Triethylamine → HCID 18980001, compound

HRID 2392564Notes

Reaction equation

HRID 2392564 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cl:20][C:21]1[CH:22]=[CH:23][C:24]2[C:30](=[O:31])[C:29](I)=[C:28]([O:33][CH3:34])[C:27](=[O:35])[NH:26][C:25]=2[CH:36]=1.[C:37]([O:41][CH2:42][CH3:43])(=[O:40])[CH:38]=[CH2:39].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]>[Cl:20][C:21]1[CH:22]=[CH:23][C:24]2[C:30](=[O:31])[C:29](/[CH:39]=[CH:38]/[C:37]([O:41][CH2:42][CH3:43])=[O:40])=[C:28]([O:33][CH3:34])[C:27](=[O:35])[NH:26][C:25]=2[CH:36]=1

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 8821Ethyl Acrylate2×HCID 11776Triphenylphosphine2×HCID 18980002HCID 18980002, compound

Product 1

HCID 18980001HCID 18980001, compoundYield 12.8%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst2×HCID 1140TolueneSolvent

Procedure

A solution of tris(dibenzylideneacetone)dipalladium (O) (0.051 g) in toluene (31 mL) was treated with triphenylphosphine (0.058 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 (0.97 g) followed by ethyl acrylate (4.3 mL, 4.0 g). The mixture was then treated with triethylamine (0.37 mL, 0.27 g). The mixture was heated to 104° C. for 1.5 hours and then it was cooled to room temperature. Another portion of tris(dibenzylideneacetone)dipalladium (O) (0.025 g) and more triphenyl phosphine (0.029 g) was added to the mixture. The mixture was then treated with more ethyl acrylate (2.8 mL) and it was heated to 105° C. for 1 hour and then it was cooled to room temperature and concentrated to a brown glass. It 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 pale yellow solid (0.115 g). The solid was recrystallized from ethyl acetate (10 mL) at room temperature to give an off-white solid (0.0712 g); mp 233.8°-234.5° C.; 1NMR (CDCl3) 7.73 (d, 1, J=16), 6.69 (d, 1, J=16) for trans olefin protons; MS: m/z=336 (M+1). Analysis for C16H14ClNO5 : Calculated: C, 57.24; H, 4.20; N, 4.17; Found C, 57.09; H, 4.16; N, 4.09.

Workup

  1. temperatureThe mixture was heated to 104° C. for 1.5 hours
  2. temperatureit was cooled to room temperature
  3. temperaturewas heated to 105° C. for 1 hour
  4. temperatureit was cooled to room temperature
  5. concentrationconcentrated to a brown glass
  6. dissolutionIt was dissolved in chloroform
  7. customchromatographed on a silica gel column (5.5 cm diameter×20 cm long)

Sources & evidence

ORD record
ord-153b8f0ac9344b6e960943c71b4ec66b
Source dataset
uspto-grants-1998_09
Patent number
US05801168

Reaction notes

Loading…