SYNTHESIS OF BIOLOGICALLY ACTIVE SUBSTANCES BASED ON PHENOXYETHANOL DERIVATIVES 677
7.28 br.s (5H, Harom). Found, %: C 71.63; H 9.18.
C20H30O4. Calculated, %: C 71.86; H 9.04.
5-Oxohexanoic acid (XIX) was obtained by ozona-
tion of 2.46 g (0.03 mmol) of cycloolefin XVII was pre-
pared by ozonation of 2.88 g (0.03 mmol) of cycloolefinX
in 40 ml of cyclohexane followed by ozonide decomposi-
tion by treating in succession with 5.4 ml of AC2O and
2.3 g AcONa in 11.8 ml of ACOH. Acid XIX was iso-
lated in the same way as compound XI as a light yellow
oily substance in an yield 3.08 g (79%). IR spectrum,
2-Phenoxyethyl 6-oxononanoate (XV). The cor-
responding acyl chloride was obtained from 4.13 g
(0.024 mol) of acid XII by treatment with 2.83 g of
SOCl2 as described for compound XI. Then to the acyl
chloride solution in pentane was added at stirring 3.3 g
(0.024 mol) of phenoxyethanol. Similarly to compound
XI 5.89 g (84%) of ester XV was isolated as yellow oily
substance and purified by chromatography on SiO2 (elu-
1
cm : 1705 C, 1715 C, 24003600 br.s.
Methyl 5-oxohexanoate was obtained by treating
acid XIX with diazomethane ether solution. IR spectrum,
ent hexaneether, 3:2), nD20 1.5398. IR spectrum, cm :
1
1
cm : 715 s, 1735 s. 1H NMR spectrum, d, ppm: 1.34 m
1100 s, 1205 s, 1500 m, 1605 w, 1715 s, 1740 s. 1H NMR
spectrum, d, ppm: 0.89 t (3H, Me, J 6.5 Hz), 1.20
1.40 m (6H, CH2), 2.38 m (6H, CH2C=O), 4.26 t (2H,
CH2OAr, J 5.5 Hz), 4.44 t (2H, CH2O, J 5.5 Hz),
7.26 br.s (5H, Harom). Found, %: C 69.96; H 8.14.
C17H24O4. Calculated, %: C 69.86; H 8.21.
(2H, CH2), 2.08 s (3H, MeC=O), 2.34 m (4H, CH2C=O),
3.62 s (3H, OMe). Found, %: C 58.43; H 8.39. C7H12O3.
Calculated, %: C 58.32; H 8.39.
2-Phenoxyethyl 5-oxohexanoate (XX). The cor-
responding acyl chloride was obtained from 4.13 g
(0.024 mol) of acid XIX by treatment with 2.83 g of
SOCl2. The acyl chloride obtained was reacted with
3.3 g (0.024 mol) of phenoxyethanol to isolate 5.04 g (84%)
of ester XX as a yellow oily substance that was purified
by chromatography on SiO2 (eluent hexaneether, 3:2),
2-Phenoxyethyl 6-oxoheptanoate (XVI). The
corresponding acyl chloride was obtained from 3.46 g
(0.024 mol) of acid XIII by treatment with 2.83 g of
SOCl2 as described for compound XI. Then to the acyl
chloride solution in pentane was added at stirring 3.3 g
(0.024 mol) of phenoxyethanol. Similarly to compound
XIV 5.37 g (80%)of ester XVI was isolated as yellow
oily substance and purified by chromatography on SiO2
(eluent hexaneether, 3 : 2 ), nD20 1.5401. IR spectrum,
nD20 1.5418. IR spectrum, cm : 1090 s, 1200 s, 1500 m,
1
1605 w, 1715 s, 1745 s. 1H NMR spectrum, d, ppm: 1.26
1.40 m (2H, CH2), 2.10 s (3H, MeCO), 2.34 m (4H,
CH2C=O), 4.24 t (2H, CH2OAr, J 5.5 Hz), 4.68 t (2H,
CH2O, J 5.5 Hz), 7.28 br.s (5H, Harom). Found, %: C 67.24;
H 7.36. C14H18O4. Calculated, %: C 67.18; H 7.25.
1
cm : 1095 s, 1215 s, 1505 m, 1605 w, 1715 s, 1745 s.
1H NMR spectrum, d, ppm: 1.241.46 m (4H, CH2),
2.10 s (3H, MeCO), 2.43 m (4H, CH2C=O), 4.24 t (2H,
CH2OAr, J 5.5 Hz), 4.42 t (2H, CH2O, J 5.5 Hz),
7.28 br.s (5H, Harom). Found, %: C 68.23; H 7.49.
C15H20O4. Calculated, %: C 68.18; H 7.58.
REFERENCES
1. Kukovinets, O.S., Zainullin, R.A., Kasradze, V.G., Burov, V.N.,
Mokrousova, E.P., Odinokov, V.N., and Tolstikov, G.A.,
Agrokhimiya, 1999, vol. 9, p. 60.
2. Kuropka, G., Koch, M., and Glombitza, K.W., Planta Med.,
1986, p. 244.
3. Nakatani, N., Inatani, R., Ohta, H., and Nichioka,A., Environ.
Health Respect., 1986, vol. 67, p. 135.
4. Sheu, J.-H., Yen, C.-F., Huang, H.-C., and Hong, Y.-L. V.,
J. Org. Chem., 1989, vol. 54, p. 5126.
5. Yamansarova, E.T., Kukovinets, A.G., Kukovinets, O.S.,
Zainullin, R.A., Galin, F.Z., Kunakova, R.V., Zorin, V.V., and
Tolstikov, G.A., Zh. Org. Khim., 2001, vol. 37, p. 259.
6. Lehta, L., Mendel, T., Matei, S., and Sclifos, M., Revista de
chimie, 1987, vol. 38, p. 525.
1-Methylcyclopentene (XVIII) was prepared by
treating with 7.14 g (0.085 mol) of cyclopentanone the
Grignard reagent obtained from 14.2 g (0.10 mol) of me-
thyl iodide and 2.4 g (0.10 mol) of Mg in 50 ml of anhy-
drous ethyl ether followed by reacting the arising alcohol
with the iodine (5.4 g, 0.43 mol). Cycloolefin XVIII was
isolated as compound VIII above described. Yield 6.55 g
(94%). The characteristics of compound XVIII were con-
sistent with those published [6].
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005