Patent GB-469080-A (GB)
Title: Manufacture of new mononitroalkylanilines, mononitroalkylacylanilines and derivatives thereof
Filed: 1936-01-15
Abstract: Nitraniline derivatives are obtained by mononitrating C-alkylanilines containing 6--18 carbon atoms in the alkyl group, or their nuclearly chlorinated, brominated or methylated derivatives, or the N-acyl derivatives of any of these compounds. The nitrated N-acyl derivatives may then be deacylated, if desired.  The C-alkylanilines used as starting materials are obtainable by heating aniline or its nuclearly chlorinated, brominated or methylated derivatives with a saturated primary aliphatic alcohol of 6--18 carbon atoms and a halide of cobalt or zinc; alternatively, a N-alkylaniline containing 6--18 carbon atoms in the alkyl group, or a nuclearly chlorinated, brominated or methylated derivative thereof, may be heated with a halide of cobalt or zinc; in preparing the C-alkylanilines, the parent anilines or N-alkylanilines may be wholly or partly replaced by their hydrochlorides or hydrobromides, and the heating of the N-alkylanilines may be effected in the presence of the hydrochlorides or hydrobromides of the parent anilines.  Alcohols specified for use in the preparation of the starting materials are hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl alcohols, and these may be pure or crude products; thus, use may be made of crude hexadecyl alcohol obtained by saponifying spermaceti, or of crude dodecyl and tetradecyl alcohols (lorol) obtained by reducing the fatty acids from coconut oil.  The preparation of suitable C-alkylanilines is described in Specification 468,226.  The N - acyl - C - alkylanilines also suitable as starting materials are obtained from the C-alkylanilines by standard processes; acetyl, propionyl and benzoyl derivatives are specified.  In the examples: (1) p-dodecylaniline is acetylated, and the acetyl derivative is treated with nitric acid without isolation; 2-nitro-4-dodecylacetanilide is obtained; (2) p-dodecylaniline is acetylated, and the crude product is nitrated with copper nitrate; 2-nitro-4-dodecylacetanilide is again obtained; (3) the product of example 1 or 2 is heated with hydrochloric and acetic acids to yield 2-nitro-4-dodecylaniline; the constitution of the product is established by its behaviour on bromination, a monobromo derivative only being obtained; (4) p-dodecylaniline is nitrated in sulphuric acid; 3-nitro-4-dodecylaniline is obtained; the constitution of the product is established by its behaviour on bromination, a dibromo derivative being obtained; (5) p-decyl aniline is acetylated and nitrated, as in example 1, to yield 2-nitro-4-decylacetanilide, which (example 6) is heated with aqueous caustic soda to yield 2-nitro-4-decylaniline; (7) p-decylaniline is nitrated in sulphuric acid to yield 3-nitro-4-decylaniline; (8) p-tetradecylaniline is acetylated and nitrated, as in example 1, to yield 2-nitro-4-tetradecylacetanilide, which (example 9) yields 2-nitro-4-tetradecylaniline when saponified as in example 6; (10) p-hexadecylaniline is acetylated and nitrated as in example 1 to yield 2-nitro-4-hexadecylacetanilide, which (example 11) yields 2-nitro-4-hexadecylaniline when saponified as in example 6; (12) p-hexadecylaniline is nitrated in sulphuric and acetic acids to yield 3-nitro-4-hexadecylaniline; (13) 4 - dodecyl - 2 - methylaniline is acetylated and nitrated as in example 1 to yield 2-nitro-4-dodecyl-6-methylacetanilide, which (example 14) yields 2-nitro-4-dodecyl-6-methylaniline when saponified as in example 6; (15) 4-dodecyl-2-methylaniline is nitrated in sulphuric acid to yield 3-nitro-4-dodecyl-2- (or 6-)methylaniline. Specification 466,650 also is referred to.