Natural balsam

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

Acetophenone. Acetophenone [98-86-2] (methyl phenyl ketone) is a colorless Hquid that forms laminar crystals at low temperature (mp 20°C). It has a characteristic sweet orange blossom odor, and is soluble in alcohols and ethers. It is found in nature in oil of casatoreum, obtained from beavers oil of labdanum, recovered from plants and in buds of balsam poplar. It can be prepared by the Friedel-Crafts reaction (qv) of acetyl chloride with benzene in the presence of aluminum chloride however, this route is of Htde commercial significance. 

The function of the essential oil in the plant is not fully understood. Microscopic examination of plant parts that contain the oil sacs readily shows their presence. The odors of flowers are said to act as attractants for insects involved in pollination and thus may aid in preservation and natural selection. Essential oils are almost always bacteriostats and often bacteriocides. Many components of essential oils are chemically active and thus could participate readily in metaboHc reactions. They are sources of plant metaboHc energy, although some chemists have referred to them as waste products of plant metaboHsm. Exudates, which contain essential oils, eg, balsams and resins, act as protective seals against disease or parasites, prevent loss of sap, and are formed readily when the tree tmnks are damaged. 

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. 

Phenyl-2-propen-l-ol [104-54-1], commonly referred to as cinnamyl alcohol, is a colorless crystalline soHd with a sweet balsamic odor that is reminiscent of hyacinth. Its occurrence in nature is widespread as, for example, in Hyacinth absolute (Hyacinthus orientalis) (42), the leaf and bark oils of cinnamon Cinnamomum cassia, Cinnamomum lancium, etc), and Guava fmit [Psidiumguajava L.) (43). In many cases it is also encountered as the ester or in a bound form as the glucoside. 

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 —... 

It appeared that the impure alcohol isolated from balsam of Peru was, in fact, identical with nerolidol. When allowed to stand for three to four weeks with phenyl-isocyanate both alcohols yielded a phenyl-urethane, melting at 37" to 38°. A mixture of the two bodies suffered no depression in melting-point. The alcohols have the formula 15 260-The alcohol from balsam of Peru is therefore mixed with a small quantity -of an alcohol of higher specific gravity, the nature of which is still undetermined. Traces of benzyl alcohol were found in it, but not in sufficient quantity to account for the differences observed. Oxidation experiments did not throw any light on the question. It may therefore be safely assumed that the peruviol of Thoms consisted in the main of nerolidol, but contaminated with a substance of the same boiling-point to such an extent that its combustion figures pointed to the formula CjjH. jO instead of... 

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 —... 

Vanillin, CgHgOj, is one of the most important synthetic perfumes. It is the active odorous ingredient of the vanilla pod, in which it occurs to the extent of about 2 per cent., appearing on the surface of the bean as a fine white crystalline efflorescence. It occurs naturally also in Sumatra benzoin (about 1 per cent.), Siam benzoin (15 per cent.), and the balsams of Tolu and Peru (traces). Numerous other bodies have been recorded as containing it, such as asafoetida, beetroot and asparagus, the seeds of Lupinus albus, the seeds of Sosa canina, etc. 

In his recapitulation Franckenberg enquires as to the nature of the medicine of the wise. Answering himself, he states that it is nothing other than water, powder, or plaster derived from nature, or found by human wit. This water springs from God s Spirit, the Ruach Elohim and operates through God s Word, the name of Jesus, to heal human illness. It is also a balsam, or oil. 

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... 

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