Morpholine amide derivative and application thereof
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Embodiment 1
[0237] Synthesis of Example 1 (S)-4-(4-((3-fluorobenzyl)oxy)benzyl)morpholine-3-formamide
[0238]
[0239] Step 1) Synthesis of 4-((3-fluorobenzyl)oxy)benzaldehyde
[0240] 4-Hydroxybenzaldehyde (1.0g, 8.19mmol), 3-fluorobenzyl bromide (1.06mL, 8.64mmol), potassium carbonate (4.30g, 32.76mmol) and acetone (50mL) were successively added into a 100mL single-necked round bottom flask , reacted at 60°C for 5h, cooled to room temperature, filtered, collected the filtrate, and purified by direct column chromatography (petroleum ether / ethyl acetate (v / v)=10 / 1) to obtain the title compound as a white solid (1.78g, 94.7 %).
[0241] MS(ESI,pos.ion)m / z:231.1[M+H] + ;
[0242] 1 H NMR (400MHz, CDCl 3 )δ (ppm) 9.89 (s, 1H), 7.85 (d, J = 8.8Hz, 2H), 7.37 (td, J = 7.9, 6.0Hz, 1H), 7.20 (d, J = 7.7Hz, 1H), 7.15 (d, J = 9.4Hz, 1H), 7.08 (s, 1H), 7.06 (s, 1H), 7.03 (dd, J = 8.4, 2.2Hz, 1H), 5.15 (s, 2H).
[0243] Step 2) Synthesis of (4-((3-fluorobenzyl)oxy)phenyl)methanol
[0...
Embodiment 2
[0254] Example 2 Synthesis of (S)-4-(2-fluoro-4-((3-fluorobenzyl)oxy)benzyl)morpholine-3-formamide
[0255]
[0256] Step 1) Synthesis of 2-fluoro-4-((3-fluorobenzyl)oxy)benzaldehyde
[0257]The title compound of this step was prepared by referring to the method described in step 1 of Example 1, that is, 3-fluorobenzyl bromide (0.92mL, 7.50mmol), 2-fluoro-4-hydroxybenzaldehyde (1.00g, 7.14mmol), potassium carbonate (3.94g, 28.56mmol) and acetone (25mL) were sequentially added to a 100mL single-necked round-bottomed flask for reaction preparation, and then concentrated and mixed with column chromatography for purification (petroleum ether / ethyl acetate (v / v)=10 / 1) to obtain The title compound was a light red solid (1.48 g, 83.7%).
[0258] MS(ESI,pos.ion)m / z:249.1[M+H] + ;
[0259] 1 H NMR (400MHz, CDCl 3 )δ (ppm) 10.20 (s, 1H), 7.83 (t, J = 8.4Hz, 1H), 7.37 (td, J = 7.9, 5.9Hz, 1H), 7.18 (d, J = 7.6Hz, 1H), 7.13(d, J=9.4Hz, 1H), 7.05(td, J=8.4, 2.2Hz, 1H), 6.84(dd, ...
Embodiment 3
[0271] Embodiment 3 (S)-4-(4-((3-bromobenzyl) oxygen group) benzyl) morpholine-3-formamide synthesis
[0272]
[0273] Step 1) Synthesis of 4-((3-bromobenzyl)oxy)benzaldehyde
[0274] The title compound of this step was prepared by referring to the method described in step 1 of Example 1, that is, 3-bromobenzyl bromide (0.96mL, 6.00mmol), 4-hydroxybenzaldehyde (0.77g, 6.30mmol), potassium carbonate (0.91g, 6.60mmol) and acetone (25mL) were sequentially added to a 100mL single-necked round-bottomed flask for reaction preparation, and then concentrated and mixed with column chromatography for purification (petroleum ether / ethyl acetate (v / v)=10 / 1) to obtain the title compound as white Solid (1.61 g, 92.2%).
[0275] MS(ESI,pos.ion)m / z:292.0[M+H] + ;
[0276] 1 H NMR (400MHz, CDCl 3 )δ(ppm)9.90(s,1H),7.87(s,1H),7.85(s,1H),7.61(s,1H),7.49(d,J=7.9Hz,1H), 7.36(d,J =7.6Hz, 1H), 7.31–7.26(m, 1H), 7.09(s, 1H), 7.06(s, 1H), 5.12(s, 2H).
[0277] Step 2) Synthesis of (4-((3...
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