AMINOMETHYLATION OF THIOUREA WITH FORMALDEHYDE
REFERENCES
885
10.00 br.s (1H, NHCH2N), 10.67 br.s (1H, NHBoc).
13C NMR spectrum (DMSO-d6), δC, ppm: 24.09 (Cγ),
25.84 (2C, Cβ), 28.18 (3C, CH3), 51.50 (2C, Cα), 67.51
(NHCH2N), 82.67 (C–O), 153.22 (C=O), 180.77
(C=S). Found: m/z 274.1578 [M + H]+. C12H23N3O2S.
Calculated: M + H 274.1584.
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tert-Butyl [(morpholin-4-ylmethyl)carbamo-
thioyl]carbamate [5b, (N-tert-butoxycarbonyl)-Nʹ-
(morpholin-4-ylmethyl)thiourea] was synthesized in
a similar way using 0.523 g (6 mmol) of morpholine.
The product separated from the reaction mixture after
2 h as abundant white solid. Yield 0.97 g (59%),
1
mp 143–145°C. H NMR spectrum (DMSO-d6), δ,
ppm: 1.46 s (9H, t-Bu), 2.53 m (4H, β-H, overlapped
by the residual proton signal of the solvent), 3.57 m
(4H, α-H), 4.51 s (2H, NHCH2N), 10.04 s (1H,
NHCH2N), 10.71 s (1H, NHBoc). 13C NMR spectrum
(DMSO-d6), δC, ppm: 28.18 (3C, CH3), 50.69 (2C, Cβ),
66.48 (2C, Cα), 66.56 (NHCH2N), 82.74 (C–O),
153.17 (C=O), 181.17 (C=S). Found: m/z 276.1380
[M + H]+. C11H21N3O3S. Calculated: M + H 276.1376.
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no. 575114, 1933; Chem. Abstr., 1933, vol. 27, p. 3483.
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The X-ray diffraction data for compounds 1a and
1b were obtained at the Center for X-Ray Diffraction
Studies of the St. Petersburg State University on
a Bruker APEX-II CCD single crystal diffractometer
(Mo Kα radiation) at 150 and 293 K, respectively. The
principal crystallographic parameters and conditions of
X-ray diffraction experiments are given in Table 2.
Primary data processing was done using CrysAlisPro
(version 1.171.36.20, release 27-06-2012, Agilent
Technologies). A correction for absorption was applied
by the Multiscan method (SADABS, Bruker, 2007).
The structures were solved by the direct method and
were refined by the full-matrix least-squares method
in anisotropic approximation for non-hydrogen atoms
(SIR2014) [15]. The positions of hydrogen atoms were
calculated geometrically and were refined in the rigid
body approximation. The molecular structures were
plotted using Mercury 3.7 [16]. The X-ray diffraction
data for compounds 1a and 1b were deposited to the
Cambridge Crystallographic Data Centre (CCDC entry
nos. 1517961 and 1517960, respectively). The inter-
atomic distances and bond and dihedral angles are
available upon request.
12. Truter, M.R., Acta Crystallogr., 1967, vol. 22, p. 556.
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15. Burla, M.C., Caliandro, R., Carrozzini, B., Casca-
rano, G.L., Cuocci, C., Giacovazzo, C., Mallamo, M.,
Mazzone, A., and Polidori, G., J. Appl. Crystallogr.,
2015, vol. 48, no. 1, p. 306.
16. Macrae, C.F., Bruno, I.J., Chisholm, J.A., Edging-
ton, P.A., McCabe, P., Pidcock, E., Rodrigues-
Monge, L., Taylor, R., van de Streek, J., and Wood, P.A.,
J. Appl. Crystallogr., 2008, vol. 41, no. 2, p. 466.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 6 2018