Acrylamide synthesis

Raj, J., Shreenath, P, and Bhalla, T.C. 2006. Rhodococcus rhodochrous PA-34 A potential biocatalyst for acrylamide synthesis. Process Biochemistry, 41 1359-63. 

Shi, HY Zhang, LM. New grafted polysaccharides based on O-carboxymethyl-0-hydroxypropyl guar gum and W-isopropyl-acrylamide Synthesis and phase transition behavior in aqueous media. Carbohydrate Polymers, 2007, 67, 337-342. 

Beaded acrylamide resins (28) are generally produced by w/o inverse-suspension polymerization. This involves the dispersion of an aqueous solution of the monomer and an initiator (e.g., ammonium peroxodisulfates) with a droplet stabilizer such as carboxymethylcellulose or cellulose acetate butyrate in an immiscible liquid (the oil phase), such as 1,2-dichloroethane, toluene, or a liquid paraffin. A polymerization catalyst, usually tetramethylethylenediamine, may also be added to the monomer mixture. The polymerization of beaded acrylamide resin is carried out at relatively low temperatures (20-50°C), and the polymerization is complete within a relatively short period (1-5 hr). The polymerization of most acrylamides proceeds at a substantially faster rate than that of styrene in o/w suspension polymerization. The problem with droplet coagulation during the synthesis of beaded polyacrylamide by w/o suspension polymerization is usually less critical than that with a styrene-based resin. 

In the synthesis of polymers it is very important to control the configuration of the multiple stereogenic centers but free radical methods generally fail to give significant stereochemical control (96T(52)4181). To compare the effects of several chiral and achiral auxiliary groups, acrylamides of type 110 were studied. 

Qiu et al. [241 have reported the synthesis of macromolecules having 4-tolylureido pendant groups, such as poly(N-acryloyl-N -4-tolylurea-cvi ethyl acrylate) [po-ly(ATU-co-EA)] 18, and poly(N-methacryloyl-A/ -4-tol-ylurea-co-EA) [poly(MTU-co-EA)] 19, from the copolymerization of ATU and MTU with EA, respectively. Graft copolymerization of acrylamide onto the surface of these two copolymer films took place using the Ce(lV) ion as initiator. The graft copolymerization is proposed as Scheme (12). 

Recently, Si et al. [59,60] have investigated the synthesis of polymerizable amines, such as N-(3-dimethyl-aminopropyl) acrylamide(DMAPAA) and N-(3-dimeth-ylaminopropyl) methacrylamide (DMAPMA), and their copolymerization reaction. DMAPAA or DMAPMA in conjunction with ammonium persulfate was used as a redox initiator for vinyl polymerization. Copolymers having amino pendant groups, such as copolymer of... 

A concise total synthesis of the indole alkaloid dihydrocorynantheol (101) (Scheme 19), that features two RCM steps and a zirconocene-catalyzed carbo-magnesation [68], is a further example of Martin s interest in applying RCM as a key reaction for the construction of alkaloid frameworks [69]. The first RCM step was applied to bis-allyl amide 96. The resulting intermediate 97 was directly subjected to carbomagnesation and subsequent elimination to deliver 98 in 71% yield from 96. Amide 98 was then transformed into acrylamide 99 in... 

Uenoyama, S and Hoffman AS. Synthesis and characterization of acrylamide-N-isopropyl acrylamide copolymer grafts on silicone rubber substrates. Radiat. Phys. Chem., 1988, 32, 605-608. 

Solubilization of vinylpyrrolidone, acrylic acid, and A,A -methylene-bis-acrylamide in AOT-reversed micelles allowed the synthesis in situ of a cross-linked polymer with narrow size distribution confined in the micellar domain. These particles displayed high entrapment efficiency of small hydrophilic drugs and have been considered interesting drug delivery systems [239],... 

Co-adsorption experiments show a complex role of the nature and concentration of chemisorbed ammonia species. Ammonia is not only one of the reactants for the synthesis of acrylonitrile, but also reaction with Br()>nsted sites inhibits their reactivity. In particular, IR experiments show that two pathways of reaction are possible from chemisorbed propylene (i) to acetone via isopropoxylate intermediate or (ii) to acrolein via allyl alcoholate intermediate. The first reaction occurs preferentially at lower temperatures and in the presence of hydroxyl groups. When their reactivity is blocked by the faster reaction with ammonia, the second pathway of reaction becomes preferential. The first pathway of reaction is responsible for a degradative pathway, because acetone further transform to an acetate species with carbon chain breakage. Ammonia as NH4 reacts faster with acrylate species (formed by transformation of the acrolein intermediate) to give an acrylamide intermediate. At higher temperatures the amide may be transformed to acrylonitrile, but when Brreform ammonia and free, weakly bonded, acrylic acid. The latter easily decarboxylate forming carbon oxides. 

Z. Wang. Synthesis of AMPS/AM (acrylamide)A AC (vinyl acetate) copolymer—a filtration reducer of drilling fluid. Drilling Prod Technol, 22(4) 4A,55-56, July 1999. 

SH Gehrke, M Palasis, MK Akhtar. Effect of synthesis conditions on properties of polyfALisopropyl acrylamide) gels. Polym Int 29 29-36, 1992. 

Monofunctional and difunctional xanthates, shown in Scheme 30, were employed as chain transfer agents in the synthesis of block and triblock copolymers of acrylic acid, AA and acrylamide, AAm PAA-fr-PAAm, PAAm-fr-PAA-fo-PAAm and P(AA-sfaf-AAm)-fr-PAAm [81]. The polymerizations were conducted in aqueous solutions at 70 °C with 4,4 -azobis(4-cyanopentanoic acid) as the initiator. The yields were almost quantitative,... 

Hurtt ME, Bentley KS, Working PK. 1987. Effects of acrylamide and acrylonitrile on unscheduled DNA synthesis (UDS) in rat spermatocytes. Environ Mutagen 9 49-50. 

Dipolar cycloadditions of 2-tert-butoxycarbonyl-1 -pyrroline A -oxide (627) with several chiral acrylamides (634a-f) (Scheme 2.276) followed by hydrogenolysis of cycloadducts (635) and (636) has been used in the synthesis of enantiopure tert-butyl (2RJ R)- and (2.S. 7a.S )-2-hydroxy-3-oxo-tetrahydro-l II -pyrrolizine-7a(5// )-carboxylates, useful intermediates for the synthesis of Gly-(s-cis)Pro dipeptide mimetic (790). 

Stille employed a Heck reaction on triflate 136 to install the acrylamide side chain in his synthesis of anthramycin and analogues, as illustrated below [79, 80]. Ironically, a Stille reaction was less efficient in this transformation. 

Enantiomerically pure tetrahydro-l//-pyrrolo[2, l -acrylamides derived from proline (see Section 11.11.7.4), are versatile intermediates for the synthesis of natural products or drugs. Compound 86a was submitted to debromination with Bu3SnH followed by ring opening in KOH and further reduction with BHj to give diol 89 that was then easily transformed into (A)-4-(2,2,4-trimethyl-l,3-dioxolan-4-yl)-lT>utanol 90, a key intermediate for )-frontalin, <2002TA155>,... 

---