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Notizen zur Synthese sulfonierter Derivate von 5,6,7,8‐Tetrahydro‐1‐naphthylamin und 5,6,7,8‐Tetrahydro‐2‐naphthylamin
Author(s) -
Courtin Alfred
Publication year - 1981
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19810640221
Subject(s) - sulfonic acid , chemistry , hydrogenolysis , sulfuric acid , amino acid , organic chemistry , medicinal chemistry , catalysis , biochemistry
Notes on the Synthesis of Sulfonated Derivatives of 5,6,7,8‐Tetrahydro‐1‐naphthylamine and 5,6,7,8‐Tetrahydro‐2‐naphthylamine Sulfonation of 5,6,7,8‐tetrahydro‐1‐naphthylamine ( 1 ) with sulfuric acid gave a mixture of 1‐amino‐5,6,7,8‐tetrahydronaphthalene‐2‐sulfonic acid ( 2 ), 4‐amino‐5,6,7,8‐tetrahydronaphthalene‐2‐sulfonic acid ( 13 ) and 4‐amino‐5,6,7,8‐tetrahydronaphthalene‐1‐sulfonic acid ( 3 ). The same reaction with 5,6,7,8‐tetrahydro‐2‐naphthylamine ( 20 ) yielded 3‐amino‐5,6,7,8‐tetrahydronaphthalene‐2‐sulfonic acid ( 21 ); formation of 2‐amino‐5,6,7,8‐tetrahydronaphthalene‐1‐sulfonic acid ( 16 ) or of 3‐amino‐5,6,7,8‐tetrahydronaphthalene‐1‐sulfonic acid ( 24 ) was not observed. Treatment of 4‐bromo‐5,6,7,8‐tetrahydro‐1‐naphthylamine ( 4 ) or of its 4‐chloro analogue 5 with amidosulfuric acid gave 1‐amino‐4‐bromo‐5,6,7,8‐tetrahydronaphthalene‐2‐sulfonic acid ( 9 ) and its 4‐chloro analogue 10 , respectively, which were dehalogenated to 2 . Preparations of 13 and 24 were achieved by sulfonation of 5‐nitro‐1,2,3,4‐tetrahydronaphthalene ( 14 ) and 6‐nitro‐1,2,3,4‐tetrahydronaphthalene ( 22 ) to 4‐nitro‐5,6,7,8‐tetrahydronaphthalene‐2‐sulfonic acid ( 15 ) and 3‐nitro‐5,6,7,8‐tetrahydronaphthalene‐1‐sulfonic acid ( 23 ), respectively, followed by Béchamp reductions. The sulfonic acid 13 was also obtained by hydrogenolysis of 4‐amino‐1‐bromo‐5,6,7,8‐tetrahydronaphthalene‐2‐sulfonic acid ( 11 ) or of its 1‐chloro analogue 12 ; compounds 11 and 12 were synthesized from N ‐(4‐bromo‐5,6,7,8‐tetrahydro‐1‐naphthyl)acetamide ( 7 ) and from its 4‐chloro analogue 8 , respectively, by sulfonation with oleum and subsequent hydrolysis. By ‘baking’ the hydrogensulfate salt of 1 or 20 compounds 3 and 21 were obtained, respectively. Synthesis of 16 was achieved by sulfur dioxide treatment of the diazonium chloride derived from 2‐nitro‐5,6,7,8‐tetrahydro‐1‐naphthylamine ( 17 ) giving 2‐nitro‐5,6,7,8‐tetrahydronaphthalene‐1‐sulfonyl chloride ( 18 ), followed by hydrolysis of 18 to the corresponding sulfonic acid 19 and final reduction.