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Synthesis of Spirocyclopropanated Analogues of Imidacloprid and Thiacloprid
Author(s) -
Brackmann Farina,
Yufit Dmitrii S.,
Howard Judith A. K.,
EsSayed Mazen,
de Meijere Armin
Publication year - 2005
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/ejoc.200400599
Subject(s) - thiacloprid , chemistry , structural isomer , imidacloprid , yield (engineering) , derivative (finance) , carbamate , stereochemistry , hydroxymethyl , organic chemistry , pesticide , materials science , thiamethoxam , economics , financial economics , agronomy , metallurgy , biology
tert ‐Butyl N ‐[1‐(hydroxymethyl)cyclopropyl]carbamate ( 8 ) was converted into spirocyclopropanated analogues 14 ‐CP and 14 ‐CT of the insecticide Thiacloprid ( 2 ) in six simple steps with overall yields of 24 % each, along with their regioisomers 13 ‐CP and 13 ‐CT in overall yields of 17 and 15 %, respectively. The spirocyclopropanated analogues 27 ‐CP and 27 ‐CT of the insecticide Imidacloprid ( 1 ) were prepared from 8 in five steps in an overall yield of 10 % each, along with their regioisomers 20 ‐CP and 20 ‐CT in an overall yield of 8 and 7 %, respectively. The key step in all preparations was a cocyclization of an appropiately protected (1‐aminocyclopropyl)methyl derivative with S , S ‐dimethyl cyanodithioiminocarbonate ( 11 ) or nitroguanidine ( 22 ). The structures of several final products and by‐products were verified by X‐ray crystal structure analyses.