Triphenylphosphine → HCID 10872275, compound

HRID 1377937Notes

Reaction equation

HRID 1377937 reaction equation
O[C@@H:2]([CH3:28])[CH2:3][C:4]1[C:5]([C:13](=[N:23][NH:24][C:25](=[O:27])[CH3:26])[C:14]2[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][CH:15]=2)=[CH:6][C:7]2[O:11][CH2:10][O:9][C:8]=2[CH:12]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[C:25]([N:24]1[C@H:2]([CH3:28])[CH2:3][C:4]2[CH:12]=[C:8]3[O:9][CH2:10][O:11][C:7]3=[CH:6][C:5]=2[C:13]([C:14]2[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][CH:15]=2)=[N:23]1)(=[O:27])[CH3:26]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 131720187HCID 131720187, compound

Product 1

HCID 10872275HCID 10872275, compoundYield 51%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

1.05 grams (S)-Acetic acid [[6-[2-[hydroxy]propyl]-1,3-benzodioxol-5-yl](4-nitrophenyl)methylene]hydrazide and 0.78 grams triphenylphosphine in 70 mL tetrahydrofuran were cooled to 0° C. 0.57 grams diethyl azodicarboxylate in 5 mL tetrahydro-furan was added dropwise over 15 min. The resulting mixture was stirred for 2 h then warmed to room temperature for 2 h. The mixture was transferred to a separatory funnel and the solution was washed with 1N HCl, water and brine. The organic phase was dried over magnesium sulfate, filtered and concentrated by rotary evaporation. The residue was eluted through a silica gel column (1:1 ethyl acetate:hexane). Fractions containing the desired compound were concentrated to a yellow oil which solidified on standing. The yellow crystalline material was slurried in 30 mL of CH2Cl2 and hexane (3:7) at 0° C. The precipitate was removed by filtration and the filtrate was concentrated to a yellow foam. The residue was suspended in 10 mL ethanol which was warmed to reflux then slowly cooled to room temperature. The precipitate was collected by filtration and dried in a vacuum oven at 60° C. to give 0.51 grams (50%) of the subtitled product (100% ee) which was 98.3% pure by HPLC potency assay.

Workup

  1. customThe mixture was transferred to a separatory funnel
  2. washthe solution was washed with 1N HCl, water and brine
  3. dry with materialThe organic phase was dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated by rotary evaporation
  6. washThe residue was eluted through a silica gel column (1:1 ethyl acetate:hexane)
  7. additionFractions containing the desired compound
  8. concentrationwere concentrated to a yellow oil which
  9. customat 0° C
  10. customThe precipitate was removed by filtration
  11. concentrationthe filtrate was concentrated to a yellow foam
  12. temperaturewas warmed
  13. temperatureto reflux
  14. temperaturethen slowly cooled to room temperature
  15. filtrationThe precipitate was collected by filtration
  16. customdried in a vacuum oven at 60° C.

Sources & evidence

ORD record
ord-4055a27435f34188ac02108b81dc0bc9
Source dataset
uspto-grants-1997_09
Patent number
US05665878

Reaction notes

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