Ethanol → HCID 15280848, compound

HRID 1734652Notes

Reaction equation

HRID 1734652 reaction equation
C([O:4][C@H:5]1[C@H:9]([N:10]2[C:14]3[CH:15]=[C:16]([Cl:20])[C:17]([Cl:19])=[CH:18][C:13]=3[N:12]=[CH:11]2)[CH2:8][C@H:7]([CH2:21][O:22]C(=O)C)[C@H:6]1[O:26]C(=O)C)(=O)C.[Br:30]N1C(=O)CCC1=O.C(=O)([O-])[O-].[Na+].[Na+].C(O)C>CN(C)C=O.O.C(O)(=O)C.CO>[Br:30][C:11]1[N:10]([C@H:9]2[C@H:5]([OH:4])[C@H:6]([OH:26])[C@@H:7]([CH2:21][OH:22])[CH2:8]2)[C:14]2[CH:15]=[C:16]([Cl:20])[C:17]([Cl:19])=[CH:18][C:13]=2[N:12]=1

Participants

9

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 67184N-bromobutanimideHCID 15280845HCID 15280845, compound

Product 1

HCID 15280848HCID 15280848, compound

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

(1S, 2R, 3R, 5R)-3-(Acetoxymethyl)-5-(5,6-dichloro-1H-benzimidazol-1-yl)-1,2-cyclopentanediyl diacetate (2.00 g, 4.51 mmol) was dissolved in dry N,N-dimethylformamide (9 mL) and heated to 90° C. N-bromosuccinimide (1.62 g, 9.02 mmol) was added in four portions over 5 hours.. Volatiles were evaporated in vacuo. The residue was chromatographed on silica gel and product was eluted with 30-50% ethyl acetate-hexanes as a yellow glass (1.00 g, 43%); 1H-NMR(DMSO-d6) consistent with structure. This sample was deblocked with sodium carbonate (203 mg, 1.9 mmol) in water (3 mL)-ethanol(15 mL)-methanol(15 mL) at ambient temperature for 5 hours. The pH was adjusted to 7 with acetic acid. The solution was evaporated to dryness in vacuo and the residue was triturated with water to give white powder which was chromatographed. Elution of a silica gel column with 10-12% methanol-chloroform gave (1S, 2R, 3R, 5R)-5-(2-bromo-5,6-dichloro-1H-benzimidazol-1-yl)-3-(hydroxymethyl)-1,2-cyclopentanediol as white powder after solidification from 1:1 ethanol-methanol (410 mg, 54%), m.p. 212°-215° C.; 1H-NMR(DMSO-d6) and mass spectrum identical with those of racemate described in Example 4; [α]20589 -31.2°, [α]20578 -32.3°, [α]20546 -37.3° (c=0.260, methanol).

Workup

  1. customVolatiles were evaporated in vacuo
  2. customThe residue was chromatographed on silica gel and product
  3. washwas eluted with 30-50% ethyl acetate-hexanes as a yellow glass (1.00 g, 43%)
  4. customat ambient temperature
  5. customfor 5 hours
  6. customThe solution was evaporated to dryness in vacuo
  7. customthe residue was triturated with water
  8. customto give white powder which
  9. customwas chromatographed
  10. washElution of a silica gel column with 10-12% methanol-chloroform

Sources & evidence

ORD record
ord-2bf5ed856a2942ca9fc20fa7c77d6c4b
Source dataset
uspto-grants-1996_07
Patent number
US05534535

Reaction notes

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