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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- tions.
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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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