Trifluoromethanesulfonyl azide

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Structural formula
Structure of trifluoromethanesulfonyl azide
General
Surname Trifluoromethanesulfonyl azide
other names
  • Trifluoromethanesulfonic acid azide
  • Triflylazide
  • TfN 3
Molecular formula CF 3 N 3 O 2 S
Brief description

colorless liquid

External identifiers / databases
CAS number 3855-45-6
PubChem 10986786
ChemSpider 9161983
Wikidata Q7841504
properties
Molar mass 175.09 g mol −1
Physical state

liquid

density

1.54 g cm −3

boiling point

80-81 ° C

Vapor pressure

94.1 mmHg (21.5 ° C)

solubility

soluble in hexane, decalin, dichloromethane, THF, dioxane, acetone, acetonitrile, DMF, DMSO, methanol

safety instructions
GHS hazard labeling
no classification available
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Trifluoromethanesulfonyl azide is an organic-chemical compound, which is derived as a derivative of trifluoromethanesulfonic acid and can also be assigned to the group of azides . It is used in organic synthesis as a reagent for introducing the diazo or trifluoromethanesulfonyl function.

Presentation and extraction

Trifluoromethanesulfonyl azide can be prepared by reacting trifluoromethanesulfonic anhydride , trifluoromethanesulfonyl fluoride or trifluoromethanesulfonyl chloride with sodium azide . Purification can be carried out by careful distillation under reduced pressure .

properties

Trifluoromethanesulfonyl azide is a colorless liquid at room temperature that boils at 80–81 ° C under normal pressure . Boiling points under reduced pressure are 52.3 ° C and 444 mmHg and 45 ° C and 350 mmHg, respectively. The compound tends to decompose explosively. The pure compound can be thermally stable up to a temperature of 100 ° C. Because of its thermal instability, it is mostly produced and used in solution in dichloromethane , n- hexane , acetonitrile or 1,2-dichloroethane . A solution in dichloromethane is stable for a few weeks at -14 ° C, a solution in n- heptane at 4 ° C for a few days.

use

The compound can be used to convert primary amines to azides. This has been described with alkylamines, aminodeoxyhexose amino acids and peptides . This conversion can be significantly accelerated by adding metal catalysts (e.g. Cu 2+ , Ni 2+ , Zn 2+ ). The neomycin with six amino groups can be converted into the corresponding six-substituted azide. In addition, substituted anilines can be converted into the corresponding phenyl azides .

Trifluoromethanesulfonyl azide reaction02.svg

Trifluoromethanesulfonyl azide enters into 1,3-dipolar cycloadditions with electron-rich alkenes . Through an addition to enolates , enol ethers and enamines , a thermally unstable 1,2,3-triazoline is formed as an intermediate . Depending on the type of substitution, this breaks down into the corresponding diazo compounds, N -triflylamides or triflylamines. Similarly, a 1,3-dipolar cycloaddition with alkynes is also possible. Phenylacetylene reacts with trifluoromethanesulfonyl azide to form the two possible addition products, where the stable 4-phenyl-1 H -1,2,3-triazole can be obtained by heating in ethanol with cleavage of the trifluoromethanesulfonyl group .

Trifluoromethanesulfonyl azide reaction01.svg

At temperatures above 80 ° C., the unstable trifluoromethanesulfonyl nitrene is formed with elimination of nitrogen. With substituted benzenes, corresponding N -trifluoromethanesulfonylanilines are formed after the addition , in pyridine the pyridinium N-trifluorosulfonylaminide.

Trifluoromethanesulfonyl azide reaction03.svg

Individual evidence

  1. ↑ a b c d e f g e-EROS Encyclopedia of Reagents for Organic Synthesis , 1999-2013, John Wiley and Sons, Inc., entry for Trifluoromethanesulfonyl Azide, accessed January 15, 2015 .
  2. ↑ a b c d Nazaretyan, VP; Yagupol'skii, LM, J. Org. Chem. USSR 14 (1978) 192.
  3. ↑ Behrend, E .; Haas, A .: in Chemiker-Zeitung 95 (1971) 1009-1010.
  4. ↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
  5. ↑ a b c Cavender, CJ; Shiner, VJ, Jr .: Trifluoromethanesulfonyl azide. Its reaction with alkyl amines to form alkyl azides in J. Org. Chem. 37 (1972) 3567-3569, doi : 10.1021 / jo00795a052 .
  6. ↑ a b c d Fritschi, S .; Vasella, A .: Synthesis of N, N-Disubstituted Lactone Hydrazones via (sulfonylimino) ethers in Helv. Chim. Acta 74 (1991) 2024-2034, doi : 10.1002 / hlca.19910740837 .
  7. ↑ a b c Vasella, A .; Witzig, C .; Chiara, J.-L .; Martin-Lomas, M .: Convenient Synthesis of 2-Azido-2-deoxy-aldoses by Diazo Transfer in Helv. Chim. Acta 74 (1991) 2073-2077, doi : 10.1002 / hlca.19910740842 .
  8. ↑ a b c d Kamigata, N .; Yamamoto, K .; Kawakita, O .; Hikita, K .; Matsuyama, H .; Yoshida, M .; Kobayashi, M .: Reactions of Trifluoromethanesulfonyl Azide with Aromatic Compounds in Bull. Chem. Soc. Yep 57 (1984) 3601-3602, doi : 10.1246 / bcsj.57.3601 , pdf .
  9. ↑ a b Ruff, JK: Sulfur Oxyfluoride Derivatives. II in Inorg. Chem. 4 (1965) 567-570, doi : 10.1021 / ic50026a027 .
  10. ↑ a b Norbeck, DW; Kramer, JB: Synthesis of (-) - oxetanocin in J. Am. Chem. Soc. 110 (1988) 7217-7218, doi : 10.1021 / ja00229a048 .
  11. ↑ a b Benati, L .; Nanni, D .; Spagnolo, P .: Reactions of Benzocyclic β-Keto Esters with Sulfonyl Azides. 2. Further Insight into the Influence of Azide Structure and Solvent on the Reaction Course in J. Org. Chem. 64 (1999) 5132-5138, doi : 10.1021 / jo9901541 .
  12. ↑ Ludin, C .; Schwesinger, B .; Schwesinger, R .; Meier, W .; Seitz, B .; Weller, T .; Hoenke, C .; Haitz, S .; Erbeck, S .; Prinzbach, H .: Total syntheses of enantiomerically pure D- and L-glycosyl donors as components of sannamycin-type aminoglycoside antibiotics in J. Chem. Soc. , Perkin Trans. 1 1994, 2685-2701, doi : 10.1039 / P19940002685 .
  13. ↑ a b Zaloom, J .; Roberts, DC: Preparation of azido derivatives from amino acids and peptides by diazo transfer in J. Org. Chem. 46 (1981) 5173-5176, doi : 10.1021 / jo00338a022 .
  14. ↑ a b Alper, PB; Hung, S.-C .; Wong, C.-H .: Metal catalyzed diazo transfer for the synthesis of azides from amines in Tetrahedron Lett. 37 (1996) 6029-6032, doi : 10.1016 / 0040-4039 (96) 01307-X .
  15. ^ Liu, Q .; Tor, Y .: Simple Conversion of Aromatic Amines into Azides in Org. Lett. 2003, 5, 2571-2572, doi : 10.1021 / ol034919 + .
  16. ↑ Xu, Y .; Xu, G .; Zhu, S .; Zhu, G .; Jia, Y .; Huang, Q .: Reactions of fluoroalkanesulfonyl azides with trimethylsilyl enol ethers in J. Fluor. Chem. 96 (1999) 79-85, doi : 10.1016 / S0022-1139 (99) 00009-3 .
  17. ↑ Ondrus, TA; Pednekar, PR; Knaus, EE: Some reactions of 1-methyl-1,2-dihydropyridines with organic azides. Synthesis and reactions of 1,2,5,6-tetrahydropyridylidene-2-cyano (sulfone) amides and piperidylidene-2-cyano (sulfone) amides . In: Canadian Journal of Chemistry . 63 (9), 1985, pp. 2362-2368, doi : 10.1139 / v85-391 .
  18. ↑ Quast, H .; Ivanova, S .; Peters, E.-M .; Peters, K .: Ring Expansion of 2-Alkylidenedihydroquinolines to 2-Iminodihydro-1-benzazepines by Phenyl, Methanesulphonyl, and Trifluoromethanesulphonyl Azide in Eur. J. Org. Chem. 2000, 507-520, doi : 10.1002 / (SICI) 1099 -0690 (200002) 2000: 3 <507 :: AID-EJOC507> 3.0.CO; 2-V .
  19. ↑ Shainyan, BA; Meshcheryakov, VI: Trifluoromethanesulfonyl Azide as a Convenient Reagent for Synthesis of Triazoles in Russ. J. Org. Chem. 37 (2001) 1797-1798, doi : 10.1023 / A: 1013911615568 .
  20. ↑ Xu, Y .; Zhu, S .: Study on the reactions of fluoroalkanesulfonyl azides with pyridine and its derivatives in Tetrahedron 55 (1999) 13725-13734, doi : 10.1016 / S0040-4020 (99) 00856-X .