Expedient Synthesis of<i>t</i>-Butyl Azide

Bottaro, Jeffrey C.; Penwell, Paul E.; Schmitt, Robert J.

doi:10.1080/00397919708006078

Cited by 31 publications

(28 citation statements)

References 5 publications

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“…[15] We capitalized on the recently described simple, safe and efficient procedure for large-scale synthesis of tert-butyl azide. [16] When treated with tert-butyl azide, the nucleophilic carbenes 5 and tris(dimethylamino)phosphine quantitatively produce the corresponding tert-butyltriazenes 8 and 9 (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

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New Lipophilic 2‐Amino‐N,N′‐dialkyl‐4,5‐dimethylimidazolium Cations: Synthesis, Structure, Properties, and Outstanding Thermal Stability in Alkaline Media

Kunetskiy

Cı́sařová

Šaman

et al. 2009

Chemistry A European J

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A series of new N,N'-dialkyl-4,5-dimethylimidazolium cations possessing electron-rich 2-imidazolylidene- or phosphoranylidene-amino substituents has been efficiently synthesized from common precursors, N,N'-dialkyl-4,5-dimethylimidazol-2-ylidenes. The new lipophilic salts obtained have been found to be highly stable towards strong alkali under both biphasic and homogeneous conditions. Their exceptional aqueous base resistance, which has hitherto only been seen with peralkylated polyaminophosphazenium cations, may be attributed to three factors: aromatic stabilization, efficient resonance charge delocalization, and steric protection of the exocyclic nitrogen linkage due to bulky lipophilic N-alkyl substituents.

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Section: Resultsmentioning

confidence: 99%

“…tert-Butyl azide, [16] neopentylamine, [27] and N,N'-dineopentyl-and N,N'-dicyclohexylthioureas [28] were obtained according to the literature procedures.…”

Section: Bfmentioning

confidence: 99%

New Lipophilic 2‐Amino‐N,N′‐dialkyl‐4,5‐dimethylimidazolium Cations: Synthesis, Structure, Properties, and Outstanding Thermal Stability in Alkaline Media

Kunetskiy

Cı́sařová

Šaman

et al. 2009

Chemistry A European J

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“…The synthesis of sterically hindered alkyl azides was achieved following Bottaro's procedure 20. The starting material for tert ‐heptyl azide, 2,3,3‐trimethyl‐2‐butanol, was prepared by alkylation of pinacolone with methylmagnesium iodide.…”

Section: Resultsmentioning

confidence: 99%

“…As organic azides are important starting materials for the synthesis of nitrogen‐containing compounds, they are usually readily available, except for sterically congested alkyl azides; an effective synthetic protocol for the multi‐gram preparation of these latter compounds hardly exists 19. The only reliable and scalable method for their synthesis is Bottaro's protocol,20 in which tert ‐butyl alcohol reacts with in situ generated hydrazoic acid (HN 3 ) to give tert ‐butyl azide in quantitative yield.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Electron‐Rich Sterically Hindered P₁ Phosphazene Bases by the Staudinger Reaction

et al. 2013

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The synthesis of electron‐rich P1 phosphazene bases with a sterically protected basic center by a Staudinger reaction is reported. The initial products of the reaction between peralkylated triaminophosphanes and bulky alkyl azides, phosphazides 1a–f, were isolated in all cases in good to quantitative yield. The structures of 1d and 1e were confirmed by single‐crystal X‐ray diffraction. Acidic hydrolysis of pyrrolidino‐substituted phosphazide (pyrr)3PN3tBu 1d led to the quantitative formation of aminophosphonium salt (pyrr)3PNH2+·BF4– 8, a direct precursor to a Schwesinger's “building block” synthetic unit. Thermally induced denitrogenation of the phosphazides, which is the second step performed in most cases under solvent‐free conditions gave P1 phosphazene bases 2a–f in moderate to excellent yields. A “one‐pot” two‐step synthesis of phosphazene bases from commercially available triaminophosphanes was discovered. Most of the syntheses were performed on a large laboratory scale. The basicities of the newly synthesized bases 2e and 2f were determined. X‐ray crystal structures were obtained for base 2e and for protonated species 2d·HBF4, 2e·HBF4, and 2f·HOTs, which provided the crucial geometrical parameters around the basic center. A rationale for the higher basicity of the pyrrolidino‐ (pyrr)3P=NR than the piperidino‐ (pip)3P=NR phosphazenes is presented.

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“…TMS−N 3 and PhNCO were stored over molecular sieves (4 Å), and HCl/Et 2 O (2 m ) was used as received. t Bu−N 3 , Ph−N 3 , Mes−N 3 , anhydrous tetramethylammonium fluoride (TMAF) and t Bu 2 PCH 2 BPh 2 were prepared following literature procedures.…”

Section: Methodsmentioning

confidence: 99%

New Insights in Frustrated Lewis Pair Chemistry with Azides

Boom

Jupp

Nieger

et al. 2019

Chemistry A European J

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The geminal frustrated Lewis pair (FLP) tBu2PCH2BPh2 (1) reacts with phenyl‐, mesityl‐, and tert‐butyl azide affording, respectively, six, five, and four‐membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six‐membered ring structure, which is thermally stable with an N‐phenyl group, but rearranges when sterically more encumbered Mes−N3 and tBu−N3 are used. The reaction of 1 with Me3Si−N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four‐membered heterocycle (5), which can be considered as a formal FLP‐trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.

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Expedient Synthesis oft-Butyl Azide

Cited by 31 publications

References 5 publications

New Lipophilic 2‐Amino‐N,N′‐dialkyl‐4,5‐dimethylimidazolium Cations: Synthesis, Structure, Properties, and Outstanding Thermal Stability in Alkaline Media

New Lipophilic 2‐Amino‐N,N′‐dialkyl‐4,5‐dimethylimidazolium Cations: Synthesis, Structure, Properties, and Outstanding Thermal Stability in Alkaline Media

Synthesis of Electron‐Rich Sterically Hindered P₁ Phosphazene Bases by the Staudinger Reaction

New Insights in Frustrated Lewis Pair Chemistry with Azides

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Expedient Synthesis oft-Butyl Azide

Cited by 31 publications

References 5 publications

New Lipophilic 2‐Amino‐N,N′‐dialkyl‐4,5‐dimethylimidazolium Cations: Synthesis, Structure, Properties, and Outstanding Thermal Stability in Alkaline Media

New Lipophilic 2‐Amino‐N,N′‐dialkyl‐4,5‐dimethylimidazolium Cations: Synthesis, Structure, Properties, and Outstanding Thermal Stability in Alkaline Media

Synthesis of Electron‐Rich Sterically Hindered P1 Phosphazene Bases by the Staudinger Reaction

New Insights in Frustrated Lewis Pair Chemistry with Azides

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Synthesis of Electron‐Rich Sterically Hindered P₁ Phosphazene Bases by the Staudinger Reaction