Triethylamine → 3-(1-Undecynyl)benzaldehyde

HRID 1900332Notes

Reaction equation

HRID 1900332 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[O:6].[CH:10]#[C:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20].C(N(CC)CC)C>O1CCCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu](I)I>[C:10]([C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[O:6])#[C:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 752491-UndecyneHCID 765833-Bromobenzaldehyde

Product 1

HCID 183730913-(1-Undecynyl)benzaldehydeYield 13.2%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
55 °C

Procedure

A mixture of 3-bromobenzaldehyde (51.8 g), 1-undecyne (48.6 g), bis(triphenylphosphine)palladium(II)chloride (3.37 g), copper iodide (457 mg), and triethylamine (196 ml) in dry tetrahydrofuran (300 ml) was stirred for 4 hrs at 55° C. The reaction mixture was filtered, the filtrate was diluted with ethyl acetate, and the solution was washed with water and brine. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated in vacuo. The residue was chromatographed on 300 g of silica gel (1:4-ethyl acetate:hexane). The appropriate fractions were collected and evaporated. Distillation of a 40-g sample of the residue (81.3 g) gave 9.5 g (13%) of the product, bp 172°-174° C. (0.5 mm mercury).

Workup

  1. filtrationThe reaction mixture was filtered
  2. additionthe filtrate was diluted with ethyl acetate
  3. washthe solution was washed with water and brine
  4. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated in vacuo
  7. customThe residue was chromatographed on 300 g of silica gel (1:4-ethyl acetate:hexane)
  8. customThe appropriate fractions were collected
  9. customevaporated
  10. distillationDistillation of a 40-g sample of the residue (81.3 g)

Sources & evidence

ORD record
ord-3cf94483604b4e31898a66b698f0810d
Source dataset
uspto-grants-1996_11
Patent number
US05574164

Reaction notes

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