From Polyamines

Depending on the reaction conditions and molar ratio, mono- and bis(aminomethylenemalonates) can be obtained in the reactions of dialkyl alkoxymethylenemalonates and bisamines. 

The reaction of 1,2-diaminoethane and EMME was carried out in boiling ethanol or in a mixture of diethyl ether and ethanol at -5°C to give bis(aminomethylenemalonate) (157) in 72% and 64% yields (64JMC68 67M11). 

2-Bis(benzylamino)ethylene was reacted with 2 mol. equiv. of EMME in boiling ethanol to give bis(aminomethylenemalonate) (158) in 43% yield (64JMC68). 

Bis(phenylamines) (159) were reacted with EMME to give bis(amino-methylenemalonates) (160) (64JMC68 84MI1, 84MI5 86MI12). 

The reaction of o-phenylenediamine (R = H) and 1 mol. equiv. of EMME at 100°C for 2 hr afforded diethyl /V-(2-aminophenyl)aminomethylenemalo-nate (162, R = H) in 94% yield (57MI2 59MI1). When 2 mol. equiv. of 

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C under nitrogen, the yield is 56% A/ AT-ethylenebisstearamide [110-30-5] (57). Other polyamides can be prepared from polyamines in a similar fashion. 

Miscellaneous Applications. Polyamides, prepared from polyamines and neodecanoic acid, are used as wash-cycle antistatic agents (qv)... 

Nabeshima, Y., Ding, Z. L., Chen, G. H., Hoffman, A. S., Taira, H., Kataoka, K., and Tsuruta, T., Slow release of heparin from a hydrogel made from polyamine chains to a temperature-sensitive polymer backbone, in Advanced Biomaterials in Biomedical Engineering and Drug Delivery Systems (N. Ogata, et al., Eds.), pp. 315-316. Springer, Tokyo (1996). 

Fabric softeners - [ALKANOLAMOSIES - ALKANOLAMINES FROM OLEFIN OXIDES AND AMMONIA] (Vol 2) - [AMINES - FATTY AMINES] (Vol 2) - [SUGARALCOHOLS] (Vol 23) -from polyamines [DIAMINES AND HIGHER AMINES ALIPHATIC] (Vol 8)... 

The mechanism of polyamine hydrogenation (Fig. 6.8) is believed to involve successive electron transfer (from polyamine to fullerene) - proton transfer (from polyamine radical cation to fullerene radical anion) steps (Briggs et al. 2005 Kintigh et al. 2007). At or near room temperature, aliphatic amines and polyamines are known to hydroaminate [60]fullerene (Miller 2006), likely also involving preliminary electron transfer - proton transfer steps followed by free radical coupling of C and N based radicals (Fig. 6.8). At elevated temperatures in polyamine solution, however, this latter free radical coupling step becomes uncompetitive with... 

Geue R et al (1984) Metal-ion encapsulation cobalt cages derived from polyamines, formaldehyde, and nitromethane. J Am Chem Soc 106 5478-5488... 

Simultaneously with the Harada s report on the first polyrotaxane, Wenz reported the preparation of polyrotaxanes from polyamines and a-cyclodex-trin in an aqueous solution [108]. a-Cyclodextrin forms inclusion complexes with poly(iminoundecamethylene) and poly(iminotrimethylene-iminode-camethylene) (Scheme 17). The rates of the inclusion of poly(iminounde-camethylene) by a-cyclodextrin are slow on the H NMR time scale in D20 at pH<6. The inclusion formation between poly(iminotrimethylene-imin-odecamethylene) and a-cyclo dextrin took 170 h to reach equilibrium. Wenz... 

Cadotte ( ) presents a comprehensive review of the development of the composite membrane with emphasis on the pros and cons of the four preparation methods mentioned above and on the polymer chemistry Involved. Cadotte points out that while each of the four methods continues to receive some attention, the Interfaclal polymerization method appears to be the most versatile. This method can be used to produce skin layers from polyamines, polylmlnes, polyurethanes, polyesters and other polymers. Elsewhere In this volume, Lee and co-workers (45) discuss the advantages and problems associated with using these composite membranes for ethanol-water separations via counter-current reverse osmosis. Also, Cabasso (44) discusses double-layer composite membranes. 

The TFC-801 membranes did not exhibit any measurable CCRO effect under equivalent test conditions. These results are consistent with our previous work on osmotic membranes. (9,) Thin-film-composite desalination membranes derived from polyamine precursors (such as TFC-801) contain a gel layer within the porous sublayer formed by thermal crosslinking of the polyamine.(10) This gel layer retards the diffusion of ethanol into the membrane from the recirculation solution. Thus the ethanol concentration inside the porous sublayer is not increased effectively by increasing the concentration of the recirculation solution. By contrast, Loeb-Sourirajan-type asymmetric membranes or composite membranes derived from monomeric precursors do not contain any gel layer. Such membranes are better suited to use in the CCRO process. 

TABLE 1. Different examples of basis polymers with ligands derived from polyamines. 

At 100 °C bulk conversion of primary amines occurs quantitatively in the presence of secondary amines. Highly branched, blocked isocyanate resins are available from polyamines and polyols (Scheme 13.1). Since nontoxic components are used, biocompatible polymers are available for biomedical applications. A large variety of reactive oligomers and highly functionalized intermediates for... 

Another method of curing epoxy resins is by the use of polyamides, which are made from polyamines re-... 

For water management in agriculture, cross-linked polyacrylamides are used for water retention and for soil moisture [HOL 05]. In contrast, polymers and copolymers of ethylene glycol are used to promote infiltration of water. The recycling of wastewater uses for the step of clarification (flocculation and sludge conditioning) polymers derived from polyamines or aciylamide. 

In these molecules, several amine groups and one or more carboxylic acid groups are combined to give highly functionalized surfactants. In particular, alkyl amino acetic acids prepared from polyamines have found interest since these amphoterics show microbio-cidal properties (36). An example is dodecyl propylene diamine acetic acid, which is derived from a diamine and chloroacetic acid by carboxymethylation (Figure 15.23). 

Most spider neurotoxins characterized to date have been found to be low molecular weight organic molecules (inorganic ions and salts, free acids and ami-noacids, biogenic amines, neurotransmitters, and acylpolyamines), peptides, or proteins. Polyamines and a variety of polypeptides with a molecular mass ranging from 3000 to 8000 Da appear to represent the main toxic compounds in spiders. More than 60 peptide toxins have been described to date, whose presence can be confirmed by reversed-phase LC. Peptides can be easily distinguished from polyamines because of their different retention times and by ultraviolet detection using a diode-array detector. 

Steroidal frameworks have been much used in synthetic ion transport designs. Cholate oligomers synthesized from polyamines and cholic acid derivatives represent another class of ion transporters (Figure 12). These compounds, inspired by squalamine antibiotic, are also known as molecular umbrellas because of their amphomorphism. Depending on the polarity of the medium, the hydrophilic cholate faces are exposed or hidden to the surface of the umbrella. These compounds such as 22 are active sodium... 

Grosvenor and Gray (1990) synthesized 2,4-dinitrophenylpyridium and used it as a colorimetric or fluorometric detection reagent for amino acids. Mueller and Eckert (1989) quantified glycine betaine in plants by use of two ion-exchange columns and silica gel TLC. Surgova et al. (1990) separated histamine from polyamines and determined it by spectrodensitometric TLC after dansyl derivatization. 

Affinity columns designed from polyamine-containing synthetic toxins have already been used to isolate and purify GluR from mammalian brain. Hossain et al. 31) used a 1-naphthylacetyl spermine-formyl-cellulofine affinity column to isolate a ca... 

A number of excellent polyamides are made from polyamines and carboxylic acids. For any given amine there will be a limited range of carbon atoms in the carboxylic acid for maximum effectiveness. Similarly, for a given acid the range of amines is limited. The most effective diamides can be made from ethylenediamine or diethylenetriamine and the most effective triamides from diethylenetriamine and the distearoyl amides of dibasic acids and of alkylenediamines. 

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