<i>p</i>-Toluenesulfonyl Azide

Heydt, H.; Regitz, Manfred; Mapp, Anna K.; Chen, Bin

doi:10.1002/047084289x.rt141.pub2

Cited by 5 publications

(10 citation statements)

References 87 publications

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“…1,2 Under typical batch conditions, the diazo acceptor molecule is reacted with tosyl azide in the presence of a base, such as NEt3, DBU or K2CO3, at ambient temperature over a period of up to 24 hours. 3,4,28,[75][76][77] Reaction times longer than several hours can be difficult to achieve in tubular reactors, so we sought to optimize the continuous diazo transfer reaction over a short reaction time of 10 min (Table 1). It has previously been reported that the diazo transfer requires only catalytic quantities of base to proceed.…”

Section: Continuous Diazo Transfer Using Batch Prepared Tosyl Azidementioning

confidence: 99%

“…The preparation of sulfonyl azide diazo transfer reagents are hazardous procedures which require extreme care. 3,4,8,27,28,75 In a typical preparation of tosyl azide a solution of tosyl chloride in MeCN is added slowly to an aqueous solution of sodium azide. As the substitution reaction is exothermic, the reaction must be kept at 0 °C to prevent explosive decomposition of the heat sensitive tosyl azide.…”

Section: In Situ Generation and Use Of Tosyl Azidementioning

confidence: 99%

“…48,58,68,[84][85][86] Tosyl azide exhibits a strong N=N=N stretching mode which can be used to assess the purity of the batch prepared reagent. 3 To verify the complete formation of tosyl azide from sodium azide and tosyl chloride, the reagents were mixed and then flowed through an in-line IR spectrometer after residence times of between 10 to 120 s. The formation of tosyl azide was followed by the strong azide band at 2135 cm -1 while the consumption of sodium azide was concurrently observed by monitoring 2048 cm -1 . After only 10 s we observed approximately 60% conversion of sodium azide to tosyl azide.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

“…[1][2][3][4] The α-diazocarbonyl compounds produced by diazo transfer are an important class of versatile synthetic intermediates due to their ability to generate reactive carbenes, [5][6][7] carbenoids, [7][8][9][10][11][12][13][14][15][16][17][18][19][20] ketenes and other heteroanalogous intermediates. [21][22][23][24][25][26] Despite being routinely used in small scale α-diazocarbonyl synthesis, tosyl azide is not suitable for use at larger scales.…”

Section: Introductionmentioning

confidence: 99%

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Taming tosyl azide: the development of a scalable continuous diazo transfer process

et al. 2016

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Heat and shock sensitive tosyl azide was generated and used on demand in a telescoped diazo transfer process. Small quantities of tosyl azide were accessed in a 'one pot' batch procedure using shelf stable, readily available reagents. For large scale diazo transfer reactions tosyl azide was generated and used in a telescoped flow process, to mitigate the risks associated with handling potentially explosive reagents on scale. The in situ formed tosyl azide was used to rapidly perform diazo tranfer to a range of acceptors, including β-ketoesters, β-ketoamides, malonate esters and β-ketosulfones. An effective in-line quench of sulfonyl azides was also developed, whereby a sacrificial acceptor molecule ensured complete consumption of any residual hazardous diazo transfer reagent. The telescoped diazo transfer process with in-line quenching was used to safely prepare over 21 g of an α-diazocarbonyl in >98% purity without any column chromatography.

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Section: Continuous Diazo Transfer Using Batch Prepared Tosyl Azidementioning

confidence: 99%

Section: In Situ Generation and Use Of Tosyl Azidementioning

confidence: 99%

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Taming tosyl azide: the development of a scalable continuous diazo transfer process

et al. 2016

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“…1 TsN 3 is a colorless oil with a melting point of 21-22 ºC and boiling point of 110-115 °C at 0.001mmHg. 2 …”

Section: Introductionmentioning

confidence: 99%

p-Toluenesulfonyl Azide

Santiago

2015

Synlett

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João Victor Santiago was born in 1991 in Brasília, Brazil. He obtained his B.Sc. in Chemistry (2012) and his M.Sc. in Organic Chemistry (2014) from the University of Brasília-UnB. Currently, he works towards his Ph.D. under the guidance of Professor Antonio C. B. Burtoloso. His research focuses on the synthesis of hexahydropyridazines, 1,2-oxazinanes, and substituted cyclohexanes from α,β-unsaturated diazoketones.

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λ⁵-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules

2016

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The compounds characterized by the presence of a λ-phosphorus functionality at the α-position with respect to the diazo moiety, here referred to as λ-phosphorus-containing α-diazo compounds (PCDCs), represent a vast class of extremely versatile reagents in organic chemistry and are particularly useful in the preparation of phosphonate- and phosphinoxide-functionalized molecules. Indeed, thanks to the high reactivity of the diazo moiety, PCDCs can be induced to undergo a wide variety of chemical transformations. Among them are carbon-hydrogen, as well as heteroatom-hydrogen insertion reactions, cyclopropanation, ylide formation, Wolff rearrangement, and cycloaddition reactions. PCDCs can be easily prepared from readily accessible precursors by a variety of different methods, such as diazotization, Bamford-Stevens-type elimination, and diazo transfer reactions. This evidence along with their relative stability and manageability make them appealing tools in organic synthesis. This Review aims to demonstrate the ongoing utility of PCDCs in the modern preparation of different classes of phosphorus-containing compounds, phosphonates, in particular. Furthermore, to address the lack of precedent collective papers, this Review also summarizes the methods for PCDCs preparation.

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p-Toluenesulfonyl Azide

Cited by 5 publications

References 87 publications

Taming tosyl azide: the development of a scalable continuous diazo transfer process

Taming tosyl azide: the development of a scalable continuous diazo transfer process

p-Toluenesulfonyl Azide

λ⁵-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules

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p-Toluenesulfonyl Azide

Cited by 5 publications

References 87 publications

Taming tosyl azide: the development of a scalable continuous diazo transfer process

Taming tosyl azide: the development of a scalable continuous diazo transfer process

p-Toluenesulfonyl Azide

λ5-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules

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λ⁵-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules