Phenylacetylene → 3,4-Bis(benzyloxy)-6-(phenylethynyl)pyridazine

HRID 927058Notes

Reaction equation

HRID 927058 reaction equation
[CH2:1]([O:8][C:9]1[N:10]=[N:11][C:12](Cl)=[CH:13][C:14]=1[O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1CCN2C(=NCCC2)CC1.[C:35]([C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1)#[CH:36]>O1CCCC1.C(OCC)(=O)C.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.[Cu]I>[CH2:1]([O:8][C:9]1[N:10]=[N:11][C:12]([C:36]#[C:35][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)=[CH:13][C:14]=1[O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 3

HCID 10821PhenylacetyleneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 122134743,4-Bis(benzyloxy)-6-chloropyridazine2×

Product 1

HCID 712704193,4-Bis(benzyloxy)-6-(phenylethynyl)pyridazineYield 61%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A 20 ml microwave vial was charged with 3,4-bis(benzyloxy)-6-chloropyridazine (Intermediate 1; 440 mg, 1.35 mmol), DBU (1230 mg, 8.08 mmol) and ethynylbenzene (413 mgs, 4.04 mmol) in tetrahydrofuran (5 ml) to produce an orange solution. The mixture was purged with nitrogen and dichlorobis(triphenylphosphine)palladium(II) (47.3 mg, 0.067 mmol) and copper(I) iodide (25.6 mg, 0.135 mmol) were added before the whole was subjected to microwave radiation for 1 hour at 80° C. Upon cooling, the resulting mixture was diluted with ethyl acetate and washed with brine and the organic layer was purified by silica chromatography (eluting with 0-30% ethyl acetate-petrol) to yield 3,4-bis(benzyloxy)-6-(phenylethynyl)pyridazine (320 mg, 0.815 mmol, 61% yield).

Workup

  1. customto produce an orange solution
  2. additionwere added before the whole
  3. customfor 1 hour
  4. customat 80° C
  5. temperatureUpon cooling
  6. washwashed with brine
  7. customthe organic layer was purified by silica chromatography (eluting with 0-30% ethyl acetate-petrol)

Sources & evidence

ORD record
ord-6b99fdef50b341feae8969359f8e49d1
Source dataset
uspto-grants-2016_03
Patent number
US09290456B2

Reaction notes

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