Preparation
CAUTION: Use a well-ventilated hood and take all precautions before using phosgene.
To a flask equipped as in Preparation 3-1 is added 1.27 kg (10.0 moles) of N-cyclohexylformamide, 3.20 liters of triethylamine, and 4.50 liters of methylene chloride. The solution is stirred while phosgene is rapidly added (300-400 gm/hr) to cause vigorous refluxing. Refluxing ceases after 1.04 kg (10.2 moles) of phosgene have been added and the addition is stopped. The reaction mixture is cooled to 22-25°C, 400 gm (23.5 moles) of ammonia gas added over a period of 1-2 hr, the mixture filtered then concentrated under reduced pressure, and the residue distilled to afford 955 gm (88%), b.p. 67-72°C (14 mm Hg).
General Description
Cyclohexyl isocyanide reacts with dimethyl acetylenedicarboxylate to give a mixture of cyclopenta[
b]pyridine derivatives, azaspirononatriene derivative and the azabicyclononatriene. It reacts with dialkyl acetylenedicarboxylates to form 1:1 intermediate which on facile addition to 1-benzylisatin and tryptantrin yields highly functionalized novel unsaturated γ-spiroiminolactones.
References
[1] Khalili, Gholamhossein. “ChemInform Abstract: A Diastereoselective Synthesis of (Z)-3-[(Aryl)(hydroxyimino)methyl] -2-cyclohexyl-1-(cyclohexylamino)imidazo[5,1-a]isoquinolinium Chlorides from Isoquinoline, Chlorooximes, and Cyclohexyl Isocyanide.” ChemInform 47 25 (2016).
[2] M. Anary‐Abbasinejad, M. Heidari, N. Shams. “One-pot synthesis of highly functionalised 1H-pyrazoles from arylcarbohydrazides, cyclohexyl isocyanide, and acetylene diesters.” Arkivoc 2012 1 (2012).
[3] Anary‐Abbasinejad, M. M. Jaafari and Mahdiyeh Talebizadeh. “One-pot Four-component Reaction between Arylamines, Arylglyoxals, Cyclohexyl Isocyanide, and Acetylene Diesters: An Efficient Synthesis of 2H-iminopyran Derivatives.” 2019. 0.
[4] Alireza Hassanabadi. “ChemInform Abstract: Use of Cyclohexyl Isocyanide in the Esterification of N-Benzoyl α-Amino Acid Derivatives.” ChemInform 43 3 (2011).
[5] A. Hassanabadi. “The use of cyclohexyl isocyanide in the esterification of N -benzoyl α-amino acids derivatives.” Journal of Chemical Research-s 18 1 (2011): 468–470.
