Methods for making 4-tetrazolyl-4-phenylpiperidine compounds
A kind of technology of compound and composition, applied in the field of preparing 4-tetrazolyl-4-phenylpiperidine compound, can solve the problems such as compound synthesis without description of tetrazole part
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[0566] 4.2.7. The preparation method of compound (9)
[0567] In another embodiment, the present invention relates to a process for the preparation of compound (9) (4-phenyl-4-(2H-tetrazol-5-yl)-piperidine), comprising making compound (8) (4-cyano Base-4-phenyl-piperidinium chloride) is reacted with sodium azide in the presence of a suitable zinc salt as shown in Scheme 7 below:
[0568] Option 7
[0569]
[0570] In certain embodiments, the phenyl moiety attached to the 4-position of the piperidine ring according to compound (8) (commercially available) and other compounds formed therefrom is substituted with one or more R 2 group, where R 2 defined above.
[0571] The reaction of Scheme 7 is carried out in a solvent containing a polar aprotic solvent. Examples of suitable polar aprotic solvents for use in the reaction of Scheme 7 include, but are not limited to, dioxane, N-methylpyrrolidone, dimethylformamide, dimethylacetamide or dimethyls...
Embodiment 1
[0775] 5.1. Example 1: Synthesis of compound (2) (1-benzyl-4-phenyl-4-(2H-tetrazol-5-yl)-piperidine)
[0776] To well stirred 125.77 g of 1-benzyl-4-cyano-4-phenylpiperidine hydrochloride (the hydrochloride salt of compound (1)) (Aldrich Chemical Co., Milwaukee, Wisconsin) in 1.0 L of chloroform Add 500mL Na to the solution 2 CO 3 saturated aqueous solution. Separate the layers and recover the chloroform layer. The aqueous layer was extracted with about 200 ml of chloroform. The chloroform layers recovered twice were combined, extracted with about 500 mL of deionized water, dried over anhydrous sodium sulfate and evaporated to constant weight to obtain 109.7 g of compound (1) as a free amine, (1-benzyl-4-cyano base-4-piperidine).
[0777] The free amine compound (1) (109.7 g) was dissolved in 500 mL of 1-methyl-2-pyrrolidone and divided into two parts, and the following steps were performed in parallel on the two parts using the same flask.
[0778] A portion of compound...
Embodiment 2
[0780] 5.2. Example 2: Synthetic compound (4) (2-[5-(1-benzyl-4-phenylpiperidin-4-yl)-tetrazol-2-yl]-acetamide)
[0781]
[0782] Equipped with magnetic stirrer, temperature controller, condenser and N 2 Add compound (2) (1-benzyl-4-phenyl-4-(2H-tetrazol-5-yl)-piperidine) (234.57g, 0734mol) to an imported 3-liter round bottom flask, dimethyl Formamide (2.0 L), potassium carbonate (121.8 g, 0.881 mol) and 2-bromoacetamide (101.32 g, 0.734 mol) (Aldrich Chemical Co., Milwaukee, Wisconsin). The reaction mixture was heated to 50 °C under N 2 Incubate overnight. Analysis of a reaction sample by LC / MS indicated the reaction was complete.
[0783] The reaction mixture was cooled to room temperature and poured into 4.5 L of rapidly stirring deionized water. Ethyl acetate (2.5 L) was added and the resulting precipitate was collected by vacuum filtration and dissolved in about 6 L of ethyl acetate. The resulting layers were separated and the ethyl acetate layer was recovered, dr...
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