Formamide perchlorate

Strong organic solvents (benzene, dimethyl formamide, perchlor-oethylene, and tetrahydrofuran)... 

Pyridine Chlorosulfonic acid, chromium trioxide, formamide, maleic anhydride, nitric acid, oleum, perchromates, silver perchlorate, sulfuric acid... 

Whilst some organic compounds can be investigated in aqueous solution, it is frequently necessary to add an organic solvent to improve the solubility suitable water-miscible solvents include ethanol, methanol, ethane-1,2-diol, dioxan, acetonitrile and acetic (ethanoic) acid. In some cases a purely organic solvent must be used and anhydrous materials such as acetic acid, formamide and diethylamine have been employed suitable supporting electrolytes in these solvents include lithium perchlorate and tetra-alkylammonium salts R4NX (R = ethyl or butyl X = iodide or perchlorate). 

The Hg/dimethyl formamide (DMF) interface has been studied by capacitance measurements10,120,294,301,310 in the presence of various tetraalkylammonium and alkali metal perchlorates in the range of temperatures -15 to 40°C. The specific adsorption of (C2H5)4NC104 was found to be negligible.108,109 The properties of the inner layer were analyzed on the basis of a three-state model. The temperature coefficient of the inner-layer potential drop has been found to be negative at Easo, with a minimum at -5.5 fiC cm-2. Thus the entropy of formation of the interface has a maximum at this charge. These data cannot be described... 

Annikov, V. E. et al., Chem. Abs., 1983, 99, 73190 MRH Acetone 4.89/18, ethanol 4.73/18, ethylene glycol 4.35/26 The detonation and combustion limits of mixtures of sodium perchlorate, water and ethylene glycol, glycerol, 1,3-butylene glycol, 2,3-butylene glycol, formamide, dimethylformamide, ethanolamine, diaminoethane, acetone, urea and galactose have been studied. 

Treatment of 2-benzoylpyridine 81 with p-toluene-sulfonamide gave 1-amino-2-benzoylpyridinium tosylate 82 (X = OTs), which was cyclized with formamide in the presence of triethylamine hydrobromide to give 83 (82FRP2486942). The reaction of the perchlorate 82 (X = C104) with urea in polyphosphoric acid afforded 3-hydroxy-l-phenylpyrido[2,l-/][l,2,4]triazinium perchlorate 84. Treatment of this salt with base led to the zwitterionic l-phenylpyrido[2,l-/][l,2,4]triazin-5-ium-3-olate 85 (86JHC375). Pharmaceutical compositions contain 83 (82FRP2486942). 

Ethyl sulfate Flammable liquids Fluorine Formamide Freon 113 Glycerol Oxidizing materials, water Ammonium nitrate, chromic acid, the halogens, hydrogen peroxide, nitric acid Isolate from everything only lead and nickel resist prolonged attack Iodine, pyridine, sulfur trioxide Aluminum, barium, lithium, samarium, NaK alloy, titanium Acetic anhydride, hypochlorites, chromium(VI) oxide, perchlorates, alkali peroxides, sodium hydride... 

The film casting solution is usually a mixture of the polymer (e.g., cellulose acetate), a solvent (e.g., acetone), and an essentially nonsolvent swelling agent (e.g., aqueous solution of magnesium perchlorate, or formamide). The film making... 

In fact, this interpretation became imperative when it was found that lithium perchlorate in dimethyl formamide does not initiate the polymerisation in systems for which lithium chloride is an effident initiator. This proves that the reaction involves the negative ion, i. e. Cl- or CJ04, and not the positive Li+ ion, and while CT in dimethyl formamide is a sufficiently strong base capable of accepting a proton and initiating the process, the C104 apparently is not. Actually, one may question to what extent these salts are dissodated in dimethyl formamide. It is possible, therefore, that the reaction involves ion-pairs rather than free ions, and the Li+, Cl- ion-pair may be a more powerful proton acceptor than Li+, CI04-. 

In the interests of improved electrochemical background limits and reactant stability, it is important to employ solvents that are as free as possible of nucleophiles and proton sources. Special attention always goes to the removal of water. The most important media are carefully purified acetonitrile, dimethyl-formamide, benzonitrile, and tetrahydrofuran. Popular supporting electrolytes are tetra-n-butylammonium perchlorate (TBAP) and fluoroborate (TBABF4). Solutions are usually prepared by vacuum-line methods (Chap. 18) or in a dry box (Chap. 19) to exclude oxygen from the systems and to avoid contamination by water. 

Fig. 10.17. Nss as a function of the electrode potential. CdTe as electrode 5% aqueous dimethyl formamide (DMF) Tetraalkylam-monium perchlorates present. (Reprinted with permission from J. O M. Bockris and J. Wass, Mater. Chem. Phys. 22 249, 1989).

The behaviour of lanthanum in dimethyl formamide (DMF) is quite different from that in methanol and acetonitrile. While perchlorate forms inner sphere complexes with lanthanides in acetonitrile [31], no such complexes are formed in DMF [32]. The coordination properties in DMF solutions were studied by NMR and UV-Vis spectroscopy techniques [33,34], The rate of DMF exchange in the system ytterbium perchlorate-DMF-CD2CI2 was slow enough that 1H NMR resonances permitted the determination of the mean coordination number to be 7.8 0.2. Similar determination in the case of thulium(III) gave a mean coordination number of 7.7 0.2. Thus it was concluded that the predominant species in heavy lanthanides is Ln(DMF)g+ in DMF solutions. In the case of lighter lanthanides, the following equilibrium exists... 

Closely related to these investigations, Breslow and co-workers studied the Diels-Alder reaction of CP with methyl vinyl ketone (MVK) in water-like solvents, ethylene glycol and formamide, in the presence of lithium salts. They found clear differences and similarities between water and these two solvent systems. In the absence of Li salts, the second-order rate constant for the reaction at 20 °C increased in formamide ( 2 = 3184 X 10 m s" ), and even more in ethylene glycol (480 x 10 m" s" ), relative to a polar solvent such as methanol (75.5 x 10 m" s ) or non-polar solvent such as isooctane (5.940.3 x 10 m s ). The reactions in both polar solvents were faster in the presence of LiC104 than in the presence of LiCl, although the perchlorate ion has less salting-out effect than chloride ion in water [41]. 

Heterocycles Acetylacetone. N-Aminophthalimide. Boron trichloride. Dichloro-formoxime. Oicyanodiamide. Dicyclohexylcarbodiimide. Dietboxymethyl acetate. Diethyl oxalate. Diketene. Dimethylformaniide diethylacetal. Diphenyldiazomethene. Ethyl ethoxy-methylenecyanoacetate. Formaldehyde. Formamide. Formamidine acetate. Formic acid. Glyoxal. Hydrazine. Hydrazoic acid. Hydroxylamine. Hydroxylamine-O-sulfonic acid. Methyl vinyl ketone. o-Phenylenediamine. Phenylhydrazine. Phosphorus pentasullide. Piperidine. Folyphosphoric acid. Potassium diazomethanedisulfonate. Sodium ethoxide. Sodium nitrite. Sodium thiocyanate. Tetracyanoethylene. Thiosemicarbozide. Thiourea. Triethyl orthoformate. Tris-formaminomethane. Trityl perchlorate. Urea. Vinyl triphenyl-phosphonium bromide. 

A later development was made by Manjikian et al. ( ), in which formamide was substituted for magnesium perchlorate/water. 

Cathodic reduction of 2-phenyl-3-chloroacrylonitrile in dimethylformamide with sodium perchlorate at —1.9 V/SCE gives A-methyl-iV-[(5-pheny]-l, 2,3-dithiazin-4-yl)methyl]formamide (l).3 In an undivided cell a 35% yield can be obtained, by using a diaphragm only a 20% yield is reported. 

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