Sodium Methoxide → HCID 13728682, compound

HRID 2291146Notes

Reaction equation

HRID 2291146 reaction equation
C([C:3]1[Se:7][C:6]([C@@H:8]2[O:30][C@H:29]([CH2:31][O:32]C(=O)C3C=CC=CC=3)[C@@H:19]([O:20]C(=O)C3C=CC=CC=3)[C@H:9]2[O:10]C(=O)C2C=CC=CC=2)=[N:5]C=1C(N)=O)C.C[O-].[Na+].C1(C)C=CC=CC=1.[C:54]([O:57][CH2:58]C)(=[O:56])[CH3:55]>CO>[C@@H:8]1([C:6]2[Se:7][CH:3]=[C:55]([C:54]([O:57][CH3:58])=[O:56])[N:5]=2)[O:30][C@H:29]([CH2:31][OH:32])[C@@H:19]([OH:20])[C@H:9]1[OH:10]

Participants

5

Reactant 3

HCID 10942334Sodium MethoxideHCID 21584019Toluene ethylacetateHCID 86741092HCID 86741092, compound

Product 1

HCID 13728682HCID 13728682, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A gummy suspension of 206.3 g (75.1% pure by HPLC; 0.239 mol) of the blocked ethyl ester, IV, in 700 ml of methanol was heated and stirred on the steam bath until solution occurred. The solution was allowed to cool to room temperature during which time a finely dispersed oily suspension formed. To this suspension was added 17.2 g (318 mmol) of sodium methoxide. The addition was slightly exothermic and resulted in a brown solution. The solution was stirred at room temperature overnight. TLC (SiO2, toluene-ethyl acetate, 10:1) indicated that no starting material remained. To the reaction solution was added 100 g of Dowex 50 W×4 resin (H+) (washed with methanol) and the suspension was stirred for one hour. The resin was filtered off, washed well with methanol, and discarded. The filtrate and washings were evaporated under reduced pressure to give a two phase mixture. The upper, more liquid phase (mainly methyl benzoate) was decanted. The remaining brown viscous gum was triturated two times with ether. (The methyl benzoate was combined with the ether triturates and upon standing yielded some desired product as a solid). The brown viscous gum was treated with approximately 1 l of warm ethanol and triturated. A dark brown material was filtered from the suspension. TLC (SiO2; dichloromethane-methanol, 10:1) indicated that the dark brown material was mostly slower moving impurities in the filtrate and was discarded.

Workup

  1. customformed
  2. additionThe addition
  3. customresulted in a brown solution
  4. stirringThe solution was stirred at room temperature overnight
  5. additionTo the reaction solution was added
  6. wash100 g of Dowex 50 W×4 resin (H+) (washed with methanol)
  7. stirringthe suspension was stirred for one hour
  8. filtrationThe resin was filtered off
  9. washwashed well with methanol
  10. customThe filtrate and washings were evaporated under reduced pressure
  11. customto give a two phase mixture
  12. customThe upper, more liquid phase (mainly methyl benzoate) was decanted
  13. customThe remaining brown viscous gum was triturated two times with ether

Sources & evidence

ORD record
ord-8ce6d2d45d8b42a8b1314b3fa5a70cd3
Source dataset
uspto-grants-1986_10
Patent number
US04619996

Reaction notes

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