Trifluoromethanesulfonyl azide
Structural formula | |||||||||||||
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General | |||||||||||||
Surname | Trifluoromethanesulfonyl azide | ||||||||||||
other names |
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Molecular formula | CF 3 N 3 O 2 S | ||||||||||||
Brief description |
colorless liquid |
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External identifiers / databases | |||||||||||||
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properties | |||||||||||||
Molar mass | 175.09 g mol −1 | ||||||||||||
Physical state |
liquid |
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density |
1.54 g cm −3 |
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boiling point |
80-81 ° C |
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Vapor pressure |
94.1 mmHg (21.5 ° C) |
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solubility |
soluble in hexane, decalin, dichloromethane, THF, dioxane, acetone, acetonitrile, DMF, DMSO, methanol |
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safety instructions | |||||||||||||
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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 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 .
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.
Individual evidence
- ↑ 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 .
- ↑ a b c d Nazaretyan, VP; Yagupol'skii, LM, J. Org. Chem. USSR 14 (1978) 192.
- ↑ Behrend, E .; Haas, A .: in Chemiker-Zeitung 95 (1971) 1009-1010.
- ↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
- ↑ 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 .
- ↑ 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 .
- ↑ 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 .
- ↑ 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 .
- ↑ a b Ruff, JK: Sulfur Oxyfluoride Derivatives. II in Inorg. Chem. 4 (1965) 567-570, doi : 10.1021 / ic50026a027 .
- ↑ a b Norbeck, DW; Kramer, JB: Synthesis of (-) - oxetanocin in J. Am. Chem. Soc. 110 (1988) 7217-7218, doi : 10.1021 / ja00229a048 .
- ↑ 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 .
- ↑ 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 .
- ↑ 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 .
- ↑ 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 .
- ^ Liu, Q .; Tor, Y .: Simple Conversion of Aromatic Amines into Azides in Org. Lett. 2003, 5, 2571-2572, doi : 10.1021 / ol034919 + .
- ↑ 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 .
- ↑ 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 .
- ↑ 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 .
- ↑ 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 .
- ↑ 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 .