Hydrochloric Acid → HCID 69266508, compound

HRID 494503Notes

Reaction equation

HRID 494503 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C@:8]([CH3:28])([CH2:22][CH2:23][C:24]([CH3:27])([CH3:26])[CH3:25])[C:9]([CH:11](C(OCC)=O)[C:12](OCC)=[O:13])=[O:10])=[CH:4][CH:3]=1.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.O.Cl>CS(O)(=O)=O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.O1CCCC1>[CH3:26][C:24]([CH3:25])([CH3:27])[CH2:23][CH2:22][C@@:8]1([CH3:28])[C:5]2[C:4](=[CH:3][C:2]([F:1])=[CH:7][CH:6]=2)[C:12]([OH:13])=[CH:11][C:9]1=[O:10]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 14812Phosphorus oxide (P4O10)HCID 68870319HCID 68870319, compound

Product 1

HCID 69266508HCID 69266508, compoundYield 50.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 86584057Phosphorus Pentoxide-Methanesulfonic AcidSolvent

Conditions

Temperature
70 °C

Procedure

The compound of Example 25D (1.68 g, 4.25 mmol) was dissolved in Eaton's reagent (15 mL, 1:10 (w/w) phosphorus pentoxide in methanesulfonic acid, cf. P. E. Eaton, et al. J. Am. Chem. Soc. 1973, 38, 4071) and warmed at 70° C. for 18 h. The solution was cooled to 25° C. and added to a mixture of ice and water. The mixture was extracted with dichloromethane (3×) and the combined organic layers dried (Na2SO4) and concentrated in vacuo. The oil obtained was dissolved in tetrahydrofuran (30 mL) and treated with 1 N HCl solution, followed by warming at reflux for 18 h. The mixture was cooled and extracted with ethyl acetate (2×). The combined organic layers were extracted with water (2×) and saturated NaCl solution. Drying (Na2SO4) and concentration in vacuo afforded a brown solid, which was triturated with ether-hexane and the resulting solid collected by filtration. These procedures afforded the title compound (590 mg, 50%) as an off-white solid. 1H NMR (300 MHz, DMSO-d6): δ 0.32 (m, 1 H) 0.71 (m, 10 H) 1.43 (s, 3 H) 1.91 (s, 1 H) 2.05 (m, 1 H) 5.73 (s, 1 H) 7.43 (m, 1 H) 7.57 (dd, J=9.56, 2.57 Hz, 1 H) 7.71 (s, 1 H) 11.79 (s, 1 H). Specific rotation: [α]D−27.7°(c 2.11, EtOH).

Workup

  1. temperatureThe solution was cooled to 25° C.
  2. extractionThe mixture was extracted with dichloromethane (3×)
  3. dry with materialthe combined organic layers dried (Na2SO4)
  4. concentrationconcentrated in vacuo
  5. customThe oil obtained
  6. temperatureby warming
  7. temperatureat reflux for 18 h
  8. temperatureThe mixture was cooled
  9. extractionextracted with ethyl acetate (2×)
  10. extractionThe combined organic layers were extracted with water (2×) and saturated NaCl solution
  11. customDrying
  12. concentration(Na2SO4) and concentration in vacuo
  13. customafforded a brown solid, which
  14. customwas triturated with ether-hexane
  15. filtrationthe resulting solid collected by filtration

Sources & evidence

ORD record
ord-ffcd88f8d3504812b6f03b07e4c60d4f
Source dataset
uspto-grants-2009_05
Patent number
US07538105B2

Reaction notes

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