Stannane, tributyl(1-ethoxyethenyl)- → HCID 66832777, compound

HRID 1914522Notes

Reaction equation

HRID 1914522 reaction equation
Cl[C:2]1[CH:7]=[C:6]([C:8]2[CH:13]=[CH:12][C:11]([C:14]([F:17])([F:16])[F:15])=[CH:10][CH:9]=2)[N:5]=[CH:4][N:3]=1.C([Sn](CCCC)(CCCC)[C:23]([O:25]CC)=[CH2:24])CCC>CN(C=O)C.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>[F:15][C:14]([F:17])([F:16])[C:11]1[CH:12]=[CH:13][C:8]([C:6]2[N:5]=[CH:4][N:3]=[C:2]([C:23](=[O:25])[CH3:24])[CH:7]=2)=[CH:9][CH:10]=1

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 167478374-Chloro-6-(4-(trifluoromethyl)phenyl)pyrimidine

Product 1

HCID 66832777HCID 66832777, compoundYield 101.7%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

In a screw top flask 4-chloro-6-(4-trifluoromethyl-phenyl)-pyrimidine (1.6 g, 6.1 mmol), tributyl-(1-ethoxy-vinyl)-stannane (1.8 g, 4.8 mmol) and trans-dichlorobis(triphenylphosphine)palladium(II) (212 mg, 0.30 mmol) were combined in DMF (10 mL). Under nitrogen the flask was sealed and heated to 80° C. for 12 hours. The reaction mixture was cooled to rt, concentrated, and purified by flash column chromatography using ethyl acetate-hexanes (0%-20%) to provide the desired product as a clear oil (1.3 g, 73%). MS (ESI): mass calcd. for C15H13F3N2O, 294.0; m/z found 295.1 [M+H]+. The resulting clear oil was diluted with THF (60 mL) and 2N HCl (10 mL) and stirred. After 12 h, the resulting solution was partitioned between saturated aqueous sodium bicarbonate (50 mL) and ethyl acetate (50 mL). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (2×50 mL). The organic phases were combined, dried with Na2SO4, filtered, and concentrated. The resulting residue was purified by flash column chromatography using ethyl acetate-hexanes (0%-20%) to provide the desired product as a clear oil (1.1 g, 93%). MS (ESI): mass calcd. for C13H9F3N2O, 266.0; m/z found 267.1 [M+H]+. 1H NMR (CDCl3) δ 9.45 (d, J=1.3 Hz, 1H), 8.37 (d, J=1.3 Hz, 1H), 8.31 (d, J=8.1 Hz, 2H), 7.82 (d, J=8.2 Hz, 2H), 2.81 (s, 3H).

Workup

  1. customUnder nitrogen the flask was sealed
  2. temperatureThe reaction mixture was cooled to rt
  3. concentrationconcentrated
  4. custompurified by flash column chromatography

Sources & evidence

ORD record
ord-74783d898fea4af4b6a21f45626e2730
Source dataset
uspto-grants-2013_12
Patent number
US08614201B2

Reaction notes

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