Diethyl (ethoxymethylene)malonate → Diethyl 2-[[(6-amino-2-methylsulfanylpyrimidin-4-yl)amino]methylidene]propanedioate

HRID 16248Notes

Reaction equation

[NH2:1][C:2]1[CH:7]=[C:6]([NH2:8])[N:5]=[C:4]([S:9][CH2:10]C)[N:3]=1.CCO[CH:15]=[C:16]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[C:17]([O:19][CH2:20][CH3:21])=[O:18]>C(O)C>[NH2:8][C:6]1[N:5]=[C:4]([S:9][CH3:10])[N:3]=[C:2]([NH:1][CH:15]=[C:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH:7]=1

Participants

Conditions

Temperature: 135 °C

Procedure

A mixture of 4,6-diamino-2-ethylmercaptopyrimidine (9.95 g) and diethyl ethoxymethylene malonate (13.77 g) at 165° C. was stirred for 40 minutes, cooled to 135° C., stirred for 60 minutes, cooled to 25° C., and added to refluxing ethanol (700 mL). This mixture was treated with decolorizing carbon (NORIT®) stirred for 30 minutes, cooled, filtered, concentrated to 300 mL, heated until homogeneous, cooled, treated with water until cloudy, stored at 0° C. for 18 hours, and filtered. 1H NMR (300 MHz, DMSO-d6) δ 10.41 (d, 1H), 8.96 (d, 1H), 6.98 (s, 2H), 5.97 (s, 1H), 4.21 (q, 2H), 4.12 (q, 2H), 2.43 (s, 3H), 1.26 (t, 3H), 1.23 (t, 3H).

Workup

stirringstirred for 60 minutes
temperaturecooled to 25° C.
additionadded
additionThis mixture was treated with decolorizing carbon (NORIT®)
stirringstirred for 30 minutes
temperaturecooled
filtrationfiltered
concentrationconcentrated to 300 mL
temperatureheated until homogeneous,
temperaturecooled
additiontreated with water until cloudy
waitstored at 0° C. for 18 hours
filtrationfiltered

Sources & evidence

ORD record: ord-a449566d473a4df08420d63595ed14e4
Source dataset: uspto-grants-2010_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07737159B2

Reaction notes

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