BUSHMELEV et al.
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1
30 ml of diethyl ether was added dropwise under
stirring over a period of 30 min, and the mixture was
stirred for 2 h at room temperature and left overnight.
After appropriate treatment, a dark oily material was
isolated, and it rapidly crystallized to form fine crystals
(1.4 g, 98.4%). The product was dissolved on heating
in 100 ml of hexane, the solution was clarified with
charcoal and filtered, and the filtrate was evaporated
by half. After cooling in an ice bath, colorless crystals
separated (0.26 g). The mother liquor was evaporated
to a volume of 20 ml to isolate an additional portion
(0.74 g) of slightly colored crystals. Further evapora-
tion gave the third portion, 0.32 g of IId as light brown
crystals. IR spectrum (CHCl3), ν, cm–1: 3586 (OH),
2259 (C≡C). Found: m/z 316.1066 [M]+. C 19H15F3O.
Calculated: M 316.1070.
Cation IIIb. H NMR spectrum (–40°C), δ, ppm:
1.98 s (6H, 9-Me, JCH = 134 Hz), 2.88 s (3H, MeC≡C,
JCH = 135 Hz), 7.78 t (1H, 6-H, J = 7 Hz), 7.87 t (1H,
2-H, J = 7 Hz), 7.93 t (1H, 7-H, J = 7 Hz), 8.02 d (1H,
8-H, J = 8 Hz), 8.54 t (1H, 3-H, J = 7 Hz), 8.62 d (1H,
1-H, J = 8 Hz), 8.67 d (1H, 4-H, J = 8 Hz), 8.75 d (1H,
13
5-H, J = 8 Hz). C NMR spectrum (–52°C), δC, ppm:
31.6 (9-Me), 53.5 (C9); 125.9, 127.4, 128.0, 129.7,
131.7, 134.7, 140.3, 152.4 (C1–C8)**; 136.8, 126.7,
149.2, 149.4 (C4a, C4b, C8a, C10a)**; 203.2 (C10), 88.3
(MeC≡C), 152.9 (MeC≡C), 8.7 (MeC≡C).
1
Cation IIIc. H NMR spectrum (–42°C), δ, ppm:
2.09 s (6H, 9-Me, JCH = 133 Hz), 7.78 t (1H, 6-H, J =
7 Hz), 7.78 t (2H, m-H, J = 7 Hz), 7.86–8.00 m (3H,
2-H, 7-H, p-H), 8.04 d (1H, 8-H, J = 8 Hz), 8.14 d
(2H, o-H, J = 8 Hz), 8.50 t (1H, 3-H, J = 7 Hz), 8.61 d
(1H, 1-H, J = 8 Hz), 8.67 d (1H, 4-H, J = 8 Hz), 8.84 d
1
Conformer IId′. H NMR spectrum (–34°C), δ,
13
ppm: 1.10 s (10-Meax), 1.78 s (10-Meeq), 2.36 s
(9-OHax), 7.32–7.56 m (1-H, 2-H, 3-H, 6-H, 7-H),
7.78–7.88 m (4-H, 5-H, 8-H). 13C NMR spectrum
(–34°C), δC, ppm: 21.1 and 26.7 (10-Me), 43.1 (C10),
76.6 (C9); 124.0, 124.3, 125.8, 127.0, 127.3, 128.2,
128.9, 130.1 (C1–C8)**; 130.6, 131.6, 133.5, 140.2
(C4a, C4b, C8a, C10a)**; 86.9 q (CF3C≡C, JCF = 6 Hz),
(1H, 5-H, J = 8 Hz). C NMR spectrum (–12°C), δC,
ppm: 32.4 (9-Me), 52.4 (C9); 126.2, 127.4, 128.1,
129.9, 131.9, 134.6, 139.0, 150.7 (C1–C8)**; 127.3,
136.1, 148.0, 148.5 (C4a, C4b, C8a, C10a)**; 198.6 (C10),
101.3 (PhC≡C), 151.9 (PhC≡C), 120.4 (Ci), 130.8
(Cm), 137.1 (Co), 138.4 (Cp).
1
Cation IIId. H NMR spectrum (–47°C), δ, ppm:
75.1 q (CF3C≡C, JCF = 53 Hz), 113.7 q (CF3, JCF
=
2.03 s (9-Me, JCH = 135 Hz), 7.92 t (6-H, J = 7.6 Hz),
7.95–8.03 (2-H), 8.12 t (7-H, J = 7.5 Hz), 8.17 d (8-H,
J = 8.0 Hz), 8.68 d (1-H, J = 8.4 Hz), 8.70–8.85 (3-H,
258 Hz). 19F NMR spectrum (–34°C): δF –49.6 ppm, s.
1
Conformer IId″. H NMR spectrum (–34°C), δ,
13
ppm: 0.94 s (10-Meax), 1.66 s (10-Meeq), 2.83 s
(9-OHeq), 7.32–7.56 m (1-H, 2-H, 3-H, 6-H, 7-H),
7.68–7.88 m (4-H, 5-H, 8-H). 19F NMR spectrum
(–34°C): δF –49.8 ppm, s.
4-H, 5-H). C NMR spectrum (–83°C), δC, ppm: 29.4
(9-Me), 52.4 (C9), 80.9 q (CF3C≡C, JCF = 6 Hz),
108.6 q (CF3C≡C, JCF = 56 Hz), 114.1 q (CF3, JCF
=
261 Hz), 126–158 (C1–C8, C4a, C4b, C8a, C10a), 188.9
(C10). 19F NMR spectrum (–47°C): δF –53.0 ppm, s.
Generation of carbocations in superacid
medium. A 5-mm NMR ampule was charged with
0.13 ml of HSO3F and cooled to –30 to –50°C, and
a triple volume of SO2ClF was condensed thereto. The
mixture was stirred and cooled to –95°C, a solution of
20–30 mg of compound IIa–IId in 0.15 ml of CD2Cl2
was carefully added, and the mixture was stirred with
a glass rod (cooled with liquid nitrogen) until a colored
solution was obtained.
REFERENCES
1. Shubin, V.G., Borodkin, G.I., and Genaev, A.M., Khimiya
aromaticheskikh, geterotsiklicheskikh i prirodnykh soedi-
nenii (Chemistry of Aromatic, Heterocyclic, and Natural
Compounds), Novosibirsk: Novosib. Inst. Org. Khim.,
2009, p. 171.
2. Genaev, A.M., Sal’nikov, G.E., and Shubin, V.G., Russ. J.
Org. Chem., 2010, vol. 46, p. 311.
1
Cation IIIa. H NMR spectrum (–47°C), δ, ppm:
2.03 s (6H, 9-Me, JCH = 134 Hz), 6.39 s (1H, HC≡C,
JCH = 265 Hz), 7.85 t (1H, 6-H, J = 7 Hz), 7.93 t (1H,
2-H, J = 7 Hz), 8.02 t (1H, 7-H, J = 7 Hz), 8.10 d (1H,
8-H, J = 8 Hz), 8.65 t (1H, 3-H, J = 7 Hz), 8.71 d (1H,
1-H, J = 8 Hz), 8.75 d (1H, 4-H, J = 8 Hz), 8.83 d (1H,
3. Bushmelev, V.A., Genaev, A.M., and Shubin, V.G., Russ.
J. Org. Chem., 2006, vol. 42, p. 100.
4. Artamoshkin, V.G., Bushmelev, V.A., Genaev, A.M., and
Shubin, V.G., Russ. J. Org. Chem., 2006, vol. 42, p. 1257.
5. Luk’yanov, S.M., Koblik, A.V., and Murad’yan, L.A.,
Usp. Khim., 1998, vol. 67, p. 899.
6. Bushmelev, V.A., Genaev, A.M., and Shubin, V.G., Russ.
J. Org. Chem., 2004, vol. 40, p. 966.
13
5-H, J = 8 Hz). C NMR spectrum (–57°C), δC, ppm:
30.7 (9-Me), 53.2 (C9); 126.4, 128.1, 128.3, 130.1,
132.4, 135.9, 140.5, 155.1 (C1–C8)**; 126.9, 137.8,
150.7, 151.8 (C4a, C4b, C8a, C10a)**; 198.6 (C10), 84.2
(HC≡C), 127.7 (HC≡C).
7. Genaev, A.M. and Shubin, V.G., Russ. J. Org. Chem.,
2011, vol. 47, p. 379.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013