CN106588612A - Acidic ionic liquid catalysis method for synthesis of 5-chloro-1-indanone - Google Patents
Acidic ionic liquid catalysis method for synthesis of 5-chloro-1-indanone Download PDFInfo
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- CN106588612A CN106588612A CN201611078872.5A CN201611078872A CN106588612A CN 106588612 A CN106588612 A CN 106588612A CN 201611078872 A CN201611078872 A CN 201611078872A CN 106588612 A CN106588612 A CN 106588612A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
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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
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- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention especially relates to an acidic ionic liquid catalysis method for synthesis of 5-chloro-1-indanone, belonging to the technical field of preparation of pesticide intermediates and medical intermediates. According to the invention, 5-chloro-1-indanone is prepared through cyclization of 3-chloro-1-(4-chlorophenyl)-1-acetone under the catalysis of acidic ionic liquid (Et3NHCl-nAlCl3, wherein n is greater than 1) and the action of an organic solvent (normal octane or petroleum ether with a temperature of 90 to 120 DEG C) at a low temperature (less than 120 DEG C). Compared with an aluminium trichloride method, the acidic ionic liquid catalysis method provided by the invention has the beneficial effects of small catalyst amount, low temperature, low cost and high product yield.
Description
Technical field
The invention belongs to organic chemistry filed, more particularly to a kind of pesticide intermediate and the chloro- 1- indones of medicine intermediate 5-,
A kind of specifically presence of acidic ionic liquid catalyst method of the chloro- 1- indones of synthesis 5-.
Background technology
The chloro- 1- indones of 5- are the important intermediate of du pont company's new varieties of pesticides indoxacarb (indoxacarb), together
When be also a kind of important medicine intermediate.Indoxacarb is a kind of broad spectrum activity brand new class efficient pesticides, with structure it is new, make
The features such as with mechanism uniqueness, low consumption, environmental friendliness and person poultry safety, and there is no cross resistance with other insecticides, it is to replace
For one of organic phosphorous insecticide ideal kind, the patent (WO of indoxacarb：9211249) protection period expired in 2010,
A large amount of pesticide producing producers will produce indoxacarb, therefore the market prospect of the chloro- 1- indones of 5- will be very good.
The synthetic route of the chloro- 1- indones of 5- mainly has following several：
1) chloro-cinnamic acid method between, US：5177075 with a chloro-cinnamic acid as raw material, hydrogenated to obtain m-chloro benzenpropanoic acid, chlorination
M-chloro phenylpropyl alcohol acyl chlorides is obtained, last cyclization obtains the chloro- 1- indones of 5-.There is selectivity in the shortcoming of the method, can shape when being mainly cyclization
The chloro- 1- indones of proportional 7-, cause product impure, there is separation problem.
2)CN：104910001A disclose with formic acid, diethylamine as organic solvent in 3- chlorobenzaldehydes and malonic acid reaction
Prepared 3- chlorobenzenes propanoic acid, then with dichloromethane as organic solvent, zinc chloride is catalyst, and at -10～80 DEG C Fu Ke acyl groups are carried out
Change reaction and the chloro- 1- indones of 5- are obtained.Still there is selectivity during cyclization, the chloro- 1- indones of a certain proportion of 7- can be formed, cause
Product is impure, there is separation problem.And it is also higher with the cost of 3- chlorobenzaldehyde methods.
3) the chloro- 1- of 3- (4- chlorphenyls) -1- acetone methods
Mainly there are two：There is friedel-craft reaction in the presence of a catalyst by 3- chlorpromazine chlorides and chlorobenzene and obtain in the first,
The catalyst for using has aluminum chloride, trifluoromethanesulfonic acid, Fluohydric acid ./boron trifluoride, concentrated sulphuric acid and solid acid etc..Such as patent
GB：993055, WO：0043342, CN：103601625A、CN：1403434、WO：9620151、FR：2784986 etc., wherein three
Although fluorine methanesulfonic acid method cyclization high income, there are problems that trifluoromethanesulfonic acid must be significantly excessive and expensive；It is wherein dense
Sulfuric acid process (fine-chemical intermediate, 2006,36 (2):The problem for 26-28) existing is that the utilization rate of equipment and installations of ring-closure reaction is not high,
Sulfuric acid dosage is too big, consume substantial amounts of freezing the problems such as, need to further solve.It two also can under a certain pressure by chlorobenzene first
Acyl chlorides obtains the chloro- 1- of 3- (4- chlorphenyls) -1- acetone (DE with ethylene under Aluminium Trichloride as Catalyst：3247823).Although yield
Height, but there is a problem of that raw material is not easy to obtain and needs pressurization, therefore, it is difficult to industrialization large-scale production.
In view of above-mentioned present situation, by the comparison to synthetic route, it is considered to which cost of material and the industrialized difficulty or ease present invention are still
Take with 3- chlorpromazine chlorides, chlorobenzene as the chloro- 1- of Material synthesis 3- (4- chlorphenyls) -1- acetone.The chloro- 1- indones of 5- are obtained in cyclization
Friedel-Crafts reaction in catalyst is made using acidic ion liquid.Therefore, in terms of environment, with traditional aluminum chloride work
Skill is compared, and present invention, avoiding strong acid to the pollution problem of environment and the process of a large amount of waste water.
The content of the invention
For above-mentioned technical problem of the prior art, it is an object of the invention to provide a kind of acidic ion liquid is catalyzed
The method that the Friedel-Crafts reaction of agent obtains the chloro- 1- indones of 5- by the chloro- 1- of 3- (4- chlorphenyls) -1- acetone cyclizations.
Described acidic ion liquid belongs to the one kind in ionic liquid.Ionic liquid is as new green solvent and urges
Agent, be widely used in being acylated, be polymerized, isomerization, the reaction such as alkylation and epoxidation, and with preferable selectivity.Its
In easily industrialized belong to AlCl3And Et3The ionic liquid that NHCl is formed.Work as AlCl3And Et3The mol ratio of NHCl less than 1,
During equal to 1 and more than 1, ionic liquid is respectively in alkalescence, neutral and acid.Due to the chloro- 1- of 3- (4- chlorphenyls) -1- acetone cyclizations
The catalyst for obtaining the Friedel-Crafts reaction of the chloro- 1- indones of 5- suitably uses acidic catalyst, therefore the present invention selects AlCl3With
Et3Et of mol ratio n of NHCl more than 13NHCl-nAlCl3Ionic liquid makees catalyst.
To reach above-mentioned purpose, the technical solution used in the present invention is：
A kind of synthetic method of the chloro- 1- indones of 5-, comprises the steps：
1) Et of 10-100 mass parts is put into in cyclization kettle3NHCl-nAlCl3Ionic liquid and 10-100 mass parts it is molten
Agent such as normal octane or petroleum ether (90-120 DEG C), rise high-temperature to 70-80 DEG C under stirring；
2) slowly to step 1) in cyclization kettle in put into 100-1000 mass parts the chloro- 1- of 3- (4- chlorphenyls) -1- third
Ketone and step 1) such as normal octane or petroleum ether be the solution that solvent is formed, rise high-temperature to 110-120 DEG C, insulation reaction 3-4
Hour, the hydrogen chloride gas of generation are absorbed into water absorption tower, and course of reaction adopts chromatogram tracking, reaction to finish, and will expect
Liquid is evacuated to hydrolysis kettle；
3) hydrolysis kettle is cooled down using recirculated water, and feed liquid is maintained into temperature between 90-95 DEG C, to add 100-1000
Mass parts water is hydrolyzed, and after finishing, stops stirring, stands to divide and goes water phase, oil phase (solvent normal octane or petroleum ether phase) to proceed to
Decolouring kettle, conventional desolventing technology.
4) will be through step 3) feed liquid suction crystallization kettle after desolventing technology, 0-30 DEG C of crystallization is cooled to, centrifugal treating is dried
It is dry, get product.
Specific embodiment
Present invention also offers a kind of example of the presence of acidic ionic liquid catalyst method of the chloro- 1- indones of synthesis 5-, below leads to
Cross embodiment to illustrate the present invention, but the present invention is not limited by these.
Embodiment
50 grams of Et are added in the 500mL four-hole boiling flasks equipped with thermometer, agitator and condensing units3NHCl-
1.8AlCl3Ionic liquid (mol ratio is 1.8) and 50 grams of normal octanes, rise high-temperature to 70-80 DEG C under stirring.It is slow again
The solution that slow chloro- 1- (4- the chlorphenyls) -1- acetone of 100 grams of 3- of input and 100 grams of normal octanes are formed, rises high-temperature to 110-120
DEG C, insulation reaction 3-4 hour, the hydrogen chloride gas of generation are derived from condensing tube top and absorbed into water absorption tower, instead
Answer process to adopt the content of chromatogram tracking, the chloro- 1- of 3- (4- chlorphenyls) -1- acetone no longer to decline, after completion of the reaction take out feed liquid
It is slowly added to 100 grams of water to the hydrolysis kettle of 1000mL jacketeds, stirring to be hydrolyzed, hydrolysis kettle carries out cold using recirculated water
But, feed liquid is maintained into temperature between 90-95 DEG C, after finishing, to stop stirring, feed liquid proceeds to separatory funnel, stands to divide and remove water
Phase, normal octane mutually proceeds to decolouring kettle, the feed liquid suction crystallization kettle after conventional desolventing technology, 0-30 DEG C of crystallization is cooled to, at centrifugation
Reason, drying, obtains final product 72 grams of the chloro- 1- indones finished products of 5-.Fusing point is 92.6-93.5 DEG C, yield 72%.
Claims (3)
1. the presence of acidic ionic liquid catalyst method of the chloro- 1- indones of a kind of synthesis 5-, it is characterised in that comprise the steps：Cyclization kettle
The acidic ion liquid of middle input 10-100 mass parts and the organic solvent of 10-100 mass parts, under stirring high-temperature is risen
To 70-80 DEG C.The solution that the chloro- 1- of 3- (4- the chlorphenyls) -1- acetone and organic solvent of 100-1000 mass parts are formed is put into again,
High-temperature is risen to 110-120 DEG C, insulation reaction 3-4 hour, the hydrogen chloride gas of generation are absorbed into water absorption tower, reaction
Process adopts chromatogram tracking, reaction to finish, and feed liquid is evacuated to into hydrolysis kettle；Add 100-1000 mass parts water to be hydrolyzed, hydrolyze
Kettle is cooled down using recirculated water, and feed liquid is maintained into temperature between 90-95 DEG C, after finishing, to stop stirring, is stood to divide and is removed water
Phase, organic solvent mutually proceeds to decolouring kettle, the feed liquid suction crystallization kettle after conventional desolventing technology, is cooled to 0-30 DEG C of crystallization, centrifugation
Process, drying obtains final product the chloro- 1- indones of 5-.
2. the presence of acidic ionic liquid catalyst method of the chloro- 1- indones of a kind of synthesis 5- according to claim 1, described acidity
Ionic liquid is N,N-Diethylethanamine hydrochloride-aluminum chloride Et3NHCl-nAlCl3, for calculation in the molar ratio, the trichlorine in acidic ion liquid
Change aluminum to be more than with the ratio n of triethylamine hydrochlorate is 1.
3. a kind of presence of acidic ionic liquid catalyst method of the chloro- 1- indones of synthesis 5- according to claim 1, its feature exists
In：Described organic solvent is such as normal octane or petroleum ether (90-120 DEG C).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534971A (en) * | 2018-11-05 | 2019-03-29 | 宿迁市科莱博生物化学有限公司 | 5- chlorine indone process units and its production method |
| CN111100057A (en) * | 2019-12-04 | 2020-05-05 | 天方药业有限公司 | Method for synthesizing diclofenac sodium intermediate 1- (2, 6-dichlorophenyl) indoline-2-ketone |
| CN111285803A (en) * | 2020-03-18 | 2020-06-16 | 湖南复瑞生物医药技术有限责任公司 | Preparation method of 6-hydroxy-3, 4-dihydro-2 (1H) -quinolone |
| CN115974664A (en) * | 2023-01-18 | 2023-04-18 | 合肥工业大学 | Synthesis method of 5-chloro-1-indanone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103601625A (en) * | 2013-11-26 | 2014-02-26 | 姜堰市科研精细化工有限公司 | Method for producing 5-chloro-1-indanone |
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- 2016-11-30 CN CN201611078872.5A patent/CN106588612A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103601625A (en) * | 2013-11-26 | 2014-02-26 | 姜堰市科研精细化工有限公司 | Method for producing 5-chloro-1-indanone |
Non-Patent Citations (1)
| Title |
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| 陈晗等: "盐酸三乙胺-三氯化铝离子液体催化甲苯与氯代叔丁烷烷基化反应", 《高校化学工程学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534971A (en) * | 2018-11-05 | 2019-03-29 | 宿迁市科莱博生物化学有限公司 | 5- chlorine indone process units and its production method |
| CN109534971B (en) * | 2018-11-05 | 2021-12-28 | 宿迁市科莱博生物化学有限公司 | 5-chloro-indanone production device and production method thereof |
| CN111100057A (en) * | 2019-12-04 | 2020-05-05 | 天方药业有限公司 | Method for synthesizing diclofenac sodium intermediate 1- (2, 6-dichlorophenyl) indoline-2-ketone |
| CN111100057B (en) * | 2019-12-04 | 2021-06-11 | 天方药业有限公司 | Method for synthesizing diclofenac sodium intermediate 1- (2, 6-dichlorophenyl) indoline-2-ketone |
| CN111285803A (en) * | 2020-03-18 | 2020-06-16 | 湖南复瑞生物医药技术有限责任公司 | Preparation method of 6-hydroxy-3, 4-dihydro-2 (1H) -quinolone |
| CN111285803B (en) * | 2020-03-18 | 2024-04-09 | 湖南复瑞生物医药技术有限责任公司 | Preparation method of 6-hydroxy-3, 4-dihydro-2 (1H) -quinolone |
| CN115974664A (en) * | 2023-01-18 | 2023-04-18 | 合肥工业大学 | Synthesis method of 5-chloro-1-indanone |
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Application publication date: 20170426 |