6
12
V. V. Dotsenko et al.
N-Methylmorpholinium 4-(2-chlorophenyl)-3,5-dicyano-6-
oxo-1,4,5,6-tetrahydropyridine-2-thiolate, ((4R,5R)-(cis):
Acknowledgements
The authors are grateful to Dr. Nataliya V. Lyutenko (Clemson
University, SC, USA) for a SciFinder literature search per-
formed and to the Russian Foundation for Basic Research
(
4R,5S)-(trans) ¼ 9:10) (1a)
ꢂ
Yield: 96% (Method A) or 81% (Method B); m.p.: 197–200 C
ꢂ
(
dec.) (Ref. [15]: 210–212 C reported for cis:trans (1:1) mix-
1
(Project No. 05-03-32031) for financial support.
ture); H NMR (200 MHz, DMSO-d ): ꢀ ¼ 2.78 (s, NCH ),
6
3
3
.18 and 3.76 (both m, each 4H, O(CH CH ) N), 4.41 (d,
2 2 2
3
3
J ¼ 7.3 Hz, C(4)H ), 4.45 (q, J ¼ 11.2Hz, C(4)H
and
cis
trans
3
C(5)H ), 4.91 (d, J ¼ 7.3 Hz, C(5)H ), 7.14–7.49 (m,
trans
cis
References
4
of NH -proton was not detected, probably due to proton-
H–Ar), 9.69 and 9.71 (both br s, NH , NH ) ppm; signal
cis trans
þ
[1] For recent reviews on the 3-cyanopyridine-2(1H)-thione
chemistry, see: a) Litvinov VP, Rodinovskaya LA,
Sharanin YuA, Shestopalov AM, Senning A (1992)
Sulfur Reports 13: 1; b) Litvinov VP (1993) Phosph
Sulfur Silicon 74: 139; c) Litvinov VP, Krivokolysko SG,
Dyachenko VD (1999) Chem Heterocycl Compd 35(5):
deuterium exchange; IR (nujol): ꢁꢀ ¼ 3180 (N–H), 2247,
ꢁ
1
2
177 (2 CꢃN), 1680 (C¼O) cm
.
N-Methylmorpholinium 4-(4-chlorophenyl)-3,5-dicyano-6-
oxo-1,4,5,6-tetrahydropyridine-2-thiolate, ((4S,5R)-(cis):
5
09; d) Litvinov VP (2006) Russ Chem Rev 75(7): 645
(
4S,5S)-(trans) ¼ 1:1) (1b, C H ClN O S)
1
8
19
4
2
ꢂ
[2] For review see: Litvinov VP (1998) Russ Chem Bull Int
Ed 47: 2053
1
Yield: 78% (Method A); m.p.: 165–168 C (dec.); H NMR
(
200 MHz, DMSO-d ): ꢀ ¼ 2.78 (s, NCH ), 3.17 and 3.75 (both
6
3
[3] For reviews on the Mannich reaction, see: a) Blicke FF
(1942) The Mannich reaction. In: Adams R (ed) Organic
Reactions, Vol 1. John Wiley & Sons, New York, p 303;
b) Tramontini M (1973) Synthesis: 703; c) Tramontini
M, Angiolini L (1990) Tetrahedron 46: 1791; d) Arend
M, Westermann B, Risch N (1998) Angew Chem Int Ed
3
m, each 4H, O(CH CH ) N), 3.89 (d, J ¼ 6.3 Hz, C(4)H ),
2 2 2 cis
3
4
.22 (dd, J ¼ 11.4Hz, C(4)H
and C(5)H ), 4.80 (d,
trans
trans
3
J ¼ 6.3 Hz, C(5)H ), 7.14–7.52 (m, 4H–Ar), 9.59 (br s, NH ,
cis
cis
þ
NH overlapped) ppm; signal of NH -proton was not de-
tected, probably due to proton-deuterium exchange; IR (nujol):
trans
ꢀ¼ 3150 (N–H), 2253, 2185 (2 CꢃN), 1700 (C¼O) cmꢁ
1
.
ꢁ
3
7: 1045; e) Klienman EF (1992) The Bimolecular
Aliphatic Mannich and Related Reactions. The Bi-
molecular Aromatic Mannich Reaction. In: Trost BM
and Fleming I (eds) Comprehensive Organic Synthesis,
Vol 2. Pergamon Press, Oxford, p 893; f) Overman LE,
Ricca DJ (1992) Modern Variants of the Mannich Re-
action. In: Trost BM, Fleming I (eds) Comprehensive
Organic Synthesis, Vol 2. Pergamon Press, Oxford,
p 1007
N-Methylmorpholinium 3,5-dicyano-4-(3,4-dimethoxy-
phenyl)-6-oxo-1,4,5,6-tetrahydropyridine-2-thiolate,
(
(4S,5R)-(cis):(4S,5S)-(trans) ¼ 3:4) (1c, C H N O S)
2
0 24 4 4
ꢂ
1
Yield: 70% (Method A); m.p.: 189–192 C (dec.); H NMR
(
(
200 MHz, DMSO-d ): ꢀ ¼ 2.78 (s, NCH ), 3.17 and 3.72
2 2 2
6
3
3
both m, each 4H, O(CH CH ) N), 3.77 (d, J ¼ 6.7 Hz,
3
C(4)H ), 4.13 (dd, J ¼ 10.9 Hz, C(4)H
and C(5)H ),
trans
.71 (d, J ¼ 6.7 Hz, C(5)H ), 6.65–7.01 (m, 3H–Ar), 9.48 (br
cis
3
trans
[4] a) Dotsenko VV, Krivokolysko SG, Chernega AN,
Litvinov VP (2003) Dokl Chem 389(4–6): 92;
b) Dotsenko VV (2004) Cyanothioacetamide and its de-
rivatives in the synthesis of ring-fused sulfur-containing
pyridines. PhD Thesis, Zelinsky Institute of Organic
Chemistry, Moscow, Russian Federation, 167 pp (In
Russian)
4
s, NH , NH
cis
þ
overlapped) ppm; signal of NH -proton was
cis
trans
not detected, probably due to proton-deuterium exchange;
also a broadened peak at ꢀ ¼ 11.73 ppm corresponding to
NH proton of by-product 7 (about 6 mol%) was observed;
IR (nujol): ꢁꢀ ¼ 3150 (N–H), 2253, 2185 (2 CꢃN), 1695
C¼O) cmꢁ
1
(
.
[
5] Dotsenko VV, Krivokolysko SG, Litvinov VP (2005)
Russ Chem Bull Int Ed 54: 2692
N-Methylmorpholinium 3,5-dicyano-4-(fur-2-yl)-6-oxo-
,4,5,6-tetrahydropyridine-2-thiolate, ((4R,5R)-(cis):
4R,5S)-(trans) ¼ 2:1) (1d, C H N O S)
[
6] Dotsenko VV, Krivokolysko SG, Litvinov VP (2005)
Chem Heterocycl Compd 41(11): 1428
1
(
[7] Dotsenko VV, Krivokolysko SG, Chernega AN,
Litvinov VP (2007) Monatsh Chem 138: 35
1
6 18 4 3
ꢂ
1
Yield: 68% (Method A); m.p.: 178–180 C (dec.); H NMR
(
200 MHz, DMSO-d ): ꢀ ¼ 2.78 (s, NCH ), 3.18 and 3.76 (both
[8] For detailed reviews on the 3,7-diazabicyclo[3.3.1]no-
nane chemistry, see: a) Zefirov NS, Rogozina SV (1973)
Russ Chem Rev 42(3): 190; b) Jeyaraman R, Aliva S
(1981) Chem Rev 81: 149; c) Zefirov NS, Palyulin VA
(1991) Conformational Analysis of Bicyclo[3.3.1]no-
nanes and Their Hetero Analogs. In: Eliel EL, Wilen SH
(eds) Topics in Stereochemistry, Vol. 20. Interscience-
Wiley Publishers, New York, p 171
6
3
3
m, each 4H, O(CH CH ) N), 3.94 (d, J ¼ 6.5 Hz, C(4)H ),
2
2 2
cis
3
4
.20 (dd, J ¼ 9.7 Hz, C(4)H
and C(5)H ), 4.70 (d,
trans
trans
3
J ¼ 6.5 Hz, C(5)H ), 6.12 (m, furyl-C(3)H ), 6.24 (m,
cis
cis
furyl-C(3)H ), 6.36 (m, furyl-C(4)H and -C(4)H over-
trans
lapped), 7.55 (m, furyl-C(5)H ), 7.59 (m, furyl-C(5)H ),
9
proton was not detected, probably due to proton-deuterium
exchange; also four peaks at ꢀ ¼ 6.69, 7.12, 7.93 (fur-2-yl),
and 11.83 (NH) ppm corresponding to pyridine-2(1H)-thione
trans
cis
cis
trans
þ
.45 (br s, NH ), 9.58 (br s, NH ) ppm; signal of NH -
cis trans
[9] Dyachenko VD, Mitroshin AE, Litvinov VP (1996)
Chem Heterocycl Compd 32(9): 1058
7
(about 7 mol%) were observed; IR (nujol): ꢁꢀ ¼ 3180 (N–H),
[10] Dyachenko VD, Litvinov VP (1998) Chem Heterocycl
Compd 34(2): 183
ꢁ
1
2
250, 2183 (2 CꢃN), 1710 (C¼O) cm
.