Potassium Carbonate → HCID 59590525, compound

HRID 1804527Notes

Reaction equation

HRID 1804527 reaction equation
[Cl:1][C:2]1[N:3]=[C:4](Cl)[C:5]2[S:10][CH:9]=[CH:8][C:6]=2[N:7]=1.C([O-])([O-])=O.[K+].[K+].[CH2:18]([O:20][C:21]([Sn](CCCC)(CCCC)CCCC)=[CH2:22])[CH3:19]>O1CCOCC1.O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:1][C:2]1[N:3]=[C:4]([C:18]([O:20][CH2:21][CH3:22])=[CH2:19])[C:5]2[S:10][CH:9]=[CH:8][C:6]=2[N:7]=1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 127128322,4-Dichlorothieno[3,2-d]pyrimidine

Product 1

HCID 59590525HCID 59590525, compoundYield 65%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
100 °C

Procedure

To a solution of Example 2 (3.0 g, 14.6 mmol) in 1,4-dioxane (200 mL) was added a solution of K2CO3 (4.0 g, 29.3 mmol) in water (40 mL). The almost clear solution was placed under nitrogen atmosphere and (1-Ethoxyvinyl)-tributylstannane (5.0 mL, 14.6 mmol) and PdCl2(PPh3)2 (500 mg, 0.731 mmol). The mixture was heated to 100° C. and stirred at 100° C. for 30 min under nitrogen atmosphere. After cooling to room temp. the 1,4-dioxane was removed i. vac. The residue was re-dissolved in DCM (100 mL) and water (50 mL) and transferred to a separating funnel. The aqueous layer was extracted with DCM (30 mL), the combined organic layers were washed with water (50 mL) and sat. brine (30 mL), dried over Na2SO4 and evaporated to dryness i. vac. The residue was purified by flash column chromatography (50 g SiO2 Isolute® pre-wetted with 1CV DCM) eluting with neat DCM collecting 12 mL fractions. Desired product eluted in fractions 10 to 20 with Rf=0.31 (DCM). By-products eluted in fractions 6 to 9 (Rf=0.59 in DCM) and fractions 21-31 ((Rf=0.14 in DCM). Fractions 10 to 20 were combined and evaporated to dryness i. vac. providing 2.28 g (65% yield) 2-chloro-4-(1′-ethoxy-vinyl)-thieno[3,2-d]pyrimidine as yellow powder of 95% purity.

Workup

  1. customwas removed i
  2. dissolutionThe residue was re-dissolved in DCM (100 mL)
  3. customwater (50 mL) and transferred to a separating funnel
  4. extractionThe aqueous layer was extracted with DCM (30 mL)
  5. washthe combined organic layers were washed with water (50 mL) and sat. brine (30 mL)
  6. dry with materialdried over Na2SO4
  7. customevaporated to dryness i
  8. customThe residue was purified by flash column chromatography (50 g SiO2 Isolute® pre-wetted with 1CV DCM)
  9. washeluting with neat DCM collecting 12 mL fractions
  10. washDesired product eluted in fractions 10 to 20 with Rf=0.31 (DCM)
  11. washBy-products eluted in fractions 6 to 9 (Rf=0.59 in DCM) and fractions 21-31 ((Rf=0.14 in DCM)
  12. customevaporated to dryness i

Sources & evidence

ORD record
ord-f660aa2664ae4b3b90720ea42f0cf912
Source dataset
uspto-grants-2013_01
Patent number
US08354415B2

Reaction notes

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