Toluene → 6-nitro-3-styryl-1-[2-(trimethyl-silanyl) ethoxymethyl]-1H-indazole

HRID 724379Notes

Reaction equation

HRID 724379 reaction equation
[N+:1]([C:4]1[CH:12]=[C:11]2[C:7]([C:8](I)=[N:9][N:10]2[CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])=[CH:6][CH:5]=1)([O-:3])=[O:2].[CH:22](B(O)O)=[CH:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.C1(C)C=CC=CC=1.[OH-].[Na+]>CCOC(C)=O.O.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.CO>[N+:1]([C:4]1[CH:12]=[C:11]2[C:7]([C:8]([CH:22]=[CH:23][C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)=[N:9][N:10]2[CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

9

Reactant 4

HCID 1140TolueneHCID 14798Sodium HydroxideHCID 27343812-Phenylvinylboronic acidHCID 218774881H-Indazole, 3-iodo-6-nitro-1-[[2-(trimethylsilyl)ethoxy]methyl]-

Product 1

HCID 693543436-nitro-3-styryl-1-[2-(trimethyl-silanyl) ethoxymethyl]-1H-indazoleYield 74.1%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

To 6-nitro-3-iodo-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazole (11.0 g, 26.1 mmol), styryl boronic acid (4.64, 31.4 mmol), and Pd(PPh3)4 (1.25 g, 1.08 mmol) under an atmosphere of argon was added toluene (192 mL), MeOH (4 mL) and 2N NaOH (aq) (32.6 mL, 65.3 mmol). The resulting heterogeneous mixture was heated to 90° C. After 8 h the reaction was diluted with EtOAc (150 mL) and water (50 mL), the phases were separated and the organic was extracted 2×50 mL EtOAc. The pooled organic phase was washed with brine (50 mL), then dried with Na2SO4, filtered and concentrated under reduced pressure. The crude reaction was purified by silica gel chromatography (1:9 EtOAc:hexane) to give 6-nitro-3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazole as a yellow solid (7.65 g, 74%): 13C NMR (75 MHz, CDCl3) δ 148.3, 145.0, 141.3, 138.1, 134.2, 130.5, 129.9, 129.8, 129.5, 128.1, 127.4, 123.2, 119.8, 117.8, 108.2, 79.7, 68.5, 19.2, 0.0; MS (FAB) [M+Na]/z Calc'd 418. found 418. Anal. Calc'd: C, 63.77; H, 6.37; N, 10.62. Found: C, 64.04; H, 6.29; N, 10.56.

Workup

  1. customthe phases were separated
  2. extractionthe organic was extracted 2×50 mL EtOAc
  3. washThe pooled organic phase was washed with brine (50 mL)
  4. dry with materialdried with Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude reaction
  8. customwas purified by silica gel chromatography (1:9 EtOAc:hexane)

Sources & evidence

ORD record
ord-77edc24b5aa1464d97879ba544a1e43d
Source dataset
uspto-grants-2006_11
Patent number
US07141587B2

Reaction notes

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