Benzaldehyde → (2-Phenyl-2H,4H-[1,3]dioxino[5,4-b]pyridin-6-yl)methanol

HRID 437392Notes

Reaction equation

HRID 437392 reaction equation
[OH:1][CH2:2][C:3]1[C:8]([OH:9])=[CH:7][CH:6]=[C:5]([CH2:10][OH:11])[N:4]=1.[CH:12](=O)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.B(F)(F)F.CCOCC>>[OH:11][CH2:10][C:5]1[CH:6]=[CH:7][C:8]2[O:9][CH:12]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[O:1][CH2:2][C:3]=2[N:4]=1

Participants

4

Reactant 3

HCID 240BenzaldehydeHCID 8000Boron trifluoride etherateHCID 4173663-Hydroxypyridine-2,6-dimethanol

Product 1

HCID 428642(2-Phenyl-2H,4H-[1,3]dioxino[5,4-b]pyridin-6-yl)methanolYield 77%

Procedure

To a stirred suspension of 31 g. (0.2 mole) of 2,6-bis-(hydroxymethyl)-3-hydroxypyridine (U.S. Pat. No. 3,700,681) in 101 ml. (1 mole) of benzaldehyde at 20°-25° C. is added dropwise over 45 min. 56.7 g. (0.4 mole) of borontrifluoride etherate. The mixture is allowed to stir at room temperature for 2 hrs., and the excess benzaldehyde removed under reduced pressure. The residue, after standing at room temperature, is added to 75 ml. of a 10M aqueous sodium hydroxide solution, and the product extracted into methylene dichloride. The organic phase is separated, concentrated in vacuo to 100 ml. and the methylene dichloride diluted with n-hexane. The crude product which crystallizes is filtered and dried, 37.4 g. (77% yield), m.p. 85°-89° C. Further purification is effected by recrystallization from acetone-n-hexane, 22.1 g., m.p. 114°-118° C.

Workup

  1. additionTo a stirred suspension of 31 g
  2. custom, and the excess benzaldehyde removed under reduced pressure
  3. customafter standing at room temperature
  4. additionis added to 75 ml
  5. extractionof a 10M aqueous sodium hydroxide solution, and the product extracted into methylene dichloride
  6. customThe organic phase is separated
  7. concentrationconcentrated in vacuo to 100 ml
  8. additionand the methylene dichloride diluted with n-hexane
  9. customThe crude product which crystallizes
  10. filtrationis filtered
  11. customdried
  12. customFurther purification
  13. customis effected by recrystallization from acetone-n-hexane, 22.1 g

Sources & evidence

ORD record
ord-e7bb09834a5e4089ab6b0bdb72659232
Source dataset
uspto-grants-1977_06
Patent number
US04031108

Reaction notes

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