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Timestamp: 2019-04-24 03:51:00+00:00

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Alternate Names: FAR; CCT; Yarovenko's reagent.
Physical Data: bp 32-33 °C/6 mmHg; d 1.19 g cm-3.
Solubility: sol ether, CH2Cl2, acetonitrile.
Form Supplied in: liquid (97%).
Handling, Storage, and Precautions: store at <0 °C. Use within 4 weeks of delivery. Fluorinating agent; handle with caution in a fume hood. Readily reacts with H2O, alcohols, and amines.
N,N-Diethyl-2-chloro-1,1,2-trifluoroethylamine, also known as Yarovenko's reagent,6 is a relatively safe fluorinating agent that is easy to use. The reagent is tolerated by many functional groups including carbon-carbon double and triple bonds, aldehydes, ketones, esters, amides, and nitriles.1 It is quantitatively hydrolyzed to its amide (eq 1).2,7 This illustrates its primary reaction mode: elimination of fluorine a to nitrogen to give an iminium ion.
Reaction with Alcohols and Acids.
Alcohols react with FAR under mild conditions to give the corresponding fluorocarbons with inversion of stereochemistry (SN2 process). Yields and enantioselectivities are comparable with those obtained with phenyltetrafluorophosphorane, N,N-Diethylaminosulfur Trifluoride (DAST) and Potassium Fluoride (eq 2).2 This interconversion works well for primary, secondary, benzylic,8 and bridgehead alcohols (eq 3),9 but gives poor results with a- and b-hydroxy nitriles. DAST is superior in the latter application.10 Cyclic secondary and tertiary alcohols tend to give elimination products.
2. Leroy, J.; Hebert, E.; Wakselman, C. JOC 1979, 44, 3406.
3. Van der Steen, R.; Groesbeek, M.; Van Amsterdam, L. J. P.; Lugtenburg, J.; Van Oostrum, J.; De Grip, W. J. RTC 1989, 108, 20.
4. Wakeselman, C.; Tordeux, M. CC 1975, 956.
5. (a) Pruett, R. L.; Barr, J. T.; Rapp, K. E.; Bahner, C. T.; Gibson, J. D.; Lafferty, R. H. JACS 1950, 72, 3646. (b) Rapp, K. E.; Barr, J. T.; Pruett, R. L.; Bahner, C. T.; Gibson, J. D.; Lafferty, R. H. JACS 1952, 74, 749.
6. (a) Yarovenko, N. N.; Raksha, M. A. ZOB 1959, 29, 2159 (CA 1960, 54, 9724h). (b) Yarovenko, N. N.; Raksha, M. A. JGU 1959, 29, 2125.
7. For tetrahydrogibberellic acid derivatives, see: Cross, B. E.; Simpson, I. C. JCS(P1) 1982, 2571.
8. Hamman, S.; Barrelle, M.; Tetaz, F.; Beguin, C. G. JFC 1987, 37, 85.
9. Kopecky, J.; Smejkal, J. CCC 1980, 45, 2971 (CA 1981, 95, 24 348g).
10. Florin, C.; Chantegrel, J.; Charlon, C.; Marsura, A.; Luu-Duc, C. Ann. Pharm. Fr. 1985, 43, 595.
11. (a) Crabbe, P.; Carpino, H.; Velarde, E. CC 1971, 1028. (b) Crabbe, P.; Carpino, H.; Velarde, E. JOC 1973, 38, 1478.
12. (a) Kobayashi, T.; Maeda, M.; Komatsu, H.; Kojima, M. CPB 1982, 30, 3082. (b) Knox, L. H.; Valarde, E.; Berger, S.; Delfín, I.; Grezemkovsky, R.; Cross, A. D. JOC 1965, 30, 4160.
13. Müller, B.; Peter, H.; Schneider, P.; Bickel, H. HCA 1975, 58, 2469.
14. (a) Evelyn, L.; Hall, L. D. Carbohydr. Res. 1976, 47, 285. (b) Wood, K. R.; Fischer, D.; Kent, P. W. JCS(C) 1966, 1994.
15. Fokin, A. V.; Studnev, Yu. N.; Rapkin, A. I.; Sultanbekov, D. A.; Potarina, T. M. IZV 1984, 2, 411 (CA 1984, 100, 209 142a).
16. Takaoka, A.; Iwamoto, K.; Kitazume, T.; Ishikawa, N. JFC 1979, 14, 421.
17. (a) Gertsyuk, M. N.; Dronkina, M. I.; Samarai, L. I. ZOB 1980, 16, 1429 (CA 1981, 94, 15 177c). (b) Gertsyuk, M. N.; Gorbatenko, V. I.; Dronkina, M. I.; Samarai, L. I. ZOB 1979, 15, 1556 (CA 1979, 91, 192 748y).
18. Pasternak, V. I.; Dronkina, M. I.; Kukhar, V. P.; Yagupol'skii, L. M. ZOB 1978, 14, 2493 (CA 1979, 90, 137 372a).
19. Vcelak, J.; Chvalovsky, V. Synth. React. Inorg. Met.-Org. Chem. 1977, 7, 123.
20. Tolman, V. CCC 1977, 42, 2537 (CA 1978, 88, 6300m).
21. Folkin, A. V.; Zimin, V. I.; Studnev, Yu. N.; Sultanbekov, D. A. JGU 1968, 38, 1459.
22. Takaoka, A.; Iwakiri, H.; Ishikawa, N. BCJ 1979, 52, 3377.

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