1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) → HCID 59837686, compound

HRID 449211Notes

Reaction equation

HRID 449211 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[C:10]1[CH:20]=[C:19]([CH3:21])[C:13]2[N:14]=[C:15]([NH2:18])[N:16]=[N:17][C:12]=2[CH:11]=1.Br[C:23]1[CH:24]=[C:25]([S:29][CH2:30][CH2:31][N:32]2[CH2:36][CH2:35][CH2:34][CH2:33]2)[CH:26]=[CH:27][CH:28]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.CC(C)([O-])C.[K+]>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[C:10]1[CH:20]=[C:19]([CH3:21])[C:13]2[N:14]=[C:15]([NH:18][C:23]3[CH:28]=[CH:27][CH:26]=[C:25]([S:29][CH2:30][CH2:31][N:32]4[CH2:33][CH2:34][CH2:35][CH2:36]4)[CH:24]=3)[N:16]=[N:17][C:12]=2[CH:11]=1

Participants

7

Reactant 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 23665647Potassium tert-butoxideHCID 248227537-(2-Chloro-5-methoxyphenyl)-5-methylbenzo[e][1,2,4]triazin-3-amineHCID 59837630HCID 59837630, compound

Product 1

HCID 59837686HCID 59837686, compoundYield 74%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

7-(2-chloro-5-methoxy-phenyl)-5-methyl-benzo[1,2,4]triazin-3-ylamine (1.0 equiv., 083 mmol), 1-[2-(3-bromo-phenylsulfanyl)-ethyl]-pyrrolidine (1.5 equiv., 1.25 mmol), Xantphos (0.1 equiv., 0.084 mmol), palladium acetate (0.05 equiv., 0.042 mmol), and potassium-tert-butoxide (2.0 equiv., 1.66 mmol) were dissolved in 10 mL of dioxane, and argon was bubbled through the solution. The reaction was run under an argon blanket while refluxing at 100° C. for 18 h. The reaction was then cooled to room temperature, filtered to remove inorganics, extracted using EtOAc with saturated NaHCO3 and brine, dried over Na2SO4, and concentrated under reduced pressure. A crude material was precipitated using 1:5 (v/v) EtOAc/hexanes to afford a bright orange solid (311.8 mg, 74% yield). Rf=0.48.

Workup

  1. customargon was bubbled through the solution
  2. temperatureThe reaction was then cooled to room temperature
  3. filtrationfiltered
  4. customto remove inorganics
  5. extractionextracted
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customA crude material was precipitated

Sources & evidence

ORD record
ord-d13fd0b906d245428f84020cbe5fc065
Source dataset
uspto-grants-2013_07
Patent number
US08481536B2

Reaction notes

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