Isopropanol → 2-Chloro-9,10-dihydro-9,10-methano-9-anthracenecarboxylic acid

HRID 862721Notes

Reaction equation

HRID 862721 reaction equation
[Cl:1][C:2]1[CH:15]=[CH:14][C:13]2[CH:12]3[CH2:16][C:5]([CH:17]=[O:18])([C:6]4[C:11]3=[CH:10][CH:9]=[CH:8][CH:7]=4)[C:4]=2[CH:3]=1.CC(C)=[O:21].OS(O)(=O)=O.O=[Cr](=O)=O.CCCCCC.C(O)(C)C>CC(C)=O>[Cl:1][C:2]1[CH:15]=[CH:14][C:13]2[CH:12]3[CH2:16][C:5]([C:17]([OH:21])=[O:18])([C:6]4[C:11]3=[CH:10][CH:9]=[CH:8][CH:7]=4)[C:4]=2[CH:3]=1

Participants

6

Reactant 4

HCID 3776IsopropanolHCID 8058HexaneHCID 196986392-Chloro-9-formyl-9,10-dihydro-9,10-methanoanthraceneHCID 131709961Jones' reagent

Product 1

HCID 196986472-Chloro-9,10-dihydro-9,10-methano-9-anthracenecarboxylic acidYield 98.7%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Conditions

Temperature
10 °C

Procedure

A stirred solution of (9RS,10RS)-2-chloro-9,10-dihydro-9,10-methanoanthracene-9-carboxaldehyde prepared as in Example 1i (290.5 g, 1.14 moles) dissolved in acetone (5.0 L) was cooled to 10° C. and treated with Jones Reagent (950 ml, ~ 1.19 moles) over a period of 1 h. The reaction mixture was stirred overnight at room temperature, then analyzed by TLC [silica gel/methylene chloride:hexane (1:1)]. Conversion of the aldehyde (Rf =0.50) to the desired carboxylic acid (Rf =0.0-0.15) was shown to be complete. Isopropanol (150 ml) was added, and the mixture stirred for another 3 h to quench any excess Jones Reagent. The acetone supernatant was decanted away from the green-black sludge that had formed, and the sludge was washed with acetone (2×1 L). The combined acetone solutions were concentrated on the rotary evaporator to a volume of 1.5 L, then poured into ice/water (6 L) with vigorous stirring. A yellow-white gum precipitated and gradually solidified with continued stirring. The solid was collected by filtration, pulverized to a fine off-white powder in a mortar & pestle, then rewashed with cold water (2×1 L). Vacuum drying afforded the title compound as an off-white powder (304.8 g, 98.7%), mp 175°-178° C.

Workup

  1. stirringthe mixture stirred for another 3 h
  2. customto quench any excess Jones Reagent
  3. customThe acetone supernatant was decanted away from the green-black sludge that
  4. customhad formed
  5. washthe sludge was washed with acetone (2×1 L)
  6. concentrationThe combined acetone solutions were concentrated on the rotary evaporator to a volume of 1.5 L
  7. additionpoured into ice/water (6 L) with vigorous stirring
  8. customA yellow-white gum precipitated
  9. filtrationThe solid was collected by filtration
  10. customVacuum drying

Sources & evidence

ORD record
ord-9bdd96b5276a40959308a6558c188eb6
Source dataset
uspto-grants-1998_02
Patent number
US05719166

Reaction notes

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