Acetic Anhydride → Diethyl 2-[[(6-acetamido-2-methylsulfanylpyrimidin-4-yl)amino]methylidene]propanedioate

HRID 16249Notes

Reaction equation

HRID 16249 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([S:8][CH3:9])[N:5]=[C:4]([NH:10][CH:11]=[C:12]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH:3]=1.[C:23](OC(=O)C)(=[O:25])[CH3:24]>>[C:23]([NH:1][C:2]1[N:7]=[C:6]([S:8][CH3:9])[N:5]=[C:4]([NH:10][CH:11]=[C:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:3]=1)(=[O:25])[CH3:24]

Participants

3

Reactant 2

HCID 7918Acetic Anhydride2×HCID 302508Diethyl 2-[[(6-amino-2-methylsulfanylpyrimidin-4-yl)amino]methylidene]propanedioate

Product 1

HCID 302509Diethyl 2-[[(6-acetamido-2-methylsulfanylpyrimidin-4-yl)amino]methylidene]propanedioate

Procedure

A mixture of EXAMPLE 16A (9.91 g) and acetic anhydride (150 mL) at reflux was stirred for 16 hours, treated with additional acetic anhydride (60 mL), refluxed for 5 hours, cooled and concentrated. The concentrate was dissolved in 9:1 ethanol/ethyl acetate (100 mL), stored at 0° C. for 18 hours, and filtered. 1H NMR (300 MHz, DMSO-d6) δ 10.65 (d, 1H), 8.90 (d, 1H), 7.66 (s, 1H), 4.23 (q, 2H), 4.14 (q, 2H), 2.52 (s, 3H), 2.26 (s, 1H), 2.11 (s, 3H), 1.27 (t, 3H), 1.23 (t, 3H).

Workup

  1. temperaturerefluxed for 5 hours
  2. temperaturecooled
  3. concentrationconcentrated
  4. dissolutionThe concentrate was dissolved in 9:1 ethanol/ethyl acetate (100 mL)
  5. waitstored at 0° C. for 18 hours
  6. filtrationfiltered

Sources & evidence

ORD record
ord-d6508440841545d58cd4d94481e795dd
Source dataset
uspto-grants-2010_06
Patent number
US07737159B2

Reaction notes

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