Extractants amides

Chloro-A -hydroxy-A -(4-methylphenyl)benz amide Extraction-photometric Ce 3... 

Sugo, Y., Sasaki, Y., Kimura, T., Sekine, T. 2007. Attempts to improve a radiolytic stability of amidic extractants. GLOBAL 2007, Boise, ID, September 9-13, pp. 1870-1873. 

The exclusive isolation of uranium at the front-end by an amide extractant (BAMA process using a Branched Alkyl MonoAmide)... 

The amounts of degraded amide extractant were slightly higher than those observed with TBP in the same conditions (187,188,189,191,192,197,198). 

The nature of the alkyl group had some influence on the stability of the amide extractants (a factor of 2 has been observed for high doses), and interest had meanwhile been aroused in the establishment of tendencies (191,192,194, 200). But the effect was strongly dependent on the diluent. 

DOA was formed by the hydrolytic cleavage of the amide-bond, as observed for other amide extractants (48, 189). DOAA and DOGA were formed mutually by the cleavage of the ether-bond. The formation of DOFA was caused by the cleavage of the bond adjacent to the ether-bond. 

Different studies indicate that diluents can inhibit or sensitize an extractant s radiolysis. For example, in the cases of alkyl phosphates, amide extractants, or crown ethers, aromatic additives act as protectors (39, 84, 88, 90, 199, 254, 298), while saturated hydrocarbons often sensitize the decomposition of the extractant (90, 182, 183, 199, 299). Figure 8.18 illustrates this sensitization effect of n-dodecane on various oxygen-donor ligands (diglycolamide, malonamide, and monoamides) (199). 

The selection of a suitable diluent is important to limit radiolytic degradation. Diluents currently used in nuclear applications are hydrocarbons, despite their well-known sensitization effect on radiolysis, as mentioned for alkylphosphates or amide extractants (90, 182, 183, 199), and as discussed in Section 8.4.2. To avoid this negative effect or to enhance the solubility of ligands and metallic complexes, other diluents have been selected and their influence on degradation investigated. 

Thiollet, G., Musikas, C. 1989. Synthesis and uses of the amides extractants. Solvent Extr. Ion Exch. 7(5) 813-827. 

Defatting is a very important step in the isolation of pure alkaloid. The fats and oils present in the crop must be removed because if they were left in, a tenacious emulsion would form during the extraction of the alkaloid, and you could forget about ever getting even close to a pure amide extract. For all practical purposes, all that would be extracted would be garbage. 

Ten grams of lysergic amides extracted from the crops are dissolved in 200 ml of methanol containing 11 grams KOH. The methanol is... 

Amide extractants are receiving increased attention as potential complexants for tri-, tetra-, and hexavalent actinides. Their extraction capability and complete incinerability are import factors for their selection as novel extractants (27). Thcst characteristics prompted us to initiate studies (J.P. Shukla, Bhabha Atomic Research Centre Report, unpublished data) on amides as carriers for 5f-block elements in SLM systems. For N-methyl N-butyl decanamide (MBDA) and N,N-di(/i-octyl) hexanamide (DOEHA), the former proved to be the better carrier providing >90 % recovery of plutonium in a single run in the presence of common fission product contaminants, like Cs, and Ru. The SLM system used 4 M nitric acid as... 

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. 

Hydrolysis of a substituted amide. A. With 10 per cent, sulphuric acid. Reflux 1 g. of the compound (e.g., acetanilide) with 20 ml. of 10 per cent, sulphuric acid for 1-2 hours. Distil the reaction mixture and collect 10 ml. of distillate this will contain any volatile organic acids which may be present. Cool the residue, render it alkaline with 20 per cent, sodium hydroxide solution, cool, and extract with ether. Distil off the ether and examine the ether-soluble residue for an amine. 

Hate 1. To a suspension of 0.40 mol of lithium amide in 400 ml of liquid NH3 (see Chapter II, Exp. 11) was added 0.30 mol of HCECCH20-tert.-CitHg Subsequently 0.46 mol of CjHsBr was introduced in 30 min. After an additional 1 h the NH3 was removed by placing the flask in a water-bath at 40°C. Addition of water, extraction with diethyl ether and distillation gave C2H C=CCH20-tert.-C,H in more than 85% yield. 

To a vigorously stirred suspension of 2 mol of lithium amide in 2 1 of liquid atimonia (see II, Exp. 11) was added in 15 min 1 mol of propargyl alcohol (commercial product, distilled in a partial vacuum before use). Subsequently, 1 mol of butyl bromide was added dropwise in 75 min. After an additional 1.5 h, stirring was stopped and the ammonia was allovied to evaporate. To the solid residue were added 500 ml of ice-water. After the solid mass had dissolved, six extractions with diethyl ether were performed. The (unwashed) combined extracts were dried over magnesium sulfate and then concentrated in a water-pump vacuum. Distillation of the residue through a 40-cm Vigreux column afforded 2-heptyn-l-ol, b.p. 

A suspension of sodium amide in 500 ml of anhydrous liquid artmonia was prepared from 18 g of sodium (see Chapter II, Exp. 11). To the suspension was added in 10 min with swirling a mixture of 0.30 mol of 1-chloro-l-ethynylcyclohexane (see VIII-2, Exp. 27) and 50 ml of diethyl ether. The reaction was very vigorous and a thick suspension was formed. The greater part of the ammonia was evaporated by placing the flask in a water bath at 50°C. After addition of 500 ml of ice-water the product was extracted three times with diethyl ether. The ethereal extracts were dried over anhydrous KjCOj and subsequently concentrated in a water-pum vacuum. Distillation of the residue afforded the amine, b.p. 54°C/15 mmHg, n 1.4345, in 87% yield. 

Phenyl-3-oxopropanoic acid (25 mmol) and EtjN (87.5 mmol) were dissolved in THF (150 ml) and cooled to —40°C. Ethyl chloroformate (27.5 mmol) was added dropwise to this solution and then the reaction mixture was stirred for 30 min at —20°C. Di-n-hexylamine (27.5 mmol) was added to the suspension and it was stirred at room temperature for an additional hour. The reaction mixture was diluted with water (100 ml) and extracted with ether (400 ml). The extract was washed with aq. 5% HCl (100 ml) and brine (2 X 100 ml) and dried over NajSO. The crude amide was obtained by removal of the solvent in vacuo and phenylhydrazine (25 mmol) was added. The mixture was heated to 100°C for 30 min. The residue was held in vacuo to remove the water formed and then powdered ZnCl2 (125 mmol) was added. The mixture was heated at 170"C with manual stirring for 5 min. The cooled residue was dissolved in acetone (100 ml) and diluted with ether (500 ml). Water (100 ml) was added. The organic layer was separated and washed successively with 5% aq. HCl (100 ml) and brine (2 x 100 ml) and dried over NajSO. The solvent was removed in vacuo, and the residue was recrystallized from EtOAc-hexane. The yield was 79%. 

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. 

Miscellaneous Applications. PEIs and their derivatives ate used as cementation auxihaties in cmde oil exploration (459), and for breaking cmde oil emulsions (460) in cmde oil extraction. Seed coatings of water-soluble copolymers containing polyethyleneimine have been developed (461). Polyethyleneimine derivatives have positive photoresist properties (462) amidated polyethyleneimines improve the flow properties of cement (463) and with few exceptions, A/-acyla2iddines act as chemical sterilisers for insects (464). 

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