Alkyl amines polyamines

Primary ( ) amines e.g. alkyl amines [1—3] lipid amines [4] a, co-diamines [5, 6] polyamines [6] alkanol amines [7] subst. anilines [8] aminoglycoside antibiotics [9, 10] biogenic amines [11] hydrazines... 

A diesel fuel stabilizer containing a blend of amines, polyamines, and alkyl ammonium alkyl phosphate as specified under MIL-S-53021 is recommended for federal diesel fuel oil. This stabilizer is to be used at a treat rate of 25 lb/1,000 barrels. It is not intended for use in routine applications, but for situations where increased stability protection is required. Typical applications include fueled equipment undergoing long-term storage in a warehouse or depot, prepositioned equipment or equipment maintained in a high-temperature environment. 

The selectivity of acylations or alkylations of polyamines can also be modulated by protonation [78] or by conversion to cyclic aminals [71, 79, 80]. The latter strategy has, for instance, been used successfully for the preparation of monofunctionalized 1,4,7-triazacyclononanes (Scheme 10.18). In this reaction the first alkylation leads to the formation of an amidinium salt, which is more difficult to alkylate than a tertiary amine. Thus, the use of only one equivalent of alkylating agent leads to a clean monoalkylation. 

Acyl chlorides react with ethylenediamine and polyamines forming acylated polyamines that can be used in further syntheses. Just as ethylene oxide is added to alkyl amine, so ethyleneimine is added to it in the presence of AICI3 or other Lewis acids to produce polyamines. Polyamines can be prepared also by the reaction of alkyl amine with acrylonitrile with a subsequent catalytic hydrogenation. 

Aliphatic amines and polyamines are bases nearly as weak as ammonia. Alkyl amine hydrochlorides are used rarely now in view of the recognised toxicity. They are known in free or salt form as corrosion inhibitors, flotation collectors and adhesion promoters for asphalt coatings. Acylated polyamines are of interest for the amphoteric biocide synthesis. 

Ethylene oxide adds easlily to an alkyl amine without catalyst forming alkyl diethanol amines or ethoxylated alkyl amines as mentioned previously (pseudocationic nonionics as discussed in Sec. 1.2.6). Primary amine and acylated polyamine ethoxylation brings forth milder and low-toxic surfactants. 

Aliphatic amines are classified in primary amines (RNH2), secondary amines (R2NH), and tertiary amines (R3N), with R representing in this very general scheme an alkyl chain of any length and further functionalization. Technically interesting classes of amines are shortalkyl amines (primary, secondary, and tertiary), fatty amines, di- and polyamines, as well as aromatic amines. Table 5.3.8 highlights... 

Fuel additives - [AMNES-CYCLOALIPHATIC AMINES] (Vol 2) - [SULFONIC ACIDS] (Vol 23) -arsenic compds as [ARSENIC COMPOUNDS] (Vol 3) -boron compds as [BORON COMPOUNDS - BORIC ACID ESTERS] (Vol 4) -coordination compounds as [COORDINATION COMPOUNDS] (Vol 7) -ethers m [ETHERS] (Vol 9) -magnesium alkyls as [MAGNESIUM COMPOUNDS] (Vol 15) -polyamines as [DIAMINES AND HIGHER AMINES ALIPHATIC] (Vol 8) -htanates as [TITANIUM COMPOUNDS - ORGANIC] (Vol 24) -use of copper compounds [COPPER COMPOUNDS] (Vol 7)... 

Amines. Aliphatic mono-, di-, and polyamines derived from fatty and main acids make up this class of surfactants. Primary, secondary, and tertiary monoamines with Qg alkyl or alkenyl chains constitute the bulk of diis class. The products are sold as acetates, naphdienales, or oleates. Principal uses are as ore-flotation agents, corrosion inhibitors, dispersing agents, wetting agents for asphalt, and as intermediates for the production of more highly substituted derivatives... 

Eberhardt et al. 169 170) found that TMEDA, sparteine or other ditertiary amines enable the telomerization of ethylene with benzene by lithium alkyls to yield molecules of the general formula C6H5(CH2CH2)nH. A valuable compilation has been made of related studies employing polyamine chelated alkali metal compounds87). 

Lehn synthesised guanidinium-based cationic steroids incorporating an acylhy-drazone linker using the approach shown in Fig. 9 [141]. The synthesis was developed from a polyamine scaffold by guanidination of the primary amino groups and alkylation of the secondary amine with methyl chloroacetate to introduce the ester moiety required to form a hydrazide group by reaction with hydrazine monohydrate. Cationic steroid hydrazones were then prepared via an acetic acid catalysed reaction with cholestanones, which demonstrated high transfection efficiency and low toxicity in a variety of cell lines [141]. 

Alkylation of amines usually proceeds more slowly than acylations, and alkylating reagents can usually be thoroughly mixed with an amine before reaction is complete. Diamines or polyamines can therefore be transformed into mixtures of the statistically expected amounts of alkylated derivatives (Scheme 10.17). The use of CsOH as base has been found to be particularly conducive to the formation of monoalkylated products [72]. Some polyamines have also been monoalkylated selectively after complexation with Zn(II) [73],... 

Drandarov, K. Hesse, M. Lithium and proton templated co-polyazamacrolactamization, new general routes to macrocyclic polyamines. Tetrahedron Lett. 2002, 43, 7213-7216. Murahashi, S.-L Yoshimura, N. Tsumiyama, T. Kojima, T. Catalytic alkyl group exchange reaction of primary and secondary amines. 

Polyamines through alkylation reaction with chloromethylsilane 1 The secondary amine function of polyaza derivatives are alkylated using chloromethyltrimethyl-silane. 

The synthesis of secondary amines from azides is efficient in terms of chemos-electivity [57] and has found valuable applications in the preparation of diamines [58,59], m-alkylaminoboronic esters [60], and in Diels-Alder-based amination reactions [61]. A convenient general route to open-chain polyamines, which play major roles in cellular differentiation and proliferation, has also been developed using the reductive alkylation of aliphatic aminoazides by (co-halogenoalk-yi)dichloroboranes as a key step [62] (Scheme 21). 

In the 1970s and 1980s, a number of amphoteric surfactants were introduced to the market that were based on alkyl polyamines, primary amines upon which is condensed acrylonitrile, then hydrogenated to produce an alkyl propylenediamine and, with additional cycles, alkyl polyamines. These, in turn, are alkylated with sodium chloroacetate to produce alkyl polyamine polycarboxylates. Some of these products find utility in laundry applications, in personal care products and as industrial foamers. 

The alkylation of amines (including polyamines formed by reduction of polypeptides) was a highly popular method of derivatization in peptide chemistry before the appearance of contemporary mass-spectro-metric techniques for analysis of nonvolatile compounds (FFAB, MALDI, etc.). Direct alkylation of amines by alkyl halides (Hoffman reaction) can lead to the final nonvolatile ammonium salts and, hence, other soft reagents must be used. For example, exhaustive methylation can be provided by the mixtures CH20/NaBH4/H+ or CH20/formic add. 

The construction of cascade molecules in a systematic divergent manner has its origins in the preparation of a series of branched polyamines more than a decade ago.1-3 Starting from a primary amine, each of the available hydrogens on nitrogen was replaced by an alkyl group... 

A somewhat different aspect of the hydrophobic shielding effect of alkyl substituents was reflected in the relative hydrophilicity of aliphatic amine-cured resins. A standard room temperature-curing polyamine, triethylenetetramine (TETA), was used to cure a series of resins at room temperature. The... 

Scheme 12 Divergent construction of glycodendrimers built on polyamine scaffolds using reductive amination (67), amide formation (68), thiourea bridging with isothiocyanates (64), thioethers (70), and novel double A -alkylation strategy (71).

In another application, PEG-bound a-aminoaldehydes served as a starting point for the combinatorial synthesis of polyamines [154], Reductive amination with an amine of type 5, followed by alkylation of the formed secondary amine (via reductive amination) and cleavage of the cyclic aminal yielded the starting aldehyde for the next cycle. 

All these polyols, based on N-methyl alkylated polyamines such as N-methylpropylenediamine, N,N-dimethyldipropylenediamine, N,N dimethyl trimethylolethane and other similar polyamines, have an improved self-catalytic activity and need only a low concentration of volatile tertiary amine catalysts in the foaming process. The resulting flexible PU foams have practically none of the unpleasant odours characteristic of the conventional flexible PU foams. The low amine emission in the foaming process diminishes the risk of workers exposed to the amines, and these polyether polyols may be considered to be more environmentally friendly. 

Polyalkylene polyamines are typical by-products in the amination of dihydroxy compounds. Some of these oligomers, e. g. diethylenetriamine and triethylene-tetramine, are valuable compounds they are produced industrially from ethanol-amine (sometimes directly from ethylene oxide) and ammonia or a mixture of ammonia and ethylenediamine. Over a Ni-Re boride catalyst the selectivity for diethylenetriamine was ca 25 %, almost independent of the conversion [27]. Higher temperatures favored the formation of worthless cyclic products, mainly piperazine and its N-alkylated derivatives (Scheme 9). Recycling the cyclic byproducts can minimize their formation and the higher oligomers can be decomposed to useful dimers and trimers [26]. 

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