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

HRID 927077ノート

反応式

HRID 927077 の反応式
[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

参加物

8

反応物 4

HCID 122691-Chloro-3-iodobenzeneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 866770253,4-Bis(benzyloxy)-6-ethynylpyridazine2 回HCID 1296629601,8-Diazabicycloundec-7ene

生成物 1

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

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
80 °C

実験手順

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%).

後処理

  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)

出典と根拠

ORDレコード
ord-38160e5aef3340c1881c66303169bfe1
出典データセット
uspto-grants-2016_03
特許番号
US09290456B2

反応ノート

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