International Journal of Organic Chemistry, 2011, 1, 202-206
doi:10.4236/ijoc.2011.14029 Published Online December 2011 (http://www.SciRP.org/journal/ijoc)
The Synthesis of Arylsulfonylphthalimides and Their
Reactions with Several Amines in Acetonitrile
Seyhan Ozturk, Halil Kutuk*
Department of C hemi st ry , Faculty of Arts and Sciences, Ondokuz Mayıs University, Samsun, Turkey
Received August 24, 2011; revised October 14, 2011; accepted October 23, 2011
Abstract
In this study, several N-(p-substituted-arylsulfonyl)phthalimides (1a-e) were synthesized. The synthesized
compounds were then examined with respect to their substitution reactions with t-butylamine, diethylamine,
cyclohexylamine, and trans-1,2-diaminocyclohexane in acetonitrile. In order to determine the mechanism,
substituent effect, activation entropy, and nucleophile effect were used as criteria.
Keywords: Arylsulfonyl Phthalimides, Mechanism, Substituent Effect, Activation Entropy
1. Introduction
N-Alkyl and N-arylsulfonyl phthalimides were prepared by
Heller [1] from the reaction of potassium phthalimide and
sulfonyl chlorides. Earlier attempts by Evans and Dehn to
prepare several N-aryl derivatives [2-3] and later by
Scott and Lutz to prepare some N-alkyl derivatives by
this reaction had been unsuccessful [4]. Later, potassium
phthalimide was reported to interact with p-toluenesul-
fonyl chloride at 140˚C or in dimethylformamide at 5˚C
to 40˚C to yield N-(p-tolylsulfonyl)phthalimide [5]. The
mechanism of acid-catalyzed hydrolysis of N-(p-substi-
tuted-arylsulfonyl)phthalimides was studied in detail in
our laboratory [6]. We now report a complementary stu-
dy of the nucleophilic substitution reactions of a series of
N-(p-substituted-arylsulfonyl)phthalimides (1a-e) in ace-
tonitrile (Scheme 1).
2. Results and Discussions
In this study, N-(p-methoxyphenylsulfonyl)phthalimide
(1a), N-(p-toluenesulfonyl)phthalimide (1b), N-(phenyl-
sulfonyl)phthalimide (1c), N-(p-bromophenylsulfonyl)
phthalimide (1d) and N-(p-nitrophenylsulfonyl)phtha- li-
mide (1e) were synthesized. The synthesized compoun-
ds were examined with respect to their substitution reac-
tions with t-butylamine, diethylamine, cyclohexylamine,
and trans-1,2-diaminocyclohexane. In order to determi-
ne the mechanism, substituent effect, activation entropy
and nucleophile effect were used as criteria.
The substituent effect was investigated at 30.0˚C ±
0.1˚C in acetonitrile. Positive ρ values were obtained for
the substitution of N-(p-substituted-arylsulfonyl)phthali-
mides with t-butylamine, diethylamine, cyclohexylamine,
and trans-1,2-diaminocyclohexane. Electron withdrawing
substituents (-Br, -NO2) increased the reaction rate, while
electron donating substituents (-CH3, -OCH3) led to a de-
crease (Figures 1-4). A positive  value indicates the SN2
mechanism or an addition-elimination mechanism. The 
values for the reaction of N-(p-substituted-arylsulfonyl)
phthalimides in acetonitrile with t-butylamine, diethyl-
amine, cyclohexylamine, and trans-1,2-diaminocyclohe-
xane were 1.18, 1.12, 1.05 and 1.14 respectively. A
similar behavior was observed for the alkaline hydrolysis
of sulfonimidic esters and reactions of sulfinylphthalim-
ides with several nucleophiles [7,8].
Scheme 1. N-(p-Substitued-arylsulfonyl)phthalimides.

203 S. OZTURK ET AL.
Figure 1. Hammett Plots of logk2/k0 versus  for the reactions
of 1a-e with t-butylamine at 30.0˚C  0.1 ˚C in acetonitrile.
Figure 2. Hammett Plots of logk2/k0 versus  for the reactions
of 1a-e with diethyla mine at 30.0˚C  0.1˚C in acetonitrile.
Figure 3. Hammett Plots of logk2/k0 versus  for the reactions
of 1a-e with cyclohexylamine at 30.0˚C  0.1˚C in acetonitrile.
The activation entropy was also studied, and negative
ΔS≠ values were obtained. The ΔS≠ values for the re-
action of N-(phenylsulfonyl)phthalimides in acetonitrile
with t-butylamine, diethylamine, cyclohexylamine, and
trans-1,2-diaminocyclohexane were –148.94, –106.55,
–132.02 and –48.78 J/mol·K respectively. The negative
ΔS≠ values indicate that the reaction followed the SN2
mechanism or an addition-elimination mechanism. Similar
Figure 4. Hammett Plots of logk2/k0 versus  for the reac-
tions of 1a-e with trans-1,2-diaminocyclohexane at 30.0˚C 
0.1˚C in acetonitrile.
behavior was observed for the aminolysis of 1-tosyl-
3-methyl imidazolium chloride as well [9]. Arrhenius pa-
rameters for the reaction of N-(phenylsulfonyl)phth- ali-
mides in acetonitrile with t-butylamine, diethylamine,
cyclohexylamine, and trans-1,2-diaminocyclohexane are
shown in Table 1.
Second order kinetics, showing dependence both on the
nucleophile and on the substrate, are widely observed in
nucleophilic substitutions [10]. It was also observed that
the reactions with cyclohexylamine, and trans-1,2-dia-
minocyclohexane nucleophiles took place much faster
than those with t-butylamine and diethylamine nucleo-
philes as shown in Table 2.
In the light of the overall evidence, we propose that
the substitution reactions of a series of N-(p-substitut
ed-arylsulfonyl)phthalimides with t-butylamine, diethy-
lamine, cyclohexylamine and trans-1,2-diaminocyclohe-
xane occur with SN2 mechanism or an addition-elimina-
tion mechanism, as shown in Schemes 2 and 3 respec-
tively.
3. Experimental
3.1. Materials and Methods
N-(p-Substituted-arylsulfonyl)phthalimides 1a-e were pre-
pared from the corresponding p-substituted-arylsulfonyl
Table 1. Activation parameters for the reaction of N-(phe-
nylsulfonyl) phthalimide in acetonitrile with t-butylamine,
diethylamine, cyclohexylamine, and trans-1,2-diaminocy-
clohexane.
Nucleophile H ( kJ/mol) S (J/mol·K) R2
t-Butylamine 29.75 –148.94 0.9981
Diethylamine 39.60 –106.55 0.9978
Cyclohexylamine 20.66 –132.02 0.9928
trans-1,2-Diaminocyclohexane46.18 –48.78 0.9829
logk2/k0
logk2/k0
logk2/k0
logk2/k0

S. OZTURK ET AL.
204
Table 2. Values of k2 (M–1s–1) for the substitution of N-(p-
substitutedarylsulfonyl) phthalimides with nucleophiles at
30.0˚C  0.1˚C in acetonitrile.
chlorides with potassium phthalimides in acetonitrile as
described by Heller [1]. All melting points were deter-
mined using an electrothermal digital melting point ap-
paratus.
Nucleophile Substituent k2 (M–1s–1)
1a 0.47
1b 0.68
1c 0.87
1d 1.29
t-Butylamine
1e 3.91
1a 1.41
1b 1.91
1c 2.63
1d 6.06
Diethylamine
1e 10.51
1a 108.63
1b 147.78
1c 210.64
1d 363.74
Cyclohexylamine
1e 1093.56
1a 102.07
1b 123.40
1c 204.84
1d 276.86
trans-1,2-Diaminocyclohexane
1e 856.09
1a: m.p. 218˚C - 219˚C (Lit.11 218˚C - 219˚C). 1H NMR
(400 MHz, DMSO-d6):  7.90 - 8.10 (d, 2H), 7.80 - 8.00 (s,
2H), 7.1 - 7.3 (d, 2H), 3.8 (s, 3H); 13C NMR (400 MHz,
DMSO-d6):  164.61, 163.43, 136.27, 131.04, 130.92,
129.65, 124.70, 115.19, 56.40; IR (ATR, cm–1) 3067, 1739,
1593 - 1417, 1252 - 975, 1165, 1143, 1089, 866 - 663, 663.
1b: m.p. 240˚C - 241˚C (Lit.1 239˚C - 240˚C). 1H NMR
(200 MHz, DMSO-d6):  8.40 - 7.60 (d, 4H), 7.50 - 7.00 (dd,
J = 7.6 Hz, 4H), 2.34 (s, 3H); 13C NMR (200 MHz,
DMSO-d6):  146.04, 135.43, 134.29, 130.97, 129.92, 128.44,
124.54, 123.59, 21.30; IR (KBr disk, cm–1) 3066, 2988,
1747, 1593 - 1466, 1256 - 965, 1178, 1088, 865 - 632, 657.
1c: m.p. 202˚C - 203˚C (Lit.1 202.5˚C - 203.5˚C). 1H
NMR (200 MHz, DMSO-d6):  8.09 - 8.07 (d, 2H), 8.07
- 8.02 (dd, J = 3.4 Hz, 2H), 7.94 - 7.90 (d, 2H), 7.77 -
7.73 (d, 2H), 7.70 - 7.60 (d, 1H); 13C NMR (200 MHz,
DMSO-d6):  162.60, 137.94, 135.82, 134.90, 130.54,
129.53, 127.75, 124.28; IR (KBr disk, cm–1) 3069, 1748,
1604 - 1448, 1255 - 999, 1138, 1087, 864 - 682, 682.
Scheme 2. SN2 mechanism for N-(p-Substitued-arylsulfonyl)phthalimides with t-butylamine.

205 S. OZTURK ET AL.
S
O
N
OC
C
O
O
R
Addition
Slow
C
N
C
OO
S
OO
R
Elimination
C
NH
C
O
OR
S
O
O
N
H
H
C
N
C
OO
S
OO
R
H
N
H
H
N
H
NH
Scheme 3. An addition-elimination mechanism for N-(p-Substitued-arylsulfonyl)phthalimides with cyclohexylamine.
1d: m.p. 249˚C - 250˚C (Lit.1 247˚C - 248˚C). 1H NMR
(200 MHz, DMSO-d6):  8.00 - 7.80 (d, 2H), 7.70 - 7.50
(dd, J = 4.0 Hz, 2H), 7.50 - 7.30 (dd, J = 4.2 Hz, 2H); 13C
NMR (200 MHz, DMSO-d6):  167.34, 135.97, 131.96,
131.84, 130.59, 129.52, 129.43, 127.40; IR (KBr disk,
cm–1) 3101, 1752, 1608 - 1466, 1258 - 969, 1140, 1086,
864 - 669, 707, 600.
1e: m.p. 239˚C - 240˚C (Lit.12 238˚C - 240˚C) 1H NMR
(400 MHz, DMSO-d6):  8.40 - 8.60 (d, 2H), 8.20 - 8.40 (d,
2H), 7.80 - 8.10 (dd, J = 4.8 Hz, 4H), 13C NMR (400 MHz,
DMSO-d6):  163.13, 151.41, 143.23, 136.35, 131.24,
130.34, 125.19, 124.85; IR (ATR, cm–1) 3107, 1754, 1602 -
1466, 1528, 1252 - 964, 1138, 1084, 854 - 690, 602.
3.2. Kinetic Studies
The rates of substitution reactions of N-(p-substituted-
arylsulfonyl)phthalimides were followed spectrophoto-
metrically using a GBC Cintra 20 Model UV-VIS spec-
trophotometer with a thermostatted cell compartment
(0.05˚C). Values of k1 were calculated from the stan-
dard equation using a least-squares procedure. All kinetic
mea- surements were duplicated, and the average devia-
tion from the mean was 3%. Second-order rate con-
stants (k2) were calculated from the slope of the plots of
pseudo-first-order rate constants versus nucleophile con-
centrations (at least three different concentrations).
2exp exp
kT HS
khRT R


 (1)
where k, is Boltzman’s constant, h, Planck’s constant and
the other symbols have their usual meanings. Expressing
Equation (1) in logarithmic form, Equation (2) is ob-
tained. From a plot of Ink2 versus 1/T, ΔS≠ and ΔH≠ can

S. OZTURK ET AL.
206
be obtained from the intercept and slope respectively.
2
In kT HS khRT R



 (2)
3.3. Product Analysis
N-t-Butyltoluenesulfonamide was prepared from t-bu-
tylamine with p-toluenesulfonyl chloride and cupric ox-
ide in acetonitrile at room temperature [13]. m.p. 112˚C -
113˚C [14].
Analysis of the products was also determined by
comparing the UV spectrum obtained after completion of
the kinetic experiment with the spectrum of the expected
products at the same concentration and under the same
conditions. Thus, for the reaction of N-(p-toluenesul-
fonyl)phthalimide with t-butylamine, the UV spectrum
recorded at the end of the reaction was identical with that
of a 1:1 mixture of phthalimide and N-t-butyltoluene-
sulfonamide.
4. Acknowledgements
We would like to thank Ondokuz Mayis University (Gr-
ant No. 1904.09.007) for its financial support to our study.
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