tert-Butyl hydroperoxide → (Z)-2-(4,6-difluoro-2-hydroxy-1-indanylidene)acetamide

HRID 1954908Notes

Reaction equation

HRID 1954908 reaction equation
[F:1][C:2]1[CH:10]=[C:9]([F:11])[CH:8]=[C:7]2[C:3]=1[CH2:4][CH2:5]/[C:6]/2=[CH:12]\[C:13]([NH2:15])=[O:14].C([O:20]O)(C)(C)C.[Se](=O)=O>ClCCl.CC(C)(CC(C)C)C>[F:1][C:2]1[CH:10]=[C:9]([F:11])[CH:8]=[C:7]2[C:3]=1[CH2:4][CH:5]([OH:20])/[C:6]/2=[CH:12]\[C:13]([NH2:15])=[O:14]

Participants

6

Reactant 3

HCID 6410tert-Butyl hydroperoxide3×HCID 24007Selenium Dioxide3×HCID 101766722-(4,6-Difluoroindan-1-ylidene)-acetamide, (E)-

Product 1

HCID 69888595(Z)-2-(4,6-difluoro-2-hydroxy-1-indanylidene)acetamide

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 109072,2,4-TrimethylpentaneSolvent

Procedure

A suspension of (E)-2-(4,6-difluoro-1-indanylidene)acetamide (10.0 g, 0.05 mol, prepared as in Example 5 g in dichloromethane (250 mL) was added portionwise over a 10 min. period to a mixture of 70% aqueous t-butylhydroperoxide (19.8 mL, 0.15 mol, Aldrich) and selenium dioxide (3.7 g, 0.03 mol, Aldrich) in dichloromethane (500 mL) at ambient temperature. After 18h, additional t-butylhydroperoxide (10 mL of a 5.0M solution in 2,2,4-trimethylpentane, 0.05 mol, Aldrich) and selenium dioxide (1.8 g, 0.02 mol) were added and the mixture was stirred at ambient temperature. After 18h, additional t-butylhydroperoxide (10 mL of 70% aqueous solution, 0.08 mol) and selenium dioxide (3.7 g, 0.05 mol) were added and the mixture was stirred at ambient temperature for 8 days. The resulting solid was filtered off and washed with dichloromethane to give 5.85 g of crude (Z)-2-(4,6-difluoro-2-hydroxy-1-indanylidene)acetamide. After 7 days at ambient temperature a second crop of crude (Z)-2-(4,6-difluoro-2-hydroxy-1-indanylidene)acetamide was obtained from the filtrate. Column chromatography on silica gel using ethyl acetate as the eluent followed by a second column chromatography on silica gel using ethyl acetate:hexanes (3:2) as eluent and trituration of the resulting solid with pentane gave 2.38 g of (Z)-2-(4,6-difluoro-2-hydroxy-1-indanylidene)acetamide as a pink solid: m.p. 235-237° C.

Workup

  1. stirringthe mixture was stirred at ambient temperature for 8 days
  2. filtrationThe resulting solid was filtered off
  3. washwashed with dichloromethane

Sources & evidence

ORD record
ord-aeb307e993a74882bced1b69dd84a7f7
Source dataset
uspto-grants-2000_09
Patent number
US06124284

Reaction notes

Loading…