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Potassium Phosphate, Tribasic → {6-Fluoro-3-methyl-4-[4-(toluene-2-sulfonyl)-phenyl]-naphthalen-2-yl}-acetic acid methyl ester

HRID 1468354
ノート
印刷プレビュー

反応式

HRID 1468354 の反応式
CC1(C)C(C)(C)OB([C:9]2[CH:14]=[CH:13][C:12]([S:15]([C:18]3[C:19]([CH3:24])=[CH:20][CH:21]=[CH:22][CH:23]=3)(=[O:17])=[O:16])=[CH:11][CH:10]=2)O1.[CH3:26][O:27][C:28](=[O:50])[CH2:29][C:30]1[C:39]([CH3:40])=[C:38](OS(C(F)(F)F)(=O)=O)[C:37]2[C:32](=[CH:33][CH:34]=[C:35]([F:49])[CH:36]=2)[CH:31]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1>[Cl-].[Na+].O.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C1(C)C=CC=CC=1>[CH3:26][O:27][C:28](=[O:50])[CH2:29][C:30]1[C:39]([CH3:40])=[C:38]([C:9]2[CH:10]=[CH:11][C:12]([S:15]([C:18]3[C:19]([CH3:24])=[CH:20][CH:21]=[CH:22][CH:23]=3)(=[O:16])=[O:17])=[CH:13][CH:14]=2)[C:37]2[C:32](=[CH:33][CH:34]=[C:35]([F:49])[CH:36]=2)[CH:31]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

10

反応物 4

HCID 62657Potassium Phosphate, TribasicHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 59326772(6-Fluoro-3-methyl-4-trifluoromethanesulfonyloxy-naphthalen-2-yl)-acetic acid methyl esterHCID 866949484,4,5,5-Tetramethyl-2-[4-(toluene-2-sulfonyl)-phenyl]-[1,3,2]dioxaborolane

生成物 1

HCID 86694947
{6-Fluoro-3-methyl-4-[4-(toluene-2-sulfonyl)-phenyl]-naphthalen-2-yl}-acetic acid methyl ester
収率 31%

試薬・触媒・溶媒 5

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒HCID 57417360Sodium chloride; water溶媒

反応条件

温度
125 °C

実験手順

To a mixture of 4,4,5,5-tetramethyl-2-[4-(toluene-2-sulfonyl)-phenyl]-[1,3,2]dioxaborolane (50 mg, 0.14 mmol), (6-fluoro-3-methyl-4-trifluoromethanesulfonyloxy-naphthalen-2-yl)-acetic acid methyl ester (73 mg, 0.19 mmol), K3PO4 (81 mg, 0.38 mmol), palladium(II) acetate (14 mg, 0.06 mmol), and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (49 mg, 0.12 mmol) were added anhydrous toluene (4 mL) and water (400 uL) at room temperature. The resulting light brown solution was heated to 125° C. for 15 hours. The reaction mixture was cooled to room temperature and diluted with brine solution and ethyl acetate. The two layers were separated and the aqueous layer was extracted with ethyl acetate and the combined extracts were washed with brine solution. The organic layer was dried over anhydrous MgSO4. Filtration and concentration gave a crude residue which was purified using an ISCO (40 g) column, eluting with 0-40% ethyl acetate in hexanes, to give {6-fluoro-3-methyl-4-[4-(toluene-2-sulfonyl)-phenyl]-naphthalen-2-yl}-acetic acid methyl ester (20 mg, 31%). 1H NMR (300 MHz, CDCl3) δ ppm 8.31 (d, J=7.5 Hz, 1 H), 8.01 (d, J=7.8 Hz, 2 H), 7.80 (dd, J=8.5, 6.0 Hz, 1 H), 7.75 (s, 1 H), 7.50-7.62 (m, 1 H), 7.47 (d, J=7.5 Hz, 1 H), 7.40 (d, J=7.8 Hz, 2 H), 7.32 (d, J=7.2 Hz, 1 H), 7.19 (td, J=8.5, 2.0 Hz, 1 H), 6.72 (d, J=10.9 Hz, 1 H), 3.85 (s, 2 H), 3.73 (s, 3 H), 2.56 (s, 3 H), 2.09 (s, 3 H). HRMS calcd. for C27H24FO4S [(M+H)+] 463.1374, obsd. 463.1373.

後処理

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customThe two layers were separated
  3. extractionthe aqueous layer was extracted with ethyl acetate
  4. washthe combined extracts were washed with brine solution
  5. dry with materialThe organic layer was dried over anhydrous MgSO4
  6. filtrationFiltration and concentration
  7. customgave a crude residue which
  8. customwas purified
  9. washeluting with 0-40% ethyl acetate in hexanes

出典と根拠

ORDレコード
ord-15ac5a4a82834d8bbdd1dd42f5726466
出典データセット
uspto-grants-2015_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09000044B2

反応ノート

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