Iodine → 3(2-Propynyl)benzaldehyde ethylene acetal

HRID 414129

Reaction equation

HRID 414129 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-].[NH4+]>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 807IodineHCID 25517Ammonium ChlorideHCID 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×

Procedure

Dry Mg (0.74 g) under dry N2 in a flask is covered with THF (10 ml) and a crystal 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° with stirring over 30 minutes. Saturated aqueous ammonium 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. temperatureto warm to 20°
  6. stirringwith stirring over 30 minutes
  7. extractionthe product is extracted with ether
  8. washThe ether layer is washed with water
  9. dry with materialdried (MgSO4)
  10. distillationthe residue distilled in vacuo
  11. customYield 4.3 g (75%) 89°-96° (0.03 m Hg)

Sources & evidence

ORD record
ord-e211f82262d5466591bb47f9cc3c9d80
Source dataset
uspto-grants-1988_12
Patent number
US04789754

Linked notes

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