Triethylamine → N-[2'-(4''-Acetamidocinnamoyloxy)ethyl]-5-(alpha-hydroxy-alpha-2-pyridylbenzyl)-7-(alpha-2-pyridyl benzylidene)-5-norbornene-2,3-dicarboximide

HRID 1496799Notes

Reaction equation

HRID 1496799 reaction equation
[OH:1][C:2]([C:15]1[CH:16]2[C:21](=[C:22]([C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][N:30]=3)[C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)[CH:19]([CH:20]=1)[CH:18]1[C:35]([N:37]([CH2:40][CH2:41]OC(=O)C=CC3C=CC(C(C)C)=CC=3)[C:38](=[O:39])[CH:17]21)=[O:36])([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][N:10]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[C:56]([NH:59][C:60]1[CH:70]=[CH:69][C:63]([CH:64]=[CH:65][C:66]([OH:68])=[O:67])=[CH:62][CH:61]=1)(=[O:58])[CH3:57].C(N=C=NCCCN(C)C)C.C(N(CC)CC)C.CN(C1C=CC=CN=1)C>ClCCl>[C:56]([NH:59][C:60]1[CH:70]=[CH:69][C:63]([CH:64]=[CH:65][C:66]([O:68][CH2:41][CH2:40][N:37]2[C:38](=[O:39])[CH:17]3[CH:18]([CH:19]4[C:21](=[C:22]([C:29]5[CH:34]=[CH:33][CH:32]=[CH:31][N:30]=5)[C:23]5[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=5)[CH:16]3[C:15]([C:2]([OH:1])([C:9]3[CH:14]=[CH:13][CH:12]=[CH:11][N:10]=3)[C:3]3[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=3)=[CH:20]4)[C:35]2=[O:36])=[O:67])=[CH:62][CH:61]=1)(=[O:58])[CH3:57]

Participants

7

Reactant 5

HCID 8471TriethylamineHCID 159081-Ethyl-3-(3'-dimethylaminopropyl)carbodiimideHCID 218852-DimethylaminopyridineHCID 2515224-Acetylaminocinnamic acidHCID 1178180985-(alpha-Hydroxy-alpha-2-pyridylbenzyl)-N-[2'-(4''-isopropylcinnamoyloxy)ethyl]-7-(alpha-2-pyridyl benzylidene)-5-norbornene-2,3-dicarboximide

Product 1

HCID 117818190N-[2'-(4''-Acetamidocinnamoyloxy)ethyl]-5-(alpha-hydroxy-alpha-2-pyridylbenzyl)-7-(alpha-2-pyridyl benzylidene)-5-norbornene-2,3-dicarboximideYield 99%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A similar procedure (Schwartz, E. et al. Macromolecules 2011, 44, 4735-4741) to that previously described for the preparation of 347 was followed using 2 (1.50 g, 2.70 mmol), 4-acetamidocinnamic acid (0.50 g, 2.46 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (1.04 g, 5.60 mmol), triethylamine (1.24 mL, 8.91 mmol) and dimethylaminopyridine (60 mg, 0.49 mmol) in dichloromethane (25 mL), at room temperature for 72 h. Purification by flash chromatography (hexane/ethyl acetate 1:4) afforded 337 as a white solid (2.0 g, 2.69 mmol, 99%). mp 125-130° C.; 1H NMR (300 MHz, CDCl3) δ 2.17 (3H, s, NHAc), 3.35-3.90 (4.16H, m, NCH2CH2O, H-2, H-3, W/H-4), 3.83-3.95 (0.84H, m, U/H-1, V/H-1, Y/H-4), 4.14 (0.14H, m, U/H-4), 4.28-4.38 (2.32H, m, NCH2CH2O, V/H-4), 4.43-4.47 (0.54H, m, W/H-1, Y/H-1), 5.53 (0.32H, dd, J=3.4 and 1.2 Hz, V/H-6), 5.55 (0.38H, dd, J=3.4 and 1.2 Hz, Y/H-6), 5.59 (s, OH), 5.60 (s, OH), 5.63 (s, OH), 5.69 (s, OH), 6.06 (0.14H, dd, J=3.4 and 1.2 Hz, U/H-6), 6.06 (0.16H, dd, J=3.4 and 1.2 Hz, W/H-6), 6.17 (0.30H, d, J=15.8 Hz, COCH═CH), 6.26 (0.70H, d, J=15.8 Hz, COCH═CH), 6.74-7.61 (21H, m, Ar and COCH═CH), 8.40-8.63 (2H, m, αPyr); m/z (ESI, 70 eV) 765 (MNa+, 100%); (Found MNa+ 765.2684, C46H38N4NaO6 requires 765.2687).

Workup

  1. customPurification by flash chromatography (hexane/ethyl acetate 1:4)

Sources & evidence

ORD record
ord-c5c0c240d7984bc9ba23c5777f8f08c7
Source dataset
uspto-grants-2015_12
Patent number
US09198420B2

Reaction notes

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