Preparation method of alfentanil and sufentan and compounds used for preparation of sufentanil and alfentan
A compound and methylation technology, applied in the field of sufentanil compound and preparation of alfentanil, can solve the problems of safety, harsh reaction conditions, cumbersome operation, etc.
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[0079] (1) According to the method for preparing the compound shown in the formula V described above, prepare the compound shown in the formula V or the oxalate of the compound shown in the formula V;
[0080] (2) contacting ethyl isocyanate with azidotrimethylsilyl to obtain 4-ethyl-1H-tetrazol-5-one;
[0081] (3) contacting 4-ethyl-1H-tetrazol-5-one with 1.4-dihaloalkane so as to obtain the compound shown in formula XII; and
[0082] (4) making the compound shown in formula V or the oxalate salt of the compound shown in formula V condense with the compound shown in formula XII, so as to obtain the compound shown in the formula VI,
[0083]
[0084] Wherein, the group Z in formula XII is halogen.
[0085] According to the embodiments of the present invention, the method can be used to conveniently, efficiently and safely prepare the compound shown in the formula VI, which is the intermediate product of alfentanil synthesis, and then, the compound shown in the formula VI c...
Embodiment 1
[0178] Example 1 Preparation of 4-anilino-1-tert-butoxycarbonyl-piperidine-4-carboxylic acid (compound shown in formula I)
[0179]
[0180] Aniline (20g, 215mmol), sodium hydroxide (30g, 750mmol), and N-Boc piperidone (90g, 452mmol) were added to a three-necked flask filled with tetrahydrofuran (1200ml), cooled to 0°C, and slowly added dropwise with chloroform (90 g, 75 mmol). After the dropwise addition, the reaction solution was a yellow transparent liquid, and the reaction was maintained at 0° C. for 1 h. Then, react at room temperature for 12h. Post-treatment: Stand still to produce precipitation, filter with suction, dissolve the filter cake in water (400ml), extract impurities 2 times with an appropriate amount of ether, adjust the pH value of the aqueous phase to 3, and use ethyl acetate (100ml / time, 3 times) ) to extract the product, wash the organic phase twice with water, dry over anhydrous magnesium sulfate, filter, and concentrate to obtain a yellow oil, add ...
Embodiment 2
[0182] Embodiment 2 prepares the compound shown in formula II
[0183] 1. Preparation of methyl 1-BOC-4-phenylaminopiperidine-4-carboxylate
[0184]
[0185] Add 4-phenylamino-1-tert-butoxycarbonyl-piperidine-4-carboxylic acid (16g, 50mmol) into a reaction flask filled with N,N-dimethylformamide (150ml), stir at room temperature to dissolve, Then potassium carbonate (21g, 152mmol) was added, stirred at room temperature for 0.5h, the reaction solution became turbid, then methyl iodide (15g, 106mmol) was added, stirred at room temperature for 12h. Post-processing: add water (300ml) to the reaction solution, separate out oil, extract with ether (100ml / time, 3 times), wash with water, dry over anhydrous magnesium sulfate, filter, concentrate to get yellow oil, add n-hexane ( 100ml) was stirred and beaten to obtain 14.5 g of a milky white solid, with a yield of 87%, an HPLC purity of 99.1%, and a melting point of 92-93°C.
[0186] 1H NMR (400MHz, CDCl3) δ7.21–7.10 (m, 2H), 6.7...
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