Tert-butyl 4-cyanophenylcarbamate → Tert-butyl N-(4-(aminomethyl)phenyl)carbamate

HRID 1191033

反応式

HRID 1191033 の反応式
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:16]=[CH:15][C:12]([C:13]#[N:14])=[CH:11][CH:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]>C1COCC1.C(O)(C)C.[Pd]>[C:1]([O:5][C:6]([NH:8][C:9]1[CH:10]=[CH:11][C:12]([CH2:13][NH2:14])=[CH:15][CH:16]=1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

参加物

4

反応物 1

HCID 10130644Tert-butyl 4-cyanophenylcarbamate

生成物 1

HCID 2794659Tert-butyl N-(4-(aminomethyl)phenyl)carbamate収率 36%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 22597222Tetrahydrofuran 2-propanol溶媒

実験手順

Add a solution of 4-(tert-butoxycarbonylamino)-benzonitrile (1 g, 4.58 mmol) in THF/iso-propanol (1:1, 142 mL) to 10% Pd/C (Degussa type E101, 0.56 g, 0.26 mmol) via syringe under N2. Purge the reaction mixture with nitrogen and submit the mixture to hydrogenation at 50 psi overnight. Filter the catalyst through Celite® and wash thoroughly with iso-propanol (100 mL) and THF (100 mL). Concentrate in vacuo and purify the crude mixture by chromatography on silica gel eluting with DCM/2M ammonia in methanol (1:0 to 95:5 gradient over 30 min; 95:5 over 3 min; 95:5 to 9:1 gradient over 30 min and 9:1 over 30 min) to obtain the desired intermediate (0.364 g, 36%). MS (ES−) m/z: 220.1 (M−2H)−.

後処理

  1. customPurge the reaction mixture with nitrogen
  2. customat 50 psi overnight
  3. filtrationFilter the catalyst through Celite®
  4. washwash thoroughly with iso-propanol (100 mL) and THF (100 mL)
  5. concentrationConcentrate in vacuo
  6. custompurify the crude mixture by chromatography on silica gel eluting with DCM/2M ammonia in methanol (1:0 to 95:5 gradient over 30 min; 95:5 over 3 min; 95:5 to 9:1 gradient over 30 min and 9:1 over 30 min)

出典と根拠

ORDレコード
ord-b422fa9a063a46dda99a9947d3e0f552
出典データセット
uspto-grants-2014_03
特許番号
US08680091B2

関連ノート

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