Pyrrolidine → 2-(Pyrrolidin-1-yl)-4-amino-m-xylene

HRID 1182266ノート

反応式

HRID 1182266 の反応式
Br[C:2]1[C:3]([CH3:10])=[C:4]([NH2:9])[CH:5]=[CH:6][C:7]=1[CH3:8].[NH:11]1[CH2:15][CH2:14][CH2:13][CH2:12]1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1>[N:11]1([C:2]2[C:3]([CH3:10])=[C:4]([NH2:9])[CH:5]=[CH:6][C:7]=2[CH3:8])[CH2:15][CH2:14][CH2:13][CH2:12]1

参加物

5

反応物 3

HCID 31268PyrrolidineHCID 123959063-Bromo-2,4-dimethylanilineHCID 23676156Sodium t-butoxide

生成物 1

HCID 204949532-(Pyrrolidin-1-yl)-4-amino-m-xylene

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
100 °C

実験手順

To a solution of the 3-bromo-2,4-dimethylphenylamine (0.6 g, 3.0 mmol) in toluene (10 mL) and pyrrolidine (1.25 mL, 15 mmol) was added sodium-t-butoxide (0.86 g, 9 mmol, 3eq). The suspension was deoxygenated by passing a stream of N2 gas through the mixture for approximately 5–10 minutes before introducing the tris(dibenzilidene)dipalladium(0) (Pd2(dba)3) (27 mg) and rac-2,2′Bis(diphenylphosphino)-1,1′binaphthyl (BINAP) (25 mg). The nitrogen stream continued 10 minutes before heating at 100° C. overnight. The reaction mixture was cooled, acidified with HCl (2N) and extracted with diethyl ether. The aqueous layer was adjusted basic and re-extracted with ethyl acetate. The organic layer was dried over sodium sulfate, decanted and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, gradient elution with 6:1 to 4:1 hexanes to ethyl acetate) to give the desired 2-(pyrrolidin-1-yl)-4-amino-m-xylene.

後処理

  1. customThe suspension was deoxygenated
  2. customfor approximately 5–10 minutes
  3. additionbefore introducing the tris(dibenzilidene)dipalladium(0) (Pd2(dba)3) (27 mg) and rac-2,2′Bis(diphenylphosphino)-1,1′binaphthyl (BINAP) (25 mg)
  4. temperatureThe reaction mixture was cooled
  5. extractionextracted with diethyl ether
  6. extractionre-extracted with ethyl acetate
  7. dry with materialThe organic layer was dried over sodium sulfate
  8. customdecanted
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by flash chromatography (silica gel, gradient elution with 6:1 to 4:1 hexanes to ethyl acetate)

出典と根拠

ORDレコード
ord-760f60a7e9f14de4be0929e705825a2b
出典データセット
uspto-grants-2007_10
特許番号
US07288538B2

反応ノート

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