Triethylamine → HCID 18358906, compound

HRID 2257010Notes

Reaction equation

HRID 2257010 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11](=[O:12])[C:10](I)=[C:9]([O:14][CH3:15])[C:8](=[O:16])[NH:7][C:6]=2[CH:17]=1.[C:18]([O:22][C:23](=[O:27])[C:24](C)=[CH2:25])([CH3:21])([CH3:20])[CH3:19].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.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.[Pd]>[C:18]([O:22][C:23](=[O:27])/[CH:24]=[CH:25]/[C:10]1[C:11](=[O:12])[C:5]2[CH:4]=[CH:3][C:2]([Cl:1])=[CH:17][C:6]=2[NH:7][C:8](=[O:16])[C:9]=1[O:14][CH3:15])([CH3:21])([CH3:20])[CH3:19]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 11448tert-Butyl methacrylateHCID 80271Tri-o-tolylphosphineHCID 18980002HCID 18980002, compound

Product 1

HCID 18358906HCID 18358906, compound

Reagents, catalysts & solvents 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
104 °C

Procedure

The title compound was prepared in the manner described in Example 44 using the 8-chloro-4-iodo-3-methoxy-2,5-dioxo-2,5-dihydro-1H-benz[b]azepine (2.18 g) and tert-butylmethacrylate (17.1 g) in toluene (70 mL) with tris (dibenzylideneacetone)dipalladium (O) (0.10 g) and tri-orthotolylphosphine (0.13 g). The mixture was treated with triethylamine (0.84 mL, 0.61 g) and heated at 104° C. for 3.7 hours. The mixture was concentrated to a dark solid which was dissolved in chloroform and chromatographed on a silica gel column (5.5 cm diameter×18 cm long) using 25% ethyl acetate in hexane. Concentration of the main fraction gave a white solid (0.77 g). A portion (0.21 g) of the solid was dissolved in hot ethyl acetate (7 mL). The solution was diluted with hexane (5 mL) and the crystals formed at room temperature. The solid was filtered off, washed with ethyl acetate, washed with hexane, and air-dried to give white crystals (0.11 g); mp=189.1°-199.8° C.; 1H NMR(CDCl3) 7.27 (s,1) for olefin proton; MS: m/z=322 (base peak), 378 (M+1). Analysis for C19H20ClNO5 : Calculated: C, 60.40; H, 5.34; N, 3.71; Found: C, 60.18; H, 5.43; N, 3.72.

Workup

  1. concentrationThe mixture was concentrated to a dark solid which
  2. dissolutionwas dissolved in chloroform
  3. customchromatographed on a silica gel column (5.5 cm diameter×18 cm long)

Sources & evidence

ORD record
ord-9d6e5587382e4aae84ce8b0e00d53369
Source dataset
uspto-grants-1997_08
Patent number
US05656626

Reaction notes

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