4442-90-4

Upstream product

• 4435-18-1 2-cyclohexylideneacetonitrile 
• 108-94-1 cyclohexanone 
• 138313-56-1 N-(2-Cyclohexylidenethyl)phthalimid 
• 6318-49-6 1-vinylcyclohexyl acetate 

Downstream Products

• 59874-98-5 2,2,2-trichloro-N-(2-cyclohexylideneethyl)acetamide 
• 1599461-71-8 (Z)-ethyl 3-((2-cyclohexylideneethyl)amino)-3-phenylacrylate 
• 138313-50-5 2-Cyclohexylidenethylisocyanid 
• 138313-51-6 2-Cyclohexylidenethylcyanid 
• 138313-52-7 N-(2-Cyclohexylidenethyl)formamid 

Relevant academic research and scientific papers

Amination of Carbenium Ions Generated by Directed Protonolysis of Cyclopropane

Directed intramolecular protonolyis of the cyclopropane C-C bond is demonstrated as a strategy to generate carbenium ions. This intermediate can be subjected to amination with nitriles under Ritter reaction conditions. Directing groups such as carbamate, carboxamide, urea, ester, and ketone were found to be efficient for regioselective anti-Markovnikov cleavage of cyclopropane. Depending on the directing group, the amination provided orthogonally protected 1,4-diamine, ?-amino carboxylic, and ?-amino ketone derivatives.

New Syntheses of Isomerically Pure Allyl and Propargyl Cyanides by Isocyanide-Cyanide Rearrangement

A new route for the synthesis of isomerically pure allyl and propargyl cyanides has been developed.Allylic amines are synthesized from the corresponding alcohols by Mitsunobu or by Overman reaction.Formylation with formic acid derivatives provides N-substituted formamides, which are dehydrated to isocyanides. 1,2-Sigmatropic rearrangement by flash pyrolysis provides the isomerically pure allyl and propargyl cyanides. Key Words: Isocyanide-cyanide rearrangment / Cyanides, allyl- and propargyl-

Palladium(0)-Catalyzed Azidation of Allyl Esters. Selective Synthesis of Allyl Azides, Primary Allylamines, and Related Compounds

Palladium(0)-catalyzed reaction of allyl esters such as phosphates, carbonates, and carboxylates with sodium azide gives allyl azides.The azidation proceeds with retention of configuration at the allylic carbon.Optically active (R)-(E)-(+)-4-phenyl-3-buten-2-yl azide (19) is obtained from (R)-(E)-(+)-4-phenyl-3-buten-2-yl acetate (18) stereoselectively.Sequential substitution of (Z)-4-acetoxy-2-buten-1-yl diethyl phosphate (24) with nucleophiles and subsequently azide ion gives (E)-4-substituted-2-buten-1-yl azides 27.The reaction of allyl azides with triphenylphosphine gives iminotriphenylphosphoranes, which are versatile synthetic intermediates of primary allylamines, N-allylamines, and N-allylamides.Treatment of allyl azides with triphenylphosphine and subsequently with aqueous ammonium solution gives primary allylamines.Other synthetic applications of allyl azides are also described.

PALLADIUM(0) CATALYZED AZIDATION AND AMINATION OF ALLYL ACETATES. SELECTIVE SYNTHESIS OF ALLYL AZIDES AND PRIMARY ALLYLAMINES

Palladium catalyzed reaction of allyl acetates with azide ion gives allyl azides, which are readily converted into the corresponding primary allylamines upon treatment with PPh3/NaOH.