Imidazole-1-sulfonyl azide

Last updated
Imidazole-1-sulfonyl azide
Imidazole-1-sulfonyl azide.png
Imidazole-1-sulfonyl-azide-3D-spacefill.png
Names
Preferred IUPAC name
1H-Imidazole-1-sulfonyl azide
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/C3H3N5O2S.ClH/c4-6-7-11(9,10)8-2-1-5-3-8;/h1-3H;1H Yes check.svgY
    Key: XYURSCOGYWBRDR-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C3H3N5O2S.ClH/c4-6-7-11(9,10)8-2-1-5-3-8;/h1-3H;1H
    Key: XYURSCOGYWBRDR-UHFFFAOYAJ
  • Cl.O=S(=O)(N=[N+]=[N-])n1ccnc1
Properties
C3H3N5O2S
Molar mass 173.15 g·mol−1
AppearanceColourless Liquid
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Potentially explosive, Harmful
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Imidazole-1-sulfonyl azide is an organic azide compound that can be used as an alternative to trifluoromethanesulfonyl azide. It is an explosive colorless liquid, but some of its organic-soluble salts can be safely handled and stored as a solid.

Contents

Preparation

The hydrochloride salt of this compound is also available commercially, but can degrade to release explosive byproducts. [1]

Preparation of imidazole-1-sulfonyl azide.png

Reactions

Like trifluoromethanesulfonyl azide, this compound generally converts primary amines or ammonium salts to azides when catalyzed by copper(II), nickel(II), zinc(II), and cobalt(II) salts. [2] This reaction is effectively the reverse of the Staudinger reaction. Similarly, it is able to transfer the diazo group (=N2) under basic conditions. [2]

Safety

As with all organic azides, this compound is potentially explosive both in use and in preparation. The hydrochloride salt was initially reported to be insensitive to impact, vigorous grinding, and prolonged heating at 80 °C, although heating above 150 °C resulted in violent decomposition. Further reported impact studies indicated otherwise, showing the sensitivity to be similar to RDX. [3] Subsequent reports noted that the hydrochloride salt is hygroscopic, and upon prolonged storage was hydrolyzed to produce hydrazoic acid, which made the material sensitive. [2] [3] Synthesis of the HCl salt has led to a significant explosion, with expected explosive byproducts of sulfonyl diazide or hydrazoic acid being present. [4]

Recent studies have shown the hydrogen sulfate salt to be significantly less hazardous to handle with decomposition temperature of 131 °C, insensitivity to impact, and low electrostatic discharge and friction sensitivities. [3] Further improvements have led to its synthesis with increased safety, making the hydrogen sulfate salt a relatively safe diazo-transfer reagent to both synthesize and handle. [5]

Related Research Articles

In chemistry, azide is a linear, polyatomic anion with the formula N−3 and structure N=N+=N. It is the conjugate base of hydrazoic acid HN3. Organic azides are organic compounds with the formula RN3, containing the azide functional group. The dominant application of azides is as a propellant in air bags.

<span class="mw-page-title-main">Sulfonate</span> Organosulfur compound of the form R–S(=O)2–O (charge –1)

In organosulfur chemistry, a sulfonate is a salt or ester of a sulfonic acid. It contains the functional group R−S(=O)2−O, where R is an organic group. Sulfonates are the conjugate bases of sulfonic acids. Sulfonates are generally stable in water, non-oxidizing, and colorless. Many useful compounds and even some biochemicals feature sulfonates.

<span class="mw-page-title-main">Imidazole</span> Chemical compound

Imidazole (ImH) is an organic compound with the formula C3N2H4. It is a white or colourless solid that is soluble in water, producing a mildly alkaline solution. In chemistry, it is an aromatic heterocycle, classified as a diazole, and has non-adjacent nitrogen atoms in meta-substitution.

<span class="mw-page-title-main">Sodium azide</span> Chemical compound

Sodium azide is the inorganic compound with the formula NaN3. This colorless salt is the gas-forming component in legacy car airbag systems. It is used for the preparation of other azide compounds. It is an ionic substance, is highly soluble in water and is very acutely poisonous.

The diazogroup is an organic moiety consisting of two linked nitrogen atoms (azo) at the terminal position. Overall charge neutral organic compounds containing the diazo group bound to a carbon atom are called diazo compounds or diazoalkanes and are described by the general structural formula R2C=N+=N. The simplest example of a diazo compound is diazomethane, CH2N2. Diazo compounds (R2C=N2) should not be confused with azo compounds of the type R-N=N-R or with diazonium compounds of the type R-N2+.

<span class="mw-page-title-main">Hydrazoic acid</span> Unstable and toxic chemical compound

Hydrazoic acid, also known as hydrogen azide or azoimide, is a compound with the chemical formula HN3. It is a colorless, volatile, and explosive liquid at room temperature and pressure. It is a compound of nitrogen and hydrogen, and is therefore a pnictogen hydride. It was first isolated in 1890 by Theodor Curtius. The acid has few applications, but its conjugate base, the azide ion, is useful in specialized processes.

<span class="mw-page-title-main">Bamford–Stevens reaction</span>

The Bamford–Stevens reaction is a chemical reaction whereby treatment of tosylhydrazones with strong base gives alkenes. It is named for the British chemist William Randall Bamford and the Scottish chemist Thomas Stevens Stevens (1900–2000). The usage of aprotic solvents gives predominantly Z-alkenes, while protic solvent gives a mixture of E- and Z-alkenes. As an alkene-generating transformation, the Bamford–Stevens reaction has broad utility in synthetic methodology and complex molecule synthesis.

<span class="mw-page-title-main">Dimethyl sulfate</span> Chemical compound

Dimethyl sulfate (DMS) is a chemical compound with formula (CH3O)2SO2. As the diester of methanol and sulfuric acid, its formula is often written as (CH3)2SO4 or Me2SO4, where CH3 or Me is methyl. Me2SO4 is mainly used as a methylating agent in organic synthesis.

<span class="mw-page-title-main">Diazonium compound</span> Diazonium salts of formula R-N≡N+

Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group [R−N+≡N]X where R can be any organic group, such as an alkyl or an aryl, and X is an inorganic or organic anion, such as a halide.

A triazole is a heterocyclic compound featuring a five-membered ring of two carbon atoms and three nitrogen atoms with molecular formula C2H3N3. Triazoles exhibit substantial isomerism, depending on the positioning of the nitrogen atoms within the ring.

<span class="mw-page-title-main">Seyferth–Gilbert homologation</span> Chemical compound

The Seyferth–Gilbert homologation is a chemical reaction of an aryl ketone 1 with dimethyl (diazomethyl)phosphonate 2 and potassium tert-butoxide to give substituted alkynes 3. Dimethyl (diazomethyl)phosphonate 2 is often called the Seyferth–Gilbert reagent.

In organic chemistry, the Baudisch reaction is a process for the synthesis of nitrosophenols using metal ions. Although the products are of limited value, the reaction is of historical interest as an example of metal-promoted functionalization of aromatic substrates.

<span class="mw-page-title-main">Trifluoromethanesulfonyl azide</span> Chemical compound

Trifluoromethanesulfonyl azide or triflyl azideCF3SO2N3 is an organic azide used as a reagent in organic synthesis.

Electrophilic amination is a chemical process involving the formation of a carbon–nitrogen bond through the reaction of a nucleophilic carbanion with an electrophilic source of nitrogen.

<span class="mw-page-title-main">Methyl azide</span> Chemical compound

Methyl azide is an organic compound with the formula CH3N3. It is a white solid and it is the simplest organic azide.

<span class="mw-page-title-main">Tosyl azide</span> Chemical compound used in organic synthesis

Tosyl azide is a reagent used in organic synthesis.

A tosylhydrazone in organic chemistry is a functional group with the general structure RR'C=N-NH-Ts where Ts is a tosyl group. Organic compounds having this functional group can be accessed by reaction of an aldehyde or ketone with tosylhydrazine.

Nickel boride is the common name of materials composed chiefly of the elements nickel and boron that are widely used as catalysts in organic chemistry. Their approximate chemical composition is Ni2.5B, and they are often incorrectly denoted "Ni
2
B
" in organic chemistry publications.

<span class="mw-page-title-main">Cyanogen azide</span> Chemical compound

Cyanogen azide, N3CN or CN4, is an azide compound of carbon and nitrogen which is an oily, colourless liquid at room temperature. It is a highly explosive chemical that is soluble in most organic solvents, and normally handled in dilute solution in this form. It was first synthesised by F. D. Marsh at DuPont in the early 1960s.

An organic azide is an organic compound that contains an azide functional group. Because of the hazards associated with their use, few azides are used commercially although they exhibit interesting reactivity for researchers. Low molecular weight azides are considered especially hazardous and are avoided. In the research laboratory, azides are precursors to amines. They are also popular for their participation in the "click reaction" and in Staudinger ligation. These two reactions are generally quite reliable, lending themselves to combinatorial chemistry.

References

  1. van Delft, Floris. "SX-B1001". Synaffix. Retrieved 30 January 2014.
  2. 1 2 3 E. D. Goddard-Borger and R. V. Stick (2007). "An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent:  Imidazole-1-sulfonyl Azide Hydrochloride". Organic Letters . 9 (19): 3797–3800. doi:10.1021/ol701581g. PMID   17713918.
    E. D. Goddard-Borger and R. V. Stick (2011). "An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent:  Imidazole-1-sulfonyl Azide Hydrochloride". Addition/Correction. Organic Letters . 13 (9): 2514. doi:10.1021/ol2007555.
  3. 1 2 3 Fischer, Niko; Goddard-Borger, Ethan D.; Greiner, Robert; Klapötke, Thomas M.; Skelton, Brian W.; Stierstorfer, Jörg (2012). "Sensitivities of Some Imidazole-1-sulfonyl Azide Salts". J. Org. Chem. 77 (4): 1760–1764. doi:10.1021/jo202264r. PMID   22283437.
  4. Goddard-Borger, Ethan D.; Stick, Robert V. (2011-03-29). "An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent: Imidazole-1-sulfonyl Azide Hydrochloride". Organic Letters. 13 (9): 2514. doi:10.1021/ol2007555.
  5. Potter, Garrett T.; Jayson, Gordon C.; Miller, Gavin J.; Gardiner, John M. (2016-03-29). "An Updated Synthesis of the Diazo-Transfer Reagent Imidazole-1-sulfonyl Azide Hydrogen Sulfate" (PDF). The Journal of Organic Chemistry. 81 (8): 3443–3446. doi: 10.1021/acs.joc.6b00177 . PMID   26998999.