Method for reducing aromatic nitro groups

Abstract: A method of reducing an aromatic nitro (-NO₂) group to the corresponding amine (-NH₂) group by treatment with iron or zinc metal and a halogen-containing aliphatic carboxylic acid provides amines in good yield and free from unwanted anilides.

Description: The invention relates to a method of reducing compounds containing aromatic nitro groups to the corresponding amines. The iron/acid reduction of aromatic nitro compounds to amines has been used extensively since its discovery by Bechamp over 100 years ago (see A. Bechamp, Ann. Chim. (Paris) 1854, 42, 180 and A. Bechamp, Justus Liebigs Ann. Chem. 1854, 92, 401). However, the first published systematic study of the reduction of nitro compounds by iron/acetic acid did not appear until 1977 (see D.C. Owsley and J J Bloomfield, Synthesis 1977, 2, 118). This later reference indicates that use of neat acetic acid leads to the formation of anilides as the major or exclusive product, whereas use of acetic acid in ethanol leads predominately rather than exclusively to the aniline. Similar methods involving mixtures of acetic acid and a mineral acid are known, eg EP 0 221 021 in which a mixture of acetic acid and sulphuric acid is said to be cheaper than acetic acid alone. US Patent 4 066 660 uses acetic acid and ethanol, while US Patent 3 798 271 uses formic or acetic acid in the presence of water and an organic solvent such as xylene, benzene or toluene. The present invention relates to a method of reducing aromatic nitro groups to form amines in good yields and free from unwanted anilides. According to the present invention there is provided a method of reducing an aromatic nitro (-NO₂) group to the corresponding amine (-NH₂) group by treatment with iron or zinc metal and a halogen-containing aliphatic carboxylic acid. The halogen-containing acids may, for example, be trichloro-, dichloro- or trifluoro- acetic acid or mixtures thereof. Mixtures of such halogenated acids with non-halogenated acids, eg. acetic acid, may also be used. The reaction mixture may also contain water and/or organic solvents. The reaction may take place at ambient or elevated temperatures, for example, in the range 20 to 100°C, preferably at 65-85°C, especially at 70-75°C. The invention is illustrated by the following examples: Example 1 1-(2,3,4,5,6-Pentachloropheny)-3-(2'-chloro-5′-amino-anilino)-2-pyrazolin-5-one. Iron powder (3.5g) was added in portions over five minutes to a slurry of 1-(2,3,4,5,6-pentachlorophenyl)- 3-(2′-chloro-5′- nitroanilino)-2-pyrazoline-5-one (5g) in trifluoracetic acid (50ml) at 70°C. The yellow colour of the nitropyrazolone rapidly disappeared, and after stirring at 70-75°C. for ten minutes the hot solution was separated from any unreacted iron and added to stirred ice-water (400ml). The resultant off-white precipitate of the aminopyrazolone was filtered off, washed with water and dried. The yield was 4.6g (98%); single spot by thin layer chromatography. Example 2 The title compound from Example 1 was prepared by the method described therein, except that DICHLOROACETIC ACID was used instead of TRIFLUOROACETIC ACID. The yield was 91%, with similar purity to the Example 1 product.

Claims: A method of reducing an aromatic nitro (-NO₂) group to the corresponding amine (-NH₂) group by treatment with iron or zinc metal and a halogen-containing aliphatic carboxylic acid. A method as claimed in claim 1 in which the halogen-containing acid is trichloro-, dichloro- or trifluoro-acetic acid. A method as claimed in claim 1 or 2 in which the reaction mixture also contains another acid, water and/or an organic solvent. A method as claimed in any of claims 1-3 in which the reaction takes place at a temperature of from 65 to 85°C. A method as claimed in any of claims 1-4 in which the reaction takes place at a temperature of from 70 to 75°C.

Inventors: BUCKLAND PAUL RICHARD, GOURLEY ROBERT NICHOLAS, BUCKLAND, PAUL RICHARD, GOURLEY, ROBERT NICHOLAS
Applicants: EASTMAN KODAK CO, KODAK LTD, EASTMAN KODAK COMPANY (A NEW JERSEY CORPORATION), KODAK LIMITED
Application year: 1989
Main classification: C07C209
IPC codes: C07D231, C07C209, C07B43