Sodium Carbonate → HCID 86722502, compound

HRID 516489Notes

Reaction equation

HRID 516489 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:24]([NH:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][C:28]=2[NH:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)=O)[CH:5]=[C:6]([CH:23]=1)[C:7]([NH:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[NH:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=O.O=P(Cl)(Cl)Cl.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1>[Br:1][C:2]1[CH:3]=[C:4]([C:24]2[N:33]([C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][C:27]=3[N:26]=2)[CH:5]=[C:6]([C:7]2[N:16]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[C:11]3[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=3[N:9]=2)[CH:23]=1

Participants

5

Reactant 3

HCID 10340Sodium CarbonateHCID 24813Phosphorus oxychlorideHCID 86722503HCID 86722503, compound

Product 1

HCID 86722502HCID 86722502, compoundYield 67.1%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a suspension of Compound 6 (30 g, 52 mmol) in anhydrous 1,4-dioxane (300 mL), POCl3 (30.6 g, 18.6 mL, 200 mmol) was added slowly with water bath cooling. The resulting mixture was then maintained at 100° C. After cooling to room temperature, the mixture was poured into ice (ca. 300 g) and neutralized with Na2CO3, followed by extraction with CH2Cl2 (2×300 mL). The organic phase was then washed with brine, dried over Na2SO4 and concentrated in vacuo. To the mixture, acetonitrile (300 mL) was added and stirred, then filtered. The solid was collected and recrystallized in CH2Cl2/hexane to afford a white solid (18.9 g). The filtrant was purified by flash chromatography (SiO2, 100% hexanes to 9:1 to 4:1-hexanes/ethyl acetate). The main fraction was collected and concentrated to give additional product, white solid (5.17 g). Total amount is 24.1 g (86%): confirmed by LCMS (APCI): calculated for C32H21BrN4 (M+): 541; Found: 541.

Workup

  1. additionwas added slowly with water bath
  2. temperaturecooling
  3. temperatureAfter cooling to room temperature
  4. extractionfollowed by extraction with CH2Cl2 (2×300 mL)
  5. washThe organic phase was then washed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated in vacuo
  8. additionTo the mixture, acetonitrile (300 mL) was added
  9. filtrationfiltered
  10. customThe solid was collected
  11. customrecrystallized in CH2Cl2/hexane

Sources & evidence

ORD record
ord-cdc3ae81c61d4f4a9547df07fe4283b0
Source dataset
uspto-grants-2015_08
Patent number
US09112159B2

Reaction notes

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