Nitrogen → 2-(Thiophen-2-yl)aniline

HRID 2060350

반응식

HRID 2060350 반응식
N#N.Br[C:4]1[S:5][CH:6]=[CH:7][CH:8]=1.CC1(C)C(C)(C)OB([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=2[NH2:23])O1.C([O-])(O)=O.[Na+]>COCCOC.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[S:5]1[CH:6]=[CH:7][CH:8]=[C:4]1[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[NH2:23]

참가 물질

7

반응물 4

HCID 947NitrogenHCID 138512-BromothiopheneHCID 516892Sodium BicarbonateHCID 27346522-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

생성물 1

HCID 41160972-(Thiophen-2-yl)aniline수율 92%

시약·촉매·용매 2

HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 80711,2-Dimethoxyethane용매

실험 절차

AB427 (The following reaction is carried out in an N2 atmosphere.) Dissolve Tetrakis-(triphenylphosphine)-palladium(0) (297 mg, 0.26 mmol) and 2-Bromo-thiophene (837 mg, 5.13 mmol) in DME (42 mL), degas the reaction mixture carefully (5 times) and flush with N2. After 10 min stirring add 2-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenylamine (1.24 g, 5.64 mmol) and a 1M aqueous NaHCO3 solution (15.4 mL, 15.4 mmol), degas the reaction mixture again carefully (5 times) and flush with N2. Stir the mixture for 3 h at 95° C. Cool mixture to rt, remove solvent under reduced pressure and partition the residue between EtOAc and water. Extract the separated aqueous layer with EtOAc (3 times). Wash combined organic layer with brine and dry it with Na2SO4. Purify the crude product by flash chromatography (silica gel 60, CyH/EtOAc 15+1] to obtain 2-Thiophene-2-yl-phenylamine (55) as a brown solid (825 mg, 92%). 1H NMR (400 MHz, CDCl3): 4.40-6.00 (m, 2H); 6.88 (td, 1H, J1=7.6 Hz, J2=1.0 Hz); 6.93 (dd, 1H, J1=8.0 Hz, J2=1.0 Hz); 7.07 (dd, 1H, J1=5.3 Hz, J2=3.5 Hz); 7.17 (td, 1H, J1=8.0 Hz, J2=1.5 Hz) 7.22 (dd, 1H, J1=3.5 Hz, J2=1.3 Hz); 7.30 (dd, 1H, J1=7.6 Hz, J2=1.5 Hz); 7.33 (dd, 1H, J1=5.3 Hz, J2=1.3 Hz).

후처리

  1. customAB427 (The following reaction
  2. customdegas the reaction mixture carefully (5 times)
  3. customflush with N2
  4. customflush with N2
  5. stirringStir the mixture for 3 h at 95° C
  6. customremove solvent under reduced pressure
  7. custompartition the residue between EtOAc and water
  8. extractionExtract the separated aqueous layer with EtOAc (3 times)
  9. washWash
  10. dry with materialdry it with Na2SO4
  11. customPurify the crude product by flash chromatography (silica gel 60, CyH/EtOAc 15+1]

출처 및 근거

ORD 기록
ord-f3be26f8bf7745048b3502a9a75cf83b
출처 데이터셋
uspto-grants-2012_10
특허 번호
US08278356B2

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