Preparation salts

Vanadium IV) forms blue VOSO4, (0, 3 and 5H2O), vanadyl sulphate, which forms ranges of double salts, Prepared by SO, reduction of V2O5 in H2SO4. 

These are ionic solids and can exist as the anhydrous salts (prepared by heating together sulphur with excess of the alkali metal) or as hydrates, for example Na2S.9HjO. Since hydrogen sulphide is a weak acid these salts are hydrolysed in water,... 

Industrial Applications. Perfluoroacylbenzene sulfonates, used as additives in fire-extinguishing compounds and galvanizing baths have been prepared (88). Perfluoroacylbenzenesulfonate salts prepared by Friedel-Crafts reaction of perfluoroacyl haUdes and benzene, and subsequent sulfonation have been used as surfactants (89). 

Other Salts. Indium nitrate trihydrate [13770-61 -1], In(N02)3 3H20, is a soluble salt prepared by dissolution of the metal or oxide in nitric acid. Indium phosphate [14693-82-4], InPO, is precipitated by adding phosphate ions to a solution of an indium salt. It is soluble in water. 

Antisyphilitics. Mercuric sahcyiate/T77(9-72-/] (6) and mercuric succinimide [584 3-0] (7) are simple salts prepared by the reaction ia water of mercuric oxide and sahcyhc acid or succinimide, respectively. Use as antisyphilitics has been substantially eliminated by virtue of the discovery of more potent and effective nonmetaUic biocides. 

Amine salts, especially acetate salts prepared by neutralization of a fatty amine with acetic acid, are useflil as flotation agents (collectors), corrosion inhibitors, and lubricants (3,8). Amine acetates are commercially available from a number of suppHers Akzo Chemicals Inc. (Armac) (73) Henkel Corporation (formerly General Mills) (Alamac) (74) Jetco Chemicals Inc. (The Procter Gamble Company) (fet Amine) (75) Sherex (Adogen) (76) and Tom ah Products (Exxon Chemical Company) (Tomah) (77). 

Pyrrohdinone forms alkaU metal salts by direct reaction with alkaU metals or their alkoxides or with their hydroxides under conditions in which the water of reaction is removed. The potassium salt prepared in situ serves as the catalyst for the vinylation of 2-pyrrohdinone in the commercial production of A/-vinylpyrrohdinone. The mercury salt has also been described, as have the N-bromo and N-chloro derivatives (61,62). 

Silver Phosphates. Silver phosphate [7784-09-0], or silver orthophosphate, Ag3P04, is a bright yellow material formed by treating silver nitrate with a soluble phosphate salt or phosphoric acid. Silver pyrophosphate [13465-97-9], is a white salt prepared by the addition of a soluble... 

Recovery Process. Figure 5 shows a typical scheme for processing sodium chlodde. There are two main processes. One is to flood solar ponds with brine and evaporate the water leaving sodium chlodde crystallized on the pond floor. The other is to artificially evaporate the brine in evaporative crystallizers. Industrial salt is made from solar ponds, whereas food-grade salt, prepared for human consumption, is mosdy produced in the crystallizers. 

Permanent coloration can also be achieved by exposing hair to certain metals copper, silver, and especially lead salts. Preparations containing aqueous solutions of lead acetate may include a source of sulfur, usually thiosulfate, which may react with cystine in the hair to produce some cysteine or may react directiy with the metal ion to form dark metallic sulfides. Preparations of this type, which darken hair gradually, are not universally considered safe. 

Many of the surfactants made from ethyleneamines contain the imidazoline stmcture or are prepared through an imidazoline intermediate. Various 2-alkyl-imidazolines and their salts prepared mainly from EDA or monoethoxylated EDA are reported to have good foaming properties (292—295). Ethyleneamine-based imida zolines are also important intermediates for surfactants used in shampoos by virtue of their mildness and good foaming characteristics. 2- Alkyl imidazolines made from DETA or monoethoxylated EDA and fatty acids or their methyl esters are the principal commercial intermediates (296—298). They are converted into shampoo surfactants commonly by reaction with one or two moles of sodium chloroacetate to yield amphoteric surfactants (299—301). The ease with which the imidazoline intermediates are hydrolyzed leads to arnidoamine-type stmctures when these derivatives are prepared under aqueous alkaline conditions. However, reaction of the imidazoline under anhydrous conditions with acryflc acid [79-10-7] to make salt-free, amphoteric products, leaves the imidazoline stmcture essentially intact. Certain polyamine derivatives also function as water-in-oil or od-in-water emulsifiers. These include the products of a reaction between DETA, TETA, or TEPA and fatty acids (302) or oxidized hydrocarbon wax (303). The amidoamine made from lauric acid [143-07-7] and DETA mono- and bis(2-ethylhexyl) phosphate is a very effective water-in-od emulsifier (304). 

Benzo[b]thiophenium, 1,2,3,5-tetramethyl-theoretical methods, 4, 3 Benzo[b]thiophenium salts preparation, 4, 723-724 Ben2o[b]thiophen-4-one, 4,5,6,7-tetrahydro-synthesis, 4, 905-906 5H-Benzo[b]thiophen-4-one, 6,7-dihydro-synthesis, 4, 900 Benzo[b]thiophyne, 4, 750 1H- 1,3,4-Benzotriazepine, 2,3-dihydro-synthesis, 7, 637 1H-1,2,4-Benzotriazepines synthesis, 7, 638 1,2,5-Benzotriazepines synthesis, 7, 640... 

Poroidine, C42H2i02N. The synthetic product was isolated as the hydrobromide, colourless plates, m.p. 224-5°. A mixture (10 parts) of this with synthetic isoporoidine hydro bromide (1 part) had m.p. 220° which was not depressed by addition of the hydro bromide of either natural or racemised base Z. The other salts prepared included oxalate, m.p. 301-2°, picrate, m.p. 172° and methiodide, m.p. 289°. 

Table 14. Synthetic Utility of Fluorinated Phosphonium Salts Prepared From Dibromodifluoromethane [40 ...

A recent adaptation of the procedure employing perchlorate and fluoro-borate salts has been reported by Leonard and Paukstelis (J5). This report includes proof of structure by direct comparison to iminium salts prepared by protonation of enamines. The general reaction reported was that of a ketone or aldehyde with a secondary amine perchlorate to give iminium salts. A large structural variety of carbonyl compounds and several amine... 

A representative list of aziridinium salts prepared by reaction of iminium salts with diazomethane is given in Table 9. The reactions of aziridinium salts are many and varied, but will not be given here since their synthetic utility has been explored and reported elsewhere 109,112-114). The products from the reaction of iminium chlorides and diazomethane are reported in Table 10. Many more examples are available in the literature 16). 

When the 1-monoximes or dioximes of 4-acetyl-l-tetralones are hydrogenated in the presence of palladium, mixtures of diastereoisomeric 1-aminotetralones are formed. The m-aminoketone isomers readily form dehydrobenzoisoquinuclideines (3,4-disubstituted-1,4-dihydro-1,4-ethano-isoquinolines). Quaternary immonium salts prepared from these bicyclic imines are then converted by bases to bicyclic enamines [2,4-disubstituted-3-alkylidene-1,4-ethano-1,2,3,4-tetrahydroisoquinolines (25)]. 

The 2,7-naphthyridine system 53 (Scheme 8.4.18) was combined with 2,4-dinitrochlorobenzene and 2-amino glycerol for in situ reaction of the resulting Zincke salt. The resulting naphthyridinium 54 was trapped by Bradsher cycloaddition with (Z)-vinyl ether 55, providing tetracycle 56 (X-ray) upon internal addition of one of the diastereotopic hydroxymethyl groups to the resulting iminium. This approach was also extended to the use of chiral 2,7-naphthyridinium salts, prepared via the analogous Zincke process. ... 

Less reactive electrophilic reagents like those involved in acylation or alkylation apparently do not react with phenyl-substituted pyrylium salts the p-acylation of a phenyl group in position 3 of the pyrylium salt obtained on diacylation of allylbenzene (Section II, I), 3, a), and the p-l-butylation of phenyl groups in y-positions of pyrylium salts prepared by dehydrogenation of 1,5-diones by means of butyl cations (Section II, B, 2, f) probably occur in stages preceding the pyrylium ring closure. 

Benzoxepin (4) was obtained in 55% yield by the reaction of phthalaldehyde with the bis-ylide generated from the bis(triphenylphosphonium) salt prepared from bis(bromomethyl) ether and triphenylphosphane.93,94... 

Although the decompositions of FeS04 and Fe2(S04)3 have received considerable attention, there is a lack of close agreement between isothermal and non-isothermal measurements [528]. Kinetic parameters are sensitive to the nature of the prevailing atmosphere and the particular salt preparation used [381]. The decomposition of iron(II) sulphate [319, 381,524] in vacuum or in an inert atmosphere (748—848 K) proceeds with the transitory formation of the intermediate Fe202(S04), viz. 

At 951 K, the reaction rate is directly proportional to Ph2o a catalytic effect that is attributed [808] to the role of water as an oxygen carrier. The reaction rate was also influenced by the method of salt preparation but for a given sample the effect of particle size was small. 

The stoichiometry of decomposition of [Ni(NH3)4](NCS)2 was dependent on the method of salt preparation [1126]. Ammonia was lost in three successive steps (—NH3, —NH3, —2 NH3) from the solution-prepared salt, but the first intermediate could not be isolated from the similar reaction of material prepared by heterogenous reaction. The difference in behaviour was ascribed to differences in perfection of the crystallites resulting from the alternative preparative methods. 

Chiral alcohols have also been used in an asymmetric synthesis of sulphoxides based on halogenation of sulphides. Johnson and coworkers have found319 that the reaction of benzyl p-tolyl sulphide with JV-chlorobenzotriazole (NCBT) followed by addition of (—) menthol and silver tetrafluoroborate afforded diastereoisomeric menthoxysulphonium salts 267 which, upon recrystallization and hydrolysis, gave benzyl p-tolyl sulphoxide with 87% optical purity (equation 145). More recently, Oae and coworkers reported320 that optically active diaryl sulphoxides (e.e. up to 20%) were formed either by hydrolysis or thermolysis of the corresponding diaryl menthoxysulphonium salts prepared in situ from diaryl sulphides using ( —) menthol and t-butyl hypochlorite. 

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