Benzene → 4,6-Dichloro-5-(1,3-dioxolan-2-yl)pyrimidine

HRID 1804534Notes

Reaction equation

HRID 1804534 reaction equation
[CH:1]1[CH:6]=CC=CC=1.[Cl:7][C:8]1[C:13]([CH:14]=[O:15])=[C:12]([Cl:16])[N:11]=[CH:10][N:9]=1.O.C1(C)C=CC(S(O)(=O)=[O:25])=CC=1.C([O-])(O)=O.[Na+]>O.C(O)CO>[Cl:7][C:8]1[C:13]([CH:14]2[O:25][CH2:1][CH2:6][O:15]2)=[C:12]([Cl:16])[N:11]=[CH:10][N:9]=1

Participants

7

Reactant 4

HCID 241BenzeneHCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 8196914,6-Dichloro-5-pyrimidinecarbaldehyde

Product 1

HCID 595944404,6-Dichloro-5-(1,3-dioxolan-2-yl)pyrimidine

Reagents, catalysts & solvents 2

HCID 174Ethylene GlycolSolventHCID 962WaterSolvent

Procedure

A mixture of 300 ml benzene and 8.2 ml ethylene glycol was heated to reflux and 100 ml solution was distilled off. To the hot solution was added 4,6-dichloro-5-pyrimidinecarbaldehyde (Bionet, 8.6 g, 48.6 mmol) and p-toluenesulfonic acid monohydrate (Aldrich, 150 mg, 0.8 mmol). The mixture was returned to reflux and water was removed via Dean-Stark trap over 3 h. After cooling, the solvents were removed under vacuum to yield a dry, yellow solid. The solids were slurried in H2O (30 ml)/saturated NaHCO3 solution (30 ml). White solid 107 was filtered off and dried under vacuum (8.8 g, 82%). Compound 107: mp 108-110° C.; MS (ES+ calculated: 221.04; found: 221/223 M+H). 1H NMR (400 MHz, DMSO-d6) δ 8.95 (s, 1H), 6.26 (s, 1H), 4.23 (m, 2H), 4.05 (m, 2H).

Workup

  1. temperaturewas heated
  2. temperatureto reflux
  3. distillation100 ml solution was distilled off
  4. temperatureto reflux
  5. customwater was removed via Dean-Stark trap over 3 h
  6. temperatureAfter cooling
  7. customthe solvents were removed under vacuum
  8. customto yield a dry, yellow solid
  9. filtrationWhite solid 107 was filtered off
  10. customdried under vacuum (8.8 g, 82%)

Sources & evidence

ORD record
ord-3883ee95e7354900909544e877e865d6
Source dataset
uspto-grants-2013_01
Patent number
US08354414B2

Reaction notes

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