Ethanol → Methyl 3-(benzyloxy)-6-[4-methoxy-2-methyl-3-(3,3,6,6-tetramethyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)phenyl]pyridine-2-carboxylate

HRID 873528Notes

Reaction equation

HRID 873528 reaction equation
N1CCCC1.[CH2:6]([O:13][C:14]1[C:15]([C:31]([O:33][CH3:34])=[O:32])=[N:16][C:17]([C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[C:22]([CH:28]=O)[C:21]=2[CH3:30])=[CH:18][CH:19]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[CH3:35][C:36]1([CH3:44])[CH2:41][C:40](=[O:42])[CH2:39][C:38](=[O:43])[CH2:37]1.O.[C:46]1([CH3:56])[CH:51]=C[C:49](S(O)(=O)=O)=[CH:48][CH:47]=1.[CH2:57]([OH:59])[CH3:58]>C(Cl)(Cl)Cl.CCCCCC.O>[CH2:6]([O:13][C:14]1[C:15]([C:31]([O:33][CH3:34])=[O:32])=[N:16][C:17]([C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[C:22]([CH:28]3[C:49]4[C:57](=[O:59])[CH2:58][C:46]([CH3:56])([CH3:51])[CH2:47][C:48]=4[O:42][C:40]4[CH2:41][C:36]([CH3:44])([CH3:35])[CH2:37][C:38](=[O:43])[C:39]3=4)[C:21]=2[CH3:30])=[CH:18][CH:19]=1)[C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1

Participants

9

Reactant 5

HCID 702EthanolHCID 31268PyrrolidineHCID 31358DimedoneHCID 521998p-Toluenesulfonic acid monohydrateHCID 117700526HCID 117700526, compound

Product 1

HCID 117700825Methyl 3-(benzyloxy)-6-[4-methoxy-2-methyl-3-(3,3,6,6-tetramethyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)phenyl]pyridine-2-carboxylateYield 81%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6212ChloroformSolventHCID 8058HexaneSolvent

Conditions

Temperature
80 °C

Procedure

Pyrrolidine (0.057 ml, 0.69 mmol) was added to a suspension of the methyl 3-(benzyloxy)-6-(3-formyl-4-methoxy-2-methylphenyl)pyridine-2-carboxylate produced in Example 11-1 (3.02 g) and 5,5-dimethylcyclohexane-1,3-dione (2.23 g, 15.92 mmol) in ethanol (60 ml) at room temperature, and the mixture thus obtained was then stirred at 80° C. for 2 hours. After air-cooling, the solvent was distilled away from the reaction solution under reduced pressure. The residue thus obtained was dissolved in chloroform (60 ml), and p-toluenesulfonic acid monohydrate (0.357 g, 2.08 mmol) was then added to the solution obtained above at room temperature. The mixture thus obtained was stirred at 70° C. for 1.5 hours. After air-cooling, water was added to the reaction solution, and the mixed solution was then extracted with ethyl acetate. The organic layer thus obtained was dried over anhydrous sodium sulfate. The solvent was distilled away under reduced pressure, and the residue thus obtained was then purified by silica gel column chromatography (ethyl acetate:hexane=2:3 to 1:1, v/v) to obtain the title compound (3.56 g, yield: 81%).

Workup

  1. customthe mixture thus obtained
  2. temperatureAfter air-cooling
  3. distillationthe solvent was distilled away from the reaction solution under reduced pressure
  4. customThe residue thus obtained
  5. customobtained above at room temperature
  6. customThe mixture thus obtained
  7. stirringwas stirred at 70° C. for 1.5 hours
  8. temperatureAfter air-cooling
  9. extractionthe mixed solution was then extracted with ethyl acetate
  10. customThe organic layer thus obtained
  11. dry with materialwas dried over anhydrous sodium sulfate
  12. distillationThe solvent was distilled away under reduced pressure
  13. customthe residue thus obtained
  14. customwas then purified by silica gel column chromatography (ethyl acetate

Sources & evidence

ORD record
ord-013fb76550024df8acebec0f52d71f12
Source dataset
uspto-grants-2015_03
Patent number
US08975263B2

Reaction notes

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