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(cell drainings) were drained from the cell after completion
of the electrolysis. The work-up gave the following products
in the À78 8C trap (14.0g): 13 (5.0 g), 25 (1.4 g), 4 (4.9 g)
and unidentified products (1.5 g). Cell drainings (11.0 g)
consisted of 4 (0.2 g), perfluoro(2-methyl-1,3,5-trioxa-
spiro[4.4]nonane) (15) (8.2 g) and unidentified product
(2.6 g). The GC yields of 4 and 15 were 15 and 18%,
respectively.
Physicochemical properties and spectral data (IR and
MS) of 30 and 19 are shown below. 19F NMR of 30 and 19
are shown in Table 3.
Methyl perfluoro(oxane-2-yl-carboxylate) (30) (nc): bp
93.5–94.5 8C, d420 1.6579, n2D0 1.3211. IR (capillary film):
2972 (w) n(CH), 1790 (s) [n(C=O)], 1443 (m), 1342–1135
(vs–s), 1057 (ms), 988 (s), 957 (ms), 894 (m), 779 (ms), 642
+
(m), 613 (m). MS: 247 [M–C(O)OMe]+ (1.4), 131 C3F5
+
+
Perfluoro(2-methyl-1,3,5-trioxa-spiro[4.4]nonane) (15)
was separated from other products by use of semi-
preparative GLC. Physicochemical properties and spectral
data (IR and MS) of 15 are shown below. 19F NMR data of 15
are shown in Table 3.
(17.7), 100 C2F4 (18.5), 69 CF3 (41.3), 59 C(O)OMe+
(100). Analysis: Calc. for C7F9O3H3: C, 27.45%; F, 55.88%.
Found: C, 27.3%; F, 56.2%.
Perfluoro(2-methyl-1,3,5-trioxa-spiro[4.5]decane) (22)
(nc): bp 93.5–94.5 8C, d420 1.774, nD20 1.2856. IR (gas):
1301 (m), 1246 (vs), 1223 (s), 1204 (s), 1161 (s), 1122 (ms),
1107 (vs), 1182 (s), 989 (ms). MS: 391 [M–F]+ (1.3), 341
Perfluoro(2-methyl-1,3,5-trioxa-spiro[4.4]nonane) (15)
(nc): bp 70.5–72.5 8C, d420 1.7075, nD20 < 1.28. IR (gas):
1331 (m), 1300 (m), 1244 (vs), 1225 (s, sh), 1194 (ms), 1182
(ms), 1155 (ms), 1130 (m), 1088 (s), 1034 (s), 1007 (m). MS:
375 [M–F]+ (4.2), 325 [M–CF3]+ (17.9), 259 C6F9O+ (12.9),
209 C5F7O+ (23.7), 181 C4F7+ (32.0), 131 C3F5+ (100), 119
+
+
[M–CF3]+ (5.7), 131 C3F5 (49.7), 100 C2F4 (100), 97
C2F3O+ (5.6), 78 C2F2O+ (31.1), 69 CF3+ (83.4), 47 C(O)F+
(38.4). Analysis: Calc. for C8F14O3: C, 23.41%; F, 64.88%.
Found: C, 23.3%; F, 65.3%.
C2F5+ (28.0), 109 C3F3O+ (34.9), 100 C2F4+ (40.1), 69 CF3
+
(65.7). Analysis: Calc. for C7F12O3: C, 23.33%; F, 63.33%.
Found: C, 23.3%; F, 63.5%.
3.8. Fluorination of oxane-2-yl-methyl trifluoroacetate
(12)
3.6. Fluorination of oxolane-2-yl-methyl
trifluoroacetate (10)
Sample 12 (27.9 g, 0.131 mol) was fluorinated similarly
under the following conditions; 1.98 A/dm2, 5.1–5.6 V,
7–8 8C, 349 min (88 Ah). The work-up gave the following
products in the À78 8C trap (7.0 g): 25 (1.0 g), 27 (2.2 g), 28
(0.9 g), 29 (0.6 g), 5 (1.1 g) and unidentified products
(1.2 g). Cell drainings (9.6 g) consisted of 27 (0.3 g), 28
(0.7 g), 29 (0.6 g), 5 (2.0 g), 22 (3.8 g) and unidentified
products (2.2 g). The GC yields of 5 and 22 were 8 and 7%,
respectively.
Sample (29.8 g, 0.151 mol) was fluorinated similarly
under the following conditions: 1.98 A/dm2, 5.2–6.0 V,
7 ꢀ 8 8C, 282 min (71 Ah). The work-up gave the following
products in the À78 8C trap (7.6 g): 13 (2.6 g), 25 (0.5 g), 4
(3.3 g) and unidentified products (0.7 g). Cell drainings
(4.5 g) consisted of 4 (0.5 g), 15 (3.2 g) and unidentified
product (0.8 g). The GC yields of 4 and 15 were 10 and 7%,
respectively.
3.9. Fluorination of cyclopentylmethyl acetate (16)
3.7. Fluorination of oxane-2-yl-methyl acetate (11)
Sample 16 (20.0 g, 0.141 mol) was fluorinated similarly
under the following conditions: 1.98 A/dm2, 5.4–7.3 V,
7–8 8C, 369 min (90 Ah). The work-up gave the following
products in the À78 8C trap (6.8 g): perfluorocyclopentane
(19) (1.4 g), perfluoro(2-methylcyclopentane) (20) (1.5 g),
perfluoro(cyclopentylcarbonyl fluoride) (17) (3.2 g) and
unidentified products (0.4 g). Cell drainings (4.3 g) con-
sisted of 17 (0.5 g), perfluoro(1,3-dioxa-2-methyl[4.4.0]no-
nane) (18) (2.7 g) and unidentified products (1.1 g). The GC
yields of 17 and 18 were 9 and 5%, respectively.
Perfluoro(cyclopentyl carbonylfluoride) (17) showed
following IR spectra (gas): 1881 (m) [n(C=O)], 1312
(ms), 1258 (s), 1227 (vs), 1207 (s, sh), 1138 (ms), 980 (s).
Methyl ester of 17 (31) was prepared for further
characterization in a similar manner as explained for 4.
Physicochemical properties and spectral data (IR and MS) of
18 and 31 are shown below. 19F NMR data of 18 and 31 are
shown in Table 3.
Sample 11 (19.9 g, 0.127 mol) was fluorinated similarly
under the following conditions: 1.98 A/dm2, 5.4–5.5 V,
7–8 8C, 357 min (89.9 Ah). In this case, a high boiling
products (cell drainings) were drained from the cell after the
completion of the electrolysis similarly. The work-up gave
the following products in the À78 8C trap (9.0 g): 25 (1.5 g),
perfluorooxane (27) (3.1 g), perfluoro(2-ethyloxolane) (28)
(1.2 g), perfluoro(2-methyloane) (29) (0.7 g), perfluoro(ox-
ane-2-yl-carbonylfluoride) (5) (1.1 g) and unidentified
products (1.3 g). Cell drainings (14.1 g) consisted of 27
(0.3 g), 28 (0.8 g), 29 (0.7 g), 5 (1.8 g), 22 (7.8 g) and
unidentified products (2.7 g). The GC yields of 5 and 22
were 8 and 7%, respectively.
Perfluoro(oxane-2-yl-carbonylfluoride) (5) showed fol-
lowing IR spectra (gas): 1886 (m) [n(C=O)], 1355 (w), 1340
(w), 1286 (ms), 1254 (ms, sh), 1286 (s, sh), 1207 (s), 1140
(vs), 1055 (ms), 986 (ms), 899 (ms), 802 (w). Methyl ester of
5 (30) was prepared for further characterization in a similar
manner as explained for 4.
Perfluoro(2-methyl-1,3-dioxa-spiro[4.4]nonane) (18)
(nc): bp 88.0–89.0 8C, d420 1.7823, n2D0 1.2876. IR (gas):
1319 (ms), 1271 (m), 1244 (vs), 1225 (s), 1138 (m), 978