Reactions of Schiff bases. V. The conversion of benzyl idenearylamines with Mg-MgI2 mixtures

Thies, Heinrich, Schönenberger, Helmut and Bauer, K. H. (1958) Reactions of Schiff bases. V. The conversion of benzyl idenearylamines with Mg-MgI2 mixtures. Archiv der Pharmazie und Berichte der Deutschen Pharmazeutischen Gesellschaft 291, pp. 620-627.

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Abstract

Abstract

cf. CA 53, 3112a. Reaction of benzylidenearylamines with Mg-MgI2 mixt. proceeded faster and with better yields than that of benzylidenealkylamines. Lower yields were obtained with halogen-, MeO- or dimethylamino-substituted benzylideneanilines. A mixt. of 2.4 g. Mg and of 12.7 g. iodine in 20 ml. anhyd. Et2O and 30 ml. anhyd. C6H6 was stirred until the iodine color disappeared, 0.1 mole Schiff base in 30 ml. anhyd. C6H6 added under N, the mixt. stirred until all Mg dissolved, then hydrolyzed with cold H2O and the pptd. Mg(OH)2 dissolved with 16 g. 30% AcOH. After sepn. of the org. layer, the aq. phase was extd. 2-3 times with C6H6, the combined exts. dried (Na2SO4), the solvent distd., the residue boiled shortly with MeOH, cooled overnight and the pptd. ethylenediamine deriv. recrystd. (MeOH). Following this procedure benzylideneaniline gave 16.7 g. N,N',alpha ,alpha '-tetraphenylethylenediamine (I), m. 134-6 Deg, n195-9 1.5700, n173-5 1.5794; benzylidene-p-toluidine gave 17 g. N,N'di-p-tolyl-alpha ,alpha '-diphenylethylenediamine (II), m. 138-40 Deg, n159-61 1.5700, n139-421.5794; benzylidene-o-toluidine gave 15.7 g. N,N'-di-o-tolyl-alpha ,alpha '-diphenylethylenediamine (III), m. 124 Deg n160-31.5700, n39-42 1.5794; N-(4-methylbenzylidene)aniline gave 1.2 g. N,N'-diphenyl-alpha ,alpha '-di-p-tolylethylenediamine (IV), m. 130 Deg, n154-7 1.5700, n135-71.5794; N-(4-methylbenzylidene)-p-toluidine gave 0.9 g. N,N',alpha ,alpha '-tetra-p-tolylethylenediamine (V), m. 155-8 Deg, n162-51.5609, n139-41 1.5700. For Cl substituted benzylidenearylamines the procedure was changed as follows. The reaction time was prolonged to 6 hrs. and the residue obtained after removal of the solvents heated 5 min. with 30 ml. concd. HCl on the steam bath to cleave the unchanged material; the mixt. was cooled, extd. with ligroine, the aq. phase sepd. and neutralized, the resulting suspension extd. 3 times with 10 ml. C6H6, the exts. combined, the solvents distd., the residue boiled shortly with MeOH, chilled overnight and the ethylenediamine deriv. recrystd. (MeOH). N-(4-Chlorobenzylidene)-4-chloroaniline gave 2.2 g. N,N',alpha ,alpha '-tetrakis-(p-chlorophenyl)ethylenediamine (VI), m. 190-2 Deg, n201-4 1.5794, n184-7 1.5898; N-(4-chlorobenzylidene)aniline gave 4.6 g. N,N'-diphenyl-alpha ,alpha '-bis(p-chlorophenyl)ethylenediamine (VII), m. 194-5 Deg, n198-91 1.5794, n167-70 1.5898; benzylidene-4-chloroaniline gave 9.4 g. N,N'-bis(p-chlorophenyl)-alpha ,alpha '-diphenylethylehediamine (VIII), m. 200-2 Deg, n204-7 1.5700, n184-6 1.5794; benzylidene-3-chloroaniline gave 3.8 g. N,N'-bis(m-chlorophenyl)-alpha ,alpha '-diphenylethylenediamine (IX), m. 153-5 Deg, n200-3 1.5700, n182-5 1.5794; benzylidene-2-chloroaniline gave 1.4 g. N,N'-bis(o-chlorophenyl)-alpha ,alpha '-diphenylethylenediamine (X), m. 132 Deg, n187-9 1.5700, n170-2 1.5794. Reaction times were reported. Eutectic m.p. of I, II, III, IV, V, IX and X with acetanilide and phenacetin and of VI, VII, VIII with dicyanamide and salophen were also tabulated. An exptl. procedure for the study of reaction of benzylideneaniline in dependence of time, together with an app. for filtration under N, were described.

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Article

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1958

Additional Information (public):

CAN 54:97388 10E Organic Chemistry: Benzene Derivatives 10377-58-9; 103043-89-6 (Derived from data in the 6th Collective Formula Index (1957-1961); 538-51-2 (Aniline, N-benzylidene-) (and derivs., reaction with Mg-MgI2 mixts.); 2879-66-5 (Ethylenediamine, N,N',1,2-tetraphenyl-); 56644-01-0 (Ethylenediamine, 1,2-diphenyl-N,N'-di-p-tolyl-); 83871-63-0 (Ethylenediamine, N,N'-diphenyl-1,2-di-p-tolyl-); 83871-64-1 (Ethylenediamine, N,N',1,2-tetra-p-tolyl-); 115228-56-3 (Ethylenediamine, N,N'-bis[o-chlorophenyl]-1,2-diphenyl-); 115228-94-9 (Ethylenediamine, N,N'-bis[m-chlorophenyl]-1,2-diphenyl-); 116027-50-0 (Ethylenediamine, 1,2-diphenyl-N,N'-di-o-tolyl-) (and eutectics with acetanilide and phenacetin); 2948-39-2 (Ethylenediamine, N,N'-bis(p-chlorophenyl)-1,2-diphenyl-); 96003-68-8 (Ethylenediamine, 1,2-bis(p-chlorophenyl)-N,N'-diphenyl-); 103051-28-1 (Ethylenediamine, N,N',1,2-tetrakis(p-chlorophenyl)-) (and eutectics with dicyanamide and phenetsal); 62-44-2 (Phenacetin) (eutectics of, with N,N',1,2-tetraarylethylenediamines); 103-84-4 (Acetanilide); 118-57-0 (Phenetsal); 504-66-5 (Dicyanamide) (eutectics with N,N',1,2-tetraarylethylenediamines)

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Chemistry and Pharmacy > Institute of Pharmacy > Alumni or Retired Professors > Prof. Schönenberger

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