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3F), À114.9 (m, 2F), À122.4 (s, 2F), À123.21 (s, 2F),
À124.0 (s, 2F), À126.6 (s, 2F).
on silica gel (petroleum ether:ethyl acetate = 12:1) to give
compound 18 (0.6 g, 95%) as a colorless oil. 1H NMR
(400 MHz, CDCl3) d: 1.38 (m, 2H), 1.51 (m, 2H), 1.61 (m,
2H), 2.05 (m, 2H), 2.44 (t, J = 3.2 Hz, 2H), 3.08 (d,
3.8. Toluene-4-sulfonic acid 6,6,7,7,8,8,9,9,10,10,
11,11,11-tridecanfluoro-undecyl ester (16)
J = 6.8 Hz, 4H), 5.13–5.20 (m, 4H), 5.81–5.91 (m, 2H). 19
F
NMR (376 MHz, CDCl3) d: À80.78 (s, 3F), À114.36 (m,
2F), À121.92 (m, 2F), À122.88 (m, 2F), À123.53 (s, 2F),
À126.14 (s, 2F). IR (thin film) 3080, 2947, 2800, 1644,
1419, 1240, 1145, 995, 920, 811, 707, 653 cmÀ1. MR m/z
100 (100), 41 (36), 42 (11), 68 (8), 69 (5), 55 (4). Anal.
Calcd. for C17H20F13N: C, 42.07; H, 4.15; N, 2.89. Found: C,
42.04; H, 4.12; N, 2.85%.
Alcohol 14 (2.72 g, 6.7 mmol) and toluene-4-sulfonyl
chloride (1.95 g, 10.2 mmol) were dissolved in CHCl3
(10 mL). Anhydrous pyridine (5 mL) was then added, and
the reaction mixture was stirred at room temperature until no
compound 14 was detected by TLC. The suspension was
decanted. The organic phase was washed three times with
water (30 mL), brine, dried over anhydrous MgSO4 and
concentrated in vacuo. The residue was purified by column
chromatography on silica gel (petroleum ether:ethyl acet-
ate = 10:1) to give compound 16 (2.40 g, 64%) as a white
solid. M.p. 42.5–43.5 8C; 1H NMR(300 MHz, CDCl3) d: 1.45
(m, 2H), 1.57 (m, 2H), 1.72 (m, 2H), 2.03 (m, 2H), 2.47 (s,
3H), 4.07 (t, J = 6.6 Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H), 7.82 (d,
J = 8.1 Hz, 2H). 19F NMR (282 MHz, CDCl3) d: À81.66 (s,
3F), À115.32 (s, 2F), À122.84 (s, 2F), À123.79 (s, 2F),
À124.43 (s, 2F), 127.01 (s,2F). IR(thin film) 2962, 1599,
1479, 1360, 1260, 1174, 1142, 1047, 959, 840, 816, 698,
653 cmÀ1. MS m/z 173 (100), 172 (49), 155 (68), 91 (92),
65(34), 55 (23), 41 (20). Anal. Calcd. for C18H17F13SO3: C,
38.58; H, 3.06. Found: C, 38.45; H, 3.21%.
3.11. N-(6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12, 13, 13,
13-Heptadecanfluorotridecyl)-N, N-diallylamine (19)
Compound 19 (1.10 g, 80%) was prepared as a colorless
oil from compound 17 (1.55 g, 2.3 mmol), diallylamine
(0.54 g, 5.5 mmol) and potassium carbonate (0.68 g,
4.9 mmol) using the same conditions as described for
compound 18. 1H NMR (400 MHz, CDCl3) d: 1.38 (m, 2H),
1.49 (m, 2H), 1.60 (m, 2H), 2.05 (m, 2H), 2.43 (t, J = 7.5 Hz,
2H), 3.08 (d, J = 6.5 Hz, 4H), 5.12–5.19 (m, 4H), 5.84 (m,
2H). 19F NMR (376 MHz, CDCl3) d: À80.76 (t, J = 11.3 Hz,
3F), À114.93 (m, 2F), À121.92 (m, 6F), À122.71 (s, 2F),
À123.53 (s, 2F), À126.10 (s, 2F). IR (thin film) 3080, 2946,
2801, 1643, 1419, 1241, 1208, 1149, 995, 920, 704,
655 cmÀ1. MS m/z 586 (M+ + 1, 4), 110 (100), 69 (3), 68 (4),
41 (28), 42 (8), 39 (6). Anal. Calcd. for C19H20F17N: C,
38.99; H, 3.44; N, 2.39. Found: C, 39.11; H, 3.42; N, 2.68%.
3.9. Toluene-4-sulfonic acid 6, 6, 7, 7, 8, 8, 9, 9, 10, 10,
11, 11, 12, 12, 13, 13, 13-heptadecanfluoro tridecyl ester
(17)
Compound 17 (1.75 g, 89%) was prepared as a white
solid from compound 15 (1.51 g, 3.0 mmol), TsCl (1.14 g,
6.0 mmol) and pyridine (3 mL) using the same conditions as
described for compounds 16. M.p. 50–52 8C. 1H NMR
(400 MHz, CDCl3) d: 1.42 (m, 2H), 1.55 (m, 2H), 1.68 (m,
2H), 2.03 (m, 2H), 2.45 (s, 3H), 4.05 (t, J = 3.4 Hz, 2H), 7.35
(d, J = 8.0 Hz, 2H), 7.79 (d, J = 8.0 Hz, 2H). 19F NMR
(376 MHz, CDCl3) d: À80.72 (t, J = 7.5 Hz, 3F), À114.41
(m, 2F), À121.73 (m, 6F), À122.69 (s, 2F), À123.50 (s, 2F),
À126.08 (s, 2F). IR (thin film) 2961, 2876, 1598, 1476,
1359, 1256, 1214, 1150, 1046, 961, 838, 814, 702,
656 cmÀ1. MS m/z 173 (82), 172 (48), 155 (62), 91
(100), 69 (22), 65 (38), 55 (24), 41 (24). Anal. Calcd. for
C20H17F17SO3: C, 36.38; H, 2.59. Found: C, 36.46; H,
2.81%.
3.12. N-(6,6,7,7,8,8,9,9,10,10,11,11,11-Tridecan-
fluoroundecyl)-N,N-diallylmethyl ammonium iodide (3)
A mixture of compound 18 (1.52 g 3.1 mmol), CH3I
(0.89 g, 6.3 mmol) and anhydrous CH3CN (8 mL) was
refluxed for 24 h under nitrogen. The solvent was removed
in vacuo. The residue was washed with anhydrous ether
(3 Â 10 mL) to give quaternary ammonium salt 3 (1.77 g,
90%) as a pale yellow dope. 1H NMR (400 MHz, CDCl3) d:
1.53 (m, 2H). 1.72 (m, 2H), 1.94 (m, 2H), 2.10 (m, 2H), 3.30
(s, 3H), 3.50 (m, 2H), 4.29 (m, 4H), 5.75–5.92 (m, 4H),
6.11–6.10 (m, 2H). 19F NMR (376 MHz, CDCl3) d: À80.83
(t, J = 9.8 Hz, 3F), À114.22 (s, 2F), À121.93 (m, 2F),
À122.90 (m, 2F), À123.46 (s, 2F), À126.15 (s, 2F). MS m/z
110 (9), 84 (100), 69 (6), 42 (23), 41 (51), 39 (22). IR (thin
film) 2954, 1640, 1467, 1203, 1145, 1050, 953, 732, 696,
653 cmÀ1. Anal. Calcd. for C18H23F13NI: C, 34.47; H, 3.70;
N, 2.23. Found: C, 34.27; H, 3.76, N, 2.21%.
3.10. N-(6,6,7,7,8,8,9,9,10,10,11,11,11-
Tridecanfluoroundecyl)-N,N-diallylamine (18)
A
suspension of toluene-4-sulfonate 16 (0.70 g,
3.13. N-(6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12, 13,
13, 13-Heptadecanfluorotridecyl)-N, N-diallylmethyl
ammonium iodide (4)
1.3 mmol), diallylamine (0.27 g, 2.7 mmol), and potassium
carbonate (0.35 g, 2.6 mmol) in anhydrous CH3CN (10 mL)
was heated to reflux for 24 h under nitrogen. The reaction
mixture was filtered. The filtrates were concentrated in
vacuo. The residue was purified by column chromatography
Compound 4 (0.95 g, 89%) was prepared from compound
19 (0.87 g, 1.5 mmol) and CH3I (1.20 g, 8.5 mmol) using the