H. K. OH ET AL.
95
IR(cmϪ1 ) 1450, 1596 (phenyl), 1395, 1179 (SO–O ), 818
(S–O ).
Methyl cyclopentylmethyl ether. Liquid; ␦H (CDCl3 )
1·17–1·99 (9H, m, cyclic ring), 3·20 (2H, d, —CH2—O,
J=7·33 Hz), 3·28 (3H, s, OCH3 ).
Cyclohexylmethyl p-chlorobenzenesulfonate. Liquid,
␦H(CDCl3 ) 1·09–1·25(10H, m, cyclic ring), 1·16–1·72(1H,
m, t-H), 3·84 (2H, d, —CH2—O, J=5·86 Hz), 7·53 (2H, d,
Methyl cyclohexylmethyl ether. Liquid; ␦H (CDCl3 )
1·11–1·86 (11H, m, cyclic ring), 3·19 (2H, d, —CH2—O,
J=5·86 Hz), 3·33 (3H, s, OCH3 ).
m-H, J=8·79 Hz), 7·84(2H, d, o-H, J=8·79 Hz); IR (cmϪ1
)
1477, 1595 (phenyl), 1364, 1185 (SO–O ), 1091 (Cl ), 852
(S–O).
Methyl cycloheptylmethyl ether. Liquid; ␦H (CDCl3 )
1·10–1·78 (13H, m, cyclic ring), 3·15 (2H, d, —CH2—O,
J=6·60 Hz), 3·32 (3H, s, OCH3 ).
Cyclohexylmethyl
p-nitrobenzenesulfonate.
M.p.
102–104 °C; ␦H (CDCl3 ) 1·08–1·28 (10H, m, cyclic ring),
1·65–1·74 (1H, m, t-H), 3·92 (2H, d, —CH2—O,
J=5·87 Hz), 8·11 (2H, d, m-H, J=8·80 Hz), 8·41 (2H, d,
oϪH, J=8·79 Hz); IR (cmϪ1 ) 1456, 1608 (phenyl), 1361,
1182 (SO–O ), 850 (S–O ).
Aminolysis product. Cyclobutylmethyl benzenesulfonate
was reacted with excess aniline with stirring for more than
15 half-lives at 65·0 °C in methanol and the products were
isolated by evaporating the solvent under reduced pressure.
The product mixture was subjected to column chromatog-
raphy (silica gel, 5% ethyl acetate–n-hexane). Analysis of
the product gave the following results.
Cycloheptylmethyl benzenesulfonate. Liquid; ␦H (CDCl3 )
1·10–1·69 (12H, m, cyclic ring), 1·83 (1H, m, t-H), 3·82
(2H, d, —CH2—O, J=6·59 Hz), 7·56 (2H, t, J=7·32 Hz),
7·65 (H, t, p-H, J=8·06 Hz), 7·92 (2H, d, o-H, J=7·33 Hz);
IR (cmϪ1 ) 1441, 1633 (phenyl), 1366, 1180 (SO–O ), 811
(S–O ).
Cyclobutylmethyl anilide. Liquid; ␦H (CDCl3 ) 1·02–1·59
(6H, m, cyclic ring), 1·74–1·98 (1H, m, t-H), 3·16 (2H, d,
—CH2—N, J=7·32 Hz), 3·69 (1H, broad, NH), 6·63 (2H, t,
m-H, J=8·86 Hz), 6·73 (1H, t, p-H, J=7·33 Hz), 7·21 (2H,
d, o-H, J=8·79 Hz).
Cycloheptylmethyl tosylate. Liquid; ␦H(CDCl3 ) 1·09–1·68
(12H, m, cyclic ring), 1·81 (1H, m, t-H), 2·45 (3H, s, CH3 ),
3·79 (2H, d, —CH2—O, J=6·60 Hz), 7·34 (2H, d, m-H,
Cyclopentylmethyl anilide. Liquid; ␦H (CDCl3 ) 1·24–1·63
(8H, m, cyclic ring), 1·80–1·81 (1H, M, t-H), 3·00 (2H, d,
—CH2—O, J=7·32 Hz), 6·58 (2H, d, m-H, J=8·06 Hz),
6·67 (1H, t, p-H, J=7·33 Hz), 7·15 (2H, t, o-H,
J=7·32 Hz).
J=8·06 Hz), 7·78 (2H, d, oϪH, J=8·06 Hz); IR (cmϪ1
1459, 1652 (phenyl), 1378, 1184 (SO–O ), 816 (S–O ).
)
Cycloheptylmethyl p-chlorobenzenesulfonate. M.p.
51–53 °C; ␦H (CDCl3 ) 1·13–1·69 (12H, m, cyclic ring), 1·83
(1H, m, t-H), 3·83 (2H, d, —CH2—O, J=6·60 Hz), 7.54
(2H, d, m-H, J=7·89 Hz), 7.85 (2H, d, o-H, J=8·06 Hz); IR
(cmϪ1 ) 1461, 1650 (phenyl), 1363, 1181 (SO–O ), 1088 (Cl ),
816 (S–O ).
Cyclohexylmethyl anilide. Liquid, ␦H (CDCl3 ) 1·01–1·80
(10H, m, cyclic ring), 1·81–1·87 (1H, m, t-H), 2·98 (2H, d,
—CH2—N, J=6·84 Hz), 3·73 (1H, broad, NH), 6·64 (2H, t,
m-H, J=7·81 Hz), 6·72 (1H, t, p-H, J=7·32 Hz), 7·21 (2H,
d, p-H, J=7·61 Hz).
Cycloheptylmethyl
p-nitrobenzenesulfonate.
M.p.
Cycloheptylmethyl anilide. Liquid; ␦H (CDCl3 ) 1·23–1·77
(12H, m, cyclic ring), 1·79–1·88 (1H, m, t-H), 2·96 (2H, d,
—CH2—O, J=6·59 Hz), 3·60–3·80 (1H, broad NH), 6·61
(2H, d, m-H, J=8·06 Hz), 6·71 (1H, t, p-H, J=7·33 Hz),
7·22 (2H, t, o-H, J=8·06 Hz).
100–102 °C; ␦H (CDCl3 ) 1·14–1·58 (12H, m, cyclic ring),
1·66 (1H, m, t-H), 3·92 (2H, d, —CH2—O, J=6·59 Hz),
8·11 (2H, d, o-H, J=7·33 Hz), 8·41 (2H, d, m-H,
J=8·79 Hz); IR (cmϪ1 ) 1456, 1608 (phenyl), 1361, 1182
(SO–O ), 850 (S–O ).
Kinetic procedure. Rates were measured conductimet-
rically at 65·0 °C in methanol. The k2 values were
determined [equation (3)] with at least four nucleophile
(aniline) concentrations using the procedure described
previously.(4–6, 10)
ACKNOWLEDGEMENT
We thank the Ministry of Education for a Basic Science
Research Grant (BSRI-96-3431) and Inha University for
support of this work.
Product analysis
REFERENCES
Solvolysis product. The TLC analysis of the reaction
mixture showed spots corresponding to anilide, salt and
unreacted substrate and nucleophile. The ether spot was
confirmed by GC and was separated by chromatography.
The NMR analytical data for the ethers are as follows.
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© 1997 by John Wiley & Sons, Ltd.
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, VOL. 10, 91–96 (1997)