Alkyl Imidazoline Amines

Tertiary Amines Alkyl Imidazoline Amines  

Coco Hydroxyethyl Imidazoline Liquid/Solid % Active 92 Lbs./Gallon 7.8 

Chemical intermediate, acid detergents, agricultural sprays, metal and textile processing. 

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LONZA, INC. Tertiary Amines Alkyl Imidazoline Amines ... 

In the selection of an appropriate corrosion inhibitor, an important consideration is the problem of adverse competition with other additives designed to adsorb on the liquid-metal interface. Extreme pressure and/or antiwear agents compete for the same sites as the corrosion inhibitor. Eatty amines are good corrosion inhibitors in this type of environment. However, their adverse effect on the performance of ZDDP additives often prohibits their use. Half esters or amides of dodecylsuccinic acid, phosphate esters or thiophosphates are frequently employed. A combination of inhibitors is sometimes used, for example, fatty carboxylic acids or the dimer/trimer analogues of the unsaturated acids, e.g. oleic, used in conjunction with an amine such as an ethanolamine or alkyl amine, or amide such as alkyl imidazoline and sarcosines, Eig. 6.7. Shorter chain carboxylic acid and amines are used as volatile corrosion inhibitors. 

Nearly all hair care products incorporate one or more cationic conditioning agents, where the latter can be either cationic surfactants or cationic polymers. The cationic surfactants can be further divided into four major classes, i.e. alkylamines, ethoxylated amines, alkyl imidazolines, and quaternaries. The quaternaries are the most widely used in the personal care industry because of their strong affinity to the hair fibre surface. 

The process is outlined in Figure 6.7 it is based on the thermal decomposition of indene carboxylic acids in the presence of amines such as monazolines, a range of commercially available detergents (l-hydroxyethyl-2-alkyl-imidazolines). 

Carboxy amphoteric surfactants based on fatty alkyl imidazolines (imidazolinium surfactants) make up a large part of the amphoteric surfactants. Materials of this surfactant class are based on the imidazolines obtained by the condensation of fatty acids or their esters with aminoethyl ethanol amine. 

Imidazolinium betaines were initially obtained from the reaction of fatty alkyl imidazolines with sodium chloroacetate [10,11]. Their preparation in this manner, however, is not practiced. They can be prepared by the reaction of imidazoline with acrylic acid (Figure 12.11). The corresponding carboxyl ethyl betaine may be obtained, in —65% yield, by the electrophilic addition of acrylic acid on tertiary amine [35] (Figure 12.12). 

Nitrogen derivatives can be made directly from fatty acids and esters by reaction with polyamines and alcoholamines. Reaction of fatty acids with polyamines such as diethylenetriamine or aminoethylethanolamine leads to the formation of amidoamines, which can be cyclized through further condensation to give alkyl imidazolines [12-15]. Condensation with dimethylaminopropylamine affords alkylamidodimethylaminopropy-lamines, which are popular precursors to betaines and amine oxides (Figure 2.2). While imidazolines and amidoamine derivatives have lost ground to esterquats in fabric... 

As yet, a number of experiments have failed to convert ureas 205 such as N-phenylurea or imidazolin-2-one by silylation amination with excess amines R3NHR4 such as benzylamine or morpholine and excess HMDS 2 as well as equivalent amounts of NH4X (for X=C1, I) via the silylated intermediates 206 and 207 in one reaction step at 110-150°C into their corresponding guanidines 208 with formation of NH3 and HMDSO 7 [35] (Scheme 4.13). This failure is possibly due to the steric repulsion of the two neighbouring bulky trimethylsilyl groups in the assumed activated intermediate 207, which prevents the formation of 207 in the equilibrium with 206. Thus the two step Rathke-method, which demands the prior S-alkylation of 2-thioureas followed by amination with liberation of alkyl-mercaptans, will remain one of the standard syntheses of guanidines [21, 35a,b,c]. 

Compositions and functions of typical commercial products in the 2-alkyl-l-(2-hydroxyethyl)-2-imidazolines series are given in Table 29. 2-Alkyl-l-(2-hydroxyethyl)-2-imidazolines are used in hydrocarbon and aqueous systems as antistatic agents, corrosion inhibitors, detergents, emulsifiers, softeners, and viscosity builders. They are prepared by heating the salt of a carboxylic acid with (2-hydroxyethyl)ethylenediamine at 150—160°C to form a substituted amide 1 mol water is eliminated to form the substituted imidazoline with further heating at 180—200°C. Substituted imidazolines yield three series of cationic surfactants by ethoxylation to form more hydrophilic products quatemization with benzyl chloride, dimethyl sulfate, and other alkyl halides and oxidation with hydrogen peroxide to amine oxides. 

Industrial surfactants find uses in almost every industry, from asphalt manufacturing to carpet fibers, from pulp and paper production to leather processing. Examples of the types of chemicals used as surfactants are fatty alcohol sulfates, alkanolamides, alkoxylates, sulfosuccinates, amines, quaternaries, phosphate esters, acid esters, blockcopolymers, betaines, imidazolines, alkyl sulfonates, etc. 

Nitrogen cationic surfactants can also be created by the use of difunctional small molecule amines which, after formation of an amide or ester bond, leave an amine residue which is suitable for quaternization as shown in eqs 6.1.9-6.1.11. The amine residue is then reacted with a suitable alkylating agent to form the cationic. Similarly, reaction of a triglyceride with diethylene triamine gives initially the diamide which, under appropriate conditions, can be cyclized to imidazoline [16] ... 

Two major classes of amphoteric surfactants are derived from fatty alkyl hydroxyethyl imidazolines which, in turn, are produced from fatty acids and low molecular weight amines. Because fatty acids are fairly economic, the imidazoline derived amphoacetates tend to be less expensive than the iminodipropionates discussed above. Most imidazoline derived... 

The other major class of fatty imidazoline derived amphoteric surfactants is the amphopropionates. Again, the ampho portion of the name indicates that they are derived from imidazolines but, rather than being alkylated with sodium chloroacetate, they are carboxy-lated with an acrylate via the Michael reaction. A primary or secondary amine is added across the double bond of the acrylate to yield the beta-alanine derivative. 

There are a number of synthetic procedures which give reduced imidazoles as the primary products, and it is usually not too difficult to aromatize these. For example, 2-alkyl-2-imidazolines can be made by heating acylethylenedi-amines in the presence of magnesium powder [11]. Barium manganate in dry... 

Regiochemical synthesis of 1-substituted imidazole-4-carboxylates can be achieved by treatment of a (Z)-)3-dimethylamino-of-isocyanoacrylate with an alkyl or acyl halide (see Section 2.1.1 and Scheme 2.1.8), by cyclization of 3-alkylamino-2-aminopropanoic acids with triethyl orthoformate followed by dehydrogenation of the initially formed imidazoline (see Section 3.1.1 and Scheme 3.1.2), by condensation of 3-arylamino-2-nitro-2-enones with ortho esters in the presence of reducing agents (see Section 3.1.1 and Scheme 3.1.4), by reaction of an alkyl A -cyanoalkylimidate with a primary amine (see Section 3.2 and Scheme 3.2.1), the poor-yielding acid-catalysed cyclization of a 2-azabutadiene with a primary amine (see Section 3.2 and Scheme 3.2.3), the cyclocondensation of an isothiourea with the enolate form of ethyl isocyanoacetate (see Section 4.2 and Scheme 4.2.5), and from the interaction of of-aminonitrile, primary tunine and triethyl orthoformate (see Chapter 5, Scheme 5.1.5, and Tables 5.1.1 and 5.1.2). 

The reaction conditions can be selected to maximise the formation of imidazoline cationics quatemised derivatives of which have some importance as cationic fabric softeners [22c, 98, 99, 102]. Surface-active tertiary amines can be formed from alkyl chlorides, acyl chlorides or fatty esters as can be illustrated by the following reactions ... 

These types of surfactants exhibit anionic properties at high pH and cationic properties at low pH and may be categorized as [87] jS-iV-alkylaminopropionic acids, TZ-alkyl-yS-iminodipropionic acids, imidazoline carboxylates, W-alkylbetaines and amine oxides. The sulfobetaines are amphoteric at all values of pH. These surfactants are not commonly used in emulsion polymerization formulations. 

Owing to their compatibility with cationic biocides, amphoteric and amine oxide surfactants continue to be used widely in the development and formulation of disinfectants and sanitizers for personal care, household, industrial, and institutional markets. For instance, substituted imidazoline amphoteric surfactants, in combination with didecyl dimethyl ammonium chloride, have been found to display unexpected synergistic irritation reduction compared to formulas with alkyl dimethyl benzyl ammonium chlorides [57]. Also, imidazoline derivatives and betaines are known to impart moderate cleansing without causing skin roughness, stickiness, or irritating reactions with cationic disinfectants [58], Amphoteric surfactants are also suitable for use in antimicrobial medications requiring subcutaneous, cutaneous, or mucosal membrane administration [36]. 

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