2,4-Dibenzyloxy-6-(2-dimethylaminovinyl)-5-nitropyrimidine → 5H-Pyrrolo3,2-dpyrimidine, 2,4-bis(phenylmethoxy)-

HRID 57784Notes

Reaction equation

HRID 57784 reaction equation
[CH2:1]([O:8][C:9]1[N:14]=[C:13]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:12]([N+:23]([O-])=O)=[C:11]([CH:26]=[CH:27]N(C)C)[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>CC(O)=O.C(Cl)Cl.[Zn]>[CH2:1]([O:8][C:9]1[N:14]=[C:13]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:12]2[NH:23][CH:27]=[CH:26][C:11]=2[N:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 1

HCID 541062272,4-Dibenzyloxy-6-(2-dimethylaminovinyl)-5-nitropyrimidine

Product 1

HCID 109255905H-Pyrrolo3,2-dpyrimidine, 2,4-bis(phenylmethoxy)-Yield 90%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 176Acetic AcidSolventHCID 6344DichloromethaneSolvent

Procedure

To a suspension of 2,4-Bis-O-Benzyl-5-nitro-6-β-dimethylaminovinyl pyrimidine 14 (2 g, 4.9 mmol) in AcOH (40 ml), Zn (4 g) was added in lot of 2 g with an interval of 4 hrs. The reaction mixture was stirred overnight at room temperature during which a dark yellow suspension became pale yellow suspension. The reaction mixture was filtered and the filtrate concentrated in vacuo to obtain syrup which was dissolved in CH2Cl2 then washed with saturated aq. NaHCO3 followed by brine. The organic phase was dried over MgSO4 and loaded on silica. The product 15 was purified using column chromatography eluting with 4:1 and 1:1 hexanes/EtOAc to obtain product as pale-yellow solid (1.45 g, 90%). Rf 0.3 in 1:3 hexanes/EtOAc. 1H NMR (400 MHz, CDCl3): δ 5.47 (s, 2H), 5.54 (s, 1H), 6.50-6.51 (dd, 1H, J=1.84, 2.28), 7.29-7.38 (m, 7H), 7.43-7.45 (m, 2H), 7.52-7.53 (m, 2H), 8.41 (br s, 1H, NH). 13C NMR (400 MHz, CDCl3): δ 68.3, 69.0, 102.6, 111.9, 127.8, 128.3, 128.4, 128.5, 128.6, 128.7, 128.8, 136.1, 137.3, 151.8, 156.79, 159.7. FAB-MS for C20H17N3O2 calculated [M+H]+ 332.1394. found 332.1398.

Workup

  1. additionwas added in lot of 2 g with an interval of 4 hrs
  2. filtrationThe reaction mixture was filtered
  3. concentrationthe filtrate concentrated in vacuo
  4. customto obtain syrup which
  5. washthen washed with saturated aq. NaHCO3
  6. dry with materialThe organic phase was dried over MgSO4
  7. customThe product 15 was purified
  8. washeluting with 4:1 and 1:1 hexanes/EtOAc

Sources & evidence

ORD record
ord-e39ed5e3e0144488af9bba3b4987c15b
Source dataset
uspto-grants-2016_09
Patent number
US09434742B1

Reaction notes

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