6324-63-6

Upstream product

• 501-53-1 benzyl chloroformate 
• 106-50-3 1,4-phenylenediamine 
• 124-38-9 carbon dioxide 
• 100-44-7 benzyl chloride 
• 116015-91-9 N,N'-cyclohexa-2,5-diene-1,4-diylidene-bis-carbamic acid dibenzyl ester 
• 121-69-7 N,N-dimethyl-aniline 
• 99-97-8 Dimethyl-p-toluidine 
• 698-69-1 4-chloro-N,N-dimethylaniline 
• 701-56-4 4-methoxy-N,N-dimethylanilne 

Downstream Products

• 116015-99-7 [4-(Benzyloxycarbonyl-{[(4-chloro-phenyl)-methyl-amino]-methyl}-amino)-phenyl]-carbamic acid benzyl ester 
• 116015-97-5 (4-{Benzyloxycarbonyl-[(methyl-p-tolyl-amino)-methyl]-amino}-phenyl)-carbamic acid benzyl ester 

Relevant academic research and scientific papers

Carbon Dioxide as a Phosgene Replacement: Synthesis and Mechanistic Studies of Urethanes from Amines, CO2, and Alkyl Chlorides

Several carbamate esters were synthesized from amines, carbon dioxide, and alkyl chlorides.The effect of added base on the yield and selectivity of carbamate ester formation was found to be highly important with the use of sterically hindered guanidine bases giving the best results.Relative rate studies were carried out giving the following order of reactivity between carbamate anions in acetonitrile with benzyl chloride giving carbamate esters: Et2NCO2(-) = Bu2NCO2(-) > t-BuNHCO2(-) = CyNHCO2(-) = s-BuNHCO2(-) > PhNHCO2(-) > CyCH2NHCO2(-) = n-octylNHCO2(-) = n-BuNHCO2(-).Rate studies were carried out with the diethyl, s-butyl, phenyl, and n-butyl carbamates and activation parameters were determined to be Et2NCO2(-), ΔH(excit.) = 11.8 kcal/mol, ΔS(excit.) = -33 eu; s-BuNHCO2(-), ΔH(excit.) = 12.8 kcal/mol, ΔS(excit.) = -33 eu; PhNHCO2(-), ΔH(excit.) = 14.3 kcal/mol, ΔS(excit.) = -28 eu; n-BuNHCO2(-), ΔH(excit.) = 23.4 kcal/mol, ΔS(excit.) = -3 eu.The unusual results obtained from the use of n-BuNHCO2(-) prompted further studies which showed that the rate of the reaction was inversely dependent on carbon dioxide pressure (20 psig CO2, k = 4.84E-4 M-1 s-1; 120 psig CO2, k = 1.83E-4 M-1 s-1).Nitrogen NMR spectroscopy indicated, via a labeling study with 15N amines and 13C enriched carbon dioxide, the formation of doubly inserted product from the addition of two carbon dioxides to ethylamine in acetonitrile.

Highly Selective Generation of Urethanes from Amines, Carbon Dioxide and Alkyl Chlorides

Generation of carbamate anions from either a primary or secondary amine, carbon dioxide and a stoichiometric amount of a pentaalkylguanidine followed by the addition of alkyl chlorides gives high yields of urethanes.

Reactions of p-Benzoquinone Diimine Derivatives with N,N-Dimethylanilines

N,N'-Bisalkoxycarbonyl-p-benzoquinone diimine underwent a thermal addition reaction with N,N-dimethylanilines to form an N-C bond between an imino group and an N-methyl group.Upon irradiation the reaction was accelerated.The reaction did not proceed with N-alkyl substituted anilines other than methyl.