Synthesis, structure, and alkylation of N-methylmorpholinium 5-2-cyanoethyl-1-(4-hydroxy-3-methoxyphenyl)-2-thiocarbamoyl]-2,2-dimethyl-6 -oxo-1,3-dioxa-4-cyclohexen-4-olate

Article abstract of DOI:10.1023/A:1021745916815

N-Methyhlmorpholinium 5-[-2cyanoethyl-1-(4-hydroxy-3-methoxyphenyl)-2-thiocarbamoyl]-2,2-dimethyl- 6-oxo-1,3-dioxa-4-cyclohexen-4-olate was obtained from the reaction of 4-hydroxy-3-methoxybenzaldehyde with cyanothioacetamide and Meldrum's acid in the presence of N-methylmorpholine. The molecular and crystal structure of the title compound have been established and its alkylation has been studied.

Full text of DOI:10.1023/A:1021745916815

Chemistry of Heterocyclic Compounds, Vol. 38, No. 10, 2002
SYNTHESIS, STRUCTURE, AND ALKYLATION
OF N-METHYLMORPHOLINIUM 5-[2-CYANOETHYL-
1-(4-HYDROXY-3-METHOXYPHENYL)-
2-THIOCARBAMOYL]-2,2-DIMETHYL-
6-OXO-1,3-DIOXA-4-CYCLOHEXEN-4-OLATE
S. G. Krivokolysko1, A. N. Chernega2 and V. P. Litvinov3
N-Methylmorpholinium 5-[2-cyanoethyl-1-(4-hydroxy-3-methoxyphenyl)-2-thiocarbamoyl]-2,2-dimethyl-
6-oxo-1,3-dioxa-4-cyclohexen-4-olate was obtained from the reaction of 4-hydroxy-3-
methoxybenzaldehyde with cyanothioacetamide and Meldrum's acid in the presence of
N-methylmorpholine. The molecular and crystal structure of the title compound have been established
and its alkylation has been studied.
Keywords:
4-hydroxy-3-methoxybenzaldehyde,
Meldrum's
acid,
tetrahydropyridines,
cyanothioacetamide, cyclohexan-4-olate, X-ray crystallographic analysis.
Recently the reaction of structural analogs – dimedone and Meldrum's acid – with
arylmethylenecyanothioacetamides, or aromatic aldehydes and cyanothioacetamide in the presence of secondary
and tertiary amines, which produce the corresponding adducts of Michael addition, has been described. The
conversion of the latter into substituted tetrahydropyridines and hexahydroquinolines [1-7] has been studied,
but a number of questions remain open with respect to their structure and the direction of cyclization and
alkylation [8]. Recently the structure of adducts obtained from dimedone has been established. The preparation
of the previously unknown sulfur-containing octahydroquinolines [9] has necessitated a study of their structure
and the corresponding Michael adducts formed with the participation of Meldrum's acid.
We have synthesized N-methylmorpholinium 5-[2-cyanoethyl-1-(4-hydroxy-3-methoxyphenyl)-2-
thiocarbamoyl]-2,2-dimethyl-6-oxo-1,3-dioxa-4-cyclohexen-4-olate (4) from the reaction of 4-hydroxy-3-
methoxybenzaldehyde (1) with cyanothioacetamide (2) and Meldrum's acid (3) in ethanol (~20°C) in the
presence of N-methylmorpholine. Its structure has been determined unambiguously by X-ray crystallography.
The six-membered heterocycle O(3)O(4)C(12-15) is distinctly non-planar: the atoms O(3), O(4), C(12), C(13) and
C(15) are coplanar within limits of 0.017 Å, but atom C(14) is 0.55 Å out of this plane. The modified Kremer-
Pople parameters [10] calculated for this ring (S = 0.65, θ = 41.5°, Ψ = 4.1) correspond to a conformation of a
somewhat compressed "semi-chair". The interatomic distances O(5)=C(13) 1.241(5), C(12)–C(13) 1.385(6),
C(12)=C(15) 1.398(6), O(6)–C(15) 1.227(5) Å indicate the considerable delocalization of electron density in this
system of bonds.
__________________________________________________________________________________________
1
2
Eastern Ukraine State University, Lugansk 91034, Ukraine. Institute of Organic Chemistry, Ukraine
National Academy of Sciences, Kiev, 02094, Ukraine; e-mail: iochkiev@ukrpack.net. 3 N. D. Zelinsky Institute
of Organic Chemistry, Russian Academy of Sciences, Moscow 117913, Russia; e-mail: vpl@cacr.ioc.ac.ru.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1438-1444, October, 2002. Original article
submitted February 8, 2000.
0009-3122/02/3810-1269$27.00©2002 Plenum Publishing Corporation
1269

O
OMe
CN
HO
O
+
+
CSNH2
Me
Me
O
O
CHO
1
2
3
OH
OH
OH
Me
N
OMe
CN
OMe
CN
OMe
_
Hal
R
O
5
O
CN
S
O
Me
CSNH
2H
O
N
H
S
H
Me
N
O
O
+
O
N
H
6
R
N
+
4
O
O
7
5 a,c-g Hal = Cl, b Hal = Br; 5, 6 a R = Ph, b R = CH2=CH, c R = COOEt, d R = CONH2,
e R = 4-BrC6H4CONH, f R = 2,5-Me2C6H3CONH, g R = 2-MeC6H4CONH
The geometric parameters of the morpholinium cation are normal. In the crystal the cations and the anions form
pairs linked by very strong [11, 12] hydrogen bond O(5)···H(4)–N(3) [O(5)···N(3) 2.730(5), O(5)···H(4) 1.74(5), N(3)–H(4)
1.00(5) Å, angle O(5)H(4)N(3) 170(3)° (N(3) is the nitrogen atom of the N-methylmorpholinium cation (see Fig. 2)].
In their turn weaker H-bonds O(6)···H(2)–N(1) [O(6)···N(1) 2.888(5), O(6)···H(2) 1.95(5), N(3)-H(4) 1.00(5) Å, angle
O(6)H(2)N(1) 173(3)°] couple the anions into centrosymmetric dimers. In addition the geometric parameters
[O(1)···O(3) 3.051(6), O(1)–H(1) 0.82(5), O(3)···H(1) 2.305 Å, angle O(1)H(1)O(3) 152.2(3)°] indicate the possibility of
formation in the crystal of compound 4 of an infinite network on account of relatively weak [11, 12]
intermolecular hydrogen bonds, O(1)–H(1)···O(3).
Fig. 1 General view of molecule 4 with numbering of atoms.
1270

Fig. 2. Crystal packing (projection on bc) of compound 4. The broken lines represent hydrogen bonds.
The 1H NMR spectrum of compound 4 contains signals of the diastereomers A and B (3JH
= 12.2 Hz)
(1)-H(2)
and the enethiol C. It is interesting that compound 4 consists of isomer B only in the crystalline state (the
corresponding torsion angles have the following values: C(5)C(1)C(2)C(3) -54.59°, C(5)C(1)C(2)C(4) -175.74°,
H(11)C(1)C(2)C(3) 63.23°, H(11)C(1)C(2)C(4) -57.91°, H(11)C(1)C(2)H(21) -174.75°, H(21)C(2)C(1)C(5) 67.44°, H(21)C(2)C(1)C(12)
-62.10°).
TABLE 1. Basic Bond Lengths (d) and Bond Angles (ω) in the Molecule of
Compound 4
Bond
d, Å
Angle
ω, deg
S(1)–C(3)
O(1)–C(8)
O(2)–C(9)
1.660(5)
1.380(6)
1.374(6)
1.368(7)
1.383(5)
1.436(5)
1.417(5)
1.379(5)
1.241(5)
1.227(5)
1.307(6)
1.127(7)
1.385(6)
1.398(6)
C(13)–O(3)–C(14)
C(14)–O(4)–C(15)
S(1)–C(3)–N(1)
116.9(4)
117.0(4)
124.7(4)
121.1(4)
114.2(4)
178.2(3)
117.9(4)
121.7(4)
120.4(4)
114.0(4)
118.4(4)
127.5(4)
114.6(4)
117.9(4)
127.5(5)
O(2)–C(11)
O(3)–C(13)
O(3)–C(14)
O(4)–C(14)
O(4)–C(15)
O(5)–C(13)
O(6)–C(15)
N(1)–C(3)
N(2)–C(4)
C(12)–C(13)
C(12)–C(15)
S(1)–C(3)–C(2)
N(1)–C(3)–C(2)
N(2)–C(4)–C(2)
C(1)–C(12)–C(13)
C(1)–C(12)–C(15)
C(13)–C(12)–C(15)
O(3)–C(13)–O(5)
O(3)–C(13)–C(12)
O(5)–C(13)–C(12)
O(4)–C(15)–O(6)
O(4)–C(15)–C(12)
O(6)–C(15)–C(12)
1271

It is known that reactions of compounds like 4 with α-bromoketones in DMF is accompanied by loss of
Meldrum's acid and leads to the formation of substituted 2-thiazolylcyanoethylenes [4, 5, 8]. The results of
interaction of Michael adducts with other alkyl halides have not been described. Tetrahydropyridones 6 were
obtained by heating salt 4 with alkyl halides 5 for a short time. It is probable that an intermediate 7 is formed in
the course of the above reaction, as has been noted earlier for isostructural analogs of compound 4 [6, 7].
_
H
Me
Me
O
O
O
O
Ar
O
O
Ar
CN
SH
O
O
Me
Me
NH2
CN
Me
H2NSC
Me
H
H
+
N
H
+
N
C
O
A
O
_
H
Me
Me
O
O
O
O
Ar
CSNH2
NC
Me
H
H
+
N
B
O
TABLE 2. Atomic Coordinates and Equivalent Isotropic Thermal
Parameters, Ueq, for the Structure 4
Atom
1
x
2
y
3
z
4
Ueq, Å2
5
S(1)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
N(1)
N(2)
N(3)
C(1)
C(2)
C(3)
C(4)
C(5)
0.14971(17)
-0.4012(5)
-0.3691(4)
0.3328(3)
0.2273(4)
0.3097(3)
0.0908(4)
0.1807(6)
-0.0247(5)
0.3834(6)
0.3652(5)
0.1191(5)
0.1344(6)
0.0791(6)
0.2752(9)
-0.0217(5)
-0.00815(12)
0.2392(4)
0.4045(4)
0.3989(3)
0.5640(3)
0.1942(3)
0.5279(3)
0.2621(5)
0.1910(4)
0.2368(5)
0.0868(4)
0.2478(4)
0.2548(4)
0.1477(4)
0.2431(5)
0.2489(4)
0.63578(14)
0.9722(4)
0.7394(3)
0.8741(3)
0.7034(3)
0.9277(3)
0.5911(3)
1.2749(5)
0.5095(4)
0.5269(5)
1.1789(4)
0.7433(4)
0.6004(4)
0.5776(4)
0.5584(5)
0.7991(4)
0.0611
0.0503
0.0863
0.0412
0.0450
0.0447
0.0498
0.0974
0.0451
0.0676
0.0491
0.0279
0.0320
0.0362
0.0423
0.0286
1272

TABLE 2 (continued)
1
2
3
4
5
C(6)
C(7)
C(8)
C(9)
-0.0434(6)
-0.1689(6)
-0.2753(7)
-0.2548(7)
-0.1300(6)
-0.3875(7)
0.1838(5)
0.2727(5)
0.2667(5)
0.1610(5)
0.1483(6)
0.3681(7)
0.2291(9)
0.1381(7)
0.3066(9)
0.4054(6)
0.4630(7)
-0.456(6)
-0.054(5)
-0.060(6)
0.349(5)
0.1677(4)
0.1647(4)
0.2442(5)
0.3272(5)
0.3311(4)
0.4178(7)
0.3489(4)
0.3074(4)
0.5324(4)
0.4791(4)
0.5550(5)
0.6135(5)
0.0597(6)
0.1857(8)
0.2887(6)
0.1670(6)
-0.0355(6)
0.287(5)
0.9230(4)
0.9813(5)
0.9158(5)
0.7923(5)
0.7359(4)
0.6165(6)
0.7619(4)
0.8564(4)
0.8287(4)
0.6823(4)
0.9161(5)
0.8186(6)
1.2312(6)
1.2156(7)
1.2231(6)
1.2409(5)
1.1894(6)
0.922(5)
0.0348
0.0386
0.0343
0.0431
0.0391
0.0945
0.0280
0.0325
0.0402
0.0370
0.0608
0.0695
0.0742
0.0929
0.0800
0.0624
0,0956
0.07(2)
0.07(2)
0.07(2)
0.06(2)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
H(1)
H(2)
H(3)
H(4)
0.282(5)
0.476(5)
0.136(5)
0.134(4)
0.485(5)
1.087(5)
EXPERIMENTAL
1H NMR spectra of DMSO-d6 solutions with TMS as internal standard were recorded with a Bruker
AM-300 (300 MHz) apparatus, IR spectra of nujol mulls were recorded on an IKS-29 spectrophotometer.
Elemental analysis was carried out on Perkin-Elmer C,H,N Analyser. The course of reactions and the purity of
products were monitored by TLC on Silufol UV-254 strips using 3:5 acetone–hexane as eluent. Melting points
were measured on a Kofler block.
X-ray diffraction analysis of a monocrystal of compound 4 with linear dimensions 0.19×0.34×0.47 mm
was carried out at 20°C on an automatic four-circle Enraf-Nonius CAD-4 diffractometer (MoKα radiation,
relative rate of scanning ω/2θ = 1.2, θmax = 23°, segment of sphere 0
h
12, -13
k
13, -13
l
13).
≤
≤
≤
≤
≤
≤
2572 reflexions were collected, of which 2359 were symmetrically independent (Rint = 0.017). Crystals of
compound 4 are triclinic, a = 10.348(1), b = 11.134(3), c = 11.206(1) Å; α = 69.49(1), β = 82.51(1),
γ = 77.56(2)°; V = 1182.8 Å3; M = 479.55; Z = 2; dcalc = 1.34 g/cm3; µ = 1.74 cm-1; space group P(1) (No. 2). The
structure was solved by direct method and refined by least squares in the full-matrix anisotropic approximation
using the CRYSTALS suite of programmes [13]. 1523 reflexions with I > 3(I) were used in the refinement. All
H atoms were found from difference synthesis of the electron density and were included in the calculation with
fixed positional and thermal parameters. Only atoms H(1-4), bonded to atoms O(1), N(1), and N(3) were refined
isotropically. Calculation of absorption in the crystal was carried out by the azimuthal scanning method [14]. A
unit weighting scheme was used in the refinement. The final residual factors were R = 0.038 and Rw = 0.038.
Residual electron densities from the final Fourier difference synthesis were 0.19 and -0.17 e/Å3. Atomic
coordinates are cited in Table 2.
N-Methylmorpholinium 5-[2-Cyanoethyl-1-(4-hydroxy-3-methoxyphenyl)-2-thiocarbamoyl]-2,2-
dimethyl-6-oxo-1,3-dioxa-4-cyclohexen-4-olate (4). Mixture of aldehyde 1 (3.04 g, 20 mmol),
cyanothioacetamide (2) (2 g, 20 mmol), Meldrum's acid (3) (2.88 g, 20 mmol), and N-methylmorpholine
1273

(2.53 ml, 25 mmol) in ethanol (30 ml) (~20°C) was stirred until the starting materials dissolved and was then
kept for 12 h. The precipitate formed was filtered off, and washed with ethanol and hexane. Yield of salt 4 8.54
g (89%); mp 185-187°C. IR spectrum, ν, cm-1: 3240, 3450 (OH, NH2, NH+); 2243 (C≡N); 1680 (C=O). 1H NMR
spectrum, δ, ppm, J (Hz): signals of the major diastereomer: 1.46 and 1.69 (6H, both br. s, Me2); 2.68 (3H, s,
3
NMe); 2.84 (4H, m, CH2NCH2); 3.68 (4H, m CH2OCH2); 3.74 (3H, s, OMe); 4.51 (1H, d, J = 12.2, CHAr);
3
3
5.39 (1H, d, J = 12.2, CHCN); 6.46 d and 6.77 d (both J = 8.2); 7.18 (3H, s, H arom); 8.34 (1H, br. s, OH);
9.35 (2H, br. s, NH2); signals of the minor diastereomer: 1.46 and 1.69 (6H, both br. s, Me2); 2.68 (3H, s, NMe);
2.84 (4H, m, CH2NCH2); 3.68 (4H, m, CH2OCH2); 3.74 (3H, s, OMe); 4.28 (1H, d, 3J = 12.2, CHAr); 5.29 (1H,
d, 3J = 12.2, CHCN); 6.59 d and 6.87 d (both 3J = 8.2); 7.78 (3H, s, H arom); 8.52 (1H, br. s, OH); 9.64 and 9.88
(2H, both s, NH2); signals of the enethiol: 1.38 and 1.73 (6H, both br. s, Me2); 2.68 (3H, s, NMe); 2.84 (4H, m
3
CH2NCH2); 3.68 (4H, m, CH2OCH2); 3.82 (3H, s OMe); 4.01 (1H, s CHAr); 7.44 d and 7.79 d (both J = 8.2);
8.06 (3H, s, H arom); 8.91 (1H, s, OH); 9.35 (2H, br. s, NH2). Ratio of the diastereomers and the enethiol –
5:3:2. Found, %: C 55.26; H 5.89; N 8.88. C17H17N2O6S·C5H12NO. Calculated, %: C 55.10; H 6.10; N 8.76.
Tetrahydropyridones 6 (General Method). Mixture of salt 4 (2.4 g, 5 mmol) and the corresponding
halide 5 (5 mmol) in 80% ethanol (15 ml) was boiled for 2 min and filtered through paper. After 12 h, the
precipitate formed in the filtrate was separated and washed with ethanol and hexane.
6-Benzylthio-5-cyano-4-(4-hydroxy-3-methoxyphenyl)-1,2,3,4-tetrahydropyridin-2-one (6a).
Yield 1.15 g (63%); mp 195-197°C. IR spectrum, ν, cm-1: 3210, 3450 (OH, NH); 2200 (C≡N); 1678 (C=O).
3
3
2
1H NMR spectrum, δ, ppm, J(Hz): 2.43 (dd, J = 7.9) and 2.63 (dd, J = 9.2) (2H, both J = 15.7, C(3)H2); 3.73
3
3
(1H, dd, J = 7.9 and 9.2, C(4)H); 3.79 (3H, s, OMe); 4.29 (2H, s, SCH2); 6.39 (d, J = 8.3); 6.63, s, 6.68 (d,
3J = 8.3) (3H, H arom); 7.32 (5H, m, Ph); 8.63 (1H, br. s, OH); 10.54 (1H, s, NH). Found, % C 65.72; H 5.12;
N 7.42. C20H18N2O3S. Calculated, %: C 65.56; H 4.97; N 7.64.
6-Allylthio-5-cyano-4-(4-hydroxy-3-methoxyphenyl)-1,2,3,4-tetrahydropyridin-2-one
(6b).
Yield 1.06 g (67%); mp 141-143°C. IR spectrum, ν, cm-1: 3240-3269 (OH, NH); 2200 (C≡N); 1710 (C=O).
1H NMR spectrum, δ, ppm, J (Hz): 2.58 (dd, 3J = 7.7) and 2.82 (dd, 3J = 9.1) (2H, both 2J = 16.6, C(3)H2); 3.75
(6H, m, C(4)H, SCH2, OMe); 5.17 (d, 3J = 8.9) and 5.22 (d, 3J = 14.1) (2H, CH2=); 5.86 (1H, m, CH=); 6.58 (d,
3J = 8.4); 6.73 s, 6.75 d (3J = 8.4) (3H arom); 8.64 (1H, br. s, OH); 10.54 (1H, s, NH). Found, %: C 60.61;
H 5.32; N 8.95. C16H16N2O3S. Calculated, %: C 60.74; H 5.10; N 8.85.
5-Cyano-6-ethoxycarbonylmethylthio-4-(4-hydroxy-3-methoxyphenyl)-1,2,3-4-tetrahydropyridin-
2-one (6c). Yield 1.4 g (77%); mp 131-133°C. IR spectrum, ν, cm-1: 3180, 3450 (OH, NH); 2190 (C≡N); 1680,
1
3
3
1728 (2 C=O). H NMR spectrum, δ, ppm, J (Hz): 1.27 (3H, t, J = 6.4, Me); 2.63 (dd, J = 7.4) and 2.83 (dd,
3J = 9.1) (2H, both J = 17.5, C(3)H2); 3.81 (3H, s, OMe); 3.89 (3H, m, C(4)H, SCH2); 4.17 (2H, q, J = 6.4,
2
3
3
3
OCH2); 6.59 (d, J = 8.3); 6.74 (d, J = 8.4); 6.77 (3H, s, H arom); 8.67 (1H, br. s, OH); 10.44 (1H, s, NH).
Found, %: C 56.52; H 5.16; N 7.64. C17H18N2O5S. Calculated, %: C 56.34; H 5.01; N 7.73.
6-Carbamoylmethylthio-5-cyano-4-(4-hydroxy-3-methoxyphenyl)-1,2,3,4-tetrahydropyridin-2-one
(6d). Yield 1.2 g (72%); mp 142-144°C. IR spectrum, ν, cm-1: 3240-3420 (OH, NH, NH2); 2190 (C≡N); 1680,
1720 (2 C=O). 1H NMR spectrum, δ, ppm, J (Hz): 2.63 (dd, 3J = 7.2) and 2.85 (dd, 3J = 9.2) (2H, both 2J = 16.8,
2
3
C(3)H2); 3.64 and 3.74 (2H, both d, J =15.8, SCH2); 3.84 (4H, m, C(4)H, OMe); 6.59 (d, J = 8.3); 6.73 (d,
3J = 8.3); 6.78 (3H, s, H arom); 7.42 and 7.79 (2H, both br. s, CONH2); 8.65 (1H, br. s, OH); 11.01 (1H, s, NH).
Found, %: C 54.21; H 4.73; N 12.55. C15H15N3O4S. Calculated, %: C 54.04; H 4.54; N 12.60.
6-(4-Bromophenyl)carbamoylmethylthio-5-cyano-4-(4-hydroxy-3-methoxyphenyl)-1,2,3,4-tetrahydro-
pyridin-2-one (6e). Yield 2.05 g (84%); mp 217-219°C. IR spectrum, ν, cm-1: 3305, 3450 (OH, 2NH); 2210
(C≡N); 1675, 1706 (2 C=O). 1H NMR spectrum, δ, ppm, J (Hz): 2.62 (dd, 3J = 6.9) and 2.87 (dd, 3J = 8.8) (2H,
2
3
both J = 16.9, C(3)H2); 3.79 (3H, s, OMe); 3.85 (1H, dd, J = 6.9 and 8.8, C(4)H); 3.93 (2H, s, SCH2); 6.59 (d,
3J = 8.3); 6.74 (d, 3J = 8.3); 6.78 (3H, s, H arom); 7.44 and 7.57 (4H, both d, 3J = 8.1, H arom); 8.63 (1H, br. s,
OH); 10.37 and 10.58 (2H, both br. s, 2 NH). Found, %: C 51.88; H 3.55; N 8.71. C21H18BrN3O4S.
Calculated, %: C 51.65; H 3.72; N 8.60.
1274

5-Cyano-4-(4-hydroxy-3-methoxyphenyl)-6-(2,5-dimethylphenyl)carbamoylmethylthio-1,2,3,4-
tetrahydropyridin-2-one (6f). Yield 1.77 g; mp 233-235°C. IR spectrum, ν, cm-1: 3270-3360 (OH, 2NH); 2210
1
(C≡N); 1695, 1718 (2 C=O). H NMR spectrum, δ, ppm, J (Hz): 2.21 and 2.32 (6H, both s, 2 Me); 2.62 (dd,
3J = 6.8) and 2.88 (dd, 3J = 8.9) (2H, both 2J = 16.9, C(3)H2); 3.78 (3H, s, OMe); 3.84 (1H, dd, 3J = 6.8 and 8.9,
C(4)H); 3.94 (2H, s, SCH2); 6.61 (d, 3J = 8.2); 6.72 (d, 3J = 8.2); 6.75 (3H, s, H arom); 6.92 (d, 3J = 8.1); 7.19 (d,
3J = 8.1); 7.27 (3H, s, H arom); 8.78 (1H, br. s, OH); 9.59 and 10.74 (2H, both br. s, 2 NH). Found, %: C 63.31;
H 5.22; N 9.73. C23H23N3O4S. Calculated, %: C 63.14; H 5.30; N 9.60.
5-Cyano-4-(4-hydroxy-3-methoxyphenyl)-6-(2-methylphenyl)carbamoylmethylthio-1,2,3,4-tetra-
hydropyridin-2-one (6g). Yield 1.88 g (89%); mp 212-215°C. IR spectrum, ν, cm-1: 3390, 3475 (OH, 2 NH);
2205 (C≡N); 1667, 1725 (2 C=O). 1H NMR spectrum, δ, ppm, J (Hz): 2.27 (3H, s, Me); 2.61 (dd, 3J = 6.9) and
3
2
3
2.86 (dd, J = 8.7) (2H, both J = 17.2, C(3)H2); 3.78 (3H, s, OMe); 3.86 (1H, dd, J = 6.9 and 8.7, C(4)H); 3.97
(2H, s, SCH2); 6.59 (d, J = 8.3); 6.71 (d, J = 8.3); 6.73 (3H, s, H arom); 7.15 m and 7.43 d (3J = 8.1) (4H,
H arom); 8.77 (1H, br. s, OH); 9.66 and 10.72 (2H, both br. s, 2 NH). Found, %: C 62.64; H 5.21; N 10.11.
C22H21N3O4S. Calculated, %: C 62.40; H 5.00; N 9.92.
3
3
This work was carried out with financial support from the Russian Fund for Fundamental Research
(project No. 99-03-32965).
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