Ethyl Acetate → HCID 90018918, compound

HRID 1506952Notes

Reaction equation

HRID 1506952 reaction equation
[C:1]([O-:4])([O-])=O.[K+].[K+].CS(N)(=O)=O.COC(=O)/C=C/[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[Cl:23].S([O-])([O-])=[O:26].[Na+].[Na+].C[CH2:32][O:33][C:34]([CH3:36])=[O:35]>CC[C@H]1[C@H]2C[C@H]([C@H](OC3C4C(=CC=CC=4)C(O[C@H](C4C=CN=C5C=4C=C(OC)C=C5)[C@@H]4N5C[C@H](CC)[C@@H](CC5)C4)=NN=3)C3C=CN=C4C=3C=C(OC)C=C4)N(CC2)C1.O.C(O)(C)(C)C>[CH3:32][O:33][C:34](=[O:35])[C@H:36]([OH:26])[C@H:1]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[Cl:23])[OH:4]

Participants

9

Reactant 5

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 24437Sodium SulfiteHCID 72879MethanesulfonamideHCID 11063366HCID 11063366, compound

Product 1

HCID 90018918HCID 90018918, compoundYield 7,090%

Reagents, catalysts & solvents 3

HCID 510036741-((1R)-((2R,4R,5S)-5-ethylquinuclidin-2-yl)(6-methoxyquinolin-4-yl)methoxy)-4-((1R)-((2R,4S,5R)-5-ethylquinuclidin-2-yl)(6-methoxyquinolin-4-yl)methoxy)phthalazineCatalystHCID 962WaterSolvent2×HCID 6386tert-ButanolSolvent

Conditions

Temperature
0 °C

Procedure

A 1000 ml round-bottomed flask, equipped with a magnetic stirrer, was filled with 362 ml of tert-butyl alcohol, 362 ml of water, K3Fe(CN)6 (135.53 g, 411.63 mmol), K2CO3 (56.89 g, 411.63 mmol), (DHQ)2PHAL (1.06 g, 1.37 mmol), K2OsO2(OH)4, (0.1 g, 0.27 mmol), and Methanesulfonamide (13.05 g, 137.21 mmol) and stirred at 0° C. (E)-Methyl-3-(2-chlorophenyl)acrylate (26.98 g, Preparation example 24) was added at once, and the mixture was stirred vigorously at 0° C. overnight. While the mixture was stirred at 0° C., solid sodium sulfite (Na2SO3, 24.4 g, 193.5 mmol), EtOAc and water was added and the mixture was allowed to warm to room temperature and stirred. After the separation of the layer, the aqueous layer was added to EtoAc, and the aqueous layer was separated. The combined organic layers were washed with 0.3M H2SO4/Na2SO4 solution (H2SO4 76 ml, H2O 2 L, Na2SO4 360 g) twice. After separation of the organic layer, the organic layer was washed with H2O. After separating of the layer, the organic layer were dried over anhydrous MgSO4, filtered and concentrated under vacuum. The crude compound was purified by a silica gel column to produce the title compound (24.42 g, 7090%)

Workup

  1. customA 1000 ml round-bottomed flask, equipped with a magnetic stirrer
  2. additionwas added at once, and the mixture
  3. stirringWhile the mixture was stirred at 0° C.
  4. temperatureto warm to room temperature
  5. stirringstirred
  6. customAfter the separation of the layer
  7. additionthe aqueous layer was added to EtoAc
  8. customthe aqueous layer was separated
  9. washThe combined organic layers were washed with 0.3M H2SO4/Na2SO4 solution (H2SO4 76 ml, H2O 2 L, Na2SO4 360 g) twice
  10. customAfter separation of the organic layer
  11. washthe organic layer was washed with H2O
  12. customAfter separating of the layer
  13. dry with materialthe organic layer were dried over anhydrous MgSO4
  14. filtrationfiltered
  15. concentrationconcentrated under vacuum
  16. customThe crude compound was purified by a silica gel column

Sources & evidence

ORD record
ord-d57a5c45e23c4bf2b5db081b67d1215a
Source dataset
uspto-grants-2015_12
Patent number
US09221783B2

Reaction notes

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