CN102850187A - Method for preparing 9-fluorenylmethanol - Google Patents
Method for preparing 9-fluorenylmethanol Download PDFInfo
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- CN102850187A CN102850187A CN2011101805803A CN201110180580A CN102850187A CN 102850187 A CN102850187 A CN 102850187A CN 2011101805803 A CN2011101805803 A CN 2011101805803A CN 201110180580 A CN201110180580 A CN 201110180580A CN 102850187 A CN102850187 A CN 102850187A
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- lumefantrine
- filtrate
- hour
- water
- ethyl acetate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for preparing 9-fluorenylmethanol. The method includes 1) adding industrial fluorene, dimethylsulfoxide, inorganic salts and polyethylene glycol at a ratio of 20 g:200 ml:(20-40) g:(4-8) g in a four-mouth flask; 2) reacting at 75-80 DEG C., cooling, and dropping ethyl formate; 3) reacting for 1-2 h, adding paraformaldehyde, and adding water to terminate reaction; 4) performing pump filtration, performing pump filtration to the filtrate again to obtain a filter cake m1, performing pump filtration to the second filtrate to obtain solid 2<#>, extracting the third filtrate with ethyl acetate, and distilling to remove azeotrope of ethyl acetate and water, to obtain m2; and 5) merging m1, m2 and 2<#>, which are obtained in the former step, and performing recrystallization, to obtain white acicular 9-fluorenylmethanol. The inorganic salts are NaCl, KCl and CaCl. Compared with existing technologies, the invention has the advantages of one-step production, safe production process, easily-obtained and cheap catalyst, and 9-fluorenylmethanol product content greater than 95%.
Description
Technical field
The present invention relates to technical field of coal chemical industry, relate in particular to a kind of preparation method of 9-Lumefantrine.
Background technology
The main raw material of preparation 9-Lumefantrine is fluorenes, and present industrial fluorenes is inexpensive unsalable.In recent years, the utilization of continually developing owing to the 9-Lumefantrine, attracted a lot of scientists to be engaged in the research of this respect, domesticly start late in this work, some scientific research institutions have obtained some achievements, have successively synthesized the 9-Lumefantrine with diverse ways such as the scientific research personnel of the units such as Zhongshan University, Yangzhou chemical engineering school.At present, the method for preparing the 9-Lumefantrine can be divided into two-step approach and single stage method.
1) two-step approach: at first prepare 9-fluorenes formaldehyde by fluorenes, then prepare the 9-Lumefantrine by 9-fluorenes formaldehyde.Use different solvent, catalyzer, reductive agent according to document announcement, yield is different, and also has certain potential safety hazard, and simultaneously, this kind method needs the 9-fluorenes formaldehyde that the first step generates is separated, and then carries out reduction reaction, complex technical process.
2) single stage method: by fluorenes one-step synthesis 9-Lumefantrine, this method need not the 9-fluorenes formaldehyde that generates is separated, technological process is relatively simple, but adopt the bibliographical information of this method seldom, also exist simultaneously catalyzer expensive, be difficult for making, storage inconvenience, operational condition is harsh, has the problems such as production safety hidden danger.
Summary of the invention
The preparation method that the purpose of this invention is to provide a kind of 9-Lumefantrine adopts the synthetic 9-Lumefantrine of single stage method, and catalyzer is cheap and easy to get, synthesis route stable reaction, easy-to-operate.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of preparation method of 9-Lumefantrine may further comprise the steps:
1) gets industrial fluorenes, dimethyl sulfoxide (DMSO), inorganic salt and polyoxyethylene glycol, the ratio of these four kinds of components is 20g: 200ml: (20-40) g: (4-8) g, above-mentioned four kinds of components are joined in the four-hole bottle, install thermometer, prolong at four-hole bottle, inorganic salt are as catalyzer, and PEG is as promotor;
2) begin to stir, after 1-1.5 hour, will be cooled to 55-60 ℃ 75-80 ℃ of lower reaction, drip the 5-10ml ethyl formate;
3) continue to stir, react again 1-2 hour after, add the Paraformaldehyde 96 of 20-30g, continue reaction after 0.5-1 hour, add entry 300ml termination reaction;
4) carry out suction filtration, get solid-state 1 after its filter cake washes with water
#, its filtrate leaves standstill that suction filtration gets filter cake m after 1 hour
1With secondary filtrate, secondary filtrate again after static 12 hours suction filtration get solid-state 2
#, three times filtrate is poured in the separating funnel, uses ethyl acetate extraction three times, and combining extraction liquid adds the azeotrope that water steams ethyl acetate and water, obtains solid-state m
2, main composition is the 9-Lumefantrine;
5) with step 4) in m
1, m
2, 2
#Merge, recrystallization can obtain the 9-Lumefantrine of white needles.
Described inorganic salt are one or two or more kinds among NaCl, KCl, the CaCl.
Compared with prior art, the invention has the beneficial effects as follows: adopt One-step production 9-Lumefantrine, production process safety, easy to operate, the catalyzer that adopts is cheap to be easy to get, and can obtain content greater than 95% 9-Lumefantrine product, and the simple easily control of process, product yield is high, be easy to industrialization.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
Get raw material: industrial fluorenes 20g; Solvent: dimethyl sulfoxide (DMSO) 200ml; Catalyzer: NaCl 20g; Promotor: PEG4g joins and begins in the four-hole bottle to stir, and after 1.5 hours, is cooled to 60 ℃ 80 ℃ of lower reactions, drips the 5ml ethyl formate, react again 1 hour after, add the 20g Paraformaldehyde 96, continue reaction and add water termination reaction, suction filtration half an hour.
Filter cake wash with water solid-state 1
#, filtrate is left standstill rear suction filtration, and filter cake is m
1Secondary filtrate again after static 12 hours suction filtration get solid-state 2
#, filtrate is poured in the separating funnel, uses ethyl acetate extraction three times, and combining extraction liquid adds the azeotrope that water steams ethyl acetate and water, obtains solid-state m
2, with m
1, m
2, 2
#Merge, recrystallization can obtain the 9-Lumefantrine of white needles.
Embodiment 2
Get raw material: industrial fluorenes 20g; Solvent: dimethyl sulfoxide (DMSO) 200ml; Catalyzer: KCl 30g; Promotor: PEG 6g joins and begins in the four-hole bottle to stir, and after 1 hour, is cooled to 58 ℃ 78 ℃ of lower reactions, drips the 8ml ethyl formate, react again 2 hours after, add the 25g Paraformaldehyde 96, continue reaction and add water termination reaction, suction filtration half an hour.
Filter cake wash with water solid-state 1
#, filtrate is left standstill rear suction filtration, and filter cake is m
1Secondary filtrate again after static 12 hours suction filtration get solid-state 2
#, filtrate is poured in the separating funnel, uses ethyl acetate extraction three times, and combining extraction liquid adds the azeotrope that water steams ethyl acetate and water, obtains solid-state m
2, with m
1, m
2, 2
#Merge, recrystallization can obtain the 9-Lumefantrine of white needles.
Embodiment 3
Get raw material: industrial fluorenes 20g; Solvent: dimethyl sulfoxide (DMSO) 200ml; Catalyzer: CaCl 40g; Promotor: PEG8g joins and begins in the four-hole bottle to stir, and after 1 hour, is cooled to 55 ℃ 75 ℃ of lower reactions, drips the 10ml ethyl formate, react again 1 hour after, add the 30g Paraformaldehyde 96, continue reaction and add water termination reaction, suction filtration half an hour.
Filter cake wash with water solid-state 1
#, filtrate is left standstill rear suction filtration, and filter cake is m
1Secondary filtrate again after static 12 hours suction filtration get solid-state 2
#, filtrate is poured in the separating funnel, uses ethyl acetate extraction three times, and combining extraction liquid adds the azeotrope that water steams ethyl acetate and water, obtains solid-state m
2, with m
1, m
2, 2
#Merge, recrystallization can obtain the 9-Lumefantrine of white needles.
Claims (2)
1. the preparation method of a 9-Lumefantrine is characterized in that, may further comprise the steps:
1) gets industrial fluorenes, dimethyl sulfoxide (DMSO), inorganic salt and polyoxyethylene glycol, the ratio of these four kinds of components is 20g: 200ml: (20-40) g: (4-8) g, above-mentioned four kinds of components are joined in the four-hole bottle, install thermometer, prolong at four-hole bottle, inorganic salt are as catalyzer, and PEG is as promotor;
2) begin to stir, after 1-1.5 hour, will be cooled to 55-60 ℃ 75-80 ℃ of lower reaction, drip the 5-10ml ethyl formate;
3) continue to stir, react again 1-2 hour after, add the Paraformaldehyde 96 of 20-30g, continue reaction after 0.5-1 hour, add entry 300ml termination reaction;
4) carry out suction filtration, get solid-state 1 after its filter cake washes with water
#, its filtrate leaves standstill that suction filtration gets filter cake m after 1 hour
1With secondary filtrate, secondary filtrate again after static 12 hours suction filtration get solid-state 2
#, three times filtrate is poured in the separating funnel, uses ethyl acetate extraction three times, and combining extraction liquid adds the azeotrope that water steams ethyl acetate and water, obtains solid-state m
2, main composition is the 9-Lumefantrine;
5) with step 4) in m
1, m
2, 2
#Merge, recrystallization can obtain the 9-Lumefantrine of white needles.
2. the preparation method of a kind of 9-Lumefantrine according to claim 1 is characterized in that, described inorganic salt are one or two or more kinds among NaCl, KCl, the CaCl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101805803A CN102850187A (en) | 2011-06-29 | 2011-06-29 | Method for preparing 9-fluorenylmethanol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101805803A CN102850187A (en) | 2011-06-29 | 2011-06-29 | Method for preparing 9-fluorenylmethanol |
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| CN102850187A true CN102850187A (en) | 2013-01-02 |
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| CN2011101805803A Pending CN102850187A (en) | 2011-06-29 | 2011-06-29 | Method for preparing 9-fluorenylmethanol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351280A (en) * | 2013-06-17 | 2013-10-16 | 张家港威胜生物医药有限公司 | Simple preparation process of 9-fluorenemethanol |
| CN112724003A (en) * | 2020-12-29 | 2021-04-30 | 常州吉恩药业有限公司 | Preparation method of 9-fluorenylformaldehyde |
| CN112898130A (en) * | 2021-02-26 | 2021-06-04 | 太原理工大学 | Method for synthesizing 9-fluorenemethanol with high selectivity |
| CN113121316A (en) * | 2021-04-01 | 2021-07-16 | 孝义市金精化工有限公司 | Device and process for industrial synthesis of 9-fluorenylmethanol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884242A (en) * | 2005-06-22 | 2006-12-27 | 上海宝钢化工有限公司 | Method for preparing 9-fluorenylmethanol |
-
2011
- 2011-06-29 CN CN2011101805803A patent/CN102850187A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884242A (en) * | 2005-06-22 | 2006-12-27 | 上海宝钢化工有限公司 | Method for preparing 9-fluorenylmethanol |
Non-Patent Citations (4)
| Title |
|---|
| 肖瑞华编: "《煤焦油化工学》", 31 January 2009 * |
| 郑其煌等: "芴甲醇合成方法的改进", 《化学试剂》 * |
| 金寄春等译: "《有机化学》", 31 December 1985 * |
| 陈叶飞等: "固体碱催化合成9-芴甲醇", 《上海化工》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351280A (en) * | 2013-06-17 | 2013-10-16 | 张家港威胜生物医药有限公司 | Simple preparation process of 9-fluorenemethanol |
| CN112724003A (en) * | 2020-12-29 | 2021-04-30 | 常州吉恩药业有限公司 | Preparation method of 9-fluorenylformaldehyde |
| WO2022141699A1 (en) * | 2020-12-29 | 2022-07-07 | 常州吉恩药业有限公司 | Method for preparing 9-fluorenyl formaldehyde |
| CN112898130A (en) * | 2021-02-26 | 2021-06-04 | 太原理工大学 | Method for synthesizing 9-fluorenemethanol with high selectivity |
| CN112898130B (en) * | 2021-02-26 | 2023-05-16 | 太原理工大学 | Method for synthesizing 9-fluorenylmethanol with high selectivity |
| CN113121316A (en) * | 2021-04-01 | 2021-07-16 | 孝义市金精化工有限公司 | Device and process for industrial synthesis of 9-fluorenylmethanol |
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Application publication date: 20130102 |