C. Naud et al. / Journal of Fluorine Chemistry 104 (2000) 173±183
177
NMR: d 2.3 (s, 3H, CH3); 2.4 (m, 2H, CF2CH2CH2); 3.05
(m, 2H, CH2SC(O)CH3). 13C NMR: d 20.55 (s,CH2 S),
30.72 (s, CH3); 31.9 (m, CH2 CF2); between 105 and 128
broad peak corresponding to the ¯uorinated carbons; 195.14
(s, C=O). Similar spectroscopic data have been observed for
2-per¯uoroalkyundecanethiolacetates.
C10H5F17S: C,25.01; H, 1.05; F, 67.26; S, 6.67. Found:
C, 24.85; H, 1.02; F, 66.93; S, 6.61%.
2.4.1.4. 12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-
Henreicosafluorododecanethiol F(CF2)10(CH2)2SH. White
1
solid, yield: 8.12 g, 70%. mp 688C. H NMR: as for the
Step 2: F(CF2)n(CH2)mSC(O)CH3 was dissolved in
methanol (50 ml for 0.01 mole of starting product) in a
250 ml three-necked ¯ask, equipped with a re¯ux condenser
and a dropping funnel containing 1.5 eq of NaOH in a
minimum of water, and kept under nitrogen at room tem-
perature. The aqueous solution of NaOH was added to the
reaction ¯ask and the mixture was allowed to re¯ux for 3 h.
The reaction was cooled in an ice bath and poured with
stirring into a 250 ml beaker containing ice water (100 ml),
concentrated HCl (10 ml) and diethyl ether (150 ml). The
ethereal layer was separated and washed with saturated
aqueous NaCl (3 mlÂ150 ml), dried over anhydrous sodium
sulfate, ®ltered and then vacuum evaporated. The crude
product was puri®ed by distillation of the thiol under
vacuum for n4, 6, 8 m2 and n6 m11. For n10
m2 and for n8, 10 m11 the disul®des are separated
from the corresponding thiols, taking advantage of the poor
solubility of the disul®des in ethanol (1 g of crude product
for 50 ml of ethanol, except for n10, m11: 100 ml).
Indicated yields are relative to the starting 1-iodoper¯uoro-
alkylalkane.
preceding compound. 19F NMR: d 126.77 (m, 2F,
CF2CF3); 124.16 (m, 2 F, CF2CF2CF3); 123.33 (m, 2
F, CF2ꢀCF26CH2); 122.39 (m, 10 F, ꢀCF23CF2CH2);
115.07 (m, 2 F, CF2CH2); 81.42 (m, 3 F, CF3). MS
(EI, 70 eV, 29.28C) (m/z): 579 (10) (M) ; 69 (8) (CF3) ; 61
(20) (C2H5S) ; 47 (100) (CH3S) .
2.4.1.5. 15,15,15,14,14,13,13,12,12-Nonafluoro-
pentadecanethiol F(CF2)4(CH2)11SH. Colorless liquid. bp:
858C 0.1 mmHg. 1H NMR: d 1.3 (m, 15 H, (CH2)7 and SH);
1.55 (m, 4H, CH2CH2CF2 and 2H, CH2CH2SH); 2 (m, 2H,
CH2CF2); 2.52 (td, 2H, JH JH
7.3 Hz, CH2SH). 19
F
H
SH
NMR: d 126.61 (m, 2F, CF2CF3); 125.07 (m, 2F,
CF2CF2CH2); 115.19 (m, 2F, CF2CH2); 81.57 (m, 3F,
CF3). MS (FAB , matrix NBA) (m/z): 405 (10) (M H) ;
403 (6.6) (C4F9(CH2)10CS) ; 55 (100) (C4H7) .
2.4.1.6. 17,17,17,16,16,15,15,14,14,13,13,12,12-Trideca-
fluoroheptadecanethiol F(CF2)6(CH2)11SH. Colorless
1
liquid. bp: 1158C 0.1 mmHg. H NMR: d 1.3 (m, 15 H,
(CH2)7 and SH); 1.55 (m, 4H, CH2CH2CF2 and 2H,
CH2CH2SH);
2 (m, 2H, CH2CF2); 2.52 (td, 2H,
JH JH
7.3 Hz, CH2SH). 19F NMR: d 126.7 (m,
H
SH
2.4.1.1. 6,6,6,5,5,4,4,3,3- Nonafluorohexanethiol F(CF2)4-
(CH2)2SH. Colorless liquid, yield: 3.36 g, 60%. bp: 358C
10 mmHg. 1H NMR: d 1.6 (t, 1H, J8 Hz, SH); 2.4 (m, 2H,
CF2CH2CH2); 2.75 (m, 2H, CH2SH).19F NMR: d 126.83
(m, 2F, CF2CF3); 125.18 (m, 2F, CF2CF2CH2); 115.4
(m, 2F, CF2CH2); 81.9 (m, 3F, CF3). MS (EI, 70 eV,
2F, CF2CF3); 125.13 (m, 2F, CF2CF2CF3); 123.45 (m,
2F, CF2(CF2)2CH2); 122.5 (m, 2 F, CF2 CF2CH2); 115
(m, 2F, CF2CH2); 81.34 (m, 3F, CF3). MS (FAB , matrix
NBA) (m/z): 505 (10) (M H) ; 503 (6.6)
(C6F13(CH2)10CS) ; 55 (100) (C4H7) .
24.18C) (m/z): 280 (54.5) (M) ꢁ; 69 (21) (CF3) ; 61 (20)
(C2H5S) ; 47 (100) (CH3S) .
2.4.1.7. 19,19,19,18,18,17,17,16,16,15,15,14,14,13,13,12,
12-heptadecafluorononadecanethiol F(CF2)8(CH2)11SH.
1
White solid, yield: 6.06 g, 50%. mp: 49.78C. H NMR: as
for the preceding compound. 19F NMR: d 126.57 (m, 2F,
CF2CF3); 123.99 (m, 2F, CF2CF2CF3); 123.17 (m, 2F,
2.4.1.2. 8,8,8,7,7,6,6,5,5,4,4,3,3-Tridecafluorooctanethiol
F(CF2)6(CH2)2SH. Colorless liquid, yield: 4.5 g, 60%. bp:
618C 10 mmHg. 1H NMR: as for the preceding compound.
19F NMR: d 126.94 (m, 2F, CF2CF3); 124.55 (m, 2 F,
CF2CF2CF3); 124 (m, 2F, CF2(CF2)2CH2); 122.6 (m, 2
F, CF2CF2CH2); 115.5 (m, 2 F, CF2CH2); 81.64 (m, 3 F,
CF2(CF2)4CH2);
114.86 (m, 2F, CF2CH2); 81.13 (m, 3F, CF3). MS
122.37 (m, 6 F, (CF2)3CF2CH2);
(FAB , matrix NBA) (m/z): 605 (10) (M H) ; 603
(6.6) (C8F17(CH2)10CS) ; 55 (100) (C4H7) . HRMS:
caldfor 605, 1171(M H) . Obsd for C19H22F17S: 605,
1125.
CF3). MS (EI, 30 eV, 48.78C) (m/z): 380 (58.2) (M) ꢁ; 69
(29) (CF3) ; 61 (53.6) (C2H5S) ; 47 (100) (CH3S) .
2.4.1.3. 10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-Heptadeca-
fluorodecanethiol F(CF2)8(CH2)2SH. Colorless liquid,
2.4.1.8. 21,21,21,20,20,19,19,18,18,17,17,16,16,15,15,
14,14,13,13,12,12-Heneicosafluoroheneicosanethiol
F(CF2)10(CH2)11SH. White solid, yield: 5.65 g, 40%. mp:
73.48C. 1H NMR: as for the preceding compound. 19F
NMR: d 126.77 (m, 2F, CF2CF3); 124.16 (m, 2F,
CF2CF2CF3); 123.33 (m, 2F, CF2(CF2)6CH2); 122.39
(m, 10 F, (CF2)5CF2CH2); 115.07 (m, 2F, CF2CH2);
81.42 (m, 3F, CF3). MS (FAB , matrix NBA) (m/z):
1
yield: 7.68g, 80%. bp: 898C 10 mm Hg. H NMR: as for
the preceding compound. 19F NMR: d 127.1 (m, 2F,
CF2CF3); 124.37 (m, 2F, CF2CF2CF3); 123.67 (m, 2
F, CF2(CF2)4CH2); 122.83 (m, 6 F, ꢀCF23CF2CH2);
115.55 (m, 2F, CF2CH2); 81.61 (t, 3 F, CF3). MS (EI,
30 eV, 48.78C) (m/z): 480 (55) (M) ꢁ; 69 (21) (CF3) ; 61
705 (20) (M H) ; 703 (11, 4) (C10F21(CH2)10CS) ; 55
(54) (C2H5S) ; 47 (100) (CH3S) . Anal. Calc. for