3-Bromobenzoic acid → HCID 66588027, compound

HRID 1408127Notes

Reaction equation

HRID 1408127 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6].[CH2:11]([OH:15])[CH2:12][C:13]#[CH:14]>C(N(CC)CC)C.CN(C)C=O.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[OH:15][CH2:11][CH2:12][C:13]#[C:14][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6]

Participants

6

Reactant 2

HCID 114563-Bromobenzoic acidHCID 135663-Butyn-1-OL

Product 1

HCID 66588027HCID 66588027, compoundYield 105.7%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 22056947triethylamine N,N-dimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

Into a 500-mL round bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 3-bromobenzoic acid (10 g, 49.75 mmol, 1.00 equiv) in triethylamine/N,N-dimethylformamide (100/20 mL), but-3-yn-1-ol (6.98 g, 99.57 mmol, 2.00 equiv), copper(I) iodide (1.90 g, 9.97 mmol, 0.20 equiv), Pd(PPh3)2Cl2 (6.98 g, 9.94 mmol, 0.20 equiv). The resulting solution was stirred overnight at 80° C. The resulting mixture was concentrated under vacuum. The resulting solution was diluted with 100 mL of water. The pH value of the solution was adjusted to 11-12 with sodium hydroxide (1 mol/L). The resulting solution was extracted with 3×300 mL of dichloromethane and the aqueous layers combined. The solution was adjusted to pH 1-2 with hydrochloric acid (1 mol/L). The resulting solution was extracted with 5×300 mL of dichloromethane and the organic layers combined, dried over sodium sulfate, and concentrated under vacuum. This resulted in 10 g crude product as brown oil.

Workup

  1. customInto a 500-mL round bottom flask purged
  2. temperaturemaintained with an inert atmosphere of nitrogen
  3. concentrationThe resulting mixture was concentrated under vacuum
  4. additionThe resulting solution was diluted with 100 mL of water
  5. extractionThe resulting solution was extracted with 3×300 mL of dichloromethane
  6. extractionThe resulting solution was extracted with 5×300 mL of dichloromethane
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-ae31d2f66e5c402c982f2f39073fc281
Source dataset
uspto-grants-2014_12
Patent number
US08916569B2

Reaction notes

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