Tributylvinyltin → 6-Ethenylpyrido[2,3-b]pyrazine

HRID 1175730노트

반응식

HRID 1175730 반응식
Cl[C:2]1[CH:3]=[CH:4][C:5]2[C:6]([N:11]=1)=[N:7][CH:8]=[CH:9][N:10]=2.[CH:12]([Sn](CCCC)(CCCC)CCCC)=[CH2:13]>C1COCC1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH:12]([C:2]1[CH:3]=[CH:4][C:5]2[C:6]([N:11]=1)=[N:7][CH:8]=[CH:9][N:10]=2)=[CH2:13]

참가 물질

5

반응물 2

HCID 81998TributylvinyltinHCID 6408346-Chloropyrido[2,3-b]pyrazine2회

생성물 1

HCID 574168446-Ethenylpyrido[2,3-b]pyrazine수율 81%

시약·촉매·용매 2

HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 8028Tetrahydrofuran용매

반응 조건

온도
65 °C

실험 절차

6-chloropyrido[2,3-b]pyrazine (Intermediate 4.2) (3 g, 18.12 mmol, 1.00 eq.) was dissolved in THF (150 mL) and degassed with nitrogen at rt for 10 minutes. Tetrakis (triphenylphosphine) palladium(0) (1.46 g, 1.27 mmol, 0.07 eq.) and vinyltributylstannane (7.47 mL, 23.5 mmol, 1.3 eq.) were added and reaction mixture was stirred at 65° C. for 3 hours. THF was evaporated and crude purified directly by flash chromatography using cyclohexane/ethyl acetate (8/2) to give 2.3 g of the expected compound (Intermediate 4.3) as an orange oil. Amount: 2.3 g; Yield: 81%; Formula: C9H7N3; HPLC Purity: 98%; HPLC H2O TFA 0.1%-ACN TFA 0.05%): Rt (min); Area %=1.32 min; 98%; 1H NMR (DMSO-d6) δ 9.10 (s, 1H), 8.98 (s, 1H), 8.46 (d, 1H, J=8 Hz), 7.95 (d, 1H, J=8 Hz), 6.90 (dd, 1H, Jtrans=17 Hz, Jcis=10 Hz), 6.50 (dd, 1H, Jtrans=17 Hz, Jgem=1.5 Hz), 5.80 (dd, 1H, Jcis=10 Hz, Jgem=1.5 Hz). LC-MS: M/Z ESI: Rt (min) 0.78 min, 158.13 (M+1).

후처리

  1. customdegassed with nitrogen at rt for 10 minutes
  2. customreaction mixture
  3. customTHF was evaporated
  4. customcrude purified directly by flash chromatography

출처 및 근거

ORD 기록
ord-403f50eeb9d9475f9e8ceb10894fc18f
출처 데이터셋
uspto-grants-2010_11
특허 번호
US07842698B2

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