Perfluoroalkylquinones by Perfluoroalkyl Radicals – Enthalpic and Polar Effects
FULL PAPER
CCl
F, F
), –106.0 to –106.2 (m, 2 F, F
ppm. C13 (368.19): calcd. C 42.41, H 2.46, F 46.44, O 8.69;
found C 42.30, H 2.45, F 46.50, O 8.66.
Benzoquinone 5: M.p. 42–44 °C. GC-MS: m/z = 500 [M] , 485, 480,
3
F): δ = –127.8 to –128.0 (m, 2 F, F
), –122.9 to –123.7 (m, 2 F, F ), –121.4 to –121.5 (m, 2 F,
), –82.5 (t, J = 9.8 Hz, 3 F, F
ε 3
), –124.4 to –124.9 (m, 2 CDCl ): δ = 2.34 (s, 3 H), 2.58–2.69 (m, 1 H), 2.88–3.00 (m, 2 H),
δ
γ
3.11–3.16 (m, 1 H), 3.70–3.76 (br., 1 H), 7.73–7.76 (m, 2 H), 8.06
F
β
α
ζ
)
(dd, J = 6.5, J = 2.5 Hz, 1 H), 8.11 (dd, J = 6.5, J = 2.5 Hz, 1 H)
1
9
H
9
F
9
O
2
ppm. F NMR (470 MHz, CCl
), –124.3 to –124.6 (m, 2 F, F
122.6 to –123.1 (m, 2 F, F ), –114.3 to –115.1 (m, 2 F, F ), –81.8
3
F): δ = –126.9 to –127.4 (m, 2 F,
F
ε
δ
), –123.7 to –124.1 (m, 2 F, F ), –
γ
+
·
β
α
1
ζ 21 12 13 3
(t, J = 9.8 Hz, 3 F, F ) ppm. C H F NO (573.30): calcd. C
2
3
31, 186, 119, 69. H NMR (500 MHz, CDCl
3
): δ = 2.27 (t, J =
.8 Hz, 3 H), 4.02 (s, 3 H), 4.03 (s, 3 H) ppm. 19F NMR (470 MHz,
43.99, H 2.11, F 43.08, N 2.44, O 8.37; found C 43.85, H 2.11, F
3.13, N 2.43, O 8.40.
4
CCl
3
F): –127.8 to –128.0 (2 m, 2 F, F ), –124.4 to –124.9 (m, 2 F,
), –122.9 to –123.7 (m, 2 F, F ), –121.4 to –121.5 (m, 2 F, F ), –
05.8 to –106.0 (m, 2 F, F ), –82.0 (t, J = 9.8 Hz, 3 F, F ) ppm.
(500.21): calcd. C 36,02, H 1.81, F 49.38, O 12.79;
found C 36,12, H 1.80, F 49.25, O 12.89.
Naphthoquinone 6: Oil. GC-MS: m/z = 506 [M] , 486, 456, 267,
ε
F
δ
γ
β
+
·
Naphthoquinone 12: Oil. GC-MS: m/z = 590 [M] , 534, 490, 321,
1
α
ζ
1
2
0
1
3
7
3
57, 200, 187, 172, 104, 76, 69. H NMR (500 MHz, CDCl ): δ =
15 9 13 4
C H F O
.86 (t, J = 7.0 Hz, 3 H), 1.24–1.34 (m, 4 H), 1.66–1.73 (m, 1 H),
.81–1.90 (m, 1 H), 2.32–2.43 (m, 1 H), 2.82–2.97 (m, 1 H), 3.67–
.76 (br., 1 H), 4.14 (s, 3 H), 7.69 (td, J = 1.7, J = 7.3 Hz, 1 H),
+
·
1
237, 151, 104, 76, 69. H NMR (500 MHz, CDCl
3
): δ = 4.29 (s, 3
19
.72 (t, J = 1.7, J = 7.3 Hz, 1 H), 8.03–8.08 (m, 2 H) ppm.
F): δ = –126.6 to –127.5 (m, 2 F, F
), –124.0 to –124.3 (m, 2 F, F ), –121.4 to –
), –114.7 (q, J = 272 Hz, 2 F, F ), –82.1 (t, J =
) ppm. C23 (590.37): calcd. C 46.79, H
.24, F 41.83, O 8.13; found C 46.67, H 3.23, F 41.96, O 8.12.
F
H), 7.73 (td, J = 1.4, J = 7.6 Hz,1 H), 7.78 (td, J = 1.4, J = 7.6 Hz,
NMR (470 MHz, CCl
to –125.0 (m, 2 F, F
1
1
3
3
ε
), –124.7
1
7
1
H), 8.04 (dd, J = 1.0, J = 7.6 Hz, 1 H), 8.09 (dd, J = 1.0, J =
.6 Hz,1 H) ppm. 19F NMR (470 MHz, CCl
F): δ = –127.3 to –
27.5 (m, 2 F, F ), –124.1 to –123.6 (m, 2 F, F ), –123.0 to –123.5
), –121.9 to –122.2 (m, 2 F, F ), –107.6 to –107.9 (m, 2
), –82.1 (t, J = 9.8 Hz, 3 F, F ) ppm. C17 (506.21):
δ
γ
3
21.5 (m, 2 F, F
0.6 Hz, 3 F, F
β
α
ε
δ
19 13 3
H F O
ζ
(m, 2 F, F
γ
β
F, F
α
ζ
7 13 3
H F O
+
·
calcd. C 40.34, H 1.39, F 48.79, O 9.48; found C 40.42, H 1.39, F
8.63, O 9.51.
Naphthoquinone 7: Oil. GC-MS: m/z = 460 [M] , 445, 431, 241,
Naphthoquinone 13: M.p. 86–88 °C. GC-MS: m/z = 573 [M] , 304,
1
4
3
240, 214, 200, 172, 104, 76, 69. H NMR (500 MHz, CDCl ): δ =
+
·
2.55–2.61 (m, 1 H), 2.83 (d, J = 6.6 Hz,1 H), 2.86 (d, J = 6.6 Hz,1
H), 3.11–3.16 (m, 1 H), 3.70–3.76 (br., 1 H), 4.28 (s, 3 H), 7.71–7.76
1
1
3
3
3
57, 76, 69. H NMR (500 MHz, CDCl ): δ = 1.32 (t, J = 7.0 Hz,
1
9
(
=
1
m, 2 H), 8.05–8.08 (m, 2 H) ppm. F NMR (470 MHz, CCl
–127.1 to –127.4 (m, 2 F, F ), –124.4 to –124.6 (m, 2 F, F
23.8 to –124.1 (m, 2 F, F ), –122.7 to –123.1 (m, 2 F, F ), –114.6
), –81.9 (t, J = 9.8 Hz, 3 F, F ) ppm.
3
F): δ
H), 1.63–1.84 (m, 4 H), 2.15–2.28 (m, 2 H), 2.82–2.94 (m,1 H),
.07–3.21 (m, 1 H), 3.73–3.79 (br., 1 H), 7.26 (s, 1 H), 8.17–8.21
ε
δ
), –
γ
β
(
m, 2 H), 8.53 (dd, J = 2.4, J = 5.5 Hz,1 H), 8.57 (dd, J = 2.4, J =
19
to –115.0 (m, 2 F, F
α
ζ
5
1
2
.5 Hz, 1 H) ppm. F NMR (470 MHz, CCl
27.4 (m, 2 F, F ), –125.7 to –125.9 (m, 2 F, F
17 9 2
72 Hz, 2 F, F ), –82.5 (t, 3 F, J = 6.6 Hz, F ) ppm. C20H F O
3
F): δ = –127.2 to –
C
21
H
12
F13NO
2
(557.30): calcd. C 45.26, H 2.17, F 44.32, N 2.51,
γ
β
), –114.3 (q, J =
O 5,74; found C 45.45, H 2.17, F 44.38, N 2.50, O 5,73.
α
δ
(
460.33): calcd. C 52.18, H 3.72, F 37.14, O 6.95; found C 52.10,
H 3.73, F 37.22, O 6.96.
Naphthoquinone 8: Oil. GC-MS: m/z = 474 [M] , 459, 445, 405,
[
1] S. Patai, Z. Rappoport, The Chemistry of the Quinonoid Com-
+
·
pounds, Wiley, Chichester, 1988.
55, 157, 76, 69. 1H NMR (500 MHz, CDCl
[2] F. Coppa, F. Fontana, F. Minisci, M. C. Nogueira Barbosa, E.
2
7
1
3
3
): δ = 0.84 (t, J =
Vismara, Tetrahedron 1991, 47, 7343.
.0 Hz, 3 H), 1.14–1.34 (m, 4 H), 1.76–1.83 (m, 1 H), 1.92–2.00 (m,
H), 2.24 (s, 3 H), 2.37–2.52 (m, 1 H), 2.93–3.10 (m, 1 H), 3.24–
[
[
[
3] J. A. Gladysz, D. P. Curran, I. T. Horvath (Eds.), Handbook of
Fluorous Chemistry, Wiley-VCH, Weinheim, 2004.
4] A. Dardin, J. B. Cain, J. M. DeSimone, C. S. Johnson, E. T.
Sanulski, Macromolecules 1997, 30, 3592.
1
9
.38 (br., 1 H), 7.64–7.68 (m, 2 H), 8.02–8.07 (m, 2 H) ppm.
F): δ = –127.3 to –127.5 (m, 2 F, F ), –125.7
), –114.9 (q, J = 269 Hz, 2 F, F ), –82.6 (t, J
) ppm. C21 (474.36): calcd. C 53.17, H
.04, F 36.05, O 6.75; found C 52.99, H 4.05, F 36.12, O 6.73.
F
NMR (470 MHz, CCl
to –125.9 (m, 2 F, F
9.6 Hz, 3 F, F
3
γ
β
α
5] W. R. Sanderson, in: J. H. Clark, D. J. Macquarrie (Eds.),
Handbook of Green Chemistry and Technology, Blackwell, Ox-
ford, 2002, p. 256.
=
4
δ
19 9 2
H F O
+
·
[6] W. R. Dolbier, Chem. Rev. 1996, 96, 1557.
[7] A. Bravo, H. R. Bjørsvik, F. Fontana, L. Liguori, A. Mele, F.
Minisci, J. Org. Chem. 1997, 62, 7128.
Naphtoquinone 9: Oil. GC-MS: m/z = 518 [M] , 476, 458, 255, 198,
1
1
1
2
3
04, 76, 69. H NMR (500 MHz, CDCl ): δ = 1.48–1.66 (m, 2 H),
.82–1.90 (m, 1 H), 1.97 (s, 3 H), 1.99–2.06 (m, 1 H), 2.23 (s, 3 H),
.37–2.54 (m, 1 H), 2.90–3.08 (m, 1 H), 3.24–3.39 (br., 1 H), 4.01
[
8] D. F. McMillan, D. M. Golden, Ann. Rev. Phys. Chem. 1982,
3, 493.
9] B. S. Evans, E. Whittle, Int. J. Chem. Kinet. 1981, 13, 59.
3
(
t, J = 6.6 Hz, 2 H), 7.65–7.69 (m, 2 H), 8.00–8.06 (m, 2 H) ppm.
[
1
9
F NMR (470 MHz, CCl
25.5 to –125.9 (m, 2 F, F
t, J = 9.3 Hz, 3 F, F ) ppm. C22
H 3.69, F 32.99, O 12.35; found C 51.02, H 3.71, F 33.11, O 12.32.
3
F): δ = –127.0 to –127.3 (m, 2 F, F
), –114.7 (q, J = 272 Hz, 2 F, F ), –82.3
(518.37): calcd. C 50.97,
γ
), – [10] O. Dobis, S. W. Benson, J. Phys. Chem. A 1997, 101, 6030.
1
β
α
[11] L. Liguori, H. R. Bjorsvik, A. Bravo, F. Fontana, F. Minisci,
(
δ
H
19
F
9
O
4
Chem. Commun. 1997, 16, 1501.
[
[
[
12] F. Minisci, Substituent Effects in Free Radical Chemistry (Ed.:
H. G. Viehe), Reidel Publishing Co., Dordrecht, 1986, p. 391.
13] A. Citterio, F. Minisci, O. Porta, G. Sesana, J. Am. Chem. Soc.
+
·
Naphthoquinone 10: Oil. GC-MS: m/z = 448 [M] , 430, 417, 229,
1
1
98, 171, 104, 76, 69. H NMR (500 MHz, CDCl
H), 2.49–2.66 (m, 1 H), 2.87–3.05 (m, 1 H), 3.63–3.72 (br., 1 H),
.44 (d, J = 7.5 Hz, 2 H,), 7.70–7.75 (m, 2 H), 8.04–8.12 (m, 2 H)
3
): δ = 2.27 (s, 3
1977, 99, 7960.
14] F. Antonietti, A. Mele, F. Minisci, C. Punta, F. Recupero, F.
4
Fontana, J. Fluorine Chem. 2004, 125, 205.
[15] D. V. Avila, K. U. Ingold, J. Lusztyk, W. R. Dolbier, H.-Q. Pan,
19
ppm. F NMR (470 MHz, CCl
), –125.3 to –125.6 (m, 2 F, F ), –114.2 (q, J = 272 Hz, 2 F, F
2.1 (t, J = 9.2 Hz, 3 F, F ) ppm. C18 (448.28): calcd. C
8.23, H 2.92, F 38.14, O 10.71; found C 48.11, H 2.91, F 38.09,
3
F): δ = –127.0 to –127.2 (m, 2 F,
M. Miur, J. Am. Chem. Soc. 1994, 116, 99.
F
γ
β
α
), –
[
16] Landolt-Börnstein (New Series), Radical Reaction Rates in Li-
quids (Ed.: H. Fisher), Springer-Verlag, Berlin, 1984, vol. 13,
part a, p. 160.
8
4
δ
13 9 3
H F O
O 10.72.
[
17] G. F. Pedulli, personal communication. From the formation en-
+
·
–1
Naphthoquinone 11: M.p. 114–115 °C. GC-MS: m/z = 557 [M] ,
thalpies of hydroquinone (–64.4 kcalmol ) and benzoquinone
1
–1
5
38, 530, 288, 224, 198, 169, 119, 104, 76, 69. H NMR (500 MHz,
(–29.4 kcalmol ) and the BDE of the O–H bond of hydroqui-
Eur. J. Org. Chem. 2005, 4434–4440
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