Ortho-para-isomerism in the preparataion of diaminodiphenylmethane / by Harold King.

  • King, Harold
Date:
1920.]
Catalogue details

Licence: Public Domain Mark

Credit: Ortho-para-isomerism in the preparataion of diaminodiphenylmethane / by Harold King. Source: Wellcome Collection.

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    boiling methyl alcohol, in which it dissolves to the extent of 12 per cent, in pale buff-coloured, woolly needles melting at 239—240° (corr.) (Found: C = 62*2; H = 5*3. C17H1704N3 requires C = 62-4; H = 52 per cent.). The tetra-acetyl derivative obtained when the diacetyl deriv¬ ative is boiled with excess of acetic anhydride is soluble in about one hundred times its weight of boiling alcohol, and separates in clear, oblique prisms melting at 201*5—202'5° (corr.) (Found: C = 61*6; 11 = 5*4. C21H2]0GN3 requires C = 61*3; H = 5T per cent.). 4 : 3'-Dinitro-2 : 47-diacetylaminodiphenylmethane. 4-Nitro-2 : 4'-diacetylaminodiphenylm ethane (1*3 grams), when nitrated with a mixture of sulphuric and nitric acids, gave 1*45 grams of the crude dinitrated anilide. It was recrystallised twice from glacial acetic acid, yielding, finally, 1T5 grams. It dissolves, in fifty volumes of the boiling solvent, and crystallises as a voluminous mass of golden needles melting at 264—265° (corr.). A mixture with the isomeric 3:3/-dinitro*-4 :4,-diacetylaminodi- phenylmethane, which melts at 259—260° (uncorr.), melted at 233° (Found: C = 55*3; H = 4*4. C17H160GN4 requires C = 54*8; H = 4*3 per cent.). 3': 4t-Dinitro~2 ■A'-diaminodipheMylmethane. The free aniline prepared from the above anilide, when recrystal¬ lised from boiling alcohol (twenty-four parts), separates in glisten¬ ing, orange needles, very similar in appearance to 4-nitro-2 :4;- diaminodiphenylmethane. It melts at 148*5—149*5° (corr.) (Found: C = 54*5; H = 4*2. C13H1204N4 requires C = 54*2; II =4 2 per cent.). 4-^4 cetylamiuodiphenylmethane. 4-Nitro-2:4/-diaminodiphenylmethane was deprived of the amino-groups by the diazo-reaction, the product reduced, and acetylated. Purification by recrystallisation from alcohol gave the compound in the form of large, pearly leaflets melting at 128—129° (corr.), and a mixed melting point with 4-acetylaminodiphenyl- methane, prepared from benzene and /?-nitrobenzyl chloride by the Friedel and Crafts synthesis, followed by reduction and acetyl¬ ation, showed no depression (Found: N = 6*2. C15H1:-ON requires N = 6'2 per cent.).