Water → 1-Benzyl-4-butylidenepiperidine

HRID 1859617Notes

Reaction equation

HRID 1859617 reaction equation
[H-].[Na+].[H][H].[CH2:5]([N:12]1[CH2:17][CH2:16][C:15](=O)[CH2:14][CH2:13]1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.O>[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)CCC.CS(C)=O>[CH2:5]([N:12]1[CH2:17][CH2:16][C:15](=[CH:5][CH2:6][CH2:7][CH3:8])[CH2:14][CH2:13]1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

7

Reactant 4

HCID 962WaterHCID 192201-Benzyl-4-piperidoneHCID 24758Sodium hydrideHCID 178418361HCID 178418361, compound

Product 1

HCID 149666561-Benzyl-4-butylidenepiperidineYield 449%

Reagents, catalysts & solvents 2

HCID 159628Butyltriphenylphosphonium bromideCatalystHCID 679Dimethyl SulfoxideSolvent2×

Procedure

A 500 mL 3-necked flask fitted with a stirrer, was charged with sodium hydride (1.61 g, 67 mmol) and DMSO (40 mL). The resulting suspension was heated to 90° C. for 30 min, until the evolution of hydrogen ceased. The suspension was cooled on an ice-bath for 20 min followed by addition of a slurry of butyltriphenylphosphonium bromide (26.6 g, 67 mmol) in DMSO (70 mL). The red mixture was stirred for 15 min at rt. 1-Benzyl-4-piperidone 1 (14.0 g, 74 mmol) was slowly added over 30 min, and the mixture was stirred at room temperature over night. H2O (200 mL) was added to the reaction mixture followed by extraction with heptane (4×100 mL) and ethyl acetate (2×100 mL). The combined organic phases were dried and evaporated to dryness, producing 38.1 g of a yellow oil. The oil was distilled to give 14.9 g (88%) of 2, bp 101-105° C. (0.1 mm Hg). 1H NMR (CDCl3) δ 0.90-0.95 (t, 3H), 1.25-1.41 (m, 2H), 1.90-2.20 (m, 2H), 2.18-2.30 (m, 4H), 2.40-2.45 (m, 4H), 2.50 (s, 2H), 5.17 (t, 1H), 7.20-7.42 (m, 5H).

Workup

  1. customA 500 mL 3-necked flask fitted with a stirrer
  2. temperatureThe suspension was cooled on an ice-bath for 20 min
  3. stirringthe mixture was stirred at room temperature over night
  4. extractionfollowed by extraction with heptane (4×100 mL) and ethyl acetate (2×100 mL)
  5. customThe combined organic phases were dried
  6. customevaporated to dryness

Sources & evidence

ORD record
ord-64652fad56594ca393b537642810c12d
Source dataset
uspto-grants-2003_03
Patent number
US06528529B1

Reaction notes

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