A new series of bis-triazenes, the 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes has been synthesized from the reaction of diazonium salts with a mixture of 1,4-diaminobutane and formaldehyde. The structures of 1(p-bromophenyl)-2-[3-{3-[2-(p-bromophenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene((1) under bar), 1-(p-cyanophenyl)-2-[3-{3-[2-(p-cyanophenyl)-1-diazenyl]1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene((2) under bar), and 1-(p-methoxyphenyl)-2[3-{3-[2-(p-methoxy-phenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1 diazene((3) under bar) have been unequivocally determined by X-ray crystallography. The new bis-triazenes are important since the structure contains the novel saturated heterocycle, 1,3- diazepane. The general conclusion of this study is that alkanediamines with 3 or 4 carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type (5) under bar, in contrast to the case of ethylenediamine (spacer link 2 carbon atoms), which affords molecules of type (6) under bar, which exemplify the general cage structure of type (4) under bar. The crystal structures of 1, 2 and 3 are compared with the previously reported structure of the hexahydropyrimidine analogue (8a) under bar (X = CN); compounds 2 and (8a) under bar (X = CN) are homologous with respect to the alkane spacer moiety. The structures of (2) under bar and (8a) under bar (X = CN) are very different in one respect; in (2) under bar the aryldiazenyl-1,3-diazepanyl groups are in the s-trans orientation around the central methylene group whereas in (8a) under bar (X = CN) the arrangement of the aryldiazenyl-hexahydropyrimidinyl groups is the s-cis orientation.
X-Ray crystal structure determination of a series of 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1, 3-diazepan-1-yl]-1-diazenes obtained from the reaction of diazonium salts with mixtures of formaldehyde and 1,4-diaminobutane
BERTOLASI, Valerio;
2006
Abstract
A new series of bis-triazenes, the 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes has been synthesized from the reaction of diazonium salts with a mixture of 1,4-diaminobutane and formaldehyde. The structures of 1(p-bromophenyl)-2-[3-{3-[2-(p-bromophenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene((1) under bar), 1-(p-cyanophenyl)-2-[3-{3-[2-(p-cyanophenyl)-1-diazenyl]1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene((2) under bar), and 1-(p-methoxyphenyl)-2[3-{3-[2-(p-methoxy-phenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1 diazene((3) under bar) have been unequivocally determined by X-ray crystallography. The new bis-triazenes are important since the structure contains the novel saturated heterocycle, 1,3- diazepane. The general conclusion of this study is that alkanediamines with 3 or 4 carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type (5) under bar, in contrast to the case of ethylenediamine (spacer link 2 carbon atoms), which affords molecules of type (6) under bar, which exemplify the general cage structure of type (4) under bar. The crystal structures of 1, 2 and 3 are compared with the previously reported structure of the hexahydropyrimidine analogue (8a) under bar (X = CN); compounds 2 and (8a) under bar (X = CN) are homologous with respect to the alkane spacer moiety. The structures of (2) under bar and (8a) under bar (X = CN) are very different in one respect; in (2) under bar the aryldiazenyl-1,3-diazepanyl groups are in the s-trans orientation around the central methylene group whereas in (8a) under bar (X = CN) the arrangement of the aryldiazenyl-hexahydropyrimidinyl groups is the s-cis orientation.I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
