CN108586189A - A kind of recovery and treatment method of 2,7- dichloros fluorenes reaction mother liquor - Google Patents
A kind of recovery and treatment method of 2,7- dichloros fluorenes reaction mother liquor Download PDFInfo
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- CN108586189A CN108586189A CN201810562616.6A CN201810562616A CN108586189A CN 108586189 A CN108586189 A CN 108586189A CN 201810562616 A CN201810562616 A CN 201810562616A CN 108586189 A CN108586189 A CN 108586189A
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- fluorenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
Abstract
This application involves a kind of recovery and treatment method of 2,7 dichloro fluorenes reaction mother liquors, the method that specifically a kind of waste reaction solution recycles after processing.By 2,7 dichloro fluorene acetic acid mother liquors through zinc powder reduction dechlorination, the mixed liquor based on 2 chlorine fluorenes and fluorenes is obtained, which is removed by filtration zinc powder and zinc acetate, then direct chlorination or 2, the 7 dichloro fluorenes of chlorination preparation together with raw material fluorenes.The application is applied to the recycling of 2,7 dichloro fluorenes reaction mother liquors, has many advantages, such as that easy to operate, processing is cheap.
Description
Technical field
This application involves the recovery and treatment method of one kind 2,7- dichloro fluorenes reaction mother liquors, specifically a kind of waste reaction solution warp
The method recycled after processing.
Background technology
Compound medicine Artemether (Artemether adds lumefantrine) is the pioneering antimalarial in China, and is obtained in the world at present
The original drug of China that must be widely recognized as, effective speed is identical as Artemether, and radical rate is high, and overcomes Artemether recurrence
The disadvantage that rate is high and lumefantrine is markedly slow, reaches mutual supplement with each other's advantages, the effect maximized favourable factors and minimized unfavourable ones, and prevents or controls to be widely used in
Treat the malaria of potential multiple drug resistance.
2,7- dichloro fluorenes is the important intermediate of lumefantrine.At present industrially using fluorenes as raw material, glacial acetic acid is solvent, is led to
2,7- dichloro fluorenes is prepared in 40 DEG C of chlorinations, then cooling recrystallization in chlorine.Since fluorenes has multiple chlorization activity sites, and
Chlorine activity is higher, and selectivity is poor, which only has 40% or so yield, generates a large amount of mother liquor；Contain 2- in mother liquor
Chlorine fluorenes, 4- chlorine fluorenes, 2,7- dichloros fluorenes, 2,5- dichloros fluorenes and 2, the compositions such as 4,7- trichlorine fluorenes, it is difficult to detach；At previous mother liquor
Reason method is：It is first distilled to recover solvent acetic acid, then by residue burning disposal, since amount of waste is big, complicated component, not only
Processing cost is high, is also easy to pollution environment.
Based on this, the application is made.
Invention content
The purpose of the present invention is overcoming the problems of the above-mentioned prior art, provide a kind of easy to operate, low-cost
The recovery and treatment method of 2,7- dichloro fluorene acetic acid mother liquors.
The structural formula of fluorenes (I) is shown below,
Mainly there are 2,4,5,7 four sites in its chlorization activity site.Through analysis, 2,7- dichloro fluorene acetic acid mother liquors mainly at
It is divided into 2- chlorine fluorenes (II), 4- chlorine fluorenes (III), 2,7- dichloros fluorenes (IV), 2,5- dichloros fluorenes (V) and 2,4,7- trichlorines fluorenes (VI).Respectively
Component structure formula is as follows：
For this purpose, the present invention adopts the following technical scheme that：
The recovery and treatment method of one kind 2,7- dichloro fluorenes reaction mother liquors, includes the following steps：2,7- dichloros fluorene acetic acid is female
Liquid is directly handled with zinc powder, reduction dechlorination, obtains the reduction reaction liquid based on 2- chlorine fluorenes and fluorenes, which removes through filtering
It goes zinc powder and zinc acetate, then direct chlorination that can prepare 2,7- dichloro fluorenes, or adds chlorination again after a certain amount of raw material fluorenes
(this mode is more suitable for industrial production).
Further, as preferred：
In above-mentioned reduction reaction, reaction temperature is 0-30 DEG C, preferably 10-20 DEG C.
In above-mentioned reduction reaction, the mole of zinc powder and the molar ratio (amount when by original feeding intake) of fluorenes are 1-5:1,
It is preferred that 1.5-2.5:1 and/or 1.8-2.2:1.
Beneficial effects of the present invention are as follows：
1. raw material used in the present invention is chlorination reaction waste liquid, at low cost and realize waste reclamation, alleviate
Environmental protection pressure.
2. the present invention in addition to product, only generates a small amount of solid mixture containing zinc (zinc, zinc acetate and zinc chloride), filtering is
It can remove, reaction solution post-processing is simple, environmental-friendly.
3. the method for the present invention is easy to operate, of low cost, there is larger industrial value.
The invention will be further described With reference to embodiment.
Specific implementation mode
Embodiment 1
The analytical instrument and equipment used in the present embodiment：Gas chromatography mass spectrometry, (U.S.'s Agilent is public by MS5973N-GC6890N
Department)；Nuclear Magnetic Resonance, II I 400M of AVANCE DMX (TMS internal standards, Bruker companies)；High performance liquid chromatograph：
Agilent Technologies 1200 Series；Infrared spectrometer, NICOLET 360FT-IR (U.S. Buddhist nun high-tensile strength instruments
Company).
Embodiment 1：The chlorination of fluorenes
It by glacial acetic acid 1200mL, fluorenes (I) 166.2g (1 mole) and is added in 2500mL four-hole bottles, maintains interior warm 40 DEG C of left sides
Chlorine, high performance liquid chromatography tracing detection reaction, until the reaction was complete for 2- chlorine fluorenyls sheet are passed through under right mechanical agitation.Stop leading to chlorine,
2h is stirred at 40 DEG C, temperature rising reflux is complete molten transparent to reaction solution, is cooled to room temperature, filters, solid 2,7- dichloro fluorenes, after drying
98 grams, liquid content 98.2% (0.409 mole), yield 40.9%.Mother liquor is yellow transparent liquid, through liquid chromatographic detection,
Each related component content such as table 1.
Each component ratio in table 1, mother liquor
By mother liquor be equally divided into 10 parts it is spare.
Embodiment 2：2,7- dichloro fluorene acetic acid mother liquor zinc powder reduction dechlorinations
The mother liquor in 1 part of embodiment 1 is taken, is added in 250mL four-hole bottles, is criticized at 20 DEG C under stirring and adds 13.1g zinc powders
(0.2 mole), about 30min is added.Then at 15 DEG C of reaction 2h, filtering, 10 milliliters of acetic acid foam washings of solid, merging filtrate is nothing
Color transparency liquid.Through liquid chromatographic detection, each related component content such as table 2.
Table 2, mother liquor each component ratio after zinc powder is handled
Embodiment 3：The chlorination again of the mother liquor of reduction dechlorination
Mother liquor in above-described embodiment 2 after reduction dechlorination is added in 250mL four-hole bottles, interior 40 DEG C or so of temperature is maintained
Chlorine, high performance liquid chromatography tracing detection reaction, until the reaction was complete for 2- chlorine fluorenyls sheet are passed through under stirring.Stop leading to chlorine, at 40 DEG C
2h (each related component content such as table 3 of liquid chromatographic detection) is stirred, 60 DEG C lower prior to pump vacuum or less are recovered under reduced pressure 50mL second
Acid, then temperature rising reflux is complete molten transparent to reaction solution, is cooled to room temperature, filters, solid 2,7- dichloro fluorenes, 5.6 grams after drying,
Liquid content 98.0% (0.023 mole).Mother liquor is yellow transparent liquid (each related component content such as table of liquid chromatographic detection
4), can continue to be applied mechanically with zinc powder reduction dechlorination.
Table 3, zinc powder treated mother liquor each component ratio after chlorination again
Each component ratio in Mother liquor is filtered in table 4, again chlorination
Through a reduction dechlorination, after leading to chlorine again, product total recovery is increased to 63.9% by original 40.9%, simultaneously
Organic mixing solid waste is greatly reduced.
Embodiment 4：2,7- dichloro fluorene acetic acid mother liquor zinc powder reduction dechlorinations
The mother liquor in 1 part of embodiment 1 is taken, is added in 250mL four-hole bottles, is criticized at 20 DEG C under stirring and adds 13.1 grams of zinc powders
(0.2 mole), about 30min is added.Then at 20 DEG C of reaction 2h, filtering, 10 milliliters of acetic acid foam washings of solid, merging filtrate is nothing
Color transparency liquid.Through liquid chromatographic detection, each related component content is as shown in table 5.
Table 5, mother liquor each component ratio after zinc powder is handled
Embodiment 5：Chlorination again after raw material is added in the mother liquor of reduction dechlorination
Mother liquor in above-described embodiment 4 after reduction dechlorination is added in 250mL four-hole bottles, 6.7 grams of fluorenes (0.041 are added
Mole), after stirring evenly, maintain to be passed through chlorine under 40 DEG C or so the stirrings of interior temperature, the reaction of high performance liquid chromatography tracing detection, until
The reaction was complete for 2- chlorine fluorenyls sheet.Stop leading to chlorine, 2h (each related component content such as table 6 of liquid chromatographic detection) is stirred at 40 DEG C, so
Temperature rising reflux is complete molten transparent to reaction solution afterwards, is cooled to room temperature, filters, solid 2,7- dichloro fluorenes, 10.8 grams after drying, liquid phase
Content 98.3% (0.045 mole), once through yield 109.8% (6.7 grams of calculating of raw material are newly added), total recovery after conversion
45% (being started with the fluorenes one contained in mother liquor with being newly added).Mother liquor is yellow transparent liquid (each related component of liquid chromatographic detection
Content such as table 7), it can continue to be applied mechanically with zinc powder reduction dechlorination.
Table 6, zinc powder treated mother liquor each component ratio after chlorination again
Each component ratio in Mother liquor is filtered in table 7, again chlorination
Embodiment 6-11：The mother liquor of reduction dechlorination is repeatedly applied mechanically
The mother liquor (being known as a mother liquor) in 1 part of embodiment 1 is taken, is handled by 4 conditional reduction dechlorination of above-described embodiment,
6.7 grams of fluorenes (0.041 mole) are added later, after stirring evenly, maintain to be passed through chlorine, efficient liquid under 40 DEG C or so the stirrings of interior temperature
Phase chromatogram tracking detection reaction, until the reaction was complete for 2- chlorine fluorenyls sheet.Stop leading to chlorine, 2h is stirred at 40 DEG C, then temperature rising reflux is extremely
Reaction solution is complete molten transparent, is cooled to room temperature, filters, and it is 2,7- dichloro fluorenes to obtain solid, and drying is weighed, and surveys liquid content and (obtains
Solid be known as 2 solids).Mother liquor then again according to above-mentioned reduction dechlorination condition, continues reduction dechlorination and (is known as secondary mother
Liquid), 6.7 grams of fluorenes are added later, repeats the above process, respectively obtains the product (3-7 solid) of different batches；Each batch obtains
To solid and related yield be shown in Table 8.
The multiple reduction dechlorination of table 8, mother liquor, the input raw material each batch product and content of chlorination again again
It summarizes：
1. using the processing method of the application, the recycling of 2,7- dichloro fluorene acetic acid mother liquors, a side can be effectively realized
Face reduces waste discharge, alleviates environmental protection pressure, on the other hand can effectively improve the reaction yield of 2,7- dichloro fluorenes, and
And the processing method of the present invention, cost is relatively low, the product of processing in addition to product, only generate a small amount of solid mixture containing zinc (zinc,
Zinc acetate and zinc chloride), filtering can remove, and reaction solution post-processing is simple, environmental-friendly.
2, the application method is easy to operate, has larger industrial value.
The processing method of the present invention is very suitable for industrial production, by through reduction dechlorination, then pressing centainly mother liquor
After amount supplement raw material, total raw material (containing each intermediate) amount in system can be made to keep stablizing, after leading to chlorine again, newly to put into
Raw material calculate, once through yield is very high, and product adds up total recovery and greatly improve (such as to apply mechanically 6 times, then improved by initial 40.9%
To 80.0%), organic mixing solid waste is greatly reduced.It is worth with essential industry.
Claims (6)
1. one kind 2, the recovery and treatment method of 7- dichloro fluorenes reaction mother liquors, which is characterized in that include the following steps：By 2,7- dichloros
Fluorene acetic acid mother liquor obtains the mixed liquor based on 2- chlorine fluorenes and fluorenes through zinc powder reduction dechlorination, which is removed by filtration zinc powder
And zinc acetate, then direct chlorination or chlorination preparation 2, the 7- dichloro fluorenes together with raw material fluorenes.
2. the recovery and treatment method of one kind 2,7- dichloro fluorenes reaction mother liquors as described in claim 1, it is characterised in that：It is described to go back
In original reaction, reaction temperature is 0-30 DEG C.
3. the recovery and treatment method of one kind 2,7- dichloro fluorenes reaction mother liquors as claimed in claim 2, it is characterised in that：It is described to go back
The temperature of original reaction is 15-20 DEG C.
4. the recovery and treatment method of one kind 2,7- dichloro fluorenes reaction mother liquors as described in claim 1, it is characterised in that：It is described to go back
In original reaction, the mole of zinc powder and the molar ratio of fluorenes are 1-5:1.
5. the recovery and treatment method of one kind 2,7- dichloro fluorenes reaction mother liquors as claimed in claim 4, it is characterised in that：It is described to go back
In original reaction, the mole of zinc powder and the mole ratio of fluorenes are 1.8-2.2:1.
6. the recovery and treatment method of one kind 2,7- dichloro fluorenes reaction mother liquors as claimed in claim 4, it is characterised in that：It is described to go back
In original reaction, the mole of zinc powder and the mole ratio of fluorenes are 1.5-2.5:1.
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| CN201810562616.6A CN108586189A (en) | 2018-06-04 | 2018-06-04 | A kind of recovery and treatment method of 2,7- dichloros fluorenes reaction mother liquor |
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| CN201810562616.6A CN108586189A (en) | 2018-06-04 | 2018-06-04 | A kind of recovery and treatment method of 2,7- dichloros fluorenes reaction mother liquor |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786399A (en) * | 2011-05-16 | 2012-11-21 | 湖南斯威森生化技术有限公司 | New synthesis method for benflumetol intermediate 2,7-dichloro-4-chloroacetylfluorene |
| CN105001044A (en) * | 2015-06-30 | 2015-10-28 | 杭州巴洛特生物科技有限公司 | Synthesis method of 2,7-dichlorofluorene |
| CN107285990A (en) * | 2017-06-24 | 2017-10-24 | 江西科美香料有限公司 | A kind of preparation method of 2,7 dichloro fluorenes |
-
2018
- 2018-06-04 CN CN201810562616.6A patent/CN108586189A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786399A (en) * | 2011-05-16 | 2012-11-21 | 湖南斯威森生化技术有限公司 | New synthesis method for benflumetol intermediate 2,7-dichloro-4-chloroacetylfluorene |
| CN105001044A (en) * | 2015-06-30 | 2015-10-28 | 杭州巴洛特生物科技有限公司 | Synthesis method of 2,7-dichlorofluorene |
| CN107285990A (en) * | 2017-06-24 | 2017-10-24 | 江西科美香料有限公司 | A kind of preparation method of 2,7 dichloro fluorenes |
Non-Patent Citations (1)
| Title |
|---|
| 谢凝子 等: "锌粉对1,2,4-三氯苯的脱氯性能", 《化工环保》 * |
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Application publication date: 20180928 |