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V. K. Yadav et al. / Tetrahedron 57 (2001) 7047±7051
7-methyl-2-oxepanone :0.256 g, 2 mmol) in Et2O :5 mL)
was added. The mixture was graduallywarmed to 25 8C
and then re¯uxed for 2 h. The reaction mixture was cooled
to 258C and mixed with saturated aqueous NH4Cl :5 mL)
and stirred for 10 min. The layers were separated and the
organic layer was washed with H2O :2£5 mL) and brine
:1£5 mL). This was dried and concentrated to furnish a
residue which was chromatographed over Al2O3 to isolate
the product, 0.255 g, liquid; 80% yield.
NMR d 5.46 :1H, bs), 5.24 :1H, bs), 2.04 :3H, s), 2.03±
1.86 :2H, m), 1.70 :3H, d, J0.08 Hz), 1.82±1.60 :4H, m).
13C NMR d 170.9, 141.1, 120.0, 68.8, 29.9, 28.0, 23.7, 21.5,
19.0. Anal. Calcd for C9H14O2: C, 70.08; H, 9.16. Found: C,
69.90; H, 8.96.
4.5.8. 1,6-Heptanediol diacetate 1liquid). 1H NMR d
4.93±4.85 :1H, m), 4.05 :2H, t, J6.6 Hz), 2.05 :3H, s),
2.03 :3H, s), 1.65±1.27 :8H, m), 1.20 :3H, d, J6.4 Hz). 13C
NMR d 171.2, 170.7, 70.8, 64.4., 35.7, 28.5, 25.7, 25.0,
21.3, 20.9, 19.9. Anal. Calcd for C11H20O4: C, 61.07; H,
9.33. Found: C, 59.90; H, 9.20.
1H NMR d 3.82±3.60 :1H, m), 1.65±1.25 :10H, m), 1.21
:6H, s), 1.19 :3H, d, J6.4 Hz). 13C NMR d 70.9, 67.9,
43.8, 39.2, 29.2, 29.1, 26.2, 24.2, 23.5. Anal. Calcd for
C9H20O2: C, 67.44; H, 12.59. Found: C, 67.32; H, 12.40.
1
4.5.9. 2-Methyl-2,7-octanediol monoacetate 1liquid). H
NMR d 4.94±4.86 :1H, m), 2.03 :3H, s), 1.21 :6H, s),
1.65±1.20 :9H, m), 1.16 :3H, d, J7.3 Hz). 13C NMR d
170.8, 70.91, 70.90, 43.7, 35.8, 29.21, 29.17, 25.9, 24.1,
21.3, 19.9. Anal. Calcd for C11H22O3: C, 65.30; H, 10.97.
Found: C, 65.15; H, 10.80.
4.5.3. Ethyl 3-12-Hydroxyphenyl)acrylate. Salicycl-
aldehyde :0.610 g, 5 mmol) was added to a stirred solution
of Ph3PvCHCO2Et :3.48 g, 10 mmol) in MeOH :15 mL).
After 30 min, the solvent was removed and the oilyresidue
was puri®ed bysilica gel chromatographyto furnish pure
ethyl 3-:2-hydroxyphenyl)acrylate, 0.865 g, liquid; 90%
yield.
4.5.10. 1-Phenyl-1,2-ethanediol diacetate 1liquid). 1H
NMR d 7.36±7.26 :5H, m), 6.02 :1H, dd, J7.9, 3.9 Hz),
4.36±4.26 :2H, m), 2.11 :3H, s), 2.05 :3H, s). 13C NMR d
170.5, 169.9, 136.4, 128.5, 126.6, 73.2, 66.0, 21.0, 20.6.
Anal. Calcd for C12H14O4: C, 58.04; H, 7.58. Found: C,
57.90; H, 7.45.
1H NMR d 8.08 :1H, d, J16.1 Hz), 7.65 :1H, s), 7.44 :1H,
dd, J7.8, 1.5 Hz), 7.24±7.19 :1H, dt, J7.7, 1.7 Hz),
6.91±6.86 :2H, m), 6.65 :1H, d, J16.1 Hz), 4.28 :2H, q,
J7.1 Hz), 1.34 :3H, t, J7.1 Hz). 13C NMR d 168.9,
155.8, 141.2, 131.5, 129.1, 121.6, 120.4, 117.9, 116.4,
60.8, 14.2.
1
4.5.11. 7-Methyl-6-octene-2-ol acetate 1liquid). H NMR
d 5.09 :1H, t, J7.0 Hz), 4.93±4.85 :1H, m), 2.03 :3H, s),
2.00±1.94 :2H, m), 1.69 :3H, s), 1.60 :3H, s), 1.65±1.55
:2H, m), 1.55±1.40 :2H, m), 1.40±1.25 :2H, m), 1.20 :3H,
d, J6.3 Hz). 13C NMR d 170.8, 131.7, 124.2, 71.0, 35.5,
27.7, 25.66, 25.60, 21.3, 19.9. Anal. Calcd for C11H20O2: C,
71.68; H, 10.95. Found: C, 71.54; H, 10.80.
4.5.4. 3-12-Hydroxyphenyl)propanol. A solution of ethyl
3-:2-hydroxyphenyl)acrylate :0.540 g, 2.82 mmol) in dry
THF :10 mL) was added slowlyto a suspension of LAH
:0.078 g, 2 mmol) in THF :5 mL) at 08C. The reaction
mixture was allowed to reach 258C and re¯uxed for 4 h. It
was brought back to 08C and the excess LAH was destroyed
byadding EtOAc. The contents were ®ltered and the solid
washed with Et2O. The solvents were removed and the
residue was puri®ed bysilica gel column chromatography
to obtain the desired product, 0.345 g, liquid; 80% yield.
4.5.12. tert-Butyl amine acetate 1mp 95±978C). 1H NMR d
5.69 :1H, bs), 1.92 :3H, s), 1.34 :9H, s). 13C NMR d 169.6,
51.2, 28.7, 24.4. Anal. Calcd for C6H13NO: C, 62.55; H,
11.38. Found: C, 62.40; H, 11.15.
1
4.5.13. p-Bromophenol acetate 1liquid). H NMR d 7.47
:2H, d, J8.5 Hz), 6.97 :2H, d, J8.5 Hz), 2.28 :3H, s). 13C
NMR d 169.1, 149.6, 132.4, 123.3, 118.9, 21.0.
1H NMR d 7.76 :1H, bs), 7.08±7.04 :2H, m), 6.86±6.80
:2H, m), 3.60 :2H, t, J5.9 Hz), 2.74 :2H, t, J7.1 Hz),
1.87±1.81 :2H, m). 13C NMR d 154.2, 130.6, 127.4,
120.7, 115.8, 60.9, 32.2, 25.3. Anal. Calcd for C9H12O2:
C, 71.01; H, 7.95. Found: C, 70.85; H, 7.78.
Acknowledgements
The authors thank the Council of Scienti®c and Industrial
Research, Government of India, for ®nancial support and
Department of Science and Technology, Government of
India, for funding a 400 MHz NMR spectrometer.
4.5.5. b-Citronellol acetate 1liquid). 1H NMR d 5.08 :1H,
t, J7.1 Hz), 4.15±4.05 :2H, m), 2.03 :3H, s), 2.00±1.87
:2H, m), 1.68 :3H, s), 1.70±1.62 :1H, m), 1.60 :3H, s),
1.58±1.50 :1H, m), 1.47±1.41 :1H, m), 1.40±1.30 :1H,
m), 1.23± 1.14 :1H, m), 0.91 :3H, d, J6.4 Hz). 13C
NMR d 171.1, 131.3, 124.5, 63.0, 36.9, 35.4, 29.4, 25.7,
25.3, 21.0, 19.4, 17.6. Anal. Calcd for C12H22O2: C, 72.67;
H, 11.19. Found: C, 72.45; H, 10.96.
References
1. Protecting Groups; Kocienski, P. J., Ed.; George Thieme:
Stuttgart, 1994; p. 23.
4.5.6. Methyl mandelate acetate 1liquid). 1H NMR d
7.47±7.44 :2H, m), 7.39±7.36 :3H, m), 5.92 :1H, s), 3.69
:3H, s), 2.17 :3H, s). 13C NMR d 170.1, 169.1, 133.6, 129.1,
128.6, 127.5, 74.3, 52.4, 20.5. Anal. Calcd for C11H12O4: C,
63.44; H, 5.81. Found: C, 63.30; H, 5.65.
2. Ho¯e, G.; Steglich, V.; Vorbruggen, H. Angew. Chem., Int.
Ed. Engl. 1978, 17, 569±583.
3. Vedej, E.; Diver, S. T. J. Am. Chem. Soc. 1993, 115, 3358±
3359.
4. Vedejs, E.; Daugulis, O. J. Org. Chem. 1996, 61, 5702±5703.
5. D'Sa, B. A.; Verkade, J. G. J. Org. Chem. 1996, 61, 2963±
2966.
4.5.7. 3-Methyl-2-cyclohexen-1-ol acetate 1liquid). 1H