GB2199034A - Process of preparing 4-trifluoromethyl-3-nitrobenzoic acid via novel nitrobenzene derivative - Google Patents
Process of preparing 4-trifluoromethyl-3-nitrobenzoic acid via novel nitrobenzene derivative Download PDFInfo
- Publication number
- GB2199034A GB2199034A GB08728747A GB8728747A GB2199034A GB 2199034 A GB2199034 A GB 2199034A GB 08728747 A GB08728747 A GB 08728747A GB 8728747 A GB8728747 A GB 8728747A GB 2199034 A GB2199034 A GB 2199034A
- Authority
- GB
- United Kingdom
- Prior art keywords
- trifluoromethyl
- process according
- preparing
- trichloromethyl
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/58—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
- C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
14 1 11 2 19 9 0 34 PROCESS OF PREPARING 4-TRIFLUOROMETHYL-3-NITROBENZOIC
ACID VIA NOVEL NITROBENZENE DERIVATIVE This invention relates to a process of preparing 4-trifluoromethyl-3- nitrobenzoic acid (abbreviated to 4TFM-3-NBA) and to 5-trichloromethyl-2- trifluoromethylnitrobenzene (abbreviated to 5-TCM-2-TFMNB) which is a novel compound formed in said process as an-intermediate.
4-TFM-3-NBA, a novel compound discovered in our laboratory, is expected to be useful as an intermediate material of some medicines, agricultural chemicals and liquid crystals.
It is known that 4-trifluoromethyl-2-nitrobenzoic acid (4-TFM-2-NBA) is formed by nitrating 4-trifluoro- methylbenzoic acid (Chem. Abstr., 64, 3487f (1966) According toa method devised in our laboratory, a mixture of 4-TFM-2-NBA and 4-TFM-3-NBA is obtained by nitrating either 4-trifluoromethylbenzoyl halide or 4trifluoromethylbenzotrihalide and simultaneously hydrolyzing the halogenated radical of the starting compound. However, for the preparation of 4-TFM-3-NBA this method-is not very favorable because a larger part of the obtained mixture is 4-TFM-2-NBA and also because some treatments have to be made for isolation of 4-TFM- 3-NBA and/or 4-TFM-2-NBA.
It is an object of the present invention to provide a process of preparing 4-TFM-3-NBA without forming unwanted isomers.
It is another object of the invention to provide a novel nitrobenzene derivative which can easily be converted into 4-TFM-3-NBA.
According to the invention there is provided a process of preparing 4-TFM-3-NBA, comprising the steps of (a) reacting 2,5-bis(trifluoromethyl)nitrobenzene (abbreviated to 2,5-TFMNB) with a metal chloride to form 5-trichloromethyl-2-trifluoromethylnitrobenzene (abbreviated to 5-TCM-2-TFMNB), and (b) hydrolyzing the trichloromethyl group of 5-TCM-2-TFMNB in the presence of a Lewis acid.
5-TCM-2-TFMNB formed by the reaction of the step (a) of this process is a novel compound.
CF3 CC1 3 5-TCM-2-TFMNB NO 2 The process according to the invention is represented by the following formulas.
NO 3 NO 3 NO 3 2 0 A1C13 2 H + 2 0 0 W 3 cl OOH 4 1 nv 1 As is known, 2,5-TEMNB as the starting material of this process can easily be formed by nitrating 1,4-bis(trifluoromethyl)benzene. The first step of this process is reacting 2,5-TFMNB with a metal chloride which is employed as a halogen exchange reagent. It is the point of the invention that by this reaction only the trifluoromethyl group at the 5- position of the starting compound selectively undergoes halogen exchange with the metal chloride and turns into trichloromethyl group. That is-, the reaction product is always 5-TCM-2TFMNB free from other isomers. The second step of the process is hydrolyzing 5-TCM-2- TFMNB by using a Lewis acid such as, for example, ferric chloride as a hydrolysis catalyst. By this reaction the trichloromethyl group of.5-TCM-2-TFMNB undergoes hydrolysis to turn into carboxylic group, so that the reaction product is always 4-TFM-3-NBA not containing any other isomer.
Thus, the process according to the invention provides 4-TFM-3-NBA at good yield and does not need complicated operations for isolation of 4-TFM-3NBA from the final reaction product.
For the halogen exchange reaction of 2,5-TFMNB in this invention a metal chloride is employed as the halogen exchange reagent. Good examples of useful metal 1 chlorides are AlCl 3' SbCl 5 and TiCl 4' and AlCl 3 is preferred. The quantity of the metal chloride must be at least 1 mol per mol of 2,5-TFMNB and does not need to be more than 2 mols, though there arises no problem by using a larger quantity. It is convenient to carry out the halogen exchange reaction by dissolving 2,5-TFMNB in an inactive solvent such as dichloromethane, dichloro ethane or carbon tetrachloride. The reaction is carried out at a temperature not higher than 70 0 C, and preferably around 0 0 C.
To hydrolyze the trichloromethyl group of 5-TCM-2TFMNB, a Lewis acid is used as a hydrolysis catalyst. Good examples of useful Lewis acids are FeCl 3' FeCl 2' Fe 2 (SO 4) 3 and SbCl 3' and FeCl 3 is preferred. A suitable quantity of the Lewis acid is from 0.001 to 50 wt% of 5-TCM-2TFMNB to be hydrolyzed. This reaction is carried out at a temperature in the range from about 80 0 C to about 250 0 C, and preferably in the range from 100 to 150 0 C.
The invention is further illustrated by the following nonlimitative examples. EXAMPLE 1 A solution of 7.8 g of 2,5-TFMNB in 36 ml of dichloroethane was cooled to 0 0 C, and 8.0 g of AlCl 3 was added to the solution for reaction with 2, 5-TFMNB.
1 111 1 1 k After the lapse of 2 hr the reaction liquid was poured into 20 g of crushed ice, and the resultant liquid mixture was separated into organic and aqueous layers. The organic layer was dried with anhydrous magnesium sulfate, conc, - entrated and then distilled to thereby obtain 3.0 g of 5-TCM-2-TFMNB.
Analysis of the obtained 5-TCM-2-TFMNB gave the following data. Boiling point: 1030C at 1 mmHg.
1 H-NMR (standard substance was TMS, in CDC1 3 J 7.5-8.5 (3H, m).
19 F-NMR (standard substance was CFC1 2' in CDC1 3 60.67 ppm (3F, s).
IR (KBr pellet): 1565 cm- 1, 1375 cm- 1 W NO 2 EXAMPLE 2
A solution of 9.1 g of 2,5-TFMNB in 42 ml of f 0 dichloromethane was cooled to 0 C, and 9.3 g of AlCl 3 was added to the solution for reaction with 2,5-TFMNB for 2 hr. After that the reaction liquid was poured into 25 g of crushed ice, and the resultant liquid mixture was separated into organic and aqueous layers. The organic layer was dried with anhydrous magnesium sulfate, concentrated and then distilled to thereby obtain 2.8 g of 5-TCM-2-TFMNB.
-6 EXAMPLE 3
A mixture of 1 g of 5-TCM-2-TFMNB and 100 mg of FeCl 3 was heated to 150 0 C, and 0.1 ml of water was added to the heated mixture for hydrolyzing 5-TCM-2-TFMNB at its trichloromethyl radical. After the hydrolyzing reaction ether was added to the reaction system to dissolve organic matter, and the ether solution was washed with water, dried with anhydrous magnesium sulfate and concentrated. As the result 0.6 g of 4- TFM- 3-NBA was obtained. Analysis of this 4-TFM-3-NBA gave the following data. Melting point: 169 0 C. 1 H-NMR (standard substance was TMS, in CDC1 3): 8.1-8.5 M, m); S 9.9 (1H, s).
19 F-NMR (standard substance was CF 3 CO 2 H, in CDC1 3 -15.5 ppm (3F, s).
IR (KBr pellet): 2510-3130 cm, 921 cm (V OH); - 1 1 - 1 1730 cm (V C=O); 1562 cm-, 1375 cm (V NO 2) 4
Claims (1)
- CLAIMS 1. A process of preparing 4-trifluoromethyl-3-nitrobenzoic acid,comprising the steps of:(a) reacting 2,5-bis(trifluoromethyl)nitrobenzene with a metal chloride to form 5-trichloromethyl-2trifluoromethy1nitrobenzene; and (b) hydrolyzing the trichloromethyl group of 5trichloromethyl-2trifluoromethylnitrobenzene in the presence of a Lewis acid. 2. A process according to Claim 1, wherein said metal chloride is selected from AlCl 3' SbC1 5 and TiCl 4' 3. A process according to Claim 1 or 2, wherein the reaction at step (a) is carried out at a temperature not higher than 70 0 C. 4. A process according to Claim 1, 2 or 3, wherein said 2,5bis(trifluoromethyl)nitrobenzene at step (a) is in the form of a solution in an organic solvent. S. A process according to Claim 4, wherein said solvent is selected from dichloromethane, dichloroethane and carbon tetrachloride. 6. A process according to any of the preceding claims, wherein said Lewis acid is selected from FeCl 3' FeCl 2- Fe 2 (SO 4)3 and SbC1 3' 7. A process according to any of the preceding claims, wherein the reaction at step (b) is carried out at it a temperature in the range from 80 0 C to 250 0 C.8. A process according to Claim 7, wherein said temperature is in the range from 100 to 150 0 C.9. A process of preparing 4-trifluoromethyl-3-nitro benzoic acid from 5-trichloromethyl-2-trifluoromethyl- nitrobenzene, substantially as hereinbefore described in Example 3.10. 5-Trichloromethyl-2-trifluoromethylnitrobenzene.11. A process of preparing 5-trichloromethyl-2 trifluoromethylnitrobenzene, substantially as hereinbefore described in Example 1 or 2.1-ublished 1988 at TI'ie Patent Offace. SLate liouse. 66 71 High Holborn, London WC I R 4TP Further copies may be obtained frOM The Patent Office, SaLles Branch, St Mary Cray, orpington, Kent BR5 3RD Printed by Multiplex techniques ItA. St May Cray, Kent. Con. 1187.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61305278A JPH0768183B2 (en) | 1986-12-23 | 1986-12-23 | 5-Trichloromethyl-2-trifluoromethylnitrobenzene and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8728747D0 GB8728747D0 (en) | 1988-01-27 |
| GB2199034A true GB2199034A (en) | 1988-06-29 |
Family
ID=17943171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08728747A Withdrawn GB2199034A (en) | 1986-12-23 | 1987-12-09 | Process of preparing 4-trifluoromethyl-3-nitrobenzoic acid via novel nitrobenzene derivative |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH0768183B2 (en) |
| DE (1) | DE3743610A1 (en) |
| FR (1) | FR2609288A1 (en) |
| GB (1) | GB2199034A (en) |
| IT (1) | IT1233421B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6930214B2 (en) * | 2002-01-25 | 2005-08-16 | Asahi Glass Company, Limited | Process for producing 2,5-bis(trifluoromethyl)nitrobenzene |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0622605Y2 (en) * | 1989-05-24 | 1994-06-15 | 小島プレス工業株式会社 | Vehicle storage device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1075300A (en) * | 1965-06-14 | 1967-07-12 | Smith Kline French Lab | N-substituted-5-sulfamoyl-4-trifluoromethylanthranilic acids |
| US3906034A (en) * | 1972-03-21 | 1975-09-16 | Hoechst Ag | Trifluoromethyl-salicylanilides |
-
1986
- 1986-12-23 JP JP61305278A patent/JPH0768183B2/en not_active Expired - Fee Related
-
1987
- 1987-12-09 GB GB08728747A patent/GB2199034A/en not_active Withdrawn
- 1987-12-11 IT IT8722959A patent/IT1233421B/en active
- 1987-12-22 DE DE19873743610 patent/DE3743610A1/en not_active Withdrawn
- 1987-12-22 FR FR8717935A patent/FR2609288A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6930214B2 (en) * | 2002-01-25 | 2005-08-16 | Asahi Glass Company, Limited | Process for producing 2,5-bis(trifluoromethyl)nitrobenzene |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8728747D0 (en) | 1988-01-27 |
| JPS63159352A (en) | 1988-07-02 |
| IT8722959A0 (en) | 1987-12-11 |
| DE3743610A1 (en) | 1988-07-07 |
| FR2609288A1 (en) | 1988-07-08 |
| JPH0768183B2 (en) | 1995-07-26 |
| IT1233421B (en) | 1992-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH01104045A (en) | Manufacture of 2,5-bis(2,2,2-trifluoroethoxy)- n-(2-piperidylmethyl)benzamide | |
| GB2199034A (en) | Process of preparing 4-trifluoromethyl-3-nitrobenzoic acid via novel nitrobenzene derivative | |
| JPH08310987A (en) | Intermediate for producing insecticide | |
| US4331820A (en) | Cis-6-undecene-1-chloride and a method for the preparation thereof | |
| DE69206423T2 (en) | Process for the preparation of 5- (2,4-difluorophenyl) salicylic acid. | |
| JPS6334856B2 (en) | ||
| JP2698306B2 (en) | Method for producing 2-methyl-3-aminobenzotrifluoride | |
| JPH06340675A (en) | Production of perfluoroalkyltrimethylsilane | |
| US4845279A (en) | Method of preparing 4-trifluoromethyl-2-nitrobenzoic acid and novel isomer | |
| JP2517304B2 (en) | Method for producing bromoacetonitrile | |
| JPS59137429A (en) | Nucleus halogenated 3-fluorotoluenes and manufacture | |
| JP2793090B2 (en) | Method for producing bromopentafluorobenzene | |
| US4324931A (en) | 1-Halo-4-decene compounds | |
| GB2200632A (en) | Novel fluorobenzophenones and fluorobenzoic acid fluorophenylester | |
| JPH09124538A (en) | Production of aromatic dialdehyde | |
| JP2807780B2 (en) | Method for producing aromatic fluorine compound | |
| JP3230099B2 (en) | A new method for producing aromatic flor compounds. | |
| JPH0449534B2 (en) | ||
| JPH0662469B2 (en) | Process for producing bis (trifluoromethylphenyl) methanol | |
| JP4034889B2 (en) | Process for producing trifluorophenols | |
| US3372202A (en) | Preparation of ar-halophenethyl alcohols | |
| JPH0249293B2 (en) | ||
| JPS6122045A (en) | Production of biphenyltetracarboxylic acid | |
| GB2204313A (en) | Bisbenzotrifluoride derivatives and method of preparing same | |
| JPH07304738A (en) | Production of trifluoromethylpyridines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |