Squaric acid → HCID 18402114, compound

HRID 1018772Notes

Reaction equation

HRID 1018772 reaction equation
[C:1]1([OH:8])[C:5](=O)[C:3](=[O:4])[C:2]=1[OH:7].[CH3:9][C:10]([C:13]1[S:14][C:15]([C:28]([CH3:31])([CH3:30])[CH3:29])=[CH:16][C:17](=[CH:19]C2C(Cl)(Cl)C(=O)C=2Cl)[CH:18]=1)([CH3:12])[CH3:11].FC(F)(F)S(O)(=O)=O>O>[CH3:12][C:10]([C:13]1[S:14][C:15]([C:28]([CH3:31])([CH3:30])[CH3:29])=[CH:16][C:17](=[CH:19][C:5]2[C:3](=[O:4])[C:2](=[O:7])[C:1]=2[OH:8])[CH:18]=1)([CH3:9])[CH3:11]

Participants

5

Reactant 3

HCID 17913Squaric acidHCID 62406Trifluoromethanesulfonic acidHCID 18402145HCID 18402145, compound

Product 1

HCID 18402114HCID 18402114, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
90 °C

Procedure

This Example illustrates the preparation, by a reaction analogous to D→E shown in FIG. 1, of the squaric acid derivative of Formula II in which Q1 is a 2,6-bis(1,1-dimethylethyl)-4-thiopyrylidene grouping and R1 is ahydrogen atom. 3-[2,6-Bis(1,1-dimethylethyl)-(4H-thiopyran-4-ylidene)methyl]-2,4,4-trichlorocyclobut-2-en-1-one (279 mg, 0.59 mmole, prepared in Example 51 above) was added to a solution of trifluoromethane sulfonic acid (1.0 mL) in water (35 mg). The colorless reaction mixture was stirred under nitrogen with heating to 90° C. for 5 hours, after which it was cooled to 20° C. and stirred for 12 hours at that temperature. The reaction mixture was quenched into ice/water (15 mL) dropwise, with efficient agitation. A brown precipitate formed which was initially crystalline, but become gummy after standing for several minutes. This was separated by filtration, washed with dilute aqueous sodium sulfate, and separated into two portions. One portion was dried, to give a red-brown amorphous solid (110 mg). The second portion was partly purified by flash chromatography on silica gel with 10-16-20 % methanol/dichloromethane as eluent to yield a still impure product (55 mg, exhibiting, inter alia, mle 363 in the mass spectrum), which was used directly in Example 70 without further purification.

Workup

  1. customthe preparation
  2. customby a reaction analogous
  3. temperatureafter which it was cooled to 20° C.
  4. stirringstirred for 12 hours at that temperature
  5. customThe reaction mixture was quenched into ice/water (15 mL) dropwise
  6. customA brown precipitate formed which
  7. waitafter standing for several minutes
  8. customThis was separated by filtration
  9. washwashed with dilute aqueous sodium sulfate
  10. customseparated into two portions
  11. customOne portion was dried

Sources & evidence

ORD record
ord-9df945cde41b419ead38d90f1ff2d7c3
Source dataset
uspto-grants-2002_11
Patent number
US06482950B1

Reaction notes

Loading…