900
R.W. Winter, G.L. Gard / Journal of Fluorine Chemistry 128 (2007) 896–901
m–s; 1130, s; 1058, w–m; 1009, w; 935, vw–w; 908, w; 875, m–
s; 838, vs; 814, s–vs; 717, w–m; 703, w–m; 668, w–m; 606, m;
600, m; 577, m.
(3ꢂ 100 ml) with ethyl acetate; the combined extracts were
brought to a small volume, and the residue passed through a
short column of Kieselgel. Re-crystallization of the dried
residue from acetone (ꢁ11 8C) left 0.54 g (16%) of brownish
needles, mp = 182–183 8C.
Mass spectrum (ion (m/z), %, assignment), Rt = 5.20 min:
+
+
180, 39, (M ꢁ SO2)+; 127, 8, SF5 ; 89, 11, SF3 ; 72, 40,
+
+
(C3H3S + H)+; 64, 15, SO2 ; 53, 100, C4H5 ; 51, 18, SF+,
Infrared spectrum (cmꢁ1): 3101, w; 3085, w; 3079, w; 3042,
w; 3012, vw; 1677, s; 1590, m; 1332, m; 1320, m; 1295, s; 1267,
w–m; 1175, w–m; 1130, vw; 1119, w; 1082, w–m; 965, s; 934,
w; 924, w; 840, b, vs with sh. at 865; 793, vs; 726, m; 711,
s; 696, w–m; 662, m; 645, m; 632, w–m; 598, m; 583, w–m;
573, w.
+
+
C4H3 ; 39, C3H3 .
High-resolution mass spectrum—calcd. for 12C4 H619F5
O232S (M + H): 244.97234. Found: 244.97160.
1
16
3.5. 4-SF5-1,2,3,6-tetrahydrophthalic anhydride (6)
1H NMR spectrum (CDCl3, 500 MHz, Si(CH3)4): d1 = 8.697
(d, 1H); d3 = 8.163 (d, d, J13 = 2.30 Hz, J34 = 8.40, 1H);
d4 = 8.424 (d, br., 1H); d5 = 8.358; d8 = 8.341 (m, overlapping
H5 with H8, 2H); d6 = 7.878; d7 = 7.876 (m, overlapping H6
with H7, J56 = J78 = 8.2, J58 = 0.4, J67 = 10.6, 2H).
19F NMR spectrum (84.7 MHz, CDCl3, CCl3F): dA = 80.8
(nine lines, 1F); dB = 61.66 (dm, JAB = 152 Hz).
Benzene (10 ml), 3-SF5-3-sulfolene (4) (0.54 g, 2.21 mmol)
and maleic anhydride (0.22 g, 2.24 mmol) are heated in a
40 ml Carius tube (three fourths of the Carius tube was
immersed in an oil bath) at 130 8C for 5 h; after 5 h no more
(4) could be detected by GC–MS. The solvent was removed
under reduced pressure and the residue pale brown solid,
0.54 g (87%), virtually pure by GC–MS was re-crystallized
(much loss) from C6H12 (4 8C), yielding shiny platelets,
mp = 115 8C.
Mass spectrum (ion (m/z), %, assignment), Rt = 13.78 min:
334, 100, M+; 206, 30, (M ꢁ CO)+; 207, 25, (M ꢁ SF5)+; 198,
41, (M ꢁ 5F–CO–CH)+; 179, 24, (M ꢁ SF5–CO)+; 170, 42,
+
+
1H NMR spectrum (CDCl3, 500 MHz, Si(CH3)4 = 0):
(M ꢁ 5F–2CO–CH)+; 151, 83, C5H2SF3 , C2SF5 ; 150, 56,
+
C5HSF3 ; 127, 1, SF5 ; 125, 8, C3SF3 ; 99, 14, C8H3 ; 89, 12,
+
+
+
0
d1 = 3.56 (d–d–d, J12 = 10.8 Hz, J16 = 7.3 (trans), J16 = 3.4
+
+
+
(cis), 1H); d2 = 3.47 (d–d–d, J24 = 8.10, J23 = 3.3 (trans), 1H);
d3 = 2.560 (d–m, J33 ꢀ 16.6, 1H); d3 = 2.910 (d–m, 1H);
SF3 ; 85, 16, C7H+; 76, 14, C6H4 ; 75, 32, C6H3 ; 73, 10, C6H+;
51, 4, SF+, C4H3 ; 50, 7, C4H2 ; 28, 4, CO+.
High-resolution mass spectrum—calcd: for
16O232S (M + H): 335.01652. Found: 335.01736.
+
+
0
0
12
d5 = 6.727 (m, 1H); d6 = 2.74 (d–d–d–d, J56 = 2.2, J36 = 2.2,
0
C
14
1H819F5
0
1H); d6 = 3.19 (d–d, J66 = 16.6, 1H).
19F NMR spectrum (84.7 MHz, CDCl3, CCl3F): dA = 81.9
(nine lines, 1F); dB = 56.8 (dm, JAB = 150 Hz, 4F).
3.7. Reaction of sulfolene (4) with methyl acrylate
preparation of (9) and (10)
Infrared spectrum (cmꢁ1); 3094, vvw; 2989, vw; 2968, vw;
1845, w–m; 1787, m; 1774, m; 1448, w; 1440, w; 1358, vw;
1342, vw; 1312, w; 1242, m; 1208, w–m; 1197, w; 1173, w–m;
1109, vw–w; 1096, w–m; 1080, vw–w; 1015, m; 967, w; 958,
m; 946, w; 931, w; 876, m; 860, m; 841, m–s; 833, s; 826, vs;
773, m; 711, w–m; 669, w; 665, w; 650, vw; 626, vw; 602, w;
598, w; 587, w–m; 576, w–m; 567, w.
Sulfolene 4 (0.33 g, 1.3 mmol), benzene (10 ml), hydro-
quinone (14 mg) and methyl acrylate (0.39 g, 4.5 mmol) are
heated in a 30 ml Carius tube in an oil bath at 125–135 8C for
4 h. The benzene is distilled away at atmospheric pressure and
the residue was taken up in 2 ml of methylene chloride; this
solution was passed through 2 g of Kieselgel, and after
evaporation, 0.24 g of a colorless oil (65%) remained; an
isomeric mixture of compounds (9) and (10).
Mass spectrum (ion (m/z), %, assignment); Rt = 9.25 min:
258, <1, (M ꢁ HF)+; 230, 4, (M ꢁ HF–CO)+; 206, 24,
(M ꢁ CO–CO2)+; 127, 5, SF5 ; 122, 27, (M ꢁ SF5–CO–H)+;
+
105, 12, C7H5O+ C6H5CO+; 97, 9, C4HO3 ; 89, 9, SF3 ; 79,
Mass spectrum (ion (m/z), %, assignment), only one band
eluted, Rt = 5.92 min: 235, 10, (M ꢁ CH3O)+; 207, 8,
+
+
+
100, C6H7 ; 78, 35, C6H6 ; 77, 55, C6H5 ; 70, 2, SF2 ; 51, 11,
+
+
+
SF+; 39.8, C3H3 .
(M ꢁ COOCH3)+; 138, 21, (M ꢁ SF5–H)+; 127, 1, SF5 ;
+
+
High-resolution mass spectrum—calcd: for 12C8 H719F5
110, 19, C6H6S+; 107, 12, C6H7CO+; 95, 5, C5H3S+; 89, 3,
1
16
O332S: 278.00362. Found: 278.00417.
SF3 ; 79, 100, C6H7 ; 59, 20, COOCH3 ; 51, 2, SF+; 39, 4,
+
+
+
+
C3H3 .
3.6. 2-SF5-anthraquinone (8)
1H NMR spectrum (500 MHz, CDCl3, Si(CH3)4): series of
multiplets from d = 1.7 to 2.85 (asym., m at 6.52 and two
singlets at d = 3.718 and 3.724, ratio 3:4).
3-SF5-3-sulfolene (2.40 g, 9.8 mmol), p-naphthoquinone
(1.55 g, 9.9 mmol) and 60 ml of toluene were heated in a
200 ml Carius tube in an oil-bath at 150 8C for 2.5 h and then
for 4 h at 160–165 8C. There was very little of the sulfolene left,
but extensive tar formation had taken place. The solvent was
removed under diminished pressure, the residue containing
compound (7) taken up in 200 ml of acetone and this solution
(homogeneous, wine-red) stirred together with 50 ml (1.0N)
KOH, while air was bubbled through the solution. After 2 h, the
volume was halved by evaporation, and the solution extracted
19F NMR spectrum (84.7 MHz, CDCl3, CCl3F): two signals,
evident in the A-portion of the AB4-spectra: dA1 = 85.12,
d
A2 = 85.02 (nine lines), respectively, area A1:A1 ꢀ 4:3;
dB1 = dB2 = 55.8 (dm); area A:B = 1:4; J ꢀ 148 Hz in both
cases.
Infrared spectrum (cmꢁ1): 3088, vvw; 3001, vw; 2958, w–
m; 2871, w; 2850, w; 1740, vs; 1457, w–m, sh.; 1440, m; 1382,
w; 1365, w; 1323, w–m; 1311, w–m; 1256, w–m; 1250, m;
1197, m; 1175, m; 1152, w–m, sh.; 1076, w; 1030, w; 1000, w;