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N. Iranpoor et al. / Tetrahedron 65 (2009) 3893–3899
Table 4 (continued )
Entry
Acid
Amine
Product
Yieldb (%)ref
O
O
H
N
14
9323
OH
N
O2N
O2N
O
O
H
N
15
9023
OH
N
a
All the reactions were finished in 1 min.
Isolated yield.
b
3.1.1. Typical procedure for N-benzylation of 4-amino-2,3-
dimethyl-1-phenyl-3-pyrazolin-5-one
3.1.4. Typical procedure for the conversion of benzoic acid to
benzanilide
To a flask containing a stirred mixture of Ph3P (1.2 mmol, 0.314 g)
and DDQ (1.2 mmol, 0.272 g) in dichloromethane (5 mL) was added 4-
amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (1.2 mmol, 0.244 g)
at room temperature. Benzyl alcohol (1.0 mmol, 0.1 mL) was then
addedtothereactionmixture. TLCmonitoringshowedthecompletion
of thereactionafter1 min. Thesolventwasevaporatedandtheresidue
was chromatographed on a silica gel column using n-hexane/ethyl
acetate (4:1) as eluent. 4-(N-Benzylamino)-2,3-dimethyl-1-phenyl-3-
pyrazolin-5-one was obtained in 86% yield (0.30 g). IR (neat) 3403,
To a stirred solution of Ph3P (1.2 mmol, 0.314 g) and DDQ
(1.2 mmol, 0.272 g) in 5 mL dichloromethane at room temperature
was added aniline (1.2 mmol, 0.11 mL) and benzoic acid (1 mmol,
0.122 g) successively. After completion of the reaction, the residue
was washed with 4% aq HCl to remove the excess of aniline and
dried with anhydrous Na2SO4. Evaporation of the solvent followed
by column chromatography of the crude mixture on silica gel using
n-hexane/ethyl acetate (3:1) as eluent gave benzanilide in 90% yield
(0.177 g) (mp 161 ꢀC, lit.10 mp 163 ꢀC). IR (neat) 3350, 2933, 2869,
3054, 2986, 2928, 1662, 1594, 1455, 1359 cmꢁ1
CDCl3):
(ppm)¼1.86 (3H, s), 2.06 (1H, s), 2.60 (3H, s), 5.18 (2H, s),
7.07–7.42 (10H, m); 13C NMR (62.9 MHz, CDCl3):
;
1H NMR (250 MHz,
1654, 1603, 1456, 1434, 720 cmꢁ1 1H NMR (250 MHz, CDCl3):
;
d
d
(ppm)¼7.15–8.08 (11H, Complex); 13C NMR (62.9 MHz, CDCl3):
d
(ppm)¼9.75, 36.32,
d
(ppm)¼120.26, 124.57, 127.04, 128.44, 128.76, 131.83, 133.56,
57.81, 113.45, 123.34, 126.04, 126.82, 127.65, 127.93, 128.10, 128.82,
129.00,139.83, 154.59. Anal. Calcd for C18H19N3O: C, 73.69; H, 6.53; N,
14.32%. Found: C, 73.46; H, 6.57; N, 14.22%.
137.90, 165.85. Anal. Calcd for C13H11NO: C, 79.16; H, 5.62; N, 7.10%.
Found: C, 79.07; H, 5.59; N, 7.13%.
Acknowledgements
3.1.2. Typical procedure for the conversion of aniline to N,N-
dimethylaniline
We are thankful to the Organization of Management and
Planning of Iran and Shiraz University Research Council for the
support of this work.
To a stirred solution of Ph3P (3.0 mmol, 0.78 g), DDQ (3.0 mmol,
0.68 g), and aniline (1.0 mmol, 0.09 mL) in dichloromethane (5 mL)
at room temperature was added methanol (3.0 mmol, 0.12 mL). The
reaction was monitored by TLC. After 30 min, the solvent was
evaporated. Column chromatography of the crude mixture on silica
gel using n-hexane/ethyl acetate (3:1) as eluent gave N,N-dime-
thylaniline in 66% yield (0.08 g) (bp 193 ꢀC, lit.10 bp 194.15 ꢀC). IR
(neat) 3025, 2888, 2809, 1605, 1513, 1440, 1341, 753 cmꢁ1; 1H NMR
References and notes
1. Seayad, A. M. A.; Klein, H.; Jackstell, R.; Gross, T.; Beller, M. Science 2002, 297,1676.
2. Smith, M. B.; March, J. Advanced Organic Chemistry, 5th ed.; Wiley: New York,
NY, 2001; p 499.
3. (a) Smith, M. B.; March, J. Advanced Organic Chemistry, 5th ed.; Wiley: New
York, NY, 2001; p 1187; (b) Abdel-Magid, A. F.; Carson, K. G.; Harris, B. D.;
Maryanoff, C. A.; Shah, R. D. J. Org. Chem. 1996, 61, 3849; (c) Firouzabadi, H.;
Iranpoor, N.; Alinejhad, H. Bull. Chem. Soc. Jpn. 2003, 76, 143.
4. Salomaa, S. In The Chemistry of Carbonyl Group; Patai, S., Ed.; Wiley: New York,
NY, 1966; Vol. 1, pp 177–210.
5. Rice, R. G.; Kohn, E. J. J. Am. Chem. Soc. 1955, 77, 4052.
(CDCl3, 250 MHz)
d
(ppm)¼3.07 (s, 6H), 7.00–7.05 (m, 2H), 7.24–7.28
(m, 1H), 7.70–7.74 (m, 2H); 13C NMR (62.9 MHz, CDCl3)
d
(ppm)¼29.30,111.17,116.08,127.39,148.40. Anal. Calcd for C8H11N:
C, 79.29; H, 9.15; N, 11.56%. Found: C, 79.16; H, 9.20; N, 11.40%.
6. (a) Watanabe, Y.; Tsuji, Y.; Ohsugi, Y. Tetrahedron Lett. 1981, 22, 2667; (b)
Murahashi, S. I.; Kondo, K.; Hakata, T. Tetrahedron Lett. 1982, 23, 229; (c) Wa-
tanabe, Y.; Tsuji, Y.; Ige, H.; Ohsugi, Y.; Ohta, T. J. Org. Chem. 1984, 49, 3359; (d)
Bitsi, G.; Schleiffer, E.; Antoni, F.; Jenner, G. J. Organomet. Chem. 1989, 373, 343;
(e) Watanabe, Y.; Moriaki, Y.; Kondo, T.; Mitsudo, T. J. Org. Chem. 1996, 61, 4214;
(f) Jun, C.; Hwang, D.; Na, S. Chem. Commun. 1998, 1405.
3.1.3. Typical procedure for the conversion of aniline to N-benzyl-N-
methylaniline
Methanol (0.04 mL, 1.0 mmol) was added to a mixture of tri-
phenylphosphine (0.314 g, 1.2 mmol), DDQ (0.272 g, 1.2 mmol),
and aniline (0.09 mL, 1.0 mmol) in dichloromethane (5 mL). The
reaction was stirred at room temperature. After 15 min, this
mixture was added to a flask containing Ph3P (0.392 g, 1.5 mmol)
and DDQ (0.34 g, 1.5 mmol) in CH2Cl2 (4 mL). Benzyl alcohol
(1.0 mmol, 0.1 mL) was then added to this flask. After 10 min, the
solvent was evaporated. The crude product was purified by col-
umn chromatography using n-hexane/ethyl acetate (3:1) as eluent
to give N-benzyl-N-methylaniline in 55% yield (0.1 g). IR (neat)
3033, 2892, 1594, 1506, 1443, 1361, 751, 693 cmꢁ1; 1H NMR (CDCl3,
7. Grigg, R.; Mitchell, T. R. B.; Sutthivaiyakit, S.; Tongpenyai, N. J. Chem. Soc., Chem.
Commun. 1981, 611.
8. (a) Siswanto, C.; Rathman, J. F. J. Colloid Interface Sci. 1997, 196, 99; (b) Salvatore,
R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1893; (c) Earle, M. J.;
McCormac, P. B.; Seddon, K. R. Chem. Commun. 1998, 2245; (d) Johnstone, R. A.
W.; Payling, D. W.; Thomas, C. J. Chem. Soc. 1969, 2223; (e) Chiappe, C.; Pier-
accini, D. Green Chem. 2003, 5, 193; (f) Valot, F.; Fache, F.; Jacquot, R.; Spagnol,
M.; Lemaire, M. Tetrahedron Lett. 1999, 40, 3689.
9. (a) Iranpoor, N.; Firouzabadi, H.; Aghapour, Gh.; Vaes Zadeh, A. R. Tetrahedron
2002, 58, 8689; (b) Iranpoor, N.; Firouzabadi, H.; Akhlaghinia, B.; Nowrouzi, N.
J. Org. Chem. 2004, 69, 2562; (c) Iranpoor, N.; Firouzabadi, H.; Akhlaghinia, B.;
Nowrouzi, N. Tetrahedron Lett. 2004, 45, 3291; (d) Iranpoor, N.; Firouzabadi, H.;
Nowrouzi, N. Tetrahedron 2006, 62, 5498; (e) Iranpoor, N.; Firouzabadi, H.;
Akhlaghinia, B.; Azadi, R. Synthesis 2004, 92; (f) Iranpoor, N.; Firouzabadi, H.;
Nowrouzi, N. Tetrahedron Lett. 2006, 8247; (g) Iranpoor, N.; Firouzabadi, H.;
Nowrouzi, N.; Firouzabadi, D. Tetrahedron Lett. 2006, 6879.
250 MHz)
d
(ppm)¼2.93 (s, 3H), 4.45 (s, 2H), 6.66–6.80 (m, 4H),
7.16–7.35 (m, 6H); 13C NMR (62.9 MHz, CDCl3)
d
(ppm)¼38.54,
60.54, 112.45, 116.64, 126.88, 127.03, 128.55, 128.67, 129.18, 135.98.
Anal. Calcd for C14H15N: C, 85.24; H, 7.66; N, 7.10%. Found: C, 85.10;
H, 7.70; N, 7.02%.
10. CRC Handbook of Chemistry and Physics, 87th ed.; Lide, D. R., Ed.; CRC: London,
2006–2007.
11. Hamid, M. S. A.; Williams, J. M. J. Chem. Commun. 2007, 725.