511302-28-6

Upstream product

• 3186-53-6 O-methyl S-p-methylphenyl thiocarbonate 
• 4152-90-3 m-chlorobenzylamine 
• 3186-65-0 O-methyl S-p-chlorophenyl thiocarbonate 
• 3186-52-5 O-methyl-S-phenyl thiolcarbonate 
• 65398-61-0 O-methyl S-p-bromophenyl thiocarbonate 
• 67-56-1 methanol 
• 58357-84-9 2-(3-chlorophenyl)acetamide 
• 1529-41-5 3-chloro-benzeneacetonitrile 

Relevant academic research and scientific papers

Hypervalent iodine catalyzed hofmann rearrangement of carboxamides using oxone as terminal oxidant

Hofmann rearrangement of carboxamides to carbamates using Oxone as an oxidant can be efficiently catalyzed by iodobenzene. This reaction involves hypervalent iodine species generated in situ from catalytic amount of PhI and Oxone in the presence of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) in aqueous methanol solutions. Under these conditions, Hofmann rearrangement of various carboxamides affords corresponding carbamates in high yields.

Kinetics and mechanism of the aminolysis of O-methyl S-aryl thiocarbonates in acetonitrile

The aminolysis of O-methyl S-aryl thiocarbonates with benzylamines are studied in acetonitrile at -45.0°C. The βX (βnuc) values are in the range 0.62-0.80 with a negative cross-interaction constant, ρXZ = -0.42, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles (XC6H 4CH2ND2) are large, kH/kD = 1.29-1.75, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the MeO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.