Ammonium nitrate-Trifluoroacetic anhydride

Tetrachlorooxanthrene has been dinitrated with either nitric acid/acetic anhydride or with ammonium nitrate/trifluoroacetic anhydride to give the 2,7-dinitro compound, and dinitration of the... 

Acetamido-3,4-di-61-acetyl-6-deoxy-D-glucal on reaction with ammonium nitrate-trifluoroacetic anhydride in aqueous sodium bicarbonate affords the unsaturated pentose compound 31 whereas reaction with mercury(II) sulfate and sulfuric acid gave the expected -alkene 32. ... 

Several electrophiles, such as acetic anhydride, nitric acid or alternative nitrating agents, such as ammonium nitrate in trifluoroacetic anhydride (41), or sodium hypochlorite, react at N-1, which is followed by reaction at N-3 under suitable conditions. In the case of acetic anhydride, the reaction can take place exclusively at N-3 if N-1 is hindered this fact has served as a criterion for studying the stereochemistry of 5-spirohydantoin derivatives (42,43). 

Nitration of the potassium enolates of cycloalkanones with pentyl nitrate81 or nitration of silyl enol ethers with nitronium tetrafluoroborate82 provides a method for the preparation of cyclic a-nitro ketones. Trifluoroacetyl nitrate generated from trifluoroacetic anhydride and ammonium nitrate is a mild and effective nitrating reagent for enol acetates (Eq. 2.41).83... 

A mixture of silver nitrite and iodine reacts with alkenes to give jS-nitroalkyl iodides, and therefore, provides a convenient route to a-nitroalkenes. Treatment of alkenes with ammonium nitrate and trifluoroacetic anhydride in the presence of ammonium bromide, followed by... 

A mixture of anhydrous lithium nitrate and trifluoroacetic anhydride in acetonitrile in the presence of sodium carbonate has been used to convert alcohols to nitrate esters for a range of peptide, carbohydrate and steroid substrates. Yields are good to high but products need puritication to remove trifluoroacetate ester impurities, which can be signiflcant in the absence of the carbonate. A similar system used for the nitration of electron-rich aromatic heterocycles employs trifluoroacetic anhydride with ammonium or potassium nitrate. ... 

Toluene, Sulfuric acid. Nitric acid Nitric acid. Sulfuric acid. Toluene Toluene, Sulfuric acid. Nitric acid. Methylene chloride Toluene, Sulfuric acid. Potassium nitrate. Methylene chloride Toluene, Sulfuric acid. Sodium nitrate. Methylene chloride Toluene, Sulfuric acid. Nitric acid. Premium unleaded gasoline Trifluoroacetic anhydride, Nitromethane, Ammonium nitrate, NIHT HCL, Ethyl acetate... 

TNTC Trifluoroacetic anhydride, Nitromethane, Ammonium nitrate, NIHT HCL, Ethyl acetate Secondary high explosive ... 

Among other oxidizing agents286 that have been used to accomplish the conversion of ArCHj to ArCHO are ceric ammonium nitrate,287 ceric trifluoroacetate,288 benzeneseleninic anhydride,257 KMnCV-EtjN,289 and silver(II) oxide.290 Oxidation of ArCHj to carboxylic acids is considered at 9 11. 

W. W. Zajac, P. Dampawan, and D. Ditrow, Reaction of glycals with trifluoroacetic anhydride and ammonium nitrate a novel cleavage reaction of glycals, J. Org. Chem., 51 (1986) 2617-2618. 

Ac, acetyl AIBN, azobis(isobutanonitrile) All, allyl AR, aryl Bn, benzyl f-BOC, ferf-butoxycarbonyl Bu, Butyl Bz, benzoyl CAN, ceric ammonium nitrate Cbz, benzyloxycarbonyl m-CPBA, m-chloroperoxybenzoic acid DAST, diethylaminosulfur trifluoride DBU, l,8-diazabicyclo[5.4.0]undec-7-ene DCC, /V. /V - d i eye I oh e x y I c ar bo -diimide DCM, dichloromethyl DCMME, dichloromethyl methyl ether DDQ, 2,3-dichloro-5,6-dicyano-l,4-benzoquinone DEAD, diethyl azodicarboxylate l-(+)-DET, L-(+)-diethyl tartrate l-DIPT, L-diisopropyl tartrate d-DIPT, D-diisopropyl tartrate DMAP, 4-dimethylaminopyridine DME, 1,2-dimethoxyethane DMF, /V./V-dimethylformamide DMP, 2,2-dimethoxypropane Et, ethyl Im, imidazole KHMDS, potassium hexamethyldisilazane Me, methyl Me2SO, dimethyl sulfoxide MOM, methoxymethyl MOMC1, methoxymethyl chloride Ms, methylsulfonyl MS, molecular sieves NBS, N-bromosuccinimide NIS, /V-iodosuccinimide NMO, /V-methylmorpho-line N-oxide PCC, pyridinium chlorochromate Ph, phenyl PMB, / -methoxvbenzyl PPTs, pyridiniump-toluenesulfonate i-Pr, isopropyl Py, pyridine rt, room temperature TBAF, tetrabutylammonium fluoride TBS, ferf-butyl dimethylsilyl TBDMSC1, f-butylchlorodimethylsilane Tf, trifhioromethylsulfonyl Tf20, trifluoromethylsulfonic anhydride TFA, trifluoroacetic acid THF, tetrahydrofuran TMS, trimethylsilyl TPAP, tetra-n-propylammonium perruthenate / -TsOH. / -toluenesulfonic acid... 

Summary TNTC is prepared by treating NIHT.HC1 with nitromethane and ammonium nitrate in the presence of trifluoroacetic anhydride. After the reaction, the TNTC is contaminated with a by-product and hence needs to be purified. To do this, the contaminated TNTC is treated with ethyl acetate, and reciystallized. Commercial Industrial note For related, or similar information, see Application No. 471,906, January 29, 1990, by Gencorp Aerojet, to Der-Shing Hunag, Folsom, CA. Part or parts of this laboratory process may be protected by international, and/or commercial/industrial processes. Before using this process to legally manufacture the mentioned explosive, with intent to sell, consult any protected commercial or industrial processes related to, similar to, or additional to, the process discussed in this procedure. This process may be used to legally prepare the mentioned explosive for laboratory, educational, or research purposes. 

Trifluoroacetyl nitrate, CF3COONO2 (1). The reagent is prepared in situ from ammonium nitrate (NH4NO3) and trifluoroacetic anhydride. 

Direct N-nitration of secondary amines by nitric acid is possible only for weakly basic amines. The more basic amines can be nitrated under neutral conditions widi reagents such as dinitrogen pentoxide and nitronium tetrafluoroborate, but nitrosamines are significant by-products. The nitrate ester CF3CMe20N02 has been recommended as a nonacidic nitrating agent for secondary amines which avoids the problem of contamination of the products by A(-nitrosamines piperidine and pyrrolidine were nitrated in yields of 75% and 72%, respectively. Amides and imides are efficiendy N-nitrated using ammonium nitrate in trifluoroacetic anhydride. ... 

Most aromatic compounds, whether of high or low reactivity, can be nitrated, because a wide variety of nitrating agents is available. For benzene, the simple alkylbenzenes, and less reactive compounds, the most common reagent is a mixture of concentrated nitric and sulfuric acids,but for active substrates, the reaction can be carried out with nitric acid alone, or in water, acetic acid, acetic anhydride, or chloroform.Nitric acid in acetic anhydride/trifluoroacetic anhydride on zeolite H-(3 was used to convert toluene to 2,4-dinitrotoluene, and AcONOi on clay converted ethylbenzene to ortho-para nitro ethylbenzene. " In fact, these milder conditions are necessary for active compounds, such as amines, phenols, and pyrroles, since reaction with mixed nitric and sulfuric acids would oxidize these substrates. With active substrates, such as amines and phenols, nitration can be accomplished by nitrosation under oxidizing conditions with a mixture of dilute nitrous and nitric acids.A mixture of N02/02/Fe(acac)3 can be used for active compounds, as can NaN02 with trichloroisocyanuric acid on wet silica gel, or N2O4 and silica acetate. Trimethoxybenzenes were nitrated easily with ceric ammonium nitrate on silica gel, and mesitylene was nitrated in an... 

Nitric acid salts in the presence of other acids have been previously described (Vol. I, p, 46). It was recently reported by Crivello [125] that metal nitrates in trifluoroacetic anhydride (TFAA) can nitrate aromatic compounds at room temperature in very good yields. Thus ammonium nitrate with TFAA nitrated benzene to nitrobenzene with a yield of 95%. 

It has been demonstrated that a mixture of ammonium nitrate and trifluoroacetic anhydride is a very effective system for the nitration of enol acetates. It is assumed that trifluoroacetyl nitrate is produced, which is a much more powerful nitrating agent than acetyl nitrate. So, 2-methyl-2-nitrocyclohexanone... 

Trifluoroacetic nitrate, prepared in situ from ammonium nitrate and trifluoroacetic anhydride, has been used for nitration of aromatic compounds at room temperature with high yields. While benzoic acid gives m-nitrobenzoic acid nearly quantitatively, nitrobenzene is not reactive under these conditions. Attack at the ortho position rather than the para position is observed with activated benzene derivatives like anisole. However, this system oxidizes phenols to quinoid products. ... 

The esters were prepared from the phenol and the acid chloride plus DM AP (or from the acid plus trifluoroacetic anhydride). In these esters the steric hulk of the ortho substituents protects the carhonyl from nucleophilic reagents, making them difficult hydrolyze. Although the diisopropyl derivative can be cleaved with hot aqueous NaOH, the di-f-butyl derivatives could only be cleaved with NaOMe in a mixture of toluene and HMPA. The related 2,6-di-f-butyl-4-methoxyphenyl ester can be cleaved oxidatively with ceric ammonium nitrate. These hindered esters have found utility in directing the aldol condensation. ... 

OXIDATION, REAGENTS Acetyl nitrate. Bis(tri-n-butyltin)oxide. Bromine-Hexameth-ylphosphoric triamide. f-Butyl perbenzoate. Ceric ammonium nitrate. N-chlorosuc-cinimide-Dimethyl sulfide. Chromic add. Chromic anhydride. Chromic anhydride-Acetic anhydride. Chromic anhydride-Hexamethylphosphoric triamide. 2,3-Dichloro-5,6-dicyano-l,4-benzoquinone. Dimethyl sulfoxide. Dimethyl sulfoxide-Trifluoro-acetic anhydride. Diphenylseleninlc anhydride. Iodine tris(trifluoroacetate). Lead tetraacetate. N-Methylmorpholine -N-oxide. p-NitrobenzenesulfonyI peroxide. Oxygen, singlet. Palladlumfll) chloride. Peroxybcnzimidic acid. Phenylseleninyl chloride. N-Phenyl-l,2,4-triazoline-3,5-dione. Potassium chromate. Potassium superoxide. Pyri-dinium chlorodiromate. Salcomine. Silver carbonate-Celite. Sodium hypochlorite. Sulfuryl chloridc-Silica gel. Thallium(III) acetate. ThaUium(III) nitrate. Triphenyl phosphite ozonide. Trltyl tetrafluoroborate. Uranium hexafluoride. 

Ammonium nitrate in trifluoroacetic anhydride (TFAA) is a particularly good nitrating agent of aromatics [13]. 

The commonest methods presently used involve removal of a hydride anion directly from cycloheptatriene. Both Organic Syntheses and Synthetic Communications contain reports of convenient preparations, the former making use of phosphorus pentachloride [22] and the latter ammonium nitrate and trifluoroacetic anhydride in chloroform [23] ... 

Treatment of tri- -acetyl-D-glucal with trifluoroacetic anhydride and ammonium nitrate gives isomeric 2-deoxy-2-nitrato-glycosyl tri-fluoroacetates which, with base, undergo very efficient Grob fragmentation as indicated in Scheme 2. Glycal esters with 3, -cis... 

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