Thallium hydroxide → HCID 69082823, 화합물

HRID 2362408노트

반응식

HRID 2362408 반응식
[F:1][C:2]1[CH:12]=[CH:11][C:5](/[CH:6]=[CH:7]/B(O)O)=[CH:4][CH:3]=1.Br[C:14]1[CH:19]=[C:18]([Br:20])[CH:17]=[CH:16][N:15]=1.[OH-].[Tl+]>O1CCCC1.O.ClCCl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:20][C:18]1[CH:17]=[CH:16][N:15]=[C:14](/[CH:7]=[CH:6]/[C:5]2[CH:11]=[CH:12][C:2]([F:1])=[CH:3][CH:4]=2)[CH:19]=1

참가 물질

8

반응물 3

HCID 160963Thallium hydroxideHCID 8171042,4-DibromopyridineHCID 5706776trans-2-(4-Fluorophenyl)vinylboronic acid

생성물 1

HCID 69082823HCID 69082823, 화합물

시약·촉매·용매 4

HCID 178418397HCID 178418397, 화합물촉매HCID 962Water용매HCID 6344Dichloromethane용매HCID 8028Tetrahydrofuran용매

실험 절차

A solution of (E)-4-fluorostyrylboronic acid (5 g, 30.1 mmol) and 2,4-dibromopyridine (6.49 g, 27.4 mmol) in tetrahydrofuran (150 mL) was purged with nitrogen for 20 min. To this was added Pd(Ph3P)4 (2.37 g, 2.05 mmol) and a 10% w/w solution of thallium(I) hydroxide (137 g, 62 mmol) in water. The reaction was stirred under nitrogen at room temperature. After 3 h, the gray suspension was diluted with dichloromethane and filtered through celite. The organics were washed with water, dried over magnesium sulfate, and concentrated. The resulting residue was purified by column chromatography (5%→13% EtOAc/Hex) to give 2.65 g (33%). 1H NMR (CDCl3) Shift: 8.43 (d, J=5.2 Hz, 1H), 7.64 (d, J=15.9 Hz, 1H), 7.50-7.59 (m, 3H), 7.34 (dd, J=5.3, 1.7 Hz, 1H), 7.10 (t, J=8.7 Hz, 2H), 7.02 (d, J=16.2 Hz, 1H). 13C NMR (CDCl3) Shift: 163.1, 157.0, 150.4, 133.3, 133.2, 132.5, 129.0, 126.4, 125.3, 116.0. 19F NMR (CDCl3) Shift: −112.69 (bs, 1F). Mass spec.: 278.2 (MH)+.

후처리

  1. filtrationfiltered through celite
  2. washThe organics were washed with water
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated
  5. customThe resulting residue was purified by column chromatography (5%→13% EtOAc/Hex)
  6. customto give 2.65 g (33%)

출처 및 근거

ORD 기록
ord-8f3cf4511f184a62babe2d9c3ab4e68b
출처 데이터셋
uspto-grants-2014_04
특허 번호
US08691821B2

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