Benzene → HCID 66627125, compound

HRID 1913847Notes

Reaction equation

HRID 1913847 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([S:19](Cl)(=[O:21])=[O:20])[C:5]([C:8]2[C:9]([S:15](Cl)(=[O:17])=[O:16])=[CH:10][C:11]([Cl:14])=[CH:12][CH:13]=2)=[CH:6][CH:7]=1.[CH:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.[Cl-].[Al+3].[Cl-].[Cl-].Cl>[N+](C)([O-])=O>[C:23]1([S:19]([C:4]2[CH:3]=[C:2]([Cl:1])[CH:7]=[CH:6][C:5]=2[C:8]2[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][C:9]=2[S:15]([C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)(=[O:17])=[O:16])(=[O:21])=[O:20])[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

6

Reactant 4

HCID 241BenzeneHCID 313Hydrochloric AcidHCID 6451240Aluminum(III) ChlorideHCID 25111428HCID 25111428, compound

Product 1

HCID 66627125HCID 66627125, compoundYield 154.8%

Reagents, catalysts & solvents 1

HCID 6375NitromethaneSolvent

Conditions

Temperature
100 °C

Procedure

Inside a glove box, a 125 mL round-bottom flask equipped with a stirring bar, reflux condenser, and gas inlet was charged with 4,4′-dichlorobiphenyl-2,2′-disulfonyl dichloride (15.4 g, 36.7 mmoles), benzene (25 mL, 280 mmoles), and anhydrous nitromethane (75 mL). Aluminum chloride (11 g, 81 mmoles) was added and the mixture stirred until dissolved under nitrogen. The solution was heated to 100° C. for 8 hours. The solution was cooled to room temperature and poured onto 200 g ice mixed with 100 mL hydrochloric acid. The mixture was extracted several times with dichloromethane. The organic extracts were washed with water, dried with sodium carbonate, filtered to give a dark solution. The solution was treated with decolorizing carbon and heated to a reflux, then filtered through filter aid, evaporated, and the solids dried at 150° C. in a vacuum oven for 8 hr to give 18.02 g (97% crude yield). The mixture was purified by column chromatography using silica gel and dichloromethane (Rf 0.28) to give 14.3 g (77% yield) of 2,2′-bis-benzenesulfonyl-4,4′-dichlorobiphenyl. The solids were recrystallized from xylenes to give 13.08 g (71%). 1H NMR (DMSO-d6): 6.96 (d, 8.2 Hz, 2H), 7.55 (bs, 4H), 7.56 (m, 8.1 Hz, 4H), 7.69 (m, 2H), 7.74 (dd, 8.2, 2.2 Hz, 2H), 8.13 (d, 2.2 Hz, 2H). 13C NMR (CDCl3): 128.42 (4CH), 129.14 (4CH), 129.58 (2CH), 132.21 (2CH), 133.84 (2CH), 134.13 (2CH), 134.68 (2C), 135.61 (2C), 140.42 (2C), 141.42 (2C). MS (M+H+): m/e 502.99 (100%), 504.99 (75%), exact mass for C24H17O4Cl2S2, 502.99 (100%), 504.99 (72.9%).

Workup

  1. customInside a glove box, a 125 mL round-bottom flask equipped with a stirring bar
  2. temperaturereflux condenser, and gas inlet
  3. dissolutionuntil dissolved under nitrogen
  4. temperatureThe solution was cooled to room temperature
  5. extractionThe mixture was extracted several times with dichloromethane
  6. washThe organic extracts were washed with water
  7. dry with materialdried with sodium carbonate
  8. filtrationfiltered
  9. customto give a dark solution
  10. additionThe solution was treated with decolorizing carbon
  11. temperatureheated to a reflux
  12. filtrationfiltered
  13. filtrationthrough filter aid
  14. customevaporated
  15. customthe solids dried at 150° C. in a vacuum oven for 8 hr
  16. customto give 18.02 g (97% crude yield)
  17. customThe mixture was purified by column chromatography

Sources & evidence

ORD record
ord-aa7a97945b8c4647a6a62b58995fad78
Source dataset
uspto-grants-2013_12
Patent number
US08609804B2

Reaction notes

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