Ethylamine → HCID 86631947, compound

HRID 906138Notes

Reaction equation

HRID 906138 reaction equation
I[C:2]1[C:3]([CH3:20])=[C:4]([CH:12]=[C:13]([CH3:19])[C:14]=1[C:15]([O:17][CH3:18])=[O:16])[C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6].C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:27]([NH2:29])[CH3:28].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>O1CCOCC1.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].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[CH2:27]([NH:29][C:2]1[C:3]([CH3:20])=[C:4]([CH:12]=[C:13]([CH3:19])[C:14]=1[C:15]([O:17][CH3:18])=[O:16])[C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6])[CH3:28]

Participants

8

Reactant 4

HCID 6341Ethylamine2×HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 86631946HCID 86631946, compound

Product 1

HCID 86631947HCID 86631947, compoundYield 67%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

1-tert-Butyl 4-methyl 3-iodo-2,5-dimethylterephthalate (300 mg, 0.769 mmol) was dissolved in dioxane (3 mL) and sparged with nitrogen for 15 minutes. XANTPHOS (18 mg, 0.031 mmol), cesium carbonate (326 mg, 1.00 mmol), ethylamine (0.1 mL) and tris(dibenzylideneacetone)dipalladium (14 mg, 0.015 mmol) were added, and the mixture was stirred in a sealed tube at 95° C. for 19 h. XANTPHOS (36 mg, 0.062 mmol), ethylamine (0.1 mL) and tris(dibenzylideneacetone)dipalladium (28 mg, 0.030 mmol) were added and the mixture was stirred in a sealed tube at 95° C. for a further 20 h. The reaction mixture was cooled to ambient temperature and was filtered through celite. The filter cake was washed with ethyl acetate, and the filtrate was concentrated to afford an orange oil which was purified by column chromatography (silica gel, 2-10% ethyl acetate in hexanes) to afford 1-tert-butyl 4-methyl 3-(ethylamino)-2,5-dimethylterephthalate (158 mg, 0.515 mmol, 67% yield) as a yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.08 (s, 1H), 3.91 (s, 3H), 3.83 (br s, 1H), 3.00 (q, 2H), 2.36 (s, 3H), 2.29 (s, 3H), 1.59 (s, 9H), 1.14 (t, 3H); MS (EI) for C17H25NO4: 308 (MH+).

Workup

  1. customsparged with nitrogen for 15 minutes
  2. stirringthe mixture was stirred in a sealed tube at 95° C. for a further 20 h
  3. temperatureThe reaction mixture was cooled to ambient temperature
  4. filtrationwas filtered through celite
  5. washThe filter cake was washed with ethyl acetate
  6. concentrationthe filtrate was concentrated
  7. customto afford an orange oil which
  8. customwas purified by column chromatography (silica gel, 2-10% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-eb857370b1724637a257388ce4221654
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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