Aldehydes cinnamic

Claisen reaction Condensation of an aldehyde with another aldehyde or a ketone in the presence of sodium hydroxide with the elimination of water. Thus benzaldehyde and methanal give cinnamic aldehyde, PhCH CH-CHO. 

Other botanical varieties are caUed cassia, but the leaves of these varieties differ in flavor components from those of the bark. Saigon cinnamon, C. loureirii Nees, from Viet Nam, closely resembles Chinese cassia in appearance but is grown on the other side of the mountains and has an entirely different flavor character, containing no orthomethoxy cinnamic aldehyde. C. burmani B/ume, ie, Korintje or Kerintje cinnamon and Padang or Batavia cinnamon, is from Sumatra and Indonesia. C. sintok B/ume is native to Malaysia and of minor commercial importance. 

Zeylanicum. The second type of cinnamon is the dried inner bark of the shoots of the tree Cinnamonium lanicum Nees, a moderately sized coppiced evergreen bush of the laurel family cultivated in Sri Lanka. The bark is stripped, roUed into quills, dried, and then shipped in large bundles. The aroma and flavor of the lanicum type, which contains eugenol as well as cinnamic aldehyde, is much milder than the cassia type. 

There are at least two routes currently being used to produce natural benzaldehyde. Principal flavor houses are reported to market a product which is derived from cassia oil. The chief constituent of cassia oil is cinnamic aldehyde which is hydrolyzed into its benzaldehyde and acetaldehyde constituents. This is a fermentative retroaldol reaction. Whether this hydrolysis allows the final benzaldehyde product to be considered natural is of great concern. The FDA has reportedly issued an opinion letter that benzaldehyde produced from cassia oil is not natural (15). 

Pyrolytic Decomposition. The pyrolytic decomposition at 350—460°C of castor oil or the methyl ester of ricinoleic acid spHts the ricinoleate molecule at the hydroxyl group forming heptaldehyde and undecylenic acids. Heptaldehyde, used in the manufacture of synthetic flavors and fragrances (see Elavors and spices Perfumes) may also be converted to heptanoic acid by various oxidation techniques and to heptyl alcohol by catalytic hydrogenation. When heptaldehyde reacts with benzaldehyde, amyl cinnamic aldehyde is produced (see Cinnamic acid, cinnamaldehyde, and cinnamyl... 

One of the first practical methods for the manufacture of cinnamyl alcohol involved reduction of cinnamic aldehyde diacetate with iron filings in acetic acid. This approach suffered from low yields and Hberation of a significant amount of the starting aldehyde. 

It may be prepared synthetically by reducing cinnamic aldehyde diacetate, and saponifying the resulting cinnamyl esters. Cinnamic alcohol is a crystalline body, although commercial specimens frequently contain traces of impurities which prevent crystallisation. It has the following characters —... 

Pyruvic Acid Compounds.—Lubrzynska and Smedley have recently shown that a number of aldehydes such as heliotropin, anisic aldehyde, benzaldehyde, and cinnamic aldehyde, condense with pyruvic acid in slightly alkaline solution, with the formation of )8-unsaturated-a-ketonic acids. For example, if heliotropin and pyruvic acid in alkaline solution be left standing for about eight days at ordinary temperature, dihydroxy-methylene-benzal-pyruvic acid is formed. This body forms yellow needles, melting at 163° Similarly, anisic aldehyde yields methoxy-benzal-pyruvic acid, melting at 130° and cinnamic aldehyde yields cinnamal-pyruvic acid, melting at 73°. 

Cimiamic aldehyde. Furfurol p-Aminophenylglycine 120° Cinnamic aldehyde anilglycine ... 

Cinnamic aldehyde. Furfurol 11 11 125° Cinnamic aldehyde aniloxamic acid it k... 

Cinnamic aldehyde, C HgO, is the principal odorous constituent of dnnamon and cassia oils, and is manufactured to a considerable extent, artificially. It can be extracted from the oils in which it occurs by means of sodium bisulphite, the sodium bisulphite compound being decomposed with dilute sulphuric acid, and distilled in a current of steam. The preparation of artificial cinnamic aldehyde, which is used in perfumery as a substitute for the natural oils, is usually carried out. by a condensation of benzaldehyde and acetaldehyde, according to the following reaction —... 

A mixture of 10 parts of benzaldehyde, 15 parts of acetaldehyde, 900 parts of water, and 10 parts of 10 per cent, solution of caustic soda are allowed to stand for ten days at 30° with constant stirring. The cinnamic aldehyde formed is extracted with ether and purified by fractional distillation. 

Cinnamic aldehyde is a sweet, odorous liquid, resembling cinnamon oil, but without its delicacy of odour. It has the following constitution —... 

Ortho-methoxy-cinnamic aldehyde is present in small amount in cassia oil. It has the composition Cj( Hjq02, and its physical characters are as follows —... 

Para-methoxy-cinnamic aldehyde has been isolated from tarrago oU. It has the following characters —... 

An aldehyde was isolated from the oil of the root of a variety of Chlorocodon, by Goulding and Pelly,i which Friedlander has shown to be p-methoxy-cinnamic aldehyde. This aldehyde has been obtained artificially by Tiemann and Parrisius by acting with chloroform on an alkaline-solution of methylresorcmol. 

Sadtler concluded finally that double bonds seem to aid in bringing about reaction when close to the. CHO group, e.g., citral, cinnamic aldehyde, and that proximity of the benzene nucleus to the. CHO group, as. in the case of benzaldehyde and vanillin, was also probably a factor, while the only active ketones were those containing double bonds near to the. CO group. 

Semioxamazide.—A gravimetric method for the estimation of cinnamic-aldehyde in cassia and cinnamon oils, but which appears to apply only to this aldehyde, has been devised by Hanus based on the formation of a crystalline semioxamazone when cinnamic aldehyde is treated -with semioxamazide, the reaction being—... 

Sodium Salicylate.—When an aldehyde is shaken with a saturated solution of sodium salicylate, there seems to be evidence of the formation of a weak molecular compound, and with cinnamic aldehyde well-defined crystals have been obtained which give on analysis —... 

Zimt, m. cinnamon. — weisser —, canella bark, canella. — chinesischer cassia bark. Zimt-. cinnamic cinnamon. -aldehyd, n. cinnamaldehyde, cinnamic aldehyde, -alko-hol, m. cinnamic alcohol, -blute,/. cinnamon flower, cassia bud. -bliltendl, n. cassia oil. zimtbraun, a. cinnamon-brown. Zimtcarbonsaure, /. carboxycinnamic acid, zimt-farbig, -farben, a. cinnamon-colored. Zimt-kaneel, m. canella bark, canella. -kassia, /. cassia bark, cassia, -kassienbl, n. oil of cassia. 

Essential oils are known to have detrimental effects on plants. The inhibitory components have not been identified, but both alde-hydic (benzol-, citrol-, cinnamal-aldehyde) and phenolic (thymol, carvacol, apiol, safrol) constituents are suspected. Muller et al. (104) demonstrated that volatile toxic materials localized in the leaves of Salvia leucophylla, Salvia apiana, and Arthemisia californica inhibited the root growth of cucumber and oat seedlings. They speculated that in the field, toxic substances from the leaves of these plants might be deposited in dew droplets on adjacent annual plants. In a subsequent paper, Muller and Muller (105) reported that the leaves of S. leucophylla contained several volatile terpenes, and growth inhibition was attributed to camphor and cineole. 

As shown in Schemes 10-44 and 10-45, two products may be formed in a Meerwein reaction Scheme 10-44 shows a simple aryl-de-hydrogenation of cinnamic aldehyde, whereas Scheme 10-45 shows an aryl-de-hydrogenation combined with the addition of HC1 to the double bond of the methyl ester of cinnamic acid. No systematic studies have been made as to which of the two products will be formed in a given reaction, what experimental conditions will favor one or the other product, and what substituents or other structural characteristics of the alkene influence the ratio of the two types of product. The addition product can, in most cases, easily be converted... 

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