Hydrochloric Acid → HCID 68407900, compound

HRID 2270534Notes

Reaction equation

HRID 2270534 reaction equation
[CH3:1]C(C)([O-])C.[K+].[CH3:7][C@@:8]12[C:24](=O)[CH2:23][CH2:22][C@H:21]1[C:20]1[C@@H:11]([C:12]3[CH:13]=[CH:14][C:15](O)=[CH:16][C:17]=3[CH2:18][CH:19]=1)CC2.Cl.N1C=CC=CC=1.[C:34]([O:37][C:38](=[O:40])[CH3:39])(=O)[CH3:35]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CS(C)=O.C[C@H]1O[C@H]2[C@H](O)[C@@H](O)[C@H](OC3C4C(=CC5OCOC=5C=4)[C@@H](C4C=C(OC)C(O)=C(OC)C=4)[C@@H]4[C@@H]3COC4=O)O[C@@H]2CO1.C1COP(NCCCl)(=O)N(CCCl)C1.[NH2-].[NH2-].Cl[Pt+2]Cl>[C:38]([O:37][C:34]1[CH:15]=[CH:16][C:17]2[C@@H:12]3[C:13]([C@H:22]4[C@@:21]([CH2:20][CH2:11]3)([CH3:1])[C:8](=[CH2:7])[CH2:24][CH2:23]4)=[CH:14][CH2:19][C:18]=2[CH:35]=1)(=[O:40])[CH3:39]

Participants

9

Reactant 5

HCID 313Hydrochloric Acid2×HCID 1049PyridineHCID 7918Acetic AnhydrideHCID 223368EquilinHCID 23665647Potassium tert-butoxide

Product 1

HCID 68407900HCID 68407900, compoundYield 86%

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 56841950ICE protocol 1CatalystHCID 679Dimethyl SulfoxideSolvent2×

Conditions

Temperature
78 °C

Procedure

Methyltriphenylphosphonium bromide (3.33 g, 9.32 mmol) and potassium t-butoxide (1.05 g, 9.36 mmol) suspended in 10 ml of anh. DMSO under argon was stirred 1 h in an oil bath (77-79° C.), following which equilin (500.0 mg, 1.863 mmol) in 10 ml of anh. DMSO was added via syringe. See FIG. 161. After stirring a further hour the cooled reaction mixture was poured into 50 ml of ice-1 N hydrochloric acid and extracted three times with 25 ml portions of ether. The combined organic extracts were washed with 25 ml of brine, dried over magnesium sulfate, and filtered through diatomaceous earth. The residue was washed with 10 ml of ether and combined filtrates concentrated under reduced pressure. The resulting light yellow syrup was taken up in anh. pyridine (6.3 ml, 78 mmol), acetic anhydride was added (0.88 ml, 9.3 mmol), and the reaction mixture was stirred 16 h. The mixture was then poured into 100 ml of 1 N hydrochloric acid and extracted three times with 50 ml portions of ether. The combined organic extracts were washed with 100 ml of saturated sodium bicarbonate+100 ml of brine, dried over magnesium sulfate, and filtered through diatomaceous earth. The residue was washed with 25 ml of ether and the combined filtrates were concentrated under reduced pressure. The crude acetate was flash chromatographed (5% ethyl acetate/hexanes on silica gel) to give a yellow resin (494.7 mg, 1,604 mmol, 86%).

Workup

  1. additionwas added via syringe
  2. stirringAfter stirring a further hour
  3. customthe cooled reaction mixture
  4. extractionextracted three times with 25 ml portions of ether
  5. washThe combined organic extracts were washed with 25 ml of brine
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered through diatomaceous earth
  8. washThe residue was washed with 10 ml of ether and combined filtrates
  9. concentrationconcentrated under reduced pressure
  10. stirringthe reaction mixture was stirred 16 h
  11. extractionextracted three times with 50 ml portions of ether
  12. washThe combined organic extracts were washed with 100 ml of saturated sodium bicarbonate+100 ml of brine
  13. dry with materialdried over magnesium sulfate
  14. filtrationfiltered through diatomaceous earth
  15. washThe residue was washed with 25 ml of ether
  16. concentrationthe combined filtrates were concentrated under reduced pressure
  17. customchromatographed (5% ethyl acetate/hexanes on silica gel)

Sources & evidence

ORD record
ord-f0e8e6320cc640ba95d33ccea70abfa7
Source dataset
uspto-grants-2001_12
Patent number
US06331534B1

Reaction notes

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