Hydrochloric Acid → Scopine-2,2-dithienyl glycolate

HRID 914637Notes

Reaction equation

HRID 914637 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]([C:12]1[S:13][CH:14]=[CH:15][CH:16]=1)([OH:11])[C:7]([O:9][CH3:10])=[O:8].[CH3:17][N:18]1[C@@H:23]2[C@@H:24]3[O:26][C@@H:25]3[C@H:19]1[CH2:20]C(O)[CH2:22]2.[Na].Cl>C1(C)C=CC=CC=1>[CH3:17][N:18]1[C@@H:23]2[C@@H:24]3[O:26][C@@H:25]3[C@H:19]1[CH2:20][CH:10]([O:9][C:7]([C:6]([OH:11])([C:12]1[S:13][CH:14]=[CH:15][CH:16]=1)[C:2]1[S:1][CH:5]=[CH:4][CH:3]=1)=[O:8])[CH2:22]2

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 1274465(1α,2β,4β,5α)-9-Methyl-3-oxa-9-azatricyclo[3.3.1.02,4]nonan-7α-olHCID 5360545SodiumHCID 11414137Methyl alpha-hydroxy-alpha-2-thienyl-2-thiopheneacetate

Product 1

HCID 29927228Scopine-2,2-dithienyl glycolate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

38.15 g (0.15 mole) of methyl di-(2-thienyl)glycolate and 23.28 g (0.15 mole) of scopine are mixed, 0.34 g (0.015 gram atom) of sodium is added and the mixture is melted in a heating bath at 90° C. under a water jet vacuum. The reaction lasts 2.5 hours. 100 ml of absolute toluene are then added and the mixture is stirred at a heating bath temperature of 90° C. until a solution is produced. The reaction solution is cooled to room temperature and stirred into a mixture of ice and hydrochloric acid cooled using ice. The hydrochloride of the basic ester crystallising out is filtered off under suction and washed using a small amount of water and a large amount of diethyl ether. The filtrate phases are separated off and the aqueous phase is extracted using diethyl ether. The hydrochloride filtered off under suction is suspended in the (acid) aqueous phase and converted to the base while monitoring the temperature and adding the corresponding amount of sodium carbonate; the base is extracted using methylene chloride. The combined methylene chloride phases are dried over sodium sulphate. After distilling off the methylene chloride, crystals remain which are purified over active charcoal and recrystallised from acetonitrile. Pale yellow crystals (from acetonitrile), m.p. 148°-49° C.;

Workup

  1. customthe mixture is melted in a heating bath at 90° C. under a water
  2. customis produced
  3. temperatureThe reaction solution is cooled to room temperature
  4. temperaturecooled
  5. filtrationThe hydrochloride of the basic ester crystallising out is filtered off under suction
  6. washwashed
  7. customThe filtrate phases are separated off
  8. extractionthe aqueous phase is extracted
  9. filtrationThe hydrochloride filtered off under suction
  10. additionadding the corresponding amount of sodium carbonate
  11. extractionthe base is extracted
  12. dry with materialThe combined methylene chloride phases are dried over sodium sulphate
  13. distillationAfter distilling off the methylene chloride, crystals
  14. customare purified over active charcoal
  15. customrecrystallised from acetonitrile

Sources & evidence

ORD record
ord-74d0b292d78240bbb536d8aebe2bba9a
Source dataset
uspto-grants-2007_09
Patent number
USRE039820E1

Reaction notes

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