Flavor Chemistry 风味化学.ppt

FlavorChemistryOctober7 2009YuanLiu Orisit Mold Dicoumarol Coumadin Coumarin Majormetaboliteinman Isithepatoxic 1954 FDABANSCOUMARIN ReflectionsonaHalfCenturyofFlavorChemistry 1954 televisionscreensweresmallroundandblack white 1954 thefirsttransistorradio TheRegency isintroducedinOctober1954 transistorsweredevelopedatBellLabsin1948byShockley Brattain BardeenforwhichtheyreceivedtheNobelPrizeinPhysics1956 TomWatson Jr atIBMgaveRegencyradiostohisengineersandtoldthemtoputtransistorsincomputers By1954overamillionpeopleayearweredesertingthebigcitiesforaffordablehomesinsuburbia MajorAdvancesinInstrumentation MajorAdvancesinInstrumentation NMR GasChromatography MassSpectrometry 12 00 14 00 16 00 18 00 20 00 22 00 24 00 26 00 28 00 30 00 32 00 34 00 36 00 0 2000000 4000000 6000000 8000000 1e 07 1 2e 07 1 4e 07 1 6e 07 Time Abundance GC MSAnalysisofaMeatFlavor PeakIdentifiedasFurfurylMercaptanPowerfulCoffeeAroma Peaksare2 Methyl 2 3 dihydrofuran 3 thiolisomers Powerfulmeat likearoma MajorAdvancesinInstrumentation 1958 FoodAdditivesAmendment FoodAdditivesAmendmentenacted requiringmanufacturersoffoodadditivestoestablishsafety FEMAbeginsprocessforestablishmentofaGRASlistforflavoringsincooperationwiththeFDA 1960 FEMApublishesfirst tentative listofGRASflavorants 1961 FEMApublishesfirst expertcommitteepeerreviewed listofGRASflavorants 662items 1965 FEMApublishesexpandedGRASlist 1124items 2004 FEMAGRASlistsnowcontain 2066items 1955 ButterFlavorandthedelta lactones Bythemid 50 smargarinewaspoisedtoovertakebutterasthetablespreadofchoice About1955itwasrecognizedthatdelta dodecalactonewasanimportantbutterflavorandcombinationsofdelta decalactone delta dodecalactonewouldsoonbethekeytoimprovedacceptability In1926 Reichstein StaudingerpatentedtheuseoffurfurylmercaptanandothercoffeeisolatesincludingaseriesofalkylpyrazinesforuseinartificialcoffeeflavorButthevalueofpyrazinesasflavorantswasoverlookeduntilthemid50 swhentheywererediscoveredasimportantcontributorstococoabyDietrich etal atFirmenich Subsequentlymanyhundredsofpublicationshaveappearedontheflavorpropertiesofpyrazines Incoffee cocoaandteaalone 100monocyclicpyrazines 15bicyclicpyrazinesand12quinoxalineshavebeenidentified AdvancesinFlavoringMaterials Pyrazines AdvancesinFlavoringMaterials Green Bellpepper Galbanum Roastedpeanut hazelnut Popcorn nutty bready Cocoa darkchocolate nutty Earthy rawpotato aromaofdampblackearth Nutty brown roasted earthyandmusty 1950 s 1960 s Pyrazines Todayabout60differentpyrazinesareemployedinflavorcreation AdvancesinFlavoringMaterials 2 acetylthiazoleNutty popcorn bread toastedcereal 2 isobutylthiazoleGreentomatoaromaandtaste tomatoleafaroma Sulfurolmeaty beeflikewithnuttynote 2 4 Dimethyl 5 vinylthiazoleNutty meatlikenotes 1950 s 1970 s Thiazoles Todayabout45differentthiazolesareemployedinflavorcreation AdvancesinFlavoringMaterials 1950 s Mushroomalcohol 1 octen 3 ol AlthoughfirstisolatedfromArmillariamatsutakein1937andLater in1944 fromlavender thismaterialwasvirtuallyunknowntomostFlavoristsuntilthelate1950 s Naturalmushroomodor slightlyfruity Herbaceous green musty Today weknowthattheracematesodorisdominatedbytheolfactivelymorepowerful R enantiomer AdvancesinFlavoringMaterials beta Pinene Myrcene Linalool Geraniol Citronellol Citronellal Menthol LinalylAcetate 1959 Bain Webb TurpentineintoFragrance Flavor 1959 RocheProcessforLinalool CitralviaAcetylene AdvancesinFlavoringMaterials AdvancesinFlavoringMaterials 1959 DiscoveryofMethylDihydrojasmonateHedione 1971 IntroductionofHedione AdvancesinFlavoringMaterials 1959 DiscoveryofRoseOxide 1960 SafroleBanned RootBeermanufacturersshudder Keyingredientbanned Manufacturersandflavorcompaniesscrambletoreformulate Solution Methylsalicylatewithotheritemssuchasmethylchavicolandanethole Methylsalicylate Anethole Methylchavicol Safrole LeafAlcohol Althoughtheexactstructureofleafalcoholwasestablishedin1938 itwasnotwidelyavailableuntilBedoukian sprocessin1961 Leafalcoholwasessentialforthedevelopmentofmanyfruitflavors especiallystrawberryTheestersareimportantinmanytropicalflavors AdvancesinFlavoringMaterials Discoveredin1937 theFirstPublicationonRaspberryKetoneappearsin1961 AdvancesinFlavoringMaterials AdvancesinFlavoringMaterials 1962 FirstpublicationsappearonMethylJasmonate MethylDihydrojasmonate 1R 2R Z methyljasmonate1S 2S Z methyljasmonate 1R 2S Z methylepijasmonate1S 2R Z methylepijasmonate MethylJasmonate odorant insectpheromone plantgrowthregulator AdvancesinFlavoringMaterials Chirality Odor MethylJasmonate MethylDihydrojasmonate ConfigurationOdorDescriptionOdorThreshold inPPB Methyljasmonates1R 2R Weakodor 70 1S 2S OdorlessOdorless1S 2R epi OdorlessOdorless1R 2S epi Strongodor floral truejasmin like3 Ref T E Acreeet al J Agric Food Chem 1985Methyldihydrojasmonates1R 2R Floral sweet jasminelike240 1S 2S Floral fatty cis jasmone haycharacter 15 360 teanote slightlylemonpeellike weak 1S 2R epi Herbal fatty tea like tobacco 12 500 damascone cis jasmone1R 2S epi Intenselyfloral jasmine like bright cis 15 jasmone slightlyfatty woody ionone like extremelylonglastingRef Werkhoff P et al FoodReviewsInternational 2002 detectionthreshold recognitionthreshold 1964 IntroductionofFuraneol 1965 FirstpublicationsonisolationofFuraneol fromstrawberryandpineapple AdvancesinFlavoringMaterials 1965 66 Sinensalisolatedfromorangeoil AdvancesinFlavoringMaterials 1950 s 60 s SyntheticCarvones AdvancesinFlavoringMaterials By1957acommerciallyviableroutetol carvonewasavailableandinthe1960 sbothsyntheticl carvoneandd carvonewereitemsofcommerce Butonlyin1971wasitunequivocallyproventhattheodordifferenceswereduetotheenantioselectiveodorperceptionofthedifferingchiralforms AdvancesinFlavoringMaterials 1960 s Nootkatone Firstisolatedin1962 it simportancetocitrusflavorwasunknownuntilit sisolationfromgrapefruitbyMcleodin1964 In1966 Coca ColaintroducedFresca By1970 NootkatonewasGRASandbecameakeyingredientinFresca Coca ColamanufacturedNootkatoneformanyyearsandsoonmadeitavailabletotheflavorindustry Nootkatonestronggrapefruitodor bitterintaste Nootkatoneweakwoody vetivernote nograpefruitcharacter virtuallynotaste Threshold 60 000ppb800ppb 1968 PfizerpatentsEthylmaltol Ethylmaltol VeltolPlus wastoutedtobeabout6XstrongerthanmaltolandanimportantsubstituteforCoumarin Well atleastitisstrongerthanmaltol AdvancesinFlavoringMaterials AdvancesinFlavoringMaterials 1960 s 80 s Importantmeatycompounds 2 methylthiophene 3 thiolCookedmeat Ortho toluenthiolMeaty liver 2 methylfuran 3 thiolCookedmeat 2 methyl 4 5 dihydrofuran 3 thiolCookedmeat DecadienalMeat poultryfat 2 pentylpyridineTallowflavor AdvancesinFlavoringMaterials 1970 s 80 s OtherFuranones Sotolon caramelfuranone Maplefuranoneidentifiedincanesugar powerfulcaramelmaplenotes Sotolon MapleFuranone Abhexone Threshold 0 003ppb0 00005ppb Sotolon keyflavorantoffenugreek sake sherrywine AdvancesinFlavoringMaterials 1970 DiscoveryDamascenone Damascone AdvancesinFlavoringMaterials 1965 Haarmann Reimerbeginsstudyonsynthesisof mentholfromm cresol thymol1973 H RmentholplantbeginsproductioninHolzminden1978 H R sBushyPark SCmentholplantonstream 1973 Haarmann Reimer MentholSynthesis AdvancesinFlavoringMaterials 1974 ThiomenthonesidentifiedinBuchuoil Keycomponentforblackcurrantandthe fuzzy peachskinnote 1970 s WilkinsonSword s CoolwithoutMenthol Inthe1970 sWilkinsonSwordLtd designedandevaluatedabout1200compoundsfortheircoolingactivity Twoofthese WS 3andWS 23werecommercializedwithlimitedsuccess UponexpirationoftheWilkinsonSwordpatentsinthelate90 s aflurryofactivityresultedinexpandedinterestintheseandrelated sensate compounds suchasTakasago sCoolantAgent10andSymrise sFrescolat series WS 3 WS 23 AdvancesinFlavoringMaterials 1980 PatentonOxane 1977 Winteridentifies2 methyl 4 propyl 1 3 oxathianeasacharacterimpactcompoundinPassionfruit1984 Pickenhagendeterminesthat cis 2 methyl 4 propyl 1 3 oxathianeistheimportantdiastereomer AdvancesinFlavoringMaterials 2R 4S 2 methyl 4 propyl 1 3 oxathianeOdor powerfulsulfury tropicalfruitThreshold 2ppb 2S 4R 2 methyl 4 propyl 1 3 oxathianeOdor flat estery camphoraceous floral lesssulfuryThreshold 4ppb AdvancesinFlavoringMaterials 1981 BASFCitralPlantcomesonstream 2004 BASFopensnewcontinuousprocesscitralplantwith40 000metrictonscapacity 1982 1 p Menthene 8 thiol Demoleidentifies1 p Menthene 8 thiolasacharacterimpactcompoundinGrapefruitJuice Verypowerfulwithanodorthresholdof0 0001ppb italsorequiresstabilizationasittendstorapidlycyclizetothethioanalogofdihydropinol AdvancesinFlavoringMaterials AdvancesinFlavoringMaterials 1983 Takasago snewEnantioselectiveMethodForproducing menthol AdvancesinFlavoringMaterials 1986 H RPatentsFilbertone TheCharacterImpactCompoundofHazelnut E R Filbertone hazelnut soft butter chocolate metallic weakerimpact at25ppbinwater OdorThresholdof E R Filbertoneisabout10timeshigherthanfor E S Filbertone E S Filbertone hazelnut metallic fatty pyidine strongerimpact at25ppbinwater OdorThresholdof E S Filbertoneisabout10timeslowerthanfor E R Filbertone AdvancesinFlavoringMaterials 3 mercapto 2 methyl pentane 1 oldiastereosomersbroth like sweaty leek like 2000 The3 mercapto 2 methyl pentane 1 ols AdvancesinFlavoringMaterials 2001 2 4 6 trithiaheptane CharacterimpactcompoundofwhitetrufflesOdor Leek onion cress horseradish mushroom like earthy greentinge AdvancesinFlavoringMaterials 2001 Takasago sProfessorRyojiNoyoriwinsthe2001NobelPrizeforChemistry AdvancesinFlavoringMaterials AdvancesinanAmbergrisCompoundSynthesis 1950 Synthesisof Ambrox fromSclareolviaSclareolide 90 Ambrox 1988 IntroductionofDL Ambrox purelysynthetic 50 Ambrox 50 diastereomers 1993 IntoductionofCetalox purelysynthetic 96 Ambrox 2004 Introductionof CetaloxLeavo purelysynthetic 99 Ambrox presumablyviaresolutionofracemicSclareolideacidwithapseudoephedrineenantiomer AdvancesinFlavoringMaterials Mintlactone 1983 Dihydromintlactone 1995 Winelactone 1996 GRASNo 37644032Odor Vinous lactonicMinty coumarinic Coumarinic hay coconut tenaciouslactonic tonkaFlavor Lactonic sweet herbalCoumarinic fatty Coumarinic herballactonic coconutThreshold 0 0000016ppb0 00012ppb0 000039ppb InairRef Frerot et al FlavourFragr J 2002 17 218 226 Gaudin Tetrahedron 2000 56 4769 4776 Coumarinicp MenthaneLactones A5thtastesensationcalled Umami akaUmani isnowaccepted MostcommonexampleisMSG Monosodiumglutamate whichenhancesmeat savoryflavors TheFifthTaste Until1999 2000only4tastesensationsweregenerallyrecognized Sweet e g Sucrose AspartameSour e g Citricacid Phosphoricacid H