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

HRID 927077Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 927077
[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

Komponenten

8

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

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%).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-38160e5aef3340c1881c66303169bfe1
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09290456B2

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