ARTEMISININ

ARTEMISININ




 

 

 

 
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http://www.google.com/patents/WO2012154906A1?cl=en


To a solution of compound 10 (7 g, 15.4 mmol) and ammonium molybdate (1 .51 g, 7.7 mmol) in t-BuOH (60 mL) was added 50% H₂0₂ (10 mL, 150 mmol). The solution was stirred with additional H₂O₂ (5 ml_, 75 mmol) added every 12 hours. At 72 hours, the mixture was diluted with water (100 mL), extracted with CH₂CI₂ (3x100 mL), dried over MgS0₄, filtered and concentrated. The yellow crude mixture was dissolved in DCM (50 mL) and treated with p-toluensulfonic acid (pTSA) (285 mg, 1 .5 mmol). The resulting solution was stirred for 72 hours before being concentrated and filtered through a plug of silica (hexanes/diethyl ether 10:1 eluent). The resulting yellow oil could be purified by flash chromatography (ethyl acetate in hexanes 0% to 20%), or recrystallized from heptane to obtain 1 .26 g artemisinin (1 ) (29% yield).
[0058] NOTE: Amberlite IR120 hydrogen form and other homogenous proton sources could also be used in place of p-toluenesulfonic acid.
[0059] IR (film) v/cm^"1 2956 (m), 2933 (m), 2884 (m), 2861 (m), 1739 (s), 1201 (m), 1 1 14 (s), 1033 (m), 1028 (m), 995 (s), 883 (m). [a]_D ²⁰ = +64.0 (c 1 .20, CHCI₃) (nat.
[G]_D ²⁰ = +66.6 (c 0.90, CHCI3)). ¹H NMR (400 MHz, CDCI₃) δ 5.84 (s, 1 H), 3.38 (dq, J = 7.4, 5.5 Hz, 1 H), 2.41 (ddd, J = 14.4, 12.9, 3.9 Hz, 1 H), 2.06-1 .92 (m, 2H), 1 .90- 1 .82 (m, 1 H), 1 .79-1 .70 (m, 2H), 1 .52-1 .31 (m, 3H), 1 .42 (s, 3H), 1 .18 (d, J = 7.4 Hz, 3H), 1 .10-1 .00 (m, 2H), 0.98 (d, J = 5.9 Hz, 3H). ¹³C NMR (100 MHz, CDCI₃) δ
172.7, 106.0, 94.3, 80.1 , 50.7, 45.6, 38.2, 36.5, 34.2, 33.5, 25.8, 25.5, 24.0, 20.5, 13.2. HRMS calculated for Ci₅H₂₂0₅Na [M+ Na] 305.1365, found 305.1356.

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HSQC

COSY
 
 HMBC
 




 

 




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