CN102390874A - Preparation method of potassium chloroplatinite - Google Patents

Preparation method of potassium chloroplatinite Download PDF

Info

Publication number
CN102390874A
CN102390874A CN2011102182566A CN201110218256A CN102390874A CN 102390874 A CN102390874 A CN 102390874A CN 2011102182566 A CN2011102182566 A CN 2011102182566A CN 201110218256 A CN201110218256 A CN 201110218256A CN 102390874 A CN102390874 A CN 102390874A
Authority
CN
China
Prior art keywords
acid
solution
platinum
reaction
potassium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011102182566A
Other languages
Chinese (zh)
Inventor
苏曼
尚林峰
孙庆伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Boyuan Chemical Co Ltd
Original Assignee
Shandong Boyuan Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shandong Boyuan Chemical Co Ltd filed Critical Shandong Boyuan Chemical Co Ltd
Priority to CN2011102182566A priority Critical patent/CN102390874A/en
Publication of CN102390874A publication Critical patent/CN102390874A/en
Pending legal-status Critical Current

Links

Abstract

The invention discloses a preparation method of potassium chloroplatinite. The preparation method comprises the following steps of: (1) putting spongy platinum and nitromurlatic acid to a reactor, heating to 100 DEG C and reacting to prepare a chloroplatinic acid solution; (2) adding a 10% oxalic acid solution to the chloroplatinic acid solution in the step (1), and reducing to generate a chloroplatinous acid solution; and (3), adding a saturated potassium chloride solution to the chloroplatinous acid solution in the step (2) to generate the potassium chloroplatinite, wherein the reaction temperature in the step (2) is 50-60 DEG C, the reaction temperature in the step (2) is 50-60 DEG C, and reactions of all steps are carried out in the same reactor, wherein the weight ratio of the platinum to the nitromurlatic acid to the oxalic acid to the potassium chloride is 1: (8-10): (0.64-0.66): (0.76-0.8). The potassium chloroplatinite prepared by using the method disclosed by the invention has the advantages of low cost, low pollution and simpleness in operation.

Description

A kind of preparation method of potassium chloroplatinite
Technical field
The present invention relates to medicine intermediate, is a kind of preparation method of medicine intermediate potassium chloroplatinite.
Background technology
Potassium chloroplatinite is the important midbody of a kind of preparation platinum series antineoplastic medicament (like carboplatin, cis-platinum, oxaliplatin etc.).Since U.S. scientist Rosenberg in 1967 finds that cis-platinum has the activity that suppresses the tumour cell growth; Research and the clinical application of platinum medicine in oncotherapy obtained development rapidly; Characteristics such as platinum series antineoplastic medicament is wide with its antitumor spectrum, anti-tumor activity is strong, untoward reaction is low; Become a line medication of a lot of malignant tumor chemotherapies of generally acknowledging in the world at present, such clinical drug consumption increases year by year.In order to reduce patient's treatment cost, various countries are all actively producing platinum series antineoplastic medicament.The preparation method of the key intermediate potassium chloroplatinite in the disclosed platinum medicine all exists and adopts hydrazine hydrogen chloride, two hydrazine hydrogen chloride to make reductive agent in deficiency: CN101279772b and the JN03131529A disclosed method respectively; Other has bibliographical information to adopt Hydrazine Hydrate 80 or hydrazonium sulfate as reductive agent, and hydrazine is to have genotoxic material, and is residual as if in the end product platinum medicine, having, and poisons bigger to human body; Simultaneously, the preparation method adopts stepwise synthesis, needs 2-3 reactor drum to accomplish; I.e. reaction obtains needing purified processing to obtain the potassium platinichloride solid behind the potassium platinichloride solution; Drop into next reaction vessel again and carry out reduction reaction, complicated operation, production cost is high; Serious environment pollution needs higher cost of investment and running cost in Pollution abatement.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of potassium chloroplatinite, the cost of the potassium chloroplatinite of this method preparation of usefulness is low, pollutes low, simple to operate.
The present invention is for realizing above-mentioned purpose, and realize through following technical scheme: a kind of preparation method of potassium chloroplatinite comprises the steps:
1. spongy platinum and chloroazotic acid are inserted in the reactor drum, be heated to, produce platinum acid chloride solution to 100 ℃ of reactions;
2. get 10% oxalic acid aqueous solution and join in the platinum acid chloride solution of step in 1., reduction generates chloro-platinous acid solution;
3. the potassium chloride saturated aqueous solution joins in the chloro-platinous acid solution of step in 2., generates potassium chloroplatinite;
The temperature of reaction of step in 2. is 50 ℃-60 ℃; The temperature of reaction of step in 2. is 50 ℃-60 ℃;
The reaction of above-mentioned each step is all carried out in same reactor drum, wherein platinum: chloroazotic acid: oxalic acid: the weight ratio of Repone K is 1:8-10:0.64-0.66:0.76-0.8.
The preparation method of described a kind of potassium chloroplatinite, concrete steps are following:
1. get 1000 gram spongy platinums and divide and slowly join for 5 times in the 9000 gram chloroazotic acid, add 200 grams at every turn, add in 10 minutes; Be heated to 100 ℃ of reactions then, after the platinum total overall reaction dissolving, with the gained solution concentration to there being crystal to separate out; Drip again till concentrated hydrochloric acid (concentration is 37.5%) to system no longer includes brown gas and emerge; The reconcentration reaction solution drips purified water then and catches up with acid to there being crystal to separate out, and obtains platinum acid chloride solution;
2. get oxalic acid 655 gram and be made into 10% the aqueous solution; With 10% oxalic acid aqueous solution 50 ℃-60 ℃, be added drop-wise in 1 hour under stirring in the platinum acid chloride solution that step obtains in 1.; Dripped the continued stirring reaction 3 hours, half of concentration of reaction solution to original volume obtains chloro-platinous acid solution;
3. potassium chloride 770 gram is mixed with saturated aqueous solution, with the Repone K saturated aqueous solution 40 ℃-50 ℃, stir and be added drop-wise to down in the chloro-platinous acid solution of step in 2., drip off continued and reacted 1 hour, make to react completely; Then 1/3rd of concentration of reaction solution to original volume, be cooled to normal temperature, drip the ethanol that concentrates the long-pending 2 times of amounts of afterreaction liquid again; Separate out crystal, be cooled to 0-5 ℃, filter; With the ice ethanol filter wash cake that concentrates the long-pending 0.3 times of amount of afterreaction liquid, after the vacuum-drying, obtain potassium chloroplatinite 2053 grams again.
Preparing method of the present invention is the new technical scheme of making to the deficiency of prior art.The preparation method of the present invention and existing reaction of spongy platinum and chloroazotic acid is generated Platinic chloride, adds that Repone K generates potassium platinichloride, the method that generates potassium chloroplatinite with hydrazine hydrogen chloride or two hydrazine hydrogen chloride or Hydrazine Hydrate 80 or hydrazonium sulfate reduction again is diverse; After prior art need be come out the potassium platinichloride purifying; Restore into potassium chloroplatinite; Preparing method of the present invention then is to be starting raw material with the spongy platinum, and material such as used raw material, reductive agent all generates the finished product in this reactor drum in this method in a reactor drum.Preparing method of the present invention thoroughly avoided in the production process because of shift, purifying mass causes such as deficiencies such as product loss, processing safety are low, seriously polluted; Facility investment is few; Significantly reduced production cost; Pollution-free to production environment, and the disposal of pollutants of production process is extremely low; The reductive agent that preparation method of the present invention selects for use is an oxalic acid, has thoroughly avoided the residual of hydrazine in the end product platinum series antineoplastic medicament, has reduced the infringement to human body; Oxalic acid is the mildness reductive agent in addition, and reaction is easy to control; With the potassium chloroplatinite product yield of method of the present invention preparation up to more than 96%.
Embodiment
The preparing method's of potassium chloroplatinite according to the invention chemical reaction process is: spongy platinum and chloroazotic acid reaction are generated Platinic chloride, generate chloro-platinous acid with the oxalic acid reduction again, generate potassium chloroplatinite with the Repone K reaction then:
3Pt?+?4HNO 3?+?18HCl?=?3H 2PtCl 6?+?4NO↑?+?8H 2O
H 2PtCl 6?+?H 2C 2O 4?=?H 2PtCl 4?+?2HCl?+?2CO 2
H 2PtCl 4?+?2KCl?=?K 2PtCl 4?+?2HCl。
The preparation method of potassium chloroplatinite of the present invention comprises the steps:
1. spongy platinum and chloroazotic acid are inserted in the reactor drum, be heated to, produce platinum acid chloride solution to 100 ℃ of reactions;
2. get 10% oxalic acid aqueous solution and join in the platinum acid chloride solution of step in 1., reduction generates chloro-platinous acid solution;
3. the potassium chloride saturated aqueous solution joins in the chloro-platinous acid solution of step in 2., generates potassium chloroplatinite;
The temperature of reaction of step in 2. is 50 ℃-60 ℃; The temperature of reaction of step in 2. is 50 ℃-60 ℃;
The reaction of above-mentioned each step is all carried out in same reactor drum, wherein platinum: chloroazotic acid: oxalic acid: the weight ratio of Repone K is 1:8-10:0.64-0.66:0.76-0.8.
The preparing method's of potassium chloroplatinite according to the invention preferred concrete steps are:
1. get 1000 gram spongy platinums and divide and slowly join for 5 times in the 9000 gram chloroazotic acid, add 200 grams at every turn, add in 10 minutes; Be heated to 100 ℃ of reactions then, treat platinum total overall reaction dissolving after, with the gained solution concentration to there being crystal to separate out; Drip again till concentrated hydrochloric acid (concentration is 37.5%) to system no longer includes brown gas and emerge; The reconcentration reaction solution drips purified water then and catches up with acid to there being crystal to separate out, and obtains platinum acid chloride solution;
2. get oxalic acid 655 gram and be made into 10% the aqueous solution; With 10% oxalic acid aqueous solution 50 ℃-60 ℃, be added drop-wise in 1 hour under stirring in the platinum acid chloride solution that step obtains in 1.; Dripped the continued stirring reaction 3 hours, half of concentration of reaction solution to original volume obtains chloro-platinous acid solution;
3. potassium chloride 770 gram is mixed with saturated aqueous solution, with the Repone K saturated aqueous solution 40 ℃-50 ℃, stir and be added drop-wise to down in the chloro-platinous acid solution of step in 2., drip off continued and reacted 1 hour, make to react completely; Then 1/3rd of concentration of reaction solution to original volume, be cooled to normal temperature, drip the ethanol that concentrates the long-pending 2 times of amounts of afterreaction liquid again; Separate out crystal, be cooled to 0-5 ℃, filter; With the ice ethanol filter wash cake that concentrates the long-pending 0.3 times of amount of afterreaction liquid, after the vacuum-drying, obtain potassium chloroplatinite 2053 grams again.Product is 46.7% through detecting platinum content, potassium content is 18.6%, and product yield is 96.5%.
The preparation method of potassium chloroplatinite according to the invention can also have following preferred concrete steps:
1. 500 gram spongy platinums are divided slowly to join for 5 times in the 4000 gram chloroazotic acid, add 100 grams at every turn, add in 10 minutes; Be heated to 100 ℃ of reactions then, treat platinum total overall reaction dissolving after, with the gained solution concentration to there being crystal to separate out; Drip till concentrated hydrochloric acid (concentration is 37.5%) to system no longer includes brown gas and emerge; The reconcentration reaction solution drips purified water then and catches up with acid to there being crystal to separate out, and gets platinum acid chloride solution;
2. get oxalic acid 325 grams; Be mixed with 10% the aqueous solution, with 10% oxalic acid aqueous solution 50 ℃-60 ℃, be added drop-wise in 1 hour under stirring in the platinum acid chloride solution that step obtains in 1., dripped the continued stirring reaction 3 hours; Half of concentration of reaction solution to original volume obtains chloro-platinous acid solution;
3. potassium chloride 380 gram is mixed with saturated aqueous solution, with the Repone K saturated aqueous solution 40 ℃-50 ℃, stir and be added drop-wise to down in the chloro-platinous acid solution of step in 2., drip off continued and reacted 1 hour, make to react completely; Then 1/3rd of concentration of reaction solution to original volume, be cooled to normal temperature, drip the ethanol that concentrates the long-pending 2 times of amounts of afterreaction liquid again; Separate out crystal, be cooled to 0-5 ℃, filter; With the ice ethanol filter wash cake that concentrates the long-pending 0.3 times of amount of afterreaction liquid, after the vacuum-drying, obtain potassium chloroplatinite 1022 grams again.Product is through detecting platinum content 46.6%, potassium content 18.7%, and product yield is 96.1%.
The preparation method of potassium chloroplatinite according to the invention can also have following preferred concrete steps:
1. 1000 gram spongy platinums are divided slowly to join for 5 times in 10 kilograms of chloroazotic acid, add 200 grams at every turn, add in 10 minutes; Be heated to 100 ℃ of reactions then, treat platinum total overall reaction dissolving after, with the gained solution concentration to there being crystal to separate out; Drip till concentrated hydrochloric acid (concentration is 37.5%) to system no longer includes brown gas and emerge; The reconcentration reaction solution drips purified water then and catches up with acid to there being crystal to separate out, and gets platinum acid chloride solution;
2. get oxalic acid 650 gram, be mixed with 10% the aqueous solution, 10% oxalic acid aqueous solution is added drop-wise in the step platinum acid chloride solution 1. under agitation 1 hour; 50 ℃-60 ℃ of controlled temperature after dropwising, continued stirring reaction 3 hours; Half of concentration of reaction solution to original volume gets chloro-platinous acid solution;
3. potassium chloride 770 gram is mixed with saturated aqueous solution, with the Repone K saturated aqueous solution 40 ℃-50 ℃, stir and be added drop-wise to down in the chloro-platinous acid solution of step in 2., drip off continued and reacted 1 hour, make to react completely; Then 1/3rd of concentration of reaction solution to original volume, be cooled to normal temperature, drip the ethanol that concentrates the long-pending 2 times of amounts of afterreaction liquid again; Separate out crystal, be cooled to 0-5 ℃, filter; With the ice ethanol filter wash cake that concentrates the long-pending 0.3 times of amount of afterreaction liquid, after the vacuum-drying, obtain potassium chloroplatinite 2066 grams again.Product is through detecting platinum content 46.6%, potassium content 18.8%, and product yield is 97.1%.

Claims (2)

1. the preparation method of a potassium chloroplatinite is characterized in that: comprise the steps:
1. spongy platinum and chloroazotic acid are inserted in the reactor drum, be heated to, produce platinum acid chloride solution to 100 ℃ of reactions;
2. get 10% oxalic acid aqueous solution and join in the platinum acid chloride solution of step in 1., reduction generates chloro-platinous acid solution;
3. the potassium chloride saturated aqueous solution joins in the chloro-platinous acid solution of step in 2., generates potassium chloroplatinite;
The temperature of reaction of step in 2. is 50 ℃-60 ℃; The temperature of reaction of step in 2. is 50 ℃-60 ℃;
The reaction of above-mentioned each step is all carried out in same reactor drum, wherein platinum: chloroazotic acid: oxalic acid: the weight ratio of Repone K is 1:8-10:0.64-0.66:0.76-0.8.
2. the preparation method of a kind of potassium chloroplatinite according to claim 1, it is characterized in that: concrete steps are following:
1. get 1000 gram spongy platinums and divide and slowly join for 5 times in the 9000 gram chloroazotic acid, add 200 grams at every turn, add in 10 minutes; Be heated to 100 ℃ of reactions then, after the platinum total overall reaction dissolving, with the gained solution concentration to there being crystal to separate out; Drip again till concentrated hydrochloric acid (concentration is 37.5%) to system no longer includes brown gas and emerge; The reconcentration reaction solution drips purified water then and catches up with acid to there being crystal to separate out, and obtains platinum acid chloride solution;
2. get oxalic acid 655 gram and be made into 10% the aqueous solution; With 10% oxalic acid aqueous solution 50 ℃-60 ℃, be added drop-wise in 1 hour under stirring in the platinum acid chloride solution that step obtains in 1.; Dripped the continued stirring reaction 3 hours, half of concentration of reaction solution to original volume obtains chloro-platinous acid solution;
3. potassium chloride 770 gram is mixed with saturated aqueous solution, with the Repone K saturated aqueous solution 40 ℃-50 ℃, stir and be added drop-wise to down in the chloro-platinous acid solution of step in 2., drip off continued and reacted 1 hour, make to react completely; Then 1/3rd of concentration of reaction solution to original volume, be cooled to normal temperature, drip the ethanol that concentrates the long-pending 2 times of amounts of afterreaction liquid again; Separate out crystal, be cooled to 0-5 ℃, filter; With the ice ethanol filter wash cake that concentrates the long-pending 0.3 times of amount of afterreaction liquid, after the vacuum-drying, obtain potassium chloroplatinite 2053 grams again.
CN2011102182566A 2011-08-01 2011-08-01 Preparation method of potassium chloroplatinite Pending CN102390874A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011102182566A CN102390874A (en) 2011-08-01 2011-08-01 Preparation method of potassium chloroplatinite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011102182566A CN102390874A (en) 2011-08-01 2011-08-01 Preparation method of potassium chloroplatinite

Publications (1)

Publication Number Publication Date
CN102390874A true CN102390874A (en) 2012-03-28

Family

ID=45858285

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011102182566A Pending CN102390874A (en) 2011-08-01 2011-08-01 Preparation method of potassium chloroplatinite

Country Status (1)

Country Link
CN (1) CN102390874A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102774894A (en) * 2012-08-21 2012-11-14 天津市风船化学试剂科技有限公司 Joint preparation method of potassium chloroplatinite and potassium chloroplatinate
CN103253718A (en) * 2013-05-24 2013-08-21 陕西煤业化工技术开发中心有限责任公司 Preparation method of potassium chloroplatinite
CN104140131A (en) * 2014-08-20 2014-11-12 山东铂源药业有限公司 Preparation method of potassium chloroplatinite
CN104310498A (en) * 2014-10-13 2015-01-28 浙江省冶金研究院有限公司 Preparation method of platinum nitrate
CN109437342A (en) * 2018-11-22 2019-03-08 沈阳有色金属研究院有限公司 A kind of preparation method of high activity potassium chloroplatinite
CN109761290A (en) * 2019-03-15 2019-05-17 西安凯立新材料股份有限公司 A kind of preparation method of potassium chloroplatinite
CN113929158A (en) * 2021-10-28 2022-01-14 浙江微通催化新材料有限公司 Preparation method of platinum nitrate
CN114315912A (en) * 2021-12-28 2022-04-12 江西贝特利新材料有限公司 Preparation method of cis-dichlorobis (diethyl sulfide) platinum (II)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332780A (en) * 1979-08-16 1982-06-01 Mpd Technology Corporation Preparation of cis-diammine diodo platinum (II)
JPH03131529A (en) * 1989-10-13 1991-06-05 Tanaka Kikinzoku Kogyo Kk Production of potassium tetrachloroplatinate
JPH04349125A (en) * 1991-05-22 1992-12-03 Tanaka Kikinzoku Kogyo Kk Production of tetraammine-platinum dichloride solution
CN101279772A (en) * 2008-05-15 2008-10-08 金川集团有限公司 Preparation of potassium platinochloride

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332780A (en) * 1979-08-16 1982-06-01 Mpd Technology Corporation Preparation of cis-diammine diodo platinum (II)
JPH03131529A (en) * 1989-10-13 1991-06-05 Tanaka Kikinzoku Kogyo Kk Production of potassium tetrachloroplatinate
JPH04349125A (en) * 1991-05-22 1992-12-03 Tanaka Kikinzoku Kogyo Kk Production of tetraammine-platinum dichloride solution
CN101279772A (en) * 2008-05-15 2008-10-08 金川集团有限公司 Preparation of potassium platinochloride

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
余建民: "《贵金属化合物及配合物合成手册》", 28 February 2009, 化学工业出版社 *
武汉大学等: "《无机化学》", 30 September 1984, 高等教育出版社 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102774894B (en) * 2012-08-21 2014-04-30 天津市风船化学试剂科技有限公司 Joint preparation method of potassium chloroplatinite and potassium chloroplatinate
CN102774894A (en) * 2012-08-21 2012-11-14 天津市风船化学试剂科技有限公司 Joint preparation method of potassium chloroplatinite and potassium chloroplatinate
CN103253718B (en) * 2013-05-24 2015-04-15 陕西煤业化工技术开发中心有限责任公司 Preparation method of potassium chloroplatinite
CN103253718A (en) * 2013-05-24 2013-08-21 陕西煤业化工技术开发中心有限责任公司 Preparation method of potassium chloroplatinite
CN104140131B (en) * 2014-08-20 2015-09-16 山东铂源药业有限公司 A kind of preparation method of potassium chloroplatinite
CN104140131A (en) * 2014-08-20 2014-11-12 山东铂源药业有限公司 Preparation method of potassium chloroplatinite
CN104310498A (en) * 2014-10-13 2015-01-28 浙江省冶金研究院有限公司 Preparation method of platinum nitrate
CN104310498B (en) * 2014-10-13 2016-06-29 浙江省冶金研究院有限公司 A kind of preparation method of platinum nitrate
CN109437342A (en) * 2018-11-22 2019-03-08 沈阳有色金属研究院有限公司 A kind of preparation method of high activity potassium chloroplatinite
CN109761290A (en) * 2019-03-15 2019-05-17 西安凯立新材料股份有限公司 A kind of preparation method of potassium chloroplatinite
CN109761290B (en) * 2019-03-15 2021-03-23 西安凯立新材料股份有限公司 Preparation method of potassium platinochloride
CN113929158A (en) * 2021-10-28 2022-01-14 浙江微通催化新材料有限公司 Preparation method of platinum nitrate
CN113929158B (en) * 2021-10-28 2023-10-03 浙江微通催化新材料有限公司 Preparation method of platinum nitrate
CN114315912A (en) * 2021-12-28 2022-04-12 江西贝特利新材料有限公司 Preparation method of cis-dichlorobis (diethyl sulfide) platinum (II)

Similar Documents

Publication Publication Date Title
CN102390874A (en) Preparation method of potassium chloroplatinite
CN102797018B (en) A kind of method adopting controlling potential separating-purifying platinum
WO2017185435A1 (en) Composite mineralized ceramic material capable of producing active hydrogen healthcare water
CN111840574A (en) Preparation and application of 5-aminolevulinic acid-camptothecin small-molecule prodrug
CN105417497A (en) Production device and technology for high-concentration steady chlorine dioxide solution
CN107325201A (en) A kind of preparation method of chitosan salicylic acid rare earth compounding
CN101289467A (en) Platinum salts of organic acids, preparation thereof and applications in preparation of anticancer drugs
CN102443034B (en) Cholesterol hybrid compound of molybdenum-containing polyoxometallate and preparation method of cholesterol hybrid compound
CN107190147B (en) A method of selective dissolution recycles platinum from platinum-containing waste catalyst
CN105440035A (en) Low-energy-consumption preparation method for synthesizing high-purity folic acid
CN103880889A (en) Precursor for preparing platinized catalyst and synthesis method thereof
CN101830933A (en) Novel method for synthesizing antitumor medicament platinum
CN101190925B (en) Copper complex, preparation method and application thereof
CN102774894B (en) Joint preparation method of potassium chloroplatinite and potassium chloroplatinate
CN108555313B (en) Preparation method of medical high-purity platinum powder
CN103059072A (en) Preparation method of raw medicine of environment-friendly iron sucrose
CN102766169A (en) New method for synthesizing anti-tumor drug miboplatin
CN101160310B (en) Method for producing alpha form crystals of sapropterin hydrochloride
Yan et al. A new paratungstate-A-based organic–inorganic hybrid compound: Synthesis, structure and photocatalytic property of [Co (en) 3] 2 [H2W7O24]· 8H2O
CN102516311A (en) Preparation method of miriplatin hydrate
CN106349169A (en) Flucytosine preparation method applicable to industrial production
CN101302236B (en) Novel method for synthesizing antineoplastic medicine nedaplatin
CN102417522A (en) Preparation method of nedaplatin with extremely low silver content
CN1321646C (en) Oral zinc reinforcing agent using hydrotalcite as carrier, its preparation and using method thereof
CN110423253A (en) A kind of platinum complex of the base containing single silane and its application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent of invention or patent application
CB02 Change of applicant information

Address after: Strong Street Jibei Economic Development Zone in Ji'nan City, Shandong province 251400

Applicant after: Shandong Boyuan Pharmaceutical Co., Ltd.

Address before: Strong Street Jibei Economic Development Zone in Ji'nan City, Shandong province 251400

Applicant before: Shandong Boyuan Chemical Co., Ltd.

COR Change of bibliographic data

Free format text: CORRECT: APPLICANT; FROM: SHANDONG BOYUAN CHEMICAL CO., LTD. TO: SHANDONG BOYUAN PHARMACEUTICAL CO., LTD.

C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20120328