Amides nitration

Hyman code name for N-nitro-N-methylgly col amide nitrate... 

Numerous additional solution studies on mixed ligand, nitrate complexes have been performed in the development and performance testing of extractants. Most notably these include tributyl-phosphate (TBP) and other phosphine oxides. As other examples, a variety of mixed amide, nitrate complexes have been proposed based upon NMR, IR and extraction behavior. " " The composition and proposed structures of these types of species are described in the sections corresponding to the functionality of the extractant. 

Amides, nitrates (except ammonium nitrate), nitrites, azides... 

Primary aromatic amides are crystaUine sohds with definite melting points. Upon boiling with 10-20 per cent, sodium or potassium hydroxide solution, they are hydrolysed with the evolution of ammonia (vapour turns red htmus paper blue and mercurous nitrate paper black) and the formation of the alkah metal salt of the acid ... 

Rearrangement of the diazo ketone, with loss of nitrogen, in the presence of suitable reagents and a catalyst (colloidal silver, silver oxide, or silver nitrate in the presence of ammonia solution). An acid is formed In the presence of water, an amide results when ammonia or an amine is used, and an ester is produced in the presence of an alcohol ... 

The conversion of a diazo ketone to an acid amide may be accomplished by treating a warm solution in dioxan with 10-28 per cent, aqueous ammonia solution containing a small amount of silver nitrate solution, after which the mixture is heated at 60°-70° for some time. Precautions should be taken (by use of a. safety glass shield) when heating mixtures containing ammoniacal silver nitrate. 

It is conveniently prepared in the laboratory by the interaction of sulphanil-amide and guanidine (from guanidine nitrate and sodium methoxide solution) the resulting guanidine salt of sulphanilamlde decomposes upon heating at 150-160° into sulphaguanidine and ammonia ... 

Anhydrous liquid ammonia (note 2) (900 ml) was drawn from a cylinder and introduced into the flask. Iron(III) nitrate (lOO mg) was added and, as soon as a uniformly brown solution had formed (after stirring for a few seconds), about 0.7 g of lithium (from the starting amount of 7 g) was cut into two or three pieces and immediately introduced into the flask. After 10-15 min the blue colour had disappeared completely and a white suspension of lithium amide had formed. The remainder of the 7 g (1 mol) of lithium was then cut up and introduced. In most cases the conversion was finished v/ithin about 30 min (note 3). 

In contrast to the reaction with lithium amide, the sodium amide suspension immediately settles out after stopping the stirring and the supernatant ammonia has a grey or black colour, due to colloidal iron. In some cases it took a long time before all of the sodium had been converted (note 4). A further 0.1 g of iron(III) nitrate was then added to accelerate the reaction and some liquid ammonia was introduced to compensate for the losses due to evaporation. 

Analytical Procedures. Standard methods for analysis of food-grade adipic acid are described ia the Food Chemicals Codex (see Refs, ia Table 8). Classical methods are used for assay (titration), trace metals (As, heavy metals as Pb), and total ash. Water is determined by Kad-Fisher titration of a methanol solution of the acid. Determination of color ia methanol solution (APHA, Hazen equivalent, max. 10), as well as iron and other metals, are also described elsewhere (175). Other analyses frequendy are required for resia-grade acid. For example, hydrolyzable nitrogen (NH, amides, nitriles, etc) is determined by distillation of ammonia from an alkaline solution. Reducible nitrogen (nitrates and nitroorganics) may then be determined by adding DeVarda s alloy and continuing the distillation. Hydrocarbon oil contaminants may be determined by ir analysis of halocarbon extracts of alkaline solutions of the acid. 

The hydroxyl groups on glycols undergo the usual alcohol chemistry giving a wide variety of possible derivatives. Hydroxyls can be converted to aldehydes, alkyl hahdes, amides, amines, a2ides, carboxyUc acids, ethers, mercaptans, nitrate esters, nitriles, nitrite esters, organic esters, peroxides, phosphate esters, and sulfate esters (6,7). 

Poly(phenylene oxide)s undergo many substitution reactions (25). Reactions involving the aromatic rings and the methyl groups of DMPPO include bromination (26), displacement of the resultant bromine with phosphoms or amines (27), lithiation (28), and maleic anhydride grafting (29). Additional reactions at the open 3-position on the ring include nitration, alkylation (30), and amidation with isocyanates (31). 

A more recent patent describes the production of titanyl nitrate by electrolysis of titanium tetrachloride or titanyl chloride (37). Other titanium nitrogen compounds that have been described include titanous amide [15190-25-9] Ti(NH2)3, titanic amide [15792-80-0] Ti(NH)2, and various products in which amines have reacted with titanium tetrachloride (38). 

Inhibition of Nitrosamine Formation. Nitrites can react with secondary amines and A/-substituted amides under the acidic conditions of the stomach to form /V-nitrosamines and A/-nitrosamides. These compounds are collectively called N-nitroso compounds. There is strong circumstantial evidence that in vivo A/-nitroso compounds production contributes to the etiology of cancer of the stomach (135,136), esophagus (136,137), and nasopharynx (136,138). Ascorbic acid consumption is negatively correlated with the incidence of these cancers, due to ascorbic acid inhibition of in vivo A/-nitroso compound formation (139). The concentration of A/-nitroso compounds formed in the stomach depends on the nitrate and nitrite intake. 

A number of compounds of the types RBiY2 or R2BiY, where Y is an anionic group other than halogen, have been prepared by the reaction of a dihalo- or halobismuthine with a lithium, sodium, potassium, ammonium, silver, or lead alkoxide (120,121), amide (122,123), a2ide (124,125), carboxylate (121,126), cyanide (125,127), dithiocarbamate (128,129), mercaptide (130,131), nitrate (108), phenoxide (120), selenocyanate (125), silanolate (132), thiocyanate (125,127), or xanthate (133). Dialkyl- and diaryUialobismuthines can also be readily converted to secondary bismuthides by treatment with an alkali metal (50,105,134) ... 

The solution in the left flask is stirred for 30 minutes after all the potassium amide has been added. The nitrogen inlet is briefly removed and 120 g. (1.5 moles) of ammonium nitrate is added this discharges the ehartreuse color. (Caution Vigorous foaming occurs.) Ethyl ether (500 ml.) is added and the dry iee condenser is replaced by a standard water-cooled condenser. I he ammonia is evaporated by allowing the stirred reaction mixture to warm to room temperature this takes several hours iti(l it is convenient to have it occur overnight. 

A more recent derivative with activities typical of the class is nitrazepam (21). Reaction of 2-amino-5-nitrobenzophe-none (19) with bromoacetylbromide affords the amide, 20. Ring closure in liquid ammonia gives nitrazepam (21). More simply, diazepinone, 22, can be nitrated directly at the more reactive C7 position with potassium nitrate in sulfuric acid. 

Samal et al. [25] reported that Ce(IV) ion coupled with an amide, such as thioacetamide, succinamide, acetamide, and formamide, could initiate acrylonitrile (AN) polymerization in aqueous solution. Feng et al. [3] for the first time thoroughly investigated the structural effect of amide on AAM polymerization using Ce(IV) ion, ceric ammonium nitrate (CAN) as an initiator. They found that only acetanilide (AA) and formanilide (FA) promote the polymerization and remarkably enhance Rp. The others such as formamide, N,N-dimethylformamide (DMF), N-butylacetamide, and N-cyclohexylacetamide only slightly affect the rate of polymerization. This can be shown by the relative rate (/ r), i.e., the rate of AAM polymerization initiated with ceric ion-amide divided by the rate of polymerization initiated with ceric ion alone. Rr for CAN-anilide system is approximately 2.5, and the others range from 1.04-1.11. 

A suspension of sodium amide2 (0.1 mole) in liquid ammonia is prepared in a 500-ml. three-necked, round-bottomed flask fitted with a West condenser, a ball and socket glass mechanical stirrer (Note 1), and a dropping funnel. In the preparation of this reagent a small piece of clean sodium metal is added to 350 ml. of commercial anhydrous liquid ammonia. After the appearance of a blue color, a few crystals of hydrated ferric nitrate are added, whereupon the blue color is discharged. The remainder of the 2.3 g. (0.1 mole) of sodium (Note 2) is then rapidly added as small pieces. After all the sodium has been converted to sodium amide (Note 3), a solution of 16.4 g. (0.1 mole) of ethyl phenyl-acetate (Note 4) in 35 ml. of anhydrous ethyl ether is added dropwise over a 2-minute period, and the mixture is stirred for 20 minutes. To the dark green suspension is added over an 8-minute period a solution of 18.5 g. (0.1 mole) of (2-bromo-... 

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