7625-64-1

Upstream product

• 106-49-0 p-toluidine 
• 501-53-1 benzyl chloroformate 
• 2101-86-2 p-methylazidobenzene 
• 124-38-9 carbon dioxide 
• 100-44-7 benzyl chloride 
• 621-84-1 O-benzyl carbamate 
• 75337-05-2 4-methyl-2-cyclohexenone 
• 622-58-2 p-Tolylisocyanate 
• 100-51-6 benzyl alcohol 
• 104-57-4 benzyl formate 
• 14618-59-8 N-(tert-butoxycarbonyl)-4-methylaniline 
• 624-31-7 4-tolyl iodide 
• 13139-17-8 N-(Benzyloxycarbonyloxy)succinimide 
• 3422-03-5 benzyloxycarbonyl azide 

Downstream Products

• 622-58-2 p-Tolylisocyanate 
• 100-51-6 benzyl alcohol 
• 1118917-04-6 methyl p-tolyl carbamic acid 1-benzyl ester 
• 103-84-4 Acetanilid 
• 6876-50-2 isovaleric acid p-toluidide 
• 71231-25-9 N-(4-methylphenyl)-3-phenylpropanamide 
• 6876-59-1 N-(4-methylphenyl)-cyclohexanecarboxamide 
• 20172-29-6 N-(p-tolyl)butyramide 
• 22671-74-5 N-butyl-N’-(4-methylphenyl)urea 
• 681810-40-2 C₁₅H₁₄FNO₂ 
• 106-49-0 p-toluidine 
• 1359874-38-6 benzyl allyl(p-tolyl)carbamate 
• 1428098-75-2 5-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-3-p-tolyloxazolidin-2-one 
• 1428098-65-0 5-(3-chloro-2,2,3,3-tetrafluoropropyl)-3-p-tolyloxazolidin-2-one 

Relevant academic research and scientific papers

One stone two birds: Cobalt-catalyzed in situ generation of isocyanates and benzyl alcohols for the synthesis of N-aryl carbamates

An efficient method for the synthesis of N-aryl carbamates from N-Boc-protected amines has been developed. The cobalt-catalyzed in situ generation of isocyanates from N-Boc-protected amines and benzyl alcohols from benzyl formates has been achieved for the first time, which in turn furnished the corresponding benzyl carbamates in moderate to high yields. The reaction was catalyzed by CoI2 with tris-(4-dimethylaminophenyl)-phosphine as the ligand and zinc powder as the reductant. The developed reaction conditions were found to be compatible for aromatic amines with both electron-donating and -withdrawing substituents.

Au(i)/Au(iii)-Catalyzed C-N coupling

Cycling between Au(i) and Au(iii) is challenging, so gold-catalyzed cross-couplings are rare. The (MeDalphos)AuCl complex, which we showed was prone to undergo oxidative addition, is reported here to efficiently catalyze the C-N coupling of aryl iodides and amines. The transformation does not require an external oxidant or a directing group. It is robust and works with a wide scope of aryl iodides and N-nucleophiles under mild conditions. Mechanistic studies, including the NMR and MS characterization of a key aryl amido Au(iii) complex, strongly support a 2e redox cycle in which oxidative addition precedes transmetalation and reductive elimination is the rate-determining step.

Selective Synthesis of Secondary Arylcarbamates via Efficient and Cost Effective Copper-Catalyzed Mono Arylation of Primary Carbamates with Aryl Halides and Arylboronic Acids

Abstract: An efficient, selective and cost-effective procedure has been developed for mono N-arylation of primary alkyl and benzyl carbamates with aryl iodides and bromides by incorporating CuI as an inexpensive and commercially available catalyst. Despite previous reports on C–N coupling reactions, this process does not need expensive ligands and takes advantage of readily available and inexpensive ethylenediamine (EDA) as the ligand. Reaction times were relatively short and related N-arylated carbamates were obtained in excellent yields. Interestingly, replacing CuI with Cu(OAc)2 allowed us to use arylboronic acids as coupling partner for this reaction. All products are well characterized by 1H- and 13C-NMR, MS, melting point, IR and CHNS techniques.

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.

N-Urethane protection of amines and amino acids in an ionic liquid

An efficient, solvent-free protocol for the N-fluorenylmethoxycarbonylation and N-benzyloxycarbonylation of amines is described. The reaction of aliphatic and aromatic amines with FmocOSu and Cbz-Osu in [Bmim][BF4] at room temperature afforded the corresponding N-urethane derivatives in excellent yields and do not require any further purification. The method has been extended to the N-Fmoc and N-Cbz protection of amino acids. Absence of bases, very short reaction times, high yields, selectivity and ease of product separation are some advantages of this protocol.

A synthetic approach to N -aryl carbamates via copper-catalyzed Chan-Lam coupling at room temperature

A mild and efficient synthesis of N-arylcarbamates was achieved by reacting azidoformates with boronic acids in the presence of 10 mol % of copper chloride catalyst. The reaction proceeds readily in an open flask at room temperature without additional base, ligand, or additive. Rapid access to urea analogues via a two-step one-pot procedure is enabled by reacting N-arylcarbamates with aluminum-amine complexes. In addition, among several boronic acid derivatives prepared, dimethylphenyl boronate was found to react rapidly in its reaction with benzyl azidoformate, invoking in situ generation of this species in the catalytic cycle.

Reaction of organozinc halides with aryl isocyanates

Reformatsky reagent, benzylzinc bromide or alkylzinc iodides react with aryl isocyanates directly to give corresponding N-substituted carbamates under mild reaction conditions. However, the reaction of allylzinc bromide or propargylzinc bromide with aryl isocyanates produces the corresponding N-substituted amides. The reactions provide alternative methods for the synthesis of N-substituted carbamates or amides.

Microwave-assisted expeditious synthesis of 5-fluoroalkyl-3-(aryl/alkyl)- oxazolidin-2-ones

An efficient and convenient protocol for synthesis of 5-fluoroalkyl-3- (aryl/alkyl)-oxazolidin-2-ones is described. The reaction of allyl (aryl/alkyl) carbamates with fluoroalkyl iodide initiated by sodium dithionite in aqueous acetonitrile resulted in adducts that undergoes a cyclization assisted by microwave irradiation to form 5-fluoroalkyl-3-(aryl/alkyl)-oxazolidin-2-ones with high yields. It was also found that the products can be more efficiently formed via an AIBN-initiated one-pot addition-cyclization sequence from benzyl allyl(aryl/alkyl) carbamates and fluoroalkyl iodide.

Palladium-catalyzed carbonylation of amines: Switchable approaches to carbamates and N,N′-disubstituted ureas

Switchable access to carbamates and ureas has been developed by solvent control palladium-catalyzed carbonylation of aromatic amines under an atmosphere of carbon monoxide. A variety of N-phenylcarbamates and N,N′- diphenylureas was easily synthesized in good to excellent yields from readily available aromatic amines under mild conditions. Copyright

A facile protocol for N-Cbz protection of amines in PEG-600

An efficient and eco-friendly protocol for the chemoselective N-benzyloxycarbonylation of amines was described. The reaction of amines with benzyl chloroformate (Cbz-Cl) in the presence of PEG-600 at room temperature afforded the corresponding N-Cbz derivatives in excellent yields. The method is applicable to the N-Cbz protection of aliphatic (acyclic and cyclic) and aromatic amines.