76543-27-6Relevant articles and documents
Gold-Catalyzed Oxidative Aminocyclizations of Propargyl Alcohols and Propargyl Amines to Form Two Distinct Azacyclic Products: Carbene Formation versus a 3,3-Sigmatropic Shift of an Initial Intermediate
Chao, Tzu-Hsuan,Chen, Mu-Jeng,Liu, Rai-Shung,Raj, Antony Sekar Kulandai,Sasane, Amit Vijay
, p. 16932 - 16938 (2020/11/30)
Gold-catalyzed oxidations of propargyl alcohols with nitrones by using a P(tBu)2(o-biphenyl)Au+ catalyst, afforded bicyclic annulation products from the Mannich reactions of gold enolates. The same reactions of propargyl amines with nitrones by using the same gold catalyst gave distinct oxoarylation products. Our DFT calculations indicate that oxidation of propargyl alcohols with nitrones by using electron-rich gold catalysts lead only to gold carbenes, which can generate gold enolates or oxoarylation intermediates with enolate species having a barrier smaller than that of oxoarylation species.
Regioselective Synthesis of 3-Hydroxy-4,5-alkyl-Substituted Pyridines Using 1,3-Enynes as Alkynes Surrogates
Barday, Manuel,Ho, Kelvin Y. T.,Halsall, Christopher T.,A?ssa, Christophe
, p. 1756 - 1759 (2016/05/19)
The poor regioselectivity of the [4 + 2] cycloaddition of 3-azetidinones with internal alkynes bearing two alkyl substituents via nickel-catalyzed carbon-carbon activation is addressed using 1,3-enynes as substrates. The judicious choice of substitution on the enyne enables complementary access to each regioisomer of 3-hydroxy-4,5-alkyl-substituted pyridines, which are important building blocks in medicinal chemistry endeavors.
1,5-rhodium shift in rearrangement of N -arenesulfonylazetidin-3-ols into benzosultams
Ishida, Naoki,Shimamoto, Yasuhiro,Yano, Takaaki,Murakami, Masahiro
, p. 19103 - 19106 (2014/01/17)
Benzosultams are synthesized in an enantiopure form starting from α-amino acids through a rhodium-catalyzed rearrangement reaction of N-arenesulfonylazetidin-3-ols. Mechanistically, this reaction involves C-C bond cleavage by β-carbon elimination and C-H bond cleavage by a 1,5-rhodium shift.
Thermal decomposition of 1,3,3-trinitroazetidine in the gas phase, solution, and melt
Nedel'Ko,Korsunskii,Makhova,Chukanov,Larikova,Ovchinnikov,Tartakovsky
experimental part, p. 2028 - 2034 (2011/01/09)
1,3,3-Trinitroazetidine (TNAZ) was synthesized using the alternative approach based on the transformation of 3-oximino-1-(p-toluenesulfonyl)azetidine in the reaction with nitric acid through intermediate pseudonitrol. The thermal decomposition of TNAZ in the gas phase, melt and m-dinitrobenzene solution in a wide concentration range (5-80%) was studied by manometry, volumetry, thermogravimetry, IR spectroscopy, and mass spectrometry. In the gas phase in the temperature range from 170 to 220°C the thermal decomposition proceeds according to the first-order kinetic law with the activation energy 40.5 kcal mol-1 and pre-exponential factor 1015.0 s-1. The major gaseous reaction products are N2, NO, NO2, CO2, H2O, and nitroacetaldehyde, and trace amounts of CO and HCN are formed. The rate-determining step of the process is the homolytic cleavage of the N-NO2 bond in the TNAZ molecule. In melt at 170-210 °C the thermal decomposition proceeds with the pronounced self-acceleration and the maximum reaction rates are observed at conversions 53.9-67.4%. The solid decomposition products accelerate the reaction. It is most likely that the autocatalysis of TNAZ decomposition in the liquid phase is due to the autocatalytic decomposition of 1-nitroso-3,3-dinitroazetidine, which is formed by the thermal decomposition of TNAZ. In m-dinitrobenzene TNAZ also decomposes with self-acceleration. The higher the concentration in the solution, the more pronounced the self-acceleration. Additives of picric acid moderately accelerate the thermal decomposition of TNAZ, whereas hexamethylenetetraamine additives exert a strong acceleration.
Improved synthesis of an energetic material, 1,3,3-trinitroazetidine (TNAZ) exploiting 2-iodoxy benzoic acid (IBX) as an oxidising agent
Singh, Alok,Sikder, Nirmala,Sikder, Arun K.
, p. 2560 - 2563 (2007/10/03)
Tetrahydropyranyl protected 1,3-dihalo-2-propanol reacts with p-toluene sulfonamide in the presence of K2CO3 to give corresponding N-p-tosyl-3-azetidinol. Deprotection and oxidation with iodoxy benzoic acid followed by oximation of N-p-tosyl-3-azetidinone readily affords the corresponding azetidine oxime in almost quantitative yield. The subsequent oxidative nitrolysis of oxime gives 1,3,3-trinitroazetidine (TNAZ) through a new sequence of reactions with excellent purity (> 99%) and moderate yield (40%).
Diazo decomposition in the presence of tributyltin hydride. Reduction of α-diazo carbonyl compounds
Tan, Zhongping,Qu, Zhaohui,Chen, Bei,Wang, Jianbo
, p. 7457 - 7461 (2007/10/03)
The diazo group of a series of α-diazo carbonyl compounds can be reduced to the corresponding CH2 group by Bu3SnH under Cu(acac)2-catalytic or photochemical conditions. The mechanistic aspects of this reaction were investigated in some detail, and a possible reaction pathway was discussed. (C) 2000 Elsevier Science Ltd.
Intramolecular N-H insertion of α-diazocarbonyls catalyzed by Cu(acac)2: An efficient route to derivatives of 3-oxoazetidines, 3-oxopyrrolidines and 3-oxopiperidines
Wang, Jianbo,Hou, Yihua,Wu, Peng
, p. 2277 - 2280 (2007/10/03)
Cu(acac)2 was found to be an efficient catalyst for the intramolecular N-H insertion by carbenoids. The competitive intramolecular C-H insertion by carbenoids is not a problem in the diazo decomposition reaction with Cu(acac)2 as catalyst. The reaction provided derivatives of 3-oxoazetidine, 3-oxopyrrolidine and 3-oxopiperidine in moderate to good yields.
Wolff rearrangement of diazo ketones derived from N-p-tolylsulfonyl-protected α- and β-amino acids
Wang, Jianbo,Hou, Yihua
, p. 1919 - 1923 (2007/10/03)
Diazo ketones derived from N-p-tolylsulfonyl (tosyl)-protected α- and β-amino acids have been synthesized and their diazo decomposition under standard Wolff rearrangement conditions, PhCO2Ag-Et3N-MeOH, has been investigated. It is observed that, under these conditions, several different reaction pathways, including direct carbene N-H insertion, are possible. The reaction is markedly affected by the N-protecting group, the substrate structure and solvent. For those diazo ketones derived from N-tosyl-protected β-amino acids, the diazo decomposition with anhydrous THF as solvent and PhCO2Ag dissolved in Et3N as catalyst gives the corresponding 5-substituted pyrrolidinones in excellent yields.
Synthesis of 1,3,3-Trinitroazetidine via the Oxidative Nitrolysis of N-p-Tosyl-3-azetidinone Oxime
Axenrod, T.,Watnick, C.,Yazdekhasti, H.,Dave, P. R.
, p. 1959 - 1964 (2007/10/02)
The tert-butyldimethylsilyl ether of 1,3-dibromo-2-propanol reacted with p-toluenesulfonamide in the presence of K2CO3 to give the corresponding N-p-tosyl-3-azetidinol.The same azetidinol was obtained when the similarly silyl-protected 3-(p-toluenesulfonamido)propan-2-ol 1(p-toluenesulfonate) was treated with LiH.Desilylation and oxidation of the N-p-tosyl-3-azetidinol followed by oximation readily afforded N-p-tosyl-3-azetidinone oxime.Oxidative nitrolysis of the latter intermediate delivered 1,3,3-trinitroazetidine through a new sequence of reactions.
Novel Syntheses of 1,3,3-Trinitroazetidine
Katritzky, Alan R.,Cundy, Darren J.,Chen, Jie
, p. 271 - 276 (2007/10/02)
Alternative methods for the synthesis of 1,3,3-trinitroazetidine (TNAZ) from epichlorohydrin, and benzhydrylamine have been developed.These approaches employ N-sulfonyl-3-(hydroxyimino)azetidines as penultimate intermediates and represent an improvement over previously published methods which require either diazo containing intermediates or involve low yielding procedures.Parallel methods employing N-benzhydryl- and N-benzyl-3-(hydroxyimino)azetidine were also investigated as alternate routes to TNAZ
