Organic Lab Reactions 291

Organic Lab Reactions 291 - tions. In addition to benzene,...

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286 THE AROMATIC PRIMARY AMINO GROUP - TREATMENT WITH SODIUM STANNITE In this reduction aqueous stannite is added to an alkaline solution of the diazo compound, the temperature being kept in the neighborhood of 0°; the reaction proceeds rapidly. 6 Few sodium stannite deaminations are to be found in the litera- ture, and of these a substantial fraction concerns unsubstituted amines and their homologs. Thus, benzene is obtained from aniline in 60% yield, 102 - 1S and the hydrocarbons derived from 2,3-dimethylaniline and 2,4,5-trimethylaniline are produced in "satisfactory yields" and in a high state of purity. 103 The conversion of l,3-dimethyl-4-amino-6-bromobenzene to 1,3-di- methyl-5-bromobenzene occurs in 73% yield, 104 but the yield is consid- erably lower (ca. 38%) in the case of the nitroaminostilbene XXIII. 106 NH 2 TYTTT In the following instances, failures have been recorded for sodium stannite: 3-nitro-4-aminotoluene, 106 p-aminophenylarsonic acid, 92 trans- o-aminocinnamic acid. 93 - * A number of by-products may be isolated from sodium stannite reduc-
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Unformatted text preview: tions. In addition to benzene, aniline gives phenol, azobenzene, phenyl azide, and phenylhydrazine. 107-1M-108-109 The danger of hydrolytic cleavage in alkaline media, previously discussed in connection with the * The first of these compounds is successfully deaminated either by ethanol or hypo-phosphorous acid; with the last two, hypophosphorous acid is effective in bringing about the desired reaction. 1M Koenigs and Carl, Ber., 23, 2672 (1890). 103 von Auwers, Ann., 419, 96 (1919). " 104 Fieser and Heymann, J. Am. Chem. Soc, 64, 380 (1942); Heymann, Ph.D. thesis, Harvard University, 1941. A detailed description of this deamination will be found on p. 298. 106 Pfeiffer and Monath, Ber., 39, 1305 (1906). 10 Bigelow, J. Am. Chem. Soc, 41, 1566 (1919). l07 Eibner, Ber., 36, 813 (1903). 108 Bamberger and Meimberg, Ber., 26, 497 (1893). 109 Culmann and Gasiorowski, J. praM. Chem., [2] 40, 108 (1889)....
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This note was uploaded on 11/20/2011 for the course CHM 2210 taught by Professor Reynolds during the Fall '01 term at University of Florida.

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