A kind of preparation method of deuterated compound
A technology of deuterated compounds and deuterated methanol, applied in the field of preparation of deuterated compounds, can solve the problems of high price, expensive metal catalysts, long synthesis routes, etc., and achieves simple and easy operation and preparation, short deuteration time, and deuterium. high generation effect
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[0120] In another aspect, the present invention provides a method for preparing deuterated compound III, which includes reacting deuterated compound I in the presence of a reducing agent to prepare deuterated compound III;
[0121] The deuterated compound I is a compound obtained by replacing all the hydrogen atoms on the atom directly connected to N with deuterium atoms in the structural elements of the non-deuterated compound Ia, the compound containing at least one structure of the formula CNX Element, and wherein the C atom of the structural element of the formula CNX is connected to at least one deuterium atom, the N atom of the structural element of the formula CNX is not connected to a deuterium atom or a hydrogen atom, and the atom directly connected to N is not connected to Hydrogen atom connection;
[0122] The deuterated compound III is that all structural elements of the formula C-N-X of the deuterated compound I are transformed into the formula C-N-NH 2 The compound or...
Embodiment 1
[0326] Example 1: N-[D 3 ] Preparation of methylaniline (compound of formula IV-1)
[0327]
[0328] (E / Z) Preparation of N-nitroso-N-methylaniline (compound of formula II-1): NaNO 2 (7.84g, 112mmol) and water (20mL) are slowly added dropwise to the solution composed of N-methylaniline (8.0g, 74.68mmol), water (9.6mL) and acetic acid (48mL), after the addition is complete The reaction was stirred at 0°C for 2 hours. After the reaction was completed, it was extracted 4 times with dichloromethane (20 mL each time). The dichloromethane layer was washed twice with a saturated aqueous sodium chloride solution (10 mL each time). Anhydrous sodium carbonate and The aqueous magnesium sulfate was dried, filtered, and the filtrate was concentrated under reduced pressure. The concentrate was dissolved in dichloromethane and adjusted to a pH greater than 7 with saturated sodium carbonate solution. After the organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate w...
Embodiment 2
[0334] Example 2: Two-[D 3 ] Preparation of methylamine hydrochloride (compound of formula VIII-1)
[0335]
[0336] (E / Z) Preparation of N-nitrosodimethylamine (compound of formula VI-1): Weigh the compound of formula V-1 (45g, 0.552mol) and 2mol / L HCl aqueous solution (165mL) in 500mL two In a neck flask, cool down to 0℃, and put NaNO 2 (57g, 0.826mol) dissolved in 180mL of water, added dropwise to the reaction flask at 0°C, kept at 0°C and reacted for 2 hours after the dropwise addition, stirred overnight at room temperature, and extracted 4 times with dichloromethane after the reaction was completed. The dichloromethane layer was dried by adding anhydrous sodium carbonate and anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure at not higher than 30°C to obtain a compound of formula VI-1 (29.33g, yellow-green liquid).
[0337] 1 HNMR(300MHz, CDCl 3 ): δ3.04 (s, 3H, the same isomer with the N=O group), 3.76 (ms, 3H, the reverse isomer w...
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