940-38-5Relevant academic research and scientific papers
Copper-Catalyzed Nitrogenation of Aromatic and Aliphatic Aldehydes: A Direct Route to Carbamoyl Azides
Bao, Hongli,Ge, Liang,Li, Yajun,Liao, Saihu,Wei, Rongbiao
, p. 4645 - 4649 (2019/12/11)
An efficient copper-catalyzed synthesis of carbamoyl azides directly from aldehydes has been developed. Both aromatic aldehydes and aliphatic aldehydes, together with other commercially available reactants, can be used as substrates in this radical relay reaction. Broad substrate scope, simple operation, readily available reagents, and good functionality tolerance make this method very attractive.
Pathways in the Degradation of Geminal Diazides
Holzschneider, Kristina,H?ring, Andreas P.,Haack, Alexander,Corey, Daniel J.,Benter, Thorsten,Kirsch, Stefan F.
, p. 8242 - 8250 (2017/08/14)
The degradation of geminal diazides is described. We show that diazido acetates are converted into tetrazoles through the treatment with bases. The reaction of dichloro ketones with azide anions provides acyl azides, through in situ formation of diazido ketones. We present experimental and theoretical evidence that both fragmentations may involve the generation of acyl cyanide intermediates. The controlled degradation of terminal alkynes into amides (by loss of one carbon) or ureas (by loss of two carbons) is also shown.
KI Catalyzed Nitrogenation of Aldehydes and Alcohols: Direct Synthesis of Carbamoyl Azides and Ureas
Song, Song,Feng, Peng,Zou, Miancheng,Jiao, Ning
supporting information, p. 845 - 848 (2017/06/27)
An efficient KI catalyzed nitrogenation of aldehydes and alcohols for the direct synthesis of carbamoyl azides and ureas via a radical process has been developed. The simple operating procedures, the readily available starting materials including aldehydes, alcohols and amines, as well as the utility of the products all make this strategy very attractive.
One-Pot Synthesis of Carbamoyl Azides via Palladium-Catalysed Azidocarbonylation of Haloarenes Using N-Formylsaccharin as a CO Surrogate
Yadav, Vinod K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
, p. 2826 - 2830 (2016/12/14)
A highly efficient one-pot synthesis of carbamoyl azides from haloarenes and sodium azide has been developed. The protocol involves palladium-catalysed azidocarbonylation of haloarenes utilizing N-formylsaccharin as a CO source to form acyl azides, which undergo in situ Curtius rearrangement to afford the desired carbamoyl azides. N-Formylsaccharin is an easy-to-handle solid alternative to CO gas.
Ceric ammonium nitrate (CAN) catalyzed modification of ketones via two C-C bond cleavages with the retention of the oxo-group
Feng, Peng,Sun, Xiang,Su, Yijin,Li, Xinyao,Zhang, Li-He,Shi, Xiaodong,Jiao, Ning
supporting information, p. 3388 - 3391 (2014/07/08)
A simple ceric ammonium nitrate (CAN) catalyzed functionalization of ketones through double C-C bond cleavage strategy has been disclosed. This reaction provides a mild, practical method toward carbamoyl azides, which are versatile intermediates and building blocks in organic synthesis. Based on relevant mechanistic studies, a unique and plausible C-C bond and N-O bond cleavage process is proposed, where the oxyamination intermediate plays an important role in this reaction.
Silicon-mediated direct conversion of acyl chlorides to carbamoyl azides or/and tetrazolinones under mild conditions
Salama, Tarek A.,Elmorsy, Saad S.,Khalil, Abdel-Galil M.,Ismail, Mohamed A.
experimental part, p. 1149 - 1151 (2012/08/07)
A simple and mild one-pot procedure for the synthesis of carbamoyl azides from acyl chlorides utilizing a combination of tetrachlorosilane and sodium azide in acetonitrile at ambient temperature is reported. Under gentle heating 1-aryltetrazolin-5- ones were also obtained in one-pot process presumably via a [3 + 2] cycloaddition step.
Synthesis of (-)-oseltamivir by using a microreactor in the curtius rearrangement
Ishikawa, Hayato,Bondzic, Bojan P.,Hayashi, Yujiro
experimental part, p. 6020 - 6031 (2011/12/15)
A microflow reaction of the Curtius rearrangement by using trimethylsilyl azide as an azide source, followed by trapping of the generated isocyanate with a nucleophile was established, which is safe, inexpensive, and suitable for large-scale synthesis. By this flow reaction in the Curtius rearrangement and recrystallization of the late-stage acetamide intermediate the third-generation synthesis of (-)-Oseltamivir has been established, which is efficient, practical, and safe. A safe and efficient total synthesis of (-)-Oseltamivir has been developed by using the Curtius rearrangement with a microflow system, which avoids the isolation of a hazardous and potentially explosive intermediate. In addition, the product, possessing an acetamide group, was easily purified by recrystallization. Thus, this procedure can be scaled up as an industrial process.
One-pot synthesis of carbamoyl azides directly from primary alcohols and oxidation of secondary alcohols to ketones using iodobenzene dichloride in combination with sodium azide
Li, Xiao-Qiang,Wang, Wei-Kun,Zhang, Chi
experimental part, p. 2342 - 2350 (2009/12/27)
An effective synthesis of carbamoyl azides directly from primary alcohols using iodobenzene dichloride in combination with sodium azide has been developed. Moreover, the same regent combination was also efficient for the oxidation of secondary alcohols to the corresponding ketones.
Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of in3
Pedersen, Christian Marcus,Marinescu, Lavinia Georgeta,Bols, Mikael
, p. 816 - 822 (2007/10/03)
TMSN3 and PhI(OAc)2 were found to promote high-yield azide substitution of ethers, aldehydes and benzal acetals. The reaction is fast and occurs at zero to ambient temperature in acetonitrile. However, it is essential for the reaction that TMSN3 is added subsequent to the mixture of PhI(OAc)2 and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with σ+ constants giving with ρ-values of -0.47 for TMSN 3-PhI(OAc)2 and -0.39 for IN3. On this basis a radical mechanism of the reaction was proposed. The Rayal Society of Chemistry 2005.
Relative migratory aptitudes of hydrogen, benzoyl, 4-methoxyphenyl and 4-nitrophenyl groups in some unsaturated carbenes (vinylidenes)
Bertha, Ferenc,Fetter, József,Lempert, Károly,Kajtár-Peredy, Mária,Czira, Gábor,Koltai, Erno
, p. 8889 - 8895 (2007/10/03)
([5-13C] Tetrazol-5-yl)methyl ketones were prepared and subjected to oxidative fragmentation induced by lead tetraacetate. The resulting intermediate [1-13C]-3-oxoprop-1-en-1-ylidenes rearrange, depending on the relative migratory aptitudes of the benzoyl group and the ligands R, either to [3-13C]prop-2-yn-1-ones or to [2-13C]prop-2-yn-1-ones or to mixtures of the two isomers. The 1H and/or 13C NMR spectra of the products allow the three cases to be distinguished. The relative migratory aptitudes were found to be H>PhCO, 4-MeOC6H4>4-O2NC6H 4.
