Phosphorus pentachloride → Methyl 1-chloro-6-methoxy-2-naphthaleneacetate

HRID 1284376Notes

Reaction equation

HRID 1284376 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[C:9](=O)[CH:8]([CH2:14][C:15]([O:17][CH3:18])=[O:16])[CH2:7][CH2:6]2.P(Cl)(Cl)(Cl)(Cl)[Cl:20]>C1C=CC=CC=1>[Cl:20][C:9]1[C:10]2[C:5](=[CH:4][C:3]([O:2][CH3:1])=[CH:12][CH:11]=2)[CH:6]=[CH:7][C:8]=1[CH2:14][C:15]([O:17][CH3:18])=[O:16]

Participants

4

Reactant 2

HCID 24819Phosphorus pentachlorideHCID 13934507Methyl 1,2,3,4-tetrahydro-6-methoxy-1-oxo-2-naphthaleneacetate

Product 1

HCID 54157069Methyl 1-chloro-6-methoxy-2-naphthaleneacetate

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a mixture of 25 g. of 6-methoxy-2-(methoxycarbonylmethyl)-1-tetralone and 150 ml. of benzene, 21 g. of phosphorus pentachloride are slowly added. After the addition, the chlorination mixture is allowed to stand for an additional 5 hours; then it is added to 500 g. of ice and extracted with xylene. The extracts, containing methyl 1-chloro-6-methoxy-3,4-dihydro-2-naphthylacetate, are combined, washed with water to neutrality and dried over sodium sulfate; the 23 g. of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone are added and the resulting mixture is refluxed for 5 hours. The dehydrogenation mixture is cooled, filtered, and evaporated. The residue is taken up in acetone and chromatographed on alumina and evaporated to yield methyl 1-chloro-6-methoxy-2-naphthylacetate.

Workup

  1. additionTo a mixture of 25 g
  2. additionAfter the addition
  3. additionthen it is added to 500 g
  4. extractionof ice and extracted with xylene
  5. additionThe extracts, containing methyl 1-chloro-6-methoxy-3,4-dihydro-2-naphthylacetate
  6. washwashed with water to neutrality
  7. dry with materialdried over sodium sulfate
  8. additionof 2,3-dichloro-5,6-dicyano-1,4-benzoquinone are added
  9. temperaturethe resulting mixture is refluxed for 5 hours
  10. temperatureThe dehydrogenation mixture is cooled
  11. filtrationfiltered
  12. customevaporated
  13. customchromatographed on alumina
  14. customevaporated

Sources & evidence

ORD record
ord-c55ac0033b9f4df2bbd816ca95024c56
Source dataset
uspto-grants-1976_08
Patent number
US03978124

Reaction notes

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