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ChemicalBook CAS DataBase List 4-(Hydroxymethyl)piperidine-1-carbaldehyde
835633-50-6

4-(Hydroxymethyl)piperidine-1-carbaldehyde synthesis

3synthesis methods
4-Piperidinemethanol

6457-49-4

Methyl formate

107-31-3

4-(Hydroxymethyl)piperidine-1-carbaldehyde

835633-50-6

The general procedure for the synthesis of 4-(hydroxymethyl)piperidine-1-carbaldehyde from 4-(hydroxymethyl)piperidine and methyl formate was as follows: 4-(hydroxymethyl)piperidine (10 g, 87 mmol) was dissolved in methyl formate (7 mL, 113 mmol) at 0 °C and the reaction was maintained at this temperature for 30 min. The reaction system was then warmed to 20 °C and stirring was continued for 90 min. Solid sodium hydroxide pellets (0.87 g) were added to the reaction mixture and the mixture was allowed to stand overnight. Upon completion of the reaction, it was diluted with the addition of dichloromethane and the solid sodium hydroxide was removed by filtration. The filtrate was treated with an ether solution (10 mL) of 1 M hydrochloric acid and subsequently filtered through diatomaceous earth. Finally, the solvent was removed by distillation under reduced pressure to give the crude product 4-(hydroxymethyl)piperidine-1-carbaldehyde. The product was characterized by 1H NMR (400 MHz, CDCl3) with the following chemical shifts: 0.85-1.1 (2H, m); 1.55-1.85 (3H, m); 2.5-2.7 (1H, m); 2.95-3.1 (1H, m); 3.3 (2H, d, J=7 Hz); 3.6-3.7 (1H, m); 4.1-4.3 ( 1H, m); 8 (1H, s).

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Yield:835633-50-6 100%

Reaction Conditions:

Stage #1: 4-piperidinemethanol;Methyl formate at 0 - 20; for 2 h;
Stage #2: with sodium hydroxide
Stage #3: with hydrogenchloride in diethyl ether;dichloromethane;

Steps:

F

4-Piperidinemethanol (10 g, 87 mmol) was dissolved in methyl formate (7 mL, 113 mmol) 0 °C, and maintained at that temperature for 30 min, then allowed to reach 20 °C and stirred 90 min. Solid sodium hydroxide was added (0.87 g, pellets) and the mixture was left overnight. Dichloromethane was added, the NAOH removed by filtration and the solution treated with 1M HCL in ether (10 mL). The mixture was filtered through Celite and the solvent was removed under reduced pressure to afford the crude title COMPOUND. 1H NMR (400 MHz, CDC13) : 0. 85-1. 1 (2H, m); 1.55-1. 85 (3H, m); 2.5-2. 7 (1H, m); 2.95-3. 1 (1H, m); 3.3 (2H, D, J7 Hz); 3.6-3. 7 (1H, m); 4.1-4. 3 (1H, m); 8 (1H, s)

References:

WO2005/9443,2005,A1 Location in patent:Page/Page column 57

6457-49-4 Synthesis
4-Piperidinemethanol

6457-49-4
356 suppliers
$18.00/25g

201230-82-2 Synthesis
carbon monoxide

201230-82-2
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4-(Hydroxymethyl)piperidine-1-carbaldehyde

835633-50-6
30 suppliers
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