Convenient preparation of N-monosubstituted S,S-diarylsulfodiimides using fluoro-λ6-sulfanenitriles

Article abstract of DOI:10.1055/s-2008-1067090

The reaction of fluorodiphenyl-λ⁶-sulfanenitrile with primary alkyl- or aryl-amines in the presence of acid catalysts or tertiary amines gave N-monosubstituted S,S-diphenylsulfodiimides effectively.

Full text of DOI:10.1055/s-2008-1067090

PAPER
1835
Convenient Preparation of N-Monosubstituted S,S-Diarylsulfodiimides Using
Fluoro-l6-sulfanenitriles
?
?? oshiaki Yoshimura,* Hiroki Ishikawa, Tetsuo Fujie, Eiichi Takata, Ryuta Miyatake, Hiroshi Kita,
Eiichi Tsukurimichi
Department of Applied Chemistry, Graduate School of Science and Engineering, University of Toyama, Gofuku, Toyama 930-8555, Japan
Fax +81(76)4456850; E-mail: yosimura@eng.u-toyama.ac.jp
Received 11 January 2008; revised 29 February 2008
The reactions of fluorodiphenyl-l6-sulfanenitrile (1) with
Abstract: The reaction of fluorodiphenyl-l6-sulfanenitrile with
three equivalents of either butylamine or aniline, were
primary alkyl- or aryl-amines in the presence of acid catalysts or
carried out under the various conditions shown in Table 1.
tertiary amines gave N-monosubstituted S,S-diphenylsulfodiimides
The reaction with butylamine in acetonitrile gave the cor-
responding N-butyl-S,S-diphenylsulfodiimide in only
12% yield, with the remainder of the reaction mixture
consisting of unreacted l6-sulfanenitrile (Table 1, entry
1). Interestingly, since N-arylsulfodiimides are difficult to
prepare by other methods, the reaction with aniline under
the same reaction conditions gave N-arylsulfodiimides in
62% yield (entry 13). Attempts to synthesize N-phenyl-
S,S-diphenylsulfodiimide by Furukawa’s method5 using
N-bromo-S,S-diphenylsulfimide and aniline without sol-
vent gave the desired product in only 3% yield
(Scheme 1).
effectively.
Key words: fluorodiphenyl-l6-sulfanenitrile, acid catalyst, N-
monosubstituted S,S-diphenylsulfodiimides
The chemistry of sulfodiimides1 is interesting from the
point of view that they have structures which are isoelec-
tronic with sulfones, are very stable and react through the
two basic functionalities in the molecule. Such com-
pounds can be expected to have characteristic reactions
and applications. Recently we reported a synthetic appli-
cation of N-monosubstituted S,S-diphenylsulfodiimides
in N-sulfenylation, which afforded the corresponding N-
sulfenylsulfodiimides. These compounds, upon moderate
thermolysis, generated sulfenylnitrenes, which could be
trapped with olefins to give N-sulfenylazyridines ste-
reospecifically in high yields.2
Since no X-ray crystal structures are available for diaryl-
sulfodiimides, the structure of the N-phenylsulfodiimide
was also confirmed by X-ray crystallographic analysis.
An ORTEP drawing and some selected bond lengths and
angles are listed in Figure 1. The S–N bond lengths are
Though there are some reports on the synthesis of S,S-di-
alkylsulfodiimides,3 only a few S,S-diarylsulfodiimides
have been prepared. Furukawa et al.4 prepared N-p-tosyl-
S,S-diarylsulfodiimides by the reaction of N-unsubstitut-
ed S,S-diarylsulfimides with chloramine-T. However, di-
rect N-monoalkylation of sulfodiimides is very difficult to
control and the only example of N-monoalkyl-S,S-diaryl-
sulfodiimides came from the reaction of N-halo-S,S-diar-
ylsulfimides with primary alkylamines.5 However, this
method is not suitable for the synthesis of N-monoarylsul-
fodiimides. Recently, we have prepared an unusual type
of compound, l6-sulfanenitriles, bearing a sulfur–nitro-
gen triple bond, and have investigated their reactivity.6
Our discovery of fluoro-l6-sulfanenitriles7 inspired us to
prepare N-monosubstituted S,S-diarylsulfodiimides. Pre-
viously we reported that the reaction of fluorodiphenyl-
l6-sulfanenitrile with primary amines gave the corre-
sponding N-monosubstituted sulfodiimides, including N-
arylsulfodiimides.7a In this paper, we report the prepara-
tion of a further variety of N-monosubstituted sulfodiim-
ides. Furthermore, we report an improvement of the yields
through the use of acid catalysts and base.
Ph
N
Ph
S
N
Ph
Br
+
Ph NH2
excess
Ph
S
Ph
40 °C, 20 h
NH
2
3%
Scheme 1
Figure 1 The molecular structure of N-phenyl-S,S-diphenylsulfodi-
imide. Selected bond lengths (Å) and bond angles (°): S(1)–N(1),
1.546(1); S(1)–N(2), 1.526(2); S(1)–C(1), 1.798(2); S(1)–C(2),
1.788(2); N(1)–S(1)–N(2), 126.02(9); C(1)–S(1)–C(2), 104.10(8);
N(1)–S(1)–C(1), 99.71(8); N(1)–S(1)–C(2), 110.46(8); N(2)–S(1)–
C(1), 112.91(9); N(2)–S(1)–C(2), 102.01(9).
SYNTHESIS 2008, No. 12, pp 1835–1840
x
x.
x
x
.
2
0
0
8
Advanced online publication: 16.05.2008
DOI: 10.1055/s-2008-1067090; Art ID: F00108SS
© Georg Thieme Verlag Stuttgart · New York

1836
T. Yoshimura et al.
PAPER
Table 1 Reaction of Fluorodiphenyl-l6-sulfanenitrile (1) with Butylamine or Aniline
R
F
S
N
O
N
Ph
Ph
+
R
NH2
+
Ph
S
Ph
Ph
S
Ph
Ph
S
Ph
+
NH
NH
(3.0 equiv)
1
2
3
4
Entry
R
Conditions
Yield (%)a
Solvent
MeCN
MeCN
MeCN
none
Temp (°C)
30
Catalyst (1.2 equiv) Time (h)
2
3
4
Recovered
1
2
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
Ph
–
16
16
8
12
51
90
20
73
98
18
59
46
87
14
38
62
50
64
49
92
90
86
62
85
29
13
84
98
0
–
–
0
0
0
0
0
0
0
0
0
0
–
–
1
85
–
30
AcOH
TFA
–
3
30
–
4
30
8
76
0
5
none
30
AcOH
TFA
Et3N
Et3N
DABCO
DABCO
pyridine
pyridine
–
8
24
0
3
6
4
4
5
5
2
2
–
–
2
2
6
–
0
–
5
8
0
6
none
30
4
0
7
none
30
8
76
32
40
0
8
none
30
24
8
9
none
30
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
none
30
24
8
none
30
72
51
0
none
30
24
16
16
16
8
MeCN
MeCN
MeCN
MeCN
none
30
11
22
8
Ph
50
–
0
Ph
30
AcOH
TFA
–
–
Ph
30
15
5
–
Ph
30
1
0
Ph
none
30
–
20
7
0
Ph
none
30
AcOH
AcOH
TFA
TFA
Et3N
DABCO
pyridine
0.5
6
0
Ph
none
30
8
12
11
41
0
–
Ph
none
30
0.5
4
0
Ph
none
30
–
Ph
none
30
8
80
2
Ph
none
30
8
0
Ph
none
30
1
0
0
a Determined by 1H NMR analysis.
very similar to those found in of S,S-dimethylsulfodiimide of sulfide 3 (entry 14). Subsequent reactions were, there-
(1.536 Å).8,9
fore, all carried out at 30 °C.
In the case of the reaction in acetonitrile, the yield of N- Addition of acids such as acetic (AcOH) or trifluoroacetic
phenylsulfodiimide formation was better than that of the (TFA) acid greatly accelerated the formation of the N-bu-
N-butylsulfodiimide, however, the reaction of aniline tylsulfodiimide, the effect of the latter being larger than
gave the by-product diphenyl sulfide (3; entry 13). Con- that of the former (entries 2 and 3). The acceleration
ducting the reaction at 50 °C reduced the yield of the N- caused by TFA in the reaction with butylamine is clearly
phenylsulfodiimide and gave rise to increased formation demonstrated in Figure 2. In the case of an aromatic
Synthesis 2008, No. 12, 1835–1840 © Thieme Stuttgart · New York

PAPER
N-Monosubstituted S,S-Diarylsulfodiimides
1837
amine, although the reaction was also accelerated by acid, action as a form of conjugate acid of the amine. Addition
the use of the strong acid TFA reduced the yield of the N- of triethylamine (1.2 equiv) to the reaction with aniline,
phenylsulfodiimide compared to the use of AcOH, and in- retarded the reaction and gave only 13% of the sulfodiim-
creased the amount of by-product (PhSPh) and tar (entries ide and 80% recovered starting material after 8 hours (en-
15 and 16).
try 23). This result provides evidence for the catalytic role
of HF. The acid catalysts are thus actually the conjugate
acid of the strongest basic amines in the system. There are
two possible catalytic mechanisms. One involves protona-
tion of the thiazyl nitrogen atom and the other involves
general acid catalysis to assist removal of the fluoride an-
ion. Loss of a fluoride anion is known to be catalyzed by
acid in the hydrolysis of acetyl fluoride in aqueous solu-
tion.10 Furthermore, we have previously reported that the
fluoro-l6-sulfanenitrile (1) undergoes hydrolysis in aque-
ous solvent through a dissociative mechanism catalyzed
by acid.11 The reaction of 1 with aniline, without the addi-
tion of acid, is considered to be catalyzed by aniline hy-
drofluoride as shown in Figure 3, however, in the
presence of triethylamine, its hydrofluoride is formed in-
stead of aniline hydrofluoride. Since the acidity of the
conjugate acid of triethylamine is weaker than that of
aniline and thus the catalytic activity is smaller, the rate of
the reaction is retarded. The acid catalysts are also effec-
tive in the reaction with aromatic amines, however, acid-
catalyzed decomposition of N-arylsulfodiimides to give
diphenyl sulfide and a tarry product, limited the product
yields. The results suggest that the HF generated effec-
tively catalyzes this reaction to afford N-arylsulfodiim-
ides in moderate yields.10,11
Figure 2 Time dependence of yields (%) of N-butylsulfodiimide in
the reaction of fluorodiphenyl-l6-sulfanenitrile (1) with butylamine at
30 °C in MeCN.
In order to examine the possibility that the use of acid
causes the decomposition of the product N-phenylsulfodi-
imide, the decomposition of 2 in an NMR tube at 30 °C
was followed for 16 hours. The formation of PhSPh (2%
yield), together with an unidentified tarry product
(Scheme 2) suggested that decomposition of the N-phe-
nylsulfodiimide was indeed catalyzed by an acid, though
the reaction conditions were not same. The formed prod-
uct 2 also decomposed in the presence of TFA when the
reaction in Table 1, entry 21 was continued for longer
times (Table 1, entry 22).
Ar
Ar
Bu
NH2
NH2
NH2
Ph
Ph
Ph
N
N
S
F
N
S
F
S
F
Ph
Ph
Ph
Ph
N
TFA (1.2 equiv)
F –
H
F –
F –
Ph
S
Ph
tarry product
+
Ph
S
Ph
+
H
H
CDCl3, 30 °C, 16 h
+
+
NH2
Ar
NH
Et3N
BuNH2
2
3
2%
weaker acidic
weaker acidic
Scheme 2
Figure 3 Catalytic action of the conjugate acids of amines
The reaction was greatly improved when performed with-
out solvent. The time required for the aliphatic amine to
react in the absence of solvent was found to be reduced
compared to that in acetonitrile; addition of acid further
improved the results compared to the reaction in acetoni-
trile (entries 4–6). These results may be an effect of con-
centration. In the case of an aromatic amine, when the
reaction was performed without solvent an exothermic re-
action occurred and the rate of the reaction significantly
increased; the reaction was almost complete in one hour,
even without addition of acid (entry 17). Longer reaction
times (20 h) afforded only a small increase in the amount
of decomposition products (entry 18). Addition of acid re-
sulted in faster reaction times (<30 min), but also in-
creased the formation of PhSPh; prolonged reaction times
gave large amounts of decomposition products (entries
19–22). However, even in the absence of acid, the reaction
can be considered to be catalyzed by HF formed in the re-
In spite of the stronger nucleophilicity of the alkylamine
compared to the aromatic amine, the reaction with butyl-
amine was slower than that with aniline. This result may
be explained by the weaker catalytic effect of conjugate
acid (hydrofluoride) from the more basic butylamine than
that of the aromatic amine as shown in Figure 3. When
both butylamine and aniline were mixed in the same reac-
tion system, without solvent, at 30 °C for 24 hours the N-
butylsulfodiimide was afforded in 36% yield; only 3% of
the N-phenylsulfodiimide together with 5% of 4 and 50%
starting materials were recovered, suggesting that the
weaker nucleophilic aniline reacts slower than the stron-
ger butylamine under the same weaker catalytic condi-
tions. Although the reaction was slow in the presence of
triethylamine, the interesting result that HF was trapped
by the more basic amine, thus inhibiting the formation of
diphenyl sulfide and tarry product, lead us to investigate
the use of various tertiary amines as shown in entries 7–12
Synthesis 2008, No. 12, 1835–1840 © Thieme Stuttgart · New York

1838
T. Yoshimura et al.
PAPER
and 23–25. Though none of the tert-amines studied signif- densed at low temperature and the reactions were carried
icantly affected the rate of reaction with butylamine (en- out from –80 °C to room temperature under normal pres-
tries 7–12), alkyl tert-amines slowed down the rate of sure. The formation of the sulfoximides 4 reduced the
formation of N-phenylsulfodiimide (entries 23 and 24) yield of the desired sulfodiimides 2 (Table 2). In the pres-
and all tert-amines were found to inhibit the formation of ence of pyridine, the rate of the reactions were found to be
the sulfide 3. The use of pyridine was found to give the slower with some ortho-substituted anilines, in these cas-
maximum yield of the N-phenylsulfodiimide, whilst not es, the reaction time was extended to three hours, to give
retarding the rate of the reaction (entry 25). Therefore, the the corresponding N-arylsulfodiimides in very good
best conditions for the reaction with aromatic amines in- yields. The reaction with other substituted anilines seems
volves the use of pyridine, while those for the reaction to be accelerated by the addition of pyridine, to give the
with aliphatic amines are to use TFA without solvent. The sulfodiimides in very good yields. None of the reactions
reaction of 1 with various aliphatic amines in the presence in the presence of pyridine gave the decomposition prod-
of TFA (1.2 equiv) are shown in Table 2 and the reaction uct, PhSPh.
with various aromatic amines in the presence of pyridine
In summary, N-monosubstituted S,S-diphenylsulfodiim-
(1.2 equiv) without using solvent are shown in Table 3. In
ides have been conveniently prepared in high yields by the
the case of gaseous amines, the amines were once con-
Table 2 Reaction of 1 with Aliphatic Amines in the Presence of TFA without Solvent
R
F
S
N
1
N
O
TFA (1.2 equiv)
+
Ph
Ph
+
Alkyl NH2
(3.0 equiv)
Ph
S
Ph
Ph
S
Ph
Ph
S
Ph
+
NH
2
NH
4
3
Amine
R
Conditions
Yield (%)a
Temp (°C)
–80 to r.t.
–80 to –40
30
Time (h)
2
3
0
0
0
0
4
Recovered
Hb
8
4
4
4
4
74
22
17
0
0
0
0
0
Meb
n-Pr
n-Bu
t-Bu
79
96
30
98
0
30
no reaction
a Determined by 1H NMR analysis.
b Due to the difficulty of measuring exact amounts of gaseous amines, an excess of amine was used.
Table 3 Reaction of 1 with Aromatic Amines in the Presence of Pyridine without Solvent at 30 °C
Ar
F
S
N
1
N
O
pyridine (1.2 equiv)
30 °C
+
Ph
Ph
+
Ar NH2
Ph
S
Ph
+
Ph
S
Ph
Ph
S
Ph
NH
2
NH
4
(3.0 equiv)
3
Amine
Ar
Time (h)
Yield (%)a
2
3
4
Recovered
o-MeC6H4
1
3
38
94
0
0
2
4
57
0
p-MeC6H4
o-MeC6H4
p-MeC6H4
o-ClC6H4
1
1
1
96
93
92
0
0
0
1
5
1
0
0
5
1
3
57
93
0
0
5
6
37
0
m-ClC6H4
p-ClC6H4
1
1
96
97
0
0
2
2
0
0
a Determined by 1H NMR analysis.
Synthesis 2008, No. 12, 1835–1840 © Thieme Stuttgart · New York

PAPER
N-Monosubstituted S,S-Diarylsulfodiimides
1839
1H NMR (400 MHz, CDCl3): d = 0.97 (t, J = 7.2 Hz, 3 H), 1.54
(sext, J = 7.2 Hz, 2 H), 3.01 (t, J = 7.2 Hz, 2 H), 7.41–7.46 (m, 6 H),
8.01–8.11 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 12.0, 26.3, 44.9, 128.0, 128.9,
131.5, 143.3.
reaction of fluorodiphenyl-l6-sulfanenitriles (1) with var-
ious primary amines. The reaction was found to be cata-
lyzed either by HF generated in the reaction, or by
additional acids such as trifluoroacetic acid or acetic acid.
N-Alkylsulfodiimides were best prepared under solvent-
free conditions in the presence of small amounts of TFA,
while N-arylsulfodiimides were optimally prepared under
solvent-free conditions in the presence of small amount of
pyridine. Use of organic solvent was found to reduce the
yield of N-substituted sulfodiimides.
Anal. Calcd for C15H18N2S: C, 69.73; H, 7.02; N, 10.84. Found: C,
70.06; H, 6.98; N, 10.74.
N-Butyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 93–94 °C (C6H6–hexane) (Lit.5 97.5–
98.0 °C).
IR (KBr): 3150, 2930, 1442, 1180, 1082, 1020, 982 cm–1 (Lit.5
3160, 1180, 1085, 1060, 1025, 985 cm–1).
All reagents and solvents were obtained commercially and were pu-
rified by general methods when necessary. Analytical TLC was per-
formed on Merck plastic sheets coated in Silica gel 60 F254. Merck
silica gel (60) was used for column chromatography. Infrared spec-
tra (IR) were recorded on a Horiba FT-710 spectrometer. 1H NMR
(400 MHz) and 13C NMR (100 MHz) spectra were obtained on a
JEOL-JNM-A400 NMR spectrometer in CDCl3 with TMS as an in-
ternal standard. Chemical shifts (d) are measured in ppm and cou-
pling constants (J) are in hertz (Hz). Mass spectra (MS) were
recorded on a JEOL-JMS-D300 mass spectrometer. Melting point
were measured on a Yanaco Mp-j3 melting point apparatus.
Elemental analysis were performed on a Yanaco MT-5 CHN
CORDER.
1H NMR (400 MHz, CDCl3): d = 0.91 (s, 3 H), 1.42 (sext, J = 7.2
Hz, 2 H), 1.63 (quint, J = 7.2 Hz, 2 H), 3.04 (t, J = 7.2 Hz, 2 H),
7.41–7.47 (m, 6 H), 8.08–8.10 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 13.4, 20.5, 35.3, 42.8, 128.0,
128.8, 131.5, 143.2.
Anal. Calcd for C16H20N2S: C, 70.54; H, 7.40; N, 10.28. Found: C,
70.68; H, 7.31; N, 10.16.
N-Phenyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 154 °C (MeOH).
IR (KBr): 3170, 1598, 1485, 1441, 1287, 1260, 1081, 959 cm–1.
Preparation of N-Alkyl- and N-Aryl-S,S-diphenylsulfodiimides
2; Typical Procedure
1H NMR (400 MHz, CDCl3): d = 6.83–6.88 (m, 1 H), 7.11–7.12 (m,
4 H), 7.43–7.50 (m, 6 H), 8.16–8.21 (m, 4 H).
To fluorodiphenyl-l6-sulfanenitrile (1; 1.00 g, 4.57 mmol) was add-
ed a solution of TFA (0.42 mL, 5.48 mmol, 1.2 equiv) in butylamine
(1.37 mL, 13.8 mmol, 3.0 equiv) and the mixture was allowed to re-
act at 30 °C whilst monitoring by TLC (CHCl3–MeOH, 20:1). The
solution was diluted with CHCl3 (50 mL), washed with dilute HCl
(3%, 20 × 5 mL) and extracted with CHCl3 (20 × 2 mL). The com-
bined organic layers were dried over anhydrous MgSO4, filtered
and the filtrate was evaporated. The residue was purified by silica
gel column chromatography (CHCl3–MeOH, 8:1) to give the crude
N-butyl-S,S-diphenylsulfodiimide, which was further recrystallized
from MeOH (82% yield, 1.02 g, 3.74 mmol).
13C NMR (100 MHz, CDCl3): d = 120.8, 123.3, 128.8, 129.1, 132.0,
143.1, 145.7.
Anal. Calcd for C18H16N2S: C, 73.94; H, 5.52; N, 9.58. Found: C,
74.11; H, 5.65; N, 9.26.
X-ray crystal data; Empirical formula: C18H16N2S; Formula weight
292.40; Crystal system = triclinic; Space group P1 (#2); Unit cell di-
mensions: a = 6.446(1) Å, b = 10.772(2) Å, c = 12.241(2) Å;
a = 106.21(1)°, b = 101.64(2)°, g = 105.67(2)°; V = 749.8(2) Å3;
T = 296 K; Z = 2; m(Mo Ka) = 2.10 cm–1; 4573 reflections mea-
sured, 3156 unique (Rint = 0.043); final R value 0.060. Crystallo-
graphic data has been deposited with the Cambridge
Crystallographic Data Centre, CCDC No. 679450.
S,S-Diphenylsulfodiimide
Colorless crystals; mp 88–90 °C (C6H6) (Lit.5 91.0–92.0 °C).
IR (KBr): 3155, 3067, 1446, 1130, 1092, 1024, 928 cm–1 (Lit.5
N-o-Tolyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 119 °C (MeOH).
IR (KBr): 3185, 1596, 1480, 1254, 1180, 1075, 950 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.50 (s, 3 H), 6.75–6.79 (td,
J = 7.2, 1.2 Hz, 2 H), 6.86–6.90 (td, J = 7.2, 1.2 Hz, 2 H), 7.13–
7.16 (m, 2 H), 7.42–7.49 (m, 6 H), 8.19–8.23 (m, 4 H).
3160, 1130, 1090, 1065, 930 cm–1).
1H NMR (400 MHz, CDCl3): d = 2.32 (br, 1 H), 7.27–7.47 (m, 6 H),
8.13–8.16 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 127.3, 128.9, 131.8, 145.2.
13C NMR (100 MHz, CDCl3): d = 19.0, 120.5, 120.7, 126.0, 128.0,
N-Methyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 115–117 °C (C6H6).
IR (KBr): 3149, 3059, 2960, 1444, 1180, 1092, 1022, 993 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.81 (s, 3 H), 7.43–7.47 (m, 6 H),
8.06–8.09 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 29.1, 127.9, 128.9, 131.7, 142.5.
129.1, 130.2, 131.9, 132.8, 143.5, 144.0.
Anal. Calcd for C19H18N2S: C, 74.47; H, 5.92; N, 9.14. Found: C,
74.49; H, 6.00; N, 8.95.
N-p-Tolyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 124 °C (MeOH).
Anal. Calcd for C13H14N2S: C, 67.79; H, 6.13; N, 12.16. Found: C,
68.13; H, 6.22; N, 12.16.
IR (KBr): 3210, 3040, 1610, 1505, 1475, 1445, 1280, 1255, 1180,
1140, 950, 820 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.22 (s, 3 H), 6.94 (d, J = 7.6 Hz,
2 H), 7.05 (d, J = 7.6 Hz, 2 H), 7.44–7.48 (m, 6 H), 8.17–8.19 (m,
4 H).
13C NMR (100 MHz, CDCl3): d = 20.6, 123.2, 128.0, 129.1, 129.4,
130.1, 131.9, 142.9, 143.2.
N-Propyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 118–119 °C (C6H6–hexane) (Lit.5 117.5–
118.5 °C).
IR (KBr): 3155, 2950, 1445, 1168, 1121, 1082, 1019 cm–1 (Lit.5
3160, 1170, 1110, 1035, 1010 cm–1).
Synthesis 2008, No. 12, 1835–1840 © Thieme Stuttgart · New York

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Anal. Calcd for C19H18N2S: C, 74.47; H, 5.92; N, 9.14. Found: C,
74.51; H, 5.88; N, 9.15.
1H NMR (400 MHz, CDCl3): d = 6.82 (td, J = 7.2, 1.6 Hz, 1 H),
7.00–7.06 (m, 2 H), 7.19 (s, 1 H), 7.43–7.52 (m, 6 H), 8.13–8.20
(m, 4 H).
N-o-Methoxyphenyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 111 °C (MeOH).
13C NMR (100 MHz, CDCl3): d = 120.7, 121.1, 123.4, 127.9, 129.2,
129.6, 132.2, 134.2, 142.6, 147.3.
IR (KBr): 3278, 3056, 3000, 1500, 1492, 1444, 1255, 1232, 1084,
1045, 1028, 949 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.35 (br, 1 H), 3.83 (s, 3 H), 6.68–
6.72 (m, 1 H), 6.83–6.88 (m, 2 H), 7.13–7.15 (dd, J = 6.8, 1.2 Hz,
1 H), 7.42–7.48 (m, 6 H), 8.19–8.23 (m, 4 H).
Anal. Calcd for C18H15N2ClS: C, 66.15; H, 4.63; N, 8.57. Found: C,
66.37; H, 4.74; N, 8.42.
N-p-Chlorophenyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 154 °C (MeOH).
13C NMR (100 MHz, CDCl3): d = 55.7, 111.5, 120.7, 121.7, 123.7,
128.0, 129.0, 131.8, 134.6, 143.5, 153.8.
IR (KBr): 3150, 3040, 1585, 1480, 1440, 1280, 1250, 1180, 1140,
1080, 1020, 950 cm–1.
Anal. Calcd for C19H18N2OS: C, 70.78; H, 5.63; N, 8.69. Found: C,
70.59; H, 5.83; N, 8.39.
1H NMR (400 MHz, CDCl3): d = 2.21 (br, 1 H), 7.06–7.11 (m, 4 H),
7.44–7.50 (m, 6 H), 8.16 (dd, J = 6.4, 1.2 Hz, 4 H).
13C NMR (100 MHz, CDCl3): d = 124.4, 125.8, 128.0, 128.8, 129.2,
N-p-Methoxyphenyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 111 °C (MeOH).
132.2, 142.7, 145.5.
MS: m/z = 328, 326 [M+].
IR (KBr): 3225, 3050, 3000, 1500, 1470, 1440, 1255, 1230, 1080,
1030, 950 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.72 (s, 3 H), 6.85 (td, J = 8.8, 2.4
Hz, 2 H), 7.08 (td, J = 8.8, 2.4 Hz, 2 H), 7.43–7.48 (m, 6 H), 8.18
(dd, J = 8.8, 2.4 Hz, 4 H).
13C NMR (100 MHz, CDCl3): d = 55.4, 114.3, 124.4, 128.1, 129.1,
131.9, 138.6, 143.1, 154.2.
Anal. Calcd for C18H15N2ClS: C, 66.15; H, 4.63; N, 8.57. Found: C,
66.26; H, 4.60; N, 8.59.
References
(1) Haake, M. The Chemistry of S,S-Diorgano-Sulfodiimides,
In Topics in Sulfur Chemistry, Vol. 1; Senning, A., Ed.;
Georg Thieme: Stuttgart, 1976, Chap. 3, 185.
MS: m/z = 292 [M+].
(2) Yoshimura, T.; Fujie, T.; Fujii, T. Tetrahedron Lett. 2007,
Anal. Calcd for C19H18N2OS: C, 70.78; H, 5.63; N, 8.69. Found: C,
70.59; H, 5.71; N, 8.60.
48, 427.
(3) (a) Appel, R.; Fehlhaber, H. W.; Hnssgen, D.; Schöllhorn, R.
Chem. Ber. 1966, 99, 3108. (b) Laughlin, R. G.; Yellin, W.
J. Am. Chem. Soc. 1967, 89, 2435.
(4) (a) Furukawa, N.; Akutagawa, K.; Yoshimura, T.; Akasaka,
T.; Oae, S. Synthesis 1979, 4, 289. (b) Furukawa, N.;
Omata, T.; Oae, S. Chem. Commun. 1973, 590.
(5) Furukawa, N.; Akutagawa, K.; Oae, S. Phosphorus Sulfur
Relat. Elem. 1984, 20, 1.
(6) Yoshimura, T. Rev. Heteroat. Chem. 2000, 22, 101.
(7) (a) Yoshimura, T.; Kita, H.; Takeuchi, K.; Takata, E.;
Hasegawa, K.; Shimasaki, C.; Tsukurimichi, E. Chem. Lett.
1992, 8, 1433. (b) Yoshimura, T.; Ohkubo, M.; Fujii, T.;
Kita, H.; Wakai, Y.; Ono, S.; Morita, H.; Shimasaki, C.;
Horn, E. Bull. Chem. Soc. Jpn. 1998, 71, 1629.
N-o-Chlorophenyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 144 °C (MeOH).
IR (KBr): 3199, 3056, 1581, 1469, 1309, 1286, 1248, 1153, 1128,
1082, 1060, 958 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.77 (td, J = 7.6, 1.6 Hz, 1 H), 6.92
(td, J = 7.6, 1.6 Hz, 1 H), 7.32 (dd, J = 7.6, 1.6 Hz, 1 H), 7.36 (dd,
J = 7.6, 1.6 Hz, 1 H), 7.43–7.50 (m, 6 H), 8.21–8.26 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 121.4, 122.5, 126.9, 128.2,
129.16, 129.20, 129.8, 132.2, 142.7, 142.8.
Anal. Calcd for C18H15N2ClS: C, 66.15; H, 4.63; N, 8.57. Found: C,
66.13; H, 4.68; N, 8.47.
(8) Webb, N. S.; Gloss, R. A. Tetrahedron Lett. 1967, 1043.
(9) Prince, E. Acta Crystallogr., Sect. B 1975, 31, 2536.
(10) Bunton, C. A.; Fendler, J. H. J. Org. Chem. 1966, 31, 2307.
(11) Dong, T.; Fujii, T.; Murotani, S.; Dai, H.; Ono, S.; Morita,
H.; Shimasaki, C.; Yoshimura, T. Bull. Chem. Soc. Jpn.
2001, 74, 945.
N-m-Chlorophenyl-S,S-diphenylsulfodiimide
Colorless crystals; mp 139 °C (MeOH).
IR (KBr): 3155, 1585, 1485, 1470, 1360, 1259, 970 cm–1.
Synthesis 2008, No. 12, 1835–1840 © Thieme Stuttgart · New York