CN1357529A - Prepn process of 2,3,4-trifluoro nitrobenzene - Google Patents
Prepn process of 2,3,4-trifluoro nitrobenzene Download PDFInfo
- Publication number
- CN1357529A CN1357529A CN 01127016 CN01127016A CN1357529A CN 1357529 A CN1357529 A CN 1357529A CN 01127016 CN01127016 CN 01127016 CN 01127016 A CN01127016 A CN 01127016A CN 1357529 A CN1357529 A CN 1357529A
- Authority
- CN
- China
- Prior art keywords
- trifluoronitrobenzene
- fluorine
- nitrated
- production method
- fluoro
- 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
Abstract
The preparation of 2,3,4-trifluoro nitrobenzene, as the main intermediate for preparing ofloxacin, with 2,6-dibromoaniline as raw material includes the steps of: diazotization of the 2,6-dibromoaniline material and fluorination and decomposition to prepare 2,6-dibromofluorobenzene; nitrating 2,6-dibromofluorobenzene into 2,4-dibromo-3-fluoro nitrobenzene; and final fluorosubstituting bromine to prepare 2,3,4-trifluoro nitrobenzene. The present invention has high product yield, over 37 % and low cost.
Description
(1) technical field
The present invention relates to preparation method a kind of 2,3,4-trifluoro nitre benzene, belong to the synthetic method of fine chemical product.
(2) background technology
2,3, the 4-trifluoronitrobenzene is the important intermediate of synthetic Ofloxacine USP 23, Ofloxacine USP 23 (ofloxacin) has has a broad antifungal spectrum, germ resistance is strong, bioavailability is good, oral safety, and toxic side effect is low, advantage such as have no drug resistance is large medicine of present clinical use.Existing synthetic method mainly be with 2, the 6-dichlorphenamide bulk powder is through diazotization, fluorine decomposes, nitrated and fluoridize and make.React as follows:
The weak point of aforesaid method is that the low and raw material 2 of product yield, 6-dichlorphenamide bulk powder are more expensive, thereby the finished product cost is higher.
(3) summary of the invention
The present invention for solve the low and raw material 2 of currently available products yield, the 6-dichlorphenamide bulk powder is more expensive, thereby causes the finished product cost problem of higher.The technical scheme that is adopted is: with 2, the 6-dibromo aniline is raw material, decompose through diazotization, fluorine, make 2,6-two bromofluoro benzenes, again through nitrated one-tenth 2,4-two bromo-3-fluoro-oil of mirbane, fluoridize at last and replace that bromine makes 2,3, the 4-trifluoronitrobenzene, its reaction formula is as follows:
For realizing the aforesaid method route, the method condition of each reactions steps of the present invention is:
1,2,6-dibromo aniline diazotization, fluorine decompose the reaction conditions of preparation 2,6-two bromofluoro benzenes and be: diazotization is used hydrochloric acid and equimolar Sodium Nitrite, fluorizating agent is 40% fluoborate aqueous solution, diazotizing temperature is 0～40 degree centigrade, and the time is 30 minutes～1.5 hours.The fluorine resolving time is 3 hours, and temperature is 200～250 degrees centigrade.
2, with 2, the method condition of 6-two bromofluoro benzenes preparation 2,4-two bromo-3-fluoro-oil of mirbane is: sulfuric acid with 98% and equimolar 63% nitric acid are made nitrating agent, and temperature is 20～100 degrees centigrade, and the nitrated time is 30～200 minutes.
3,2, the processing condition of 4-two bromo-3-fluoro-oil of mirbane preparation 2,3,4-trifluoronitrobenzene are: fluorizating agent is KF, fluorinated dielectric is polar solvent such as DMSO or DMF or tetramethylene sulfone etc., fluorination catalyst is with quaternary ammonium salt-type phase transfer catalyst or need not, fluoridizing temperature is 120～240 degrees centigrade, and the time of fluoridizing is 1～8 hour.
Because product yield height of the present invention, product yield can reach more than 37%, therefore can reduce cost, and raw material 2 of the present invention again, 6-dibromo aniline price are lower, therefore can reduce product cost greatly.Bring favorable economic benefit for enterprise, society.
(4) embodiment
The present invention describes in further detail below in conjunction with embodiment:
Embodiment: with 2,1 mole of input reaction flask of 6-dibromo aniline, the hydrochloric acid that adds 200 ml distilled waters and 1.9 mole 37%, 60 degrees centigrade were stirred 30 minutes down, are cooled to 0 degree centigrade, drip the mixed solution of 1 mole of Sodium Nitrite and 60 ml waters, holding temperature drips 3.0 mole 40% fluoroboric acid at 0～10 degree centigrade, filters out precipitation, behind 120 degrees centigrade of finish-dryings, drop in the reaction flask, be heated to 250 degrees centigrade, the product of generation with steam distillation handle 2,6-two bromofluoro benzenes.
Again with 2,1 mole of 6-two bromofluoro benzene, (63%) 1 mole in nitric acid, in 2 moles of input reaction flasks of 98% sulfuric acid, 60 degrees centigrade were stirred 1 hour, filter intermediates 2,4-two bromo-3-fluoro-oil of mirbane.
At last with 2,1 mole in 4-two bromo-3-fluoro-oil of mirbane, drop among the DMSO that is equipped with 300 milliliters, drop into the KF2.5 mole, be warming up to 190 degrees centigrade, be incubated 6 hours after-filtration, underpressure distillation gets product 2,3,4-trifluoronitrobenzene.
Claims (4)
- One kind prepare 2,3, the production method of 4-trifluoronitrobenzene, it is characterized in that: with 2, the 6-dibromo aniline is raw material, decomposes through diazotization, fluorine, make 2,6-two bromofluoro benzenes, again through nitrated one-tenth 2,4-two bromo-3-fluoro-oil of mirbane, fluoridize at last and replace that bromine makes 2,3, the 4-trifluoronitrobenzene.
- 2. according to the production method of right 1 described preparation 2,3,4-trifluoronitrobenzene, it is characterized in that: 2, the diazotization of 6-dibromo aniline, fluorine decomposition condition are: earlier with 1.5 times hydrochloric acid and 2,6-dibromo aniline salify, the back drips Sodium Nitrite diazotization under 0～40 degree centigrade condition, drip the fluoroboric acid salify subsequently, the amount of substance of fluoroboric acid is 2,1.5～3.0 times of the 6-dibromo aniline, and the salt that is used for the fluorine decomposition must anhydrate by finish-drying, the fluorine decomposition temperature is at 200～250 degrees centigrade, and the time that fluorine decomposes is 3 hours.
- 3. according to the production method of right 1 described preparation 2,3,4-trifluoronitrobenzene, it is characterized in that: the reaction conditions of 2, the nitrated generation 2 of 6-two bromofluoro benzenes, 4-two bromo-3-fluoro-oil of mirbane is: nitrating agent is a nitration mixture, nitrated temperature is 20～100 degrees centigrade, and the nitrated time is 30～200 minutes.
- 4. the production method of preparation 2,3 according to claim 1,4-trifluoronitrobenzene, it is characterized in that: 2, the fluorination conditions of 4-two bromo-3-fluoro-oil of mirbane is: fluorizating agent is KF, fluorinated dielectric is polar solvent such as dimethyl sulfoxide (DMSO) (DMSO) or dimethylformamide (DMF) or tetramethylene sulfone etc., fluorination catalyst can use quaternary ammonium salt-type phase transfer catalyst or need not, fluoridizing temperature is 120～240 degrees centigrade, fluoridizes 1～8 hour time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011270160A CN1158242C (en) | 2001-07-20 | 2001-07-20 | Prepn process of 2,3,4-trifluoro nitrobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011270160A CN1158242C (en) | 2001-07-20 | 2001-07-20 | Prepn process of 2,3,4-trifluoro nitrobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1357529A true CN1357529A (en) | 2002-07-10 |
| CN1158242C CN1158242C (en) | 2004-07-21 |
Family
ID=4667014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011270160A Expired - Fee Related CN1158242C (en) | 2001-07-20 | 2001-07-20 | Prepn process of 2,3,4-trifluoro nitrobenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1158242C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420842A (en) * | 2013-08-01 | 2013-12-04 | 上虞市临江化工有限公司 | Preparation method for 2,3,4-trifluoronitrobenzene |
-
2001
- 2001-07-20 CN CNB011270160A patent/CN1158242C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420842A (en) * | 2013-08-01 | 2013-12-04 | 上虞市临江化工有限公司 | Preparation method for 2,3,4-trifluoronitrobenzene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1158242C (en) | 2004-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102781920B (en) | Process for synthesis of fipronil | |
| US5294742A (en) | Process for preparing 3,5-difluoroaniline | |
| CN102336689A (en) | Preparation and refining method of 4-Cl-(trifluoromethyl) benzene sulfonyl chloride | |
| ROCKLIN | Substitution reactions of hexachlorobenzene | |
| CN1158242C (en) | Prepn process of 2,3,4-trifluoro nitrobenzene | |
| JPS5967281A (en) | 3-methylflavone-8-carboxylic acid derivative and its preparation | |
| WO2014103947A1 (en) | Halogenated aniline and method for producing same | |
| CN101265224A (en) | Method for preparing 4-trifluoromethylmercaptoaniline | |
| EP0118971B1 (en) | Process for the preparation of cyanotetrachlorobenzenes | |
| CN1357530A (en) | Process of preparing 2,3,4-trifluoro nitrobenzene using o-chloro nitrobenzene | |
| JPH0247990B2 (en) | ||
| JPS6210046A (en) | Nitration of phenol compound | |
| JPS6212750A (en) | Manufacture of 3-amino-4-hydroxybenzoic acid | |
| JPS6335548A (en) | Production of triarylamine | |
| JP2001151736A (en) | Method for producing trifluoromethylaniline | |
| JP3076991B2 (en) | Method for producing fluorophenols | |
| CN104961638A (en) | Synthetic method of 2, 3, 4-trifluoroaniline | |
| CN110590571A (en) | Preparation method of 4-amino-5, 6,7, 8-tetrahydro-1-naphthol | |
| CN116836060A (en) | Preparation method of 2,3, 4-trifluoro nitrobenzene | |
| JP4022316B2 (en) | Method for producing fluorophenols | |
| EP0596130B1 (en) | Production of 2-halo-3,5-difluoroaniline, intermediate for producing the same, and production of said intermediate | |
| KR890000365B1 (en) | Process for the preparation of disfluorobenzonitrile | |
| JPH0144692B2 (en) | ||
| JPS63303958A (en) | Production of 2-amino-4,6-dichloro-5-alkylphenol | |
| JPS62178551A (en) | Fluorine-containing amine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |