Potassium Fluoride → 1,1'-(4H-thieno[3,2-c]chromene-2,7-diyl)diethanone

HRID 1521795Notes

Reaction equation

HRID 1521795 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[C:6]3[S:14][C:13]([C:15](=[O:17])[CH3:16])=[CH:12][C:7]=3[CH2:8][O:9][C:10]=2[CH:11]=1.C([Sn](CCCC)(CCCC)[C:23]([O:25]CC)=[CH2:24])CCC.[F-].[K+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[S:14]1[C:6]2[C:5]3[CH:4]=[CH:3][C:2]([C:23](=[O:25])[CH3:24])=[CH:11][C:10]=3[O:9][CH2:8][C:7]=2[CH:12]=[C:13]1[C:15](=[O:17])[CH3:16]

Participants

7

Reactant 3

HCID 522689Potassium FluorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 897389921-(7-bromo-4H-thieno[3,2-c]chromen-2-yl)ethanone

Product 1

HCID 897392211,1'-(4H-thieno[3,2-c]chromene-2,7-diyl)diethanoneYield 93.2%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 178418807HCID 178418807, compoundCatalystHCID 312751,4-DioxaneSolvent2×

Procedure

A solution of 1-(7-bromo-4H-thieno[3,2-c]chromen-2-yl)ethanone (1b) (14 g, 45.3 mmol) in 300 ml of anhydrous dioxane was degassed by passing nitrogen gas for 45 min. Tributyl(1-ethoxyvinyl)stannane (16.35 g, 45.3 mmol) was added to it followed by Pd(PPh3)4 (4.19 g, 3.62 mmol) and PdCl2(dppf)-CH2Cl2 adduct (2.65 g, 3.62 mmol) and the solution was heated at 90 OC for overnight. After cooling, the volume of dioxane was reduced, and a saturated solution of KF was added to it and stirred for 15 min., after which the mixture was passed through a pad of celite and washed with ethyl acetate. The combined filtrate was stirred with 4N HCl solution for 1 h and the organic layer was dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography to obtain the diacetyl compound (1c) (11.5 g, 68%). m/z 272.9 (M+H)+.

Workup

  1. customfor 45 min
  2. temperaturethe solution was heated at 90 OC for overnight
  3. temperatureAfter cooling
  4. washwashed with ethyl acetate
  5. stirringThe combined filtrate was stirred with 4N HCl solution for 1 h
  6. dry with materialthe organic layer was dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-193d7f7582db42dc91f950281941d8e7
Source dataset
uspto-grants-2015_07
Patent number
US09073942B2

Reaction notes

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