Preparation and use of thiocarbonyl compound
A thiocarbonyl, compound technology, applied in the field of tumor-related drugs
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preparation example Construction
[0043] Reference example 1 (preparation of intermediate 1)
[0044]
[0045] 3,4 difluorobenzaldehyde as the starting material reacts with hydroxylamine hydrochloride under alkaline and room temperature conditions to generate 3,4 difluorobenzoxime (intermediate 2), and then reacts with N-chlorosuccinimide to generate 3 , 4 difluorobenzoxime chloride (intermediate 3), 3 and allyl acetamide carry out cyclization reaction under low temperature conditions to obtain intermediate 5: (±)-N-5-(acetamidomethyl)-3- (3,4 difluorophenyl) isoxazoline, 5 reacts with anhydrous piperazine heating to generate intermediate 1: (±)-N-[[3-[3-fluoro-4-(1-piperazinyl) )phenyl]-4,5 dihydro-5-isoxazolyl]methyl]acetamide. m.p.160.5-161.3°C, 1 H-NMR (DMSO-d 6 , 400MHz) δ: 1.81 (s, 3H, CH 3 ), 3.04-3.62 (m, 8H, Piperazinyl-H), 4.68-4.72 (m, 1H, CH), 7.06-7.42 (m, 3H, Ar-H), 8.09 (t, 1H, NH).
Embodiment 1
[0047] Ij: (±)-N-[[3-[3-fluoro-4-[4-[(p-fluorobenzaldehyde hydrazone)thiocarbonyl]-1-piperazinyl]phenyl]-4,5- Dihydro-5-isoxazolyl]methyl]acetamide.
[0048]
[0049] Dissolve 1g of intermediate 1 and 0.71g of methyl p-fluorobenzaldehyde hydrazone dithiocarbamate in 40ml of absolute ethanol, pass through nitrogen protection, connect the airway tube at the end of the condenser, and connect an inverted suspension at the end of the airway tube Put a glass funnel in a beaker filled with ethanol, react at 30-50°C for 5-6 hours, then heat up, reflux for 5-24 hours, TLC detects that the reaction is complete, filter while hot, and rinse the filter cake with a small amount of ethyl acetate , and dried to obtain 1.08 g of yellow solid with a yield of 69.9%. m.p.208.8-209.8℃, HPLC99.1%, 1 H-NMR (DMSO-d6, 400MHz) δ: 1.80(s, 3H, CH 3 ), 3.19-3.25 (m, 2H, Isoxazole-CH 2 ), 3.31-4.07 (m, 8H, Piperazinyl-H), 4.67-4.74 (m, 1H, CH), 7.10-7.72 (m, 7H, Ar-H), 8.10 (t, 1H, NHC=O), 8.16 (s,...
Embodiment 2-4
[0051] With reference to the operation of Example 1, the difference is that the methyl dithioformate compound containing different substituents is selected to replace the methyl p-fluorobenzaldehyde hydrazone dithioformate in Example 1, and react with intermediate 1 to prepare the following formula I compound.
[0052]
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