Methanol → HCID 22012605, compound

HRID 1533122Notes

Reaction equation

HRID 1533122 reaction equation
[CH2:1]([NH:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([F:15])[C:10]=1[CH:16]=NCC1C=CC=CC=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.C(O)(=O)C(O)=[O:28].CO>O1CCOCC1>[CH2:1]([NH:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([F:15])[C:10]=1[CH:16]=[O:28])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 962Water2×HCID 971Oxalic AcidHCID 22012607HCID 22012607, compound

Product 1

HCID 22012605HCID 22012605, compoundYield 786.3%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent3×

Procedure

To a solution of Example 1A (11.95 g, 3.9 mmol) in dioxane was added water (40 mL) until the solution just clouded and then dioxane was added until the solution became clear again(˜5 mL). Oxalic acid (9.83 g, 78.0 mmol) was added in a single portion to give a dark orange solution which became a thick slurry. To the slurry was added in sequence: water (110 mL), dioxane (60 mL), and methanol (20 mL). This gave a mostly homogeneous solution with some small crystals which eventually dissolved as the reaction mixture was stirred for 1 hour. The volume of the reaction was reduced to ⅓ of the original volume by concentration under vacuum. The resulting solution was extracted (3×, ethyl acetate). The organic extracts were combined and washed (2×, 10% aqueous HCl; 2×, saturated aqueous NaHCO3; 2×, brine), dried (Na2SO4), filtered and concentrated under vacuum to give a thick orange-yellow oil which was dried under vacuum at 45° C. to a constant weight providing the title compound (7.03 g, 79%) as a orange-yellow solid. This material was pure by 1H NMR. A small portion was recrystallized from ether/hexanes.

Workup

  1. customto give a dark orange solution which
  2. additionTo the slurry was added in sequence
  3. customThis gave a mostly homogeneous solution with some small crystals which
  4. dissolutioneventually dissolved as the reaction mixture
  5. concentrationto ⅓ of the original volume by concentration under vacuum
  6. extractionThe resulting solution was extracted (3×, ethyl acetate)
  7. washwashed (2×, 10% aqueous HCl; 2×, saturated aqueous NaHCO3; 2×, brine)
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated under vacuum
  11. customto give a thick orange-yellow oil which
  12. customwas dried under vacuum at 45° C. to a constant weight

Sources & evidence

ORD record
ord-45aa1884b7de44c8b5836f0105385014
Source dataset
uspto-grants-2001_03
Patent number
US06207701B1

Reaction notes

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