CN104059036A - Synthetic method of 5-[(dimethylamino) methyl]-2-furfuryl alcohol - Google Patents
Synthetic method of 5-[(dimethylamino) methyl]-2-furfuryl alcohol Download PDFInfo
- Publication number
- CN104059036A CN104059036A CN201410325160.3A CN201410325160A CN104059036A CN 104059036 A CN104059036 A CN 104059036A CN 201410325160 A CN201410325160 A CN 201410325160A CN 104059036 A CN104059036 A CN 104059036A
- Authority
- CN
- China
- Prior art keywords
- dimethylamino
- methyl
- furfuralcohol
- synthetic method
- reaction
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
Abstract
The invention discloses a synthetic method of 5-[(dimethylamino) methyl]-2-furfuryl alcohol. The synthetic method comprises the following steps: mixing a reactant with a reaction solution, distilling and recycling a solvent after heating reaction, regulating the pH value of residues to be 11-12 by using a sodium hydroxide solution, performing extraction by using ethyl acetate, steaming the solvent, and performing reduced pressure distillation to obtain 5-[(dimethylamino) methyl]-2-furfuryl alcohol, wherein the reactant is one of glucose, fructose, saccharose, fructose, 5-hydroxymethylfurfural and the like; the reaction solution is a mixed solution obtained by mixing one of N,N-dimethylformamide and N,N-dimethylacetamide with methanoic acid and water. According to the synthetic method disclosed by the invention, raw materials such as glucose, fructose, saccharose and a degradation product of sugar namely 5-hydroxymethylfurfural which are ordinary on the market are adopted as the reactants, the mixed solution obtained by mixing one of N,N-dimethylformamide and N,N-dimethylacetamide with methanoic acid and water is adopted as the reaction solvent, and the synthetic method is simple in process, is based on one-pot process production, and is short in reaction time, mild in reaction condition and high in yield.
Description
Technical field
The present invention relates to 5-[(dimethylamino) methyl]-2-furfuralcohol, especially relate to a kind of 5-[(dimethylamino) methyl] synthetic method of-2-furfuralcohol.
Background technology
5-[(dimethylamino) methyl]-2-furfuralcohol is synthetic H
2the important intermediate of-receptor antagonist Ranitidine HCL.Ranitidine HCL is the common drug for the treatment of gastric and duodenal ulcer, and effective, untoward reaction is few, has obtained FDA approval.At present, also there is manufacturer production in China.Important intermediate 5-[(dimethylamino as synthetic Rayleigh for fourth) methyl] preparation method of-2-furfuralcohol mainly contains:
(1) taking dimethylamine agueous solution, formalin and furfuralcohol as raw material, more than reaction 20h, obtain product (Price B.J. through alkalization, extraction, distillation, Clitherow J.W., Bradshaw J.B..Aminoalkyl furanderivatives.US4128658A, 1978; Chen Yubin, wishes the improvement of new extra large .5-dimethylamino methyl-2-furfuralcohol synthesis method. Chinese Journal of Pharmaceuticals .1991,22 (7), 319-320).
(2) taking dimethylamine agueous solution, the paraformaldehyde aqueous solution and furfuralcohol as raw material, a large amount of alcoholic solvents as Virahol, ethanol or methanol solution in more than back flow reaction 18h, obtain product through alkalization, extraction, distillation.
(3) utilize two diformazan ammonia methane in a large amount of acetic aid mediums, to react 18h with furfuralcohol, obtain product (Liu Fude through the alkalization of Distillation recovery acetic acid, extraction, distillation, Liu Yan, Li Baoli, Duan Yanxin, Xu Guofeng .5-dimethylamino methyl-2-furfuralcohol new synthetic process. chemistry circular, 66 (121), 1-3; Cooper J., Lee D.V..Process for thepreparation of5-dimethylaminomethyl-2-furanmethanol.US4347191A.1980; Cooper J., Lee D.V..Process for preparing5-dimethylaminomethyl-2-furanmethanol.EP0036716 A1.1980).
Summary of the invention
The object of the present invention is to provide a kind of 5-[(dimethylamino) methyl] synthetic method of-2-furfuralcohol.
The present invention includes following steps:
Reactant is mixed with reaction soln, after reacting by heating, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with sodium hydroxide solution, extract by ethyl acetate, boil off solvent, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol; Described reactant is the one in glucose, fructose, sucrose, fructose, 5 hydroxymethyl furfural etc., described reaction soln is N, N – dimethyl formamide (DMF) or N, the mixing solutions of the one in N – N,N-DIMETHYLACETAMIDE (DMAC) and formic acid (FA), water.
The mass ratio of described reactant and reaction soln can be 1: (1.5～4); Described N, N – dimethyl formamide or N, the mass ratio of N – N,N-DIMETHYLACETAMIDE and formic acid and water can be 1: (0.8～8.9): (0.01～0.2).
The temperature of described reacting by heating can be 50～120 DEG C, and the time of reacting by heating can be 1～10h.
Described sodium hydroxide solution can adopt 40% sodium hydroxide solution.
The condition of described underpressure distillation can be at 130～133 DEG C, underpressure distillation under 2000Pa condition.
The present invention is with the common raw material in market as glucose, fructose, sucrose, and the degradation product 5 hydroxymethyl furfural of sugar is reactant, N, N – dimethyl formamide or N, one and formic acid in N – N,N-DIMETHYLACETAMIDE, the mixing solutions of water is reaction solvent, temperature of reaction is 50～120 DEG C, reaction times is 1～10h, can obtain product, and feature is that technological process is simple, one kettle way is produced, reaction times is short, reaction conditions gentleness, and yield is high.Compared with the existing methods, there is comparatively significantly advantage.
Brief description of the drawings
Fig. 1 is the synthetic 5-[(dimethylamino of the embodiment of the present invention) methyl]-2-furfuralcohol gas chromatogram.
Embodiment
Below in conjunction with embodiment, the invention will be further described, it should be noted that, embodiment does not form the restriction to the claimed scope of the present invention.
Embodiment 1
In the round-bottomed flask of 500mL, add formic acid 210g, water 28.64g, N, N – dimethyl formamide: 111.36g, then puts into 60g dextrose anhydrous, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 120 DEG C, and the reaction times is 3h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol (Fig. 1), product yield exceedes 72%.
Embodiment 2
In the round-bottomed flask of 500mL, add formic acid 210g, water 28.64g, N, N – dimethyl formamide: 111.36g, then puts into 60g without Fruit candy, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 120 DEG C, and the reaction times is 3h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, and under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol, product yield exceedes 83%.
Embodiment 3
In the round-bottomed flask of 500mL, add formic acid 210g, water 28.64g, N, N – dimethyl formamide: 111.36g, then puts into 60g sucrose, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 120 DEG C, and the reaction times is 3h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, and under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol, product yield exceedes 85%.
Embodiment 4
In the round-bottomed flask of 50mL, add formic acid 21g, water 2.86g, N, N – dimethyl formamide: 11.14g, then puts into 6g5-hydroxymethylfurfural, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 120 DEG C, and the reaction times is 3h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, and under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol, product yield exceedes 95%.
Embodiment 5
In the round-bottomed flask of 50mL, add formic acid 21g, water 2.86g, N, N – dimethyl formamide: 11.14g, then puts into 6g5-hydroxymethylfurfural, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 50 DEG C, and the reaction times is 10h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, and under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol, product yield exceedes 33%.
Embodiment 6
In the round-bottomed flask of 50mL, add formic acid 21g, water 2.86g, N, N – dimethyl formamide: 11.14g, then puts into 6g5-hydroxymethylfurfural, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 50 DEG C, and the reaction times is 10h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, and under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol, product yield exceedes 29%.
Embodiment 7
In the round-bottomed flask of 50mL, add formic acid 21g, water 2.86g, N, N – N,N-DIMETHYLACETAMIDE: 11.14g, then puts into 6g5-hydroxymethylfurfural, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 100 DEG C, and the reaction times is 6h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, and under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol, product yield exceedes 90%.
Embodiment 8
In the round-bottomed flask of 50mL, add formic acid 21g, water 2.86g, N, N – N,N-DIMETHYLACETAMIDE: 11.14g, then puts into 6g5-hydroxymethylfurfural, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 100 DEG C, and the reaction times is 6h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, and under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol, product yield exceedes 87%.
Embodiment 9
In the round-bottomed flask of 50mL, add formic acid 7g, water 0.96g, N, N – dimethyl formamide: 27.04g, then puts into 6g5-hydroxymethylfurfural, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 120 DEG C, and the reaction times is 6h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, and under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol, product yield exceedes 27%.
Embodiment 10
In the round-bottomed flask of 50mL, add formic acid 28g, water 3.96g, N, N – dimethyl formamide: 3.18g, then puts into 6g5-hydroxymethylfurfural, fully dissolves.Flask is placed in to oil bath reacting by heating, and temperature is 120 DEG C, and the reaction times is 6h.After completion of the reaction, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with 40% sodium hydroxide solution, extract 3 times by 100mL ethyl acetate, combined ethyl acetate layer, distillating recovering solvent ethyl acetate boils off solvent, obtain 5-[(dimethylamino) methyl]-thick the product of 2-furfuralcohol exists, thick product is at 130～133 DEG C, and under 2000Pa condition, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol, product yield exceedes 25%.
Claims (6)
1. 5-[(dimethylamino) methyl] synthetic method of-2-furfuralcohol, it is characterized in that its concrete steps are as follows:
Reactant is mixed with reaction soln, after reacting by heating, distillating recovering solvent, it is 11～12 that resistates is regulated to pH value with sodium hydroxide solution, extract by ethyl acetate, boil off solvent, underpressure distillation obtains 5-[(dimethylamino) methyl]-2-furfuralcohol; Described reactant is the one in glucose, fructose, sucrose, fructose, 5 hydroxymethyl furfural, and described reaction soln is N, N – dimethyl formamide or N, a kind of and formic acid in N – N,N-DIMETHYLACETAMIDE, the mixing solutions of water.
2. a kind of 5-[(dimethylamino as claimed in claim 1) methyl] synthetic method of-2-furfuralcohol, the mass ratio that it is characterized in that described reactant and reaction soln is 1: (1.5～4).
3. a kind of 5-[(dimethylamino as claimed in claim 1) methyl] synthetic method of-2-furfuralcohol, it is characterized in that described N, N – dimethyl formamide or N, the mass ratio of N – N,N-DIMETHYLACETAMIDE and formic acid and water can be 1: (0.8～8.9): (0.01～0.2).
4. a kind of 5-[(dimethylamino as claimed in claim 1) methyl] synthetic method of-2-furfuralcohol, the temperature that it is characterized in that described reacting by heating is 50～120 DEG C, the time of reacting by heating is 1～10h.
5. a kind of 5-[(dimethylamino as claimed in claim 1) methyl] synthetic method of-2-furfuralcohol, it is characterized in that described sodium hydroxide solution adopts 40% sodium hydroxide solution.
6. a kind of 5-[(dimethylamino as claimed in claim 1) methyl] synthetic method of-2-furfuralcohol, the condition that it is characterized in that described underpressure distillation is at 130～133 DEG C, underpressure distillation under 2000Pa condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410325160.3A CN104059036B (en) | 2014-07-09 | 2014-07-09 | A kind of synthetic method of 5-[(dimethylamino) methyl]-2-furfuralcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410325160.3A CN104059036B (en) | 2014-07-09 | 2014-07-09 | A kind of synthetic method of 5-[(dimethylamino) methyl]-2-furfuralcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104059036A true CN104059036A (en) | 2014-09-24 |
| CN104059036B CN104059036B (en) | 2015-12-02 |
Family
ID=51547005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410325160.3A Expired - Fee Related CN104059036B (en) | 2014-07-09 | 2014-07-09 | A kind of synthetic method of 5-[(dimethylamino) methyl]-2-furfuralcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104059036B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987040A (en) * | 2017-12-19 | 2018-05-04 | 厦门大学 | The synthesis of 2-N- methylaminomethyl -5-N- methyl formamino furans |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4347191A (en) * | 1980-03-08 | 1982-08-31 | Smith Kline & French Laboratories Limited | Process for the preparation of 5-dimethylaminomethyl-2-furanmethanol |
| WO2008108957A2 (en) * | 2007-03-02 | 2008-09-12 | Schering Corporation | Piperidinyl-piperidine and piperazinyl-piperidine for use in the treatment of diabetes or pain |
| CN101381351A (en) * | 2008-10-21 | 2009-03-11 | 华南理工大学 | Method for cogeneration of 5-hydroxymethyl-furfural, acetylpropionic acid and formic acid by high temperature catalytic dehydration of glucose in formic acid |
| CN101456850A (en) * | 2007-12-12 | 2009-06-17 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl-furfural |
| CN103443090A (en) * | 2010-12-16 | 2013-12-11 | 阿彻丹尼尔斯米德兰德公司 | Preparation of aminomethyl furans and alkoxymethyl furan derivatives from carbohydrates |
-
2014
- 2014-07-09 CN CN201410325160.3A patent/CN104059036B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4347191A (en) * | 1980-03-08 | 1982-08-31 | Smith Kline & French Laboratories Limited | Process for the preparation of 5-dimethylaminomethyl-2-furanmethanol |
| WO2008108957A2 (en) * | 2007-03-02 | 2008-09-12 | Schering Corporation | Piperidinyl-piperidine and piperazinyl-piperidine for use in the treatment of diabetes or pain |
| CN101456850A (en) * | 2007-12-12 | 2009-06-17 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl-furfural |
| CN101381351A (en) * | 2008-10-21 | 2009-03-11 | 华南理工大学 | Method for cogeneration of 5-hydroxymethyl-furfural, acetylpropionic acid and formic acid by high temperature catalytic dehydration of glucose in formic acid |
| CN103443090A (en) * | 2010-12-16 | 2013-12-11 | 阿彻丹尼尔斯米德兰德公司 | Preparation of aminomethyl furans and alkoxymethyl furan derivatives from carbohydrates |
Non-Patent Citations (2)
| Title |
|---|
| 刘福德等: "5-二甲氨基甲基-2-呋喃甲醇合成新工艺", 《化学通报（网络版）》 * |
| 陈玉彬等: "5-二甲胺基甲基-2-呋喃甲醇合成法的改进", 《中国医药工业杂志》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987040A (en) * | 2017-12-19 | 2018-05-04 | 厦门大学 | The synthesis of 2-N- methylaminomethyl -5-N- methyl formamino furans |
| CN107987040B (en) * | 2017-12-19 | 2020-05-29 | 厦门大学 | Synthesis of 2-N-methylaminomethyl-5-N-methylaminomethylfuran |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104059036B (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103467245B (en) | Method for complexing and removing water contained in ethanol and water mixed solution by utilizing eutectic solvent | |
| CN102558572B (en) | Method for preparing xylogen acetylated derivative in ionic liquid solvent | |
| CN104744237A (en) | Preparation method of 2-(4-bromomethylphenyl) propionic acid | |
| CN103113246A (en) | Production method of methyl cyclopentenolone via amination and step-by-step reaction | |
| CN102627608A (en) | Preparation method for analgesic and antipyretic drug-analgin | |
| CN104059036B (en) | A kind of synthetic method of 5-[(dimethylamino) methyl]-2-furfuralcohol | |
| CN105601496A (en) | Preparation method of 3,4-dimethoxy phenylpropionic acid | |
| CN102070469B (en) | Resolution method for preparing optically pure metoprolol | |
| CN104151171A (en) | Method for preparing optically pure R-1-naphthylethylamine by splitting | |
| CN103242269A (en) | Preparation method of furfural | |
| CN104496825B (en) | The preparation method of 2-fluorine ethylamine hydrochloride | |
| CN204303239U (en) | A kind ofly promote the chemical experiment device that Synthesis Diethyl ether reaction forward is carried out | |
| CN102757367A (en) | Splitting process of racemic ethyl benzene sulfonic acid | |
| CN103804178A (en) | Synthesis method for caffeic acid | |
| CN103554019B (en) | A kind of synthetic method of tilbroquinol | |
| CN102659911A (en) | Method for extracting diosgenin from turmeric | |
| CN103113234B (en) | Method for synthesizing N-methyl paranitroaniline | |
| CN101659586B (en) | Extraction separation method for salicylic acid derivatives and corresponding phenol derivatives | |
| CN110818548A (en) | Method for preparing benzylidene acetone | |
| CN104610065B (en) | A kind of 2, the preparation method of 2 '-dinitrobenzene dibenzyl | |
| CN105622679A (en) | Preparation method of edible tannic acid | |
| CN104031001B (en) | Cook different foods in one pot and prepare the method for 2-[N-(2,4,5-trimethoxy-benzene methylamino) is amino]-4-ethoxycarbonyl-1,3-thiazoles | |
| CN103387519A (en) | Preparation method for 4-hydroxybenzyl cyanide | |
| CN102442961A (en) | Production method of 1-methyl tetrazole | |
| CN104326934A (en) | Preparation method of medical intermediate 2-chlorobenzene glycine methyl hydrochloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151202 Termination date: 20210709 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |