Nitric Acid → HCID 12573606, compound

HRID 1764545Notes

Reaction equation

HRID 1764545 reaction equation
[Na+:1].[Na+].[C:3]1([S:13]([O-:16])(=[O:15])=[O:14])[CH:8]=[CH:7][CH:6]=[C:5]([S:9]([O-:12])(=[O:11])=[O:10])[CH:4]=1.S(=O)(=O)(O)O.[N+:22]([O-])([OH:24])=[O:23].[OH-].[Ca+2].[OH-]>>[Na+:1].[Na+:1].[N+:22]([C:7]1[CH:8]=[C:3]([S:13]([O-:16])(=[O:15])=[O:14])[CH:4]=[C:5]([S:9]([O-:12])(=[O:11])=[O:10])[CH:6]=1)([O-:24])=[O:23]

Participants

5

Reactant 4

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 71577Disodium benzene-1,3-disulfonateHCID 6093208Calcium Hydroxide

Product 1

HCID 12573606HCID 12573606, compound

Procedure

Additionally, the hexaphenyl ester intermediate compound of the invention is prepared by treating 1,3-benzenedisulfonic acid disodium salt with concentrated sulfuric acid at 80° C. then adding fuming nitric acid and heating at 85°-89° C. for four hours. The cooled mixture is added to ice-water, neutralized to pH 5-6 with calcium hydroxide and filtered. The aqueous mixture is adjusted to pH 10 with sodium carbonate and filtered. Evaporation of the filtrate produces a residue which is recrystallized from boiling water to give 5-nitrobenzene-1,3-disulfonic acid disodium salt. This material is refluxed 16 hours with thionyl chloride and dimethylformamide and filtered. The filtrate is concentrated to an oil which is crystallized from chloroform:carbon tetrachloride to give the disulfonyl chloride which is reacted with phenol in pyridine at elevated temperature for one hour. Addition of the cooled mixture to 10% aqueous sodium carbonate solution produces a product which is crystallized from ethanol to yield the nitro-diphenyl ester. Hydrogenation of the ester in ethyl acetate with 10% palladium on carbon catalyst for 6.5 hours yields an oil which is crystallized from benzene to give the amino-diphenyl ester. The amine in pyridine is heated with 1,3,6-naphthalenetrisulfony chloride. The mixture is poured into water and extracted with methylene chloride. The extract, after washing the dilute acid, is evaporated to a glass which is purified by column chromatography to yield the hexaphenyl ester intermediate compound of the invention. Treatment of the novel intermediate triphenyl and hexaphenyl esters with alkali metal ethoxide in dimethylsulfoxide at elevated temperature followed by acidification with acetic acid and precipitation with absolute ethanol provides the active complement inhibiting trialkali metal and hexaalkali metal salts of the invention.

Workup

  1. temperatureheating at 85°-89° C. for four hours
  2. filtrationfiltered
  3. filtrationfiltered
  4. customEvaporation of the filtrate
  5. customproduces a residue which
  6. customis recrystallized

Sources & evidence

ORD record
ord-1f9d1793387d49f19e15f883e01fc065
Source dataset
uspto-grants-1978_09
Patent number
US04117003

Reaction notes

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