Iodine → HCID 561050, compound

HRID 612444Notes

Reaction equation

HRID 612444 reaction equation
[Mg].II.Br[CH2:5][CH2:6]Br.C(Br)=C.[C:11](=[O:13])=O.C(O)C.[Cl:17][C:18]1[CH:32]=[CH:31][C:21]2[S:22][CH2:23][C:24]3[CH:30]=[CH:29][CH:28]=[CH:27][C:25]=3C[C:20]=2[CH:19]=1>O1CCCC1>[Cl:17][C:18]1[CH:19]=[CH:20][C:21]2[S:22][CH2:23][C:24]3[CH:25]=[CH:27][CH:28]=[CH:29][C:30]=3[C:11]([CH:5]=[CH2:6])([OH:13])[C:31]=2[CH:32]=1

Participants

8

Reactant 6

HCID 807IodineHCID 78391,2-DibromoethaneHCID 11641Bromoethene2×HCID 5462224MagnesiumHCID 19595484HCID 19595484, compoundHCID 19604758Methanedione--ethanol (1/1)

Product 1

HCID 561050HCID 561050, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
60 °C

Procedure

Magnesium (4.94 g, 0.203 mol) under tetrahydrofuran (15 ml) was activated with a grain of iodine and 1,2-dibromoethane (0.4 ml). After the reaction was finished, 10% of a solution of vinylbromide (21.4 g, 0.2 mol) in tetrahydrofuran (70 ml) was added (dry ice-ethanol condenser, nitrogen atmosphere). The reaction started immediately, and the remaining part of the vinylbromide solution was added dropwise under stirring at such a rate (over 45 minutes) as to maintain the temperature at 58-62° C. The mixture was heated at reflux temperature for 30 minutes and then cooled to 30° C. Over 1 h, a solution of 2-chloro-6,11-dihydrodibenzo[b,e]thiepine (28.9 g, 0.1 mol, prepared as described in Es. farmacie 11, 451, 1962) in tetrahydrofuran (70 ml) was added dropwise under stirring (30-35° C.). The mixture was allowed to stand overnight at room temperature and then quenched under cooling (ice and sodium chloride) with a solution of ammonium chloride (21 g) in water (100 ml). Toluene (100 ml) was added, the mixture was filtered and the aqueous layer was extracted with toluene (3×100 ml). The toluene solutions were combined, dried (MgSO4) and evaporated. The residue was crystallised from a mixture of benzene (50 ml) and hexane (100 ml) to give 27.4 g (95%) of 2-chloro-11-vinyl-6,11-dihydrodibenzo[b,e]thiepin-11-ol.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux temperature for 30 minutes
  3. temperaturecooled to 30° C
  4. waitOver 1 h
  5. stirringunder stirring (30-35° C.)
  6. waitto stand overnight at room temperature
  7. customquenched
  8. temperatureunder cooling (ice and sodium chloride) with a solution of ammonium chloride (21 g) in water (100 ml)
  9. additionToluene (100 ml) was added
  10. filtrationthe mixture was filtered
  11. extractionthe aqueous layer was extracted with toluene (3×100 ml)
  12. dry with materialdried (MgSO4)
  13. customevaporated
  14. customThe residue was crystallised from a mixture of benzene (50 ml) and hexane (100 ml)

Sources & evidence

ORD record
ord-57298a3bc45f474982d2c16f269e4c81
Source dataset
uspto-grants-1999_12
Patent number
US06004983

Reaction notes

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