Chloride → 3(2-Propynyl)benzaldehyde ethylene acetal

HRID 1981910Notes

Reaction equation

HRID 1981910 reaction equation
II.[CH2:3]1[O:14][CH:6]([C:7]2[CH:12]=[CH:11][CH:10]=[C:9](Br)[CH:8]=2)[O:5][CH2:4]1.CO[CH:17]=[C:18]=[CH2:19].[Cl-]>C1COCC1.[Cu]Cl>[CH2:3]1[O:14][CH:6]([C:7]2[CH:12]=[CH:11][CH:10]=[C:9]([CH2:19][C:18]#[CH:17])[CH:8]=2)[O:5][CH2:4]1

Participants

7

Reactant 4

HCID 312ChlorideHCID 807IodineHCID 873062-(3-Bromophenyl)-1,3-dioxolaneHCID 1394031-Methoxypropa-1,2-diene

Product 1

HCID 212828573(2-Propynyl)benzaldehyde ethylene acetal

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
20 °C

Procedure

Dry Mg (0.74 g) under dry N2 in a flask is covered with THF (10 ml) and a crystal of I2 added. 5 ml of a solution of 3-bromobenzaldehyde ethylene acetal (7.0 g) in THF (30 ml) is added and kept until it becomes warm, when it is cooled to 15°, and the remainder of the acetal solution added over 15 minutes, then stirred for an additional 1 hour. A mixture of methoxyallene (2.45 g), copper (1)chloride (0.30 g) and THF (30 ml) is cooled to -20°. The above Grignard solution (under moisture excluding conditions) is then added to this solution during 5 minutes, and allowed to warm to 20° C. with stirring over 30 minutes. Saturated aqueous ammnium chloride is added and the product is extracted with ether. The ether layer is washed with water, dried (MgSO4) and the residue distilled in vacuo. Yield 4.3 g (75%) 89°-96° (0.03 m Hg), nD20 1.5422.

Workup

  1. temperaturebecomes warm
  2. temperaturewhen it is cooled to 15°
  3. temperatureis cooled to -20°
  4. additionThe above Grignard solution (under moisture excluding conditions) is then added to this solution during 5 minutes
  5. stirringwith stirring over 30 minutes
  6. extractionthe product is extracted with ether
  7. washThe ether layer is washed with water
  8. dry with materialdried (MgSO4)
  9. distillationthe residue distilled in vacuo
  10. customYield 4.3 g (75%) 89°-96° (0.03 m Hg)

Sources & evidence

ORD record
ord-80d5428756d94e04aea1cbb298067e4d
Source dataset
uspto-grants-1986_06
Patent number
US04594355

Reaction notes

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