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Cesium carbonate → 3-[3-(Tert-butyldimethylsilanyloxy)-4-methoxyphenyl-amino]phthalic acid dimethyl ester

HRID 448342
Notes
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Reaction equation

HRID 448342 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:5](=[C:10](I)[CH:11]=[CH:12][CH:13]=1)[C:6]([O:8][CH3:9])=[O:7].[Si:16]([O:23][C:24]1[CH:25]=[C:26]([NH2:32])[CH:27]=[CH:28][C:29]=1[O:30][CH3:31])([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17].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+]>C1(C)C=CC=CC=1.C(Cl)Cl.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]>[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:5](=[C:10]([NH:32][C:26]2[CH:27]=[CH:28][C:29]([O:30][CH3:31])=[C:24]([O:23][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[CH:25]=2)[CH:11]=[CH:12][CH:13]=1)[C:6]([O:8][CH3:9])=[O:7]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 2326127Dimethyl 3-iodophthalateHCID 154537193-[(Tert-butyldimethylsilyl)oxy]-4-methoxyaniline

Product 1

HCID 583073223-[3-(Tert-butyldimethylsilanyloxy)-4-methoxyphenyl-amino]phthalic acid dimethyl esterYield 71%

Reagents, catalysts & solvents

3
HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of 3-iodophthalic acid dimethyl ester (1.0 g, 3.1 mmol), 3-(tert-butyldimethylsilanyloxy)-4-methoxyphenylamine (0.79 g, 3.1 mmol), Pd2(dba)3 (0.13 g, 0.14 mmol), rac-BINAP (0.058 g, 0.093 mmol), and cesium carbonate (1.4 g, 4.3 mmol), in 6 mL toluene was heated to reflux under nitrogen for 24 hours. The reaction mixture was cooled, diluted with CH2Cl2 (10 mL), and filtered through Celite, and the filter was washed with additional CH2Cl2 (30 mL). The filtrate was evaporated, and the residue was chromatographed using a hexanes-ethyl acetate gradient, eluting 1.0 g of the product at 90:10 hexanes-ethyl acetate, in 71% yield: 1H NMR (CDCl3) δ 0.16 (s, 6H), 0.98 (s, 9H), 3.81 (s, 3H), 3.87 (s, 3H), 3.88 (s, 3H), 6.69-6.75 (m, 2H), 6.82 (d, J=8.2 Hz, 1H), 6.95 (dd, J=7.3 Hz, J=1.1 Hz, 1H), 7.12 (dd, J=7.0 Hz, J=1.1 Hz, 1H), 7.24 (t, J=7.8 Hz, 1H), 8.04 (s, 1H).

Workup

  1. temperatureto reflux under nitrogen for 24 hours
  2. temperatureThe reaction mixture was cooled
  3. filtrationfiltered through Celite
  4. washthe filter was washed with additional CH2Cl2 (30 mL)
  5. customThe filtrate was evaporated
  6. customthe residue was chromatographed
  7. washeluting 1.0 g of the product at 90:10 hexanes-ethyl acetate

Sources & evidence

ORD record
ord-86ddb96d98634825b607272499b5fa37
Source dataset
uspto-grants-2013_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08481568B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes