Cinnamic acid storax

The principal constituent of storax is cinnamic acid and for laboratory purposes styrene is still most easily obtained in high purity but dry distillation of cinnamic acid and its salts under atmospheric pressure (Figure 16.1). 

It is a very aromatic oil, useful in some bouquets, and is found naturally in storax and other balsamic substances. It is prepared by various methods, amongst them being the heating of cinnamic acid with lime to 200°. It is a colourless, highly refractive liquid having the following characters —... 

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. 

Ethyl Cinnamate.—The cinnamic ester of ethyl alcohol is a natural constituent of a few essential oils, including camphor oil and storax. It is formed synthetically by condensing cinnamic acid and ethyl alcohol by dry hydrochloric acid gas. It has a soft and sweet odour, and is particularly suitable for blending in soap perfumes. It is an oil at ordinary temperatures, melting at 12°, and boiling at 271°. Its specific gravity is 1 0546, and its refractive index 1 5590. 

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 —... 

Storax resin is extracted from Liquidambar orientalis (Hammamelidiaceae) and Altingia and its major components are cinnamyl cinnamate and 3-phenylpropanyl cinnamate, with significant amounts of benzoic and cinnamic acids, and 3-phenylpropanol and cinnamyl alcohols [130,131]. The volatile content is very low and triterpenes (oleanonic and 3-epioleanolic acids and liquid ambronovic acid) have also been observed [130,132]. 

N.A. Liquidambar orientalis Mill. L. styraciflua L. Levant storax cinnamic acid, cinnamyl cinnamate, phenylprepyl cinnamate, triterpene acid.99 Internally for strokes, infantile convulsions, coma, heart disease, and pruritus. 

Ethyl dnnamate occurs in small amounts in storax.1 It has been prepared by the action of ethyl alcohol on cinnamic acid in the presence of dry hydrochloric or sulfuric acid 2 by the distillation of the copper salt of the monoethyl ester of benzylidene oxalacetic acid3 and by the condensation of ethyl acetate and benzaldehyde in the presence of sodium.4 The method described in the procedure is a slight modification of the one originally described by Claisen.5... 

St3rrene, Phenyl Ethylene.— The first of these hydrocarbons is known as st3rrene. It is obtained from storax a resin found in the plant, Styrax officinalis. It is also present in coal tar. It is related to, and also prepared from, cinnamic acid, an important acid to be considered later. Styrene is a liquid boiling at 140 . Its constitution is proven by its synthesis from benzene and ethylene when a mixture of the two compounds is passed through a red hot tube. 

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. 

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. 

Styrene was first reported by Neuman in the late eighteenth century from storax. Storax is a balsam derived from the trees of Liquamber orientalis which are native to Asia Minor. His experiments were confirmed years later. In 1839 Simon named the product "styrol" and noted that after a few months it became jellylike. In 1841 Gerhardt and Cahours arrived at the correct formula, CgHg, and prepared the dibromlde derivative. In 1845 Blyth and Hofmann confirmed that a solid mass resulted when styrene was heated. Additional work was done in which styrene was prepared from cinnamic acid by decarboxylation. In 1866 Berthelot prepared styrene from the reaction of benzene and ethylene in a hot tube. Thus, at the turn of the century the following chemistry was known ... 

Styrene, CeHs.CH = CH2, phenylethylene, or styrole, derives its name from its occurrence in storax. It can be prepared by methods which are indicated by its structure. The hydrocarbon bears the same relation to cinnamic acid, C6H5CH = CHC00H, that benzene bears to benzoic acid. It can be prepared by heating sodium cinnamate with sodium hydroxide, or by simply distilling the free acid —... 

Cinnamyl Alcohol, CeHs.CH =CH.CH20H, may be taken as an example of the unsaturated aromatic alcohols. It occurs in storax as the ester of cinnamic acid, CeHsCH = CHCOOH. It crystallizes in needles, which possess an odor like that of hyacinths, melts at 33°, and boils at 254°. 

Cinnamic Acid, C6H5.CH = CH.COOH, is the most important member of the class of unsaturated aromatic acids. It occurs in oil of cinnamon, the balsams of Peru and Tolu, gum-benzoin, storax, and the leaves, of certain plants. The acid crystallizes from hot water, melts at 134°, and boils with partial decomposition at 300°. 

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. 

Hydrocinnamyl alcohol (3-phenyl-1-propanol). H5C6-CH2-CH2-CH2OH, C9H.20, Mr 136.19. Liquid with a pleasantly sweet, reseda-like odor, bp. 253 °C, bp. 119°C (1.6 kPa), soluble in water and alcohol. H. esteriiied with cinnamic acid occurs in benzoin gum, peru balsam and storax. H. is used in many fragrances. 

Phenylethyl isothiocyanate see mustard oils. 3-Phenyl-l-pro >anol see hydrocinnamyl alcohol. 3-Ptienylpropyl cinnamate see storax (oil). Phenylpyruvic acid (2-oxo-3-phenylpropanoic acid). 

Properties Dk. brn. vise, liq., pleasant vanilla odor sol. in fixed oils si. sol. in propylene glycol insol. in water, glycerin dens. 1.150-1.170 Toxicology LD50 (oral, rat) > 5 g/kg, (skin, rabbit) >10 g/kg low toxicity by ing. and skin contact skin irritant mild allergen can cause contact dermatitis and stuffy nose common sensitizer may cross react with benzoin, rosin, benzoic acid, benzyl alcohol, cinnamic acid, essential oils, storax, etc. TSCA listed Precaution Combustible when heated Hazardous Decomp. Prods. Heated to decomp., emits acrid smoke and irritating fumes... 

Styrene and its polymers deserve a special place in polymer science history. The polymerization of a liquid obtained by Simon by the pyrolysis of storax in 1839 was the first recoiled polymerization of a vinyl monomer (1). Since he confused the polymer with an oxidation product, he called it styrene oxide. Blythe and Hofmann (2) suggested the name meta-styrol and Kopp (3) showed that this product and cinnanol, obtained by the distillation of cinnamic acid to be identical. Erlenmeyer (4) described this product as vinyl benzene. 

Storax oil, american Liquidambar styraciflua Balsam WD Esters of cinnamic acid... 

American storax and Levant storax are reported to contain similar constituents in highly variable concentrations, including free cinnamic acid (5-15%), 5-10% styracin (cinna-myl cinnamate), about 10% phenylpropyl cinnamate, a resin (storesin) consisting of triterpenic acids (oleanolic and 3-epioleanolic acids) and their cinnamic acid esters, and a volatile oil. The volatile oil present in Levant storax is usually less than 1%, but that in American storax has been reported to range from less than 7% to over 20% (arctander ... 

Andrew lire s Dictionary of Chemistry and Minerology of 1831 lists Storax as the resinous exudate of the Sweetgum (Liquidambar) tree [19]. The sweet fragrance is due to cinnamic acid. When pure cinnamic acid is heated in a steam distillation it readily decarboxylates to yield styrene. 

Benzyl Alcohol, NF. Ben/yl alcohol (phenylcarbinol. phenylmethanol) occurs naturally as the unesteriried form in oil of jasmine and in esters of acetic, cinnamic, and benzoic acids in gum benzoin,. storax re.sin. Peru balsam, tolu balsam, and some volatile oils. It is. soluble in water and alcohol and is a clear liquid with an aromatic odor. 

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