CN100415738C - Pyrazole contained diheterocyclic compound, its preparation and use - Google Patents
Pyrazole contained diheterocyclic compound, its preparation and use Download PDFInfo
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- CN100415738C CN100415738C CNB2004100933310A CN200410093331A CN100415738C CN 100415738 C CN100415738 C CN 100415738C CN B2004100933310 A CNB2004100933310 A CN B2004100933310A CN 200410093331 A CN200410093331 A CN 200410093331A CN 100415738 C CN100415738 C CN 100415738C
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Abstract
The present invention discloses a bioactive double heterocyclic compound containing pyrazole, a preparation method thereof and an application 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 a heterocyclic ring containing nitrogen carry out a condensation reaction in an organic solvent at the temperature of 0 to 20 DEGC 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 pyrazole contained diheterocyclic compound, preparation method and application.
(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 bis-heterocyclic compounds 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
The object of the invention is to provide a kind of pyrazole contained diheterocyclic compound, preparation method and application thereof of biologically active.
Described bis-heterocyclic compounds is suc as formula shown in (I):
Wherein X represents H or electron-withdrawing group, is preferably one of following: H, NO
2, Cl, Br; Y, Z independently represent O or S separately.
A kind of preparation method of above-mentioned pyrazole contained diheterocyclic compound, comprise the steps: suc as formula the 1-methyl shown in (II)-3-ethyl-4-replacement-5-pyrazol formyl chloride and suc as formula the nitrogen heterocyclic ring shown in (III) under the acid-capture agent effect, carry out condensation reaction at 0～20 ℃ in organic solvent, aftertreatment gets product;
Wherein X, Y, Z define 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: nitrogen heterocyclic ring: 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 nitrogen heterocyclic ring 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 pyrazole contained diheterocyclic compound.
The preparation method of described pyrazole contained diheterocyclic compound recommends to be undertaken by following parameter:
Described 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride: nitrogen heterocyclic ring: 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 nitrogen heterocyclic ring quality; Setting-up point is 5～15 ℃, 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-replacement-5-pyrazole carboxylic acid and excess chlorination sulfoxide are joined in the 100mL there-necked flask, back flow reaction under agitation, reaction finishes, concentrating under reduced pressure gets light yellow 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride transparent liquid.Use method for preparing 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride, yield generally reaches more than 90%.
Above-mentioned pyrazole contained diheterocyclic compound is as the application of insectofungicide.
Adopt toxic potato agar substratum (PDA) method that the fungicidal activity that the synthetic compound has carried out Pyricularia oryzae (Pyricularia oryzae), fusarium graminearum (Gibberella zeae), Phytophthora capsici germ (Phytophthora capsici) and botrytis cinerea pers (Botrytis cinerea) 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 described pyrazole contained diheterocyclic compound does not have preventive effect effect (X=NO substantially to fusarium graminearum, Phytophthora capsici germ
2, Y=S, Z=O and X=NO
2, except the Y=S, the formula of Z=S (I) compound), and rice blast fungus, botrytis cinerea pers, wheat powdery mildew are had different preventive effect effects.
Adopt the Potter spray method that the synthetic compound has been 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).The result shows that described pyrazole contained diheterocyclic compound does not have insecticidal activity substantially to mythimna separata, and leafhopper is had certain insecticidal activity, and is best with formula (I) compound effect of X=Br especially.
(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.
2.06g (20mmol) 2-thiazolidone 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, ethyl alcohol recrystallization obtains yellow solid.Yield is 89%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；4.36(t，2H，N-CH
2-C)，3.79(s，3H，N-CH
3)，3.48(t，2H，S-CH
2-C)，2.95(q，2H，CH
2-C)，1.29(t，3H，C-CH
3)
IR(KBr，V
CO)cm
-1；1723，1677
Embodiment 2
19mmol 1-methyl-3-ethyl-5-pyrazole carboxylic acid and 200mmol sulfur oxychloride are joined in the 100mL there-necked flask, and under agitation back flow reaction 3h reacts and finishes, and concentrating under reduced pressure gets light yellow 1-methyl-3-ethyl-5-pyrazol formyl chloride transparent liquid.
2.06g (20mmol) 2-thiazolidone 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；6.45(s，1H，heterocyclic?H)，4.18(t，2H，N-CH
2-C)，4.00(s，3H，N-CH
3)，3.36(t，2H，S-CH
2-C)，2.65(q，2H，CH
2-C)，1.23(t，3H，C-CH
3)
IR(KBr，V
CO)cm
-1；1712，1674
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.
2.06g (20mmol) 2-thiazolidone 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 67%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；4.22(t，2H，N-CH
2-C)，3.99(s，3H，N-CH
3)，3.46(t，2H，S-CH
2-C)，2.72(q，2H，CH
2-C)，134(t，3H，C-CH
3)
IR(KBr，V
CO)cm
1；1716，1675
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-bromo-5-pyrazol formyl chloride transparent liquid.
2.06g (20mmol) 2-thiazolidone 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 64%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；4.12(t，2H，N-CH
2-C)，3.91(s，3H，N-CH
3)，3.40(t，2H，S-CH
2-C)，2.62(q，2H，CH
2-C)，1.23(t，3H，C-CH
3)
IR(KBr，V
CO)cm
-1；1717，1677
Embodiment 5
The trichloromethane consumption changes 50 times of 2-thiazolidone quality into, and other is operated with embodiment 1.Yield is 89%.
Embodiment 6
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-bromo-5-pyrazol formyl chloride transparent liquid.
2.38g (20mmol) 2-thiazole thione and 3.59g (26mmol) Anhydrous potassium carbonate 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 84%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；4.52(t，2H，N-CH
2-C)，3.89(s，3H，N-CH
3)，3.52(t，2H，S-CH
2-C)，2.59(q，2H，CH
2-C)，1.23(t，3H，C-CH
3)
IR(KBr，V)cm
1；1686(CO)，1227(CS)
Embodiment 7
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.
2.38g (20mmol) 2-thiazole thione and 3.59g (26mmol) Anhydrous potassium carbonate are joined in the 40mL tetrahydrofuran solution, drip 1-methyl-3-ethyl-4-chloro-5-pyrazol formyl chloride under ice bath stirs, 30min drips complete, reacts 10h then in about 6 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, concentrate, use ethyl alcohol recrystallization, obtain yellow crystals.Yield is 87%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；4.52(t，2H，N-CH
2-C)，3.90(s，3H，N-CH
3)，3.50(t，2H，S-CH
2-C)，2.60(q，2H，CH
2-C)，1.22(t，3H，C-CH
3)
IR(KBr，V)cm
1；1680(CO)，1149(CS)
Embodiment 8
19mmol 1-methyl-3-ethyl-5-pyrazole carboxylic acid and 200mmol sulfur oxychloride are joined in the 100mL there-necked flask, and under agitation back flow reaction 3h reacts and finishes, and concentrating under reduced pressure gets light yellow 1-methyl-3-ethyl-5-pyrazol formyl chloride transparent liquid.
2.38g (20mmol) 2-thiazole thione and 2.4g (24mmol) triethylamine are joined in the 40mL tetrahydrofuran solution, drip 1-methyl-3-ethyl-5-pyrazol formyl chloride under ice bath stirs, 30min drips complete, reacts 10h 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 43%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；6.45(s，1H，heterocyclic?H)，4.47(t，2H，N-CH
2-C)，3.97(s，3H，N-CH
3)，3.46(t，2H，S-CH
2-C)，2.63(q，2H，CH
2-C)，1.23(t，3H，C-CH
3)
IR(KBr，V)cm
-1；1686(CO)，1157(CS)
Embodiment 9
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.
2.38g (20mmol) 2-thiazole thione and 2.0g (22mmol) lutidine are joined in the 50mL chloroform soln, drip 1-methyl-3-ethyl-4-nitro-5-pyrazol formyl chloride under ice bath stirs, 30min drips complete, reacts 15h then in about 12 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, concentrate, use ethyl alcohol recrystallization, obtain yellow crystals.Yield is 92%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；4.77(t，2H，N-CH
2-C)，3.77(s，3H，N-CH
3)，3.59(t，2H，S-CH
2-C)，2.93(q，2H，CH
2-C)，1.27(t，3H，C-CH
3)
IR(KBr，V)cm
-1；1685(CO)，1210(CS)
Embodiment 10
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.
1.74g (20mmol) 2-oxazolidone and 2.0g (22mmol) lutidine are joined in the 40mL chlorobenzene solution, drip 1-methyl-3-ethyl-4-nitro-5-pyrazol formyl chloride under ice bath stirs, 30min drips complete, reacts 15h then in about 12 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, concentrate, use ethyl alcohol recrystallization, obtain yellow crystals.Yield is 92%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；4.40(t，2H，O-CH
2-C)，4.05(t，2H，N-CH
2-C)，3.80(s，3H，N-CH
3)，2.53(q，2H，CH
2-C)，1.14(t，3H，C-CH
3)
IR(KBr，V
CO)cm
-1；1791，1682
Embodiment 11
19mmol 1-methyl-3-ethyl-5-pyrazole carboxylic acid and 200mmol sulfur oxychloride are joined in the 100mL there-necked flask, and under agitation back flow reaction 3h reacts and finishes, and concentrating under reduced pressure gets light yellow 1-methyl-3-ethyl-5-pyrazol formyl chloride transparent liquid.
1.74g (20mmol) 2-oxazolidone and 2.3g (23mmol) triethylamine are joined in the 40mL toluene solution, drip 1-methyl-3-ethyl-5-pyrazol formyl chloride under ice bath stirs, 35min drips complete, reacts 11h then in about 8 ℃, 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 45%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；6.60(s，1H，heterocyclic?H)，4.48(t，2H，O-CH
2-C)，4.14(t，2H，N-CH
2-C)，4.02(s，3H，N-CH
3)，2.66(q，2H，CH
2-C)，1.24(t，3H，C-CH
3)
IR(KBr，V
CO)cm
-1；1790，1677
Embodiment 12
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.
1.74g (20mmol) 2-oxazolidone 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, 40min drips complete, reacts 13h then in about 5 ℃, 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；4.43(t，2H，O-CH
2-C)，4.09(t，2H，N-CH
2-C)，3.86(s，3H，N-CH
3)，2.63(q，2H，CH
2-C)，1.24(t，3H，C-CH
3)
IR(KBr，V
CO)cm
-1；1791，1683
Embodiment 13
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-bromo-5-pyrazol formyl chloride transparent liquid.
1.74g (20mmol) 2-oxazolidone and 1.85g (23mmol) pyridine are joined 40mL tetrahydrochysene fluorine mutters in the solution, drip 1-methyl-3-ethyl-4-bromo-5-pyrazol formyl chloride under ice bath stirs, 40min drips complete, reacts 16h 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 74%.
This compound
1H NMR and IR are as described below,
1H?NMR(CDCl
3)δppm；4.58(t，2H，O-CH
2-C)，4.27(t，2H，N-CH
2-C)，3.82(s，3H，N-CH
3)，2.96(q，2H，CH
2-C)，1.29(t，3H，C-CH
3)
IR(KBr，V
CO)cm
1；1793，1703
The test of embodiment 14 fungicidal activities
Adopt toxic potato agar substratum (PDA) method that the fungicidal activity that embodiment 1～13 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 pyrazole contained diheterocyclic compound is to the restraining effect of germ
The test of embodiment 15 insecticidal activities
Adopt the Potter spray method that embodiment 1～13 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 pyrazole contained diheterocyclic compound is to the killing action of insect
Claims (9)
1. suc as formula the pyrazole contained diheterocyclic compound shown in (I):
Wherein X representative is one of following: H ,-NO
2, Cl, Br, Y, Z independently are O or S separately.
2. pyrazole contained diheterocyclic compound as claimed in claim 1 is characterized in that described X representative-NO
2
3. pyrazole contained diheterocyclic compound as claimed in claim 1 is characterized in that described X represents Br.
4. preparation method of pyrazole contained diheterocyclic compound 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 suc as formula the nitrogen heterocyclic ring shown in (III) under the acid-capture agent effect, carry out condensation reaction at 0～20 ℃ in organic solvent, aftertreatment gets product;
Wherein X representative is one of following: H ,-NO
2, Cl, Br, Y, Z independently are O or S separately.
5. the preparation method of pyrazole contained diheterocyclic compound as claimed in claim 4, it is characterized in that described 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride: nitrogen heterocyclic ring: the molar ratio of acid-capture agent is 1: 1.0～1.5: 1.0～2.0, described consumption of organic solvent is 20～60 times of nitrogen heterocyclic ring quality, and the described reaction times is 1～50 hour.
6. the preparation method of pyrazole contained diheterocyclic compound as claimed in claim 4, it is characterized in that described acid-capture agent is one of following: triethylamine, pyridine, lutidine, Anhydrous potassium carbonate, described organic solvent are one of following: tetrahydrofuran (THF), ethyl acetate, toluene, chlorobenzene, trichloromethane.
7. as the preparation method of the described pyrazole contained diheterocyclic compound of one of claim 4～6, it is characterized in that described aftertreatment is: extremely neutral with dilute hydrochloric acid washing reaction liquid, layering, the organic phase drying is filtered, and concentrates, column chromatography for separation gets described pyrazole contained diheterocyclic compound.
8. as the preparation method of the described pyrazole contained diheterocyclic compound of one of claim 4～6, it is characterized in that described 1-methyl-3-ethyl-4-replacement-5-pyrazol formyl chloride: nitrogen heterocyclic ring: 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 nitrogen heterocyclic ring quality; Setting-up point is 5～15 ℃, and the reaction times is 10～20 hours.
9. the described pyrazole contained diheterocyclic compound of claim 1 is as the application of insectofungicide, and described desinsection is for killing leafhopper.
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| CN103554089B (en) * | 2013-11-26 | 2015-04-08 | 黑龙江大学 | Diheterocyclic compound as well as synthesis method and application thereof |
Citations (3)
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| JPH06116264A (en) * | 1983-08-02 | 1994-04-26 | American Cyanamid Co | Dihydroimidazopyrroropyridines and their derivatives |
| CN1091239A (en) * | 1993-02-16 | 1994-08-31 | 南开大学元素有机化学研究所 | Plant growth regulating agent of cell division factor type |
| WO1994029300A1 (en) * | 1993-06-07 | 1994-12-22 | Rhone Poulenc Agrochimie | Pyrazole fungicides 3-substituted by a heterocyclic ring |
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