meta), 141.92 (Ph ipso), 149.1 (C-6), 155.5 (C-2), 171 (C-4); m/z
(Ph ipso), 160.5 (C-2); m/z (EI) 202 (Mϩ, 100%), 171 (21), 145
(42), 130 (32), 104 (18), 77 (43), 51 (18).
(EI) 202 (Mϩ, 100%), 144 (36), 116 (18), 110 (45), 77 (58).
1-Phenyl-4-(2-trimethylsilylethoxy)pyrimidin-2(1H)-one 2k.
Eluent hexane–EtOAc 6:1; oil (Found: Mϩ, 288.1296. C15H20-
N2O2Si requires 288.1294); δH (300 MHz, acetone-d6) 0.02 (9H,
s, Si(CH3)3), 1.03–1.12 (2H, m, CH2Si), 4.32–4.40 (2H, m,
OCH2), 6.49 (1H, d, H-5, J 5.7), 7.16–7.26 (3H, m, Ph), 7.39–
7.43 (2H, m, Ph), 8.20 (1H, d, H-6, J 5.7); δC (75 MHz, acetone-
d6) Ϫ1.4 (SiCH3), 17.7 (CH2Si), 65.4 (OCH2), 103.9 (C-5), 122.5
(Ph ortho), 125.7 (Ph meta), 130.1 (Ph para), 154.2 (Ph ipso),
159.8 (C-6), 165.9 (C-2), 172.1 (C-4); m/z (EI) 288 (Mϩ, 4%),
259 (36), 245 (100), 218 (10), 188 (41), 151 (34), 145 (57), 77
(13), 73 (95).
5-Methoxy-2-methylthio-4-phenoxypyrimidine 4n. Eluent
CH2Cl2–MeOH 40:1; mp 58–60 ЊC (Found: Mϩ, 248.0611.
C12H12N2O2S requires 248.0619); δH (300 MHz, acetone-d6) 2.27
(3H, s, SCH3), 3.97 (3H, s, OCH3), 7.20–7.29 (3H, m, Ph), 7.42–
7.47 (2H, m, Ph), 8.23 (1H, s, H-6); δC (75 MHz, acetone-d6)
14.1 (SCH3), 57.1 (OCH3), 122.5 (Ph ortho), 126.2 (Ph meta),
130.2 (Ph para), 140.4 (C-5), 141.6 (C-6), 153.3 (Ph ipso), 160.0
(C-2), 161.8 (C-4); m/z (EI) 248 (Mϩ, 100%), 233 (17), 215 (14),
202 (11), 140 (11), 86 (11), 77 (22).
References
1 A. Varvoglis, The Organic Chemistry of Polycoordinated Iodine,
VCH Publishers, Inc., New York, 1992.
2 (a) Ref. 1, pp. 207; (b) R. M. Moriarty and R. K. Vaid, Synthesis,
1990, 431; (c) A. Varvoglis, Synthesis, 1984, 709.
4-Amino-1-phenylpyrimidin-2(1H)-one 21. The crude product
was purified by spinning first in CHCl3 and then in 0.1 M
NaOH; δH (300 MHz, DMSO-d6) 5.77 (1H, d, H-5, J 7.3), 7.21
(2H, s, NH2), 7.29–7.48 (5H, m, Ph),7.61 (1H, d, H-6, J 7.3);
δC (75 MHz, DMSO-d6) 93.8 (C-5), 126.2 (Ph ortho), 127.00 (Ph
para), 128.5 (Ph meta), 141.2 (Ph ipso), 145.4 (C-6), 154.6 (C-2),
165.9 (C-4); m/z (EI) 187 (Mϩ, 100%), 185 (63), 145 (26), 144
(24), 143 (14), 117 (16), 114 (12), 104 (7).
3 (a) A. McKillop and R. J. Kobylecki, J. Org. Chem., 1974, 39, 2710;
(b) W.-Y. Chen and N. W. Gilman, J. Heterocycl. Chem., 1983, 20,
663; (c) S. Bátori and A. Messmer, J. Heterocycl. Chem., 1988, 25,
437.
4 Direct O/N-arylation of amides has been achieved with aryl halides
catalyzed by copper salts: B. Renger, Synthesis, 1985, 856; A.
Greiner, Synthesis, 1989, 312; with tetraphenylbismuth trifluoro-
acetate: D. H. R. Barton, J.-P. Finet, W. B. Motherwell and
C. Pichon, J. Chem. Soc., Perkin Trans. 1, 1987, 251 and with
p-tolyllead triacetate: P. López-Alavardo, C. Avendaño and J. C.
Menéndez, Tetrahedron Lett., 1992, 33, 6875.
5 (a) D. J. Brown and T.-C. Lee, Aust. J. Chem., 1968, 21, 243;
(b) C. Kashima, A. Katoh, Y. Yokota and Y. Omote, Synthesis, 1983,
151; (c) J. Solberg, PhD Thesis, University of Oslo, 1988.
6 D. J. Brown, The Pyrimidines, Supplement II, Wiley & Sons,
New York, 1985, p. 205 and references therein.
7 A. N. Nesmeyanov, L. G. Makarova and T. P. Tolstaya, Tetrahedron,
1957, 145.
4-(N,N-Dimethylamino)-1-phenylpyrimidin-2(1H)-one
2m.
Eluent CH2Cl2–MeOH 40:1; mp 153–155 ЊC (Found: Mϩ,
215.1051. C12H13N3O requires 215.1059); νmax/cmϪ1 1653 (CO);
δH (300 MHz, DMSO-d6) 3.07 (6H, s, N(CH3)2), 6.11 (1H, d,
H-5, J 7.6), 7.32–7.47 (5H, m, H-Ph), 7.72 (1H, d, H-6, J 7.6);
δC (75 MHz, DMSO-d6) 36.6 (CH3), 37.6 (CH3), 91.5 (C-5),
126.5 (Ph para), 127.3 (Ph meta), 128.8 (Ph ortho), 141.0 (Ph
ipso), 145.7 (C-6), 154.0 (C-2), 163.5 (C-4); m/z (EI) 215 (Mϩ,
72%), 200 (9), 144 (11), 123 (100), 77 (26).
2-Phenoxypyrimidine 3a.27 Eluent CH2Cl2–MeOH 40:1; δH
(300 MHz, acetone-d6) 7.16–7.26 (4H, m, Ph), 7.41–7.46 (2H,
m, Ph/H-5), 8.58 (2H, d, H-4/H-6, J 4.7); δC (75 MHz, acetone-
d6) 117.4 (C-5), 122.5 (Ph ortho), 125.8 (Ph meta), 130.3 (Ph
para), 154.3 (Ph ipso), 160.6 (C-4/C-6), 166.3 (C-2); m/z (EI) 172
(Mϩ, 100%), 171 (60), 144 (46), 117 (11), 77 (36), 51 (19).
8 D. D. Perrin, B. Dempsey and E. P. Serjeant, pKa Prediction of
Organic Acids and Bases, Chapman and Hall, London, 1981.
9 A. Albert and J. N. Phillips, J. Chem. Soc., 1956, 1294.
10 D. J. Brown, The Pyrimidines, Wiley & Sons, New York, 1962,
Table XVI, pp. 472.
11 D. J. Brown, The Pyrimidines, Supplement I, Wiley & Sons,
New York, 1970, Table XVI, pp. 369.
12 M. F. Beringer, A. Brierley, M. Drexler, E. M. Grindler and C. C.
Lumpkin, J. Am. Chem. Soc., 1953, 75, 2705.
5-Chloro-2-phenoxypyrimidine 3b. Eluent hexane–EtOAc
2:1; δH (300 MHz, CDCl3) 7.22 (3H, m, Ph), 7.43 (1H, m, Ph),
8.47 (2H, s, H-4/H-6); δC (75 MHz, CDCl3), 121.4 (Ph ortho),
125.3 (C-5), 125.8 (Ph para), 129.73 (Ph meta), 152.6 (Ph ipso),
157.8 (C-4, C-6), 163.5 (C-2); m/z (EI) 206 (Mϩ, 100%), 205
(37), 178 (27), 171 (37), 164 (27), 143 (19), 104 (31).
13 J. L. Dektar and N. P. Hacker, J. Org. Chem., 1990, 55, 639.
14 D. G. Crosby and R. V. Berthold, J. Org. Chem., 1960, 25, 1916.
15 W. Franke and R. Kraft, Chem. Ber., 1953, 86, 797.
16 G. E. Hilbert and T. B. Johnson, J. Am. Chem. Soc., 1930, 52, 2001.
17 M. Prystas, Collect. Czech. Chem. Commun., 1975, 40, 1786.
18 M. L. Falck-Pedersen, T. Benneche and K. Undheim, Acta Chem.
Scand., 1993, 47, 72.
19 W. Szar and D. Shugar, Acta Biochim. Pol., 1966, 13, 177.
20 Z. Budésinsky, V. Bydzovsky, J. Kopecky, A. Sváb and J. Vavrina,
Cesk. Farm., 1961, 10, 241.
21 Z. Budésinsky, J. Prikryl and E. Svátek, Collect. Czech. Chem.
Commun., 1964, 29, 2980.
22 Z. Budésinsky, J. Prikryl and E. Svátek, Collect. Czech. Chem.
Commun., 1967, 32, 1637.
23 A Novácek and M. Lisserová, Collect. Czech. Chem. Commun.,
1968, 33, 1003.
5-Bromo-2-phenoxypyrimidine 3c. Eluent hexane–EtOAc 2:1
(Found: Mϩ, 251.9737. C10H7BrN2O requires 251.9721); δH
(300 MHz, CDCl3) 7.18 (3H, m, Ph), 7.24 (1H, m, Ph), 8.54
(2H, s, H-4/H-6); δC (75 MHz, CDCl3) 113.1 (C-5), 121.4 (Ph
ortho), 125.1 (Ph para), 129.7 (Ph meta), 152.6 (Ph ipso), 160.0
(C-4, C-6), 163.9 (C-2); m/z (EI) 252/250 (Mϩ, 56/61%), 224/222
(5/4), 210/208 (7/7), 172 (12), 171 (100), 143 (11), 116 (14), 104
(20).
24 T. Nishio, K. Katahira and Y. Omote, J. Chem. Soc., Perkin Trans. 1,
1981, 943.
25 M. R. Atkinson, M. J. Maguire, R. K. Ralph, G. Shaw and R. N.
Warrener, J. Chem. Soc., 1957, 2363.
26 Y. F. Shealy and C. A. O’Dell, J. Heterocycl. Chem., 1976, 13, 1041.
27 T. Joijima and S. Tamura, Agric. Biol. Chem., 1966, 30, 896.
5-Methoxy-2-phenoxypyrimidine 3d. Eluent hexane–
EtOAc 2:1; oil (Found: Mϩ, 202.0757. C11H10N2O2 requires
202.0742); δH (300 MHz, acetone-d6) 3.92 (3H, s, OCH3), 7.11–
7.22 (3H, m, Ph), 7.37–7.43 (2H, m, Ph), 8.29 (2H, s, H-4/H-6);
δC (75 MHz, acetone-d6) 57.0 (OCH3), 122.0 (Ph ortho), 125.3
(Ph para), 130.2 (Ph meta), 146.3 (C-4/C-6), 151.5 (C-5), 155.1
Paper 9/05519C
3268
J. Chem. Soc., Perkin Trans. 1, 1999, 3265–3268