1-Chloro-3-iodobenzene → 3,4-Bis(benzyloxy)-6-((3-chlorophenyl)ethynyl)pyridazine

HRID 927077노트

반응식

HRID 927077 반응식
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4](I)[CH:3]=1.N1(C2CCCCCCCCCC2)CCCN=CCCCCC1.C1CCN2C(=NCCC2)CC1.[CH2:42]([O:49][C:50]1[N:51]=[N:52][C:53]([C:64]#[CH:65])=[CH:54][C:55]=1[O:56][CH2:57][C:58]1[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=1)[C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1>O1CCCC1.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:42]([O:49][C:50]1[N:51]=[N:52][C:53]([C:64]#[C:65][C:4]2[CH:5]=[CH:6][CH:7]=[C:2]([Cl:1])[CH:3]=2)=[CH:54][C:55]=1[O:56][CH2:57][C:58]1[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=1)[C:43]1[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=1

참가 물질

8

반응물 4

HCID 122691-Chloro-3-iodobenzeneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 866770253,4-Bis(benzyloxy)-6-ethynylpyridazine2회HCID 1296629601,8-Diazabicycloundec-7ene

생성물 1

HCID 712699503,4-Bis(benzyloxy)-6-((3-chlorophenyl)ethynyl)pyridazine수율 30%

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매HCID 8028Tetrahydrofuran용매

반응 조건

온도
80 °C

실험 절차

To a solution of 1-chloro-3-iodobenzene (0.862 g, 3.62 mmol) in dry tetrahydrofuran (11 ml) was added copper(I) iodide (0.063 g, 0.33 mmol), bis(triphenylphosphine)-palladium(II) chloride (0.115 g, 0.16 mmol) and 1,8-diazabicycloundec-7-ene and (DBU; 2.97 ml, 19.72 mmol). The reaction was then purged and evacuated with nitrogen several times before 3,4-bis(benzyloxy)-6-ethynylpyridazine (Intermediate 5; 1.04 g, 3.29 mmol) was added. The reaction vessel was sealed and heated to 80° C. for 1 hour. Upon cooling, the resultant mixture was partitioned between ethyl acetate and water. The combined organic portions were washed with water (×2) and brine, dried (MgSO4), filtered and concentrated to give a brown oil. The crude oil was purified by silica chromatography (eluting with 0-20% ethyl acetate in petrol) to yield 3,4-bis(benzyloxy)-6-((3-chlorophenyl)ethynyl)pyridazine as a yellow solid (yield=30%).

후처리

  1. customThe reaction was then purged
  2. additionwas added
  3. customThe reaction vessel was sealed
  4. temperatureUpon cooling
  5. customthe resultant mixture was partitioned between ethyl acetate and water
  6. washThe combined organic portions were washed with water (×2) and brine
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give a brown oil
  11. customThe crude oil was purified by silica chromatography (eluting with 0-20% ethyl acetate in petrol)

출처 및 근거

ORD 기록
ord-38160e5aef3340c1881c66303169bfe1
출처 데이터셋
uspto-grants-2016_03
특허 번호
US09290456B2

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