Flavor and Fragrance Materials of Natural rigin
Expression
Enfleurage
Jasmine
Jasmine
Distillation
Steam Distillation $30 $300/kg 250 300 tonnes/yr Steam/il vapor mixture Plant material H 2 out Condensor Still H 2 in Steam Essential oil Water of Cohobation
Lavendar
Sandalwood
Fractional Distillation Water condensor Water condensor Condensor/ Fractionating column
Extraction/Isolation ethanol extraction Natural Material Tincture distillation solvent extraction enfleurage Essential il distillation Concrete (Resinoid) ethanol extraction Pomade ethanol extraction Absolute
Gas Chromatography / Mass Spectrometry (GCMS)
Headspace analysis
GC-MS of Soft Soap
GC-MS of Multipurpose cleaner
GC-MS of Dishwashing detergent
Figure 1. Column A 160 I40 I20 100 00 G _I-/ TIME, PAINUTES Gas chromatogram of a concentrate of volatile constituents from roast beef drippings. Attenuation 256, sample size 0.3 p1,
Peak no. 1 5 7 8 9 10 12 12 13 14 15 16 17 18 Table I. Volatile Constituents of Roast Beef and Roast Beef Drippings Compd Sample Peak no. Compd Diethyl ether (solvent) M, D 23 It-Nonanal Ethyl acetate (solvent M, D 24 2-ctenal impurity) 25 1-Heptanol Ethanol (solvent impurity) 2-Methylbutanal M, D M, D 26 Benzaldehyde 2-n-Hept ylfuran 3-Met hylbutanal M, D Ca-benzene 2,3-Butanedione M 2,4-ctadienal (tent,) n-pentanal M, D 2,3-Butanediol n-nonane M, D 2-Decanone 1-Propanol 2,3-Pentanedione D M rz-tetradecane rz-decanal Toluene M, D 28 y-butyrolactone Dimethyl disulfide M 29 2-Nonenal n-hexanal M, D 30 1-ctanol n-decane M, D 31 2-n-ctylfuran n-butanol 1,4-DimethyIbenzene M, D M, D Butyric acid 6(?)-Methyltetradecane 1,ZDimethylbenzene 3-Heptanone M D 32 Phenylacetaldehyde 2-cten- 1-01 n-undecane M, D n-pentadecane 2-Heptanone M, D 34 2-Undecanone n-heptanal M, D y-hexalactone 2-Hexenal D n-undecanal 3-Hydroxy-2-butanone M, D 35 2-Decenal 1-Pentanol M, D 36 2,4-Nonadienal 2-n-Pentylfuran M, D 6-Valerolactone (tent.) Trimethylbenzene M y-heptalactone Methylethylbenzene M Dimethyl sulfone 3-ctanone M, D 2-Dodecanone Trimethylbenzene M, D n-hexadecane 4-Heptanol (tent.) D 39 2,4-Decadienal 3-Heptanol D n-dodecanal 2-ctanone M, D 40 2-Undecenal n-dodecane M, D 41 2,4-Decadienal 6-Heptalactone n-ctanal M, D n-heptadecane 2-Heptenal M, D Heptadecene 2,3-ctanedione M Acetylpyrrole Dieth ylbenzene M y-ctalactone 1-Hexanol M, D 43 2-Tridecanone Acetic acid D 12-Tridecanal 19 C8-benzene M 44 2-Dodecenal 20 2-n-Hexylfuran D 6-ctalactone n-butylbenzene M 45 2,4-Undecadienal Ca-benzene M n-ctadecane Dimethylpyrazine (tent.) D 47 y-nonalactone 4-ctanol (tent.) D 2-Tridecenal 3-ctanol D 2,4-Dodecadienal 2-n-butox yet hano M 6-Nonalactone 22 2-Nonanone M, D y-decalactone n-tridecane M, D 2-Pentadecanone a M: Compo lund was found in roast beef meat; D: Compound was found in roast beef drippings. D D M, D D D D D D
Volatile Composition of Some Brazilian Fruits: Umbu-caja (Spondias citherea), Camu-camu (Myrciaria dubia), Araça-boi (Eugenia stipitata), and Cupuaçu (Theobroma grandiflorum) Maria Regina B. Franco*, and Takayushi Shibamoto Faculdade de Engenharia de Alimentos, UNICAMP, Campinas-SP, CP 6121, CEP 13081-970, Brazil, and Department of Environmental Toxicology, University of California, Davis, California 95616-8588 1264 J. Agric. Food Chem., Vol. 48, No. 4, 2000 Franco and Shibamoto Table 1. Volatile Composition of the Umbu-caja Sample compound Kovats index % area NI a 725 0.42 ethyl acetate 824 1.71 NI 900 0.21 NI 925 0.20 NI 932 0.23 R-pinene 1010 1.48 NI 1038 0.29 ethyl butyrate 1043 1.90 toluene 1055 3.60 butyl acetate 1100 0.72 β-pinene 1100 0.43 β-myrcene 1154 1.29 d-limonene 1184 7.09 β-phellandrene 1192 tr c cis-β-ocimene 1236 36.30 trans-β-ocimene 1250 7.45 ethyl hexanoate 1252 0.77 hexyl acetate 1289 0.20 1,5,5,6-tetramethyl-1,3-cyclohexadiene b 1365 0.62 ethyl octanoate 1442 tr R-copaene 1450 0.59 β-caryophyllene 1556 26.8 R-caryophyllene 1606 4.49 β-selinene 1679 1.22 1,2,3,4,4a,5,6,8a-octahydro-4a,8-1685 1.65 dimethylnaphthalene b δ-cadinene 0.32 Table 2. Volatile Composition of the Camu-camu Sample compound Kovats index % area ethyl acetate 820 0.17 R-pinene 1009 66.2 R-fenchene 1029 0.09 ethyl butyrate 1048 0.16 camphene 1052 0.20 NI a 1065 tr b β-pinene 1102 0.48 car-3-ene 1142 tr β-myrcene 1155 1.11 R-phellandrene 1160 0.27 NI 1162 0.33 R-terpinene 1169 0.11 d-limonene 1195 23.72 β-phellandrene 1200 0.29 eucalyptol 1208 tr γ-terpinene 1238 0.58 p-cimene 1267 0.31 terpinolene 1271 0.40 fenchol 1554 tr β-caryophyllene 1563 4.61 4-terpineol 1574 tr humulene 1606 tr NI 1636 0.20 NI 1744 0.16 a NI, not identified. b Traces. There was an inversion in the order of elution of ethyl
GC-lfactory (GC-)
Infrared Spectroscopy
Limonene
Citronellol H
Carvone
Nuclear Magnetic Resonance (NMR)
2-D NMR
Biosynthesis
Cellulose Glucose Acetyl Coenzyme A Biosynthesis
Terpene Biosynthesis CoAS + CoAS Claisen condensation (substitution) CoAS Acetoacetyl-CoA
Terpene Biosynthesis CoAS + CoAS Claisen condensation (substitution) CoAS Acetoacetyl-CoA CoAS Acetoacetyl-CoA + SCoA Acetyl-CoA Aldol reaction (addition) CoAS H SCoA H 2 (hydrolysis) H H SCoA b-hydroxy-b-methyl-glutaryl-coa
Terpene Biosynthesis CoAS + CoAS Claisen condensation (substitution) CoAS Acetoacetyl-CoA CoAS Acetoacetyl-CoA + SCoA Acetyl-CoA Aldol reaction (addition) CoAS H SCoA H 2 (hydrolysis) H H SCoA b-hydroxy-b-methyl-glutaryl-coa H H SCoA NADPH + H + (reduction) H H H mevalonic acid ATP (convert to good leaving group) H H PP mevalonic acid diphosphate PP = P P H H H
Terpene Biosynthesis CoAS + CoAS Claisen condensation (substitution) CoAS Acetoacetyl-CoA CoAS Acetoacetyl-CoA + SCoA Acetyl-CoA Aldol reaction (addition) CoAS H SCoA H 2 (hydrolysis) H H SCoA b-hydroxy-b-methyl-glutaryl-coa H H SCoA NADPH + H + (reduction) H H H mevalonic acid ATP (convert to good leaving group) H H PP mevalonic acid diphosphate PP = P P H H H H H PP (decarboxylation) PP PP mevalonic acid diphosphate isopentyl-pyrophosphate dimethylallyl-pyrophosphate
Isoprene Units PP + PP PP PP prenyl pyrophosphate isopentyl pyrophosphate geranyl pyrophosphate farnesyl pyrophosphate PP H H Acyclic Monoterpenoids geranyl pyrophosphate geraniol (rose) H citral (lemon) H H citronellol (rose) citronellal (lemon/citrus) linalool (floral) geranyl acetate (floral)
Cyclic Monoterpenoids H limonene α-terpineol α-pinene (citrus) (lilac) (pine) β-pinene camphor H l-(-) menthol (mint) (S)-carvone d-(+) (R)-carvone l-(-)
Sesquiterpenoids H H α-bisabolol cedrol chamomile oil (anti-inflammatory) Virginian and Chinese cedarwood oil H PP farnesyl pyrophosphate H H patchouli alcohol patchouli oil α-santalol East Indian sandalwood oil zizinal vetiver oil
H H ambreine H H Ambergris dihydro-γ-ionone ambrinol H ambrox Moist, soft, creamy, persistent, warm, animalic, woody, amber
Australian beach, 2006 32 lb Ambergris = $750,000
Polyketide, Terpenoide or Shikimate? H CoA acetylcoenzyme A (polyketide) CoA PP PP prenyl pyrophosphate isopentyl pyrophosphate (terpenoid) H H H shikimic acid (shikimate) H 3 C ethyl everninate CH 3 methyl jasmonate Me Me Me β-asarone H H H H polyketide polyketide H H H H H shikimate
deodarone dehydrocostus lactone