Ethyl Acetate → [6-Chloro-3-methyl-4-(4-nitro-phenyl)-naphthalen-2-yl]-acetic acid methyl ester

HRID 1468352ノート

反応式

HRID 1468352 の反応式
[CH3:1][O:2][C:3](=[O:25])[CH2:4][C:5]1[C:14]([CH3:15])=[C:13](OS(C(F)(F)F)(=O)=O)[C:12]2[C:7](=[CH:8][CH:9]=[C:10]([Cl:24])[CH:11]=2)[CH:6]=1.[N+:26]([C:29]1[CH:34]=[CH:33][C:32](B(O)O)=[CH:31][CH:30]=1)([O-:28])=[O:27].C(=O)([O-])[O-].[Cs+].[Cs+].C(OCC)(=O)C>C(COC)OC.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:1][O:2][C:3](=[O:25])[CH2:4][C:5]1[C:14]([CH3:15])=[C:13]([C:32]2[CH:33]=[CH:34][C:29]([N+:26]([O-:28])=[O:27])=[CH:30][CH:31]=2)[C:12]2[C:7](=[CH:8][CH:9]=[C:10]([Cl:24])[CH:11]=2)[CH:6]=1

参加物

7

反応物 4

HCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 27735524-Nitrophenylboronic acidHCID 86694933(6-Chloro-3-methyl-4-trifluoromethanesulfonyloxy-naphthalen-2-yl)-acetic acid methyl ester

生成物 1

HCID 86694945[6-Chloro-3-methyl-4-(4-nitro-phenyl)-naphthalen-2-yl]-acetic acid methyl ester収率 74.6%

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 80711,2-Dimethoxyethane溶媒

実験手順

To a mixture of (6-chloro-3-methyl-4-trifluoromethanesulfonyloxy-naphthalen-2-yl)-acetic acid methyl ester (200 mg, 0.5 mmol), 4-nitrophenylboronic acid (170 mg, 1.1 mmol) and cesium carbonate (331 mg, 1 mmol) in dimethoxyethane (3 mL) was added [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (55.3 mg, 0.07 mmol) at room temperature under nitrogen. The resulting mixture was reacted using a microwave reactor (Personal Chemistry) at 120° C. for 30 minutes. Ethyl acetate (10 mL) was added and the organic layer was washed with water (20 mL) and brine solution (20 mL). The organic layers were dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to give the crude product which was purified by using an ISCO (40 g) column chromatography eluting with 5-15% ethyl acetate in hexanes to give [6-chloro-3-methyl-4-(4-nitro-phenyl)-naphthalen-2-yl]-acetic acid methyl ester (138 mg, 74%) as a light yellow solid. 1H NMR (300 MHz, CDCl3), δ ppm 8.40 (d, J=8.6 Hz, 2 H), 7.82 (dd, J=8.9, 5.7 Hz, 1 H), 7.77 (s, 1 H), 7.46 (d, J=8.6 Hz, 2 H), 7.21 (td, J=8.9, 2.4 Hz, 1 H), 6.76 (dd, J=11.2, 2.4 Hz, 1 H), 3.87 (s, 2 H), 3.74 (s, 3 H), 2.14 (s, 3 H). HRMS calcd. for C20H15ClNO4 [(M−H)−] 368.0695, obsd. 368.0695.

後処理

  1. customThe resulting mixture was reacted
  2. customat 120° C.
  3. customfor 30 minutes
  4. washthe organic layer was washed with water (20 mL) and brine solution (20 mL)
  5. dry with materialThe organic layers were dried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give the crude product which
  9. customwas purified
  10. washeluting with 5-15% ethyl acetate in hexanes

出典と根拠

ORDレコード
ord-4e473206438d4f04a97bf3003b71510c
出典データセット
uspto-grants-2015_04
特許番号
US09000044B2

反応ノート

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