Acrylate guanidine

Keywords acrylate- and methacrylate guanidines radical polymerization poly (meth) acrylate guanidines, conformational behavior, micro-heterogeneity... 

Keywords poly (meth) acrylate guanidines, poly (diallyldimethylammonium chloride)-copolyacrylate guanidines, poly (diallyldimethylammonium chloride)-copolymethacrylate guanidines, poly (diallyldimethylammonium chloride)-copolydiallylguanidine acetates, biocide properties, toxicity... 

New acrylate and methacrylate monomer derivatives (meth) acrylate guanidines, methacryloyl guanidine and it s hydrochloride and also a number of model (meth) acrylate compounds (corresponding acids, salts and amides, methacryloyl chloride, methylmethacrylate, guanidine and it s hydrochloride) were investigated by NMR spectroscopy method. Structure of synthesized monomers was determined, and dependence of spectral characteristics on structure of investigated compounds and used solvent was shown. 

Keywords NMR spectroscopy, (meth) acrylate guanidines, methacryloyl guanidines, methacryloyl guanidines hydrochloride, (meth) acrylic acids, (meth)acryl amides, guanidine hydrochloride, chemical shifts... 

Keywords polyelectrolytes, diallylguanidine (tryfluoro)acetates, diallyl(methyl)ammonium tryfluoroacetates, (meth) acrylate guanidines, guanidine containing (co) polymers, (meth)acryloyl guanidines... 

Use of sodium sulfite allows selective replacement of iodine by hydrogen at C4 without affecting the ortho-position in 4-iodo-3-(2-iodophenyl)sydnone <2005SC639>. Acrylate groups attached at the C4 position of 4-arylsydnones reacted with guanidine hydrochloride but the result was replacement of the G4 substituent by hydrogen instead of formation of the planned pyrimidinone products <2003T4103>. 

Ma and co-workers extended use of chiral guanidine catalysts to the addition of glycine derivatives to acrylates [121], Addition products were achieved in high yield with modest enantioselectivity (Scheme 67). The ferf-butyl glycinate benzophenone imines generally provided better enantiomeric ratios than the ethyl glycinate benzophenone imines. Based on this observation, the authors hypothesized that an imine-catalyst complex determines the stereochemical outcome of the product. 

Another structurally modified guanidine was reported by Ishikawa et al. as a chiral superbase for asymmetric silylation of secondary alcohols [122]. Soon after, Ishikawa discovered that the same catalyst promoted asymmetric Michael additions of glycine imines to acrylates [123]. The additions were promoted in good yield and great asymmetric induction under neat reaction conditions with guanidine catalyst 250 (Scheme 68). The authors deduced that the high conversion and selectivity were due to the relative configuration of the three chiral centers of the catalyst in... 

Ishikawa and co-workers also reported a class of structurally modified guanidines for promotion of the asymmetric Michael reaction of ierf-butyl-diphenylimino-acetate to ethyl acrylate [124,125]. In addition to a polymer support design (Scheme 69), an optical resolution was developed to achieve chiral 1,2-substituted ethylene-l,2-di-amines, a new chiral framework for guanidine catalysis. The authors discovered that incorporating steric bulk and aryl substituents in the catalyst did improve stereoselec-tivitity, although the reactivity did suffer (Scheme 70, Table 4). 

The asymmetric addition of glycine enolates to acrylates was also achieved by use of the tartaric acid-derived phase-transfer catalysts 27 and 28 (Scheme 4.9). Arai, Nishida and Tsuji [13] showed that the C2-symmetric ammonium cations 27a,b afford up to 77% ee when t-butyl acrylate is used as acceptor. The cations 28 are the most effective/selective PTC identified by broad variation of the substituents present on both the acetal moiety and nitrogen atoms [14], In this study by Shibasaki et al. enantiomeric excesses up to 82% were achieved by use of the catalyst 28a (Scheme 4.9) [14], Scheme 4.9 also shows the structure of the guanidine 29 prepared by Ma and Cheng in the absence of additional base this also catalyzes the Michael addition of the glycine derivative 22 to ethyl acrylate, albeit with modest ee of 30% [15],... 

Modified guanidines 3 efficiently catalyzed the asymmetric Michael addition of a prochiral glycine derivatives with acrylate, acrylonitrile and methyl vinyl ketone under simple and mild conditions. Remarkably, both product formation and enantioselectivity were dramatically improved using solvent-free conditions (Scheme 12) [34]. The addition of alcohols to methyl propiolate was performed using fluorous phosphines such as P[(CH2)2 (CF2)7 CF3]3 and again better yields of 99% have been obtained under solvent-free conditions. Toluene was added to efficiently separate the product from the solid catalyst, which was then reused without loss of activity [35],... 

Scheme 12. Guanidine-catalyzed asymmetric Michael-addition of tert.-butyl diphenyliminoacetate with ethyl acrylate [34].

Similar chiral catalysts 7 were used in the Michael addition of glycine derivatives to acrylic esters to obtain functionalised oc-aminoacids5 here, the guanidines were prepared from chiral amines or diamines in one step but using cyanogen bromide, which is a noxious reagent (Figure 4). 

PEP-2 PEP-3 PIPE = mixtures of PETN and Gulf Crown Oil (USA) perchlorate d ammonium 17 perchlorate de barium 29 perchlorate explosives 247 perchlorate de guanidine 157 perchlorate d hydrazine 182 perchlorate de lithium 205 perchlorate de potassium 263 perchlorate de sodium 292 percussion cap percussion primer 95 201 202 247 267 288 289 perforation of oil and gas wells 247 perle d allumage = squib 43, 236 Perlit = picric acid (german) 256 permissibles permitted explosives 14 75 86 88 248 370 peroxides 31 170 252 346 371 peroxide de benzoyle 31 peroxide de tricycloacetone 346 peroxide de zinc = zinc peroxide 371 Perspex = acrylic acid methylester polymer (same as Plexiglas ... 

Azirine, formation, 56, 372 2W-Azirine-2-acrylates, 3-phenyl-reaction with formamidine, 57, 62, 63 guanidine, 57, 63 hydrazine, 57, 62... 

When the less hindered 2,4-tolylene diisocyanate is reacted with a phospholene oxide catalyst linear oligomeric carbodiimides are obtained which have been reacted with a variety of nucleophiles to give poly(ureas), poly(acyl ureas), poly(formamidines) and poly-(guanidines) by addition across the N=C=N group. Also, reaction of the oligomeric carbodiimides with acrylic or methacrylic acid affords linear polymers, which can be further polymerized by free-radical type processes. Also, reaction of the carbodiimide oligomers obtained from 2,4-TDI with adipic acid in DMF produces a polyureid. ... 

Acrylates can also be used in Michael addition with primary amine and, after further reaction with isothiocyanate, supported thioureas are isolated. These can then undergo a cleavage under basic conditions leading to cyclisation and formation of tetrahydrothioxopyrimidinones [129], Onium salts supported isothiocyanates can also be used with this methodology and lead to the formation of various guanidines [130] (Fig. 41). 

For revealing of influence of conformational state of macro-radicals on kinetics of radical polymerization of acrylate- and methacrylate-guanidines in water mediums with the help of viscosimetry method the values of macroscopic viscosities in solutions modeling reaction mixtures at low conversion degrees were measured and obtained data were compared with kinetic ones. 

On the base of said above we may conclude that synthesis of novel guanidine containing polyelectrolytes on the base of monomers of acrylic type and dialkyldiallylammonium derivatives with the use of radical polymerization and investigation of scientific bases of these processes, and also the developing of methods of novel guanidine containing biocide polyelectrolytes reception are very relevant problems. 

Thus, combination of high bactericide activity (at the expense of guanidine groups presence) with high ability to bond with bacterial cells due to DADMAC units in obtained copolymers allows us to synthesis the novel effective guanidine-containing biocide polymers. The presence in copolymer chain of acrylate units allows obtaining of such preparations with low toxicity. 

The investigation of monomers structure is necessary for correct choice of pomerization system for concrete monomer. In this work NMR spectral characteristics were studied for a number of new guanidine containing monomer compounds, and also for a number of (meth) acrylic acids derivatives (scheme 1) and guanidine (G) and guanidine hydrochloride (GHC). 

Peculiarities of Radical Polymerization Reactions of Acrylate- and Methacrylate Guanidines... 

Acrylate- and methacrylate guanidines (AG and MAG) were prepared with high yield (to 80%) by reaction of acrylic acids and guanidine according to method elaborated by authors of this article and described in work [1], Kinetics of AG and MAG monomers polymerization was studied by dilatometry method in bidistillated water (pH 6.5, 60°C) on low conversion degrees (< 5%) after preliminary degassing of reaction mixtures on vacuum equipment (103 millimeters of mercury). Ammonium persulfate (APS) was used as initiator. The degree of conversion of monomer into polymer was determined on the base of contraction values determined by densimetry method which for GA polymerization reaction in water was 10.8%, and for MAG - 7.0%. Intrinsic viscosities [r ] of polymers were determined IN solution of NaCl in water at 30°C. Relative viscosities r rei of reaction solutions were determined at 30°C. 

More recently it has been reported that the reaction of methyl ( >3-(3-phenylazirin-2-yl)-acrylate (40) with guanidine in dimethyl sulfoxide at room temperature for five days gives the 4-alkyl-6-aryl-l,3,5-triazin-2-aminc 41 in 35% yield.442... 

Ma et al. examined guanidine catalysed Michael reaction of ferf-butyl glycinate Schiff base with ethyl acrylate in THF and observed 30% ee as the asymmetric induction when an acyclic guanidine (2) was used as a catalyst [10b]. Ishikawa et al. succeeded in greatly improving the asymmetric induction by the use of guanidine 17a, originally prepared based... 

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