CN103242152A - Method for synthesizing compound 3-(benzyloxy)-1-cyclobutanone - Google Patents
Method for synthesizing compound 3-(benzyloxy)-1-cyclobutanone Download PDFInfo
- Publication number
- CN103242152A CN103242152A CN2013101639200A CN201310163920A CN103242152A CN 103242152 A CN103242152 A CN 103242152A CN 2013101639200 A CN2013101639200 A CN 2013101639200A CN 201310163920 A CN201310163920 A CN 201310163920A CN 103242152 A CN103242152 A CN 103242152A
- Authority
- CN
- China
- Prior art keywords
- benzyloxy
- cyclobutanone
- ether
- phenmethyl
- compound
- 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
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a new method for synthesizing compound 3-(benzyloxy)-1-cyclobutanone, belonging to the technical field of organic synthesis. The method comprises the steps of performing five steps of reaction, namely etherification, halogenation, elimination, ring closure and dechloridation by taking halogenated methyl benzene as an initial raw material, and synthesizing to obtain the target product 3-(benzyloxy)-1-cyclobutanone with high yield and high purity. According to the method, the raw materials are low-cost and easily available, the reaction conditions are mild (especially the ring closure reaction is carried out at room temperature), the synthesis cost can be effectively lowered, the requirement on equipment can be reduced, and the method has good industrialization production prospects.
Description
Technical field
The invention belongs to the organic chemical synthesis field, relate to the synthetic method of a kind of compound 3-(benzyloxy)-1-cyclobutanone.
Background technology
Compound 3-(benzyloxy)-1-cyclobutanone is important organic synthesis intermediate, is the synthesis material of a lot of medicines and auxiliary, for example preparation of HIV-1 reverse transcriptase inhibitors, PLK inhibitor etc.; Also can be used for the preparation of medicine and medical developer.Its structural formula is:
Synthetic for 3-(benzyloxy)-1-cyclobutanone, domestic do not have a bibliographical information, abroad more existing documents or patent report,
Bioorganic ﹠amp; Biological and the pharmaceutical chemistry wall bulletin of Medicinal Chemistry Letters(), 22 (12), 4064-4067; 2012 have reported the synthetic method of 3-(benzyloxy)-1-cyclobutanone; be with semi-synthetic intermediate 2-benzyloxy-1; 3-dibromopropane and methyl sulfo-first sulfone are raw material; under the butyllithium effect; subzero 78 ℃ of degree reactions; make 1-methylsulfinyl-1-methylthio group-3-benzyloxy tetramethylene, obtained 3-(benzyloxy)-1-cyclobutanone by the perchloric acid oxidation then.Because semi-synthetic intermediate 2-benzyloxy-1,3-dibromopropane and methyl sulfo-first sulfone are difficult in market buy, cost is higher, and the condition harshness, is not easy to amplify produce; Total recovery is not high yet.Its circuit is as follows:
WO2009114512 provides the method for a kind of synthetic 3-(benzyloxy)-1-cyclobutanone; be raw material with brooethyl propylene oxide and cylite; reaction makes 2-benzyloxy-1 under 160 ℃ under the effect of mercury chloride; the 3-dibromopropane; again under the butyllithium effect; 2-benzyloxy-1; 3-dibromopropane and methyl sulfo-first sulfone are in-78 ℃ of reactions down; make 1-methylsulfinyl-1-methylthio group-3-benzyloxy tetramethylene, obtained 3-(benzyloxy)-1-cyclobutanone by the perchloric acid oxidation then, this method has been finished reaction by three steps; purifying products uses column chromatography; the cost height, yield is low, is unfavorable for suitability for industrialized production.Its synthetic line is as follows:
Summary of the invention
The objective of the invention is the problem at the prior art existence, the novel method of synthetic compound 3-(benzyloxy)-1-cyclobutanone that a kind of cost is low, yield is high is provided.
The synthetic method of The compounds of this invention 3-(benzyloxy)-1-cyclobutanone comprises following processing step:
(1) preparation of BOE
Under the mineral alkali condition, monochloromethyl benzene and ethylene glycol are with the mol ratio of 1:2 ~ 1:10, and ℃ reaction 1 ~ 6h in room temperature ~ 70 obtains BOE---intermediate 2;
Described monochloromethyl benzene is chloromethylbenzene or brooethyl benzene;
Described mineral alkali is sodium hydroxide or potassium hydroxide; The molar weight of mineral alkali is 1 ~ 1.5 times of monochloromethyl benzene.
(2) preparation of haloethyl phenmethyl ether
In organic solvent, BOE, triphenylphosphine, halogen in room temperature reaction 1 ~ 5h, obtain haloethyl phenmethyl ether---intermediate 3 with the mol ratio of 1:1:0.5 ~ 1:1.5:1.5;
Described halogen is chlorine, bromine or iodine;
Described organic solvent is methylene dichloride, trichloromethane or tetracol phenixin.
(3) preparation of phenmethyl vinyl ether
Be solvent with the trimethyl carbinol, haloethyl phenmethyl ether and potassium tert.-butoxide are with the mol ratio of 1:1.0 ~ 1:1.5, and ℃ reaction 2 ~ 8h in room temperature ~ 70 obtains the phenmethyl vinyl ether---intermediate 4.
(4) benzyloxy-2, the preparation of 2-dichloro cyclobutanone
Under the nitrogen protection, in organic solvent, be catalyzer with the zinc-copper, phenmethyl vinyl ether and trichoroacetic chloride are with the mol ratio of 1:1 ~ 1:3, and room temperature reaction 1 ~ 3h gets benzyloxy-2,2-dichloro cyclobutanone---intermediate 5;
Or under the nitrogen protection, in organic solvent, be catalyzer with the zinc-copper, make phenmethyl vinyl ether, trichoroacetic chloride, phosphorus oxychloride with the mol ratio of 1:1:0.2 ~ 1:3:0.3, in room temperature reaction 0.5 ~ 3.0h, get benzyloxy-2,2-dichloro cyclobutanone---intermediate 5;
Described zinc-copper catalyst consumption is 0.4 ~ 1 times of phenmethyl vinyl ether molar weight;
Described organic solvent is methyl tertiary butyl ether, ether or isopropyl ether.
(5) preparation of 3-(benzyloxy)-1-cyclobutanone
Be solvent with the aqueous acetic acid, benzyloxy-2,2-dichloro cyclobutanone and metallic zinc are with the mol ratio of 1:2 ~ 1:3.5, and room temperature reaction 1 ~ 3h gets final product 6---3-(benzyloxy)-1-cyclobutanone;
In the described aqueous acetic acid, the percent by volume of acetic acid is 40 ~ 60%.
The synthetic route of 3-of the present invention (benzyloxy)-1-cyclobutanone is as follows:
Synthetic product of the present invention is through proton nmr spectra, and high resolution gas chromatography is measured, and shows that the finished product that the present invention synthesizes are 3-(benzyloxy)-1-cyclobutanone, and purity is 95 ~ 98%, and yield is more than 50%.
The present invention is starting raw material with monochloromethyl benzene, pass through into ether, halo, elimination, pass ring, dechlorination five steps reaction, high yield, high purity have been synthesized target product 3-(benzyloxy)-1-cyclobutanone, its raw material is cheap and easy to get, reaction conditions gentleness (particularly ring closure reaction is at room temperature to carry out), effectively reduce synthetic cost, reduced the requirement to equipment simultaneously, have good industrial production foreground.
Description of drawings
Fig. 1 is the gas-chromatography of synthetic product of the present invention;
The nuclear magnetic spectrogram that Fig. 2 synthesizes for the present invention.
Embodiment
Be further described below by the synthetic method of specific embodiment to 3-of the present invention (benzyloxy)-1-cyclobutanone.
(1) BOE is synthetic
In the reaction flask that thermometer, prolong are housed, add 800mL(15.74mol) ethylene glycol, 285.6g(7.14mol) sodium hydroxide, be stirred to dissolving in 40 ℃, slowly add brooethyl benzene 684g(4mol), stirred 1 hour, add 2000mL water, use extracted with diethyl ether, anhydrous sodium sulfate drying, precipitation, get BOE 556g, yield 91%;
(2) the bromo ethyl phenenyl methyl ether is synthetic
Take by weighing triphenylphosphine 832g(3.58mol) be dissolved among the chloroform 2000mL, drip bromine 290g(1.79mol) to the solution becomes yellowly, drip 400g(2.62mol under the room temperature) BOE, 400mL triethylamine and 600mL chloroform mixed solution, dripped off in 1 hour, reacted 0.5 hour, the decompression precipitation, residuum adds chloroform 1000mL, wash anhydrous sodium sulfate drying, distillation with water, get product bromo ethyl phenenyl methyl ether 544g, yield 97%;
(3) the phenmethyl vinyl ether is synthetic
Take by weighing bromo ethyl phenenyl methyl ether 450g(2.1mol) be dissolved in the 1000mL trimethyl carbinol, add potassium tert.-butoxide 330g(2.9mol), 55 ℃ of stirring reactions 2 hours, reaction solution is poured in the 3000mL water, uses petroleum ether extraction, washing, anhydrous sodium sulfate drying, precipitation gets phenmethyl vinyl ether 247g, yield 88%;
(4) benzyloxy-2,2-dichloro cyclobutanone synthetic
Under nitrogen protection, with 160g(1.2mol) the phenmethyl vinyl ether is dissolved in the 3000mL ether, adds zinc-copper catalyzer 50g(0.77mol), drip 300mL(2.7mol under the room temperature) trichoroacetic chloride and 30mL(0.33mol) phosphorus oxychloride, stirred 1 hour, and added sodium bicarbonate aqueous solution 1000mL, get with sherwood oil, washing, anhydrous sodium sulfate drying, precipitation gets benzyloxy-2,2-dichloro cyclobutanone 250g, yield 85%;
(5) 3-(benzyloxy)-1-cyclobutanone is synthetic
With 250g(1mol) benzyloxy-2,2-dichloro cyclobutanone is dissolved in 2000mL water and the 2000mL acetic acid, slowly add zinc powder 200g(3.07mol), stirring at room 1 hour is filtered, filtrate is used extracted with diethyl ether, washing, anhydrous sodium sulfate drying, distillation, get 3-(benzyloxy)-1-cyclobutanone 150g, yield 84%.The end product total recovery is 55.46%.
(1) BOE is synthetic
Thermometer is being housed, add 800mL(15.74mol in the reaction flask of prolong) ethylene glycol, 400g(7.14mol) potassium hydroxide, 70 ℃ are stirred to dissolving, slowly add 522.0g(4.1mol) chloromethylbenzene, stirred 1 hour, and added the water of 2000mL, use extracted with diethyl ether, anhydrous sodium sulfate drying, precipitation gets BOE 586g, yield 96%.
(2) the bromo ethyl phenenyl methyl ether is synthetic
Triphenylphosphine 832g(3.58mol) be dissolved among the methylene dichloride 3000mL Dropwise 5 72g(3.5mol) to the solution becomes yellowly, drip 400g(2.62mol under the room temperature) BOE, 400mL triethylamine and 600mL methylene dichloride mixed solution, dripped off in 1 hour, and dripped off reaction 0.5 hour, the decompression precipitation, residuum adds ether 1000mL, wash anhydrous sodium sulfate drying, distillation with water, get product bromo ethyl phenenyl methyl ether 521g, yield 93%.
(3) the phenmethyl vinyl ether is synthetic
Take by weighing bromo ethyl phenenyl methyl ether 450g(2.1mol) be dissolved in the 1000mL trimethyl carbinol, add potassium tert.-butoxide 330g(2.9mol), 60 ℃ of stirring reactions 2 hours, reaction solution is poured in the 3000mL water, uses petroleum ether extraction, washing, anhydrous sodium sulfate drying, precipitation gets phenmethyl vinyl ether 252g, yield 90%.
(4) 3-(benzyloxy)-1-cyclobutanone is synthetic
Under nitrogen protection, with 160g(1.2mol) the phenmethyl vinyl ether is dissolved in the 3000mL ether, adds zinc-copper catalyzer 50g(0.77mol), drip 300mL(2.7mol under the room temperature) trichoroacetic chloride, stirred 1 hour, and added sodium bicarbonate aqueous solution 1000mL, get with sherwood oil, washing, anhydrous sodium sulfate drying, precipitation gets benzyloxy-2,2-dichloro cyclobutanone 232g, yield 79%;
(5) 3-(benzyloxy)-1-cyclobutanone is synthetic
With 125g(0.5mol) benzyloxy-2,2-dichloro cyclobutanone is dissolved in 1000mL water and the 1000mL acetic acid, slowly add zinc powder 100g(1.5mol), stirring at room 1 hour is filtered, filtrate is used extracted with diethyl ether, washing, anhydrous sodium sulfate drying, distillation, get 3-(benzyloxy)-1-cyclobutanone 77.6g, yield 87%.The end product total recovery is 55.22%.
(1) BOE is synthetic
Thermometer is being housed, add 800mL(15.74mol in the reaction flask of prolong) ethylene glycol, 400g(7.14mol) potassium hydroxide, stirring at room to the dissolving, slowly add 522.0g(4.1mol) chloromethylbenzene, stirred 6 hours, and added the water of 2000mL, use extracted with diethyl ether, anhydrous sodium sulfate drying, precipitation gets BOE 525g, yield 86%.
(2) the bromo ethyl phenenyl methyl ether is synthetic
Triphenylphosphine 832g(3.58mol) be dissolved among the methylene dichloride 3000mL Dropwise 5 72g(3.5mol) to the solution becomes yellowly, drip 400g(2.62mol under the room temperature) BOE, 400mL triethylamine and 600mL methylene dichloride mixed solution, dripped off in 1 hour, and dripped off reaction 0.5 hour, the decompression precipitation, residuum adds ether 1000mL, wash anhydrous sodium sulfate drying, distillation with water, get product bromo ethyl phenenyl methyl ether 521g, yield 93%.
(3) the phenmethyl vinyl ether is synthetic
Take by weighing bromo ethyl phenenyl methyl ether 450g(2.1mol) be dissolved in the 1000mL trimethyl carbinol, add potassium tert.-butoxide 330g(2.9mol), stirring at room reaction 8 hours, reaction solution is poured in the 3000mL water, uses petroleum ether extraction, washing, anhydrous sodium sulfate drying, precipitation gets phenmethyl vinyl ether 246g, yield 88%.
(4) benzyloxy-2,2-dichloro cyclobutanone synthetic
Under nitrogen protection, with 160g(1.2mol) the phenmethyl vinyl ether is dissolved in the 3000mL ether, adds zinc-copper catalyzer 78g(1.2mol), drip 300mL(2.7mol under the room temperature) trichoroacetic chloride, stirred 1 hour, and added sodium bicarbonate aqueous solution 1000mL, get with sherwood oil, washing, anhydrous sodium sulfate drying, precipitation gets benzyloxy-2,2-dichloro cyclobutanone 246g, yield 84%;
(5) 3-(benzyloxy)-1-cyclobutanone is synthetic
With 125g(0.5mol) benzyloxy-2,2-dichloro cyclobutanone is dissolved in 1000mL water and the 1000mL acetic acid, slowly add zinc powder 112g(1.75mol), stirring at room 1.5 hours is filtered, filtrate is used extracted with diethyl ether, washing, anhydrous sodium sulfate drying, distillation, get 3-(benzyloxy)-1-cyclobutanone 78.5g, yield 88%.The end product total recovery is 52%.
Claims (8)
1. the synthetic method of compound 3-(benzyloxy)-1-cyclobutanone comprises following processing step:
(1) preparation of BOE: under the mineral alkali condition, monochloromethyl benzene and ethylene glycol are with the mol ratio of 1:2~1:10, and ℃ reaction 1~6h obtains BOE in room temperature~70;
(2) preparation of haloethyl phenmethyl ether: in organic solvent, BOE, triphenylphosphine, halogen in room temperature reaction 1~5h, obtain haloethyl phenmethyl ether with the mol ratio of 1:1:0.5~1:1.5:1.5;
(3) preparation of phenmethyl vinyl ether: be solvent with the trimethyl carbinol, haloethyl phenmethyl ether and potassium tert.-butoxide are with the mol ratio of 1:1.0~1:1.5, and ℃ reaction 2~8h obtains the phenmethyl vinyl ether in room temperature~70;
(4) benzyloxy-2, the preparation of 2-dichloro cyclobutanone: under the nitrogen protection, in organic solvent, be catalyzer with the zinc-copper, phenmethyl vinyl ether and trichoroacetic chloride are with the mol ratio of 1:1~1:3, and room temperature reaction 1~3h gets benzyloxy-2,2-dichloro cyclobutanone; Or under the nitrogen protection, in organic solvent, be catalyzer with the zinc-copper, make phenmethyl vinyl ether, trichoroacetic chloride, phosphorus oxychloride with the mol ratio of 1:1:0.2~1:3:0.3, in room temperature reaction 0.5~3.0h, get benzyloxy-2,2-dichloro cyclobutanone;
(5) preparation of 3-(benzyloxy)-1-cyclobutanone: be solvent with the aqueous acetic acid, benzyloxy-2,2-dichloro cyclobutanone and metallic zinc are with the mol ratio of 1:2~1:3.5, and room temperature reaction 1~3h gets end product 3-(benzyloxy)-1-cyclobutanone.
2. the synthetic method of compound 3-(benzyloxy)-1-cyclobutanone according to claim 1, it is characterized in that: the described monochloromethyl benzene of step (1) is chloromethylbenzene or brooethyl benzene.
3. the synthetic method of compound 3-(benzyloxy)-1-cyclobutanone according to claim 1, it is characterized in that: the described mineral alkali of step (1) is sodium hydroxide or potassium hydroxide; The molar weight of mineral alkali is 1~1.5 times of monochloromethyl benzene.
4. the synthetic method of compound 3-(benzyloxy)-1-cyclobutanone according to claim 1, it is characterized in that: the described halogen of step (2) is chlorine, bromine or iodine.
5. the synthetic method of compound 3-(benzyloxy)-1-cyclobutanone according to claim 1, it is characterized in that: the described organic solvent of step (2) is methylene dichloride, trichloromethane or tetracol phenixin.
6. the synthetic method of compound 3-(benzyloxy)-1-cyclobutanone according to claim 1, it is characterized in that: the described zinc-copper catalyst consumption of step (4) is 0.4~1 times of phenmethyl vinyl ether molar weight.
7. the synthetic method of compound 3-(benzyloxy)-1-cyclobutanone according to claim 1, it is characterized in that: the described organic solvent of step (4) is methyl tertiary butyl ether, ether or isopropyl ether.
8. the synthetic method of compound 3-(benzyloxy)-1-cyclobutanone according to claim 1, it is characterized in that: in the described aqueous acetic acid of step (5), the percent by volume of acetic acid is 40~60%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310163920.0A CN103242152B (en) | 2013-05-07 | 2013-05-07 | The synthetic method of compound 3-(benzyloxy)-1-cyclobutanone |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310163920.0A CN103242152B (en) | 2013-05-07 | 2013-05-07 | The synthetic method of compound 3-(benzyloxy)-1-cyclobutanone |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103242152A true CN103242152A (en) | 2013-08-14 |
CN103242152B CN103242152B (en) | 2015-12-02 |
Family
ID=48922061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310163920.0A Expired - Fee Related CN103242152B (en) | 2013-05-07 | 2013-05-07 | The synthetic method of compound 3-(benzyloxy)-1-cyclobutanone |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103242152B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002060362A (en) * | 2000-08-17 | 2002-02-26 | Nippon Synthetic Chem Ind Co Ltd:The | Method for producing ethylene glycol monobenzyl ether |
WO2004056725A1 (en) * | 2002-12-20 | 2004-07-08 | Ge Healthcare Limited | Solid-phase preparation of 18f-labelled amino acids |
WO2011006000A1 (en) * | 2009-07-08 | 2011-01-13 | Haiyan Liu | Berberine derivatives useful for modulating lipid levels and their methods of synthesis |
-
2013
- 2013-05-07 CN CN201310163920.0A patent/CN103242152B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002060362A (en) * | 2000-08-17 | 2002-02-26 | Nippon Synthetic Chem Ind Co Ltd:The | Method for producing ethylene glycol monobenzyl ether |
WO2004056725A1 (en) * | 2002-12-20 | 2004-07-08 | Ge Healthcare Limited | Solid-phase preparation of 18f-labelled amino acids |
WO2011006000A1 (en) * | 2009-07-08 | 2011-01-13 | Haiyan Liu | Berberine derivatives useful for modulating lipid levels and their methods of synthesis |
Non-Patent Citations (2)
Title |
---|
LAURENT MARTARELLO等: "Synthesis of syn- and anti-1-Amino-3-[18F]fluoromethyl-cyclobutane-1-carboxylic Acid (FMACBC), Potential PET Ligands for Tumor Detection", 《J. MED. CHEM.》, vol. 45, no. 11, 26 April 2002 (2002-04-26), pages 2250 - 2259, XP 002276531, DOI: doi:10.1021/jm010242p * |
VIJAY KAIWAR等: "Synthesis of 9- [ cis-3-(hydroxymethyl)cyclobutyl] -adenine and-guanine", 《J . CHEM. SOC. PERKIN TRANS.》, vol. 1, 31 December 1995 (1995-12-31), pages 2281 - 2287, XP 000926767, DOI: doi:10.1039/p19950002281 * |
Also Published As
Publication number | Publication date |
---|---|
CN103242152B (en) | 2015-12-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107629032A (en) | A kind of preparation method of cyclic sulfates | |
CN103641722B (en) | A kind of production method of adjacent nitro bromobenzyl | |
CN104496959A (en) | Method for preparing cyclic carbonate by reacting normal pressure carbon dioxide with epoxide | |
CN102850325B (en) | Preparation method of Dabigatran etexilate key intermediate | |
CN106748921B (en) | A kind of virtue sulfuryl difluoroacetic acid salt compounds, preparation method and applications | |
CN108558916B (en) | Synthesis process of p-phenylbutoxy benzoic acid | |
CN105218544A (en) | A kind of synthetic method of Eliquis intermediate | |
CN103242152B (en) | The synthetic method of compound 3-(benzyloxy)-1-cyclobutanone | |
CN104447621A (en) | Preparation method of Vortioxetine | |
CN104447277B (en) | A kind of method of coproduction capacitor stage 2-butyl sebacic acid and 2,9-dibutyl sebacic acid | |
CN102503794B (en) | Method for preparing fluorine-containing substituted phenyl ketone | |
Crumrine et al. | Catalytic decomposition of diphenyldiazomethane by Lewis acids, cyclopropanation reactions of a diphenylcarbenoid species | |
CN110041176B (en) | Preparation method of thermosensitive paper sensitizer ethylene glycol diphenyl ether | |
CN109422709A (en) | A kind of synthetic method of oxetanone | |
CN103145540B (en) | The preparation method of a kind of optical activity 7-halo-6-hydroxyl-heptan-3-alkene-2-ketone | |
CN101768109A (en) | Bi-methyl fluoride sulfones compound and application thereof | |
CN104529726A (en) | Preparation method of hydroxyacetophenone | |
CN104961629A (en) | Synthetic method of pentafluorophenol | |
CN104262450A (en) | Method for preparing and refining eplerenone | |
CN103539666B (en) | Preparation method of 2-methyl-3-butenoic acid ester | |
CN104557653A (en) | Preparation method for 7-methyl-aza-bicyclo[4,1,0]heptane | |
CN102276550B (en) | The synthetic method of 2-aryl nitrile thiazole derivative and intermediate thereof | |
CN103193729B (en) | Preparation method of (2-hydrocarbon sulfenyl thiazoline-5-yl) methanol and carboxylic ester thereof | |
CN106316745A (en) | Preparing method of biphenyl compound | |
CN106365998A (en) | Preparation method of iodomethyl pivalate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C41 | Transfer of patent application or patent right or utility model | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20150915 Address after: 730010 Gansu Province Chengguan District of Lanzhou City Yantan Power Plant Road Building Room 2404 Applicant after: LANZHOU AGLI BIOCHEMICAL TECHNOLOGY Co.,Ltd. Address before: 730020, Gansu Province, Chengguan District, Lanzhou Province, 177 section 7, 3 floor, 301 Jia Lu Road House Applicant before: LANZHOU SHUYA BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
|
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151202 |