Dollars from Scents MARIAN DRAKE HALL Industry Analysis Section, Ofice of Domestic Commerce
W h m the war made impoaible thc importation qf thrcc-fourthj of the usual supplizs qf cs~cntialoils, it war ound that t h i d&icncy ~ could be made up from various ~cctionrd o u r own country. The ewntial-oil industry modc use qf oils from oranges, lcmonr and grapefruit, pepprrmmt, ~pcarminf,ccdnr, msmfrar, and birch fo supply mw materials fo manufadurers qf perfume, c o ~ m c t i u soap , food, and medicine. The current annual value qf the cs~entialoiLr from domestic m w products L w t i m a t ~ dat $20,000,000. Agricultural schools and colleges arc conducting experimental program in the cultivation q f f i w e r r and shrubrfor the production qfe.wntia1 oils.
A WHIFF .
of some floral-scented perfume often brings t o mrnd the flowers of southern France. Italy, or Spaintraditional sources of essential oils. However, when three-fourths of the usual supplies of essential oils were cut off hy wartime trade dislocations, the essential-oil industry in the United States really came into its own. Oranges, lemons, and grapefruit from California and Florida; peppermint and spearmint from the Middle West; cedar, sassafras, and birch trees from Maine to Florida--dl these helped to fill the raw-material shelves of the manufacturers of perfumes, cosmetics, soap, foods, and medicine, Formerly, these manufacturers were largely dependent upon imports for aromas and flavors, Reliable trade sources estimate a t $20,000,000 the current annual value of essential ails from domestic raw products. In 1939, the value of essential oils distilled in the United States from both domestic and imported basic materials was only $9,800,000. United States orange and lemon oils were offered in the 1920's after special interest was aroused by the dwindling imports of Italian citrus oils during World War I. In 1937 somewhat more than half the consumption of oil of sweet orange in the United States was met by domestic output, hut after the war began, California and Florida geared their well-organized orange-gming industry to a productive capacity capable of supplying the entire home market for the oil. Recent estimates place the annual yield of oil of sweet orange a t about 700,000 €0 800.000 pounds. Of this amount, Florida furnishes approximately 250.000 pounds and California accounts for the remainder. Although the hulk of oil of sweet orange is cold-pressed in machine-equipped factories, small quantities are distilled on the west coast from the residue left after cold-pressing. This type of oilis sold separately. Even more important than sweet-orange oil is oil of lemon, produced entirely in California. Since 1939 apparent annual output has ranged from ahaut 700,000 pounds to as much as 1,700,000 pounds. Furnishing about two-thirds of domestic demand in 1937, California expanded its production during the war to satisfy total requirements. Oil of lemon also is cold-pressed. . Other citrus fruits yielding aromatic by-products are grapefruit and lime. Lime ail, processed only in limited quantities in the United States. is made entirely in the Florida Keys. In 1944-45 production dropped to 475 pounds, from 1060 pounds in the preceding year. Florida grapefruit gives us most of our grapefruit oil, annual production of which averages about 50,000 poundsobtained throueh cold-oressine. I x ~ n o ndrops and oranKs ' pup" are only two of the well-known fmgl products flavored with citrus oils. Gelatin desserts, bakery goods, powdered cornstarch pudding, lotions, a n d perfume banquets may also contain oils from lemons, oranges, limes, or grapefruit. A popular aromatic ingredient in perfumes and cosmetics, orange ail is used in even larger quantities for flavoring tobacco. Although the resumption of imports of citrus oils from
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Italy may provide competition for United Starer products domestic output-particularly of orange and lemon o i l s i s now established on a h basis. The woods of our northeastern and southeastern states provide us with another source of fragrant oils-the cedar tree. From the leaves of the white cedar in northern New York State and Vermont cedarleaf oil or oil of thuja is distilled. Annual production in 1944 was estimated a t 75,000 to 100,000 pounds. much of it compounded in perfumes. The red cedars of Florida, the Carolinas, Georgia, Tennessee, and Virginia yield another aromatic product, oil of cedarwood. Some of this oil, very similar t o the cedarleaf type, is distilled from waste farmed during the manufacture of pencils, hut most of it is made from regular distillation of the chips of the red-care wood. Output of this commodity reaches 200,000 pounds yearly, an amount adequate far domestic needs. Both cedarleaf and cedarwwd oils are lowcost "country" oils brought to the market hv manv small farmers who Droduce it as a side line. Cedarwood ail is employed in many perfumes, being valuable in the heavier types. Because it is relatively inexpensive, cedarwood oil is used extensively in soaps. Such prosaic household items as mothballs, fly sprays, and shoe polish are scented with this oil. From our southern states comes oil of pine, derived from the hvpentiue industry, which in turn yields terpineol, a synthetic lilac. Pine oil is used in insecticides and medicinal preparations, while terpineol is employed in lilac formulas and as an adjuvant in a great many other types of perfume odors. It is used especially in soaps because of its law price and pleasing odor. From the sassafras trkind of laurel-sassafras oil is produced in homemade stills on the east coast from Maine to Florida and in the hills of Kentucky and the rolling country of Ohio. Beverages of the root-beer type, such as sarsaparilla, and candies, chewing gum, mouthwashes, and toothpastes are flavored with oil of sassafras. Soaps and perfumes also are often compounded with this oil. The United States produces ahaut 25,000 pounds of the oil each year, according to trade sources. Other products of the woods are ails of sweet birch, spruce, and hemlock-the first coming from Pennsylvania and North Carolina, and the other two from the farming and lumbering areas of the region from the Great Lakes east t o the Atlantic coast and south to Virginia. Small operators process these oils in crude distilleries and then sell them. In 1944 production of oil of sweet hirch was placed a t 10,000 pounds, while spruce and hemlock together total 50,000 pounds. The uses of sweet-birch oil are similar to those of oil of sassafras. Spruce and hemlock oils give a woodsy tank t o perfumes and toilet preparations. Kalamazoo, Michigan, has the largest peppermint distillery in the world. The principal variety of peppermint in the United States is Mentha piperika, grown for the most part on the black velvet muckland of northern Indiana and southern Michigan. Oregon and Washington also contribute to the domestic supplies of peppermint ail. Some successful attempts have been made to raise the Japanese type, Menlha amensis, in California. Production of peppermint oil in 1945is estimated to have been 1,603,000 pounds, an increase of 31 per cent over the 1944 figure. The area under cultivation in 1945 totaled 47,660 acres, the largest proportion-19,500 acres-being in Indiana. Some 42,880 acres were cultivated in 1944, of which 17,700 acres were planted in Indiana. Another familiar mint oil is that of spearmint. highly publicized in the development of the chewing-gum industry. Michi-
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JOURNAL OF CHEMICAL EDUCATION
gan and Indiana are the centers of the cultivation of Mentha viridis and Mentha spkata, the most important varieties of spearmint plants whose leaves and flowering tops, when distilled, yield oil of spearmint. The 1945production of spearmint oil amounted
to 312,000 pounds, a gain of more than one-third over the preceding year's total. I n 1945 about 8600 acres were devoted to spearmint, compared with 7700 in 1944. Spearmint oil is also used t o flavor dentifrices, medicinals, andcandies.
THE SIGNIFICANCE OF STEROLS IN FOODSTUFFS
We commonly associate starch, sugar, fat protein, and mineral matter as the chief components of foodstuffs that enterinmetaholism processes of animal and vegetable life. There are, however, certain other substances, related t o each other, of a complex nature that prove t o be vital and indispensable factors in animal metabolism, and those are sterols and bile acids. The sterols in general are water-insoluble solid alcohols, of quite high melting points. The name sterol is derived from stereos, the Greek word for solid, and the ending "01" denotes an alcoholic OH group in the chemical structure. The term sterol is prefaced by another term when i t is desired t o denote the ljnd of sterol; for example, prefaced by the Greek word, chole, meaning bile, as in cholesterol. Cholesterol which is commonly pronounced "cho1'-esterol," has been known since the 18th century as the chief constituent of human gallstones. It is known t o be a common constitutent of the blood, the brain, and nerve tissue. In the late 19th century sterols were isolated from the seeds, pollen, and roots of plants. At first i t was believed that none of the plant sterols would match the composition of the animal sterols. The first of the plant sterols was named pkyto-sterol, the word being derived from the Greek word phyto, meaning plant, and sterol. Soon all plant sterois were referred t o as phyto-sterols. It was shown by A. Windaus, University of Freiburg, early in the 20th century that the phyto-sterol of thecalabat bean and cholesterol were one and the same thing, thus hridging the gap between the sterols of the animal with those of the vegetable kingdom. Yet, still very little of the complex chemical structure of the sterols was known a t the time, and these mysteries were not unfolded until about ten years ago. The determination of these complex structures of the sterols by famous chemists such as Burian, Molinari, Hess. Flury, Salkowski, Klobh, Zellner, Power, Jones, Meakins, King, Ball, Anderson, Heilbron, and oarticularlv Ruzicka. has led to the develo~mentof the ereatest mlvances in t h e i,iochernical T.elcl. ' l l c structure of the srerolr now hccatnes comparntively sirnplc and hasi: fur the dcterminztion of the more complex structures of the hormones, some of the vitamins, and the sepogenins. Sterols are often associated with fats and oils, and there are apout 50 different ones recorded as existing in nature. The natural sterols are sometimes referred t o as metasterols, to distinguish them from those made synthetically. There are hundreds of svnthetic ones. few of which are of ohvsioloeical value.
point of 160°C., and is called faemsterol. There exist optically inactive forms in the colocynth apple and in pumpkin seed. Of themetasterols that have 29 instead of 27 carbon atoms with the formula GH.0, the most important is sitosterpl, the term heing derived from the Greek, sito, meaning grain, and sterol. A very pure form may be prepared from barley rootlets by saponifying the ether extracted fatty substance and removing the sitosterol by petroleum ether and recrystallizing from alcohol. Sitosteral is found in soybean oil, rape seed oil, sunflower oil, pine ail, corn ail, in scopola root, and cinchona hark. The sitosterol of the latter goes under the name of cinchol. The sitosterols usually have a laevorotary power of about 33, and a melting point qf 139°C. They have one conjugated double carbon hand. There are others which have two conjugated double bonds, giv!ng the formula G H t s O . One such compound in ostreasterol whxh was isolated from the oyster and other mollusks. It has been found that man does not ingest the ordinary plant sterols. They are just so much waste going through his system. Man manufactures his own sterols from the sugars or related principles with slight exceptions. One exception is ostreasterol, making shellfish such as oysters popular as an article of diet. Stigmasterol. almost identical in chemical composition to ortreasterol is found in rice bran, alfalfa seed, soybean and sugar cane wax, but in smaller amounts than the metasterol of gastropods. Fucorterol of algae is quite similar to stigmasterol. A sterol with twodouble conjugated bonds. GIHuO, is zynrorterol, obtained from yeast. This, however, has a dextrorotary power of +37 and a melting point of 1 3 6 T . Wheat germ oil contains a double bonded sterol of 30 carbon atoms, known as tritirterol, CsoHsnO. There are but few sterols with three conjugated double bonds, the one of most significance heing ergosterol, GaH4.0, which has a highlaevorotary power, -133. and a melting point of 163 It is found in ergot and is the chief sterol in yeast. Peculiarly the snail and earth worm contain i t also. Ergosterol provides a source of vitamin D as will he later explained. One of the most important vitamins, as we already know, is "vitamin D." The individual members of the group are Dz. Ds, Dc etc. Vitamin D2 is called "calciferol" in England, and has been given the name "viosterol" in America. I t is an antirachitic vitamin. I n 1822, Trousseau recommended cod-liver oil as a remedy far the cure of rickets, and Sniadecki wrote on the irradiated comoound that can be readilv absorbed bv the in-
jambul seed, soybeans cotton oil, linseed oil, walnut oil, corn oil, in linden tree wood, musk root, cone-flower root, etc., always in the loeuo form, an optical form which turns a beam of polarized light to the left. the same as is true of cholesterol. There are, however, some very slight differences between the phyto-sterol and cholesterol. The former shows about a -34 angle deflection and the latter a -38 deflection. The melting point of the former is about,l40"C., and the latter 150°C. Recently i t has been shown that the plant sterols have several components of slightly different configuration in their chemical strnctwe, and this may well explain the slight differences referred to. All of the aforementioned sterols have the constitutional formula CprHlsO also written CnrH4s(OH) t o show that the compounds are alcohols. The right-handed optical form of the same phytosteral is found in yeast fat. It has a dextrorotary power of f42, a melting
provitamin. How much provitamin or specific sterol is found in animal and vegetable material? In the vertebrates the various organs cantain less than 0.2 per cent. Peculiarly chicken feet do contain several per cent. The invertebrates such as shellfish contain over 4 per cent. I n fact, mussels contain 9 to 10 per cent and make a good source for producing through irradiation another curative effect of sunlight. I t was not until 1925 that it was found that the sterol fraction of foodstuffs could be made antirachitically active by irradiation by sunlight or ultraviolet light although it was not active itself. These discoveries were made by Hess and several other workers in the field. It was McCullum who named the antirachitic material "vitamin D." Metasterols that are the source of making the vitamins D are given the name provitemins. E?gostwol is a provitamin and can
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beackvated by ultraviolet light to become vitamin Dn. Ergosterol, t o hegin with, is extracted from yeast as the yeast microorganism manufactures i t in substantially large quantities. A sterol t o answer the requirements of a provitamin must have the OH group in the 3-position, and two conjugated double bonds that are in the 5.6 and 7,s positions. What the ultraviolet light does to produce vitamin D is t o break the methyl group a t 10-position, and bridge the 9,10 position with a C = H 2 group. It is only the vitamin D, although much of the sterol content is really active in the beginning. Plants usually contain a fraction of one per cent of provitamins with but few sources available for the production of vitamins. Periwinkles can be used to produce a periwinkle vitamin D. Vitamins A, B, and C are entirely different compounds, bearing no relation t o vitamin D except, again, the provitamin A must be converted t o vitamin A or a t least assisted
by irradiated provitamin D to make i t readily ingested by the human. Vegetables and fruits when first withdrawn from sun expwure do have much of the provitamin A content already naturally irradiated although it is small in amount. The quantity of vitamin D of any kind in most fresh green vegetables is exceedingly small, since the phytosterols present are not of'the provitamin classification. All vitamins D have the same constitution with the exception of differentstructures of the side chain. Much is still unknown concerning the exact differences in behavior between some of the provitamins and their related vitamins, and these seem linked up with the degree of resonance produced by compounds that have all of the carbon atoms of the tetracyclic structure fully saturated with hydrogen atoms. Eventually such differences will become well understood.-Reprinted from the C r o m (June, 1916).
SPEED
The Englishman and the Chinaman ran helter-skelter down the escalator, crashed their way through a mass of people leaving an underground train, and dashed, hot and dishevelled, through the closing door. As they flung themselves into a seat, the Englishman said, "There. We've saved two minutes by that." "Good," said the Chinaman, "what shall we do with them?" This ancient story of the different views on hurry of eastem and western mentalities came inevitably and unbidden to our mind when, the other day, we took a busman's holiday t o hear Major Halford, chairman and managing director of De Havilland, speak upon the subject of "Jet Propulsion." The chair was taken by no less a person than Air Commodore Whittle. The kings of speed were assembled and seemed not a whit surprised by what they heard. I t is not so very long ago since any form of human travel a t speeds over 100 miles an hour seemed enormous; 150 miles an hour was outside the bounds of imagination. Yet a "ear am. when Air Commodore Whittle flew into his home
really trying." Major Halford already has designs for a transoceanic passenger machine holding 50 people t o cross the Atlantic a t 6000 m.p.h. It will take less time t o travel from London to New York than i t did 40 years ago from London to Paris. Six of these passenger machines, costing together about 3,000,000 pounds, could take each year, without hurrying themselves t o change round quickly, as many passengers as the Queen Mary, costing perhaps four times as much today. Moreover, because the plane would fly sufficiently high to he out of theweather and in rarefied air, and because of its quick change-round, the passenger fares would be less for this high speed than a t present for air travel a t today's speeds. Jet propulsion, there can be no doubt, has brought upon us a complete revolution in travel. I t has brought countries nearer t o each other. I t has increased their risks in war. I t has increased their contacts in peace. We shall have to adjust ourselves t o a world in which speeds are normal that were undreamed of in our youth. Whether that is a good thing or a bad one we forbear t o argue; it is a fact that we have to face. The human heing will adapt himself t o the changed conditions. That in itself is rather a wonderful thing. For eons Nature has been adapting her children slowly through the ways of evolution t o changed environments. Now, within the short space of less than a lifetime, the human race can adapt itself to a tempo of life which would have seemed impossible a century ago. Nor, strangely enough, has our span of life been shortened by the speed a t which we live. We crowd far more into the day than our ancestors could possibly have done. Verily. we live! Yet the human frame does not wear out more quickly; on the contrary, our expectation of life has increased.
What is the explanation? Is it not in the application of science? Not the application of a particular science, but the continued advance of science all along the front. Without advances in medical science we could not have taken advantage of the advances in physical science that have enabled us t o live fuller lives-to save our two minutes here and there, t o crowd so much mare into the day's work and play. All the sciences help us to live more dangerously, more adventurously, "to fill the unforgiving minute with 60 seconds' worth of distance run." I t has become a condition of survival, in this turbulent and hurrying age, that the production of goods should be speeded up t o the same extent as the jet propulsion experts are speeding up air transport. To accomplish that increased rate of production is the function of modern management and of modern industrial science. There is no room for the slow, for the slacker, in these days of speed. Those who remember the spacious life of 50 years ago, when we kept business appointments by train or drove t o them in a horsed cab-ome of us walked and that hzlped t o keep us fitl-will understand the contrast between the "naughty nineties" and the "ferocious forties" in which we live today. Those who have never known the more leisurely days of the Victorians, a t once more gracious and more squalid, cannot fully understand the change; and that in itself is a tribute to the resilience of the human body and the human mind. But, what shall we do with the two minutes we have saved by our rush and bustle? One answer is that we shall use it t o do some more work. That is the very general reply and the usual oractice. In itself. however. i t means that leisure when it comes must also be put t o good use. "To live remains an art," a philosopher has told us, "an art which everyone must learn and which no one can teach." If science shows us how t o bustle, compels us t o Live a t high pressure, and enables us to do s-high pressures being the fashion today in chemistry and as in life-it is the arts which show us how to use our leisure. Leisure and contemplation have gone out of fashion, hut there is much to he said for using in this way some a t least of the two minutes we save by hustling. We recollect words written hy Sir James Fraser while he was a professor a t Cambridge University: "The windows of my study look on to the tranquil court of an ancient college, where . Here, if the sundial marks the silent passage of the hours. anywhere, remote from the tumult and battle of the world, with its pomps and vanities and ambitions, the student may hope t o hear the still voice of truth, t o penetrate through the little transitory questions of the hour t o the realities which abide, while generations come and go." Without a breathing space for contemplation and quiet thought, all our modern speed ends in heating the air.
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-Reprinted
from The Chemical Age
