Ethyl chloroacetate → HCID 53893019, compound

HRID 1578818Notes

Reaction equation

HRID 1578818 reaction equation
[CH2:1]([CH2:11]/[C:12](/[CH3:24])=[CH:13]/[CH2:14][CH2:15]/[C:16](/[CH3:23])=[CH:17]/[CH2:18][CH2:19]C(=O)C)/[CH:2]=[C:3](/[CH2:5][CH2:6][CH:7]=[C:8]([CH3:10])[CH3:9])\[CH3:4].ClCC([O:29][CH2:30][CH3:31])=O.[O-][CH2:33]C.[Na+].[OH-].[K+]>CO.O>[CH3:33][CH:31]([CH2:19][CH2:18][CH:17]=[C:16]([CH3:23])[CH2:15][CH2:14][CH:13]=[C:12]([CH3:24])[CH2:11][CH2:1][CH:2]=[C:3]([CH3:4])[CH2:5][CH2:6][CH:7]=[C:8]([CH3:10])[CH3:9])[CH:30]=[O:29]

Participants

7

Reactant 4

HCID 7751Ethyl chloroacetateHCID 14797Potassium HydroxideHCID 2723922Sodium ethoxideHCID 5282199(5E,9E,13E)-6,10,14,18-Tetramethyl-5,9,13,17-nonadecatetraen-2-one

Product 1

HCID 53893019HCID 53893019, compoundYield 70.9%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
150 °C

Procedure

To a mixture of geranylgeranylacetone (32.2 g) and ethyl monochloroacetate (17.2 g), sodium ethoxide (8.85 g) is portionwise added at -10°C in nitrogen stream. The resultant mixture is stirred for 7 hours, a solution of potassium hydroxide (99 g) in methanol (560 ml) is added thereto, stirring is continued for 3 hours and then the resulting mixture is allowed to stand overnight. Then, the reaction mixture is poured into water, washed with petroleum ether, neutralized with acetic acid and extracted with ether. The ether extract is washed with water, dried and evaporated. The residue is heated at 150°C for 30 minutes for decarboxylation. The resulting crude produce (31 g) is purified by chromatography on silica gel (300 g) using benzene to give 2,6,10,14,18-pentamethyl-5,9,13,17-nonadecatetraenal (23.8 g). IR: 2680, 1720 cm-1 (CHO).

Workup

  1. additionis portionwise added at -10°C in nitrogen stream
  2. waitto stand overnight
  3. washwashed with petroleum ether
  4. extractionextracted with ether
  5. extractionThe ether extract
  6. washis washed with water
  7. customdried
  8. customevaporated
  9. customThe resulting crude produce (31 g)
  10. customis purified by chromatography on silica gel (300 g)

Sources & evidence

ORD record
ord-e1c70bef2cfa4bf98b32ebc4d1016c3f
Source dataset
uspto-grants-1976_02
Patent number
US03939202

Reaction notes

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