1857
REACTION OF CARBODIIMIDES WITH TRIFLUOROMETHANESULFONIC ACID
1
1030, 636, 516. Н NMR spectrum, δ, ppm: 7.38 d
(1H, NH, J 7.2 Hz), 3.80–3.70 m (0.5H, CHNTf),
3.70–3.50 m (1.5H, СHNН), 1.87–1.07 m (20H, СH2).
13С NMR spectrum, δC, ppm: 154.16 and 153.99
(С=O), 121.64 q (CF3, J 319.8 Hz), 58.75 (TfNC),
51.71 (CNH), 33.61, 32.43, 32.10, 26.31, 26.18, 26.02,
25.84, 25.65, 25.41. 19F NMR spectrum: δF –78.78 ppm.
Found, %: С 45.91; Н 6.50; F 15.92; N 7.77; S 8.84.
C14H23F3N2O3S. Calculated, %: С 47.18; Н 6.50; F
15.99; N 7.86; S 9.00.
NH). 13С NMR spectrum (DMSO-d6), δC, ppm:
1
155.74, 154.70, 120.92 q (CF3, JCF 321.6 Hz). 19F
NMR spectrum: δF –77.85 ppm. Found, %: С 14.63; Н
2.10; F 25.63; N 21.72; S 12.07. Calculated for the
IX:X = 4:1 mixture of salts, %: С 14.81; Н 2.03; F
25.40; N 22.06; S 14.29.
Reaction of cyanamide (II) with TfOH was
carried out as above described for the reaction of Id
with one equivalent of TfOH (b). Conversion of cyan-
amide 100%. IR specrum (KBr), ν, cm–1: 3422, 3364,
3227, 1734, 1696, 1590, 1280, 1251, 1173, 1028, 640,
N-Trifluoromethylsulfonyl-N,N'-diphenyl urea
(IIIc). To the suspension of 0.39 g (2.0 mmol) of
carbodiimide Ic in 3 ml of CH2Cl2 0.30 g (2.0 mmol,
18 ml) of TfOH was added at vigorous stirring and
cooling with cold water, the reaction mixture was
stirred for 3 h at room temperature and left overnight.
Yield of product IIIc after evaporation of solvent 0.69 g
(100%), yellow crystals, mp 120°С. IR spectrum
(KBr), ν, cm–1: 3432, 1674, 1637, 1612, 1587, 1492,
1285, 1242, 1227, 1172, 1030, 756, 691, 636. 1Н NMR
spectrum, δ, ppm: 10.52 br.s (1H, NH), 8.15–7.00 m
(10H, Ph). 13С NMR spectrum, δC, ppm: 149.91
(С=O), 140.57, 135.42, 131.96, 131.80, 130.06, 128.77,
127.19, 125.43. 19F NMR spectrum: δF –79.32 ppm.
Found, %: С 48.39; Н 3.11; N 7.47; S 8.84.
C14H11F3N2O3S. Calculated, %: С 48.84; Н 3.22; F
16.55; N 8.14; S 9.31.
1
518. Н NMR spectrum (DMSO-d6), δ, ppm: 7.97 br.s
(2Н, NH), 7.1 br.s (1Н, NH). 13С NMR spectrum
(DMSO-d6), δC, ppm: 162.98, 161.87, 155.77, 154.68,
1
19
120.94 q (CF3, JCF 321.9 Hz). F NMR spectrum: δF
–77.84 ppm.
ACKNOWLEDGMENTS
This work was performed with the financial support
from the Russian Foundation for Basic Research (grant
no. 13-03-00055).
REFERENCES
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Reaction of bis(trimethylsilyl)carbodiimide (Id)
with TfOH. а. To 0.37 g (2.0 mmol) of carbodiimide
Id in 5 ml of CH2Cl2 with stirring and cooling with
cold water 0.30 g (2.0 mmol, 0.18 ml) of TfOH was
added, the mixture was stirred for 2 h and left
overnight. After removal of the solvent 0.4 g of white
viscous residue was obtained, which solidified upon
storage. IR spectrum (film), ν, cm–1: 2962, 2230, 1658,
1555, 1388, 1259, 1224, 1172, 1041, 846, 768, 640,
519. 13С NMR spectrum (DMSO-d6), δC: 156.89 ppm.
19F and 29Si NMR spectra see in the text.
4. Ulrich, H., Chemistry and Technology of Carbodi-
imides, Chichester: Wiley, 2007.
5. Benfodda, Z., Delon, L., Guillen, F., and Blancou, H.,
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b. To 0.37 g (2.0 mmol) of carbodiimide Id in 5 ml
of CH2Cl2 0.60 g (4.0 mmol, 0.36 ml) of TfOH was
added at stirring and cooling with cold water, the
reaction mixture was stirred for 2.5 h and left
overbight. The formed fine-dispersed precipitate was
filtered off, dried, washed with hot ethyl acetate, and
dried to obtain 0.36 g of white fine-dispersed powder,
mp 202–204°С. IR spectrum (KBr), ν, cm–1: 3429,
3385, 3348, 3242, 1735, 1696, 1592, 1278, 1244,
1228, 1171, 1031, 640, 518. 1Н NMR spectrum
(DMSO-d6), δ, ppm: 8.0 br.s (2Н, NH), 7.1 br.s (1Н,
9. Roesky, H.W. and Giere, H.H., Z. Naturforsch. B, 1970,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013