Parfumuri

Mirosul(olfactia)-Rol -Protectie - Fiziologic- Natura - Adaptare - Memorie - Sensibilitate - Selectivitate - Intensitate, caliate

Mirosul organismului:-Determinant genetic-Modificat de stilul de viata, in special de cel alimentar

- Carne- Peste- Condimente( usturoi)

Mirosul

Cãile senzitive1- odorant; 2- aroma; 3- pata galbenã; 4,8- traseu

neuronic; 5- zona corticalã de analizã; 6- papile gustative linguale; 7- papile gustative paletale; 9- formaţii intermediare

Structura şi modul de acţiune al semnalului olfactiv A-vector-semnal; AC-adenilciclazã; C-proteinã canal; G-proteina de legare a guanozin-trifosfatului

Istoria parfumurilor

5000 BC – Egyptian First Dynasty – earliest evidence3000 BC – Mesopotamia: extraction pots, early apparatus1400 BC – Book of Exodus “anointing with oils”370 BCE – Theophrastus writings on use of oils to make fragrances

longer lasting.800 AD – Alembic distillation apparatus – Jabir ibn Hayyan1200 AD – Essential oils produced in pharmacies1600 AD – Quality of many natural extracts established1860 AD – First synthetics (naturally occuring materials)1900 AD – First non-natural synthetics (ionones, nitro-musks)

Alembic Distillation Appratus

• Popularity of perfume waned in Europe after the fall of the Roman empire, returned with the crusaders

• Distillation of essential oils• Attributed to Avicenna, Arab,

late 900’s

Perfumes in 18th century Europe• More flowery as

opposed to heavier scents

• Numerous ways to use perfumes, elaborate containers

• Vinaigrettes• Pommanders go out of

style with availability of liquid perfume

Eau de Cologne

• Germany, invented an 1709 by an Italian barber

• Rosemary, orange flower, and bergamot oils distilled in grape spirits

• Non-greasy• Napolean decreed the

formula must be public in 1810

Perfume odorant types today

• Concretes– purest, soft plant parts are placed in solvent

• Absolutes– concretes concentrated in alcohol

• Resinoids– extracted like concretes, from plant secretions

• Tinctures– direct extraction with ethanol

• Distilled essential oils– most common modern methods

Types of fragances

Concentraţie şi compoziţii

Extras de parfum: 20%-40% compuşi aromaticiApă de parfum (Eau de parfum): 10-30% compuşi aromaticiApă de toaletă (Eau de toilette: 5-20% compuşi aromaticiApă de colonie (Eau de Cologne): 2-3% compuşi aromatici

Perfume anatomy• Top notes

– immediately perceived, highly volatile, bright, often citrus, ginger

• Middle notes– a minute to an hour; often rose, lavender

• Bottom notes– often animal, resin scents, perhaps vanilla, sandlewood

Business of scents (perfumes)

• 10-20 billion dollar industry• Only a few companies are doing smell R & D• They work for two main client groups;

household products companies, and perfume companies

• Lots of secrecy

Grasse, in Provence, France

• Started with tannery perfumes– for scenting gloves?

• A local company got a patent on the distillation system

• 1720’s become a local industry

• Good sources for jasmine, rose, orange

• Modern perfume industry started here

- Grasse has had a prospering perfume industry since the end of the 18th century.

- Grasse is the centre of the French perfume industry and is known as the world's perfume capital (la capitale mondiale des parfums).

- Many "noses" (or, in French, "Les nez" (plural)/"Le nez" (singular)) are trained or have spent time in Grasse to distinguish over 2,000 kinds of scent.

- Grasse produces over two-thirds of France's natural aromas (for perfume and for food flavourings).

- This industry turns over more than 600 million euros a year.

-Grasse's particular microclimate encouraged the flower farming industry. It is warm and sufficiently inland to be sheltered from the sea air.

-Jasmine, a key ingredient of many perfumes, was brought to southern France in the 16th century.

-Twenty-seven tonnes of jasmine are now harvested in Grasse annually.

- There are numerous old 'parfumeries' in Grasse, such as Molinard, Fragonard and Galimard, each with tours and a museum.

Materii primeOdoranti, diluanti, fixatori

-Ingrediente aromatice naturale-Ingrediente aromatice sintetice-Fixatori- permit parfumului sa se evapore incet si sa

miroase cat mai mult timp-Solvent(apa si alcool)

What are Fragrance Ingredients?

ROH

RCHO

R

O

R O

O

RO

O

alcohols

aldehydes

ketones

estersR

SH

OH

N

R

phenolics

olefins

mercaptans

amines

- Chemicals having 6 – 18 carbon atoms (mostly), and usually one oxygenated functional group. - There are also some multi-functional materials as well as a few sulfur- and nitrogen containing chemical compound.

Performance in Use

• Volatility– Function of molecular weight (how many carbons)

and chemical type.

• Stability– Function of chemical type and use condition (acidity,

alkalinity, oxidizing, open, closed).

• Odor Threshold and dose/response– Function of chemical structure (molecular shape and

chemical type).

Clasificarea materiilor prime odorante• Naturale -Vegetale

-flori ( trandafir, iasomie, mimoze, narcise, lacrimioare, tuberose, plumeria, muscata, flori de salcam ,flori de portocal, flori de ylang-ylang, cuisoara)-fructe (citrice, fructe de ienupar, vanilie) - frunze si parti lemnoase( lavanda, salvie, rozmarin, viola(panseluta), frunze de citrice) - scoarta de copac( scortisoara, casarila)- lemn (santal, palisandru, cedru, mesteacan, ienupar, pin)- radacini, rizomi si bulbi (rizomi de iris, radacini de vetiver, rizomi de ghimbir)- seminte (boabe de cumaru, seminte de morcov, coriandru, cacao, chimen, nucsoara, anason)- rasini(tamaie, mir, rasini de pin si brad, etc. )

- Animale (secretii)- musk (mosc), civet(zibeta), ambergris (ambra)(casalot), castoreum(castor), fagure

• Sintetice- calone, linalool, cumarina, salicilati, etc.

Obtinerea parfumului- composing perfumes

Obtinerea parfumului- composing perfumes-poate dura ani de zile-poate contine pana la 800 de ingrediente

- expert- parfumator- nez(nas)- parfumuri functionale- parfumuri fine

-Colectarea- plantele sunt culese(adesea cu mana) si aduse din toate zonele lumii -ingredientele sintetice- obtinute in laborator

-Extractia- obtinerea ingredientelor aromatice prin diferite metode de extractie-Amestecarea- rolul parfumatorului-Imbatranirea parfumului- poate dura luni sau ani-Controlul calitatii

Metode de obtinere a odorantilor naturali

- Macerarea(extractie cu solvent)- cea mai folosita metoda de obtinere- dureaza de la ore la luni- hexan, dimetil eter- "concret"

- extractie cu lichide supercritice- CO2-"absolut"- extractie cu etanol- "tinctura"- extractie cu grasime- "pomada"

- Distilarea- antrenarea cu vapori ( hidrodistilare) - distilarea uscata - distilarea fractionata

- Expresie- Enfleurage

Extractia - extractoare statice- materialul vegetal este imobil, imersat în solvent

- recirculare exterioara- extractoare mobile (rotative)- materialul vegetal este încãrcat într-un

tambur rotativ, venind permanent în contact cu o cantitate de solvent - cantitate mai mica de solventi

Narcisse Concrete

Avantaje: -consum termic redus, - posibilitatea excluderii contactului cu oxigenul, - inexistenţa problemelor derivate din prezenţa rezidurilor de

solvenţi în extract - utilizarea unor gaze netoxice -CO2 - CO2- nepolar- folosit la extractia aromaticelor nepolare - temperatura mica- putere de solvatare mare

- compusi extrasi raman nealterati- absolut - se recupereaza "solventul"

Extractie cu lichide supercritice

Advantages of CO2- It is a natural product- chemically inert, non-flammable- non-toxic- easy to completely eliminate- selective- readily available- Inexpensive

Extractie cu lichide supercritice- CO2

- extracţia prin SFE se compune din douã etape: extracţia şi colectarea analitului- colectarea analitului: - “on-line” în gaz-cromatograf sau SFC (supercriticalfluid-cromatograf),

- “off-line” prin depresurizarea lichidului supercritic într-un vas colector.

Extractie cu lichide supercritice

Disadvantage: Technical constraints- High cost of initial investment

Advantages:- obtain extracts which are very close in composition to the natural product.- It is possible to adjust the selectivity & viscosity, etc by fine tuning the temperature & pressure- All result in the increase of popularity of this type of method

Antrenarea cu vapori de apã

Antrenarea cu vapori de apã se practicã în cinci variante diferite:- antrenarea la foc direct- antrenarea în curent de vapori- antrenarea cu vapori sub presiune- antrenarea la presiune redusã - procedeu nou de antrenare cu vapori de apã

Florentine vessel

Expresie

-metoda -”cold pressed”-oil is forced from the material under high mechanical pressure and generally produces a good quality oil

Enfleurage

- grasimile absorb componentii odoranti- grasimea se depune pe placi de sticla montata in rame de lemn- startul de grasime se zgarie cu un pieptene- se depun petalele de flori pe suprafata de grasime- 3 luni- ramele se intorc si se bat pentru a provoca desprinderea petalelor epuizate- se inlocuiesc cu unele noi- un kg grasime- 3 kg petale- grasimea parfumata se extrage cu alcool- absolut

Lavender

• Mint family• Sterile hybrid of two species (L.

angustifolia and L. latifolia) most often used today

• Obtained by steam distillation• More than 300 components,

linalool important• In many men’s fragrances (fern

note)

Rose• Rosa centifolia and

damascena• Petals extracted with

steam or solvents• Used in many perfumes,

foods

RoseMost important constituents:

OH

OH

OOH

b-phenethyl alcohol

citronellollinalool

b-damascenone

Geranium

• Pelargonium graveolens• Oils distilled from leaves and

stems• Much cheaper than rose,

similar fragrance in some types

• Essence from Reunion island especially fruity

• Also in drinks, insect repellent

Geraniol and related compounds

• Found in a variety of plants

• Also produced synthetically

Jasmine• Jasminum grandiflorum• Volatile solvents now used,

used to be enfleurage• A ton of flowers to yield a

kilo of essence• Extremely expensive• Wide range of “jasmonoid”

compounds, biosynthesis perhaps similar to prostaglandins

• Benzyl acetate and related compounds common

Jasmine

Most important constituents

O O

COOCH3

NH

cis-jasmone methyl jasmonate

indole

Tuberose

• Polyanthes tuberosa• Amaryllis relative• Expensive, low yield to

extract, done by enfleurage until relatively recently

• Many fragrance compounds (eugenols, nerol) also some weird tuberose lactones

Orange

• Citrus species• Flowers, leaves, fruits, even

bark all used• Distillation or solvents used• Wide range of compounds

isolated, including linalool

Bergamot

• Citrus bergamia• Zests from unripe fruits

used• Harmonious with many

other compounds; contains linalool, limonene does not dominate in this as it does in orange oil

• Coumarins removed from essence (photosensitizing)

• In Earl Grey tea, as well as perfumes, soaps

• Eau de Colognes

Iris of Florence

• Iris pallida• Violet-scented rhizomes

(orris root) used to produce a concrete with iron in myristic acid (called a butter)

• In perfume with heavy, woody notes

ylang-ylang

• Cananga odorata, related plants

• From SE Asia (?)• Annonaceae• Very floral scent• Several common

compounds (eugenols, linalool) also

• p-Cresyl methyl ether – stinks by itself, but blends

well

Patchouli

• Shrub in the mint family• Pogostemon cablin • Distilled dried leaves yield

several important fragrances

• Distinctive strong odor, but also mixes well

Patchouli

Most important constituents:

tricyclic sesquiterpene alcohols

HO HO HO

Vanilla• Native to Mexico, much

now grown in Madagascar• More than 200 compounds

have been identified• Extract used in small

amounts in perfumes; it’s very strong

• Lots of synthetic vanillin relatives used

vanillin

Vanillin analogs, some with carnation, cocoa butter overtones

Oakmoss

• Evernia prunastri • A lichen found in

much of Europe• Some constituents

now synthesized

Olibanum (incense tree)

• Resin from a Boswellia tree

• Resinous, woody smell• Used in some perfumes

(Opium, Jicky)

Sandalwood• Alpha Santalol:

• Beta Santalol:

OH

OH

Fixatives

• Various animal products– Ambergis, musk, castoreum, civet– synthetics often used now– e.g. ambergris compound from sage

GINGER: Zingiber officinale• Definition: Ginger is the peeled or unpeeled

rhizome of Zingiber officinale (Zingiberaceae).

• Common Names: Jamaican ginger, Ginger• Geographical sources

• Jamaica• China• India Africa

• HistoryCultivated in India from the earliest times. Used

by Greeks and Romans and was a common article of commerce in the European Middle Ages.

Zingiber officinale - CONSTITUENTS• Volatile oils (1 – 2%)

– Camphene– Cineole– Citral– Borneol

• Gingerol – pungent component – Anti-inflammatory• Shogaols – increases bile secretion

• Sesquiterpene HC’s– Zingiberene & Zingiberol (Sesquiterpene alcohol)

• Resins• Starch • Mucilage

CINNAMON: Cinnamomum zeylanicum

• DEFINITION: Cinnamon is the dried bark of Cinnamomum zeylanicum (Lauraceae).

• GEOGRAPHICAL SOURCESCultivated in Sri Lanka, South India, Seychelles, Madagascar, Martinique, Cayenne, Jamaica & Brazil.

Cinnamomum - CONSTITUENTS

• Volatile oils (at least 1.2 %)

• Phlobaphenes• Mucilage• Calcium Oxalate• Starch

CLOVEDEFINITION: Cloves are the dried flower buds

of Syzygium aromaticum (Eugenia caryophyllus), (Myrtaceaea).

Geographical SourcesMolucca or Clove Islands, Zanzibar, Pemba,

Madagascar, Indonesia & Brazil.

CONSTITUENTS14-21% Volatile oils• Mainly eugenol & isoeugenol• Sitosterol• Stigmasterol• Campesterol

Terpene derivatives

CH3

OH

H3C CH3

Menthol

(peppermint oil)

CH3

O

H3C CH2

Carvone

(caraway oil)

CH3

H3C CH3

OH

Thymol

(thyme oil)

Others-Ginger, cardamom, pepper (Piper nigrum), clove

Aromatic compounds

OH

OCH3

Eugenol(clove oil)

OCH3

CH3

Anethole(anise oils)

CHO

Cinnamaldehyde(cinnamon oil)

CH2

First Synthetics

ONO2

O2N NO2

methyl ionone gamma musk xylol

HO

OO

O O

vanillin coumarin

H3C

Synthesis of Vanillin

HO

O

HO

O

HO

OO

eugenol(from clove oil)

isoeugenol

CrVI or MnVII

H3C H3C

H3C

OH-

Synthesis of Coumarin

CHO

OH O

O O

O O

+

(Perkin condensation)

salicylaldehydeaceticanhydride

KOAc

Synthesis of Ionones

OO

O

O

S/A

+

citral 2-butanone

"gamma methyl ionone"

H3PO4

OH-

Sandalwood

• Alpha Santalol:

• Beta Santalol:

OH

OH

Musks

O

O2N NO2

O

O

O

O

muscone muskalactone

musk ketone Galaxolide

Research and Development• Analytical

– Application of new GC methods (head space with SPME)

– Use of more sensitive and better computerized instrumentation: GC-MS, NMR, FT-IR.

• Live flowers – above methods used to analyze odors of flowers before picking.

• New extraction methods for naturals: supercritical CO2

Synthetic Research

Considerations:• Structure – relationship to materials of

known value – natural or synthetic• Raw materials • Process

(often a combination of all three)

Synthetic ResearchPractical only for largest companies.• Hundreds of materials synthesized each

year for evaluation.• In-depth evaluation must include testing in

fragrances and in applications.• Decision to develop cannot be taken

lightly.

Development of New Synthetics

• Processes must be very well worked out in laboratory, pilot plant and factory.

• Best economics, safety and workplace hygiene.

• Testing is required to meet industry safety standards and international PMN requirements for all new chemicals.

• Cost to register new ingredients worldwide is well over $300,000.

Synthetic vs natural: what are the issues?

• “The truth about fragrance oils” “Each essential oil comes from just one source, a living plant.

There are no chemicals involved.”

• Remember, they are all chemicals!• We may actually know more about the synthetic

mixtures than the natural ones

Concerns

• Toxicity to people?• Allergens?• Increasing asthma incidence?• Unknown compounds in the mix?• Persistence in the environment?

– Example: synthetic musk