Hydrochloric Acid → HCID 68481886, compound

HRID 1470893Notes

Reaction equation

HRID 1470893 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1B(O)O.Br[C:13]1[CH:14]=[CH:15][C:16]([CH2:32][CH3:33])=[C:17]([CH:19]2[C:24](=[O:25])[C:23]([CH3:27])([CH3:26])[C:22](=[O:28])[C:21]([CH3:30])([CH3:29])[C:20]2=[O:31])[CH:18]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].Cl>ClCCl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Na].[Na].[Na].S(C1C=C(P(C2C=CC=C(S(O)(=O)=O)C=2)C2C=CC=C(S(O)(=O)=O)C=2)C=CC=1)(O)(=O)=O.O>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:13]1[CH:14]=[CH:15][C:16]([CH2:32][CH3:33])=[C:17]([CH:19]2[C:20](=[O:31])[C:21]([CH3:29])([CH3:30])[C:22](=[O:28])[C:23]([CH3:27])([CH3:26])[C:24]2=[O:25])[CH:18]=1

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 62657Potassium Phosphate, Tribasic2×HCID 2734659(2,4-Dichlorophenyl)boronic acid2×HCID 684845366-(5-Bromo-2-ethylphenyl)-2,2,4,4-tetramethylcyclohexane-1,3,5-trione

Product 1

HCID 68481886HCID 68481886, compoundYield 37.4%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 86657037CID 86657037CatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
160 °C

Procedure

To a microwave vial is added palladium(II) acetate (1.1 mg, 0.0049 mmol), tris(3-sulfophenyl)phosphine trisodium salt (5.1 mg, 0.0099 mmol), 2,4-dichlorophenylboronic acid (0.099 g, 0.5 mmol), 6-(5-bromo-2-ethylphenyl)-2,2,4,4-tetramethylcyclohexane-1,3,5-trione (0.19 g, 0.5 mmol) and potassium phosphate (0.53 g, 2.5 mmol). Degassed water (0.75 ml) is next added (washing-down any solids from the slides of the vial), followed by stirring for 5 minutes and flushing with argon. This mixture is then heated at 160° C. under microwave irradiation for 15 minutes. A further quantity of 2,4-dichlorophenylboronic acid (0.099 g, 0.5 mmol) and potassium phosphate (0.095 g, 0.5 mmol) are added, the reaction mixture again blanketed under an atmosphere of argon, and the mixture is heated at 160° C. for a further 15 minutes. After cooling to room temperature the reaction mixture is diluted with dichloromethane (5 ml) and acidified with 2M aqueous hydrochloric acid. The organic phase is separated, dried over anhydrous magnesium sulfate, and filtered through a plug of silica gel. The filtrate is concentrated under reduced pressure and the residue is dissolved in N,N-dimethylformamide (approximately 1 ml) and purified by preparative reverse phase HPLC to afford 6-(2′,4′-dichloro-4-ethylbiphenyl-3-yl)-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione as a colourless oil (80.6 mg).

Workup

  1. washwashing-down any solids from the slides of the vial),
  2. customflushing with argon
  3. temperaturethe mixture is heated at 160° C. for a further 15 minutes
  4. temperatureAfter cooling to room temperature the reaction mixture
  5. customThe organic phase is separated
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered through a plug of silica gel
  8. concentrationThe filtrate is concentrated under reduced pressure
  9. dissolutionthe residue is dissolved in N,N-dimethylformamide (approximately 1 ml)
  10. custompurified by preparative reverse phase HPLC

Sources & evidence

ORD record
ord-e86fa4106ae64c74952452bcbdbf4074
Source dataset
uspto-grants-2015_04
Patent number
US09006429B2

Reaction notes

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