STEREOSELECTIVE SYNTHESIS OF 2-ARYL-4-EN-1-OLS, PROMISING SYNTHONS
173
1
1704 (С=О), 1603 (С=С). Н NMR spectrum, δ, ppm:
0.83 t (3Н, СН3, J 6.8 Hz), 1.18–1.24 m (2Н, СН2),
1.45–1.53 m (2Н, СН2), 1.81 s (3Н, СН3С=С), 2.18 d
(2Н, СН2С=С, J 6.3 Hz), 2.28 с (3Н, СН3arom), 2.35 t
(2Н, СН2С=О, J 7.2 Hz), 3.70 t (1Н, СНarom, J 6.2 Hz),
4.78 d (1Н, СН=С, J 8.6 Hz), 4.92 d (1Н, СН=С,
J 8.6 Hz), 7.22–7.34 m (4Нarom). Mass spectrum, m/z
(Irel, %): 245 (100) [M + Н]+. Found, %: С 83.48; Н
9.95. С17Н24О. Calculated, %: С 83.55; Н 9.90. M
244.37.
1.43–1.54 m (2Н, СН2), 1.57 s (3Н, СН3С=С), 1.63 s
(3Н, СН3С=С), 2.29 s (3Н, СН3arom), 2.35–2.43 m (3Н,
СН2С=О, СНС=С), 2.70–2.79 m (1Н, СНС=С), 3.64 t
(1Н, СНarom, J 6.5 Hz), 5.03 t (1Н, СН=С, J 6.6 Hz),
7.19–7.27 m (4Нarom). Mass spectrum, m/z (Irel,
%): 259 (100) [M + Н]+. Found, %: С 83.48; Н
10.21. С18Н26О. Calculated, %: С 83.67; Н 10.14. M
258.40.
9-Methyl-6-(4-chlorophenyl)dec-8-en-5-one (5с).
Yield 84%, light-yellow oil. IR spectrum, ν, cm–1:
1
2-Methyl-4-(4-chlorophenyl)non-1-en-5-one (4с).
Yield 84%, colorless oil. IR spectrum, ν, cm–1: 1706
(С=О), 1606 (С=С). 1Н NMR spectrum, δ, ppm: 0.84 t
(3Н, СН3, J 6.9 Hz), 1.19–1.23 m (2Н, СН2), 1.46–
1.55 m (2Н, СН2), 1.83 s (3Н, СН3С=С), 2.18 d (2Н,
СН2С=С, J 6.3 Hz), 2.36 t (2Н, СН2С=О, J 7.4 Hz),
3.81 t (1Н, СНarom, J 6.5 Hz), 4.79 d (1Н, СН=С,
J 9.1 Hz), 4.94 d (1Н, СН=С, J 9.1 Hz), 7.22 d
(2Нarom, J 8.8 Hz), 7.35 d (2Нarom, J 8.8 Hz). Mass
spectrum, m/z (Irel, %): 265 (100) [M + Н]+. Found, %:
С 72.63; Н 8.06; Cl 13.44. С16Н21ClО. Calculated, %:
С 72.57; Н 7.99; Cl 13.39. M 264.79.
1705 (С=О), 1606 (С=С). Н NMR spectrum, δ, ppm:
0.84 t (3Н, СН3, J 6.8 Hz), 1.20–1.28 m (2Н, СН2),
1.45–1.56 m (2Н, СН2), 1.57 s (3Н, СН3С=С), 1.64 s
(3Н, СН3С=С), 2.38–2.45 m (3Н, СН2С=О, СНС=С),
2.73–2.81 m (1Н, СНС=С), 3.71 t (1Н, СНarom, J
6.8 Hz), 5.05 t (1Н, СН=С, J 6.7 Hz), 7.22 d (2Нarom, J
9.2 Hz), 7.38 d (2Нarom, J 9.2 Hz). Mass spectrum, m/z
(Irel, %): 279 (100) [M + Н]+. Found, %: С 73.18; Н
8.43; Cl 12.64. С17Н23ClО. Calculated, %: С 73.23; Н
8.31; Cl 12.72. M 278.82.
6-(4-Bromophenyl)-9-methyldec-8-en-5-one (5d).
Yield 42%, yellow oil. IR spectrum, ν, cm–1: 1704
(С=О), 1605 (С=С). 1Н NMR spectrum, δ, ppm: 0.84 t
(3Н, СН3, J 6.8 Hz), 1.21–1.27 m (2Н, СН2), 1.45–
1.54 m (2Н, СН2), 1.57 s (3Н, СН3С=С), 1.64 s (3Н,
СН3С=С), 2.37–2.47 m (3Н, СН2С=О, СНС=С), 2.73–
2.80 m (1Н, СНС=С), 3.71 t (1Н, СНarom, J 6.8 Hz),
5.04 t (1Н, СН=С, J 6.8 Hz), 7.22 d (2Нarom, J 7.9 Hz),
7.41 d (2Нarom, J 7.9 Hz). Mass spectrum, m/z (Irel, %):
324 (100) [M + Н]+. Found, %: С 62.94; Н 7.09; Br
24.63. С17Н23BrО. Calculated, %: С 63.16; Н 7.17; Br
24.72. M 323.27.
4-(4-Bromophenyl)-2-methylnon-1-en-5-one
(4d). Yield 56%, light-yellow oil. IR spectrum, ν, cm–1:
1
1705 (С=О), 1606 (С=С). Н NMR spectrum, δ, ppm:
0.85 t (3Н, СН3, J 6.9 Hz), 1.18–1.24 m (2Н, СН2),
1.48–1.56 m (2Н, СН2), 1.83 s (3Н, СН3С=С), 2.19 d
(2Н, СН2С=С, J 6.3 Hz), 2.34 t (2Н, СН2С=О,
J 7.2 Hz), 3.82 t (1Н, СНarom, J 6.4 Hz), 4.78 d (1Н,
СН=С, J 9.1 Hz), 4.95 d (1Н, СН=С, J 9.1 Hz), 7.18 d
(2Нarom, J 8.6 Hz), 7.42 d (2Нarom, J 8.6 Hz). Mass
spectrum, m/z (Irel, %): 310 (100) [M + Н]+. Found, %:
С 61.87; Н 6.75; Br 25.61. С16Н21BrО. Calculated, %:
С 62.14; Н 6.84; Br 25.84. M 309.24.
5-Methyl-1,3-diphenylhex-5-en-2-one (6а). To
15 mL (0.03 mol) of 2 M BnMgCl solution in THF at
0°С was added 4.66 g (0.02 mol) of compound 2а in
30 mL of anhydrous THF, the mixture was stirred for
20 h at room temperature (TLC monitoring). The work
up was the same as in the synthesis of ketone 4a,
eluent hexane–ethyl acetate, 5 : 1. Yield 83%,
colorless oil. IR spectrum, ν, cm–1: 1708 (С=О), 1602
(С=С). 1Н NMR spectrum, δ, ppm: 1.82 s (3Н,
СН3С=С), 2.21 d (2Н, СН2С=С, J 6.6 Hz), 3.66 t (1Н,
СНarom, J 6.6 Hz), 3.78 s (2Н, СН2С=О), 4.76 d (1Н,
СН=С, J 8.7 Hz), 4.92 d (1Н, СН=С, J 8.7 Hz), 7.15–
7.34 m (10Нarom). Mass spectrum, m/z (Irel, %): 265
(100) [M + Н]+. Found, %: С 86.21; Н 7.55. С19Н20О.
Calculated, %: С 86.32; Н 7.63. M 264.36.
9-Methyl-6-phenyldec-8-en-5-one (5а). Yield 95%,
colorless fluid. IR spectrum, ν, cm–1: 1705 (С=О),
1603 (С=С). Н NMR spectrum, δ, ppm: 0.84 t (3Н,
1
СН3, J 6.5 Hz), 1.19–1.26 m (2Н, СН2), 1.46–1.54 m
(2Н, СН2), 1.57 s (3Н, СН3С=С), 1.64 s (3Н,
СН3С=С), 2.35–2.42 m (3Н, СН2С=О, СНС=С), 2.71–
2.81 m (1Н, СНС=С), 3.69 t (1Н, СНarom, J 6.5 Hz),
5.04 t (1Н, СН=С, J 6.6 Hz), 7.15–7.24 m (5Нarom).
Mass spectrum, m/z (Irel, %): 245 (100) [M + Н]+.
Found, %: С 83.41; Н 9.87. С17Н24О. Calculated, %: С
83.55; Н 9.90. M 244.37.
9-Methyl-6-(4-methylphenyl)dec-8-en-5-one
(5b). Yield 93%, colorless fluid. IR spectrum, ν, cm–1:
1
1704 (С=О), 1602 (С=С). Н NMR spectrum, δ, ppm:
Compounds 6b–6d and 7a–7d were synthesized
0.85 t (3Н, СН3, J 6.7 Hz), 1.18–1.26 m (2Н, СН2),
similarly.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017