Lithium Chloride → 13-(1-Ethoxyethenyl)-12-methyl-4-[3-methyl-1-(propan-2-yl)-1H-1,2,4-triazol-5-yl]-9-oxa-3,6-diazatricyclo[8.4.0.02,6]tetradeca-1(14),2,4,10,12-pentaene

HRID 1530705Notes

Reaction equation

HRID 1530705 reaction equation
Br[C:2]1[CH:15]=[C:14]2[C:5]([O:6][CH2:7][CH2:8][N:9]3[C:13]2=[N:12][C:11]([C:16]2[N:20]([CH:21]([CH3:23])[CH3:22])[N:19]=[C:18]([CH3:24])[N:17]=2)=[CH:10]3)=[CH:4][C:3]=1[CH3:25].C([Sn](CCCC)(CCCC)[C:31]([O:33][CH2:34][CH3:35])=[CH2:32])CCC.[Li+].[Cl-].[F-].[K+]>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:34]([O:33][C:31]([C:2]1[CH:15]=[C:14]2[C:5]([O:6][CH2:7][CH2:8][N:9]3[C:13]2=[N:12][C:11]([C:16]2[N:20]([CH:21]([CH3:22])[CH3:23])[N:19]=[C:18]([CH3:24])[N:17]=2)=[CH:10]3)=[CH:4][C:3]=1[CH3:25])=[CH2:32])[CH3:35]

Participants

7

Reactant 4

HCID 433294Lithium ChlorideHCID 522689Potassium FluorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 683128519-Bromo-2-(2-isopropyl-5-methyl-2H-[1,2,4]triazol-3-yl)-8-methyl-4,5-dihydro-6-oxa-1,3a-diazabenzo[e]azulene

Product 1

HCID 6831273413-(1-Ethoxyethenyl)-12-methyl-4-[3-methyl-1-(propan-2-yl)-1H-1,2,4-triazol-5-yl]-9-oxa-3,6-diazatricyclo[8.4.0.02,6]tetradeca-1(14),2,4,10,12-pentaeneYield 136.3%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 13-bromo-12-methyl-4-[3-methyl-1-(propan-2-yl)-1H-1,2,4-triazol-5-yl]-9-oxa-3,6-diazatricyclo[8.4.0.02,6]tetradeca-1(14),2,4,10,12-pentaene (1.50 g, 3.73 mmol), tributyl(1-ethoxyvinyl)stannane (1.35 g, 3.74 mmol), LiCl (472 mg, 11.2 mmol), Pd(PPh3)4 (130 mg, 0.120 mmol) in THF (30 mL) was stirred at 80° C. for 16 hrs under N2 atmosphere in a sealed tube. After being cooled to room temperature, the mixture was treated with aq. KF (2.0 M, 50.0 mL). The resulting mixture was stirred at room temperature for 1 h and then filtered. The filtrate was extracted with ethyl acetate (5×50 mL). The combined organic layer was washed with brine and dried over MgSO4. Removal of the solvent gave the crude product (2.0 g, over 100% yield) as pale yellow oil, which was used directly in the next step without further purification. LCMS m/z [M+H]+ 395.3.

Workup

  1. temperatureAfter being cooled to room temperature
  2. stirringThe resulting mixture was stirred at room temperature for 1 h
  3. filtrationfiltered
  4. extractionThe filtrate was extracted with ethyl acetate (5×50 mL)
  5. washThe combined organic layer was washed with brine
  6. dry with materialdried over MgSO4
  7. customRemoval of the solvent

Sources & evidence

ORD record
ord-f3d3734d57f74a84a2b86791f11ba5c7
Source dataset
uspto-grants-2015_07
Patent number
US09090628B2

Reaction notes

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