Hydrochloric Acid → 1-Trifluoromethyl2,4,6-trinitrobenzene

HRID 981405Notes

Reaction equation

HRID 981405 reaction equation
[F:1][C:2]([F:7])([F:6])[C:3]([O-])=O.[K+].[N+:9]([C:12]1[CH:17]=[C:16]([N+:18]([O-:20])=[O:19])C=[C:14]([N+:21]([O-:23])=[O:22])[CH:13]=1)([O-:11])=[O:10].C(OCl)(C)(C)C.Cl>CN(C)C=O.CS(C)=O>[F:1][C:2]([F:7])([F:6])[C:3]1[C:16]([N+:18]([O-:20])=[O:19])=[CH:17][C:12]([N+:9]([O-:11])=[O:10])=[CH:13][C:14]=1[N+:21]([O-:23])=[O:22]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 74341,3,5-TrinitrobenzeneHCID 521297Tert-Butyl hypochloriteHCID 23662811Potassium trifluoroacetate

Product 1

HCID 117809461-Trifluoromethyl2,4,6-trinitrobenzeneYield 40%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 6228DimethylformamideSolvent2×

Procedure

A mixture of potassium trifluoroacetate (210 mg, 1.4 mmol and 1,3,5-trinitrobenzene (100 mg, 0.47 mmol) in one mL of N,N-dimethylformamide (DMF) or in one mL of dimethylsulfoxide (DMSO) was heated at 150° C. for one hour. A deep red solution of a Meisenheimer complex of formula (II) above (Z=nitro; Q=trifluoromethyl; R and R'=H; M=K; and n=1) was obtained. The structure of the complex was verified by NMR spectroscopy. Oxidation of a DMF solution of this complex by dropwise addition of tert-butylhypochlorite until the red color disappeared (about seven drops) followed by aqueous workup (10 mL of 1M HCl, extracted with three portions of diethyl ether afforded an oil. This was purified by preparative thin layer chromatography (one 2 mm silica gel plate eluted with 50% petroleum ether/50% dichloromethane) to give 53 mg (40% yield) of 1-trifluoromethyl2,4,6-trinitrobenzene.

Workup

  1. customand n=1) was obtained
  2. extractionextracted with three portions of diethyl ether
  3. customafforded an oil
  4. customThis was purified by preparative thin layer chromatography (one 2 mm silica gel plate eluted with 50% petroleum ether/50% dichloromethane)

Sources & evidence

ORD record
ord-773f3854f4e7459a94d45244a025c257
Source dataset
uspto-grants-1991_02
Patent number
US04990699

Reaction notes

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