Hydrochloric Acid → HCID 67527954, compound

HRID 2261823Notes

Reaction equation

HRID 2261823 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([OH:17])[CH:5]=[CH:6][C:7]=1B1OC(C)(C)C(C)(C)O1.[CH3:18][O:19][C:20](=[O:29])[C:21]1[CH:26]=[CH:25][C:24](Br)=[CH:23][C:22]=1[CH3:28].N#N.C([O-])([O-])=O.[Na+].[Na+].Cl>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>[CH3:18][O:19][C:20]([C:21]1[CH:26]=[CH:25][C:24]([C:7]2[CH:6]=[CH:5][C:4]([OH:17])=[CH:3][C:2]=2[CH3:1])=[CH:23][C:22]=1[CH3:28])=[O:29]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 947NitrogenHCID 10340Sodium CarbonateHCID 22031226Methyl 4-bromo-2-methylbenzoateHCID 574432723-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol

Product 1

HCID 67527954HCID 67527954, compoundYield 75.4%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

A solution of 3-methyl-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenol (0.241 g, 1.03 mmol) and 4-bromo-2-methyl-benzoic acid methyl ester (0.236 g, 1.03 mmol) in 1,4-dioxane (20 mL) is evacuated and re-filled with N2 3 times. To this solution, Pd(PPh3)4 (0.010 g) and aqueous Na2CO3 (1.0 mL, 2.0 M) are added. The resulting mixture is heated at 90° C. for 24 hours under N2. The reaction mixture is cooled to room temperature, neutralized with HCl (1.0 M, 3.0 mL), and concentrated. The residue is extracted with ethyl acetate (30 mL×2) and the combined organic layers are dried over sodium sulfate and concentrated. The residue is purified via silica gel chromatography eluting with 25-30% ethyl acetate in hexanes to give the title compound (0.199 g, 75%). 1H NMR (400 MHz, CDCl3): δ 7.95-7.91 (d, 1H), 7.18 (s, 1H), 7.18 (d, 1H), 7.08 (d, 1H), 6.75 (d, 1H), 6.72 (d, 1H), 3.90 (s, 3H), 2.61 (s, 3H).

Workup

  1. temperatureThe reaction mixture is cooled to room temperature
  2. concentrationconcentrated
  3. extractionThe residue is extracted with ethyl acetate (30 mL×2)
  4. dry with materialthe combined organic layers are dried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue is purified via silica gel chromatography
  7. washeluting with 25-30% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-0e567bc274104ccf836caae0a36fe7c5
Source dataset
uspto-grants-2010_12
Patent number
US07846960B2

Reaction notes

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