1,2-Dichloroethane → HCID 57712917, compound

HRID 1983430Notes

Reaction equation

HRID 1983430 reaction equation
[C:1]1(=[O:11])[O:6][C:4](=[O:5])[C:3]2=[CH:7][CH:8]=[CH:9][CH:10]=[C:2]12.ClCCCl.[Cl-].[Al+3].[Cl-].[Cl-].[OH:20][C:21]1[CH:26]=[C:25]([OH:27])[CH:24]=[CH:23][C:22]=1[CH2:28][CH2:29][CH2:30][CH2:31][C:32]([O:34][CH3:35])=[O:33]>ClC(Cl)C.ClCCl>[OH:27][C:25]1[CH:26]=[C:21]([OH:20])[C:22]([CH2:28][CH2:29][CH2:30][CH2:31][C:32]([O:34][CH3:35])=[O:33])=[CH:23][C:24]=1[C:4]([C:3]1[CH:7]=[CH:8][CH:9]=[CH:10][C:2]=1[C:1]([OH:6])=[O:11])=[O:5]

Participants

7

Reactant 4

HCID 111,2-DichloroethaneHCID 6811Phthalic AnhydrideHCID 6451240Aluminum(III) ChlorideHCID 23195023HCID 23195023, compound

Product 1

HCID 57712917HCID 57712917, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 63651,1-DichloroethaneSolvent

Procedure

A 2-liter round-bottomed flask was charged with 12.83 g (86.6 mmoles) of phthalic anhydride and a stir bar. Anhydrous 1,2-dichloroethane (190 ml) was added. The flask was flushed with argon, and a reflux condenser was added to the flask. A drying tube was added to the top of the condenser. The mixture was stirred for 30 minutes. (The solid did not dissolve completely.) Then 28.6 g (214.5 mmoles) of aluminum chloride was added (by momentarily removing the condenser). Most solids were dissolved; a greenish-yellow solution results. Stirring was continued for another 30 minutes while a solution of 18.5 g (82.5 mmoles) of methyl-5-(2,4-dihydroxyphenyl)-pentanoate (5a) in 130 ml of dichloroethane was made. This solution was poured into the flask, the headspace was flushed with argon, and the condenser was replaced. With good stirring, the solution in the flask was heated to a light reflux for 30 to 60 minutes. The solution in the flask became slightly warm and turned dark. HCl gas was evolved for about 10-20 minutes. Then the solution was cooled to room temperature. A tarry precipitate formed. The reaction was concentrated to a gum. To this material a mixture of ice (400 g) and concentrated HCl (200 ml) was added followed by 500 ml of ethyl acetate. The flask was capped with a septum and placed on an orbital shaker until all solid dissolved. The mixture was transferred to a 2-liter separatory funnel. The organic layer was separated, washed with 400 ml of 1 N HCl, 2×200 ml of saturated NaCl and dried over sodium sulfate. Concentration afforded an oil. To this material, 200 ml of dichloromethane was added. The resulting solution was sonicated for 30 minutes, and then cooled to −20° C. for 2 hours. The crystalline precipitate was filtered off, washed with 2:1 hexanes/dichloromethane, followed by 4:1 hexanes/dichloromethane and dried. Yield was 20.0 g (65%).

Workup

  1. customThe flask was flushed with argon, and a reflux condenser
  2. additionwas added to the flask
  3. additionA drying tube was added to the top of the condenser
  4. dissolution(The solid did not dissolve completely
  5. customby momentarily removing the condenser)
  6. dissolutionMost solids were dissolved
  7. customa greenish-yellow solution results
  8. stirringStirring
  9. additionThis solution was poured into the flask
  10. customthe headspace was flushed with argon
  11. temperatureWith good stirring, the solution in the flask was heated to a light
  12. temperaturereflux for 30 to 60 minutes
  13. temperatureThe solution in the flask became slightly warm
  14. waitHCl gas was evolved for about 10-20 minutes
  15. customA tarry precipitate formed
  16. concentrationThe reaction was concentrated to a gum
  17. additionTo this material a mixture of ice (400 g) and concentrated HCl (200 ml)
  18. additionwas added
  19. customThe flask was capped with a septum
  20. dissolutiondissolved
  21. customThe mixture was transferred to a 2-liter separatory funnel
  22. customThe organic layer was separated
  23. washwashed with 400 ml of 1 N HCl, 2×200 ml of saturated NaCl
  24. dry with materialdried over sodium sulfate
  25. concentrationConcentration
  26. customafforded an oil
  27. customThe resulting solution was sonicated for 30 minutes
  28. temperaturecooled to −20° C. for 2 hours
  29. filtrationThe crystalline precipitate was filtered off
  30. washwashed with 2:1 hexanes/dichloromethane
  31. customdried

Sources & evidence

ORD record
ord-2a177fec8d22453aa8aeca31c4d751db
Source dataset
uspto-grants-2009_06
Patent number
US07541454B2

Reaction notes

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