The mere retention of the same crystal form by homologous substances is not a sufficient reason for denying a morphotropic effect to the substituent group; for, in the case of certain substances crystallizing in the cubic system, although the crystal form remains unaltered, yet the structures vary.
Other substituent groups exercise morphotropic effects similar to those exhibited by the alkyl radicles; investigations have been made on halogen-, hydroxy-, and nitro-derivatives of benzene and substituted benzenes.
Soc. 61, p. 367): If the hydrogen compound of the substituent already in the benzene nucleus can be directly oxidized to the' corresponding hydroxyl compound, then meta-derivatives predominate on further substitution, if not, then orthoand paraderivatives.
If, however, one of the para positions in the hydrazo compound is substituted, then either diphenyl derivatives or azo compounds are formed, or what is known as the semidine change takes place (P. Jacobson, Berichte, 1892, 2 5, p. 99 2; 1893, 26, p. 681; 1896, 29, p. 2680; Annalen, 1895, 287, p. 97; 1898, 3 0 3, p. 290) A para mono substituted hydrazo compound in the presence of a hydrochloric acid solution of stannous chloride gives either a para diphenyl derivative (the substituent group being eliminated), an ortho-semidine, a para-semidine, or a diphenyl base, whilst a decomposition with the formation of amines may also take place.
From acetylene and acetone); but according to Baeyer (Ber., 1886, 9, 1797) it fails to explain the formation of dioxyterephthalic ester from succinosuccinic ester, unless we make the assumption that the transformation of these substances is attended by a migration of the substituent groups.
The magnitude of this separation would obviously depend on the magnitude of the substituent group, which may be so large (in this case propyl is sufficient) as to cause unequal horizontal deformation and at the same time a change in the vertical direction.
Starting with a monoderivative, we have seen that a substituent group may enter in either of three positions to form an ortho-, meta-, or paracompound.
Intermolecular transformations-migrations of substituent groups from one carbon atom to anotherare of fairly common occurrence among oxy compounds at elevated temperatures.
Not only does the substituent group modify the readiness with which the derivative is attacked, but also the nature of the product.
The nature of the substituent exerts a specific influence on the reaction; thus with chlorine or bromine, ortho-semidines and the diphenyl bases are the chief products; the dimethylamino, -N(CH 3) 2, and acetamino, -NHCOCH3, groups give the diphenyl base and the para-semidine respectively.