CN1289462C - Trifluoromethyl benzols, preparing process and application thereof - Google Patents
Trifluoromethyl benzols, preparing process and application thereof Download PDFInfo
- Publication number
- CN1289462C CN1289462C CN 03115499 CN03115499A CN1289462C CN 1289462 C CN1289462 C CN 1289462C CN 03115499 CN03115499 CN 03115499 CN 03115499 A CN03115499 A CN 03115499A CN 1289462 C CN1289462 C CN 1289462C
- Authority
- CN
- China
- Prior art keywords
- acid
- trifluoromethyl
- compounds
- preparation
- application
- 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.)
- Expired - Lifetime
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses trifluoromethyl benzene compounds and a preparation method thereof and the application thereof. The preparation method comprises the following steps: di-trifluoromethyl diphenyl ketone reacts with an oxidant in a solvent, then, the trifluoromethyl benzene compounds can be gathered from reaction products, and the trifluoromethyl benzene compounds can be used for the preparation of trifluoromethylbenzoic acid and trifluoromethylphenol. The present invention has the main advantage of the comprehensive utilization of the di-trifluoromethyl diphenyl ketone with the defects of harmfulness to environment and no economic value, and intermediate products which are never reported are synthesized by a convenient oxidation method and a hydrolytic method so that the di-trifluoromethyl diphenyl ketone are converted into the trifluoromethylbenzoic acid and the trifluoromethylphenol with high utilization value. Furthermore, the present invention is easily industrialized, and is particularly convenient for preparing the trifluoromethylphenol. In a word, the method with superiority provides a unique approach for comprehensive utilization, and the trifluoromethyl benzene compounds of the present invention are compounds of which the general structural formulas are shown as follows.
Description
Technical field
The present invention relates to a kind of trifluoromethyl benzene-like compounds and its production and application
Background technology
Trifluoromethylbenzoic acid and trifloro methyl phenol are obligato intermediates during the fluorine fine chemistry industry is produced, and they are synthetic for fluoro-containing pesticide and fluorine-containing medicines, all are to have important use value.
Synthesizing of trifluoromethylbenzoic acid has many reports, under lab, can carry out grignard reaction to corresponding halogenation phenylfluoroform, generates corresponding Grignard reagent, and hydroxy acidization can obtain (US3052603,1962) again, but unsuitable industrialization.Also can prepare (Neth.Appl 6402896,1964), but cost is higher with corresponding 4-trifluoromethylbenzonitrile hydrolysis.Once the someone reported (fine chemistry industry 2,2000,17,82-83), adopt electrochemical method (J.Electro-anal.chem, 1994,379,111,20), use the halogenation phenylfluoroform, feed carbonic acid gas, carry out electrochemical reaction, can obtain the yield of 70-80%, but the difficult control of electrochemical effect, industrialization acquires a certain degree of difficulty.
Synthesizing of trifloro methyl phenol is generally all comparatively difficult, and mostly yield is not high simultaneously, is difficult to industrialization.Directly using trifluoromethyl sulfonate as phenol, oxidation trifluoromethylation (EP458684,1991), but yield is not high, and also the orthoformic acid acyl chlorides of useful corresponding benzenyl trichloride is fluoridized with hydrofluoric acid, also can obtain (Gerl257784,1968; Fr2585353,1987), yield is also undesirable.The corresponding halogenation trifluoromethylbenzene of human was once arranged, the ether of elder generation and the reaction of benzyl acid sodium, capable again catalytic hydrogenolysis, and obtain corresponding trifloro methyl phenol (Org.prepd.Proced.Int, 1979,11,23), two of this method goes on foot yield and has only 42～57%.With corresponding trifluoromethyl aromatic amine, through diazotization, prepare trifloro methyl phenol (Can666608,1963) (Brit934577,1963), yield still can, but operate cumbersome.So trifloro methyl phenol does not still have the ideal industrial method.
In sum, the raw material that utility value is higher adopts more loaded down with trivial details method to prepare this two middle intermediates, and its utility value is more limited.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of trifluoromethyl benzene-like compounds;
Two of the technical issues that need to address of the present invention are preparation methods of the open trifluoromethyl benzene-like compounds of being addressed;
The invention still further relates to the application of trifluoromethyl benzene-like compounds in preparation trifluoromethylbenzoic acid and trifloro methyl phenol of being addressed,, satisfy requirements of large-scale industrial production to overcome the defective that prior art exists.
The chemical name of the trifluoromethyl benzene-like compounds that reaches of the present invention is trifluoromethylbenzoic acid-trifluoromethyl phenyl ester, for having the compound of following general structure:
Wherein: x=o, m, p, o represents the ortho position, position between the m representative, p represents contraposition.
The preparation method of the trifluoromethyl benzene-like compounds of being addressed comprises the steps:
With the by product in the fluorine chemical production, the bis trifluoromethyl benzophenone, in solvent, use oxygenant, as oxygen, potassium bichromate, potassium permanganate, oleum, hydrogen peroxide, sulphur trioxide or nitrosonitric acid etc., under 20-100 ℃, reacted 2～30 hours, from reaction product, collect the trifluoromethyl benzene-like compounds of being addressed then, the mol ratio of bis trifluoromethyl benzophenone and oxygenant is suitable with 1: 1～10, said solvent comprises acetic anhydride, acetic acid, sulfuric acid, nitric acid, a kind of and composition thereof in various longer chain fatty acids or the aromatic acid, its reaction expression is:
The trifluoromethyl benzene-like compounds that reaches of the present invention can be used for preparing trifluoromethylbenzoic acid and trifloro methyl phenol.
Pour trifluoromethylbenzoic acid-trifluoromethyl phenyl ester of collecting in frozen water crystallization, collect crystalline solid, be trifluoromethylbenzoic acid;
From mother liquor, collect residue then, add acidic substance and be hydrolyzed, under 70-150 ℃ condition, refluxed 4～10 hours, adopt conventional method from hydrolysate, to collect trifloro methyl phenol then.Said acidic substance comprise a kind of in hydrochloric acid, sulfuric acid, acetic acid or the phenylformic acid.
The yield of the trifluoromethylbenzoic acid that is obtained is at 80-90%; The yield of trifloro methyl phenol is 70-80%.
Major advantage of the present invention is to utilize environment harmful, still find no the comprehensive utilization of the bis trifluoromethyl benzophenone of economic worth, adopt the easier oxidation and the method for hydrolysis, synthesized the intermediate of not reported, be translated into trifluoromethylbenzoic acid and trifloro methyl phenol with higher utility value, and be easy to industrialization, this process is not seen bibliographical information.Especially can make trifloro methyl phenol easily, present method has more superiority, is the comprehensive Utilization Ways of a uniqueness.
Embodiment
Embodiment 1
The preparation of m-trifluoromethyl phenylformic acid one trifluoromethyl phenyl ester:
In a liter four-hole bottle of thermometer, agitator, dropping funnel and reflux exchanger is housed, add 200 milliliters of acetic anhydride and 250 milliliters of acetic acid, then under agitation, add 3 of 510 grams (0.16 mole), 3-bis trifluoromethyl benzophenone after treating to dissolve fully, drips the hydrogen peroxide of 120ml30% (about 1 mole), under 80 ℃, reacted 15 hours, and steamed part acetic acid, residuum is cooled off, separate out solid filtering, promptly obtain m-trifluoromethyl phenylformic acid one trifluoromethyl phenyl ester;
MW.C
15H
8F
6O
Z334; n
o 251.4793.b.p 154-156 ℃ of ultimate analysis (calculated value):
C
153.90, H
12.42, F
134.11; Measured value: C
153.73, H
12.65, F
134.25
1HNMR (COCl
3, 360MHZ), and δ (ppm) 7.5-8.5 (8H, ArH, m)
19FNMR (COCl
3, 360MHZ), δ (ppm)-13.8 (CF
3, S) ,-14.0 (CF
3, S), IR (film), 1748,1452,1329,1327cm
-1MS
m/ z (%), M
t: 334 (1.18), 173 (100), 145 (48.68).
Can prepare neighbour, right-trifluoromethylbenzoic acid one trifluoromethyl phenyl ester with identical method.
Embodiment 2
The benzoic preparation of m-trifluoromethyl:
In a liter four-hole bottle of thermometer, agitator, dropping funnel and reflux exchanger is housed, add 200 milliliters of acetic anhydride and 250 milliliters of acetic acid, then under agitation, add the m-trifluoromethyl phenylformic acid one trifluoromethyl phenyl ester of embodiment 2 acquisitions of 510 grams (0.16 mole), after treating to dissolve fully, dropwise add 100 milliliters of vitriol oils, the control rate of addition, make temperature of reaction be controlled at 55 ℃, after adding, under this temperature, continue reaction 10 hours.
Reactant reclaims most acetic acid and aceticanhydride at 75 ℃ of following concentrating under reduced pressure.About 300 milliliters of residue.Pour in 500 milliliters the frozen water, hydrolyzate filters out crystalline solid, m-trifluoromethylbenzoic acid 13.0 grams.
M.p.104-106 ℃, productive rate 73.8%.
Embodiment 3
The crystalline mother solution that contains organic liquor is used dichloromethane extraction three times, united extraction liquid, and normal pressure concentrates, and behind the recovery solvent, gets residue 28.5 grams.
The residue of above gained adds 74 milliliters of formic acid, and backflow is after 6 hours down at 115 ℃ for mixture, and concentrating under reduced pressure, residue add 100 ml waters, acidolysis solution dichloromethane extraction, and the alkalization washing merges the alkali lye that, and uses hcl acidifying, and phenol is easily separated out.Obtain m-trifluoromethyl phenol 16.0 grams, thick productive rate 61.5%.
Claims (8)
1. trifluoromethyl benzene-like compounds is characterized in that for having the compound of following general structure:
Wherein: x=o, m, p, o represents the ortho position, position between the m representative, p represents contraposition.
2. the preparation method of compound according to claim 1 is characterized in that comprising the steps:
With the bis trifluoromethyl benzophenone, in solvent, use oxygenant under 20-100 ℃, reacted 2～30 hours, from reaction product, collect the trifluoromethyl benzene-like compounds of being addressed then;
Said oxygenant is selected from a kind of in oxygen, potassium bichromate, potassium permanganate, oleum, hydrogen peroxide, sulphur trioxide or the nitrosonitric acid.
3. preparation method according to claim 2 is characterized in that, the mol ratio of bis trifluoromethyl benzophenone and oxygenant is 1: 1～10.
4. preparation method according to claim 2 is characterized in that, said solvent is selected from a kind of or its mixture in acetic anhydride, acetic acid, sulfuric acid, nitric acid, various longer chain fatty acid or the aromatic acid.
5. application of compound according to claim 1 is characterized in that being used to prepare trifluoromethylbenzoic acid and trifloro methyl phenol.
6. application of compound according to claim 5 is characterized in that pouring the described trifluoromethyl benzene-like compounds of collecting of claim 1 in frozen water crystallization, collects crystalline solid, is trifluoromethylbenzoic acid.
7. application of compound according to claim 6, it is characterized in that, from crystalline mother solution, collect residue, add acidic substance and be hydrolyzed, under 70-150 ℃ condition, refluxed 4～10 hours, and adopted conventional method from hydrolysate, to collect trifloro methyl phenol then.
8. application of compound according to claim 7 is characterized in that, said acidic substance are selected from a kind of in hydrochloric acid, sulfuric acid, acetic acid or the phenylformic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115499 CN1289462C (en) | 2003-02-24 | 2003-02-24 | Trifluoromethyl benzols, preparing process and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115499 CN1289462C (en) | 2003-02-24 | 2003-02-24 | Trifluoromethyl benzols, preparing process and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1524844A CN1524844A (en) | 2004-09-01 |
| CN1289462C true CN1289462C (en) | 2006-12-13 |
Family
ID=34284313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03115499 Expired - Lifetime CN1289462C (en) | 2003-02-24 | 2003-02-24 | Trifluoromethyl benzols, preparing process and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1289462C (en) |
-
2003
- 2003-02-24 CN CN 03115499 patent/CN1289462C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1524844A (en) | 2004-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1613849A (en) | Preparation of 2-Cl-5-F-nicotinate and nicotonic acid | |
| JP2014514269A (en) | Method for producing difluoroacetonitrile and its derivatives | |
| CN1800193A (en) | 2-deoxidized glucose preparation method | |
| CN1226259C (en) | Preparing method for 1,2-pentadiol | |
| CN1289462C (en) | Trifluoromethyl benzols, preparing process and application thereof | |
| CN1847223A (en) | Production process of tetrabromobispheno S bis (2,3-dibromopropyl) ether | |
| CN101585762B (en) | Method for synthesizing 2-(4-cyclopropoxycarbonylphenyl)-2-methylpropanoic acid | |
| CN1283605C (en) | Process for preparing meta-trifluoromethyl benzyl alcohol | |
| CN104311432B (en) | ADZ6140 important intermediate (1R, 2S)-2-(3,4-difluoro-benzene base) preparation method of cyclopropylamine | |
| CN101585768B (en) | Method for synthesizing 2-[4-(4-chlorobutyryl)phenyl]-2-methacrylate | |
| CN100351226C (en) | Method for preparing 2,6- dialkoxy benzene nitrile | |
| CN100465149C (en) | Preparation method of chlorophenyl acetic acid | |
| CN1927801A (en) | Preparation method of methylphenyl acetic acid | |
| CN100500629C (en) | Method for preparing 2-Methyl-1[4-(trifluoromethoxy)phenyl] propan-1-one | |
| CN1274650C (en) | Method for preparing 4-bromine-3-fluorine methylbenzene | |
| CN1070842C (en) | Process for preparing diethyl alpha-methyl diglycollat | |
| CN1034659C (en) | One-step synthesis of ortho-formate | |
| CN101585764B (en) | Method for synthesizing 2-[4-(4-chlorobutyryl)phenyl]-2-methylpropanoic acid | |
| CN107880011A (en) | The synthetic method of Shandong agate Kato key intermediate | |
| CN112961030B (en) | Method for catalytic synthesis of 4- (trans-4-alkyl cyclohexyl) cyclohexanone | |
| CN1463961A (en) | Process for preparing phenol derivative | |
| CN1199941C (en) | Method for preparing 2,6-difluorobenzonitrile by using 2,6-dichlorobenzonitrile fluoro | |
| CN101585767B (en) | Method for synthesizing 2-[4-(4-chlorobutyryl)phenyl]-2-methacrylate | |
| CN1865217A (en) | Method for manufacturing monochloroacetic acid based on continuous catalytic chlorination process | |
| CN108947797A (en) | A kind of preparation method of chlorine phenoxy carboxylic acid herbicides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI HETENG FINE CHEMICAL CO., LTD. Free format text: FORMER OWNER: SHANGHAI HETENG HIGH SCIENCE AND TECHNOLOGY CO.,LTD. Effective date: 20080530 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20080530 Address after: No. 4688 Jinshan Road, Shanghai, Jinshan District Patentee after: Shanghai Heteng Fine Chemical Co.,Ltd. Address before: Shanghai city Tianlin Road Xinye Building No. 388 room 1011 Patentee before: Shanghai High Victory Science & Technology Co.,Ltd. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20061213 |
|
| CX01 | Expiry of patent term |