VINOGRADOV et al.
350
a fraction with bp 107–108°C (0.68 g) was collected; it
contained (GLC) ~99% of ketone XVIII (yield 24%).
IR spectrum, ν, cm–1: 2986, 2943, 2908, 1746, 1724,
1477, 1313, 1227, 1117, 985. UV spectrum, λmax, nm
(logε): 204 (3.90), 228 (3.88), 285 (3.14). H NMR
spectrum, δ, ppm: 1.21 t (3H, CH2CH3, JHH = 7.2 Hz),
1.40 t (3H, CH2CH3, JHH = 7.1 Hz), 2.83 q (2H,
water, and subjected to steam distillation. We isolated
1.94 g of a material containing (GLC) 87% of ketone
XXI (yield 50%). The product was distilled under
reduced pressure (~3 mm), and a fraction with bp 68–
70°C (1.01 g) was collected; it contained (GLC) ~98%
of ketone XXI (yield 30%). IR spectrum, ν, cm–1:
2987, 2944, 1727, 1650, 1492, 1352, 1351, 1257,
1205, 1163, 1126, 1048. UV spectrum, λmax, nm (logε):
1
CH2CH3, JHH = 7.2 Hz), 4.41 q (2H, OCH2, JHH
=
7.1 Hz). 19F NMR spectrum, δF, ppm: 20.0 m (2F),
23.3 m (2F). Mass spectrum, m/z (Irel, %): 279 (3), 278
(24) [M]+, 249 (100) [M – Et]+, 233 (15) [M – C2H5O]+,
221 (34) [M – COEt]+, 57 (2) [COEt]+. Found, %:
C 52.26; H 3.53; F 27.50. M+ 278.0563. C12H10F4O3.
Calculated, %: C 51.81; H 3.62; F 27.32. M 278.0561.
207 (3.97), 276 (3.24). H NMR spectrum, δ, ppm:
1
1.25 t (3H, CH2CH3, JHH = 7.2 Hz), 2.86 q (2H,
CH2CH3, JHH = 7.2 Hz). 19F NMR spectrum, δF, ppm:
21.9 d.d.t (1F, 7-F), 31.6 quint (2F, 2-F), 37.0 d.d (1F,
6-F), 44.2 d.d.t (1F, 4-F), 53.7 m and 54.5 m (2F, 1-F,
3-F); JFF, Hz: 6-F–7-F 21.4, 4-F–7-F 21.4, 3-F–4-F
6.9, 1-F–7-F 6.9, 4-F–6-F 4.4, 2-F–1(3)-F) 4.0 Hz.
Mass spectrum, m/z (Irel, %): 337 (1), 336 (9) [M]+, 307
(100) [M – Et]+, 279 (2) [M – COEt]+, 57 (3) [COEt]+,
29 (4) [Et]+. Found, %: C 43.42; H 1.46; F 50.86.
M+ 336.0195. C12H5F9O. Calculated, %: C 42.88;
H 1.50; F 50.87. M 336.0191.
1,1,2,2,3,3,4,6,7-Nonafluoroindan-5-yl(phenyl)-
methanone (XX). A mixture of 7.14 g (10.0 mmol) of
organozinc compounds XIX [a solution in DMF con-
taining 96% of XIX and 4% of 1,1,2,2,3,3,4,5,7-nona-
fluoroindan (XXXII)], 2.11 g (15.0 mmol) of benzoyl
chloride (Ia), and 0.01 g (0.10 mmol) of CuCl was
heated for 4 h at 60–65°C under argon. The mixture
was cooled to room temperature, 10 ml of water was
added, and the mixture was subjected to steam distilla-
tion. A solid crystallized in the receiver and was
filtered off and dried in air. According to the GLC data,
the product, 1.87 g, contained 85% of ketone XX
(yield 41%). Sublimation of the still residue gave an
additional portion, 0.21 g, of XX. After recrystalliza-
tion from hexane, yield 1.15 g (35%), purity ~99%
(GLC), mp 82.5–83.5°C. IR spectrum, ν, cm–1: 3070,
1690, 1599, 1583, 1495, 1452, 1339, 1231, 946. UV
spectrum, λmax, nm (logε): 203 (4.41), 261 (4.11).
1H NMR spectrum, δ, ppm: 7.53 m (2H, 3′-H, 5′-H),
7.68 m (1H, 4′-H), 7.82 m (2H, 2′-H, 6′-H). 19F NMR
spectrum, δF, ppm: 21.8 d.d.t (1F, 7-F), 31.7 quintet
(2F, 2-F), 38.8 d.d (1F, 6-F), 45.9 d.d.t (1F, 4-F), 53.9 m
and 54.7 m (2F, 1-F, 3-F); JFF, Hz: 6-F–7-F 21.6,
4-F–7-F 21.1, 3-F–4-F 7.0, 1-F–7-F 7.0, 4-F–6-F 5.2,
2-F–1(3)-F 4.3. Mass spectrum, m/z (Irel, %): 385 (5),
384 (28) [M]+, 307 (9) [M – Ph]+, 279 (2) [M – COPh]+,
105 (100) [COPh]+, 77 (43) [Ph]+, 51 (13). Found, %:
C 50.25; H 1.36; F 44.67. M+ 384.0190. C16H5F9O.
Calculated, %: C 50.02; H 1.31; F 44.50. M 384.0191.
Phenyl(2,3,5,6-tetrafluoropyridin-4-yl)metha-
none (XXIII). A mixture of 8.85 g (10.0 mmol) of
organozinc compounds XXII (a solution in DMF
preliminarily treated with CaCl2; fraction of XXII
93%, fraction of XXV 7%), 1.55 g (11.0 mmol) of
benzoyl chloride (Ia), and 0.01 g (0.10 mmol) of CuCl
was heated for 2 h at 55–60°C under argon. The mix-
ture was cooled to room temperature, 10 ml of water
was added, and the mixture was subjected to steam
distillation. The organic phase was separated and dried
over MgSO4. We isolated 1.86 g of a mixture contain-
ing (92%) of ketone XXIII (yield 76%) and 2% of
XXV. Vacuum sublimation at 75°C (~2 mm) gave
1.65 g (65%) of ketone XXIII with a purity of ~98%
(GLC). IR spectrum, ν, cm–1: 3067, 2610, 1694, 1599,
1583, 1492, 1465, 1411, 1289, 970, 686, 683. UV
spectrum, λmax, nm (logε): 204 (4.09), 261 (4.11).
1H NMR spectrum, δ, ppm: 7.52 m (2H, 3-H, 5-H),
7.67 m (1H, 4-H), 7.81 m (2H, 2-H, 6-H) [11].
19F NMR spectrum, δF, ppm: 19.6 m (2F, 3′-F, 5′-F),
73.6 m (2F, 2′-F, 6′-F). Mass spectrum, m/z (Irel, %):
256 (5), 255 (38) [M]+, 178 (2) [M – Ph]+, 150 (4)
[M – COPh]+, 105 (100) [COPh]+, 77 (73) [Ph]+, 51
(30). Found, %: C 56.03; H 1.99; F 30.48; N 5.18.
M+ 255.0304. C12H5F4NO. Calculated, %: C 56.48;
H 1.98; F 29.78; N 5.49. M 255.0307.
1-(1,1,2,2,3,3,4,6,7-Nonafluoroindan-5-yl)pro-
pan-1-one (XXI). A mixture of 7.14 g (10.0 mmol) of
organozinc compounds XIX [a solution in DMF con-
taining 96% of XIX and 4% of 1,1,2,2,3,3,4,5,7-nona-
fluoroindan (XXXII)], 1.39 g (15.0 mmol) of propi-
onyl chloride Ic, and 0.01 g (0.10 mmol) of CuCl was
heated for 2 h at 60–65°C under argon. The mixture
was cooled to room temperature, treated with 10 ml of
1-(2,3,5,6-Tetrafluoropyridin-4-yl)propan-1-one
(XXIV). a. A mixture of 9.05 g (14.48 mmol) of
organozinc compounds XXII (97% of XXII and 3% of
XXV; a solution in DMF without preliminary treat-
ment with CaCl2), 2.78 g (30.0 mmol) of propionyl
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010