J. CHEM. RESEARCH (S), 1999 123
Table 2 Reactions of 2-alkylcycloalkanones with I2±CST in R3OHa
Substrate
Solvent
T/8C
t/h
Products (%)b
1a
1a
1b
1b
1b
1b
1b
1b
1f
EtOH
PrnOH
EtOH
65
65
20
21
4d
20
6d
20
6d
20
18
7
3a11b (61)
4a
(63)
Room temp.
65
Room temp.
65
Room temp.
65
65
65
3b11d (66)
7b (16)
8b (27)
EtOH
3b
4b
4b
5b
5b
(57)
(36)
(51)
(43)
(44)
PrnOH
PrnOH
PriOH
PriOH
EtOH
3f11h (90)
1f
PrnOH
4f
(98)
aSubstrate (2.72 mmol) with I2 (0.54 mmol)±CST (2.72 mmol) in alcohol (20 ml). bIsolated yield.
2 H), 1.74±1.83 (m, 2 H), 1.40±1.54 (m, 1 H) and 1.13 (d, 3 H); dC
(CDCl3) 203.9, 44.5, 42.3, 37.5, 36.1, 27.9 and 15.9 (Found: M ,
237.9831. C7H11OI requires Mr, 237.9855).
summarized in Table 2. For the more bulky alkoxy groups,
the yields of the oxo esters are diminished compared with
those for the methoxy reactions. However, in the case of
2-phenylcyclohexanone, the yields were not aected.
In conclusion, the present method provides a new alterna-
tive to others previously reported for the preparation of oxo
esters from cyclic ketones by using I2±cerium(IV) salts in
alcohol.
1
4f: Pale yellow oil; ꢀmax/cm (NaCl) 1731 and 1685; dH (CDCl3)
7.93±7.96 (2 H), 7.52±7.55 (1 H), 7.42±7.47 (2 H), 4.00±4.04 (t, 2 H),
2.97±3.00 (t, 2 H), 2.35±2.38 (t, 2 H), 1.71±1.80 (m, 4 H), 1.61±1.67
(m, 2 H) and 0.91±0.95 (t, 3 H); dC (CDCl3) 199.7, 173.5, 136.9,
133.0, 128.6, 128.6, 128.0, 128.0, 65.9, 38.1, 34.1, 24.7, 23.7, 22.0
and 10.4; MS (EI): m/z 248 [M ], 189(M
(CI): m/z 249 [M+1] .
59), 105 and 77; MS
1
5f: Colorless plates; mp 73±76 8C; ꢀmax/cm (KBr): 1712; dH
(CDCl3) 7.33±7.39 (m, 2 H), 7.25±7.31 (m, 1 H), 7.11±7.17 (m, 2 H),
4.78±4.82 (m, 1 H), 4.75 (dd, 1 H) and 1.89±2.32 (m, 6 H); dC
(CDCl3) 204.6, 137.8, 128.7, 128.4, 127.2, 50.4, 37.0, 34.8, 31.4 and
Experimental
IR spectra were measured using a Jasco FT-IR 230. NMR
spectra were measured on a JEOL GSX 400 spectrometer with the
samples dissolved in deuteriochloroform with Me4Si as the internal
standard. High-resolution mass spectra were recorded at 75 eV on a
JEOL JMS-O1 SG-2 instrument with a direct inlet.
22.0 (Found: M , 299.9985. C12H13OI requires Mr, 300.0011).
We thank Professor Sukekatsu Nozaki, Josai University,
for his measurements of the high-resolution mass spectra.
This work was supported by Rikkyo University Grant for
the Promotion of Research.
General Procedure. Reaction of 2-Methylcyclohexanone with
CST±I2 in MeOH.ÐA mixture of 2-methylcyclohexanone 1b
(0.305 g, 2.72 mmol), iodine (0.138 g, 0.54 mmol) and cerium(IV) sul-
fate tetrahydrate (1.099 g, 2.72 mmol) in MeOH (20 ml) was stirred
at room temperature for 4 days. The white precipitate of CeIII salt
was ®ltered o and the solvent was evaporated under reduced press-
ure. The residue was poured into water (20 ml) and extracted with
dimethyl ether (50 ml). The ethereal solution was washed succes-
sively with aq. sodium thiosulfate (10 ml), saturated aq. NaCl
(10 ml) and water (10 ml) and dried (Na2SO4). Evaporation of the
solvent gave a pale yellow oil. Methyl benzoate was added as an
internal standard if the yield was to be estimated by 1H NMR spec-
troscopy. The oil was chromatographed on silica gel with hexane±
ether (4:1) as the eluent to give the corresponding compound 2b as
a pale yellow oil (0.225 g, 52%).
Received, 10th August 1998; Accepted, 26th October 1998
Paper E/8/06288I
References
1 S. Ito and M. Matsumoto, J. Org. Chem., 1983, 48, 1133.
2 T. Hirao, M. Mori and Y. Oshiro, Bull. Chem. Soc. Jpn., 1989,
62, 2399.
3 T. Shono, Y. Matsumura, T. Imanishi and K. Yoshida, Bull.
Chem. Soc. Jpn., 1979, 51, 2179.
1
Spectroscopic and Analytical Data.Ð4a: Pale yellow oil, ꢀmax/cm
(NaCl) 1718 and 1172; ꢁH (CDCl3) 4.01±4.06 (t, 2 H), 2.50±2.54
(t, 2 H), 2.32±2.36 (t, 2 H), 2.15 (s, 3 H), 1.87±1.91 (m, 2 H),
1.62±1.68 (m, 2 H) and 0.92±0.96 (t, 3 H); ꢁC (CDCl3) 208.0, 173.3,
4 K. Kaneda, N. Kii, K. Jitsukawa and S. Teranishi, Tetrahedron
Lett., 1981, 22, 2595.
66.0, 42.5, 33.3, 29.9, 22.0, 19.0 and 10.4 (Found: M , 172.1086.
C9H16O3 requires Mr, 172.1100).
5 B. El Ali, J-M. Bregeault, J. Mercier, J. Martin, C. Martin and
O. J. Convert, J. Chem. Soc., Chem. Commun., 1989, 825.
6 A. Atlamsani and J.-M. Bregeault, J. Org. Chem., 1993, 58, 5663.
7 (a) C. A. Horiuchi, Y. Suzuki, M. Takahashi and J. Y. Satoh,
Chem. Lett., 1987, 393; (b) C. A. Horiuchi and Y. Suzuki,
Bull. Chem. Soc. Jpn., 1989, 62, 2919; (c) C. A. Horiuchi,
H. Kiyomiya, M. Takahashi and Y. Suzuki, Synthesis, 1989, 785.
8 (a) C. A. Horiuchi and S. Kiji, Chem. Lett., 1988, 31; (b) C. A.
Horiuchi, Y. Nishio, D. Gong, T. Fujisaki and S. Kiji, Chem.
Lett., 1991, 607; (c) C. A. Horiuchi, K. Ochiai and H. Fukunishi,
Chem. Lett., 1994, 185; (d) C. A. Horiuchi, H. Fukunishi,
M. Kajita, A. Yamaguchi, H. Kiyomiya and S. Kiji, Chem.
Lett., 1991, 1921; (e) C. A. Horiuchi and E. Takahashi, Bull.
Chem. Soc. Jpn., 1994, 67, 271.
1
4b: Pale yellow oil, ꢀmax/cm (NaCl) 1735 and 1716; dH (CDCl3)
4.01±4.04 (t, 2 H), 2.45±2.48 (t, 2 H), 2.30±2.34 (t, 2 H), 2.14
(s, 3 H), 1.60±1.68 (m, 6 H), and 0.92±0.96 (t, 3 H); dC (CDCl3)
208.5, 173.5, 65.9, 43.3, 34.1, 29.9, 24.5, 23.2, 22.0 and 10.4 (Found:
M , 186.1227. C10H18O3 requires Mr, 186.1256).
1
5b: Pale yellow oil, ꢀmax/cm (NaCl) 1727 and 1719; dH (CDCl3)
4.97±5.02 (m, 1 H), 2.45±2.48 (t, 2 H), 2.26±2.29 (t, 2 H), 2.14
(s, 3 H), 1.60±1.61 (m, 4 H) and 1.21±1.27 (d, 6 H); dC (CDCl3)
208.4, 172.8 67.5, 43.2, 34.4, 29.8, 24.5, 23.2, 21.8 and 21.8; MS
(EI): m/z 186 [M ], 127, 58, 43; MS (CI): m/z 187 [M 1] .
1
6b: ꢀmax/cm (NaCl) 1740 and 1156; dH (CDCl3) 4.48 (t, 1 H),
3.68 (s, 3 H), 2.43 (s, 3 H), 2.36 (t, 2 H), 1.88±2.02 (m, 2 H), 1.72±
1.84 (m, 1 H) and 1.54±1.68 (m, 1 H); dC (CDCl3) 202.2, 173.3,
51.6, 33.7, 33.0, 32.2, 26.1 and 24.6 (Found: M , 283.9939.
C8H13O3I requires Mr, 283.9909).
7b: ꢀmax/cm (NaCl) 1732; dH (CDCl3) 4.48 (t, 1 H), 4.13 (q,
1 H), 2.43 (s, 3 H), 2.35 (dt, 2 H), 1.88±2.02 (m, 2 H), 1.72±1.84
9 C. A. Horiuchi and S. Kiji, Bull. Chem. Soc. Jpn., 1997, 70, 421.
10 C. A. Horiuchi, A. Ikeda, M. Kanamori, H. Hosokawa,
T. Sugiyama and T. Takahashi, J. Chem. Res. (S), 1997, 60.
11 (a) W. G. Daub, R. N. Zuckermann and W. S. Johnson, J. Org.
Chem., 1985, 50, 1599; (b) T. Ishida and K. Wado, J. Chem.
Soc., Perkin Trans. 1, 1979, 323; (c) R. S. Randad, N. G. Bhat
and G. H. Kulkarni, Indian J. Chem., Sect. B, 1984, 22, 947;
(d) K. I. Kohdair, A. A. Magd, K-K. S. Hussain, H. M. Khairy
and E-K. M. Ahmed, Rev. Roumaine Chim., 1983, 28, 921;
(e) A. E. Berhanu and G. Sendaba, J. Chromatogr., 1985, 3, 440;
( f ) S. Takano, K. Masuda and K. Ogasawara, Heterocycles,
1981, 16, 1509; (g) B. M. Vivekananda, M. Ravindranathan,
S. Viswanatha and R. G. Venkoba, J. Org. Chem., 1984, 49,
3170; (h) T. Mukaiyama, M. Araki and H. Takei, U.S. Nat.
3,867,453, (Cl. 260-570AB; C07c), 18 Feb. 1975.
1
(m, 1 H), 1.55±1.68 (m, 1 H) and 1.26 (t, 3 H); dC (CDCl3) 202.2,
172.9, 60.5, 33.8, 33.3, 32.4, 26.1, 24.6 and 14.2 (Found: M ,
298.0038. C9H151O3I requires Mr, 298.0066).
8b: ꢀmax/cm (NaCl) 1732; dH (CDCl3) 4.50 (t, 1 H), 4.04 (t,
2 H), 2.43 (s, 3 H), 2.36 (dt, 2 H), 1.91±2.03 (m, 2 H), 1.71±1.84
(m, 1 H), 1.55±1.71 (m, 1 H) and 0.94 (t, 3 H); dC (CDCl3) 202.2,
172.9, 66.1, 33.7, 33.2, 32.3, 26.1, 24.6, 21.9 and 10.4 (Found: M ,
312.0209. C10H17O3I requires Mr, 312.0222).
9b: Colorless plates; mp 63±64 8C; ꢀmax/cm (KBr) 1716; dH
(CDCl3) 4.88 (d, 1 H), 2.74 (m, 1 H), 2.60 (m, 1 H), 2.11±2.31 (m,
1