Benzyl Azide Research Articles

Benzylic azide functionalization of tautomeric o-acyl-benzoic acid, -benzamide, and -nicotinic acid derivatives, and thermal decomposition of the derived azides

A series of benzylic azido compounds were prepared by the reactions of o-acyl-benzoic acids and -benzamides and pyridine analogues with sodium azide, diphenylphosphoryl azide, and trimethylsilyl azide. Thermal decomposition of the derived benzylic azides afforded three types of rearrangement products. The selectivity of rearrangement depended on the migratory aptitude of substituents and on stereoelectronic factors.

1 4N nuclear quadrupole resonance and a b i n i t i o MO study of organic azides

An ab inito SCF-MO calculation of the electric field gradient (EFG) using a double zeta basis set with polarization is reported for N−3, HN3 NCN3, and H3CN3. A similar calculation using a Dunning set with polarization is also reported for N−3, HN3, and H3CN3. Excellent correlation was found between the calculated and the components obtained from gas phase microwave data. The calculation showed that the terminal N atom had a positive nuclear quadrupole coupling constant and its pincipal z axis was found to be perpendicular to the NNN direction in substituted azides. The changes in the charge distribution of HN3 and NCN3 obtained from the analysis of the atomic multipoles was shown to be in general agreement with the variations found in the N EFG components calculated for these azides. The 14N nuclear quadrupole resonance frequencies of the terminal and the first N atom of the azide group have been measured at 77 K for phenyl, benzyl, triphenylmethane, and tosyl azide. An analysis based on the Townes and Dailey approach of the measured NQR data showed that the terminal N atom have lost more σ than π orbital population. A similar analysis for the first N atom of azides showed strong inductive and resonance interactions with the substituents.

Effect of high pressure on the reaction of dipolar 1,3-cycloaddition between 4-nitrophenyl cyanate and benzyl azide and the role of the solvent

1. The observed volume activation effect (ΔV0≠) of the reaction of dipolar 1,3-cycloraddition between 4-nitrophenyl cyanate and benzyl azide in acetonitrile is a function of the ratio of the reagents and is 40–60% of the change in the volume in the reaction (ΔV0). 2. The accelerating effect of high pressure increases in conducting the reaction in conditions of the existence of the solvent (benzene) in the supercooled state; ¦ΔV0≠¦ is only 15% less than ¦ΔV0¦. 3. In consideration of the change in the viscosity with a change in the pressure (ΔVη≠), the volume activation effect (ΔVr≠) is similar to the volume effect of the reaction studied (ΔV0), which supports a cyclic transition state.

Experimental and Theoretical Investigation of the Azide Anion (N−3) in the Gas Phase

AbstractWe report the formation of the azide anion (N−3) in the gas phase by dissociative electron attachment to benzyl azide in a beam experiment. The electron photodetachment cross section of N−3, generated analogously in an ion cyclotron resonance (ICR) spectrometer has been measured. A threshold of 2.76 ± 0.04 eV was obtained corresponding to the vertical detachment energy in N−3. Ab initio calculations on N−3 and N3 predict similar geometries for both compounds, indicating that the photodetachment threshold can be equated with the electron affinity of the azide radical.

Synthesis of 5H‐tetrazolo[5,1‐c][1,4]benzodiazepines

AbstractA three step synthesis of 5H‐tetrazolo[5,1‐c][1,4]benzodiazepin‐11‐ones 8a‐d via the reaction of a substituted benzyl azide and ethyl cyanoformate is described. The derived lactams are converted to the corresponding 11‐thiones 9a‐d and, through the S‐methylated derivatives, to the 11‐amino analogs 11a‐f. All of the described compounds are representatives of a novel ring system.

β-Carboxyaspartic acid

β-Carboxyaspartic acid (Asa) is a congener of γ-carboxyglutamic acid (Gla), formed by the vitamin-K mediated post-translational γ-carboxylation of glutamyl residues. Asa is synthesized in 200-mg quantities and 46% overall yield by the transesterification of 1,1,2-tris(carbomethoxy)ethane with benzyl alcohol, followed by bromination at the 1-position, dehydrobromination with triethylamine, Michael addition of hydrazoic acid, and simultaneous catalytic hydrogenolysis of the benzyl esters and azide functional groups. The presence of Asa in derivatized base hydrolysates of E. coli ribosomal proteins is unambiguously established by gas chromatography-mass spectrometry (GC-MS). The conditions for the gas chromatographic separation are critical for the successful determination of nanogram quantities of Asa in a complex biological matrix. Asa is the most acidic natural amino acid presently known. Asa efficiently decarboxylates to aspartic acid upon heating in acidic medium and eliminates ammonia to give tricarboxyethylene upon heating in moderately basic medium. In strong base, Asa is reasonably stable even at 100° for 24 hr. Moreover, acid-catalyzed decarboxylation of Asa to Asp is a qualitative test for the presence of Asa.

Spin-trapping of α-azidoalkyl radicals

Spin-trapping with 2-methyl-2-nitrosopropane of the α-azidoalkyl radicals derived from isopropyl and benzyl azides competes effectively with loss of nitrogen from these radicals at 313 K.

Nitroxide chemistry. Part 15. Reactions between bistrifluoromethyl nitroxide and benzyl alcohol, azide, chloride, and cyanide

Bistrifluoromethyl nitroxide readily attacks benzyl cyanide and benzyl chloride at room temperature to give the α-bistrifluoromethylamino-oxy-derivatives PhCHRCN and PhCHRCl [R =–ON(CF3)2] respectively; treatment of the former product with the nitroxide yields benzoyl cyanide and the di-substituted derivative PhCR2CN. Abstraction of a benzylic hydrogen atom by the nitroxide from benzyl alcohol and benzyl azide leads, respectively, to the formation of benzaldehyde (and hence PhCOR) and benzonitrile.

1,3‐Dipolar cycloadditions to alkyldicyanamides

AbstractThe 1,3‐dipoles 2,4,6‐trimethylbenzonitrile oxide and benzyl azide react with alkyldicyanamides (1) to give the 3,5‐disubstituted 1,2,4‐oxadiazoles 2 and the 1,5‐disubstituted tetrazole 4, respectively, by (3 + 2)‐cycloaddition. The structure of 4 has been determined by a single crystal X‐ray analysis.

Addition d'azides a des olefines trisubstituees par des groupements electroattracteurs

The reaction of benzyl, methyl and phenyl azide, with olefins substituted by three electron-withdrawing groups, has been studied. This reaction gives in certain cases only one triazoline (single orientation of the cycloaddition). In other cases, a mixture of a triazoline and a diazocompound (double orientation of the cycloaddition) is obtained. The structure assignment of the triazolines is confirmed using chemical methods and 13C-NMR. Thermally, diazocompounds rearrange to enaminoesters which cyclise at high temperature to quinolines.

Alkylating nucleosides. 1. Synthesis and cytostatic activity of N-glycosyl(halomethyl)-1,2,3-triazoles. A new type of alkylating agent

1,3-Dipolar cycloaddition of benzyl azide or peracetylated glucopyranosyl azides to propargyl halides or 1,4-dihalobutynes yielded 1-benzyl- or 1-glycosyl(halomethyl)-1,2,3-triazoles. Alkylating chloromethyl- bromomethyl- and iodomethyl-1,2,3-triazoles were also obtained from the corresponding hydroxymethyl derivatives by treatment with (C6H5)3P/CCl4, (C6H5O)3P/Br2, and (C6H5O)3P/I2, respectively. 1-Benzyl-4-(fluoromethyl)-1,2,3-triazole was obtained from 1-benzyl-4-(bromomethyl)-1,2,3-triazole by treatment with KF and 18-crown-6. Chloromethyl-, bromomethyl-, and iodomethyl-1,2,3-triazole derivatives inhibited the "in vitro" growth of HeLa cells. Some of these compounds increased the life span of mice bearing tumors.

The synthesis of d-ribofuranosyl derivatives of methyl propiolate and a study of the activating influence of the ester group in cylcoaddition reactions

2,3,5-Tri- O-benzyl- D-ribofuranosyl bromide ( 17) has been converted into methyl 3-(2,3,5-tri- O-benzyl-β- d-ribofuranosyl)propiolate ( 8) and its α anomer 10 in 21 and 42% yields, respectively, by reaction with the silver salt of methyl propiolate. Attemps to prepare 8 from (β- d-ribofuranosyl)ethyne ( 1) by standard methods were unsuccesful. The reactions of the esters 8 and 10 and the ethyne 1 with several 1,3-dipoles have been examined. With diazomethene, 8 and 10 gave the pyrazole esters 20 and 28, respectively, whereas the ethyne 1 reacted more slowly to give a mixture of 23 (37%) and 26(31%). The ester 10 was converted into the triazoles 32 (51%) and 36 (34%) by reaction with benzyl azide. Treatment of the ester 10 with phenylhydrazine gave the pyrazolone 38 in 71% yield. A number of the products of dipolar addition have been converted into new d-ribofuranosyl-pyrazoles and -triazoles by hydrogenolysis.

ChemInform Abstract: PALLADIUM‐CATALYZED DECOMPOSITION OF AZIDES. I. FORMATION OF NITRILES

AbstractBenzylchlorid (I) wird mit Na‐azid umgesetzt und der Benzolextrakt des Benzylazid enthaltenden Reaktionsgemisches der Pd‐katalysierten Zersetzung unterworfen; als Hauptprodukt entsteht Ben‐zonitril (II), dessen Ausbeute in Gegenwart von H‐ Acceptoren (A) wie 2,5‐Dimethyl‐3‐hexin‐2,5‐diol oder Diphenylacetylen noch erhöht werden kann.

Palladium-catalyzed Decomposition of Azides. I. Formation of Nitriles

Abstract Palladium metal catalyzes the decomposition of benzyl azide affording benzonitrile, benzylamine, and N-benzylidenebenzylamine. The presence of a suitable hydrogen-acceptor improves the yield of benzonitrile at the sacrifice of benzylamine, whereas the yield of N-benzylidenebenzylamine remains constant. The reaction is applied to the preparation of other nitriles.

Synthesis of D-ribofuranosyl derivatives of methyl propiolate as C-nucleoside precursors

The synthesis of methyl 4,7-anhydro-5,6,8-tri-O-benzyl-2,3-dideoxy-D-allo-oct-2-ynoate (2) and its D-altro isomer (5) is reported; the ester (5) reacts with benzyl azide to give two isomeric triazoles (10) and (11).

C-nucleoside studies. Part I. Synthesis of [2,3,5-tri-O-benzyl-α(and β)-D-ribofuranosyl]ethyne

Ethynylmagnesium bromide reacted with 2,3,5-tri-O-benzyl-D-ribofuranose (1) in tetrahydrofuran to give, in quantitative yield, a mixture of 4,5,7-tri-O-benzyl-1,2-dideoxy-D-altro- and D-allo-hept-1-ynitol [(2) and (7)] in the ratio 7:3. Treatment of the mixture with toluene-p-sulphonyl chloride in pyridine afforded (2,3,5-tri-O-benzyl-β-D-ribofuranosyl)ethyne (13)(52%) and its α-anomer (16)(13%), together with 4,5,7-tri-O-benzyl-1,2-dideoxy-3,6-bis-O-p-tolylsulphonyl-D-altro-hept-1-ynitol (4)(16%). 2,3,5-Tri-O-benzyl-D-ribofuranosyl chloride (12) and ethynylmagnesium bromide gave the ethynes (13) and (16) in 8 and 63% yield, respectively.Hydrogenation of the ethynes (13) and (16)(Pd–C) afforded β-D-ribofuranosylethane (15) and the crystalline anomer (18), respectively, together with 5,6,7-trideoxy-L-ribo-heptitol (27), characterised as the tetra-acetate (28).The β-ethyne (13), on treatment with benzyl azide, was converted into 1-benzyl-4(and 5)-(2,3,5-tri-O-benzyl-β-D-ribofuranosyl)-1,2,3-triazole [(30) and (31)] in approximately equal amounts.

THE ISOLATION AND CHARACTERIZATION OF 1,4-DIBENZYL-5,6-DIPHENYL-1,2,3,4-TETRAAZA-2-CYCLOHEXENE

Abstract The reaction of 1,1,4,4-tetrabenzyl-2-tetrazene with sulfuryl chloride in benzene at room temperature gave benzyl azide, dibenzylamine and benzaldehyde. In addition, another compound was isolated as a very minor product. On the basis of its elemental analysis and spectral data, this compound was assigned the structure of 5,6-diphenyl-1,4-dibenzyl-1,2,3,4-tetraaza-2-cyclohexene, the first cyclic 2-tetrazene ever reported.

Reactions of the nitrosonium ion. II. Reactions of triphenylmethyl, benzhydryl, and benzyl azides with nitrosonium compounds

Reactions of the nitrosonium ion. II. Reactions of triphenylmethyl, benzhydryl, and benzyl azides with nitrosonium compounds

Synthesis of 2,3,5-tri-O-benzyl-α-(and β-)-D-ribofuranosylethyne, potential intermediates for the synthesis of C-nucleosides

Two methods are described for the synthesis of the anomers of 2,3,5-tri-O-benzyl-D-ribofuranosyelthyne; the β-anomer has been converted into 1,2,3-triazole derivatives by reaction with benzyl azide.

Novel oxidative fragmentation. The formation of benzyl azide from the reaction of 1,1,4,4-tetrabenzyltetrazene with lead tetraacetate

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNovel oxidative fragmentation. The formation of benzyl azide from the reaction of 1,1,4,4-tetrabenzyltetrazene with lead tetraacetateGen Koga and Jean P. AnselmeCite this: J. Am. Chem. Soc. 1969, 91, 15, 4323–4324Publication Date (Print):July 1, 1969Publication History Published online1 May 2002Published inissue 1 July 1969https://doi.org/10.1021/ja01043a071RIGHTS & PERMISSIONSArticle Views117Altmetric-Citations6LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (286 KB) Get e-Alerts Get e-Alerts