl;
Said alkyl is C
1~ C
6straight or branched alkyl, thiazolinyl is
thiazolinyl, alkynyl is C
3~ C
6alkynyl.
Described compound, is characterized in that:
R
1be preferably methyl, n-propyl, phenyl, m-trifluoromethylphenyl;
X
1be preferably chlorine;
X
2be preferably methoxycarbonyl oxygen base, ethoxycarbonyl-oxygen base, sec.-propyl oxygen base, allyl group oxygen base, propargyloxy, cyclopentyloxy, isopentyl oxygen base;
X
1and X
2also can form benzo 6-unit heterocycle with phenyl ring, its general formula is (II), and R is preferably n-propyl, allyl group, propargyl, ethoxycarbonylmethyl group.
Described 1-replaces-N-substituted-phenyl-5-amino-1H-pyrazole-4-carboxamide compounds and can prepare as follows: be dissolved in by compound (a) in solvent, add mineral alkali, be heated to 40 ~ 80 DEG C, hydrolysis obtains compound (b), compound (b) obtains compound (c) through sulfur oxychloride chloride, then is obtained by reacting 1-with (d) and replaces-N-substituted-phenyl-5-amino-1H-pyrazole-4-carboxamide compounds (I).Solvent is: toluene, benzene, acetonitrile, tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, water or above-mentioned solvent are with the mixed solvent of arbitrary proportion; Mineral alkali is sodium hydroxide, potassium hydroxide.
The present invention goes back the compound listed in free list 1 and illustrates, but does not limit the present invention.
It is different from those known compounds that 1-provided by the invention replaces-N-substituted-phenyl-5-amino-1H-pyrazole-4-carboxamide compounds, and structure is completely novel, has good fungicidal activity.
The application of compound of the present invention on agricultural chemicals is as sterilant.
[embodiment]:
Further illustrate the present invention below in conjunction with embodiment, in following embodiment, fusing point is not calibrated.
The synthesis of embodiment 1:1-methyl-5-amino-1H-pyrazoles-4-formic acid (b1)
In the round-bottomed flask of 500mL, add the aqueous sodium hydroxide solution of 8.45g 1-methyl-5-amino-1H-pyrazoles-4-ethyl formate (a1), 50mL tetrahydrofuran (THF), 50mL anhydrous methanol and 50mL 2.5mol/L, be heated to 60 DEG C, temperature control 4 hours, most of solvent is sloughed in decompression, debris with 6mol/L hcl acidifying to pH=1, there is milky white precipitate, filter, use water, washed with dichloromethane respectively, drying obtains white solid b1 (5.55g), yield 78.7%, fusing point 67-68 DEG C.
The synthesis of embodiment 2:1-methyl-5-amino-1H-pyrazoles-4-formyl chloride (c1)
In the round-bottomed flask of 50mL, add 0.71g 1-methyl-5-amino-1H-pyrazoles-4-formic acid (b1), under cryosel bath cooling, drip 10mL thionyl chloride, drip and finish, naturally room temperature is risen to, stir 3 hours, thionyl chloride is taken out in decompression, obtains yellow solid c1 (0.98g), quantitatively complete reaction, fusing point 128-130 DEG C.
The synthesis of embodiment 3:1-methyl-5-amino-N-(the fluoro-4-of 2-chloro-5-allyloxy propyl group)-1H-pyrazole-4-carboxamide (I4)
In 50mL round-bottomed flask, add the fluoro-4-of 0.40g 2-chloro-5-allyloxy aniline, 10mL methylene dichloride and 1mL pyridine, cryosel bath is cooled to less than 0 DEG C, add 0.39g 1-methyl-5-amino-1H-pyrazoles-4-formyl chloride (c1), naturally room temperature is risen to, TLC detection reaction, after question response, decompression sloughs solvent, debris 30mL 1mol/L salt acid elution, filter, solid is again with saturated sodium bicarbonate solution washing, and filter, drying obtains pale solid I4 (0.52g), yield is 80.1%, fusing point 184-186 DEG C.
Equally, other compounds of the present invention can be synthesized, in table 1 according to similar method.
The physical properties of table 1 Compound I characterizes
Embodiment 4: fungicidal activity is tested
By a certain amount of medicament dissolution in appropriate DMF, be then diluted to 50mg/L with emulsified water.Adopt in vitro Plating, the results are shown in Table 2.For examination pathogenic bacteria: cucumber fusarium axysporum (C.cucumerinum), peanut Cercospora bacteria (C.rachidicola), Botryosphaeria berengeriana f. sp (P.piricol), tomato early epidemic germ (A.solani), fusarium graminearum (G.zeae), phytophthora infestans (P.infestans), Sclerotinia sclerotiorum (S.sclerotiorum), botrytis cinerea pers (B.cinerea), Rhizoctonia solani Kuhn (R.solani), P. capsici (P.capsici).
Adopt biomass growth rate assay method (mycelium growth rate test).Detailed process is: aseptically respectively draw 1mL liquid and inject in culture dish, add 9mL PDA substratum, make 50mg/L pastille dull and stereotyped, do blank with the flat board adding 1mL aqua sterilisa after shaking up.Cut bacterium dish with the punch tool of diameter 4mm along mycelia outer rim, move on pastille flat board, each process in triplicate.Culture dish is placed in 24 ± 1 DEG C of constant incubators and cultivates.72h " Invest, Then Investigate " respectively processes bacterium dish expansion diameter, averages, compares calculate relative bacteriostasis rate with blank.A: >=50%; B: >=20%; C: be less than 20%.
Table 2: fungicidal activity inhibiting rate (%) (the concentration 50mg/L) of Compound I
Claims (3)
1. the 1-with fungicidal activity replaces-N-substituted-phenyl-5-amino-1H-pyrazole-4-carboxamide a compounds, it is characterized in that it has structure shown in following general formula (I):
In formula,
R
1for alkyl, substituted-phenyl etc.;
X
1for halogen;
X
2for alkoxyl group, alkene oxygen base, alkynyloxy group, haloalkene oxygen base etc.;
X
1and X
2also can form benzo 6-unit heterocycle with phenyl ring, its general formula is (II);
Wherein,
R is alkyl, thiazolinyl, alkynyl;
Said alkyl is C
1~ C
6straight or branched alkyl, thiazolinyl is C
3 ~ C
6thiazolinyl, alkynyl is C
3~ C
6alkynyl.
2. compound according to claim 1, is characterized in that:
R
1be preferably methyl, n-propyl, phenyl, m-trifluoromethylphenyl;
X
1be preferably chlorine;
X
2be preferably methoxycarbonyl oxygen base, ethoxycarbonyl-oxygen base, sec.-propyl oxygen base, allyl group oxygen base, propargyloxy, cyclopentyloxy, isopentyl oxygen base;
X
1and X
2also can form benzo 6-unit heterocycle with phenyl ring, its general formula is (II), and R is preferably n-propyl, allyl group, propargyl, ethoxycarbonylmethyl group.
3. 1-described in claim 1 replaces the application of-N-substituted-phenyl-5-amino-1H-pyrazole-4-carboxamide compounds, it is characterized in that fungicidal activity.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484614A (en) * | 2018-05-23 | 2018-09-04 | 南开大学 | Pyrazolo [3,4-d] pyrimidine -4 (5H) -one derivative and its preparation method and application |
Citations (5)
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| WO1996016954A1 (en) * | 1994-12-02 | 1996-06-06 | Agrevo Uk Limited | Derivatives of anthranilic acid useful as fungicides |
| CN1533380A (en) * | 2001-07-25 | 2004-09-29 | �ݶ�ũ�����ѧ�ɷݹ�˾ | N-pyrazolylcarboxanilides as fungicides |
| CN1646494A (en) * | 2002-02-19 | 2005-07-27 | 拜尔农作物科学股份公司 | Disubstituted pyrazolyl carboxanilides |
| CN101215289A (en) * | 2008-01-11 | 2008-07-09 | 南开大学 | 3-substituted phenyl-pyrazolo[3,4-d][1,2,3]triazin-4-one compounds with PPO restraining activity and weeding activity |
| CN105017258A (en) * | 2014-12-30 | 2015-11-04 | 南开大学 | Prepartion and application of pyrazolo[3,4-d][1,2,3]triazine-4-one derivative |
-
2014
- 2014-12-31 CN CN201410852814.8A patent/CN104529900A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996016954A1 (en) * | 1994-12-02 | 1996-06-06 | Agrevo Uk Limited | Derivatives of anthranilic acid useful as fungicides |
| CN1533380A (en) * | 2001-07-25 | 2004-09-29 | �ݶ�ũ�����ѧ�ɷݹ�˾ | N-pyrazolylcarboxanilides as fungicides |
| CN1646494A (en) * | 2002-02-19 | 2005-07-27 | 拜尔农作物科学股份公司 | Disubstituted pyrazolyl carboxanilides |
| CN101215289A (en) * | 2008-01-11 | 2008-07-09 | 南开大学 | 3-substituted phenyl-pyrazolo[3,4-d][1,2,3]triazin-4-one compounds with PPO restraining activity and weeding activity |
| CN105017258A (en) * | 2014-12-30 | 2015-11-04 | 南开大学 | Prepartion and application of pyrazolo[3,4-d][1,2,3]triazine-4-one derivative |
Non-Patent Citations (1)
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|---|
| 李华斌等: "3-(2-氟-4-氯-5-取代基苯基)-7-甲基-3H-吡唑并[3,4-d][1,2,3]三嗪-4(7H)-酮化合物的合成及其对原卟啉原氧化酶的抑制活性", 《有机化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484614A (en) * | 2018-05-23 | 2018-09-04 | 南开大学 | Pyrazolo [3,4-d] pyrimidine -4 (5H) -one derivative and its preparation method and application |
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