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MENVOL AND THE DESIGN OF MENTbWLATED CIGARETTES COURSE Module 1. Menthol and Mint Flavor Additives - General History and Applications , OUTLINE - I~ Introduction of Topics for Diacuaaion A. Mints/Menthol in History B. Mint as a Taste 1. Mentha arvensis. (a). Dementholated M. arvensis Oil '2. Mentba piperita (a). Dementholated M. piperita Oil C. The Mint/Menthol Market D. M. arvensis vs. M.•piperita Oils E. Coaiposition of Peppermint Oil II. Sumsa III. Bibliopraphy

Madt'.1a 1. Menthol and Mint Fibvor Additives - General History and Applicatious Menthol can be obtained from natural products (Mentha species) or it can be syn- thesised: This section will describe the history of the Mentha species, the characteristics of the dementholated oil fraction from these species, their -econooic-i.portance and commercial value, differences between--the major types of peppermint oils (in terms of flavor profiles and chemical composition), the role that menthol has played as an important by-product from these Mentha species, and how synthetic menthol has stabilized the world market for peppermint oil and natural menthol. A. Mints/Menthol in History Menthol is the major by-product of the Mentha species which has been used since the beginning of recorded history. Forr example, the remains of Mentha species have been found in $eYPtian graves. It has also been described in ancient Chinese literature. Historioally,- the YAntha species was used as herbs for coo]cinQ and in preparations for illnesses. Today, Mentha arven- sis and Mentha piperita are the primary mint species in use. From tLse sources, peppermint oils and menthol are extracted and used in a wide variety of commercial products. Figure 1 Peppermint Oils Menthol H&R is recommended for use in the following types of products at the dosage ranges dsted below. Dosage Drugs 0.1% Compresses 0.1-0.2% Medicated oifs' 2.0-4.0 96 Analgesic balms 2.0-3.0 96 Rubbing akohol 1.0-1.2 96 Toothpaste• 0.5 96 Mouthwashes• 1.0-2.0% oraf sprays' 0.3 96 Regular Cigarettes 0.03% Menthol Cigarettes Pipe Tobacco 0.196-0.2 % weak effect 0.2 %-0.45 % strong effect 0.3 96 chewinp Tobacco 0.05 96-0.196 Chewing Gum' 0.5% Hard candies' 0.05 96-0.196 Cough Drops' 0.1% Lozenges' 0.1% Licorice• 0.05 96-0.196 Lotions 0.05% Pre-shave Lotlons' 02-0.3 96 Handkerchiefs' 0.1-02 96 Foot Sprays• 0.5% Shampoo 0.2-0.5 96 Refreshing Towels 1.0 96 Cooling Gels_ 1.0% Menthol H&R and its derivates can also be added to various peppermint type compositions to enhance the cooling and freshening effects. - in addiaon to Peppermint Oils and compounds -4- Suggested Uses Pharmaceutical Products Oral Products Tobacco Goods Confectionary Goods Perfumed Products

B. Mint as a Taste(1) The desire for mint (especially peppermint) as a flavorant was originally , an English phenomenon. . The Mentha piperita plant was first cultivated in Mitcham, a town southeast of London. From Mitcham, use of this oil as a flavorant spread throughout all English-speaking overseas countries, e.g., Australia, South Africa, and the IInited States. 0n- the--Europeaa---contiaent, the taste for mint is still---relatively underdeveloped in comparison with its use in England and the United States, however, in recent years it has increased in popularity. In numerous other countriev-:throughout the world, mint is making significant gains in popularity as incomes of populations increase. In the Near East, for example, such traditional taste trends as lemon and li.e now frequently also incorporate a mint component. Today, mint (both peppermint andd apearmint) represents the third largest taste trend worldwide. It is surpassed oaly by vanilla and citrus. As opposed to many other taste trends, mint appeals to all consumer Voups, irrespective of age, sex, and ethnic background. Yet the popularity of mint is based not only on its pleasant taste and easy digestibility, but also on its increasing association with freshness, cleanliness, and hygiene. 1. Mentha arvensis As a result of its high menthol content (approximately 70-80% L-menthol), the crude oil is always used as the raw material for extraction of menthol. Only after the L-menthol has been partially frozen out of Mentha arvensis is the "residual" oil offered in the form of "dementholated peppermint oil" which has a menthol content of 4S-S0%. la. Dementholated M. arvensis Oil For many years, Brazil was the major supplier of Mentha arvensis. In 1970, Brazil produced a peak output of over 3,000 tons. As a result of destructive cultivation methods (destructive monoculture) and the resulting decline in areas available for cultivation, production has gradually shifted across the Parana River to Paraguay. However, in 1982, Brazil and Paraguay (although primarily Paraguay) produced only one tenth of the 1970 production level, i.e., somewhat more than 300 tons. Land which is suitable for the cultivation of peppermint is disappearing and arable land will eventually be required for products having greater economic value. Therefore, the mint oil industry is increasingly of the opinion that "Brazilian Mentha arvensis" will be a thing of the past in a few years. In the meantime, China has become the largest supplier of M. arvensis oil, with a reported annual production level of up to 2,000 tons of dementholated oil. However, the oil produced in China differs considerably from the South American product because of different climatic conditions and inherent differences in the nature of the oil. The Chinese oil has more earthy, .ushroomy, and bitter notes. This shift from South America to China is thus .posing major difficulties in terms of quality as well as availability and price for the traditional user market. -5-

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The homeland and major supplier of M. piperita oils is North America. The main production territories are located in the Midwest (i.e., the states of Indiana, Michigan, and Wisconsin) and in the Northwest (i.e., Oregon, Washington, and . Idaho). - The North American M. piperita crops are cultivated by ultramodern agricultural methods unlike the cultivation methods for M. arvensis in South America. Therefore, M._piperita oils are relatively expensive. 2a. Dementholated M. piperita Oils In 1982, total production of M. piperita oils in the United States amounted to approximately 1800 tons. (This was slightly lower than in previous years). M. piperita oils from the United States and other smaller producing countries such as Italy, France, and Bulgaria are not employed for the production of menthol because their menthol content is only 4S-S0x. In 1982, the total production of- M. piperita oils and dementholated M. arvensis oils was approximately 4500 tons. Including the addition of other flavors, these oils were used to compound an estimated 9000 tons of mint flavorings worldwide. ?he_main applications for mint are in oral hygiene products (57%), chewing gum (35%), and other confectionaries (8%). Figure 4 ApOication of Mint flavours 0 -7-

The use of L-menthol as a single flavor or in conjLinction with mint oils ' comprises an even' larger market segment, approximately 5,000-6,000 tons. Currently, menthol is widely used in pharmaceutical, oral, -tobacco, eoafeetionary, and perfumed(~Foducts. (See Hd~A Bulletin oa~ Menthol, for suggested uses and dosaBes). 1. D. M. arvensis vs. M. piperita Oils M.-arvensis -aad M. piperita oils produce'different characteristic flavor profiles. The taste profile of M. arvensis oils is characterised by pronounced earthy, mushroomy, phenolic, and bitter notes. However, positive taste characteristics such as i.pact, freshness, taste.volu.e (fullness), ete., are lower in M. arvensis oils. Soaie of these differences can be corrected, however, the correction is very limited. Therefore, M. arvensis oils are used merely as extenders for M. piperita oils. M. piperita oils are significantly higher in quality and are therefore more valuable. Their flavor is sweeter and more well rounded. The tea and herbal components are more pronounced and produce a fullness of taste. Their impression of freshness, and.thus their cooling effect'and i.pact, is more intense than the dementholated oils of M.*arvensis. Figure 5 TL of sW nV 7I 1 sdtsion NPlow~h N MWnt.

In most cases, rectified oils or "blends" of both M. arvensis and M. piperita are actually employed. Although the oils ere customarily subfected to a 6-9 Montr, maturing process, both steps are an absolute necessity in order to compensate for fluctuations from harvest to harvest caused by weather conditions. However, blending and particularly the tedious maturing process represent tie-ups of capita~ that few companies can afford. Prices_are_determined by supply_and_demand as well as speculation. Since 1960. fluctuations in the average price of the ma3or.oils has ranged from $2 per pound tc $21 per pound. For many years, L-menthol, the most important component in pepper- mint oils, was subjected to similar fluctuations. This instability did not enc until manufacturers introduced synthetic L-menthol on the market. Since about 1974, the price of L-menthol has steadily decreased to about $5-6 per pound. To- day, production of synthetic L-menthol accounts for nearly one-third of the world's demand and thus simultaneously ensures that the world,.aarket price balances at a more economical and stable level. -9-

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E. Composition of Peppermint Oils .- The largest and most important component of peppermint oil is L-menthol which comprises 43-50% of the oil. It is an optically active substance in which 8 stereoisomers or 4 racemic compounds exist. (The stereoisomers of •enthol will be discussed in a later section). Since all development processes in nature occur in one direction, only one specific form is created in natural peppermint oil, namely L-menthol. FiBure 8 QwnbM OOmDOSdion of PecDertnirrt 01 ,loo oomponwNs WoompaWns "M.ewhoAiran. euaWa, UWa,«y "A«rna

The characteristic flavor of L-menthol is dependent c.n its -conforoation.. Only L-menthol imparts the well known desired cooling effect. (This topic will be discussed further in a later section.) hydrate, piperitone, and pulegone each- account for about 1% of the composition of peppermint oil. Eucalyptol and menthofuran 'are also important to taste. Normally, M. piperita oils contain 1-3% of menthofuran, however, the percentage can reach 10% dependent on the origin of the oils.- (Yakima oils routinely eontain 10% menthofuran.) Menthofuran, while important for reasons of taste, is also known to spoil both the oil and the finished product through oxidation and subsequent discoloration. The stability. of natural oils and thus their shelf life are influenced considerably by oxidation of the, terpene hydrocarbons naturally present. Finally, mint oils contain approximately 2% of other compounds.- It is estimated that there may be as many as 1600 compounds comprising this fraction. It is this fraction that separates reconstructed peppermint oils from naturally obtained peppermint oils. coaprise__10%. The terpenes, alpha and' beta pinene, limonene, sabinene Another 20-25% of peppermint oil is composed of the menthol derivatives menthone and isomenthone. Menthyl, acetate, neomenthol, and isomenthol II. Summary o Mints/menthol have been used since the beginning of recorded history. 0 Historically, mints and menthol were primarily used for herbs in medicine and in cooking. 0 0 0 0 0 0 Two main mints are used today for the production of menthol and for use in industry - Mentha arvensis and Mentha piperita. Menthol is extracted from these two int species. The remaining dementholated oils are used as peppermint oils, although these oils still contain considerable menthol - 20-40%. Main sources of raw mints are Brazil, Paraguay, U. S., Japan, India, and China, although other countries do produce mints at lower levels. Total production of mint oils is approximately 4500"tons. Total production of ¢atural menthol is approximately 3000-4000 tons. Production of synthetic menthol stabilized the mint/menthol market. Current price is approximately $5-6/pound. Composition of mint oils is approximately 50% menLhol, 35% menthol derivatives, approximately 13% comprising 10 components (e.g., menthofuran, eucalyptal, limonene, etc.), and approximately 2% which comprises approximately 1600 other components which are very important to the taste properties/qualities of particular mints from various areas of the world. - -12-