Trichloroethanol → (2',2',2'-Trichloroethyl)7-acetoxycoumarin-4-acetate

HRID 1472930Notes

Reaction equation

HRID 1472930 reaction equation
[C:1]([O:4][C:5]1[CH:14]=[C:13]2[C:8]([C:9]([CH2:16][C:17]([OH:19])=[O:18])=[CH:10][C:11](=[O:15])[O:12]2)=[CH:7][CH:6]=1)(=[O:3])[CH3:2].[Cl:20][C:21]([Cl:25])([Cl:24])[CH2:22]O.C1(N=C=NC2CCCCC2)CCCCC1>ClCCl>[Cl:20][C:21]([Cl:25])([Cl:24])[CH2:22][O:18][C:17](=[O:19])[CH2:16][C:9]1[C:8]2[C:13](=[CH:14][C:5]([O:4][C:1](=[O:3])[CH3:2])=[CH:6][CH:7]=2)[O:12][C:11](=[O:15])[CH:10]=1

Participants

5

Reactant 3

HCID 8259TrichloroethanolHCID 10868DicyclohexylcarbodiimideHCID 12514017(7-Acetoxy-2-oxo-2H-chromen-4-yl)-acetic acid

Product 1

HCID 86644260(2',2',2'-Trichloroethyl)7-acetoxycoumarin-4-acetateYield 96.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

To a suspension of 7-acetoxycoumarin-4-acetic acid 5 (945 mg, 3.6 mmol, 1 eq) in 47 mL of anhydrous dichloromethane at room temperature under nitrogen was added 2,2,2-trichloroethanol (431 μL, 4.5 mmol, 1.25 eq). A solution of N,N′-dicyclohexylcarbodiimide (818 mg, 4 mmol, 1.1 eq) in 10 mL of anhydrous dichloromethane was added. The reaction mixture was stirred for 15 min, after which it was diluted with dichloromethane and filtered. The filtrate was concentrated under vacuum. Column chromatography on silica gel (CH2Cl2 then CH2Cl2:EtOAc, 10:1) afforded product 6a (1.37 g, 96%): Rƒ 0.78 (CH2Cl2:EtOAc, 5:1); 1H NMR (300 MHz, CDCl3): δ 7.61 (d, 1 H, J5,6 8.7 Hz, H-5), 7.15 (d, 1 H, J6,8 2.1 Hz, H-8), 7.07 (dd, 1 H, J6,8 2.3, J5,6 8.7 Hz, H-6), 6.42 (s, 1 H, H-3), 4.77 (s, 2 H, CH2CCl3), 3.91 (2 s, 2 H, CH2CO2), 2.33 (s, 3 H, OAc); 13C NMR (75 MHz, CDCl3): δ 168.6, 167.0, 154.5, 153.5, 146.5, 125.5, 118.5, 117.0, 116.5, 110.9, 74.6, 37.7, 21.2; ESI-MS: m/z 393 [M+H]+.

Workup

  1. filtrationfiltered
  2. concentrationThe filtrate was concentrated under vacuum

Sources & evidence

ORD record
ord-2d60d2cb495141ea8bae0c57d6359874
Source dataset
uspto-grants-2015_04
Patent number
US09012663B2

Reaction notes

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