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{{Chembox {{Chembox
| Verifiedfields = changed
⚫ | verifiedrevid = 420135754
| Watchedfields = changed
⚫ | verifiedrevid = 476995490
| ImageFile = Imidazole-1-sulfonyl azide.png | ImageFile = Imidazole-1-sulfonyl azide.png
| ImageAlt = Space-filling model of the imidazole-1-sulfonyl azide molecule
| ImageSize =
| ImageFile1 = Imidazole-1-sulfonyl-azide-3D-spacefill.png
| IUPACName =
| ImageSize1 = 180
| ImageAlt1 = Space-filling model of the imidazole-1-sulfonyl azide molecule
| PIN = 1''H''-Imidazole-1-sulfonyl azide
| OtherNames = | OtherNames =
| Section1 = {{Chembox Identifiers |Section1={{Chembox Identifiers
| InChI = 1/C3H3N5O2S.ClH/c4-6-7-11(9,10)8-2-1-5-3-8;/h1-3H;1H | InChI = 1/C3H3N5O2S.ClH/c4-6-7-11(9,10)8-2-1-5-3-8;/h1-3H;1H
| InChIKey = XYURSCOGYWBRDR-UHFFFAOYAJ | InChIKey = XYURSCOGYWBRDR-UHFFFAOYAJ
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} | StdInChI_Ref = {{stdinchicite|correct|chemspider}}
Line 12: Line 17:
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = XYURSCOGYWBRDR-UHFFFAOYSA-N | StdInChIKey = XYURSCOGYWBRDR-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|??}} | CASNo_Ref = {{cascite|correct|PubChem}}
| CASNo = 952234-37-6 | CASNo = 952234-37-6
| PubChem = | PubChem = 23583981
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID=21374920 | ChemSpiderID=21374920
| SMILES = Cl.O=S(=O)(N==)n1ccnc1 | SMILES = Cl.O=S(=O)(N==)n1ccnc1
}} }}
| Section2 = {{Chembox Properties |Section2={{Chembox Properties
| C = 3 | H = 3 | N = 5 | O = 2 | S = 1 | C=3 | H=3 | N=5 | O=2 | S=1
| Appearance = | Appearance = Colourless Liquid
| Density = | Density =
| MeltingPt = | MeltingPt =
| BoilingPt = | BoilingPt =
| Solubility = | Solubility =
}} }}
| Section3 = {{Chembox Hazards |Section3={{Chembox Hazards
| MainHazards = Potentially explosive | MainHazards = Potentially explosive, Harmful
| FlashPt = | FlashPt =
| Autoignition = | AutoignitionPt =
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}} }}


'''Imidazole-1-sulfonyl azide''' is an organic ] compound that can be used as an alternative to ]. It is a colorless liquid; it may also be used as a better-handled ] salt. '''Imidazole-1-sulfonyl azide''' is an organic ] compound that can be used as an alternative ] reagent to ]. It is an explosive colorless liquid, but some of its organic-soluble salts can be safely handled and stored as a solid.


==Preparation== ==Preparation==
The hydrochloride salt of this compound is also available commercially, but can degrade to release explosive byproducts.<ref>{{cite web|last=van Delft|first=Floris|title=SX-B1001|url=http://synaffix.biedmeer.nl/Webwinkel-Category-1120834/SX-B1001.html|work=Synaffix|accessdate=30 January 2014}}</ref>
This compound is not readily available commercially. It may be prepared by reacting ] with ] in ], followed by the addition of excess ]. The hydrochloride salt may be obtained by precipitating with an ethanol solution of HCl.<ref name = Goddard-Borger>{{cite journal | author = E. D. Goddard-Borger and R. V. Stick | title = An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent:&nbsp; Imidazole-1-sulfonyl Azide Hydrochloride | journal = ] | volume = 9 | issue = 19 | pages = 3797–3800 | doi = 10.1021/ol701581g | pmid = 17713918 | year = 2007}}<br>
⚫ {{cite journal | author = E. D. Goddard-Borger and R. V. Stick | title = An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent:&nbsp; Imidazole-1-sulfonyl Azide Hydrochloride | journal = ] | volume = 13 | issue = 9 | pages = 2514 | doi = 10.1021/ol2007555 | year = 2011 | format = Addition/Correction}}</ref>


:] :]


==Reactions== ==Reactions==
Like ], this compound generally converts primary amines or ammonium salts to azides.<ref name = Goddard-Borger/> This reaction is effectively the reverse of the ]. Similarly, it is able to transfer the ] group (=N<sub>2</sub>) when catalyzed by copper(II), nickel(II), zinc(II), and cobalt(II) salts.<ref name = Goddard-Borger/> Like ], this compound generally converts primary amines or ammonium salts to azides when catalyzed by copper(II), nickel(II), zinc(II), and cobalt(II) salts.<ref name = Goddard-Borger>{{cite journal | author = E. D. Goddard-Borger and R. V. Stick | title = An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent:&nbsp; Imidazole-1-sulfonyl Azide Hydrochloride | journal = ] | volume = 9 | issue = 19 | pages = 3797–3800 | doi = 10.1021/ol701581g | pmid = 17713918 | year = 2007}}<br>
⚫ {{cite journal | author = E. D. Goddard-Borger and R. V. Stick | title = An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent:&nbsp; Imidazole-1-sulfonyl Azide Hydrochloride | journal = ] | volume = 13 | issue = 9 | pages = 2514 | doi = 10.1021/ol2007555 | year = 2011 | url = https://figshare.com/articles/journal_contribution/2986117 | department = Addition/Correction}}</ref> This reaction is effectively the reverse of the ]. Similarly, it is able to transfer the ] group (=N<sub>2</sub>) under basic conditions.<ref name = Goddard-Borger/>


==Safety== ==Safety==
As with all organic azides, this compound is potentially explosive. 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. Subsequent reports noted that upon storage, the hydrochloride salt hydrolyzed to produce ], which made the material sensitive.<ref name = Goddard-Borger/><ref>{{cite journal | doi = 10.1021/jo202264r | journal = J. Org. Chem. | title = Sensitivities of Some Imidazole-1-sulfonyl Azide Salts | year = 2012 | last1 = Fischer | first1 = Niko | last2 = Goddard-Borger | first2 = Ethan D. | last3 = Greiner | first3 = Robert | last4 = Klapötke | first4 = Thomas M. | last5 = Skelton | first5 = Brian W. | last6 = Stierstorfer | first6 = Jörg | volume = 77 | issue = 4 | pages = 1760}}</ref> 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&nbsp;°C, although heating above 150&nbsp;°C resulted in violent decomposition. Further reported impact studies indicated otherwise, showing the sensitivity to be similar to ].<ref name=":0" /> Subsequent reports noted that the hydrochloride salt is ], and upon prolonged storage was hydrolyzed to produce ], which made the material sensitive.<ref name = Goddard-Borger/><ref name=":0">{{cite journal | doi = 10.1021/jo202264r | journal = J. Org. Chem. | title = Sensitivities of Some Imidazole-1-sulfonyl Azide Salts | year = 2012 | last1 = Fischer | first1 = Niko | last2 = Goddard-Borger | first2 = Ethan D. | last3 = Greiner | first3 = Robert | last4 = Klapötke | first4 = Thomas M. | last5 = Skelton | first5 = Brian W. | last6 = Stierstorfer | first6 = Jörg | volume = 77 | issue = 4 | pages = 1760–1764| pmid = 22283437 }}</ref> Synthesis of the HCl salt has led to a significant explosion, with expected explosive byproducts of ] or hydrazoic acid being present.<ref>{{Cite journal|last1=Goddard-Borger|first1=Ethan D.|last2=Stick|first2=Robert V.|date=2011-03-29|title=An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent: Imidazole-1-sulfonyl Azide Hydrochloride|journal=Organic Letters|language=EN|volume=13|issue=9|pages=2514|doi=10.1021/ol2007555|url=https://figshare.com/articles/journal_contribution/2986117 }}</ref>

Recent studies have shown the hydrogen sulfate salt to be significantly less hazardous to handle with decomposition temperature of 131&nbsp;°C, insensitivity to impact, and low electrostatic discharge and friction sensitivities.<ref name=":0" /> 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.<ref>{{Cite journal|last1=Potter|first1=Garrett T.|last2=Jayson|first2=Gordon C.|last3=Miller|first3=Gavin J.|last4=Gardiner|first4=John M.|date=2016-03-29|title=An Updated Synthesis of the Diazo-Transfer Reagent Imidazole-1-sulfonyl Azide Hydrogen Sulfate|journal=The Journal of Organic Chemistry|language=EN|doi=10.1021/acs.joc.6b00177|volume=81|issue=8|pages=3443–3446|pmid=26998999|url=https://www.research.manchester.ac.uk/portal/files/33083992/JOC_note_jo_2016_00177a.pdf|doi-access=free}}</ref>


==References== ==References==
<references/> <references/>


] ]
] ]
]
]

Latest revision as of 04:42, 17 November 2023

Imidazole-1-sulfonyl azide
Space-filling model of the imidazole-1-sulfonyl azide molecule
Space-filling model of the imidazole-1-sulfonyl azide molecule
Names
Preferred IUPAC name 1H-Imidazole-1-sulfonyl azide
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
PubChem CID
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C3H3N5O2S.ClH/c4-6-7-11(9,10)8-2-1-5-3-8;/h1-3H;1HKey: XYURSCOGYWBRDR-UHFFFAOYSA-N
  • InChI=1/C3H3N5O2S.ClH/c4-6-7-11(9,10)8-2-1-5-3-8;/h1-3H;1HKey: XYURSCOGYWBRDR-UHFFFAOYAJ
SMILES
  • Cl.O=S(=O)(N==)n1ccnc1
Properties
Chemical formula C3H3N5O2S
Molar mass 173.15 g·mol
Appearance Colourless 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 , 100 kPa). ☒N verify (what is  ?) Infobox references
Chemical compound

Imidazole-1-sulfonyl azide is an organic azide compound that can be used as an alternative organic synthesis reagent 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.

Preparation

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

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. This reaction is effectively the reverse of the Staudinger reaction. Similarly, it is able to transfer the diazo group (=N2) under basic conditions.

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. Subsequent reports noted that the hydrochloride salt is hygroscopic, and upon prolonged storage was hydrolyzed to produce hydrazoic acid, which made the material sensitive. Synthesis of the HCl salt has led to a significant explosion, with expected explosive byproducts of sulfonyl diazide or hydrazoic acid being present.

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. 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.

References

  1. van Delft, Floris. "SX-B1001". Synaffix. Retrieved 30 January 2014.
  2. ^ 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. ^ 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.
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