The Journal of Organic Chemistry
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8.20 (d, 2H, J = 9.3 Hz), 9.71 (s, 1H); 13C NMR (acetone-d6, 300
MHz) δ 20.1, 30.4, 38.7, 118.6, 124.7, 128.2, 129.0, 135.3, 138.0,
142.8, 145.4, 171.2; LRMS (EI) m/z 284 (M+), 267, 254, 239, 226,
138, 119, 105, 91; HRMS C16H16O3N2 calcd 284.11610, found
284.11729.
(7) Klumpp, D. A.; Rendy, R.; Zhang, Y.; Gomez, A.; McElrea, A.
Org. Lett. 2004, 6, 1789.
(8) Hutchby, M.; Houlden, C. E.; Haddow, M. F.; Tyler, S. N. G.;
Lloyd-Jones, G. C.; Booker-Milburn, K. I. Angew. Chem., Int. Ed. 2012,
51, 548.
3-(4-Methoxyphenyl)-N-(4-nitrophenyl)propanamide (5).
Using general procedure B, 3-(4-methoxyphenyl)propionic acid (0.1
g, 0.56 mmol) provided compound 5 (0.16 g, 5.3 mmol, 95%) as a
yellow solid: mp = 140−143 °C; 1H NMR (CDCl3, 300 MHz) δ 2.71
(t, 2H, J = 7.5 Hz), 3.02 (t, 2H, J = 7.5 Hz), 3.79 (s, 3H), 6.84 (d, 2H,
J = 8.7 Hz), 7.15 (d, 2H, J = 8.4 Hz), 7.59 (s, 1H), 7.63 (d, 2H, J = 9.3
Hz), 8.17 (d, 2H, J = 9.3 Hz); 13C NMR (CDCl3, 300 MHz) δ 30.4,
39.8, 55.3, 113.4, 114.1, 119.0, 125.1, 126.4, 129.3, 132.1, 143.4, 143.6,
158.3, 171.0; HRMS C16H16O4N2 calcd 300.11101, found 300.10967.
3-(4-Bromophenyl)-N-(4-nitrophenyl)propanamide (6).
Using general procedure B, 3-(4-bromophenyl)propionic acid (0.4 g,
1.75 mmol) provided compound 6 (0.47 g, 1.35 mmol, 77%) as a
(9) Hutchby, M.; Houlden, C. E.; Ford, J. G.; Tyler, S. N. G.; Gagne,
M. R.; Lloyd-Jones, G. C.; Booker-Milburn, K. I. Angew. Chem., Int. Ed.
2009, 48, 8721.
(10) Ashley, A. E.; Herrington, T. J.; Wildgoose, G. G.; Zaher, H.;
Thompson, A. L.; Rees, N. H.; Kramer, T.; O’Hare, D. J. Am. Chem.
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Soc. 2011, 133, 14727.
(11) Zhang, Y.; Briski, J.; Zhang, Y.; Rendy, R.; Klumpp, D. A. Org.
Lett. 2005, 7, 2505.
(12) (a) Ohta, T.; Shudo, K.; Okamoto, T. Tetrahedron Lett. 1984,
25, 325. (b) Ohta, T.; Machida, R.; Takeda, K.; Endo, Y.; Shudo, K.;
Okamoto, T. J. Am. Chem. Soc. 1980, 102, 6386.
(13) Koltunov, K. Yu.; Walspurger, S.; Sommer, J. Eur. J. Org. Chem.
2004, 69, 4039.
1
yellow solid: mp = 182−184 °C; H NMR (acetone-d6,, 300 MHz) δ
2.78 (t, 2H, J = 7.8 Hz), 3.01 (t, 2H, J = 7.5 Hz), 7.25 (d, 2H, J = 8.4
Hz), 7.45 (d, 2H, J = 8.4 Hz), 7.88 (d, 2H, J = 9.3 Hz), 8.20 (d, 2H, J
= 9.3 Hz), 9.72 (s, 1H; 13C NMR (acetone-d6,, 300 MHz) δ 30.1, 38.2,
112.6, 112.7, 118.6, 118.7, 119.4, 124.7, 126.0, 130.5, 131.3, 140.6,
142.8, 145.3, 170.9; LRMS (EI) m/z 350, 290, 211, 183, 171, 138, 122,
104, 90, 77, 63; LRMS (EI) m/z 350/348 (M+), 320/318, 213/211,
1171/169, 138; HRMS C15H13O3N2Br calcd 348.01096, found
348.01053.
(14) Booth, B. L.; El-Fekky, T. A. J. Chem. Soc., Perkin Trans. 1 1979,
2441.
(15) Hosseini-Sarvari, M.; Sodagar, E.; Doroodmand, M. M. J. Org.
Chem. 2011, 76, 2853.
(16) See the Supporting Information.
(17) (a) Gauvreau, D.; Dolman, S. J.; Hughes, G.; O’Shea, P. D.;
Davies, I. W. J. Org. Chem. 2010, 75, 4078. (b) Effenberger, F.; Gleiter,
R. Chem. Ber. 1964, 97, 472.
(18) Olah, G. A.; Prakash, G. K. S.; Molnar, A.; Sommer, J. Superacid
Chemistry, 2nd ed.; Wiley: New York, 2009.
(E)-N-(4-Nitrophenyl)-4-phenylbut-3-enamide (14). Using
general procedure B, styrylacetic acid (0.10 g, 0.62 mmol) provided
1
compound 14 (0.093 g, 0.33 mmol, 53%) as a yellow oil: H NMR
(19) (a) Gaussian 09, Revision A.1: Frisch, M. J.; Trucks, G. W.;
Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.;
Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji,
H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.;
Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.;
Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,
O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.;
Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.;
Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.;
Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega,
N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;
Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.;
(CDCl3, 300 MHz) δ 3.40 (dd, 2H, J = 1, 7.2 Hz), 6.32−6.42 (m, 1H),
6.63−6.68 (m, 1H), 7.27−7.43 (m, 5H), 7.73 (d, 2H, J = 9.3 Hz), 7.87
(s, 1H), 8.20 (d, 2H, J = 9 Hz); 13C NMR (CDCl3, 300 MHz) δ 42.0,
113.4, 119.2, 120.8, 125.1, 126.4, 128.26, 129.0, 136.1, 143.5, 143.6,
169.4; HRMS C16H14O3N2 calcd 282.10045, found 282.10067.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C NMR spectra for compounds 1b, 3−6, and 14;
computation methods and results. This material is available free
AUTHOR INFORMATION
Corresponding Author
̈
Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.;
■
Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc.,
Wallingford, CT, 2009. (b) Stephens, P. J.; Devlin, F. J.; Chabalowski,
C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623. (c) Kutzelnigg, W.;
Fleischer, U.; Schindler, M. In NMR, Basic Principles and Progress;
Notes
The authors declare no competing financial interest.
Diehl, P., Fluck, E., Gunther, H., Kosfield, R., Seelig, J., Eds.; Springer-
̈
Verlag: Berlin, 1990; Vol. 23, pp 165−262.
ACKNOWLEDGMENTS
(20) Arnett, E. M. Prog. Phys. Org. Chem. 1963, 1, 223.
(21) Sargeant, E. P.; Dempsey, B. Ionisation Constants of Organic
Acids in Aqueous Solution; Pergamon Press: Oxford, 1979.
(22) Examination of the calculated shifts for ions 27 and 26 raises the
following question: Why is 27 more shielded than 26 especially since
27 has a nitro substituent? This may be related to the most stable
conformation(s) arising from the calculations. In 27, the amide bond is
in the same plane as the phenyl ring, while in 26 the amide bond is
almost perpendicular to the phenyl ring plane (see the Supporting
Information).
■
The financial support from the Åke Wiberg Foundation (S. O.
N. L.) and the NIH-National Institute of General Medical
Sciences (GM085736-01A1; D.A.K.) is gratefully acknowl-
edged.
DEDICATION
■
Dedicated to Professor George A. Olah on the occasion of his
85th birthday.
(23) Olah, G. A.; Burrichter, A.; Rasul, G.; Gnann, R.; Christe, K. O.;
Prakash, G. K. S. J. Am. Chem. Soc. 1997, 119, 8035.
REFERENCES
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(24) Acetyl chloride (ca. 50 mg, 0.64 mmol) was dissolved in 1 mL of
FSO3H at 0 °C, and the spectrum was taken at 25 °C (acetone-d6,
external standard). For comparison: acetyl chloride, carbonyl 13C at δ
170.4; acetic anhydride, carbonyl 13C at δ 166.2.
(25) Cox, C.; Lectka, T. Acc. Chem. Res. 2000, 33, 849.
(26) Olah, G. A.; Klumpp, D. A. Superelectrophiles and Their
Chemistry; Wiley: New York, 2008.
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