Preparation of N-alkyl-S,S-diphenylsulfimides by the reaction of N-unsubstituted S,S-diphenylsulfimide with borane-pyridine

Article abstract of DOI:10.1055/s-2008-1067004

The reaction of an N-unsubstituted S,S-diphenylsulfimide¹ with aldehydes or ketones in the presence of a borane-pyridine complex and acetic acid in benzene at 40°C affords the corresponding N-alkyl-S,S- diphenylsulfimides. Since this reaction does not form the N,N-dialkylated aminosulfonium salt, this method provides a convenient preparation of N-monoalkylsulfimides without the necessity for a difficult separation of the products by column chromatography due to their similar R_f values. The mechanism of formation is discussed. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1067004

PAPER
1565
Preparation of N-Alkyl-S,S-diphenylsulfimides by the Reaction of
N-Unsubstituted S,S-Diphenylsulfimide with Borane–Pyridine
Preparationof
N
e
-Alkyl-
S
,
S
t
-
diphen
s
ylsulfimid
u
e
s
o Fujie, Tsunehisa Iseki, Hirofumi Iso, Yasushi Imai, Eiichi Tsukurimichi, Toshiaki Yoshimura*
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 26 December 2007; revised 8 February 2008
Before examination of the reductive alkylation of the
Abstract: The reaction of an N-unsubstituted S,S-diphenyl-
sulfimide, direct alkylation of N-unsubstituted sulfimide 1
with benzyl chloride was carried out in an NMR tube at
room temperature. The NMR spectrum showed a mixture
sulfimide1 with aldehydes or ketones in the presence of a borane–
pyridine complex and acetic acid in benzene at 40 °C affords the
corresponding N-alkyl-S,S-diphenylsulfimides. Since this reaction
does not form the N,N-dialkylated aminosulfonium salt, this meth- of partially protonated N-unsubstituted sulfimide (30%),
od provides a convenient preparation of N-monoalkylsulfimides
N-monobenzylsulfimide (39%) and N,N-dibenzylamino-
without the necessity for a difficult separation of the products by
sulfonium salt (31%) in the ratio 30:39:31. As expected
column chromatography due to their similar Rf values. The mecha-
the alkylation was very difficult to control; separation of
nism of formation is discussed.
this mixture by silica gel column chromatography is te-
dious because the products have similar Rf values and tail-
ing occurs.
Key words: N-alkyl-S,S-diphenylsulfimides,
monoalkylation, N-unsubstituted S,S-diphenylsulfimide
borane–pyridine,
Reaction of 1 with 1.2 equivalent amounts of 2 or 3 was
carried out in the presence of 1.5 equivalents of 4 and ace-
tic acid at 40 °C for two hours in benzene (Table 1). After
the disappearance of 1, the reaction mixture was treated
with dilute acid and extracted with chloroform to remove
by-products. The aqueous solution was made alkaline and
extracted with chloroform. The organic layer was evapo-
rated to give almost pure N-alkylsulfimide 5 and a small
amount of pyridine. Therefore, if the sulfimide is allowed
to react until it is completely consumed, separation by col-
umn chromatography is not required. No N,N-dialkylami-
nosulfonium salt was formed. The products were
identified by IR, 1H NMR, 13C NMR, and elemental anal-
yses. General by-products are diphenyl sulfide and nitriles
formed by the known reductive cleavage of the S–N bond
by aldehydes.6 Diphenyl sulfide is not considered to be
formed by the simple reduction of the N-unsubstituted
sulfimide 1 with borane–pyridine and acetic acid, because
no reaction occurred without the aldehyde, which was in
this case benzaldehyde. The reaction of 1 with paraform-
aldehyde gave the corresponding N-methylsulfimide 5a in
44% yield. The reaction with ketones such as acetone and
cyclohexanone under the same or higher conditions af-
forded also the corresponding N-(secondary alkyl)sulf-
imides 5k,l. However, aromatic ketones such as
benzophenone or anthraquinone did not react.
The chemistry of the sulfimides has been developed using
mainly N-acyl-substituted and N-unsubstituted sulfim-
ides.1c Among these, examples of N-alkylsulfimides have
been very limited because of difficulties in their prepara-
tion. Since N-alkylsulfimides have interesting reactions,
such as the formation of 2,3-dibenzoyl-1-benzylaziridine2
by the reaction of N-benzylsulfimide with trans-1,2-
dibenzoylethene, general methods for the preparation of
N-alkylsulfimides are required. In 1975, Frantz and
Martin3 obtained various N-alkyl-S,S-diphenylsulfimides
by treatment of S,S-dialkoxy-S,S-diphenylsulfuranes with
primary alkylamines. However, the preparation of the sul-
furane is troublesome and limited because of its moisture
sensitivity. On the other hand, the N-alkylation of N-un-
substituted S,S-diarylsulfimides with alkyl halides would
be expected to be difficult to control by stopping the reac-
tion at the monoalkylation stage and instead would afford
a mixture of the corresponding N-mono- and N-dialkyla-
tion products and unreacted sulfimide, which is difficult
separate without using column chromatography.2 The
conjugate addition of (S,S)-diphenylsulfimide (1) with
electrophilic vinyl compounds giving the corresponding
N-alkylsulfimides is only available to the vinyl-type con-
jugative electrophilic alkenes.4 In 1984, Pelter et al.5 pre-
pared N-monoalkylaniline by the reaction of aniline with
aldehydes 2 in the presence of borane–pyridine complex
(4) and acetic acid. This paper will report a more conve-
nient synthesis of N-alkylsulfimides by the reaction of
sulfimide 1 with aldehydes 2 or ketones 3 in the presence
of borane–pyridine complex (4) and acetic acid.
Without acetic acid the reaction was about ten times slow-
er and gave a complex mixture with side reactions like the
reductive amination of carbonyl compounds with borane–
pyridine. Pelter et al.5 reported that in the presence of ace-
tic acid the reductive amination of aldehydes and ketones
with borane–pyridine occurred much faster than the re-
duction without acetic acid. Meanwhile, Chen et al.7 re-
ported that presence of acetic acid accelerates the
reduction of aldehydes with borane–pyridine and claimed
the acetic acid activates borane–pyridine. In order to ex-
SYNTHESIS 2008, No. 10, pp 1565–1569
x
x.
x
x
.
2
0
0
8
Advanced online publication: 27.03.2008
DOI: 10.1055/s-2008-1067004; Art ID: F23907SS
© Georg Thieme Verlag Stuttgart · New York

1566
T. Fujie et al.
PAPER
of reductive amination using sodium cyanoborohydride
instead of borane–pyridine.
Table 1 Reaction of N-Unsubstituted S,S-Diphenylsulfimide (1)
with Aldehydes 2 or Ketones 3 in the Presence of Borane–Pyridine
Complex (4) and Acetic Acid
A possible mechanism for the reaction is consider to in-
volve initial nucleophilic attack of the sulfimide nitrogen
to afford an N-(1-hydroxyalkyl)sulfimide followed by de-
hydroxylation to give an iminosulfonium salt, which fur-
ther undergoes proton abstraction by a base, such as a
sulfimide, to give the nitrile or undergoes reduction with
the activated borane–pyridine complex to afford the N-
alkylsulfimide (Scheme 2).
N
BH3
Ph
S
N
Ph
4
R1
C
O
R2
Ph
S
Ph
CH R2
R1
benzene, AcOH,
MS 3A
NH
5
1
2 or 3
R1
R2
Product Temp
(°C)
Time Yielda
(h)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
(%)
Ph
S
Ph
R1
H
H
H
H
H
H
H
H
H
H
H
Me
5a
5b
5c
5d
5e
5f
40
40
40
40
40
40
40
40
40
40
40
40
40
40
44
Ph
S
N
Ph
R1
Ph
S
Ph
NH
HN
H
Me
Et
Pr
87 (26)b
C
R1
H
C
H
C
O
66 (16)b (57)c
O
(AcOH)
H
70
Ph
S
N
Ph
Ph
S
Ph
(CH2)4Me
Ph
45
N
R1
C
H
R1
C
H
76 (24)b
80
base
H
4-O2NC6H4
4-ClC6H4
4-BrC6H4
4-MeC6H4
Me
5g
5h
5i
(borane–pyridine complex)
64
47
Ph
S
N
Ph
R1
C
N
Ph
S
Ph
5j
47
H
C
H
R1
5k
5l
60
Scheme 2
–(CH2)5–
Ph
34
Ph
5m
5n
0
All reagents and solvents were obtained commercially and were fur-
ther purified by general methods when necessary. Analytical TLC
was performed on Merck plastic sheets, Silica gel 60 F254 plates. IR
anthraquinone
a Isolated yield.
0
b Results in the reaction with NaBH3CN (1.5 equiv) instead of
borane–pyridine complex under the same conditions.
c Without MS 3A.
1
spectra were recorded on a Horiba FT-710 spectrophotometer, H
NMR (400 MHz) and 13C NMR (100 MHz) spectra were obtained
on a Jeol-JNM-A400 NMR spectrometer in CDCl3 with TMS as an
internal standard. Melting point was measured on a Yanaco Mp-j3
melting point apparatus. Elemental analysis was performed on a
Yanaco MT-5 CHN CORDER.
amine the dynamic behavior of this reaction, the forma-
tion of the N-alkylsulfimides and by-products was
followed in an NMR tube. Without borane–pyridine the
reaction of 1 with benzaldehyde gave benzonitrile and
diphenyl sulfide,7 but the rate was slow and further re-
duced when acetic acid was used (Scheme 1).
Synthesis of N-Alkyl-S,S-diphenylsulfimide; General Proce-
dure
N-Unsubstituted S,S-diphenylsulfimide (1.0 g, 4.6 mmol) was dis-
solved in benzene (25 mL). To this soln was added aldehyde or ke-
tone 2 or 3 (1.2 equiv), AcOH (2.5 mL) as a catalyst, and borane–
pyridine complex (4, 1.0 mL, 0.69 mmol). MS 3A were added to the
soln. The soln was stirred at 40 °C for 2 h. The soln was filtered to
remove the molecular sieves and extracted with 3% HCl. The acidic
soln was treated with charcoal, filtered, neutralized with 10%
NaOH, and extracted with CHCl3. The chloroform extracts were
dried (anhyd MgSO4), filtered, and concentrated to give the oily N-
alkyl-S,S-diphenylsulfimide in the yield shown in Table 1.
Ph
C
N
Ph
C
O
2
H
Ph
S
Ph
Ph
S
Ph
CDCl3
NH
1
Scheme 1
The reaction with acetaldehyde, propanal, or benzalde-
hyde using sodium cyanoborohydride instead of borane–
pyridine complex under the same conditions gave also the
corresponding N-alkylsulfimides 5b,c,f, but the yields
were lower than those for the borane–pyridine complex
and, instead, a much higher amount of diphenyl sulfide
was formed. This result is similar to Pelter’s5 lower yield
Picrate of S,S-Diphenyl-N-propylsulfimide (5c); Typical Proce-
dure
N-Propylsulfimide 5c (0.176 g, 0.73 mmol) was added to picric acid
(0.167 g, 0.73 mmol) dissolved in a minimum quantity of acetone at
r.t. to give yellow soln. To this was added small amount of H2O to
give the crystalline picrate salt, which was filtered and recrystal-
lized (EtOH).
Synthesis 2008, No. 10, 1565–1569 © Thieme Stuttgart · New York

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Preparation of N-Alkyl-S,S-diphenylsulfimides
1567
N-Methyl-S,S-diphenylsulfimide (5a)3
13C NMR (100 MHz, CDCl3): d = 14.0, 20.6, 35.0, 48.0, 128.6,
129.2, 130.4, 138.9.
White solid; yield: 44%; mp 79–80 °C (Lit.3 79–80 °C).
IR (KBr): 1080 cm–1 (S=N) (Lit.3 1080 cm–1).
1H NMR (400 MHz, CDCl3): d = 2.64 (s, 3 H), 7.47–7.54 (m, 10 H).
13C NMR (100 MHz, CDCl3): d = 33.9, 129.0, 129.1, 130.7, 137.2.
Picrate of 5d
Yellow solid; mp 81–82 °C.
1H NMR (400 MHz, CDCl3): d = 0.87 (t, J = 7.6 Hz, 3 H), 1.36
(sext, J = 7.6 Hz, 2 H), 1.67 (quint, J = 7.6 Hz, 2 H), 3.29 (td,
J1 = 7.6 Hz, J2 = 5.2 Hz, 2 H), 7.62–7.72 (m, 6 H), 7.84 (dd, J1 = 7.6
Hz, J2 = 1.2 Hz, 4 H), 8.69 (t, J = 5.2 Hz, 1 H), 8.82 (s, 2 H).
Picrate of 5a
Yellow solid; mp 95–96 °C.
1H NMR (400 MHz, CDCl3): d = 2.97 (d, J = 4.8 Hz, 3 H), 7.65–
7.76 (m, 6 H), 7.82 (dd, J1 = 7.6 Hz, J2 = 1.6 Hz, 4 H), 8.78 (q,
J = 4.8 Hz, 1 H), 8.85 (s, 2 H).
13C NMR (100 MHz, CDCl3): d = 32.1, 126.6, 127.4, 128.0, 129.4,
130.8, 134.3, 141.7, 162.1.
13C NMR (100 MHz, CDCl3): d = 13.5, 19.8, 32.1, 47.5, 126.5,
127.3, 129.1, 129.8, 130.8, 134.1, 141.7, 161.8.
Anal. Calcd for C22H22N4O7S: C, 54.31; H, 4.56; N, 11.52. Found:
C, 54.26; H, 4.57; N, 11.62.
N-Hexyl-S,S-diphenylsulfimide (5e)2a
Colorless oil; yield: 45%.
IR (neat): 1080 cm–1 (S=N) (Lit.2a 1095 cm–1).
1H NMR (400 MHz, CDCl3): d = 0.84 (t, J = 7.2 Hz, 3 H), 1.16–
1.34 (m, 6 H), 1.54 (quint, J = 7.2 Hz, 2 H), 2.83 (t, J = 7.2 Hz, 2
H), 7.44–7.49 (m, 6 H), 7.53–7.55 (m, 4 H).
Anal. Calcd for C19H16N4O7S: C, 51.35; H, 3.63; N, 12.61. Found:
C, 51.46; H, 3.64; N, 12.76.
N-Ethyl-S,S-diphenylsulfimide (5b)
Colorless oil; yield: 87%.
IR (neat): 1070 cm–1 (S=N).
1H NMR (400 MHz, CDCl3): d = 1.19 (t, J = 7.2 Hz, 3 H), 2.91 (q,
J = 7.2 Hz, 2 H), 7.47–7.51 (m, 6 H), 7.58–7.60 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 17.7, 42.4, 128.8, 129.2, 130.7,
138.1.
13C NMR (100 MHz, CDCl3): d = 14.0, 22.6, 27.2, 31.8, 32.7, 48.2,
128.7, 129.0, 130.5, 138.8.
Picrate of 5e
Yellow solid; mp 45–46 °C.
1H NMR (400 MHz, CDCl3): d = 0.83 (t, J = 6.4 Hz, 3 H), 1.20–
1.34 (m, 6 H), 1.67 (quint, J = 7.6 Hz, 2 H), 3.29 (td, J1 = 7.6 Hz,
J2 = 5.6 Hz, 2 H), 7.62–7.72 (m, 6 H), 7.84 (dd, J1 = 7.6 Hz, J2 = 1.2
Hz, 4 H), 8.68 (t, J = 5.6 Hz, 1 H), 8.81 (s, 2 H).
13C NMR (100 MHz, CDCl3): d = 13.9, 22.4, 26.2, 30.1, 31.2, 47.9,
126.4, 127.3, 129.1, 129.9, 130.7, 134.1, 141.7, 161.8.
Picrate of 5b
Yellow solid; mp 81–82 °C.
1H NMR (400 MHz, CDCl3): d = 1.34 (t, J = 7.2 Hz, 3 H), 3.36 (qd,
J1 = 7.2 Hz, J2 = 5.2 Hz, 2 H), 7.62–7.73 (m, 6 H), 7.84 (dd, J1 = 7.6
Hz, J2 = 1.6 Hz, 4 H), 8.71 (t, J = 5.2 Hz, 1 H), 8.82 (s, 2 H).
13C NMR (100 MHz, CDCl3): d = 15.5, 42.7, 126.5, 127.3, 129.1,
129.7, 130.8, 134.2, 141.7, 161.9.
Anal. Calcd for C24H26N4O7S: C, 56.02; H, 5.09; N, 10.89. Found:
C, 56.16; H, 5.15; N, 10.91.
Anal. Calcd for C20H18N4O7S: C, 52.40; H, 3.96; N, 12.22. Found:
C, 52.29; H, 3.95; N, 12.24.
N-Benzyl-S,S-diphenylsulfimide (5f)2a,3
Colorless oil; yield: 76%.
S,S-Diphenyl-N-propylsulfimide (5c)
IR (neat): 1060 cm–1 (S=N) (Lit.2a 1060 cm–1).
Colorless oil; yield: 66%.
IR (neat): 1070 cm–1 (S=N).
1H NMR (400 MHz, CDCl3): d = 0.88 (t, J = 7.2 Hz, 3 H), 1.57
(sext, J = 7.2 Hz, 2 H), 2.81 (t, J = 7.2 Hz, 2 H), 7.44–7.49 (m, 6 H),
7.53–7.56 (m, 4 H).
1H NMR (400 MHz, CDCl3): d = 4.10 (s, 2 H), 7.17 (tt, J = 7.6 Hz,
1 H), 7.26 (tt, J1 = 7.6 Hz, J2 = 1.6 Hz, 2 H), 7.34 (tt, J1 = 7.6 Hz,
J2 = 1.6 Hz, 2 H), 7.46–7.49 (m, 6 H), 7.58–7.61 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 52.4, 126.3, 127.8, 128.1, 128.6,
129.2, 130.7, 134.2, 138.4.
13C NMR (100 MHz, CDCl3): d = 12.0, 25.9, 50.3, 128.7, 129.1,
130.5, 138.7.
Picrate of 5f
Yellow solid; mp 97–98 °C.
Picrate of 5c
1H NMR (400 MHz, CDCl3): d = 4.54 (d, J = 4.4 Hz, 2 H), 7.26–
7.33 (m, 5 H), 7.56–7.68 (m, 6 H), 7.79 (dd, J1 = 7.6 Hz, J2 = 1.6
Hz, 4 H), 8.81 (s, 2 H), 9.45 (t, J = 4.4 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 51.4, 126.5, 127.4, 128.6, 128.8,
129.0, 129.1, 129.9, 130.7, 134.1, 135.5, 141.7, 161.8.
Yellow solid; mp 114–115 °C.
1H NMR (400 MHz, CDCl3): d = 0.94 (t, J = 7.2 Hz, 3 H), 1.71
(sext, J = 7.2 Hz, 2 H), 3.36 (td, J1 = 7.2 Hz, J2 = 5.2 Hz, 2 H), 7.62–
7.72 (m, 6 H), 7.85 (dd, J1 = 7.6 Hz, J2 = 1.6 Hz, 4 H), 8.69 (t,
J = 5.2 Hz, 1 H), 8.81 (s, 2 H).
13C NMR (100 MHz, CDCl3): d = 11.1, 23.5, 49.6, 126.4, 127.2,
129.1, 129.9, 130.7, 134.1, 141.7, 161.8.
Anal. Calcd for C25H20N4O7S: C, 57.69; H, 3.87; N, 10.76. Found:
C, 57.58; H, 3.97; N, 10.81.
Anal. Calcd for C21H20N4O7S: C, 53.38; H, 4.27; N, 11.86. Found:
C, 53.29; H, 4.28; N, 11.89.
N-(4-Nitrobenzyl)-S,S-diphenylsulfimide (5g)
Colorless oil; yield: 80%.
IR (neat): 1060 cm–1 (S=N).
1H NMR (400 MHz, CDCl3): d = 4.20 (s, 2 H), 7.46–7.52 (m, 8 H),
7.54–7.58 (m, 4 H), 8.09 (d, J = 8.4 Hz, 2 H).
N-Butyl-S,S-diphenylsulfimide (5d)3
Colorless oil; yield: 70%.
IR (neat): 1080 cm–1 (S=N) (Lit.3 1097 cm–1).
1H NMR (400 MHz, CDCl3): d = 0.85 (t, J = 7.2 Hz, 3 H), 1.34
(sext, J = 7.2 Hz, 2 H), 1.53 (quint, J = 7.2 Hz, 2 H), 2.83 (t, J = 7.2
Hz, 2 H), 7.43–7.49 (m, 6 H), 7.52–7.53 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 51.8, 123.2, 128.1, 128.5, 129.2,
130.7, 130.9, 140.1, 147.1.
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Picrate of 5g
Yellow solid; mp 134–135 °C.
Picrate of 5j
Yellow solid; mp 141–142 °C.
1H NMR (400 MHz, CDCl3): d = 4.69 (d, J = 4.8 Hz, 2 H), 7.53 (d,
J = 8.4 Hz, 2 H), 7.60–7.72 (m, 6 H), 7.83 (dd, J1 = 7.2 Hz, J2 = 1.2
Hz, 4 H), 8.12 (d, J = 8.4 Hz, 2 H), 8.81 (s, 2 H), 9.92 (t, J = 4.8 Hz,
1 H).
1H NMR (400 MHz, CDCl3): d = 2.30 (s, 3 H), 4.48 (d, J = 4.0 Hz,
2 H), 7.07 (d, J = 8.0 Hz, 2 H), 7.18 (d, J = 8.0 Hz, 2 H), 7.56–7.68
(m, 6 H), 7.79 (dd, J1 = 7.6 Hz, J2 = 1.6 Hz, 4 H), 8.79 (s, 2 H), 9.29
(t, J = 4.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 50.7, 124.0, 126.4, 127.9, 129.1,
129.2, 129.4, 130.9, 134.5, 141.6, 143.1, 147.8, 161.6.
13C NMR (100 MHz, CDCl3): d = 21.1, 51.0, 126.4, 127.4, 128.8,
129.1, 129.6, 129.9, 130.7, 132.3, 134.0, 138.6, 141.7, 161.8.
Anal. Calcd for C25H19N5O9S: C, 53.10; H, 3.39; N, 12.38. Found:
C, 52.88; H, 3.46; N, 12.63.
Anal. Calcd for C26H22N4O7S: C, 58.42; H, 4.15; N, 10.48. Found:
C, 58.25; H, 4.23; N, 10.39.
N-(4-Chlorobenzyl)-S,S-diphenylsulfimide (5h)
Colorless oil; yield: 64%.
N-Isopropyl-S,S-diphenylsulfimide (5k)3
Colorless oil; yield: 60%.
IR (neat): 1080 cm–1 (S=N).
IR (neat): 1120 cm–1 (S=N) (Lit.3 1120 cm–1).
1H NMR (400 MHz, CDCl3): d = 4.05 (s, 2 H), 7.21 (dt, J1 = 8.4 Hz,
J2 = 2.0 Hz, 2 H), 7.26 (dt, J1 = 8.4 Hz, J2 = 2.0 Hz, 2 H), 7.46–7.50
(m, 6 H), 7.55–7.58 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 51.9, 127.0, 128.1, 128.5, 129.1,
129.2, 131.0, 138.6, 141.1.
1H NMR (400 MHz, CDCl3): d = 1.09 (d, J = 6.4 Hz, 6 H), 3.42
(sept, J = 6.4 Hz, 1 H), 7.42–7.47 (m, 6 H), 7.58–7.62 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 26.3, 51.8, 127.8, 129.3, 130.6,
138.0.
Picrate of 5k
Yellow solid; mp 93–94 °C.
Picrate of 5h
Yellow solid; mp 135–136 °C.
1H NMR (400 MHz, CDCl3): d = 1.36 (d, J = 6.4 Hz, 6 H), 3.78
(sept, J = 6.4 Hz, 1 H), 7.59–7.68 (m, 6 H), 7.88 (dd, J1 = 7.2 Hz,
J2 = 1.2 Hz, 4 H), 8.78 (s, 2 H).
13C NMR (100 MHz, CDCl3): d = 23.3, 51.2, 126.3, 127.1, 128.8,
130.7, 131.0, 133.9, 141.7, 161.6.
1H NMR (400 MHz, CDCl3): d = 4.50 (d, J = 4.0 Hz, 2 H), 7.22–
7.27 (m, 4 H), 7.57–7.70 (m, 6 H), 7.81 (dd, J1 = 7.2 Hz, J2 = 1.6
Hz, 4 H), 8.80 (s, 2 H) 9.54 (t, J = 4.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 50.7, 126.4, 127.5, 129.08,
129.11, 129.7, 130.0, 130.8, 134.15, 134.23, 134.6, 141.6, 161.7.
Anal. Calcd for C21H20N4O7S: C, 53.38; H, 4.27; N, 11.86. Found:
C, 53.36; H, 4.31; N, 11.81.
Anal. Calcd for C25H19ClN4O7S: C, 54.11; H, 3.45; N, 10.10.
Found: C, 54.10; H, 3.59; N, 10.16.
N-Cyclohexyl-S,S-diphenylsulfimide (5l)
Colorless oil; yield: 34%.
N-(4-Bromobenzyl)-S,S-diphenylsulfimide (5i)
Colorless oil; yield: 47%.
IR (neat): 1060 cm–1 (S=N).
1H NMR (400 MHz, CDCl3): d = 4.06 (s, 2 H), 7.21 (d, J = 8.4 Hz,
2 H), 7.36 (d, J = 8.4 Hz, 2 H), 7.45–7.51 (m, 6 H), 7.57–7.60 (m, 4
IR (neat): 1080 cm–1 (S=N).
1H NMR (400 MHz, CDCl3): d = 1.08–1.37 (m, 5 H), 1.53 (m, 1 H),
1.67–1.74 (m, 4 H), 3.01 (m, 1 H), 7.42–7.47 (m, 6 H), 7.64–7.66
(m, 4 H).
H).
13C NMR (100 MHz, CDCl3): d = 27.7, 30.8, 34.9, 58.6, 127.8,
129.3, 130.6, 132.0.
13C NMR (100 MHz, CDCl3): d = 51.8, 120.0, 128.6, 129.3, 129.5,
130.9, 131.1, 138.3, 141.2.
Picrate of 5l
Yellow solid; mp 79–81 °C.
Picrate of 5i
Yellow solid; mp 139–140 °C.
1H NMR (400 MHz, CDCl3): d = 1.16–1.37 (m, 3 H), 1.47–1.63 (m,
3 H), 1.78–1.82 (m, 2 H), 3.02 (dd, J1 = 11.2 Hz, J2 = 2.4 Hz, 2 H),
3.38 (m, 1 H), 7.59–7.68 (m, 6 H), 7.86 (dd, J1 = 7.6 Hz, J2 = 1.6
Hz, 4 H), 8.67 (d, J = 5.2 Hz, 1 H), 8.95 (s, 2 H).
13C NMR (100 MHz, CDCl3): d = 24.9, 33.7, 58.2, 64.8, 126.3,
127.2, 128.8, 130.7, 131.2, 133.9, 141.7, 161.6.
1H NMR (400 MHz, CDCl3): d = 4.50 (d, J = 4.0 Hz, 2 H), 7.19 (d,
J = 8.4 Hz, 2 H), 7.39 (dd, J1 = 8.4 Hz, J2 = 1.6 Hz, 2 H), 7.58–7.70
(m, 6 H), 7.80 (dd, J1 = 7.2 Hz, J2 = 1.6 Hz, 4 H), 8.81 (s, 2 H) 9.56
(t, J = 4.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 50.8, 122.7, 126.4, 127.6, 129.1,
129.7, 130.3, 130.8, 132.0, 134.3, 134.7, 141.7, 161.7.
Anal. Calcd for C24H24N4O7S: C, 56.24; H, 4.72; N, 10.93. Found:
C, 56.03; H, 4.66; N, 10.96.
Anal. Calcd for C25H19BrN4O7S: C, 50.09; H, 3.19; N, 9.35. Found:
C, 50.01; H, 3.19; N, 9.36.
References
N-(4-Methylbenzyl)-S,S-diphenylsulfimide (5j)
Colorless oil; yield: 47%.
(1) (a) Furukawa, N.; Omata, T.; Yoshimura, T.; Aida, T.; Oae,
S. Tetrahedron Lett. 1972, 13, 1619. (b) Yoshimura, T.;
Omata, T.; Furukawa, N.; Oae, S. J. Org. Chem. 1976, 41,
1728. (c) Gilchrist, T. L.; Moody, C. J. Chem. Rev. 1977, 77,
409.
(2) (a) Tamura, Y.; Matsushima, H.; Ikeda, M.; Sumoto, K.
Tetrahedron 1976, 32, 431. (b) Tamura, Y.; Sumoto, K.;
Matsushima, H.; Taniguchi, H.; Ikeda, M. J. Org. Chem.
1973, 38, 4324. (c) Tamura, Y.; Miyamoto, T.; Eiho, J.;
Taniguchi, H.; Nishimura, T.; Kita, Y. J. Chem. Soc., Perkin
IR (neat): 1060 cm–1 (S=N).
1H NMR (400 MHz, CDCl3): d = 2.29 (s, 3 H), 4.04 (s, 2 H), 7.07
(d, J = 8.0 Hz, 2 H), 7.22 (d, J = 8.0 Hz, 2 H), 7.44–7.48 (m, 6 H),
7.57–7.59 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 20.1, 52.1, 126.9, 127.6, 128.6,
128.8, 129.1, 130.6, 135.6, 138.8.
Synthesis 2008, No. 10, 1565–1569 © Thieme Stuttgart · New York

PAPER
Trans. 1 1974, 105. (d) Gilchrist, T. L.; Moody, C. J.; Rees,
C. W. J. Chem. Soc., Perkin Trans. 1 1975, 1964.
(3) Franz, J. A.; Martin, J. C. J. Am. Chem. Soc. 1975, 97, 583.
(4) Furukawa, N.; Oae, S.; Yoshimura, T. Synthesis 1976, 30.
(5) Pelter, A.; Rosser, R. M. J. Chem. Soc., Perkin Trans. 1
1984, 717.
Preparation of N-Alkyl-S,S-diphenylsulfimides
1569
(6) Furukawa, N.; Fukumura, M.; Akasaka, T.; Yoshimura, T.;
Oae, S. Tetrahedron Lett. 1980, 21, 761.
(7) Chen, J.; Wayman, K. A.; Belshe, M. A.; DiMare, M. J. Org.
Chem. 1994, 59, 523.
Synthesis 2008, No. 10, 1565–1569 © Thieme Stuttgart · New York