Nitrogen → [5-(3-Nitro-phenyl)-thiophen-2-yl]acetic acid methyl ester

HRID 1256689

反応式

HRID 1256689 の反応式
N#N.[CH3:3][O:4][C:5](=[O:13])[CH2:6][C:7]1[S:8][C:9](Br)=[CH:10][CH:11]=1.[N+:14]([C:17]1[CH:18]=[C:19](B(O)O)[CH:20]=[CH:21][CH:22]=1)([O-:16])=[O:15].C([O-])([O-])=O.[Na+].[Na+]>C1(C)C=CC=CC=1.CCO.[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>[CH3:3][O:4][C:5](=[O:13])[CH2:6][C:7]1[S:8][C:9]([C:21]2[CH:20]=[CH:19][CH:18]=[C:17]([N+:14]([O-:16])=[O:15])[CH:22]=2)=[CH:10][CH:11]=1

参加物

8

反応物 4

HCID 947NitrogenHCID 16773-Nitrophenylboronic AcidHCID 10340Sodium CarbonateHCID 12403315Methyl 2-(5-bromothiophen-2-yl)acetate

生成物 1

HCID 59786790[5-(3-Nitro-phenyl)-thiophen-2-yl]acetic acid methyl ester収率 58.4%

試薬・触媒・溶媒 3

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 702Ethanol溶媒HCID 1140Toluene溶媒

反応条件

温度
100 °C

実験手順

FR544 (The following reaction is carried out in an N2 atmosphere.) Dissolve Tetrakis-(triphenylphosphine)-palladium(0) (1.12 g, 0.97 mmol) and ester (43) (4.57 g, 19.44 mmol) in toluene (200 mL) and EtOH (20.0 mL), degas the reaction mixture carefully (5 times) and flush with N2. Add 3-nitrophenylboronic acid (3.57 g, 21.38 mmol) and a 3 M aqueous Na2CO3 solution (18.1 mL, 54.3 mmol), degas the reaction mixture again carefully (5 times) and flush with N2. Stir the mixture for 18 h at 100° C. Partition the reaction solution between EtOAc and water and extract the separated aqueous layer with EtOAc (3 times). Wash combined organic layer with brine and dry it with Na2SO4. Purify the obtained crude product by preparative radial chromatography (silica gel, EtOAc/CyH 1+5) to obtain [5-(3-nitro-phenyl)-thiophen-2-yl]acetic acid methyl ester (56) as a yellow solid (3.15 g, 58%). 1H NMR (400 MHz, CDCl3): 3.75 (s, 3H); 3.85 (s, 2H); 6.94 (br.d, 1H, J=3.8 Hz); 7.27 (d, 1H, J=3.8 Hz); 7.51 (t, 1H, J=8.0 Hz); 7.84 (ddd, 1H, J1=7.8 Hz, J2=1.5 Hz, J3=0.8 Hz); 8.08 (ddd, 1H, J1=8.3 Hz, J2=2.1 Hz, J3=1.0 Hz); 8.39 (t, 1H, J=1.9 Hz).

後処理

  1. customFR544 (The following reaction
  2. customdegas the reaction mixture carefully (5 times)
  3. customflush with N2
  4. customflush with N2
  5. customPartition the reaction solution between EtOAc and water
  6. extractionextract the separated aqueous layer with EtOAc (3 times)
  7. washWash
  8. dry with materialdry it with Na2SO4
  9. customPurify the
  10. customobtained crude product by preparative radial chromatography (silica gel, EtOAc/CyH 1+5)

出典と根拠

ORDレコード
ord-0652c2030faf4ce181f454d758323aba
出典データセット
uspto-grants-2013_06
特許番号
US08461207B2

関連ノート

読み込み中…