Lily of the Valley (Muguet) in

Perfumery

By Danute Pajaujis Anonis, Consulting Chemist Perfumer,

Ridge Park, New York

Lilyo~thev#yi s an important floraf odor in Chemical Compoeltion

per ume . The natural flower oil is not As early as 1836, a crystalline substance pos-
commercially available afthough a&empts have sessing a strong odor was reported in a study on
been made to obtain the concrete of lily of the the composition of the lily of the valley?
valley. At the beginning of this century in another
In the early part of this century, a product study, the presence of famesol was indicated.’
called Muguet de Mai was commercially avail- This was later disputed.
able, but it was a lily of the valley-like extract In tbe last three decades, new research work in
produced in Grasse from the hyacinth-like lily of the vafley was done in Japan? in Ger-
freesia.’ many,g and in Holland,l” and over fifty compo-
The advent of aromatic chemicals paved the nents were reported. Previously identified main
way for synthetic lily of the valley compounds components were comfirmed, and a number of
which are now being used in perfumery. new components present in low concentrations
were found. Some of these are significant to the
Botanical Origin
odor of lily of the valley.
Lily of the vafley, Conoaltaria maialis L. (fmn. Components found in both species reported in
Liliaceae) originated in Asia Minor, or Persia the above studies are listed in Table I; additional
(now Iran), and is known in Europe as a wild components found only in Convallatia Maialis L.
growing plant? Another species of lily of the are shown in Table H; those found only in Con-
vafley is Conwdlaria keikusei Miq, (Japanese lily oaltaria kekusei Miq. are shown in Table III.
of valley).s

Mode of Production, Yield, Type of 011

Synthetic Compounds
Steam distillation can not be applied to obtain
the lily of the valley oil. As no natural lily of tbe valley flower oil was
Attempts have been made to extract the flower commercially available, synthetic compounds
oil with petroleum ether. The yield of the con- had to be developed. The base of the early lily of
c~te obtained from the flowers and stafks was the valley compounds consisted of hydroxycitro-
0.42 to 0.55 per cent. Extraction of the flowers nellal combined with jasmin and rose compo-
alone gave 0.9 to 1.05 per cent of the concrete.4 nents to which Iinalool, terpineol and ionone
Another method which tried to obtain the con- were added. Cinnamic alcohol, famesol, methyl
crete was butane extraction of the flowers.5 heptin- and octin carbonates, guaiacwood ace-
Lily of the valley oil produced by these tate, indol and cresol esters, nonafactone, alde-
methods was and still is being used only for sci- hydes C-8, C-9, C-n (enic), and C-12(MNA)
entific research, were used in smaller amounts to add nuance.

Vol. 11, December 1986/Jcmuory 1987 0272-2666/86/00W3101 S02.00/0+0 1986 Allured PublishingCorp. Perfumer & Flavc.risr/31
 Lilyof the Valley

Table 1.Identlcel Component of Convellerle

Teble Ill. Additional Component of Convelleria
melelle L. end Convellerie kekueei Mlq.
kekuaei Mlq.
~ me!!lm G,~,V191 m.ll,,~(lol
Bmmldehyde + + + WzQm@s Lam
Citral + + W.ZY1 C* Pro”ate +

Citm”ellal + + + Ci””aulyl capronate +

Be”zyl alcohol + + LI”.l Y1 acetate +

Cinnmic alcohol + + 3-Metw Prowl acetate +

Citro”,llol + + +
Gerani.1 . +
Linalml + + +
Neml + +
PIww1 ethyl alcohol + + +
Plwwl prowl alcohol + + +
c,,.,. ) + +
Bm,Yl acetate + . + For the green note, phenylacetaldehyde di-
Cinnmyl acetate + + methvl acetal was imDortant. Later. aromatic car-
Citrmellyl acetate + + bino~s and their aceti-tes were used. Phenyl prD-
wr,”yl acetate + + + pyl aldehyde and dimethyl octanol were sDme of
CIS-3-IWX,”YI acet,te + + +
the other aromatics used.
Methyl anthrani late + +
. +
Fixatives were civet, olibanum, balsam tolu
methyl salicylat,
New1 acetate . + +
and s~rax resirmid, as well as crystalline aroma-
N,.Y1 format, + + + tics, i.e., musk ketone and vanillin. Later, musk
Phenyl Prowl acetate + . and civet specialties were used as fixatives, re-
placing natural civet and musk.
Among trace components, are cardamon, cel-
Teble Il. Addltlonel Compcmente of Convellerie eri, clary sage, coriander, cuminic cddebyde,
maialie L. neroli and ylang. Of the absolutes, cassie,
mimosa, orange flower, rose, reseda, tuberose
~ Germm, (9) H,lland[l OL
and vicdet leaves may be cited,
Lirmnmw + + As new aromatics became available, they were
a-Ph,l Ia”dre”e . used in lily of the vafley compounds.
Fa,”,,ol .
GIYCO1 derivatives became important, for
Ci, -3-heX,”.31 + .
example, phenyl glycol acetate, pbenyl glycol
O,tene-1 -.1-3 t.
acetal of phenylacetaldehyde and propylene
n-Pe”tanol .

a-Te T.lneol .
glycol acetal of phenylacetaldehyde.
0-TerPine.l t, The foHDwing are among less cDmmon aroma-
a-Te W.fne”e . tics that have been used to capture the elusive
.,
Pheno 1 Dolor Of ]ily Df the Va]ley: aniSyl aCe@te, aniSyl
Ci””mic aldehyie .
fonnate, cinnamyl acetate, cinnamyl butyrate,
Benzyl mproat, .

Bmzyl f.mte +
citronellyl formate, Iinalyl isobutyrate and
Cinnmyl CWmate + phenyl ethyl salicylate,
Cinlwwl Fm’mte + The following percentages of less knDwn
Far”esyl OCetate + aromatics have been recommended in lily of the
G,?a”yl fomt, .
valley compmitions:”
Ge.,nyl heoty late +

Ci, -3-bexe”Y1 benzmte t,

C1, -3-IWX,”Y1 Pr.Dimate t.

citmnellyl cinnamate (l-3%)
I,mmyl ProDionate t.
dimethyl octanyl pbenyl acetate (3%)
Methyl “o”Y1 ketone t. geranyl cinnamate (0.570)
Ne.yl f,mate + kmafyl anthranilate (2%)
PhenY1 ethyl acetate + . neryl isovaferate (4%)
PhenY1 ethyl Fomte .

LI”,1oo1 OXfde + Examples of few conventional illustrative lily

R.,, oxide ,
Df the va.fley compounds are shown in Formula
Bmzyl cyanide + +

lnd.le + +
1-3.
2,2,6-trimethyl-6-Vinyl hyd.ofurane + New research on lily of the valley has shown
that its main constituents are rose alcohols (gera-
. not specified niol, citmnellol and nerol), and their acetates,
comprising 70 per cent of the flower 0iL8

321Perf.mer & Flavorisi Vol. II, December 1986/Janwmy 1987

 Lilyof the Valley

Accordingly, modem lily of’ the valley com-

pounds are being reformulated to include a
higher percentage of rose alcohols and their es- Lily of the Valley Formula 1
ters, and smaller amounts of hydroxycitronelbd.
The later bas not been identified in tbe lily of the w
valley flower oil. As more stable aromatic chemi- Hydmw. itr.”ellal 150
cals became available, i.e., cyclamen aldehyde, Sem”fol 30

Lilial and Lyral, they were used in lily of the Ylmg 30

L{”,1oo1 30
valley compounds. More recent arnmatics in the
TerP1”eol 30
hydroxycitronellal odor type are: Dupiccd (Naar-
R.,, Wnthet!c 15
den), cis-dihydro shiseol (Mayol-Finnenich), and B,”,.{” re, i”oid, 20% 15
Bourgeonal (Naarden) among others. The use of Cwimde? 0.4

ionones has also declined.

Hexenol and nonadienol and their esters
brought a new gamut of green and folial odors.
Several green type aromatics are cited:lz trans- Lily of the valley Formula 2
2-hexanyl acetate, cis-bexenyl ethyl acetal of
m
phenylacetaldebyde, dihydrodicyclopentadienyl
Hydr.XYCit,O”ellal 350
acetate, and acetaldehyde ethyl phenyletbyl mm” Sy”thetlc 100
acetal, to mention but a few, encompass fruit-, RhOdi”Ol 100

flowery-, herbal-, cucumber- and violet-green Te.P{nml 30

20
odor types. Gemnio1
Lfnalml 20
Cis-r-decenal, timethyl undecylenic aldebyde
Cyclamen aldehyde 7
are among the newer aldehydes available. Oxy- 5
PhmY1 ethyl alcohol
acetaldehydes, including cis-hexenyl oxyacetal- GuaiacYl acetate 5
dehyde, bring new possibilities. .-10”0”, 5

Dihydrolinalool and piperonyl propanal are Rose absolute 3

W,anyl acetate 2
few examples of replacements for older aromatic
cmintc aldehyde 0.5
chemicals.
Methyl dihydrojasmonate (Hedione), jasmo-
lactone and derivatives of cyclopentenone, Lily of the VallOy FOrlllUla 3
among others, me used per se or as components of m
jasmin compounds in lily of the valley formulas. Hydmxyc{tr. nel1.1 320

Analogically, rose oxides and damascenones are Uenzyl acetate 10

PhenY1 ethyl alcohol 30
used for the rose note, and neroli oxide in the
Imone 25
orange flower. Two more recent groups of aro-
L1”,1oo1 25
matics used in perfumery are furan and pyrazine Jamin synthetic 20
derivatives. Among the later, 2-methoxy-3-iso- Rose synthetic 15
butyl pyrazine of a green odor tonality may be RhOdi”O1 12
Temi”e.al 10
mentioned, and 2,2,6 -trimethyl-6-vinyl hydro-
Citr.a”,llyl ,Xyacetald,hyd, 10
furan (listed in Table H) was newly discovered in
Ge,anyl acetate 6
lily of the valley oil. Row absolute 5
Tbe majority of components of modem lily of Bemmmt, de,e”,lti ,,d 5
the valley compounds being rose alcohols pre- sweet .r,”ge, terDe”el,s, 4
sents no problems of stability in alkali. The same RoseOtto 2
G“aiacyl acetate 2
may be said of most bydroxycitronellal replace-
OrangeF10!+,, absolwt, 1.5
ments. Ylmg 1
In regard to sensitization, several perfume l,oewenol 1
materials previously used in lily of the valley Isowwyl Ndmtmnlc aldekyd, 1
compounds have been eliminated; others are Huskketone 0.5
used in purified form, in limited concentration or
in conjunction with quenchers. Among the first
are coumarin, famesol, heliotmpin, methyl hep-
tine carbonate, musk ambrette, orris concrete and
balsam Peru. Bergamot and styrax resinoid be- In the beginning of this century, synthetic lily
long to the second group. Cinnamic alcohol, iso- of tbe valley compounds were produced by the
eugenol, and phenylacetaldehyde may serve as German chemical industw. Lily of the valley
examples of the third group. (known as muguet) was offered in the form of a

Vol. II, December 1986/Jon.my 1987 Perfumer & Flavorist/33

 Lily of the Valley

straight perfume oil, along with jasmin, rose, car-

nation, heliotrope, and violet in small vials as fra-
grance. Another application was to mix these
perfume oils with a specified amount of eau de
cologne or alcohol to obtain what were known at
that time as “triple extracts”}’
Before World War II, innovative perfumes
without alcohol, adaptable for export, were avail-
able in Germany. Diethyl phtalate, castor oil and
others were used as solvents. Lily of the valley
was included among other floral fmgrances.]4
Among single lily of the valley fragrances of
the past, Muguet (Coty), Premier Mai (Houbig-
ant), and Muguet de Chaville (Cheramy) may be
cited.
Lily of the vafley compounds were valuable
components of past perfumes, as they still are in
modem fragrances. Among the early perfumes,
containing lily of the valley or its components,
Quelques Fleurs, Amour Amour, Chanel 5, Ar-
p>ge and Je Reviens maybe mentioned.
In the 1940s and 1950s, White Shoulders, R6-
plique, Chantilly, L’air du Temps, Wind Song,
Intimate, and especially Diorissimo—a reborn
muguet fragrance-are good examples.
Among fragrances of the 1960s and 1970s,
Fidgi, Madame Rochas, Rive Gauche, Charlie,
Aliage, White Linen and Adolfo may serve as
examples.
Of the newer modem fragrances we cite two
examples, in Premi&re, lily of the valley is
blended with gardenia and honeysuckle; in
Armani-with jasmin, orange flower and hya-
cinth.
In general, lily of the valley is osmotically
compatible with many floral notes, among them,
besides the above mentioned, jonquil, reseda,
mse and violet; it also blends well with alde-
bydic and green, as well as folial notes.
Lily of the valley cream perfumes, containing
undecalactone, aldehyde C-12(L), vetyver ace-
tate, and benzyl salicylate have a good coverage
of the lanolin odor. Dihydrocitronellal, terpineol,
and phenylacetaldehyde dimethyl acetal are
other aromatics used in traditional lily of the
valley type of cream perfumes.
Lily of the valley is also used to perfume lo-
tions. Some lily of the valley compositions con-
tained lilac compounds, older ones were fixed
with musk and civet infusions and tolu resinoid,
and some contained methyl heptine carbonate.
Lily of the valley fragrances for powder contain
terpineol, linalool, benzyl acetate and hydroxy-
citronellal as base, and among other components
are heliotropic, coumarin, musk ambrette, tolu
balsam, cinnamic alcohol, ylang and aldehyde
C-12(L).

34/Perfumer & Flovorist Vol. II, December 198#Jon.aw 1987

 Lily of the Valley

Conclusion
In spite of a number of new aromatics iden-
tified in the lily of the valley oil, none of them
suggests the basic scent of the flowers.
The unique characteristic of the lily of the
valley flowers, as observed by the writer, is that
the dry blossoms, while losing part of the ethereal
green-floral odor, retain a musky sweetness with
alight green note for weeks when enclosed in a
plastic envelope. In contrast, lilac blossoms lose
all odor and change to a rusty color when wilting.
Present aromatic research concentrates mostly on
analyzing head space constituents of the flower
oils. Perhaps new residual components of the lily
of the valley would help to better reproduce the
elusive odor of lily of the valley.
Lily of the valley has not lost its importance in
perfumery, It has found a more universal appli-
cation. Previously there was a clear division of
two main groul?s of fragrances: the heavier sultry
orientals and chypre-derived types, and the light
floral-aldehydic-green types, Lily of the valley
belonged to the latter group of fragrances and
found extensive application inthe’’green” type
fragrances of the1970s. Inthelast decade, semi-
oriental, fruity-floral-green fragrance types have
evolved, and lily of the valley became part of
the se fragrances.
Asmen’s line fragrances became more sophis-
ticated, lily of the valley components found their
way into these fragrances.

Rstemnces
Address correspmdenm to Ms. Dame Pajaujis Armnis, 98-n —
64th Road, Rego Park,NY11374, U.S.A.

1. O. Gerhardt, DasK.nnpimier6ninderPatfumetie,Aktiomkti
Veriagsgesellschaft, M. B.H., Leipzig (1931 ), p. 62
2. ltid., p.62
3. M. Soelens, H. J. WtibenandJ. Heydel, Petium. Flavor.,5(5),
14, Octobor/November 1960
4, Naves and Mazuyer, Les Parfums Naturals, Pans (1939), p.
250
5. M. Mounier, lnd. Perlum.,5,26,1930
6. S, Herberger, Rept. Pharm.,2,397 ,1636
7. M. Kerschbaum, Chem. Ber.46,1732 ,1913
6. S. Wakayamaand S. Namba, NippOn Kagaku Z6.Sshi90(ll)
1160-3, 1969
9. H. Mackand M. Kopsel, Patt. Kosm.,548/73,233, 1973
10. M. Boelensetal., ibid.
11. E. S, Maurer, Perfumes andtheir Production, United Trade
Press, Ltd., London, 1956, 125-160
12. A. F. MOrris, Perfum. Flavor.,6(1 ),1-7, FebrLIarY/Marchl%1
13. LeNouveau FJrWiaire.dela Seaut4, G. Clacks, Paris,89,l76
14. H, Fouquet, La Technique Modemeet Ies Fonmdesdela
Parfumerie, Paris &LitIge, tibrairie Polylechnique Ch. S.3-
ranger, 1951, p. 141.

26/Perf.mer 2. Flavorist Vol. 11, December 196d/Jmw.my1967