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