Azlactones, alkenyl

Reactions of amine nucleophiles with alkenyl azlactones (2-alkenyl-2-... 

The present report deals with the reaction of alkenyl azlactones with... 

Starting Materials Alkenyl Polyamine Azlactone (eq.wt.) la Jeffamine M-300 ( ) Acrylamide-Functional Adducts Unsaturation 30 Equlv. Wt. Appearance (poises) d Pred. Obs. colorless 31.35 1.4690 422 447 liquid ... 

The overall reaction of alkenyl azlactones (J ) and amine-terminated oligomers -6 is depicted in Equation 1, with actual reactants listed in Table 1. 

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. 

FUNCTIONAL, TELECHELIC POLYMERS DERIVED FROM REACTIONS OF NUCLEOPHILIC OLIGOMERS AND ALKENYL AZLACTONES, PART II MULTIAZLACTONES-ALTERNATIVES TO ISOCYANATE AND EPOXY RESINS ... 

Alkenyl azlactones were prepared according to literature proce-12 13... 

Subsequently, a number of additional multiazlactones were synthesized from various polythiols and alkenyl azlactones (Table 1). In those cases where the addition of a catalyst was required, ethanesulfonic acid was found to be quite satisfactory. With the exception of bisazlactone 4 (a low melting solid), all of these multiazlactones were fluid materials. 

Table 1. Multlazlactones from Polythiols and Alkenyl Azlactones... 

Michael addition to alkenyl azlactones is not limited to mercaptans, but also occurs to a significane extent with secondary amines. This was first observed upon attempted reaction of azlactone with Jeffamlne CD-2000 (Texaco Chemical, Inc.) (Scheme 9). Initially, no reaction was observed at room temperature over two days time. However, heating the mixture at 50-70°C overnight resulted in clean conversion to the corresponding bisazlactone. As might be expected, the source of the azlactone appears to have no effect upon the course of this reaction. 

To gain further insight into the reactions of alkenyl azlactones with secondary amines, reaction of 2 with a variety of simple amines was studied. Table 3 lists the results as the ratio of Michael addition to ring-opening as estimated by 100 MHz H-NMR. As can be seen from the... 

Both in Chapter 10 and this chapter, we have described new techniques for the preparation of functional, telechelic oligomers and polymers based on reactions of alkenyl azlactones (Scheme 10). Nucleophilic ring-opening reactions can be utilized for the preparation of fluid acrylamides for potential use in a variety of free radical curable resin systems whereas, Michael addition leads to fluid multiazlactones which may be subsequently cured via nucleophilic addition. Further investigations concerning the chemistry and practical utility of these novel resin systems are ongoing in our laboratories. 

Chemistry of Alkenyl Azlactones VI. For previous paper in this... 

Buck ME, Zhang J, Lynn DM (2007) Layer-by-layer assembly of reactive ultrathin films mediated by click-type reactions of poly(2-alkenyl azlactone)s. Adv Mater 19 3951-3955... 

Buck ME, Breitbach AS, Belgrade SK, Blackwell HE, Lyim DM (2009) Chemical modification of reactive multilayered films fabricated from poly(2-alkenyl azlactone)s design of... 

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