Potassium Carbonate → tert-butyl 4-(2-bromo-5-(trifluoromethyl)phenyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 2172287ノート

反応式

HRID 2172287 の反応式
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][C:3]=1I.CC1(C)C(C)(C)OB([C:21]2[CH2:26][CH2:25][N:24]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:23][CH:22]=2)O1.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.O.C(OCC)(=O)C.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].C(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][C:3]=1[C:21]1[CH2:26][CH2:25][N:24]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:23][CH:22]=1

参加物

8

反応物 3

HCID 11430Potassium CarbonateHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 467352311-Bromo-2-iodo-4-(trifluoromethyl)benzene

生成物 1

HCID 71259576tert-butyl 4-(2-bromo-5-(trifluoromethyl)phenyl)-5,6-dihydropyridine-1(2H)-carboxylate収率 73.1%

試薬・触媒・溶媒 4

HCID 178418807HCID 178418807、化合物触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

実験手順

A solution of 1-bromo-2-iodo-4-(trifluoromethyl)benzene (1.408 ml, 8.55 mmol), tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1(2H)-carboxylate (Frontier Scientific, Logan, Utah, 2.78 g, 8.98 mmol), Pd(dppf)Cl2—CH2Cl2 adduct (Strem Chemicals Inc., Newburyport, Mass., 0.349 g, 0.427 mmol), and potassium carbonate (2.052 g, 34.2 mmol) in dioxane (32.1 ml) and water (10.69 ml) was stirred at 70° C. for three hours. (LC-MS MH+ 430.1) The reaction was diluted with ethyl acetate and washed with water. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried with sodium sulfate, filtered, and concentrated. The material was purified via column chromatography (silica gel 80 g, gradient elution 0 to 100% Et2O:Heptane) to afford tert-butyl 4-(2-bromo-5-(trifluoromethyl)phenyl)-5,6-dihydropyridine-1(2H)-carboxylate (2.54 g, 6.25 mmol) as a light yellow oil. [M+H]+=428.0. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm=7.69 (d, J=8.3 Hz, 1H), 7.43 (d, J=2.2 Hz, 1H), 7.41-7.36 (m, 1H), 5.69 (br. s., 1H), 4.08 (q, J=2.7 Hz, 2H), 3.66 (t, J=5.6 Hz, 2H), 2.48-2.40 (m, 2H), 1.52 (s, 9H)

後処理

  1. washwashed with water
  2. extractionThe aqueous layer was extracted with ethyl acetate
  3. dry with materialthe combined organic layers were dried with sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe material was purified via column chromatography (silica gel 80 g, gradient elution 0 to 100% Et2O:Heptane)

出典と根拠

ORDレコード
ord-a1332cb5926143df9a30b096116d0319
出典データセット
uspto-grants-2015_06
特許番号
US09051311B2

反応ノート

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