Thionyl Chloride → HCID 172035639, compound

HRID 2309118Notes

Reaction equation

HRID 2309118 reaction equation
[Cl:1][C:2]1[CH:42]=[CH:41][C:5]([CH2:6][N:7]2[CH2:12][CH2:11][N:10]([CH2:13][CH2:14][CH2:15][O:16][C:17]3[CH:18]=[C:19]([CH:38]=[CH:39][CH:40]=3)[O:20][C:21]3[N:25](CC4C=CC(OC)=CC=4)[N:24]=[N:23][C:22]=3[C:35](O)=[O:36])[CH2:9][CH2:8]2)=[CH:4][CH:3]=1.S(Cl)(Cl)=O.[Cl-].[Al+3].[Cl-].[Cl-]>ClCCl.CN(C)C=O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:6][N:7]2[CH2:8][CH2:9][N:10]([CH2:13][CH2:14][CH2:15][O:16][C:17]3[CH:40]=[CH:39][C:38]4[C:35](=[O:36])[C:22]5[NH:23][N:24]=[N:25][C:21]=5[O:20][C:19]=4[CH:18]=3)[CH2:11][CH2:12]2)=[CH:41][CH:42]=1

Participants

6

Reactant 3

HCID 24386Thionyl ChlorideHCID 6451240Aluminum(III) ChlorideHCID 20186857HCID 20186857, compound

Product 1

HCID 172035639HCID 172035639, compoundYield 35%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Procedure

The carboxylic acid from example 3 (10.0 g, 16.89 mmol) was dissolved in dry dichloromethane (450 ml) and thionyl chloride (2.742, 20.27 mmole) was added together with 10 drops of N,N-dimethylformamide. The mixture was refluxed with stirring for 4 hours under nitrogen and the solvent and excess thionyl chloride were removed in vacuo. Fresh dichloromethane (500 ml) was added and the freshly ground anhydrous aluminium chloride (7.88 g, 59.1 mmole, 3.5 equiv.) was added in three portions (over 20 minutes) at room temperature whilst under nitrogen. After a further 30 minutes the supernatant was separated from the brown oil which separated and 2M hydrochloric acid was added (250 ml). Trituration afforded a white solid which was partitioned between water and dichloromethane. Evaporation of the dried organic phase afforded crude title compound which after silica gel chromatography gave 2.68 g (35%) of material identical with that previously described in European Pat. No. 34,004.

Workup

  1. temperatureThe mixture was refluxed
  2. customthe solvent and excess thionyl chloride were removed in vacuo
  3. additionFresh dichloromethane (500 ml) was added
  4. customAfter a further 30 minutes the supernatant was separated from the brown oil which
  5. customseparated
  6. addition2M hydrochloric acid was added (250 ml)
  7. customTrituration afforded a white solid which
  8. customwas partitioned between water and dichloromethane
  9. customEvaporation of the dried organic phase
  10. customafforded crude title compound which after silica gel chromatography

Sources & evidence

ORD record
ord-9708f6af162741229d1b01276ec54a7b
Source dataset
uspto-grants-1987_09
Patent number
US04692526

Reaction notes

Loading…