CN102924339A - Mitoguazone preparing method - Google Patents
Mitoguazone preparing method Download PDFInfo
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- CN102924339A CN102924339A CN2012104814194A CN201210481419A CN102924339A CN 102924339 A CN102924339 A CN 102924339A CN 2012104814194 A CN2012104814194 A CN 2012104814194A CN 201210481419 A CN201210481419 A CN 201210481419A CN 102924339 A CN102924339 A CN 102924339A
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- mitoguazone
- methyl alcohol
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- hydrochloric acid
- reaction solution
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Abstract
The invention aims to solve the technical problem by providing a mitoguazone preparing method, which has the advantages that the yield and product quality are improved, the cost is reduced, the reaction medium, the cleaning solvent and the purifying solvent can be recovered for reuse, and the pollution on the environment is alleviated. The method includes the following steps: composing mitoguazone under the condition that hydrochloric acid exists by taking industrial pyruvic aldehyde dimethyl acetal and aminoguanidine bicarbonate as raw materials and methanol as a reaction medium, filtering the formed mitoguazone reaction liquid through cooling and washing, and obtaining mitoguazone by purifying and drying the filter cake.
Description
Technical field
The present invention relates to a kind of preparation method of compound, especially the preparation method of mitoguazone.
Background technology
The preparation method who relates to mitoguazone in the prior art mainly contains following two kinds: a kind of is the pyruvic aldehyde method, and another kind is the pyruvic aldehyde dimethyl acetal method.
Document 1: (chapter is thought rule to the pyruvic aldehyde method, " the organic volume of practical fine chemicals handbook, 1757), take pyruvic aldehyde, aminoguanidine sulfate, hydrochloric acid as raw material condensation in the medium of dehydrated alcohol, after filtration, with absolute ethanol washing, drying, again decolouring, in acetone recrystallization and getting, yield is 65%.
Document 2:US5659083,1997.8.19, relate to the pyruvic aldehyde dimethyl acetal method, take pyruvic aldehyde dimethyl acetal, aminoguanidine sulfate, hydrochloric acid as raw material condensation in the medium of Virahol, filtration, usefulness low-density oil ether washing, air-dry, purified rear respectively with Virahol, Virahol-ether, ether washing again, vacuum-drying and get yield 86.87%, purity (HPLC) 99.9%.
During the synthetic mitoguazone of above-mentioned two kinds of preparation methods, all exist wastewater discharge large, reaction medium can't reclaim reusable problem, and is larger to the harm of environment.
Summary of the invention
The present invention will provide a kind of raising yield and quality product exactly, has reduced cost, and reaction medium, cleaning solvent, purification solvent is recyclable reuses, and has reduced the mitoguazone preparation method to the pollution of environment.In order to solve the problems of the technologies described above, technical scheme of the present invention is:
A kind of method for preparing mitoguazone, the method may further comprise the steps: take industrial acetone methylal, aminoguanidine sulfate as raw material, take methyl alcohol as reaction medium, synthetic mitoguazone under the hydrochloric acid existence condition, formed mitoguazone reaction solution, through freezing, washing and filtering, purified, the dry mitoguazone that gets of gained filter cake.
Preferably, gained filtrate is reclaimed methyl alcohol through air distillation.
Preferably, the environmental PH of described mitoguazone reaction solution=1.
Preferably, the content of described industrial acetone methylal 〉=98%.
Preferably, the methyl alcohol that reclaims take this synthetic method is as reaction medium.
Preferably, the concentration of described hydrochloric acid is more than 36%.
Preferably, the freezing temp 5-10 of described mitoguazone reaction solution ℃.
Preferably, the used solvent of described washing and purifying is methyl alcohol.
Preferably, described filtrate, cleaning solvent and purification solvent merge by the air distillation recovery, recycle.
Present method has improved yield and quality product, has reduced cost, and reaction medium, cleaning solvent, purification solvent is recyclable reuses, and has reduced the mitoguazone preparation method to the pollution of environment.
Embodiment
The synthetic method of the mitoguazone that uses among the present invention: be furnished with reflux exchanger, thermometer, dropping funnel, add aminoguanidine sulfate in the 500ml four-hole boiling flask of magnetic stirring apparatus, methyl alcohol (can or reclaim), start is stirred, dripped concentrated hydrochloric acid at 22 ~ 28 ℃ with 2 hours and make PH=1, hydrochloric acid dropwises at 22 ~ 30 ℃ and continues to stir 30 minutes, slowly be warmed up to 60 ± 2 ℃ and keep 30 minutes after, cool to 22 ~ 28 ℃, with 3 hours dropping pyruvic aldehyde dimethyl acetals, maintain the temperature at 22 ~ 28 ℃ in the process of dropping pyruvic aldehyde dimethyl acetal, pyruvic aldehyde dimethyl acetal dropwises to continue to stir and spends the night, next day, reaction solution was chilled to 5 ~ 10 ℃, filter, with methanol wash 3 times, each 10ml.Filtrate often pushes back to receive and reuses; Filter cake is soaked in the 100ml methyl alcohol, through washing and filtering, vacuum-drying, gets mitoguazone, and purity is up to (HPLC) more than 99.5%.
Carry out the mol ratio of pyruvic aldehyde dimethyl acetal and the aminoguanidine sulfate of this reaction, 1:2.0 ~ 2.5 are preferably: 2.1 ~ 2.3.The consumption of reaction medium methyl alcohol (by 1 mole of acetone methylal) 420 ~ 530ml, preferred 460 ~ 500ml; 36% hydrochloric acid content (every mole of aminoguanidine sulfate), 90 ~ 110ml; Preferred 99 ~ 102ml; 20 ~ 30 ℃ of the temperature of dropping hydrochloric acid, preferred 22 ~ 28 ℃; Time for adding 1.5 ~ 2.5 hours, preferred 2 hours; 20 ~ 30 ℃ of temperature of reaction, preferred 22 ~ 28 ℃; 2 ~ 4 hours reaction times, preferred 3 hours.
The invention will be further elaborated below by specific embodiment.
Embodiment one
Is being furnished with reflux exchanger, thermometer, dropping funnel, add the 50g aminoguanidine sulfate in the 500ml four-hole boiling flask of magnetic stirring apparatus, 80ml methyl alcohol, start is stirred, at 26 ℃ with dripping concentrated hydrochloric acid 37ml in 2 hours, survey PH=1, hydrochloric acid dropwises at 26 ℃ and continues to stir 30 minutes, slowly be warmed up to 60 ℃ and keep 30 minutes after, cool to 26 ℃, dripped pyruvic aldehyde dimethyl acetal 20 with 3 hours and restrain, maintain the temperature at 26 ℃ in the process of dropping pyruvic aldehyde dimethyl acetal, pyruvic aldehyde dimethyl acetal dropwises to continue to stir and spends the night, next day, reaction solution was chilled to 5 ℃, filter, use methanol wash 3 times, each 10ml.Filtrate often pushes back to receive and reuses; Filter cake is soaked in the 100ml methyl alcohol, through washing and filtering, vacuum-drying, gets mitoguazone 45.5g, yield 97.66%, purity (HPLC) 99.55%.
Embodiment two
Is being furnished with reflux exchanger, thermometer, dropping funnel, add the 50g aminoguanidine sulfate in the 500ml four-hole boiling flask of magnetic stirring apparatus, the methyl alcohol that 80ml reclaims, start is stirred, at 26 ℃ with dripping concentrated hydrochloric acid 37ml in 2 hours, survey PH=1, hydrochloric acid dropwises at 26 ℃ and continues to stir 30 minutes, slowly be warmed up to 60 ℃ and keep 30 minutes after, cool to 26 ℃, dripped pyruvic aldehyde dimethyl acetal 20 with 3 hours and restrain, maintain the temperature at 26 ℃ in the process of dropping pyruvic aldehyde dimethyl acetal, pyruvic aldehyde dimethyl acetal dropwises to continue to stir and spends the night, next day, reaction solution was chilled to 5 ℃, filter, with reclaiming methanol wash 3 times, each 10ml.Filtrate often pushes back to receive and reuses; Filter cake is soaked in 100ml and reclaims in the methyl alcohol, through washing and filtering, vacuum-drying, gets mitoguazone 45.0g, yield 96.50%, purity (HPLC) 99.50%.
Embodiment three
Is being furnished with reflux exchanger, thermometer, dropping funnel, add the 50g aminoguanidine sulfate in the 500ml four-hole boiling flask of magnetic stirring apparatus, the methyl alcohol that 75ml reclaims, start is stirred, at 28 ℃ with dripping concentrated hydrochloric acid 40ml in 2.5 hours, survey PH=1, hydrochloric acid dropwises at 26 ℃ and continues to stir 30 minutes, slowly be warmed up to 60 ℃ and keep 30 minutes after, cool to 26 ℃, dripped pyruvic aldehyde dimethyl acetal 20 with 4 hours and restrain, maintain the temperature at 28 ℃ in the process of dropping pyruvic aldehyde dimethyl acetal, pyruvic aldehyde dimethyl acetal dropwises to continue to stir and spends the night, next day, reaction solution was chilled to 10 ℃, filter, with reclaiming methanol wash 3 times, each 10ml.Filtrate often pushes back to receive and reuses; Filter cake is soaked in 100ml and reclaims in the methyl alcohol, through washing and filtering, vacuum-drying, gets mitoguazone 44.8g, yield 96.08%, purity (HPLC) 99.56%.
More than a kind of method for preparing mitoguazone provided by the present invention is described in detail, used specific example herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, the general technology foundation thought of the present invention for this area will change in particular implementation and range of application, and in sum, this description should not be construed as limitation of the present invention.
Claims (9)
1. method for preparing mitoguazone, it is characterized in that, take industrial acetone methylal, aminoguanidine sulfate as raw material, take methyl alcohol as reaction medium, synthetic mitoguazone reaction solution under the hydrochloric acid existence condition, formed mitoguazone reaction solution, through freezing, washing and filtering, purified, the dry mitoguazone that gets of resulting filter cake.
2. method according to claim 1, resulting filtrate is reclaimed methyl alcohol through air distillation.
3. method according to claim 1, the environmental PH=0.8-1.1 of described mitoguazone reaction solution.
4. method according to claim 1, the content of described industrial acetone methylal 〉=98%.
5. method according to claim 2, the methyl alcohol that reclaims take this synthetic method is as reaction medium.
6. method according to claim 1, the concentration of described hydrochloric acid is more than 36%.
7. method according to claim 1, the freezing temp 5-10 of described mitoguazone reaction solution ℃.
8. method according to claim 1, the used solvent of described washing and purifying is methyl alcohol.
9. method according to claim 2, the solvent that described filtrate, washing are used and the used solvent of purifying merge by air distillation and reclaim, and recycle.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB819587A (en) * | 1956-06-15 | 1959-09-09 | Ici Ltd | Bis-amidinohydrazones |
| US3673241A (en) * | 1968-04-04 | 1972-06-27 | Ciba Geigy Corp | Substituted benzaldehyde guanylhydrazones |
| CN85101799A (en) * | 1985-04-01 | 1987-01-17 | 拜尔股份公司 | With 1,2,3,4, the preparation method of the guanylhydrazones of tetrahydro chennai, benzene-r-pyrone, sulfo--r-pyrone and tetrahydroquinoline derivative and in pharmaceutically application |
| EP0782984A2 (en) * | 1996-05-30 | 1997-07-09 | Sanofi | Process of preparing 2-2'-(1-Methyl-1,2-Ethanediylidene) bis (Hydrazine carboximidamide) |
| US5693673A (en) * | 1996-05-30 | 1997-12-02 | Sanofi | Process of preparing 2,2'-(1-methyl-1,2-ethanediylidene)bis hydrazine caroximidamide! |
-
2012
- 2012-11-23 CN CN201210481419.4A patent/CN102924339B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB819587A (en) * | 1956-06-15 | 1959-09-09 | Ici Ltd | Bis-amidinohydrazones |
| US3673241A (en) * | 1968-04-04 | 1972-06-27 | Ciba Geigy Corp | Substituted benzaldehyde guanylhydrazones |
| CN85101799A (en) * | 1985-04-01 | 1987-01-17 | 拜尔股份公司 | With 1,2,3,4, the preparation method of the guanylhydrazones of tetrahydro chennai, benzene-r-pyrone, sulfo--r-pyrone and tetrahydroquinoline derivative and in pharmaceutically application |
| EP0782984A2 (en) * | 1996-05-30 | 1997-07-09 | Sanofi | Process of preparing 2-2'-(1-Methyl-1,2-Ethanediylidene) bis (Hydrazine carboximidamide) |
| US5693673A (en) * | 1996-05-30 | 1997-12-02 | Sanofi | Process of preparing 2,2'-(1-methyl-1,2-ethanediylidene)bis hydrazine caroximidamide! |
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