4
Tetrahedron
ACCEPTED MANUSCRIPT
(CDCl3): Z-isomer: 2.42 (s, 3H, Me-C=O), 3.69 (s, 3H, MeO),
(CDCl3): Z-isomer: 1.39 (t, J = 7.0, 3H, Me), 4.17 (q, J = 7.0,
6.14 (s, 1H, =CH), 6.72-6.74 (m, 2H, o-CH, MeOC6H4O), 6.83-
6.85 (m, 2H m-CH, MeOC6H4O), 7.26-7.53 ( m, 5H, Ph); E-
isomer: 1.89 (s, 3H, Me-C=O), 3.80 (s, 3H, MeO), 5.45 (s, 1H,
=CH), 6.73-6.75 (m, 2H, o-CH, MeOC6H4O), 6.83-6.85 (m, 2H
m-CH, MeOC6H4O), 7.26-7.53 (m, 3H, Ph), 7.55-7.57 (m, 2H,
Ph). 13C NMR (CDCl3): Z-isomer: 30.9 (Me-C=O), 55.5 (MeO),
114.7 (m-CH, MeOC6H4O), 117.0 (=CH), 117.9 (o-CH,
MeOC6H4O), 127.7 (o-Ph), 128.7 (m-Ph), 130.5 (p-Ph), 133.9 (i-
Ph), 149.8 (i-C, MeOC6H4O), 155.3 (MeO-C) 161.6 (O-C=),
198.0 (C=O); E-isomer: 30.9 (Me-C=O), 55.6 (MeO), 107.7
(=CH), 115.1 (m-CH, MeOC6H4O), 122.3 (o-CH, MeOC6H4O),
128.2 (o-Ph), 129.0 (p-Ph), 129.4 (m-Ph), 134.2 (i-Ph), 147.3 (i-
C, MeOC6H4O), 157.2 (MeO-C) 170.1 (O-C=), 197.6 (C=O). IR
(ν, cm-1): 1465, 1504, 1576, 1625, 1661. MS (EI, m/z (%)): 268
(14, M+), 226 (5), 124 (100), 109 (20), 105 (17), 43 (25). Calc.
for C17H16O3: C 76.10; H 6.01. Found: C 76.23; H 6.11.
2H, CH2), 6.49 (s, 1H, =CH), 7.32-7.50 (m, 6H, Ph), 7.69-7.74
(m, 2H, Ph), 7.97-8.02 (m, 2H, Ph); E-isomer: 1.50 (t, J = 7.0,
3H, Me), 4.16 (q, J = 7.0, 2H, CH2), 6.21 (s, 1H, =CH), 7.32-7.50
(m, 8H, Ph), 7.84-7.92 (m, 2H, Ph). 13C NMR (CDCl3): Z-
isomer: 15.6 (Me), 70.1 (CH2O), 103.7 (=CH), 127.8, 128.5,
128.5, 128.7, 130.7, 132.3, 136.4, 139.7 (Ph, Ph’), 168.0 (O-C=),
189.8 (C=O); E-isomer: 14.6 (Me), 65.2 (CH2O), 99.1 (=CH),
128.0, 128.4, 128.4, 129.1, 130.0, 132.1, 135.7, 140.0 (Ph, Ph’),
171.0 (O-C=), 190.9 (C=O). IR (ν, cm-1): 1465, 1486, 1556,
1565, 1600. MS (EI, m/z (%)): 252 (32, M+), 251 (58), 235 (61),
147 (54), 105 (100), 77 (88). Calc. for C17H16O2: C 80.93; H
6.39. Found: C 80.72; H 6.16.
3-Bromo-4-(4-methoxyphenyl)butanone-2 5: A mixture of 3-
bromobuten-3-one-2 4 (2 mmol) and 4-methoxyphenol (2 mmol)
was refluxed for 3 h. The solvent was evaporated and the residue
was chromatographed (silica gel, CHCl3/MeOH = 98:2) to yield
oxa-Michael adduct 5. Light yellow oil, 168 mg (31%). 1H NMR
(CDCl3): 2.39 s (3H, Me), 3.74 (s, 3H, MeO), 4.21 (dd, J = 10.2,
5.7, 1H, CH), 4.39 (dd, J = 10.2, 7.6, 1H, CH), 4.48 (dd, J = 7.6,
5.7, 1H, CH), 6.80 – 6.85 (m, 5H, m,o,p-Ph). 13C NMR (CDCl3):
27.0 (Me), 48.4 (CHBr), 55.8 (MeO), 69.3 (CH2O), 114.9 (m-
CH, MeOC6H4O), 116.3 (o-CH, MeOC6H4O), 152.1 (i-C,
MeOC6H4O), 154.7 (MeO-C), 200.5 (C=O). IR (ν, cm-1): 1718
(C=O). MS (EI, m/z (%)): 274 (30, M++1), 272 (30, M+-1), 231
(16), 229 (16), 150 (55), 123 (100), 43 (60). Calc. for
C11H13BrO3: C 48.37; H 4.80. Found: C 48.34; H 4.65.
4-(4-Nitrophenoxy)-4-phenylbuten-3-one-2 2d: Yellow oil,
1
(4:1) mixture of Z,E-isomers, 55 mg (20%). H NMR (CDCl3):
Z-isomer: 2.32 (s, 3H, Me), 6.37 (s, 1H, =CH), 7.01-7.03 (m,
2H, o-CH, NO2C6H4O), 7.36-7.58 (m, 5H, Ph), 8.14-8.16 (m, 2H
m-CH, NO2C6H4O); E-isomer: 2.00 (s, 3H, Me), 5.78 (s, 1H,
=CH), 7.19-7.21 (m, 2H, o-CH, NO2C6H4O), 7.36-7.58 (m, 5H,
Ph), 8.23-8.25 (m, 2H m-CH, NO2C6H4O). 13C NMR (CDCl3): Z-
isomer: 31.3 (Me), 116.8 (o-CH, NO2C6H4O), 116.9 (=CH),
126.2 (m-CH, NO2C6H4O), 127.2 (o-Ph), 129.3 (m-Ph), 131.4 (p-
Ph), 132.8 (i-Ph), 143.2 (NO2-C), 158.9 (O-C=), 161.2 (i-C,
NO2C6H4O), 196.4 (C=O); E-isomer: 31.1 (Me), 112.8 (=CH),
120.6 (o-CH, NO2C6H4O), 126.0 (m-CH, NO2C6H4O), 128.6 (m-
Ph), 129.1 (o-Ph), 130.6 (p-Ph), 134.4 (i-Ph), 144.1 (NO2-C),
159.0 (O-C=), 159.6 (i-C, NO2C6H4O), 198.3 (C=O). IR (ν, cm-
1): 1490, 1519, 1578, 1590, 1609, 1626, 1665, 1693. MS (EI, m/z
(%)): 283 (39, M+), 282 (42), 268 (12), 222 (10), 194 (9), 145
(18), 105 (48), 103 (6), 102 (19), 77 (33), 76 (8), 43 (100).
Acknowledgement
This work was supported by the Russian Foundation for Basic
Research (Grant no. 13-03-00063a).
References and notes
1. For the fundamental reviews, see: (a) Fernández, I.; Bickelhaupt,
F. M.; Uggerud, E. J. Org. Chem. 2013, 78, 8574; (b) Bernasconi,
C. F.; Rappoport, Z. Acc. Chem. Res. 2009, 42, 993; (c)
Rappoport, Z. Recl. Trav. Chim. Pays–Bas 1985, 104, 309; (d)
Rappoport, Z. Acc. Chem. Res. 1981, 14, 7; (e) Okuyama, Т.;
Lodder, G. Adv. Phys. Org. Chem. 2002, 37, 1; (f) Cohen, D.; Bar,
R.; Shaik, S. S. J. Amer. Chem. Soc. 1986, 108, 231; (g) Shainyan,
B. A. Russ. Chem. Rev. 1986, 55, 511; (h) Modena, G. Acc.
Chem. Res. 1971, 4, 73.
2. (a) Brahma, S.; Ray, J. K. Tetrahedron 2008, 64, 2883; (b)
Bamwell, M. G.; Lupton, D. W.; Ma, X.; Renner, J.; Sydnes, M.
O. Org. Lett. 2004, 6, 2741.
3. For reviews, see: (a) Rulev, A. Yu. Usp. Khim. 1998, 67, 317;
Russ. Chem. Rev. 1998, 67, 279; (b) Rulev, A. Yu. Usp. Khim.
2002, 71, 225; Russ. Chem. Rev. 2002, 71, 195.
4. (a) Rulev, A. Yu.; Maddaluno, J. J. Phys. Org. Chem., 2002, 15,
590; (b) Rulev, A. Yu.; Fedorov, S. V.; Chuvashov, Yu. A.;
Voronkov, M. G. Zh. Org. Khim. 2003, 39, 691; (c) Rulev, A. Yu.;
Ushakov, I. A.; Nenajdenko, V. G.; Balenkova, E. S.; Voronkov,
M. G. Eur. J. Org. Chem. 2007, 6039; (d) Rulev, A. Yu.;
Ushakov, I. A.; Nenajdenko, V. G. Tetrahedron 2008, 64, 8073.
5. (a) Greenhill, J. V. Chem. Soc. Rev., 1977, 6, 277; (b) Kuckländer,
U. In: The Chemistry of enamines; Rappoport, Z., Ed.; Wiley:
New York, 1994; pp 523-636.
6. Dufraisse, C., Moureu, H. Bull. Soc. Chim. France 1927, 41, 850.
7. (a) Rosnati, V.; Saba, A.; Salimbeni, A. Tetrahedron Lett. 1981,
22, 167; (b) Rosnati, V.; Saba, A.; Salimbeni, A.; Vettori, U.
Gazz. Chim. Ital. 1981, 111, 249.
3-(4-Methoxyphenoxy)-1,3-diphenylpropen-2-one-1
2e:
1
Yellow oil, (1:5.5) mixture of Z,E-isomers, 230 mg (35%). H
NMR (CDCl3): Z-isomer: 3.66 (s, 3H, MeO), 6.67-6.69 (m, 2H,
o-CH, MeOC6H4O), 6.80-6.82 (m, 2H, m-CH, MeOC6H4O), 6.85
(s, 1H, =CH), 7.31-7.38 (m, 3H, m,p-Ph), 7.38-7.40 (m, 2H, m-
Ph’), 7.49-7.51 (m, 1H, p-Ph’), 7.63-7.65 (m, 2H, o-Ph) 7.90-
7.92 (m, 2H, o-Ph’); E-isomer: 3.81 (s, 3H, MeO), 6.07 (s, 1H,
=CH), 6.95-6.97 (m, 2H, o-CH, MeOC6H4O), 7.02-7.04 (m, 2H,
m-CH, MeOC6H4O), 7.31-7.38 (m, 5H, m,p-Ph, m-Ph’), 7.41-
7.44 (m, 1H, p-Ph’), 7.62-7.64 (m, 2H, o-Ph), 7.73-7.75 (m, 2H,
o-Ph’). 13C NMR (CDCl3): Z-isomer: 55.6 (MeO), 110.3 (=CH),
114.6 (m-CH, MeOC6H4O), 117.9 (o-CH, MeOC6H4O), 127.6 (o-
Ph), 128.5 (o,m-Ph’), 128.9 (m-Ph), 130.6 (p-Ph), 132.6 (p-Ph’),
134.9 (i-Ph), 138.9 (i-Ph’), 151.2 (i-C, MeOC6H4O), 155.0
(MeO-C), 161.8 (O-C=), 189.9 (C=O); E-isomer: 55.7 (MeO),
103.6 (=CH), 115.2 (m-CH, MeOC6H4O), 122.3 (o-CH,
MeOC6H4O), 128.1 (m-Ph), 128.3 (o-Ph’), 128.4 (m-Ph’), 129.4
(o-Ph), 130.4 (p-Ph), 132.4 (p-Ph’), 134.3 (i-Ph), 139.2 (i-Ph’),
147.7 (i-C, MeOC6H4O), 157.3 (MeO-C), 170.8 (O-C=), 190.8
(C=O). IR (ν, cm-1): 1448, 1504, 1572, 1588, 1663. MS (EI, m/z
(%)): 330 (11, M+), 225 (5), 124 (32), 105 (100), 77 (29), 51 (3).
Calc. for C22H18O3: C 79.98; H 5.49. Found: C 80.34; H 5.46.
3-Ethoxy-1,3-diphenylpropene-2-one-1 3.[13] A suspension of
potassium hydrocarbonate (4.75 mmol) and 1,4-diphenylbut-3-
yn-2-one (0.48 mmol) in ethanol (2 mL) was refluxed for 6 h.
The precipitate was filtered and washed 2×3 mL of diethyl ether.
Then filtrate was concentrated in vacuo and the residue (112 mg)
was purified by column chromatography (SiO2, Et2O:hexane =
1:2). 3-Ethoxy-1,3-diphenylpropene-2-one-1 3 was obtained as a
8. Salimbeni, A.; Manghisi, E.; Fregnan, G. B.; Prada, M. J. Med.
Chem. 1987, 30, 773.
9. Rulev, A. Yu.; Mokov, A. S.; Krivdin, L. B.; Keiko, N. A.;
Voronkov, M. G. Magn. Res. Chem. 1997, 35, 533.
10. Fedor, R. L.; De, N. C.; Gurwara, S. K. J. Am. Chem. Soc. 1973,
95, 2905.
11. Gelin, R.; Makula, D. Bull. Soc. Chim. France 1966, 2347.
12. Suwiński, J.; Świerczek, K. Tetrahedron 2001, 57, 1639.
13. Spassky, A. Bull. Soc. Chim. France 1970, 2954.
1
mixture of Z,E-isomers (1:7). Yield 42 mg (35%). H NMR