1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) → HCID 57551219, compound

HRID 1644645Notes

Reaction equation

HRID 1644645 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([S:8]([NH:11][C:12]2[S:13][CH:14]=[CH:15][N:16]=2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1.[Cl:59][C:60]1[CH:73]=[CH:72][C:63]([CH2:64][C:65]2[CH:66]=[C:67]([NH2:71])[N:68]([CH3:70])[N:69]=2)=[CH:62][CH:61]=1.CC(C)([O-])C.[Na+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Cl:59][C:60]1[CH:73]=[CH:72][C:63]([CH2:64][C:65]2[CH:66]=[C:67]([NH:71][C:2]3[CH:7]=[CH:6][C:5]([S:8]([NH:11][C:12]4[S:13][CH:14]=[CH:15][N:16]=4)(=[O:10])=[O:9])=[CH:4][CH:3]=3)[N:68]([CH3:70])[N:69]=2)=[CH:62][CH:61]=1

Participants

7

Reactant 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 10193184-Iodo-N-(thiazol-2-yl)benzenesulfonamideHCID 23676156Sodium t-butoxideHCID 575512163-(4-Chlorobenzyl)-1-methyl-1H-pyrazol-5-ylamine

Product 1

HCID 57551219HCID 57551219, compoundYield 6.5%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
150 °C

Procedure

To a mixture of 4-iodo-N-thiazol-2-yl-benzenesulfonamide (100 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium(0) (10 mg, 0.01 mmol, 0.04 equiv), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (19 mg, 0.033 mmol, 0.12 equiv) and 5-(4-chloro-benzyl)-2-methyl-2H-pyrazole-3-ylamine (80 mg, 0.36 mmol, 1.2 equiv) in 4.0 mL of anhydrous 1,4-dioxane was added sodium tert-butoxide (100 mg, 0.90 mmol, 3.0 equiv). The vial was capped, and the reaction mixture was heated 30 min at 150° C. in the microwave. The crude reaction mixture was filtered through celite then concentrated in vacuo. The residue was taken up in chloroform-methanol, concentrated onto celite, and purified via automated flash chromatography (12 g SiO2, gradient from hexanes to ethyl acetate). The appropriate fractions were collected, concentrated in vacuo, then purified further via reverse phase HPLC. The appropriate fractions were lyophilized from water-acetonitrile to afford the product as a white solid (9 mg, 6%).

Workup

  1. customThe vial was capped
  2. customThe crude reaction mixture
  3. filtrationwas filtered through celite
  4. concentrationthen concentrated in vacuo
  5. concentrationconcentrated onto celite
  6. custompurified
  7. customThe appropriate fractions were collected
  8. concentrationconcentrated in vacuo
  9. custompurified further via reverse phase HPLC

Sources & evidence

ORD record
ord-8c4a60578d1743f886295e0317cab88b
Source dataset
uspto-grants-2012_02
Patent number
US08124610B2

Reaction notes

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