Cinnamic alcohol/esters

Synthesis in the presence of undissolved substrates has proven useful also in the lipase-catalyzed syntheses of surfactants such as glucose esterified with fatty acids or esters of glycosides [71], but also in more unusual examples such as ibuprofen resolution [72] and the syntheses of the cinnamic alcohol ester of glucuronic acid... 

Which of the two is the cis form and which the trans form has not been determined. A third cinnamic acid, viz., iso-cinnamic acid, is also known, but the constitution of it has not been established. Cinnamic acid is found in nature in the resin storax both as the free acid and as the cinnamic alcohol ester, styrin. It is also found in Peru and Tolu balsams as the free acid and as the benzyl alcohol ester, the benzoic acid ester of benzyl alcohol being present also. Thus benzyl alcohol, benzoic acid, cinnamic alcohol and cinnamic acid are all constituents of esters present in these plant resins. Allo-cinnamic acid, the geometric isomer, is obtained from coca leaves from which the alkaloid cocaine is also obtained (p. 896). When cinnamic acid is heated with lime it loses carbon dioxide and yields the unsaturated side-chain hydrocarbon st3rrene, or phenyl ethylene, CeHs—CH = CH2. On reduction it yields first cinnamic aldehyde, found in oil of cinnamon (p. 842) and then cinnamic alcohol. Both cinnamic acid and allo-cinnamic acid yield anhydrides. 

Some of the widely used synthetic fixatives are amyl benzoate, phenethyl, phenyl acetate, cinnamic alcohol esters, acetophenone, musk ambrette, musk ketone, musk xylols, vanillin, coumarin, etc. [41]. 

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. 

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 —... 

Benzyl Ginnamate.—The cinnamic acid ester of benzyl alcohol is a natural constituent of storax, tolu, and Peru balsams. It is a crystalline Bubstance with a characteristic sweet balsamic odour. It may be prepared by heating sodium cinnamate, alcohol, and benzyl chloride together under a reflux condenser. It is a useful ester where a sweet balsamic odour is required to be introduced into a perfume, especially cf the heavy type. It forms white, glistening prisms, which melt at 39°, and.decompose when heated to 350°. The best commercial specimens have the following characters —... 

Ir-catalyzed allylic substitutions employing allylic alcohols as substrates and diethyl malonate as pronucleophile were first reported by Takeuchi and coworkers [11]. Here, the substitution step was found to be preceded by OH activation via transesterification to a malonic ester derivative. The asymmetric alkylation of cinnamic alcohol was similarly accomplished by Helmchen and colleagues, using a PHOX ligand and the procedure described in Section 9.2.3 [19]. 

Phenethyl alcohol is qualitatively and quantitatively one of the most important fragrance substances that belongs to the class of araliphatic alcohols. Its lower homologue (benzyl alcohol) and higher homologue (dihydrocinnamic alcohol) also have characteristic odor properties, but are more frequently used in the form of their esters. Cinnamic alcohol, the most important unsaturated araliphatic alcohol, is valuable for both fragrances and flavors. 

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. 

Uses. Cinnamic alcohol is valuable in perfumery for its odor and fixative properties. It is a component of many flower compositions (lilac, hyacinth, and lily of the valley) and is a starting material for cinnamyl esters, several of which are valuable fragrance materials. In aromas, the alcohol is used for cinnamon notes and for rounding off fruit aromas. It is used as an intermediate in many syntheses (e.g., for pharmaceuticals such as the antibiotic Chloromycetin). 

L. M. Minsk, W. P. Van Deusen, E. M. Robertson, Printing-Plate Resists of Cinnamic Acid Esters of Polyvinyl Alcohol and Cellulose, US Patent 2, 610, 120, 1952. 

The suffix -yl is normally used in conjunction with alcohols and their derived esters. This is the form given in most of the samples below. The -ic suffix is normally used in conjunction with aldehydes, and for acids. In some cases, however, the two forms are used alternatively, for example, as with cinnamyl or cinnamic alcohol. 

Phenylpropynoic acid (13) can be prepared from cinnamic acid esters by the addition of bromine to the double bond followed by dehy-drobromination with alcoholic potassium hydroxide (Scheme 5.14). 

This procedure illustrates a general method for the preparation of phenylcyclopropanes from cinnamic acids, esters, aldehydes, or alcohols. It complements the Simmons-Smith reaction as a general method for the preparation of such cyclopropanes. It offers advantages over the Simmons-Smith method in cases in... 

Homologues.—The homologues of benzyl alcohol result from substitution of the hydroxyl group in one of the methyl groups of xylene, mesitylene, etc., or, as in the examples previously given of secondary and tertiary aromatic alcohols, by the substitution of hydroxyl in a poly-carbon side chain either saturated or unsaturated. These need not be discussed further except to mention that both phenyl propanol, CeHs—CH2—CH2—CH2OH, and phenyl propenol, CeHs—CH = CH— CH2OH, are also found as cinnamic acid esters in storax. 

For a series of cinnamic acid esters formed from chiral alcohols, reduction in DMF gave the CHD with from 0% de for the (—)-menthyl ester up to >95% de for the (—)-endo-hoxny ester [66] (Table 4). The menthyl and the bornyl cinnamates have virtually... 

Baizer and coworkers established the most brilliant industrial electroorganic synthesis of the hydrodimerization of acrylonitrile to adiponitrile. They extended this hydrodimerization to a variety of activated olefins and in some cases [41 3] paid attention to the stereochemistry of products. However, their stereochemical data were not enough to discuss the stereochemical course of the reaction. Afterward, an attempt was made to provide a working hypothesis in the hydrodimerization of cinnamates by considering an orientated adsorption of radical anion intermediates on a cathode surface, but this was not persuasive because of a lack of experimental data on the stereochemistry of both the starting olefins and products. Recently Utley and coworkers [44-46] have reported stereochemical data of hydrodimers derived from a variety of cinnamic acid esters with chiral alcohol components. 

Main components During fermentation, vanillin (up to app. 2.5%) is formed from the odourless glucovanillin by enzymatic hydrolysis. Its aroma is rounded-off and modified by p-hydroxybenzoic acid, p-hydroxybenzaldehyde, p-hydroxybenzyl methyl ether, vanillyl alcohol, vanillic acid, cinnamic acid ester and various other trace constituents [291, 292], Also the resins, gums, amino acids and other organic acids contribute to the typical flavour of the cured beans [293[. For further constituents and characterisations of fruits from different growing areas see [294[. 

C11H12O2, Mr 176.21, bpi z kpa 139-140 °C, d22 1.0520, rag0 1.5420, is the only ester of cinnamic alcohol of any importance. fraras-Cinnamyl acetate occurs in cassia oil and is a colorless liquid with a sweet-flowery-fruity, slightly balsamic odor. It is a good fixative and is used in blossom compositions (e.g., lilac and jasmine) and for oriental notes. In aroma compositions, it is used for cinnamon-fruity effects. 

Ckmamyl alcohol (cinnamic alcohol, 3-phenyl-2-pro-pen-l-ol). H5C -CH=CH-CH20H, C,H, 0, Mr 134.17, ( )-form needles with a sweet-balsamy, hyacinth-like odor, mp. 33°C, bp. 258°C, bp. 142-145 C (1.86 kPa), readily soluble in alcohol and ether, it is slowly oxidized by atmospheric oxygen under warmer conditions and on exposure to light. It occurs mostly in the form of cinnamic acid esters (see cinnamic acid) in storax (oil), peru balsam, cinnamon leaf, narcissus, and hyacinth oils. 

Cinnamic acid, 3-phenyl propyl ester. See 3-Phenylpropyl cinnamate Cinnamic alcohol. SeeCinnamyl alcohol, Cinnamic aldehyde. See Cinnamal Cinnamic aldehyde ethylene glycol acetal. See Cinnamaldehyde ethylene glycol acetal Cinnamic chloride. See Cinnamoyl chloride Cinnamol. See Styrene Cinnamomum camphora. See Camphor Cinnamomum camphora oil. See Camphor (Cinnamomum camphora) oii Cinnamomum cassia. See Cinnamon (Cinnamomum cassia) extract Cinnamon (Cinnamomum cassia) Cinnamon (Cinnamomum cassia) oii... 

Synonyms Butanoic acid, 3-methyl-, 3-phenyl-2-propenyl ester Cinnamyl 3-methyl butyrate Isovaleric acid, cinnamyl ester 3-Methylbutanoic acid 3-phenyl-2-propenyl ester 3-Phenylallyl isovalerate 3-Phenylallyl 3-methylbutanoate 3-Phenyl-2-propenyl 3-methylbutanoate Definition Obtained by esterification of cinnamic alcohol with isovaleric acid Empiricai C14H18O2... 

Other minor components characterized include tocopherols (90 mg/kg), triterpenol alcohols and cinnamic acid esters, sterols and 4-methylsterols. These are characteristic of the oil (Derbesy and Richert, 1979 Peers, 1977 Itoh et al, 1974). The major triterpene alcohols are a- and jS-amyrin, butyrospermol and lupeol. The major sterols are a-spinasterol, previously confused with )8-sito-sterol and A7-stigmasterol (Derbesy and Richert, 1979 Itoh era/., 1974). (Tables 3.145-3.147). 

Different organic groups have been used in synthetic perfumes hydrocarbons, terpenes, sesquiterpenes, alcohols (dtronelol, geraniol, cinnamic alcohol), fenols (p-cresol, thymol), aldehydes (cuminaldehyde, vanillin), ketones (carvone, muscone, ionones, metilion-ones), lactones (nonalactone, undecalactone), esters (acetates, formates, butyrates), nitrogen compounds (indol, methyl anthranilate, musk xylol, quinoHnes). 

In nature, terpenoids are found to occur both in free and combined states. Most of the terpenoids that are not highly functionalized occur free. Carboxylic acids invariably occur in a free state, though occasional occurrence of methyl and other esters is known. Alcohols often occur both in the free state and as esters, in which the acid moiety is usually a simple aliphatic acid (e.g., acetic, tiglic, angelic, etc.) or less often an aromatic acid (e.g., benzoic, cinnamic), though esters... 

This oil consists principally of benzyl cinnamate and benzyl benzoate, with a small amount of free benzoic and cinnamic acids. Dihydro-benzoic acid is also probably present in the form of esters. Cinnamic alcohol, vanillin, and farnesol are also present in very small amoilnt. 

The principal odorous constituent of the oil is styrol, or phenylethy-lene OgHj. CH. - CH, an optically inactive hydrocarbon boiling at 146. The cinnamic acid esters of ethyl, benzyl, phenyl-propyl, and cinnamyl alcohols are also present, as well as the free alcohols, and traces of vanillin. 

The typical constituents are cinnamic alcohol and esters of cinnamic acid, such as methyl and ethyl cinnamate. Styrax oil, steam-distilled from styrax balsam, is a pale yellow to almost water-white viscous liquid with a similar odor profile to s., except for greater diffusion and a more floral-spicy note. Both products are used in floral (jasmine, hyacinth, lilac) notes and in floral-oriental ( odor description) fragrances as booster and as a pleasant addition to the drydown (->odor description) notes. 

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