Carbamates as btk inhibitors
A technology of carbadithioformic acid and dithioformic acid, which is applied in the field of preparation of new carbamate compounds for the treatment or prevention of cancer, and can solve the problem of under-immunity, lack of antibodies, and B cell death And other issues
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[0063] Next, the present invention will be described in further detail through examples, but the present invention is not limited to these examples.
[0064] In an exemplary embodiment, the compound of the present invention is synthesized by the following method, wherein each substituent is as defined in the general formula (I).
preparation Embodiment 1
[0065] Preparation Example 1: 2-Chloro-5-fluoro-N-(3-nitrophenyl)pyrimidin-4-amine
[0066]
[0067] Dissolve 2,4-dichloro-5-fluoropyrimidine (2g, 12mmol) and m-nitroaniline (1.38g, 10mmol) in 20ml of isopropanol, then add DIEA (1.6ml, 10mmol), and heat at 90°C Reflux for 6 hours until a large number of yellow solids are formed, cool to room temperature, filter with suction, wash the solid with 95% ethanol and ether, and dry to obtain a light yellow flocculent solid (1.77g, yield 66%). 1 H NMR (400MHz, DMSO-d 6 )δ10.38(s,1H),8.72(t,J=2.1Hz,1H),8.41(d,J=3.3Hz,1H),8.14(dd,J=8.2,1.4Hz,1H),7.98– 7.89 (m, 1H), 7.65 (t, J=8.2Hz, 1H).
preparation Embodiment 2a
[0068] Preparative Example 2a: 1-(2-Chloroethoxy)-4-nitrobenzene
[0069]
[0070] Add p-nitrophenol (1.39g, 10mmol) and potassium carbonate (1.38g, 10mmol) to 25ml of acetonitrile, then dropwise add 1-bromo-2-chloroethane (2.5ml, 30mmol), and reflux overnight at 80°C. After the reaction, add water to dissolve potassium carbonate, extract with ethyl acetate, wash the organic phase with saturated sodium bicarbonate and brine, evaporate to dryness under reduced pressure to give a white solid (1.69g, yield 84%), the product is directly used without purification react in the next step.
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