16744-99-3

Upstream product

• 79-22-1 methyl chloroformate 
• 371-40-4 4-fluoroaniline 
• 67-56-1 methanol 
• 590-28-3 potassium cyanate 
• 1765-93-1 4-fluoroboronic acid 
• 1195-45-5 para-fluorophenyl isocyanate 
• 201230-82-2 carbon monoxide 
• 681-84-5 tetramethylorthosilicate 
• 124-38-9 carbon dioxide 
• 824-75-9 p-fluorobenzamide 
• 74-88-4 methyl iodide 
• 6294-89-9 hydrazinecarboxylic acid methyl ester 

Downstream Products

• 330-91-6 bis-(4-fluoro-phenyl)-amine 
• 95017-63-3 3-bromo-N,N-bis(4-fluorophenyl)propanamide 
• 409313-68-4 [3-(cis-3,5-dimethyl-1-piperazinyl)propyl]-N,N-bis(4-fluorophenyl)amine 
• 409313-67-3 3-(3,5-dimethyl-piperazin-1-yl)-N,N-bis-(4-fluoro-phenyl)-propionamide 
• 409313-70-8 1-((2R,6S)-4-{3-[Bis-(4-fluoro-phenyl)-amino]-propyl}-2,6-dimethyl-piperazin-1-yl)-3-phenyl-propan-1-one 
• 409313-69-5 1-((2R,6S)-4-{3-[Bis-(4-fluoro-phenyl)-amino]-propyl}-2,6-dimethyl-piperazin-1-yl)-2-(3,4-dichloro-phenyl)-ethanone 
• 1357510-83-8 3-(4-fluorophenyl-3-nitrophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione 
• 1048953-79-2 3-(3-amino-4-fluorophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione 
• 1048953-55-4 2-(2,4-dichlorophenoxy)-N-(2-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-2,3-dihydro-pyrimidin-1(6H)-yl)phenyl)propanamide 
• 1048953-54-3 N-(2-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-2,3-dihydro-pyrimidin-1(6H)-yl)phenyl)-2-(2-methoxyphenoxy)propanamide 
• 1048953-51-0 N-(2-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-2,3-dihydro-pyrimidin-1(6H)-yl)phenyl)-2-(m-tolyloxy)propanamide 
• 1048953-52-1 N-(2-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-2,3-dihydro-pyrimidin-1(6H)-yl)phenyl)-2-(para-tolyloxy)propanamide 
• 1048953-50-9 N-(2-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-2,3-dihydro-pyrimidin-1(6H)-yl)phenyl)-2-(3-fluorophenoxy)propanamide 
• 1048953-70-3 N-(2-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-2,3-dihydro-pyrimidin-1(6H)-yl)phenyl)-2-phenoxypropanamide 

Relevant academic research and scientific papers

METHOD FOR PRODUCING CARBAMATE

PROBLEM TO BE SOLVED: To provide a method that can produce carbamate with high yield and high selectivity, and excellent economical efficiency, using more different kinds of amines. SOLUTION: A method for producing carbamate has a reaction step where, in the presence of calcium carbide and potassium carbonate, a reaction is induced among amine, methanol, and carbon dioxide. The reaction step is preferably performed at a temperature of 165-180°C. The reaction step is preferably performed at a carbon dioxide pressure of 3-5 MPa. The reaction step is preferably performed using an acetonitrile solvent. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2021,JPOandINPIT

Copper-Catalyzed Coupling of Amines with Carbazates: An Approach to Carbamates

A new approach for the preparation of carbamatesviathe copper-catalyzed cross-coupling reaction of amines with alkoxycarbonyl radicals generated from carbazates is described. This environmentally friendly protocol takes place under mild conditions and is compatible with a wide range of amines, including aromatic/aliphatic and primary/secondary substrates.

Atomically Dispersed Copper on N-Doped Carbon Nanosheets for Electrocatalytic Synthesis of Carbamates from CO2 as a C1 Source

The synthesis of carbamates by electrocatalytic reduction of CO2 is an effective method to realize the utilization of CO2 resources. The development of high-performance electrocatalysts to complete this process more efficiently is of great significance to sustainable development. Owing to their unique structural characteristics, single-atom catalysts are expected to promote the reaction process more efficiently. In this study, an atomically dispersed Cu species on N-doped carbon nanosheet composite material (Cu?N?C) was prepared by metal-organic framework derivatization. Compared with traditional Cu bulk electrodes, the Cu?N?C material has better catalytic performance for the synthesis of methyl N-phenylcarbamate; and the optimized yield reached 71 % at room temperature and normal pressure. The Cu?N?C material has good stability that the catalytic performance does not decrease after repeated use for 10 times. In addition, the Cu?N?C material has good applicability to this catalytic system, and a variety of amines can be smoothly converted into corresponding carbamates.

N-Aryl and N-Alkyl Carbamates from 1 Atmosphere of CO2

We have successfully isolated and characterized the zinc carbamate complex (phen)Zn(OAc)(OC(=O)NHPh) (1; phen=1,10-phenanthroline), formed as an intermediate during the Zn(OAc)2/phen-catalyzed synthesis of organic carbamates from CO2, amines, and the reusable reactant Si(OMe)4. Density functional theory calculations revealed that the direct reaction of 1 with Si(OMe)4 proceeds via a five-coordinate silicon intermediate, forming organic carbamates. Based on these results, the catalytic system was improved by using Si(OMe)4 as the reaction solvent and additives like KOMe and KF, which promote the formation of the five-coordinated silicon species. This sustainable and effective method can be used to synthesize various N-aryl and N-alkyl carbamates, including industrially important polyurethane raw materials, starting from CO2 under atmospheric pressure.

Calcium carbide as a dehydrating agent for the synthesis of carbamates, glycerol carbonate, and cyclic carbonates from carbon dioxide

Carbon dioxide (CO2) is a nontoxic and inexpensive C1 building block, which can be used for the synthesis of valuable chemicals such as aromatic carbamates from anilines and methanol (MeOH), glycerol carbonate from glycerol, and cyclic carbonates from diols. However, these reactions generate water as the byproduct and suffer from thermodynamic limits, which lead to low yields. Calcium carbide (CaC2) is a renewable chemical, which can be recycled from calcium that is abundant in the Earth's crust. Furthermore, CaC2 rapidly reacts with water. In this work, we used CaC2 as a dehydrating agent for the direct synthesis of carbamates (including polyurethane precursors) from amines, CO2, and MeOH. All reagents were commercially available. In addition, CaC2 was employed for the synthesis of glycerol carbonate from glycerol and CO2 with a zinc catalyst and N-donor ligand. A similar protocol was applied to synthesize cyclic carbonates from diols and CO2.

Direct Catalytic Synthesis of N-Arylcarbamates from CO2, Anilines and Alcohols

The direct catalytic synthesis of carbamates from CO2, amines and methanol was achieved by controlling both the reaction equilibrium and the reactivity of the three components. The combination of CeO2 and 2-cyanopyridine was an effective catalyst, providing various carbamates including N-arylcarbamates in high selectivities.

Electrochemical Hofmann rearrangement mediated by NaBr: Practical access to bioactive carbamates

An electrochemical Hofmann rearrangement is reported. With the mediation of NaBr, highly corrosive and toxic halogens are avoided. Moreover, this efficient and green approach is well compatible with a broad range of amides, including several commercial medicine derivatives, and provides direct access to synthetically useful carbamates. The synthetic utility of this method is also demonstrated by the preparation of 15N labeling carbamate and gram-scale synthesis of Amantadine.

A Simple Zinc Catalyst for Carbamate Synthesis Directly from CO2

Several zinc salts were employed as catalysts for the synthesis of carbamates directly from aromatic amines, CO2, and silicate esters. Zn(OAc)2 offered the best performance among the salts tested. The addition of an N-donor ligand such as 1,10-phenanthroline increased the yield. The best catalytic performance of Zn(OAc)2 can be explained by carboxylate-assisted proton activation. The interaction between the substrate and the catalyst can be observed by chemical shifts in 1H and 15N NMR spectra. Isocyanate was a key intermediate, which was generated from amine and CO2. Silicate ester was finally converted to siloxane, which was determined by 29Si NMR. The commercially available catalyst system could be reused. The yield of isolated carbamate could reach up to 96 % with various substrates, and the catalytic reaction was amine-selective in the presence of other functional groups.

Synthesis of carbamates from carbon dioxide promoted by organostannanes and alkoxysilanes

A cooperative methoxy transfer between orthosilicate esters and organotin oxides was developed for the synthesis of various N-alkyl and N-aryl carbamates from carbon dioxide in up to 97% isolated yield. The reaction is highly selective and N-alkylated amines are not observed. Density functional theory calculations of the reaction were performed and, together with NMR observations, a plausible mechanism featuring the catalytic regeneration of dialkyltin dialkoxide is proposed.

Copper-catalyzed mild nitration of protected anilines

A practical copper-catalyzed direct nitration of protected anilines, by using one equivalent of nitric acid as the nitrating agent, has been developed. This procedure features mild reaction conditions, wide structural scope (with regard to both N-protecting group and arene substitution), and high functional-group tolerance. Dinitration with two equivalents of nitric acid is also feasible. Practical and reliable: A Cu-catalyzed selective nitration of para- and ortho-substituted aniline derivatives by using one equivalent of HNO3 has been developed that produces water as the only stoichiometric byproduct (see scheme; PG=protecting group). This method is compatible with strongly electron-deficient substrates, enabling dinitration (by using 2.0 equiv of HNO3). This method allows for a rapid access to relevant nitrogen-containing heterocyclic architectures.