Sodium amide → HCID 12812405, compound

HRID 848190Notes

Reaction equation

HRID 848190 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([OH:16])=[C:6]([CH:8]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[OH:9])[CH:7]=1.[NH2-].[Na+].Cl[CH:20](Cl)[C:21]([O-:23])=[O:22].[K+].[K]>C1(C)C=CC=CC=1.O.C(OCC)(=O)C.CN(C)P(N(C)C)(N(C)C)=O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[O:16][CH:20]([C:21]([OH:23])=[O:22])[O:9][CH:8]([C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=3)[C:6]=2[CH:7]=1

Participants

9

Reactant 4

HCID 24533Sodium amideHCID 5462222PotassiumHCID 12577118HCID 12577118, compoundHCID 23681501Potassium dichloroacetate

Product 1

HCID 12812405HCID 12812405, compoundYield 14.2%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 1140TolueneSolvent2×HCID 8857Ethyl AcetateSolventHCID 12679HexamethylphosphoramideSolvent

Procedure

A solution of 30.1 g of 5-chloro-2-hydroxy-α-phenyl-benzene-methanol in 200 ml of anhydrous toluene was added dropwise with stirring at room temperature to a mixture of 10.35 g of sodium amide and 100 ml of toluene and the mixture was stirred for 2 hours at room temperature and was then refluxed for 6 hours. After cooling the mixture to room temperature, 22.3 g of potassium dichloroacetate were added thereto in small portions and 20 ml of hexamethylphosphoramide were added. The mixture was stirred for 20 hours at room temperature and was then refluxed for 4 hours and then returned to room temperature. 20 ml of ethyl acetate were added thereto followed by show addition of 250 ml of water and the aqueous phase containing the potassium salt of the desired acid was extracted 3 times with 100 ml of ether and acidified by bubbling sulfur dioxide therethrough. The mixture was then extracted 3 times with 100 ml of ether and the combined ether extracts were washed 3 times with 100 ml of water, dried over magnesium sulfate, treated with activated carbon and evaporated to dryness under reduced pressure. The 24 g of residue were effloresced in cyclohexane to obtain crystals which were crystallized from 520 ml of a 7-3 benzene-cyclohexane mixture to obtain 5.3 g of 6-chloro-4-phenyl-[4H]-1,3-benzodioxin-2-carboxylic acid melting at 194° C.

Workup

  1. temperaturewas then refluxed for 6 hours
  2. temperatureAfter cooling the mixture to room temperature
  3. stirringThe mixture was stirred for 20 hours at room temperature
  4. temperaturewas then refluxed for 4 hours
  5. customreturned to room temperature
  6. extractionwas extracted 3 times with 100 ml of ether
  7. customby bubbling sulfur dioxide
  8. extractionThe mixture was then extracted 3 times with 100 ml of ether
  9. washthe combined ether extracts were washed 3 times with 100 ml of water
  10. dry with materialdried over magnesium sulfate
  11. additiontreated with activated carbon
  12. customevaporated to dryness under reduced pressure
  13. customto obtain crystals which
  14. customwere crystallized from 520 ml of a 7-3 benzene-cyclohexane mixture

Sources & evidence

ORD record
ord-e3c5fd7fcd324cd89bc26c9546ef05ca
Source dataset
uspto-grants-1981_10
Patent number
US04294845

Reaction notes

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