Trimethylsilylacetylene → 3,4-Bis(benzyloxy)-6-((trimethylsilyl)ethynyl)pyridazine

HRID 927060Notes

Reaction equation

HRID 927060 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.[C:24]([Si:26]([CH3:29])([CH3:28])[CH3:27])#[CH:25].C1CCN2C(=NCCC2)CC1>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:25]#[C:24][Si:26]([CH3:29])([CH3:28])[CH3:27])=[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 66111TrimethylsilylacetyleneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 122134743,4-Bis(benzyloxy)-6-chloropyridazine2×

Product 1

HCID 712704503,4-Bis(benzyloxy)-6-((trimethylsilyl)ethynyl)pyridazineYield 70.6%

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, 3.06 mmol) and ethynyltrimethylsilane (902 mg, 9.18 mmol) in tetrahydrofuran (5 ml) to afford an orange solution. The reaction was purged with nitrogen before DBU (2.77 ml, 18.36 mmol), dichlorobis(triphenylphosphine)palladium(II) (107 mg, 0.153 mmol) and copper(I) iodide (58.3 mg, 0.306 mmol) were added and the whole was subjected to microwave radiation for 1 hour at 80° C. Upon cooling, the reaction mixture was diluted with ethyl acetate and washed with brine. The organic layer was purified by silica chromatography (eluting with 0-30% ethyl acetate in petrol) to yield 3,4-bis(benzyloxy)-6-((trimethylsilyl)ethynyl)pyridazine (838 mg, 2.16 mmol, 70% yield)

Workup

  1. customto afford an orange solution
  2. additionwere added
  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 in petrol)

Sources & evidence

ORD record
ord-0f513fa4349f4459bafd33c3fbd25728
Source dataset
uspto-grants-2016_03
Patent number
US09290456B2

Reaction notes

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