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

HRID 2172287노트

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HRID 2172287 반응식
[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

참가 물질

8

반응물 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

생성물 1

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

시약·촉매·용매 4

HCID 178418807HCID 178418807, 화합물촉매HCID 962Water용매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

실험 절차

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)

후처리

  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)

출처 및 근거

ORD 기록
ord-a1332cb5926143df9a30b096116d0319
출처 데이터셋
uspto-grants-2015_06
특허 번호
US09051311B2

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