CN108707121B - Method for preparing 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one - Google Patents
Method for preparing 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one Download PDFInfo
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- CN108707121B CN108707121B CN201810875887.7A CN201810875887A CN108707121B CN 108707121 B CN108707121 B CN 108707121B CN 201810875887 A CN201810875887 A CN 201810875887A CN 108707121 B CN108707121 B CN 108707121B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/14—Nitrogen atoms
Abstract
The invention discloses a method for preparing 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one, which comprises the following steps: step 1, reacting isobutyric acid and hydrazine hydrate in a n-butyl alcohol solvent at the reaction temperature of 50-150 ℃ to generate isobutyrylhydrazide; step 2, reacting the isobutyryl hydrazide reaction liquid synthesized in the step 1 with phosgene or solid light and n-butyl alcohol serving as a solvent at the reaction temperature of 0-60 ℃ to generate 2-isobutyl hydrazino butyl formate; and 3, reacting the 2-isobutyl hydrazino butyl formate synthesized in the step 2 with hydrazine hydrate in an alkali solution at the reaction temperature of 80-120 ℃ to generate 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one and n-butyl alcohol. The invention uses single n-butanol as solvent in the whole reaction process, the intermediate process is not separated, and the invention has the advantages of simple reaction system, high reaction speed and less three wastes; the n-butanol can be repeatedly used; and the yield of the synthetic method is as high as 85 percent.
Description
Technical Field
The invention belongs to the field of pesticide synthesis, and particularly relates to a method for preparing 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one.
Background
The 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one is a substance with very strong chemical activity, is an important intermediate of a plurality of herbicides and insecticides which are commonly used in agricultural production, such as amicarbazone, propoxycarbazone, sulfentrazone, carfentrazone-ethyl and the like, and has wide application range.
This compound is usually obtained by using isobutyric acid or isobutyrylhydrazide as a starting material and by the following reaction.
The above process was first developed by Bayer AG, Germany, and its patents US5756752 and US5693821 mention that isobutyric acid (I) is reacted with hydrazine hydrate in toluene to give isobutyrohydrazide (II), which is then reacted with phosgene to give compound (V), which is subsequently desolventized and finally reacted with hydrazine hydrate under alkaline conditions to give compound (IV).
The solvent toluene recovered by the route is acidic, and if the solvent toluene is repeatedly used, the solvent toluene can be reused for synthesizing isobutyrylhydrazide (II) after alkali treatment. Obviously, this route adds a certain cost to the equipment to be industrialized.
The synthesis of isobutyrylhydrazide using n-butanol as solvent is also mentioned in Bayer patent US5756752, but there is no mention of the use of n-butanol as solvent in the whole route,
the above route is a route mentioned in KS test research corporation patent CN 103717580B, wherein R represents methyl, ethyl, isopropyl or butyl. Isobutyryl hydrazide (II) reacts with a carbamation reagent to obtain a compound (III), and related solvents are dichloromethane, methanol and toluene.
Another patent CN 104968649B from KS testing research corporation also mentions this route without major changes, only extending its scope from chloroformates to haloformates.
In patent US 9332762B 2, it is mentioned that n-butyl chloroformate is reacted with isobutyryl hydrazide (II) to produce 2-isobutylhydrazinobutyl formate (III), and a common solvent such as methylene chloride, methanol and the like is used as a solvent.
As is well known, the boiling point of dichloromethane is only 40 ℃, the industrial production is rarely applied due to the high volatility and low-temperature storage, methanol is miscible with water, and the separation is difficult, so that the recovery rate is reduced; according to the above patent, the former and latter solvents are not uniform, methylene chloride or methanol is often used as the solvent for the synthesis of the compound (III), and toluene is often used as the solvent for the synthesis of the compound (IV), so that various operations such as separation and rectification occur, which increases equipment cost. On the raw material side, the carbamation reagent is more costly than light-curing or phosgene.
Disclosure of Invention
In order to solve the problems in the industrialization, the invention provides a method for preparing 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one by a one-pot method which uses n-butyl alcohol as a solvent in the whole process.
The method for preparing 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one adopts the following route:
the method comprises the following steps:
step 1, reacting isobutyric acid and hydrazine hydrate in a n-butyl alcohol solvent at a reaction temperature of 50-150 ℃ to generate isobutyrylhydrazine, wherein the weight of the n-butyl alcohol is 2.0-10.0 times that of the isobutyric acid, and the molar equivalent of the hydrazine hydrate is 1.00-2.00 on the basis of the isobutyric acid.
The n-butyl alcohol has a higher boiling point, can be well separated from water, has a high recovery rate, and also gives consideration to the unification of solvents in subsequent operations, so the n-butyl alcohol is selected as the solvent.
And 2, reacting the isobutyrylhydrazide synthesized in the step 1 with phosgene or solid light and n-butyl alcohol serving as a solvent at the reaction temperature of 0-60 ℃, preferably 10-25 ℃ to generate 2-isobutylhydrazinobutyl formate, wherein the molar equivalent of the phosgene is 0.90-1.50 and the molar equivalent of the solid light is 0.30-0.50 based on isobutyric acid.
In this step, part of n-butanol theoretically reacts with phosgene (or light-fixing) and isobutyrylhydrazide which are cheap raw materials, and butyl 2-isobutylhydrazinoformate can be generated. The experiment proves that the n-butyl alcohol is used as the solvent to successfully obtain the 2-isobutyl hydrazino butyl formate, and the reaction effect is good. In addition, the use of n-butanol has the advantage that even if slightly more phosgene (or phosgene fixing) is introduced, n-butanol will consume the reaction and no risk of leakage will occur. In addition, after the 2-isobutyl hydrazinobutyl formate is obtained, the solvent does not need to be separated and can be directly used for subsequent reaction.
And 3, reacting the 2-isobutyl hydrazino butyl formate synthesized in the step 2 with hydrazine hydrate in an alkali solution at the reaction temperature of 80-120 ℃ to generate 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one and n-butyl alcohol, wherein the molar equivalent of the alkali is 0.10-1.00 and the molar equivalent of the hydrazine hydrate is 0.90-1.50 based on isobutyric acid.
In the step, standing and layering are carried out after the reaction is finished, the n-butyl alcohol on the upper layer almost has no product, the product can be directly applied to the preparation of the isobutyrylhydrazide in the first step without purification, the n-butyl alcohol generated in the step is the n-butyl alcohol reacted in the step 2, and the n-butyl alcohol almost has no loss; the lower layer is water phase, and the compound can be obtained by cooling, crystallization and filtration.
In order to keep the solvent of the whole route consistent, facilitate the operation and directly use the solvent as the reaction raw material, the solvent is a single solvent of n-butyl alcohol.
In order to make the reaction smoothly proceed, the alkali solution is a single solution or a mixed solution of any two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia water or triethylamine.
Has the advantages that: the invention uses single n-butanol as solvent in the whole course of the whole reaction, thereby simplifying the reaction system, reducing complex separation operation and equipment, having fast reaction speed and less three wastes; the n-butanol participates in the reaction and is finally generated by the reaction, and the n-butanol can be repeatedly applied without loss; and the yield of the synthetic method is as high as 85 percent, so that the method is a green industrial production route with low cost and high yield.
Detailed Description
The present invention will be described in detail with reference to the following examples, but is not limited thereto.
Example 1
44.5g (0.50mol) of isobutyric acid and 222.5g of n-butanol were introduced into a 500mL reaction flask at room temperature, and 32.9g (0.525mol) of 80% hydrazine hydrate was slowly added dropwise while stirring was turned on. After the dropwise addition, the temperature is raised to reflux for dehydration. And when 23mL of water is removed, the heating is closed, and the temperature is reduced to 15-20 ℃ in a water bath to obtain a product 1. And (3) slowly introducing 50.0g (0.50mol) of phosgene at the temperature of 15-20 ℃, using for 1 hour, and keeping the temperature for 3 hours to obtain a product 2. Then 31.3g (0.50mol) of 80% hydrazine hydrate and 8.0g (0.1mol) of 50% sodium hydroxide are added, the temperature is raised to 105-110 ℃, reflux is carried out for 3 hours, and the reaction is finished. Standing for layering, and separating out n-butanol on the upper layer. And continuously cooling the lower water phase to 20-40 ℃, adjusting the pH value to 6-7 with 30% hydrochloric acid, then continuously cooling to 0-5 ℃, continuously stirring for half an hour at the temperature, performing suction filtration, washing with a small amount of water, and drying to obtain a product 3 (the yield is 83.8%, and the purity is 99.5%).
GC-MS analysis was performed on products 1,2 and 3, respectively, and the data for product 1 was: 102.0,89.0,71.0,43.0, identified as isobutyrylhydrazide; data for product 2 was 202.2,132.1,71.1,43.0, identifying 2-isobutylhydrazinobenzoic acid butyl ester; product 3 has data of 142.1,127.1,114.1,96.0,82.0,70.0,43.0 and was identified as 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one.
Example 2
44.5g (0.50mol) of isobutyric acid and 133.5g of n-butanol were put into a 500mL reaction flask at room temperature, and 46.9g (0.75mol) of 80% hydrazine hydrate was slowly added dropwise while stirring was turned on. After the dropwise addition, the temperature is raised to reflux for dehydration. And when 35mL of water is removed, closing the heating, and cooling in a water bath to 15-20 ℃ to obtain a product 1. Slowly adding 55.0g (0.183mol) of solid light at 15-20 ℃, using for 1 hour, and keeping the temperature for 3 hours to obtain a product 2. Then 31.3g (0.50mol) of 80% hydrazine hydrate and 24.0g (0.3mol) of 50% sodium hydroxide are added, the temperature is raised to 100-105 ℃, reflux is carried out for 3 hours, and the reaction is finished. Standing for layering, and separating out n-butanol on the upper layer. Continuously cooling the lower water phase to 20-40 ℃, adjusting the pH value to 6-7 with 30% hydrochloric acid, then continuously cooling to 0-5 ℃, continuously stirring for half an hour at the temperature, performing suction filtration, washing with a small amount of water, and drying to obtain a product 3 (the yield is 84.2%, and the purity is 99.5%)
GC-MS analysis of products 1,2 and 3, respectively, gave the same data as in example 1 for products 1,2 and 3.
Example 3
44.5g (0.50mol) of isobutyric acid and 133.5g of n-butanol were placed in a 500mL reaction flask at room temperature, and 32.9g (0.525mol) of 80% hydrazine hydrate was slowly added dropwise while stirring was turned on. After the dropwise addition, the temperature is raised to reflux for dehydration. And when 23mL of water is removed, the heating is closed, and the temperature is reduced to 10-15 ℃ in a water bath to obtain a product 1. And (3) slowly introducing 52.5g (0.525mol) of phosgene at the temperature of 10-15 ℃, using for 2 hours, and keeping the temperature for 3 hours to obtain a product 2. Then 31.3g (0.50mol) of 80% hydrazine hydrate and 10.7g (0.1mol) of sodium carbonate are added, the temperature is raised to 95-100 ℃ and the mixture is refluxed for 3 hours, and the reaction is finished. Standing for layering, and separating out n-butanol on the upper layer. And continuously cooling the lower water phase to 20-40 ℃, adjusting the pH value to 6-7 with 30% hydrochloric acid, then continuously cooling to 0-5 ℃, continuously stirring for half an hour at the temperature, performing suction filtration, washing with a small amount of water, and drying to obtain a product 3 (the yield is 85.3%, and the purity is 99.5%).
GC-MS analysis of products 1,2 and 3, respectively, gave the same data as in example 1 for products 1,2 and 3.
Example 4
44.5g (0.50mol) of isobutyric acid and 178g of n-butanol were put into a 500mL reaction flask at room temperature, and 34.4g (0.55mol) of 80% hydrazine hydrate was slowly added dropwise while stirring was turned on. After the dropwise addition, the temperature is raised to reflux for dehydration. And when 25mL of water is removed, the heating is closed, and the temperature is reduced to 5-10 ℃ in a water bath to obtain a product 1. And (3) slowly introducing 52.5g (0.525mol) of phosgene at the temperature of 5-10 ℃, using for 2 hours, and keeping the temperature for 3 hours to obtain a product 2. Then 31.3g (0.50mol) of 80% hydrazine hydrate and 71.4g (0.2mol) of 30% sodium carbonate are added, the temperature is raised to 90-95 ℃ and the mixture is refluxed for 3 hours, and the reaction is finished. Standing for layering, and separating out n-butanol on the upper layer. And continuously cooling the lower water phase to 20-40 ℃, adjusting the pH value to 6-7 by using 30% hydrochloric acid, then continuously cooling to 5-10 ℃, continuously stirring for half an hour at the temperature, performing suction filtration, washing with a small amount of water, and drying to obtain a product 3 (the yield is 84.8%, and the purity is 99.5%).
GC-MS analysis of products 1,2 and 3, respectively, gave the same data as in example 1 for products 1,2 and 3.
Example 5
44.5g (0.50mol) of isobutyric acid and 178g of n-butanol were put into a 500mL reaction flask at room temperature, and 34.4g (0.55mol) of 80% hydrazine hydrate was slowly added dropwise while stirring was turned on. After the dropwise addition, the temperature is raised to reflux for dehydration. And when 25mL of water is removed, the heating is closed, and the temperature is reduced to 15-20 ℃ in a water bath to obtain a product 1. 52.0g (0.173mol) of solid light is slowly put into the reactor at 15-20 ℃ for 1.5 hours, and the temperature is kept for 4 hours to obtain a product 2. Then 31.3g (0.50mol) of 80% hydrazine hydrate and 15.3g (0.15mol) of triethylamine are added, the temperature is raised to 100-110 ℃ and the mixture is refluxed for 3 hours, and the reaction is finished. Standing for layering, and separating out n-butanol on the upper layer. And continuously cooling the lower water phase to 20-40 ℃, adjusting the pH value to 6-7 by using 30% hydrochloric acid, then continuously cooling to 5-10 ℃, continuously stirring for half an hour at the temperature, performing suction filtration, washing with a small amount of water, and drying to obtain a product 3 (the yield is 82.5%, and the purity is 99.5%).
GC-MS analysis of products 1,2 and 3, respectively, gave the same data as in example 1 for products 1,2 and 3.
Example 6
44.5g (0.50mol) of isobutyric acid and 133.5g of n-butanol were placed in a 500mL reaction flask at room temperature, and 32.9g (0.525mol) of 80% hydrazine hydrate was slowly added dropwise while stirring was turned on. After the dropwise addition, the temperature is raised to reflux for dehydration. And when 23mL of water is removed, the heating is closed, and the temperature is reduced to 10-15 ℃ in a water bath to obtain a product 1. And (3) slowly introducing 52.5g (0.525mol) of phosgene at the temperature of 10-15 ℃, using for 3 hours, and keeping the temperature for 2 hours to obtain a product 2. Then 31.3g (0.50mol) of 80% hydrazine hydrate and 10.7g (0.1mol) of sodium carbonate are added, the temperature is raised to 100-110 ℃ and the mixture is refluxed for 3 hours, and the reaction is finished. Standing for layering, and separating out n-butanol on the upper layer. And continuously cooling the lower water phase to 20-40 ℃, adjusting the pH value to 6-7 by using 30% hydrochloric acid, then continuously cooling to 0-5 ℃, continuously stirring for half an hour at the temperature, performing suction filtration, washing with a small amount of water, and drying to obtain a product 3 (the yield is 83.0%, and the purity is 99.5%).
GC-MS analysis of products 1,2 and 3, respectively, gave the same data as in example 1 for products 1,2 and 3.
Example 7
44.5g (0.50mol) of isobutyric acid and 178g of n-butanol recovered were put into a 500mL reaction flask at room temperature, and 34.4g (0.55mol) of 80% hydrazine hydrate was slowly added dropwise while stirring was turned on. After the dropwise addition, the temperature is raised to reflux for dehydration. And when 25mL of water is removed, the heating is closed, and the temperature is reduced to 15-20 ℃ in a water bath to obtain a product 1. And (3) slowly introducing 52.0g (0.52mol) of phosgene at the temperature of 15-20 ℃, using for 2 hours, and keeping the temperature for 4 hours to obtain a product 2. Then 31.3g (0.50mol) of 80% hydrazine hydrate and 15.3g (0.15mol) of triethylamine are added, the temperature is raised to 95-100 ℃ and the mixture is refluxed for 3 hours, and the reaction is finished. Standing for layering, and separating out n-butanol on the upper layer. And continuously cooling the lower water phase to 20-40 ℃, adjusting the pH value to 6-7 with 30% hydrochloric acid, then continuously cooling to 5-10 ℃, continuously stirring for half an hour at the temperature, performing suction filtration, washing with a small amount of water, and drying to obtain a product 3 (the yield is 83.1%, and the purity is 99.5%).
GC-MS analysis of products 1,2 and 3, respectively, gave the same data as in example 1 for products 1,2 and 3.
Example 8
44.5g (0.50mol) of isobutyric acid and 133.5g of recovered n-butanol were put into a 500mL reaction flask at room temperature, and 46.9g (0.75mol) of 80% hydrazine hydrate was slowly added dropwise while stirring was turned on. After the dropwise addition, the temperature is raised to reflux for dehydration. And when 36mL of water is removed, closing the heating, and cooling in a water bath to 15-20 ℃ to obtain a product 1. 52.0g (0.173mol) of solid light is slowly put into the reactor at 15-20 ℃ for 1 hour, and the temperature is kept for 3 hours to obtain a product 2. Then 31.3g (0.50mol) of 80% hydrazine hydrate and 16.8g (0.15mol) of 50% potassium hydroxide are added, the temperature is raised to 100-105 ℃, reflux is carried out for 3 hours, and the reaction is finished. Standing for layering, and separating out n-butanol on the upper layer. And continuously cooling the lower water phase to 20-40 ℃, adjusting the pH value to 6-7 by using 30% hydrochloric acid, then continuously cooling to 0-5 ℃, continuously stirring for half an hour at the temperature, performing suction filtration, washing with a small amount of water, and drying to obtain a product 3 (the yield is 84.0%, and the purity is 99.5%).
GC-MS analysis of products 1,2 and 3, respectively, gave the same data as in example 1 for products 1,2 and 3.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited thereto. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. A process for preparing 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one comprising:
step 1, reacting isobutyric acid and hydrazine hydrate in a n-butyl alcohol solvent at a reaction temperature of 50-150 ℃ to generate isobutyrylhydrazine, wherein the weight of the n-butyl alcohol is 2.0-10.0 times that of the isobutyric acid, and the molar equivalent of the hydrazine hydrate is 1.00-2.00 on the basis of the isobutyric acid;
step 2, reacting the isobutyrylhydrazide synthesized in the step 1 with phosgene or solid light and n-butyl alcohol serving as a solvent at the reaction temperature of 0-60 ℃ to generate 2-isobutyl hydrazino butyl formate, wherein the molar equivalent of the phosgene is 0.90-1.50 and the molar equivalent of the solid light is 0.30-0.50 based on isobutyric acid;
and 3, reacting the 2-isobutyl hydrazino butyl formate synthesized in the step 2 with hydrazine hydrate in an alkali solution at the reaction temperature of 80-120 ℃ to generate 3-isopropyl-4-amino-1, 2, 4-triazolin-5-one and n-butyl alcohol, wherein the molar equivalent of the alkali is 0.10-1.00 and the molar equivalent of the hydrazine hydrate is 0.90-1.50 based on isobutyric acid.
2. The process according to claim 1, characterized in that the solvent is n-butanol single solvent.
3. The method according to claim 1, wherein the alkali solution is a single solution or a mixed solution of any two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia water, or triethylamine.
4. The method according to claim 1, wherein the reaction temperature in the step 2 is 10 to 25 ℃.
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| US5057144A (en) * | 1988-05-09 | 1991-10-15 | Bayer Aktiengesellschaft | Sulphonylaminocarbonyltriazolinones |
| CN1136558A (en) * | 1995-02-13 | 1996-11-27 | 拜尔公司 | Process for preparing triazolinone and new intermediate |
| US5756752A (en) * | 1997-04-15 | 1998-05-26 | Bayer Corporation | Process for preparing substituted oxadiazolones |
| CN103717580A (en) * | 2011-07-28 | 2014-04-09 | Ks试验研究株式会社 | Method for preparing amino-triazolinone |
| CN104968649A (en) * | 2013-01-25 | 2015-10-07 | Ks试验研究株式会社 | Method for preparing amicarbazone |
| CN107162993A (en) * | 2017-06-06 | 2017-09-15 | 无锡市稼宝药业有限公司 | The synthetic method of amicarbazone |
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2018
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| US5057144A (en) * | 1988-05-09 | 1991-10-15 | Bayer Aktiengesellschaft | Sulphonylaminocarbonyltriazolinones |
| CN1136558A (en) * | 1995-02-13 | 1996-11-27 | 拜尔公司 | Process for preparing triazolinone and new intermediate |
| US5756752A (en) * | 1997-04-15 | 1998-05-26 | Bayer Corporation | Process for preparing substituted oxadiazolones |
| CN103717580A (en) * | 2011-07-28 | 2014-04-09 | Ks试验研究株式会社 | Method for preparing amino-triazolinone |
| CN104968649A (en) * | 2013-01-25 | 2015-10-07 | Ks试验研究株式会社 | Method for preparing amicarbazone |
| CN107162993A (en) * | 2017-06-06 | 2017-09-15 | 无锡市稼宝药业有限公司 | The synthetic method of amicarbazone |
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