3-Nitrobenzoic acid → 3-Nitrosobenzoic acid

Temperature

0 °C

As an alternative method of forming azo compounds, nitroso compounds are coupled to amines in glacial acetic acid by the Mills reaction. Badger, G. et al., Aust. J. Chem. 17: 1036 (1964). Nitroso compounds are made by the method of Coleman et al., Organic Synthesis Collective Vol. III: p668. For example, 3-nitrobenzoic acid (Aldrich Chem. Co., Milwaukee, Wis.) (2.44 mmoles) and a solution of 150 mg of NH4Cl in 5 ml of water are combined in a 50 ml round-bottomed flask and stirred vigorously. Zinc dust (372 mg) is added in small portions over 5 minutes. After the addition of zinc is complete the temperature begins to rise, but is kept between 50 and 55° C. by the use of an ice bath. The mixture is stirred at that temperature for 20 minutes and then the zinc residues are filtered and washed with boiling water. The combined filtrate and washings are cooled to 0° C. in a beaker by the addition of ice. To this cold mixture of the hydroxylamine, a cold solution of sulfuric acid (750 μl of concentrated acid plus enough ice to bring the temperature to −5° C.) is added with stirring. An ice-cold solution of 170 mg of sodium dichromate dihydrate in 750 μl of water is added all at once with stirring. The resulting 3-nitrosobenzoic acid thus obtained is combined with one-half of an equivalent of benzidine, 2,7-diaminofluorene or another benzidine derivative in glacial acetic acid and warmed to 70-80° C. for 7 hrs and then allowed to stand at room temperature overnight. The mixture is diluted with water and extracted with ethyl acetate giving 4,4′-bis(3-carboxy-phenylazo)-biphenyl), 2,7-bis(3-carboxy-phenylazo)-fluorene, or the corresponding bis(3-carboxy-phenylazo) derivative of the particular benzidine derivative employed.

1. customis kept between 50 and 55° C. by the use of an ice bath
2. stirringThe mixture is stirred at that temperature for 20 minutes
3. filtrationthe zinc residues are filtered
4. washwashed with boiling water
5. additionTo this cold mixture of the hydroxylamine
6. customto −5° C.
7. additionis added
8. stirringwith stirring
9. additionAn ice-cold solution of 170 mg of sodium dichromate dihydrate in 750 μl of water is added all at once
10. stirringwith stirring

ORD record

ord-247129bfd23f4d2ebe39c24ed9dd046c

Source dataset

uspto-grants-2002_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06417178B1