8216 J . Org. Chem., Vol. 63, No. 23, 1998
Ranu and J ana
5.97-6.10 (m, 1H), 6.92 (d, J ) 9 Hz, 2H), 7.11 (d, J ) 9 Hz,
1H), 9.62 (d, J ) 0.9 Hz, 1H); 13C NMR δ 14.5 (CH3), 52.0 (CH),
68.7 (CH2), 115.3 (2 CH), 117.5 (CH2), 133.1 (CH), 158.0 (C),
129.71 (2 CH), 130.5 (C), 200.9 (CH). Anal. Calcd for
OMe, CO2Me, and double and triple bonds. We believe
this method will find many useful applications in organic
synthesis.
C
12H14O2: C, 75.75; H, 7.42. Found: C, 75.48; H, 7.46.
Exp er im en ta l Section
2-[4-(2-P r op yn oxy)p h en yl]p r op a n a l (en tr y 7): IR (neat)
1510, 1610, 1720 cm-1; H NMR δ 1.34 (d, J ) 7.2 Hz, 3H),
2.45 (t, J ) 2.4 Hz, 1H), 3.51 (m, 1H), 4.62 (d, J ) 2.4 Hz,
2H), 6.92 (d, J ) 8.4 Hz, 2H), 7.07 (d, J ) 6.6 Hz, 2H), 9.57 (d,
J ) 0.9 Hz, 1H); 13C NMR δ 15.0 (CH3), 52.5 (CH), 56.2 (CH2),
76.0 (CH), 97.4 (C), 115.0 (2 CH, C), 129.9 (2 CH, C), 201.4
(CH). Anal. Calcd for C12H12O2: C, 76.56; H, 6.43. Found: C,
76.78; H, 6.54.
2-(3-Ca r boeth oxycycloh exyl)-2-p h en yleth a n a l (en tr y
10): IR (neat) 1450, 1600, 1730 (broad) cm-1; 1H NMR δ 1.27
(t, J ) 7 Hz, 3H), 1.54-2.32 (m, 10H), 3.66 (m, 1H), 4.15 (q, J
) 7 Hz, 2H), 7.17-7.58 (m, 5H), 9.70 (d, J ) 3.3 Hz, 1H); 13C
NMR δ 14.1 (CH3), 21.9 (CH2), 25.0 (CH2), 28.2 (CH2), 30.9
(CH2), 38.9 (CH), 42.5 (2 CH), 127.2 (CH), 128.66 (CH), 128.9
(CH), 129.3 (CH), 129.4 (CH), 132.9 (2 C), 175.1 (C), 200.3
(CH). Anal. Calcd for C17H22O3: C, 74.41; H, 8.09. Found: C,
74.63; H, 8.18.
1
Gen er a l. 1H and 13C NMR spectra were recorded in CDCl3
solution at 300 and 75 MHz, respectively. Analyses were done
on a Perkin-Elmer 2400 autoanalyzer. Indium(III) chloride
was purchased from Aldrich and used as such. Tetrahydro-
furan (THF) was distilled over potassium-benzophenone
immediately before use. Thin-layer chromatography was done
on precoated silica gel plates (E. Merck). Silica gel (60-120
mesh, SRL, India) was used for column chromatography.
Epoxides used in this investigation were prepared either
from olefins or from carbonyl compounds following reported
procedures.2,5,7,8 A few epoxides which were not previously
reported in the literature have been identified from their 1H
NMR spectra and analysis. These data are included in
Supporting Information.
Gen er a l P r oced u r e for Rea r r a n gem en t of Ep oxid es.
Rep r esen ta tive P r oced u r e. A solution of styrene oxide (240
mg, 2 mmol) in THF (2 mL) was added to a stirred suspension
of InCl3 (265 mg, 1.2 mmol) in THF (3 mL) at room temper-
ature (25 °C) under nitrogen, and stirring was continued for
15 min for a complete reaction (TLC). The reaction mixture
was quenched with brine and extracted with ether. The ether
extract was dried over Na2SO4 and evaporated to leave a crude
product which was purified by column chromatography over
silica gel to afford pure phenylacetaldehyde (204 mg, 85%)
which is easily identified by comparison of its spectra (IR and
NMR) with those of an authentic sample.14
2,2-Dip h en ylp r op a n a l (en tr y 16): IR (neat) 1450, 1490,
1600, 1725 cm-1; 1H NMR δ 1.78 (s, 3H), 7.10-7.40 (m, 10H),
9.93 (s, 1H); 13C NMR δ 22.5 (CH3), 65.5 (C), 126.4 (2 C), 127.5
(2 CH), 127.7 (4 CH), 128.1 (4 CH), 199.6 (CH). Anal. Calcd
for C15H14O: C, 85.67; H, 6.72. Found: C, 85.36; H, 6.54.
Meth yl (3-ch lor o-2-h yd r oxy-3-p h en yl)p r op ion a te (a 2:1
m ixtu r e of syn :a n ti by NMR) (en tr y 19): IR (neat) 700,
1455, 1495, 1600, 1750, 3300-3600 (braod) cm-1; H NMR δ
1
3.08 (broad, 1H), 3.74 (s, <3H), 3.86 (s, <3H), 4.54 (d, J ) 2.4
Hz, <1H), 4.66 (d, J ) 4.2 Hz, <1H), 5.23 (d, J ) 4.2 Hz, <1H),
5.33 (d, J ) 2.4 Hz, <1H), 7.33-7.54 (m, 5H). Anal. Calcd
for C10H11O3Cl: C, 56.06; H, 5.18. Found: C, 55.76; H, 5.28.
This procedure is followed for the rearrangement of all the
epoxides included in Table 1. Many of these products are
known compounds and were easily characterized by compari-
son with authentic samples. Those which are unknown have
been identified by their spectral (IR, 1H and 13C NMR) and
analytical data. These data are presented below in order of
their entries in Table 1.
3-Ch lor o-3-p h en yl-2-p r op a n on e (en tr y 20): IR (neat)
700, 1350, 1610, 1720 cm-1; H NMR δ 2.22 (s, 3H), 5.35 (s,
1
1H), 7.37-7.49 (m, 5H); 13C NMR δ 25.7 (CH3), 66.5 (C), 127.8
(2 CH, C), 129.0 (2 CH, C), 200.1 (C). Anal. Calcd for C9H9-
OCl: C, 64.27; H, 5.40. Found: C, 64.36; H, 5.42.
2-(4-Meth oxyp h en yl)eth a n a l (en tr y 2):IR (neat) 1515,
3-Meth yl-3-n a p h th yl-2-bu ta n on e (en tr y 21): IR (neat)
1
1610, 1725 cm-1; H NMR δ 3.69 (d, J ) 2.4 Hz, 2H), 3.80 (s,
1
1600, 1650, 1710 cm-1; H NMR δ 1.61 (s, 6H), 1.96 (s, 3H),
7.28-7.30 (m, 1H), 7.51 (m, 2H), 7.88-7.96 (m, 4H); 13C NMR
δ 25.0 (2 CH3), 25.6 (CH3), 52.6 (C), 124.1 (CH), 124.5 (CH),
125.9 (CH), 126.2 (CH), 127.5 (CH), 127.6 (CH), 128.4 (CH),
132.2 (C), 133.4 (C), 141.5 (C), 211.3 (C). Anal. Calcd for
3H), 6.94 (d, J ) 6.3 Hz, 2H), 7.13 (d, J ) 6.9 Hz, 2H), 9.72 (t,
J ) 2.4 Hz, 1H); 13C NMR δ 48.3 (CH2), 53.9 (CH3), 112.5 (C),
113.0 (2 CH), 126.2 (C), 129.3 (2 CH), 198.3 (CH). Anal. Calcd
for C9H10O2: C, 71.97; H, 6.72. Found: C, 72.15; H, 6.78.
2-(3,4-Dim eth oxyp h en yl)eth a n a l (en tr y 3): IR (neat)
C
15H16O: C, 84.86; H, 7.60. Found: C, 85.04; H, 7.70.
1
1520, 1610, 1725 cm-1; H NMR δ 3.63 (d, J ) 2.4 Hz, 2H),
3.87 (s, 6H), 6.70-6.89 (m, 3H), 9.73 (t, J ) 2.4 Hz, 1H); 13C
NMR δ 50.1 (CH2), 55.8 (2 CH3), 110.3 (C), 111.4 (CH), 112.4
(CH),121.0 (CH), 126.8 (C), 124.0 (C), 199.5 (CH). Anal. Calcd
for C10H12O3: C, 66.64; H, 6.72. Found: C, 66.82; H, 6.74.
2-[4-(2-P r op en oxy)p h en yl]p r op a n a l (en tr y 6): IR (neat)
1510, 1580, 1610, 1650, 1720 cm-1; 1H NMR δ 1.40 (d, J ) 6.9
Hz, 3H), 3.56 (m, 1H), 4.51-4.53 (m, 2H), 5.25-5.43 (m, 2H),
Ack n ow led gm en t. We are pleased to acknowledge
the financial support from CSIR, New Delhi [Grant 01-
(1504)/98]. U.J . is also thankful to CSIR for this fellow-
ship.
Su p p or tin g In for m a tion Ava ila ble: Spectroscopic and
analytical data for epoxides (entries 3, 6, 7, 10, and 13)
included in Table 1 (1 page). This material is contained in
libraries on microfiche, immediately follows this article in the
microfilm version of the journal, and can be ordered from the
ACS; see any current masthead page for ordering information.
(14) Pouchert, C. J . The Aldrich Library of NMR Spectra, 2nd ed.;
Aldrich Chemical Co., Inc.: Milwaukee, 1983; Vol. 1 and 2.
(15) Moffett, R. B.; Shriner, R. L. Organic Syntheses; Wiley: New
York, 1955; Collect. Vol. III, p 562.
(16) Funekawa, N.; Ogawa, S.; Kawai, T. J . Chem. Soc., Perkin
Trans. 1 1984, 1833.
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