Cesium carbonate → HCID 71269993, compound

HRID 927076Notes

Reaction equation

HRID 927076 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(=O)([O-])[O-].[Cs+].[Cs+].[CH2:30](B1C2CCCC1CCC2)[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1>O1CCCC1.O.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:30]([C:12]1[N:11]=[N:10][C:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[C:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:13]=1)[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 41509249-Benzyl-9-borabicyclo(3.3.1)nonaneHCID 122134743,4-Bis(benzyloxy)-6-chloropyridazine2×

Product 1

HCID 71269993HCID 71269993, compoundYield 64%

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 3,4-bis(benzyloxy)-6-chloropyridazine (Intermediate 1: 0.22 g, 0.67 mmol) in tetrahydrofuran (6 ml) and water (0.6 ml) was added cesium carbonate (0.66 g, 2.01 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.049 g, 0.067 mmol). The reaction was then purged and evacuated with nitrogen several times before 9-benzyl-9-borabicyclo[3.3.1]nonane (9-BBN; 4.02 ml, 2.01 mmol) was added. The reaction vessel was then sealed and heated to 60° C. for 1 hour. Upon cooling, the resulting mixture was diluted with ethyl acetate and washed 5 times with a 1:1 mixture of water and saturated aqueous brine. The organics portion was dried (MgSO4), filtered and concentrated to give an orange oil. The crude oil was purified by silica chromatography (eluting with 0-80% ethyl acetate in petrol) to yield 6-benzyl-3,4-bis(benzyloxy)pyridazine as a colourless oil (yield=64%).

Workup

  1. customThe reaction was then purged
  2. additionwas added
  3. customThe reaction vessel was then sealed
  4. temperatureUpon cooling
  5. washwashed 5 times
  6. additionwith a 1:1 mixture of water and saturated aqueous brine
  7. dry with materialThe organics portion was dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give an orange oil
  11. customThe crude oil was purified by silica chromatography (eluting with 0-80% ethyl acetate in petrol)

Sources & evidence

ORD record
ord-8772ec888e864b0ab7ab1dc24334623a
Source dataset
uspto-grants-2016_03
Patent number
US09290456B2

Reaction notes

Loading…