N-HYDROXYMETHYLATION OF 3-ARYL-2-CYANOPROP-2-ENETHIOAMIDES
1415
powder. IR spectrum, ν, cm–1: 3390, 3325 (O–H, N–H),
2222 (C≡N). 1Н NMR spectrum (200 MHz, DMSO-d6),
N 10.66. С12Н12N2О3S. Calculated, %: С 54.53; H 4.58;
N 10.60. Mcalc 264.30.
3
δ, ppm: 5.00–5.06 m (2H, СH2), 6.32 t (1H, OH, J =
Interaction of 3-(2-chlorophenyl)-2-cycnoprop-
2-enethioamide 2a with formaldehyde and
1Н-benzotriazole. Excess (1.0 mL) of 37% aqueous
solution of formaldehyde was added at stirring to
a suspension of 500 mg (2.25 mmol) of compound
2a and 270 mg (2.27 mmol) of 1H-benzotriazole in
5 mL of 96% ethanol. The mixture was refluxed during
5 min. Upon ~ 15 min cooling, the precipitate was
formed from the light red solution; it was filtered off,
washed with ethanol, and dried. 379 mg of orange
powder was obtained, which was identified (1Н NMR
data) as a mixture of N-(hydroxymethyl)thioamide 6a
(~37 mol %), 1Н-benzotriazol-1-ylmethanol 15
(~40 mol %), starting thioamide 2a (~14 mol %), and
the product of aminomethylation 14 (~9 mol %). The
following signals of the components were identified in
3
7.1 Hz), 7.64 d (2H, H3,5Ar, J = 8.6 Hz), 7.90 s (1H,
3
CH=), 7.92 d (2H, H2,6Ar, J = 8.6 Hz), 10.90–10.92 m
(1H, NH). 1Н NMR spectrum (400 MHz, CDCl3), δ, ppm:
3
4.29 t (1H, OH, J = 8.4 Hz), 5.22–5.26 m (2H, СH2),
7.49 d (2H, H3,5Ar, 3J = 8.6 Hz), 7.93 d (2H, H2,6Ar, 3J =
8.6 Hz), 8.59–8.62 m (1H, NH), 8.72 s (1H, CH=). Mass
spectrum, m/z (Irel, %): 235.3 [M – H2O + H]+, 253.1
[M + H]+, 331.1 [M + DMSO + H]+, 487.3 [2M – H2O +
H]+, 522.3 [2M + NH4]+. Found, %: С 52.26; H 3.63; N
11.05. С11Н9ClN2ОS. Calculated, %: С 52.28; H 3.59;
N 11.08. Mcalc 252.72.
(E)-N-(Hydroxymethyl)-3-(furan-2-yl)-2-cyano-
prop-2-enethioamide (6c). Yield 54%, orange-brown
powder. IR spectrum, ν, cm–1: 3420, 3210 (O–H, N–H),
2215 (C≡N). 1Н NMR spectrum (200 MHz, DMSO-d6),
1
the Н NMR spectrum (400 MHz, DMSO-d6), δ, ppm:
3
δ, ppm: 5.00–5.04 m (2H, СH2), 6.20 t (1H, OH, J =
compound 2a, 8.27 s (1Н, CH=), 9.73 br. s (CSNH2),
10.25 br. s (CSNH2); compound 6a, 5.03–5.07 m (2H,
СH2), 6.32 m (1H, OH), 8.10 s (1H,CH=), 10.98–10.99 m
(1H, NH); 1Н-benzotriazol-1-ylmethanol 15, 6.02 d
(2H, CH2OH, 3J = 7.0 Hz), 7.19 t (1H, OH, 3J = 7.0 Hz),
7.2 Hz), 6.83–6.84 m (1H, H4furyl), 7.41 d (1H, H3furyl, 3J =
3.7 Hz), 7.90 s (1H, CH=), 8.13–8.14 m (1H, H5furyl),
10.63–10.64 m (1H, NH). Mass spectrum, m/z (Irel, %):
209.1 [M + H]+, 269.3 [M –H2O + DMSO + H]+, 287.1
[M + DMSO + H]+, 399.1 [2M – H2O + H]+, 434.4 [2M +
NH4]+, 607.5 [3M – H2O + H]+. Found, %: С 51.87; H
3.93; N 13.46. С9Н8N2О2S. Calculated, %: С 51.91; H
3.87; N 13.45. Mcalc 208.24.
3
8.06 d (1H, H4Ar, J = 8.6 Hz); compound 14, 6.60 d
3
(2H, CH2NH, J = 5.1 Hz), 8.17 s (1H, CH=), 11.66
3
(1H, CH2NH, J = 5.1 Hz). Mass spectrum, m/z: 120.4
[M (BtH) + H]+, 150.1 [M (15) + H]+, 223.3 [M (2a) +
H]+, 331.1 [M (6a) + DMSO + H]+, 354.1 [M (14) + H]+,
487.0 [2M (6a) – H2O + H]+, 522.2 [2M (6a) + NH4]+,
709.2 [2M (14) + H]+, 1062.2 [3M (14) + H]+.
(E)-N-(Hydroxymethyl)-3-[(4-dimethylamino)-
phenyl]-2-cyanoprop-2-enethioamide (6d). Yield 60%,
red crystals. 1Н NMR spectrum (400 MHz, DMSO-d6),
3
FUNDING
δ, ppm: 5.02–5.05 m (2H, СH2), 6.07 t (1H, OH, J =
3
7.1 Hz), 6.82 d (2H, H3,5Ar, J = 8.8 Hz), 7.87 d (2H,
This study was financially supported by the Ministry
of Education and Science of Russian Federation (project
no. 0795-2020-0031).
3
H2,6Ar, J = 8.8 Hz), 7.96 s (1H, CH=), 10.31–10.32 m
(1H, NH). Mass spectrum, m/z (Irel, %): 262.3 [M + H]+,
379.5 [M + DMSO + K]+, 397.3 [M + H2O + DMSO +
K]+, 523.3 [2M + H]+. Found, %: С 59.70; H 5.83; N
16.11. С13Н15N3ОS. Calculated, %: С 59.74; H 5.79; N
16.08. Mcalc 261.34.
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
REFERENCES
(E)-3-(4-Hydroxymethyl-3-methoxyphenyl)-N-
(hydroxymethyl)-2-cyanoprop-2-enethioamide (6e).
Yield 51%, yellow powder. 1Н NMR spectrum (400 MHz,
DMSO-d6), δ, ppm: 5.06–5.07 m (2H, СH2), 5.87 t (1H,
OH, 3J = 7.0 Hz), 6.89 d (1H, H5Ar, 3J = 8.4 Hz), 7.40 d
1. Litvinov, V.P., Russ. Chem. Rev., 1999, vol. 68, no. 9,
p. 737.
2. Dyachenko,V.D., Dyachenko, I.V., and Nenajdenko,V.G.,
Russ. Chem. Rev., 2018, vol. 87, no. 1, p. 1.
3. Magerramov, A.M., Shikhaliev, N.G., Dyachenko, V.D.,
Dyachenko, I.V., and Nenajdenko, V.G., α-Tsianotio-
atsetamid (α-Cyanothioacetamide), Moscow: Tekhno-
sfera, 2018.
3
(1H, H6Ar, J = 8.4 Hz), 7.71 s (1H, H3Ar), 8.03 s (1H,
CH=), 10.02 br. s (1Н,ArOH), 10.22–10.23 m (1H, NH).
Mass spectrum, m/z (Irel, %): 265.3 [M + H]+, 382.3 [M +
NH4]+, 546.3 [2M + NH4]+. Found, %: С 54.61; H 4.55;
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 8 2020