CN1300138C - Diheterocyclic compound, its preparing method and use - Google Patents
Diheterocyclic compound, its preparing method and use Download PDFInfo
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- CN1300138C CN1300138C CNB2004100930454A CN200410093045A CN1300138C CN 1300138 C CN1300138 C CN 1300138C CN B2004100930454 A CNB2004100930454 A CN B2004100930454A CN 200410093045 A CN200410093045 A CN 200410093045A CN 1300138 C CN1300138 C CN 1300138C
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Abstract
The present invention relates to a double heterocyclic compound with bioactivity and a preparation method thereof. The double heterocyclic compound is disclosed in the formula (I). The preparation method comprises the following steps: 1-methyl-3-ethyl-4-substituent-5-pyrazolyl formyl chloride and imidazole react by condensation in an organic solvent at the temperature of 0 to 15 DEG C under the action of an acid catalyst, and a product is obtained by post processing. The double heterocyclic compound has different prevention effects on paddy rice blast, botrytis cinerea pers and wheat powdery mildew and has certain insecticidal activity for leaf hoppers.
Description
(1) technical field
The present invention relates to a kind of bis-heterocyclic compounds, 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.Synthetic and the bioactivity research of pyrazole contained diheterocyclic compound has become an important directions of heterocyclic pesticide.Before the present invention makes, after the nineties, there is the pesticide patent of relevant two heterocycle structures to occur abroad, two heterocycles are connected pyrazoles by groups such as methylene radical, sulfuryls in the patent report with nitrogen heterocyclic ring.Domestic Lee rectifies name etc. pyrazoles directly is connected with heterocycle, obtains the bis-heterocyclic compounds of a series of biologically actives; Liu Zhao outstanding persons etc. have synthesized the acid amides series bis-heterocyclic compounds of a class biologically active.
(3) summary of the invention
Bis-heterocyclic compounds that provides a kind of biologically active and preparation method thereof is provided the object of the invention.
Described bis-heterocyclic compounds is suc as formula shown in (I):
Wherein X representative is one of following: H, NO
2, Cl, Br.
A kind of preparation method of above-mentioned bis-heterocyclic compounds, comprise the steps: suc as formula the 1-methyl shown in (II)-3-ethyl-4-replacement-5-pyrazol formyl chloride and imidazoles under the acid-capture agent effect, carry out condensation reaction at 0～15 ℃ in organic solvent, aftertreatment gets product;
Wherein the X definition is the same.
Based on the consideration of productive rate and cost, the described reaction times was good with 1～50 hour.
Described 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride: imidazoles: the molar ratio of acid-capture agent is preferably 1: 1.0～and 1.5: 1.0～2.0, described consumption of organic solvent is preferably 20～60 times of imidazoles quality.
It is one of following that described acid-capture agent is preferably: triethylamine, pyridine, lutidine, Anhydrous potassium carbonate.
It is one of following that described organic solvent is preferably: tetrahydrofuran (THF), ethyl acetate, toluene, chlorobenzene, trichloromethane.
Described aftertreatment can be: use dilute hydrochloric acid washing reaction liquid to neutral, and layering, the organic phase drying is filtered, and concentrates, and column chromatography for separation gets described bis-heterocyclic compounds.
The preparation method of described bis-heterocyclic compounds recommends to be undertaken by following parameter:
Described 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride: imidazoles: the molar ratio of acid-capture agent is 1: 1.0～1.1: 1.2～1.4, and described consumption of organic solvent is 30～50 times of imidazoles quality; Setting-up point is 0～10 ℃, and the reaction times is 10～20 hours.
Described 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride can adopt following method to make:
1-methyl-3-ethyl-4-nitro-5-pyrazole carboxylic acid and excess chlorination sulfoxide are joined in the 100mL there-necked flask, and under agitation back flow reaction is reacted and is finished, and concentrating under reduced pressure gets light yellow 1-methyl-3-ethyl-4-nitro-5-pyrazol formyl chloride transparent liquid.The molar ratio of sulfur oxychloride and 1-methyl-3-ethyl-4-nitro-5-pyrazole carboxylic acid is generally 5～15: 1.Use method for preparing 1-methyl-3-ethyl-4-nitro-5-pyrazol formyl chloride, yield reaches more than 90%.
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, described bis-heterocyclic compounds does not have the preventive effect effect substantially to fusarium graminearum, Phytophthora capsici germ, Rhizoctonia solani Kuhn, Sclerotinia sclerotiorum, and rice blast fungus, botrytis cinerea pers, wheat powdery mildew are had different preventive effect effects.
Adopt the Potter spray method synthetic compound to be carried out the insecticidal activity assay of mythimna separata (Mythimna separata), adopt leaf worm with soaking method has been carried out black bean aphid (Aphisfabae) to the synthetic compound insecticidal activity assay, adopt dipping plant method that the synthetic compound has been carried out the insecticidal activity assay of green rice leafhopper (Nephotettix cincticeps), adopt leaf worm the synthetic compound to be carried out two-spotted spider mite (Tetranchus urticae) with the method for soaking.The result shows that described bis-heterocyclic compounds does not have insecticidal activity substantially to mythimna separata, aphid, red spider, and leafhopper is had certain insecticidal activity (except the formula of X=Cl (I) compound).
(4) embodiment
Below by embodiment the present invention is further specified, but protection scope of the present invention is not limited to this.
Embodiment 1
19mmol 1-methyl-3-ethyl-4-nitro-5-pyrazole carboxylic acid and 200mmol sulfur oxychloride are joined in the 100mL there-necked flask, back flow reaction 3h under agitation, reaction finishes, and concentrating under reduced pressure gets light yellow 1-methyl-3-ethyl-4-nitro-5-pyrazol formyl chloride transparent liquid.
1.36g (20mmol) imidazoles and 2.4g (24mmol) triethylamine are joined in the 40mL chloroform soln, drip 1-methyl-3-ethyl-4-nitro-5-pyrazol formyl chloride under ice bath stirs, 30min drips complete, reacts 20h then in about 7 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, concentrate, column chromatography [V (sherwood oil): V (ethyl acetate)=2: 1] separates, and obtains pure product.Yield is 87%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δppm；8.09，7.55，7.23(s，3H，imidazole-H)，3.84(s，3H，N-CH
3)，2.86(q，2H，CH
2-C)，1.28(t，3H，C-CH
3)
IR(KBr)cm
-1；3150，2982，1702，1560
Embodiment 2
19mmol 1-methyl-3-ethyl-5-pyrazole carboxylic acid and 200mmol sulfur oxychloride are joined in the 100mL there-necked flask, back flow reaction 3h under agitation, reaction finishes, and concentrating under reduced pressure gets light yellow 1-methyl-3-ethyl-4-nitro-5-pyrazol formyl chloride transparent liquid.
1.36g (20mmol) imidazoles and 2.0g (22mmol) lutidine are joined in the 40mL toluene solution, ice bath stirs down and drips 1-methyl-3-ethyl-5-pyrazol formyl chloride, and it is complete that 40min drips, and reacts 10h then in about 3 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, concentrate, column chromatography [V (sherwood oil): V (ethyl acetate)=2: 1] separates, and obtains pure product.Yield is 32%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δppm；8.04，7.48，7.10(s，3H，imidazole-H)，6.50(s，1H，pyrazole-H)，4.02(s，3H，N-CH
3)，2.65(q，2H，CH
2-C)，1.24(t，3H，C-CH
3)
IR(KBr)cm
-1；3136，2968，1693，1560
Embodiment 3
19mmol 1-methyl-3-ethyl-4-chloro-5-pyrazole carboxylic acid and 200mmol sulfur oxychloride are joined in the 100mL there-necked flask, back flow reaction 3h under agitation, reaction finishes, and concentrating under reduced pressure gets light yellow 1-methyl-3-ethyl-4-chloro-5-pyrazol formyl chloride transparent liquid.
1.36g (20mmol) imidazoles and 1.85g (23mmol) pyridine are joined in the 40mL ethyl acetate solution, drip 1-methyl-3-ethyl-4-chloro-5-pyrazol formyl chloride under ice bath stirs, 30min drips complete, reacts 15h then in about 10 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, concentrate, column chromatography [V (sherwood oil): V (ethyl acetate)=2: 1] separates, and obtains pure product.Yield is 77%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δppm；8.07，7.52，7.18(s，3H，imidazole-H)，4.0(s，3H，N-CH
3)，2.69(q，2H，CH
2-C)，1.29(t，3H，C-CH
3)
IR(KBr)cm
-1；3128，2977，1702，1558
Embodiment 4
19mmol 1-methyl-3-ethyl-4-bromo-5-pyrazole carboxylic acid and 200mmol sulfur oxychloride are joined in the 100mL there-necked flask, back flow reaction 3h under agitation, reaction finishes, and concentrating under reduced pressure gets light yellow 1-methyl-3-ethyl-4-chloro-5-pyrazol formyl chloride transparent liquid.
1.36g (20mmol) imidazoles and 1.85g (23mmol) pyridine are joined in the 40mL chlorobenzene solution, drip 1-methyl-3-ethyl-4-bromo-5-pyrazol formyl chloride under ice bath stirs, 30min drips complete, reacts 16h then in about 6 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, concentrate, column chromatography [V (sherwood oil): V (ethyl acetate)=2: 1] separates, and obtains pure product.Yield is 74%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δppm；8.05，7.50，7.15(s，3H，imidazole-H)，3.95(s，3H，N-CH
3)，2.79(q，2H，CH
2-C)，1.27(t，3H，C-CH
3)
IR(KBr)cm
-1；3140，2972，1668，1550
Embodiment 5
The trichloromethane consumption changes 50 times of imidazoles quality into, and other is operated with embodiment 1.Yield is 86%.
Embodiment 6
Acid-capture agent is used Anhydrous potassium carbonate 3.59g (26mmol) instead, and the imidazoles consumption is (21mmol)
Other operation is with embodiment 1.Yield is 85.0%.
Embodiment 7
Organic solvent changes tetrahydrofuran (THF) 40ml into, and other is with embodiment 1.Yield is 85%.
The test of embodiment 8 fungicidal activities
Adopt toxic potato agar substratum (PDA) method that the fungicidal activity that embodiment 1～4 synthetic compound has carried out Pyricularia oryzae (Pyricularia oryzae), fusarium graminearum (Gibberella zeae), Phytophthora capsici germ (Phytophthora capsici) and botrytis cinerea pers (Botrytiscinerea) is measured, general sieve concentration is 25ppm; 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 (Rhizoctoniasolani) is measured, general sieve concentration is 500ppm; Adopt potted plant toxic potato agar substratum (PDA) method that the fungicidal activity that the synthetic compound has carried out Sclerotinia sclerotiorum (Sclerotoniasclerotiorum) is measured, general sieve concentration is 500ppm; 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, general sieve concentration is 500ppm.Test result sees Table 1.
Table 1 bis-heterocyclic compounds is to the restraining effect of fungi
| The embodiment title | Compound | Concentration (ug/ml) | Fusarium graminearum | The Phytophthora capsici germ | Rice blast fungus | Botrytis cinerea pers | Concentration (ug/ml) | Rhizoctonia solani Kuhn | Wheat powdery mildew | Sclerotinia sclerotiorum |
| X 1 | ||||||||||
| Preventive effect (%) | Preventive effect (%) | Preventive effect (%) | Preventive effect (%) | Preventive effect (%) | Preventive effect (%) | Preventive effect (%) | ||||
| Embodiment 3 | Cl | 25 | 0 | 0 | 4.4 | 15.9 | 500 | 0 | 15.0 | 0 |
| Embodiment 2 | H | 25 | 0 | 0 | 4.2 | 16.5 | 500 | 0 | 17.3 | 0 |
| Embodiment 1 | NO 2 | 25 | 0 | 0 | 4.4 | 15.9 | 500 | 0 | 5.0 | 0 |
| Embodiment 4 | Br | 25 | 4.5 | 0 | 17.5 | 0 | 500 | 0 | 15.0 | 0 |
The test of embodiment 9 insecticidal activities
Adopt the Potter spray method that embodiment 1～4 synthetic compound has been carried out the insecticidal activity assay of mythimna separata (Mythimnaseparata), working concentration is 1000mg/L; Adopt leaf worm with soaking method the synthetic compound to be carried out the insecticidal activity assay of black bean aphid (Aphis fabae), working concentration is 500mg/L; Adopt dipping plant method that the synthetic compound has been carried out the insecticidal activity assay of green rice leafhopper (Nephotettixcincticeps), working concentration is 500mg/L; Adopt leaf worm with the method for soaking the synthetic compound to be carried out two-spotted spider mite (Tetranchus urticae), working concentration is 500mg/L.Test result sees Table 2.
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%.
Table 2 bis-heterocyclic compounds is to the killing action of insect
| The embodiment title | Compound | Mythimna separata | Aphid | Leafhopper | Red spider | ||||
| Mortality ratio | Virulence | Mortality ratio | Virulence | Dead | Virulence | Dead | Virulence | ||
| X 1 | (％) | Rank | (％) | Rank | Rate (%) | Rank | Rate (%) | Rank | |
| Embodiment 3 | Cl | 0 | 0 | 0 | 0 | ||||
| Embodiment 2 | H | 0 | 0 | 39.7 | 0 | ||||
| Embodiment 1 | NO 2 | 0 | 0 | 53.57 | C | 0 | |||
| Embodiment 4 | Br | 0 | 0 | 43.57 | D | 0 |
Claims (9)
1, suc as formula the bis-heterocyclic compounds shown in (I):
Wherein X representative is one of following: H, NO
2, Cl, Br.
2, a kind of preparation method of bis-heterocyclic compounds according to claim 1, it is characterized in that comprising the steps: suc as formula the 1-methyl shown in (II)-3-ethyl-4-replacement-5-pyrazol formyl chloride and imidazoles under the acid-capture agent effect, carry out condensation reaction at 0～15 ℃ in organic solvent, aftertreatment gets product;
Wherein the X definition is with claim 1.
3, the preparation method of bis-heterocyclic compounds as claimed in claim 2 is characterized in that the described reaction times is 1～50 hour.
4, the preparation method of bis-heterocyclic compounds as claimed in claim 2, it is characterized in that described 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride: imidazoles: the molar ratio of acid-capture agent is 1: 1.0～1.5: 1.0～2.0, and described consumption of organic solvent is 20～60 times of imidazoles quality.
5, the preparation method of bis-heterocyclic compounds as claimed in claim 2 is characterized in that described acid-capture agent is one of following: triethylamine, pyridine, lutidine, Anhydrous potassium carbonate.
6, the preparation method of bis-heterocyclic compounds as claimed in claim 2 is characterized in that described organic solvent is one of following: tetrahydrofuran (THF), ethyl acetate, toluene, chlorobenzene, trichloromethane.
7,, it is characterized in that described aftertreatment is as the preparation method of the described bis-heterocyclic compounds of one of claim 2～6: use dilute hydrochloric acid washing reaction liquid to neutral, layering, the organic phase drying is filtered, and concentrates, and column chromatography for separation gets described bis-heterocyclic compounds.
8, the preparation method of bis-heterocyclic compounds as claimed in claim 7, it is characterized in that described 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride: imidazoles: the molar ratio of acid-capture agent is 1: 1.0～1.1: 1.2～1.4, and described consumption of organic solvent is 30～50 times of imidazoles quality; Setting-up point is 0～10 ℃, and the reaction times is 10～20 hours.
9, the described bis-heterocyclic compounds of claim 1 is as the application of agricultural chemicals in Pesticidal and sterilizing.
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| JPS57106665A (en) * | 1980-12-23 | 1982-07-02 | Showa Denko Kk | 3-pyrazolecarboxamide derivative, its preparation, and herbicide |
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| EP0462573A1 (en) * | 1990-06-18 | 1991-12-27 | Mitsubishi Chemical Corporation | Pyrazolecarboxamide, insecticidal and miticidal composition, and fungicidal composition for use in agriculture and horticulture |
| US5201932A (en) * | 1989-09-22 | 1993-04-13 | Basf Aktiengesellschaft | Carboxamides |
| WO2002089583A1 (en) * | 2001-05-07 | 2002-11-14 | Mitsubishi Chemical Corporation | Bactericide containing pyrazole amide compound as active ingredient |
-
2004
- 2004-12-10 CN CNB2004100930454A patent/CN1300138C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4134987A (en) * | 1976-01-14 | 1979-01-16 | Huppatz John L | Compounds and compositions |
| JPS57106665A (en) * | 1980-12-23 | 1982-07-02 | Showa Denko Kk | 3-pyrazolecarboxamide derivative, its preparation, and herbicide |
| JPS6034949A (en) * | 1983-08-05 | 1985-02-22 | Nissan Chem Ind Ltd | Pyrazolecarboxyanilide derivative and fungicide |
| CN88102427A (en) * | 1987-04-24 | 1988-11-09 | 三菱化成工业株式会社 | Pyrazole derivatives and insecticidal or acaricidal compositions containing them |
| US5201932A (en) * | 1989-09-22 | 1993-04-13 | Basf Aktiengesellschaft | Carboxamides |
| EP0462573A1 (en) * | 1990-06-18 | 1991-12-27 | Mitsubishi Chemical Corporation | Pyrazolecarboxamide, insecticidal and miticidal composition, and fungicidal composition for use in agriculture and horticulture |
| WO2002089583A1 (en) * | 2001-05-07 | 2002-11-14 | Mitsubishi Chemical Corporation | Bactericide containing pyrazole amide compound as active ingredient |
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