Amine-formaldehyde-reaction-products

The antimicrobial efficacy of the amine - formaldehyde reaction products essentially corresponds to the formaldehyde content of these compounds. Known exceptions are HTA, hexahydro-oxadiazines and octahydro-s-tetrazines, which derive from ammonia respectively certain alkylolhydrazines (Paulus, 1980) here the detection of formaldehyde by the Tanenbaum methods gives a negative result, which means that these substances have no significant antimicrobial effect at neutral to alkaline pH they release formaldehyde in acidic media only. This pH dependency is broken off, if, for example, HTA is quaternized (Jacobs et al., 1916). In contrast to HTA the quaternary hexaminium salts release formaldehyde widely independent of pH and therefore may be used as 

The 3 m NH3 and 6 m CH2O first liberated during hydrolytic cleavage at pH values 7 will soon become rearranged to form 0.75 m hexamethylenetetramine and 1.5 m CH2O, the latter remaining available for the antimicrobial efficacy. Examination of MICs of different quaternary hexaminium salts confirms that in actual fact a mere 25% (approx.) of the hexaminium salts calculated formaldehyde content is available for the antimicrobial efficacy (see Table 24). 

Secondary 2-hydroxy-alkylamines react with formaldehyde to 1,3-oxazolidines, too, but constitutionally not to dioxazolidinylmethanes, or 1,3,5-hexahydro-triazines. 

3-oxazolidines listed here are highly soluble in water and polar solvents, and in oils, too. Aqueuos solutions have a basic pH. The formaldehyde releasable is detectable by the Tanenbaum method in consequence the antimicrobial effectiveness of the 1,3-oxazolidines corresponds to their formaldehyde content. 

Chemical name Chemical formula Structural formula 

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If after the addition of IM formaldehyde to IM l-amino-2-methy 1-propanol from the resulting 2-(N-hydro-xymethyl)-2-methyl-propanol 1 M H2O is eliminated, the condensation reaction leads to 100% 4,4-dimethyl-1,3-oxazohdine which, compared with other amine-formaldehyde-reaction-products, where water is not completely ehminated and an equilibrium exists between the N-hydroxymethyl compound and the condensation product, has solubility properties favouring its incorporation in to oil concentrates (e.g. lubricoolants) and its application in fuels to inhibit microbial growth in fuel oil bottom water. 

The microbicide is listed here under the amine-formaldehyde-reaction-products, because it is synthesized by condensation of formaldehyde with methyl amine and carbon disulphide. 

Pr)4, " borohydride-exchange resin,and formic acid. When the last is used, the process is called the Wallach reaction. Conjugated aldehydes are converted to alkenyl-amines with the amine/silica gel followed by reduction with zinc borohydride.In the particular case where primary or secondary amines are reductively methylated with formaldehyde and formic acid, the method is called the Esch-weiler-Clarke procedure. It is possible to use ammonium (or amine) salts of formic acid, " or formamides, as a substitute for the Wallach conditions. This method is called the Leuckart reaction,and in this case the products obtained are often the N-formyl derivatives of the amines instead of the free amines. Primary and secondary amines can be iV-ethylated (e.g., ArNHR ArNREt) by treatment with NaBH4 in acetic acid. Aldehydes react with aniline in the presence of Mont-morillonite KIO clay and microwaves to give the amine. Formaldehyde with formic acid converts secondary amines to the N-methyl derivative with microwave irradiation. 

The two key isocyanates that are used in the greatest volumes for polyurethane polymers are toluene diisocyanate (TDl) and methylene diphenyl diisocyanate (MDl). Both isocyanates are produced first by nitration of aromatics (toluene and benzene, respectively), followed by hydrogenation of the nitro aromatics to provide aromatic amines. In the case of MDl, the aniline intermediate is then condensed with formaldehyde to produce methylene dianiline (MDA), which is a mixture of monomeric MDA and an oligomeric form that is typical of aniline/formaldehyde condensation products [2]. The subsequent reaction of phosgene with the aromatic amines provides the isocyanate products. Isocyanates can also be prepared by the reaction of aromatic amines with dimethylcarbonate [3, 4]. This technology has been tested at the industrial pilot scale, but is not believed to be practiced commercially at this time. 

The commercially important representatives of group 4 are diphenyl guanidine and diortho tolyl guanidine. Group 5 includes a number of aldehyde aniline reaction products such as formaldehyde aniline, ethyledene aniline, butraldehyde aniline, heptaldehyde aniline hexa methylenetetraamine and acet-aldehydeaniline. Aetaldehyde, butraldehyde and heptaldehyde derivatives of aromatic amines are powerful accelerators. 

Cyclization of allo-ocimene, using alkali metal amines, may give cycloheptadienes or acyclic dienes depending upon the conditions used 1,2,4-trimethylcyclohepta-1,3-diene may be obtained exclusively with sodium-piperidine, and 2,6-dimethylocta-2,4-diene (predominantly trans) is the major product using sodium-morpholine.129 The Prins formaldehyde reaction on myrcene (12), on the chelo-tropic adduct (42), and on the Diels-Alder adduct (43), has been investigated 130... 

When a Mannich reaction is carried out between a substrate containing at least two active hydrogen atoms and a primary or a bis-secondary amine, a polycondensation takes place with production of a polymeric derivative. Fhe polycondensation can also occur when both an NH group and one active hydrogen atom arc present in the same molecule. The reaction product is thus characterized by the presence of the methylene moiety, whieh is derived from the formaldehyde, and forms the polymer backbone, with the consequent possibility of polymer degradation by deamination or dcaminomethy-lation both of these reactions are typical of Mannich bases (Chap. II, A). 

A somewhat similar reaction is the conversion of substituted benzyl-amines to the corresponding benzaldehydes by treating their formaldehyde condensation product with hexamine. ... 

Attempts to synthesize the clathrochelate complexes of lanthanide ions via template condensation of the tripodal amine tren with formaldehyde bis-(dimethylamino)methane derivative on the rare-earth metal ion were successful only for ytterbium. The [Yb(metr)](CF3S03)3 AN clathrochelate was obtained in 3-5% yield [165]. With ytterbium cation, as well as with cerium, praseodymium, europium, yttrium, and lanthanum ions, the major reaction products proved to be mono- and dibridged semiclathrochelate complexes with ligands 1 and 2 (Scheme 71). 

Other complex mixtures involving Mannich reaction products of use as anti-rust additives in lubricating oils have included the reaction of fatty acids (RCO2H), nonylphenol, with diethylenetriamine or triethylenetriamine and aqueous formaldehyde. It would appear that the primary amine groups result in amide formation at 160-180°C and the residual secondary amine group then undergoes a Mannich reaction in the usual way with t-octyllphenol and... 

With formaldehyde and amines such as dimethylamine, diethylamine, or pentaethylenehexamine, Mannich reactions have been carried out on poly(sty-rene-co-acrylamide) latex particles. The expected tertiary amines were accompanied by hydrolysis products. Thus both the Hofmann rearrangement and the Mamiich reactions led to amphoteric latex particles. When attempts were made to alkylate the Maimich reaction product, soluble products (presumably quarternary ammoniitm salts) were formed. 

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