CN102718681A - Method for purifying yellowed benzophenone hydrazone - Google Patents
Method for purifying yellowed benzophenone hydrazone Download PDFInfo
- Publication number
- CN102718681A CN102718681A CN2012102239535A CN201210223953A CN102718681A CN 102718681 A CN102718681 A CN 102718681A CN 2012102239535 A CN2012102239535 A CN 2012102239535A CN 201210223953 A CN201210223953 A CN 201210223953A CN 102718681 A CN102718681 A CN 102718681A
- Authority
- CN
- China
- Prior art keywords
- benzophenonehydrazones
- organic solvent
- obtains
- white solid
- purification
- 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
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for purifying benzophenone hydrazone yellowed after being placed for certain time. The method comprises the following steps of: adding 1 part of yellowed benzophenone hydrazone sample and 0.03 to 0.1 part of active carbon into 7 to 20 parts of organic solvent together, controlling the temperature to be between 85 and 90 DEG C, stirring, refluxing, and performing suction-filtration with heat; cooling the filtrate, crystallizing, performing suction-filtration till dryness, washing the filter cakes by using a pure organic solvent till dryness, and thus obtaining white solid; and drying the obtained white solid, discontinuously turning over the solid during drying till constant weight, and thus obtaining the purified white benzophenone hydrazone. The method is easy and convenient to operate and high in purifying yield, the total impurity content of the purified benzophenone hydrazone is low, the recovery rate of the organic solvent is high, and the recovered organic solvent can be continuously used without affecting the purifying effect. The method can be applied to large-scale treatment of the yellowed benzophenone hydrazone.
Description
Technical field
The present invention relates to a kind of method of purification of Organic Chemicals, more precisely is a kind of method of purification of placing the Benzophenonehydrazones of its colour changed into yellow after for some time.
Background technology
Benzophenonehydrazones is a kind of important Organic Chemicals, is widely used in synthetic sensitive materials, spices, UV light absorber, pigment dyestuff, medicine and agrochemical.In medicine industry; Benzophenonehydrazones is except that can be used for producing perhexiline, diphenhydramine hydrochlorate and the cardiovascular agent cibenzoline etc., can also draw the carboxyl-protecting group of 6-APA and 7-ACA in the building-up processes such as hydrazone and beta-lactamase inhibitor Tazobactam Sodium as antibiotic medicine such as Cefixime Micronized, cephalo and is widely used.In addition, Benzophenonehydrazones can also generate stable aromatic series imines with the primary amine reaction, is the important source material of preparation peptide presoma diphenyl diazomethane.
The method of synthetic Benzophenonehydrazones mainly contains three kinds: be that raw material makes with the diphenylketoxime; With the diphenyl diazomethane is that raw material makes, and reaching with the UVNUL MS-40 is that raw material makes.Because of preceding two kinds of compound method expensive raw materials; Be not suitable for large-scale industrial production, so the industriallization Benzophenonehydrazones mainly is to be that raw material makes with the UVNUL MS-40 at present, its productive rate can be up to 96%; But because the Benzophenonehydrazones of white is after placement for some time; The easy yellowing of its color relation, and being abandoned by enterprise has so not only been wasted raw material but also has been reduced the productive rate of actual available Benzophenonehydrazones.
The research of relevant Benzophenonehydrazones both at home and abroad mainly concentrates on the improvement synthesis of benzophenone hydrazone at present, how the xanchromatic Benzophenonehydrazones is become white again, makes it be back to Chemical Manufacture, becomes problem demanding prompt solution.Those skilled in the art does not know the reason of its jaundice always now, therefore is difficult to find out terms of settlement yet.
Summary of the invention
The objective of the invention is provides a kind of simple to operate to the problems referred to above; Can realize the method for mass-producing purification jaundice Benzophenonehydrazones; Obtaining highly purified Benzophenonehydrazones, thereby the Benzophenonehydrazones of jaundice is become white again, make it be reused for Chemical Manufacture.
The present invention realizes like this.A kind of method of purification of Benzophenonehydrazones of jaundice, it comprises the steps: (consumption is a weight part)
1) the Benzophenonehydrazones sample with 1 part of jaundice joins in 7-20 part organic solvent with 0.03-0.1 part gac, and controlled temperature is 85 ℃ of-90 ℃ of stirring and refluxing, then suction filtration while hot; Can remove impurity with this understanding.Preferably the Benzophenonehydrazones sample with 1 part of jaundice joins in 10 parts of organic solvents with 0.1 part of gac, and is relatively good according to the product appearance that this proportioning is handled, and is pure white.
2) crystallisation by cooling of will filtrating, suction filtration is to doing again, and filter cake to doing, obtains white solid with purified organic solvent drip washing;
3) white solid that obtains is carried out drying, in the drying process, that is interrupted stirs solid, gets final product to constant weight.
In the aforesaid method, gac contains a large amount of micropores, has huge specific surface area, can adsorb those and not be dissolved in inorganic impurity and part organic impurity in the organic solvent, effectively removes colourity.Wherein, the rational proportion of Benzophenonehydrazones sample, gac and consumption of organic solvent adds suitable reflux temperature; Absorption and follow-up crystallisation process have greatly been optimized; Make that the Benzophenonehydrazones total impurities content of purification gained is low, purification efficiency is high, and the machine solvent refining effect after reclaiming is constant; Can continue to use, thereby reduce production cost and reduced operation easier.The inventive method is fit to the large-scale Benzophenonehydrazones of handling jaundice, is back to Chemical Manufacture after it is bleached.
Further, said organic solvent is hexanaphthene, normal hexane, Skellysolve A, chloroform or benzene, preferred hexanaphthene, more preferably hexanaphthene and chloroform according to the mixture of mass ratio 1:1 as solvent.These organic solvents near the boiling point to Benzophenonehydrazones solubleness high and during at low temperature solubleness very little, can effectively the Benzophenonehydrazones Crystallization Separation be come out, increase purification efficiency, also make Recovery of Organic Solvent rate and purity all very high, improved Production Gain.
Said return time is 1-3 hour, and preferred 2 hours, the crystallisation by cooling time was 1-2 hour.The processing condition of purifying have further been optimized
Said drying temperature is 40 ℃-50 ℃, and be 3-4 hour time of drying.Thoroughly remove, further improve product purity attached to the organic solvent on the Benzophenonehydrazones.
Embodiment
Below in conjunction with embodiment the present invention is further described, but the present invention is not limited to following embodiment.
Except as otherwise noted, the percentage ratio that is adopted among the present invention is weight percentage.
Embodiment 1
(sample quality: HPLC purity 97%), 1250g hexanaphthene and 10g gac, controlled temperature are 85 ℃, stirring and refluxing 2 hours, suction filtration while hot in the flask of 2000ml, to add the Benzophenonehydrazones sample 125g that turns to be yellow; Then solution is placed room temperature, make its cooling crystallization 2 hours, suction filtration is to doing, and filter cake to doing, obtains 121g weight in wet base white solid with the purified hexanaphthene drip washing of 200g; With the solid that obtains in baking oven 40 ℃ dry 4 hours down, in the drying process, that is interrupted stirs solid, to constant weight, obtains the 113g white solid.
Benzophenonehydrazones sample yield: 90.4%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.8%, color: white;
The hexanaphthene recovery: 88.7%.
Embodiment 2
(sample quality: HPLC purity 97%), 1375g hexanaphthene and 10g gac, controlled temperature are 90 ℃, stirring and refluxing 2 hours, suction filtration while hot in the flask of 2000ml, to add the Benzophenonehydrazones sample 125g that turns to be yellow; Then solution is placed room temperature, make its cooling crystallization 2 hours, suction filtration is to doing, and filter cake to doing, obtains 120g weight in wet base white solid with the purified hexanaphthene drip washing of 200g; With the solid that obtains in baking oven 50 ℃ dry 3 hours down, in the drying process, that is interrupted stirs solid, to constant weight, obtains the 112g white solid.
Benzophenonehydrazones sample yield: 89.6%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.9%, color: white; The hexanaphthene recovery: 88.5%.
Embodiment 3
(sample quality: HPLC purity 97%), 1125g hexanaphthene and 10g gac, controlled temperature are 90 ℃, stirring and refluxing 2 hours, suction filtration while hot in the flask of 2000ml, to add the Benzophenonehydrazones sample 125g that turns to be yellow; Then solution is placed room temperature, make its cooling crystallization 2 hours, suction filtration is to doing, and filter cake to doing, obtains 120g weight in wet base white solid with the purified hexanaphthene drip washing of 200g; With the solid that obtains in baking oven 50 ℃ dry 3 hours down, that is interrupted in the drying stirs solid, to constant weight, obtains the 110g white solid.
Benzophenonehydrazones sample yield: 88%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.8%, color: white;
The hexanaphthene recovery: 88.3%.
Embodiment 4
(sample quality: HPLC purity 97%), 875g hexanaphthene and 3.75g gac, controlled temperature are 88 ℃, stirring and refluxing 3 hours, suction filtration while hot in the flask of 2000ml, to add the Benzophenonehydrazones sample 125g that turns to be yellow; Then solution is placed room temperature, make its cooling crystallization 1.5 hours, suction filtration is to doing, and filter cake to doing, obtains 121g weight in wet base white solid with the purified hexanaphthene drip washing of 200g; With the solid that obtains in baking oven 45 ℃ dry 3.5 hours down, that is interrupted in the drying stirs solid, to constant weight, obtains the 114g white solid.
Benzophenonehydrazones sample yield: 91.2%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.6%, color: white;
The hexanaphthene recovery: 88.5%.
Embodiment 5
(sample quality: HPLC purity 97%), 2500g hexanaphthene and 12.5g gac, controlled temperature are 86 ℃, stirring and refluxing 1 hour, suction filtration while hot in the flask of 2000ml, to add the Benzophenonehydrazones sample 125g that turns to be yellow; Then solution is placed room temperature, make its cooling crystallization 1 hour, suction filtration is to doing, and filter cake to doing, obtains 120g weight in wet base white solid with the purified hexanaphthene drip washing of 200g; With the solid that obtains in baking oven 48 ℃ dry 3 hours down, that is interrupted in the drying stirs solid, to constant weight, obtains the 112g white solid.
Benzophenonehydrazones sample yield: 89.6%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.8%, color: white;
The hexanaphthene recovery: 88.8%.
Embodiment 6
(sample quality: HPLC purity 97%), 1000g normal hexane and 11g gac, controlled temperature are 86 ℃, stirring and refluxing 3 hours, suction filtration while hot in the flask of 2000ml, to add the Benzophenonehydrazones sample 125g that turns to be yellow; Then solution is placed room temperature, make its cooling crystallization 2 hours, suction filtration is to doing, and filter cake to doing, obtains 119g weight in wet base white solid with the purified normal hexane drip washing of 200g; With the solid that obtains in baking oven 40 ℃ dry 4 hours down, in the drying process, that is interrupted stirs solid, to constant weight, obtains the 108g white solid.
Benzophenonehydrazones sample yield: 86.4%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.7%, color: white;
The normal hexane recovery: 88.7%.
Embodiment 7
(sample quality: HPLC purity 97%), 1500g Skellysolve A and 5g gac, controlled temperature are 87 ℃, stirring and refluxing 2 hours, suction filtration while hot in the flask of 2000ml, to add the Benzophenonehydrazones sample 125g that turns to be yellow; Then solution is placed room temperature, make its cooling crystallization 2 hours, suction filtration is to doing, and filter cake to doing, obtains 121g weight in wet base white solid with the purified Skellysolve A drip washing of 200g; With the solid that obtains in baking oven 42 ℃ dry 4 hours down, in the drying process, that is interrupted stirs solid, to constant weight, obtains the 113g white solid.
Benzophenonehydrazones sample yield: 90.4%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.5%, color: white;
The Skellysolve A recovery: 88.2%.
Embodiment 8
(sample quality: HPLC purity 97%), 1625g chloroform and 5g gac, controlled temperature are 85 ℃, stirring and refluxing 1.5 hours, suction filtration while hot in the flask of 2000ml, to add the Benzophenonehydrazones sample 125g that turns to be yellow; Then solution is placed room temperature, make its cooling crystallization 2 hours, suction filtration is to doing, and filter cake to doing, obtains 118g weight in wet base white solid with the purified chloroform drip washing of 200g; With the solid that obtains in baking oven 40 ℃ dry 3 hours down, in the drying process, that is interrupted stirs solid, to constant weight, obtains the 109g white solid.
Benzophenonehydrazones sample yield: 87.2%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.8%, color: white;
The chloroform recovery: 88.8%.
Embodiment 9
(sample quality: HPLC purity 97%), 2250g benzene and 4g gac, controlled temperature are 88 ℃, stirring and refluxing 2 hours, suction filtration while hot in the flask of 2000ml, to add the Benzophenonehydrazones sample 125g that turns to be yellow; Then solution is placed room temperature, make its cooling crystallization 2 hours, suction filtration is to doing, and filter cake to doing, obtains 120g weight in wet base white solid with the purified benzene drip washing of 200g; With the solid that obtains in baking oven 50 ℃ dry 4 hours down, in the drying process, that is interrupted stirs solid, to constant weight, obtains the 110g white solid.
Benzophenonehydrazones sample yield: 88%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.5%, color: white;
The benzene recovery: 88.1%.
Embodiment 10
The Benzophenonehydrazones sample 125g (sample quality: HPLC purity 97%) that in the flask of 2000ml, adds jaundice; Add 1500g hexanaphthene and chloroform according to the mixture of mass ratio 1:1 as solvent and 5g gac; Controlled temperature is 87 ℃, stirring and refluxing 2 hours, suction filtration while hot; Then solution is placed room temperature, make its cooling crystallization 2 hours, suction filtration is to doing, and filter cake to doing, obtains 121g weight in wet base white solid with the purified Skellysolve A drip washing of 200g; With the solid that obtains in baking oven 42 ℃ dry 4 hours down, in the drying process, that is interrupted stirs solid, to constant weight, obtains the 113g white solid.
Benzophenonehydrazones sample yield: 91.5%;
The Benzophenonehydrazones specification of quality after the purification: HPLC purity 99.5%, color: white.
Claims (4)
1. the method for purification of the Benzophenonehydrazones of a jaundice, it comprises the steps:
1) the Benzophenonehydrazones sample with 1 part of jaundice joins in 7-20 part organic solvent with 0.03-0.1 part gac, and controlled temperature is 85 ℃ of-90 ℃ of stirring and refluxing, then suction filtration while hot; Said organic solvent is hexanaphthene, normal hexane, Skellysolve A, chloroform or benzene;
2) crystallisation by cooling of will filtrating, suction filtration is to doing again, and filter cake to doing, obtains white solid with purified organic solvent drip washing;
3) white solid that obtains is carried out drying, in the drying process, that is interrupted stirs solid, gets final product to constant weight.
2. the method for purification of the Benzophenonehydrazones of a kind of jaundice according to claim 1, it is characterized in that: return time is 1-3 hour, the crystallisation by cooling time is 1-2 hour.
3. the method for purification of the Benzophenonehydrazones of a kind of jaundice according to claim 1, it is characterized in that: drying temperature is 40 ℃-50 ℃, and be 3-4 hour time of drying.
4. the method for purification of the Benzophenonehydrazones of a kind of jaundice according to claim 1, it is characterized in that: described organic solvent is a hexanaphthene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102239535A CN102718681A (en) | 2012-07-02 | 2012-07-02 | Method for purifying yellowed benzophenone hydrazone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102239535A CN102718681A (en) | 2012-07-02 | 2012-07-02 | Method for purifying yellowed benzophenone hydrazone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102718681A true CN102718681A (en) | 2012-10-10 |
Family
ID=46944587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102239535A Pending CN102718681A (en) | 2012-07-02 | 2012-07-02 | Method for purifying yellowed benzophenone hydrazone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102718681A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082750A (en) * | 2017-05-18 | 2017-08-22 | 三斯达（江苏）环保科技有限公司 | The preparation of benzophenone hydazone derivative and its application in anti-aging expanded material |
| CN108663246A (en) * | 2018-05-18 | 2018-10-16 | 中国烟草总公司郑州烟草研究院 | Benzophenone purity rubric substance and preparation method thereof |
| CN111451254A (en) * | 2020-05-01 | 2020-07-28 | 东阳市聚冉电子科技有限公司 | Method for recycling industrial waste residue containing benzophenone hydrazone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3732307A (en) * | 1970-09-24 | 1973-05-08 | Du Pont | Benzophenone hydrazones containing perfluoroalkyl,perfluoroalkoxy,and perfluoroalkylthio substituents |
| CN102503853A (en) * | 2011-11-22 | 2012-06-20 | 太仓市运通化工厂 | Synthesis method of benzophenone hydrazone |
-
2012
- 2012-07-02 CN CN2012102239535A patent/CN102718681A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3732307A (en) * | 1970-09-24 | 1973-05-08 | Du Pont | Benzophenone hydrazones containing perfluoroalkyl,perfluoroalkoxy,and perfluoroalkylthio substituents |
| CN102503853A (en) * | 2011-11-22 | 2012-06-20 | 太仓市运通化工厂 | Synthesis method of benzophenone hydrazone |
Non-Patent Citations (2)
| Title |
|---|
| 杨秉一: "二苯甲酮腙的合成工艺改进", 《中国药物化学杂志》, vol. 13, no. 1, 28 February 2003 (2003-02-28), pages 46 - 47 * |
| 梁亮: "《化学化工专业实验》", 31 March 2009, 化学工业出版社, article "活性炭脱色", pages: 57 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082750A (en) * | 2017-05-18 | 2017-08-22 | 三斯达（江苏）环保科技有限公司 | The preparation of benzophenone hydazone derivative and its application in anti-aging expanded material |
| CN108663246A (en) * | 2018-05-18 | 2018-10-16 | 中国烟草总公司郑州烟草研究院 | Benzophenone purity rubric substance and preparation method thereof |
| CN111451254A (en) * | 2020-05-01 | 2020-07-28 | 东阳市聚冉电子科技有限公司 | Method for recycling industrial waste residue containing benzophenone hydrazone |
| CN111451254B (en) * | 2020-05-01 | 2021-09-03 | 东阳市聚冉电子科技有限公司 | Method for recycling industrial waste residue containing benzophenone hydrazone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107337618B (en) | Production method for simultaneously improving purity and yield of metformin hydrochloride | |
| CN108129346A (en) | A kind of green synthesis method of D-VB5 calcium | |
| CN102718681A (en) | Method for purifying yellowed benzophenone hydrazone | |
| CN102372626A (en) | Preparation method of phthalic acid | |
| CN102584693B (en) | Preparation method for high purity 2-chlorine-3-aminopyridine hydrochloride | |
| CN108997211A (en) | A kind of method of solvent crystallisation by cooling separation 4- cyanopyridine | |
| CN106065005B (en) | Preparation method of R- (+) -2- [4- (hydroxyphenoxy) ] propionate | |
| CN102557980B (en) | Method for preparing high-purity capsaicine monomer by crystallization | |
| CN108586493A (en) | A kind of preparation method of crystal type CEFUROXIME AXETIL | |
| CN110128285B (en) | Preparation method of D-phenylglycine methyl ester hydrochloride/D-dihydrophenylglycine methyl ester hydrochloride | |
| CN109265413B (en) | Preparation method and refining method of difenidol hydrochloride | |
| CN106928018B (en) | Preparation method of 1-bromoadamantane | |
| CN104355990B (en) | Method for recycling and mechanically using L- (+) -tartaric acid in D-ethyl ester production | |
| CN103204522A (en) | Preparation method of high-purity mass potassium nitrate | |
| CN108727319A (en) | A kind of preparation method of 3- nitrophthalic acids acid anhydride | |
| CN108690077A (en) | A kind of synthetic method of the right amine salt of the left phosphine of intermediate | |
| CN104447758A (en) | Synthesis process of pyrazolo[3,4-d]pyrimidine compounds | |
| CN112745246A (en) | Purification method of shakubiqu intermediate | |
| CN108863856B (en) | Purification method of analytically pure reagent 5-sulfosalicylic acid | |
| CN113185387A (en) | Preparation method of high-purity octabromoether | |
| CN102675175B (en) | Method for separating and purifying cilastatin | |
| CN104513251A (en) | Nalmefene hydrochloride preparation method | |
| CN104109131A (en) | Method for preparing N-formyl phenothiazine | |
| CN105566349A (en) | Synthesis process of o-chloro-benzathine penicillin | |
| CN109422679B (en) | Purification of bedaquiline and preparation method of stable crystal form |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20121010 |