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1
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0000399002
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Avila, D. V.; Ingold, K. U.; Lusztyk, J.; Dolbier, W. R.; Pan, H.-Q. J. Am. Chem. Soc. 1993, 115, 1577-1579.
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(1993)
J. Am. Chem. Soc
, vol.115
, pp. 1577-1579
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Avila, D.V.1
Ingold, K.U.2
Lusztyk, J.3
Dolbier, W.R.4
Pan, H.-Q.5
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2
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0028224332
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Avila, D. V.; Ingold, K. U.; Lusztyk, J.; Dolbier, W. R., Jr.; Pan, H.-Q.; Muir, M. J. Am. Chem. Soc. 1994, 116, 99-104.
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J. Am. Chem. Soc
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-
Avila, D.V.1
Ingold, K.U.2
Lusztyk, J.3
Dolbier Jr., W.R.4
Pan, H.-Q.5
Muir, M.6
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3
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0026000469
-
-
For α,α-difluoro-n-alkyl radical cyclizations see, e.g., Cavicchio, G.; Marchetti, V.; Arnone, A.; Bravo, P.; Viani, F. Tetrahedron 1991, 47, 9439-9448
-
(a) For α,α-difluoro-n-alkyl radical cyclizations see, e.g., Cavicchio, G.; Marchetti, V.; Arnone, A.; Bravo, P.; Viani, F. Tetrahedron 1991, 47, 9439-9448
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-
-
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4
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70350449831
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Arnone, A.; Bravo, P.; Cavicchio, G.; Frigerio, M.; Viani, F. Tetrahedron 1992, 48, 8523-8540.
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(1992)
Tetrahedron
, vol.48
, pp. 8523-8540
-
-
Arnone, A.1
Bravo, P.2
Cavicchio, G.3
Frigerio, M.4
Viani, F.5
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5
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0026649490
-
-
For β,β-difluoro-n-alkyl radical cyclizations see, e.g., Morikawa, T.; Kodama, Y.; Uchida, J.; Takano, M.; Washio, Y.; Taguchi, T. Tetrahedron 1992, 48, 8915-8926.
-
(b) For β,β-difluoro-n-alkyl radical cyclizations see, e.g., Morikawa, T.; Kodama, Y.; Uchida, J.; Takano, M.; Washio, Y.; Taguchi, T. Tetrahedron 1992, 48, 8915-8926.
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-
-
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6
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76049093553
-
-
The modified (see footnote b to Table 1) rate constant for addition of a non-fluorinated n-alkyl radical to α-methylstyrene is probably about a factor of 5 lower than the true value. Certainly, it seems very improbable that addition to this substrate could be slower than addition to styrene.
-
The "modified" (see footnote b to Table 1) rate constant for addition of a non-fluorinated n-alkyl radical to α-methylstyrene is probably about a factor of 5 lower than the true value. Certainly, it seems very improbable that addition to this substrate could be slower than addition to styrene.
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-
-
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7
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76049089403
-
-
This extension of the α-fluoroalkyl radical series can be justified by the fact that CH2F• and CHF2F• have reactivities roughly comparable to those of RCH2CH 2CHFF• and RCH2CH2CF2F•, respectively.8
-
8
-
-
-
-
8
-
-
76049119180
-
-
For example, in acetonitrile kadd (CH 2FF•, C6F5CH=CH2, 0.35 ± 0.04) × 106 M-1 s-1, kadd (CHF2F•, C6H 5CH=CH2, 4.1 ± 0.4) × 106 M-1 s-1 and kadd (CHF2F•, C6F5CH=CH2, 5.5 ± 0.7) × 106 M-1 s-1 cf, Table 1
-
-1 (cf., Table 1).
-
-
-
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9
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76049126145
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Fischer, H. In Magnetic Properties of Free Radicals; Landolt-Börnstein, New Series; Fischer, H., Hellwege, K.-H., Eds.; Springer-Verlag: Berlin, 1977; 9, Part b, Chapter 3.
-
Fischer, H. In Magnetic Properties of Free Radicals; Landolt-Börnstein, New Series; Fischer, H., Hellwege, K.-H., Eds.; Springer-Verlag: Berlin, 1977; Vol. 9, Part b, Chapter 3.
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-
-
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10
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76049091870
-
-
E.g.,9 CH3CH2•, a (2Hα, 22.2 G, a (13Cα), 39.1 G, g, 2.0026; CH 3CH2CH2bull;, a (2Hα, 22.1 G, g, 2.0026; CF3CH2•, a (2Hα, 23.8 G, g) 2.0023; CF3CF2CH2•, a 2Hα, 22 G
-
2•, a (2Hα) = -22 G.
-
-
-
-
11
-
-
76049124396
-
-
E.g.,9 RCH2CH2•;10 CH2F•, a (2Hα, 21.1 G, a (Fα), 64.3 G, a (13Cα, 54.8 G, g, 2.0045; CF 3OCH2CHF•, a (Hα, 21.4 G, a (Fα, 63.5 G; CHF2•, a (Hα, 22.2 G, a (2Fα, 84.2 G, a (13Cα, 148.8 G, g) 2.0041; CF3OCH2CF2•, a (2Fα, 90.6 G; CF3•, a (3Fα, 142.4 G, a 13Cα, 271.6 G, g, 2.0031
-
13Cα) = +271.6 G, g = 2.0031.
-
-
-
-
12
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-
76049107057
-
-
The greater reactivity of bent σ-radicals relative to planar π-radials has been noted earlier in studies on aryl radicals, 13 and the influence of pyramidality on radical reactivities has been previously suggested in a study of α-hydroxyalkyl radicals.14
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14
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13
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0000370082
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-
Madhaven, V.; Schuler, R. H.; Fessenden, R. W. J. Am. Chem. Soc. 1978, 100, 888-893.
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(1978)
J. Am. Chem. Soc
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, pp. 888-893
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Madhaven, V.1
Schuler, R.H.2
Fessenden, R.W.3
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14
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37049090815
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-
Gilbert, B. C.; Lindsay Smith, J. R.; Milne, E. C.; Whitwood, A. C.; Taylor, P. J. Chem. Soc., Perkin Trans. 2 1993, 2025-2031.
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(1993)
J. Chem. Soc., Perkin Trans. 2
, pp. 2025-2031
-
-
Gilbert, B.C.1
Lindsay Smith, J.R.2
Milne, E.C.3
Whitwood, A.C.4
Taylor, P.5
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15
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0001051921
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-
Wong, M. W.; Pross, A.; Radom, L. J. Am. Chem. Soc. 1994, 116, 6284-6292.
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(1994)
J. Am. Chem. Soc
, vol.116
, pp. 6284-6292
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Wong, M.W.1
Pross, A.2
Radom, L.3
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16
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0041059705
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Wong, M. W.; Pross, A.; Radom, L. J. Am. Chem. Soc. 1994, 116, 11938-11943.
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(1994)
J. Am. Chem. Soc
, vol.116
, pp. 11938-11943
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Wong, M.W.1
Pross, A.2
Radom, L.3
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17
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0001049639
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-
For an earlier study, see
-
For an earlier study, see: Dewar, M. J. S.; Olivella, S. J. Am. Chem. Soc. 1978, 100, 5290-5295.
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(1978)
J. Am. Chem. Soc
, vol.100
, pp. 5290-5295
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-
Dewar, M.J.S.1
Olivella, S.2
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18
-
-
76049089664
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-
2•, a (2Fα) = 86.2 G, g = 2.0039.
-
2•, a (2Fα) = 86.2 G, g = 2.0039.
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-
-
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22
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0000520481
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-
Martell, J. M.; Boyd, R. J.; Shi, Z. J. Phys. Chem. 1993, 97, 7208-7215.
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(1993)
J. Phys. Chem
, vol.97
, pp. 7208-7215
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Martell, J.M.1
Boyd, R.J.2
Shi, Z.3
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23
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33845554482
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Chatgilialoglu, C.; Ingold, K. U.; Scaiano, J. C. J. Am. Chem. Soc. 1982, 104, 5123-5127.
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(1982)
J. Am. Chem. Soc
, vol.104
, pp. 5123-5127
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Chatgilialoglu, C.1
Ingold, K.U.2
Scaiano, J.C.3
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24
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76049083729
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As would be expected for a reaction with a polar transition state the addition of perfluoroalkyl radicals to alkenes are faster in CH3CN than in Freon 113 with this solvent effect being greater for the more electron-rich alkenes. For example, the rate acceleration in CH3CN relative to the Freon solvent for addition to styrene by CF3• and CF3CF2CF2• is about a factor of 3, but for the addition of these two radicals to pentafluorostyrene the rate acceleration is only ca. 50, For comparison, Salikhov and Fischer22 have found that the rate of addition of the nucleophilic tert-butyl radical to (electron-deficient) acrylonitrile (IP, 10.9 eV) is also somewhat accelerated in more polar solvents, e.g, kadd (CH3CN)/kadd (c-C6H12), 2.8. In connection with the foregoing, we note that solvent effects on the rates of radical additions to alkenes
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24
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26
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76049100168
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Unpublished results from this laboratory.
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Unpublished results from this laboratory.
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27
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0000681444
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Avila, D. V.; Ingold, K. U.; Lusztyk, J.; Green, W. H.; Procopio, D. R. J. Am. Chem. Soc. 1995, 117, 2929-2930.
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(1995)
J. Am. Chem. Soc
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Avila, D.V.1
Ingold, K.U.2
Lusztyk, J.3
Green, W.H.4
Procopio, D.R.5
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28
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0028339426
-
-
2 and related groups) preferentially exhibit nucleophilic character, see: Buttle, L. A.; Motherwell, W. B. Tetrahedron Lett. 1994, 35, 3995-3998. For other studies on the intramolecular cyclization of α,α- difluoroalkenyl radicals, see: ref 5a.
-
2 and related groups) preferentially exhibit nucleophilic character, see: Buttle, L. A.; Motherwell, W. B. Tetrahedron Lett. 1994, 35, 3995-3998. For other studies on the intramolecular cyclization of α,α- difluoroalkenyl radicals, see: ref 5a.
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-
-
-
29
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76049112959
-
-
30 It is clear that one or two α-fluorine atoms do not make an alkyl radical more electrophilic than the corresponding nonfluorinated species and may even make them slightly more nucleophilic.
-
30 It is clear that one or two α-fluorine atoms do not make an alkyl radical more electrophilic than the corresponding nonfluorinated species and may even make them slightly more nucleophilic.
-
-
-
-
31
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76049128599
-
-
NIST Standard Reference Database 25. NIST Structures and Properties Database and Estimation Program 1991; U. S. Department of Commerce: Gaithersburg, MD.
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NIST Standard Reference Database 25. NIST Structures and Properties Database and Estimation Program 1991; U. S. Department of Commerce: Gaithersburg, MD.
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-
-
-
32
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76049124915
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-
Buckley, T.; Johnson, R., III; Huie, R.; Zhang, A.; Kuo, S.; Klemm, B. (NIST) Unpublished results.
-
Buckley, T.; Johnson, R., III; Huie, R.; Zhang, A.; Kuo, S.; Klemm, B. (NIST) Unpublished results.
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-
-
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33
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33645901990
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Rodriquez, C. F.; Sirois, S.; Hopkinson, A. C. J. Org. Chem. 1992, 57, 4869-4876.
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(1992)
J. Org. Chem
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, pp. 4869-4876
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Rodriquez, C.F.1
Sirois, S.2
Hopkinson, A.C.3
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34
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76049090856
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3 = 3.0 (see March, J. Advanced Organic Chemistry, 3rd ed., Wiley: New York, 1985; p 14).
-
3 = 3.0 (see March, J. Advanced Organic Chemistry, 3rd ed., Wiley: New York, 1985; p 14).
-
-
-
-
35
-
-
76049123391
-
-
3 is slightly more electron-withdrawing than F.
-
3 is slightly more electron-withdrawing than F.
-
-
-
-
36
-
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0028059645
-
-
Polar effects have also been demonstrated to be important in H-atom abstractions by perfluoroalkyl radicals, see: Dolbier, W. R, Jr, Rong, X. X. Tetrahedron Lett. 1994, 35, 6225-6228
-
Polar effects have also been demonstrated to be important in H-atom abstractions by perfluoroalkyl radicals, see: Dolbier, W. R., Jr.; Rong, X. X. Tetrahedron Lett. 1994, 35, 6225-6228.
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-
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37
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0001610327
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Kazanis, S.; Azarani, A.; Johnston, L. J. J. Phys. Chem. 1991, 95, 4430-4435.
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(1991)
Phys. Chem
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, pp. 4430-4435
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Kazanis, S.1
Azarani, A.2
Johnston, L.J.J.3
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33845552922
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Zhao, C.; Zhou, R.; Pan. H.; Jin, X.; Qu, Y.; Wu, C.; Jiang, X. J. Org. Chem. 1982, 47, 2009-2013.
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Zhao, C.1
Zhou, R.2
Pan, H.3
Jin, X.4
Qu, Y.5
Wu, C.6
Jiang, X.7
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40
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33845561336
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Olah, G. A.; Welch, J. T.; Vankar, Y. D.; Nojima, M.; Kerekes, I.; Olah, J. A. J. Org. Chem. 1979, 44, 3872-3881.
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Olah, G.A.1
Welch, J.T.2
Vankar, Y.D.3
Nojima, M.4
Kerekes, I.5
Olah, J.A.6
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41
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76049084719
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Bloshachitsa, F. A.; Burmakov, A. I.; Kunshenko, B. V.; Alekeeva, L. A.; Yagupolskii, L. M. J. Org. Chem., USSR 1982, 18, 679-684.
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Bloshachitsa, F.A.1
Burmakov, A.I.2
Kunshenko, B.V.3
Alekeeva, L.A.4
Yagupolskii, L.M.5
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Fortes, C. C.; Souto, C. R. O.; Okino, E. A. Synth. Commun. 1991, 21, 2045-2052.
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Synth. Commun
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Fortes, C.C.1
Souto, C.R.O.2
Okino, E.A.3
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0003905534
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5th ed, Longman Scientific and Technical: Essex, England
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Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.; Tatchell, A. R. Vogel's Textbook of Practical Organic Chemistry, 5th ed.; Longman Scientific and Technical: Essex, England, 1989; pp 692-693.
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Vogel's Textbook of Practical Organic Chemistry
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Furniss, B.S.1
Hannaford, A.J.2
Smith, P.W.G.3
Tatchell, A.R.4
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