2-(4-Bromophenyl)-1,3-dioxolane → HCID 86607749, compound

HRID 1767164Notes

Reaction equation

HRID 1767164 reaction equation
[CH3:1][CH2:2][CH2:3][CH2:4][N:5]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6]1[S:7][CH:8]=[CH:9][C:10]=1[CH3:11].Br[C:19]1[CH:24]=[CH:23][C:22](C2OCCO2)=[CH:21][CH:20]=1.[C:30]([O:34][Na])(C)(C)C>C1(C)C=CC=CC=1.C(OCC)C.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].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2]>[CH3:1][CH2:2][CH2:3][CH2:4][N:5]([C:12]1[CH:13]=[CH:14][C:15]([CH:30]=[O:34])=[CH:16][CH:17]=1)[C:6]1[S:7][CH:8]=[C:9]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:10]=1[CH3:11]

Participants

8

Reactant 3

HCID 27738422-(4-Bromophenyl)-1,3-dioxolaneHCID 86607748HCID 86607748, compoundHCID 178418730sodium 2-methylpropan-2-olate

Product 1

HCID 86607749HCID 86607749, compound

Reagents, catalysts & solvents 4

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 1.65 g (6 mmol) of N-4-butylphenyl-N-3-methylthiophenylamine (3), 2.04 g (5.3 mmol) of 2-(4-bromophenyl)-[1,3]dioxolane (4), 23 mg (0.025 mmol) of Pd2(dba)3, 42 mg (0.075 mmol) of DPPF and 1.34 g (14 mmol) of t-BuONa in 20 mL of toluene was stirred for 24 h at 90° C. The reaction mixture was allowed to cool down to room temperature and was diluted with 150 mL diethyl ether. After filtration, the solvent was evaporated and the residue was purified by liquid chromatography on silica gel. The product was then dissolved in 20 mL of THF and 10 mL of 10% HCl was added. After stirring for 12 h at room temperature, the mixture was diluted with 150 mL of chloroform, washed twice with equal amounts of sat. NaHCO3 aqueous solution and once with water. The organic phase was dried over MgSO4, evaporated and the crude product was filtered over a short column of silica gel with chloroform. 1H-NMR (400 MHz, CDCl3): δ 7.67 (m, 2 H), 7.245 (m, 1 H), 7.16 (m, 2H), 7.07(m, 2), 7.05 (m, 1 H), 7.03-6.99 (m, 3 H), 2.617 (t, J=7.6 Hz, 2H), 2.42 (s, 3 H), 1.62 (m, 2 H), 1.39 (tq,J1,J2=7.2Hz, 2H), 0.95 (t, J=7.2 Hz, 3H). GC-MS: m/z=375 (M+).

Workup

  1. temperatureto cool down to room temperature
  2. filtrationAfter filtration
  3. customthe solvent was evaporated
  4. customthe residue was purified by liquid chromatography on silica gel
  5. dissolutionThe product was then dissolved in 20 mL of THF
  6. addition10 mL of 10% HCl was added
  7. stirringAfter stirring for 12 h at room temperature
  8. additionthe mixture was diluted with 150 mL of chloroform
  9. washwashed twice with equal amounts of sat. NaHCO3 aqueous solution and once with water
  10. dry with materialThe organic phase was dried over MgSO4
  11. customevaporated
  12. filtrationthe crude product was filtered over a short column of silica gel with chloroform

Sources & evidence

ORD record
ord-389af6e506f247faad816a92f47c7727
Source dataset
uspto-grants-2007_06
Patent number
US07232913B2

Reaction notes

Loading…