Synthesis and Hydrolysis of Phenyl Arylsulfonyl-alkyl-dithiocarbamates
FULL PAPER
Conclusions
In conclusion, phenyl arylsulfonyl-alkyl-dithiocarba-
mates 3 give thiophenol and the corresponding sulfon-
amides when hydrolysed in basic media. The kinetic para-
meters, solvent isotope effect in hydroxide media and hydro-
peroxide effectiveness support a BAC2 mechanism involving
Scheme 3. Rate-determining step of BAC2 with nucleophilic cataly-
sis mechanism.
Table 2. Physicochemical properties and corresponding yields of compounds 3a–h.
IR
ν(S=O) [cm–1]
HRMS [M + H]+
R1
R2
Yield [%]
M.p. [°C]
–
1
ν(C=S) [cm ]
1089
Calcd.
Exp.
3
3
3
3
3
3
3
3
a
b
c
d
e
f
H
CH
CH
CH
CH
CH
CH
3
3
3
3
3
3
40
40
25
69
14
26
22
24
107.4–109.4
86.5–87.6
85.0–87.0
126.7–127.4
109.0–110.0
81.0–83.0
83.7–84.7
86.8–87.7
1362, 1170
1368, 1158
1314, 1176
1368, 1170
1359, 1173
1326, 1179
1386, 1182
1383, 1182
324.0187
354.0292
338.0343
369.0037
357.9797
392.0061
352.0500
366.0656
324.0184
354.0305
338.0356
369.0034
357.9795
392.0070
352.0512
366.0667
OCH
3
1086
CH
3
1053
NO
2
1089
Cl
1053
CF
CH
CH
3
1068
g
h
3
3
C
2
3
H
5
7
1092
C
H
1092
Table 3. H NMR and 13C NMR chemical shifts observed for 3a–h.
1
δ
H
(CDCl
3
) [ppm] (400 MHz)
δ
C
(CDCl
3
) [ppm] (100 MHz)
4
1
1
1.41 (N-Me), 129.01 (C-2,6, Ar-SO
30.37 (C-2,6, Ar-S), 131.30 (C-3,5, Ar-S), 132.17 (C-1, Ar-S),
35.19 (C-3,5, Ar-SO ), 137.11 (C-4, Ar-SO ), 139.14 (C-1, Ar-
), 203.09 (C=S)
41.49 (N-Me), 56.38 (O-Me), 115.35 (C-3,5, Ar-SO
, Ar-S), 1, Ar-SO ), 130.34 (C-4, Ar-S), 131.24 (C-3,5, Ar-S), 131.62 (C-
, Ar-S), 8.03 (d, 2 H, J = 8.9 Hz, 2,6, Ar-S), 132.47 (C-1, Ar-S), 137.20 (C-2,6, Ar-SO ), 165.24
(C-4, Ar-SO ), 202.96 (C=S)
1.75 (Me-Ar-SO ), 40.95 (N-Me), 128.38 (C-2,6, Ar-SO
29.44 (C-3,5, Ar-SO ), 129.72 (C-4, Ar-S), 130.42 (C-2,6, Ar-S),
31.43 (C-1, Ar-S), 135.06 (C-1, Ar-SO ), 136.37 (C-3,5, Ar-S),
45.30 (C-4, Ar-SO
0.55 (N-Me), 125.25 (C-3,5, Ar-SO
30.55 (C-2,6, Ar-S), 131.01 (C-1, Ar-S), 131.59 (C-4, Ar-S),
37.18 (C-2,6, Ar-SO ), 144.52 (C-1, Ar-SO ), 151.57 (C-4, Ar-
), 202.41 (C=S)
0.50 (N-Me), 129.36 (C-2,6, Ar-SO
29.84 (C-4, Ar-S), 130.62 (C-2,6, Ar-S), 130,85 (C-1, Ar-S),
36.60 (C-1, Ar-SO ), 136.36 (C-3,5, Ar-S), 140.75 (C-4, Ar-
), 201.96 (C=S)
0.27 (N-Me), 126.17 (C-2,6, Ar-SO
29.63 (C-4, Ar-S), 130.63 (C-2,6, Ar-S), 130.51 (C-1, Ar-S),
35.29 (C-1, Ar-SO ), 136.33 (C-3,5, Ar-S), 141.88 (C-4, Ar-
), 201.92 (C=S)
4.73 (N-CH CH ), 21.72 (CH
C-2, C-6, Ar-SO ), 129.40 (C-3, C-5, Ar-SO
S), 130.42 (C-2, C-6, Ph-S), 131.08 (C-1, Ph-S), 135.73 (C-1, Ar-
SO ), 136.52 (C-3, C-5 Ph-S), 145.05 (C-4, Ar-SO ), 201.14
C=S)
11.06 (N-CH
), 4.40 (t, J = CH CH CH
), 7.33 (d, J = 8.0 Hz, 2 H, SO ), 129.40 (C-3, C-5, Ar-SO
), 7.36 (m, 5 H, H , H , H , H , H , Ph-S), 2, C-6, Ph-S), 131.08 (C-1, Ph-S), 135.73 (C-1, Ar-SO
.88 (d, J = 8.4 Hz, 2 H, H , H , Ar-SO (C-3, C-5 Ph-S), 144.97 (C-4, Ar-SO ), 201.37 (C=S)
2
), 130.21 (C-4, Ar-S),
3
.87 (s, 3 H, N-Me), 7.27 (d, 2 H, H
, H , H , Ar-S), 7.73 (m, 2 H, H
d, 1 H, H , Ar-SO ), 8.08 (d, 2 H, H , H
2
, H
, H
, Ar-SO
6
, Ar-S), 7.49 (m, 3
3
3
3
3
3
3
a
H, H
(
3
4
5
3
5
, Ar-SO
2
), 7.80
2
2
4
2
2
6
2
)
SO
2
3
8
7
.82 (s, 3 H, N-Me), 3.93 (s, 3 H, O-Me), 7.18 (d, J =
.3 Hz, 2 H, H , H , Ar-SO ), 7.28 (d, 2 H, H , H
.45 (m, 3 H, H , H , H
, H , Ar-SO
2
), 130.18 (C-
b[a]
2
6
2
2
6
2
3
4
5
2
H
2
6
2
)
2
2
1
1
1
4
1
1
2
2
),
2
.46 (s, 3 H, Me-Ar-SO
H, H , H ,H , H , H , Ar-S), 7.39 (d, J = 9 Hz, 2 H, H
, Ar-SO ), 7.89 (d, J = 9 Hz, 2 H, H
2
), 3.83 (s, 3 H, N-Me), 7.38 (m, 5
2
c
2
3
4
5
6
3
,
2
H
5
2
2
6 2
, H , Ar-SO )
2
)
2
), 130.51 (C-3,5, Ar-S),
3
.96 (s, 3 H, N-Me), 7.31 (d, 2 H, H
H, H , H , H
SO ), 8.49 (d, J = 4.4 Hz, 2 H, H
2
, H
6
, Ar-S), 7.48 (m, 3
, H , Ar-
d[a]
, Ar-S), 8.33 (d, J = 4.4 Hz, 2 H, H
, H , Ar-SO
3
4
5
2
6
2
2
2
3
5
2
)
SO
2
4
1
1
2
), 129.57 (C-3,5, Ar-SO
2
2
),
),
3.86 (s, 3 H, N-Me), 7.38 (m, 5 H, H
2
, H
3
,H
4 5 6
, H , H , Ar-
e
S), 7.53 (d, J = 8.8 Hz, 2 H, H , H , Ar-SO
3
5
2
), 7.94 (d, J =
2
2 6 2
8.8 Hz, 2 H, H , H , Ar-SO )
SO
2
4
1
1
SO
1
2
), 128.90 (C-3,5, Ar-SO
3.90 (s, 3 H, N-Me), 7.37 (m, 5 H, H
2
, H
3
,H
4 5 6
, H , H , Ar-
f
S), 7.82 (d, J = 8.4 Hz, 2 H, H
3
, H , Ar-SO
5
2
), 8.11 (d, J =
2
2 6 2
8.0 Hz, 2 H, H , H , Ar-SO )
2
2
3
3
2 3
-Ar), 49.05 (N-CH CH ), 128.53
1
.53 (t, J = 6.8 Hz, 3 H, N-CH
), 4.55 (q, J = 6.8 Hz, 2 H, N-CH
8.4 Hz, 2 H, H , H , Ar-SO ), 7.37 (m, 5 H, H
, H , Ph-S), 7.90 (d, J = 8.0 Hz, 2 H, H , H , Ar-SO
2
CH
3
), 2.45 (s, 3 H, CH
CH ), 7.34 (d, J
4
, H , H ,
3
–
(
2
2
), 129.56 (C-4, Ph-
Ar–SO
=
H
2
2
3
3
g
h
3
5
2
2
3
2
,
2
5
6
2
6
2
)
(
1
.01 (t, J = 7.2 Hz, 3 H, N-CH
2
CH CH ), 2.45 (s, 3 H,
), 1.99 (m, 2 H, N-CH CH CH
8.0 Hz, 2 H, N-CH CH CH
, H , Ar-SO
2
3
2
CH
2
CH
3
), 21.72 (CH
CH CH
), 129.51 (C-4, Ph-S), 130.40 (C-
), 136.47
3
-Ar), 22.72 (N-
CH –Ar–SO
3
2
2
2
3
2
2
3
), 55.02 (N-CH
2
2
3
), 128.55 (C-2, C-6, Ar-
3
2
2
3
2
2
H
3
5
2
2
3
4
5
6
2
7
2
6
2
)
,
2
[
a] Spectra obtained in (CD CO.
3 2
)
Eur. J. Org. Chem. 2005, 4710–4714
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4713