Nucleophilic Substitution Reactions of Aryl Benzenesulfonates
J . Org. Chem., Vol. 67, No. 4, 2002 1281
p-ClC6H4SO2OC6H4-p-NO2: mp 114 °C; IR (KBr)/cm-1
1605, 1510 (CC aromatic), 1515, 1345 (NO2), 1365, 1175 (SO2);
1H NMR (60 MHz, CDCl3) 6.8-8.2 (phenyl, 8H, m). Anal. Calcd
for C12H8ClNO5S: C, 45.9; H, 2.6; N, 4.5. Found: C, 45.7; H,
2.6; N, 4.4.
(phenyl, 9H, m). Anal. Calcd for C14H15NO3S: C, 60.6; H, 5.5;
N, 5.1. Found: C, 60.7; H, 5.4; N, 5.1.
C6H5SO2NHCH2C6H4-p-CH3: IR (KBr)/cm-1 1590, 1490
1
(CC aromatic), 1345, 1160 (SO2); H NMR (60 MHz, CDCl3)
2.4 (p-CH3, 3H, s), 2.8 (CH2, 2H, s), 3.8 (NH, H, s) 6.8-7.8
(phenyl, 9H, m). Anal. Calcd for C14H15NO2S: C, 64.3; H, 5.8;
N, 5.4. Found: C, 64.4; H, 5.6; N, 5.4.
p-NO2C6H4SO2OC6H4-p-CH3: mp 98 °C; IR (KBr)/cm-1
1600, 1538 (CC aromatic), 1510, 1340 (NO2), 1360, 1170 (SO2);
1H NMR (60 MHz, CDCl3) 1.4 (CH3, 3H, d), 2.4 (p-CH3, 3H, s),
7.0-8.0 (phenyl, 8H, m). Anal. Calcd for C13H11NO5S: C, 53.2;
H, 3.8; N, 4.8. Found: C, 53.0; H, 3.6; N, 4.5.
C6H5SO2NHCH2C6H5: IR (KBr)/cm-1 1600, 1490 (CC aro-
matic), 1350, 1175 (SO2); 1H NMR (60 MHz, CDCl3) 2.8 (CH2,
2H, s), 3.8 (NH, H, s) 6.8-7.8 (phenyl, 10H, m). Anal. Calcd
for C13H13NO2S: C, 63.1; H, 5.3; N, 5.7. Found: C, 63.4; H, 5.3;
N, 5.7.
p-NO2C6H4SO2OC6H5: mp 92 °C; IR (KBr)/cm-1 1600, 1510
1
(CC aromatic), 1500, 1340 (NO2), 1360, 1170 (SO2); H NMR
C6H5SO2NHCH2C6H4-p-Cl: IR (KBr)/cm-1 1580, 1495 (CC
aromatic), 1350, 1175 (SO2); 1H NMR (60 MHz, CDCl3) 2.8
(CH2, 2H, s), 3.9 (NH, H, s), 6.9-7.9 (phenyl, 9H, m). Anal.
Calcd for C13H12ClNO2S: C, 55.4; H, 4.3; N, 5.0. Found: C, 55.2;
H, 4.2; N, 5.0.
(60 MHz, CDCl3) 1.4 (CH3, 3H, d), 2.4 (p-CH3, 3H, s), 7.0-8.0
(phenyl, 8H, m). Anal. Calcd for C12H9NO5S: C, 51.6; H, 3.2;
N, 5.0. Found: C, 51.3; H, 3.3; N, 5.3.
p-NO2C6H4SO2OC6H4-p-Cl: mp 114 °C; IR (KBr)/cm-1
1605, 1510 (CC aromatic), 1515, 1345 (NO2), 1365, 1175 (SO2);
1H NMR (60 MHz, CDCl3) 7.1-8.1 (phenyl, 8H, m). Anal. Calcd
for C12H8ClNO5S: C, 45.9; H, 2.6; N, 4.5. Found: C, 46.2; H,
2.8; N, 4.6.
p-CH3C6H4SO2NHCH2C6H5: IR (KBr)/cm-1 1595, 1510 (CC
aromatic), 1350, 1170 (SO2); 1H NMR (60 MHz, CDCl3) 2.3 (p-
CH3, 3H, s), 2.8 (CH2, 2H, s), 3.8 (NH, H, s), 6.8-7.8 (phenyl,
9H, m). Anal. Calcd for C14H15NO2S: C, 64.3; H, 5.8; N, 5.4.
Found: C, 64.4; H, 5.7; N, 5.3.
p-NO2C6H4SO2OC6H4-p-NO2: mp 139 °C; IR (KBr)/cm-1
1605, 1510 (CC aromatic), 1525, 1345 (NO2), 1370, 1180 (SO2),
850 (SOC); 1H NMR (60 MHz, CDCl3) 7.1-8.2 (phenyl, 8H,
m). Anal. Calcd for C12H8N2O7S: C, 44.4; H, 2.5; N, 8.6. Found:
C, 44.4; H, 2.6; N, 8.8.
C6H5NHCH2C6H4-p-OCH3: IR (KBr)/cm-1 1600, 1500 (CC
aromatic); 1H NMR (60 MHz, CDCl3) 2.8 (CH2, 2H, s), 3.8 (NH,
H, s), 6.9-7.9 (phenyl, 9H, m). Anal. Calcd for C14H15NO: C,
78.8; H, 7.1; N, 6.6. Found: C, 78.9; H, 7.0; N, 6.6.
C6H5NHCH2C6H4-p-CH3: IR (KBr)/cm-1 1590, 1495 (CC
aromatic); 1H NMR (60 MHz, CDCl3) 2.8 (CH2, 2H, s), 3.8 (NH,
H, s), 6.9-7.8 (phenyl, 9H, m). Anal. Calcd for C14H15N: C,
85.2; H, 7.7; N, 7.1. Found: C, 85.3; H, 7.6; N, 7.1.
C6H5NHCH2C6H5: IR (KBr)/cm-1 1600, 1490 (CC aromatic);
1H NMR (60 MHz, CDCl3) 2.8 (CH2, 2H, s), 3.9 (NH, H, s),
6.9-7.9 (phenyl, 10H, m). Anal. Calcd for C13H13N: C, 85.2;
H, 7.2; N, 7.6. Found: C, 85.3; H, 7.0; N, 7.7.
Kin etic P r oced u r e. Rates were measured conductometri-
cally at 65.0 °C. The conductivity due to cation (benzylam-
moinum ion) and anions (ZC6H4O- and YC6H4SO3-) produced
increases with the progress of reaction. Pseudo-first-order rate
constants, kobs, were determined by the Guggenheim method
with a large excess of benzylamine; [aryl benzenesulfonate] )
10-3M and [benzylaime] ) 0.1-0.25 M. Second-order rate
constants, kN, were obtained from the slope of a plot of kobs vs
[N] (eq 3) with more than four concentrations of benzylamine.
The reported values of kN are the averages of more than
duplicate runs and were reproducible to within (3%.
P r od u ct An a lysis. Upon completion of rate measurements,
the products were separated using HP5890A gas chromato-
graph. A HP-1 (5 m × 0.53 mm × 2.65 µm) column and FID
(350 °C) detector were used. The injector temperature was 250
°C. The oven temperature was 100 °C initially and was
increased to 140 °C at a rate of 10 °C/min and to 200 °C at
the rate of 2 °C/min. The flow rate of carrier gas, He, was 20
mL/min. The two possible benzylamides products, YC6H4SO2-
NHCH2C6H4X and XC6H4CH2NHC6H4Z, were prepared by the
Tipson method and recrystallized over ethanol. These stan-
dards were then used to identify the reaction products from
the kinetic measurements. The areas of the two peaks were
used to determine percentage (or fraction) contributions of kS-O
and kC-O paths, which are listed in Table 3. The individual
rate constants, kS-O and kC-O, were then obtained by multiply-
ing the fractions to kN. Analysis of the products gave the
following results:
C6H5NHCH2C6H4-p-Cl: IR (KBr)/cm-1 1575, 1490 (CC
aromatic); 1H NMR(60 MHz, CDCl3) 2.8 (CH2, 2H, s), 3.8 (NH,
H, s), 6.9-7.9 (phenyl, 9H, m). Anal. Calcd for C13H12ClN: C,
71.7; H, 5.6; N, 6.4. Found: C, 71.9; H, 5.5; N, 6.3.
p-CH3C6H4NHCH2C6H5: IR (KBr)/cm-1 1590, 1515 (CC
aromatic); 1H NMR (60 MHz, CDCl3) 2.8 (CH2, 2H, s), 3.9 (NH,
H, s), 6.9-7.9 (phenyl, 9H, m). Anal. Calcd for C14H15N: C,
85.2; H, 7.7; N, 7.1. Found: C, 85.3; H, 7.6; N, 7.1.
p-ClC6H4NHCH2C6H5: IR (KBr)/cm-1 1590, 1495 (CC aro-
1
matic); H NMR (60 MHz, CDCl3) 2.8 (CH2, 2H, s), 3.8 (NH,
H, s), 6.9-8.0 (phenyl, 9H, m). Anal. Calcd for C13H12ClN: C,
71.7; H, 5.6; N, 6.4. Found: C, 71.9; H, 5.5; N, 6.6.
p-NO2C6H4NHCH2C6H5: IR (KBr)/cm-1 1590, 1500 (CC
aromatic), 1515, 1300 (NO2); 1H NMR (60 MHz, CDCl3) 2.8
(CH2, 2H, s), 3.9 (NH, H, s), 7.1-8.0 (phenyl, 9H, m). Anal.
Calcd for C13H12N2O2: C, 68.4; H, 5.3; N, 12.3. Found: C, 68.4;
H, 5.5; N, 12.3.
Ack n ow led gm en t. We thank Choongbuk National
University and Inha University for support of this work.
C6H5SO2NHCH2C6H4-p-OCH3: IR (KBr)/cm-1 1600, 1510
1
(CC aromatic), 1350, 1175 (SO2); H NMR (60 MHz, CDCl3)
2.7 (CH2, 2H, s), 3.5 (p-OCH3, 3H, s), 3.9 (NH, H, s), 6.5-7.6
J O0161835