Benzophenone imine → HCID 23114409, compound

HRID 1787183Notes

Reaction equation

HRID 1787183 reaction equation
Br[C:2]1[C:3]([CH3:21])=[CH:4][C:5]2[S:9][CH2:8][CH:7]([C:10]3[CH:15]=[CH:14][C:13]([CH:16]([CH3:18])[CH3:17])=[CH:12][CH:11]=3)[C:6]=2[C:19]=1[CH3:20].[C:22](=[NH:35])([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][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+]>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[C:29]1([C:22]([C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)=[N:35][C:2]2[C:3]([CH3:21])=[CH:4][C:5]3[S:9][CH2:8][CH:7]([C:10]4[CH:15]=[CH:14][C:13]([CH:16]([CH3:18])[CH3:17])=[CH:12][CH:11]=4)[C:6]=3[C:19]=2[CH3:20])[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1

Participants

8

Reactant 4

HCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 23114102HCID 23114102, compoundHCID 23676156Sodium t-butoxide

Product 1

HCID 23114409HCID 23114409, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

To a solution of 5-bromo-3-(4-isopropylphenyl)-4,6-dimethyl-2,3-dihydro-1-benzothiophene obtained in Reference Example 259 (870 mg, 2.41 mmol) and benzophenone imine (0.76 mL, 2.89 mmol) in toluene (15 mL) were added tris(dibenzylideneacetone)dipalladium (22 mg, 0.024 mmol) and BINAP (45 mg, 0.072 mmol) at room temperature, and the mixture was stirred under argon atmosphere for 15 minutes. To the reaction solution was added sodium tert-butoxide (324 mg, 3.37 mmol) at room temperature, and the mixture was heated under reflux under argon stream for 16 hours. Water was added to the reaction solution, which was extracted with ethyl acetate, and the organic layer was washed with water and a saturated brine, was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain the crude product of N-(diphenylmethylene)-3-(4-isopropylphenyl)-4,6-dimethyl-2,3-dihydro-1-benzothien-5-amine. This compound was dissolved in THF (10 mL), to which 1 N hydrochloric acid (2 mL) was added, and the mixture then was heated under reflux for 30 minutes. The solvent was concentrated under reduced pressure to obtain the residue, which was neutralized with 1 N aqueous sodium hydroxide solution. The product was extracted with ethyl acetate. The combined extract was washed with water, dried over magnesium sulfate, and then concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:10) to obtain 521 mg (yield 73%) of the title compound. Melting point: 121-122° C. (hexane-ethyl acetate).

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux under argon stream for 16 hours
  3. extractionwas extracted with ethyl acetate
  4. washthe organic layer was washed with water
  5. dry with materiala saturated brine, was dried over anhydrous sodium sulfate
  6. distillationthe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-3219bdee6e9749aa83f465b79f66172e
Source dataset
uspto-grants-2009_03
Patent number
US07507841B2

Reaction notes

Loading…