Ethanol → (+/-)-9-Bromo-9,10-dihydropyrrolo[2,1-b][1,3]benzothiazepine

HRID 1936559Notes

Reaction equation

HRID 1936559 reaction equation
O[CH:2]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[S:6][C:5]2=[CH:13][CH:14]=[CH:15][N:4]2[CH2:3]1.P(Br)(Br)[Br:17].C(O)C.C([O-])([O-])=O.[Na+].[Na+]>C(OCC)C>[Br:17][CH:2]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[S:6][C:5]2=[CH:13][CH:14]=[CH:15][N:4]2[CH2:3]1

Participants

6

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 24614Phosphorus tribromideHCID 10680299(+/-)-9,10-Dihydro-9-hydroxypyrrolo[2,1-b][1,3]benzothiazepine

Product 1

HCID 10802668(+/-)-9-Bromo-9,10-dihydropyrrolo[2,1-b][1,3]benzothiazepineYield 142.8%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To a solution of 24a (0.26 g, 1.0 mmol) in anhydrous ethyl ether (4 ml) was added dropwise a solution of PBr3 (0.13 g, 0.5 mmol) in anhydrous ethyl ether (1 ml) and the reaction mixture was kept at reflux temperature for 2 hours under nitrogen. Anhydrous ethanol was added (0.2 ml) and the resulting solution was heated to reflux temperature for another hour. Five ml of an aqueous solution of 5% Na2CO3 were then added, the organic phase was separated, anhydrified and evaporated. The crude product was chromatographed (hexane and chloroform 1:1) to give 25a (0.2 g, 64% yield) as colourless prisms: melting point 115-116° C. (cyclohexane); 1H NMR (CDCl3) δ7.46-7.09 (m, 4H); 6.93 (m, 1H), 6.39 (m, 1H), 6.12 (m, 1H), 5.75 (dd, 1H, J=6.9, 2.6 Hz), 5.07 (dd, 1H, J=14.7, 2.6 Hz), 4.61 (dd, 1H, J=14.7, 6.9 Hz). Anal. (C12H10BrNOS): C, H, N.

Workup

  1. temperatureat reflux temperature for 2 hours under nitrogen
  2. temperaturethe resulting solution was heated
  3. temperatureto reflux temperature for another hour
  4. customthe organic phase was separated
  5. customevaporated
  6. customThe crude product was chromatographed (hexane and chloroform 1:1)

Sources & evidence

ORD record
ord-b59124fbe9de4ff9b5181c26f7127e4d
Source dataset
uspto-grants-2002_05
Patent number
US06391870B2

Reaction notes

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