HCID 86752885, compound → HCID 86752884, compound

HRID 1955478Notes

Reaction equation

HRID 1955478 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([N:10]=[N:11][C:12]2([O:39]CC3C=CC=CC=3)[CH:17]=[CH:16][C:15]([N:18]([C:25]3[CH:30]=[CH:29][C:28]([O:31]CC4C=CC=CC=4)=[CH:27][CH:26]=3)[C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[CH:14][CH2:13]2)=[CH:6][CH:5]=1)([O-:3])=[O:2]>FC(F)(F)C(O)=O>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([N:10]=[N:11][C:12]2([OH:39])[CH:13]=[CH:14][C:15]([N:18]([C:25]3[CH:26]=[CH:27][C:28]([OH:31])=[CH:29][CH:30]=3)[C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[CH:16][CH2:17]2)=[CH:8][CH:9]=1)([O-:3])=[O:2]

Participants

3

Reactant 1

HCID 86752885HCID 86752885, compound

Product 1

HCID 86752884HCID 86752884, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

To a 500 mL flask equipped with a nitrogen inlet and a magnetic stir was added 20 g (0.033) dibenzyl ether 2 from Example 1B and 330 mL (0.3M) trifluoroacetic acid (Aldrich). The dark blue mixture was allowed to stir at room temperature for 48 hours after which all of 2 had been consumed as measured by LC in addition to one minor impurity (monobenzyl ether). The reaction was quenched with 1 L ice water and the bisphenol was extracted into 300 mL Et2O. The organic layer was washed 2×100 mL H2O 5×100 mL aq. sodium bicarbonate (sat.) and 2×100 mL H2O dried over MgSO4, filtered and reduced in vacuo giving ca. 20 g crude 3 as a dark red powder (ca. 60 percent by LC). All attempts at recrystallization failed and the two components were separated by high pressure flash chromatography (Biotage) on silica with CH3 CN/CH2Cl2 (20/80 percent) TLC ΔRf =0.119) giving 3.2 g of BHPD as a red powder (m.p. 237°-240° C.) in 25 percent isolated yield (99+ percent by LC). It had the following spectral properties. 1H NMR (250 MHz, DMSO-d6): δ6.7 (d,2H), 6.82 (d,4H), 7.1 (d,4H), 7.75 (d,2H), 7.91 (d, 2H), 8.32 (d,2H), 9.55 (d, 2H, OH). 13C NMR (63 MHz, DMSO-d6): δ115.5, 116.5, 122.6, 124.9, 125.5, 128.4, 136.6, 144.3, 147.4, 153.1, 155.6, 156.9. GCMS (EI) m/z calcd (found) for C24H18N4O4 =426 (426 w/276 at 100 percent).

Workup

  1. customTo a 500 mL flask equipped with a nitrogen inlet
  2. stirringto stir at room temperature for 48 hours after which all of 2
  3. customhad been consumed
  4. additionas measured by LC in addition to one minor impurity (monobenzyl ether)
  5. customThe reaction was quenched with 1 L ice water
  6. extractionthe bisphenol was extracted into 300 mL Et2O
  7. washThe organic layer was washed 2×100 mL H2O 5×100 mL aq. sodium bicarbonate (sat.) and 2×100 mL H2O
  8. dry with materialdried over MgSO4
  9. filtrationfiltered

Sources & evidence

ORD record
ord-a93795d8adfd4bb0bd6ae23ddcc02547
Source dataset
uspto-grants-1998_07
Patent number
US05776374

Reaction notes

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