201024-81-9Relevant articles and documents
Enthalpies of combustion of 2,4,6-trimethylbenzonitrile, 2,4,6-trimethylbenzonitrile N-oxide, 2,6-dimethylbenzonitrile, 2,4,6-trimethoxybenzonitrile, and 2,4,6-trimethoxybenzonitrile N-oxide: the dissociation ethalpies of the (N-O) bonds
Acree, W. E.,Tucker, Sheryl A.,Zvaigzne, Anita I.,Meng-Yan, Yang,Pilcher, G.,Ribeiro da Silva, Maria D. M. C.
, p. 31 - 36 (1991)
The standard (pdeg = 0.1 MPa) molar enthalpies of combustion at 298.15 K were measured by static-bomb calorimetry and the standard molar enthalpies of sublimation at 298.15 K were measured by microcalorimetry for the following aromatic nitriles and aromatic nitrile N-oxides: .From the standard molar enthalpies of formation of the gaseous compounds, the molar dissociation enthalpies of the (N-O) bonds were derived: D(N-O)/(kJ*mol-1): trimethylbenzonitrile N-oxide, (222.2 +/- 4.6); trimethoxybenzonitrile N-oxide, (232.8 +/- 3.8).
N-Arylalkyl-N-phenylhydroxylamines as novel photo-induced DNA-cleaving agents
Hwu,Tsay,Chen,Patel,Chou
, p. 1427 - 1428 (1994)
Single-strand cleavage of DNA was accomplished by photolysis of various N-arylalkyl-N-phenylhydroxylamines under aerobic conditions for 3 h with 312 nm UV light, which functioned as the trigger to initiate the new and controllable DNA cleavage process.
Gold-Catalyzed Bicyclic and [3+2]-Annulations of Internal Propargyl Alcohols with Nitrones and Imines To Yield to Two Distinct Heterocycles
More, Sayaji Arjun,Chao, Tzu-Hsuan,Cheng, Mu-Jeng,Liu, Rai-Shung
supporting information, p. 525 - 531 (2020/12/01)
A gold-catalyzed synthesis of 1,3-dihydrooxazolo[3,4-a]indoles from 1-oxo-3-yn-4-ols and nitrones is described; this new bicyclic annulation presents the first examples that internal alkynes can react with nitrones to undergo an oxoarylation route. DFT calculations indicate a [3,3]-sigmatropic shift of initial alkenylgold intermediates to elude the intermediacy of gold carbenes. We also developed new [3+2]-annulations of the same 1-oxo-3-yn-4-ols with imines, yielding oxazolidin-4-ylidene derivatives efficiently. The tethered alcohols of these 1-oxo-3-ynes allow trapping of their metastable 2-azadienium intermediates to enable a novel annulation. Our mechanistic analysis indicates that the two products, despite their structural relevance, are produced from two independent systems. (Figure presented.).
Polyfunctionalized biaryls accessed by a one-pot nucleophilic aromatic substitution and sigmatropic rearrangement reaction cascade under mild conditions
Liang, Dong-Dong,Guo, Shen-Yi,Tong, Shuo,Wang, Mei-Xiang
supporting information, (2021/02/09)
A practical synthetic method has been developed for polyfunctionalized biaryls based on a facile one-pot nucleophilic aromatic substitution (SNAr) reaction and [5,5]- or [3,3]-sigmatropic rearrangement reaction cascade. Under mild basic conditions, N-arylhydroxylamines reacted with o-activated fluoro (het)arenes to form N,O-diarylhydroxylamine intermediates which underwent spontaneously selective [5,5]-sigmatropic rearrangement reaction to produce diverse functionalized 4-amino-4′-hydroxy-1,1′-biaryls. A sequential SNAr reaction and [3,3]-sigmatropic rearrangement took place between N-arylhydroxylamines and 2-fluoropyridine derivatives or 4-fluorobenzonitrile to afford functionalized 2-amino-2′-hydroxy-1,1′-biaryls. As invaluable and unique building blocks, the resulting biaryls were applied in the straightforward synthesis of N2,O2-coronarene, carbazole, aza- and diaza carbazole derivatives.
Gold Catalysts Can Generate Nitrone Intermediates from a Nitrosoarene/Alkene Mixture, Enabling Two Distinct Catalytic Reactions: A Nitroso-Activated Cycloheptatriene/Benzylidene Rearrangement
Cheng, Mu-Jeng,Kardile, Rahul Dadabhau,Kuo, Tung-Chun,Liu, Rai-Shung,More, Sayaji Arjun
supporting information, p. 5506 - 5511 (2021/07/31)
Gold-catalyzed reactions of cycloheptatrienes with nitrosoarenes yield nitrone derivatives efficiently. This reaction sequence enables us to develop gold-catalyzed aerobic oxidations of cycloheptatrienes to afford benzaldehyde derivatives using CuCl and nitrosoarenes as co-catalysts (10-30 mol %). Our density functional theory calculations support a novel nitroso-activated rearrangement, tropylium → benzylidene. With the same nitrosoarenes, we developed their gold-catalyzed [2 + 2 + 1]-annulations between nitrosobenzene and two enol ethers to yield 5-alkoxyisoxazolidines using 1,4-cyclohexadienes as hydrogen donors.
Hydrazones as Substrates in the Synthesis of Isoxazolidines via a KOH-Promoted One-Pot Three-Component Cycloaddition with Nitroso Compounds and Olefins
Chen, Wenwen,Li, Wenhui,Li, Xing,Lin, Jianying,Wei, Wen-Long,Zhai, Pingan
, p. 17710 - 17721 (2021/12/09)
Hydrazones have been employed as the starting materials in a KOH-mediated one-pot three-component cycloaddition with readily accessible nitroso compounds and olefins to construct various isoxazolidines. Compared with diazo compounds as starting materials, this methodology could afford a wider range of products in good to excellent yields and diastereoselectivities for most substrates, and hydrazones are cheaper, more accessible, and safer substrates. The experimental study shows that the choice of suitable hydrazones is crucial.
S -Tetrazine: Robust and Green Photoorganocatalyst for Aerobic Oxidation of N,N-Disubstituted Hydroxylamines to Nitrones
Allain, Clémence,Audebert, Pierre,Claraz, Aurélie,Le, Tuan,Lyu, Jiyuan,Masson, Géraldine
supporting information, (2021/12/06)
Efficient photocatalytic aerobic oxidative dehydrogenation reactions of N,N-disubstituted hydroxylamines to nitrones were developed with an in situ generated photocatalyst based on commercially available 3,6-dichlorotetrazine. This process affords a wide range of nitrones in high yields under mild conditions. In addition, an oxidative (3+3) cycloaddition between an oxyallyl cation precursor and a hydroxylamine was also developed.
Method for converting terminal alkyne into carboxylic acid and application of method in construction of gene coding library
-
Paragraph 0056-0058, (2021/11/27)
The invention provides a method for converting terminal alkyne into carboxylic acid in construction of a gene coding compound library. The method has the advantages of good universality, mild conditions, convenient operation and high yield, and is suitable for synthesis of the gene coding compound library by a porous plate. According to the method for converting terminal alkyne into carboxylic acid in construction of the gene coding compound library, the reaction types which can be successfully applied in the gene coding library technology are increased, and the synthesis method of the gene coding compound library is simplified.
Method for converting terminal alkyne into amide and application of method in construction of gene coding library
-
Paragraph 0057-0059, (2021/12/07)
The invention provides a method for converting terminal alkyne into amide on oligomeric nucleic acid, and has good universality. The method is mild in condition, convenient to operate and high in yield, and is suitable for synthesis of a gene coding compound library carried out on a porous plate. The invention increases the reaction type which can be successfully applied in the gene coding library technology, and particularly provides a method for directly carrying out amide coupling reaction of free carboxylic acid and an unprotected primary or secondary amine small molecule compound. Thus, the synthesis step of the gene coding compound library is simplified, and the synthesis efficiency of the gene coding compound library and the quality of the oligomeric nucleic acid product are improved.
Single-Step Approach toward Nitrones via Pyridinium Ylides: The DMAP-Catalyzed Reaction of Benzyl Halides with Nitrosoarenes
Jung, Yeonghun,Hong, Jee Eun,Kwak, Jae-Hwan,Park, Yohan
, p. 6343 - 6350 (2021/05/29)
A single-step approach is reported for the preparation of nitrones from benzyl halides and nitrosoarenes via pyridinium ylides, utilizing 4-dimethylaminopyridine (DMAP) catalyst and mild reaction conditions (Li2CO3, dimethylacetamide, and room temperature). The reaction provides both keto-and aldonitrones in high yields with a wide scope for benzyl halides and nitrosoarenes. In the same reaction system, 2-methyl-2-nitrosopropane, which does not have an aryl group, also affords the corresponding N-tert-butyl nitrones from primary benzyl bromides that have an electron-withdrawing group. As an application of the reaction, methyl 2-bromo-2-phenylacetate was used to prepare the corresponding isoxazolidine by a sequential one-pot synthesis.
