Methoxymethyl-triphenylphosphonium chloride → 1-(4-Chlorocinnamyl)-4-[1-methoxy-methylidene]-3-methyl-piperidine

HRID 1875548Notes

Reaction equation

HRID 1875548 reaction equation
CC(C)([O-])C.[K+].[Cl-].[CH3:8][O:9][CH2:10][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cl:30][C:31]1[CH:47]=[CH:46][C:34]([CH:35]=[CH:36][CH2:37][N:38]2[CH2:43][CH2:42][C:41](=O)[CH:40]([CH3:45])[CH2:39]2)=[CH:33][CH:32]=1.CC1C(=O)CCNC1.ClC1C=CC(C=CCCl)=CC=1>O1CCCC1.O>[Cl:30][C:31]1[CH:47]=[CH:46][C:34]([CH:35]=[CH:36][CH2:37][N:38]2[CH2:43][CH2:42][C:41](=[CH:8][O:9][CH3:10])[CH:40]([CH3:45])[CH2:39]2)=[CH:33][CH:32]=1

Participants

8

Reactant 5

HCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 122842773-Methylpiperidin-4-oneHCID 23665647Potassium tert-butoxideHCID 53728250p-Chlorocinnamyl chlorideHCID 687996701-(4-Chlorocinnamyl)-3-methyl-piperidin-4-one

Product 1

HCID 688000601-(4-Chlorocinnamyl)-4-[1-methoxy-methylidene]-3-methyl-piperidine

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Potassium t-butoxide (1.56 g) was added portionwise to a stirred suspension of methoxymethyltriphenylphosphonium chloride (4.76 g) in tetrahydrofuran (30 ml) at 0° C. under argon. The resulting orange mixture was stirred at 0° C. for 30 min., then 1-(4-chlorocinnamyl)-3-methyl-piperidin-4-one (1.83 g, prepared by alkylation of 3-methyl-piperidin-4-one [CAS No 5773-58-0] with 4-chloro-cinnamyl chloride) dissolved in a minimum volume of tetrahydrofuran was added dropwise and the resulting solution was stirred at room temperature for 1 hour, poured into water and extracted twice with ether. The combined organic layers were dried over sodium sulphate and concentrated in vacuo. The residue was purified by silica gel chromatography (cyclohexane:ethyl acetate 75:25) to afford 1-(4-chlorocinnamyl)-4-[1-methoxy-methylidene]-3-methyl-piperidine as a mixture of diastereoisomers. MS (ES+) 292/294 (M+H+).

Workup

  1. additionwas added dropwise
  2. stirringthe resulting solution was stirred at room temperature for 1 hour
  3. extractionextracted twice with ether
  4. dry with materialThe combined organic layers were dried over sodium sulphate
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by silica gel chromatography (cyclohexane:ethyl acetate 75:25)

Sources & evidence

ORD record
ord-54744d90d98b412b996c1a0cc6d3edbb
Source dataset
uspto-grants-2012_11
Patent number
US08309567B2

Reaction notes

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