Bromide ion → HCID 88669256, compound

HRID 247761Notes

Reaction equation

HRID 247761 reaction equation
[C:1]([O-])([O-:3])=[O:2].[Na+].[Na+].[C:7]([O:10][CH2:11]Br)(=[O:9])[CH3:8].[Br-].[CH3:14]/[CH:15]=[CH:16]/[C:17]1(C(O)=O)[CH2:37][S:36][CH:20]2[CH:21]([NH:24][C:25](/[C:27](/[C:30]3[N:34]=[C:33]([NH2:35])[S:32][CH:31]=3)=[N:28]\[OH:29])=[O:26])[C:22](=[O:23])[N:19]2[CH2:18]1>CN(C=O)C.CCOC(C)=O.O.CC#N>[NH2:35][C:33]1[S:32][CH:31]=[C:30](/[C:27](=[N:28]/[OH:29])/[C:25]([NH:24][CH:21]2[C:22](=[O:23])[N:19]3[C:18]([C:1]([O:3][CH2:11][O:10][C:7](=[O:9])[CH3:8])=[O:2])=[C:17](/[CH:16]=[CH:15]\[CH3:14])[CH2:37][S:36][C@H:20]23)=[O:26])[N:34]=1

Participants

9

Reactant 4

HCID 259Bromide ionHCID 10340Sodium Carbonate2×HCID 68536Bromomethyl acetateHCID 178439797HCID 178439797, compound

Product 1

HCID 88669256HCID 88669256, compoundYield 14%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred suspension of Ia (R2 =R3 =H) (280 mg, 0.68 m mole) and Na2CO3 (36 mg, 0.34 m mole) in dry DMF (5 ml) was added at -10° C. over 10 min. a solution of acetoxymethyl bromide in dry DMF (104 mg, 0.68 m mole/100 μl). After 30 min, additional Na2CO3 (18 mg, 0.17 m mole) and the bromide solution (52 mg, 0.34 m mole/50 μl) were added in small portions over 10 min. The mixture was stirred at the same temperature for 30 min. The reaction mixture showing four spots at Rf 0.10 (BMY-28232), 0.15, 0.60 and 0.75 by TLC (Merck Kieselgel 60 F254, 10:1 MeCN--H2O) was diluted with AcOEt (25 ml), washed with water (×3) and a saturated NaCl solution, dried over MgSO4 and evaporated. The residue was dissolved in a small amount of CHCl3 and charged on a column of Kieselgel 60 (18 g), which was washed with CHCl3 (50 ml) and eluted with MeOH--CHCl3 (1:20, 250 ml). The fractions showing a spot at Rf 0.60 by TLC were combined and evaporated in vacuo. The residue was dissolved in benzene and lyophilized to afford 45 mg (14%) of the title compound. M.p. 107-110° C. Estimated purity 70%. HPLC (Lichrosorb 4×300 mm, 2:3 MeCN--H2O): retention time, 6.0 min.

Workup

  1. washwashed with water (×3)
  2. dry with materiala saturated NaCl solution, dried over MgSO4
  3. customevaporated
  4. dissolutionThe residue was dissolved in a small amount of CHCl3
  5. additioncharged on a column of Kieselgel 60 (18 g), which
  6. washwas washed with CHCl3 (50 ml)
  7. washeluted with MeOH--CHCl3 (1:20, 250 ml)
  8. customevaporated in vacuo
  9. dissolutionThe residue was dissolved in benzene

Sources & evidence

ORD record
ord-68dd7f670ac74f3e9fca8db153785982
Source dataset
uspto-grants-1987_11
Patent number
US04708955

Reaction notes

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