Cinnamic acid, 2-phenyl

Methyl, ethyl, n-propyl, isopropyl, n-hutyl, benzyl, cyclohexyl esters of formic, acetic, oxalic, succinic, tartaric, citric, benzoic, salicylic (and other substituted benzoic acids), phthalic and cinnamic acids phenyl esters of acetic, benzoic and salicylic acids. 

The a-carbon atom of the phenylacetyl group is more susceptible to attack by the basic catalyst (triethylamine) than the acetyl group hence a-phenyl-cinnamic acid, but no cinnamic acid, is obtained. 

Chapter IV. a-Chloromethylnaphthalene (IV,23) benzylamine (Gabriel synthesis) (IV,39) i r.N -dialkylanilines (from amines and trialkyl orthophosphates) (IV,42) a-naphthaldehyde (Sommelet reaction) (IV,120) a-phenyl-cinnamic acid (Perkin reaction using triethylamine) (IV,124) p-nitrostyrene (IV,129) p-bromonaphthalene and p naphthoic acid (from 2 naphthylamine-1 -sulphonic acid) (IV,62 and IV,164) diphenic acid (from phenanthrene) (IV,165). 

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. 

Radicaloid substitution has not been extensively studied in the thiophene series. Molecular orbital calculations indicate that substitution should occur in the a-position. This has been found to be the case in the Gomberg-Bachmann coupling of diazohydroxides with thiophenes which has been used for the preparation of 2-(o-nitro-phenyl) thiophene, 2-(p-toluyl) thiophene, " " and 2-(p-chloro-phenyl)thiophene. " Coupling in the /8-position has been used for the preparation of 1,3-dimethyl-4,5-benzisothionaphthene (148) from 2-amino-tt-(2,5-dimethyl-3-thienyl)cinnamic acid (149). A recent investigation describes the homolytic phenylation of 2- and 3-phenyl-... 

Phenyl-propyl alcohol, CgH. CHj. CH.2. CHj. OH, is the next highest homologue of phenyl-ethyl alcohol, and is also known as hydro-cinnamyl alcohol. Like the last described bodies it has been known for many years, its first preparation being described in the Aivnalen (188, 202). It occurs as a cinnamic acid ester in storax, and as an acetic ester in cassia oil. It is prepared synthetically by the reduction of cinnamyl alcohol with sodium amalgam and water, or by the reduction of cinnamic or benzyl acetic esters with sodium and absolute alcohol. It has the following characters —... 

Cinnamic alcohol, C Hj. CH CH. CH OH, or y-phenyl-allyl alcohol, is found in the form of esters, principally of either acetic or cinnamic acid in storax, balsam of Peru, and in hyacinth and other essential oils. 

Cinnamic alcohol forms a phenyl-urethane, melting at 90° to 91°, and a diphenyl-urethane, melting at 97° to 98°. On oxidation it yields cinnamic acid, melting at 133°, and by more thorough oxidation, benzoic acid, melting at 120°. 

In this section, we will neglect the crystal structures of the mesogenic perfluorinated phenyl benzoates [23-27], benzoic acids [6, 28-31], cinnamic acids [7, 32, 33], dicarboxylic acids [34, 35], and cinnamate compounds [8, 36-40]. The single crystal X-ray analyses of chiral mesogenic carboxylates are described in Sect. 6. 

The trans cinnamic acid and phenyl propiolic acid data involve fits of essentially the same precision at o-, m-, and p- positions (SD =. 05 . 02). However, the RMS of these sets is quite low, and consequently, / values of. 200 prevail. The interpretation of these results is therefore uncertain. To the extent that the results of Table VII are meaningful, it is of particular interest that Kj =p°Ip =. 68 for the phenyl propiolic acid, whereas for the tram cinnamic acids, K° = 1.02. These results suggest that in contrast to the ortho substituted benzoic acids, the lines of field forces in the ortho substituted phenyl propiolic acids do (partly at least) penetrate regions of hi dielectric solvent. The results for the tram cinnamic acids would then indicate some (but not complete) exclusion of solvent resulting from the presence of the vinyl hydrogens. These interesting results from the application of eq. (1) clearly need to be confirmed by additional studies. 

Figure 1. Linear regression plot of tomato and radish seedling root growth inhibition with varying concentrations of phenyl aliphatic acids. Benzoic acid (V) phenylacetic acid (X) 3-phenyIpiropanoic acid (A) 4-phenylbutanoic acid ( ) trans-cinnamic acid (----) (1).

An example of this reveals an additional substituent effect (Fig. 2.18).121 Ordinarily, the phenyl and carboxyl groups anchor the double bond approximately equally (notice the sixth entry in Table 2.3 and cinnamic acid in Fig. 

Phenyl aryl cyclopropenones16 were cleaved by methanolic KOH to a mixture of cis aryl cinnamic acids (318/319 R = phenyl, R = aryl), whose rates of formation gave rise to a linear Hammett-type correlation with a values in the range of -0.268 to +0.373 and p = 0.75. This also indicates that cleavage yielding the more stable carbanion is preferred. Interestingly, ortho-substituted aryl phenyl cyclopropenones gave only a-phenyl-0-aryl acrylic acids (319 R = phenyl, R = aryl), which was explained in terms of steric interactions. 

The procedure described is essentially that of Ballard and Dehn.1 Stilbene has also been prepared by reduction of desoxy-benzoin,20 benzaldehyde,23 and benzil 2o-2c by dehydrogenation of ethyl benzene,30 toluene,30- 33- 3, and bibenzyl 33-3alkaline reduction of phenylnitromethane,40 phenylnitroacetonitrile,40 and desoxybenzoin 43 by distillation of benzyl sulfone,50 benzyl sulfide,60-63 calcium cinnamate,5 cinnamic acid,5d phenyl cinna-mate,6e-6/ and diphenyl fumarate ie by dehydrohalogenation of a,a -dichlorobibenzyl60 and benzyl chloride 63 by dehalogenation of a,a,c/,a -tetrachlorobibenzyl70 and benzal chloride 73 by the coupling of cinnamic acid and phenyldiazonium chloride 8 by de-... 

The reaction was followed by chiral GC (SE 30, 220 °C, nitrogen mobile phase). R (a-acetamido cinnamic acid) 3.70 min Rt (/V-acetyl-L-phenyl-alanine) 5.4 min. 

DMA in 500 ml ether mix rapidly with 270 ml 0.9 M phenyl-Li, boil fifteen hours and extract as for (VI) or as described previously to get 8 g oily 4-methoxy-indoline (or its 1-methyl derivative) (VII). Alternatively, add 36 g naphthalene to 300 ml tetrahydrofuran and add 11 g Na metal cut in small pieces. Reflux and stir three hours and add 18 g (VI) and 8 g DEA in 200 ml tetrahydrofuran rapidly and boil twelve hours. Evaporate in vacuum, dissolve the oily residue in 2N HCI and extract with ether. Proceed as described to get (VII). 4 g (VII) in 200 ml dry pyridine add to 6 g Cu chloride in 400 ml pyridine and reflux 1 xh hours. Pour on water and extract with ether. Wash extract with 4N HCI and then water and dry and evaporate in vacuum the ether to get 2 g of the indole (VIII). Alternatively, dissolve 4 g (VII) and 9.5 g cinnamic acid in 700 ml mesitylene, add 1 g 5% palladium-carbon and reflux five hours. Filter, wash with HCI and NaHC03 and dry and evaporate in vacuum the mesitylene to get the red, oily (VIII) (can chromatograph on alumina and elute with benzene-petroleum ether). 

But catalytic reduction of the same phenyl propionic acid gives cis cinnamic acid. Therefore by adding hydrogen under various conditions, one can obtain a desired isomer. The conversion of acetylene into olefinic compounds has been carried out not only for the sake of obtaining the adduct, but Michael studied the various addition reactions for the sake of obtaining a desired product cis or trans. For example, he found that the addition of bromine to acetylene-dicarboxylic acid leads predominantly to the formation of trans isomer. 

Figure 39. Four ribbons of cinnamide (phenyl = ) molecules. Ribbons / and l, d and d are related by translation. Ribbons d and /, d and l make plane-to-plane contacts of 4 A across centers of symmetry. Ribbon / is above d, and ribbon d is below l. Cinnamic acid molecules (filled circles) have been introduced into the structure in the allowed sites, assuming the crystal grows from the center in the two opposite directions +b and —b. The dimers obtained at the two opposite sides are enantiomeric.

Kinetics of the reaction of diazodiphenylmethane (92) in a wide range of alcohols with pyridine and pyridine-A -oxide 3- and 4-carboxylic acids (84)-(87), 4-substituted benzoic acids (88)," cw -substituted cinnamic acids (89), 2-(4-phenyl-substituted)cyclohex-l-enyl carboxylic acids (90), and 4 -substituted-biphenyl-2-carboxylic acids (91)" have been reported. Comparison of the new results for 4-substituted benzoic acids with the published results of data for 3-substituted benzoic acids was made, " and it was concluded that the most important solvent property influencing the rate of reaction appears to be the polarity of the alkyl group expressed as Taft s polar constant a. Transmission coefficients in the cinnamic acids (89) were compared with those in the bicyclic acids (90) and... 

A study of the regioselectivity of the 1,3-dipolar cycloaddition of aliphatic nitrile oxides with cinnamic acid esters has been published. AMI MO studies on the gas-phase 1,3-dipolar cycloaddition of 1,2,4-triazepine and formonitrile oxide show that the mechanism leading to the most stable adduct is concerted. An ab initio study of the regiochemistry of 1,3-dipolar cycloadditions of diazomethane and formonitrile oxide with ethene, propene, and methyl vinyl ether has been presented. The 1,3-dipolar cycloaddition of mesitonitrile oxide with 4,7-phenanthroline yields both mono-and bis-adducts. Alkynyl(phenyl)iodonium triflates undergo 2 - - 3-cycloaddition with ethyl diazoacetate, Ai-f-butyl-a-phenyl nitrone and f-butyl nitrile oxide to produce substituted pyrroles, dihydroisoxazoles, and isoxazoles respectively." 2/3-Vinyl-franwoctahydro-l,3-benzoxazine (43) undergoes 1,3-dipolar cycloaddition with nitrile oxides with high diastereoselectivity (90% de) (Scheme IS)." " ... 

The first reactions concerned (Simons and Archer, 27) alkylation of benzene with propylene to form isopropylbenzene, with isobutene to form f-butylbenzene and di-f-butylbenzene, and trimethylethylene to form amylbenzene. Later on (Simons and Archer, 28) studied these and other reactions in more detail and showed that high yields could be obtained and that the product was not contaminated with tars or other obnoxious impurities. It was shown that the products obtained with trimethylethylene were mono- and di-f-amylbenzene, that phenyl-pentane resulted from the use of pentene-2, and that cyclohexene produced cyclohexylbenzene. Cinnamic acid reacted with benzene (Simons and Archer, 29) to form /3-phenylpropionic acid and allyl benzene reacted with benzene to form 1,2-diphenylpropane. It is interesting to note that although allyl alcohol reacted with benzene to form 1,2-diphenylpropane, the intermediate in the reaction, allylbenzene, was isolated and identified. This shows that in this case the hydroxyl reacted at a more rapid rate than the double bond. Both di- and triisobutylene reacted with phenol (Simons and Archer, 30) at 0°, when using hydrogen fluoride containing only relatively small quantities of water, to form f-butyl-benzene, but diisobutylene with 70% hydrogen fluoride produced p-f-octylphenol. Cyclohexene reacted with toluene to form cyclohexyl-toluene and octene-1 rapidly reacted with toluene to form 2-octyltoluene (Simons and Basler, 31). 

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