3-Pyridinecarboxaldehyde → HCID 13590429, compound

HRID 1252694Notes

Reaction equation

HRID 1252694 reaction equation
[CH2:1]1[O:13][CH:4]([C:5]2[CH:10]=[CH:9][C:8]([CH2:11]Cl)=[CH:7][CH:6]=2)[O:3][CH2:2]1.P(OCC)(OCC)OCC.C[O-].[Na+].[N:27]1[CH:32]=[CH:31][CH:30]=[C:29]([CH:33]=O)[CH:28]=1>CN(C)C=O.C1(C)C=CC=CC=1>[CH2:1]1[O:13][CH:4]([C:5]2[CH:10]=[CH:9][C:8](/[CH:11]=[CH:33]/[C:29]3[CH:28]=[N:27][CH:32]=[CH:31][CH:30]=3)=[CH:7][CH:6]=2)[O:3][CH2:2]1

Participants

7

Reactant 4

HCID 103713-PyridinecarboxaldehydeHCID 31215Triethyl phosphiteHCID 3578782-(4-(Chloromethyl)phenyl)-1,3-dioxolaneHCID 10942334Sodium Methoxide

Product 1

HCID 13590429HCID 13590429, compoundYield 84.9%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
5 °C

Procedure

10.11 g (50.9 mmol) of 4-chloromethylbenzaldehyde ethylene acetal and 8.46 g (50.9 mmol) of triethyl phosphite were heated without solvent, with magnetic stirring, at an oil bath temperature of 200°-210° C. until gas evolution was complete (about 1 h). After cooling, 70 ml of dimethylformamide (filtered through basic alumina, activity I) and 5.5 g (102.0 mmol) of sodium methylate were added. The mixture was cooled to 5° C. and, with magnetic stirring and cooling, a solution of 5.45 g (50.9 mmol) of pyridine-3-aldehyde in 20 ml of dimethylformamide was added dropwise within 15 min (during which the temperature rose to 25° C.), and the mixture was then stirred at room temperature for 1 h. The reaction mixture was diluted with 250 ml of toluene and washed twice with water. The combined wash phases were extracted twice with toluene. Drying of the combined organic phases over magnesium sulfate and removal of the solvent in vacuo provided 10.94 g of a yellowish solid. Recrystallization from cyclohexane produced 8.74 g, and working up of the mother liquor produced a further 0.60 g.

Workup

  1. custom(about 1 h)
  2. temperatureAfter cooling
  3. temperaturecooling
  4. customrose to 25° C.
  5. stirringwas then stirred at room temperature for 1 h
  6. washwashed twice with water
  7. washThe combined wash phases
  8. extractionwere extracted twice with toluene
  9. dry with materialDrying of the combined organic phases over magnesium sulfate and removal of the solvent in vacuo

Sources & evidence

ORD record
ord-4bc8407933904ecb9628eab8e0594375
Source dataset
uspto-grants-1988_05
Patent number
US04745120

Reaction notes

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