R. Winter et al. / Journal of Fluorine Chemistry 107 (2001) 23±30
27
1
H NMR spectrum: d 1:1±2.3 (1.33 and 2.07 ppm(s);
vessel was heated at 658C for 17 h. The product was distilled
at reduced pressure to provide 2.13 g (21% yield) of
SF CH CHCl(CH ) OH; bp 95±978C at 0.04 mm Hg.
1
1
6
7.3H), d2 4:10(t; 2H, J 6:4 Hz; CH OAc), d3 4:9±
2
.2 (m, 3H, CH=CH ), d1 2:02(s; CH CO), d2 4:05 (t;
2
3
5
2
2 8
19
J 6:5 Hz; CH OAc), d3 4:75±6.10 (m; 3H, CH=CH )
F NMR spectrum (CDCl , CCl3F 0): AB -spectrum
2
2
3
4
�
� 1
1
[
29]. Infrared spectrum:
n
:
1743 cm
;
n
:
[13,14], j 83:10 ppm (9 lines, 1.0 F); j 65:9 ppm
C=O
C=C
A
B
�
1
� 1
1
double-bond vibration at 1642 cm
642 cm ; nC=O: 1750 cm ; nC=C: 1645 cm [27]. A
(skewed d, 4.0 F); JAB 146:0 Hz.
�
1
� 1
with additional
bands at 994 and 910 cm , is observed, consistent with
Infrared spectrum (cm ): 3624, vw,br; 3362, m,br; 3023,
vw; 2933, s; 2859, s; 1734, vw; 1467, m; 1434, m; 1417, w;
1376, w; 1319, w; 1252, w; 1194, w; 1103, w; 1059, m; 951,
m; 933, m; 875, vs; 846, vs; 826, vs; 770, w; 725, w; 695, w;
673, w; 659, w; 636, m; 619, m; 598, s; 573, m; 564, m.
GC±MS: Rt 12:61 min: (and several small additional
peaks nearby, probably due to reaction of the compound in
the injection port), (m/z, species, related abundance): 137,
�
1
terminal ole®ns [30]. No evidence was found for any iso-
merization. Refractive index: n25 1:4350, lit. value is
D
1
ꢁ
.4350, [31]; GC±MS:Rt 10:9 min., single peak; 138
M� CH3COOH , 4%, 43 ꢁCH3CO , 100%.
3
.3.2. 2-Chloro-1-SF -hexane
5
C H , 6%; 127, SF5 , 3%; 109, C H , 19%; 95,
10 17 8
Into a 75 ml Hoke stainless steel reaction vessel was
13
C H , 23%; 89, SF3 , 11%; 87, C H OH , 5%; 83,
7 11 5 10
added 4.16 g (49.5 mmol) of 1-hexene. The vessel was then
cooled to � 1968C, evacuated and warmed to room tem-
perature. This freeze-thaw process was repeated twice more
to remove air from the vessel. After cooling to � 1968C,
C H , 18%; 82, C H , 6%; 81, C H9 , 32%; 79,
6
6
11
6
10
C H , 7%; 73, C H OH , 7%; 71, C H , 5%; 70,
11
6
7
4
8
5
SF2 , C H , 16%; 69, C H , 47; 68, C H8 , 19%; 67,
5
5
10
5
9
3
.53 g (21.7 mmol) of SF Cl was condensed into the
C H , 34%; 59, C H OH , 9%; 57, C H , 13%; 56,
9
5
5
7
3
6
4
vessel and then heated at 55±608C for 47 h. Distillation
at reduced pressure provided 4.77 g (89% yield) of
C H , 26%; 55, C H , 88; 54, C H , 19%; 53,
4
8
4
7
4 6
C H , 16%; 51, SF , C H ,4%; 45, C H OH , 5%; 44,
4 5 4 3 2 4
1
CS , 5%; 43, C H , 33%; 42, C H , 43%; 41, C H ,
5
SF CH CHCl(CH ) CH ; bp 55±578C at 10 mm Hg. H
5
2
2 3
3
3
7
3
6
3
100%; 40, C H , 9%; 39, C H , 34%; 31, CH OH , 98%;
3 4 3 3 2
NMR spectrum (CDCl , 400 MHz): d 0:93 ppm, t;
3
29, C H5 , 41%; 28, C H4 , 11%; 27, C H3 , 33%.
2 2 2
J 7:2 Hz, 3.0 H (CH ); d 1:2±2.0 ppm, several m, 6.4
3
H, (±(CH ) ±; d 3:94 ppm, m, 2.1 H; (SF CH ).
Elemental analysis: calculated for C H ClF OS: C,
10 20 5
2
3
5
2
d 4:34 ppm, m, 1.0H, (CHCl). Infrared spectrum: 3030,
37.67; H, 6.34; S, 10.06; F, 29.80%. Found: C, 38.33; H,
6.20; S, 9.82; F, 29.50%.
vw; 2964, s; 2937, s; 2878, s; 2868, s; 2739, vw; 1470, m;
1
1
1
8
6
5
464, m; 1436, m; 1429, m; 1418, m; 1384, w; 1360, vw;
345, vw; 1318, w; 1278, w; 1247, w; 1239, w; 1193, m;
108, w; 1077, w; 1022, m; 976, m; 954, s; 938, s; 875, vs;
45, vs; 825, vs; 751, w; 735, w; 718, w; 701, m; 695, m;
73, w; 661, w; 636, s; 620, s; 598, s; 573, m; 565, s; 530, w;
20, w. 19F NMR spectrum (CDCl , CCl F 0): AB -
3.3.4. 9-Chloro-10-SF -decyl-1-acetate
5
Into a 75 ml steel bomb tube containing 21.0 g
(106 mmol) of 9-decenyl acetate was condensed at
� 1968C 18.3 g (113 mmol) of SF Cl and the container
5
was then allowed to reach ꢂ08C (ꢀ1.5 h), and kept in an
ice bath in a beaker overnight (the ice melted). A check of
the gas pressure (by expanding into a space with attached
manometer) showed that the pressure was still high. It was
then heated for 2 days at ꢀ908C (oil bath); gas chromato-
graphy-mass spectrometry showed that only a trace of ole®n
remained. Distillation afforded 31.96 g (84%) of a colorless
3
3
4
spectrum [12,13], j 83:30 ppm(9 lines, 1.0 F);
A
j 66:0 ppm (skewed d, 4.0 F); JAB 146:2 Hz,
B
JFAH1 7:9 Hz.
GC±MS: Rt 6:25 min., single peak: (m/z, species, %
abundance): 127, SF , 9%; 89, SF , 16%; 84, C H ,
12
5
3
6
%; 83, C H , 80%; 82, C H , 27%; 81, C H9 , 7%; 74,
6 11 6 10 6
5
(C H SH) , 10%; 73, C H S , 7%; 70, C H , 3%; 69,
C H , 3%; 68, C H , 2%; 67, C H ,32%; 63, CSF , 5%;
6
5
3
3
oil, boiling range 116±1288C at 11±14 mm Hg.
3
5
3
5
5
10
1
H NMR spectrum (90 MHz): d 1:36±2.00 (broad
5
9
5
8
5
7
1
2, ?, 7; 57, C H , 41; 56, C H , 12%; 55, C H , 98%;
multiplet, 14 H), d2 2:07(s; CH C=O, 3H), d3 3:8±
4
9
4
8
4
7
3
4, C H , 7%; 53, C H , 14%; 51, SF , 5%;43, C H ,
7
4.3 m, CH2OAc SF5CH2, (4H); d4 4:3±4.6 m, CHCl,
4
6
4
5
3
19
0%; 42, C H , 44%; 41, C H , 100%; 40, C H , 5%;
4
(1H). F NMR spectrum: AB -spectrum, j 83:83 ppm
3
6
3
5
3
4
A
9, C H , 34%; 29, C H , 48%; 28, C H , 9%; 27,
4
(9 lines, 1.0 F); j 66:33 ppm (skewed d, 4.0 F);
3
3
2
5
2
B
C H , 40%; 26, C H , 4%; 15, CH3 , 4%.
2
JAB 154:8 Hz:
3
2 2
�
1
Elemental analysis: calculated for C H ClF S: C, 29.21;
6
Infrared spectrum (cm ): 3022, vw; 2934, s; 2860, m;
1739, s-vs; 1467, w-m; 1437, w-m; 1418, w; 1389, w-m;
1367, m; 1245, vs; 1040, m; 955, vw; 933, w-m; 874, s-vs;
12
5
H, 4.91; S, 13.00; F, 38.51%. Found: C, 29.32; H, 4.96; S,
1
3
4
3.84; F, 38.80%.
8
46, vs; 827, vs; 725, w; 693, w; 635, m-s; 618, m; 597, m-s;
.3.3. 9-Chloro-10-SF -decanol
5
571, w; 564, m. GC-MS: R 13:6 min:, single peak:
t
35
To a 75 ml Hoke stainless steel bomb tube was added
.93 g (31.6 mmol) of 9-decen-1-ol. The vessel was chilled
361 ꢁMꢁ Cl H: <1%; 43 ꢁCH CO : 100%.
3
Elemental analysis: calculated for C H ClF O S, C,
22
12
5 2
(
condensed into it. After warming to room temperature, the
� 1968C), evacuated, and 5.37 g (33.0 mmol) of SF Cl was
39.95; H, 6.15; F, 26.3; S, 8.89. Found, C, 39.89; H,
6.39; F, 24.6; S, 8.25%.
5