N-Methyl p-methoxy-ꢀ-chloroacetanilide. Light brown oil;
Anal. Found: C, 56.1; H, 5.5; N, 6.4. Calcd. for C10H12NO2Cl:
C, 56.22; H, 5.66; N, 6.56%. IR (KBr film) νmax (Neat) 840 (C–N
1
stretching), 1742 cmϪ1 (C᎐O stretching); H NMR (200 MHz,
᎐
CDCl3) δ 3.28 (s, 3H), 3.84 (s, 5H), 6.95 (d, J = 8.8 Hz, 2H), 7.17
(d, J = 9.2 Hz, 2H); m/z (EI) 213 (Mϩ).
N-Methyl p-methyl-ꢀ-chloroacetanilide. Brown oil; Anal.
Found: C, 60.8; H, 6.3; N, 7.2. Calcd. for C10H12NOCl:
C, 60.77; H, 6.12; N, 7.09%. IR (KBr film) νmax (Neat) 827
1
(C–N stretching), 1746 cmϪ1 (C᎐O stretching); H NMR (200
᎐
MHz, CDCl3) δ 2.40 (s, 3H), 3.30 (s, 3H), 3.87 (s, 2H), 7.13 (d,
J = 8.2 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H); m/z (CI) 198 (Mϩ).
N-Methyl ꢀ-chloroacetanilide. Light brown solid; mp 66–67
ЊC; Anal. Found: C, 58.7; H, 5.5; N, 7.5. Calcd. for C9H10NOCl:
C, 58.87; H, 5.49; N, 7.63%. IR (KBr disk) νmax 801 (C–N
Fig. 3 A plot of kobsd vs. concentration of p-chlorobenzylamine.
1
stretching), 1686 cmϪ1 (C᎐O stretching); H NMR (200 MHz,
᎐
Reaction: α-chloroacetanilide (≈ 0.001 M) with p-chlorobenzylamine in
DMSO at 55.0 ЊC. Slope = kN = 5.17 × 10Ϫ3 MϪ1 sϪ1; intercept = 4.28 ×
10Ϫ5 ≈ 0; r = 0.9993.
CDCl3) δ 3.32 (s, 3H), 3.85 (s, 2H), 7.23–7.47 (m, 5H); m/z (EI)
183 (Mϩ).
N-Methyl p-chloro-ꢀ-chloroacetanilide. Pale brown solid; mp
54–55 ЊC; Anal. Found: C, 49.4; H, 4.3; N, 6.2. Calcd. for
Product analysis
p-Methyl- and N-methyl p-methyl- α-chloroacetanilide (0.05 M)
were reacted with benzylamine (0.5 M), in acetonitrile at 55.0.
After more than 15 half-lives, solvent was removed under
reduced pressure and the product was separated by column
chromatography. Analytical data of the product gave the
following results:
C9H9NOCl2: C, 49.57; H, 4.16; N, 6.42%. IR (KBr disk)
1
νmax 850 (C–N stretching), 1681 cmϪ1 (C᎐O stretching); H
᎐
NMR (200 MHz, CDCl3) δ 3.30 (s, 3H), 3.86 (s, 2H), 7.22 (d,
J = 8.8 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H); m/z (CI) 218 (comp.)
(Mϩ), 184 (base).
N-Methyl p-nitro-ꢀ-chloroacetanilide. Light brown solid; mp
111–112 ЊC; Anal. Found: C, 47.1; H, 4.1; N, 12.1. Calcd. for
p-CH C H NHC(᎐O)CH NHCH C H . White solid (silica
᎐
3
6
4
2
2
6
5
gel, 10% acetonitrile–diethyl ether, Rf = 0.13); mp 80–81 ЊC;
Anal. Found: C, 75.8; H, 7.2; N, 11.2. Calcd. for C16H18N2O: C,
75.56; H, 7.13; N, 11.02%. 1H NMR (200 MHz, CDCl3), δ 1.96
(s, 1H), 2.31 (s, 3H), 3.38 (s, 2H), 3.81 (s, 2H), 7.10–7.47
(m, 9H), 9.20 (s, 1H); m/z 254 (Mϩ).
C9H9N2O3Cl: C, 47.28; H, 3.97; N, 12.25%. IR (KBr disk)
1
νmax 861 (C–N stretching), 1681 cmϪ1 (C᎐O stretching); H
᎐
NMR (200 MHz, CDCl3) δ 3.40 (s, 3H), 3.95 (s, 2H), 7.50 (d,
J = 9.2 Hz, 2H), 8.34 (d, J = 10.6 Hz, 2H); m/z (EI) 228 (Mϩ).
Kinetic measurement
p-CH C H N(CH )C(᎐O)CH NHCH C H . Brown oil (silica
᎐
3
6
4
3
2
2
6
5
Rates were measured conductometrically in dimethyl sulfoxide
at 55.0 0.1 ЊC (Fig. 2). A computer connected automatic A/D
converter conductivity-bridge was used in this work. Pseudo-
first-order rate constants, kobsd, were determined with large
excess of benzylamine; [Substrate] = 1–5 × 10Ϫ3 and [BnA] =
0.05–0.12 M. The second-order rate constants, kN, were
obtained from the slopes of plots of kobsd vs. [BnA] with more
than five concentrations of benzylamine (Fig. 3). Pseudo-first-
order rate constant values were average of two (or three) runs
which were reproducible to 3%.
gel, 50% ethyl acetate–n-hexane, Rf = 0.23); Anal. Found: C,
75.9; H, 7.4; N, 10.2. Calcd. for C17H20N2O: C, 76.09; H, 7.51;
N, 10.44%. 1H NMR (200 MHz, CDCl3), δ 2.33 (s, 1H), 2.39 (s,
3H), 3.17 (s, 2H), 3.30 (s, 3H), 3.80 (s, 2H), 7.08–7.27 (m, 9H);
m/z 268 (Mϩ).
Acknowledgements
This work was supported by Korea Research Foundation Grant
(KRF-2002-070-C00061).
References
1 (a) J. B. Conant and W. R. Kirner, J. Am. Chem. Soc., 1924, 46, 232;
(b) A. Streitwieser, Jr., Solvolytic Displacement Reactions, McGraw-
Hill, New York, 1962; (c) S. D. Ross, M. Finkelstein and R. C.
Petersen, J. Am. Chem. Soc., 1968, 90, 6411; (d ) A. Halvorsen and
J. Songstad, J. Chem. Soc., Chem. Commun., 1978, 327.
2 (a) F. Carrion and M. J. S. Dewar, J. Am. Chem. Soc., 1984, 106,
3531; (b) R. D. Back, B. A. Coddens and G. J. Wolber, J. Org. Chem.,
1986, 51, 1030; (c) T. I. Yousaf and E. S. Lewis, J. Am. Chem. Soc.,
1987, 109, 6137.
3 (a) T. K. Brunck and F. Weinhold, J. Am. Chem. Soc., 1979, 101,
1700; (b) A. E. Reed and L. E. Curtiss, Chem. Rev., 1988, 88, 735.
4 (a) J. W. Baker, Trans. Faraday Soc., 1951, 37, 643; (b) C. A. Bunton,
Nucleophilic Substitution at a Saturated Carbon Atom, Elsevier,
New York, 1963, p. 5; (c) S. Winstein, E. Grunwald and H. W. Jones,
J. Am. Chem. Soc., 1951, 73, 2700.
5 (a) M. J. S. Dewar, The Electronic Theory of Organic Chemistry,
Oxford University Press, Oxford, 1949, p. 73; (b) D. J. McLennan
and A. Pross, J. Chem. Soc., Perkin Trans. 2, 1984, 981.
6 H. J. Koh, K. L. Han, H. W. Lee and I. Lee, J. Org. Chem., 2000, 65,
4706.
7 (a) I. Lee, Chem. Soc. Rev., 1990, 19, 317; (b) I. Lee, Adv. Phys. Org.
Chem., 1992, 27, 57; (c) I. Lee and H. W. Lee, Collect. Czech. Chem.
Commun., 1999, 64, 1529.
Fig. 2 A typical plot of conductivity (λ × 10Ϫ6/S cmϪ1) vs. time
(interval 3 s) for the reaction of α-chloroacetanilides with p-chloro-
benzylamine in DMSO at 55.0 ЊC. Black line: experimental, red line:
curve by Origin method. [α-Chloroacetanilide] ≈ 0.001 M; [p-chloro-
benzylamine] = 0.1583 M. kobsd = 0.00256/3 = 8.53 × 10Ϫ4 sϪ1
.
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 9 8 9 – 1 9 9 4
1993