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Synthesis and Structural Properties of Bridged 1,8‐Diazacyclotetradeca‐4,11‐diynes
Author(s) -
Wolfart Volker,
Gleiter Rolf,
Irngartinger Hermann,
Oeser Thomas,
Krieger Claus
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199812)1998:12<2803::aid-ejoc2803>3.0.co;2-c
Subject(s) - chemistry , isopropyl , nitrogen atom , nitrogen , bicyclic molecule , stereochemistry , atom (system on chip) , crystallography , ammonia , crystal structure , medicinal chemistry , ring (chemistry) , organic chemistry , computer science , embedded system
The synthesis of 1,8‐diazacyclotetradeca‐4,11‐diyne ( 4 ) was accomplished by reaction of 1,6‐dibromo‐3‐hexyne ( 11 ) with ammonia. Similarly, the preparation of 1‐azacyclotetradeca‐4,11‐diyne ( 5 ) was achieved from 1,13‐dibromotrideca‐3,11‐diyne ( 10 ) and ammonia. The reaction of α,ω‐diamines of linear hydrocarbons of the chain length C 4 to C 10 with 11 yielded the corresponding bicyclic diynes 23‐29 . The reaction of 4 with 11 yielded 1,8‐diazabicyclo[6.6.6]icosa‐4,11,16‐triyne ( 14 ). Similarly, the reaction of 4 with 1,4‐dibromo‐2‐butyne yielded 1,8‐diazabicyclo[6.6.4]octadeca‐4,11,16‐triyne ( 31 ). The molecular structures of 1,8‐diisopropyl‐1,8‐diazacyclotetradeca‐4,11‐diyne ( 13a ), as well as of 14 , 24 , 27 and 31 were studied by means of the X‐ray technique. It was found that 13a adopts a chair‐like conformation ( C 2h ) with an equatorial orientation of the isopropyl groups. In 14 , 24 , 27 , and 31 the 14‐membered rings adopt a twist‐boat conformation. The distance between the nitrogen atoms varies between 4.662(2) and 5.189(2) Å. In the case of 14 , 24 and 27 the nitrogen atoms are pyramidalized and point inside the cage while in 31 the substituents at each nitrogen atom and the nitrogen atoms are situated in one plane.