Triethylamine → HCID 25100879, compound

HRID 1967666Notes

Reaction equation

HRID 1967666 reaction equation
I[C:2]1[CH:3]=[C:4]([CH:15]=[CH:16][CH:17]=1)/[CH:5]=[CH:6]/[C:7]1[C:12]([CH3:13])=[CH:11][CH:10]=[CH:9][C:8]=1[CH3:14].[CH3:18][CH2:19][N:20](CC)CC.C(OC)(=O)C[SH:27]>CN1C(=O)CCC1.O.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(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH3:14][C:8]1[CH:9]=[CH:10][CH:11]=[C:12]([CH3:13])[C:7]=1/[CH:6]=[CH:5]/[C:4]1[CH:3]=[C:2]([S:27][CH2:18][CH2:19][NH2:20])[CH:17]=[CH:16][CH:15]=1

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 16907Methyl ThioglycolateHCID 57766464HCID 57766464, compound

Product 1

HCID 25100879HCID 25100879, compoundYield 101.1%

Reagents, catalysts & solvents 4

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
80 °C

Procedure

To a stirred solution of (E)-2-(3-iodostyryl)-1,3-dimethylbenzene (4) (0.551 g, 1.65 mmol) in NMP (10 mL) was added Et3N (0.501 g, 4.95 mmol). The resulting solution was purged with nitrogen for 2 min and tris(dibenzylideneacetone)dipalladium(0) (0.076 g, 0.083 mmol) was added followed by 1,1′-bis(diphenylphosphino)ferrocene (0.183 g, 0.330 mmol). After 0.5 h methyl thioglycolate (0.531 g, 5.00 mmol) was added and the reaction mixture was heated at 80° C. After 26 h the reaction mixture was cooled to room temperature and diluted with water (50 mL). The resulting mixture was extracted with ethyl acetate (3×50 mL) and the combined organics were dried (Na2SO4), filtered and concentrated. The residue was purified by flash column chromatography (silica gel, 90:10 hexanes/ethyl acetate) to provide (E)-2-(3-(2,6-dimethylstyryl)phenylthio)ethylamine (18) (0.473 g, 92%) as a colorless oil: 1H NMR (500 MHz, CDCl3) δ 7.54 (s, 1H), 7.34 (m, 3H), 7.12 (d, J=16.4 Hz, 1H), 7.08 (m, 3H), 6.55 (d, J=16.4 Hz, 1H), 3.73 (s, 3H), 3.69 (s, 2H), 2.36 (s, 6H).

Workup

  1. customThe resulting solution was purged with nitrogen for 2 min
  2. temperatureAfter 26 h the reaction mixture was cooled to room temperature
  3. extractionThe resulting mixture was extracted with ethyl acetate (3×50 mL)
  4. dry with materialthe combined organics were dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by flash column chromatography (silica gel, 90:10 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-2b68af23710e42d585f9f8c105a44103
Source dataset
uspto-grants-2013_04
Patent number
US08420863B2

Reaction notes

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