Formaldehyde → HCID 20475366, compound

HRID 2295398Notes

Reaction equation

HRID 2295398 reaction equation
O.[Br-].[CH3:3][C:4]1[C:5]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][N:31]=2)=[N:6][C:7]([CH:10]=[C:11]2C=CC=CC2[PH+](C2C=CC=CC=2)C2C=CC=CC=2)=[CH:8][CH:9]=1.C=O.ClCCl.[OH-].[Na+]>[C-]#N.C([N+](CCCC)(CCCC)CCCC)CCC.O.C(C1C(C)=CC=C(O)C=1C(C)(C)C)(C)(C)C>[CH3:3][C:4]1[C:5]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][N:31]=2)=[N:6][C:7]([CH:10]=[CH2:11])=[CH:8][CH:9]=1

Participants

8

Reactant 4

HCID 712FormaldehydeHCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 86739171HCID 86739171, compound

Product 1

HCID 20475366HCID 20475366, compoundYield 71.9%

Reagents, catalysts & solvents 3

HCID 165872Tetrabutylammonium CyanideCatalystHCID 3034427Phenol, bis(1,1-dimethylethyl)-4-methyl-CatalystHCID 962WaterSolvent

Conditions

Temperature
23 °C

Procedure

0.9 g (1.7 mmols) of [3-methyl-2,2'-bipyridin-6-yl-(methylene)]-triphenylphosphonium bromide monohydrate is dissolved in a well stirred emulsion consisting of 15 ml of 35% formaldehyde solution, 20 ml of dichloromethane, 5 mg of di-tert.-butyl-p-cresol and 22 mg of tetrabutylammonium cyanide. A solution of 0.5 g of sodium hydroxide in 2.5 ml of water is added dropwise at 25° C. After stirring for 1 hour at 23° C., the dichloromethane phase is separated off and washed with 20 ml of water. After the addition of 5 mg of di-tert.-butyl-p-cresol, the mixture is concentrated in vacuo and 20 ml of dilute hydrochloric acid are added to the residue. The precipitating crystalline triphenylphosphine oxide is washed with three times 20 ml of ethyl acetate. The aqueous phase is covered with a layer of 20 ml of ethyl acetate and rendered alkaline with potassium carbonate. The organic phase is dried over sodium sulfate and freed from solvent in vacuo. After renewed addition of 5 mg of di-tert.-butyl-p-cresol, the residue is distilled in a bulb tube oven at a maximum of 150° C./0.93 Pa. 0.24 g (71% of theory) of 3-methyl-6-vinyl-2,2'-bipyridine are obtained as a colourless liquid. UV absorption (in chloroform): λ=250 nm (ε=15,450); λ=293 nm (ε=7,700).

Workup

  1. customthe dichloromethane phase is separated off
  2. washwashed with 20 ml of water
  3. additionAfter the addition of 5 mg of di-tert.-butyl-p-cresol
  4. concentrationthe mixture is concentrated in vacuo and 20 ml of dilute hydrochloric acid
  5. additionare added to the residue
  6. washThe precipitating crystalline triphenylphosphine oxide is washed with three times 20 ml of ethyl acetate
  7. dry with materialThe organic phase is dried over sodium sulfate
  8. additionaddition of 5 mg of di-tert.-butyl-p-cresol
  9. distillationthe residue is distilled in a bulb tube oven at a maximum of 150° C./0.93 Pa

Sources & evidence

ORD record
ord-2be2887ed9894898a55cc1add646b2f0
Source dataset
uspto-grants-1984_01
Patent number
US04424359

Reaction notes

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