Methyl-cinnamate

As a typical example, the catalytic reaction of iodobenzene with methyl acrylate to afford methyl cinnamate (18) is explained by the sequences illustrated for the oxidative addition, insertion, and /3-elimination reactions. 

Benzaldehyde s most important use is in organic synthesis, where it is the raw material for a large number of products. In this regard, a considerable amount of benzaldehyde is utilized to produce various aldehydes, such as cinnamic, methyl cinnamic, amyl cinnamic, and hexyl cinnamic. 

Phenyl-2-propenoic acid [621 -82-9] commonly referred to as cinnamic acid, is a white crystalline soHd having a low intensity sweet, honeylike aroma. It has been identified as a principal constituent in the botanical exudates from Styrax IJquidamber orientalis) Benzoin Styrax ben in Pern Balsam [Myroxylon pereirae and Tolu Balsam (]Ayro>ylon balsamum) (4,5). In these, as well as numerous other natural products, it exists both as the free acid and in the form of one or more of its esters, as for example, methyl cinnamate, ben2yl cinnamate [103 1 -3] and cinnamyl cinnamate. 

Esters can be obtained from halogenated olefins using a metal carbonyl catalyst (87), eg, /n j -l-bromo-2-phenylethylene is treated with nickel carbonyl in the presence of methanol to afford the corresponding methyl cinnamate (see Cinnamic acid). 

Further evidence showed this mechanism to be incorrect, especially the fact that it was methyl cinnamate and not (347) which was isolated from the reaction (73CPB2026). Also 1-phenylpyrazoles did not react with DMAD under the reaction conditions (74BSF2547). The origin of (346) remains obscure, but in no circumstances does it imply a Diels-Alder reaction of a pyrazole. For Ogura et al., it has its origin in an intermediate A -pyrazoline (73CPB2026). 

Methyl cinnamate (16 parts) is dissolved in methyl alcohol (20 parts) and treated with bromine (20 parts). The mixture solidifies in the cold. It is shaken with a solution of caustic soda (12 parts) in water (24 parts), the temperature being kept down to 40°. After two hours the mixture is neutralised with dilute sulphuric acid, and an oily layer separates. This is mixed with water (to 250 parts) and sodium carbonate (5-5 parts) added, and the aldehyde distilled in a current of steam, and extracted with ether, and the ether evaporated. The yield is about 75 per cent, of the theoretical. 

To a stirred slurry of copper(i) cyanide (110 mmol) in THF (100 ml), cooled to 0 °C, was added a solution of dimethylphenylsilyl lithium (220 mmol, 1.3 m in THF), and the mixture was stirred at 0°C for a further 30min. After cooling to —78°C, a solution of methyl cinnamate (100mmol) in THF (50 ml) was added, and stirring was continued at —78°Cfor6h. At this time, iodomethane (300 mmol) (CAUTION—CANCER SUSPECT AGENT) was added, and the mixture allowed to warm to ambient temperature with... 

The combination of CsF with Si(OMe)4 58 is an efficient catalyst for Michael additions, e.g. of tetralone 130 to methacrylamide, followed hy cyclization of the addition product to the cyclic enamide 131 in 94% yield [67]. Likewise, addition of the lactone 132 to methyl cinnamate affords, after subsequent cyclization with tri-fluoroacetic acid, the lactam 133 in 58% yield [68] whereas < -valerolactam 134, with ethyl acrylate in the presence of Si(OEt)4 59/CsF, gives 135 in 98% yield [69]. Whereas 10mol% of CsF are often sufficient, equivalent amounts of Si(OEt)4 59 seem to be necessary for preparation of 135 [69] (Scheme 3.11). 

During the photoreaction of ethyl methyl 1,4-phenylenediacrylate crystals (3 OEtMe), in which the distances of intermolecular double bonds are 3.891 A between two methyl cinnamate groups and 4.917 A between two... 

One of the distinguishing features of liverworts is their capacity to produce a variety of volatile, often very fragrant, oils that occur in oil bodies distributed over much of the surface of the organism. Several of these volatile compounds figure prominently in defining geographically different chemotypes in several countries. Toyota et al. (1997) examined 280 specimens of C. conicum collected at Kamikatsu-cho and Katsuura-cho, both Katsuura-gun, Tokushima. Three chemotypes were identified based upon their major components. Chemotype-I-accumulated (-)-sabinene [420], chemotype-II-accumulated (H-)-bomyl acetate [421], and chemotype III was characterized by methyl cinnamate [422] (see Pig. 5.4 for structures). In addition to a number of compounds known from previous studies of C. conicum, three... 

Wood, W. E., Lancaster, W. C., Eisher, C. O. and Stotler, R. E. 1996. frans-Methyl cinnamate the major volatile from some populations of the liverwort Conocephalum conicum. Phytochemistry 42 241-242. 

By heterogeneous reaction of methyl cinnamate, the C=C double bond is selectively hydrogenated [26] and methyl 3-phenylpropionate is formed the ester function is not affected. 

Similar behavior has been observed in the formation of methyl cinnamate from iodobenzene and methyl acrylate... 

Table 3. Reaction between iodobenzene and methyl acrylate to methyl cinnamate in the presence of palladium catalysts...

In one study, the mechanisms of the reaction of methyl cinnamate and cyclopen-tadiene with BF3, A1C13, and catecholborane bromide as catalysts were compared.29 According to these computations (B3LYP/6-31G ), the uncatalyzed and BF3- and AlCl3-catalyzed reactions proceed by asynchronous concerted mechanisms, but a... 

Other ketones besides acetone can be used for in situ generation of dioxi-ranes by reaction with peroxysulfate or another suitable peroxide. More electrophilic ketones give more reactive dioxiranes. 3-Methyl-3-trifluoromethyldioxirane is a more reactive analog of DMDO.99 This reagent, which is generated in situ from 1,1,1-trifluoroacetone, can oxidize less reactive compounds such as methyl cinnamate. 

Acrylic acid (AA) and methacrylic acid (MAA) (purchased from Merck) are freed from inhibitor on a neutral aluminium oxid column and distilled. Acrylamide (AM) from Kebo, Stockholm, is recrystallized once from chloroform solution before use. Other monomers of analytical grade were purchased from Merck and used as received crotonic acid (CA), tiglic acid (TA), 3-methyl crotonic acid (3-MCA), and a-methyl cinnamic acid (oi-MCia) (Table 1). Benzophenone (analytical grade, Kebo) and acetone (spectroscope grade, Merck) were used as supplied. 

In 1989, Isayama and Mukaiyama reported a related Co-catalyzed coupling reaction that employs a,b-unsaturated nitriles, amides, and esters with PhSiLb as a hydrogen source [9]. Cobalt-bis(diketonato) complex, Co(II)(dpm)2 [dpm = bis(dipivaloylmethanato)] (5mol%), exhibited high catalytic activity at 20 °C in the coupling of excess acrylonitrile and ben-zaldehyde to provide b-hydroxy nitrile 4 in 93% yield (syn anti = 50 50) (Scheme 5). N,N-Dimethylacrylamide and methyl cinnamate both reacted... 

Similarly, methyl methacrylate reacts with ketones and TMSH/RuCE-SlEO to give /l-trimethylsiloxy-2,2-dimethyl methyl esters in good yields. A lactone example is shown in Eq. 292.473 Methyl acrylate, trans methyl ( )-cinnamate, and 3,4-dehydro-S-lactone react in an analogous manner, albeit in lower yields.473... 

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