Putrescine Dihydrochloride → N'-(2,4-difluorophenyl)butane-1,4-diamine

HRID 2239808ノート

反応式

HRID 2239808 の反応式
Cl.Cl.[NH2:3][CH2:4][CH2:5][CH2:6][CH2:7][NH2:8].CC(C)([O-])C.[Na+].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.Br[C:62]1[CH:67]=[CH:66][C:65]([F:68])=[CH:64][C:63]=1[F:69]>C(OCC)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[F:68][C:65]1[CH:64]=[C:63]([F:69])[CH:62]=[CH:67][C:66]=1[NH:3][CH2:4][CH2:5][CH2:6][CH2:7][NH2:8]

参加物

7

反応物 4

HCID 9532Putrescine DihydrochlorideHCID 676741-Bromo-2,4-difluorobenzeneHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxide

生成物 1

HCID 68414832N'-(2,4-difluorophenyl)butane-1,4-diamine

試薬・触媒・溶媒 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium触媒HCID 3283Diethyl Ether溶媒

反応条件

温度
110 °C

実験手順

1,4-Diaminobutane dihydrochloride (0.97 g, 6 mmol), sodium t-butoxide (1.87 g, 19.5 mmol), rac-BINAP (61.0 mg, 0.09 mmol), and Pd(dba)2 (35.0 mg, 0.06 mmol) are charged to a flame dried screw-cap vial. The vial is vacuumed and back filled with nitrogen. Then anhydrous toluene (15 mL) is added, followed by the addition of 1-bromo-2,4-difluorobenzene (0.34 mL, 3.00 mmol). The mixture is stirred under nitrogen at 110° C. overnight. The reaction mixture is diluted with 80 mL of diethyl ether and filtered through a pad of celite 545. The filtrate is extracted with 6N aqueous HCl (10 mL×3). The combined aqueous layers are washed twice with diethyl ether and adjusted with 1M aqueous NaOH to pH>12. The aqueous layer was extracted with diethyl ether three times. The combined ether phase is dried over anhydrous Na2SO4, filtered, and concentrated to obtain N′-(2,4-difluorophenyl)butane-1,4-diamine as a brown oil: 1H NMR (CDCl3) δ 1.55 (m, 2H), 1.66 (m, 2H), 2.74 (t, 2H), 3.12 (t, 2H), 6.55 (m, 1 H), 6.73 (m, 2H).

後処理

  1. customdried
  2. customscrew-cap vial
  3. additionback filled with nitrogen
  4. additionThen anhydrous toluene (15 mL) is added
  5. filtrationfiltered through a pad of celite 545
  6. extractionThe filtrate is extracted with 6N aqueous HCl (10 mL×3)
  7. washThe combined aqueous layers are washed twice with diethyl ether
  8. extractionThe aqueous layer was extracted with diethyl ether three times
  9. dry with materialThe combined ether phase is dried over anhydrous Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated

出典と根拠

ORDレコード
ord-541bf923969d4d12853860da84c113ae
出典データセット
uspto-grants-2010_05
特許番号
US07723343B2

反応ノート

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