CN1687036A - Method for preparing 4,6 dichloropyridine - Google Patents
Method for preparing 4,6 dichloropyridine Download PDFInfo
- Publication number
- CN1687036A CN1687036A CN 200510077242 CN200510077242A CN1687036A CN 1687036 A CN1687036 A CN 1687036A CN 200510077242 CN200510077242 CN 200510077242 CN 200510077242 A CN200510077242 A CN 200510077242A CN 1687036 A CN1687036 A CN 1687036A
- Authority
- CN
- China
- Prior art keywords
- pyrimidine
- triphosgene
- dihydroxy
- trichloromethylchloroformate
- alkali
- 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
Abstract
The present invention relates to a method capable of using diphosgene or triphyosgene to chlorinate 4,6-dihydroxypyrimidine to obtain 4,6-dichloropyrimidine in the presence of proper alkali and a certain solvent or mixed solvent.
Description
Invention field
The present invention relates to use trichloromethylchloroformate or triphosgene, in the presence of suitable alkali, with 4, the 6-dihydroxy-pyrimidine is converted into 4, the method for 6-dichloro pyrimidine.4, the 6-dichloro pyrimidine can be used as the chemical intermediate of agricultural chemicals and medicine industry, as can be used for preparing sterilant Azoxystrobin, nucleoside analog and at activated compound of central nervous system (CNS) etc.
Background technology
Because 4, the 6-dichloro pyrimidine is purposes and importance economically widely, many synthesizing chlorinated pyrimidines particularly 4, the method for 6-dichloro pyrimidine has obtained exploitation.
WO 02/04428 (Chinese patent 01812416.X) has disclosed and has a kind ofly generated the imido acyl chloride compound by organic amide (as methane amide, ethanamide) and phosgene or by organic nitrile (as butyronitrile) and hcl reaction, the imido acyl chloride compound generates 4 with phosgene reaction subsequently, the preparation method of 6-dichloro pyrimidine.But this patent does not provide its result data (yield, content etc.).This method has big distance apart from industrialization.
Therefore by 4, the 6-dihydroxy-pyrimidine carries out chlorination reaction and generates 4, and the 6-dichloro pyrimidine is still the preparation method who generally adopts at present.
Relate generally in the presence of suitable alkali, by 4,6-dihydroxy-pyrimidine and phosphoryl chloride prepared in reaction 4, the method for 6-dichloro pyrimidine comprise Kenner etc. (J.CHEM.SOC., Nov.1943, pp574-575); Hull (J.CHEM.SOC., Aug.1951, p2214); English Patent GB2287466; United States Patent (USP) 5,583,226,5,723,612,6,018,045 etc.When the problem of these methods is to use on a large scale, produce quite a large amount of phosphoric acid by products, these by products must be disposed in a certain way.
The United States Patent (USP) 5,677,453 (Chinese patent 96109338.2) of Cramm etc. has proposed by 4, and 6-dihydroxy-pyrimidine and the reaction of excessive phosphoryl chloride are synthetic 4, the method for 6-dichloro pyrimidine.In this synthetic method, do not add alkali, but adopt excessive phosphorus and muriate (with respect to 4, the 6-dihydroxy-pyrimidine) to keep phosphorus trichloride to be in excess in chlorine in the reaction mixture by phosphorus trichloride and chlorine are added to.Yet this method need distill out large numbers of excessive phosphorus trichlorides and phosphoryl chloride at last, product 4, and the 6-dichloro pyrimidine also will be separated by distillation, therefore uses this method that bigger energy consumption problem is arranged.
WO such as Jones 95/29166 (United States Patent (USP) 5,750,694; 6-dihydroxy-pyrimidine and phosgene reaction preparation 4, the method for 6-dichloro pyrimidine are disclosed in the presence of suitable alkali by 4 Chinese patent 20031012068.7).Suitable alkali comprises tertiary amine and heterocyclic amine, and the molar ratio range of preferred bases and phosgene is 1: 10 to 10: 1.Preferred this is reflected in a kind of solvent or the mixed solvent and carries out.But, be that some height of the relevant phosgene transportation that produces therefrom, storage, use aspect are restrictive, the safety rule system of legislation on the other hand, thereby the use of this method is subjected to bigger restriction on the one hand because phosgene toxicity height.
Summary of the invention
The object of the present invention is to provide a kind of easy and simple to handle, be suitable for industrialized 4, the preparation method of 6-dichloro pyrimidine.
Of the present invention 4, the preparation method of 6-dichloro pyrimidine is in the presence of suitable alkali, with trichloromethylchloroformate or triphosgene processing 4,6-dihydroxy-pyrimidine.The trichloromethylchloroformate (superpalite) and the crystalline triphosgene (two (trichloromethyl) carbonic ether) that under the standard state are liquid are the stable phosgene substitutes.Under the condition that certain catalyzer exists, trichloromethylchloroformate and triphosgene can be converted into phosgene quantitatively.
4, the 6-dihydroxy-pyrimidine also can tautomeric forms exist, and comprises its all tautomeric forms.
Trichloromethylchloroformate and triphosgene are the phosgene substitutes of safety and stability, are convenient to store, transport and use.Have found that trichloromethylchloroformate or triphosgene can replace phosgene to finish chlorination 4, the 6-dihydroxy-pyrimidine generates 4, the reaction of 6-dichloro pyrimidine, and need be with the usage quantity (with respect to 4, the 6-dihydroxy-pyrimidine) of excessive several times.Triphosgene is used in special recommendation of the present invention, on the one hand because its better security can provide better yield and higher product purity owing to it on the other hand.Certainly using trichloromethylchloroformate to finish this reaction also is that right of the present invention is desired.
Suitable alkali is tertiary amine and heterocyclic amine.Tertiary amine comprises triethylamine, N, and accelerine, N, N-diisopropylethylamine, heterocyclic amine comprise pyridine, 2-picoline, 4-picoline, imidazoles and N-crassitude.Preferred triethylamine and pyridine.
Present method is preferably carried out in solvent or mixed solvent.Solvent can be aprotonic solvent, for example normal hexane, toluene, dimethylbenzene etc.; Chlorinated solvent is methylene dichloride, chloroform, 1 for example, 2-ethylene dichloride, chlorobenzene etc.Mixed solvent comprises the double solvents of being made up of above-mentioned two or more solvents, for example the mixture of normal hexane and ethylene dichloride.
The usage quantity of triphosgene is in present method: triphosgene: 4, and 6-dihydroxy-pyrimidine=2/3: 1 to 2: 1 (mol ratio), preferred 2/3: 1 to 1: 1.The usage quantity of trichloromethylchloroformate is: trichloromethylchloroformate: 4, and 6-dihydroxy-pyrimidine=1: 1 to 3: 1 (mol ratio), preferred 1: 1 to 2: 1.The usage quantity of alkali is in present method: alkali: triphosgene=1: 1 to 7: 1 (mol ratio), preferred 1: 1 to 3: 1; Or alkali: trichloromethylchloroformate=0.5: 1 to 5: 1 (mol ratio), preferred 0.5: 1 to 2: 1.Therefore their threes' ratio is preferred 4, and 6-dihydroxy-pyrimidine: suitable alkali: the mol ratio of triphosgene is 1: (2/3~3): (2/3~1); Or 4,6-dihydroxy-pyrimidine: suitable alkali: the mol ratio of trichloromethylchloroformate is 1: (0.5~4): (1~2).
Present method is preferably carried out in-20 ℃~120 ℃ temperature ranges, and especially 0~100 ℃, particularly 0~70 ℃.Reactant should place ice bath before heating.
Of the present invention in the presence of suitable alkali, with trichloromethylchloroformate or triphosgene chlorination 4, the 6-dihydroxy-pyrimidine generates 4, the method of 6-dichloro pyrimidine comprises trichloromethylchloroformate or triphosgene is added to 4, in the mixture of 6-dihydroxy-pyrimidine and alkali, also comprise alkali is added to 4, in the mixture of 6-dihydroxy-pyrimidine and trichloromethylchloroformate or triphosgene.The present invention can provide more than 85%, usually is to surpass 90% yield.
Embodiment
The following example is used to illustrate the present invention, but is not limited in the scope of illustrating in the claim.In the following example used plant and instrument with preceding should be dry, reaction will be carried out under anhydrous condition.
Embodiment 1
Imposing ice bath, stirring under the good condition, to 4,6-dihydroxy-pyrimidine (34.2g, 0.3mol) and triphosgene (90g, 0.3mol) in the mixture of ethylene dichloride (400ml), be added dropwise to triethylamine (126ml, 0.9mol) and the immiscible material of ethylene dichloride (150ml), temperature control is adding more than 30 minutes below 5 ℃.With the mixture of gained restir below 5 ℃ 30 minutes.Remove ice bath and at room temperature stirred 1 hour, and then stirred 2 hours at 60 ℃.The cooling reactant, then water (3 * 300ml) washings, water layer use again ethylene dichloride (2 * 100ml) extractions merge organic extract liquid, water (200ml) washing again, anhydrous magnesium sulfate drying, the precipitation drying obtains 4,6-dichloro pyrimidine solid crystal 42.3g.It is 99% that HPLC analyzes content, and productive rate is corresponding to 93.6% of theory.
Embodiment 2
Imposing ice bath, stirring under the good condition, to 4,6-dihydroxy-pyrimidine (34.2g, 0.3mol) and trichloromethylchloroformate (81g, 0.4mol) in the mixture of ethylene dichloride (400ml), be added dropwise to triethylamine (112ml, 0.8mol) and the immiscible material of ethylene dichloride (150ml), temperature control is adding more than 1 hour below 5 ℃.With the mixture of gained restir below 5 ℃ 30 minutes.Remove ice bath and at room temperature stirred 1 hour, and then stirred 1 hour, stirred 1 hour at 70 ℃ at 50 ℃.The cooling reactant, then water (3 * 300ml) washings, water layer use again ethylene dichloride (2 * 100ml) extractions merge organic extract liquid, water (200ml) washing again, anhydrous magnesium sulfate drying, the precipitation drying obtains 4,6-dichloro pyrimidine solid crystal 41.3g.It is 98% that HPLC analyzes content, and productive rate is corresponding to 90.7% of theory.
Embodiment 3
Imposing ice bath, stirring under the good condition, to 4,6-dihydroxy-pyrimidine (34.2g, 0.3mol) and triethylamine (126ml, 0.9mol) in the mixture of ethylene dichloride (250ml), be added dropwise to the triphosgene that is dissolved in the ethylene dichloride (300ml) (90g, 0.3mol), temperature control is adding more than 30 minutes below 5 ℃.With the mixture of gained restir below 5 ℃ 30 minutes.Remove ice bath and at room temperature stirred 1 hour, and then stirred 2 hours at 60 ℃.As described in embodiment 1, handle, obtain 4,6-dichloro pyrimidine solid crystal 42.7g.It is 99% that HPLC analyzes content, and productive rate is corresponding to 94.5% of theory.
Embodiment 4
Imposing ice bath, stirring under the good condition, to 4,6-dihydroxy-pyrimidine (34.2g, 0.3mol) and pyridine (73.5ml, 0.9mol) in the mixture of ethylene dichloride (250ml), be added dropwise to the triphosgene that is dissolved in the ethylene dichloride (300ml) (90g, 0.3mol), temperature control is adding more than 30 minutes below 5 ℃.With the mixture of gained restir below 5 ℃ 30 minutes.Remove ice bath and at room temperature stirred 1 hour, and then stirred 2 hours at 60 ℃.As described in embodiment 1, handle, obtain 4,6-dichloro pyrimidine solid crystal 42.0g.It is 99% that HPLC analyzes content, and productive rate is corresponding to 93.0% of theory.
Embodiment 5
Imposing ice bath, stirring under the good condition, to 4,6-dihydroxy-pyrimidine (34.2g, 0.3mol) and triethylamine (126ml, 0.9mol) in the mixture of normal hexane (250ml), be added dropwise to the triphosgene that is dissolved in the normal hexane (300ml) (90g, 0.3mol), temperature control is adding more than 30 minutes below 5 ℃.With the mixture of gained restir below 5 ℃ 30 minutes.Remove ice bath and at room temperature stirred 1 hour, and then stirred 2 hours at 60 ℃.The cooling reactant, then water (3 * 300ml) washings, water layer use again normal hexane (2 * 100ml) extractions merge organic extract liquid, water (200ml) washing again, anhydrous magnesium sulfate drying, the precipitation drying obtains 4,6-dichloro pyrimidine solid crystal 41.7g.It is 99% that HPLC analyzes content, and productive rate is corresponding to 92.5% of theory.
Claims (6)
1. one kind prepares 4, and the method for 6-dichloro pyrimidine is characterized in that in the presence of suitable alkali, handles 4, the 6-dihydroxy-pyrimidine with trichloromethylchloroformate or triphosgene.The usage quantity of triphosgene is: triphosgene: 4, and 6-dihydroxy-pyrimidine=2/3: 1 to 2: 1 (mol ratio), the usage quantity of trichloromethylchloroformate is: trichloromethylchloroformate: 4,6-dihydroxy-pyrimidine=1: 1 to 3: 1 (mol ratio); The usage quantity of alkali is: alkali: triphosgene=1: 1 to 7: 1 (mol ratio), or alkali: trichloromethylchloroformate=0.5: 1 to 5: 1 (mol ratio); Be reflected in solvent or the mixed solvent and carry out; Be reflected in-20 ℃~120 ℃ temperature ranges and carry out, reactant should place ice bath before heating.
2. according to the method for claim 1, it is characterized in that the usage quantity of triphosgene is: triphosgene: 4,6-dihydroxy-pyrimidine=2/3: 1 to 1: 1.The usage quantity of trichloromethylchloroformate is: trichloromethylchloroformate: 4, and 6-dihydroxy-pyrimidine=1: 1 to 2: 1.
3. according to the method for claim 1, it is characterized in that above-mentioned suitable alkali is tertiary amine and heterocyclic amine.The usage quantity of alkali is: alkali: triphosgene=1: 1 to 3: 1; Or alkali: trichloromethylchloroformate=0.5: 1 to 2: 1.
4. according to the method for claim 1, it is characterized in that trichloromethylchloroformate or triphosgene are added to 4, in the mixture of 6-dihydroxy-pyrimidine and alkali, also comprise alkali is added to 4, in the mixture of 6-dihydroxy-pyrimidine and trichloromethylchloroformate or triphosgene.
5. according to the method for claim 1, it is characterized in that being reflected in 0~100 ℃ of temperature range and carry out.
6. according to the method for claim 1, it is characterized in that being reflected in 0~70 ℃ of temperature range and carry out.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2005100772421A CN1321986C (en) | 2005-06-20 | 2005-06-20 | Method for preparing 4,6 dichloropyridine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2005100772421A CN1321986C (en) | 2005-06-20 | 2005-06-20 | Method for preparing 4,6 dichloropyridine |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1687036A true CN1687036A (en) | 2005-10-26 |
CN1321986C CN1321986C (en) | 2007-06-20 |
Family
ID=35305078
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2005100772421A Active CN1321986C (en) | 2005-06-20 | 2005-06-20 | Method for preparing 4,6 dichloropyridine |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1321986C (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101898925A (en) * | 2009-05-27 | 2010-12-01 | 韶远化学科技(上海)有限公司 | Green synthesis and industrialization method of chloro-substituted heterocyclic ring |
CN102070536A (en) * | 2011-02-14 | 2011-05-25 | 符爱清 | Method for preparing 2,4-dichloro-5-fluoropyrimidine compound |
CN104211648A (en) * | 2014-08-25 | 2014-12-17 | 天津市中央药业有限公司 | Synthetic process method of erlotinib intermediate |
CN105439963A (en) * | 2016-01-29 | 2016-03-30 | 河南中医学院 | Method for preparing 4,6-dichloropyrimidine under sulfuric acid catalysis |
CN105859636A (en) * | 2016-05-13 | 2016-08-17 | 安徽广信农化股份有限公司 | Synthesis method of 4,6-dichloropyrimidine with 4,6-dihydroxypyrimidine serving as midbody |
CN105859637A (en) * | 2016-05-13 | 2016-08-17 | 安徽广信农化股份有限公司 | Synthesis of 4,6-dichloropyrimidine and process optimization |
CN105906570A (en) * | 2016-05-13 | 2016-08-31 | 安徽广信农化股份有限公司 | Synthesis technology of 4,6-dichloropyrimidine |
CN106045917A (en) * | 2016-07-19 | 2016-10-26 | 安徽广信农化股份有限公司 | Synthetic process for preparing 4,6-dichloropyrimidine through one-step method |
CN106053691A (en) * | 2016-07-19 | 2016-10-26 | 安徽广信农化股份有限公司 | Method for measuring content of 4,6-dichloropyrimidine |
CN108341784A (en) * | 2017-01-24 | 2018-07-31 | 重庆紫光化工股份有限公司 | The synthetic method of 4,6- dichloro pyrimidines |
CN109796413A (en) * | 2019-01-24 | 2019-05-24 | 安徽广信农化股份有限公司 | A kind of triethylamine recovery process for the synthesis of 4,6- dichloro pyrimidine |
CN110204495A (en) * | 2019-06-03 | 2019-09-06 | 浙江工业大学 | A kind of preparation method of chloro polyhydroxy nitrogen heteroaromatic rings compound |
CN113912550A (en) * | 2021-11-11 | 2022-01-11 | 浙江先锋科技股份有限公司 | Method for preparing 2,4, 5-trichloropyrimidine |
CN114644591A (en) * | 2020-12-17 | 2022-06-21 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of dichloropyrimidine |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9408270D0 (en) * | 1994-04-26 | 1994-06-15 | Zeneca Ltd | Chemical process |
-
2005
- 2005-06-20 CN CNB2005100772421A patent/CN1321986C/en active Active
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101898925B (en) * | 2009-05-27 | 2013-10-02 | 韶远化学科技(上海)有限公司 | Green synthesis and industrialization method of chloro-substituted heterocyclic ring |
CN101898925A (en) * | 2009-05-27 | 2010-12-01 | 韶远化学科技(上海)有限公司 | Green synthesis and industrialization method of chloro-substituted heterocyclic ring |
CN102070536A (en) * | 2011-02-14 | 2011-05-25 | 符爱清 | Method for preparing 2,4-dichloro-5-fluoropyrimidine compound |
CN104211648A (en) * | 2014-08-25 | 2014-12-17 | 天津市中央药业有限公司 | Synthetic process method of erlotinib intermediate |
CN105439963B (en) * | 2016-01-29 | 2018-02-02 | 河南中医学院 | The method that 4,6 dichloro pyrimidines are prepared under sulfuric acid catalysis |
CN105439963A (en) * | 2016-01-29 | 2016-03-30 | 河南中医学院 | Method for preparing 4,6-dichloropyrimidine under sulfuric acid catalysis |
CN105859636A (en) * | 2016-05-13 | 2016-08-17 | 安徽广信农化股份有限公司 | Synthesis method of 4,6-dichloropyrimidine with 4,6-dihydroxypyrimidine serving as midbody |
CN105859637A (en) * | 2016-05-13 | 2016-08-17 | 安徽广信农化股份有限公司 | Synthesis of 4,6-dichloropyrimidine and process optimization |
CN105906570A (en) * | 2016-05-13 | 2016-08-31 | 安徽广信农化股份有限公司 | Synthesis technology of 4,6-dichloropyrimidine |
CN106045917A (en) * | 2016-07-19 | 2016-10-26 | 安徽广信农化股份有限公司 | Synthetic process for preparing 4,6-dichloropyrimidine through one-step method |
CN106053691A (en) * | 2016-07-19 | 2016-10-26 | 安徽广信农化股份有限公司 | Method for measuring content of 4,6-dichloropyrimidine |
CN108341784A (en) * | 2017-01-24 | 2018-07-31 | 重庆紫光化工股份有限公司 | The synthetic method of 4,6- dichloro pyrimidines |
CN109796413A (en) * | 2019-01-24 | 2019-05-24 | 安徽广信农化股份有限公司 | A kind of triethylamine recovery process for the synthesis of 4,6- dichloro pyrimidine |
CN110204495A (en) * | 2019-06-03 | 2019-09-06 | 浙江工业大学 | A kind of preparation method of chloro polyhydroxy nitrogen heteroaromatic rings compound |
CN114644591A (en) * | 2020-12-17 | 2022-06-21 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of dichloropyrimidine |
CN114644591B (en) * | 2020-12-17 | 2023-12-29 | 北京颖泰嘉和生物科技股份有限公司 | Process for preparing dichloropyrimidine |
CN113912550A (en) * | 2021-11-11 | 2022-01-11 | 浙江先锋科技股份有限公司 | Method for preparing 2,4, 5-trichloropyrimidine |
Also Published As
Publication number | Publication date |
---|---|
CN1321986C (en) | 2007-06-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1687036A (en) | Method for preparing 4,6 dichloropyridine | |
EP1658299B1 (en) | Method for the production of cyclic phosphonic acid anhydrides | |
Blagden et al. | Disappearing polymorphs and the role of reaction by-products: the case of sulphathiazole | |
CN100509771C (en) | Method for the production of sulphamic acid halogenides | |
EP2334645B1 (en) | Process for the synthesis of fluorinated cyclic compounds | |
EP2128122B1 (en) | Process for producing carboxylic acid chloride | |
CN1944408A (en) | Process for preparing symmetric tetrachloro pyridine | |
EP2655360B1 (en) | Method for producing n-sulfonyl-substituted oxindoles | |
Salinas-Hernández et al. | Synthesis, crystal structure and Hirshfeld surface analysis of the 1-(3, 6-dihydropyrimidin-2-yl) urea salt structurally related to dihydropyrimidinon-2-ylurea-type RNA-binding ligands | |
EP1731510B1 (en) | Process for producing n,n'-carbonyldiimidazole | |
CN109942416A (en) | A kind of preparation method of aroyl chloride | |
CN100427470C (en) | Synthesis technology of 1,3-dimethyl-2-chloroimidazoline chloride | |
US20080004444A1 (en) | Process for the Preparation of Phenyl 2-Pyrimidinyl Ketones and Their Novel Intermediates | |
CN100593538C (en) | Method for preparing N-substituted acryloyl-2,5-pyrrole-dione compound | |
DE102006027089A1 (en) | Process for the preparation of fluorinated molecules | |
JPS62249991A (en) | Production of oxadinobenzothiazine-6, 6-dioxide derivative | |
CN114644591B (en) | Process for preparing dichloropyrimidine | |
CN1301976C (en) | Synthesis of chlorinated pyrimidines | |
CN114644590B (en) | Process for preparing dichloropyrimidine | |
JP2000191634A (en) | Production of trifluoromethane sulfonyl chloride | |
EP1210337A1 (en) | Method for producing 4,6-dichloropyrimidine with sulfur compounds and phosphorous compounds | |
JPH1192121A (en) | Method for purifying phosphorus oxychloride | |
CN112654600A (en) | Preparation method of fluoroalkyl nitrile and application of fluoroalkyl nitrile in preparation of related fluoroalkyl tetrazole | |
CN118146056A (en) | Catalytic synthesis method of nitrogen-containing aromatic heterocyclic chlorinated organic compound | |
Ríos-Guerra et al. | Synthesis, Hirshfeld atom refinement of crystal structure, and Hirshfeld surface analysis of 5-ethoxycarbonyl-6-methyl-4-(2-(trifluoromethyl) phenyl)-3, 4-dihydropyrimidin-2-(1H)-one formic acid monosolvate |
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 | ||
C56 | Change in the name or address of the patentee | ||
CP03 | Change of name, title or address |
Address after: 213200 No. 95 Park North Road, Jintan Economic Development Zone, Jiangsu, China Patentee after: Jiangsu Institute of Ecomones Co.,Ltd. Address before: 213022 No. 98 Minjiang Road, Changzhou New District, Jiangsu, Changzhou Patentee before: Jiangsu Prov. Hormone Inst., Co., Ltd. |