CN108203385A - A kind of method for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone - Google Patents
A kind of method for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone Download PDFInfo
- Publication number
- CN108203385A CN108203385A CN201611180982.2A CN201611180982A CN108203385A CN 108203385 A CN108203385 A CN 108203385A CN 201611180982 A CN201611180982 A CN 201611180982A CN 108203385 A CN108203385 A CN 108203385A
- Authority
- CN
- China
- Prior art keywords
- fluoro
- nitrobenzophenones
- catalyst
- acetone
- reaction
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Synthetic method more particularly to large porous strong acid type catalytic resin the invention discloses a kind of pesticide intermediate is preparing the method for 3 (4 fluorine, 2 nitrobenzophenone) acetone：Using 3 (4 fluorine, 2 nitrobenzophenone) 4 hydroxyl, 3 amylene, 2 ketone as raw material, acetic acid is reaction medium, and large porous strong acid type catalytic resin is catalyst, prepares target compound.Preparation method provided by the invention, reaction condition is mild, it is easy to operate, greatly reduce quantity of three wastes and the corrosion to equipment.
Description
Specification
Technical field
The invention belongs to organic synthesis field, more particularly to a kind of method for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone.
Technical background
2- nitrophenylacetone class compounds since intramolecular is there are nitro and carbonyl Liang Zhong functional groups, be prepare it is various miscellaneous
Change the important intermediate of class compound.3- (the fluoro- 2- nitrobenzophenones of 4-) acetone (3- (4-fluoro-2-nitrophenyl)
Propan-2-one organic synthesis intermediate) is important, all there is larger application in terms of the production of medical and pesticide etc.
Value.It is the important intermediate for synthesizing amisulbrom especially in terms of pesticide.Amisulbrom (Amisulbrom) is a kind of
Triazolylsulfonamide series bactericidal agent, the fungicide have higher activity to the vegetable plague as caused by Oomycete and downy mildew.But
So far, the medicament that can effectively prevent oomycetes diseases is not very much, and the appearance of amisulbrom can be to a certain degree
Upper this problem of solution.The compound annual growth rate of the fungicide is very high, has very big development potentiality in particular market.But
The synthesis technology of domestic 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone is very immature, seriously limits the use of amisulbrom.Cause
This, it is very urgent to the improvement in synthesis work of 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone.
CN1646522 provides a kind of preparation method of 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, is solvent with acetic acid, dilute
Sulfuric acid is catalyst, by 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyl -3- amylene -2- ketone by de-carbonyl reaction synthesis 3- (4-
Fluoro- 2- nitrobenzophenones) acetone, yield 89%.This method uses a large amount of sulfuric acid, and high temperature is needed first to deviate from after reaction
Most acetic acid water, then plus toluene extracts product, not only cumbersome, and with the abjection of dampening, sulfuric acid concentration increases,
Product section is caused to be carbonized, tar content increases, and processing sulfuric acid generates a large amount of waste water and waste coke oil.It is special that processing procedure needs
Equipment, and it is very big to operation equipment corrosion.Therefore, problems existing for this method, especially sulfuric acid usage amount is big, causes
Acid-bearing wastewater amount it is big the problem of need to improve.
Macroporous strong acid resin catalyst styrene type cation exchange resin, the resin have suitable macroporous netlike knot
Structure and higher catalytic activity and stronger wearability and inoxidizability, it is corrosion-free to equipment, it is liquid strong acid catalyst
Upgrade substitute products, be widely used in field of fine chemical etherificate produce MTBE, alkylation, esterification, ester-type hydrolysis, alkene
The organic reactions processes such as hydration, alcohols dehydration, ammonification, acetone double focusing.
Invention content
The object of the present invention is to provide a kind of preparations that can simplify operation, reduce three wastes yield, reduce equipment corrosion
The method of 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone.
Purpose to realize the present invention, the present invention use technical solution for：
A kind of catalyst synthesizes 3- (the fluoro- 2- nitre of 4- for 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyl -3- amylene -2- ketone
Base phenyl) acetone method, reaction equation is as follows：
Using 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyl -3- amylene -2- ketone as raw material, acetic acid is solvent, large porous strong acid type
Resin is catalyst, and 1-12h is reacted at 80-200 DEG C, and decrease temperature crystalline filters, dry, obtains 3- (the fluoro- 2- nitrobenzophenones of 4-)
Acetone.
Macroporous strong acid resin catalyst is using the polymer of styrene and divinylbenzene as carrier, after sulfonated reaction
Macropore strong acid cation exchanger resin obtained.This patent relates generally to commercially available common D001, D002, D61, and D62 etc. is
Row resin, but it is not limited only to these types of resin, preferably D002.
The additive amount of resin catalyst is preferably relative to 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyl -3- amylene -2- ketone
0.01-5 times, more preferably 0.1-1 times.
The reaction temperature is 80-200 DEG C, preferably 90-120 DEG C.The reaction time is 1-12h, preferably 3-8h.
Solvent for use usage amount is preferably 1-12 times relative to 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyl -3- amylene -2- ketone, more excellent
It is selected as 1-6 times.
As the processing method of reaction solution after reaction, catalyst is filtered out after reaction, distillation removes filtrate as needed
Remove solvent, added in coarse reactants after water and solvent unmixing with water fully wash, organic layer is distilled, crystallization and purification or
Person's decrease temperature crystalline as needed filters, dry, obtains target compound 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone.
The catalyst of recycling, not being poisoned can multiple Reusability.Processing method as poisoned catalyst：Recycling
Catalyst through solvent soaking 1-24 hours, preferably 1-10 hours, filter, drying, you can reuse.Solvent for use, can be with
Enumerate such as toluene, dimethylbenzene, trimethylbenzene, acetone, butanone, methylisobutylketone, cyclohexanone, methyl formate, Ethyl formate, acetic acid
The alcohols such as ethyl ester, methyl acetate, butyl acetate, ethyl propionate, methanol, ethyl alcohol, isopropanol, butanol, formic acid, acetic acid, propionic acid etc.
Organic acid, n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone can also use the mixed of these
Bonding solvent.
The invention has the advantages that：
The present invention replaces sulfuric acid or hydrochloric acid to carry out decarbonylation base experiment using specific macroporous strong acid resin as catalyst.
By a large amount of condition test, suitable response parameter and reaction condition are determined, reduce quantity of three wastes, simplify operation, reduce environment
Pollution and equipment corrosion.It is specific as follows：
1st, hard resin is added in reaction unit as catalyst, is directly filtered after reaction, filtrate abjection part
Direct crystallization after solvent, is obtained by filtration product, improves product content and yield.It avoids using inorganic acid catalyst to environment
Pollution and the corrosion to production equipment, and are easily isolated, and the catalyst filtered out, which can directly cover to use down, to be criticized, can be used 30 times with
On.
2nd, reaction condition it is mild, it is easy to operate, greatly reduce waste liquid amount, have larger industrial application value.
Specific embodiment
The following examples are used to the present invention be further described, but do not form limitation of the invention.
Embodiment 1
240g acetic acid, 41.2g 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyls -3- penta are added in the reaction bulb of 500ml
Alkene -2- ketone, 10g resin catalyst D001 are stirred and are gradually heating to 110 DEG C, reaction 3h, liquid chromatogram tracking 3- (the fluoro- 2- of 4-
Nitrobenzophenone) -4- hydroxyl -3- amylene -2- ketone content<When 0.2%, reaction terminates.Reaction solution filters while hot, and with 20g second
Acid washing catalyst, the solvent of filtrate abjection about 2/3, is cooled to 25-30 DEG C, a large amount of solids is precipitated, and filters, after filtration cakes torrefaction
To 32.2g3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, content 95%, yield 90%, filtrate precipitation, solvent and catalyst directly cover
It uses down and criticizes, residue 8g.The method 100g products generate 25g organic detritus, and (catalyst is according to using 30 times for 1g dead catalyst
Discarded meter), this step reaction does not generate exhaust gas and waste water.
Embodiment 2
400g acetic acid, 82.4g 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyls -3- penta are added in the reaction bulb of 1000ml
Alkene -2- ketone, 20g resin catalyst D002 are stirred and are gradually heating to 112 DEG C, reaction 3h, liquid chromatogram tracking 3- (the fluoro- 2- of 4-
Nitrobenzophenone) -4- hydroxyl -3- amylene -2- ketone content<When 0.2%, reaction terminates.Reaction solution filters while hot, and with 40g second
Acid washing catalyst, filtrate deviate from the solvent of about half, are cooled to 25-30 DEG C, and a large amount of solids are precipitated, filtering, after filtration cakes torrefaction
66.9g3- (the fluoro- 2- nitrobenzophenones of 4-) acetone is obtained, content 97%, yield 95.5%, filtrate precipitation, solvent and catalyst are straight
Female connector, which is used down, to be criticized, residue 12g.The method 100g products generate 18g organic detritus, and (catalyst is according to making for 1g dead catalyst
With 30 discarded meters), this step reaction does not generate exhaust gas and waste water.
Embodiment 3
500g acetic acid, 82.4g3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyls -3- penta are added in the reaction bulb of 1000ml
Alkene -2- ketone, 40g resin catalyst D61 are stirred and are gradually heating to 90 DEG C, reaction 6h, liquid chromatogram tracking 3- (the fluoro- 2- nitre of 4-
Base phenyl) -4- hydroxyl -3- amylene -2- ketone content<When 0.2%, reaction terminates.Reaction solution filters while hot, and with 40g acetic acid
Washing catalyst, the solvent of filtrate abjection about 2/3, is cooled to 25-30 DEG C, a large amount of solids is precipitated, and filters, and is obtained after filtration cakes torrefaction
65.8g3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, content 95%, yield 92%, filtrate precipitation, solvent and catalyst are directly applied mechanically
To lower batch, residue 15g.The method 100g products generate 23g organic detritus, and (catalyst is according to using 30 times for 2g dead catalyst
Discarded meter), this step reaction does not generate exhaust gas and waste water.
Embodiment 4
300g acetic acid, 82.4g 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyls -3- penta are added in the reaction bulb of 500ml
Alkene -2- ketone, 50g resin catalyst D62 are stirred and are gradually heating to 120 DEG C, react 5.5h, (4- is fluoro- by liquid chromatogram tracking 3-
2- nitrobenzophenones) -4- hydroxyl -3- amylene -2- ketone content<When 0.2%, reaction terminates.Reaction solution filters while hot, and uses 40g
Acetic acid washing catalyst, filtrate deviate from the solvent of about half, are cooled to 25-30 DEG C, and a large amount of solids are precipitated, filtering, filtration cakes torrefaction
After obtain 67.2g 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, content 94%, yield 93%, filtrate precipitation, solvent and catalyst are straight
Female connector, which is used down, to be criticized, residue 20g.The method 100g products generate 30g organic detritus, 2.5g dead catalyst (catalyst according to
Use 30 discarded meters), this step reaction does not generate exhaust gas and waste water.
Embodiment 5
Using the method for CN1646522,400g acetic acid, 41.2g 3- (the fluoro- 2- nitre of 4- are added in the reaction bulb of 1000ml
Base phenyl) -4- hydroxyl -3- amylene -2- ketone, 320g50% aqueous sulfuric acids, stirring and gradual temperature rising reflux, react 4h, liquid phase
The content of chromatogram tracking 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyl -3- amylene -2- ketone<When 0.2%, reaction terminates.Reaction solution
Precipitation removes part water and acetic acid, puts into 800ml toluene and 1600ml water, liquid separation, and water layer is extracted 2 times with 1200ml toluene, is closed
And toluene layer, with 1200ml water washings 3 times, 600ml saturated common salts water washing 1 time, anhydrous sodium sulfate drying, after filtering precipitation,
Obtain 30.4g 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone.The method 100g products generate 1000g or so acid-bearing wastewater and 3500g
Neutral waste water (water jacket of washing organic layer is with three times).
Claims (7)
- A kind of 1. method for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, it is characterised in that：Reaction equation is as follows：Using 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyl -3- amylene -2- ketone as raw material, acetic acid is solvent, macroporous strong acid resin For catalyst, 1-12h is reacted at 80-200 DEG C, decrease temperature crystalline filters, dry, obtains 3- (the fluoro- 2- nitrobenzophenones of 4-) third Ketone.
- 2. the method according to claim 1 for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, it is characterised in that：Described Macroporous strong acid resin catalyst be using the polymer of styrene and divinylbenzene as carrier, it is obtained big after sulfonated reaction Hole storng-acid cation exchange resin, this patent relate generally to the series plastics such as commercially available common D001, D002, D61, D62, but It is not limited only to these types of resin.
- 3. the method according to claim 1 for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, it is characterised in that：The tree The additive amount of fat catalyst is 0.01-5 times relative to 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyl -3- amylene -2- ketone.
- 4. the method according to claim 1 for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, it is characterised in that：Described Reaction temperature is 80-200 DEG C, and the reaction time is 1-12h.
- 5. the method according to claim 1 for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, it is characterised in that：It is used molten Agent is acetic acid, and solvent usage amount is 1-12 times relative to 3- (the fluoro- 2- nitrobenzophenones of 4-) -4- hydroxyl -3- amylene -2- ketone.
- 6. the method according to claim 1 for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone, it is characterised in that：As anti- The processing method of reaction solution, filters out catalyst, solvent is distilled off in filtrate as needed, in crude reaction after reaction after answering After addition water and solvent unmixing with water fully wash in object, organic layer is distilled, crystallization and purification or as needed cooling Crystallization filters, dry, obtains target compound 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone.
- 7. resin catalyst according to claim 2, it is characterised in that：The catalyst of recycling, not being poisoned can be more Secondary Reusability.Processing method as poisoned catalyst：The catalyst of recycling is filtered, drying through solvent soaking 1-24 hours, It is i.e. reusable.Solvent for use can enumerate such as toluene, dimethylbenzene, trimethylbenzene, acetone, butanone, methylisobutylketone, ring Hexanone, methyl formate, Ethyl formate, ethyl acetate, methyl acetate, butyl acetate, ethyl propionate, methanol, ethyl alcohol, isopropanol, The organic acids such as the alcohols such as butanol, formic acid, acetic acid, propionic acid, n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl Pyrrolidones can also use these mixed solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611180982.2A CN108203385B (en) | 2016-12-20 | 2016-12-20 | Method for preparing 3- (4-fluoro-2-nitrophenyl) acetone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611180982.2A CN108203385B (en) | 2016-12-20 | 2016-12-20 | Method for preparing 3- (4-fluoro-2-nitrophenyl) acetone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108203385A true CN108203385A (en) | 2018-06-26 |
| CN108203385B CN108203385B (en) | 2021-03-09 |
Family
ID=62601942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611180982.2A Active CN108203385B (en) | 2016-12-20 | 2016-12-20 | Method for preparing 3- (4-fluoro-2-nitrophenyl) acetone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108203385B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004099A (en) * | 2019-12-09 | 2020-04-14 | 浙江利化新材料科技有限公司 | Method for preparing hexafluoroacetone by taking perfluoroepoxypropane as raw material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1646522A (en) * | 2002-04-01 | 2005-07-27 | 日产化学工业株式会社 | Processes for producing indole compound |
-
2016
- 2016-12-20 CN CN201611180982.2A patent/CN108203385B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1646522A (en) * | 2002-04-01 | 2005-07-27 | 日产化学工业株式会社 | Processes for producing indole compound |
Non-Patent Citations (1)
| Title |
|---|
| 霍稳周,: "强酸型阳离子交换树脂催化剂预处理研究", 《工业催化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004099A (en) * | 2019-12-09 | 2020-04-14 | 浙江利化新材料科技有限公司 | Method for preparing hexafluoroacetone by taking perfluoroepoxypropane as raw material |
| CN111004099B (en) * | 2019-12-09 | 2022-07-26 | 浙江利化新材料科技有限公司 | Method for preparing hexafluoroacetone by taking perfluoroepoxypropane as raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108203385B (en) | 2021-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102417498B (en) | The synthetic method of 3-(α-methoxyl group) methene cumarone-2 (3H)-one | |
| CN109232178B (en) | Novel method for preparing high-purity hydroxytyrosol | |
| CN105254544A (en) | Preparing method for bisphenol S | |
| CN101781235A (en) | Method for preparing 2-cyanophenol | |
| CN101845017A (en) | Preparation method of atracurium besilate intermediates | |
| CN105130926A (en) | Preparation method of methylene blue | |
| US8754256B2 (en) | Process for preparation of L-Arginine α-ketoglutarate 1:1 and 2:1 | |
| CN108203385A (en) | A kind of method for preparing 3- (the fluoro- 2- nitrobenzophenones of 4-) acetone | |
| CN101260092B (en) | Method for preparing cinepazide maleate | |
| CN112552244A (en) | Production process of 4, 6-dimethoxy-2-methylsulfonyl pyrimidine | |
| CN108026051A (en) | Prepare 1- methyl -3-（Trifluoromethyl）The method of -1H- pyrazoles -5- alcohol | |
| CN103772189B (en) | Synthesis method of diethylstilbestrol compound methyl pigeon pea ketonic acid A | |
| CN102382050A (en) | Preparation method of substituted 1, 2, 3 and 4- tetrahydroquinoline -4-one hydrochloride | |
| CN102040572A (en) | Production method of benzofuranone | |
| CN110330422B (en) | Preparation method of 2, 6-diethyl-4-methylphenylacetic acid | |
| EP4118068A1 (en) | Method for preparing benzamide compound | |
| CN110272451B (en) | Preparation method of tetraphenylphenol phosphonium salt | |
| CN103087033A (en) | Synthesis method of poly-substituted oxacycloheptatriene-3(2H) ketone compounds | |
| CN101302150B (en) | Synthetic method of 2-(2,4- dichlorophenoxy) propionic acid | |
| CN106866384B (en) | Preparation method of hydroxytyrosol | |
| CN106317042B (en) | A kind of synthetic method of the fluoro- 6- amino -4- of 7- (2- propargyls) -1,4- benzoxazines -3 (4H) -one derivative | |
| CN104926702A (en) | Preparation method for 2-methylmercapto-4-thrifluoromethyl benzoate | |
| CN100564340C (en) | (2E, 4E)-preparation method of 2-methyl-6-oxo-2 | |
| CN106748912B (en) | A kind of synthesis technology of sodium azulenesulfonate monohydrate | |
| CN104262332A (en) | Preparation method of olmesartan medoxomil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210204 Address after: No.12 Haipu North Road, Xinhe eco chemical technology industrial base, Pingdu City, Qingdao City, Shandong Province 266700 Applicant after: Qingdao hengning Biotechnology Co.,Ltd. Address before: 266109 Chengdong Industrial Park, Chengyang District, Qingdao, Shandong Province Applicant before: HAILIR PESTICIDES AND CHEMICALS Group |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |