C. Gentilini, M. Boccalon, L. Pasquato
FULL PAPER
(S)-[2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Hexadecafluoro-10-(2-{2-[2-(2- F, CF2), –123.0 (m, 2 F, CF2), –122.6–121.8 (m, 8 F, CF2), –120.4
(m, 2 F, CF CH O), –112.8 (m, 2 F, CF CH S) ppm. IR (film): ν
methoxyethoxy)ethoxy]ethoxy}ethoxy)decyl] Thioacetate (7b): To a
solution of 5b (previously coevaporated with dry toluene in order
to remove any trace of water; 1.15 g, 1.76 mmol) in dry dichloro-
methane (8 mL) was dropwise added trifluoromethanesulfonyl
chloride (0.56 mL, 5.28 mmol) under an argon atmosphere; the
mixture was then cooled to 0 °C, and a solution of triethylamine
(1.96 mL, 14.0 mmol) in dichloromethane (3 mL) was added drop-
wise; a yellow precipitate was observed. The mixture was stirred at
room temperature for 18 h. Another portion of trifluoromethanes-
ulfonyl chloride (0.18 mL, 1.76 mmol) and triethylamine (1.2 mL,
8.8 mmol) was added at 0 °C. The reaction was monitored by TLC;
when the reagent was completely converted, the precipitate was fil-
tered off, the solvent was removed under reduced pressure and the
residue was redissolved in N,NЈ-dimethylformamide under an ar-
gon atmosphere. Potassium thioacetate (0.4 g, 3.5 mmol) was
added to the solution. The mixture was protected from light and
stirred at room temperature for 4 h. Then, ethyl acetate (30 mL)
and water (30 mL) were added, and the phases were separated. The
aqueous phase was extracted with ethyl acetate (3ϫ30 mL); the
organic layer was washed with water (8ϫ30 mL) and brine (30 mL)
and dried with Na2SO4. After solvent removal, the crude product
was purified by flash chromatography (chloroform to chloroform/
methanol, 98.5:1.5) to yield a brown oil (0.54 g). Yield: 40%. 1H
NMR (400 MHz, CDCl3): δ = 2.43 (s, 3 H, CH3C=O), 3.37 (s, 3
H, CH3O), 3.53 (m, 2 H, CH2O), 3.64 (m, 14 H, CH2O, CH2S),
3.78 (m, 2 H, CH2O), 4.03 (t, JH,F = 13.91 Hz, 2 H, CH2CF2)
ppm. 13C NMR (67.8 MHz, CDCl3): δ = 29.3 (t, JC,F = 23.5 Hz,
SCH2CF2), 30.1 (CH3C=O), 58.9 (CH3O), 67.8 (t, JC,F = 25.9 Hz,
CF2CH2O), 70.4–72.2 (CH2O), 110.3–115.5 (m, CF2), 191.7 (C=O)
ppm. 19F NMR (282 MHz, CDCl3): δ = –124.4 (m, 2 F, CF2),
–123.0 (m, 2 F, CF2), –123.0–121.8 (m, 8 F, CF2), –120.4 (m, 2 F,
˜
2
2
2
2
= 2873 (s), 1716 (s, νC=O), 1459 (m), 1350 (m), 1294 (m), 1212 (s,
νC–F), 1128 (s), 1140 (s), 954 (m), 854 (m) cm–1. MS (ESI, CH3CN):
m/z = 909.2, 953.3, 997.3, 1041.3, 1085.3, 1129.3, 1173.4 [M +
Na]+.
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Hexadecafluoro-10-{2-[2-(2-methoxy-
ethoxy)ethoxy]ethoxy}decane-1-thiol (1a): To a solution of 7a
(0.616 g, 0.924 mmol) in dichloromethane (60 mL) and methanol
(34 mL, 0.831 mol) was dropwise added acetyl chloride (22.6 mL,
0.318 mol) at 0 °C. The mixture was stirred at room temperature
for 12 h. Another two portions of acetyl chloride (22.6 mL each)
was added over 10 h, and the mixture was left to stir for 12 h. Then,
dichloromethane (50 mL) and water (50 mL) were added; the
phases were separated, and the aqueous phase was extracted with
dichloromethane (3ϫ20 mL). The organic layer was washed with
water (6 ϫ 40 mL) and dried with Na2SO4. The solvent was re-
moved under reduced pressure to yield a yellow oil (540 mg). Yield:
1
94%. Overall yield from 3a: 19%. H NMR (400 MHz, CDCl3): δ
= 1.74 (t, J = 8.78 Hz, 1 H, SH), 3.1 (ddt, JH,F = 16.84 Hz, JH,H
= 8.78 Hz, 2 H, CH2S), 3.36 (s, 3 H, CH3O), 3.53 (m, 2 H, CH2O),
3.64 (m, 8 H, CH2O), 3.77 (m, 2 H, CH2O), 4.03 (t, JH,F
=
14.28 Hz, 2 H, OCH2CF2) ppm. 13C NMR (100 MHz, CDCl3): δ
= 25.65 (t, JC,F = 25.37 Hz, CF2CH2S), 58.92 (CH3O), 68.27 (t,
JC,F = 25.37 Hz, CF2CH2O), 70.68 (CH2O), 71.87 (CH2O), 72.26
(CH2O), 108.49 (m, CF2), 110.82 (m, CF2), 111.12 (m, CF2), 115.43
(m, CF2), 118.18 (m, CF2) ppm. 19F NMR (282 MHz, CDCl3): δ
= –124.0 (m, 2 F, CF2), –123.0 (m, 2 F, CF2), –122.6–121.6 (m, 8
F, CF2), –120.2 (m, 2 F, CF2CH2O), –113.4 (m, 2 F, CF2CH2S)
ppm. IR (film): ν = 2882 (s), 2550 (w, νS–H), 1456 (m), 1352 (m),
˜
1210 (s, νC–F), 1145 (s), 855 (m), 649 (m) cm–1. MS (ESI, CH3CN):
m/z = 647.1 [M + Na]+, 663.1 [M + K]+.
CF CH O), –113.2 (m, 2 F, CF CH S) ppm. IR (film): ν = 3411
˜
2
2
2
2
(w), 2881 (s), 1766 (m), 1716 (s, νC=O), 1456 (m), 1352 (m), 1212
(s, νC–F), 1149 (s), 958 (m), 855 (m), 702 (m) cm–1. MS (ESI,
CH3OH): m/z = 733.1 [M + Na]+. C21H26F16O6S (710.47): calcd.
C 35.50, H 3.69, S 4.51; found C 35.03, H 3.60, S 4.45.
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Hexadecafluoro-10-(2-{2-[2-(2-meth-
oxyethoxy)ethoxy]ethoxy}ethoxy)decane-1-thiol (1b): Starting from
7b (0.23 g) and 1b (0.20 g). Yield: 95%. Overall yield from 3b: 23%.
1H NMR (400 MHz, CDCl3): δ = 1.74 (t, J = 9.15 Hz, 1 H, SH),
3.15 (ddt, JH,F = 16.84 Hz, JH,H = 9.15 Hz, 2 H, CH2S), 3.37 (s, 3
H, CH3O), 3.55 (m, 2 H, CH2O), 3.64 (m, 12 H, CH2O), 3.77 (m,
2 H, CH2O), 4.03 (t, JH,F = 13.92 Hz, 2 H, OCH2CF2) ppm. 13C
NMR (100 MHz, CDCl3): δ = 25.69 (t, JC, F = 25.37 Hz,
CF2CH2S), 58.99 (CH3O), 68.29 (t, JC,F = 24.60 Hz, CF2CH2O),
70.56 (CH2O), 71.89 (CH2O), 72.31 (CH2O), 108.44 (m, CF2),
110.87 (m, CF2), 111.12 (m, CF2), 115.61 (m, CF2), 118.17 (m,
CF2) ppm. 19F NMR (282 MHz, CDCl3): δ = –124.2 (m, 2 F, CF2),
–123.2 (m, 2 F, CF2), –122.6–121.8 (m, 8 F, CF2), –120.4 (m, 2 F,
(S)-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Hexadecafluoro-10-{2-[2-(2-{2-[2-
(2-methoxyethoxy)ethoxy]ethoxy}ethoxy)ethoxy]ethoxy}decyl)
Thioacetate (7c): Starting from 5c (0.45 g) and 7c (0.30 g). The
crude product was purified by flash chromatography (chloroform
to chloroform/methanol, 98.5:1.5). Yield: 62 %. 1H NMR
(400 MHz, CDCl3): δ = 2.44 (s, 3 H, CH3C=O), 3.37 (s, 3 H,
CH3O), 3.54 (m, 2 H, CH2O), 3.64 (m, 22 H, CH2O + CH2S), 3.78
(m, 2 H, CH2O), 4.0 (t, JH,F = 13.92 Hz, 2 H, CH2CF2) ppm. 13C
NMR (100 MHz, CDCl3): δ = 29.4 (t, JC,F = 23.7 Hz, SCH2CF2),
30.2 (CH3C=O), 59.0 (CH3O), 68.2 (t, JC,F = 24.5 Hz, CF2CH2O),
70.5–72.3 (CH2O), 111.2–115.8 (m, CF2), 193.7 (C=O) ppm. IR
CF CH O), –113.6 (m, 2 F, CF CH S) ppm. IR (film): ν = 2882
˜
2
2
2
2
(s), 2550 (w, νS–H), 1456 (m), 1352 (m), 1220 (s, νC–F), 1144 (s), 855
(m), 648 (m) cm–1. MS (ESI, CH3CN): m/z = 691.1 [M + Na]+,
707.1 [M + K]+.
(film): ν = 3391 (w), 2886 (s), 1766 (m), 1716 (s, νC=O), 1457 (m),
˜
1350 (m), 1212 (s, νC–F), 1134 (s), 958 (m), 854 (m), 702 (m) cm–1.
MS (ESI, CH3OH): m/z = 821.2 [M + Na]+. C25H34F16O8S
(798.57): calcd. for C 37.60, H 4.29, S 4.02; found C 37.25, H 4.20,
S 3.95.
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Hexadecafluoro-10-{2-[2-(2-{2-[2-(2-
methoxyethoxy)ethoxy]ethoxy}ethoxy)ethoxy]ethoxy}decane-1-thiol
(1c): Starting from 7c (0.30 g) and 1c (0.27 g). Yield: 94%. Overall
1
(S)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Hexadecafluoro-10-(methoxy- yield from 3c: 25%. H NMR (400 MHz, CDCl3): δ = 1.72 (t, J =
PEG550) Thioacetate (7d): Starting from 5d (3.00 g) and 7d 9.15 Hz, 1 H, SH), 3.11 (ddt, JH,F = 16.84 Hz, JH,H = 9.16 Hz, 2
(2.16 g). The crude product was purified by flash chromatography
(chloroform to chloroform/methanol, 97:3). Yield: 65%. H NMR
H, CH2S), 3.37 (s, 3 H, CH3O), 3.52 (m, 2 H, CH2O), 3.62 (m, 20
H, CH2O), 3.75 (m, 2 H, CH2O), 4.01 (t, JH,F = 13.92 Hz, 2 H,
1
(400 MHz, CDCl3): δ = 2.43 (s, 3 H, CH3C=O), 3.37 (s, 3 H, OCH2CF2) ppm. 13C NMR (100 MHz, CDCl3): δ = 25.62 (t, JC,F
CH3O), 3.54–3.78 (m, 42 H, CH2O), 4.0 (t, JH,F = 13.92 Hz, 2 H, = 26.13 Hz, CF2CH2S), 58.90 (CH3O), 68.24 (t, JC,F = 24.59 Hz,
CH2CF2) ppm. 13C NMR (100 MHz, CDCl3): δ = 29.2 (t, JC,F
23.8 Hz, SCH2CF2), 30.0 (CH3C=O), 58.9 (CH3O), 68.1 (t, JC,F
=
=
CF2CH2O), 70.50 (CH2O), 71.86 (CH2O), 72.25 (CH2O), 108.43
(m, CF2), 110.82 (m, CF2), 111.13 (m, CF2), 115.40 (m, CF2),
24.6 Hz, CF2CH2O), 70.2–72.2 (CH2O), 110.7–115.8 (m, CF2), 118.24 (m, CF2) ppm. 19F NMR (282 MHz, CDCl3): δ = –124.2
191.7 (C=O) ppm. 19F NMR (282 MHz, CDCl3): δ = –124.4 (m, 2 (m, 2 F, CF2), –123.2 (m, 2 F, CF2), –122.6–121.8 (m, 8 F, CF2),
3312
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Eur. J. Org. Chem. 2008, 3308–3313