Triphenylphosphine → HCID 14154745, compound

HRID 2291831Notes

Reaction equation

HRID 2291831 reaction equation
N(C(OC(C)C)=O)=NC([O:5][CH:6]([CH3:8])C)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O[CH:35]1[CH:40]2[CH2:41][CH2:42][N:37]([CH2:38][CH2:39]2)[CH2:36]1.[S:43]1C=CC=C1CC(O)=O>O1CCCC1.C(OCC)C.[OH-].[Na+]>[C:6]([S:43][CH:35]1[CH:40]2[CH2:41][CH2:42][N:37]([CH2:38][CH2:39]2)[CH2:36]1)(=[O:5])[CH3:8]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 15381(+-)-3-QuinuclidinolHCID 159702-Thiopheneacetic acidHCID 75555Diisopropyl diazene-1,2-dicarboxylate

Product 1

HCID 14154745HCID 14154745, compound

Reagents, catalysts & solvents 3

HCID 14798Sodium HydroxideCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
5 °C

Procedure

Diisopropyl azodicarboxylate (31.6 cc) is added dropwise in the course of 30 minutes to a solution, maintained at 5° C. under an atmosphere of nitrogen, of triphenylphosphine (42 g) in tetrahydrofuran (300 cc). The suspension obtained in then stirred for 30 minutes at 5° C. A solution of 3-hydroxyquinuclidine (10.2 g) and thiolacetic acid (11.4 cc) in tetrahydrofuran (600 cc) is then added to this suspension, maintained at 5° C., in the course of 30 minutes. The reaction mixture is then stirred for 20 hours at a temperature in the region of 20° C. It is then concentrated to dryness under reduced pressure (2.7 kPa) at 40° C. The oil obtained is dissolved in ethyl ether (400 cc), and then washed with hydrochloric acid (3×160 cc). The combined aqueous phases are washed with ethyl ether (100 cc) and then neutralized to a pH in the region of 7 by adding sodium bicarbonate. The pH of the solution obtained is then adjusted to about 9 by adding a few drops of 10N aqueous sodium hydroxide solution. The mixture is extracted with methylene chloride (3×200 cc). The combined organic phases are dried over sodium sulphate, filtered and concentrated to dryness under reduced pressure (2.7 kPa) at 30° C. 3-(Acetylthio)quinuclidine (14.7 g) is thereby obtained in the form of a brown oil [Rf=0.33; eluant: methylene chloride/methanol (90:10 by volume)].

Workup

  1. customThe suspension obtained
  2. temperaturemaintained at 5° C., in the course of 30 minutes
  3. stirringThe reaction mixture is then stirred for 20 hours at a temperature in the region of 20° C
  4. concentrationIt is then concentrated to dryness under reduced pressure (2.7 kPa) at 40° C
  5. customThe oil obtained
  6. washwashed with hydrochloric acid (3×160 cc)
  7. washThe combined aqueous phases are washed with ethyl ether (100 cc)
  8. additionby adding sodium bicarbonate
  9. customThe pH of the solution obtained
  10. extractionThe mixture is extracted with methylene chloride (3×200 cc)
  11. dry with materialThe combined organic phases are dried over sodium sulphate
  12. filtrationfiltered
  13. concentrationconcentrated to dryness under reduced pressure (2.7 kPa) at 30° C

Sources & evidence

ORD record
ord-26d5265a99ac4aa7b9d7544174bb9ca8
Source dataset
uspto-grants-1989_01
Patent number
US04798827

Reaction notes

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