Formaldehyde → HCID 21436304, compound

HRID 2397913Notes

Reaction equation

HRID 2397913 reaction equation
Cl.[CH3:2][O:3][C:4]1[CH:19]=[CH:18][C:7]([CH2:8][CH:9]2[C:14](=[C:15]([CH3:17])[CH3:16])[CH2:13][CH2:12][CH2:11][NH:10]2)=[CH:6][CH:5]=1.C=O.[CH2:22](N(CC)CC)C.[H][H]>C(O)C>[CH3:22][N:10]1[CH2:11][CH2:12][CH2:13][C:14](=[C:15]([CH3:17])[CH3:16])[CH:9]1[CH2:8][C:7]1[CH:6]=[CH:5][C:4]([O:3][CH3:2])=[CH:19][CH:18]=1

Participants

6

Reactant 4

HCID 712FormaldehydeHCID 8471TriethylamineHCID 21436291HCID 21436291, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 21436304HCID 21436304, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 2.8 g. of 2-(p-methoxybenzyl)-3-isopropylidenepiperidine hydrochloride, 0.8 ml. of 35% aqueous formaldehyde solution, 1.4 ml. of triethylamine, and ethanol to a total volume of 50 ml. was shaken at room temperature under 50 p.s.i. of hydrogen. The theoretical quantity of hydrogen was consumed in one hour. The reaction mixture was filtered and the residue thus collected was rinsed with a small amount of ethanol. The filtrate and rinse were combined and evaporated to dryness under reduced pressure and the residue was partitioned between dilute ammonium hydroxide and diethyl ether. The ether layer was washed with water, dried, and filtered, and the filtrate evaporated to dryness under reduced pressure to give 1.9 g of 1-methyl-2-(p-methoxybenzyl)-3-isopropylidenepiperidine as a syrup. This was taken up in 50 ml. of diethyl ether and treated with a slight excess of ethereal hydrogen chloride to precipitate a gum. Addition of 5 ml. of isopropyl alcohol and trituration caused crystallization. Recrystallization from 5 ml. of isopropyl alcohol and 50 ml. of diethyl ether afforded the pure compound which melted at 179°-183° C; ir (KBr) 1670 cm-1 (tetrasubstituted double bond); nmr (of base, CDCl3): 147 (s,3); 93 (s,3); 63 (d3, J=1-2 cps).

Workup

  1. additionA mixture of 2.8 g
  2. customThe theoretical quantity of hydrogen was consumed in one hour
  3. filtrationThe reaction mixture was filtered
  4. customthe residue thus collected
  5. washwas rinsed with a small amount of ethanol
  6. washThe filtrate and rinse
  7. customevaporated to dryness under reduced pressure
  8. customthe residue was partitioned between dilute ammonium hydroxide and diethyl ether
  9. washThe ether layer was washed with water
  10. customdried
  11. filtrationfiltered
  12. customthe filtrate evaporated to dryness under reduced pressure

Sources & evidence

ORD record
ord-7948b24b497c4578a36839718ef1b5dd
Source dataset
uspto-grants-1977_05
Patent number
US04022792

Reaction notes

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