Hydrochloric Acid → HCID 68773038, compound

HRID 1471390Notes

Reaction equation

HRID 1471390 reaction equation
[CH2:1]([Mg]Cl)[CH:2]=[CH2:3].[CH3:6][C@H:7]1[CH2:16][CH:15]=[CH:14][C:9]2([CH2:13][CH2:12][CH2:11][CH2:10]2)[C@H:8]1[C:17]([O:19]CC)=O.Cl.CC([O-])(C)C.[K+]>C1COCC1.CN(C=O)C.CC1C=CC(S(O)(=O)=O)=CC=1.O.O>[CH3:6][C@H:7]1[CH2:16][CH:15]=[CH:14][C:9]2([CH2:10][CH2:11][CH2:12][CH2:13]2)[C@H:8]1[C:17](=[O:19])/[CH:1]=[CH:2]/[CH3:3]

Participants

9

Reactant 4

HCID 313Hydrochloric Acid2×HCID 23665647Potassium tert-butoxideHCID 68769890HCID 68769890, compoundHCID 178418473HCID 178418473, compound

Product 1

HCID 68773038HCID 68773038, compoundYield 43%

Reagents, catalysts & solvents 4

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
20 °C

Procedure

At 5° C., a solution of allylmagnesium chloride (12.1 ml, 2 M in THF) was treated dropwise with a solution of rel-(6S,7S)-ethyl 7-methylspiro[4.5]dec-9-ene-6-carboxylate (1.5 g, 6.7 mmol, prepared as described in Example 19) in THF (20 ml), stirred at 20° C. for 1 h, poured into cold 2N aqueous HCl (30 ml), and extracted twice with MTBE (70 ml). The combined organic phases were washed with water (100 ml), with a saturated aqueous solution of NaCl (100 ml), dried (MgSO4), and concentrated. The crude product (1.9 g) was dissolved in DMF (10 ml) and added to a solution of KOt-Bu (1.2 g, 10.7 mmol) in DMF (10 ml). The resulting mixture was stirred for 1 h, poured into cold 2N aqueous HCl (30 ml), and extracted twice with hexane (80 ml). The combined organic phases were washed with water (100 ml), with a saturated aqueous solution of NaCl (100 ml), dried (MgSO4), and concentrated. The crude product (1.9 g) was then dissolved in toluene (15 ml) and treated with PTSA.H2O (15 mg, 0.077 mmol). The resulting solution was stirred at 60° C. for 2.75 h, poured into cold water (30 ml), and extracted with cyclohexane (20 ml). The combined organic phases were washed with a saturated aqueous solution of NaCl (20 ml), dried (MgSO4), and concentrated. FC (120 g SiO2, hexane/MTBE 25:1) of the crude product (1.38 g) gave (E)-1-(rel-(6S,7S)-7-methylspiro[4.5]dec-9-en-6-yl)but-2-en-1-one (0.63 g, 43%). Boiling point: 115° C. (0.09 mbar).

Workup

  1. extractionextracted twice with MTBE (70 ml)
  2. washThe combined organic phases were washed with water (100 ml), with a saturated aqueous solution of NaCl (100 ml)
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. dissolutionThe crude product (1.9 g) was dissolved in DMF (10 ml)
  6. stirringThe resulting mixture was stirred for 1 h
  7. extractionextracted twice with hexane (80 ml)
  8. washThe combined organic phases were washed with water (100 ml), with a saturated aqueous solution of NaCl (100 ml)
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated
  11. dissolutionThe crude product (1.9 g) was then dissolved in toluene (15 ml)
  12. stirringThe resulting solution was stirred at 60° C. for 2.75 h
  13. extractionextracted with cyclohexane (20 ml)
  14. washThe combined organic phases were washed with a saturated aqueous solution of NaCl (20 ml)
  15. dry with materialdried (MgSO4)
  16. concentrationconcentrated

Sources & evidence

ORD record
ord-4f4c9a349e1d4a0eb67cd67bb2dd9477
Source dataset
uspto-grants-2015_04
Patent number
US09012391B2

Reaction notes

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