Balsamic acids

Styrax tonkinensis Pierre. S. benzoin Dryand An Xi Xian (Styrax) (leaf) Sumaresinolic acid, coniferyl cinnamate, styracin, vanillin, alpha-phenylpropyl cinnamyl cinnamate, balsamic acid.33-50 As an aromatic stimulant, for aphrodisiac, an astringent. 

Balsamic Acid Spirit spiritus balsamico acidulus. two species) Figure 13.4 From Cartheuser [1754] vol. 4 pp. 7-75. 

The estimation of free and total balsamic acids, due to Cocking, is described under Tolu Balsam (p. 643). In the case of benzoin, the alcoholic... 

The minimum total balsamic acids calculated from those present in the individual drugs should be 3-75 per cent. 

The total balsamic acids should be determined, using 25 ml of tincture it contains theoretically at least T98 per cent w/v. 

Free and total balsamic acids should be determined, using 10 ml of tincture for each assay. Figures obtained experimentally for a series of tinctures from a reliable source showed 7 4 to 9 6 per cent total acids and 3 9 to 5 0 per cent free acids, whilst obviously inferior samples from other sources gave 4 18 to 5 98 per cent and 1 96 to 3 29 per cent for total and free acids respectively the total solids in these latter examples were not low. The minimum total balsamic acids calculated from those present in the individual drugs used in the preparation is 4 6 per cent. 

The B.P. estimation of total balsamic acids is due to Cocking. The acids from the saponified balsams are converted into the corresponding magnesium salts and the salts of the balsamic acids are separated from the salts of the resin acids by filtration and from aromatic alcohols by extraction with sodium bicarbonate. The B.P. quantities directed to be used must be adhered to and the manipulative details must be closely followed to prevent precipitation of gummy matter and formation of clots. 

Cocking used ether for extraction of the purified balsamic acids and this solvent is preferable. Further, the B,P, directs the mixed benzoic and cinnamic acids to be titrated but they should be weighed after drying in zacuo over sulphuric acid as they are present in variable proportions the amount of cinnamic acid present may be determined by bromination,... 

Tolu balsam contains 35 per cent to 50 per cent of total balsamic acids, calculated on the dry alcohol-soluble matter. 

In the original method Cocking included a determination of free balsamic acids ... 

Dissolve 2-5 g of balsam of tolu, or the alcoholic extractive from 2-5 g of benzoin, in 15 ml of hot 95 per cent ethanol in a 300-ml flask. Add all at once a mixture of 10 ml of 5 per cent potassium hydroxide solution and 50 ml of water mix and dilute with 150 ml of water. To the mixture add 2 5 g of magnesium sulphate dissolved in 50 ml of water, and stand the flask on a water-bath for five minutes. Cool, and continue the determination of total balsamic acids as given above. 

Assayed for total balsamic acids by the method given above for balsam of tolu. Prepared storax should contain at least 30 per cent of total balsamic acids calculated on the substance dried on a water-bath for one hour. 

Benzoic acid had been known for several hundred years by the time of Mitscher lich s experiment Many trees exude resinous materials called balsams when cuts are made m their bark Some of these balsams are very fragrant which once made them highly prized articles of commerce especially when the trees that produced them could be found only m exotic faraway lands Gum benzoin is a balsam obtained from a tree that grows m Java and Sumatra Benzoin is a word derived from the Erench equivalent benjoin which in turn comes from the Arabic luban jawi meaning incense from Java Benzoic acid is itself odorless but can easily be isolated from gum benzoin... 

Vanillin is known to cause allergic reactions in people previously sensiti2ed to balsam of Pern, ben2oic acid, orange peel, cinnamon, and clove, but vanillin itself is not an allergic sensiti2er. 

Benzoic acid in the free state, or in the form of simple derivatives such as salts, esters, and amides, is widely distributed in nature. Gum benzoin (from styrax ben in) may contain as much as 20% benzoic acid in the free state or in combinations easily broken up by heating. Acaroid resin (from anthorrhoca haslilis) contains from 4.5 to 7%. Smaller amounts of the free acid are found in natural products including the scent glands of the beaver, the bark of the black cherry tree, cranberries, pmnes, ripe cloves, and oil of anise seed. Pern and Tolu balsams contain benzyl benzoate the latter contains free benzoic acid as well. The urine of herbivorous animals contains a small proportion of the glycine derivative of benzoic acid, hippuric acid [495-69-2] (CgH CONHCH2COOH). So-called natural benzoic acid is not known to be available as an item of commerce. 

Ben /ben ate [120-51-4] CgH COOCH2CgH, mp, 21°C, cff , 1.118 bp, 323—324°C at 101.3 kPa , 1.5681. This is a colorless, oily liquid with a faiat, pleasant aromatic odor and a sharp, burning taste. It occurs naturally iu Pern and Tolu balsams, is spariugly volatile with steam, and is iusoluble iu water. Benzyl benzoate is prepared commercially by the direct esterification of benzoic acid and benzyl alcohol or by reaction of benzyl chloride and sodium benzoate. The pleasant odor of benzyl benzoate, like other benzoic esters, has long been utilized iu the perfume iadustry, where it is employed as a solvent for synthetic musks and as a fixative. It has also been used iu confectionery and chewing gum flavors. 

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. 

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 —... 

When rectified gurjun balsam oil, that is, a mixture of a- and /3-gurjunene, is saturated in ethereal solution with hydrochloric acid gas, and the mixture is left standing for two days at room temperature, and the hydrochloric acid abstracted by heating with sodium acetate, the regenerated sesquiterpene appears to be a bicyclic compound having 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. 

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 —... 

Cinnamic acid Natural balsam, cocoa leaves, cinnamol oil Carlina oxide Carline aeaulis L. 

Although the mass spectra of aged diterpenoid resins are generally not characteristic enough for a clear identification, some natural products show characteristic peaks above m/z 325. These signals can be explained by particular constituents of the respective resins, so-called biomarkers. For example, copaiba balsam shows an intense peak at m/z 385, which can be attributed to 3-acetoxy-copaiferic acid [51] (see Figure 5.11). Another... 

Figure 5.11 GALDI mass spectrum of copaiba balsam. The most intense peak (m/z 385) can be attributed to 3 acetoxy copaiferic acid...

A number of important resins are composed of triterpenoids, including the dammar resins which derive from a sub-family of the family Dipterocarpaceae. Dammar resins are fluid, balsamic oleoresins highly suited for caulking and waterproofing. Frankincense (olibanum) is known as a gum-resin collected from various Boswellia spp. and contains amyrin epimers and triterpenoid acids. The gum component is polysaccharide in origin and is water soluble. The Anacardiaceae family contains the genus Pistacia (Mills and White, 1977 21 Mills and White, 1989). 

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