Benzylidenebarbituric and -thiobarbituric Acids
CDCl
3
): δ 19.7 (CH
3
), 28.4, 28.5 (NCH
3
), 40.3, 51.2, 51.7, 83.5,
MHz, CDCl
(CH), 55.3 (OCH
H), 150.7, 160.1, 167.0, 167.3. C16
H 5.48, N 12.03; found C 54.66, H 5.61, N 11.85.
3
): δ 19.7 (CH
), 83.4 (CH), 114.8 (CAr-H), 125.4, 129.5 (CAr
(349.2): calcd C 55.01,
3 3
), 28.3, 28.5 (NCH ), 50.9 (C-5), 51.3
(CH), 112.5 (CAr-H), 119.9, 129.0 (CAr-H), 150.7, 151.0, 167.2,
3
-
167.4. C17
H N O
22 4 5
(362.4): calcd C 56.35, H 6.12, N 15.46; found
19 3 6
H N O
+
C 56.17, H 6.14, N 15.16. HR-MS (EI) [M ]: calcd 362.1590;
found 362.1565.
1-(4-Dimethylaminophenyl)-2,2′-dicyanoethene (7bh). 62%
yield, mp 179-180 °C (EtOH, 179 °C).7 The H NMR spectrum
4
1
1,3-Dimethyl-5-[(4,4′-dimethyl-2,6-dioxocyclohexyl)(4-meth-
oxyphenyl)methyl]-pyrimidine-2,4,6(1H,3H,5H)-trione (5cb). Col-
orless crystals, 93% yield, mp 146-147 °C (EtOH). H NMR (400
is consistent with that reported in ref 74.
1
1-(4-Methoxyphenyl)-2,2′-dicyanoethene (7ch). 21% yield, mp
113-114 °C (EtOH, 115-116 °C).76 The H NMR spectrum is
consistent with that reported in ref 76.
1
MHz, CDCl
H, CH ), 3.35 (s, 3H, NCH
OCH ), 5.51 (s, 1H, CH), 6.82 (d, J ) 8.8 Hz, 2H, Ar), 7.02 (d,
J ) 8.8 Hz, 2H, Ar), 11.32 (br. s, 1H, OH), 12.82 (s, 1H, 6-OH).
3
): δ 1.13 (s, 3H, CH
3
), 1.26 (s, 3H, CH
3
), 2.40 (m,
4
2
3
), 3.44 (s, 3H, NCH ), 3.78 (s, 3H,
3
3
3
1
-(4-Methoxyphenyl)-2-cyano-2-ethoxycarbonylethene (7ci).
3
75
1
8
3% yield, mp 79-81 °C (EtOH, 81-82 °C). The H NMR
spectrum is consistent with that reported in ref 75.
-Amino-5-(4-methoxyphenyl)-1,3-dimethyl-2,4-dioxo-1,3,4,5-
tetrahydro-2H-pyrano[2,3-d]-pyrimidine-6-carbonitrile (8ch).
13
C NMR (75.5 MHz, CDCl
3
): δ 27.3, 29.0, 29.4, 30.2, 31.4, 33.1,
), 92.8 (C-5), 113.9 (CAr-H),
4
1
1
1
1
6.2 (CH ), 47.2 (CH ), 55.4 (OCH
16.8 (C-1), 127.8 (CAr-H), 129.1, 150.9, 158.1, 162.5, 164.3, 190.9,
2
2
3
7
91.4. IR (KBr): ν˜ ) 3428, 3055, 3001, 2959, 2839, 2632, 1702,
1
Colorless crystals, 47% yield, mp 225-227 °C (EtOH). H NMR
400 MHz, d -DMSO): δ 3.08 (s, 3H, NCH ), 3.34 (s, 3H, NCH ),
.72 (s, 3H, OCH ), 4.27 (s, 1H, CH), 6.83 (d, J ) 8.8 Hz, 2H,
609, 1510, 1466, 1421, 1389, 1305, 1264, 1249, 1178, 1154, 1117,
(
3
6
3
3
095, 1031, 938 cm- . C22
1
H N O
26 2 6
(414.4): calcd C 63.77, H 6.32,
3
3
N 6.76; found C 63.50, H 6.33, N 6.55.
-[2-Acetyl-1-(4-methoxyphenyl)-3-oxobutyl]-1,3-dimethylpy-
rimidine-2,4,6(1H,3H,5H)-trione (5ce). Colorless crystals, 93%
3
13
Ar), 7.15 (d, J ) 8.8 Hz, 2H, Ar), 7.30 (br s, 2H, NH
100 MHz, d -DMSO): δ 27.7 (NCH ), 29.1 (NCH ), 35.8 (CH),
), 58.9 (C-CN), 89.1, 113.6 (CAr-H), 115.2 (CN), 119.2,
28.4 (CAr-H), 133.4, 136.2, 150.0, 150.9, 157.6, 158.1, 160.5. IR
2
). C NMR
5
(
5
1
6
3
3
5.0 (OCH
3
1
yield, mp 116-118 °C (EtOH). H NMR (400 MHz, CDCl
3
): δ
), 3.10 (s,
), 3.73 (d, J ) 4.4 Hz, 1H, 5-H),
1
3
4
.88 (s, 3H, CH
H, NCH ), 3.69 (s, 3H, OCH
.28 (dd, J ) 12.0 Hz, J ) 4.4 Hz, 1H, CH), 4.79 (d, J ) 12.4
3 3 3
), 2.36 (s, 3H, CH ), 2.92 (s, 3H, NCH
(
1
KBr): ν˜ ) 3419, 3306, 3190, 2950, 2194, 1687, 1639, 1611, 1511,
3
-1
3
3
3
493, 1461, 1388, 1304, 1262, 1244, 1230, 1181, 1037, 970 cm
(340.3): calcd C 59.99, H 4.74, N 16.46; found C
.
3
17 21 3 6
C H N O
3
3
Hz, 1H, CH), 6.70, (d, J ) 8.8 Hz, 2H, Ar), 6.85 (d, J ) 8.8 Hz,
H, Ar). 13C NMR (100 MHz, CDCl
): δ 28.1 (NCH ), 28.2
), 46.5 (CH), 51.1 (CH), 55.3
), 70.7 (CH), 114.4 (CAr-H), 126.5, 129.1 (CAr-H), 150.8,
), 202.4 (COCH ).
IR (KBr): ν˜ ) 3409, 2943, 2843, 1744, 1678, 1611, 1570, 1540,
514, 1424, 1380, 1363, 1256, 1185, 1140, 1120, 1085, 1022, 994
60.18, H 4.73, N 16.65.
2
3
3
Reaction of 8ch with Cyclohexanone to 9ch. Compound 8ch
(
(
NCH
OCH
3
3 3
), 28.5 (CH ), 30.6 (CH
(0.130 g, 0.382 mmol) and cyclohexanone (0.043 mL, 0.42 mmol)
3
were added to a suspension of AlCl (0.056 g, 0.42 mmol) in 5
3
158.8, 159.9, 167.6 (2 × CO), 201.4 (COCH
3
3
mL of 1,2-dichloroethane. The mixture was then refluxed for 3.5
h in a nitrogen flow. After cooling, 3 mL of aqueous THF (65%)
and 3 mL of sodium hydroxide solution (10%) were added, and
the resulting mixture was extracted with ethyl acetate (3 × 50 mL).
The combined organic layers were washed with water and dried
1
-
1
22 2 6
cm . C19H N O (374.4): calcd C 60.95, H 5.92, N 7.48; found
C 60.90, H 5.86, N 7.57.
Ethyl 2-[(1,3-Dimethyl-2,4,6-trioxohexahydropyrimidine-5-
yl)(4-methoxyphenyl)-methyl]-3-oxobutanoate (5cg). Colorless
2
over CaCl . After removal of the solvent, the residue was purified
by column chromatography (silica gel, CHCl
recrystallization from ethanol.
3
/EtOH 50:1) and
crystals, 88% yield, isolated as mixture of diastereomers (4:3).
Major diastereomer: 1H NMR (400 MHz, CDCl
): δ 0.93 (t, J )
3
3
6-Amino-5-(4-methoxyphenyl)-1,3-dimethyl-1,5,7,8,9,10-hexahy-
7
.2 Hz, 3H, CH
NCH ), 3.72 (s, 3H, OCH
CH), 4.64 (d, J ) 12.4 Hz, 1H, CH), 6.72 (d, J ) 8.8 Hz, 2H,
2
CH
3
), 2.42 (s, 3H, CH
3
), 2.95, 3.14 (2s, 6H, 2 ×
dro-12-oxa-1,3,11-triaza-naphthacene-2,4-dione (9ch). Colorless
3
3
), 3.83-4.33 (m, 4H, CH
2
+ 5-H +
1
crystals, 69% yield, mp >240 °C (EtOH). H NMR (600 MHz,
3
3
CDCl
H, CH
OCH ), 4.17 (br. s, 2H, NH
Hz, 2H, Ar), 7.30 (d, J ) 9.0 Hz, 2H, Ar). C NMR (150 MHz,
CDCl ): δ 22.4 (CH ), 22.7 (CH ), 23.1 (CH ), 28.3 (NCH ), 29.6
NCH ), 32.7 (CH ), 35.3, 55.4 (OCH ), 91.0, 99.7, 114.3 (CAr
H), 115.1, 129.6 (CAr-H), 134.4, 150.9, 151.2, 152.6, 153.7, 154.5,
3
): δ 1.83 (m, 4H, 2 × CH
), 3.27 (s, 3H, NCH
), 4.91 (s, 1H, CH), 6.81 (d, J ) 8.4
2
), 2.30 (m, 2H, CH
2
), 2.79 (m,
3
13
Ar), 6.90 (d, J ) 8.8 Hz, 2H, Ar). C NMR (75.5 MHz, CDCl
CH ), 28.2, 28.3 (NCH ), 30.2 (CH ), 45.9 (CH), 50.8
C-5), 55.3 (OCH ), 61.5 (CH), 61.8 (CH ), 114.1 (CAr-H), 127.4,
29.1 (CAr-H), 150.9, 159.7, 166.9, 167.7, 168.0, 201.6. Minor
3
):
2
2
3
), 3.59 (s, 3H, NCH
3
), 3.74 (s, 3H,
δ 13.9, (CH
2
3
3
3
3
3
2
(
1
3
2
3
13
3
2
2
2
3
1
3
diastereomer: H NMR (400 MHz, CDCl
Hz, 3H, CH CH ), 2.01 (s, 3H, CH
), 2.99, 3.15 (2s, 6H, 2 ×
NCH ), 3.71 (s, 3H, OCH ), 3.83-4.33 (m, 4H, CH + 5-H +
CH), 4.64 (d, J ) 12.4 Hz, 1H, CH), 6.71 (d, J ) 8.8 Hz, 2H,
3
): δ 1.29 (t, J ) 7.2
(
3
2
3
-
2
3
3
3
3
2
1
1
1
59.0, 162.0. IR (KBr): ν˜ ) 3502, 3393, 2937, 1709, 1664, 1627,
3
3
510, 1491, 1447, 1420, 1376, 1320, 1301, 1260, 1237, 1204, 1186,
3
13
Ar), 6.91 (d, J ) 8.8 Hz, 2H, Ar). C NMR (75.5 MHz, CDCl
CH ), 28.2, 28.3 (NCH ), 30.9 (CH ), 46.4 (CH), 51.4
C-5), 55.3 (OCH ), 60.6 (CH), 62.1 (CH ), 114.4 (CAr-H), 127.4,
29.1 (CAr-H), 151.0, 159.7, 166.9, 167.7, 167.9, 168.0, 201.3.
(404.4): calcd C 59.40, H 5.98, N 6.93; found C 59.00,
H 5.82, N 6.82.
-[1-(4-Methoxyphenyl)-2-nitropropyl]-1,3-dimethylpyrimi-
3
):
-1
24 4 4
084, 1046, 1030, 976 cm . C23H N O (420.45): calcd C 65.70,
δ 14.2 (CH
(
2
3
3
3
H 5.75, N 13.32; found C 65.51, H 5.79, N 13.02.
Reactions of 1c with 10a-c and 13a to the Corresponding
Compounds 11 and 14ca according to General Procedure C.
3
2
1
20 24 2 7
C H N O
1,3-Dimethyl-5-(4-methoxyphenyl-3-oxo-1-phenylpropyl)pyrimi-
dine-2,4,6(1H,3H,5H)-trione (11ca). Colorless crystals, 87% yield,
5
57 1
3
mp 140-141 °C). H NMR (400 MHz, CDCl ): δ 3.07, 3.12
3
dine-2,4,6-(1H,3H,5H)-trione (5cm). Colorless crystals, 74% yield,
isolated as mixture of diastereomers (7:2). Major diastereomer: H
2
(
2s, 2 × 3 H, NCH
3
), 3.48 (dd, J ) 18.2 Hz, J ) 5.8 Hz, 1H,
3
1
CH ), 3.75 (s, 3H, OCH
(
2
3
), 3.96 (d, J ) 4.0 Hz, 1H, 5-H), 4.48
3
NMR (300 MHz, CDCl
.14, (2s, 6H, NCH
OCH ), 4.01-4.11 (m, 1H, CH), 5.44-5.55 (m, 1H, CHCH
3
): δ 1.90 (d, J ) 6.6 Hz, 3H, CH
3
), 3.02,
2
3
dd, J ) 18.2 Hz, J ) 9.0 Hz, 1H, CH ), 4.29-4.34 (m, 1 H,
2
3
3
3
), 3.73 (d, J ) 3.3 Hz, 1H, 5-H), 3.72 (s, 3H,
3
3
CH), 6.78 (d, J ) 8.8 Hz, 2H, Ar-H), 7.01 (d, J ) 8.8 Hz, 2H,
3
3
), 6.73
13
Ar-H), 7.45-7.59 (m, 3H, Ar-H), 7.99-8.02 (m, 2H, Ar-H).
NMR (75.5 MHz, CDCl ), 40.9 (CH ), 44.0
), 114.2, 128.2, 128.6, 128.8, 130.2
C
3
3
13
(
(
5
d, J ) 8.7 Hz, 2H, Ar), 6.91 (d, J ) 8.7 Hz, 2H, Ar). C NMR
75.5 MHz, CDCl ): δ 18.9 (CH ), 28.3, 28.6 (NCH ), 50.6 (C-5),
1.8 (CH), 55.3 (OCH ), 84.9 (CH), 114.5 (CAr-H), 125.2, 128.8
CAr-H), 150.5, 160.2, 167.0, 167.3. Minor diastereomer: H NMR
3
): δ 28.2, 28.4 (NCH
CH), 53.3 (C-5), 55.4 (OCH
3
2
3
3
3
(
3
3
1
(
(
(
3
(74) Posner, T. B.; Hall, C. D. J. Chem. Soc., Perkin Trans 2 1976, 729-
32.
75) Lee, J.; Gauthier, D.; Rivero, R. A. J. Org. Chem. 1999, 64, 3060-
3065.
(76) Lord, E.; Naan, M. P.; Hall, C. D. J. Chem. Soc. B 1971, 213-219.
300 MHz, CDCl
2s, 6H, NCH ), 3.68 (d, J ) 3.3 Hz, 1H, 5-H), 3.75 (s, 3H, OCH
3
): δ 1.37 (d, J ) 6.6 Hz, 3H, CH
3
), 3.04, 3.16
),
7
3
3
3
3
(
4
3
.01-4.11 (m, 1H, CH), 5.55-5.64 (m, 1H, CHCH ), 6.79 (d, J
8.7 Hz, 2H, Ar), 6.93 (d, J ) 8.7 Hz, 2H, Ar). C NMR (75.5
3
13
)
J. Org. Chem, Vol. 72, No. 24, 2007 9179