R. Olivera et al. / Tetrahedron 58 +2002) 3021±3037
3029
3.1.5.
4-72-Bromo-4,5-dimethoxyphenyl)-5-72-bromo-
43.49; H, 2.84; N, 5.64. Found: C, 43.53; H, 2.88; N,
5.51.
phenyl)pyrimidine 73e). 73%; colorless powder; mp
104±1058C :MeOH); Rf 0.42 :20% hexane/EtOAc); 1H
NMR :CDCl3) d 3.60:3H, s), 3.85 :3H, s), 6.58 :1H, s),
7.02 :1H, s), 7.14±7.24 :3H, m), 7.55 :1H, dd, J7.8,
1.5 Hz), 8.86 :1H, s), 9.32 :1H, s); 13C NMR :CDCl3) d
55.4, 55.6, 113.0, 114.9, 121.4, 126.8, 129.8, 129.9, 132.3,
138.5, 147.5, 149.0, 156.9, 158.9, 164.1; FTIR :neat ®lm,
cm21): 1601; EIMS :m/z, %) 452 :M12, 9), 450:M 1, 19),
448 :M22, 9), 290:M 22Br, 100). Anal. Calcd for
C18H14Br2N2O2: C, 48.03; H, 3.13; N, 6.22. Found: C,
48.08; H, 3.19; N, 6.16.
3.1.10. 5-72-Bromo-4,5-dimethoxyphenyl)-4-72-iodo-
phenyl)pyrimidine 73j). 76%; yellow powder; mp 114±
1
1158C :MeOH); Rf 0.33 :50% hexane/EtOAc); H NMR
:CDCl3) d 3.64 :3H, s), 3.85 :3H, s), 6.62 :1H, s), 7.00
:1H, ddd, J7.7, 7.6, 2.0 Hz), 7.02 :1H, s), 7.09 :1H, dd,
J7.7, 1.7 Hz), 7.24 :1H, ddd, J7.6, 7.6, 1.7 Hz), 7.86
:1H, dd, J7.9, 1.0Hz), 8.86 :1H, s), 9.33 :1H, s); 13C
NMR :CDCl3) d 55.5, 55.6, 96.1, 113.0, 113.3, 114.7,
126.7, 127.5, 129.0, 129.6, 132.5, 138.7, 141.7, 147.5,
148.9, 156.8, 159.0, 165.9; FTIR :neat ®lm, cm21): 1598;
EIMS :m/z, %) 498 :M11, 6), 496 :M21, 6), :M2Br±I,
100). Anal. Calcd for C18H14BrIN2O2: C, 43.49; H, 2.84; N,
5.64. Found: C, 43.19; H, 2.96; N, 5.69.
3.1.6. 4-74,5-Dimethoxy-2-iodophenyl)-5-72-iodophenyl)-
pyrimidine 73f). 66%; colorless powder; mp 80±828C
:MeOH); Rf 0.41 :40% hexane/EtOAc); H NMR :CDCl3)
1
d 3.62 :3H, s), 3.83 :3H, s, OMe), 6.63 :1H, s), 6.97 :1H,
ddd, J7.9, 7.5, 1.6 Hz), 7.13 :1H, dd, J7.5, 1.6 Hz), 7.23
:1H, s), 7.24 :1H, ddd, J7.5, 7.5, 1.2 Hz), 7.88 :1H, d,
J7.9, 1.2 Hz), 8.74 :1H, s), 9.35 :1H, s); 1H NMR
:CDCl3) d 55.8, 56.0, 84.8, 99.5, 112.3, 121.6, 128.3,
130.0 130.7, 133.8, 136.3, 139.2, 140.0, 148.5, 149.3,
157.6, 159.1, 165.4; FTIR :neat ®lm, cm21): 1595; EIMS
:m/z, %) 544 :M1, 16), 290:M 22I, 100). Anal. Calcd for
C18H14I2N2O2: C, 39.73; H, 2.59; N, 5.15. Found: C, 39.79;
H, 2.48; N, 5.15.
3.1.11. 4-72-Bromophenyl)-5-75-bromo-1,3-benzodioxol-
6-yl)pyrimidine 73k). 66%; colorless powder; mp 159±
1608C :MeOH); Rf 0.41 :50% hexane/EtOAc); H NMR
1
:CDCl3) d 5.94 :2H, s), 6.59 :1H, s), 7.01 :1H, s), 7.14±
7.25 :3H, m), 7.57 :1H, dd, J8.0, 1.6 Hz), 8.76 :1H, s),
9.31 :1H, s); 13C NMR :CDCl3) d 102.0, 110.6, 112.8,
114.4, 121.7, 127.1, 128.5, 130.1, 130.3, 133.0, 133.6,
138.2, 147.2, 148.6, 157.5, 159.4, 164.4; FTIR :neat ®lm,
cm21): 1594; EIMS :m/z, %) 436 :M12, 3), 434 :M1, 6),
432 :M22, 3), 274 :M22Br, 100). Anal. Calcd for
C17H10Br2N2O2: C, 47.04; H, 2.32; N, 6.45. Found: C,
47.17; H, 2.09; N, 6.49.
3.1.7. 5-72-Bromo-4,5-dimethoxyphenyl)-4-72-bromo-
phenyl)pyrimidine 73g). 79%; colorless powder; mp 65±
1
678C :MeOH); Rf 0.28 :30% hexane/EtOAc); H NMR
:CDCl3) d 3.65 :3H, s), 3.84 :3H, s), 6.66 :1H, s), 6.99
:1H, s), 7.10±7.23 :3H, m), 7.60 :1H, dd, J7.1, 2.0Hz),
8.78 :1H, s), 9.34 :1H, s); 13C NMR :CDCl3) d 55.8, 56.0,
112.2, 112.8, 115.4, 123.4, 127.3, 129.9, 130.0, 131.4,
132.7, 133.8, 136.0, 147.7, 149.6, 157.5, 158.7, 163.4;
FTIR :neat ®lm, cm21): 1600; EIMS :m/z, %) 452 :M12,
11), 450:M 1, 21), 448 :M22, 11), 290:M 22Br, 100).
Anal. Calcd for C18H14Br2N2O2: C, 48.03; H, 3.13; N,
6.22. Found: C, 48.19; H, 3.16; N, 6.08.
3.1.12. 4,5-Diphenylpyrimidine 73l). 67%; colorless
powder; mp 130±1318C :MeOH) :lit.41 130±1318C
:MeOH)).
3.1.13. 4,5-Bis73,4-dimethoxyphenyl)pyrimidine 73m).
78%; colorless powder; mp 143±1458C :MeOH):lit.42
125±1278C :EtOH)); Rf 0.30 :30% EtOAc/CH2Cl2); 1H
NMR :CDCl3) d 3.67 :6H, s), 3.87 :3H, s), 3.89 :3H, s),
7.11 :6H, m), 8.63 :1H, s), 9.20:1H, s); 13C NMR :CDCl3) d
55.5, 55.7, 110.3, 111.3, 112.3, 112.4, 121.5, 122.9, 128.9,
129.5, 132.4, 148.3, 148.8, 148.9, 150.0, 156.9, 157.9,
162.5; FTIR :neat ®lm, cm21): 1620; EIMS :m/z, %) 353
:M11, 21), 352 :M1, 97), 351 :M21, 100). Anal. Calcd for
C20H20O4N2: C, 68.17; H, 5.72; N, 7.95. Found: C, 68.34; H,
5.50; N, 7.66.
3.1.8. 5-74,5-Dimethoxy-2-iodophenyl)-4-72-iodophenyl)-
pyrimidine 73h). 61%; colorless powder; mp 148±1498C
:MeOH); Rf 0.36 :40% hexane/EtOAc); 1H NMR :CDCl3) d
3.64 :3H, s), 3.84 :3H, s), 6.66 :1H, s), 7.00 :1H, ddd,
J7.5, 7.5, 1.6 Hz), 7.12 :1H, dd, J7.5, 1.6 Hz), 7.21±
7.26 :2H, m), 7.87 :1H, d, J7.5 Hz), 8.83 :1H, s), 9.34
:1H, s); 13C NMR :CDCl3) d 55.9, 56.0, 87.2, 96.5, 113.2,
121.1, 128.0, 129.2, 130.2, 131.6, 135.7, 139.2, 142.2,
148.8, 149.2, 157.4, 159.7, 166.2; FTIR :neat ®lm, cm21):
1591; EIMS :m/z, %) 544 :M1, 16), 290:M 22I, 100). Anal.
Calcd for C18H14I2N2O2: C, 39.73; H, 2.59; N, 5.15. Found:
C, 39.44; H, 2.32; N, 5.07.
3.1.14. 4-73,4-Dimethoxyphenyl)-5-phenylpyrimidine
73n). 78%; colorless powder; mp 115±1168C :MeOH); Rf
1
0.40 :30% EtOAc/CH2Cl2); H NMR :CDCl3) d 3.57 :3H,
s), 3.85 :3H, s), 6.76 :1H, d, J8.4 Hz), 6.93 :1H, d,
J1.8 Hz), 7.14 :1H, dd, J8.5, 1.8 Hz), 7.21±7.42
:5H, m), 8.65 :1H, s), 9.19 :1H, s); 13C NMR :CDCl3) d
55.4, 55.7, 110.5, 112.8, 123.1, 127.9, 128.8, 129.2,
129.4, 132.7, 136.7, 148.2, 150.2, 157.2, 158.0, 162.5;
FTIR :neat ®lm, cm21): 1684; EIMS :m/z, %) 293 :M11,
18), 292 :M1, 93), 291 :M21, 100). Anal. Calcd for
C18H16O2N2: C, 73.95; H, 5.52; N, 9.58. Found: C, 73.68;
H, 5.50; N, 9.35.
3.1.9. 4-72-Bromophenyl)-5-74,5-dimethoxy-2-iodophenyl)-
pyrimidine 73i). 66%; yellow powder; mp 134±1358C
:MeOH); Rf 0.29 :50% hexane/EtOAc); H NMR :CDCl3)
1
d 3.61 :3H, s), 3.84 :3H, s), 6.62 :1H, s), 7.15±7.23 :4H, m),
7.56 :1H, dd, J7.5, 2.4 Hz), 8.84 :1H, s), 9.33 :1H, s); 13C
NMR :CDCl3) d 55.6, 55.9, 87.2, 113.0, 121.0, 121.7,
127.1, 129.8, 130.2, 131.4, 132.6, 136.0, 138.5, 148.7,
149.1, 157.2, 159.4, 164.1; FTIR :neat ®lm, cm21): 1594;
EIMS :m/z, %) 498 :M11, 8), 496 :M21, 10), 290
:M2Br±I, 100). Anal. Calcd for C18H14BrIN2O2: C,
3.1.15.
5-73,4-Dimethoxyphenyl)-4-72,3,4-trimethoxy-
phenyl)pyrimidine 73o). 75%; colorless oil; Rf 0.20 :30%
EtOAc/CH2Cl2); 1H NMR :CDCl3) d 3.44 :3H, s), 3.58 :3H,
s), 3.66 :3H, s), 3.80:3H, s), 3.82 :3H, s), 6.58 :1H, s), 6.64