CN103910650A - Preparation method for 4-chlorophenylhydrazine hydrochloride - Google Patents
Preparation method for 4-chlorophenylhydrazine hydrochloride Download PDFInfo
- Publication number
- CN103910650A CN103910650A CN201210594118.2A CN201210594118A CN103910650A CN 103910650 A CN103910650 A CN 103910650A CN 201210594118 A CN201210594118 A CN 201210594118A CN 103910650 A CN103910650 A CN 103910650A
- Authority
- CN
- China
- Prior art keywords
- drip
- solution
- aqueous solution
- reaction
- acid amide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A provided preparation method for 4-chlorophenylhydrazine hydrochloride comprises the following steps: 1) under an acidic condition, at 5-10 DEG C, dropwise adding a sodium nitrite aqueous solution with a concentration of 20% into 4-chloroaniline to perform a diazo reaction and to generate a diazo salt; 2) under a room temperature condition, dropwise adding an ammonium sulfite aqueous solution into a solution of the diazo salt obtained in the step 1, heating to 50-60 DEG C and keeping the temperature for 3-4 h; and 3) at 50-70 DEG C, dropwise adding a hydrochloric acid solution with a concentration of 20% into the solution obtained in the step 2, keeping the temperature for 1-2 h, reducing the temperature, filtering, washing, discharging the material, and drying to obtain a finished product. The beneficial effects comprise that by using ammonium sulfite aqueous solution as a reducing agent in the reduction reaction, the problems are solved that sodium sulfite solid is easy to cake during material charging in a conventional technology and material charging is not easy to operate; ammonium chloride and ammonium hydrogen sulfate which are generated in the acidification reaction have high solubility in water, and crystallization precipitation is late, thereby facilitating performing of the acidification reaction in the solution and reducing side reactions; and the product crystallizes loosely, is good in fluidity, easy for material discharging and washing, and product quality and yield are both better than conventional production levels.
Description
Technical field
The present invention relates to chemical field, relate to particularly a kind of method of preparing p-hydrochloride.
Background technology
P-hydrochloride is an important medicine, pesticide intermediate, in prior art, take p-Chlorobenzoic acid amide as raw material, prepares p-hydrochloride through diazotization reaction, S-WAT reduction, acidification hydrolization.The raw material adopting is that p-Chlorobenzoic acid amide, hydrochloric acid, Sodium Nitrite, S-WAT react, and concrete technological process is
1. p-Chlorobenzoic acid amide is under acidic conditions, and 0～10 ℃ drips 20% sodium nitrite in aqueous solution reaction, generates diazonium salt;
2. under room temperature condition, under strong mixing, slowly in water, drop into S-WAT solid, rise to 70 ℃, drip after diazonium salt, be incubated 4 hours.
3. the reduced liquid that step 2 obtains, in the time of 80 ℃, drips after technical hydrochloric acid, is incubated 1 hour, and cooling, filtration, pickling, discharging, dry to obtain finished product.
The shortcoming that this technique exists:
1, while reduction, S-WAT solid feeds intake, and its solubleness in the aqueous solution is little, very easily caking, and be difficult for dissolving after caking, therefore rate of feeding is had to requirement while operation, make troubles to production operation;
2, make reductive agent with S-WAT, when acidifying, the sodium-chlor of generation and the sodium pyrosulfate poor solubility in sour water, material is very thick, poor fluidity, discharging again after needing to process;
3, crystallization thickness, bad washing.
Summary of the invention
The object of this invention is to provide a kind of convenient operation, condition and be easy to the p-hydrochloride preparation method who controls.
For realizing above-mentioned goal of the invention, technical scheme of the present invention is as follows:
A preparation method for p-hydrochloride, comprises the steps:
1) p-Chlorobenzoic acid amide, under acidic conditions, 5～10 ℃, drips 20% sodium nitrite in aqueous solution and carries out doazo reaction, generation diazonium salt;
2) after the diazonium salt solution obtaining to ammonium sulphite aqueous solution dropping step 1 under room temperature condition, be warming up to 50-60 ℃, insulation 3～4h;
3) step 2 gained solution, in the time of 50-70 ℃, drips 20% hydrochloric acid soln, insulation 1-2h, and cooling, filtration, washing, discharging, dry to obtain finished product.
Further, comprise the steps:
1) p-Chlorobenzoic acid amide is dropped in a certain amount of water, open and stir, drip the hydrochloric acid soln of the amount of substance that is three times in p-Chlorobenzoic acid amide, drip and finish, be warming up to 60 ℃, after p-Chlorobenzoic acid amide hydrochloride all dissolves, be cooled to 5-10 ℃, now separate out as seen p-Chlorobenzoic acid amide hydrochloride fine crystals, drip 20% sodium nitrite in aqueous solution, drip terminal starch kI test paper and become blue, maintain this thermotonus architecture heat preservation 1 hour, keeping system pH is 1-2;
2) under room temperature, in the ammonium sulphite aqueous solution, drip the diazonium salt solution that step 1 obtains, it is yellow muddy that reaction solution is, and drips to finish to regulate pH=6.5-8, is warming up to 50-60 ℃ of reaction 3-4h, transparent to reaction solution;
3) under 50-70 ℃ of condition, step 2 gained reaction solution drips 20% hydrochloric acid, and along with adding of hydrochloric acid, reaction solution crystallization, is incubated 1 hour, is cooled to 15 ℃, discharging, and suction filtration, washing, obtains p-hydrochloride crude product; Dry to obtain finished product in 80 ℃.
Further, comprise the steps:
1) p-Chlorobenzoic acid amide 38.7kg is dropped in 82kg water, p-Chlorobenzoic acid amide amount of substance is 300mol, open and stir, dropping is three times in 30% hydrochloric acid soln 109kg of the amount of substance of p-Chlorobenzoic acid amide, contain hydrochloric acid 900mol, drip and finish, be warming up to 60 ℃, after p-Chlorobenzoic acid amide hydrochloride all dissolves, be cooled to 5-10 ℃, now separate out as seen p-Chlorobenzoic acid amide hydrochloride fine crystals, drip 20% sodium nitrite in aqueous solution, drip terminal starch kI test paper and become blue, maintain this thermotonus architecture heat preservation 1 hour, keeping system pH is 1-2;
2) under room temperature, in retort, drop into ammonium sulphite aqueous solution 220kg, containing ammonium sulphite 750mol, in the ammonium sulphite aqueous solution, drip the diazonium salt solution that step 1 obtains, it is yellow muddy that reaction solution is, and drips to finish to regulate pH=6.5-8, be warming up to 50-60 ℃ of reaction 3-4h, transparent to reaction solution;
3) under 50-70 ℃ of condition, step 2 gained reaction solution drips 20% hydrochloric acid 280kg, and along with adding of hydrochloric acid, reaction solution crystallization, is incubated 1 hour, is cooled to 15 ℃, discharging, and suction filtration, washing, obtains p-hydrochloride crude product; Dry to obtain finished product net weight 47kg in 80 ℃, purity 99.2%, yield reaches 86.8%.
The p-Chlorobenzoic acid amide solid purity that the present invention uses is 99%; Hydrochloric acid is except special mentioning, concentration is 31%; Sodium Nitrite is technical pure 99%; The ammonium sulphite aqueous solution is prepared in advance, and concentration is 33-37%; Above-mentioned raw materials is conventional known chemical feedstocks, all can be buied by market.
The invention has the beneficial effects as follows: in the preparation method who announces in the present invention, reduction reaction is that step 2 is used the ammonium sulphite aqueous solution to make reductive agent, save the former technique S-WAT solids easily not easy-operating difficult problem of caking that feeds intake, be convenient to production operation; In step 3, after acidification reaction, the ammonium chloride of generation and monoammonium sulfate solubleness in water is large, crystallization evening, is conducive to acidification reaction and carries out in solution, has reduced the generation of side reaction; The more former technique of product crystallization is loose, good fluidity, and easily discharging, washing, and quality product and yield are all better than existing production level; Due to the raw material ammonium sulphite aqueous solution can request for utilization people plant area acyl chloride reaction tail gas recycle the ammonium sulphite aqueous solution, can greatly reduce production costs, play the effect of recycle, energy-conserving and environment-protective.
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
A preparation method for p-hydrochloride, comprises the steps:
1) diazotization reaction: p-Chlorobenzoic acid amide 38.7kg is dropped in 82kg water, open and stir, drip the hydrochloric acid soln 109kg of the amount of substance that is three times in p-Chlorobenzoic acid amide, drip and finish, be warming up to 60 ℃, after p-Chlorobenzoic acid amide hydrochloride all dissolves, be cooled to 5-10 ℃, now separate out as seen p-Chlorobenzoic acid amide hydrochloride fine crystals, drip 20% sodium nitrite in aqueous solution, drip terminal starch kI test paper and become blue, maintain this thermotonus architecture heat preservation 1 hour, keeping system pH is 1-2;
2) reduction reaction: under room temperature, in retort, drop into ammonium sulphite aqueous solution 220kg, containing ammonium sulphite 750mol, in the ammonium sulphite aqueous solution, drip the diazonium salt solution that step 1 obtains, it is yellow muddy that reaction solution is, drip and finish pH=6.5-8, be warming up to 50-60 ℃ of reaction 3-4h, transparent to reaction solution;
3) acidification reaction: step 2 gained reaction solution drips 20% hydrochloric acid 280kg under 50-70 ℃ of condition, along with adding of hydrochloric acid, reaction solution crystallization, from crystallization, continue insulation 1 hour, be cooled to 15 ℃, discharging, suction filtration, washing, obtains p-hydrochloride crude product; Use baking oven to dry to obtain finished product, net weight 47kg, purity 99.2% in 80 ℃.
The foregoing is only preferred embodiment of the present invention, be not limited to the present invention, within the spirit and principles in the present invention all, any modification of making and be equal to replacement, within all should being included in protection scope of the present invention.
Claims (3)
1. a preparation method for p-hydrochloride, is characterized in that: comprise the steps:
1) p-Chlorobenzoic acid amide, under acidic conditions, 5～10 ℃, drips 20% sodium nitrite in aqueous solution and carries out doazo reaction, generation diazonium salt;
2) after the diazonium salt solution obtaining to ammonium sulphite aqueous solution dropping step 1 under room temperature condition, be warming up to 50-60 ℃, insulation 3～4h;
3) step 2 gained solution, in the time of 50-70 ℃, drips 20% hydrochloric acid soln, insulation 1-2h, and cooling, filtration, washing, discharging, dry to obtain finished product.
2. the preparation method of a kind of p-hydrochloride according to claim 1, is characterized in that: further, comprise the steps:
1) p-Chlorobenzoic acid amide is dropped in a certain amount of water, open and stir, drip the hydrochloric acid soln of the amount of substance that is three times in p-Chlorobenzoic acid amide, drip and finish, be warming up to 60 ℃, after p-Chlorobenzoic acid amide hydrochloride all dissolves, be cooled to 5-10 ℃, now separate out as seen p-Chlorobenzoic acid amide hydrochloride fine crystals, drip 20% sodium nitrite in aqueous solution, drip terminal starch kI test paper and become blue, maintain this thermotonus architecture heat preservation 1 hour, keeping system pH is 1-2;
2) under room temperature, in the ammonium sulphite aqueous solution, drip the diazonium salt solution that step 1 obtains, it is yellow muddy that reaction solution is, and drips and finish, and pH=6.5-8, is warming up to 50-60 ℃ of reaction 3-4h, transparent to reaction solution;
3) under 50-70 ℃ of condition, step 2 gained reaction solution drips 20% hydrochloric acid, and along with adding of hydrochloric acid, reaction solution crystallization, continues insulation 1 hour, is cooled to 15 ℃, discharging, and suction filtration, washing, obtains p-hydrochloride crude product; Dry to obtain finished product in 80 ℃.
3. the preparation method of a kind of p-hydrochloride according to claim 1, is characterized in that: further, comprise the steps:
1) p-Chlorobenzoic acid amide 38.7kg is dropped in 82kg water, open and stir, drip the hydrochloric acid soln 109kg of the amount of substance that is three times in p-Chlorobenzoic acid amide, drip and finish, be warming up to 60 ℃, after p-Chlorobenzoic acid amide hydrochloride all dissolves, be cooled to 5-10 ℃, now separate out as seen p-Chlorobenzoic acid amide hydrochloride fine crystals, drip 20% sodium nitrite in aqueous solution, drip terminal starch kI test paper and become blue, maintain this thermotonus architecture heat preservation 1 hour, keeping system pH is 1-2;
2) under room temperature, in retort, drop into ammonium sulphite aqueous solution 220kg, containing ammonium sulphite 750mol, in the ammonium sulphite aqueous solution, drip the diazonium salt solution that step 1 obtains, it is yellow muddy that reaction solution is, and drips and finish pH=6.5-8, be warming up to 50-60 ℃ of reaction 3-4h, transparent to reaction solution;
3) under 50-70 ℃ of condition, step 2 gained reaction solution drips 20% hydrochloric acid 280kg, and along with adding of hydrochloric acid, reaction solution crystallization, continues insulation 1 hour, is cooled to 15 ℃, discharging, and suction filtration, washing, obtains p-hydrochloride crude product; Dry to obtain finished product net weight 47kg, purity 99.2% in 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210594118.2A CN103910650A (en) | 2012-12-29 | 2012-12-29 | Preparation method for 4-chlorophenylhydrazine hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210594118.2A CN103910650A (en) | 2012-12-29 | 2012-12-29 | Preparation method for 4-chlorophenylhydrazine hydrochloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103910650A true CN103910650A (en) | 2014-07-09 |
Family
ID=51036701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210594118.2A Pending CN103910650A (en) | 2012-12-29 | 2012-12-29 | Preparation method for 4-chlorophenylhydrazine hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103910650A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565534A (en) * | 2016-10-28 | 2017-04-19 | 浙江奇彩环境科技股份有限公司 | Synthesis method for aromatic hydrazine sulfate |
| CN116119623A (en) * | 2023-01-29 | 2023-05-16 | 西陇科学股份有限公司 | Production method of environment-friendly high-purity potassium persulfate |
-
2012
- 2012-12-29 CN CN201210594118.2A patent/CN103910650A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565534A (en) * | 2016-10-28 | 2017-04-19 | 浙江奇彩环境科技股份有限公司 | Synthesis method for aromatic hydrazine sulfate |
| CN106565534B (en) * | 2016-10-28 | 2018-10-30 | 浙江奇彩环境科技股份有限公司 | A kind of synthetic method of aryl hydrazine sulfate |
| CN116119623A (en) * | 2023-01-29 | 2023-05-16 | 西陇科学股份有限公司 | Production method of environment-friendly high-purity potassium persulfate |
| CN116119623B (en) * | 2023-01-29 | 2023-08-15 | 西陇科学股份有限公司 | Production method of environment-friendly high-purity potassium persulfate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102993044A (en) | Preparation method of 4-chlorophenylhydrazine hydrochloride | |
| JP5850550B2 (en) | Method for producing taurine | |
| CN106565534B (en) | A kind of synthetic method of aryl hydrazine sulfate | |
| CN108191688A (en) | A kind of method synthesized and crystallize D-VB5 calcium | |
| CN106699570A (en) | Synthesis method for (2-chloro-5-iodophenyl)(4-fluorophenyl)ketone | |
| CN108329205A (en) | It is double（Aspirin）The preparation method of calcium carbamide compound | |
| CN101659635A (en) | Preparation method of methyl p-tolyl sulfone | |
| CN103102351B (en) | Refining method for preparing high-purity folic acid | |
| CN109053535A (en) | A kind of preparation method of n-acetyl-5-methoxytryptamine | |
| CN102558040A (en) | Method for preparing pirfenidone | |
| CN103910650A (en) | Preparation method for 4-chlorophenylhydrazine hydrochloride | |
| CN104355990B (en) | Method for recycling and mechanically using L- (+) -tartaric acid in D-ethyl ester production | |
| CN103145645A (en) | Preparation technology of mercapto-5-methyl-1,3,4-thiadiazole | |
| WO2015039266A1 (en) | Method for synthesising 2-thiopheneacetic acid | |
| CN103848752A (en) | Novel synthesis process of P-chlorophenylhydrazine hydrochloride | |
| CN107698651B (en) | A kind of production technology of high-purity dutasteride | |
| CN107686445A (en) | A kind of method for improving sodium acetate crystallographic granularity | |
| CN104557685A (en) | Method for producing nicotinic acid by using nicotinamide mother solution | |
| CN102093292B (en) | Method for synthesizing DL-alpha-amino caprolactam | |
| CN103483261A (en) | Preparation method of 1-substitued phenyl-3-carboxymethyl-5-pyrazolone | |
| CN105837452B (en) | 2- methyl-5-nitro phenol production process | |
| CN103980166B (en) | A kind of novel crystal forms of florfenicol and preparation method thereof | |
| CN109593060A (en) | A kind of preparation method of anti-fibrosis medicine | |
| CN106928146A (en) | A kind of purification process of lemon yellow | |
| CN109400491A (en) | A kind of crystallization preparation method of D-HPG methyl esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140709 |