Ammonium Chloride → tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aminomethyl)-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

HRID 405100ノート

反応式

HRID 405100 の反応式
O[N:2]=[CH:3][C@:4]12[CH2:42][CH2:41][C@@H:40]([C:43]([CH3:45])=[CH2:44])[C@@H:5]1[C@@H:6]1[C@@:19]([CH3:22])([CH2:20][CH2:21]2)[C@@:18]2([CH3:23])[C@@H:9]([C@:10]3([CH3:39])[C@@H:15]([CH2:16][CH2:17]2)[C:14]([CH3:25])([CH3:24])[C:13]([C:26]2[CH:38]=[CH:37][C:29]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])=[CH:28][CH:27]=2)=[CH:12][CH2:11]3)[CH2:8][CH2:7]1.[NH4+].[Cl-].[Na]>[Cl-].[Ti+3].[Cl-].[Cl-].CCO>[NH2:2][CH2:3][C@:4]12[CH2:42][CH2:41][C@@H:40]([C:43]([CH3:45])=[CH2:44])[C@@H:5]1[C@@H:6]1[C@@:19]([CH3:22])([CH2:20][CH2:21]2)[C@@:18]2([CH3:23])[C@@H:9]([C@:10]3([CH3:39])[C@@H:15]([CH2:16][CH2:17]2)[C:14]([CH3:25])([CH3:24])[C:13]([C:26]2[CH:38]=[CH:37][C:29]([C:30]([O:32][C:33]([CH3:34])([CH3:35])[CH3:36])=[O:31])=[CH:28][CH:27]=2)=[CH:12][CH2:11]3)[CH2:8][CH2:7]1

参加物

6

反応物 3

HCID 25517Ammonium ChlorideHCID 5360545SodiumHCID 86676421tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((hydroxyimino)methyl)-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

生成物 1

HCID 86676419tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aminomethyl)-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

試薬・触媒・溶媒 2

HCID 10313229titanium(III) trichloride触媒HCID 702Ethanol溶媒

実験手順

To the crude product from above containing tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((hydroxyimino)methyl)-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 (100 mg, 0.163 mmol) in a 100 mL pear shape flask was added EtOH (12 mL) to form a clear solution. To this was added excess of NH4Cl (400 mg, 5.19 mmol) and sodium cyanoborohydre (300 mg, 4.77 mmol). The mixture was stirred in an ice bath until cold. To this suspension was added titanium(III) chloride (4 mL, 0.163 mmol) 20% solution. The resulting mixture was blanketed with nitrogen. The ice bath was removed and the stirring was continued at rt for an hour. LCMS show the reaction was complete. At this point, the mixture was dark greenish-blue-purple. A solution of sodium hydroxide (3 mL, 10N in 25 mL water) was added into the reaction mixture, along with methylene chloride (30 mL).

後処理

  1. customto form a clear solution
  2. customThe ice bath was removed
  3. waitthe stirring was continued at rt for an hour
  4. additionA solution of sodium hydroxide (3 mL, 10N in 25 mL water) was added into the reaction mixture, along with methylene chloride (30 mL)

出典と根拠

ORDレコード
ord-d32393327a9a49439416ade6c55c209b
出典データセット
uspto-grants-2014_06
特許番号
US08748415B2

反応ノート

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