Lithium Chloride → (S)-3-chloromethyl-1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthalene

HRID 35748Notes

Reaction equation

HRID 35748 reaction equation
C([CH2:4][C@@H:5]1[C:14]([CH3:16])([CH3:15])[C:13]2[C:8](=[CH:9][CH:10]=[C:11]([CH3:17])[CH:12]=2)[C:7]([CH3:19])([CH3:18])[CH2:6]1)(O)=O.C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.[Pb+4].[Cl-:37].[Li+]>C1C=CC=CC=1>[Cl:37][CH2:4][C@@H:5]1[C:14]([CH3:16])([CH3:15])[C:13]2[C:8](=[CH:9][CH:10]=[C:11]([CH3:17])[CH:12]=2)[C:7]([CH3:19])([CH3:18])[CH2:6]1

Participants

5

Reactant 3

HCID 433294Lithium ChlorideHCID 13175026(R)-3-carboxymethyl1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthaleneHCID 178418268HCID 178418268, compound

Product 1

HCID 13175029(S)-3-chloromethyl-1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthaleneYield 77%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a solution of (R)-3-carboxymethyl1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthalene ([α]546 -23.8° (C=1 in benzene)) (2.00 g; 7.69 mmol) in benzene (30 ml), lead tetraacetate (4.00 g; 9.02 mmol) and anhydrous lithium chloride (0.80 g; 18.9 mmol) were added, and the resultant mixture was refluxed for 6 hours. The reaction mixture was washed with water, dilute hydrochloric acid and 6% ammonia water in order. The benzene layer was dried, concentrated and purified on column chromatography to give (S)-3-chloromethyl-1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthalene (1.22 g; 4.87 mmol). From the ammonia water layer, there was recovered the unreacted carboxylic acid (0.35 g; 1.34 mmol). The yield was 77% (based on the consumed carboxylic acid). [α]546 +26.1° (C=1 in n-hexane).

Workup

  1. washThe reaction mixture was washed with water, dilute hydrochloric acid and 6% ammonia water in order
  2. dry with materialThe benzene layer was dried
  3. concentrationconcentrated
  4. custompurified on column chromatography

Sources & evidence

ORD record
ord-ff8d4725456f4a2a9adef143198fa8b5
Source dataset
uspto-grants-1988_08
Patent number
US04767882

Reaction notes

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