Amides described

The diacid-diamine amidation described in reaction 2 in Table 5.4 has been widely studied in the melt, in solution, and in the solid state. When equal amounts of two functional groups are present, both the rate laws and the molecular weight distributions are given by the treatment of the preceding sections. The stoichiometric balance between reactive groups is readily obtained by precipitating the 1 1 ammonium salt from ethanol ... 

In addition to the amides described in ref. [72], further examples prepared by means of CDI from amino compounds of the cephalosporin or penicillin type, and various heterocyclic carboxylic acids, are reported in ref [86] and [87] and ref. [88] and [89], respectively. 

One of the procedures for converting sodium to sodium amide described in Organic Syntheses is used.4 5... 

Nitration can be conducted by the same method as was used by Aaronson in prepn of N,N -Dinitro-N,N -dimethyl-su If amide, described in this Vol under N,N -Dimethyl-sulf amide... 

Arsenic Imide, As2(NH)3, is obtained by heating to 60° C. the amide described below. It is a pale yellow amorphous powder, stable in air up to 100° C., but above that temperature it decomposes forming the nitride. It is slowly decomposed by water into arsenious oxide and ammonia.3... 

Sodamide is a white substance. According to Wohler and Stang-Lund,12 it melts at 210° C., and not between 149° and 155° C., as stated by Titherley13 but McGee14 found that it melts sharply at 208° C. He was unable to prepare the blue solutions of sodium in the amide described by Titherley,15 and found no solvent action on glass below 240° C. Contact of the amide with glass for several days at 270°... 

So far, the amides described have all been in the -1-4 state, but one rare three coordinate compound is U N(SiMe3)2 3(pyramidal, like the lanthanide analogues). Unusual amides... 

An attempt to prepare pentanamide from ethyl pentanoate led to a mixture of products. Two molecules were separated the ester and the amide. Describe the spectroscopic differences in the IR spectrum and proton NMR spectrum that will allow you to distinguish them. 

In organic chemistry the term is used to describe the conversion of an ester to an acid and an alcohol (saponification), the addition of the elements of water to a molecule, e.g. the conversion of a nitrile to an amide... 

In some extremely iimovative recent experiments, Hochstrasser and co-workers [ ] have described IR transient hole-burning experiments focused on characterizing inliomogeneous broadening in the amide 1... 

The experimental conditions for conducting the above reaction in the presence of dimethylformamide as a solvent are as follows. In a 250 ml. three-necked flask, equipped with a reflux condenser and a tantalum wire Hershberg-type stirrer, place 20 g. of o-chloronitrobenzene and 100 ml. of diinethylform-amide (dried over anhydrous calcium sulphate). Heat the solution to reflux and add 20 g. of activated copper bronze in one portion. Heat under reflux for 4 hours, add another 20 g. portion of copper powder, and continue refluxing for a second 4-hour period. Allow to cool, pour the reaction mixture into 2 litres of water, and filter with suction. Extract the solids with three 200 ml. portions of boiling ethanol alternatively, use 300 ml. of ethanol in a Soxhlet apparatus. Isolate the 2 2- dinitrodiphenyl from the alcoholic extracts as described above the 3ueld of product, m.p. 124-125°, is 11 - 5 g. 

A suspension of 0.40 mol of sodium amide in 300 ml of liquid ammonia was prepared as described in Chapter II, Exp. 11. To the suspension was added with swirling a mixture of 0.25 mol of CHgCeC-S-Ph (see Chapter IV, Exp. 14) and 40 ml of THE in about 2 min (note 1). Swirling was continued after the addition. Three minutes later (note 1) the stopper with glass tube was placed on the flask. The brown solution was forced through the glass tube and the plastic tube, connected to it under 400 g of finely crushed ice, which was contained in a 3-1 conical flask (see Chapter I, Fig. 3, and accompanying description of this operation). The flask was placed for... 

S—Cg is perpendicular to the amide plane of the / -lactam and therefore weakened. The S—bond, on the other hand, is not affected by electronic interactions with the benzamide plane. It was now thought, that a bridging of the thiazolidine moiety would bring the —S bond into a more orthogonal position with respect to the amide plane of the new lactam and make this bond more fragile. The tricyclic thiazolidine was synthesized as described above and fulfilled the predictions (J.E. Baldwin, 1978). 

Most of the known acylations have been described for 2-aminothiazoles, the activity of the acylating agent being in the order, acid halides > anhydrides > esters > acids — amides. 

Aromatic thioamides can be prepared as described in the literature by different ways, either by S -> O exchange between the corresponding benzamides and phosphorus pentasulfide in pyridine solution in the presence of triethylamine (65, 646) as strong base, or by action of H2S on the appropriate nitrile with pyridine and triethylamine solvents using the method of Fairfull et al. (34, 374, 503). In this reaction, thioacetamide in acidic medium can also be used as a H2S generator with dimethylform-amide as the solvent (485). 

The preparation of amines by the methods described m this section involves the prior synthesis and isolation of some reducible material that has a carbon-nitrogen bond an azide a nitrile a nitro substituted arene or an amide The following section describes a method that combines the two steps of carbon-nitrogen bond formation and reduction into a single operation Like the reduction of amides it offers the possibility of prepar mg primary secondary or tertiary amines by proper choice of starting materials... 

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. 

Selected physical properties of various methacrylate esters, amides, and derivatives are given in Tables 1—4. Tables 3 and 4 describe more commercially available methacrylic acid derivatives. A2eotrope data for MMA are shown in Table 5 (8). The solubiUty of MMA in water at 25°C is 1.5%. Water solubiUty of longer alkyl methacrylates ranges from slight to insoluble. Some functionalized esters such as 2-dimethylaniinoethyl methacrylate are miscible and/or hydrolyze. The solubiUty of 2-hydroxypropyl methacrylate in water at 25°C is 13%. Vapor—Hquid equiUbrium (VLE) data have been pubHshed on methanol, methyl methacrylate, and methacrylic acid pairs (9), as have solubiUty data for this ternary system (10). VLE data are also available for methyl methacrylate, methacrylic acid, methyl a-hydroxyisobutyrate, methanol, and water, which are the critical components obtained in the commercially important acetone cyanohydrin route to methyl methacrylate (11). 

Polymerization by Transimidization Reaction. Exchange polymerization via equihbrium reactions is commonly practiced for the preparation of polyesters and polycarbonates. The two-step transimidization polymerization of polyimides was described in an early patent (65). The reaction of pyromellitic diimide with diamines in dipolar solvents resulted in poly(amic amide)s that were thermally converted to the polyimides. High molecular weight polyimides were obtained by employing a more reactive bisimide system (66). The intermediate poly(amic ethylcarboamide) was converted to the polyimide at 240°C. 

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