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The Reaction of Cyclohexanone Azine with PCl 3 . Synthesis of Annulated Dichlorodiazaphosphole and its Unusual Transannulation
Author(s) -
Kornev Alexander N.,
Gorak Olga Y.,
Lukoyanova Olga V.,
Sushev Vyacheslav V.,
Panova Julia S.,
Baranov Evgenii V.,
Fukin Georgy K.,
Ketkov Sergei Y.,
Abakumov Gleb A.
Publication year - 2012
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200042
Subject(s) - azine , cyclohexanone , chemistry , yield (engineering) , pyridine , adduct , derivative (finance) , molecule , crystal structure , intermolecular force , medicinal chemistry , crystal (programming language) , crystallography , organic chemistry , materials science , catalysis , computer science , economics , financial economics , programming language , metallurgy
The N, N′‐annulated dichlorodiazaphosphole 1 was prepared in 55 % yield by the reaction of cyclohexanone azine ( c ‐HA) with two equivalents of PCl 3 in pyridine. Compound 1 revealed one‐dimensional chains in crystal with short intermolecular interactions [3.194(1) Å] between phosphorus atoms of adjacent molecules. Treatment of c ‐HA with MeLi (2 equiv. in Et 2 O) followed by addition of PCl 3 gave 1 in 33 % yield. An amount of c ‐HA isomerizes in these conditions to form corresponding hexahydroindazole derivative 3 , which further reacts with 1 to give diazaphosphole 5 as transannulation product. Copper monochloride forms an (1:1) adduct with 5 , which was characterized by its X‐ray crystal structure. Only one equivalent of PCl 3 reacts with c ‐HA in Et 2 O/Et 3 N mixture to form diazaphospholium chloride 2 and hexahydroindazole 3 .