CN102746238A - Preparation method of pyrimethanil - Google Patents
Preparation method of pyrimethanil Download PDFInfo
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- CN102746238A CN102746238A CN2012102677690A CN201210267769A CN102746238A CN 102746238 A CN102746238 A CN 102746238A CN 2012102677690 A CN2012102677690 A CN 2012102677690A CN 201210267769 A CN201210267769 A CN 201210267769A CN 102746238 A CN102746238 A CN 102746238A
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Abstract
The invention discloses a preparation method of pyrimethanil, which comprises the steps of: carrying out addition and salification reaction on aniline, hydrochloric acid, mono-cyanamide and sodium carbonate to generate aniline guanidine carbonate; carrying out cyclization reaction on aniline guanidine carbonate and acetyl benzophenone to generate pyrimethanil crude product; and directly adding water and alcohol mixed solvent to pyrimethanil crude product without separation, cooling, filtering and drying to obtain pyrimethanil. The content of pyrimethanil is more than 99%, and the total yield achieves more than 96% based on aniline. According to the invention, the process is simple and easy to operate, has the advantages of high product content, high yield, short reaction time, few side reactions and the like, and has significant economic benefit.
Description
Technical field
The present invention relates to the agricultural chemicals preparation field, specifically, relate to a kind of preparation technology of sterilant.
Background technology
Phonetic mould amine is the PYRIMITHAMINE sterilant by the exploitation of German Ai Gefu company; Chemical name N-(4,6-dimethyl pyrimidine-ethyl) aniline, CA accession number: 533112-28-0; Be mainly used in diseases such as the gray mold of preventing and treating various crop, black spot; Be a kind of good wide spectrum, efficient, low toxicity, systemic fungicide, and obtaining unusual effect aspect the sterilization of crop, the raising the output, thus countries in the world with phonetic mould amine as first-selected sterilant.Its physico-chemical property is: former medicine is clear crystal or white crystal, can be dissolved in organic solvent, is slightly soluble in water, and (25 ℃) solubleness in water is 0.12Kg/L under the room temperature, in 96.3 ℃ of 25 ℃ of following fusing points (pure article), vp 2.2 * 10
-3Pa (25 ℃), stable under weak acid and weak base property condition, proportion 11.15 (20 ℃) can reach 3 years at normal temperatures storage period.
The compound method of external phonetic mould amine is to be starting raw material with aniline, and for example: it is the synthetic phonetic mould amine of starting raw material that EP560726 and US4906778 patent application document disclose with aniline, cyanamide, and total recovery is only 67.2%, and content is about 95%.It is the method for the synthetic phonetic mould amine of raw material that EP29510 and EP310550 application documents disclose benzene guanidine supercarbonate, methyl ethyl diketone, and its yield is 87.2%, and content is about 96%.Because world market, particularly European Union market are strengthened phonetic mould amine market demand, require high-content (content >=98%) simultaneously, yet domestic many enterprises do not reach content requirement at present, thereby lose the world market, therefore must improve present production technique.
In the preparation method of general employing at present, there is following shortcoming:
1, aniline and cyanamide addition reaction temperature are low, and aniline is transformed not exclusively, bring in next step reaction, with the methyl ethyl diketone reaction, generate side reaction, are present in the product;
2, guanidines carbonate is directly synthetic without drying, so that residual too much moisture content in the wet article of guanidines, causes ring-closure reaction speed slow, and side reaction is many;
3, phonetic mould amine cyclization process does not adopt high vacuum, and the water that causes ring-closure reaction to generate can not shift out reactive system, and the long reaction time side reaction is many
4, phonetic mould amine ring-closure reaction finishes to adopt water, dichloromethane extraction, the hexanaphthene recrystallization, and yield is low, and product content is low;
5, phonetic mould amine total recovery is not high, can not reach high-content (content >=98%) product by present phonetic mould amine preparation method, influences the former medicine of phonetic mould amine and gets into world market, particularly European Union and Mei Jia market smoothly, therefore must improve present production technique.
Summary of the invention
Shortcomings such as the aniline transformation efficiency that prior art exists is low in order to solve, long reaction time, water generation reaction can not in time shift out, total recovery is low; The invention provides a kind of phonetic mould amine preparation method; Product content is reached more than 99%, guarantee that again yield is higher than the existing manufacturing technique level simultaneously.
The present invention relates to a kind of preparation method of phonetic mould amine, realize through following technical scheme:
A kind of preparation method of phonetic mould amine may further comprise the steps:
Aniline, hydrochloric acid, cyanamide and yellow soda ash are carried out the addition salt-forming reaction, generate the aniline guanidine carbonate;
Said aniline guanidine carbonate and acetyl benzophenone are carried out ring-closure reaction generate phonetic mould amine bullion;
Said phonetic mould amine bullion is directly added water and alcohols mixed solvent without separating, and cooling, filtration, drying obtain phonetic mould amine.
Said addition salt-forming reaction further may further comprise the steps:
Aniline is added in the reaction kettle, stirs and dripping hydrochloric acid, drip and finish back maintenance reaction;
After said maintenance reaction finishes, heat up, drip cyanamide then, drip and temperature increase to 100 is carried out insulation reaction by ℃-105 ℃ after finishing;
After said insulation reaction finished, cooling dripped sodium carbonate solution, stirring, cooling, centrifugal, washing, dried, and generated the aniline guanidine carbonate; And
The reaction formula of said addition salt-forming reaction is following:
Said guanidines carbonate is carried out further vacuum-drying, and being dried to the water cut mass percent is below 1%.
Said ring-closure reaction carries out under high vacuum condition, and vacuum tightness remains on-0.098Mpa, and the reaction formula of ring-closure reaction is following:
Said water and alcohols mixed solvent are the mixed solvents of alcohols materials such as water and Virahol, methyl alcohol, ethanol, and wherein by mass percentage, alcohols material is 85%, and water is 15%.
Said water and alcohols mixed solvent further are water and alcohol mixed solvent, and wherein the ethanol mass percent is 85%.
Compared with prior art, the present invention has the following advantages:
1. addition reaction process holding temperature of the present invention is 100-105 ℃, owing to improve temperature of reaction, makes aniline and cyanamide speed of response fast; Aniline reaction is complete; Transformation efficiency is high, otherwise aniline is followed in next step reaction of midbody entering aniline and methyl ethyl diketone reaction generation by product.Technology of the present invention is simple, and is easy to operate, shortens the reaction times, reduces side reaction, has economic benefit significantly to reducing cost;
2. after the guanidines vitriol drying, with the methyl ethyl diketone reaction, can reduce guanidines carbonate water cut again, reduce the methyl ethyl diketone hydrolysis, side reactions such as self-polymerization improve product content and yield, have economic benefit significantly;
3. in the ring-closure reaction process of the present invention, adopt high vacuum, the water that ring-closure reaction is generated can in time shift out reactive system, and fast reaction speed shortens reaction time, improves yield and content, has remarkable economic efficiency;
4. after the product end of synthesis, do not adopt water, dichloromethane extraction, hexanaphthene recrystallization, and adopt water and 85% ethanol to make solvent; Water can dissolve the inorganic impurity of solubility in the product on the one hand; Like guanidines carbonate, ethanol can dissolve organic side reaction impurity on the other hand, can significantly improve product content; Product content is reached more than 99%, and total recovery reaches (in aniline) more than 96%.
Embodiment
The present invention is described further the present invention in order better to explain below in conjunction with specific embodiment.In the following example, like no specified otherwise, " % " representation quality percentage ratio.
Embodiment 1
In 3000L lass lining aerofoil profile stirred autoclave, add 385Kg (99%) aniline, and stir, controlled temperature is below 60 ℃, drips 450L (30%) hydrochloric acid, drips and finishes, and keeps reaction 30 minutes; Open steam, temperature increase to 80-85 ℃, is begun to drip cyanamide 680Kg (30%), the continuously and smoothly drips in 2 hours; After drip finishing, with temperature increase to 100-105 ℃, insulation reaction 5 hours; Insulation reaction is cooled to 40-45 ℃ after finishing, and in 30 minutes, drips the solution that is made into by 270Kg (96%) yellow soda ash and 450Kg water continuously; Stirred 30 minutes, and fed 30 ℃ of recirculated waters and make temperature reduce to 35 ℃, after cooling finishes; Use SGZ type 3-foot automatic scraper bottom conveyer centrifugal to carry out centrifugal, drying mother liquor; After mother liquor dries, adopt the clear water washing material of 300 Kg, the use supercentrifuge dries material with 1200 revolutions per seconds rotating speed; Obtain wet article guanidines carbonate, water cut is 15%; Send into vacuum rake dryer to wet article guanidines carbonate dry 3 hours, use the SH10A KETT that the water-content of guanidines carbonate is analyzed.According to above step,, aniline and cyanamide holding temperature experimentize under being 85-90 ℃ and 100-105 ℃ of condition, and the result sees table 1.
Aniline that table 1 is different and cyanamide holding temperature experimental result
| Batch | The cyanamide dropping temperature | Holding temperature | The guanidines carbonate content | The aniline transformation efficiency |
| 1 | 80-85℃ | 85-90℃ | 89.25% | 90.6% |
| 2 | 80-85℃ | 85-90℃ | 88.78% | 90.5% |
| 2 | 80-85℃ | 85-90℃ | 89.68% | 90.7% |
| 4 | 80-85℃ | 100-105℃ | 98.78% | 99.5% |
| 5 | 80-85℃ | 100-105℃ | 98.89% | 99.3% |
| 6 | 80-85℃ | 100-105℃ | 98.12% | 99.6% |
Table 1 experimental result shows, guanidines carbonate content the when holding temperature when aniline and cyanamide reaction is 100-105 ℃ and aniline transformation efficiency guanidines carbonate content and the aniline transformation efficiency when holding temperature is 85-90 ℃.Specifically, under identical dropping temperature condition, when holding temperature is 100-105 ℃, guanidines carbonate content average out to 98.60%, aniline transformation efficiency average out to 99.5%; When holding temperature is 85-90 ℃, guanidines carbonate content average out to 89.24%, aniline transformation efficiency average out to 90.6%.Obviously, when holding temperature was 100-105 ℃, the guanidines carbonate content reached more than 98%, and the aniline transformation efficiency reaches more than 99%.
Embodiment 2
The guanidines carbonate that embodiment 1 reaction generates is put into 3000L stainless steel anchor formula stirring synthesis reactor; The methyl ethyl diketone that adds 580Kg (99%); Stir, be evacuated to-0.098MPa, open steam temperature increase to 75 ℃ is carried out cyclization; Back flow reaction 6 hours; Add water, dichloromethane extraction, hexanaphthene recrystallization, use 300 order SGZ type 3-foot automatic scraper bottom conveyer centrifugals to filter then, adopt vacuum rake dryer to obtain the phonetic mould amine of white powder in dry 3.5 hours at last.
With water cut is that 50%, 20%, 10%, 1%, 0.8% and 0.9% guanidines carbonate experimentizes, and the result sees table 2.
Table 2 guanidines carbonate water cut experimental result
| Batch | The guanidines water cut | Phonetic mould amine weight | Phonetic mould amine content | Phonetic mould amine yield |
| 1 | 50% | 711 kilograms | 91.2% | 79.5% |
| 2 | 20% | 728 kilograms | 93.5% | 83.5% |
| 3 | 10% | 764 kilograms | 94.6% | 88.6% |
| 4 | 1% | 774 kilograms | 96.2% | 91.3% |
| 5 | 0.8% | 777 kilograms | 96.0% | 91.5% |
| 6 | 0.9% | 772 kilograms | 96.5% | 91.4% |
Table 2 experimental result shows that the synthetic phonetic mould amine content that obtains of guanidines carbonate of process exsiccant low water content and yield are apparently higher than synthetic phonetic mould amine content and the yield that obtains of the guanidines carbonate of high-moisture.Specifically; Under identical synthesis temperature and vacuum degree condition; When water cut was respectively the synthetic phonetic mould amine of 1%, 0.9% and 0.8% guanidines carbonate, phonetic mould amine content was respectively 96.2%, 96.5% and 96.0%, and phonetic mould amine yield is respectively 91.3%, 91.4% and 91.5%; And water cut is when being respectively the synthetic phonetic mould amine of 10%, 20% and 50% guanidines carbonate, and phonetic mould amine content is respectively 94.6%, 93.5% and 91.2%, and phonetic mould amine yield is respectively 88.6%, 83.5% and 79.5%.Obviously, water cut is the synthetic phonetic mould amine of the guanidines carbonate below 1%, and phonetic mould amine content reaches more than 96%, and phonetic mould amine yield reaches more than 91%.
Adopt the dry guanidines carbonate of crossing, vacuum tightness be 0MP and-carry out the ring-closure reaction experiment under the 0.098MP condition, the result sees table 3.
The different vacuum tightness experimental results of table 3
| Batch | Vacuum tightness | Phonetic mould amine weight | Phonetic mould amine content | Phonetic mould amine yield |
| 1 | 0MP | 780 kilograms | 93.5% | 89.5% |
| 2 | 0MP | 789 kilograms | 92.6% | 89.6% |
| 3 | 0MP | 791 kilograms | 92.8% | 90.0% |
| 4 | -0.098MP | 777 kilograms | 96.3% | 91.6% |
| 5 | -0.098 MP | 776 kilograms | 96.0% | 91.3% |
| 6 | -0.098 MP | 776 kilograms | 96.2% | 91.5% |
Table 3 experimental result shows, phonetic mould amine content and yield that phonetic mould amine content that obtains when vacuum tightness is for-0.098MP in the building-up process and yield obtain during for 0MP apparently higher than vacuum tightness.Specifically, adopt the dry guanidines carbonate of crossing, under identical synthesis temperature condition, vacuum tightness be-during 0.098MP, synthesize phonetic mould amine content average out to 96.2%, phonetic mould amine yield average out to 91.5%; When vacuum tightness is 0MP, synthetic phonetic mould amine content average out to 93.0%, phonetic mould amine yield average out to 89.7%.Obviously, vacuum tightness during for-0.098MP synthetic phonetic mould amine content reach more than 96%, and phonetic mould amine yield reaches more than 91%.
Embodiment 3
The embodiment 1 dry guanidines carbonate of crossing is put into 3000L stainless steel anchor formula stir synthesis reactor; Add 580Kg (99%) methyl ethyl diketone, stir and be evacuated to-0.098MPa, open steam heating temperature increase to 75 ℃ is carried out cyclization; Back flow reaction 6 hours; After reaction finished, solubilizing agent stirring and dissolving 30 minutes was cooled to 0 ℃ then; Use 300 order SGZ type 3-foot automatic scraper bottom conveyer centrifugals to filter, adopt vacuum rake dryer to obtain the phonetic mould amine of white powder in dry 3.5 hours.Use hexanaphthene, sherwood oil and water+ethanol (ethanol is 85%) to experimentize respectively as solvent, the result sees table 4.
Table 4 different solvents experimental result
| Batch | Solvent | Phonetic mould amine weight | Phonetic mould amine content | Phonetic mould amine yield |
| 1 | Hexanaphthene | 775 kilograms | 96.3% | 91.5% |
| 2 | Hexanaphthene | 776 kilograms | 96.0% | 91.4% |
| 3 | Sherwood oil | 777 kilograms | 96.2% | 91.6% |
| 4 | Water+ethanol | 793 kilograms | 99.8% | 97% |
| 5 | Water+ethanol | 797 kilograms | 99.5% | 97.2% |
| 6 | Water+ethanol | 794 kilograms | 99.3% | 97.6% |
Table 4 experimental result shows, makes phonetic mould amine content that water+ethanol (ethanol is 85%) crystallization obtains and yield apparently higher than the phonetic mould amine content and the yield that use other solvent (hexanaphthene, sherwood oil) crystallization to obtain.Specifically, under identical synthesis temperature and vacuum degree condition, the phonetic mould amine that water+ethanol (ethanol is 85%) crystallization obtains, phonetic mould amine content average out to 99.5%, phonetic mould amine yield average out to 97.3%; With the phonetic mould amine content average out to 96.2% that hexanaphthene, sherwood oil crystallization obtain, phonetic mould amine yield average out to 91.5%.Obviously, the phonetic mould amine result that water+ethanol (ethanol is 85%) crystallization obtains is best, and phonetic mould amine content reaches more than 99%, and phonetic mould amine yield reaches more than 97%.
Though illustrate and described certain exemplary embodiment of the present invention; But those skilled in the art should know; Under the situation that does not break away from principle of the present invention and spirit, can make change to these exemplary embodiments, scope of the present invention is limited claim and equivalent thereof.
Claims (6)
1. the preparation method of a phonetic mould amine said method comprising the steps of:
Aniline, hydrochloric acid, cyanamide and yellow soda ash are carried out the addition salt-forming reaction, generate the aniline guanidine carbonate;
Said aniline guanidine carbonate and acetyl benzophenone are carried out ring-closure reaction generate phonetic mould amine bullion;
Said phonetic mould amine bullion is directly added water and alcohols mixed solvent without separating, and cooling, filtration, drying obtain phonetic mould amine.
2. the preparation method of phonetic mould amine according to claim 1 is characterized in that, saidly aniline, hydrochloric acid, cyanamide and yellow soda ash are carried out the addition salt-forming reaction further may further comprise the steps:
Aniline is added in the reaction kettle, stirs and dripping hydrochloric acid, drip and finish back maintenance reaction;
After said maintenance reaction finishes, heat up, drip cyanamide then, drip and temperature increase to 100 is carried out insulation reaction by ℃-105 ℃ after finishing;
After said insulation reaction finished, cooling dripped sodium carbonate solution, stirring, cooling, centrifugal, washing, dried, and generated the aniline guanidine carbonate; And
The reaction formula of said addition salt-forming reaction is following:
3. the preparation method of phonetic mould amine according to claim 1 and 2 is characterized in that, said guanidines carbonate is carried out further vacuum-drying, and being dried to the water cut mass percent is below 1%.
4. the preparation method of phonetic mould amine according to claim 1; It is characterized in that; Saidly said aniline guanidine carbonate and acetyl benzophenone are carried out ring-closure reaction under high vacuum condition, carry out, and vacuum tightness remains on-0.098Mpa, the reaction formula of ring-closure reaction is following:
5. the preparation method of phonetic mould amine according to claim 1 is characterized in that, said water and alcohols mixed solvent are the mixed solvents of alcohols materials such as water and Virahol, methyl alcohol, ethanol, and wherein by mass percentage, alcohols material is 85%, and water is 15%.
6. the preparation method of phonetic mould amine according to claim 5 is characterized in that, said water and alcohols mixed solvent further are water and alcohol mixed solvent, and wherein the ethanol mass percent is 85%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145589A (en) * | 2013-03-14 | 2013-06-12 | 黄河三角洲京博化工研究院有限公司 | Synthesis method of phenylguanidine bicarbonate |
| CN104610165A (en) * | 2015-02-02 | 2015-05-13 | 利民化工股份有限公司 | Preparation method of high-purity pyrimethanil and equipment used for preparing high-purity pyrimethanil |
| CN107879953A (en) * | 2017-10-28 | 2018-04-06 | 南通江山农药化工股份有限公司 | Phenyl guanidine carbonate recovery method and its device in waste water |
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| CN1631882A (en) * | 2004-12-02 | 2005-06-29 | 江苏耕耘化学有限公司 | Preparation method of agricultural fungicide N-(4,6-dimethyl pyrimidine-2-yl) aniline |
| WO2012082372A1 (en) * | 2010-12-16 | 2012-06-21 | Dow Agrosciences Llc | Synergistic fungicidal interactions of aminopyrimidines and other fungicides |
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2012
- 2012-07-31 CN CN2012102677690A patent/CN102746238A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1631882A (en) * | 2004-12-02 | 2005-06-29 | 江苏耕耘化学有限公司 | Preparation method of agricultural fungicide N-(4,6-dimethyl pyrimidine-2-yl) aniline |
| WO2012082372A1 (en) * | 2010-12-16 | 2012-06-21 | Dow Agrosciences Llc | Synergistic fungicidal interactions of aminopyrimidines and other fungicides |
Non-Patent Citations (1)
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| 王惠芳等: "《嘧霉胺盐的合成及其杀菌活性测试》", 《合成化学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145589A (en) * | 2013-03-14 | 2013-06-12 | 黄河三角洲京博化工研究院有限公司 | Synthesis method of phenylguanidine bicarbonate |
| CN104610165A (en) * | 2015-02-02 | 2015-05-13 | 利民化工股份有限公司 | Preparation method of high-purity pyrimethanil and equipment used for preparing high-purity pyrimethanil |
| CN107879953A (en) * | 2017-10-28 | 2018-04-06 | 南通江山农药化工股份有限公司 | Phenyl guanidine carbonate recovery method and its device in waste water |
| CN107879953B (en) * | 2017-10-28 | 2023-07-28 | 南通江山农药化工股份有限公司 | Method and device for recycling phenylguanidine carbonate in wastewater |
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Application publication date: 20121024 |