Esters cinnamate, reaction with

Sulphinylacetic esters are converted in a one-pot reaction into cinnamic esters, when alkylated with benzyl halides [50],... 

The reactivity of phenylacetic esters with electron-deficient alkenes is generally fairly poor, even under phase-transfer catalytic conditions. The reaction with cinnamic esters is often accompanied by hydrolysis and the yield of the adduct with chalcone is generally <60% [10]. The activity of the methylene group towards alkylation has been enhanced by the initial complexation of the phenyl ring with chromium tricarbonyl (see Section 6.2), but this procedure has not been applied to the Michael reaction. 

Cinnamic alcohol can be dehydrogenated to give cinnamaldehyde and oxidized to give cinnamic acid. Hydrogenation yields 3-phenylpropanol and/or 3-cyclo-hexylpropanol. Reaction with carboxylic acids or carboxylic acid derivatives results in the formation of cinnamyl esters, some of which are used as fragrance materials. 

Accordingly, the synthesis of novel cinnamate polymers with high functionality and performance is very important from the viewpoint of both polymer chemistry and practical use. Recently, we have reported the synthesis of polymers with pendant photosensitive moieties such as cinnamic ester and suitable photosensitizer groups by radical copolymerizations of 2-(cinnamoyloxy) ethyl methacrylate with photosensitizer monomers (9), by copolymerizations of chloromethylated styrene with the photosensitizer monomers followed by the reactions of the copolymers with salts of... 

This topological rule readily explained the reaction product 211 (>90% stereoselectivity) of open-chain nitroolefins 209 with open-chain enamines 210. Seebach and Golinski have further pointed out that several condensation reactions can also be rationalized by using this approach (a) cyclopropane formation from olefin and carbene, (b) Wittig reaction with aldehydes yielding cis olefins, (c) trans-dialkyl oxirane from alkylidene triphenylarsane and aldehydes, (d) ketenes and cyclopentadiene 2+2-addition, le) (E)-silyl-nitronate and aldehydes, (f) syn and anti-Li and B-enolates of ketones, esters, amides and aldehydes, (g) Z-allylboranes and aldehydes, (h) E-alkyl-borane or E-allylchromium derivatives and aldehydes, (i) enamine from cyclohexanone and cinnamic aldehyde, (j) E-enamines and E-nitroolefins and finally, (k) enamines from cycloalkanones and styryl sulfone. 

Compound 85 was dehydrogenated at 300° over palladium black under reduced pressure to a pyridine derivative 96 which was independently synthesized by the following route. Anisaldehyde (86) was treated with iodine monochloride in acetic acid to give the 3-iodo derivative 87. The Ullmann reaction of 87 in the presence of copper bronze afforded biphenyldialdehyde (88). The Knoevenagel condensation with malonic acid yielded the unsaturated diacid 91. The methyl ester (92) was also prepared alternatively by a condensation of 3-iodoanisaldehyde with malonic acid to give the iodo-cinnamic acid (89), followed by the Ullmann reaction of its methyl ester (90). The cinnamic diester was catalytically hydrogenated and reduced with lithium aluminium hydride to the diol 94. Reaction with phosphoryl chloride afforded an amorphous dichloro derivative (95) which was condensed with 2,6-lutidine in liquid ammonia in the presence of potassium amide to yield pyridine the derivative 96 in 27% yield (53). 

The benzylic free radical produced by the addition of the carbamoyl radical to the ethyl cinnamate molecule is more stable than the alternative radical alpha to the ester group. With such an orientation of addition to the a,p-unsaturated ester, this reaction should lead to derivatives of malonic acid. However, it has been found that the intermediate radical, being a stable benzylic free radical, fails to perform the subsequent abstraction of a hydrogen atom from formamide, and thus no chain-transfer step takes place. Instead of performing this step it favours the combination with a semi-pinacol radical, which is present in solution, to yield the hydroxy ester which subsequently lactonizes to give the major product of the reaction (67). 

Cinnamic esters 691 react with aryl halides via a domino Heck reaction-lactonization process in molten //-Iki () c///-B111 hr to yield 4-arylcoumarins (Scheme 170) <2005ASC308>. Likewise, the palladium(n)-cata-lyzed reaction of cinnamic esters with vinyl triflates yields 4-vinyl coumarins <1996SL568>. 

Other preparations of 2-iminothiazolidin-4-ones which are discussed in the review by Brown utilize the reactions of thiourea with a-hydroxy acids,ethyl diazoacetate,glycidic esters, - cinnamic acid, unsaturated diacids (fumaric, maleic, and citraconic) or their esters or imides, and propiolic esters. There has been considerable controversy in the literature surrounding the propiolic ester synthesis since many workers have proposed that the products are 1,3-thiazines (see Section IV, B, 1). The pertinent papers in this controversy have been summarized by Cain and Warrener. Nagase has recently settled the argument in favor of the 2-iminothiazolidin-4-... 

The photocrosslinking of poly(vinyl cinnamate) was assumed by Minsk to involve reactions which led to the disappearance of the double bond. A number of studies have confirmed that ultraviolet irradiation of poly(vinyl cinnamate) causes diminution of the value of absorbance in the region characteristic of the cinnamate ester group. Typical experiments involved the irradiation of coatings of poly(vinyl cinnamate) on quartz plates. It was then possible to follow the disappearance of the cinnamate ester absorption spectra with irradiation time. The photoreaction taking place has been presumed by Tsuda 41> to be analogous to dimerization of low molecular weight cinnamate esters. 

The preparation of chelating surface-active diphosphines proved to be more successful. The BDPP analogue R,R-(9) was synthesized by lithiation of tris[p-(3-phe-nylpropyl)phenyl]phosphine, reaction with (R,R)-2,4-pentane-diylditosylate and subsequent sulfonation with concentrated sulfuric acid [16]. Hydrogenation of the prochiral olefin (Z)-2-(N-acetamido)cinnamic acid ester in a two-phase system (ET0Ac/H20) with Rh complexes derived from R,R-(9) was accomplished with identical selectivity compared with the unsulfonated BDPP and improved reactivity compared with BDPPTS (2). 

One of the most important transformations catalysed by palladium is the Heck reaction. Oxidative addition of palladium(O) into an unsaturated halide (or tri-flate), followed by reaction with an alkene, leads to overall substitution of a vinylic (or allylic) hydrogen atom with the unsaturated group. For example, formation of cinnamic acid derivatives from aromatic halides and acrylic acid or acrylate esters is possible (1.209). Unsaturated iodides react faster than the corresponding bromides and do not require a phosphine ligand. With an aryl bromide, the ligand tri-o-tolylphosphine is effective (1.210). The addition of a metal halide or tetra-alkylammonium halide can promote the Heck reaction. Acceleration of the coupling can also be achieved in the presence of silver(I) or thallium(I) salts, or by using electron-rich phosphines such as tri-tert-butylphosphine. ... 

The second series has been prepared from isocyanates 247, which were readily produced by Cuitius rearrangement of cinnamic acid with diphenylphosphoryl azide in the presence of triethylamine (Scheme 49). Isocyanates 247 were engaged with lithium derivatives 244 or 246. After deprotective reaction of phosphinate ester, phosphinic acids 242a-f were obtained [172]. One example of saturated structure 242d was synthesized by reduction of the alkene [172]. 

A wide range of 4-aryl-3,4-dihydrocoumarins were synthesized through a molecular iodine-catalyzed reaction of cinnamic acids with phenols (14T5221), or iron(III) chloride-promoted reaction of cirmamate esters with phenols, in moderate-to-good yields (140BC4347). Other 4-aryl-... 

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