Acrylamide, phenylation

In 1994, Kataoka et al. demonstrated the thermosensitive behavior of a copolymer 9 of N,N-dimethylacrylamide containing 15 mol% of 3-(acrylamide)phenyl-boronic acid with glucose (Figure 5.14). They controlled the LCST by changing the concentration of glucose. In the absence of glucose, 9 demonstrated an LCST around 27°C in HEPES-buffered saline (pH 7.4). Since the homopolymer of N,N-dimethylacrylamide did not show LCST behavior in water, the phenylboronic acid moieties in 9 played a key role in the appearance of the LCST. 

AJ-methyl-AJ-phenyl-methacrji amide -methylenebis-methacrjiamide -ethylenebismeth-acrylamide A/-(diethylphosphono)-methacr5iamide N- tert-hutyl-N- (diethyl-pho sphono)meth -acrylamide ... 

The initiating radicals are assumed to be SCN, ONO or N3 free radicals. Tris oxalate-ferrate-amine anion salt complexes have been studied as photoinitiators (A = 436 nm) of acrylamide polymer [48]. In this initiating system it is proposed that the CO2 radical anion found in the primary photolytic process reacts with iodonium salt (usually diphenyl iodonium chloride salt) by an electron transfer mechanism to give photoactive initiating phenyl radicals by the following reaction machanism ... 

Vinylphenyl-terminated PBE dendrons were prepared as polymerizable den-drons from 4-vinylbenzyl chloride [37]. The vinylphenyl-terminated PBE dendrons are useful to make the lanthanide-cored dendrimer complexes polymerizable. The Ist-generation Tb +-cored dendrimer complex bearing the vinyl-phenyl terminal on the dendron subunits (Fig. 5) was copolymerized with N-iso-propylacrylamide in the presence of methylene bis-acrylamide (as crosslinker) in DMSO to give a green-luminescence transparent gel. The DMSO gel was con-... 

Azetidones (p-lactams) are generally obtained in high yield from (3-halopropion-amides (Table 5.18) and the low yield from the reaction of N-phenyl (3-chloropropi-onamide can be reconciled with the isolation of A-phenyl acrylamide in 58% yield [34]. The unwanted elimination reaction can be obviated by conducting the cyclization in a soliddiquid system under high dilution [35, 36]. Azetidones are also formed by a predominant intramolecular cyclization of intermolecular dimerization to yield piperazine-2,5-diones, or intramolecular alkylation to yield aziridones. Aone-pot formation of azetidones in 45-58% yield from the amine and P-bromocarboxylic acid chloride has also been reported [38]. 

Phenylation of styrene, acrylic esters, and acrylamide with Ph3Bi(02CCF3)2 was examined using palladium nanoparticles immobilized in spherical polyelectrolyte brushes (Pd SPB) (Scheme 7) [21], The reaction can be conducted under air, and... 

When acrylamides are used as dipolarophUes, FMO theory predicts that the 4-amido isomer should be preferred, which is contrary to the results found with tertiary amides (129). Semiempirical, ab initio, and density functional theory (DFT) calculations were applied to the regioisomeric transition state stmctures of benzonitrile oxide cycloadditions (129-131). The results suggest that there is an unfavorable steric repulsion between the phenyl ring of the nitrile oxide and the methyl group of the ester (or amide) functionalities of the dipolarophile in the transition state leading to the 4-acyl regioisomer (Scheme 6.17). 

Aryliodonium salts have been found to be coinitiators for photooxidizable dye sensitization (105). Smith polymerized aerylamide-bis(acrylamide) mixtures using acridine, xanthene, or cyanine dyes and, for example, diphenyllodonium chloride as an electron acceptor. Reduction of the salt results in the formation of phenyl radicals. 

Functionalized alkenes are used for the cooligomerization. Phenyl-1,4,8-decatriene (104) is obtained by the Ni-catalysed 1 2 addition of styrene and butadiene [42a], Pd catalyst affords the 1 1 adduct [43], Co or Fe catalyst gives the 1 1 adducts 105 and 106 of methyl acrylate and butadiene [44,42a], The 1 1 adducts 107 and 108 are obtained by the Ru-catalyzed coupling of butadiene and acrylamide [45]. Reaction of methyl methacrylate affords the 1 2 adduct 109 with Ni—PhjP catalyst at 0°C, whereas the oligomer 110 is obtained at higher temperature [46],... 

Since the amide group and the aromatic ring are perpendicular (atropisomer) in N-methyl-Af-(2-iodo-4,6-dimethyl)phenyl acrylamide, free rotation between the C-N bond does not occur, so each enantiomer can be separated. Once an sp2 carbon-centered radical... 

More or less similar behavior has been observed (8) in the blends of the copolymer or the terpolymer with the following bis-A polycarbonate, polyvinyl chloride, poly (ethyl methacrylate), and a terpolymer made from methyl methacrylate, N,N -dimethyl acrylamide, and N-phenyl-maleimide. Because of this unique miscibility characteristic of the a-methyl styrene interpolymers, an attempt was made at compati-bilizing polyarylethers with the interpolymers by attaching pendant chemical groups known to exist in systems with which the interpolymers are miscible. 

The reaction of enamines and imines with acrylamide results in aza-annulation120,121. Other electrophilic alkenes which have been used to alkylate enamines and the products used in hetero- or carbocyclic synthesis include ethyl / -nitroacrylate122, where reaction occurs beta to the nitro not the ester group, 2-(phenylseleno)prop-2-enenitrile [CH2 = C(SePh)CN]123,124, phenyl a-phenylselenovinyl sulphone [CH2 = C(SePh)-S02Ph]124 and phenyl a-bromovinyl sulphone124. An electrophilic allene, phenylsulpho-nylpropadiene, has also been used to alkylate enamines125 (Scheme 44). 

NPPEGE PA-6 PAA P(AA8iVAC) PACA nonyl phenyl poly(ethylene glycol ether) polyamide-6 po y(acrylic acid) poly(acrylic acid-co-vinyl acetate) poly(acrylamide)... 

Organocopper compounds react slowly with nitriles or not at all 124, 233). Only a low yield of benzanilide was obtained from the reaction between phenylcopper and phenyl isocyanate 124). Isocyanate insertion reactions with vinylcopper compounds in HMPT in the presence of P(0C2H5)3 afford acrylamides 225a). 

Neurotoxic chemicals and motor neuropathy Chlorpyrifos, dichlorvos (DDVP), EPN, n-hexane, 2-hexanone, lead, lead chromate, lead II thiocyanate, leptophos, methamidophos, mipafox, omethoate, parathion, trichlor-fon, trichloronate, triorthocresyl phosphate Neurotoxic chemicals and sensorimotor neuropathy acrylamide, allyl chloride, arsenic and compounds, arsenic trichloride, calcium arsenate, carbon disulfide, dichloroacetylene, ethylene oxide, gallium arsenide, lead arsenate, mercuric chloride, mercuric nitrate, mercurous nitrate, mercury, nitrous oxide, phenyl arsine oxide, thallium and soluble compounds, thallous nitrate... 

Metal salts and complexes continue to attract interest as radical/ionic initiators. Trisoxalatoferrate/amine anion salts have been studied as initiators of the polymerization of acrylamide. Here the anion salts react with photolytically formed COa " radicals by an electron transfer mechanism to give photoactive initiating phenyl radicals by the set of reactions shown in Scheme 9. Ferric o-phenanthroline has been shown to be a good photoinitiator for... 

Poly(methyl acetoxy silylene) [poly(MASi)] is also claimed [130] to initiate the polymerization of cyclohexyl methacrylate upon UV irradiation and to crosslink the resulting polymer by air exposure. Finally, the pyridinium salt of partially chloromethylated poly(methyl phenyl silylene) (Q-PMPSi) is reported [131] to initiate the polymerization, in aqueous solution, of hydrophilic vinyl monomers such as methacrylic acid, acrylamide, 2-hydroxyethyl methacrylate and 1 -vinyl-2-pyrrolidone. 

Support for this mechanism stems from isolation of diazo compound 181b from the analogous reaction of diester 180b. By comparison adduct 182 (from tetrachlorocyclopropene and phenyl azide) is extremely labile and gives acrylamide 183 upon nitrogen loss and hydrolysis. ... 

---