Nitrogen → 2-(Thiophen-2-yl)aniline

HRID 2060350

反応式

HRID 2060350 の反応式
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]

参加物

7

反応物 4

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

生成物 1

HCID 41160972-(Thiophen-2-yl)aniline収率 92%

試薬・触媒・溶媒 2

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 80711,2-Dimethoxyethane溶媒

実験手順

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).

後処理

  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]

出典と根拠

ORDレコード
ord-f3be26f8bf7745048b3502a9a75cf83b
出典データセット
uspto-grants-2012_10
特許番号
US08278356B2

関連ノート

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