Amine group , reactivity

Arylamines contain two functional groups the amine group and the aromatic ring they are difunctional compounds The reactivity of the amine group is affected by its aryl substituent and the reactivity of the ring is affected by its amine substituent The same electron delocalization that reduces the basicity and the nucleophilicity of an arylamme nitrogen increases the electron density in the aromatic ring and makes arylamines extremely reactive toward electrophilic aromatic substitution... 

Reactive Polyamide Resins. Another significant commercial appHcation of dimer acids is in reactive polyamide resins. These are formed by the reaction of dimer acids with polyamines such as diethylenetriamine to form polyamides containing reactive secondary amine groups (see DiAMlNES AND HIGHER AMINES, aliphatic). In contrast to nonreactive polyamides, these materials are generally Hquids at 25°C. 

The adventitious discovery of the antitumor action of the nitrogen mustard poison war gases led to intensive investigation of the mode of action of these compounds. In brief, it has been fairly well established that these agents owe their effect to the presence of the highly reactive bis(2-chloroethyl)amine group. The cytotoxic activity of... 

The kinetics of the reactive compatibilization of nylon-6-PP by acrylic acid modified PP was investigated by Dagli et al. [47]. The compatibilization reaction in this system involved the reaction between the acid group of acrylic acid modified PP and the amine group of nylon-6. A typical intensive batch mixer torque (t) vs time (t) trace for a ternary blend showing an increase in mixing torque upon the addition of PP-g-AA to a binary PP-NBR (85 7.5) blend is shown in Fig. 3. The kinetic... 

The isocyanate group is more reactive than the epoxy group in that it will react at room temperature with water and hydroxyl groups as well as with amine groups. However, the latter reaction is too fast to be practicable so the standard two-pack coatings are based on isocyanate and polyhydroxyl prepolymers such as hydroxyl terminated polyesters or polyethers as in the last example given in the section on epoxy resins. 

Acid chlorides are very reactive and have as a condensation product hydrochloric acid.4,7 9 This hydrochloric acid can form an amine salt with unreacted amine groups, which should be avoided. To prevent this happening, acid binders, which are more reactive than the amines, are added. Polyamidation can be earned out using a solution and with an interfacial method. With the interfacial method one has the choice between a stirred and an unstirred process. In an unstirred process, the polymerization is at the interface and a rope can be drawn from the interface,... 

Acid chlorides are very reactive and at room temperature react readily with amines. Synthesis by interfacial and solution methods is possible. However, care should be taken that the hydrochloric acid produced does not react with unreacted amine groups. With the strong basic aliphatic diamines, the acid binder must preferably be even more basic. The attainable molecular weights are strongly dependent on the concentrations this is particularly the case for easily precipitated terephthalamide polymers. Possible problems with the acid binder can be overcome by starting with silylated diamines.33,34 A typical example for interfacial polymerization of terephthalamides is PA-2,T.66... 

Because aromatic purines and purine nucleosides and free purines such as hypo-xanthine and guanine 242 are readily silylated-aminated [64] (cf Scheme 4.24), it is obvious that 6-membered hydroxy-N-heterocycles are analogously silylated-aminated, with reactivity in the order given in Scheme 4.25 [73] X=OTf is the best leaving group and X=NHSiMe3 (cf the transamination as discussed in Section 4.2.4) is the weakest. 

To determine the rate behavior of chain growth polymerization reactions, we rely on standard chemical techniques. We can choose to follow the change in concentration of the reactive groups, such as the carboxylic acid or amine groups above, with spectroscopic or wet lab techniques. We may also choose to monitor the average molecular weight of the sample as a function of time. From these data it is possible to calculate the reaction rate, the rate constant, and the order of the reacting species. 

Carbohydrate molecules containing amine groups, such as D-glucosamine, easily may be conjugated to other macromolecules using a number of amine reactive chemical reactions and crosslinkers (Chapter 2, Section 1 and Chapter 3). Some polysaccharides containing acetylated... 

Dimethyl suberimidate, DMS, is a homobifunctional crosslinking agent-containing amine-reactive imidoester groups on both ends. The compound is reactive toward the s-amine groups... 

React for 30 minutes to create the SASD derivative, coupled through the NHS ester-reactive group of the crosslinker onto available amine groups of the protein (forming amide bonds). 

Figure 5.25 The reaction of sulfo-SAPB with an amine group is done first to form an amide bond derivative through its NHS ester end. Subsequent exposure to UV light causes the phenyl azide group to ring-expand to a highly reactive dehydroazepine, which can couple to nucleophiles, such as amines.

Photolyzing with UV light may result in immediate reaction of the nitrene intermediate with a target molecule within Van der Waals distance, or may result in ring expansion to the nucleophile-reactive dehydroazepine. The ring-expanded product is reactive primarily with amine groups (Figure 5.31). 

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