3770-95-4Relevant articles and documents
HIGH-PRESSURE SYNTHESIS OF CARBAMATES BY THE CARBONYLATION OF AROMATIC NITRO COMPOUNDS IN CYCLOHEXANOL
Lapidus, A. L.,Pirozhkov, S. D.,Tumanova, A. R.,Dolidze, A. V.,Yukhimenko, A. M.
, p. 1672 - 1674 (1991)
A study was carried out on the high-pressure carbonylation of nitrobenzene and 3-chloronitrobenzene by CO in cyclohexanol in the presence of PdCl2-FeCl3-pyridine with the formation of cyclohexyl-N-phenylcarbamate and cyclohexyl-N-3-chlorophenylcarbamate i
Disparate behavior of carbonyl and thiocarbonyl compounds: Acyl chlorides vs thiocarbonyl chlorides and isocyanates vs isothiocyanates
Wiberg, Kenneth B.,Wang, Yi-Gui,Miller, Scott J.,Puchlopek, Angela L. A.,Bailey, William F.,Fair, Justin D.
, p. 3659 - 3664 (2009)
(Figure Presented) The reaction of benzoyl chloride with methanol catalyzed by pyridine is 9 times more rapid than is the same reaction with thiobenzoyl chloride. The difference in reactivity, as well as the dealkylation reactions that occur when the reaction of thiobenzoyl chloride is catalyzed by bases such as Et3N, can be understood in terms of the charge distributions in the intermediate acylammonium ions. The reaction of PhNCO with ethanol occurs at a much higher rate (4.8 × 104) than that of PhNCS, corresponding to a difference in activation free energies for the additions of 6 kcal/mol. Transition states for each of these reactions were located, and each involves two alcohol molecules in a hydrogen bonded six-membered ring arrangement. Information concerning differences in reactivity was derived from analysis of Hirshfeld atomic charge distributions and calculated hydrogenolysis reaction energies.
Synthesis, crystal structure and ab initio studies of cyclohexyl n-phenylcarbamate
Pereira Silva,Ghalib, Raza Murad,Mehdi, Sayed Hasan,Hashim, Rokiah,Sulaiman, Othman,Jawad, Ali
, p. 1150 - 1154 (2010)
Cyclohexyl N-phenylcarbamate, C13H17NO2 (I), which is a useful target for biotransformations by fungi, has been synthesized and the structure has been solved by X-ray diffraction. The crystals are triclinic, space group P
Nickel-Catalyzed Synthesis of N-(Hetero)aryl Carbamates from Cyanate Salts and Phenols Activated with Cyanuric Chloride
Dindarloo Inaloo, Iman,Esmaeilpour, Mohsen,Majnooni, Sahar,Reza Oveisi, Ali
, p. 5486 - 5491 (2020/09/04)
A simple and efficient domino reaction has been designed and employed for the one-pot synthesis of N-(hetero)aryl carbamates through the reaction between alcohols and in-situ produced (hetero)aryl isocyanates in the presence of a nickel catalyst. The phenolic C?O bond was activated via the reaction of phenol with cyanuric chloride (2,4,6-trichloro-1,3,5-triazine (TCT)) as an inexpensive and readily available reagent. This strategy provides practical access to N-(hetero)aryl carbamates in good yields with high functional groups compatibility.
Carbon dioxide utilization in the efficient synthesis of carbamates by deep eutectic solvents (DES) as green and attractive solvent/catalyst systems
Dindarloo Inaloo, Iman,Majnooni, Sahar
, p. 11275 - 11281 (2019/07/31)
A green and eco-friendly solvent/catalyst system based on a deep eutectic solvent (DES) was devised and developed for the simple synthesis of carbamates through three-component coupling of amines, alkyl halides and carbon dioxide (CO2). It was found that choline chloride:zinc(ii) chloride ([ChCl][ZnCl2]2) was very proficient and effective for the activation and utilization of CO2 in carbamate formation reactions from a wide scope of amines. Surprisingly, this strategy provides the desired carbamates under atmospheric CO2 pressure at room temperature. In particular, both aromatic and aliphatic amines were effective and demonstrated excellent yields. Besides, the [ChCl][ZnCl2]2 exhibited very high stability and also could be reused for at least five consecutive cycles without any significant loss of activity. It is worth noting that this is the first solvent/catalyst system which can be recycled successfully from the reaction mixture.
An Fe3O4@SiO2/Schiff base/Cu(ii) complex as an efficient recyclable magnetic nanocatalyst for selective mono: N-arylation of primary O-alkyl thiocarbamates and primary O-alkyl carbamates with aryl halides and arylboronic acids
Sardarian, Ali Reza,Dindarloo Inaloo, Iman,Zangiabadi, Milad
, p. 8557 - 8565 (2019/06/14)
An efficient, convenient and novel method for the selective mono N-arylation of primary O-alkyl thiocarbamates and primary O-alkyl carbamates with aryl halides and arylboronic acids in the presence of a recyclable magnetic Cu(ii) nanocatalyst is described. A variety of mono N-arylated O-alkyl thiocarbamates and O-alkyl carbamates were prepared in good to excellent yields with a broad range of aryl coupling partners. The magnetic nanocatalyst can be easily recovered with an external magnetic field and reused at least five times without noticeable leaching or loss of its catalytic activity. This cost-effective and eco-friendly methodology has some other advantages, such as easy preparation of the catalyst, simple workup procedure, and easy purification, which makes this protocol interesting for the users in various fields of pharmacology and biotechnology systems.
A Fe3O4?SiO2/Schiff Base/Pd Complex as an Efficient Heterogeneous and Recyclable Nanocatalyst for One-Pot Domino Synthesis of Carbamates and Unsymmetrical Ureas
Inaloo, Iman Dindarloo,Majnooni, Sahar
, p. 6359 - 6368 (2019/11/05)
A palladium-catalyzed domino method for the direct synthesis of carbamates and ureas has been developed by using readily available and economical starting materials (aryl halide, carbon monoxide, sodium azide, amines and alcohols) in a one-pot approach. The domino process underwent carbonylation, Curtius rearrangement, and nucleophilic addition. This protocol provides a step-economical and highly efficient reaction to access the wide range of valuable carbamates, symmetrical and unsymmetrical ureas with high yields under remarkable mild reaction conditions that are important factors in pharmaceutical science, biochemistry and agricultural industries. Furthermore, the magnetically recoverable nanocatalyst (Fe3O4?SiO2/Pd(II)) can be conveniently and swiftly recycled using external magnet and reused at least for seven times without noticeable loss of its catalytic activity.
One stone two birds: Cobalt-catalyzed in situ generation of isocyanates and benzyl alcohols for the synthesis of N-aryl carbamates
Li, Sida,Khan, Ruhima,Zhang, Xia,Yang, Yong,Wang, Zheting,Zhan, Yong,Dai, Yuze,Liu, Yue-E,Fan, Baomin
, p. 5891 - 5896 (2019/06/24)
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.
Direct Catalytic Synthesis of N-Arylcarbamates from CO2, Anilines and Alcohols
Tamura, Masazumi,Miura, Ayaka,Honda, Masayoshi,Gu, Yu,Nakagawa, Yoshinao,Tomishige, Keiichi
, p. 4835 - 4839 (2018/10/15)
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.
METHOD FOR PRODUCING CARBAMATE
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Paragraph 0041; 0043, (2018/10/16)
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
