Cesium carbonate → HCID 50900631, compound

HRID 1921920Notes

Reaction equation

HRID 1921920 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N:8]([CH3:16])[C:9]1[C:10]([NH2:15])=[CH:11][CH:12]=[CH:13][CH:14]=1.I[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[N+:24]([O-:26])=[O:25].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N:8]([CH3:16])[C:9]1[C:10]([NH:15][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[N+:24]([O-:26])=[O:25])=[CH:11][CH:12]=[CH:13][CH:14]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 69115o-IodonitrobenzeneHCID 634876Binap, (A+-)-HCID 50900630HCID 50900630, compound

Product 1

HCID 50900631HCID 50900631, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

Compound 3 (0.842 g, 3.62 mmol), o-iodonitrobenzene (1.35 g, 5.43 mmol), Pd2(dba)3 (0.104 g, 5% mol), BINAP (0.170 g, 7.5%), Cs2CO3 (2.35 g, 7.42 mmol) and 12 mL of toluene were placed in a pressure tube. The mixture was purged with argon at room temperature for 15 min. The tube was sealed and placed in an oil bath at 80-90° C. for 30 h. When thin-layer chromatography (TLC) showed consumption of compound 3, the reaction mixture was filtered through silica gel with a 90:10 mixture of ethyl acetate:dichloromethane. The solvent was then removed under vacuum. The product was purified by column chromatography on silica gel using a 8:92 mixture of methyl chloride:petroleum ether as the eluent to afford the product as a red crystalline solid (0.785 g, 80% yield). 1H NMR (300 MHz, CDCl3) δ 9.03 (1H, bs), 8.07 (1H, dd, J=8.7, 1.5 Hz), 7.32-7.19 (4H, m), 7.12-6.99 (5H, m), 6.90 (1H, ddd, J=8.0, 6.9, 2.2 Hz), 6.68 (1H, ddd, J=8.4, 6.9, 1.2 Hz), 3.16 (3H, s); 13C (75 MHz, CDCl3) δ 147.2 (q), 145.1 (q), 142.4 (q), 135.2 (t), 131.6 (q), 130.7 (t), 129.5 (q), 127.4 (t), 126.5 (t), 126.5 (t), 126.0 (t), 124.8 (t), 124.0 (t), 123.2 (t), 121.7 (t), 117.0 (t), 115.8 (t), 40.6.

Workup

  1. customThe mixture was purged with argon at room temperature for 15 min
  2. customThe tube was sealed
  3. customconsumption of compound 3
  4. filtrationthe reaction mixture was filtered through silica gel with a 90:10 mixture of ethyl acetate
  5. customThe solvent was then removed under vacuum
  6. customThe product was purified by column chromatography on silica gel using
  7. additiona 8:92 mixture of methyl chloride

Sources & evidence

ORD record
ord-5827ef745bd041b9bead0444c7cd8a54
Source dataset
uspto-grants-2012_05
Patent number
US08173803B2

Reaction notes

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