457-79-4

Upstream product

• 108-23-6 isopropyl chloroformate 
• 371-40-4 4-fluoroaniline 
• 546-68-9 titanium(IV)isopropoxide 
• 1195-45-5 para-fluorophenyl isocyanate 
• 2446-83-5 di-isopropyl azodicarboxylate 
• 124-38-9 carbon dioxide 
• 67-63-0 isopropyl alcohol 

Downstream Products

• 314-83-0 (4-fluoro-phenyl)-μ-imido-dicarbonic acid diisopropyl ester 

Relevant academic research and scientific papers

METHOD FOR PRODUCING CARBAMATE

PROBLEM TO BE SOLVED: To provide a method for producing carbamate in which a high yield can be obtained and the amount of by-products produced can be reduced. SOLUTION: In the method, carbamate is synthesized using at least one member selected from the group consisting of amine and derivative thereof, alcohol having 3 or more carbon atoms and carbon dioxide as a raw material, cerium oxide as a catalyst, and 2-cyanopyridine as a dehydrating agent. By using an alcohol having 3 or more carbon atoms, a high yield can be obtained and the amount of by-products produced can be reduced. In addition, the pressure of carbon dioxide can be lowered and the production can be of ease. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2018,JPO&INPIT

Metal-Free Synthesis of Unsymmetrical Ureas and Carbamates from CO2 and Amines via Isocyanate Intermediates

A mild and metal-free synthesis of aryl isocyanates from arylamines under an atmosphere of CO2 was developed. The carbamic acid intermediate, derived from the arylamine starting material and CO2 in the presence of DBU, is dehydrated by activated sulfonium reagents to generate the corresponding isocyanate. The latter can be detected by in situ IR and trapped by various amines and alcohols to make unsymmetrical ureas and carbamates, respectively. Dicarbamates can also be prepared in good yields via the mild dehydration of the corresponding dicarbamic acids.

Copper-catalyzed carbonylation of anilines by diisopropyl azodicarboxylate for the synthesis of carbamates

A Cu-catalyzed efficient methodology for the direct carbonylation of anilines has been developed. The N-H bond cleavage and N-C bond formation were notably achieved under solvent-free conditions and a variety of carbamates were synthesized from readily available anilines using diisopropyl azodicarboxylate (DIAD) as the carbonylating source.

Reversible double insertion of aryl isocyanates into the Ti-O bond of titanium(IV) isopropoxide

The insertion of phenyl isocyanate into titanium isopropoxide leads to the formation of a dimeric complex [Ti(OiPr)2(μ-O iPr){C6H5N(OiPr)CO}]2 (1) which has been structurally characterized. Reaction of titanium isopropoxide with two and more than 2 equiv. of phenyl isocyanate is complicated by competitive, reversible insertion between the titanium carbamate and titanium isopropoxide. The ligand formed by insertion of phenyl isocyanate into the titanium carbamate has been structurally characterized in its protonated form C6H5N{C(OiPr)O}C(O)N(H)C6H 5 (3aH). Insertion into the carbamate is kinetically favored whereas insertion into isopropoxide gives the thermodynamically favored product.