Hydrochloric Acid → 6-Chloro-4,4-diphenyl-2H,4H-1,3-benzodioxine-2-carboxylic acid

HRID 848191Notes

Reaction equation

HRID 848191 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([OH:22])=[C:6]([C:8]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[OH:9])[CH:7]=1.[NH2-].[Na+].Cl[CH:26](Cl)[C:27]([O-:29])=[O:28].[K+].Cl.C(=O)(O)[O-].[Na+]>O.C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[O:22][CH:26]([C:27]([OH:29])=[O:28])[O:9][C:8]([C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=3)([C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=3)[C:6]=2[CH:7]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 24533Sodium amideHCID 516892Sodium BicarbonateHCID 13076869HCID 13076869, compoundHCID 23681501Potassium dichloroacetate

Product 1

HCID 30550676-Chloro-4,4-diphenyl-2H,4H-1,3-benzodioxine-2-carboxylic acidYield 31.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A mixture of 12.4 g of 5-chloro-2-hydroxy-α,α-diphenyl-benzene methanol, 150 ml of toluene and 3.2 g of sodium amide was refluxed for 6 hours and was then cooled to room temperature after which 6.8 g of potassium dichloroacetate were added thereto. The mixture was refluxed for another 6 hours and was cooled to room temperature after which 300 ml of water were added thereto. The mixture was slowly acidified with N hydrochloric acid solution and was then made alkaline wiith a saturated sodium bicarbonate solution. The mixture was washed twice with 100 ml of methylene chloride and was then acidified with 2 N hydrochloric acid. The mixture was extracted 3 times with 100 ml of ether and the combined ether extracts were washed twice with 80 ml of water, dried over magnesium sulfate, treated with activated carbon and evaporated to dryness under reduced pressure. The 7 g of residue were crystallized from 300 ml of benzene to obtain 4.6 g of 6-chloro-4,4-diphenyl-[4H]-1,3-benzodioxin-2-carboxylic acid melting at 226° C.

Workup

  1. temperaturewas refluxed for 6 hours
  2. additionwere added
  3. temperatureThe mixture was refluxed for another 6 hours
  4. additionwere added
  5. washThe mixture was washed twice with 100 ml of methylene chloride
  6. extractionThe mixture was extracted 3 times with 100 ml of ether
  7. washthe combined ether extracts were washed twice with 80 ml of water
  8. dry with materialdried over magnesium sulfate
  9. additiontreated with activated carbon
  10. customevaporated to dryness under reduced pressure
  11. customThe 7 g of residue were crystallized from 300 ml of benzene

Sources & evidence

ORD record
ord-ad1898264ce94127bf6106d63771b1a6
Source dataset
uspto-grants-1981_10
Patent number
US04294845

Reaction notes

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