i Urn Cornell University Library SB 411.S27 Rhodologia.A discourse on roses, a^^^^^^ 3 1924 003 062 399 ^tate College of agriculture at Cornell ©nibctsitp JUbata. M. B- ILtl)rari» RHODOLOGIA A DISCOURSE ON ROSES. THE ODOUR OF ROSE. BY J. Ch. SAWER, F.L.S AUTHOK OP " Odobogbaphia.") :il3cigbton : W J. SMITH, 43, NORTH STliBET MDCCGXCIV. A. M. Robinson and Son, Pbintebs, Duke Stbeet, Bbighton ; AND London. PREFACE. By referring to the table of General Contents on the next page, it ■will be perceived that the intention of these few Eose-leaves (culled from plants of many countries) is to interest persons located in some of our Colonies where the climate, etc., is suitable to the development of the Eose. The Eose Industry is capable of great extension, and the demand for the products of this flower is increasing. Details are also given which are intended to interest students, manufacturing chemists, and buyers of rose-products. Statistics of trade, recent discoveries, patents, etc., are, as far as possible, recorded right up to date. Classification and cultural instructions respecting hybrid roses grown for purely ornamental purposes are not here included. That work has already been very ably acco mplished by several eminent authorities who have made it their especial study. Lists of new roses are also given in the Annual Eeports of the National Eose Society and in their Catalogue of Exhibi- tion and Garden Eoses. Brighton, llth Sept., 1894. Cornell University Library The original of tiiis book is in tine Cornell University Library. There are no known copyright restrictions in the United States on the use of the text. http://www.archive.org/details/cu31924003062399 GENERAL CONTENTS Eose enthusiasm, 7 ;— The varieties of perfume in roses, 11;— Capricious nature of the perfume, 12 ;— Glandular formations secreting oleo-resins in the green parts of the plant, ] 3 { Illustrated,) ;— The oU- cells in the petals, 17 (Illustrated) ; — History of the art of distilling roses, 22 ;— The Indian method of distillation, 29 ;— The Eose Industry in Bulgaria, cultivation, distillation, adulteration, and commerce, 31 (Illustrated) ; — Map of the Bulgarian Eose-farming districts, 54 ; — The Eose Industry in Germany, explanatory of the great superiority of the German otto, and reasons of this excellence, 55 ; — The Eose Industry in France, 58;— Physical properties of the otto, tests of purity, chemical constitution, etc., 60 ; — Physical properties of Geraniol, 72 ; — Perfumes somewhat resembling that of the Eose, Geranium, 77 ( nhistrated) ; — Pelargonium cultivation and distillation, 77 ; — Glan- dular formations secreting the oil, 79 (Illustrated) ; — Chemical con- stitution and physical properties of the oil, 81 ; — Tests of purity, 83 ; — Indian Geranium (Grass-oil), 84 ; — Physical properties, and tests of purity, 87 ; — Other sources of geraniol, 88 ; — Other plants yielding a rose-like perfume, 92 ; — Definite chemical compounds possessing a rose-odour, 93. RHODOLOGIA ^,-^ HE great perfection to which rose growers (amateur I r^^ and professional) in England, Belgium and France ^^^ have now brought this magnificent flower is indeed marvellous ; the number of distinct varieties named and cultivated is over 7,000, and with every horticultural exhibition this number is increased to such an extent as to justify the existence in England, France, and Germany of periodical publications exclusively consecrated to the " Queen of Flowers." In fact, there seems to be no end to what rose growers can do in the way of novelty. A leading London paper commenting on a show of the National Eose Society, gives a glowing description of such novelties as the creamy, claret- tipped " Princess of Wales," the shell-white " Hon. Edith Gifford," the ivory Tea-rose " Souvenir de S. A. Prince," the pink-copper "Lady Penzance," and the exquisite double-yellow " Rosa Sulphurea," and remarks : — " What immortality can be more charming than that which is thus conferred by coupling some happy name with a new favourite in the world of roses." Many a London house during the month of June, at the festal hour, is converted into a perfect Gulistan with this most delicate and most delicious of ornamentation. Some of them almost rival the lavish prodigality of ancient times. Cleopatra, according to 8 Athenseus, more than once covered the floor of her dining-hall with roses a cubit thick, and the Emperor Nero expended in one feast as much as iGSO.OOO in roses alone ; while everybody remembers the gorgeous canvas upon which Mr. Alma Tadema delineated Heliogabalus overwhelming his guests with an avalanche of roses showered from above. But the ancient rose lovers never possessed or saw blooms of their favourite flower half so perfect as those which are to-day quite common. They knew next to nothing of the amazing modern variety in the Queen of the Garden — white roses, blush roses, pink roses, pied roses, crimson roses, scarlet roses, vermilion, claret, carmine, purple- striped, and black roses, and roses of burning bronze and silver satin. Many a cottager has to-day upon his wall a " Cloth of Gold " rose such as the Caesars could not have bought for a thousand sesterces; and, beyond question, the finest roses in the world are to be seen in London during the months of June and July. Well is it said by the Dean of Eochester, in his perfectly charming " Book about Eoses,"* that " he who would have beautiful flowers in his garden must have them in his heart." In this work, abounding in information concerning the culture of the choicest specimens of roses, are also to be found many anecdotes of those who have loved roses, and been successful with them (not by any means always the rich or the learned). The very reverend author tells a story of a Nottingham mechanic whose wife, with his entire consent, took a blanket from their insufficiently supplied bed to keep the frost out of the little green-house where they had their rose stocks. He tells us also how, at a June show of the Manchester Botanical Society, £1,100 was paid by the working-classes in single shillings to see the glory of the prize blossoms. Delightful indeed is the enthusiasm to which such a lover of the imperial flower attains ! If once, indeed, a man is bitten with the passion for cultivating high-bred roses, anything like a cure of it is hopeless. The Dean himself confesses that, though he commenced with a * London, 13th Edition. 9 dozen plants only (the first which enslaved him being the "D'Aguesseau Gallica"), he did not become contented when he owned 5,000. Master of many rosy legions, he frankly de- clares that if he had Nottinghamshire full of roses he would still desire to have Derbyshire for a budding-ground. If a grave and pious dignitary of the Church can fall into the splendid horticultural avarice indicated here, laymen may well be warned not to abandon themselves too lightly to the fascinations of the Heve d'Or, La Belle Lyonnaise, or Souvenir de Malmaison. Notwithstanding this great enthusiasm, it seems that both cultivators and admirers of this flower concentrate their whole attention on the development of colour, form, and size, and pay little heed to the great variety of perfumes generated in the beautiful petals. These different odours (although, of course, blended with that of rose) are distinctly recognisable, and are in some cases very marked. The organs of the sense of smell can be trained to the appreciation of perfumes, especially by young persons, as easily as the palate can be trained for business purposes to the tasting of the flavours of wines, tea, or coffee. Of course a taster, sampler, or evaluer of such beverages must naturally be possessed of a finely developed nervous susceptibility to the slight variations occurring in every sample which comes under Ms notice. Such natural perfection of susceptibility is not common, although many possess the gift without being quite aware of it : they may not be in the tea trade or the wine trade, or in any trade at all ; and so the gift is not trained, or even appreciated. To those who are not constantly occupied in the culture of the rose, it may seem that one rose is very much the same as another, and excepting a few variations in colour and liabit of growth, there is very little difference distinguishable. Probably many persons would never believe that there are not only roses perfectly devoid of odour, but there are some which stink. There are experienced gardeners who can name many Tarieties of rose in the dark : this means that the perfume of roses is very varied, and that no two varieties possess the same B 10 odour. What is called the pure odour of rose is unique, undefinable, incomparable. It is, in fact, a type, and no imitation can approach it. It may be best represented by the B. centifolia and R. Damascena. R. centifolia, Lin. Sp. 704* {R. provincialis Miller), is found in the wild state, with single flowers, in the eastern parts of the Caucasus.t Under cultivation its flowers are more or less double, and innumerable varieties of it are propagated and grown in every temperate region of the globe. In English gardens it is grown as the Cabbage Eose or Provence Eose. In the South of France it is cultivated commercially. The second type of a pure rose odour is represented by the plant grown in Bulgaria ; this is a variety of the Rosa Damascena, Miller. J Living specimens were sent from Constantinople by Professor Baur ; these flowered at Tiibingen, and were examined and identified by Hugo Mohl.§ R. Damascena is not known to exist in the uncultivated state. Koch II affirms that at a remote period it was brought from Italy into northern countries. BakerU considers R. Damascena to be merely a variety of R. Gallica which was distributed from France to Mesopotamia. * P. J. Redoute, "Les Roses" Paris, 1817 and following years. Text by Thory ; i. p. 25, t. i. p. 37, t. 7 ; p. 77, t. 26 ; p. 79, t. 27 ; and p. Ill, t. 40. t Boissier, Flora orientalis, 1872, ii. p. 676. J Redoute, as abovf, i. p. 137. t. 53 ; i. p. 107, t. 38 ; and i. p. 121, t. 45. Also Lawrence, "Collection of Roses from Nature," London, 1799, t. 38. § Wiggers and Husemann, Jahresbericht, 1867, p. 350. || Dendrologie, 1869, i. p. 250. IT Journal of Botany, Jan., 1875. For description and classification of roses the following works may also be referred to : — Guillemeau, Histoire Naturelle de la Rose, 1800 • J. P. Buchoz, Monographie de la Rose, Paris, 1804 ; Raw, Enumeratio Rosarum Wirceburg, 1816 ; Pronville, Nomenclature Raisonn^e des espeees vari^t^s and sous-varietes du genre Rosier, Paris, 1818 ; John Lindley Rosarum Monographia, London, 1820 ; L. Trattiniok, Rosacearum Monographia Vienna, 1823 ; Hariot, Notes, pour servir a I'historie des classifications dans les espeees du genre Rosa ; These de I'Ecole de Pharm. de Paris 1832 ■ Boitard, Manuel complet de I'Amateur de Rose?, Paris, 1836 ; Desgglise Catalogue raisonn^ des espeees du genre Rosier, Paris, 1877 ; Chereau Examen des roses officinales ; Journal de Pharmacie, xii. p. 436 ; S; Reynolds Hole, A Book about Roses, 12th edition, London, 1892. Good lists of new varieties are also to be found in the catalogues of Louis Van Houtte, of Ghent 11 The first attempt to classify the varieties of perfume in the rose was made as recently as 1886, by an anonymous writer in an American horticultural journal.* The subject was further studied by Dr. Blondel in 1889, t and reprinted in his admirable treatise, " Les produits odorants des Eosiers," Paris, 1889. These observers record the fact that the odour of tea is not perceptible in the so-called " Tea-roses," indeed many Tea-roses are odourless, such as the Melanie Souppert, Marie Guillot, Marie Caroline de Sertoux, and Triomphe de Milan. Some Tea- roses possess very delicate fruity odours ; for instance, the R. i^ocrates has the odour of peach ; Elizabeth Barbenzien, odour of melon ; Isabelle Narbonnand, odour of violet ; Safrano, odour of pinks. Some of the Tea-roses possess odours which are far removed from that of pure rose, but yet are particularly sweet and fruity, recalling that of the raspberry, such as the Marechal Niel amongst the yellow, Goubault amongst the red, and Madame Bravy amongst the creamy-white varieties. There are Tea-roses such as Gloire de Dijon, whose perfume is so sweet and subtle, that any definition or comparison is quite impossible. The majority of Noisette roses are inodorous, but the variety known as Unique jaune has a faint odour of hyacinth, and some, such as Celestine Forestier, Claire Garnot, and Earl ofEldon have a slight fruity odour; this is particularly noticeable in the Desprez. Amongst roses possessing fruity odours, B. hracteata and B. Macartnea are credited with possessing the odour of apricots, and Souveraine (a cross between a Tea-rose and B. centifolia) has exactly the odour of melons ; in most cases, however, the fruit odours are blended with one somewhat analagous to that of bananas or quinces. The odour of mignonette is noticeable in B. canina (especially when the petals are developed in a some- what darker shade than usual), the red B. sxpium,X and B. Alpina, Lin. (This last is now employed in the perfume industry specially by reason of its mignonette-like fragrance.) § * The Gardener's Monthly and Horticulturist, xxviii. 1886, p. 249, Phila- delphia. + Bull, de la Soc. Bot. de Prance, Pevrier, 1889. t Sowerby, Eng Bot. Sup. t. 2653. § Bot. Reg. t. 424. 12 The odour of violet, besides being developed in R. Tsabelh Nahonnand, above-mentioned, is also very noticeable in R. Banksia alba. (Banhsia lutea is perfectly inodorous.) The odour of pinks is also exhaled by the R. caryophyllea, R. Ripartii, Deseglise, and R. moschata, Miller. This last, however, does not possess the odour of musk, as one might suppose by the name. The musk odour is only clearly developed in the R. Salet, a hybrid climbing Moss-rose, bright red with a pale centre. The flowers of most of the varieties of R. ruhiginosa are inodorous, but those of R- platyacantha and R. Capucinn (/?. EglanUria, Lin.), (especially the variety feicoZor, Jacq.) belonging to this group, develop an odour of bugs and coriander. The same may be said of R. Beggerlana {R. coriosma, Decsn.).* In further illustration of the capricious nature of this perfume, and the extraordinary complexity of its forms, it is stated that not only in the whole list of roses are there no two which develop precisely the same odour, but that in the same species, and even on the same plant, there are not found two flowers absolutely identical in odour, — even yet further, that it is a well known fact amongst rose growers that at different times in the day an individual flower will emit a different perfume. As a rule the red roses are more odoriferous than the white. Cut roses placed in a vase diffuse their fragrance more powerfully than when growing on the plant. It has also been noticed that roses flowering under glass give off a greater amount of perfume than those cultivated in the open air ; the reason of this is obscure, but it is perfectly certain that under no conditions is the odour fully developed except in * This is a very remarkable coincidence ; the coriander plant and its unripe fruit both possess the intensely disgusting odour of bugs, but the fruit at complete maturity, acquires the pure odour of coriander. The nature of the chemical action producing this modification in the odour is not understood An equally curious example of the transmutation or development of odours is instanced in the Acacia Farneaiana and the Tritelia uni flora, in both of ■which plants are associated the odours of violet and of garlic. 13 very hot climates, where the power of the sun affords the maximum benefit of light and heat. The flowers of Rosa gallica (which are used officinally) are but feebly odoriferous when freshly gathered; their perfume develops gradually in the process of desiccation, while that of the Damask-rose is almost destroyed by drying. In Bulgaria the flowers grown for the distillation of the otto are gathered before they fully expand, and a little before sunrise. Were they gathered later in the day, when fully expanded by the heat, the perfume would be weaker, and not so sweet, and the resulting essence would be of less value. It has been noticed that previous to a storm, or atmospheric disturbance, the odour of the rose seems strangely increased ; this may be by reason of the oxidising influence of the ozone in the atmosphere, or it may be that our perceptive faculties are sharpened at such moments. Eosa centifolia. Transverse section of a sepal, showing the pedicellate glands on surface of epidermis, and fibro-vascular bundle within. (After Blondel.) In estimating the quality of the odour of a rose, care should 1)6 taken in handling the stalk, the calyx, or any green part, as a very slight friction breaks the pedicellate glands which abound 14 on these parts, and in which is secreted an oil or glutinous oleo- resin of powerful odour, totally different in character to that developed in the microscopic cells of the petals. In some roses. S 6- Rosa CentifoUa, var. muscosa (Moss-rose). Pig. 1.— Single tooth of a foliole (x 80) showing the pedicellate and branched glands on the margins of the tooth, and non-existence of same at the summit. The dark coloured cells at the summit of the tooth and at the base of the glands are cells secreting tannin. Fig. 2. — A single gland of the above, isolated and greatly magnified, showing the tannin-secreting cells at the base rendered opaque by their contents, and the upper cuticle raised by the accumulation of oleo-resin at the summit. Fig. 3. — Transverse section of a foliole. (This drawing is inadvertantly made xipside-down.) It shows the pedicellate, oleo-resin secreting glands on the lower surface, and the structural difference of the upper and lower parenchymatose tissue (x 300). Fig. 4. — Base of a petiole, showing the stipules, and how the entire formation is clothed with pedicellate glands. Figs. 0, 6. — Glandulous structures occurring in large quantities amongst the prickles and young thorns. such as the Moss-rose, these glandular formations attain quite a prodigious size, developing very rapidly on the young shoots, even overtopping the thorns. In some varieties the odour of the glandular secretion is very rank, and has been described as hot, peppery, clove-like and terebenaceous, but the word tere- benaceous is misplaced and misleading ; the odour may remind of the resins contained in certain woods, but it is generally more balsamic, like the odours of some varieties of pelargonium and geranium leaves. In some varieties of the group Ro^a villosa the odour approaches that of olibanum and myrrh. In R. Brunonii, Lindl. (a moss variety of R. moschata, Miller), the hispido-glandulous system which thickly covers the pedicels and sepals, develops a fine odour of pinks. Sometimes this odour is fruity, as in many varieties of R. rubiginaxa, Lin. (the " Sweetbriar ") and is developed to such an extent as to be disengaged spontaneously, especially on a warm day, and by the gentle action of the wind after a light rain. All the green parts, especially the lower part of the leaves, contain innumerable oil glands, which, being broken by the slightest friction, exhale an agreeable odour which has been very rightly compared to that of an apple called " Pomme Eeinnette," or in English " Pippin." The glands of R. micranlha, Smith ; R. graveolens, Pers, and R. glutinoxa, Sibth. secrete a very similar perfume. The composition of the body contained in these glands is apparently unstudied and little understood, but its odour is suggestive of 16 valerianate of amyl, which is now prepared on a large scale for use in flavouring sweetmeats and liqueurs with the flavour of apples.* The leaves of R. lutea, Dalech [B. Eglanteria, Lin.), (known also as R. Capucine] possess an odour which is even finer, recalling that of jasmin. The glandular structures of the green parts of the rose are minutely described by Dr. Blondel in his work above cited, he also gives details of the cellular arrangement of the epidermis of the petals, and illustrates the appearance of the same under the microscope (the accompanying illustrations are copied there- from). He found on examining the anatomical structure of a transverse section, that both sides of the petal are equally odoriferous, that is to say, the otto is secreted in epidermal cells on both surfaces, the upper ones being papillary, and the lower ones cubic, in form. To exhibit the presence of the oil, he employed a reagent of great sensitiveness, viz., a solution of osmic acid (Os O4), 1 in 200. The section of a fresh petal is plunged in this, bath for about twenty seconds, then carefully washed in distilled water and mounted in glycerine. Thus prepared, and examined under the microscope, the cells of both surfaces of the epidermis appear to be filled with an intense bluish-black pigment, due to the reduction of osmic acid by the essential oil and deposition of the osmium. The mass of osmium thus deposited is quite homogeneous in appearance, and this is thought to indicate that the oil exists in a very minute state of division, and not agglomerated in drops, as in the pedicellate glands on the leaves and other green parts of plants. In * A similar odour has been noticed inphenylnitro-ethylene chloride, which can be prepared by passing chlorine into a cooled solution of phenylnitro- ethylene in chloroform. On the evaporation of the latter it remains as a thick oil, which has a penetrating odour, resembling, when dilute, that of pippins. On standing for some time, large lustrous crystals are deposited, which are extremely soluble in ether and chloroform, and are again left on evaporation as an oil, which solidifies, when placed in contact with a fragment of the original crystals, to a mass, which melts at 30°. This odour of pippins, akin to that of sweetbriar, is noticeable in the flowers of Agrimonia eupatorium, and in all parts of the Agrimonia odorata. 17 sections of plants containing essential oil in an agglomerated mass, or even in rather large drops, the action of osmic acid is very different. For example, if a section of a leaf or petal of the orange plant be treated with this reagent, the osmic acid coming Rosa centifolia. Fig- 1. — Transverse section of a petal ( x 500,) after treatment with osmic acid ; showing the reduction of the osmium in the vessels on both' surfaces. Fig. 2. — Fragment of section of a petal at the part where it is attached to the calyx, showing (x500) the non-papillary cells of the upper epidermis filled with essential oil. Fig. 3. — Fragment of upper epidermis of a petal, dissected under the microscope, showing the formation of papillary cells. Fig.. 4.— A single eeU ( x 1000). Fig. 5. — Longibudinal section of same, and Fig. 6 upper view of same. Fig. 7. — Transverse section of filament of stamen, after treatment with osmic acid, showing the essential oil contained in the epidermal cells (x200). in contact with the drops of oil, is. only reduced by the smallest drops or particles of the oil, leaving the other drops intact and unacted upon. This is further exemplified by placing side by side, and in contact, on a slip of glass, a drop of otto of rose and 18 a drop of osmic acid solution (even a concentrated solution) , the reduction only takes place at the points of contact of the two liquids, and for the reason that they are not reciprocally miscible one with the other. To produce the complete reaction, it is necessary to actively stir the mixture of the two liquids with the point of a needle in order to produce an intimate mixture or emulsion of the oil in the aqueous solution, and so to multiply the points of contact with the reagent ; the mixture then blackens almost immediately. From this experiment we can draw a conclusion of great importance as regards the elementary biology of the epidermal cell of the petal ; viz., that as the osmium is reduced with the rapidity above stated, it is evident that the oil is located equally at all points of the substance of the phytoblast, and exists in a state of extreme division, so permitting contact to be established at innumerable points simultaneously. This proves that the cell is not only the reservoir or containing receptacle of the oil, but that it is in fact the ieat of its maniifacture, the actual locality where it is generated by a natural synthetic process, and not the simple container of products elaborated in sub-adjacent tissues. It is also inferred that as this oil does not accumulate or take the form of drops, it is given off as an odorous emanation almost as soon as it is generated, and that the formation and the dispersion by exhalation proceed simultaneously. Hence the flowers soon lose their perfume after being cut. This feasible theory applies to many other odorous flowers which exhale their perfume, are not furnished with receptacles to store their oil, and therefore cannot yield oil on distillation (or at all events very little). Considering this structural arrangement, it is not surprising that the quantity of essential oil obtainable from the rose is so very small, and if not immediately distilled the yield is even smaller. The perfume exhaling from many other flowers, such, for instance, as pinks, stocks, hyacinths, and in some instances from leaves, such as Mimulus moschatus is doubtless referable to the same cellular formation. Such flowers as those of lavender, and such leaves as those of mint, thyme, and geranium are 19 furnished with cells and glands which dore up the oil, consequently their perfume is only perceptible when these vessels are ruptured by friction. The conditions in which the various oils exist in the plant and their liability to be more or less changed or damaged by the action of heat, of course guide the manufacturer as to the process he shall adopt to extract the products. It may be remarked that as osmic acid is reduced by fixed oils and by tannin as well as by essential oils, the presence of stereoptene in the rose petals may have interfered with the accuracy of Blondel's observations, and that the conclusion he arrived at, viz., that the otto is produced in the cells of both surfaces, may be erroneous ; in any case, it has more recently been affirmed by Mesnard that the essential oil of rose is found in the papilliform epidermal cells on the upper surface of the petals, and scarcely ever on the lower side.* Mesnard conducted his investigation in the Botanical Laboratory of the Sorbonne, under the direction of Gaston Bonnier. His interesting and suggestive memoir may be abstracted as follows : — " The imperfection of the micro-chemical methods usually employed has hitherto prevented an exact knowledge being obtained of the manner in which the perfume of flowers is generated (and localised in the flower). In this particular investigation I have followed the same method of research which was adopted in the localisation of fixed oils. The method is as foUows : — The section being placed in a drop of pure glycerine is arranged upon a round cover-glass, which being then inverted, serves as a cover to a email chamber formed by cementing a glass ring to an object-slide. In the interior of this chamber is fixed another ring of smaller diameter, and somewhat less in height, thus forming an inner annular space in which the reagent may be placed. By adopting this arrangement the * Reclierclies sur le mode de production du parfum dans les fleurs, Note de E. Mesnard, presentee h I'Acad^mie par DucViartre. Comptes Bendus, 21 Nov., 1892, cxv., p. 282. 20 light passing through the central part of the cell is not weakened. The inner ring further serves to support a very small cover-glass upon which sections may be arranged which require to be exposed to the action of the reagent for some length of time, as occasionally happens in the case of fixed oils. The reagent invariably employed is pure hydrochloric acid, the hydrated acid vapours abundantly given off from which are absorbed with avidity by the glycerine. In this way, by a gentle and easily regulated action, I obtain complete hydration of sections in the presence of an acid. After a few moments of exposure to the presence of the reagent, the essential oils appear as minute spherical drops of a fine transparent golden yellow. If the action be prolonged, the drops disappear, being trans- formed into diffusible products. The disappearance or diffusion of globules of fixed oils never takes place, the process thus furnishes a means of distinguishing these two classes of products. "As regards the localisation o^ essential oils in the parts oi the flower, the following observations have been made : — " Jasmin. In this flower the oil is situated in the row of epidermal cells on the upper side of the sepals and petals. Some exist also in the corresponding layer on the under surface, where the sepals are coloured by a violet pigment. If the evolution of the cell contents in flowers at different stages of development be followed, at first nothing but chlorophyll is found in the tissue ; tannin is the next to appear, or rather intermediate glucosides, difficult to identify by means of the ordinary tests for these substances. These glucosides furnish the tannin and pigments of the lower surface of the sepals. The hydrochloric acid vapours furnish a means of distinguishing all the tannoid compounds intermediate between the chlorophyll and tannin, or pigments, on the one hand, and between the chlorophyll and essential oil on the other. The explanation of these facts seems to be as follows : — Whereas, upon the lower surface, which, in the bud, was exposed to the action of light and the oxygen of the air, the tannoid compounds were slowly oxidised, thereby generating tannin, the upper surface, on the contrary, being 21 then hidden inside the bud, these agencies were inoperative (the parts not heing exposed to the action of light and oxygen), and the same compounds were converted into essential oil, which oxidises when in contact with air, and so produces the sensation of perfumes." — [This confirms the theory of Liebig and others, that perfume is the result of eremacausis.] He then states his opinion that the essential oil is generated in the rose precisely in the same way as in the jasmin ; also from his investigations he draws the following conclusions :-^ " 1° — That the essential oil is generally found localised in the epidermal cells in the upper surface of the sepals or petals, though it may exist upon both surfaces, especially if the floral organs are completely hidden in the bud. The lower surface generally contains tannin or pigments derived from it. " 2° — The essential oil seems in all cases to be the result of a transformation of the chlorophyll. This transformation is readily understood if it be admitted, as it generally is, that the floral organs are but leaves modified for the performance of a new function. The chlorophyll being thus diverted from its original purpose or use, is transformed into permanent tannoid eompounds or into essential oils. " 3" — The liberation or disengagement of perfume from the flower only becomes perceptible when the essential oil is sufficiently freed from the intermediate compounds which generated it. Its formation is to some extent in inverse proportion to that of the tannin and colouring matters in the flower." The above opinions (of Mesnard) are of course speculative.* «■ The subject has been investigated by oihprnaturalists ; amongst the most important records of their researcheF, the following may be referred to :— Guettard : "Sur les corps ylanduleux des plantes," Mem. del' Acad. Boy. des Sc. 1745 a 1756. De Mirljel : "Mi§m. sur I'anat. des plantes, et Elements de physiol. veg. & de bot.," 1815. De Candolle : " Organogr. v6get." Meyen : " Ueber die Secretions Organe der Pflaenzen," Berlin, 1837. Ditto : ■" Neues System der Pflanzen-Physiologie;" 1837. A. Weiss : " Die Pflanzen- bafire. in Karsten's Botanische Untersuchungen," 1887. Martinet : "Organes de S^ijr^tion des v%dtaux. These de la Faculty des Sciences Paris," 1871. Eaw : "Enumeratio Eosarum," 1816. 22 HE art of distilling roses undoubtedly originated in Persia, and was practised on a large scale at a very- remote date. The earliest record of this fact was discovered by Professor Fliickiger in the National Library in Paris.* This document informs us, on the authority of Ibn. Khaldun, that between the years 810 and 817 of the Christian era, during the reign of Kaliph Mamoun, the province of Faristan was required to pay an annual tribute of 30,000 bottles of rose water to the Treasury of Bagdad. It is also stated by Istakhrif that a considerable quantity of rose water was produced throughout Faristan, and was from thence sent to China, J India, Yemen, Egypt, Andalusia, and Magreb (in the Barbary States, especially to Morocco). The most important factories were at Dschur (now called Piruzabad), situate between Shiraz and the coast, and where, even to this day, the business is not altogether extinct. § The art of distilling roses was probably introduced into Western countries by the Arabs. An important record con- cerning the early history of agricultural industries introduced by the Arabs into Spain ("le Calendrier d'Harib")|| recommends that the water, confection, syrup, and oil of roses, should be prepared in the month of April. Throughout the Middle Ages, rose water constituted an important article of commerce between Eastern and Western countries. This fact is frequently alluded to in the writings of Joannes Actuarius,1f physician at the Court of Constantinople towards the end of the twelfth century. * Notices et extraits des manuscrits de la Bibliotheque Imp^riale, xix., p. 364 (1862). t Le Livre des Compagnes, p. 73. J A proof of the intro- duction by the Arabs of rose water into China, during the dynasty of Sung, is given in a work derived from Chinese sources, entitled, " On the know- ledge possessed by the ancient Chinese of the Arabs and of the Arabian colonies, etc," by Bretschneider, London, 1871. § Fliickiger, Pharmacognosie des Pflanzenreichs, 1883, p. 159. || Durean de la Malle, " Climatologie compar6e de I'ltalie et de I'Andaloiisie," Paris, 1849, p. 65 ; " Calendrier raral, etc., d'Harib ; " Dozy, "Le Calendrier de Cordoue de I'ann^e 961 " Leyde, 1873. T" J. Aetuarius, De Methodo Medendi, lib v. cap. iv. De Medicamentorum compositione ; BasilcK, 1540, pp. 10, 19, 22, 31, etc. 23 In 1214, rose water is meDtioned amongst other aromatics, such as Balsam of Mecca, camphor, etc., in a description of a fete given at Trevise.* In 1379 "Kose water" appears on the Tariff List of the Custom House of the Port of Talamone, also in 1442 on the Custom's Eegisters of Florence, which had the control of that port.f This industry was also carried on in Mesopotamia during the fourteenth century, the town of Nisibin situated west of the Tigris, between Mosul and Diarbekir having at that period a reputation for its rose water. J Ksempfer, in his Amaenitates^ speaks with admiration of the roses of Shiraz, and of the extensive commerce dependent upon them. In point of fact, these celebrated rose plantations existed rather in the surrounding districts than in the town itself; he says: "... the rose and the vine flourish, abundantly and with equal luxuriance, but not so much in the gardens in the interior of the town as in a suburb named Kesseri Desjt, or commonly called Mescidi Berdi, situate at the foot of a mountain towards the north-west, also in the gardens of the country people and peasants bordering the road between this suburb and the town. Although this region may have many equals as regards beauty of aspect, fertility of soil or perfection of climate, the fine products of its rose plantations and vineyards are unrivalled. Even as the roses in Persia are produced in greater abundance and with finer perfume than those in any other country in the world, so also do those of this particular district in the vicinity of Shiraz, excel in profusion and in fragrance those of any other locality in Persia." The rose is not distinguished in Persia by any specific name, it is simply called gul (flower) ; that is to say, " the flower " par * " Cronica Paduana Rolandini " in Pertz Monumenta Germaniae hist, scriptores, xix. p. 46. f Heyd. Levanthandel im Mittelalter, ii. p. 297. I Voyage' d'lbn Batoutah, 1854, p. 140; trad. Defr^mery. § Ksempfer, Amoenitatum exoticarum, politico-physico-medicarum, fasc. v. quibns con- tinentur variiB relationes, observationes, et descriptiones rerum Persioarum et ulterioris Asise, multa attentions, in peregrinationibus per universum Orientem, colleclse ab auctore, Lemgoviae, 1712. 24 excellence. Its distilled water is transported to all parts of India, and is even sent into the other provinces of Persia for home use. It is much eateemed as an article of luxury at banquets and at festive meetings. It is used to sprinkle the guests on their arrival, as a sign of welcome, and flavoured with cinnamon and sweetened with white sugar it is taken as a heverage.* KsBmpfer does not give any description of the particular •species of rose cultivated in these plantations. He gives a very •detailed plan of the palace of Persepolis, and mentions the ■Garden of Eoses (rosetum) or Bagi Guldistuum annexed to the building Untsj mertebeh, which extends in the form of an •octagon, describing its dimensions, its central pavilion, its pictures and even its water cisterns, but makes no mention of its roses. Blondel says that the examination of specimens made by Olivier and Pissard during the present century, lead to the belief that the species cultivated was the R. moschata. The R. Piasardi, which, according to some botanists, is a distinct species, is a veritable R. Moschata: he adds that there exist at the present day living specimens of the Persian rose, and that they are cultivated by Godefroy-Leboeuf at Argenteuil, in France.f : * Ksempfer, Loc. cit., Fasc. ii. p. 373. t ■"• moschata, Miller, native of Barbary, is figured in Curtis' Botanical Magazine, t. 4,030, also by La'wrenee, t. 64, in her work of illustrations from nature above-quoted ; also -the double variety (fl. pleno) at t.' 53 of the same. The R. moschata Nepalensis is figured in the Botanical Register, t. 829. Previous to the commencement of the sixteenth century writers on the subject of roses generally confused R. mofchata with R. Damascena, and used either name indiscriminately. R. Indica (Lin. spec.) 705 is described and figured by Eedoute, loc. cit. i. p. 51, t. 142 ; p. 35, t. 15. The R. Indica odoratissima, Lindl. Rosarum monographia, p. 106, Bot. Reg. t. 864, also a native ci China, is the R. odoratissima of Sweet, and the R. Indica fragrans of Redouts, i. p. 6, t. 19 rthis is noticed in " Gardiners' Chronicle," 1887, ii., p. 430). By •crossing It. Indica with R. mcschata, a French cultivator, P. Noisette ■originated the " Noisette " roses, but the numerous varieties now in cultiva- tion are mostly obtained by crossing the primitive " Noisette " with Tea- roses, so producing Hybrid Noisettes. By crossing R. Indica with R. Daniascena the 'Bonrhon rose {Rosa Borbonica, Redoute) was produced in 1819 ; and by crossing U. Indica with R. Alpina the Boursault Rose {P. reclinata, Redoute) resulted. The original discovery of the possibility of separating the small drops of oily matter floating on the surface of rose water, appears to have been made by Geronimo Eossi at Eavenna, and this product is mentioned by Wecker in 1574* as " the Oil of Eoses of Eubeus" (Eossi). The discovery was afterwards recorded by Eossi himself in his book published in 1582.t The essential oil of rose was next described by Porta in 1589, t and in 1604 he writes : " Omnium difficillime extractionis est rosarum oleum atque in minima quantitate sed suavissimi odoris."^ The druggists' price lists of the commencement of the seventeenth century, in Germany, quote both the Oleum rosarum de-stillatum and the Oleum rosatum (a rose-scented fixed oil), but the infinitely higher price of the former is sufficient to identify it as the volatile oil, or " otto."|| The next mention of this essential oil appears to be made by Angelus Sala, a writer in Germany during the period of from 1610 to 1630t and then by Schroeder in 1649.** It is mentioned by Pomet, in his History of Drugs, 1694, as being well known in Paris at that date, but only obtainable in very small quantity and at a very high price. It was also described by Homberg in 1709 in a memoir entitled " Observations sur les huiles des plantes."tt It seems strange that although the rose is an oriental plant, and the art of distilling rose water was first practised in Persia, the otto of rose was known in Europe about forty years sooner than in the East, and that even then the discovery was o Wecker, '^Antidotarium," published at Colmar, 1574. f Hyeronimi Eubei Ravpnnatis, " De Destillatione liber." Kavenna, 1582, Sect. ii. cap. xvi p 102. X Porta, " Magie naturalis," lib. xx. § Porta, " De DestiUa- tione," lib. ix. Roma, 1608. || "Documente zur Geschichte der Pharmacie," Halle 1867, p. 37, by F. A. Pluckiger ; from which interesting work most of the above bibliographical references on this subject are taken. IT Angelus Sala Opera medico-chymica, Fran:forti, 1647, p. 63-79. ** Schroeder, Pharmacopoeia medico-chymica, Ulm, 1649, lib. ii. cap. Ixx. p. 241. ft M^m. de I'Aoad. Roy. des Sciences, p. 206. 26 made in Persia quite accidentally, and quite independently of any knowledge of the results attained by chemists in Western countries. The date of the discovery by the Persians of this valuable essence has been ascertained by Langles to be 1612. He was thoroughly acquainted with the languages and literature of the East, and in his excellent little book* he shows that previous to this date (1612), no mention of otto of rose is made in any work written in Oriental language, and that the circumstances attending the discovery are for the first time described in a work written in Persian by Mohammed Achem, entitled Tarykh montekheh hihdb, which is a History of the Great Moguls from the year 1525 to 1667. In this work, mention of the essence is twice made. The first time, it occurs in the chapter entitled : " Marriage of the Princess Nour-Djihan with the habitant of the paradise Djihan- guyr ; inventions and discoveries of the Queen of the World." The second mention is made in the chapter entitled: " History of the seventh year of the reign of Djihan- guyr, and Feast of the New Year." According to the translation, it appears that at the commencement of this f^te, the mother of Nour-Djihan having presented to the prince the " essence of rose water " which she had prepared, the prince thereon attached to this discovery his illustrious name, and called the perfume A'ther Djihan-guyry (Perfume of Djihanguyr) ; at the same time presenting to the princess a necklace of the value of 30,000 rupees, t Another version of the circumstances connected with this discovery is recounted by Manucci, a Venetian physician who resided about forty years in India. He bases it on the " Annals of the Mongolian Empire," an important work translated and * L. Langes, Eecherches sur la decouverte de I'Essenoe de Roses, Paris 1804. f G-ladnin, in his "History of Hindustan, i. p. 201, a work based on authentic records, such as the Maacer Djihanguyry (Acts of Djihanguyr) by Kfimgar Hocein, and the Touzouk Djihanguyry (Commentaries of Djihan- guyr) also attributes this discovery tn the mother of the Empress IS cur Djihan-Beygum, and in alm^pt the same terms. 27 abstracted by Catron.* According to this description the fete was of a very costly and magnificent character, luxurious amusements of every sort being provided, the princess even carrying her extravagance and prodigality to the extent of causing rose water to flow through a canal constructed in the flower gardens. I then happened that whilst the emperor and the princess were walking along the bank of this canal thej noticed that an oily stratum had concentrated on the rose water and was floating on its surface ; this was carefully collected and recognised by the entire Court as the most delicate of perfumes. What thus resulted from accident was afterwards imitated by art. Whichever of these two narratives is really the most truthful, it seems to be an established fact that the manufacture of the otto in Persia dates from the period of this fete, viz., 1612. At the time of Keempfer's visit to Persia in 1684, the distilleries of Shiraz were in a most flourishing condition. He says,t " TJie roses of Shiraz are remarkable for yielding on distillation a fatty matter like butter, which is called Aettr Gyl. This substance is more valuable than gold, and nothing in the world possesses a perfume so agreeable and sweet ; from this we may conclude that the rose growing in the country of Persepolis is of a strongly odoriferous nature." Kasmpfer also mentions the custom of blending the oil of santal with that of the rose (a practice which is perpetuated in India at the present day), and says: "The raspings of santal wood is sometimes added to the flowers previous to distillation. A century later (1787), this fact was confirmed by Archibald Keir,! who describes the primitive method of manufacture practised at Ohatra in Eamgur The rose water prepared in this way (with santal wood), was sold separately, under the name of Ssandali Qulab.^ Pure rose water, prepared by distilling roses alone with water is called * Manucci Histoire g^n6rale de I'Empire Monghol depuis sa formation jusqa'h present, 2 Ed. i. p. 326, 327. + Ksempfer, Amcenitatum, etc., p. 373. + Asiatic Researches, i. p. 309. § Zend-Avetta, i. Appendix, p. 525, 52& in Langlfes, loc. cit. 28 Gulab. The word Gul in Persian fOuard in Arabic), signifies in a general way "a flower," including also the idea of " perfume " or " perfumed flower," and is particularly applied to the rose (as before mentioned). The word Athr, A'thr, or O'thr is employed by the Arabs, the Turks, and the Persians to designate the essential oil of rose, even without the addition of the word Gul, but it is also applied to compound, or mixed perfumes, very much in the same way as the word Abir, which in Bombay is used to designate a compound of rose water, santal, violets, orange flower, musk and spikenard ; — therefore when pure otto of rose is solely and distinctly meant, it is necessary to add the word Gul or Gyl after the word Athr. At about the same period Porster* mentions the roses of Kashmir as being highly esteemed for their beauty, and adds that their " essence " is particularly valued. Colonel Poller, describing the manufacture of the otto,t says: — " In Kashmir they seldom use santal to adulterate the attar, but I have been informed that, to increase the quantity, they distil with the roses a sweet-scented grass, which does not communicate any unpleasant scent and gives the attar a clear green colour. This essence also does not congeal in a slight cold, as does that of roses. "J At the commencement of the present century it is reported by 01ivier§ that he found the otto of rose industry in a highly prosperous condition at Shiraz, Parisian and Karman. According to Forbes Watson, || Douglas, IT and Schlagenweit- Sakiinliinski,** the cultivation of the rose and the art of dis- tilling its flowers was introduced from Persia and Arabia into India, first to Kanauj, a town on the Ganges (which has now * Voyages de I'Inde a St. Petersbourg, i. p. 294. t Asiatic Researches, i. p. 332. X Here was evidently the origin of the -wholesale adulterations after- wards practised in Bulgarin, and which, even now, the Bulgarian Government are quite unable to put a stop to. § Voyage dans I'Empire Ottoman, 1807 V. p. 367. II Catplogue of the Indian Department, Vienna Exhibition, 1873 p. 98. IT Pharm. Journ. [i.] viii. p. 811. ** " Das genus Rosa in Hochasien| und iiber Rosenw.isser und Rosenoel," in Buchner's Repertoiium fur Pharmacie, xxiv. p. 129-143. •Id ceased to exist), and from theuce to Ghazipur, Lahore, Armritsar and other localities in India, where this industry is still carried on, but the products are not more than sufficient for native requirements, and are not exported. According to Brandis* the species cultivated is the B. Damascena. The Indian Method of Distillation was described by Colonel Poller, of Lucknow, in 1787 1 as follows: — "About forty pounds of fresh roses (including the calyces, but with the stems cut close) are put into a still with sixty pounds of water, and distillation continued until thirty pounds of water come over, which is generally in about four or five hours. This rose water is distilled again with a fresh quantity (forty pounds) of roses and from fifteen to twenty pounds of rose water drawn over. This is poured into pans either of earthenware or tinned metal, and left exposed to the fresh air for the night. Ii the morning the otto is found swimming on the surface. It is then carefully skimmed off with a thin shell and poured into a small flask, and when the water and impurities have subsided it is decanted into another flask. The impurities and water are distilled again with fresh roses. The yield of otto is about one-amd-a-half drachms from eighty pounds of roses, or, deducting the weight of the calyces, about three drachms per hundred pounds of rose leaves." The process employed by the natives at Chatra in Eamgur, was described by Archibauld Keir.J He says the bodies of the stills are constructed of earthenware, which, absorbing the heat more gradually and slowly than metal, is less apt to communicate any empyreumatic odour by burning the contents. The head of the still, called by the natives the " adkur," is constructed like the head of an alembic, i.e., with a channel running round its * Forest Flora of North-Western and Central India, 1874, p. 200. + Asiatic Researches, i. p. 332. % Asiatic Eesearcho°, i. p. 309. 80 interior to collect the condensed product. The refrigeration takes IJlace at the top of this head, -which is of copper, a stream of water is kept pouring upon it, aaid is conducted away by a channel on the outside. [The writer of this description then expresses his opinion that this method of effecting the con- densation is suj)erior to the ordinary pipe or worm method, as the vapours being condensed as suddenly as they rise, the pressure on the liquid would be diminished, and therefore permit the water to boil at a lower degree of temperature than under ordinary atmospheric pressure. He appears to be the first observer who draws attention to the injurious effect of heat on essential oils, and to the desirability of diminishing as much as possible the time in which the oil is kept in contact with hot aqueous vapour.] The requirements of Egypt, which are considerable, are supplied from Medinet Fayum, south-west of Cairo. Although, as above proved, the discovery of otto of rose was made somewhat earlier in Europe than in Persia, yet, as a manufacturing industry, it was introduced by Turkey. The oil was for some time distilled at Ohio (Ollivier mentions that it was produced in that island in the year 1800), and probably at Smyrna.* It was also produced largely in the Earbary States, and especially in Tunis, where, according to a modern traveller,! the species cultivated was the R. canina, Lin. or a very odorous variety of it (thirty pounds of flowers yielding one-and-a-half drachm of oiDJ. According to the accredited tradition, it was from Tunis, which had developed into one of the most important centres of this industry, that the culture was introduced, about two centuries ago into Bulgaria (then known as Eastern Eoumelia), by a Turk. It is also a fact that the business was introduced and established in France (in Provence), from the coast of Africa. * Pharmacographia, p. 2fi4. f Von Maltzan, Reise in den Regentschaften Tunis, und Tripolis, Leipzig, 1870. J Fliickiger and Hanbury, Hist, des Drogues, i. p. 472. •6) At the present day the odorous products of the rose are extracted in Bulgaria, France, Germany, and to some extent in India, Persia, Tunis, Algeria, Morocco, and Egypt. Having now traced the whole affair chronologically, we proceed to describe the cultivation, manufacture, etc., in Bul- garia, which is by far the most important producer (commercially considered) of the otto, and next France, which supplies the largest quantities of rose water^ pommade, and " extrait." The German production is (as yet) on a smaller scale, but by reason of the more scientific processes adopted in cultivation and manipulation, its products are of a very superior kind. The Rose Industry in Bulgaria. The region devoted to the cultivation of roses south of tlie Balkans is situate in the northern portion of the province formerly known under the Turkish rule as Eastern Eoumelia, and which is now included in Danubian Bulgaria. The acclimatisation of roses has been tried north of the Balkans, at Travna, but without success. The rose country occupies especially the two valleys of the Toundja (canton of Kezanlik) and of the Strema (canton of Karlova) both bounded on the lower side by a spur of the Balkans called Sredna-Gora. The south side of this mountain supports numerous rose farms, but their produce is inferior to that obtained from the south side of the Balkans proper, not only in consequence of less favourable climatic and geological conditions, but because the two indispensable factors of the work of distillation, namely, the water, and the wood for fuel, are much less, easy to obtain there by the distillers. The two extreme points, longitudinally, of the rose cultivation are Koprivchtiza on the west, and Tvarditza on the east. These two villages are above 130 kilometres distant one from the other. The two principal centres of the industry are Karlova and 32 (especially) Kezanlik, the finest quality of otto being produced in the mountainous zone which surrounds Kezanlik, not only by reason of its favourable southern aspect and specially suitable quality of soil, but also owing to the abundant flow of water during the harvest time, and the sufficiency of wood fuel obtain- able on the spot. The region of Kezanlik is situated about 400 metres above the level of the sea. The climate is temperate, but very variable ; the changes of temperature being frequent and singularly sudden. The thermometer falls in winter to — 20° C, and in summer reaches 40° C. The uncertainty of the weather at harvest time is a source of great anxiety to the cultivators. The mean temperature is nearly that of France, but sensibly colder than at Nice or Grasse (where the rose is largely cultivated). At Kezanlik, neither the orange, the olive, nor any of the plants indigenous to Provence are known to grow in the open air. The soil in the Kezanlik district is sandy, consequently very pervious to water. This condition is absolutely indispensable for the culture on a large scale. If the ground is calcarious or not sufficiently porous, or if a bed of clay lies at no great depth below the bed of sand and opposes the drainage of the waters by forming a basin, the roots soon decay. Hail-storms, too-pro- longed drought, and late frosts, are very common occurrences, and terrible enemies to the growers. The proximity of the mountains brings, however, frequent rains ; besides which, the snows which accumulate on the summits during the winter, produce abundant subterranean waters, the origin of numerous springs. The presence of water in a large quantity at harvest time is certainly one of the most important causes of the pros- perity of the district of Kezanlik, from the point of view of rose growing. The town of Kezanlik itself is watered by several springs of more or less importance, tapped by canals and tunnels of an age long past, which feed numerous fountains, bringing water in abundance at harvest time to each grower. The surrounding villages are equally well irrigated. All the waters 33 flow either into the river at Kezanlik, the Stara-Eeka, or into other less important ones, and from there into the Toundjha. Even in times of the greatest drought water is never wanting in in this favoured region. From this, as may be imagined, results the relative inferiority of the villages south of the Sredna-Gora, where water is wanting, and where the streams dry up during the great heats which prevail, usually at the harvest season. The rose cultivated in Bulgaria for the otto has been clearly identified by botanists as a variety of the R. Damasrena, Miller, the red damask rose. It is distinguished from tt. centifoUa by the greater size of its spines, green bark, elongated fruit, and longer reflexed sepals. It forms a branching shrub which reaches the height of five or six feet, flowering in May and sometimes again in November. This second flowering is insignificant from an industrial point of view, but exemplifies the tendency which all the descendants of the Rosa centifoUa have to revert to the original type. The branches, more or less spreading, spring from the base of the stem about the second year, and intermingling their sub-divisions form a very close thicket. The young shoots, from the time when 'they come above the ground till they have reached the height of twenty centimetres, are of a deep red colour. The branches, until they become old, are covered with brown, straight, and very closely set prickles or spines, which sometimes measure a centimetre in length. The leaves are from ten to fifteen centimetres in length, composed of seven folioles. The stipules are very wide, foliaceous, green, and prolonged to a sharp point. The median nerve is delicately velvet-like, and has numerous very small pedicellate glands mingled with the hairs. The folioles are unequal in size, elliptical, non-acuminate, and sharply serrate. The u| per surface is smooth and bright green, the lower surface is of a dull glaucous colour, the margins and nerves being finely pubescent. The petiole is furnished with recurved spines and is clothed with short glandular brown hairs similar to those on the nerves. The odour of the stalk when bruised is very slight. 34 The flowers are grouped in two — or three — flowered cymes. The branches bear on the average seven flowers, and in good vears as many as thirteen have been counted. The blooms are semi-double, and their diameter when full blown rarely exceeds four or five centimetres. The floral pedicels are about four centimetres long, and slender ; they are armed with numerous very fine spines, mingled with glandulous hairs, which render the stalk very clammy and sticky to the touch. (The workmen who gather the flowers find that their fingers become hardened so that they do not feel the pricking of the thorns, but become ■covered with a dark resinous substance emanating from the glands of the flower stalks ; the odour of this substance is strongly terebenaceous, and at the end of the day the men .scrape the substance from their fingers, roll it into balls and keep it for mixing with tobacco in cigarettes.) The receptacle (seed A'essel) is small, nearly conical and gradually diminishing to the thickness of the stalk, so blending with it ; this also is full of resinous glands. The sepals are very pointed and often attain a length of three centimetres. The margins of the two outer sepals and the exterior margin of the partly exposed inner sepal of the unopened bud are provided with numerous very long, thin, tongue-like growths, covered with hispid glands on their outer surface. The two exposed sepals of the bud, and the exposed portion of the inner sepal are simply downy. The broad inner surface of the five sepals is covered at the lower part with a delicate pale down. The petals are orbicular, of a beautiful pink colour, almost red in the bud, but becoming paler iifter expansion. They are thin, not glossy, but not velvety. The pure white showing at their base gradually merges into the full colour of the petal. Their perfume is exquisite, very closely allied to that of R. centifolia, and id especially powerful at the moment of the opening of the bud. The stamens are few in number. The styles are slightly exsert, and free in tlieir whole length. The colour of the berry is cherry red. The most suitable ground for a rose plantation is that of a sandy, porous nature, allowing of free percolation of moisture. 35 and sloping towards the south so as to be sheltered from the cold winds of winter. (Abundance of running water in the vicinity is absolutely necessary, as has already been pointed out.) Many of the grounds in Bulgaria which apparently possess the advantage of shelter by being situate on the southern slope of a mountain really are at a greater disadvantage than if situate in the middle of a plain, for the rose is indeed a delicate plant, very sensitive to atmospheric extremes at certain critical epochs of its existence, particularly at the time of its budding; thus, a white frost in April is very disastrous. Unseasonable rain, which on neighbouring high peaks easily turns to snow, suffices to effect this; the next morning a rapid clearing of the sky brings the frost, and the crop is severely damaged. What the rose needs nt this critical period is a warm sun, alternating with showers. Consular Eeport No. 1,300 states that owing to untimely rains just before the harvest the 1892 yield ■of otto in Bulgaria was very small, amounting only to 1,300 kilos. The 1893 rose crop in Bulgaria was nearly three weeks late, and fears were naturally entertained of a diminished yield, owing to the distillation taking place in a hotter period of the year than usual. But contrary to all custom, cool weather, accompanied by frequent rain showers, set in during the first ?, :iKUi« ObalojilariV:^^'^^ OrtiSSiuMI W '5ADAKU olJbvA-MAHALI^^ IcHtRPAN 55 Name of Canton. I. — Kezanlik . . II. — Strema III. — Sarijagora . . IV. — Stara Zagora v.— OvtchetHn . , VI. — Nova-Zagora Vn,— Tchirpan VIII.— Pechtera Kilos Quantity of Roses Used, in Kilos. No. of Stills. 1891. 1,752,000 1,850,000 596,900 144, OOt) 145,700 130,500 135,200 220,000 4,974,300 1892. 1,643,000 1,674,200 561,600 129,700 127,500 112,300 102,900 270,000 4,621,200 1893. 1,909,500 1,893,300 520,400 174 700 156,000 202,800 152,800 280,000 5,289,500 1892. 3,053 2,200 780 290 200 187 220 360 7,290 1893. 3,180 2,360 807 305 270 265 255 450 7,892 Rose Cultivation in Germany. In 1886 a rose plantation was established at Milfcitz, about five miles south-west from Leipzig, by Messrs. Schimmel and Co., and, owing to the great success of the experiment, was further extended in 1889. In 1891 it was reported that the extent of land under this cultivation had been increased to eighty-five acres. More recent reports confirm the general opinion that this undertaking is a growing success, a fact not to be marvelled at, considering the patient study of the subject made by this firm, the enormous outlay they have made, and the labours of the talented men in their employ. At first the Rosa centifolia was grown, but in 1888 the firm procured a consider- able number of plants of M. damascena, Miller, from Bulgaria, which increased rapidly under suitable treatment, and it was found that these roses from Kezanlik flourished excellently in the porous, chalky, loamy soil of the Saxon plains ; a widely ramified system of irrigation and drainage having been con- structed in order to ensure a supply of water t > the deep striking roots of the plants. It appears that as here grown the yield of flowers is equal in weight to that obtained in Bulgaria. 56 From 115 to 160 of such well developed flowers, just as gathered, go to the pound, but it requires as many as 275 faded ones to make up that weight.* The green parts of the flower, viz., the sepals and receptacle, constitute about seventeen per cent, by weight of a fully developed freshly gathered rose unmoistened by rain. The factory is situate close to the Klein-Miltitz station of the Thuringian Eailway at the southern end of a rose field extending without interruption over a surface of about fifty acres. This factory is constructed on the most rational ^inciples and equipped with the best modern appliances. Every forenoon during the harvest, the freshly gathered flowers reach the factory within a quarter of an hour at most of the time of being gathered, and in traversing this short distance are not tightly packed, but distributed in baskets of moderate size. The hall in which they are placed when they reach the factory faces north, and is exceedingly cool, while in the factory itself care has been taken to secure the lowest possible temperature. There are four stills which can easily accommodate a charge of thirty Mtndredweights of roses in each, and the combined plant is able to extract without difficulty the otto ixom fifty tons ofros^s in the space of twelve hours. The stills are charged and emptied automatically in the course of a few minutes, and a few hands are sufficient to deal with the output of a whole working day. The stills are heated by steam. The total heating surface of the boilers covers about 360 square yards. The method of distributing the heat, the amount of heat applied, and the duration of its action on the flowers have all been considered in the construction of these stills, in order to suit them as far as possible to the delicate nature of the otto ; nevertheless the oil does not pass through these stills without being to some extent chemically affected in a way slightly detrimental to its true odour. It is probably to the Southern French that we «re * Experience teaches that over-matured roses, showing a more or less clearly defined violet tinge, contain less oil than others. This applies in a much greater degree to the white, or only slightly pink tinged roses. indebted for the invention of treating the roses by a process which extracts the odour in an unimpaired condition. This process, known as " maceration," consists in stripping the flowers of their green parts and steeping the petals and anthers in purified grease, then extracting this grease (or pommade) with pure alcohol, so obtaining what is known as the "Extrait." Although extreme cleanliness is observed throughout the rooms used for the preparation of the oil of rose, it is nowhere carried to greater perfection than in the rooms devoted to the manufacture of the " rose pommade." In these the floor and walls are covered with China tiles, which contrast beautifully with the glittering copper of the machinery. The whole premises are lighted by electricity. The otto of rose introduced into commerce by this firm will remain liquid at ordinary temperatures, will readily dissolve in spirit, and, used in the preparation of compound bouquet perfumes, will not deposit stereoptene, by reason that the bulk of that odourless substance has, in course of manufacture, been abstracted from it. Of course this oil is more powerful than the crude oil in proportion to the amount of stereoptene abstracted, but it is also pro- portionately sensitive to oxidation in consequence of its fluid character causing it to be more exposed to the action of the oxygen of the air than is the case with the crude oil containing stereoptene, which is semi-solid at ordinary temperatures. It therefore appears necessary to store this German oil in small bottles, or of a size according to the consumption. The original bottles in which it is supplied vary in capacity down to fifty (rrammes ; they are of yellow glass, and on the white leather cap covering the stopper, is the seal of the firm. After a series of experiments, Messrs. Schimmel have succeeded in preparing an extraordinarily strong and perfectly permanent rose water. This is prepared in two strengths, viz. : — " Double " — distilled from two parts by weight of roses to one part by weight of water. " Sextuple " — distilled from six parts by weight of roses to one part by weight of water. 58 Both are obtained directly from the roses for this special pur- pose, and are not a by-product in the distillation of rose oil. The sextuple rose water represents the highest ohtainable, concen- tration. If placed in ice overnight, small drops of oil, clearly discernable, separate out on the surface. Given normal flowers, a rose water prepared from more than six times its weight of roses would only retain the whole of its oil in solution at a tem- perature above the normal point, and thus become practically useless. A great advantage of the " Sextuple " rose water is that it enables the buyer to make a considerable economy in freight and duty, as, from one kilo of this water three kilos of rose water of ordinary concentration can be prepared by the simple admixture of two kilos of distilled water (or boiled and well filtered water.) Rose Cultivation in France. In the south of France, especially in the neighbourhood of Grasse, the cultivation of the rose has enormously increased, principally for use in the manufacture of rose pommade and the spirituous extract therefrom, the demand for which is very great. Large quantities of flowers are also used in the dis- tillation of rose water, during which process otto of rose is collected as a by-product. The French otto is more green in colour than the Bulgarian, and has a greater consistence, containing more stereoptene ; this is explained by the fact that it is the first runnings of the still, and the stereoptene being insoluble in water always comes over with the first part of the distillate, and separates on the surface of the water with the otto. At Grasse 8,000 to 10,000 kilos of rose petals (without the green parts) yield only one kilo of this oil. It is of very superior odour, and, accordingly, high in price, especially considering the large amount of stereoptene it contains. The variety of rose there grown is the B. ceniifolia, Linn. The bushes are set in rows, but not so close together as to form 59 thick hedges, as in Baloraria, nor do the plants attain such a height. Ground gently sloping to the south-east is preferred. Young shoots are taken from a five year old tree, and are planted in ground which has been well broken up to a depth of three or four feet. When the young plant begins to branch out, the top of it is cut off about a foot from the ground. During the first year the farmer picks off the buds that appear, in order to develop and strengthen the plant. In the fourth or fifth year the tree is in its full yielding condition. A rose tree will live to a good age, but does not yield much after its seventh year ; at that period it is dug up and burned, and the land planted with some other plant for one year. The flowering begins about mid-April, and lasts through May to early June, a time so short that difficulty is experienced in dealing with the enormous quantity of blossom produced, for of course loss of perfume occurs if the flowers are not immediately used. The buds on the point of opening are picked in the early morning. On some days as many as 150 tons of roses are gathered in the province of the Alpes Maritimes. At the factory the petals are first completely separated from the green parts ; this work is done by women, seated at long benches under a shed. The separated petals, of which there are sometimes as much as four tons accumulated on the floor at one time in one factory, are then either distilled with water for the production of rose water, or they are subjected to the process of maceration in warm fat or in olive oil for the purpose of obtaining the perfumed pommade or oil, and these products afterwards finished off by the process of " enfleura,ge," or " absorption." This consists in spreading the grease thinly on glass trays and spreading rose petals on the surface, changing the flowers daily until the grease is sufficiently impregnated. By this cold process the natural delicacy of the perfume is in no way changed. Prom such pommade the "extrait de rose" is afterwards obtained by agitation with alcohol and then congelation; the fat being frozen the spirit is readily separated. uo Physical Properties of the Otto. Tests of Purity, Chemical Constitution, Etc. Pure otto of rose is, at the ordinary temperature, a very pale yellow, or pale green, or nearly colourless liquid, according to its source. Its specific gravity at 20° C. varies from 0*855 to 0.'865. A reduction of temperature causes it to assume the appearance of a concrete mass, by reason of the formation of crystals of stereoptene in brilliant plates and aigrettes reflecting the prismatic colours. The proportion of crystals forming in the liquid varies according to the geographical position of the country in which the flowers producing it are cultivated, the degree of temperature at the time the flowers are gathered, and other causes more obscure. According to Bauer, it solidifies at between 11° and 16° C. In some experiments made by Hanbury in 1859,* the point of solidification of pure Turkish otto varied bet\een 16° and 18° C, that, of an Indian sample was 20° C, one distilled in the south of France was between 21° and 23° C, one distilled in Paris was 29° C, and one obtained in London by distilling rose water was between 30° and 32° C. Those results indicate that the cold climates of the north are unfavourable to the production of a very odoriferous oil, the high points of solidification resulting from a larger proportion of stereoptene, which is an inodorous constituent of no value to the consumer, but valuable to the fraudulent dealer, who takes advantage of its. high proportion, and can thereby add a proportionately larger quantity of geranium oil as an adulterant. The proportion of stereoptene content is certainly very variable. The Turkish oil may contain eighteen per cent., the French thirty-five per cent., and samples produced in colder climates have been found to contain forty-two, sixty, and even sixty-eight per cent, of this inodorous substance. Thus, a rose * Pharm. Journ. [2] xviii. p. 504. 61 grown in a cold or temperate climate is not so powerfully fragrant as one grown in a warm or hot climate, even if the amount of otto produced in its petals were the same in quantity, which is not the case, the statistics given on page 40 showing that the yield in Bulgaria is over 0"03 per cent., and the yield recorded at the Leipzig plantations* is only 0"02 per cent. For many years past chemists have been occupied with researches into the composition of both the solid and fluid constituents of rose oil. As regards the solid, stereopfcene (which can be separated by mixing the oil with three times its volume of seventy per cent, alcohol, freezing, and filtering), its nature was studied by Fliickiger in 1869, t and by Gladstone in 1872. t Fliickiger says§ : — " A drop of stereoptene let fall on paper is not dissipated by the heat of a stove, even after several days. When it is carefully melted at the temperature of sun- heat and then allowed to cool, it sets in microscopic crystals of a peculiar form, most of them being truncated hexagonal pyramids, which, nevertheless, do not belong to the rhomboidal system, as their angles are manifestly unequal ; many of them are curved into the form of an S or §. Examined under the microscope by polarised light, they present, by reason of their refractive power, a very brilliant aspect. Stereoptene is a very stable, unalterable body, but on boiling it for several days in fuming nitric acid it slowly dissolves and decomposes into various acids, homologues of the fatty acids, and possibly also fumaric acid. Amongst the former, butyric and valerianic acids ' are recognisable ; the principal product, however, is succinic acid, which was found in pure crystals, giving the well known reactions. According to experiments of the same observers, there are many points of resemblance in the physical character- istics of stereoptene and paraffin." More recent experiments made by Schimmel and Co. 1| showed that by digesting stereoptene at a temperature near to its melt- ing point, it was possible to obtain, by crystallising, fractions of « Schimmel's Beport, Oct., 1893. t Pharm. Journ. [2] x. p. 147. J Journ. Chein. Soc. x. p. 12. § Hist. Des Drogues, 1878, i. p. 473. || Berioht, Oct., 1890. 62 different melting points, and by repeatedly putting the substance through these operations, two constituents were finally obtained, one of which melted at 41° C. and the other at 22° G. The result of this experiment on Turkish stereoptene was confirmed by repeating it on stereoptene of known purity resulting from the distillation of roses grown by themselves. It is, therefore, manifest that contrary to the views hitherto held, rose oil stereoptene is not a uniform substance, but a mixture of what are probably a whole series of homologous hydrocarbons. In a previous report of the same firm* the following informa- tion is given respecting the detection of spermaceti in rose oil : " The stereoptene of rose oil is not altered by boiling with alcoholic potash solution, whilst spermaceti, which is essentially palmitic-cetyl-ether, is saponified by that reagent, with the formation of potassium palmitate and cetyl alcohol. Upon this fact, the following method of examination is based : — " 1°. — Isolation and determination of the stereoptene. — Fifty grammes of oil are heated with 500 grammes of 75 per cent, spirit at a temperature of 70° to 80° C Upon cooling, the stereoptene separates nearly entirely. It is removed from the liquid and treated similarly with 200 grammes more of 75 per cent, spirit, and this operation is repeated until the stereoptene is obtained perfectly odourless ; a second treatment of the crude stereoptene being usually sufficient. 2°. — Determination of an admixture of spermaceti. — Three to five grammes of the stereoptene are boiled for five or six hours in a vessel with a reflux condenser v/ith twenty to twenty-five grammes of five per cent, alcoholic potash solution ; the alcohol is then driven off and the residue treated with hot water. Upon cooling, the greater part of the stereoptene separates on the surface as a crystalline mass. The alkaline liquor is then poured off, the stereoptene washed with some cold water, then again melted down with hot water, allowed to cool, and the water poured off, and this is repeated until the wash water is neutral. The united aqueous liquor is shaken twice with ether, to remove * Bericht, April, 1889. 63 suspended stereoptene, and after separation of the ether is acidulated with dilute sulphuric acid and again extracted with ether, which, upon evaporation should leave no residue (fat acid). As a cheek, the stereoptene, including that withdrawn from the alkaline liquid, is dried at 90" C. and weighed. There will, however, be a small loss due to the volatiHsation of some stereoptene. In a control experiment in which 1-7 per cent, of spermaceti was added to a sample of Turkish oil, 1-5 per cent, was recovered." The method in use in Bulgaria to detect the amount of adulteration with oil of geranium is very simple, and very defective ; it is called the congelation test, and is based on the fact that the addition of geranium oil lowers the temperature of congelation of the otto in proportion to the quantity added. Presuming that a perfectly pure Bulgarian otto congeals at from 14° to 16° Eeaumur it will, if geranium oil be added to it, only congeal at 13°, 12°, 11°, and even lower according to the amount of " geranium " added. The purchaser takes a twenty- gramme flask containing fifteen grammes of the otto to be tested, and plunges this bottle into a basin of water, the temperature of which is regulated by the addition of hot and cold water, and read off on a Eeaumur thermometer. In a pure oil the con- gelation commences in three minutes, and at the end of ten minutes should be so complete that on turning the flask upside down the contents should not run out. Payment is made according to the degree marked by the thermometer when this congelation is arrived at ; the degree of congelation indicating the degree of adulteration.* Christo Christoff, of Kezanlik, states that " formerly paraf&n was added to the otto, in which it dissolves very well, and in * In the Report of Christo Christoff, of Kezanlik, from which the above information is taken, the temperatures are given in degrees of Reaumur, a scale which appears to be still in use in Bulgaria. To convert degrees of R&umer to degrees of Centigrade, R -7- 4 X 5 = C. To convert Centigrade to Farenheit, C^5 x 9 -f 32 = F. 64 spite of the presence of geranium the congelation takes place at 15° E. to 16° E., but the crystals are opaque, of a dirty yellow, and break up, forming a sort of muddy substance which collects at the top of the flask. The simplest method of adulteration consists in adding to the roses to be distilled some white roses, the product from which, though less fragrant, is much richer in stereoptene than that of the red rose; furthermore, this otto, which normally would congeal at 16° E., can, by geranium, be brought down to 14° E., and still remain within the pre- scribed limits." Besides the ordinary crystallising test above explained, it would be well to examine the manner of crystallisation in order to ascertain if that crystallisation be caused by stereoptene or by spermaceti. The crystals should form in brilliant plates and in aigrettes reflecting the prismatic colours, in all parts of the liquid. Spermaceti is precipitated in a solid mass, easily recognisable, besides whicfi its melting-point is 50° C, as is that of most varieties of parafSn ; the microscopic crystals of the last, although somewhat resembling those of stereoptene, are easily distinguishable by careful comparative examination. A test for the presence of the oils of rose geranium, palma rosa, etc., is described by Ganswindt* : — "On mixing a few drops of pure oil of rose with an equal bulk of sulphuric acid, the rose odour is not changed, but oils used for adulteration change their odour ; or five drops of the oil are mixed in a dry test tube with twenty drops of pure concentrated sulphuric acid ; when the mixture is cool it is agitated with twenty grammes -of absolute alcohol, when a nearly clear solution should be obtained, which, heated to boiling and then allowed to cool, remains clear yellowish brown. In the presence of the oils of rose geranium, etc., the alcoholic mixture is turbid, and on standing separates a deposit without becoming clear." The above mentioned test has been confirmed ten years later by Panajotow,* who mentions that the brownish red fluid resulting from the mixture of equal parts of oil of rose and con- * Amer., Journ. Pharm. 1881, p. 250. 65 centrated sulphuric acid dissolves completely in ninet3'-five per cent, alcohol to an almost colourless solution, while the similar product resulting from oil of geranium is rendered turbid by the addition of alcohol, and a yellow, fatty, flocculent mass separates. 0. F. Miiller has recently observed that a number of resins, oils, and lacs yield colour reactions with fuchsin solution de- colourised by sulphurous acid, tbe so-called " Schiff's reagent." Applying this test, Panajotow foundt that if two or three drops of "Indian geranium oil" be shaken in the cold with two c.c. of the reagent, it gives at first a blue violet, and after two hours a beautiful blue colouration. Under the same conditions piore otto of rose only gives a red colouration after twenty-four hours, and hence the slightest admixture of geranium oil is recognisable, because the bluish colouration is always formed at once. This test is, however, condemned by certain distillers of otto of rose as perfectly inefl&cient and useless, by reason that the reaction is occasioned by the presence of an aldehyde, citral or geranium aldehyde, formed by oxidation of geraniol. This is coloured by the reagent at first blue violet, after some time a turbid greenish blue ; whilst the aqueous liquid assumes an intense blue violet colour. As hereafter shown, the bulk of the liquid portion of otto of rose consists of geraniol (the alcohol which Eckart called Ehodinol), and as this readily yields on oxidation citral (geranium aldehyde, or more correctly Geranial), also as this oxidation is partially effected when the otto is exposed to the air, the fuchsin- sulphurous acid test cannot be depended upon. As regards the fluid constituents of otto of rose. The papers that have been published upon this subject generally agree in describing them to consist mainly of an alcoholic body, but they contradict each other with regard to its chemical constitution. Thus : investigations made by Eckart, at the Breslau University* resulted in his arriving at the conclusion that the bulk of the liquid portion of the samples he examined consisted of a body * Berichte d. Deutscb. Chetn. Ges. xxiv. p. 2,700. t Loc. cit G6 isomeric with, or nearly related to Geraniol, to which, arguing from its chemical characteristics and from analysis, he gave the formula CioHigO, and called it Rhodinol. (He also found that both the Turkish and German oils submitted to him contained about five per cent, of ethyl alcohol, which he distilled off below 100° C. As both specimens were of undoubted purity, the source of this ethyl alcohol could only be conjectured — either ethyl alcohol is a natural constituent of rose oil, that is to say, occurs already formed in the petals, which in such quantities is very improbable, or it is formed by some kind of secondary pro- cess during the distillation or transport of the roses, which is a postulate easier of acceptance ; indeed this explanation has since been given as regards the German product by the fact that in 1892, the manipulation of the crop being effected in a more rapid and careful manner, no ethyl alcohol at all was met with. It can therefore be assumed with a certain degree of certitude that the ethyl alcohol was a product of fermentation. The roses packed in baskets one above another, or in sacks, soon undergo a spontaneous fermentation during transport in hot weather. They are also subject to the same change when piled on the floor of a factory. The German 1892 crop had not to undergo any transport, the factory being in the centre of the plantation, and the roses being thrown into the apparatus freshly plucked from the bushes, it is readily understood why no ethyl alcohol could be detected in the product.) Eckart's statements may be abstracted as follows : — " The stereoptene is separated by dissolving the otto in 75 per cent, alcohol at 70" — 80° and cooling to 0° C. The alcoholic solution is then evaporated in a vacuum to obtain the Ehodinol. The physical constants of this body vary according to its source, between the following limits: — Boiling point 216 — 217° C, refractive index 1-4710 — 1*4725; refraction equivalent 48'97 — 49"28; dispersion ll'l^ — 12-5; specific rotation — 2*7 to — 2"8. The vapour density corresponds with the molecular weight * Inaugural Dissertation, Breslau, 1891 ; Archives der Pharm. 1891, pp. 355—389 ; and Pharm. Journ. [3] xxi. p. 664. 67 142-43 (Ci„Hi8 0=154). Rhodinol shows all the reactions of an alcohol. Oxidation with potassium bichromate and sulphuric acid converts it into an aldehyde, Rhodinal, believed to be an isomer of, and closely resembling, Citral, which can be obtained from G-eraniol by similar treatment." The above statements of Eckart have subsequently been fully corroborated by Barbier,* who obtained bi-hydrochlorate of cipentene by treating rhodinol .with dry hydrochloric acid. From this combination he liberated the dipentene, which he recognised by its tetra-bromide melting at 124°. Barbier also obtained the acetic ester of rhodinol. It yielded back unaltered rhodinol upon saponification and possessed the formula Co Hi^ C2 H3 ; whereas, according to Eeformatzky and Markovnikoff, its formula is Cio H,9 C2 H3 0. These last named authorities examined three samples sent to them by the Bulgarian Government. + The following is an abstract of the most important portions of their paper : — " The crude oils turned the polarised ray of light to the left, as follows: 3° 34-5', - 3^ 53' and -3° 20'. The separation of oil and stereoptene was effected by filtration at C^ and at — 55° . Prom the liquid portion a principal fraction having a boiling point of 222° — 225° was next isolated by fractional distillation. The analysis of a fraction boiling at 224-7° gave the formula Cio H^o 0. The authors call the principal constituent, which possesses alcoholic properties, Roseol. From this roseol they prepared an acetic ester, with a boiling point between 235° and 236°. Saponification of this ester resulted in the recovery of the roseol. The action of dehydrating agents converted the alcohol into a hydrocarbon of which the analysis responded to the formula Ci„ H,8, rather than to that of C,o H16. Treated with chromic acid solution, roseol oxidised into an aldehyde of a lemon or melissa-like odour. Its sodium-bisulphite compound was crystalline." ^ Derives et constitution du Rhodinol de I'essence de roses, Comptes Rendus, cxvii. p. 771. t Ber. Deutsch. chem. ges. 1890 , p. 3191 ; Journ. f. prakt. Chem. ['2] xlviii. p. 293 ; Pharmaceutisohe Zisohr. fiir Russland xxxii. p. 102 ; and Journ. Russ. Chem. Soc. xxiv. pp. 66.3-686. 68 As, up to the time of these researches, " rhodinol " had not been found in any essential oil other than rose oil, it was generally taken for granted that this body was peculiar to the rose, and that the plebeian geraniol (supposed to bear the same relation to rhodinol as common tin to noble silver) was a characteristic constituent of other plants of a rose-like odour, such as certain species of pelargonium and andropogon. Monnet and Barbier recently opposed this opinion in a treatise bearing the title " Sur une nouvelle source du Ehodinol."* In this paper they maintained the existence of considerable proportions of rhodinol both in French and in African oil of geranium mixed with other substances which disguise its nature. It is evident that this discovery, if proved to be correct, would have been of the greatest possible practical importance ; for if rhodinol could be obtained in a pure state from geranium oil the road would have been discovered to the synthetic preparation of rose oil. Unfortunately the alleged discovery has proved to be without foundation. Shortly after the publication of the treatise in question, experiments in the isolation of rhodinol from oil of geranium were made by Drs. Bertram and Geldemeister in the laboratory of Messrs. Schimmel and Co., but without success. Messrs. Schimmel and Co. state, in their report of April, 1894 : — " We did not succeed in obtaining a body possessing the properties of Eckart's rhodinol, but we were able to satisfy ourselves that the fractions in which rhodinol should have been found consisted in reality, for the greater part, of Geraniol (the smell and other characters of which were modified by the presence of a small proportion of substance leaving an odour of mint)." They mention t that the published data relating to the physical characters of the product obtained from rose oil and named rhodinol and roseol are discrepant, as shown on the next page. * Compt. rend, cxvii. p. 1092. f Journ. f. prakt. Chem. [2] xlix. p. 185. (59 2 O I^ ■^ t^ t^ C^ TO CO CO ^ o o o '■< cq o o 1 o 1 a o Q CM to 1 o r^ 1 ■^ o -* Tj< *.~ r-^ (M cq (M =3 3 3 Pl .^ i! EH pq H H f^ p^ c3 T-l , ^ PI C3 ^^ t^ t3 r^ fl oj li si ;-( -*a o P 03 l3 u o ^ ai eH s o a « a 70 Eckart states that rhodinol cannot be distilled unaltered except under reduced pressure. Markovnikoff and Eeformatzky state that roseol can be distilled without change under ordinary- pressure. Owing to such differences in the statements of various authors, we were compelled, in the course of our investigations, to prepare the alcohol for purposes of control, from rose oil. It then appeared, to our surprise, that by far the greater part of the supposed rhodinol consisted of Geraniol, besides which only small proportions of a honey-like smelling body, which has not yet been further inquired into, are present. In conducting this investigation, Bulgarian oil of 1893 was freed from stereoptene by mixing it with three times its volume of 70 per cent, alcohol, freezing and iiltering. After distilling off the alcohol a pale yellow oil remained of sp. gr. '8863 at 15° C. Optical rotation — • 2° 56' for 100 m.m. By saponification with alcoholic potash the amount of acetic ether present was found to be only 6'3 per cent, for an alcohol of the formula C,o H,8 0. On distilling the oil at 11 m.m. pressure it began to pass over at 100° C, and when the temperature had risen to 159° there remained a thick liquid having the smell of sesquiterpene. By distilling under a pressure of 9 m.m. three fractions were obtained, the second and third being the largest : — 1. At 101° — 106° 2. „ 105° — 115° 3. „ 115° — 145° Under normal pressure the oil was separated into four fractions at the following temperatures, the second and third being largest, but no decomposition was observed : — 1. At 215° — 228° 2. „ 228° — 230° 3. „ 230° — 233° 4. „ 233° — 240° The boiling point of the principal portion of the oil being that of geraniol, the presence of that alcohol was tested for by conversion into the calcium chloride compound described by 71 Jacobsen*. From this combination geraniol was liberated by treating with water, the product boihng between 106''-8 — 107°-2 under 8 m.m., and under normal pressure between 229'^ — 230° C. It had a ap. gr. of -8817 at IS* and presented the other characters of geraniol. The amount of this constituent in Turkish rose oil was estimated at 90*4 per cent. German rose oil (distilled by ourselves, and therefore absolutely pure) examined in a similar manner, proved to have the same com- position. The geranyl acetate present amounted to 4*4 per cent. By distillation under 10 m.m. the oil almost all distilled over between 116" — 140°, the first fraction amounting to 88 per cent., passing over between 110^ — 111°, and distilling under normal pressure without residue between 228° — 232°. The difference observed in the case of Turkish oil may have been due to its distillation by open fire and partial resinification or change thus effected. Geraniol being the chief constituent of Palmarosa oil (Indian geranium oil from Andropogon Schoenanthus) the geraniol prepared from that oil was examined and found to correspond with the geraniol of rose oil. Similar results were obtained with geraniol prepared from African geranium oil, obtained in Algiers by distilling the leaves of various kinds of pelargonium with water. We have already shown that citronella oil contains geraniol, and it proves to be identical with that from other sources. Durinc^ the investigation the identity of Licarhodol (obtained by Barbier by heating Linalool with acetic anhydride) t with geraniol, was also established. The following table will be found useful for the purpose of a handy comparison of the chemical and physical properties of geraniols from different sources :— * Ann. Ohem. clvii. p. 234. f Compt. Eend. cxvi. p. 1,200. 72 •NOixovajaa av''inoa7onji; •g^.g^ sexnoepTn-ene^^ii:^^ g q:jiAi 0'*'R"'iJ ■toj ^jvouaaoaHX TUAL ECULAl. FKAC- lON. 00 -H 'O CD 01 CO 05 65 61 CO 3 S w ^ rfl Tf ■* -f ■* T< <1 cp^ § CD CD 1 CO CD CO o* 00 CO t^ t^ CD CO Q o t~ t~- t^ J-^ 1^ 1^ . ^^ ■* ■* ^ T •* ■f oi I— 1 r-t ■"^ f—l *"* '^ kO TiH rf t^ a> CO n o (N o< CO ^o 00 00 00 00 00 00 00 00 00 00 00 00 '^i 6 o 6 b 6 lJ f5 03 <: 2 > ^ci^ "O ■0 i O D-^ O Ct Of n° g ^ S O OS CO iM CO CO CO CO 3 00 CD 05 CK 05 mpp C^ 'M Ol IM (M 'M 11 oo r- da o P o a s a s a sa ^^ a 7 s. 7 a 7 a 7^ 7 a 7 a 2^ 4." ' ro 00 '^ 1 00 lo 00 1 o> c " ?-^ s,^ it "S it -t3 1^ c t— ' r—t ■"^ '"' i-H '~' CO d ,,_^ T^ •^ ri r^d as § ^ (D OS QQ s a • so d CD d .a g o ^^ i'e. EH 1 cb ir 1-& .-! CM CO Tp •^ CD 73 This table shows that the physical properties of the alcohols obtained from the different raw materials described in it are absolutely identical. The same is the case with regard to their odour, taste, solubility, &c. The slight differences in specific gravity may be due to the ready oxidation of geraniol, and to partial formation of citral and other products by exposure to air.* As to the chemical relations of the alcohol of rose oil and the geraniol from other sources, it appears from the nature of the products obtainable by the action of dehydrating agents that the composition of this body is represented by the formula CioHijO. Eckart showed that by treatment with phosphoric anhydride, rhodinol loses one molecule of water, and that dipentene is formed.! Monnet and Barbier confirmed the formation of dipentene, but they obtained this terpene by passing dry hydrochloric gas into rhodinol. I Barbier had also obtained dipentene from the geraniol of Palmarosa oil.§ Bertram and Gildemeister have since obtained terpene by the action of formic acid upon geraniol, but terpinene is also formed, and this change points to the formula Cjo H,8 0. The production of citral from "rhodinol " by oxidation is also important. Eckart obtained, II by treatment with chromic acid, an aldehyde smelling like lemon, C,„Hi6 which he named rhodinol, and sub- sequently Tieman and Semmler^ proved its identity with citral, showing that the formula of rhodinol must be do Hia instead of CoHjoO that adopted by Markovnikoff and Eeformatzky, and citral had long before been obtained by Semmler from geraniol.** The acids produced by this oxidation, called by Eckart rhodinolic acid and by Semmler geranic acid, are also the same body. Potassium permanganate oxidises geraniol to isovalerianic acid,tt aii 00 " -2 g ONIFICA- NUMBER F THE etylised Oil. r^ C5 »-^ (M CO C5 t~ IC «0 (M OS CO 00 lO Tf< ■* ■* ^ b t ■ •z) •" H ~ B ~ 6 £ '^ 6 1 J, "=■ ^ 5 '5 S 3 2 o <; 1 '^ '0 " 03 mo " '-4J M c- § 53 t. ft d p -tj ?H 'O ' CO -# o rt CO rt — 00 00 !£) UO tH 00 03 05 OS C^ OS OS OS OS o CC C5 00 00 00 00 00 CO 00 00 CO OS GO CO m -^ o 6 6 O O O O O OS o 6 6 Ed 1 Vj W ... . . - 1 -^ • ^ p 2 bp ft •rH 1-:; CI ~*^ ef-i Pi