Cinnamic acid, polymers

Truxillic Acid. 2,4-Diphenyi-t,3-cyclobulanedi-carboxylic acid. C,(Hl(04 mol wt 296.3], C 72.96%, H 5.44%, O 21,60%. Cinnamic acid polymers obtained from the minor alkaloids of cocaine Liebermann, Ber. 21, 2342 (1888), Five stereoisomers have been obtained a-, y, t. peri- and eni-isomers. Stereochemical configurations Stoermer, Bacher, Ber. 57B, 15-23 (1924). 

Samples used in this work are the binary polymer mixtures with the characteristics illustrated in Table 10.1. Here, PSA and PSAF stand, respectively, for polystyrene labeled with anthracene and polystyrene doubly labeled with anthracene and fluorescein used as a fluorescent marker. On the other hand, PSC and PVME stands respectively for polystyrene labeled with trans-cirmamic acid and poly(vinyl methyl ether). The factor a in Table 10.1 indicates the label content of anthracene in the polystyrene chain in the unit of number of labels per one chain. For PSC, the label content is 1 cinnamic acid per 28 styrene monomers. 

Photodimerization of cinnamic acids and its derivatives generally proceeds with high efficiency in the crystal (176), but very inefficiently in fluid phases (177). This low efficiency in the latter phases is apparently due to the rapid deactivation of excited monomers in such phases. However, in systems in which pairs of molecules are constrained so that potentially reactive double bonds are close to one another, the reaction may proceed in reasonable yield even in fluid and disordered states. The major practical application has been for production of photoresists, that is, insoluble photoformed polymers used for image-transfer systems (printed circuits, lithography, etc.) (178). Another application, of more interest here, is the use that has been made of mono- and dicinnamates for asymmetric synthesis (179), in studies of molecular association (180), and in the mapping of the geometry of complex molecules in fluid phases (181). In all of these it is tacitly assumed that there is quasi-topochemical control in other words, that the stereochemistry of the cyclobutane dimer is related to the prereaction geometry of the monomers in the same way as for the solid-state processes. 

The suitability of the polymer-Hnker conjugate was examined for a variety of transformations, in particular Pd°-catalyzed reactions. For instance, the polymer-bound aryl iodide (63) was transformed quantitatively in a Heck reaction to a cinnamic acid ester (64) and to biphenyl (66) in a Suzuki reaction. It gave an alkyne (65) in a Sonogashira reaction (Scheme 10.12). 

Polymers with other pendant photosensitive moieties such as 0-furylacrylic ester (2) or / -styrylacrylic ester (5) are highly photosensitive and have even higher photosensitivity after the addition of photosensitizers. However, the thermal stability of these polymers is inferior to that of the polymer with pendant cinnamic esters (4). Polymers with pendant benzalacetophenone (5), styrylpyridinium (6), a-cyanocinnamic ester (7) or a-phenylmaleimide (8) have high photosensitivity but they can not be sensitized. In addition, the photosensitive moieties that are used in the syntheses of these polymers are not commercially available, in contrast to cinnamic acid. 

Limonene -polymer permeation [BARRIER POLYMERS] (Vol 3) - [CINNAMIC ACID, CINNAMALDEHYDE AND C INN AMYL ALCOHOL] (Vol 6) - [METALLICCOATINGS - SURVEY] (Vol 16) -in tagetes oil [OILS, ESSENTIAL] (Vol 17)... 

Although actual diffusion in solids is not significant within the lifetimes of excited molecules, bimolecular reactions can take place when molecules are kept in close contact in a polymer or crystal lattice. In some crystals the molecules are ideally spaced for cycloaddition, as in the example of cinnamic acid (Figure 4.80). The geometrical requirements are quite stringent and the reaction cannot proceed if the interplane separation of the molecules exceeds about 4A. 

The photodimerization of cinnamic acid and similar molecules is observed in crystals, but reactions of the same type occur in some polymers as well. Polymers such as polystyrene are made of long, saturated hydrocarbon chains with pendant groups in close contact dangling from the chain these chromophores can then interact in bimolecular photoaddition reactions. Polyvinyl car bazole and its derivatives are important examples of polymers which lead to such bimolecular interactions (e.g. exciplex formation). 

Photo-crosslinking and the reverse process of photodissociation of pre-existing crosslinks relies on a cycloaddition reaction (and on the reverse dissociation of the cyclic adduct). For example, derivatives of vinyl cinnamic acid can form crosslinks which are dissociated by irradiation with short wavelength light (e.g. 254 nm produced by low-pressure mercury arcs). In this process the polymer chains become separated, and the polymer itself is then soluble in organic solvents. 

Neckers et al. reported the synthesis of bulk polymers imprinted with one of the three possible isomeric products of the photodimerisation of /ram-cinnamic acid... 

This polymer was able to convert more than 50% of the tnmv-cinnamic acid in 8-truxinic acid (12), an isomer that is never formed with the catalyst in solution. This demonstrated how the cavity of the imprinted polymer could control the stereochemistry of the reaction in a direction which did not occur at all using the free catalyst in solution (Scheme 3) [9]. 

Cinnamic acid derivative 36 crystallizes in the chiral space group P2t and gives the optically pure dimer 37 upon irradiation in the solid state [22], Chiral crystals of 38 gave, upon irradiation, the optically active dimer 39 of 90% ee, whereas the corresponding methyl ester gave a highly crystalline linear polymer through a typical [2 + 2] topochemical photopolymerization [23],... 

Cinnamates occupy an important place in the history of photochemistry. Schmidt and his co-workers [18] used the solid state photochemistry of cinnamic acid and its derivatives to develop the idea of topochemical control of photochemistry in the crystalline state. Minsk [19] developed poly(vinyl cinnamate) as the first polymer for photoimaging. The cinnamate chromophore is still commonly incorporated in photopolymers of all types, including LC polymers, to enable them to be photochemically cross-linked [20], and a number of reports of the photochemistry of such MCLC and SCLC polymers are summarized below. 

One of the best-studied solid-state reactions is the photopolymerization of distyrylpyrazine (9) and related compounds to give crystalline polymers containing cyclobutane rings (Scheme 10). This reaction is reminiscent of Schmidt s early work on cinnamic acids, although the presence of two double bonds per monomer can lead to oligomeric or polymeric rather than solely dimeric products. The four-center reaction of 9, and other related polymerizations, have been reviewed in detail by Hasegawa, who has played a central role in the study of these systems... 

The copolymer of glycidyl methacrylate and methyl methacrylate was treated with a mixture of monoethyl fumarate and cinnamic acid to yield a polymer capable of [2 + 2] cycloaddition with the naphthylacrylate as well as cinnamate-cinnamate and cinnamate-fumarate crosslinks. 

The alcohols formed from some cinnamic acid derivatives, namely /7-coumaryl alcohol, coniferyl alcohol (LI), and sinapyl alcohol (L2), commonly known as monolignols, undergo dimerization reactions that yield lignans such as (-l-)-pinoresinol (L3), (-l-)-sesamin (L4), (-)-matairesinol (L5), and podophyllotoxin (L6) (Fig. 13). Several thousand lignans are found to occur in nature. Lignins, the structural components of plant cell walls, are polymers of monolignols and/or lignans. 

Synthesis of New Photocrosslinkable Polymers Derived from Cinnamic Acid... 

Dimerization of trans-cinnamic acid under ultraviolet radiations is a well known phenomenon since it has been studied a long time ago by Bertram and Kursten (J ). Presence of cinnamic structures in macromolecules leads, after irradiation, to crosslinking polymers which have found applications in modern lithographic techniques and electronic microminiaturization (j.). 

Introduction of these photocrosslinkable structures in macro-molecular chains can be performed by esterification of hydroxyla-ted polymers with cinnamoyl chloride. Cellulose Q).condensation products (4, ) and mainly poly(vinyl alcohol) have Been treated( by this method. Other chemical modifications have been studied as ester interchange of poly(vinyl acetate) 7) and Knoevenagel reaction on polyesters (8). Very few results on the synthesis of such photocrosslinkable polymers by polymerization have been reported. Therefore free radical polymerization of cinnamic acid vinyl derivatives did not lead to the expected polymers, but to insolubilization reactions. Howewer cationic procedure can be a good way in some cases since Kato et al. could polymerize by this way with high yields p-vinyl phenylcinnamate (9) and B-vinyloxyethyl cinnamate (10). 

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