Cesium carbonate → 6-Ethenyl-2-methyl-3-nitropyridine

HRID 594109노트

반응식

HRID 594109 반응식
Br[C:2]1[N:7]=[C:6]([CH3:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][CH:3]=1.[CH:12](B1OC(C)(C)C(C)(C)O1)=[CH2:13].C(=O)([O-])[O-].[Cs+].[Cs+]>CC1CCCO1.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C>[CH:12]([C:2]1[N:7]=[C:6]([CH3:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][CH:3]=1)=[CH2:13]

참가 물질

8

반응물 3

HCID 10796Cesium carbonateHCID 52330122-Ethenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 247280146-Bromo-2-methyl-3-nitropyridine

생성물 1

HCID 684528106-Ethenyl-2-methyl-3-nitropyridine수율 116.3%

시약·촉매·용매 4

HCID 167845palladium(II) acetate촉매HCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl촉매HCID 962Water용매HCID 73012-Methyltetrahydrofuran용매

실험 절차

A suspension/solution of 6-bromo-2-methyl-3-nitropyridine (500 mg, 2.304 mmol), 2-ethenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.782 mL, 4.61 mmol), palladium(II) acetate (25.9 mg, 0.115 mmol), X-phos (110 mg, 0.230 mmol) and cesium carbonate (3.0 g, 9.22 mmol) in 2-methyltetrahydrofuran (2-MeTHF) (8 mL) and water (2 mL) was stirred under nitrogen at 60° C. for 1 hour. The reaction mixture was cooled then separated between ethyl acetate and water. The organic phase was washed with brine and dried over magnesium sulphate. The solvent was removed in vacuo and the residue was dissolved in DCM (5 mL). This was applied to a silica cartridge and eluted with a gradient of 0-100% ethyl acetate in cyclohexane. This gave the crude product (440 mg) as a brown liquid which was used directly in the next step with no further purification. LCMS (2 min, formic) Rt 0.91 min, m/z (ES+) 165 (M+H).

후처리

  1. temperatureThe reaction mixture was cooled
  2. customthen separated between ethyl acetate and water
  3. washThe organic phase was washed with brine
  4. dry with materialdried over magnesium sulphate
  5. customThe solvent was removed in vacuo
  6. dissolutionthe residue was dissolved in DCM (5 mL)
  7. washeluted with a gradient of 0-100% ethyl acetate in cyclohexane

출처 및 근거

ORD 기록
ord-a54ef7cd6cc04d60a0c52759cf1efeea
출처 데이터셋
uspto-grants-2016_01
특허 번호
US09242972B2

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