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in the rapid determination many substances, of particularlywhenthey are

presentonly in small concentrations.
ACKNOWLEDGMENT

The author wishesto expresshis thanks to the Directors of County Laboratories, Ltd., for permission publishthis paper. to
REFERENCES

Clark, G. R., y. Soc. Cos. Cicero.,1951, 2,290.

a Bolton & Marshall, Soap and Sanitary Chemicals, 1949, 25, 129. Hawksley, B.C.U.t?./t., 1944, 8, 245 (Review).

'"Moore& Stein,f. tiol. Chem.,1948, 176, 367.

Lederer & Tchen, Bull. Soc. Chim. Biol., 1945, 27, 419, via f.C.S., 1949, 2121 6 Anal. Meth. Comm. Rep. Analyst, 1954, 79, 397. ? Fogh, Rasmussen & Skadhauge, Anal. Chem., 1954, 26,392.

/t Lecture delivered the Societyon 5th ]kIarch, r954 to

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By J. PICKTHAnr, F.R.I.C.*
ITRODUCTION

THERE MUST be a number of non-technical members of this audience who are

interestedin perfumesand who would like to know somethingof their nature and the way in which they are employed. Further, many of our technicalmembersuseor handleperfumeswithout, perhaps,having had the opportunityof giving the subjecta comprehensive study. Nobodywould doubtthe importance perfumes the cosmetic associated of in and industries: they are as important to success attractive packingand presentation. as One might add that a perfumecontinues please to the buyer long after the appealof the container faded. has Most peoplein this world are favourablyimpressed a goodperfume, by although naturally preferences are widely divergent. Even the men, althoughoften reluctantto admit it, are influenced odour. by My aim this eveningis to introduce perfumery to those who know it only by name,to assist thosewith a workingknowledge and to interestthe
experts.

Perfumery,althoughone of the oldestarts of expression, youngin a is scientificsense. We know little of the mode of action of odourperception
and much work of a scientific nature remains to be undertaken before we

candevelop theories. Frankly, I donot believe that the manyclassifications offered have greatlyhelpedeitherthe established the buddingperfumer. or
The well-known numerical classification, I am afraid, confuses without

offeringa starting-point a language even an alphabetfor perfumers. as or It is this lack of descriptive wordsthat makesperfumeryso difficultto
* Polak & Schwarz (England) Ltd., Enfield, Middx.
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discuss. A layman with a tune running through his mind might hum or whistle the tune and enable a pianist to record his impressions. One could likewisedescribe sceneor subjectto a painter and commentupon colour a

depthsand tonesso that the impression couldbe translatedand recorded.

When one acknowledged perfumer speaksto another equally accomplished in the art, eventhey are sadlydeficientin descriptive phrases and the jargon they employwould be Greekto an outsider. We speakof top, middle and back notes,intended to convey a scaleof diminishingvolatility of the constituents. This samescaleis alsoemployedon a weight basislight, medium and heavy notes. We speakof warmth of odour,but what doesthat mean to the layman,and just how closely wouldtwo perfumers agreeon a temperature scalein describing range of chemicals oils ? a or We limit our use of colour comparisons green, a word intended to be to descriptiveof odoursassociated mainly with leaves, but how green is my Lily of the Valley ? We make half-hearteduseof linear measurements and talk vaguelyof "depth." Naturally, we bring "aromatic," "aldehydic," "phenolic," "fatty," "burnt," "leathery" and a host of partially descriptivenamesinto our conversation,but again the valuesare vague and uninformativeto the outsider and far from definite to the expert. After all, there are a great number of aldehydes,to name but one word from our dictionary. We comenearer to reality when we speakin terms of flowers,for despite the variety of odoursto be foundin onefloral type, the namingof Lavender, Rose or Carnation is certainly descriptive,although even the use of floral namesis limited to a relatively few well-knowntypes. This frustrating lack of vocabularybrings to mind a story which I am
sure will be familiar to all members of the audience. It concerns Noah and

his Ark and, incidentally, Noah must have had his problemswhere odours are concerned. The story goesthat Noah named his animalswith little or no effort, until he cameto the frog,which completely stumpedhim. Asking his wife's opinion, she immediatelysaid, "Call it a frog," and when Noah askedwhy this particular name, Mrs. Noah replied, "Because lookslike a it frog." Admitting, therefore,our lack of vocabulary,how are we to rectify this inadequacy Obviously, establishing scale unitswhichwill accurately ? by a of

and precisely describe given odour,but beforesucha step can be taken a we have still to investigate and understand just exactlywhat odour is and
how it works. ODOUR PERCEPTION

This phenomenon constitutes scientific a miracle. The ear and eye cater for a relatively small number of vibrations but the nose can receive and identify an apparentlyunlimitednumberof differentodoursor, at any rate, relay messages which the brain translatesas differences. Many theorieson
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odourhave beenput forwardand, in the main, they can be dividedinto two classes--the chemicalor corpuscular and the physical. The latter school of thoughtsuggests that odorous substances radiate high frequency vibrations and that differences wave-lengthare responsible differences odour. in for in To someextent theseideaswerefoundedon the falseassumption that certain chemicals emitted odourfor longperiodsof time without lossin weight. Thus natural and synthetic muskswere said to be capableof transferringtheir odour to grease-smeared surfaces without weight loss,when exposed the to atmosphere. Theseexperiments reflectupon the inadequacies our weighof ing equipment,althoughonemust bear in mind that 1 gm. of Musk Ambrette is theoretically capable of releasing2.7 x 102 molecules,and that one "sniff" will bring odour response when as little as 0.00000000025gms. of natural musks are presentin the air and, perhaps,ten times this amount of syntheticmusk. I was rather intrigued with the little item from February International Perfumer. This note mentions Eugene Rimmel's extraction of odorous materialsfrom petalsby meansof volatile solvents and is a quotationfrom his book, written nearly 100 years ago. Mentioningthat the process had not been put to any practicalapplicationon accountof expenses, finishes he as
follows:

"It has, however,servedto prove the imponderability of fragrant molecules, althoughthis substance for from its high state of concentration appears at first sightto be the solidified principleof scent,after it be treatedseveral times with alcohol,it gradually losesall its perfume, and yet the residueis not found to have lost one atom of its weight." I think we can accept the fact that odorous substances release molecules which are air-borneto the noseand that with somesubstances quick intake a of breath or "sniff" is required to provide the necessary concentrationof molecules evoke odour response. to E. D. Adrian writes effectively on the subject in his "Flavour Assessment" in Chemistry and Industry, November28, 1953, and describes how the essentialstep in odourperceptionmay be the contact of molecules with the millions of hairs presentin the sensorycells of the olfactory cleft and the surfacelayer of mucusand water. Just as we can acceptvolatility as an essential property,sowe can includerelativesolubilityin water and lipides.
In fact, I like to think of an odorous molecule as a kind of emulsifier, its

effect and performancedependingupon its ability to overcometension between surfacesand its relative affinity for aqueousand "oil" phases. This "fixing" of the moleculeat the surfaceor interface could determinethe setting of the angles bonding the atoms of the molecule, changesin the bonding anglessetting up variations in potential energy. Just how the released energyis transmitted and analysedis another matter. To me the whole mechanismhas somethingof the Hollarith punch-cardsystem.
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Information

in the form of molecules is fed to the nose where it is fixed via

its relativesolubilityat the interface. Here it takeson a penetrativeshape determined the bondingangles. Electric charges by are allowedto pass throughthe "punched card" and proceed the olfactoryreceptors to which relay the appropriate message the brain. It is quitebeyondme to enlarge to on thesevagueand unhelpfulideas.
DEFINITION

I have elsewhere suggested that perfumerymay be definedas the art of producing creatinga pleasant or impression blendingsome many odours by or and that a simplemixing of odoriferous ingredients may not necessarily produce a harmoniouseffect. Despite the effortsof certain modern "artists," perfectionof subject-matteris the art of the painter and sculptor, and the value of his work may be iudgedby all with eyesto see. Musicand perfumery are lesstangible to the senses and consequently lesseasy to defineanG appreciate. With music, a "mixture" of notes may or may not produce' harmony to the ear; the skill of the arrangerand dispenser will determine' this point. Even in this caseonly the expert can criticallyjudgethe quality of a pieceof musicand the way in which it is presented. In much the same way we can arrange our odour notes and presentthem for the approval of the nose,and whilst the expert will obviouslybe capable of a more critical
examination, the individual, as with music, "knows what he likes." It is

almost as easy to strike the wrongnote in perfumeryas in music,although, thankfully, I say lesspeoplewill be awareof the fact.
TRAINING

Are perfumers madeor born? I suppose eachsuccessful perfumermust "haveit in him," but, asin all walksof life, longandarduous practice the is keynoteto success. There are somany thousands ingredients consider of to
and so many ways in which to use them. Perhapsconsideration the of

trainingof a perfumer wouldofferan introduction his ultimaterequireto ments. Unfortunately, thereare no organised schools perfumery no of and accepted curriculum.Onecanonlyindicate methods would the one personally adopt or recomlnend. Let us assumethat the trainee starts with a

reasonable knowledge chemistry, of particularlyorganicchemistry--that

is the chemistry the carboncompounds of whichcomprise raw materials the
with which he will work. For the moment he is not concerned with theories

or physics, but with becoming familiar with his perfumeryingredients. What have we to offerour hopefulby way of vocabulary Precious ? little

which helphim. Classifications been will have made whilst and perfumers in general understand other a certain can each to extent, twopeople no appear
to agreeon all points. It will be necessary showhim a selectednumber to of importantingredientsthoseessential or synthetics mostcommon oils in
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use, forhimto memorise sothathewillimmediately and them recognise

them individually and in certainsimplecases whenoccurring combination in with each other. We might well selectbergamot,lemon,lavender,bols de rose, geranium, vetivert and sandalwoodfrom amongst our essential oil group. Hydroxycitronellal,benzyl acetate, linalool, linalyl acetate, amyl cinnamicaidehyde,phenyl ethyl alcohol,alpha ionone,musk ketone,musk ambrette,geraniol,terpineoland methyl nonyl acetaldehyde might form a fair selectionfrom our synthetic range. Add to this one high boiling solvent in caseour solidsexceedthe limit of solubility in our mixture and to act as a general "fixative." Benzyl benzoate may be our choice. I hope to make
mention of "fixation" later in this talk.

An association ideasis the finestbasisfor remembering identifying of or an odour. In this connection,a knowledgeof chemistry or a method of extraction or manufactureleavesan unforgettableimpression the memory on and opens way to othersimilarappreciations. expression the The "aldehydic" may meanlittle to a non-technical person, evenalthoughhe hasoftensmelled suchproducts,but to have a clear picture of an aidehyde,to visualisethat reactive carbonylgroup,its relationshipto alcohols and acids,is to retain its odourin the memory,not only for eachindividual aidehyde,but as a general classification. Most experienced perfumerswould successfully place a new chemical in the appropriate class--alcohol, aidehyde, ketone, ester, etc. Starting with the essential oils,whichare volatileproductsof vegetableorigin, our traineeis off to an easystart. The lemonsucked half-time,the piece at of lavenderhead idly pluckedfrom a convenientgarden, etc.

Synthetics more difficultto associate are with eventsor knownthings and onemay be forced cheata little and associate to them with essential
oils, fruits or flowers. Thus one can easily connectlinalool and linalyl

acetate with bergamot and lavender, oil phenylethyl alcohol with the full
note of the roseand iononewith the violet. Very many more instances may

bequoted, astheperruiner and, progresses, fieldofassociations sohis widens.

For instance,he will in time connectamyl cinnamicaidehydeand benzyl acetate with the odour of jasmin, hydroxycitronellalwith the odour of

lily of thevalleyandlilac,but onlyafterhehasmade those associations by practicalexperimentation. Undoubtedly hardest mostefficacious of remembering the but way your
raw materials is to handle them in an intimate manner, that is seek closer

contact working an analyst a finechemical by as in laboratory, operative an in a factory producing isolates synthetics.You will neverforget iso or the eugenol which refused solidify temperatures below melting-point to at far its
and then does whenyou put it away in disgust. Remember so thoseinterminable melting-points recordings results Muskambrette C., and of ? 85 muskketone136 C., muskxylol 113 C., exceptwhen it became stubborn
and reverted to its other form and melted at 105 C. ? Rememberthe way
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citral and lemongrass turned your skin yellow and anisaldehydeoxidised to a white solid, and how phenyl acetaldehydepolymerisedto a viscous liquid ? These and a hundred more experiences one remembersand forever associates with the appropriate odour. But to return to our selected ingredients, perfumer-to-be, our lackingthe background outlinedabove,sets out to memorise eachodour,makingwhat association can and by continuhe ous effort perfecting his olfactory memory. From the few ingredients already mentioned he may producea crude but identifiable range of floral or other mixtures. There are four typical floral odours which occurrepeatedly in our bouquet or fancy perfumes--rose, jasmin, lilac, muguet and, in addition, perhaps violet. The rose odour may be made basically from phenylethyl alcohol, geranioland geraniumoil. The latter oil was specially included in our limited range as it contains the indispensablealcohols rhodinol and citronellol and certain esterswhich possess intense rose the odour. The lilac impression givenby phenylethyl alcohol, is hydroxycitronellal and terpineoi. The muguet by hydroxycitronellal, terpineol, phenyl ethyl alcoholand geranium,the latter usedfor its rhodinolnotes. Jasmin is lesseasyto define termsof a few selected in items,but is typifiedby amyl cinnamic aidehyde, benzylacetate,linalooland linalyl acetateand,perhaps, hydroxycitronellal, togetherwith small amountsof the ever-present phenyl ethyl alcohol. Sweetening effects any of thesefour basicodourtypesmay to be achievedby tracesof musk ketone. Below in tabular form is shownthe four floral formulae, making use of eight synthetics(or isolates)and one
essential oil.

Phenyl ethyl alcohol.. Hydroxycitronellal ..

Geraniol ....

Rose 40 5
45

.Lilac 20 35
-

Muguet 10 40
15

Jasmin 10 5
-

Geranium

Oil ....

Terpineol .... Amyl cinnamicaidehyde Benzyl Acetate ..

Linalool Musk ketone ....

5
-

25 5 5
5

15 5 5
-

35 40
5

Linalyl Acetate
....

..

traces

5
traces

5
traces

5
traces

Violet may be built in simplefashionfrom alpha ionone.

The formulae shownare, of course, crude and only in roughproportions. Geraniol,for instance,is given only as a representativeof the rose-alcohol group. In roseit would be supplemented citronelloland rhodinol accordby ing to type and cost. Further, many refinementsand more attention to blendingproportionwouldbe necessary, the table is helpfulif only to but
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indicate how certain ingredientsoccur in each type. Thus phenyl ethyl alcohol,hydroxycitronellal and benzyl acetate are presentin all four perfumes, and amyl cinnamicaidehyde and linalyl acetate in three and the remainderin two. By makingsimplemixturesof the four basictypes many "blends" or bouquetsmay be formulated. Thesemixtures may be further modifiedby ringing the changes with bergamot oil, vetivert, sandalwood, alpha ionone,musk ketoneand musk ambrette, from the ingredients originally given to our trainee. Final sophistication eventuallybe achieved will by careful use of methyl nonyl acetaldehyde. Without doubt, a second perfumerwould approachthe subjecton very different lines and may well considerthat important basic raw materials have beenneglected that unnecessary or complications have beenintroduced at an early stage. However,many traineespassing throughour perfumery laboratories have benefitedfrom this particular approach. Having reacheda stagewherehe is reasonably well acquainted with the selected raw materialsand with an approximateidea of how his four basic floral odoursare built up, he now widens his range of raw matehals. He will come to understandthe basic odours of other floral perfumes,e.g., carnation typified by clove oil, iso eugenoland eugenol,modified by the rose complex. It will be advisablealso to attempt to imitate or modify certain essential oils and in this caselavenderis a goodexample. Lavender oil, offeredin many grades,and lavandin are in themselves excellentbasic raw materials,especially soapperfumes, for but by themselves they are but indifferentperformers. They require"buildingup," supporting and greatly modifying before they may be considered adequate soap. At the same in time it must alwaysbe remembered that the presentation a perfumein whatever of the medium should aim for an individual character: for somethingthat differs from the next preparation. Before passingfrom the types with which our trainee will become familiar, Colognesshould be mentioned. Quiteapart from the populartoilet water,the Cologne idiomis usedto give the fresh citrus note to many creations. Colognes essentially are basedon bergamot, lemon, orange,mandarin, lime and, inevitably, neroli. One of the finest training techniques and, indeed,a necessary qualification of the perfumeris the matchingor imitating of an existingperfume. Quite apart from commercial necessities training,the olfactoryexaminaor tion of a perfumeis a satisfying and excitingbusiness.It is an exercise in the knowledge raw materials,a test of memory,a battle of wits and, above of all, a test of patience. From the trainee's point of view,he startswith simple mixtures,initially of two synthetics oilsin statedproportions, problem or his beingsimplyto identify the two ingredients. Graduallymore complicated mixtures are presented,complicatedin number, type, and proportions. Perhaps work in perfumery no sharpens wits moreeffectively the than this
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matchingof a blend. Most peoplevisiting a perfumerylaboratoryshowa great interestin the identification ingredients of from a complexmixture, and I shouldlike to spendsometime on giving my own particular approach
to the problem.
IMITATING A PERFUME

The imitation of an existingperfumemay be undertakensimply as an exercise keeponefrom becoming to rusty, to keeponeup to date, asa training technique, but more often from commercial necessity. Of course, one may by chemicalor physical analysisobtain a certain amount of information regarding the constituentsof a sample. Thus chromatography, which briefly depends uponthe separation individualingredients of from a mixture by means of selectiveabsorptionon powder from solvents,offers some help. In this case,it is necessary keep very much in mind the possible to effectof the powderuponthe ingredients.Nevertheless, approach the simplifiesthe identification the mixedingredients, of althoughit is time-consuming and callsfor a delicatehandlingof an established technique. Someseparation may be made (providing samplein question sufficiently the is large) by fractional distillation. The physical constantsin certain casesmay be of help, althoughsuchcases rare. To know the total alcohol,ester,carbonyl are

(aidehydeand/or ketone)contentsmay be of somehelp, but it is very

important to realisethat chemicalchanges continuallytaking place in a are mixture of chemicals. This is our chemicalblending effect. In terms of simplechemicalchanges can expect a combinationof alcohols we and aldehydesto produce hemi-acetals, aldehydes may oxidiseor polymerise, esters may break down or more likely interchange(for instance,alcoholysis may occur). The presence a high boilingalcohol of with an esterformedfrom a low boilingalcoholmay result in a partial exchange the alcoholradicals. of Benzyl alcoholmay replacethe methyl radical from methyl salicylateto

yield methyl alcoholand benzylsalicylate. Sucha change constitution in

meansa considerable changein odour, from the strongwintergreennote of

methylsalicylate the almost to odourless benzylsalicylate. Naturally,

equilibriumwill be reached. In much the sameway, radical exchange in estersmay occur. Ethyl phenyl acetate and geranylpropionatemay well change part to ethyl propionate in and geranylphenylacetate. It must thereforebe understood that oneis not necessarily imitating a mixture as originally compounded. In point of fact, one rarely or never achievesperfectionin matching; that is, one may arrive at a satisfactory imitation by a route quite differentfrom that pursuedby the originator. The final effectis the important thing, and althoughobviously onemust be somewhere the right regionregarding in correctingredients and proportions, different approachesmay well bring success. By success meant the is productionof an imitation sufficientlyclosein odour and performance to satisfy both customerand investigatingperfumer.
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It is not necessary tell perfumers,but it may be news to some,that to when a perfumeis made to a definiteformula by two or more peoplethe final result may be different as far as odour is concerned. Mainly, this is dueto the fact that whereas commercially pure true synthetics reasonably are standardin quality, essentialoils, and more particularly, isolatesfrom these oils,vary with eachsupplier. What hopethen has a perfumerof matchinga blend made from materials differing from those he intends employing ? Here we come back to the previouslyexpressed suggestion that onemay achievegoodresultsby an alternative route. Each perfumerwill have his or her own techniquewhere matchingis concerned, dictatedby the nature of his training experience and perhaps prejudices. One can only offer one'sown ideas. Let us consider are in we possession a small sample(1 mi. may be sufficient the task is not too of if complicated) a perfume of and that the examination restricted olfactory is to analysis only. In the first place,take advantageof every availablepiece of informationregardingthe perfume. Can you ascertainits sellingprice, its originand very importantlyits intendeduse? Thesepointsmay at first glancehave little to do with analysisby the nose,but this is a game and everypieceof informationmust be usedintelligentlyand effectively. There is much of the detectiveto be found in the successful perfumer. This may requirefurther enunciation, but it is helpful to know in advancethat the price automatically reduces cuts out the use of expensive or ingredients. Knowledge the originof the compound of helpsbecause recognises one individual types and approaches clearly as one identifies a handwriting. as Knowledgeof intended use obviouslyhelpsto delete productsunsuitableto that particular product and to indicate the most likely ingredients. Using only slips of absorbentpaper by way of apparatus,one might approachan olfactoryanalysisin the followingmanner: (In the selection of these"smellingslips"it is important to keep to one gradeso that rate of evaporation from the paper is constantfor eachexamination.) The ingredientspresentin the samplewill each have their own rate of evaporation modifiedas this rate may be by blendingwith other ingredients. It followsthat if the perfumeis exposed the atmosphere to and examinedat variousintervals we are virtually examining individual fractions in much the same way as if we had performedthe fractionationby distillation or absorption. In this casewe cannotretain the individual fraction other than as an impression the nose. Further, the identificationis complicated in by the intimate presence other volatile substances, this is our separation of but and we make of it the bestwe can. If time is not an important factor dip a "smellingslip" or "blotter" into the sampleand leave it exposedto the atmosphere a few days. At the end of this periodthe slip will contain for only the relatively non-volatile constituents, the solids, i.e., musks,coumarin, heliotropin, vanillin, etc.; resoins, e.g., benzoin, labdanum, oakmoss,
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opoponax, sesqui terpenealcohols esters, and sandalwood, vetivert and patchouli oils. These nowmoreeasily are identified they are no longer as
masked the morevolatilelight andmedium by odours duringthe period lost
of standing. The examinationis made mainly by a contrasting scheme. The perfume

is gentlyrubbedinto the back of the left hand (forright-handed people),this to allowfreedomfor writing and manipulationof the normalhand. The heat
of the hand and the moisture present combine to provide a miniature but effective "steam-distillation" apparatus. The volatile products float

gently but quickly from the hand and in perhapstwenty minutes have reached stageof evaporation a whichmight require24 hourson the blotter. During this time a smellingslip is dippedinto the perfumeand constant reference this, the hand and the three-day-old to smelling slip, providesthe necessary odour contrastso essentialas a memory stimulant. Perhapsa seemingly smallpoint, but the methodof dippingthe perfumeis important. Firsfly, try to keep your techniqueautomaticallyconstant. Make your
identificationmarks on the lower end of the slip in a positionwhich will not be seenduringexamination. This to avoid an unconscious desireto cheat-a most unhelpfulpractice. Pinch the end of the slip to form about threequarter inch of channelling. Smell directly into this channelwhich concentrates and directsthe odoursto the nose. Make sure the perfumedoesnot brush the nose. It has also the advantageof keepingall the papersof a similar appearance often the slip is dippedinto the neck of a small bottle as and pouringon to the slip may be a wastefulprocedure. Often a difference in colourbetweenoriginal and experimentalsamplesmay make it difficult to avoid visual recognition.

The first stepis to identifythe class perfume of involved. In too many

cases name, evenwhen of a well-knownfloral character,may be misleadthe ing, but the important thing is to "get into the mind" of the original com-

pounder. Try to fathomjust what hehadin view. Florals,although varying immensely evenfor eachnamedtype, usuallyfollowsome basicpattern and
it is not too difficult to strip a perfume of its fineriesand to reach this basic
accord.

Complicated bouquets and fancy creations may be quite anothermatter and a more searching and critical examination called for. This may is
require segregation the .basicfloral notes. Here again we are faced with of the fact that ready blended floral perfumesmay have been used or, alternatively, the floral effects may have beenbroughtaboutby the useof similar type ingredients shown the earliertable. as in Shouldwe be dealingwith a fairly simplefloral perfumesuch as lilac, we can automaticallyexpectto encounter phenyl ethyl alcohol,hydroxycitronellal, anisaldehyde,heliotropin, terpineol and a j asmin complex. Perhaps havea perfume our shelves we on whichis reminiscent the sample. of
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A comparison between the two will soonshow where the balancesdiffer, which ingredientsare excessive deficient. In any case,we already know or from experience how to compound something least similar in odourto the at sample. The compounding the experimental sampleis often tediousand timeof consuming, and shouldbe the work of a reliablejunior or trainee, and in this connection handlingand blendingof thesesamples excellenttraining. the is Although the final productionof a perfumeon both laboratory and factory scalemust be on a weightbasis(on accountof variation in specific gravities of the ingredients) is often time-saving work by volumewherepossible it to duringearliertrials. The question orderof addingthe ingredients of may be important and specialattention has to be given to the dissolving solids of where present. In earlier trials it is not always necessary add the less to
odorous materials until the imitation reaches a reasonable standard.

When oneis dealingwith a well-blended perfumeand identification the of ingredientor even type is difficult, the previouslymentionedassociation of ideascomes handy. Each and every perfumerwill have his or her own in particular odour associations will know the ingredientsresponsible and for these effects. Towards the end of the evaporation life of a perfume I repeatedly meet a "cardboard" note, which is the result of a heliotropinvanillin combination. Chrysanthemum-like odoursarise from the use of phenyl acetate with certain essentialoils, notably lavender. Wet bathing costumes another of my association is notes, and this inevitably meansthe presence the anisyl odour grouping,e.g., anisaldehyde, of anisyl alcoholor acetate. A Plasticinenote invariably meansthe presence amyl salicylate. of One final odour which says "corduroy trousers" to me I can never describe othersand, quite frankly, I have yet completelyto identify it to to myself. So much for what, I must emphasise, rarely the sincerestform of is flattery.
USING OUR FINISHED PERFUMES

One may, of course,producea range of perfumesand let the consumers try them out for themselves their variouspreparations. This is, however, in a far from satisfactoryapproach,satisfactory that is to either produceror consumer. I have, in a previous talk, mentionedsome of the problems involved in producing perfumes for soaps,creams, lotions and powders. These are real and difficult problems indeed and call for both skill and knowledge: knowledgeof both the perfumery ingredientsand the final preparation. Perhapsan example of how one type of perfume must be modified differentproducts for wouldbe of interest. Let usselect popular the lavenderodourfor this example.For usein toilet water, that is a preparation basically5 per cent lavenderperfume,80 per cent alcoholand 15 per cent water, we could make a simpleand effectiveblend as follows:
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Lavenderoil 40/42%
Bergamot oil
Musk ketone

......

89.5
10'0
0.5
100.0

........
........

This toilet water would give the true fresh note of the lavender and might, despiteits simplicity of formulation,be regardedas an acceptable preparation. In creamsor lotionsits performance wouldbe but moderate with the initial effect fairly good. However, the perfume would be fugitive and lacking in "body", with a tendencyto become"stale." In powder, too, the effect would be disappointing, lacking in strength and depth, and
would lose its initial freshness a short time. In soapsthe blend would be in a dismalfailure. When usedat the rate of 1 per cent in a normal soapbase the odour of the tablet would be but faintly lavender and the odour of soap

wouldpreponderate.Further, the life of the faint odourof perfumewould

be short. A new techniquecalling for more raw materialsis neededfor both creamand powder,but an evenmoredrasticreformulation requiredfor a is satisfying lavenderperfumefor soap. The light pleasing notesof Frenchlavenderoil, so effectivein alcoholic media, are far lessefficacious when usedin soap. They require considerable modificationand reinforcement. One might approachthe problem in the followingmanner:

Lavenderoil 40/42 per cent Lavandin20/22 per cent

Lavender concrete

20 30
5

Lavandin

concrete

5
5

Terpineol
Bois de rose oil

..
..

5
5 7

Linalyl acetate .. Terpinyl acetate Spike lavender Spanish

Borneol Oakmoss Labdanum Coumarin Musk Musk ambrette ketone .... resoine.. resoine .. ..

10
4 4
2
1

Bornyl acetate ..

6
2

Musk xylol

..
..

4
2

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Strengthand bodyhasbeengivento the lavenderaccordby the lavandin, lavandin and lavender concretesand spike. The ester notes have been modifiedby the use of linalyl, terpinyl and bornyl acetate and the alcohol notesby the useof terpineoland borneol. The spikeand bornyl acetategive the necessary lift so essential the initial impression top for whenthe tablet is examined prior to use. The coumarin--atypical lavendernote--performs almost throughoutthe whole range of evaporationand is an essential part of a lavender soap perfume. The oakmoss,labdanum and musks assure adequateback notesand fixation and generallysweetenthe wholeaccord.
FIXATION

Earlier in this talk I mentionedfixation, a subjectwhich has beensome-

what summarilydismissed writersin the field of perfumery. Previously by brief references non-volatilesolvents,solidsand resinous to products have beenmade, but the moderntendencyappearsto be to decry the useof fixa-. tives as unscientific, which is surprising, the subjectlendsitself ideally as
to both theoretical and practical considerations.Just recently I read a pamphletwhich absolutely scoffs the existence a fixative whilst,at the at of sametime, talking of products which enhance tenacity of a givenodour. the This could be dismissed a confusion terminologyif it were not for the as in fact that the paper statesquite definitely that benzyl benzoate,when added to a perfume,will have no effecton the rate of evaporation the constituof entsof the perfume. At leastonewriter hassuggested fixationactually that takes placewithin the nose. If this effectdid in fact occurperfumers and,

indeed, all usersof perfumesmight well have causeto regret the very
existenceof such products. What exactly do we mean by fixation ? It is simply a retardingof the rate of evaporation of the constituentsof a mixture of volatile substances.

Call it "tenacity," "lengthof life" or any nameyou choose, comes it simply to the fact that we desireto maintain as far as possible constantrate of a evaporationof the individual constituents and certainly to inhibit the loss of the morevolatile members. Ideally, we shouldselecta range of ingredients,all strongin odourand possessing identicaland low vapourpressures. Such a mixture would obviouslyrequire no additional fixative. In actual fact we mustuse,in oneblend, many substances varying in vapourpressure over a considerable range, and our problem is to make sure that the more volatileingredients not lost too readily,thus upsetting balance the are the of perfume. Actually, the very mixingof two or moresubstances produce may some degree fixationor lowering the individualratesof evaporation. of of Before the molecules a pure liquid can leave the surfacethey must of
overcomethe forces of attraction of the other molecules,and this attraction

is great,asthe molecules the liquid aremuchmoreclosely of packed thanwhen in the vaporous state. In an idealsystemthe effectof dissolving substance a
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in a solvent is to lower the vapour pressureof the latter. In simple form, Raoult's Law states "the relative loweringof vapour pressure equal to the is mole fraction of solute in the solution." The relative lowering of vapour
p_p

pressure given by is

po

where P is the vapour pressure the solvent of

and P is the vapour pressure the solution(solventplus solute). The mole of fraction is the numberof molecules solutedivided by the total number of of molecules the solution. This effectis well illustratedby the way the vapour in pressure ether may be considerably of lowered by the addition of organic
chemicals.

Viewed from a perfumeryanglethis is not as helpful as it seems first at glance. The addition of a secondsubstance has certainly lowered the
desireof the moleculesof the solvent to leave the surface,but it is virtually only a questionof dilution and we are facedwith the thought that the more volatile the solutethe more effectivelywe lower the vapour pressure the of solvent, this on consideration the fact that normally, low molecularof weight bodiesare more volatile than thoseof high molecularweight. If we take two substances and B of equal molecularweight, then the lowering A of the vapour pressureof A will be proportionalto the amount of B added.

If, however,the molecularweight of B is much higherthan that of A, the lowering vapourpressure be correspondingly of will less. An examplewould be the caseof ethyl acetate (molecularweight 88, vapour pressure 72-8 mm. at 20 C.) as solvent. If we add to the ethyl acetateone-tenthof its weight of a second substance "B," alsowith a molecularweight of 88, then we have the following equation accordingto Raoult's Law.
P -- P
__

Molecules of substance B
--

P
72.8x

Molecules ethyl acetate+ molecules substance of of B

0'6 x 10 TM

72'8
x ----

6 x 10 TM 0'6 x 10 a +
66.18mm.

6 x 10a refersto the number of molecules presentin one gram molecule, i.e., 88 gms.of ethyl acetatewill contain6 x 10TM molecules. In the caseof a soluteC having a high molecularweight, say, 880, and wherean amountequalto one-tenth the ethyl acetateis added,we have of
P -- P Molecules of C

P
72-8x

Molecules ethyl acetate5- molecules C of of

0.06 x 10 a

72'8
x =

6 x 10 a 5- 0'06 x 10TM
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In other words,an additionof 10 per cent of B (molecular weight88) has loweredthe vapour pressure ethyl acetate by 6.62 mm., whilst the of additionof 10 per cent of C (molecular weight880) haslowered vapour the pressure only 0.72 mm. by Departing from ideal solutions, that is solutions which obey Raoult's Law, we enter a realm more closelyconnected with perfumes. In an ideal solution molecules the soluteare presumed haveno effectuponthe the of to
intramolecular forces of the solvent, and vice versa.

This might be the caseif both ingredientsin a two-part systemwere similarin character, e.g., both relatedpolar substances both non-polar. or
If, however, the intramolecular attraction of one constituent was much

greaterthan that existingin the second constituent, then the effectwould be to increase vapourpressure the latter and to forcethosemolecules the of out of the solutionas vapour. Such a casewould be exemplified a by mixture of a polar and non-polarcompound. On the other hand, the two, constituentsof a solutionmay have a strong attraction for one another; then the vapour pressure both constituents of will be lowerednot only by
virtue of molecular dilution, but also on account of this intermolecular
attraction.

Figs. I, II, III and IV showhow partial and total vapourpressures are
affectedaccordingto the nature of the ingredientsof the solution. Reviewing the four figures we imagine that our effective fixative will therefore have three distinct and important requirements:

(a) Low molecular weight. (b) Low vapour pressure. (c) Molecularattraction for the other constituentor constituents. When dealingwith a perfumeor mixture of perfumeryingredients, is it to be realised that the vapour pressure,or the desire of the moleculesto

escape, has, for eachindividualmember,alreadybeenreduced only by a if dilution phenomenon. Further, if the individual ingredients so selected are
that their molecules attract one another, then the fixation of the mixed

molecules enhanced. This is, of course,our physicalblendingeffect. is Additionalblendingeffects obtainedby chemical are means,e.g., the formation of hemi-acetals betweenaldehydesand alcohols,Schiff-base formation from aldehydesand amines,etc., but for the time being we are concerned with physicaleffects. Admitting, therefore,that we are, if our blending techniqueis good, automaticallyprovidingfixation in our perfume,is it possible evennecesor sary to add an additionalfixative ? In many cases answer the must be yes. There are so many individual ingredients be usedin one mixture and to their chemicaland physicalcharacteristics may vary enormously. Whilst one may aim at minimum total and partial vapour pressures the mixture in
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TOTAL

'"xN -,.. '

P7

Xn I X. =0

MOLE FRACTION

X^=O X. , I

X^ I Xe 0

MOLE FRACTION

X,O Xe

FiG.

II

Fig. I represents the vapour pressure effect when two substances, similar in character, are mixed.

Fig. II indicates how the total and partial vapour pressures a system of mayincrease
above the normal due to the presenceof
dissimilar substances in solution.

X, I X.=O

MOLE FRACTION

XaO X. --I

X^ I
X.=0

MOLE FRACTION
FIG. IV

X^0
'X.--I

Fig. III shows how two substances whose

molecules attract one another will tend

to possess relatively total andpartial low vapour pressureswhen in common

solution.

In Fig. IV the effect of mixing two substances possessing intermolecular attraction for one another is again shown,but
in this instance one ingredient is nonvolatile.

p,O Vapour pressure pure Liquid A. _--_ of B = Vapourpressure pure Liquid B. of

Xx = Mole Fraction A in mixture. X -- Mole Fraction B in mixture.

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by a carefulchoiceof ingredients, severelimit on odoureffects a wouldbe imposed too narrow a selection. The balanceof odour effectsand the by stability of theseeffectsis decidedby the compounder and thereinlies the skill of the perfumer. Let us thereforeconsider matter from the view of a perfumerwho, the from whateverthe reason,desires retard the rate of evaporation one or to of more of the ingredients his perfume; he desires add to his pre-made in to mixture a substance which we call our fixative. From previousindications this must have a low vapour pressureand a low molecularweight, two properties not often to be foundin one chemical substance, especially when oil-soluble. In most cases are forcedto userelatively non-volatilesubwe stancesof comparatively high molecular weight, although the molecular weight may not be high in comparison with otheringredients the perfume. of Our third requirementis, perhaps,the most important, and here we must select a product with physical attraction for the moleculesof the more
volatile membersof our perfume. This attraction of moleculefor molecule could be explained on the grounds dipolemoments;that is, an electrostatic of attraction between polar

molecules on the grounds hydrogen or of bonding,or possibly both. Hydrogen bondingaccounts the fact that water boilsat 100 C., whereas for other considerations would indicate a considerably lower figure. If we consider the structuralformubeof two isomeric compounds, dimethyl ether and ethyl alcohol, gathersome we idea of the way in whichbondingeffects their physical properties. Thus dimethyl ether CHOCH3 boils at --24 C., whilst ethyl alcoholCHsCHOH boilsat q-78.4 C. Turning closerto our perfumery materials we can expect an associationof moleculespossessing hydroxyl radicalsin the followingmanner:-H

R--O

....

0 .... R

0 .... R

This particular examplerefersto alcohols phenols; with carboxylic or

acids the effect would be to producea double molecule:
OH-0

/
R C

%
C R

%
o- -.HO

One more example of a bondingeffect accompanied a loweringof by vapourpressure given by a study of the properties two isomeric is of compounds,ortho and para hydroxy benzaldehyde.

The formeris very volatile in steam,whilst the para isomer not steam is
distillable.
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This effect is shown below:

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HOH

C
I
H

XH
para hydroxy benzaldehyde

ortho hydroxy benzaldehyde

Of course, this bondingor associating effectof molecules not restricted is to alcohols and phenols, but appliesto many polar compounds, it is and
important to remember that the effect will obtain also between different types of molecules. No doubt the fine blendingpropertiesof phenyl ethyl alcohol and certaincarbinols be attributed to a bondingphenomenon. can Benzyl benzoate is, perhaps,the most used of our fixatives. It is inexpensive, goodsolventfor our solidingredients, a and relatively free from
odour. It is not the ideal fixative, but it will be known to all. Let us con-

siderits practicalfunction a fixative. The following as simple example demonstratesquite clearly that benzyl benzoatedoeshave the powerto retard the
rate of evaporationof volatile substances.
Six solutions were made as follows:
A B C D E F

Ethyl alcohol .... Methyl amyl ketone .. Benzyl acetate .. Benzyl benzoate ..

9 1 -

8 1 1

9 1 -

8 1 1

8 1 1 -

7 1 1 1

The solutions were testedfrom smelling slipsand, ignoringthe odour of alcoholand benzyl benzoate,timeswere recorded the length of life of the for odourof methyl amyl ketoneand benzyl acetate.
COMPARING A WITH B

Initially A was stronger. After 3 minutesB was stronger. In 5 minutes the odour of A had gone. The odour of B lasted for 8 minutes.
COMPARING C WITH D

Initially C was stronger in benzyl acetate. Gradually the strength approached equality, and at 40 minutesthey were at the samestrength. D then becomestrongerwith time and after 75 minutes the odour of benzyl acetate in C had disappeared, whilst that in D was still strong. The odour
in D remained for at least 3 hours.
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COMPARING E WITH

Immediately E was stronger,especially methyl amyl ketone. After of 4 minutesE was strongerin both methyl amyl ketone and benzyl acetate. After 6 minutes the methyl amyl ketone was strongerin F but the benzyl acetatewasweaker. After 8 minutesonly the benzylacetatewasin evidence in E, whilst the methyl amyl ketone was still apparent in F. After 12

minutes wasstronger, bothodours E but wereof benzylacetate. E remained

strongerfor 45 minutesand at 60 minutesthe odourof benzyl acetatein F was definitely stronger. The benzyl acetate in E had disappeared 80 in
minutes, but remained in F for at least 3 hours.

On theoretical groundswe could imagine benzyl benzoate having an attraction for methyl amyl ketone as follows
CH3
+ --

0
I

CHn

I
I

OCH2CoH5

o
Methyl amyl ketone

+
CoH5

benzylbenzoate

For the benzylbenzoate/benzyl acetateassociation imagine' we

C0HsCH.Ox,

C CHa
0
--

0 l OCH.CoH

CoH5 On the evidence of these experimentsbenzyl benzoate retards the evaporation rate of both methylamyl ketoneand benzylacetate. Further, the presence benzyl acetateitself has somefixative properties the of for
methyl amyl ketone.
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We can safely say that somedegreeof fixation of certain odorous moleculesin a mixture can be accomplished, although we must, of course,be reasonable our definition of the word fixation. Benzyl benzoate,decried in in certainquarters,is a fixative, but it is, perhaps, too difficult,with the not requirements already mentioned,to indicate other and more effectivesubstances. Before ending, I must forestall the critics who will inevitably ask "how do you accountfor the fact that non-polarsubstances also act as can fixatives?" One couldquotethe well-knownexampleof paraffinwax in this connection. If volatile solventssuch as acetone, ethyl, butyl, and amyl acetatesare brushedon to paintwork they are volatilisedbefore adequate softening the paint takesplace. If a few per cent of paraffinwax is added of to the stripping solvent, then the rate of solvent lossis inhibited to such a degreethat the paint is dissolvedor softenedand may readily be removed. This could be quite a poser,but onemight draw on the experience certain of workerswho have describedthe addition compounds urea with organic of substances. Solid urea complexes with many chemicalswere found and
whilst these substances include ketones, acids, alcohols and esters, the same

effectswere found for many paraffins,includingnormal straight chain members. Urea apparently lends itself to the isolation and xamination of its complexes,and whilst other complexeswith paraffin may be difficult to investigate,their presence, the groundof hydrogenbonding,shouldnot on be ignored. This particular effect may also accountfor the fact that the stearoptenebodiesof essentialoils are in themselves fixatives. Of course,the particular "fixing" effect of paraffin wax in solventsmay be due in part to a sealingof the surface. A single perfume may well contain alcohols,esters, ketones, ethers, aldehydes,aminesand many more types of chemicals,their structure complicated by isomerisation,unsaturation, branched-chainand a host of other
considerations. Hence a forecast of the final attraction of the individual

molecules and the effect upon vapour pressure would indeedbe difficult to make. The problemsof fixation might, to someextent, be compared the to problemsof fractional distillation, in reverse. The successful loweringof the vapour pressureof one ingredient may well result in an increasedrate of vapourrelease a second. It is a common in experience findthat a substance to with a strongodourcan only be usedin tracesin somemixtures and yet in a second mixture it may be added in fairly large quantitieswithout undue prominence. Thus we are unableto selector recommend universalfixative. a The constituents the mixture in question of will decidethe type of fixative required,and here again the perfumercomesinto his own. That hydrogen bondingwill have effects uponthe ultimate odourof the perfumeis obvious and quite another story. Further, it must be clearly realisedthat we have discussed fixation as a meansof retarding odour lossfrom a liquid. The final effectsupon the olfactorynervesmust be considered from completely
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different angles, and, of course, the forces of attraction in the gaseous state cannot be compared thoseexistingin the liquid state. to
IN CONCLUSION

It is regrettablethat such expressions "creative genius," "inspiraas tion," and similar expressions have figuredso little in this talk, but it must be rememberedthat these are subjective and the aim of this talk has been strictly objective, that is to describesome of the productsused by the perfumers,the manner in which they are used and, to some extent, the requirements and training of a perfumer. If the talk has beendisconnected and given from a personalview, then that is inevitable when "talking of
perfumes."

PERFUMERY

AND COSMETICS IN AND MODERN INDIA

ANCIENT

By T. H. CRAWFORD and T. S. NAGARAJAN, B.Sc.* It is not intendedin this Paperto touchon what might be calledthe Western type of perfumeryand cosmetics India, which are undoubtedlyusedin in increasing quantitiesby Indian women. The writers feel they shouldconfine themselves the productswhich have been usedsinceearlier days by the to Indian population,still comparativelyuntouchedby Western habits in its homelife. At this stageit shouldbe mentionedthat the writers' experience hasbeenmostlywith SouthIndia, wherethe peopleare muchmoreorthodox in their religious and private lives than elsewhere. It must always be remembered that India is a vast country, and the habits and customs the of societylady of cosmopolitan Bombay are as different from those of the middle-class South-Indianhousewife are, for example,thoseof a Parisian as lady of fashionand of a Balkan farmer'swife. Almost the earliestuseof perfumeryin India occurred the ceremonial at fires used in religiousrituals. During some of these ceremonies fires of fragrant woodswere lighted at the four cardinalpoints, and the flameswere
fed with a consecrated ointment. Around the fire would be scattered a

scentedherb, possiblyRusa or Ginger Grass. It is known that some2,000 years ago Indian ladies stained their feet, a customwhich still prevails among some communitiesto-day. The use of aromaticsin religiousceremonies,particularly in the Hindu religion,is still as widespread in early as times,and the preparationof aromatics usein theseceremonies been for has
a trade from time immemorial.

* Best & Co. Ltd., Soap Factory, Ma[dras, S. India.

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