Quaternary aliphatic compounds

The most convenient way of a quat synthesis consists in the exhaustive methylation using primary or secondary fatty amines and methyl chloride to yield RN (CH3)3Cr (I) and R2N (CH3)2Cr (II), respectively [101, 102], In order to enhance the quat yield the reaction is carried out in an aqueous or alcoholic solution of sodium carbonate at 60-95 °C. Tertiary amine quatemisation with benzyl chloride gives benzylalkyldimethylammonium, or benzalkonium , chloride (III)  

Instead of alkyl halides, methyl or ethyl sulphate is often taken advantage as an alkylation agent, e.g.  

NHCH2CH2CH2N (CH3)3 CH3S04 Undecenoyl-l-aminopropyl-3-trismeihylammonium methosulphate 

Probably, the oldest source of surface-active quaternaries with biocidal, hair-conditioning and textile-softening properties is the reaction between alkyl halide and trimethylamine  

The new quats generation presents readily biodegradable surfactants the long chains of which are interrupted by ester groups, thus named esterquats [102, 108]. Esterquats are derived frequently from the diester of triethanolamines and the partially hydrogenated tallow or oleic acid followed by a diester quaternisation. The final product, N-methyl-N,N-di[2-(Ci6-i8-acyIoxy)-ethyl]-N-(2-hydroxyethyl)ammonium methosulphate (VIII), of the formula 

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Naturally occurring quaternary ammonium compounds have been reviewed (179). Many types of aliphatic, heterocycHc, and aromatic derived quaternary ammonium compounds are produced both in plants and invertebrates. Examples include thiamine (vitamin B ) (4) (see Vitamins) choline (qv) [62-49-7] (5) and acetylcholine (6). These have numerous biochemical functions. Several quaternaries are precursors for active metaboUtes. 

Because reductive cleavage of aliphatic nitro compounds with Bu3SnH proceeds via alkyl radicals, nitro compounds are also used as precursors to alkyl radicals. Reactions using nitro compounds may have some advantages over other ones, since aliphatic nitro compounds are available from various sources. For example, the sequence of the Michael additions of nitro compounds provides an excellent method for the construction of quaternary carbon compounds (Eq. 7.79).126 Newkome has used this strategy for the construction of dendritic polymers (Eq. 7.80).127... 

Many types of aliphatic, heterocyclic, and aromatic derived quaternary ammonium compounds are produced both in plants and invertebrates. Examples include thiamine (vitamin Bj) (4). See also Vitamin choline... 

The action of quaternary ammonium compounds on the dyed fiber in many cases produces a change of shade. A further disadvantage is the possible elimination of aliphatic amines, e.g., in an alkaline medium in the presence of anionic substances or at excessive drying temperatures. This can cause an unpleasant (fishy) odor to arise. In such cases, an acid aftertreatment is necessary. 

Recent examples of analytes amenable to conductivity detectors include inorganic anions [33], aliphatic long chain quaternary ammonium compounds [34], and metaUocyanide complexes of Fe(II), Ni(II), and Co(III) [35], among others. 

GiovanneUi, D. and Abballe, F. Aliphatic long chain quaternary ammonium compound analysis by ion-pair chromatography coupled with suppressed conductivity and UV detection in lysing reagents for blood cell analysers. J. Chromatogr. A. 2005, 1085,... 

With long-chain hydrocarbons, such as oil, where hydrophobic and hydrophilic portions of the molecule exist, surface-tension effects will be significant, and may result in foaming and possible acceleration of carryover. The alkalinity of the boiler water may saponify any fatty acids present, producing a crude soap that may foam. Soaps, sulfated oils and alcohol, sulfonated aliphatics and aroma.ics, quaternary ammonium compounds, nonionic organic ethers and esters, and various fine particles, act as emulsifiers that can increase foaming. 

Deodorizers are used in bathrooms, around pets, on carpets and upholstery, and for aesthetic purposes. Toxic chemicals contained in deodorizers include glycol ethers, quaternary ammonium compounds, aromatic and aliphatic hydrocarbons, alcohols, aldehydes, and esters. 1331... 

In the field of cation analysis, ion-pair chromatography is the preferred method for the separation of amines of all types. While short-chain aliphatic amines (C3 to C3) and some smaller aromatic amines [39] can also be separated on surface-sulfonated cation exchangers, ion-pair chromatographic applications have been developed for the separation of structurally isomeric amines, alkanolamines, quaternary ammonium compounds, arylalkylamines, barbiturates, and alkaloids. 

Direct replacement of an amino group by hydrogen is possible only in certain cases. Such reductive fissions are particularly well known for tertiary amines and quaternary ammonium compounds and occur especially readily with allyl- and benzyl-substituted amines. In the last-mentioned cases the benzyl group is removed as toluene, and this reaction route is used for preparation of secondary from primary aliphatic amines the primary amine is first condensed with benzaldehyde, and the resulting Schiff base is reduced to the alkylbenzylamine this is converted by alkylation into the dialkylbenzyl-amine, from which finally the benzyl group is removed by catalytic hydrogenation 544... 

HA, heterocyclic amine AA, aromatic amine PA, polyamine Al, aliphatic amine N, nitrosamine CZE, capillary zone electrophoresis MEKC, micellar electrokinetic capillary chromatography LIE, laser induced huorescence ED, electrochemical detection CD, conductivity detection AD, amperometric detection PD, potentiometric detection ALA, alkylamines AQA, alkyl and aUcylbenzyl quaternary ammonium compound A, air H, water S, soil W, waste. 

In water, tertiary amines form quaternary ammonium compounds, e. g. with methyl halogenides. In aqueous solution, secondary (aliphatic and aromatic) amines react with nitrous acid HONO (namely the nitrosonium ion NO ) as already mentioned (reaction 5.217) to generate nitrosamines ... 

Urdahl et al. studied crude oils and silica-absorbed compounds (asphaltenes and resins) using C-NMR techniques (65). It was found that the asphaltenes and resins were enriched in condensed aromatics compared to the whole crude oils. There were strong indications of a long straight-chain aliphatic compound containing a heteroatom substituent which is abundant in paraf-finic oils. There was also reason to believe that this compound was active in the formation of stable water-in-crude oil emulsions. The range from 130 to 210 ppm in the NMR spectra was particularly of interest. This region represents quaternary aromatic and heteroatom-bonded carbons. 

Ethoxylated fatty amines are 48 percent of the market, aliphatic sulfonates 25 percent, fatty acid esters 16 percent, quaternary ammonium compounds 2 percent, others 9 percent. 

Conventional cation exchangers can also be used for the analysis of aromatic amines, in which hydrophobic interactions dominate the separation mechanism. As with the separation of quaternary ammonium compounds, the elution of anilines shown in Figure 4.86 is also carried out with a solvent gradient at constant acid concentration. Anilines are detected photometrically at 210 nm. A slight elevation of the column temperature - as already discussed for the analysis of aliphatic diamines - has a positive effect on the peak form of the late-eluting components. 

In the past, these types of cationic surfactants have played only a secondary industrial role, but are increasingly employed in recent years. In the past, not many liquid chromatographic methods for separating such compounds were foimd in the literature. Because these quaternary ammonium compounds are comparably hydrophobic, hydrochloric acid is used as the ion-pair reagent in their separation. Perfluorinated carboxylic acids are also used from time to time. Because of the lack of suitable chromophores, quaternary ammonium compounds can be sensitively detected only by measuring the electrical conductivity. Figure 6.44 shows a separation of a number of aliphatic quaternary ammonium compoimds it was... 

Figure 6.44 Gradient elution of various aliphatic quaternary ammonium compounds. Separator column lonPac NS1,10 pm eluent (A) 2mmol/L perfluorobutyric acid/MeCN (80 20 v/v) and (B) 2 mmol/L perfluorobutyric acid/MeCN (20 80 v/v) gradient linear, 100% A to 100% B in lOmin flow rate 1 mlVmin detection suppressed conductivity injection volume 25 pL peaks 25 mg/L...

In addition to the anions listed under HPIC anionic sur ctants, metal-cyanide complexes, aromatic carboxylic acids In addition to the cations listed under HPIC aliphatic and aromatic amines, quaternary ammonium compounds, cationic sur ctants, sulfonium compounds, phosphonium compounds, hydrazinium compounds... 

Cation-exchange chromatography with suppressed conductivity detection can also be applied to the analysis of aliphatic quaternary ammonium compounds. Typical examples are carbachol (2-[(aminocarbonyl)oxy] A/,A/,A/-trimethyletha-naminium chloride) and bethanechol (2-[(aminocarbonyl)oxy]-A/ iV,A/-trimethyl-propan-l-aminium chloride). 

In our recent publications [4, 5] we discussed results concerning ion and molecule mobility in cationic montmorillonite film modified electrodes hydrophobized with aliphatic and aromatic quaternary ammonium compounds. We also described experiences with independent measurements by electrochemical and radiochemical methods on transport processes in humate containing montmorillonite and bentonite thin layers [6]. We interpreted the results as consequences of changes in structure which lead to changes in porosity and ditfu-sional transport [7, 8, 9]. The present paper approaches the role of film thickness, and the kinetics of the swelling of films (porodine xerogels) at different levels of hydrophobization, and also the kinetics of the penetration and release of probe molecules. 

Aliphatic quaternary ammonium compounds hexadecylcetylt-rimethylammonium bromide (CTAB) dodecyltrimethylammo-nium bromide (DTAB). 

A typical polymer-modified organoclay for the preparation of PS nanocomposites could be a PS polymer with some cationic sites to be attached to the clay surface. Polystyryl quaternary ammonium salts (PSQAS) were synthesized via three different polymerization routes anionic polymerization (AP), free radical co-polymerization (CP), and chloromethy-lation of polystyrene (CM) [67] (Table 3.6). TGA results indicated that CP-PSQAS and CM-PSQAS were thermally stable, because the C-C bonds in aromatics are much stronger than those in aliphatic compounds. The polystyryl-modified clays exhibited intercalated or partially exfoliated structures. 

Surface-active microbicides with cationic properties include not only the widely used quaternary ammonium compounds (QACs) but also long-chain (C12-C15) aliphatic alkyl amines, aliphatic diamines, guanidines and higua-... 

Skelly, N.E. Separation of aliphatic and aromatic acids, aromatic sulfonates, quaternary ammonium compounds, and chelating agents on a reversed-phase column without ion pairing, J.Chromatogr.ScL, 2003, 41, 22-25. [nonoxynol-9 citric add benzenesulfonic acid phthsilic acid hydrobromic acid nitrUotriacetic acid oxalic acid nitric acid hydriodic acid glycolic acid formic add nitrous add cyanuric acid lactic acid acetic acid NTA benzalkonium EDTA]... 

Most of the inhibitors in use are organic nitrogen compounds and these have been classified by Bregman as (a) aliphatic fatty acid derivatives, b) imidazolines, (c) quaternaries, (d) rosin derivatives (complex amine mixtures based on abietic acid) all of these will tend to have long-chain hydrocarbons, e.g. CigH, as part of the structure, (e) petroleum sulphonic acid salts of long-chain diamines (preferred to the diamines), (/) other salts of diamines and (g) fatty amides of aliphatic diamines. Actual compounds in use in classes (a) to d) include oleic and naphthenic acid salts of n-tallowpropylenediamine diamines RNH(CH2) NH2 in which R is a carbon chain of 8-22 atoms and x = 2-10 and reaction products of diamines with acids from the partial oxidation of liquid hydrocarbons. Attention has also been drawn to polyethoxylated compounds in which the water solubility can be controlled by the amount of ethylene oxide added to the molecule. 

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