Benzothiazin-4-one compound containing n-aminopiperazine fragment and preparation method thereof
A compound, piperazine technology, applied in the field of medicinal chemistry, can solve the problems of poor water solubility and in vivo activity of BTZ043 not as expected, and achieve the effects of low side effects, cost reduction, and simple operation of the synthesis process
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Embodiment 1
[0065] Example 1. 2-(4-(Cyclohexylamino)piperazin-1-yl)-8-nitro-6-(trifluoromethyl)-4H-benzo[e][1,3]thiophene oxazin-4-one
[0066] Compound 1-tert-butyloxycarbonyl-4-aminopiperazine IV (201mg, 1.0mmol) was dissolved in 10mL of dichloromethane solution, then cyclohexanone (108mg, 1.2mmol) and acetic acid (72mg, 1.2mmol) were added , after stirring at room temperature for 0.5 hours, sodium triacetoxyborohydride (318 mg, 1.5 mmol) was added, and stirring was continued for 1.5 hours. Post-processing: the reaction solution was washed with water, and the dichloromethane layer was dried over anhydrous sodium sulfate.
[0067] After the above dried solution was filtered, trifluoroacetic acid (342 mg, 3.0 mmol) was added to the system, and stirred at room temperature for 1 hour. Post-processing: The reaction solution was directly spin-dried to carry out the next reaction.
[0068] The above concentrated solution was dissolved in 5 mL of methanol, then triethylamine (303 mg, 3.0 mmo...
Embodiment 2
[0070] Example 2. 2-(4-((cyclohexylmethyl)amino)piperazin-1-yl)-8-nitro-6-(trifluoromethyl)-4H-benzo[e][1, 3] Thiazin-4-one
[0071] Referring to Example 1, compound IV was reductively aminated with cyclohexylformaldehyde, de-Boc-protected, and then reacted with compound II to obtain a light yellow solid.
[0072] 1 H NMR (600MHz, CDCl 3 ):δ9.10(s,1H),8.76(s,1H),4.20-3.88(m,4H),2.78(brs,4H),2.66(d,J=6.7Hz,2H),1.78-1.66( m,5H),1.49-1.44(m,1H),1.28-1.16(m,3H),0.97-0.90(m,2H). 13 C NMR (150MHz, CDCl 3 ): δ166.61, 162.28, 144.08, 134.13, 133.57(q, J=4.1Hz), 129.94(q, J=35.3Hz), 126.81, 126.20(q, J=4.4Hz), 122.51(q, J=273.1Hz ),55.16,51.03,46.39,37.10,31.72,26.81,26.18.MS-ESI(m / z):472.2(M+H) + .
Embodiment 3
[0073] Example 3. 2-(4-((2-cyclohexylethyl)amino)piperazin-1-yl)-8-nitro-6-(trifluoromethyl)-4H-benzo[e][ 1,3] Thiazin-4-one
[0074] Referring to Example 1, compound IV was reductively aminated with cyclohexylacetaldehyde, de-Boc-protected, and then reacted with compound II to obtain a light yellow solid.
[0075] Yellow solid; yield: 27%; 1 H NMR (600MHz, CDCl 3 ): δ9.10(d, J=2.0Hz, 1H), 8.76(d, J=2.1Hz, 1H), 4.15-3.94(m, 4H), 2.85-2.79(m, 6H), 1.72-1.62( m,5H),1.38-1.30(m,4H),1.22-1.19(m,2H),0.95-0.89(m,2H). 13 C NMR (150MHz, CDCl 3): δ166.59, 162.28, 144.09, 134.11, 133.43(q, J=3.5Hz), 129.96(q, J=35.0Hz), 126.82, 126.05(q, J=3.4Hz), 122.52(q, J=273.5Hz ), 55.26, 46.22, 36.20, 35.91, 33.60, 29.84, 26.72, 26.45. MS-ESI (m / z): 486.2 (M+H) + .
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