Formaldehyde → 4-Boc-1-methyl-2-phenylpiperazine

HRID 530623ノート

反応式

HRID 530623 の反応式
[C:1]1([CH:7]2[NH:12][CH2:11][CH2:10][N:9]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C=O.[C:22](O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>CO.C(=O)(O)[O-].[Na+].C(OCC)(=O)C>[C:16]([O:15][C:13]([N:9]1[CH2:10][CH2:11][N:12]([CH3:22])[CH:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[CH2:8]1)=[O:14])([CH3:19])([CH3:18])[CH3:17]

参加物

7

反応物 3

HCID 712FormaldehydeHCID 2735358Tert-butyl 3-phenylpiperazine-1-carboxylateHCID 5049666Sodium triacetoxyborohydride

生成物 1

HCID 771800394-Boc-1-methyl-2-phenylpiperazine収率 101%

試薬・触媒・溶媒 3

HCID 887Methanol溶媒HCID 8857Ethyl Acetate溶媒HCID 516892Sodium Bicarbonate溶媒

実験手順

To a mixture of tert-butyl 3-phenylpiperazine-1-carboxylate (288 mg, 1.1 mmol), and formaldehyde (185 mg, 6.16 mmol) in methanol (7 mL) was added sodium triacetoxyborohydride (949 mg, 4.48 mmol) at 0° C. After stirring for 3 h at room temperature, the reaction mixture was diluted with 10% sodium bicarbonate solution and ethyl acetate. The aqueous part was extracted with ethyl acetate and the combined organic part was dried over sodium sulfate, filtered, concentrated in vacuo. The residue was purified by flash chromatography (20/1 dichloromethane/methanol) to provide 4-methyl-3-phenyl-piperazine-1-carboxylic acid tert-butyl ester (307 mg, 101%). (M+H)+=277 m/e. To a solution of 4-methyl-3-phenyl-piperazine-1-carboxylic acid tert-butyl ester (307 mg, 1.11 mmol) in THF (3 mL) at 0° C. was added 4M HCl in dioxane (0.9 mL). The reaction mixture was stirred overnight and concentrated in vacuo. The residue was triturated with dichloromethane and filtered to provide 1-methyl-2-phenyl-piperazine dihydrochloride (290 mg), which was used as is for the next step.

後処理

  1. extractionThe aqueous part was extracted with ethyl acetate
  2. dry with materialthe combined organic part was dried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by flash chromatography (20/1 dichloromethane/methanol)

出典と根拠

ORDレコード
ord-83653501d9f14647b6cac6428c8e8740
出典データセット
uspto-grants-2016_05
特許番号
US09353096B2

反応ノート

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