Novel 2H-chromene derivatives as selective estrogen receptormodulators
A chromene and selected technology, applied in the field of selective estrogen receptor modulators, can solve the problems of not improving the cognitive function of elderly patients
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Embodiment 1
[0168] 4-Methyl-2-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-2H-chromene-7-ol (Compound ID#4)
[0169]
[0170] Step A: Preparation of 4-methyl-7-(2-trimethylsilyl-ethoxymethoxy)-2H-chromen-2-ol
[0171] To a solution of 4-methyl-7-(2-trimethylsilyl-ethoxymethoxy)-chromen-2-one (1.53g, 5mmol) in toluene (50mL) at -78°C A 1.5M solution of DIBAL-H in toluene (3.34 mL, 5 mmol) was added slowly. After stirring at -78 °C for 30 min, the reaction mixture was quenched with methanol (1 mL). The reaction mixture was then diluted with ethyl acetate (500 mL) and washed with saturated aqueous potassium sodium tartrate (4 x 200 mL). The organic layer was dried over sodium sulfate and concentrated to give the crude product as a colorless oil. The crude product was used in the next step without further purification.
[0172] Step B: Preparation of 4-Methyl-2-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-2H-chromen-7-ol
[0173]To a solution of 1-[2-(4-iodo-phenoxy)-ethyl]-piperidine (15 mmol) (...
Embodiment 2
[0177] 4-Methyl-2-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-3-(2-trimethylsilyl-ethoxy Methyl)-2H-chromen-7-ol (Compound ID#2)
[0178]
[0179] Step A: Preparation of 4-methyl-7-(2-trimethylsilyl-ethoxymethoxy)-3-(2-trimethylsilyl-ethoxymethyl)-chromene-2 -ketone
[0180] To a solution of 4-methyl-7-(2-trimethylsilyl-ethoxymethoxy)-chromen-2-one (306 mg, 1 mmol) in THF (10 mL) at -10°C was added LiHMDS (1.5 mL, 1.0 M in THF). The resulting yellowish solution was stirred for 30 min, then SEMCl (0.21 mL, 1.2 mmol) was added. After 2 hours, the reaction was quenched with aqueous ammonium chloride and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated. Flash column to get 4-methyl-7-(2-trimethylsilyl-ethoxymethoxy)-3-(2-trimethylsilyl-ethoxymethyl)-chromene-2- Ketones are colorless oily substances.
[0181] 1 HNMR (CDCl 3 , 400MHz) δ (ppm) 7.8 (d, J = 8.4Hz, 1H), 7.2 (d, J = 8.4Hz, 2H), 5.51 (s, 2H), 4.77 (s, 2H), 4.01 (t, J ...
Embodiment 3
[0198] S * -4-Methyl-2-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-3-(2-trimethylsilylethoxymethyl)-2H-color En-7-ol and
[0199] R * -4-Methyl-2-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-3-(2-trimethylsilylethylhydrogenmethyl)-2H-color En-7-ol (Compound ID#3 and Compound ID#11)
[0200]
[0201]The racemic compound 4-methyl-2-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-3-(2-trimethylsilylethoxymethyl) -2H-chromen-7-ol (2.5 g) was loaded onto a ChiralPak AD chiral HPLC column (5 cm I.D. x 50 cm L), and eluted with 20% MeOH / IPA at a flow rate of 90 mL / min. Under vacuum, the two peaks were separated to give the following product:
[0202] Peak 1: S * -4-Methyl-2-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-3-(2-trimethylsilylethoxymethyl)-2H-color en-7-ol
[0203] 1 HNMR (CDCl 3 , 400MHz) δ (ppm) 7.2 (d, J = 8.4Hz, 2H), 7.05 (d, J = 8.4Hz, 1H), 6.65 (d, J = 6.8Hz, 2H), 6.35 (dd, 1 J=8.4Hz, 2 J=2Hz, 1H), 6.20(d, J=2Hz, 1H), 5.75(s, 1H), 4.2(d, J=10Hz, 1H), 4.0(t, J=6Hz, 2H), 3.7(d , J=10Hz,...
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