59146-96-2Relevant articles and documents
One-pot reaction as an efficient method for rigid molecular tweezers
Havlik, Martin,Kral, Vladimir,Kaplanek, Robert,Dolensky, Bohumil
supporting information; experimental part, p. 4767 - 4769 (2009/05/31)
(Equation Presented) Rigid molecular tweezers are compounds of increasing scientific interest. As the structural requirements for such compounds are highly specific, few types of these tweezers are thus far known. The preparation of examples of rigid larg
Zur Synthese sulfonierter Derivate von 2,3-Dimethylanilin und 3,4-Dimethylanilin
Courtin, Alfred,Tobel, Hans-Rudolf von
, p. 385 - 394 (2007/10/02)
Baking the hydrogensulfate salt of 2,3-dimethylaniline (1) or of 3,4-dimethylaniline (2) led to 4-amino-2,3-dimethylbenzenesulfonic acid (4) and 2-amino-4,5-dimethylbenzenesulfonic acid (5), respectively (Scheme 1).The sulfonic acid 5 was also obtained by treatment of 2 with sulfuric acid or by reaction of 2 with amido-sulfuric acid. 3-Amino-4,5-dimethylbenzenesulfonic acid (3) and 5-amino-2,3-dimethylbenzenesulfonic acid (6) were prepared by sulfonation of 1,2-dimethyl-3-nitrobenzene (9) to 3,4-dimethyl-5-nitrobenzenesulfonic acid (11) and of 1,2-dimethyl-4-nitrobenzene (10) to 2,3-dimethyl-5-nitrobenzenesulfonic acid (12), respectively, with subsequent Bechamp reduction (Scheme 1).Preparations of 2-amino-3,4-dimethylbenzenesulfonic acid (7) and of 6-amino-2,3-dimethylbenzenesulfonic acid (8) were achieved by the sulfur dioxide treatment of the diazonium chlorides derived from 3,4-dimethyl-2-nitroaniline (24) and from 2,3-dimethyl-6-nitroaniline (31) to 3,4-dimethyl-2-nitrobenzenesulfonyl chloride (29) and 2,3-dimethyl-6-nitrobenzenesulfonyl chloride (32), respectively, followed by hydrolysis to 3,4-dimethyl-2-nitrobenzenesulfonic acid (30) and 2,3-dimethyl-6-nitrobenzenesulfonic acid (33), and final reduction (Scheme 3).Compound 7 was also synthesized by reaction of 4-chloro-2,3-dimethylaniline (23) with amidosulfuric acid to 2-amino-5-chloro-3,4-dimethylbenzenesulfonic acid (20) and subsequent hydrogenolysis (Scheme 2). 4'-Bromo-2',3'-dimethyl-acetanilide (13) and 4'-chloro-2',3'-dimethyl-acetanilide (14) on treatment with oleum yielded 5-acetylamino-2-bromo-3,4-dimethylbenzenesulfonic acid (17) and 5-acetylamino-2-chloro-3,4-dimethylbenzenesulfonic acid (18), respectively.Their structures were proven by hydrolysis to 5-amino-2-bromo-3,4-dimethylbenzenesulfonic acid (21) and 5-amino-2-chloro-3,4-dimethylbenzenesulfonic acid (22), followed by reductive dehalogenation to 3.Reaction of 1 with sulfuric acid gave a mixture of 3,4 and 7, whereas sulfonation of 2',3'-dimethyl-acetanilide with subsequent hydrolysis led to a mixture of 3 and 4.Treatment of 3',4'-dimethyl-acetanilide with oleum followed by hydrolysis resulted in the formation of mainly 5 and a small amount of unknown product.