A one-pot synthesis of ethyl 1,3-thiazole-5-carboxylates and 2-chloro-1,3-dicarbonyl compounds
211
?
EI-MS: m/z = 186 (M , 7), 171 (52), 170 (43), 156 (65),
Ethyl 2,4-dimethy-1,3-thiazole-5-carboxylate
3d, C H NO S)
1
(
141 (37), 113 (57), 45 (100); H NMR: d = 1.55 (t,
J = 9.0, Me), 2.64 (s, 3H, Me), 4.36 (q, J = 9.0, OCH ),
8
11
2
3
3
White powder: yield 0.35 g (95%); m.p. 195-197 8C. IR
2
-
1
13
(
KBr): vꢀ = 3,542, 3,169, 1,731, 1,453, 1,030 cm ; EI-
5.00 (s, 2H, NH ) ppm; C NMR: d = 13.8 (Me), 14.0
2
?
MS: m/z = 185 (M , 4), 170 (23), 155 (98), 141 (36), 114
(Me), 62.0 (OCH ), 118.9 (C), 148.3 (C), 160.9 (C=O),
2
1
3
(
18), 44 (100); H NMR: d = 1.20 (t, J = 9.0, Me), 2.53
170.1 (C=N) ppm.
3
s, 3H, Me), 2.56 (s, 3H, Me), 4.16 (q, J = 9.0, OCH )
(
2
1
3
ppm; C NMR: d = 14.5 (Me), 15.5 (Me), 17.5 (Me), 63.1
OCH ), 136.7 (C), 152.5 (C), 159.5 (C=N), 173.8 (C=O)
References
(
2
ppm.
1
. Breslow R (1958) J Am Chem Soc 80:3719
Ethyl 2-(dimethylamino)-4-hydroxy-1,3-thiazole-5-
carboxylate (3e, C H N O S)
2. Haviv F, Ratajczyk JD, DeNet RW, Kerdesky FA, Walters RL,
Schmidt SP, Holms JH, Young PR, Carter GW (1988) J Med
Chem 31:1719
8
12 2 3
Yellow oil: yield 0.30 g (70%); IR (KBr): vꢀ = 3,390,
3
. Patt WC, Hamilton HW, Taylor MD, Ryan MJ, Taylor DG Jr,
Connolly CJC, Doherty AM, Klutchko SR, Sircar I, Steinbaugh
BA, Batley BL, Painchaud CA, Rapundalo ST, Michniewicz BM,
Olson SCJ (1992) J Med Chem 35:2562
-
1
,118, 1,746, 1,658, 1,425, 1,030 cm ; EI-MS: m/z = 216
3
?
M , 5), 201 (56), 199 (10), 172 (26), 145 (67), 73 (100);
(
1
3
H NMR: d = 1.28 (t, J = 9.0, Me), 2.90 (s, 6H, 2 Me),
4
5
. Tsuji K, Ishikawa H (1994) Bioorg Med Chem Lett 4:1601
. Bell FW, Cantrell AS, Hoegberg M, Jaskunas SR, Johansson NG,
Jordon CL, Kinnick MD, Lind P, JM Morin Jr, Noreen R, Oberg
B, Palkowitz JA, Parrish CA, Pranc P, Sahlberg C, Ternansky RJ,
Vasileff RT, Vrang L, West SJ, Zhang H, Zhou X-X (1995)
J Med Chem 38:4929
3
.25 (q, J = 9.0, OCH ), 9.11 (broad s, 1H, OH) ppm;
13
4
C
2
NMR: d = 13.7 (Me), 49.4 (2 CH ), 62.8 (OCH ), 123.0
3
2
(
C), 152.6 (C), 166.7 (C=N), 168.4 (C=O) ppm.
Ethyl 2-(dimethylamino)-4-methyl-1,3-thiazole-5-
carboxylate (3f, C H N O S)
6
7
. Fink BA, Mortensen DS, Stauffer SR, Aron ZD, Katzenellenb-
ogen JA (1999) Chem Biol 6:205
. Van Muijlwijk-Koezen JE, Timmerman H, Vollinga RC, Von
Drabbe Kunzel JF, De Groote M, Visser S, Ijzerman AP (2001)
J Med Chem 44:749
9
14 2 2
Pale yellow oil: yield 0.36 g (85%); IR (KBr): vꢀ = 3,574,
-
1
,111, 1,722, 1,627, 1,463, 1,029 cm ; EI-MS: m/z = 214
3
?
M , 3), 199 (65), 184 (26), 170 (67), 73 (100); H NMR:
1
(
3
8
. Hantzsch A, Weber JH (1887) Ber Dtsch Chem Ges 20:3118
d = 1.34 (t, J = 9.0, Me), 2.73 (s, 3H, Me), 3.15 (s, 6H, 2
Me), 4.36 (q, J = 9.0, OCH ), ppm; C NMR: d = 13.2
3
13
9. Metzger JV (1984) Comprehensive heterocyclic chemistry. In:
Katritzky R, Rees CW (eds) vol 6. Pergamon, New York, pp 235–
332
2
(
Me), 19.5 (CH ), 49.6 (s, 6H, 2 Me), 62.1 (OCH ), 137.2
2
3
(
C), 149.3 (C), 160.7 (C=O), 167.6 (C=N) ppm.
10. Welton T (1999) Chem Rev 99:2071
1
1. Rogers RD, Seddon KR (eds) (2002) In ionic liquids: industrial
applications to green chemistry, ACS Symposium Series 818.
American Chemical Society, Washington
Ethyl 2-amino-4-hydroxy-1,3-thiazole-5-carboxylate
3g, C H N O S)
(
6
8 2 3
1
2. Wasserscheid P, Welton T (eds) (2003) Ionic liquids in synthesis.
Wiley-VCH, Weinheim
3. Chiappe C (2007) Monatsh Chem 138:1035
Colorless oil: yield 0.21 g (55%); IR (KBr): vꢀ = 3,321,
-
1
?
3
,159, 1,708, 1,633, 1,506, 1,030 cm ; EI-MS: 188 (M ,
); 173 (47); 172 (37); 159 (44); 142 (27); 115 (87); 45
1
1
7
4. Paczal A, Kotschy A (2007) Monatsh Chem 138:1115
0
1
3
(
3
100). H NMR: d = 1.29 (t, J = 9.0, Me), 4.33 (q,
J = 9.0, OCH ), 5.06 (broad s, 2H, NH ), 9.12 (s, 1H,
15. Meindersma GW, Sa nchez LMG, Hansmeier AR, de Haan AB
(2007) Monatsh Chem 138:1125
2
2
1
3
OH) ppm; C NMR: d = 13.7 (Me), 62.5 (OCH ), 122.9
2
(
C), 143.3 (C), 161.4 (C=O), 166.4 (C=N) ppm.
Ethyl 2-amino-4-methyl-1,3-thiazole-5-carboxylate
3h, C H N O S)
(
7
10 2 2
Yellow powder: yield 0.24 g (65%); m.p. 100–102 8C. IR
-
KBr): vꢀ = 3,372, 3,153, 1,721, 1,651, 1,429, 1,030 cm
;
1
(
123