1064
Vol. 50, No. 8
extracted with ether, washed with brine, and dried over anhydrous MgSO4.
After removal of the solvents, the crude products were purified by column
chromatography on silica-gel using ethyl acetate–n-hexane (1 : 40) to afford
a mixture of nitrated products 1 and 2 as a yellow oil (74% yield). The iso-
mer ratio of the products determined by 1H-NMR was 1 : 2ϭ16 : 84.
Spectral data and mps of the new compounds as well as those of the less
common compounds are shown below.
5) Waller F. J., Barrett A. G. M., Braddock D. C., Ramprasad D., J. Chem.
Soc., Chem. Commun., 1997, 613—614 (1997).
6) Ramprasad D., Waller F. J., Barrett A. G. M., Braddock D. C., U.S.
Patent 5728901 (1998) [Chem. Abstr., 128, 204692 (1998)].
7) Waller F. J., Barrett A. G. M., Braddock D. C., Ramprasad D., Tetrahe-
dron Lett., 39, 1641—1642 (1998).
8) Waller F. J., Barrett A. G. M., Braddock D. C., Ramprasad D., McKin-
nell R. M., White J. P., Williams D. J., Ducray R., J. Org. Chem., 64,
2910—2913 (1999).
9) Waller F. J., Ramprasad D., Barrett A. G. M., Braddock D. C., Chem.
Ind. (Dekker), 75, 289—305 (1998).
4-Methoxy-3-nitroacetophenone (13)58): mp 92—94 °C (ethyl acetate); IR
(KBr) 1680, 1535, 1275, 1240 cmϪ1; 1H-NMR (CDCl3) d: 2.61 (s, 3H), 4.04
(s, 3H), 7.17 (d, 1H, Jϭ8.5 Hz), 8.18 (dd, 1H, Jϭ8.5, 2.5 Hz), 8.43 (d, 1H,
Jϭ2.5 Hz). Anal. Calcd for C9H9NO4: C, 55.38; H, 4.65; N, 7.18%. Found:
C, 55.10; H, 4.84; N, 7.15%.
(4-Methoxy-3-nitrophenyl)-methanediol Diacetate (14): mp 69—72 °C
(ethyl acetate); IR (KBr) 1740, 1535, 1350, 1245 cmϪ1; 1H-NMR (CDCl3) d:
2.14 (s, 6H), 3.99 (s, 3H), 7.12 (d, 1H, Jϭ8.5 Hz), 7.63 (s, 1H), 7.69 (dd,
10) Waller F. J., Barrett A. G. M., Braddock D. C., McKinnell R. M., Ram-
prasad D., J. Chem. Soc., Perkin Trans. 1, 1999, 867—872 (1999).
11) Barrett A. G. M., Braddock D. C., Ducray R., McKinnell R. M.,
Waller F. J., Synlett, 2000, 57—58 (2000).
1H, Jϭ8.5, 2.0 Hz), 8.04 (d, 1H, Jϭ2.0 Hz). Anal. Calcd for C12H13NO7: C, 12) Suzuki H., Murashima T., Kozai I., Mori T., J. Chem. Soc., Perkin
50.88; H, 4.63; N, 4.95%. Found: C, 50.92; H, 4.70; N, 5.00%.
Trans. 1, 1993, 1591—1957 (1993).
13) Suzuki H., Mori T., J. Chem. Soc., Perkin Trans. 2, 1994, 479—484
(4-Methoxyphenyl)-methanediol Diacetate (15)59): mp 60—63 °C (ethyl
acetate); IR (KBr) 1750, 1545 cmϪ1; 1H-NMR (CDCl3) d: 2.09 (s, 6H), 3.80
(s, 3H), 6.89 (d, 2H, Jϭ8.5 Hz), 7.45 (d, 2H, Jϭ8.5 Hz), 7.62 (s, 1H). Anal. 14) Suzuki H., Murashima T., J. Chem. Soc., Perkin Trans. 1, 1994, 903—
(1994).
Calcd for C12H13NO7: C, 50.88; H, 4.63; N, 4.95%. Found: C, 50.92; H,
4.70; N, 5.00%.
908 (1994).
15) Suzuki H., Yonezawa S., Mori T., Maeda K., J. Chem. Soc., Perkin
Trans. 1, 1994, 1367—1639 (1994).
(E)-3-(2-Nitrophenyl)-2-propene-1,1-diol Diacetate (16)60)
: mp 75—
80 °C (ethyl acetate); IR (KBr) 1760, 1530, 1350, 1240, 1200, 1100, 1070, 16) Suzuki H., Mori T., Maeda K., Synthesis, 1994, 841—845 (1994).
1010 cmϪ1
;
1H-NMR (CDCl3) d: 2.15 (s, 6H), 6.19 (dd, 1H, Jϭ16.0,
17) Suzuki H., Mori T., J. Chem. Soc., Perkin Trans. 2, 1995, 41—44
5.5 Hz), 7.34 (d, 1H, Jϭ5.5 Hz), 7.38 (d, 1H, Jϭ16.0 Hz), 7.4—7.7 (m, 3H),
8.0 (d, 1H, Jϭ7.5 Hz).
(1995),
18) Suzuki H., Mori T., J. Chem. Soc., Perkin Trans. 1, 1995, 291—293
(E)-3-(4-Nitrophenyl)-2-propene-1,1-diol Diacetate (17)61) mp 105—
(1995).
109 °C (ether–n-hexane); IR (KBr) 1760, 1530, 1350, 1240, 1200, 1100, 19) Suzuki H., Tatsumi A., Ishibashi T., Mori T., J. Chem. Soc., Perkin
1
1070, 1010 cmϪ1; H-NMR (CDCl3) d: 2.15 (s, 6H), 6.37 (dd, 1H, Jϭ16.0,
5.5 Hz), 6.93 (d, 1H, Jϭ16.0 Hz), 7.33 (d, 1H, Jϭ6.5 Hz), 7.57 (d, 2H,
Jϭ8.5 Hz), 8.21 (d, 2H, Jϭ8.5 Hz).
Trans. 1, 1995, 339—343 (1995).
20) Suzuki H., Tomaru J., Murashima T., J. Chem. Soc., Perkin Trans. 1,
1994, 2413—2416 (1994).
(E)-3-Phenyl-2-propene-1,1-diol Diacetate (18)32): mp 81—84 °C (ethyl 21) Suzuki H., Yonezawa S., Mori T., Bull. Chem. Soc. Jpn., 68, 1535—
acetate); IR (KBr) 1760, 1680, 1625, 1490, 1455, 1375, 1245, 1195, 1130,
1060, 1000, 940, 750, 690 cmϪ1; 1H-NMR (CDCl3) d: 2.11 (s, 6H), 6.19 (dd,
1H, Jϭ16.5, 6.4 Hz), 6.90 (d, 1H, Jϭ16.5 Hz), 7.1—7.6 (m, 6H), 7.57 (d,
2H, Jϭ8.5 Hz), 8.21 (d, 2H, Jϭ8.5 Hz).
1544 (1995).
22) Suzuki Hit, Tatsumi A., Suzuki Hid, Maeda K., Synthesis, 1995,
1353—1554 (1995).
23) Suzuki H., Mori T., J. Chem. Soc., Perkin Trans. 2, 1996, 677—683
(1996).
24) Suzuki H., Yonezawa S., Nonoyama N., Mori T., J. Chem. Soc., Perkin
Trans. 1, 1996, 2385—2389 (1996).
25) Suzuki H., Mori T., J. Org. Chem., 62, 6498—6502 (1997).
1-Acetyl-7-nitroindoline (20)62): IR (KBr) 1670, 1520, 1400, 1320 cmϪ1
;
1H-NMR (CDCl3) d: 2.27 (s, 3H), 3.23 (t, 2H, Jϭ8.0 Hz), 4.24 (t, 2H,
Jϭ8.0 Hz), 7.14 (dd, 1H, Jϭ8.0, 8.0 Hz), 7.42 (ddd, 1H, Jϭ8.0, 1.5, 1.5 Hz),
7.62 (dd, 1H, Jϭ8.0, 1.5 Hz).
2-(2-Nitrophenyl)ethyl Acetate (22)63): Yellow oil; IR (neat) 1720, 1520, 26) Enya T., Suzuki H., Hisamatsu Y., Bull. Chem. Soc. Jpn., 71, 2221—
1350, 1240 cmϪ1
1.5 Hz), 4.36 (t, 2H, Jϭ8.0 Hz), 7.40 (m, 2H), 7.41 (ddd, 1H, Jϭ8.0, 8.0, 27) For example see: Deans F. B., Eaborn C., J. Chem. Soc., 1957, 498—
1.5 Hz), 7.94 (dd, 1H, Jϭ8.0, 1.5 Hz). 499 (1957).
2-(4-Nitrophenyl)ethyl Acetate (23)64): Yellow oil; IR (neat) 1720, 1520, 28) For example see: Paul M. A., J. Am. Chem. Soc., 80, 5329—5332
1350, 1240 cmϪ1 1H-NMR (CDCl3) d: 2.04 (s, 3H), 3.06 (td, 2H, Jϭ8.0,
(1958).
1.5 Hz), 4.33 (td, 2H, Jϭ8.0, 1.5 Hz), 7.40 (dd, 2H, Jϭ8.0, 1.5 Hz), 8.18 (dd, 29) For example see: Bordwell F. G., Garbisch E. W., J. Am. Chem. Soc.,
2H, Jϭ8.0, 1.5 Hz). 82, 3588—3598 (1960).
;
1H-NMR (CDCl3) d: 2.03 (s, 3H), 3.26 (td, 2H, Jϭ8.0,
2228 (1998).
;
(E)-2-Nitrocinnamyl Acetate (25): Yellow oil; IR (neat) 1740, 1520, 1345, 30) For example see: Sparks A. K., J. Org. Chem., 31, 2299—2302 (1966).
1
1230, 1440, 1030, 965, 860, 785, 740, 700 cmϪ1; H-NMR (CDCl3) d: 2.13 31) For example see: Hartshorn S. R., Moodie R. B., Schofield K., J.
(s, 3H), 4.78 (dd, 2H, Jϭ6.0, 1.5 Hz), 6.27 (dt, 1H, Jϭ16.0, 6.0 Hz), 7.14
Chem. Soc. B, 1971, 1256—1261 (1971).
(dd, 1H, Jϭ16.0, 1.5 Hz), 7.43 (ddd, 1H, Jϭ8.0, 7.5, 2.0 Hz), 7.5—7.6 (m, 32) For example see: Kurz M. E., Yang L. T. A., Zahora E. P., Adams R.
2H), 7.95 (dd, 1H, Jϭ8.0, 0.5 Hz). C., J. Org. Chem., 38, 2271—2281 (1973).
(E)-4-Nitrocinnamyl Acetate (26): Yellow oil; IR (neat) 1740, 1520, 1345, 33) For example see: Narang S. C., Thompson M. J., Aust. J. Chem., 28,
1
1230, 1440, 1030, 965, 860, 785, 740, 700 cmϪ1; H-NMR (CDCl3) d: 2.13
(s, 3H), 4.78 (dd, 2H, Jϭ6.0, 1.5 Hz), 6.46 (dt, 1H, Jϭ16.0, 6.0 Hz), 7.14
(dd, 1H, Jϭ16.0, 1.5 Hz), 7.52 (d, 2H, Jϭ8.5 Hz), 8.19 (d, 2H, Jϭ8.5 Hz).
385—389 (1975).
34) For example see: Sifniades S., J. Org. Chem., 40, 3562—3566 (1975).
35) For example see: Morzycki J. W., Lotowski Z., Stepniowska M.,
Gryszkiewicz A., Wilczewska A. Z., Tetrahedron, 53, 16161—16168
(1997).
Acknowledgements We are grateful to the SC-NMR Laboratory of
Okayama University for high-field NMR experiments.
36) For example see: Olah G. A., Malhotra R., Narang S. C., “Nitration:
Methods and Mechanisms,” VCH Publishers Inc., New York, 1989,
pp. 43—45.
References and Notes
1) Olah G. A., Malhotra R., Narang S. C., “Nitration: Methods and 37) Olah G. A., Malhotra R., Narang S. C., “Nitration: Methods and
Mechanisms,” VCH Publishers Inc., New York, 1989. Mechanisms,” VCH Publishers Inc., New York, 1989, pp. 32—36.
2) Olah G. A., “Friedel–Crafts and Related Reactions,” Vol. 3, Wiley-In- 38) Crivello J. V., J. Org. Chem., 46, 3056—3060 (1981).
terscience, New York, 1964.
3) “The Chemistry of the Nitro and Nitroso Groups,” Vol. II, ed. by Feuer
39) For example see: Kobayashi S., Hachiya I., Yamanoi Y., Bull. Chem.
Soc. Jpn., 67, 2342—2344 (1994).
H., in the series of “The Chemistry of Functional Groups,” ed. by Patai 40) For example see: Hachiya I., Kobayashi S., J. Org. Chem., 58, 6958—
S., Wiley-Interscience, New York, 1969. 6966 (1993).
4) “Supplement F: The Chemistry of Amino, Nitroso and Nitro Com- 41) For example see: Manabe K., Oyamada H., Sugita K., Kobayashi S., J.
pounds and Their Derivatives,” ed. by Patai S., in the series of “The Org. Chem., 64, 8054—8057 (1999).
Chemistry of Functional Groups,” ed. by Patai S., Wiley, New York, 42) For example see: Kobayashi S., Ishitani H., Hachiya I., Araki M.,
1982. Tetrahedron, 50, 11623—11633 (1994).