Acrylamides reaction with amines

Acromegalics treatment, 74 Acrylamide, reaction with amines to form diamides, 51... 

It has been also reported sicne 1958 [52] that itaconic anhydride (lAn), which is an another cyclic derivative of lA, polymerizes as well as other lA derivatives, but its reactivity is less than those of RII and RPhll. Poly(IAn) may be derived into some poly(IA) derivatives by reaction with amines and alcohols [63,64]. The polymerization reactivities of several itaconamides (lAm) and itaconamates (lAE) were also investigated [48]. It was found that iV, -dialkyl substituted lAm homopolymerize in the presence of a radical initiator, but iV,iV,iVj -tetraalkyl-substituted one did not give a polymer, because the latter consists of an a,7V, trisubsti-tuted acrylamide structure resemble to, y disubstituted methacrylamides. Similar results were obtained for polymerization of mono- and, V disub-stituted lAE. 

Polyamines can also be made by reaction of ethylene dichloride with amines (18). Products of this type are sometimes formed as by-products in the manufacture of amines. A third type of polyamine is polyethyleneimine [9002-98-6] which can be made by several routes the most frequently used method is the polymeriza tion of azitidine [151 -56 ] (18,26). The process can be adjusted to vary the amount of branching (see Imines, cyclic). Polyamines are considerably lower in molecular weight compared to acrylamide polymers, and therefore their solution viscosities are much lower. They are sold commercially as viscous solutions containing 1—20% polymer, and also any by-product salts from the polymerization reaction. The charge on polyamines depends on the pH of the medium. They can be quaternized to make their charge independent of pH (18). 

Dimethyl-2-vmyl-5(4/i/)-oxazolone (VDMO) 140 and 4,4-dimethyl-2-isopro-penyl-5(4//)-oxazolone 328 have been extensively investigated as monomers (Fig. 7.32). Copolymeiization of 140 or 328 with other monomers, for example, acrylates or acrylamides produces reactive polymers that are conveniently further modified by nucleophilic reaction with alcohols, amines, or other nucleophiles. ""... 

I), other important alkaloids are used as amine reagents for Mannich synthesis. Thus, demethylatcd nicotine affords aminomethylation of hydrogen cyanide (460), employed in studies of the metabolic oxidation of nicotine, and anabasinc gives, by reaction with acrylamide, the readily polymerizable monomeric species 461, the polymeric derivative of which is. 50 times less toxic than the original anabasinc. ... 

Amides (dimethyl formamide) were also detected in air (Howard 1990), whereas other amides have been found to be emitted in industrial processes (acetamide, acrylamide). The general fate of amines is similar to that of ammonia, i.e. reactions with OH. They do not photolyze. Because the C—H bond energy is smaller than the N—H bond, predominantly OH abstracts H from C—H (Chapter 5.7.2) ... 

The condensation grafting of polyethylenimine (PEI) onto poly(acrylamide-co-acryhc acid) (PAM-co-AA) was studied by FTIR spectroscopy. The reaction mechanism, which proceeded by a two-step reaction, involved the conversion of AA to acid chloride (AC) using thionyl chloride, followed by the condensation of AC onto PAM and with amine onto PEI to form the graft copolymer (125). 

The invention of Heath et al. relates to novel phosphonate allyl monomers, made from reaction of an unsaturated oxirane with amine- or hy-drojyl-functionalized phosphonic acids (Scheme 3.21). These monomers were copolymerized with other unsaturated species (acrylic acid, maleic acid, acrylamide, or monomer derivatives of sulfonic acid, etc), yielding phosphonate polymers or oligomers. Phosphorus-containing monomers were incorporated at a ratio of 0.1-30% and polymerized in aqueous media. The final polymers had a molecular weight of 800-30 000 g mol . With their phosphonic acids groups (free acid or salts forms), they are of particular use as oilfield scale inhibitors. 

We anticipated that the Michael addition which is known to occur with bis(acrylamides) and primary amines might be a troublesome side reaction, expecially in the the latter stages of reaction when the concentration of acrylamide groups is very much higher than residual azlactone groups. This Michael addition side reaction is depicted in Equation 2. 

In summary, the reaction of alkenyl azlactones with amine-terminated oligomers has been found to be an excellent method for preparing the corresponding (meth)acrylamide-terminated oligomers. The reaction is characterized by a very simple synthetic sequence in which equivalent quantities of reactants are mixed at room temperature with no catalyst reactions are complete to the almost exclusion of side reactions within 16-18 hours. Furthermore, the reaction is a nucleophilic addition. This is the same manner in which nucleophiles react with isocyanates and epoxides. Indeed, this nucleophilic addition mode of reaction which involves no by-products likely accounts for the widespread use of these latter functional groups by industry. In comparison with isocyanate and epoxide, amine nucleophiles react with azlactones at controlled and predictable rates, intermediate between the very reactive isocyanate and the slow reacting epoxide. 

First, a reactive comonomer unit can be introduced for a direct covalent immobilisation. When the material surface to be coated contains hydroxyl groups (e.g., glass, silicon, titanium alloys), the silyl-hydroxyl reaction can be used. Following this route, Yang et al. (2010) combine A-isopropyl acrylamide (NiPAAm) with a 3(trimethoxysi-lyOpropyl methacrylate unit to provide a stable thermo-responsive cell culture surface on glass carriers. On an amine-modified surface, a randomly distributed copolymer of... 

Amides derived from carboxylic acids (8-144) and the corresponding JV-substituted (8-145) and JV,JV-disubstituted amides (8-146) are polar compounds of low volatility, yet some of them may participate in the aroma of non-acidic foods. Commonly occurring compounds are mainly amides derived from formic and acetic acids. For example, beer contains hundredths to tenths mg/kg JV-methylformamide (8-145, R= H, RY CHj), JV-methylacetamide (8-145, R = rY CHj), JV ,Y-dimethylacetamide (8-146, R= R = R = CHj), JV -(2-methylbutyl)acetamide,whereR= CH3,R = CHjCH (CHj) CH2CH3, its isomer JV-(3-methylbutyl)acetamide, R = CH2 CH2CH(CHj)2 and JV -(2-phenylethyl)acetamide (8-147), which are produced by condensation of carboxylic acids with amines followed by decarboxylation (Figure 8.70). Many non-volatile JV-substituted formamides and acetamides are also produced in the Maillard reaction. Decarboxylation of asparagine catalysed by decarboxylases yields 3-aminopropionamide (8-148), which may become a precursor of acrylamide (see Section 12.2.2). 

The chemical structures of representative modified cationic polymers are shown in Fig. 4. Representative polymers are aminomethylated acrylamide homopolymer (Mannich modification) with formaldehyde and dimethyl-amine, and Hoffman-decomposed poly(acrylamide) made from the reaction of an acrylamide homopolymer with sodium perchlorate at relatively low temperature. Because the former polymer (Mannich-modified type) does not show molecular weight reduction during modification, high molecular weight modified polymers result. However, the latter example (Hoffman-decomposed type) has a shortcoming molecular weight is... 

Many of these reactions are reversible, and for the stronger nucleophiles they usually proceed the fastest. Typical examples are the addition of ammonia, amines, phosphines, and bisulfite. Alkaline conditions permit the addition of mercaptans, sulfides, ketones, nitroalkanes, and alcohols to acrylamide. Good examples of alcohol reactions are those involving polymeric alcohols such as poly(vinyl alcohol), cellulose, and starch. The alkaline conditions employed with these reactions result in partial hydrolysis of the amide, yielding mixed carbamojdethyl and carboxyethyl products. 

---