CN103936619A - Preparation method and application of pyruvate acetal p-nitrobenzoylhydrazone - Google Patents
Preparation method and application of pyruvate acetal p-nitrobenzoylhydrazone Download PDFInfo
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- CN103936619A CN103936619A CN201410150906.1A CN201410150906A CN103936619A CN 103936619 A CN103936619 A CN 103936619A CN 201410150906 A CN201410150906 A CN 201410150906A CN 103936619 A CN103936619 A CN 103936619A
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- pyruvic acid
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- nitrophenyl formyl
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Abstract
The invention discloses a preparation method and application of pyruvate acetal p-nitrobenzoylhydrazone. The preparation method comprises the following steps: (1) adding methyl 4-nitrobenzoate and hydrazine hydrate into a reaction container according to a molar ratio of 1:(1-4), by taking absolute ethyl alcohol as a solvent, slowly adding the hydrazine hydrate through a dropping funnel, reacting at the temperature of 50-80 DEG C for 2-4 hours, cooling, filtering, washing, drying and obtaining p-nitrobenzoyl formyl hydrazine; and (2) adding the p-nitrobenzoyl formyl hydrazine and pyruvic acid into the reaction container according to a molar ratio of 1:(1-3), by taking the absolute ethyl alcohol as a solvent, slowly adding the pyruvic acid through the dropping funnel, reacting at the temperature of 50-80 DEG C for 2-6 hours, cooling, filtering, washing, recrystallizing, drying to obtain the pyruvate acetal p-nitrobenzoylhydrazone which can serve as a bactericide. The preparation method is mild in reaction conditions and cheap and easily available in raw materials, the used reagent is low in toxicity or non-toxic, and the synthetic product is high in yield, high in purity and suitable for expanded production under industrial conditions.
Description
[technical field]
The invention belongs to Synthetic Organic Chemistry field, be specifically related to a kind of preparation method and application thereof of pyruvic acid contracting p-nitrophenyl formyl hydrazone.
[background technology]
Owing to containing the active substructure group of this two class of amide group and Containing Schiff-bases in acylhydrazone molecular structure, therefore most of acylhydrazone analog derivatives have diversified biological activity, as anticancer, anti-oxidant, antiviral and anti-inflammatory etc. the potential source biomolecule having based on acylhydrazone and physiologically active, make it in agricultural and the field of medicaments prospect that has a very wide range of applications. the report .2001 Easmon etc. that just had various phenylhydrazones to uproot agent as wheat leaf rust shovel as far back as 1963 has reported two lopps hydrazones, 1-methyl-2-benzoglyoxaline hydrazone has title 4-acetylpyridine-2 '-phenylpropyl alcohol thiazole hydrazones such as potential antitumour activity .2002 J.Hofmann, 3-acetyl isoquinoline 99.9-2 '-phenylpropyl alcohol oxazole hydrazone etc. is the novel antitumor and anticancer agent of a class, they present unusual leukemia, melanoma, the effect .2003 of lung cancer and kidney, what water sample etc. has been reported salicylic aldehyde salicyloyl hydrazone, the multiple hydrazone compounds such as 2-carbonyl propionic acid salicyloyl hydrazone and title complex thereof are to puccinia striiformis, phytophthora blight of pepper, the red star bacterium of cotton-wilt fusarium and tobacco etc. all has restraining effect in various degree.Some hydrazone compounds have developed into commercial agricultural chemicals, as the pyrimidine hydrazone sterilant (Blasin) of Japanese Wu Tian pharmaceutical industries company exploitation, rice tail spore on main control paddy rice, the microbial diseases of cause of disease such as rice Helminthosporium sp. and Magnaporthe grisea are as rice blast.
[summary of the invention]
The object of the invention is to overcome the defect of above-mentioned prior art, a kind of preparation method and application thereof of pyruvic acid contracting p-nitrophenyl formyl hydrazone are provided.
For achieving the above object, the inventive method adopts following technical scheme:
A preparation method for pyruvic acid contracting p-nitrophenyl formyl hydrazone, comprises the following steps:
1) be 1:(1～4 according to mol ratio) methyl p-nitrobenzoate and hydrazine hydrate are added in reaction vessel, taking dehydrated alcohol as solvent, at 50～80 DEG C of reaction 2～4h, cooled and filtered, rinses, and dries, obtain p-nitrobenzoylhydrazide, wherein, hydrazine hydrate is that dropping funnel slowly adds;
2) be 1:(1～3 according to mol ratio) p-nitrobenzoylhydrazide and pyruvic acid are added in reaction vessel, taking dehydrated alcohol as solvent, at 50-80 DEG C of reaction 2～6h, cooled and filtered, rinses recrystallization, dry, obtain pyruvic acid contracting p-nitrophenyl formyl hydrazone, wherein, pyruvic acid is that dropping funnel slowly adds.
The present invention further improves and is, in step 1), use washed with methanol filter cake, 50～70 DEG C of oven dry, obtain p-nitrobenzoylhydrazide.
The present invention further improves and is, step 2) in, use washed with methanol filter cake, recrystallization, 50～70 DEG C of oven dry, obtain pyruvic acid contracting p-nitrophenyl formyl hydrazone.
The present invention further improves and is, step 1) and 2) in, in reaction process, add inorganic or organic bases as catalyzer.
The present invention further improves and is, inorganic or organic bases is sodium hydroxide, sodium carbonate, ammoniacal liquor, triethylamine, Diethylenetriamine or pyridine.
The present invention further improves and is, step 1) and 2) in, in reaction process, add inorganic or organic acid as catalyzer.
The present invention further improves and is, inorganic or organic acid is sulfuric acid, hydrochloric acid, formic acid or Glacial acetic acid.
The present invention further improves and is, pyruvic acid contracting p-nitrophenyl formyl hydrazone crude product uses ethyl alcohol recrystallization.
Another object of the present invention, pyruvic acid contracting p-nitrophenyl formyl hydrazone is as the application of sterilant.
With respect to prior art, the present invention has following technique effect:
The preparation method of pyruvic acid contracting p-nitrophenyl formyl hydrazone of the present invention, its reaction conditions gentleness, raw material is cheap and easy to get, and agents useful for same is low toxicity or nontoxic, and sintetics yield is higher, and purity is better, is suitable for the expanding production under industrialized condition.Pyruvic acid contracting p-nitrophenyl formyl hydrazone of the present invention is as the application of sterilant, its advantage is that the preparation method of this product is simple, and preparation process does not need expensive instrument, and cost is low, and this compounds is all low toxicity or nontoxic, is used for doing sterilant and can avoids bringing pollution to environment.
[brief description of the drawings]
Fig. 1 is the crystalline structure figure of pyruvic acid contracting p-nitrophenyl formyl hydrazone of the present invention.
[embodiment]
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.
Referring to Fig. 1, the preparation method of pyruvic acid contracting p-nitrophenyl formyl hydrazone of the present invention, its reaction schematic diagram is as follows:
According to above-mentioned reaction mechanism, the preparation method of pyruvic acid contracting p-nitrophenyl formyl hydrazone of the present invention, comprises the steps:
1) be 1:(1～4 according to mol ratio) methyl p-nitrobenzoate and hydrazine hydrate are added in reaction vessel, taking dehydrated alcohol as solvent, at 50～80 DEG C of reaction 2～4h, cooled and filtered, rinses, and dries, obtain p-nitrobenzoylhydrazide, wherein, hydrazine hydrate is that dropping funnel slowly adds;
2) be 1:(1～3 according to mol ratio) p-nitrobenzoylhydrazide and pyruvic acid are added in reaction vessel, taking dehydrated alcohol as solvent, at 50-80 DEG C of reaction 2～6h, cooled and filtered, rinses recrystallization, dry, obtain pyruvic acid contracting p-nitrophenyl formyl hydrazone, wherein, pyruvic acid is that dropping funnel slowly adds.
Embodiment 1:
The preparation of p-nitrobenzoylhydrazide: add 5mmol methyl p-nitrobenzoate and 5mmol85% hydrazine hydrate in 100mL round-bottomed flask, add 30mL dehydrated alcohol, 50 DEG C of water-bath back flow reaction 3h, cooled and filtered, adopt a small amount of methanol wash, 50 DEG C of oven dry obtain white needle-like crystals, yield 50%;
The preparation of pyruvic acid contracting p-nitrophenyl formyl hydrazone: add 5mmol p-nitrobenzoylhydrazide and 5mmol pyruvic acid in 100mL round-bottomed flask, add 50mL dehydrated alcohol, 50 DEG C of water-bath back flow reaction 3h, cooled and filtered, a small amount of methanol wash, with ethyl alcohol recrystallization, 70 DEG C of oven dry obtain white needle-like crystals, yield 45%.
Embodiment 2:
The preparation of p-nitrobenzoylhydrazide: add 5mmol methyl p-nitrobenzoate and 10mmol85% hydrazine hydrate in 100mL round-bottomed flask, add 30mL dehydrated alcohol, 70 DEG C of water-bath back flow reaction 4h, cooled and filtered, a small amount of methanol wash, 70 DEG C of oven dry obtain white needle-like crystals, yield 61%.
The preparation of pyruvic acid contracting p-nitrophenyl formyl hydrazone: add 5mmol p-nitrobenzoylhydrazide and 10mmol pyruvic acid in 100mL round-bottomed flask, add 50mL dehydrated alcohol, 70 DEG C of water-bath back flow reaction 4h, cooled and filtered, a small amount of methanol wash, with ethyl alcohol recrystallization, 50 DEG C of oven dry obtain white needle-like crystals, yield 56%.
Embodiment 3:
The preparation of p-nitrobenzoylhydrazide: add 5mmol methyl p-nitrobenzoate and 10mmol85% hydrazine hydrate in 100mL round-bottomed flask, add 30mL dehydrated alcohol, 80 DEG C of water-bath back flow reaction 4h, cooled and filtered, a small amount of methanol wash, 60 DEG C of oven dry obtain white needle-like crystals, yield 65%.
The preparation of pyruvic acid contracting p-nitrophenyl formyl hydrazone: add 5mmol p-nitrobenzoylhydrazide and 10mmol pyruvic acid in 100mL round-bottomed flask, add 50mL dehydrated alcohol, 80 DEG C of water-bath back flow reaction 4h, cooled and filtered, a small amount of methanol wash, with ethyl alcohol recrystallization, 60 DEG C of oven dry obtain white needle-like crystals, yield 60%.
Embodiment 4:
The preparation of p-nitrobenzoylhydrazide: add 5mmol methyl p-nitrobenzoate and 10mmol85% hydrazine hydrate in 100mL round-bottomed flask, add 30mL dehydrated alcohol, add again a small amount of ammonia-catalyzed agent, 80 DEG C of water-bath back flow reaction 4h, cooled and filtered, a small amount of methanol wash, 70 DEG C of oven dry obtain white needle-like crystals, yield 80%.
The preparation of pyruvic acid contracting p-nitrophenyl formyl hydrazone: add 5mmol p-nitrobenzoylhydrazide and 10mmol pyruvic acid in 100mL round-bottomed flask, add 50mL dehydrated alcohol, add again a small amount of Glacial acetic acid to make catalyzer, 80 DEG C of water-bath back flow reaction 4h, cooled and filtered, a small amount of methanol wash, with ethyl alcohol recrystallization, 70 DEG C of oven dry obtain white needle-like crystals, yield 75%.
Embodiment 5:
The preparation of p-nitrobenzoylhydrazide: add 5mmol methyl p-nitrobenzoate and 10mmol85% hydrazine hydrate in 100mL round-bottomed flask, add 30mL dehydrated alcohol, add again a small amount of Triethylamine catalyst, 80 DEG C of water-bath back flow reaction 4h, cooled and filtered, a small amount of methanol wash, 60 DEG C of oven dry obtain white needle-like crystals, yield 87%.
The preparation of pyruvic acid contracting p-nitrophenyl formyl hydrazone: add 5mmol p-nitrobenzoylhydrazide and 10mmol pyruvic acid in 100mL round-bottomed flask, add 50mL dehydrated alcohol, add again a small amount of Catalyzed by Formic Acid agent, 80 DEG C of water-bath back flow reaction 4h, cooled and filtered, a small amount of methanol wash, with ethyl alcohol recrystallization, 70 DEG C of oven dry obtain white needle-like crystals, yield 83%.
The fungicidal activity test of pyruvic acid contracting p-nitrophenyl formyl hydrazone
For trying bacterial classification: red sage root wilt (extract to separate from red sage root diseased plant and obtain).
Adopt biomass growth rate assay method, pyruvic acid contracting p-nitrophenyl formyl hydrazone is mixed with to certain density methanol solution under aseptic condition, be diluted in use desired concn, the each 1mL of absorption solution injects in culture dish, add respectively again 9mL nutrient agar, after shaking up, make 0.5,5,50 and 500 μ g/mL pastille flat boards, do blank with the flat board that adds 1mL sterilizing ethanol.Cut bacterium cake with the punch tool of diameter 4mm, move on pastille flat board, every processing in triplicate, culture dish is placed in 25 ± l DEG C of constant incubator and is cultivated, within 72 hours, " Invest, Then Investigate " is respectively processed bacterium cake expansion diameter, averages, and relatively calculates relative bacteriostasis rate with blank.
Wherein, inhibiting rate (%)=[(contrast growth diameter-processing growth diameter)/contrast growth diameter] × l00%.
Table 1: the clean property of the sterilization result (%) of pyruvic acid contracting p-nitrophenyl formyl hydrazone
As can be seen from Table 1, pyruvic acid contracting p-nitrophenyl formyl hydrazone prepared by the present invention, it is as sterilant, and desired concn is extremely low, and IC50 is about 50 μ g/mL.
Claims (9)
1. a preparation method for pyruvic acid contracting p-nitrophenyl formyl hydrazone, is characterized in that, comprises the following steps:
1) be 1:(1～4 according to mol ratio) methyl p-nitrobenzoate and hydrazine hydrate are added in reaction vessel, taking dehydrated alcohol as solvent, at 50～80 DEG C of reaction 2～4h, cooled and filtered, rinses, and dries, obtain p-nitrobenzoylhydrazide, wherein, hydrazine hydrate is that dropping funnel slowly adds;
2) be 1:(1～3 according to mol ratio) p-nitrobenzoylhydrazide and pyruvic acid are added in reaction vessel, taking dehydrated alcohol as solvent, at 50-80 DEG C of reaction 2～6h, cooled and filtered, rinses recrystallization, dry, obtain pyruvic acid contracting p-nitrophenyl formyl hydrazone, wherein, pyruvic acid is that dropping funnel slowly adds.
2. the preparation method of pyruvic acid contracting p-nitrophenyl formyl hydrazone according to claim 1, is characterized in that, in step 1), uses washed with methanol filter cake, and 50～70 DEG C of oven dry, obtain p-nitrobenzoylhydrazide.
3. the preparation method of pyruvic acid contracting p-nitrophenyl formyl hydrazone according to claim 1, is characterized in that step 2) in, use washed with methanol filter cake, recrystallization, 50～70 DEG C of oven dry, obtain pyruvic acid contracting p-nitrophenyl formyl hydrazone.
4. the preparation method of pyruvic acid contracting p-nitrophenyl formyl hydrazone according to claim 1, is characterized in that step 1) and 2) in, in reaction process, add inorganic or organic bases as catalyzer.
5. the preparation method of pyruvic acid contracting p-nitrophenyl formyl hydrazone according to claim 4, is characterized in that, inorganic or organic bases is sodium hydroxide, sodium carbonate, ammoniacal liquor, triethylamine, Diethylenetriamine or pyridine.
6. the preparation method of pyruvic acid contracting p-nitrophenyl formyl hydrazone according to claim 1, is characterized in that step 1) and 2) in, in reaction process, add inorganic or organic acid as catalyzer.
7. the preparation method of pyruvic acid contracting p-nitrophenyl formyl hydrazone according to claim 6, is characterized in that, inorganic or organic acid is sulfuric acid, hydrochloric acid, formic acid or Glacial acetic acid.
8. according to the preparation method of the pyruvic acid contracting p-nitrophenyl formyl hydrazone described in claim 1-7 Arbitrary Term, it is characterized in that, pyruvic acid contracting p-nitrophenyl formyl hydrazone crude product uses ethyl alcohol recrystallization.
9. the pyruvic acid contracting p-nitrophenyl formyl hydrazone that prepared by preparation method claimed in claim 1 is as the application of sterilant.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822104A (en) * | 2018-08-03 | 2018-11-16 | 商洛学院 | A kind of anti-oxidant ternary cobalt complex of high activity, preparation method and its usage |
| CN109456226A (en) * | 2018-12-07 | 2019-03-12 | 商洛学院 | A kind of complex Er (PANH) having bacteriostatic activity3, synthetic method and the application as Fusarium solani bacteriostatic agent |
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| CN1850789A (en) * | 2006-05-19 | 2006-10-25 | 西北大学 | Dipyruvate condensed terephthaloyl hydrazone, and its preparing method and use |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850789A (en) * | 2006-05-19 | 2006-10-25 | 西北大学 | Dipyruvate condensed terephthaloyl hydrazone, and its preparing method and use |
Non-Patent Citations (3)
| Title |
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| MIN HONG ET AL.: "Weakly-bridged dimeric diorganotin(IV) compounds derived from pyruvic acid hydrazone Schiff base ligands: Synthesis, characterization and crystal structures", 《SOLID STATE SCIENCES》, vol. 13, 10 November 2010 (2010-11-10), pages 501 - 507, XP028154152, DOI: 10.1016/j.solidstatesciences.2010.11.010 * |
| 何水样等: "铜(Ⅱ) 与2-羰基丙酸水杨酰腙配合物的合成、晶体结构和抑菌活性", 《高等学校化学学报》, vol. 23, 30 June 2002 (2002-06-30), pages 991 - 995 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822104A (en) * | 2018-08-03 | 2018-11-16 | 商洛学院 | A kind of anti-oxidant ternary cobalt complex of high activity, preparation method and its usage |
| CN109456226A (en) * | 2018-12-07 | 2019-03-12 | 商洛学院 | A kind of complex Er (PANH) having bacteriostatic activity3, synthetic method and the application as Fusarium solani bacteriostatic agent |
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Application publication date: 20140723 |