Triethylamine → HCID 18358906, compound

HRID 2392565Notes

Reaction equation

HRID 2392565 reaction equation
C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[Cl:23][C:24]1[CH:25]=[CH:26][C:27]2[C:33](=[O:34])[C:32](I)=[C:31]([O:36][CH3:37])[C:30](=[O:38])[NH:29][C:28]=2[CH:39]=1.[C:40]([O:44][C:45]([CH3:48])([CH3:47])[CH3:46])(=[O:43])[CH:41]=[CH2:42].C(N(CC)CC)C>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]>[C:45]([O:44][C:40](=[O:43])/[CH:41]=[CH:42]/[C:32]1[C:33](=[O:34])[C:27]2[CH:26]=[CH:25][C:24]([Cl:23])=[CH:39][C:28]=2[NH:29][C:30](=[O:38])[C:31]=1[O:36][CH3:37])([CH3:48])([CH3:47])[CH3:46]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 18980002HCID 18980002, compound

Product 1

HCID 18358906HCID 18358906, compoundYield 76.3%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

A solution of tris(dibenzylidenacetone)dipalladium (O) (0.0163 g) in toluene (39 mL) was treated with tri-orthotolylphosphine (0.0815 g). The solution was stirred under argon at room temperature for 15 minutes and then it was treated with 8-chloro-4-iodo-3-methoxy-2,5-dioxo-2,5-dihydro-1H-benz[b]azepine (1.22 g) followed by tert-butyl acrylate (7.30 mL, 6.45 g). The mixture was then treated with triethylamine (0.47 mL, 0.34 g) and it was heated to 105° C. for 35 minutes. The mixture was cooled and concentrated to a dark solid. The solid was dissolved in chloroform and chromatographed on a silica gel column (5.5 cm diameter×20 cm long) using 25% ethyl acetate in hexane to give a light yellow solid (0.932 g). A portion of the solid (0.294 g) was dissolved in warm ethyl acetate (5 mL) and then it was concentrated to 3 mL volume. Hexane (1 mL) was added to the solution and crystals formed. The solid was filtered off, washed with cold ethyl acetate, washed with hexane, and dried to give a white solid (0.21 g); mp 213.2°-213.8° C. (dec); 1H NMR (CDCl3) 7.67 (d,1, J=16), 6.61 (d,1, J=16) for trans olefin protons; MS: m/z=308 (base peak), 364 (M+1). Analysis for C18H18ClNO5 : Calculated: C, 59.43; H, 4.99; N, 3.85; Found: C, 59.22; H, 4.92; N, 3.79.

Workup

  1. temperaturewas heated to 105° C. for 35 minutes
  2. temperatureThe mixture was cooled
  3. concentrationconcentrated to a dark solid
  4. dissolutionThe solid was dissolved in chloroform
  5. customchromatographed on a silica gel column (5.5 cm diameter×20 cm long)

Sources & evidence

ORD record
ord-baab6f5778fe4118a61e04702d4f6a0b
Source dataset
uspto-grants-1998_09
Patent number
US05801168

Reaction notes

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