◦
H
2
NC(
=
O)NHCH C H Cl-m. Mp 82–84 C, yield (38%),
2
6
4
Experimental
IR (KBr), 3436 (N–H), 1078 (C–Cl), 1649 (C=O), 1509 (C–C,
Materials
aromatic), 1490 (C=C, aromatic), 1462 (C–H, CH
), 703 (C–H,
),
2
1
aromatic); H NMR (400 MHz, CDCl
3
1
), d 4.28 (2H, s, CH
3
2
GR grade acetonitrile was used after three distillations. The ben-
zylamine nucleophiles were used without further purification.
GR grade thiophenols and potassium cyanate were used.
ca. 7.24–7.31 (4H, m, aromatic ring); C NMR (100.4 MHz,
CDCl
3
), d 154.2, 142.5, 138.1, 132.0, 129.5, 128.2, 127.8, 40.2;
+
Mass, m/z 184 (M ). Anal. calc. for C
.91. Found: C, 52.2; H, 4.90%.
8
H
9
ClN O: C, 52.0; H,
2
Preparations of aryl thiocarbamates. The aryl thiocarba-
4
mates were prepared by the literature method of Al-Rawi and
26
Williams. These substrates were prepared by adding acetic
acid (1 mL) over a period of 5 min to a stirred suspension of
thiophenol (1 g) and potassium cyanate (0.8 g) in water (10 mL).
After about 15 min, a precipitate formed which was filtered and
Acknowledgements
This work was supported by Korea Research Foundation Grant
(KRF-2002-070-C00061).
1
recrystallized. Melting point, IR (Nicolet 5BX FT-IR) and H
1
3
and C NMR (JEOL 400 MHz) data were found to agree well
26
with the literature values.
References
1
(a) C. A. Satterthwait and W. P. Jencks, J. Am. Chem. Soc, 1974, 96,
Kinetic measurement
7
1
018; (b) E. A. Castro and C. Ureta, J. Chem. Soc., Perkin Trans. 2,
991, 63; (c) E. A. Castro, C. A. Areneda and J. G. Santos, J. Org.
◦
Rates were measured conductometrically at 10.0 ± 0.05 C. The
Chem., 1997, 62, 126; (d) E. A. Castro and C. Ureta, J. Org. Chem.,
1990, 55, 1676; (e) E. A. Castro and C. Ureta, J. Org. Chem., 1989,
conductivity bridge used in this work was a self-made computer
2
7
automatic A/D converter conductivity bridge. Pseudo-first-
5
3
1
4, 1253; (f) E. A. Castro and J. G. Santos, J. Org. Chem., 1985, 50,
595; (g) H. K. Oh, C. H. Shin and I. Lee, Bull. Korean Chem. Soc.,
995, 16, 657; (h) H. K. Oh, S. Y. Woo, C. H. Shin, Y. S. Park and I.
order rate constants, kobs, were determined by the Guggenheim
28
method with large excess of benzylamine. Second-order rate
constants, k , were obtained from the slope of a plot of
obs vs. benzylamine with more than five concentrations. The
2
Lee, J. Org. Chem., 1997, 62, 5780; (i) I.-H. Um, H.-J. Kwon, D.-S.
Kwon and Y.-J. Park, J. Chem. Res. (S), 1995, 301; I.-H. Um, H.-J.
Kwon, D.-S. Kwon and Y.-J. Park, J. Chem. Res. (M), 1995, 1801;
k
values reported are averages of more than three runs and were
(
1
j) I.-H. Um, K.-E. Choi and D.-S. Kwon, Bull. Korean Chem. Soc.,
990, 11, 362.
reproducible to within ± 3%.
2
3
M. J. Gresser and W. P. Jencks, J. Am. Chem. Soc., 1977, 99, 6963;
E. A. Castro and F. J. Gil, J. Am. Chem. Soc., 1977, 99, 7611; E. A.
Castro, M. Aliaga, P. J. Campodonico and J. G. Santos, J. Org. Chem.,
Product analysis
Substrate, phenyl thiocarbamates (ca. 1.0 × 10− mol) was
3
2
002, 67, 8911; E. A. Castro, M. Andajar, A. Taro and J. G. Santos,
−
2
reacted with excess p-chlorobenzylamine (ca. 1.0 × 10 mol)
J. Org. Chem., 2003, 68, 3608; E. A. Castro, M. Andajar, A. Taro and
J. G. Santos, J. Org. Chem., 2003, 68, 5930; E. A. Castro, M. Cubillos
and J. G. Santos, J. Org. Chem., 2001, 66, 6000; P. M. Bond and R. B.
Moodie, J. Chem. Soc., Perkin Trans. 2, 1976, 66, 679.
◦
with stirring for more than 15 half-lives at 10.0 C in ca. 200 ml
acetonitrile, and the products were isolated by evaporating the
solvent under reduced pressure. The product mixture was treated
with column chromatography (silica gel, 20% ethyl acetate–n-
hexane). Analysis of the product gave the following results.
(a) E. A. Castro, F. Ibanez and J. G. Santos, J. Org. Chem., 1991, 56,
4
5
819; (b) E. A. Castro, M. Salas and J. G. Santos, J. Org. Chem., 1994,
9, 30; (c) E. A. Castro, P. Munoz and J. G. Santos, J. Org. Chem.,
◦
1999, 64, 8298; (d) E. A. Castro, M. I. Pizarro and J. G. Santos,
J. Org. Chem., 1996, 61, 5982; (e) E. A. Castro, M. Cubillos and J. G.
Santos, J. Org. Chem., 1999, 64, 6342; (f) H. K. Oh, Y. H. Lee and I.
Lee, Int. J. Chem. Kinet., 2000, 32, 132; (g) H. B. Song, M. H. Choi,
I. S. Koo, H. K. Oh and I. Lee, Bull. Korean Chem. Soc., 2003, 24,
91.
H
2
NC(=O)NHCH
2
C
6
H
4
OCH
3
-p. Mp 110–112 C, yield
(
1
7
47%), IR (KBr), 3435 (N-H), 2836 (C–H, CH
3
), 1650 (C=O),
514 (C–C, aromatic), 1491(C=C, aromatic), 1459 (C–H, CH
),
03 (C–H, aromatic); H NMR (400 MHz, CDCl ), d 3.80 (3H, s,
), 4.29 (2H, s, CH ), ca. 7.21–7.27 (4H, m, aromatic ring); C
NMR (100.4 MHz, CDCl
2
1
3
1
3
CH
3
2
4 (a) F. M. Menger and L. E. Glass, J. Org. Chem., 1974, 39, 2469;
(b) A. S. Shawali, A. Harbash, M. M. Sidky, H. M. Hassaneen and
S. S. Elkaabi, J. Org. Chem., 1986, 51, 3498; (c) H. J. Koh, O. K. Kim,
H. W. Lee and I. Lee, J. Phys. Org. Chem., 1997, 10, 725; (d) H. K.
Oh, J. E. Park, D. D. Sung and I. Lee, J. Org. Chem., 2004, 69, 3150;
3
), d 155.5, 138.4, 132.1, 128.3, 128.1,
+
5
5.6, 40.3; Mass, m/z 180 (M ). Anal. calc. for C
9
H
12
N
2
O : C,
2
6
0.0; H, 6.71. Found: C, 60.2; H, 6.72%.
◦
H
2
NC(=O)NHCH
2
C
6
H
4
CH -p. Mp 94–96 C, yield (45%),
3
(
6
e) H. K. Oh, J. E. Park, D. D. Sung and I. Lee, J. Org. Chem., 2004,
9, 9285.
I. Lee, Chem. Soc. Rev., 1990, 19, 317; I. Lee, Adv. Phys. Org. Chem.,
992, 27, 57.
IR (KBr), 3432 (N–H), 2852 (C–H, CH
), 1653 (C=O), 1511
C–C, aromatic), 1495 (C=C, aromatic), 1463 (C–H, CH
), 701
C–H, aromatic); H NMR (400 MHz, CDCl ), d 2.95 (3H, s,
), 4.25 (2H, s, CH ), ca. 7.18–7.25 (4H, m, aromatic ring);
C NMR (100.4 MHz, CDCl ), d 154.3, 137.9, 132.3, 128.4,
3
(
(
2
5
1
3
1
CH
3
2
6 (a) C. D. Ritchie, in Solute–Solvent Interactions, J. F. Coetzee and
C. D. Ritchie, eds., Marcel Dekker, New York, 1969, ch. 4; (b) J. F.
Coetzee, Prog. Phys. Org. Chem., 1967, 4, 54; (c) W. J. Spillane, G.
Hagan, P. McGrath, J. King and C. Brack, J. Chem. Soc., Perkin
Trans. 2, 1996, 2099.
1
3
3
+
1
6
28.0, 40.5; Mass, m/z 164 (M ). Anal. calc. for C
5.8; H, 7.40. Found: C, 65.6; H, 7.38%.
9
H
12
N O: C,
2
◦
H
2
NC(=O)NHCH
2
C
6
H
5
.
Mp 72–74 C, yield (50%), IR
7 H. K. Oh, M. H. Ku, H. W. Lee and I. Lee, J. Org. Chem., 2002, 67,
3
874.
(
(
KBr), 3429 (N–H), 1651 (C=O), 1513 (C–C, aromatic), 1489
1
8 S. Glasstone, K. J. Laidler and H. Eyring, The Theory of Rate
C=C, aromatic), 1458 (C–H, CH
), 702 (C–H, aromatic); H
), d 4.34 (2H, s, CH ), ca. 7.20–7.27
2
Processes, McGraw-Hill, New York, 1941, ch. IV.
I. Lee and D. D. Sung, Curr. Org. Chem., 2004, 8, 557.
NMR (400 MHz, CDCl
3
2
9
1
3
(
5H, m, aromatic ring); C NMR (100.4 MHz, CDCl
3
), d 155.2,
1
0 (a) N. D. Epiotis, W. R. Cherry, S. Shaik, R. L. Yates and F. Bernardi,
Structural Theory of Organic Chemistry, Springer-Verlag, Berlin,
1977, Part 1; (b) A. Reed, L. A. Curtiss and F. Weinhold, Chem.
Rev., 1988, 88, 899; (c) I. Fleming, Frontier Orbitals and Organic
Chemical Reactions, Wiley, London, 1976, ch. 2–4.
+
138.0, 132.2, 128.3, 128.0, 39.9; Mass, m/z 150 (M ). Anal. calc.
for C
8
H
10
N
2
O: C, 64.0; H, 6.71. Found: C, 64.2; H, 6.72%.
◦
H
2
NC(=O)NHCH
2
C
6
H
4
Cl-p. Mp 85–87 C, yield (42%),
IR (KBr), 3438 (N–H), 1085 (C–Cl), 1652 (C=O), 1512 (C–C,
11 C. Hansch, A. Leo and R. W. Taft, Chem. Rev., 1991, 91, 165.
aromatic), 1492 (C=C, aromatic), 1461 (C–H, CH
), 705 (C–H,
),
1
2 E. A. Castro, L. Leandro, R. Millan and J. G. Santos, J. Org. Chem.,
1999, 64, 1953.
2
1
aromatic); H NMR (400 MHz, CDCl
3
), d 4.31 (2H, s, CH
2
1
3
13 H. J. Koh, J.-W. Lee, H. W. Lee and I. Lee, Can. J. Chem., 1998, 76,
ca. 7.23–7.29 (4H, m, aromatic ring); C NMR (100.4 MHz,
7
10.
CDCl
3
), d 154.8, 138.2, 132.2, 128.5, 128.1, 40.1; Mass, m/z 184
ClN O: C, 52.0; H, 4.91. Found: C,
1
4 (a) E. A. Castro, P. Pavez and J. G. Santos, J. Org. Chem., 2001, 66,
3129; (b) D. Stefanidas, S. Cho, S. Dhe-Paganon and W. P. Jencks,
J. Am. Chem. Soc., 1993, 115, 1650.
+
(
M ). Anal. calc. for C
8
H
9
2
5
2.1; H, 4.92%.
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 1 2 4 0 – 1 2 4 4
1 2 4 3