1-Chloro-3-iodobenzene → HCID 11750293, compound

HRID 1296485Notes

Reaction equation

HRID 1296485 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]2[N:10]([CH3:11])[C:9](=[O:12])[O:8][C:7]([C:14]3[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=3)([CH3:13])[C:6]=2[CH:21]=1.[Cl:22][C:23]1[CH:28]=[CH:27][CH:26]=[C:25](I)[CH:24]=1.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.CC(C)([O-])C.[Na+].C1OCCOCCOCCOCCOCCOC1>C1COCC1.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]>[Cl:20][C:17]1[CH:18]=[CH:19][C:14]([C:7]2([CH3:13])[C:6]3[CH:21]=[C:2]([NH:1][C:25]4[CH:26]=[CH:27][CH:28]=[C:23]([Cl:22])[CH:24]=4)[CH:3]=[CH:4][C:5]=3[N:10]([CH3:11])[C:9](=[O:12])[O:8]2)=[CH:15][CH:16]=1

Participants

8

Reactant 5

HCID 122691-Chloro-3-iodobenzeneHCID 2855718-Crown-6HCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 69212235HCID 69212235, compound

Product 1

HCID 11750293HCID 11750293, compoundYield 18%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 6-amino-4-(4-chlorophenyl)-1,4-dimethyl-1,4-dihydro-2H-3,1-benzoxazin-2-one (0.09 g, 0.30 mmol) and 1-chloro-3-iodobenzene (0.2 mL, 1.62 mmol) in THF (2 mL) was added Pd2(dba)3 (0.03 g, 0.03 mmol), BINAP (0.03 g, 0.05 mmol), sodium t-butoxide (0.07 g, 0.45 mmol), and 18-crown-6 (0.12 g, 0.45 mmol). The reaction mixture was stirred at room temperature for 2 days, quenched with ammonium chloride solution (sat.) and extracted several times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated. Flash silica gel column separation with 20% ethyl acetate/hexane followed by trituration with hexane gave the title compound as brown solid (0.02 g, 18%). 1H NMR (DMSO-d6): δ 8.43 (s, 1H), 7.46 (dd, J=6.7, 2.0 Hz, 2H), 7.31 (dd, J=6.8, 2.2 Hz, 2H), 7.28 (m, 2H), 7.10 (d, J=10.5 Hz, 1H), 7.09 (s, 1H), 6.94 (m, 2H), 6.80 (m, 1H), 3.17 (s, 3H), 1.92 (s, 3H); MS (ESI) m/z [M+H]+ (413/415); MS (ESI) m/z [M−H]−(411/413); Anal. calcd for C22H18Cl2N2O2: C, 63.93; H, 4.39 N, 6.78. Found: C, 62.88; H, 4.72; N, 5.67.

Workup

  1. customquenched with ammonium chloride solution (sat.)
  2. extractionextracted several times with ethyl acetate
  3. dry with materialThe combined organic layers were dried over magnesium sulfate
  4. concentrationconcentrated
  5. customFlash silica gel column separation with 20% ethyl acetate/hexane

Sources & evidence

ORD record
ord-5c737605ef6241a2bcebba0e87ef5bf7
Source dataset
uspto-grants-2007_07
Patent number
US07247625B2

Reaction notes

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