Phosphoric Acid → ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-yl)-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)cyclohex-3-enecarboxylate

HRID 338653ノート

反応式

HRID 338653 の反応式
[NH2:1][C@:2]12[CH2:38][CH2:37][C@@H:36]([C:39]([CH3:41])=[CH2:40])[C@@H:3]1[C@@H:4]1[C@@:17]([CH3:20])([CH2:18][CH2:19]2)[C@@:16]2([CH3:21])[C@@H:7]([C@:8]3([CH3:35])[C@@H:13]([CH2:14][CH2:15]2)[C:12]([CH3:23])([CH3:22])[C:11]([C:24]2[CH2:29][CH2:28][CH:27]([C:30]([O:32][CH2:33][CH3:34])=[O:31])[CH2:26][CH:25]=2)=[CH:10][CH2:9]3)[CH2:6][CH2:5]1.Br[CH2:43][CH2:44]Cl.P(=O)(O)(O)O.[K]>C(#N)C>[N:1]1([C@:2]23[CH2:38][CH2:37][C@@H:36]([C:39]([CH3:41])=[CH2:40])[C@@H:3]2[C@@H:4]2[C@@:17]([CH3:20])([CH2:18][CH2:19]3)[C@@:16]3([CH3:21])[C@@H:7]([C@:8]4([CH3:35])[C@@H:13]([CH2:14][CH2:15]3)[C:12]([CH3:23])([CH3:22])[C:11]([C:24]3[CH2:29][CH2:28][CH:27]([C:30]([O:32][CH2:33][CH3:34])=[O:31])[CH2:26][CH:25]=3)=[CH:10][CH2:9]4)[CH2:6][CH2:5]2)[CH2:44][CH2:43]1

参加物

6

反応物 4

HCID 1004Phosphoric AcidHCID 78491-Bromo-2-ChloroethaneHCID 5462222PotassiumHCID 86692333ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-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)cyclohex-3-enecarboxylate

生成物 1

HCID 86692341ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-yl)-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)cyclohex-3-enecarboxylate収率 100.3%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

反応条件

温度
120 °C

実験手順

To a sealable vial was added ethyl 4-((1R,3 aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-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)cyclohex-3-enecarboxylate (0.2 g, 0.356 mmol), 1-bromo-2-chloroethane (0.295 mL, 3.56 mmol) and phosphoric acid, potassium salt (0.378 g, 1.780 mmol). The mixture was diluted with acetonitrile (5 mL), was flushed with nitrogen, then sealed and heated to 120° C. After 24 h of heating, the mixture was cooled to rt. The reaction mixture was filtered to remove solids, then the solids were washed with dichloromethane and the filtrate was concentrated under reduced pressure to give the title compound (0.21 g, 0.357 mmol, 100% yield) as an off-white solid. LCMS: m/e 588.7 (M+H)+, 2.21 min (method 5).

後処理

  1. customwas flushed with nitrogen
  2. customsealed
  3. temperatureAfter 24 h of heating
  4. temperaturethe mixture was cooled to rt
  5. filtrationThe reaction mixture was filtered
  6. customto remove solids
  7. washthe solids were washed with dichloromethane
  8. concentrationthe filtrate was concentrated under reduced pressure

出典と根拠

ORDレコード
ord-be803485e34d4809a29baca97678a3e6
出典データセット
uspto-grants-2014_11
特許番号
US08889854B2

反応ノート

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