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Ethyl Acetate → Methyl 4-tert-butyl-3-(prop-1-en-2-yl)benzoate

HRID 1675253
Notes
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Reaction equation

HRID 1675253 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]=1[C:12]([CH3:15])([CH3:14])[CH3:13])[C:5]([O:7][CH3:8])=[O:6].[C:16](B1OC(C)(C)C(C)(C)O1)([CH3:18])=[CH2:17].C(=O)([O-])[O-].[K+].[K+].CCOC(C)=O>C1(C)C=CC=CC=1.[Cl-].[Na+].O.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>[C:12]([C:11]1[CH:10]=[CH:9][C:4]([C:5]([O:7][CH3:8])=[O:6])=[CH:3][C:2]=1[C:16]([CH3:18])=[CH2:17])([CH3:15])([CH3:14])[CH3:13]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolaneHCID 11959028Methyl 3-bromo-4-(tert-butyl)benzoate

Product 1

HCID 59300653Methyl 4-tert-butyl-3-(prop-1-en-2-yl)benzoateYield 88%

Reagents, catalysts & solvents 3

HCID 178418397
HCID 178418397, compound
Catalyst
HCID 1140TolueneSolvent
HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
100 °C

Procedure

Methyl 3-bromo-4-tert-butylbenzoate (500 mg, 1.80 mmol, prepared according to the procedure of Hambley T. W. et al. Aust. J. Chem., 1990, 43, 807-814) and commercially available isopropenylboronic acid pinacol ester (0.693 mL, 3.6 mmol) were suspended in toluene (7 mL). Potassium carbonate (765 mg, 5.5 mmol) was added followed by Pd(PPh3)4 (213 mg, 0.180 mmol). The resulting mixture was heated to 100° C. and stirred for 24 hours. After cooling to room temperature, the mixture was treated with EtOAc (5 mL) and brine (5 mL). The organic layer was separated, washed twice with brine, dried with MgSO4, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (0-10% EtOAc/hexane) to give 26.2 (378 mg, 88%) as a clear oil.

Workup

  1. temperatureAfter cooling to room temperature
  2. customThe organic layer was separated
  3. washwashed twice with brine
  4. dry with materialdried with MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash chromatography on silica gel (0-10% EtOAc/hexane)

Sources & evidence

ORD record
ord-ef27c8ded03542fa8bbc083f3ee10957
Source dataset
uspto-grants-2011_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08003648B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes