Diethyl Ether → 8-Chloro-1,2,3,4-tetrahydronaphthalen-2-one

HRID 863472Notes

Reaction equation

HRID 863472 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][C:9](Cl)=[O:10].C(=O)=O.[CH3:15][C:16](C)=O.C(OCC)C>ClCCl.CCCCCC>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]2[C:3]=1[CH2:8][C:9](=[O:10])[CH2:16][CH2:15]2

Participants

6

Reactant 3

HCID 3283Diethyl EtherHCID 182669Acetyl chloride, 2-(2-chlorophenyl)-HCID 18522661Acetone cardice

Product 1

HCID 46232698-Chloro-1,2,3,4-tetrahydronaphthalen-2-one

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
5 °C

Procedure

To a slurry of 46.5 gm (0.348 mole) AlC3 in 400 mL dichloromethane at -78° C. was added a solution of 32.76 gm (0.174 mole) of the previously prepared o-chlorophenylacetyl chloride in 100 mL dichloromethane dropwise over 1 hour. The dry ice/acetone bath then was replaced with an ice/water bath and ethylene was bubbled into the reaction mixture during which time the temperature rose to 15° C. The ethylene addition was discontinued at the end of the exotherm and the reaction mixture was stirred at about 5° C. for 4 hours. Ice was then added to the reaction mixture to destroy aluminum complexes. Upon termination of the exotherm, the reaction mixture was diluted with 500 mL of water and stirred vigorously until all solids had dissolved. The phases were separated and the organic phase was washed with 3×400 mL 1N hydrochloric acid and 2×400 mL saturated aqueous sodium bicarbonate. The remaining organic phase was then dried over sodium sulfate and concentrated in vacuo to give a pale orange residue. The residue was dissolved in 1:1 hexane:diethyl ether and was poured over a flash silica column which was then eluted with 1:1 hexane:diethyl ether to give a light yellow residue which was crystallized from 4:1 hexane:diethyl ether to give 10.55 gm of the title compound.

Workup

  1. customethylene was bubbled into the reaction mixture during which time the temperature
  2. customrose to 15° C
  3. additionThe ethylene addition
  4. additionIce was then added to the reaction mixture
  5. customto destroy aluminum complexes
  6. additionUpon termination of the exotherm, the reaction mixture was diluted with 500 mL of water
  7. stirringstirred vigorously until all solids
  8. dissolutionhad dissolved
  9. customThe phases were separated
  10. washthe organic phase was washed with 3×400 mL 1N hydrochloric acid and 2×400 mL saturated aqueous sodium bicarbonate
  11. dry with materialThe remaining organic phase was then dried over sodium sulfate
  12. concentrationconcentrated in vacuo
  13. customto give a pale orange residue
  14. washwas then eluted with 1:1 hexane
  15. customdiethyl ether to give a light yellow residue which
  16. customwas crystallized from 4:1 hexane

Sources & evidence

ORD record
ord-9e377ba3c156428087c2cc434e2f0e2d
Source dataset
uspto-grants-1998_02
Patent number
US05721252

Reaction notes

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