Bài giảng tổng hợp hóa học hương liệu

Nattaya Lourith, Ph.D. 1 Basic fragrance chemistry I 2 Objectives: • Basic element • Chemical functional group of aroma compounds 3 Contents: •Introduction •Functional group 4 Flower and Chemistry •Smell a Flower – The Fragrance is Chemistry • See a Flower – The Colour is Chemistry •Touch a Flower – The Structure is Chemistry 5 Carnation •Flower •Eugenol • Perfume & Cosmetics 6 Vanilla • Seed • Vanillin •Perfume Nattaya Lourith, Ph.D. 2 7 O OH Lilial ® Florol ® Excital ® Orriniff ® Karanal ® Lyral ® Cedramber ® Boisambrebe ® Mayol ® Aldron ® 8 Functional groups with therapeutic actions Anti-infectious, immunostimulants Anti-infectious, immunostimulants Anti-infectious, immunostimulants Estrogen-like activity Anti-infections, calming, litholitic Balancing, calming Antispasmodic, calming Balancing, calming Cicatrizing (wound healing), mucolitic, litholitic, calming Expectorant, antispasmodic Anti0infectious, immunostimulants Anti-infectious, antispasmodic Anti-infectious, cortisone-like activity Antihistamines, anti-allergic Acids Aromatics aldehydes C10 Alcohols C15 & 20 Alcohols Aldehydes Coumarins Esters Lactones Ketones Oxides Phenols Phenyl methyl ethers C10 Terpenes C15 Terpenes Actions Functional group 9 Chemistry/Biology/Physiology/Psychology - Organic Chemistry – Synthetic, Molecular structure, Biochemistry, Molecular Biology, Genomics, Anatomy, Neuroscience, Bioinformatics - Analytical Chemistry – GC-MS analysis, Quality Assurance - Physical Chemistry – Emulsions, Light scattering, etc. - Psychological aspects of perception – other influences Computer Science – for all of the above + OLFACTION & GUSTATION Multidisciplinary Fields 10 Organic Chemistry Organic synthesis 11 Analytical Chemistry GC-MS analysis Volatiles from a living flower 12 Physical Chemistry Nattaya Lourith, Ph.D. 3 13 Artificial nose 14 15 16 Elements for Life • C : Carbon • H : Hydrogen • N : Nitrogen • O : Oxygen • P : Phosphorus • S : Sulfur Living organisms composed of the 6 elements in 99.9% w/w And trace 17 elements 17 18 Pork fired rice Cheese pizza Nattaya Lourith, Ph.D. 4 19 hemoglobin is bright red containing Iron (Fe) 20 Organic and Inorganic substances •Organic – C, H, N, O, P, S •Inorganic –Metal –Salt 21 Weight & Number 0Shell -1Electron 1Nucleus 0Neutron 1Nucleus+1Proton MassLocation ChargeParticle Atomic weight = Proton + Neutron Atomic number = Proton 22 Structure 23 Chemical bonds : Octet rule 24 Chemical bonds : Electronegativity Nattaya Lourith, Ph.D. 5 25 Chemical bonds Two or more elements combine to form compound -Covalent bonds -Ionic bonds - Hydrogen bonds 26 Covalent bonds 27 Ionic bonds 28 Hydrogen bonds 29 Fragrance and Chemical functional group -Hydrocarbon -Oxygen compounds - Nitrogen compounds -Sulfur compounds - Heterocyclic compounds - Halogen compounds 30 Fragrance compound name DecNonOctHepHexPentButPropEthMeth Prefix 10987654321C Start with Prefix and end up with Suffix -ate-ic-one-al-ol-yle-ene-ane Suffix Functional group Nattaya Lourith, Ph.D. 6 31 32 Structure writing 33 Isomers 34 Isomers Cis or Z Trans or E 35 Isomers R, S or (+), (-) or d, l 36 Hydrocarbon Aliphatic alkane : single bond : C n H 2n+2 alkene : double bond : C n H 2n alkyne : triple bond : C n H 2n-2 cycloalkane : C n H 2n alicyclic : aliphatic cyclic Aromatic Nattaya Lourith, Ph.D. 7 37 Alkane - 1C to 4C are colorless and odorless, flammable gases at ambient temp. & press. - 5C to 14C are colorless, flammable liquids, uninteresting odor - >15C are colorless, odorless, waxy solid Hydrocarbon : Aliphatic Lower alkanes are of no interest in perfumery, needed to remove as the extraction solvent from the extract 38 Hydrocarbon : Aliphatic Alkene -unsaturated hydrocarbon - geometric isomers - molecular parent of terpene buta-1,3-diene methylbuta-1,3-diene Alkane posses odor rather similar to the corresponding alkane but more odor strength due to double bond. Simple alkanes are not used as perfume ingredients. 39 Terpene Hydrocarbon : Aliphatic Isoprene 40 myrcene Terpene momoterpene : C 10 H 16 sesquiterpene : C 15 H 24 (one and a half) limonene -pinene Hydrocarbon : Aliphatic farnesene 41 Alkyne - unpleasant, petroleum-like odor - no application in perfumery But its derivative recently used as perfume ingredient give powerful green character Hydrocarbon : Aliphatic 42 Hydrocarbon : Aliphatic cycloalkane C n H 2n alicyclic : aliphatic cyclic Similar odor of those alkane having the same number of carbon Nattaya Lourith, Ph.D. 8 43 Hydrocarbon : Aromatic -Benzene is the prototype of aromatic compounds 1865 Friedrich August Kekulé - Bezenoid compound posses sweet and pleasant odor Dimethylbenzene or Xylene 1,2-dimethylbenzene ortho -dimethylbenzene o -dimethylbenzene 1,3-dimethylbenzene meta -dimethylbenzene m -dimethylbenzene 1,4-dimethylbenzene para -dimethylbenzene p -dimethylbenzene 44 Alcohols & Phenols : R-OH Ethers : R-O-R Aldehydes : R-CHO Acetals : R-C(OR) 2 Ketones : R-COR Carboxylic acids : R-COOH Esters : R-COOR Lactones : O O Oxygen compounds O O 45 Substitute group : R C H H C H H C H H C H H HHC H H C H H C H H C H H C H H HC H H PentylPentane 46 Alcohols & Phenols Some alcohol of interest to perfumer NACreamy mushroom3-octen-2-ol 1.2 ppb (H 2 O)Powerful mushroom1-octen-3-ol 1550 ppb (H 2 O)Green, grassy and leafy E -3-hexen-1-ol 70 ppb (H 2 O)Herbaceous, green, grassy Z -3-hexen-1-ol 400 ppb (H 2 O)Green, leafy E -2-hexanol NAFresh green, leafy Z -2-hexanol Odor detection threshold OrganolepticsAlcohol 47 Pure phenol is colorless crystal with clean and antiseptic odor Phenol was the first antiseptic ever used Pure phenol is very dangerous cause extremely painful skin burn OH Alcohols & Phenols O OH OH Eugenol Thymol Glucoside form in oil of cloves, pale yellow liquid, strong odor. Antibacterial, antifungal Perfumes, Soaps, Cosmetic Thyme and ajowan oil, white solid, thyme odor 48 Aldehydes Aldehyde = alcohol dehydrogenatum Latin = dehydrogenated alcohol English 3.0 ppb (H 2 O) Vinous fruity, coarse, very powerful CH 3 (CH 2 ) 5 CHOHeptanal 4.5 ppb (H 2 O)Fruity green, very powerfulCH 3 (CH 2 ) 4 CHOHexanal 12.0 ppb (H 2 O)Choking, pungent, fruity, oilyCH 3 (CH 2 ) 3 CHOPentanal 0.7 ppb (H 2 O)Orange peel, fatty, very powerfulCH 3 (CH 2 ) 6 CHOOctanal 9.0 ppb (H 2 O)Choking, pungent, fruityCH 3 (CH 2 ) 2 CHOButanal 9.5 ppb (H 2 O)Choking, suffocating, fruityCH 3 CH 2 CHOPropanal 8.7 ppb (H 2 O)Choking, vinous, fruityCH 3 CHOAcetaldehyde Odor detection threshold Organoleptics Formula Aldehydes Important aldehyde in perfumery = C 8 -C 13 Perfume industry tends to speak of aldehyde C 12 rather than dodecanal Nattaya Lourith, Ph.D. 9 49 Acetals R O R O H R O R O R O O Hemi-acetal Acetal - Acetal posses interesting and useful odor - Acetal is alkali stable PADMA = phenyl-acetaldehyde dimethyl acetal O O acetaldehyde di- cis -3-hexenyl acetal Perfume, green relates to hyacinth and watercress Sweet and Green 50 Ketones Acetone (aketon German ) rose to ketone Acetone has a rather harsh, etheral and unpleasant odor used as a simple and inexpensive nail varnish remover Fruity, orange like, floralCH 3 CO(CH 2 ) 7 CH 3 Decanone Fruity, floral, herbaceousCH 3 CO(CH 2 ) 6 CH 3 Nonanone Floral, green fruity, herbaceous CH 3 CO(CH 2 ) 5 CH 3 Octanone Sweet, fruity, spearmintCH 3 CO(CH 2 ) 4 CH 3 Heptanone Ethereal, fruityCH 3 CO(CH 2 ) 3 CH 3 Hexanone Fruity, orange like, waxy, floralCH 3 CO(CH 2 ) 8 CH 3 Undecanone Ethereal, not unpleasantCH 3 CO(CH 2 ) 2 CH 3 Pentanone Ethereal, not unpleasantCH 3 COCH 2 CH 3 Butanone Harsh, ethereal CH 3 COCH 3 Propanone Organoleptics Formula Ketones 51 Esters 1.0 ppb (H 2 O)Ethereal, fruity, buttery EtOOC(CH 2 ) 2 CH 3 Ethyl butyrate 1.5 ppb (H 2 O)Strong, fruity, appleEtOOC(CH 2 ) 3 CH 3 Ethyl valerate 1.0 ppb (H 2 O) Strong, fruity, wine, apple, banana, pineapple EtOOC(CH 2 ) 4 CH 3 Ethyl hexanoate 2.2 ppb (H 2 O)Strong, fruity, wine, cognacEtOOC(CH 2 ) 5 CH 3 Ethyl heptanoate 15.0 ppb (H 2 O) Fruity, wine, sweet, cognac- apricot EtOOC(CH 2 ) 6 CH 3 Ethyl octanoate 850.0 ppb (H 2 O) Fatty, oily, cognac, nutEtOOC(CH 2 ) 7 CH 3 Ethyl nonanoate 10.0 ppb (H 2 O)Strong, ethereal, fruity, rumEtOOCEtEthyl propionate 5000.0 ppb (H 2 O) Ethereal, sharp, wine-brandy like EtOAcEthyl acetate Odor detection threshold Organoleptics Formula Esters 52 Cinnamon •Bark •Cinnamaldehyde •Perfume 53 Cinnamon •Leaf •Eugenol • Vanillin raw material 54 Citronella •Leaf •Citronellol •Soap & Cosmetics Nattaya Lourith, Ph.D. 10 55 Clove •Bud •Eugenol •Perfume 56 Cumin • Seed • Cuminaldehyde •Perfume 57 Eucalyptus •Leaf •Cineole •Fixative 58 Fennel • Seed •Anethole • Oral care 59 Geranium •Stem & Leaf •Geraniol •Perfume 60 Hyacinth •Flower • Benzyl acetate •Fragrant