Dichloroacetyl chloride → 7,7-Dichloro-4-(5-methoxyheptyl)bicyclo[3.2.0]heptan-6-one

HRID 1789520Notes

Reaction equation

HRID 1789520 reaction equation
[CH3:1][O:2][CH:3]([CH2:13][CH3:14])[CH2:4][CH2:5][CH2:6][CH2:7][CH:8]1[CH2:12][CH2:11][CH:10]=[CH:9]1.[Cl:15][CH:16]([Cl:20])[C:17](Cl)=[O:18].[CH2:21](N(CC)CC)C.[CH3:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33]>>[Cl:15][C:16]1([Cl:20])[C:17](=[O:18])[CH:12]2[CH:11]1[CH2:10][CH2:9][CH:8]2[CH2:7][CH2:6][CH2:5][CH2:4][CH:3]([O:2][CH3:1])[CH2:13][CH3:14].[Cl:15][C:16]1([Cl:20])[C:29]2([CH:28]([CH2:5][CH2:4][CH:3]([O:2][CH3:1])[CH2:13][CH3:14])[CH3:21])[CH:30]([CH2:31][CH2:32][CH2:33]2)[C:17]1=[O:18].[Cl:15][C:16]1([Cl:20])[CH:12]2[CH:11]([CH2:10][CH2:9][CH:8]2[CH2:7][CH2:6][CH2:5][CH2:4][CH:3]([O:2][CH3:1])[CH2:13][CH3:14])[C:17]1=[O:18]

Participants

7

Reactant 4

HCID 6593Dichloroacetyl chlorideHCID 8058Hexane2×HCID 8471TriethylamineHCID 139240423-(5-Methoxyheptyl)cyclopent-1-ene

Product 3

HCID 139240447,7-Dichloro-4-(5-methoxyheptyl)bicyclo[3.2.0]heptan-6-oneHCID 139240487,7-Dichloro-2-(5-methoxyheptyl)bicyclo[3.2.0]heptan-6-oneHCID 201884187,7-Dichloro-(5-methoxyhept-2-yl)bicyclo[3.2.0]heptan-6-one

Procedure

To a 1,000 ml three-necked, round-bottomed flask, equipped with a reflux condenser containing 3-(5-methoxyhept-1-yl)cyclopentene {3-(5-methoxyheptyl)cyclopentene} (15.0 g, 0.076 moles) in 300 ml of hexane, freshly distilled dichloroacetyl chloride (35.1 g, 0.240 moles) is added and the solution is stirred by a mechanical stirrer and heated to reflux. Triethylamine (25.2 g, 0.249 moles), dissolved in 200 ml hexane, is added dropwise and the refluxing solution allowed to stir for 4 hours. The solvent is removed and then the residue is distilled and applied to a silica gel chromatography column of 4.5 cm diameter in a 4:1 hexane-ether solvent mixture. The product is eluted using a 4:1 hexane-ether solvent system. The fractions are monitored using vapor phase chromatography. The solvent is removed under vacuum. 6,6-Dichloro-2-(5-methoxyhept-1-yl)bicyclo[3.2.0]heptan-7-one {7,7-dichloro-4-(5-methoxyheptyl)bicyclo[3.2.0]heptan-6-one} and a smaller amount of 7,7-dichloro-(5-methoxyhept-2-yl)bicyclo[3.2.0]heptan-6-one {7,7-dichloro-2-(5-methoxyheptyl)bicyclo[3.2.0]heptan-6-one} were obtained in mainly the alpha form .

Workup

  1. customTo a 1,000 ml three-necked, round-bottomed flask, equipped with a reflux condenser
  2. temperatureheated to reflux
  3. additionis added dropwise
  4. stirringto stir for 4 hours
  5. customThe solvent is removed
  6. distillationthe residue is distilled
  7. washThe product is eluted
  8. customThe solvent is removed under vacuum

Sources & evidence

ORD record
ord-c21ededa198241be8bfe0a31117ca8c5
Source dataset
uspto-grants-1987_08
Patent number
US04689349

Reaction notes

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