Triphenylphosphine → HCID 66713532, compound

HRID 715682Notes

Reaction equation

HRID 715682 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:8]=[C:9]([O:20][CH3:21])[C:10]=1OCCN1CCOCC1)[C:6]#[N:7].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[O:41]1[CH2:46][CH2:45][CH:44](O)[CH2:43][CH2:42]1.CC(OC(/N=N/C(OC(C)(C)C)=O)=O)(C)C>O1CCCC1>[CH3:21][O:20][C:9]1[CH:8]=[C:5]([CH:4]=[C:3]([O:2][CH3:1])[C:10]=1[CH:44]1[CH2:45][CH2:46][O:41][CH2:42][CH2:43]1)[C:6]#[N:7]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 74956Tetrahydro-4H-pyran-4-olHCID 6034084Di-tert-butyl diazene-1,2-dicarboxylateHCID 58072035HCID 58072035, compound

Product 1

HCID 66713532HCID 66713532, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

15 g 3,5 Dimethoxy-4-hydroxy-benzonitrile (for synthesis see: benzonitrile for Example 18), 28 g triphenylphosphine and tetrahydro-4H-pyran-4-ol was suspended in 150 mL tetrahydrofuran at 0° C. before 25 g di-tert-butylazodicarboxylate (DBAD) was added. The reaction was stirred overnight at ambient temperature. After this time the solvent was distilled off and the residue was dissolved in ethyl acetate. The organic phase was extracted with 2N sodium hydroxide (×2), 4N hydrochloric acid (×3), saturated sodium chloride solution, dried and concentrated. The residue was purified with silica gel chromatography (SiO2: cyclohexane/ethyl acetate 5:1) and the appropriate fractions were combined and concentrated. The residue was dissolved in formic acid and stirred at 50° C. for 2 h, concentrated and dissolved in ethyl acetate. The organic phase was washed with 2N hydrochloric acid and saturated sodium chloride solution, dried and concentrated.

Workup

  1. additionwas added
  2. distillationAfter this time the solvent was distilled off
  3. dissolutionthe residue was dissolved in ethyl acetate
  4. extractionThe organic phase was extracted with 2N sodium hydroxide (×2), 4N hydrochloric acid (×3), saturated sodium chloride solution
  5. customdried
  6. concentrationconcentrated
  7. customThe residue was purified with silica gel chromatography (SiO2: cyclohexane/ethyl acetate 5:1)
  8. concentrationconcentrated
  9. dissolutionThe residue was dissolved in formic acid
  10. stirringstirred at 50° C. for 2 h
  11. concentrationconcentrated
  12. dissolutiondissolved in ethyl acetate
  13. washThe organic phase was washed with 2N hydrochloric acid and saturated sodium chloride solution
  14. customdried
  15. concentrationconcentrated

Sources & evidence

ORD record
ord-c6d06f3fc09f48b9bc296f847f72d7ab
Source dataset
uspto-grants-2015_11
Patent number
US09187478B2

Reaction notes

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