Methanol → HCID 20228201, compound

HRID 1731635Notes

Reaction equation

HRID 1731635 reaction equation
[C:1]([CH2:4][CH2:5][C:6]1[C:16]2[S:15][C:14]3[CH:17]=[C:18]([C:21](O)=O)[CH:19]=[CH:20][C:13]=3CC[C:10]=2[CH:9]=[CH:8][CH:7]=1)([OH:3])=[O:2].S(Cl)(Cl)=O.[Cl-].[Al+3].[Cl-].[Cl-].[CH3:32]O.[C:34](OCC)(=[O:36])[CH3:35]>ClCCCl>[O:36]=[C:34]1[C:17]2[C:14]3[S:15][C:16]4=[CH:10][CH2:9][CH2:8][CH:7]=[C:6]4[CH:5]=[C:4]([C:1]([O:3][CH3:32])=[O:2])[C:13]=3[CH:20]=[CH:19][C:18]=2[CH2:21][CH2:35]1

Participants

7

Reactant 5

HCID 887MethanolHCID 8857Ethyl AcetateHCID 24386Thionyl Chloride2×HCID 6451240Aluminum(III) ChlorideHCID 13746712HCID 13746712, compound

Product 1

HCID 20228201HCID 20228201, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

6-(2-Carboxyethyl)-10,11-dihydrodibenz-[b,f]thiepin-3-carboxylic acid (328 mg; 1 mmole) was treated with thionyl chloride (6 ml) and after heating the mixture under reflux for 2 hours excess thionyl chloride was removed under vacuum. The residue was dissolved in 1,2-dichloroethane and the solvent was evaporated off to remove the last traces of thionyl chloride. The crude acid chloride dissolved in 1,2-dichloroethane (5 ml) was treated at 0°-5° C. with anhydrous aluminum chloride (100 mg; 0.75 mmole) in 1,2-dichloroethane (2 ml). The mixture was stirred in the ice-bath for 2 hours and then it was treated with methanol (4 ml). The mixture was stirred in the ice-bath for 5 minutes, then at room temperature for 30 minutes and finally at 50° C. for 30 minutes. Ethyl acetate (20 ml) was added and the solution was washed in succession with 2N hydrochloric acid (2×6 ml), water (6 ml), N sodium (2×6 ml) and finally with water (6 ml). Evaporation of the dried (MgSO4) ethyl acetate solution gives 291 mg of crude product which on purification by column chromatography (10 g Merck silica gel eluted with 3% ethyl acetate in methylene chloride) gave 228 mg (70%) of solid m.p. 156°-158° C.

Workup

  1. temperatureafter heating the mixture
  2. customwas removed under vacuum
  3. dissolutionThe residue was dissolved in 1,2-dichloroethane
  4. customthe solvent was evaporated off
  5. customto remove the last traces of thionyl chloride
  6. dissolutionThe crude acid chloride dissolved in 1,2-dichloroethane (5 ml)
  7. waitfinally at 50° C. for 30 minutes
  8. washthe solution was washed in succession with 2N hydrochloric acid (2×6 ml), water (6 ml), N sodium (2×6 ml) and finally with water (6 ml)
  9. customEvaporation of the
  10. dry with materialdried (MgSO4) ethyl acetate solution
  11. customgives 291 mg of crude product which
  12. customon purification
  13. washby column chromatography (10 g Merck silica gel eluted with 3% ethyl acetate in methylene chloride)

Sources & evidence

ORD record
ord-951d403785594df0815320cd31cc3763
Source dataset
uspto-grants-1986_11
Patent number
US04622403

Reaction notes

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