Methyl iodide → 5-Benzyloxy-6-methoxy-2-methylsulfanyl-pyrimidine-4-carboxylic acid ethyl ester
Reaction equation
[CH2:1]([O:3][C:4]([C:6]1[N:7]=[C:8]([S:21][CH3:22])[NH:9][C:10](=[O:20])[C:11]=1[O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:5])[CH3:2].[H-].[Na+].I[CH3:26]>CN(C)C=O>[CH2:1]([O:3][C:4]([C:6]1[C:11]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[C:10]([O:20][CH3:26])[N:9]=[C:8]([S:21][CH3:22])[N:7]=1)=[O:5])[CH3:2]Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Procedure
5-Benzyloxy-2-methylsulfanyl-6-oxo-1,6-dihydro-pyrimidine-4-carboxylic acid ethyl ester (6.190 g, 19.32 mmol) in dry N,N-dimethylformamide (60 ml) was reacted at 10° C. with sodium hydride (0.90 g of a 60% dispersion in mineral oil, 22.5 mmol) and iodomethane (1.4 ml, 21.7 mmol) and chromatographed to give first 0.581 g (9% yield) of 5-benzyloxy-6-methoxy-2-methylsulfanyl-pyrimidine-4-carboxylic acid ethyl ester as white crystals; mp 48–49° C. (ethyl acetate-hexane). 1HNMR 400 MHz (CDCl3) δ (ppm): 1.32 (3H, t, J=7.1 Hz, CH3), 2.56 (3H, s, SCH3), 4.07 (3H, s, OCH3), 4.36 (2H, q, J=7.1 Hz, CH2), 5.04 (2H, s, OCH2), 7.3–7.45 (5H, m, aromatics). HRMS (FAB POS) calculated for C16H19N2O4S [M+H+]: 335.106554. found: 335.106641, δ −0.3 ppm. The following fractions then gave 5.836 g (90% yield) of the title ester as white needles; mp 84–85° C. (ethyl acetate-hexane). 1HNMR 400 MHz (CDCl3) δ (ppm): 1.33 (3H, t, J=7.0 Hz, CH3), 2.62 (3H, s, SCH3), 3.57 (3H, s, NCH3), 4.35 (2H, q, J=7.0 Hz, CH2), 5.22 (2 H, s, OCH2), 7.3–7.5 (5H, m, aromatics). Anal. Calcd for C16H18N2O4S: C 57.47, H 5.43, N 8.38. Found: C 57.37, H 5.42, N 8.36.
Workup
- customchromatographed
Sources & evidence
- ORD record
- ord-f31a1a8d96964857a31970acbe3e607b
- Source dataset
- uspto-grants-2006_11
- Patent number
- US07135467B2
Reaction notes
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