Trifluoromethanesulfonic acid → 2-Chlorotetracene-5,12-dione

HRID 2250147Notes

Reaction equation

HRID 2250147 reaction equation
FC(F)(F)S(O)(=O)=O.[Cl:9][C:10]1[CH:30]=[CH:29][C:13]([C:14]([C:16]2[C:17]([C:26](O)=[O:27])=[CH:18][C:19]3[C:24]([CH:25]=2)=[CH:23][CH:22]=[CH:21][CH:20]=3)=[O:15])=[CH:12][CH:11]=1.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O>>[Cl:9][C:10]1[CH:30]=[CH:29][C:13]2[C:14](=[O:15])[C:16]3[C:17](=[CH:18][C:19]4[C:24]([CH:25]=3)=[CH:23][CH:22]=[CH:21][CH:20]=4)[C:26](=[O:27])[C:12]=2[CH:11]=1

Participants

4

Reactant 3

HCID 62406Trifluoromethanesulfonic acidHCID 67749Trifluoromethanesulfonic anhydrideHCID 586407363-(4-Chlorobenzoyl)-naphthalene-2-carboxylic acid2×

Product 1

HCID 219535562-Chlorotetracene-5,12-dioneYield 73%

Conditions

Temperature
155 °C

Procedure

A 500 mL flask was successively loaded with trifluoromethanesulfonic acid (175 mL), 3-(4-chlorobenzoyl)-naphthalene-2-carboxylic acid (Formula XV, 25.5 g), and trifluoromethanesulfonic anhydride (21 mL). The mixture was heated at 155° C. for 10 hours. The violet-blue solution was gradually poured into a 2 L beaker containing 1 L of crushed ice. Additional ice was added as necessary to keep the solution cold. The brown-green mixture was poured onto a large 25-50 μm glass frit, and the isolated solid was washed with water (1 L), methanol (300 mL), and then air-dried overnight. The crude material was purified by high vacuum train sublimation (less than 10−3 Torr) at a source temperature of 165° C. to afford 17.5 g (73 percent yield) of bright yellow product. 1H NMR (400 MHz, d6-DMSO): δ 8.89 (‘s’, 6-H and 11-H), 8.36 (m, 4 lines, J=3.2 Hz, 7-H and 10-H), 8.30 (‘d’, J=8 Hz, 4-H), 8.22 (‘d’, 2 Hz, 1-H), 8.02 (‘dd’, J=2 Hz, 4 Hz), 7.82 (m, 4 lines, J=3.2 Hz, 8-H and 9-H).

Workup

  1. additionThe violet-blue solution was gradually poured into a 2 L beaker
  2. additionAdditional ice was added as necessary
  3. additionThe brown-green mixture was poured onto a large 25-50 μm glass frit
  4. washthe isolated solid was washed with water (1 L), methanol (300 mL)
  5. customair-dried overnight
  6. customThe crude material was purified by high vacuum train sublimation (less than 10−3 Torr) at a source temperature of 165° C.

Sources & evidence

ORD record
ord-eae29ba3ccc64398a41b70327a68246b
Source dataset
uspto-grants-2008_01
Patent number
US07315042B2

Reaction notes

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