Sodium Carbonate → HCID 178420200, compound

HRID 2047540Notes

Reaction equation

HRID 2047540 reaction equation
Br[C:2]1[CH:20]=[CH:19][C:5]2[N:6]=[C:7]([C@H:9]3[CH2:12][C@H:11]([N:13]4[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]4)[CH2:10]3)[S:8][C:4]=2[CH:3]=1.CC1(C)C(C)(C)OB([C:29]2[CH:30]=[N:31][N:32]([C:34]([C:47]3[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=3)([C:41]3[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=3)[C:35]3[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=3)[CH:33]=2)O1.C(=O)([O-])[O-].[Na+].[Na+]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2)CCCCC1.C(O)C.O1CCOCC1>[N:13]1([C@H:11]2[CH2:12][C@H:9]([C:7]3[S:8][C:4]4[CH:3]=[C:2]([C:29]5[CH:30]=[N:31][N:32]([C:34]([C:41]6[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=6)([C:35]6[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=6)[C:47]6[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=6)[CH:33]=5)[CH:20]=[CH:19][C:5]=4[N:6]=3)[CH2:10]2)[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 457896834-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl)-1-trityl-1H-pyrazoleHCID 178419317HCID 178419317, compound

Product 1

HCID 178420200HCID 178420200, compoundYield 70%

Reagents, catalysts & solvents 3

HCID 27342162-(Dicyclohexylphosphino)biphenylCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 22560076Dioxan ethanolSolvent

Procedure

The product of Example 44A (120 mg, 0.34 mmole), 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1-trityl-1H-pyrazole (224 mg, 0.51 mmole), dichlorobis-(triphenylphosphine)palladium(II) (14.0 mg, 0.020 mmole), 2-(dicyclohexyl-phosphino)biphenyl (7.0 mg, 0.020 mmole), sodium carbonate (1 M solution, 0.51 ml, 0.51 mmole) and 1.5 ml of ethanol/dioxane (1:1) were combined under N2 in a capped, sealed vial. The vial was sealed and was placed a commercial (i.e. Emrys Creator) microwave for 10 minutes at 140° C. The reaction mixture was quenched with water and extracted with dichloromethane (4×5 ml). The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated to give the crude product which was purified by column chromatography (1% ammonium hydroxide and 10% methanol in dichloromethane) to give 138.1 mg (70% yield) of title compound. 1H NMR (300 MHz, CDCl3) δ ppm 7.99 (s, 1H), 7.89 (d, J=8.31 Hz, 1H), 7.88 (d, J=2.03 Hz, 1H), 7.68 (s, 1H), 7.53 (dd, J=8.31, 1.87 Hz, 1H), 7.52-7.35 (m, 9H), 7.19-7.23 (m, 6H), 3.93 (m, 1H) 3.42 (m, 1H) 2.61-2.73 (m, 2H) 2.26-2.52 (m, 4H) 1.73-1.90 (m, 4H) 1.43-1.58 (m, 4H). MS: (M+H)+=581.

Workup

  1. customsealed vial
  2. customThe vial was sealed
  3. customfor 10 minutes
  4. customat 140° C
  5. customThe reaction mixture was quenched with water
  6. extractionextracted with dichloromethane (4×5 ml)
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customto give the crude product which
  12. customwas purified by column chromatography (1% ammonium hydroxide and 10% methanol in dichloromethane)

Sources & evidence

ORD record
ord-4f4b916ee4cb49cc9a7fcd9583b1ac5c
Source dataset
uspto-grants-2013_11
Patent number
US08592467B2

Reaction notes

Loading…