芥酸二十二烯酸环化研究.doc

芥酸（二十二烯酸）环化

药品: 芥酸（阿拉丁80%）, CuCl2（沃凯 99%）, PaCl2（沪试AR）, Pa/C（Sigma-Alorich 10 wt%）, Br2（西陇 AR）, KOH（科密欧 AR）, TMSCl（沪试 CP）, LiAlH4（。。。）, 正丙醇（科密欧 AR）, CH3OH（天力 AR）, DMSO（科密欧 AR）, THF（西陇 AR）, 苯（沪试 AR）, 正丁醇（科密欧 AR）
仪器: 傅立叶变换红外光谱仪（Tensor, Bruker）, 核磁共振光谱仪（Avance ⅢTM 300 MHz NB Digital, Bruker）
1. Dibromide carboxylic acid 1
Erucic acid (15.88 g, 33.6 mmol) in diethyl ether (50 mL) was colled to 0 oC in an ice-water bath. Bromine (2.7 mL, 52.3 mmol) was then removed and solytion was stirred for another 2 hrs at RT. Saturated Na2S2O3 solution (20 mL) was added to reduce the excess bromine. The resulting solution was further washed distilled water (20 mL) and diethyl ether (30 mL). The organic layer was separated, washed with brine (20 mL) and dried over MgSO4. The solvent was evaporated by reduced pressure to give pale yellow oil 1 (yield……).
2. Behenolic acid 2
Dibromide compound 1 (7.5 g, 15 mmol) was dissolved in DMSO (18 mL, 250 mmol). KOH (20g, 360 mmol) and 1-propanol (150 mL) were added. The mixture was heated at 108 oC under reflux for 4 hrs and cooled to RT. Then the solution was poured into 2N HCl (150 mL) at room temperature. The resulting solution was further washed distilled water (20 mL) and diethyl ether (30 mL). The organic layer was separated, washed with brine (20 mL) and dried over MgSO4. The solvent was evaporated by reduced pressure to give yellow oil 2 (yield……).
3. Behenolyl alcohol 3
Behenolic acid 2 (1.5 g, 4.3 mmol) was dissolved in 30 mL diethyl ether. LiAlH4 (0.2 g, 5.1 mmol) was then added. The mixture was stirred for 2 hrs at RT. Distilled water (20 mL) was added followed by 2N HCl (30 mL). The resulting solution was further washed distilled water and diethyl ether (30 mL). The organic layer was separated, washed with brine (20 mL) and dried over MgSO4. The solvent was evaporated by reduced pressure to give……3 (yield.......).
4. Behenolic ester 4
To a solution of behenolic acid 2 (1.5 g, 4.3 mmol) in methanol (50 mL) was added three drops of concentrated sulphuric acid. The reaction mixture was heated at 95 oC refluxed for 3 hrs and cooled to RT. The resulting solution was further washed distilled water (20 mL) and diethyl ether (30 mL). The organic layer was separated, washed with brine (20 mL) and dried over MgSO4. The solvent was evaporated by reduced pressure to give dark yellow oil 4 (yield……).
5. Aromatic triols 5
Behenolyl alcohol 3 (1.3 g, 4.0 mmol) was dissolved in THF (30 mL). 0.25 g of Pd/C (10%) and TMSCl (0.75 mL, 6.0 mmol) were then added. The reaction mixture was heated at 65 oC refluxed for 12 hrs and cooled to RT. The mixture was filtered to remove the Pd/C. The resulting solution was further washed distilled water (20 mL) and diethyl ether (30 mL). The organic layer was separated, washed with brine (20 mL) and dried over MgSO4. The solvent was evaporated by reduced pressure to give…….5 (yield ……).
6. Aromatic triols 6
To a solution of behenolyl alcohol 3 (1.3 g, 4.0 mmol) was dissolved in n-butyl alcohol (9 mL) and benzene (150 mL). 0.25 g of PdCl2 (0.15 g, 0.85 mmol) and CuCl2 (4.1 g, 24 mmol) were then added. The reaction mixture was heated at 40 oC refluxed for 8 hrs and cooled to RT. The mixture was filtered to remove the PdCl2 and CuCl2. The resulting solution was further washed distilled water (20 mL) and diethyl ether (30 mL). The organic layer was separated, washed with brine (20 mL) and dried over MgSO4. The solvent was evaporated by reduced pressure to give…… 6 (yield ……).
7. Aromatic triester 7
Behenolic ester 4 (1.4 g, 4.0 mmol) was dissolved in THF (30 mL). 0.25 g of Pd/C (10%) and TMSCl (0.75 mL, 6.0 mmol) were then added. The reaction mixture was heated at 65 oC refluxed for 12 hrs and cooled to RT. The mixture was filtered to remove the Pd/C. The resulting solution was further washed distilled water (20 mL) and diethyl ether (30 mL). The organic layer was separated, washed with brine (20 mL) and dried over MgSO4. The solvent was evaporated by reduced pressure to give dark red oil 7 (yield ……).
8. Aromatic triester 8
A solution of behenolic ester 4 (1.4 g, 4.0 mmol) was dissolved in n-butyl alcohol (9 mL) and benzene (150 mL). 0.25 g of PdCl2 (0.15 g, 0.85 mmol) and CuCl2 (4.1 g, 24 mmol) were then added. The reaction mixture was heated at 40 oC refluxed for 8 hrs and cooled to RT. The mixture was filtered to remove the PdCl2 and CuCl2. The resulting solution was further washed distilled water (20 mL) and diethyl ether (30 mL). The organic layer was separated, washed with brine (20 mL) and dried over MgSO4. The solvent was evaporated by reduced pressure to give dark yellow oil 8 (yield ……).