1708
Vol. 55, No. 12
127.3, 129.5, 131.8, 131.9, 133.5, 140.3; MS m/z: 426 (Mꢃ ). Anal. Calcd
for C18H16Cl2N2O4S: C, 50.59; H, 3.77; N, 6.56; Found C, 50.50; H, 3.75; N,
6.60.
·
contents were diluted with ice-cold water, acidified with conc. HCl and ex-
tracted with ethyl acetate. The organic layer was washed with brine and
dried over anhydrous Na2SO4. Removal of the solvent under vacuum af-
forded crude product which was purified by recrystallization from MeOH.
6-Imino-5,5-bis-(2ꢀ-phenylsulfonylethyl)-1,3-dimethylpyrimidine-2,4-
dione (5): White powder, yield 64%, mp 273—275 °C; IR (KBr) cmꢁ1: 3215
General Procedure of Synthesis of 6-Amino-5,5-bis-(2ꢀ-phenylsul-
fonylethyl)-2-hydroxypyrimidine-4-one (4)/6-Amino-5-(2ꢀ-arylsulfonyl-
1ꢀ-arylethyl)-2-hydroxypyrimidine-4-one (13a—b)/6-Amino-5-(2ꢀ-aryl-
methylsulfonyl-1ꢀ-arylethyl)-2-hydroxypyrimidine-4-one (14a—b) The
compound 1/7/8 (0.01 mol) was dissolved in EtOH (10 ml). To this urea
(0.01 mol) in EtOH (10 ml) and piperidine (5 ml) were added and refluxed
for 6—9 h. The contents were cooled, poured onto crushed ice containing
conc. HCl and extracted with ethylacetate. The organic layer was washed
with brine and dried over anhydrous Na2SO4. Removal of the solvent in
vacuo gave crude product which was purified by recrystallization from
MeOH.
1
(NH), 1634 (CꢂO), 1612 (CꢂN), 1327, 1133 (SO2). H-NMR (CDCl3) d:
1.88—1.96 (m, 2H, C1ꢀ-H), 2.11—2.20 (m, 2H, C1ꢀ-H), 2.70 (s, 6H, N-CH3),
2.80—2.96 (m, 4H, C2ꢀ-H), 7.44—7.87 (m, 10H, Ar-H), 9.18 (bs, 1H, NH);
13C-NMR (CDCl3) d: 23.8 (C-1ꢀ), 28.9 (N-CH3), 29.2 (N-CH3), 42.5 (C-5),
49.4 (C-2ꢀ), 158.4 (C-2), 164.2 (C-6), 178.0 (C-4), 126.6, 130.1, 132.5,
136.3; MS m/z: 491 (Mꢃ ). Anal. Calcd for C22H25N3O6S2: C, 53.75; H,
·
5.13; N, 8.55; Found C, 53.89; H, 5.15; N, 8.67.
6-Imino-5-(2ꢀ-phenylsulfonyl-1ꢀ-phenylethyl)-1,3-dimethylpyrimidine-
2,4-dione (15a): White solid, yield 64%, mp 287—288 °C; IR (KBr) cmꢁ1
:
6-Amino-5,5-bis-(2ꢀ-phenylsulfonylethyl)-2-hydroxypyrimidine-4-one
(4): White needles, yield 66%, mp 270—272 °C; IR (KBr) cmꢁ1: 3458,
3362 (NH2), 3335 (OH), 1635 (CꢂO), 1604 (CꢂN), 1335, 1145 (SO2). 1H-
NMR (CDCl3ꢃDMSO-d6) d: 1.92—2.01 (m, 2H, C1ꢀ-H), 2.15—2.22 (m,
2H, C1ꢀ-H), 2.85—3.01 (m, 4H, C2ꢀ-H), 5.94 (bs, 2H, NH2), 6.84 (s, 1H,
OH), 7.42—7.85 (m, 10H, Ar-H); 13C-NMR (CDCl3ꢃDMSO-d6) d: 24.7
(C-1ꢀ), 47.2 (C-5), 49.1 (C-2ꢀ), 157.4 (C-6), 161.2 (C-2), 178.7 (C-4), 125.8,
3212 (NH), 1641 (CꢂO), 1603 (CꢂN), 1326, 1137 (SO2). 1H-NMR
(CDCl3ꢃDMSO-d6) d: 2.73 (s, 6H, N-CH3), 3.02 (dd, 1H, C2ꢀ-H, Jꢂ4.1,
14.0 Hz), 3.75 (dd, 1H, C2ꢀ-H, Jꢂ9.6, 14.3 Hz), 4.15—4.21 (m, 1H, C1ꢀ-H),
4.34 (d, 1H, C5-H, Jꢂ5.1 Hz), 7.05—7.87 (m, 10H, Ar-H), 9.21 (bs, 1H,
NH); 13C-NMR (CDCl3ꢃDMSO-d6) d: 27.9 (N-CH3), 28.5 (N-CH3), 52.8
(C-2ꢀ), 54.1 (C-1ꢀ), 64.3 (C-5), 159.7 (C-2), 163.2 (C-6), 176.5 (C-4), 125.5,
126.4, 126.8, 127.8, 129.5, 131.3, 138.5, 141.2; MS m/z: 399 (Mꢃ ). Anal.
127.3, 131.6, 136.2; MS m/z: 463 (Mꢃ ). Anal. Calcd for C20H21N3O6S2: C,
·
·
Calcd for C20H21N3O4S: C, 60.13; H, 5.30; N, 10.52. Found C, 60.24; H,
5.28; N, 10.60.
51.82; H, 4.57; N, 9.07. Found C, 51.70; H, 4.60; N, 9.14.
6-Amino-5-(2ꢀ-phenylsulfonyl-1ꢀ-phenylethyl)-2-hydroxypyrimidine-4-
one (13a): Colourless crystals, yield 66%, mp 284—286 °C; IR (KBr) cmꢁ1
:
6-Imino-5-[2ꢀ-phenylsulfonyl-1ꢀ-(4-chlorophenyl)ethyl]-1,3-dimethyl-
pyrimidine-2,4-dione (15b): White solid, yield 67%, mp 266—267 °C; IR
(KBr) cmꢁ1: 3217 (NH), 1634 (CꢂO), 1607 (CꢂN), 1313, 1128 (SO2). 1H-
NMR (CDCl3ꢃDMSO-d6) d: 2.71 (s, 6H, N-CH3), 3.06 (dd, 1H, C2ꢀ-H,
Jꢂ4.3, 14.3 Hz), 3.78 (dd, 1H, C2ꢀ-H, Jꢂ9.7, 14.4 Hz), 4.16—4.23 (m, 1H,
C1ꢀ-H), 4.32 (d, 1H, C5-H, Jꢂ5.2 Hz), 7.01—7.88 (m, 9H, Ar-H), 9.18 (bs,
1H, NH); 13C-NMR (CDCl3ꢃDMSO-d6) d: 28.4 (N-CH3), 29.1 (N-CH3),
53.2 (C-2ꢀ), 54.7 (C-1ꢀ), 65.2 (C-5), 158.6 (C-2), 162.4 (C-6), 175.3 (C-4),
3442, 3365 (NH2), 3328 (OH), 1635 (CꢂO), 1609 (CꢂN), 1334, 1142
(SO2). 1H-NMR (CDCl3ꢃDMSO-d6) d: 3.11 (dd, 1H, C2ꢀ-H, Jꢂ4.4,
14.3 Hz), 3.79 (dd, 1H, C2ꢀ-H, Jꢂ9.4, 14.4 Hz), 4.17—4.22 (m, 1H, C1ꢀ-H),
4.33 (d, 1H, C5-H, Jꢂ5.4 Hz), 5.86 (bs, 2H, NH2), 6.92 (bs, 1H, OH), 7.11—
7.82 (m, 10H, Ar-H); 13C-NMR (CDCl3ꢃDMSO-d6) d: 52.7 (C-2ꢀ), 53.6
(C-1ꢀ), 63.9 (C-5), 158.8 (C-6), 162.5 (C-2), 176.3 (C-4), 125.3, 125.9,
126.7, 127.4, 129.1, 131.3, 137.8, 138.3; MS m/z: 371 (Mꢃ ). Anal. Calcd
for C18H17N3O4S: C, 58.21; H, 4.61; N, 11.31; Found C, 58.30; H, 4.66; N,
11.41.
·
126.5, 127.1, 127.9, 129.2, 130.5, 132.5, 138.8, 140.3; MS m/z: 433 (Mꢃ ).
·
Anal. Calcd for C20H20ClN3O4S: C, 55.36; H, 4.65; N, 9.68; Found C, 55.30;
H, 4.70; N, 9.74.
6-Amino-5-[2ꢀ-(4-chlorophenylsulfonyl)-1ꢀ-phenylethyl]-2-hydroxy-
pyrimidine-4-one (13b): White solid, yield 68%, mp 268—270 °C; IR (KBr)
cmꢁ1: 3379, 3453 (NH2), 3315 (OH), 1625 (CꢂO), 1612 (CꢂN), 1328,
1130 (SO2). 1H-NMR (CDCl3ꢃDMSO-d6) d: 3.07 (dd, 1H, C2ꢀ-H, Jꢂ4.5,
14.4 Hz), 3.74 (dd, 1H, C2ꢀ-H, Jꢂ9.5, 14.5 Hz), 4.21—4.26 (m, 1H, C1ꢀ-H),
4.31 (d, 1H, C5-H, Jꢂ5.4 Hz), 5.89 (bs, 2H, NH2), 6.87 (bs, 1H, OH), 7.04—
7.87 (m, 9H, Ar-H); 13C-NMR (CDCl3ꢃDMSO-d6) d: 52.1 (C-2ꢀ), 54.9 (C-
1ꢀ), 64.5 (C-5), 159.2 (C-6), 163.4 (C-2), 175.7 (C-4), 125.1, 126.9, 128.1,
6-Imino-5-[2ꢀ-(4-chlorophenylmethylsulfonyl)-1ꢀ-phenylethyl]-1,3-di-
methylpyrimidine-2,4-dione (16a): White solid, yield 62%, mp 270—
272 °C; IR (KBr) cmꢁ1: 3232 (NH), 1640 (CꢂO), 1615 (CꢂN), 1324, 1125
1
(SO2). H-NMR (CDCl3ꢃDMSO-d6) d: 2.74 (s, 6H, N-CH3), 3.08 (dd, 1H,
C2ꢀ-H, Jꢂ4.5, 14.5 Hz), 3.71 (dd, 1H, C2ꢀ-H, Jꢂ9.5, 14.6 Hz), 4.21—4.25
(m, 1H, C1ꢀ-H), 4.28 (s, 2H, Ar-CH2), 4.35 (d, 1H, C5-H, Jꢂ4.9 Hz), 7.06—
7.33 (m, 9H, Ar-H), 9.21 (bs, 1H, NH); 13C-NMR (CDCl3ꢃDMSO-d6) d:
27.8 (N-CH3), 28.1 (N-CH3), 52.4 (C-2ꢀ), 55.3 (C-1ꢀ), 56.8 (Ar-CH2), 63.8
(C-5), 157.4 (C-2), 163.2 (C-6), 174.9 (C-4), 125.1, 125.7, 126.6, 127.4,
129.4, 130.4, 131.8, 137.9, 140.1; MS m/z: 405 (Mꢃ ). Anal. Calcd for
·
C18H16ClN3O4S: C, 53.27; H, 3.97; N, 10.35.;Found C, 53.22; H, 4.00; N,
10.30.
128.3, 131.7, 133.8, 139.9; MS m/z: 447 (Mꢃ ). Anal. Calcd for
·
C21H22ClN3O4S: C, 56.31; H, 4.95; N, 9.38; Found C, 56.41; H, 4.94; N,
9.45.
6-Amino-5-[2ꢀ-(4-chlorophenylmethylsulfonyl)-1ꢀ-phenylethyl]-2-hy-
droxypyrimidine-4-one (14a): White crystals, yield 70%, mp 262—264 °C;
IR (KBr) cmꢁ1: 3360, 3445 (NH2), 3331 (OH), 1637 (CꢂO), 1601 (CꢂN),
1328, 1146 (SO2). 1H-NMR (CDCl3ꢃDMSO-d6) d: 3.05 (dd, 1H, C2ꢀ-H,
Jꢂ4.2, 14.1 Hz), 3.67 (dd, 1H, C2ꢀ-H, Jꢂ9.2, 14.1 Hz), 4.14—4.21 (m, 1H,
C1ꢀ-H), 4.26 (s, 2H, Ar-CH2), 4.33 (d, 1H, C5-H, Jꢂ5.2 Hz), 5.78 (bs, 2H,
NH2), 6.93 (bs, 1H, OH), 7.09—7.46 (m, 9H, Ar-H); 13C-NMR (CDCl3ꢃ
DMSO-d6) d: 53.8 (C-2ꢀ), 55.2 (C-1ꢀ), 59.8 (Ar-CH2), 63.3 (C-5), 158.7 (C-
6), 162.7 (C-2), 174.2 (C-4), 126.1, 126.9, 127.0, 127.7, 129.3, 131.3, 137.8,
6-Imino-5-[2ꢀ-(4-chlorophenylmethylsulfonyl)-1ꢀ-(4-chlorophenyl)ethyl]-
1,3-dimethylpyrimidine-2,4-dione (16b): Light yellow solid, yield 64%, mp
250—252 °C; IR (KBr) cmꢁ1: 3225 (NH), 1636 (CꢂO), 1604 (CꢂN), 1318,
1132 (SO2). 1H-NMR (CDCl3ꢃDMSO-d6) d: 2.73 (s, 6H, N-CH3), 3.13 (dd,
1H, C2ꢀ-H, Jꢂ4.7, 14.6 Hz), 3.74 (dd, 1H, C2ꢀ-H, Jꢂ9.6, 14.4 Hz), 4.11—
4.17 (m, 1H, C1ꢀ-H), 4.27 (s, 2H, Ar-CH2), 4.34 (d, 1H, C5-H, Jꢂ5.0 Hz),
7.12—7.41 (m, 8H, Ar-H), 9.18 (bs, 1H, NH); 13C-NMR (CDCl3ꢃDMSO-
d6) d: 28.9 (N-CH3), 29.4 (N-CH3), 53.3 (C-2ꢀ), 54.8 (C-1ꢀ), 57.3 (Ar-CH2),
64.2 (C-5), 157.0 (C-2), 162.6 (C-6), 175.3 (C-4), 126.4, 126.9, 127.2,
140.4; MS m/z: 419 (Mꢃ ). Anal. Calcd for C19H18ClN3O4S: C, 54.35; H,
·
4.32; N, 10.01; Found C, 54.44; H, 4.33; N, 10.08.
129.3, 130.4, 131.3, 133.6, 138.7; MS m/z: 481 (Mꢃ ). Anal. Calcd for
·
6-Amino-5-[2ꢀ-(4-chlorophenylmethylsulfonyl)-1ꢀ-(4-chlorophenyl)-
ethyl]-2-hydroxypyrimidine-4-one (14b): White crystals, yield 69%, mp
280—282 °C; IR (KBr) cmꢁ1: 1134, 1325 (SO2), 1610 (CꢂN), 1630
(CꢂO), 3324 (OH), 3372, 3443 (NH2). 1H-NMR (CDCl3ꢃDMSO-d6) d:
3.09 (dd, 1H, C2ꢀ-H, Jꢂ4.3, 14.2 Hz), 3.77 (dd, 1H, C2ꢀ-H, Jꢂ9.3, 14.2 Hz),
4.19—4.24 (m, 1H, C1ꢀ-H), 4.32 (d, 1H, C5-H, Jꢂ5.3 Hz), 4.25 (s, 2H, Ar-
CH2), 5.86 (bs, 2H, NH2), 6.89 (bs, 1H, OH), 7.04—7.39 (m, 8H, Ar-H);
13C-NMR (CDCl3ꢃDMSO-d6) d: 54.2 (C-2ꢀ), 54.4 (C-1ꢀ), 58.5 (Ar-CH2),
64.9 (C-5), 158.7 (C-6), 161.8 (C-2), 173.8 (C-4), 125.4, 126.1, 127.3,
C21H21Cl2N3O4S: C, 52.29; H, 4.39; N, 8.71; Found C, 52.21; H, 4.43; N,
8.68.
General Procedure of Synthesis of 6-Amino-5,5-bis-(2ꢀ-phenylsul-
fonylethyl)-2-mercaptopyrimidine-4-one (6)/6-Amino-5-(2ꢀ-arylsulfonyl-
1ꢀ-arylethyl)-2-mercaptopyrimidine-4-one (17a—b)/6-Amino-5-(2ꢀ-aryl-
methylsulfonyl-1ꢀ-arylethyl)-2-mercaptopyrimidine-4-one (18a—b) To
a solution of 1/7/8 (0.01 mol) in EtOH (20 ml), thiourea (0.01 mmol) and
piperidine (5 ml) were added and refluxed for 7—12 h. The reaction mixture
was cooled, poured onto crushed ice containing conc. HCl and extracted
with ethyl acetate. The organic layer was washed with brine and dried over
anhydrous Na2SO4. The solvent was removed with rotary evaporator. The re-
sulted solid was purified by recrystallization from MeOH.
128.7, 129.8, 131.7, 134.2, 138.1; MS m/z: 453 (Mꢃ ). Anal. Calcd for
·
C19H17Cl2N3O4S: C, 50.23; H, 3.77; N, 9.25; Found C, 50.29; H, 3.80; N,
9.20.
General Procedure of Synthesis of 6-Imino-5,5-bis-(2ꢀ-phenylsul-
fonylethyl)-1,3-dimethylpyrimidine-2,4-dione (5)/6-Imino-5-(2ꢀ-arylsul-
fonyl-1ꢀ-arylethyl)-1,3-dimethylpyrimidine-2,4-dione (15a—b)/6-Imino-
5-(2ꢀ-arylmethylsulfonyl-1ꢀ-arylethyl)-1,3-dimethylpyrimidine-2,4-dione
(16a—b) A mixture of 1/7/8 (0.01 mol), 1,3-dimethylurea (0.01 mol),
EtOH (15 ml) and piperidine (5 ml) was taken and refluxed for 6—10 h. The
6-Amino-5,5-bis-(2ꢀ-phenylsulfonylethyl)-2-mercaptopyrimidine-4-one
(6): White solid, yield 68%, mp 269—271 °C; IR (KBr) cmꢁ1: 3462, 3357
1
(NH), 2558 (SH), 1630 (CꢂO), 1616 (CꢂN), 1338, 1142 (SO2). H-NMR
(CDCl3ꢃDMSO-d6) d: 1.35 (s, 1H, SH), 1.83—1.94 (m, 2H, C1ꢀ-H), 2.14—
2.22 (m, 2H, C1ꢀ-H), 2.89—3.05 (m, 4H, C2ꢀ-H), 5.97 (bs, 2H, NH2), 7.37—