2-Phenylethyl acrylate

A stock mixture (50 g) of monomers suitable for preparing intraocular lens material was prepared by thoroughly mixing 2-phenylethyl acrylate (66 wt%), 2-phenylethyl methacrylate (30.5 wt%), and 1,4-butanediol diacrylate (3.5 wt%). 

The acrylate- and methacrylate-derivatized r 5-(benzene)tricarbonylchromium monomers 20 65,66,68,72 21,69>72 and 2273 (Scheme 1.2) were synthesized from benzyl alcohol or 2-phenylethanol when reacted with Cr(CO)6. The alcohols were esterified with either acrylyl or methacrylyl chloride in ether/pyridine and purified by multiple recrystallizations from CS2. Homopolymerizations proceeded in classic fashion with no special electronic effects from the rr-complexed Cr(CO)3 moiety.65,73 Acrylate 20 was copolymerized with styrene and methyl methacrylate and the reactivity ratios were obtained.65 Acrylate 21 and methacrylate, 22, copolymerized readily with styrene, methyl acrylate, acrylonitrile, and 2-phenylethyl acrylate to give bimodal molecular-weight distributions using AIBN initiation.69 Copolymerization of 20 with ferrocenylmethyl acrylate, 2, generates copolymers with varying mole ratios of two transition metals, Cr and Fe (see structure 34).65... 

Phenethyl methacrylate (2-phenylethyl methacrylate) and phenethyl acrylate (2-phenylethyl acrylate) copolymers have become one of the most widely used medical implant materials (in terms of number of devices) because of their application in intraocular lenses (AcrySol ). The special advantages of AcrySof are its flexibility (permitting folding and small incision implantation in the eye), chemical stability, and high refractive index (1.55) allowing thiimer lenses. 

Methyl acrylate Propyl acrylate Hexyl acrylate Phenyl acrylate 2-Phenylethyl acrylate Methyl methacrylate Propyl methacrylate Hexyl methacrylate Phenyl methacrylate 2-Phenylethyl methacrylate Ethyl acrylate n-Butyl acrylate 2-Ethylhexyl acrylate Benzyl acrylate Hydroxyethyl acrylate Ethyl methacrylate n-Butyl methacrylate 2-Ethylhexyl methacrylate Benzyl methacrylate 2-Hydroxyethyl methacrylate... 

Several optically active polymers of acrylates and methacrylates have been obtained by enantioselective polymerization of a racemic monomer initiated by a Grignard compound complexed with chiral reagent. Complexing agents for the polymerization of (K,S)-a-methylbenzyl methacrylate include chiral alcohols, such as quinine and cinchonine [63], (— )-sparteine and its derivatives [64-67], and other axially disymmetric biphenyl compounds [68,69]. Other racemic monomers used include (/ ,S)-a-methylbenzyl acrylate [70], (K,S)-l-phenylethyl acrylate, methacrylate and a-ethylacrylate [71], and 1,2-diphenylethylmethacrylate [72]. 

The most widely used foldable lOL, AcrySof, is fabricated from a copolymer of phenylethyl acrylate and phenylethyl methacrylate with a crosslinking... 

The Manganese(V) catalyzed oxidation of S derivatives in the presence of a nitroxide provides excellent yields of phenylethyl alkoxyamines (Scheme 9.22).175,176 Alkoxyamines can also be prepared from acrylates by... 

The Diels-Alder [4 + 2] cycloaddition of the homochiral dienophile 2-((S)-l-phenylethyl)-l,2-thiazolin-3-one-(S)-l-oxide (535) with 1.1 equiv. of 1-dimethylamino-l-azabutadiene (534) in acetonitrile at 70 °C proceeded with regioselectivity and with greater than 98% diastereoselectivity to give the adduct (536) in 85% yield (Equation (48)) <89TL306i>. In this reaction the regiochemistry is controlled by the acrylate substructure while the sulfinyl group inductively activates the C=C double bond. 

Alternate Name (17 ,2S,57 )-2-( 1-methyl-l-phenylethyl)-5-me-thylcyclohexyl acrylate. 

Table 1 displays rate data for alkoxyamine-termi-nated polymers and low molecular model compounds and shows some important trends. At about the same temperature, the dissociation rate constants Ad of alkoxyamines (Schemes 12 and 30) with the same leaving radical (polystyryl, 1-phenylethyl) increase in the order 3 (TEMPO) < 6 < 8 (DEPN) < 1 (DBNO) by a factor of about 30. Acrylate radicals dissociate markedly slower than styryl radicals from 1 (DBNO), but there is no appreciable difference for 8 (DEPN). The dependence of Ad on the nitroxide structure has been addressed by Moad et al.104 They found the order five membered ring < six membered ring < open chain nitroxides and pointed out additional steric (compare 3 and 6) and polar effects. 

In the mechanistic study of metal-catalyzed living polymerization, this method has thus far been utilized primarily for analysis of model reactions to uncover the interaction between a metal catalyst and a carbon—halogen dormant end.170 176 Typical models for the dormant end include a-haloesters, such as alkyl haloisobutyrate and MMA dimer halides 1-25 (Figure 8) (for methacrylate), alkyl 2-halopropionate (for acrylate), and a-phenylethyl halide (for styrene). 

To promote a polymerization, the newly formed carbon-halogen bond must be capable of being reactivated and the new radical must be able to add another alkene. This was accomplished for the radical polymerizations of St and methyl acrylate (MA), which were initiated by 1-phenylethyl bromide and catalyzed by a Cu(I)/2,2 -bipyridine (bpy) complex [42,79-81]. The process was called Atom Transfer Radical Polymerization (ATRP) to reflect its origins in ATRA. A successful ATRP relies on fast initiation, where all the initiator is consumed quickly, and fast deactivation of the active species by the higher oxidation state metal. The resulting polymers are well defined and have predictable molecular weights and low polydispersities. Other reports used different initiator or catalyst systems, but obtained similar results [43,82]. Numerous examples of using ATRP to prepare well-defined polymers can now be found [44-47,49]. Scheme 4 illustrates the concepts of ATRA and ATRP. To simplify schemes 3,4 and 5, termination was omitted. 

Hawker et al. prepared the 1-phenylethyl adduct of BPPN, i.e., 2,2,5-trime-thyl-3-(l-phenylethoxy)-4-phenyl-3-azahexane, (TMPAH, Fig. 13) and found that it was useful for the controlled homopolymerizations of St, nBA, acrylonitrile, and N,N-dimethylacrylamide [71]. For example, the homopolymerization of DMA resulted in polymers with Mn=4000-55,000 with Mw/Mn=l.15-1.21. TMPAH was also used to prepare random copolymers containing St or nBA and the above monomers, in addition to copolymers with MMA, acrylic acid, 2-hy-droxyethyl acrylate (HEA),and glycidyl acrylate. As with DEPN, it was necessary to add the free nitroxide to mediate the polymerization rate, but the resulting... 

The halogen end group can be transformed into other functionalities by means of standard organic procedures, such as a nucleophilic displacement reaction. Different authors have investigated this process of the nucleophilic displacement reactions with model compounds, to confirm the feasibility and selectivity. Compounds such as 1-phenylethyl halide, methyl 2-bromopropionate, and ethyl 2-bromoisobutane mimic the end groups of PSs, poly(alkyl acrylates), and poly(alkyl methacrylates), respectively. Different compounds have been tested, such as sodium azide, n-butylamine, and n-butylphosphine. 

Preparation of Phosphines by Addition of P-H to Unsaturated Compounds. -This route has not received much attention over the past year. A stereoselective synthesis of tris(Z-styryl)phosphine is offered by the addition of phosphine to phenylacetylene in a superbasic system (HMPA-H20-K0H)." In a similar vein, the reaction of phosphine with styrene and a-methylstyrene in a superbasic medium (DMSO-KOH) provides a route to the primary phosphines, (2-phenylethyl)phosphine and (2-methyl-2-phenylethyl)phosphine, respectively. 7 Transition metal phosphine complexes have been shown to catalyse the a-hydroxylation, P-cyanoethylation, and P-alkoxycarbonylethylation of phosphine. 71 Addition of primary phosphines to acrylic esters has been used for the synthesis of the phosphines (80).7 A similar addition of diphenylphosphine to acrylic esters and amides has given a series of hydrophilic phosphines (81). 72 The bis(phosphorinanyl)ethane (82) is formed in the photochemical addition of l,2-bis(phosphino)ethane to 1,4-pentadiene. ... 

Anotiier metiiod of S5mthesis of S)-DOPA and other alpha- smno acids was elaborated using hydrogenation of a precursor corresponding to the azlactone of substituted acrylic acids on a [PdCl2 (S)-(l-phenylethyl)-amine) ] complex tiiat was prepared in situ fKarpeiskaya et al. ) (Scheme 7.2.). 

Figure 7 Methacrylates and acrylates widely used In medicine and dentistry (a) PMMA, (b) poly(acrylic acid), (c) pHEMA, (d) poly(2-phenylethyl methacrylate), and (e) 2,2-bls[4-(2-hydroxy-3-methacryloyolxypropoxy)phenyl]propane monomer (BIsGMA) (also called bisphenol A-glycidyl methacrylate).

Methoxyethyl acrylate p-Methoxyethyl acrylate. See Methoxyethyl acrylate (2-Methoxyethyl) benzene. See 2-Phenylethyl methyl ether... 

The DT of acrylates (butyl acrylate and methyl acrylate) with alkyl iodides was reported by Gaynor et al. and Matyjaszewski et al in 1995. For instance, solution polymerization of butyl acrylate in benzene initiated by AIBN at 50 °C in the presence of 1-phenylethyl iodide provided poly(butyl acrylate) with 97% monomer conversion in 7.5 h and Mn = 19 SOOgmol" (close to Mn,theoredcai = 18000gmor ) (Scheme 15a). The PDI = 2.0 is large, indicating a rather low Cex value. Later on, 2-ethylhexyl acrylate and tert-butyl acrylate were also polymerized by DT in the presence of bis(iodomethyl)benzene or PS-I, respectively. ... 

For the case of acrylates, retardation with dithiobenzoate RAFT agent is independent of R and is not directly related to consumption of the initial RAFT agent, which is rapid with the dithiobenzoate being completely consumed at very low monomer conversion. Thus in polymerization of MA with benzyl (103) or cyanoisopropyl dithiobenzoate (92) as RAFT agent at 60 °C, substantial retardation of similar magnitude was found from the onset of polymetization. Use of an aliphatic dithioester, benzyl dithioacetate (113), provided substantially less retardation imder the same polymerization conditions. Quitm et observed that 1-phenylethyl... 

Chloride-capped poly(iso-butylene) (PIB) prepared via cationic polymerization was also used as macroinitiator for the copper-catalyzed radical polymerization of acrylates, methacrylates and St [140-143]. The C-Cl moiety at the end of the PIB chain cannot initiate living radical polymerization due to its lower activity for redox reactions, but it can be modified into an active form by inserting several units of St. Since the cross-reaction from the living PIB chain to St is a relatively rapid process, it is possible to add only a few St units to the PIB chain [144]. The resulting 1-chloro-l-phenylethyl end groups are potential initiating sites for ATRP of many vinyl monomers, leading to a variety of new block copolymers, such as CLB-23 (see Scheme 3.33), [140,142] which cannot be prepared by any direct polymerization techniques, because isobutylene can be polymerized only by cationic polymerization. 

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