Introduction of the Azido Group

Biffin, M. E. C.; Miller, J. A.; Paul, D. B.

doi:10.1002/9780470771266.ch2

Cited by 35 publications

(14 citation statements)

References 367 publications

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“…Synthesis of the equatorial substituted amine 30 was achieved as outlined in Scheme 4, the stereochemistry of the products being confirmed by ' H NMR studies. Reaction of the axial methanesulphonate 28 with azide ion occurred with the expected inversion (Biffin et al 1971) to the equatorial azide 29.…”

Section: Resultsmentioning

confidence: 97%

Potential Protein Kinase C Inhibitors. 8,9,10,11α:-Tetrahydro-7αH-7,11-methano-12,12-dimethylcycloocta[de]naphthyl-9-amines

Wilson

Bowman

Smith

et al. 1996

Journal of Pharmacy and Pharmacology

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Section: Resultsmentioning

confidence: 97%

Potential Protein Kinase C Inhibitors. 8,9,10,11α:-Tetrahydro-7αH-7,11-methano-12,12-dimethylcycloocta[de]naphthyl-9-amines

Wilson

Bowman

Smith

et al. 1996

Journal of Pharmacy and Pharmacology

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“…This complements the most commonly employed methods for obtaining organic azides, 11 some of which are unsuited for the preparation of the simple heteroaryl azides (i.e. S N Ar, instability of certain aminoheteroaryls).…”

Section: Methodsmentioning

confidence: 95%

Synthesis, reactivity, and electronic structure of multifarious, five-membered heteroaryl and heteroaroyl azides

Zanirato¹

2009

Arkivoc

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The aim of this account is to review our most important outcomes -published during the last 30 years -concerning the azido group that is linked to five-membered heteroaryl and heteroaroyl systems. The main focus of this manuscript is on the 'azido transfer' reaction to heteroaryl azides, and the peculiar thermal and chemical reactivities of these precursor species. In particular, the following topics are considered: (a) the ring cleavage of α-heteroaryl azides to form 4-cyano-1,3-heterodienes, (b) the reactivity of thermally generated β-nitrene, (c) the 1,3-dipolar cycloaddition of the azido group to various terminal or 1,2-disubstituted alkenes or alkynes to form nitrogen-containing biheterocycles, (d) the generation of electrophile nitrenium ions with Lewis acids, (e) the conversion of heteroaroyl azides into isocyanates, and (f) the 1,3-dipolar cycloadditions of heteroaroyl azides with 'activated' olefins. The concurrence and discordance of the thermal and chemical behaviour between heteroaryl azides, and the related substituted phenyl azides will be critically considered here.

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“…30 It has been reported that insoluble polymeric reagents can be used in large excess to complete this conversion into an alkyl azide. 30 It has been reported that insoluble polymeric reagents can be used in large excess to complete this conversion into an alkyl azide.…”

Section: Inmentioning

confidence: 99%

“…Step C, a suspension of polymer-supported azide in dichloromethane was used to convert the iodide to the azide (4a/b), which follows a well-established synthetic pathway to alkyl azides by nucleophilic substitution. 30 It has been reported that insoluble polymeric reagents can be used in large excess to complete this conversion into an alkyl azide. 31 In Step D, the residue was dissolved in tetrahydrofuran/water and polymer-supported triphenylphosphine was added to convert the azide to an amine which spontaneously lead to ring closure (imine formation) to afford the ethoxy benzodiazepine intermediate (5a/b).…”

Section: Inmentioning

confidence: 99%

An approach to shortening the timeframe between the emergence of new compounds on the drugs market and the availability of reference standards: The microscale syntheses of nitrazolam and clonazolam for use as reference materials, utilizing polymer‐supported reagents

Dowling

Kavanagh

Eckhardt³

et al. 2018

Drug Testing and Analysis

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Nitrazolam and clonazolam are 2 designer benzodiazepines available from Internet retailers. There is growing evidence suggesting that such compounds have the potential to cause severe adverse events. Information about tolerability in humans is scarce but typically, low doses can be difficult to administer for users when handling bulk material. Variability of the active ingredient in tablet formulations can also be of a concern. Customs, toxicology and forensic laboratories are increasingly encountering designer benzodiazepines, both in tablet and powdered form. The unavailability of reference standards can impact on the ability to identify these compounds. Therefore, the need arises for exploring in-house approaches to the preparation of new psychoactive substances (NPS) that can be carried out in a timely manner. The present study was triggered when samples of clonazolam were received in powdered and tablet form at a time when reference material for this drug was commercially unavailable. Therefore, microscale syntheses of clonazolam and its deschloro analog nitrazolam were developed utilizing polymer-supported reagents starting from 2-amino-2'-chloro-5-nitrobenzophenone (clonazolam) and 2-amino-5-nitrobenzophenone (nitrazolam). The final reaction step forming the 1,2,4-triazole ring moiety was performed within a gas chromatography-mass spectrometry (GC-MS) injector. A comparison with a preparative scale synthesis of both benzodiazepine derivatives showed that microscale synthesis might be an attractive option for a forensic laboratory in terms of time and cost savings when compared with traditional methods of synthesis and when qualitative identifications are needed to direct forensic casework. The reaction by-product profiles for both the micro and the preparative scale syntheses are also presented.

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Introduction of the Azido Group

Cited by 35 publications

References 367 publications

Potential Protein Kinase C Inhibitors. 8,9,10,11α:-Tetrahydro-7αH-7,11-methano-12,12-dimethylcycloocta[de]naphthyl-9-amines

Potential Protein Kinase C Inhibitors. 8,9,10,11α:-Tetrahydro-7αH-7,11-methano-12,12-dimethylcycloocta[de]naphthyl-9-amines

Synthesis, reactivity, and electronic structure of multifarious, five-membered heteroaryl and heteroaroyl azides

An approach to shortening the timeframe between the emergence of new compounds on the drugs market and the availability of reference standards: The microscale syntheses of nitrazolam and clonazolam for use as reference materials, utilizing polymer‐supported reagents

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