Potassium Phosphate, Tribasic → 3-((trimethylsilyl)ethynyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one

HRID 1413015Notes

Reaction equation

HRID 1413015 reaction equation
Cl[C:2]1[CH:3]=[CH:4][C:5]2[C:14]3[CH:13]=[C:12]4[CH2:15][CH2:16][CH2:17][C:18](=[O:19])[C:11]4=[CH:10][C:9]=3[O:8][CH2:7][C:6]=2[CH:20]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.[Si:63]([C:67]#[CH:68])([CH3:66])([CH3:65])[CH3:64]>CC#N.CC#N.Cl[Pd]Cl.C(#N)C>[CH3:64][Si:63]([C:67]#[C:68][C:2]1[CH:3]=[CH:4][C:5]2[C:14]3[CH:13]=[C:12]4[CH2:15][CH2:16][CH2:17][C:18](=[O:19])[C:11]4=[CH:10][C:9]=3[O:8][CH2:7][C:6]=2[CH:20]=1)([CH3:66])[CH3:65]

Participants

7

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 66111TrimethylsilylacetyleneHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 696733663-Chloro-10,11-dihydro-5H-benzo(d)naphtho(2,3-b)pyran-8(9H)-one

Product 1

HCID 866883743-((trimethylsilyl)ethynyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-oneYield 33.4%

Reagents, catalysts & solvents 2

HCID 6093782Bis(acetonitrile)dichloropalladiumCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
65 °C

Procedure

A 300 mL flask equipped with an overhead stirrer and a reflux condenser under an atmosphere of nitrogen was charged with 3-chloro-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one (10.0 g, 35.12 mmol), powdered anhydrous tripotassium phosphate (22.4 g, 105.4 mmol), XPhos (1.34 g, 2.81 mmol), and PdCl2(MeCN)2 (364 mg, 1.40 mmol). Acetonitrile (140 mL) was added followed by TMSacetylene (18 mL, 141 mmol). The mixture was heated to 65° C. After 6 h, the reaction was judged complete, and the mixture was cooled to 20° C. The mixture was filtered through a fitted funnel, and the filtercake was washed with acetonitrile. The filtrate was concentrated to about 150 mL under reduced pressure and extracted with heptane (50 mL, 3×100 mL). N-Acetyl cysteine (15 g) was added to the acetonitrile phase, and the mixture was agitated for 5 h at 45° C. The mixture was cooled to ambient temperature, filtered through a fitted funnel, and the filtercake was washed with acetonitrile. The filtrate was concentrated to about 120 mL under reduced pressure. Water (120 mL) was added and the mixture was agitated for 40 minutes at 45° C. and then cooled to ambient temperature. After 30 minutes the mixture was filtered through a fitted funnel to provide 3-((trimethylsilyl)ethynyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one (4.07 g, 33.4% yield) as a yellow solid: 400 MHz 1H NMR (CDCl3) δ 7.65 (d, J=8.1 Hz, 1H), 7.60 (s, 1H), 7.55 (s, 1H), 7.47 (dd, J=8.1, 1.4 Hz, 1H), 7.27 (s, 1H), 5.06 (s, 2H), 2.95 (t, J=6.1 Hz, 2H), 2.67-2.59 (m, 2H), 2.18-2.08 (m, 2H), 0.26 (s, 9H).

Workup

  1. customA 300 mL flask equipped with an overhead stirrer and a reflux condenser under an atmosphere of nitrogen
  2. temperaturethe mixture was cooled to 20° C
  3. filtrationThe mixture was filtered through a fitted funnel
  4. washthe filtercake was washed with acetonitrile
  5. concentrationThe filtrate was concentrated to about 150 mL under reduced pressure
  6. extractionextracted with heptane (50 mL, 3×100 mL)
  7. additionN-Acetyl cysteine (15 g) was added to the acetonitrile phase
  8. temperatureThe mixture was cooled to ambient temperature
  9. filtrationfiltered through a fitted funnel
  10. washthe filtercake was washed with acetonitrile
  11. concentrationThe filtrate was concentrated to about 120 mL under reduced pressure
  12. additionWater (120 mL) was added
  13. stirringthe mixture was agitated for 40 minutes at 45° C.
  14. temperaturecooled to ambient temperature
  15. filtrationAfter 30 minutes the mixture was filtered through a fitted funnel

Sources & evidence

ORD record
ord-bb9af7f5221747e8a0039fd9ded4b23e
Source dataset
uspto-grants-2014_12
Patent number
US08921341B2

Reaction notes

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