反応 #172734

反応方程式

diphenyl phosphoryl azide

(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid

triethylamine

→

title compound

収率 86.4%

methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-isocyanato-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate

収率 86.4%

溶媒

EtOAc

1,4-dioxane

反応条件

後処理

1. 1
   温度to cool to rt
2. 2
   洗浄washed with 1N NaOH (2×70 mL)
3. 3
   抽出The combined aqueous layer was extracted with EtOAc (2×150 mL)
4. 4
   乾燥The combined organic layer was dried over Na2SO4
5. 5
   ろ過filtered
6. 6
   濃縮concentrated to a slurry (75 mL) which
7. 7
   その他was stored in a refrigerator overnight
8. 8
   ろ過The slurry was filtered
9. 9
   洗浄the white solid product was washed with Et2O
10. 10
    濃縮The liquid filtrate was concentrated to a yellow slurry which
11. 11
    ろ過was filtered
12. 12
    洗浄washed with Et2O
13. 13
    その他to give more white solid product
14. 14
    その他dried in vacuo

実験手順

To a slurry of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (10 g, 17.46 mmol) in 1,4-dioxane (200 mL) was added triethylamine (4.38 mL, 31.4 mmol) followed by diphenyl phosphoryl azide (5.82 mL, 26.2 mmol). The resulting white slurry was heated to 100° C. After 5 h, the reaction was allowed to cool to rt and was then diluted with EtOAc and washed with 1N NaOH (2×70 mL). The combined aqueous layer was extracted with EtOAc (2×150 mL). The combined organic layer was dried over Na2SO4, filtered and concentrated to a slurry (75 mL) which was stored in a refrigerator overnight. The slurry was filtered and the white solid product was washed with Et2O. The liquid filtrate was concentrated to a yellow slurry which was filtered and washed with Et2O to give more white solid product. The two batches of white solid were combined and dried in vacuo to give the title compound (8.6 g, 15.09 mmol, 86% yield) as a white solid. 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 8.0 (2H, d, J=8.2 Hz), 7.2 (2H, d, J=8.2 Hz), 5.3 (1H, d, J=4.6 Hz), 4.8 (1H, s), 4.7 (1H, s), 3.9 (3H, s), 2.6 (1H, td, J=10.8, 5.8 Hz), 2.1-2.2 (2H, m), 1.8-2.0 (4H, m), 1.7-1.8 (1H, m), 1.7 (3H, s), 1.5-1.7 (5H, m), 1.4-1.5 (5H, m), 1.3-1.4 (2H, m), 1.2-1.3 (2H, m), 1.1 (3H, s), 1.1-1.1 (1H, m), 1.0 (3H, s), 1.0 (3H, s), 1.0 (3H, br. s.), 1.0 (3H, br. s.). 13C NMR (CHLOROFORM-d) δ ppm 14.2, 15.4, 16.2, 19.2, 19.5, 20.8, 21.0, 24.7, 27.4, 29.0, 29.2, 33.3, 36.0, 37.2, 39.0, 39.0, 40.3, 41.5, 41.8, 47.8, 49.0, 49.2, 51.7, 52.6, 66.8, 71.3, 110.2, 121.3, 123.7, 127.6, 128.2, 129.8, 146.0, 148.4, 148.6, 166.9.

出典