90329-57-0Relevant academic research and scientific papers
An Expeditious Approach to Tetrazoles from Amides Utilizing Phosphorazidates
Ishihara, Kotaro,Shioiri, Takayuki,Matsugi, Masato
supporting information, p. 6244 - 6247 (2020/07/24)
A novel method was developed for the synthesis of tetrazoles from amides utilizing diphenyl phosphorazidate or bis(p-nitrophenyl) phosphorazidate as both the activator of amide-oxygen for elimination and azide source. Various amides were converted into th
An Environmentally Friendly Method for N-Methylation of 5-Substituted 1H-Tetrazoles with a Green Methylating Reagent: Dimethyl Carbonate
Xie, Aming,Zhang, Qiang,Liu, Yangyang,Feng, Liandong,Hu, Xinyu,Dong, Wei
, p. 1483 - 1487 (2015/10/06)
An environmentally friendly method was established for the N-methylation of the 5-substituted 1H-tetrazoles with a green reagent: DMC. DABCO was the optimal catalyst, and hazardous chemicals were avoided in this protocol. A plausible catalytic mechanism is proposed, which consists of a DABCO-activated process and a thermally induced rearrangement of tetrazole carbamates.
Improved conditions for converting sterically hindered amides to 1,5-disubstituted tetrazoles
Schroeder, Gretchen M.,Marshall, Sydney,Wan, Honghe,Purandare, Ashok V.
experimental part, p. 1404 - 1406 (2010/04/25)
Improved conditions for converting amides into 1,5-disubstituted tetrazoles are described. The optimum reaction conditions [diisopropyl azodicarboxylate (DIAD), diphenylphosphoryl azide (DPPA), and diphenyl-2-pyridyl phosphine in THF at 45 °C] converted s
Controlled Synthesis of 5-Substituted 1-Methyl-1H-Tetrazoles and 3,5-Disubstituted 1,4-dimethyltriazolium Salts from N-Methylnitrilium Trifluoromethanesulfonate Salts.
Amer, Muhanned I. K.,Booth, Brian L.
, p. 113 - 124 (2007/10/02)
C-Alkyl and -benzyl N-methylnitrilium trifluoromethanesulfonate salts, 1C=NMe>+ OTf- (R1=Me, Prn, Pri, But, PhCH2; OTf=O3SCF3), react rapidly under mild conditions with either sodium azide or tetramethylguanidinium azide in nitromethane to give the corresponding 5-substituted 1-methyl-1H-tetrazoles as the sole product in high yields.These reactions are independent of the mode of addition.C-aryl-N-methylnitrilium trifluoromethanesulfonate salts (R1=C6H6, 2-MeC6H4, 4-MeC6H4, 2,4-Me2C6H3) give mixtures of the corresponding tetrazoles and the triazolium salts with sodium azide.With tetramethylguanidinium azide the products depend upon the mode of addition.Addition of the nitrilium salt to the azide gives only the tetrazole, while inverse addition gives the triazolium salt in high yield.
Photochemical Formation of Heteromethylenecyclopropanes, 16. - 1,4,5-Substituted Tetrazolium Salts Through Methylation of 1,5-Substituted Tetrazoles and Cycloaddition of Alkyl Azides to Nitrilium Ions
Quast, Helmut,Bieber, Lothar,Meichsner, Georg
, p. 469 - 476 (2007/10/02)
Efficient syntheses of isomerically pure 1,4,5-substituted tetrazolium salts are reported.Methylation of 1,5-substituted tetrazoles 5 affords mixtures of 1,4,5- (1) and 1,3,5-substituted tetrazolium salts 6.The ratio 1:6 depends only little on the reaction conditions as well as on the methylating agents.The isomerically pure tetrazolium salts 1a-e, g, j, k and 6j, k are isolated by fractionating crystallizations. tert-Butylation of 5a, c using tert-butyl alcohol/tetrafluoroboric acid produces only the 3-tert-butyltetrazolium tetrafluoroborates 9a, c.The N-methylnitrili um tetrafluoroborates, fluorosulfonates or trifluoromethanesulfonates 7a-c and e cycloadd the alkyl azides 8a-d regioselectively to the tetrazolium salts 1a-c, e, f, h, i.Both rate and yield of the cycloaddition decrease with increasing size of the substituents.The N-tert-butylnitrilium tetrachloroferrate 7h (X=FeCl4) reacts with methyl azide (8a) yielding the hydrogen tetrachloroferrate 4a*HFeCl4 of the imidoyl chloride 4a.
ADDITION REACTION OF TRIMETHYLSILYL AZIDE TOWARDS KETONES AND FACILE FORMATION OF TETRAZOLE DERIVATIVES
Nishiyama, Kozaburo,Watanabe, Akio
, p. 455 - 458 (2007/10/02)
In the presence of Lewis acid such as SnCl2, the reactions of trimethylsilyl azide with ketones readily gave 1:1- or 1:2-adduct, which reacted with Lewis acid to afford tetrazole.
Regiospecific Coordination of Ambidentate Tetrazoles to Cobalt Oximes
Takach, Nicolas E.,Holt, Elizabeth M.,Alcock, Nathaniel W.,Henry, Ronald A.,Nelson, John H.
, p. 2968 - 2979 (2007/10/02)
A series of complexes of the type (n-Bu3P)Co(DH)2(5R-tetrazolate) (DH is the monoanion of dimethylglyoxime; R = CF3, CH3, C6H5, C6H5CH2, (CH3)2N, 4-FC6H4, and 3-FC6H4) have been prepared and characterized by conductance studies, elemental analyses, and 1H, 13C, 31P, and 19F NMR spectroscopy.Quantum-mechanical calculations (MINDO/3) indicate that the N1 nitrogens of the aromatic tetrazolate anion are slightly more nucleophilic than the N2, yet in each complex the ambidentate tetrazolate anion is coordinated to cobalt via the N2 nitrogen, showing that regiospecific coordination is sterically induced.This is in marked contrast to tetrazole complexes of platinum and palladium wherein both N1 and N2 bound tetrazoles are found in approximately equal abundances.These cobalt complexes react with alkyl halides such as CH3I and C6H5CH2Br to produce exclusively 1,5-disubstituted tetrazoles.None of the isomeric 2,5-disubstituted tetrazole is detected in these reactions in marked contrast to the reactions of sodium tetrazolates or gold, palladium, or platinum tetrazolate complexes with alkyl halides which produce mixtures of the 1,5- and 2,5-disubstituted tetrazoles.The crystal structure of n-Bu3PCo(DH)2(5-CF3-tetrazolate) was determined using three-dimensional X-ray diffraction techniques.The molecule crystallizes in the orthorhombic space group Pbca in a unit cell of dimensions a = 12.040(2) Angstroem, b = 21.531(3) Angstroem, c = 23.536(4) Angstroem, ρcalcd = 1.368 g/cm3, ρobsd = 1.374 g/cm3.Refinement converged to 5.4percent with 2525 independent reflections.The tetrazolato ring is coordinated to cobalt via N2 and is planar.The Co-P bond (2.263 Angstroem) is one of the shortest observed in LCo(DH)2X structures.The acute dihedral angle between the planes of the two glyoximato groups (10.4 deg) is among the largest dihedral angles observed in structures of this type.Surprisingly, the tetrazolato ring does not lie in the fold of the two glyoximato rings but is nearly normal to it.Thus, the regiospecificity of the alkylations of the coordinated tetrazolate with alkyl halides is sterically promoted.
