Schönenberger, Helmut and Thies, Heinrich and Rappl, A. (1965) Cystostatic agents. III. Mechanism of reduction of Schiff bases by activated aluminum. Archiv der Pharmazie und Berichte der Deutschen Pharmazeutischen Gesellschaft 298 (6), pp. 367-371.
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cf. Schoenenberger, et al., CA 62, 6992f, 7664a, 13163g. The mechanism of redn. was investigated of benzylidenealkyl- and benzylidenearylamine-type Schiff bases with activated Al, to form mono- and dimeric secondary amines. Redn. of PhCH:NBu (I) in abs. EtOH with Al-Hg gave yields of benzylbutylamine (II) and N,N'-dibutyl-alpha ,alpha '-diphenylethylenediamine (III) (in meso- and racemic forms) which varied with the amt. of EtOH. HgCl2 (200 mg.) was dissolved in abs. EtOH (12.5-400 ml.), the soln. heated to boiling (78 Deg) under reflux, and 2 g. Al foil (0.1 mm. thick) added. After 5 min., 4 g. I in 20 ml. abs. EtOH was added to the 78 Deg mixt. with vigorous stirring. The reaction was continued at 78 Deg until the metals dissolved (.apprx.2 hrs.). Concd. HCl (40 ml.) was added to the gelatinous mixt.; the soln. was evapd. almost to dryness on a 100 Deg bath. The green residue was mixed with small vols. of 30% NaOH until the soln. was alk.; the mixt. was extd. with an equal vol. of CHCl3 (3 times), and the combined CHCl3 exts. dried over anhyd. Na2SO4. The dried CHCl3 soln. was satd. with HCl gas, and the CHCl3 distd. The residue (mainly II.HCl + III.HCl) was extd. in a Craig 34 stage countercurrent extn. app., using 40:12:28 CHCl3-MeOH-2% HCl solvent. The compn., and no., of the sepd. fractions are: (A) racemic III, 1-5; (B) meso-III, 6-21; (C) II, 22-34, resp. The av. yields of II, racemic III and meso-III, using first vols. of 12.5, 25, 50, 100, 200, 300, and 400 ml. of abs. EtOH in the redns. of I, are 10.0, 45.1, 45.4; 15.9, 41.5, 42.7; 27.2, 36.1, 36.8; 41.0, 29.0, 30.1; 59.0, 20.2, 20.8; 67.9, 15.7, 16.4; and 71.9, 13.3, 14.9%, resp. Cf. Arzneimittel-Forsch, 15(1), 30-6(1965).
|Additional information (public):||CAN 63:31027 32 Physical Organic Chemistry 2403-22-7P (Benzylamine, N-butyl-) Role: PREP (Preparation) (formation from N-benzylidenebutylamine and isopropylmagnesium halides, in N-benzylidenebutylamine redn. with Al-Hg); 544-40-1 (Butyl sulfide) (hydrogenolysis of, solvent effect in); 1165-52-2P (Ethylenediamine, N,N'-dibutyl-1,2-diphenyl-, meso-); 4169-62-4P (Ethylenediamine, N,N'-dibutyl-1,2-diphenyl-, (-)-) Role: PREP (Preparation) (prepn. of); 1077-18-5 (Butylamine, N-benzylidene-) (redn. of, by Al-Hg); 7439-97-6 (Mercury) (N-benzylidenebutylamine redn. by Al and); 7429-90-5 (Aluminum) (N-benzylidenebutylamine redn. by Hg and)|
|Institutions:||Chemistry and Pharmacy > Institute of Pharmacy > Retired Professors > Prof. Schönenberger|
|Subjects:||500 Science > 540 Chemistry & allied sciences|
|Refereed:||Yes, this version has been refereed|
|Created at the University of Regensburg:||Unknown|
|Deposited On:||19 Nov 2010 08:27|
|Last Modified:||19 Nov 2010 08:27|