Vanillin 228190 222987855 2008-07-02T01:39:00Z 132.161.136.35 /* Uses */ {{Chembox new | Name = Vanillin | ImageFile = Vanillin.png | ImageSize = 120px | ImageName = Vanillin | ImageFile1 = Vanillin-3d.png | ImageSize1 = 130px | IUPACName = 4-Hydroxy-3-methoxybenzaldehyde | OtherNames = Vanilin<br />Vanillic aldehyde<br />Methyl vanillin | Section1 = {{Chembox Identifiers | SMILES = O=CC1=CC(OC)=C(O)C=C1 | CASNo = 121-33-5 | RTECS = YW5775000 }} | Section2 = {{Chembox Properties | Formula = C<sub>8</sub>H<sub>8</sub>O<sub>3</sub> | MolarMass = 152.15 g/mol | Appearance = White or lightly yellow solid<br />(usually in needles) | Density = 1.056 g/cm³, solid | Solubility = 1 g/100 ml (25°C) | MeltingPt = 80-81°C (353-354 K) | BoilingPt = 285°C (558 K) | Viscosity = ? [[Poise|cP]] at ?°C }} | Section7 = {{Chembox Hazards | ExternalMSDS = [http://www.jtbaker.com/msds/englishhtml/v2775.htm External MSDS] | MainHazards = May cause irritation to skin,<br />eyes, and respiratory tract | NFPA-H = 1 | NFPA-F = 1 | NFPA-R = | FlashPt = 147°C | RPhrases = {{R22}}. | SPhrases = {{S24/25}}. }} | Section8 = {{Chembox Related | OtherCpds = [[Eugenol]], [[Anisaldehyde]], [[Phenol]] }} }} '''Vanillin''', '''methyl vanillin''', or ''4-hydroxy-3-methoxybenzaldehyde'', is an [[organic compound]] with the molecular formula C<sub>8</sub>H<sub>8</sub>O<sub>3</sub>. Its [[functional groups]] include [[aldehyde]], [[ether]] and [[phenol]]. It is the primary component of the extract of the [[vanilla]] bean. Synthetic vanillin is used as a [[flavoring agent]] in foods, beverages, and pharmaceuticals. Methyl vanillin is used by the food industry as well as '''[[ethyl vanillin]]'''. The ethyl is more expensive but has a stronger note, and differs by having an ethoxy group (-O-CH<sub>2</sub>CH<sub>3</sub>) instead of a methoxy group (-O-CH<sub>3</sub>). Natural [[vanilla]] extract is a mixture of several hundred different compounds in addition to vanillin. Artificial vanilla flavoring is a solution of pure vanillin, usually of synthetic origin. Because of the scarcity and expense of natural vanilla extract, there has long been interest in the synthetic preparation of its predominant component. The first commercial synthesis of vanillin began with the more readily available natural compound [[eugenol]]. Today, artificial vanillin is made from either the [[petrochemical]] [[guaiacol]], or from [[lignin]], a natural constituent of [[wood]] which is a byproduct of the [[paper industry]]. Lignin-based artificial vanilla flavoring is alleged to have a richer flavor profile than oil-based flavoring; the difference is due to the presence of [[acetovanillone]] in the lignin-derived product, an impurity not found in vanillin synthesized from guaiacol.<ref>According to [[#esposito1997|Esposito 1997]], blind taste-testing panels cannot distinguish between the flavors of synthetic vanillin from lignin and from guaicol, but can distinguish the odors of these two types of synthetic vanilla extracts. Guaiacol vanillin, adulterated with acetovanillone, has an odor indistinguishable from lignin vanillin.</ref> ==History== Vanilla was cultivated as a flavoring by pre-Columbian Mesoamerican peoples; at the time of their conquest by [[Hernán Cortés]], the [[Aztecs]] used it as a flavoring for [[chocolate]]. Europeans became aware of both chocolate and vanilla around the year 1520.<ref>[[#esposito1997|Esposito 1997]]</ref> Vanillin was first isolated as a relatively pure substance in 1858 by [[Nicolas-Theodore Gobley]], who obtained it by evaporating a vanilla extract to dryness, and [[recrystallization|recrystallizing]] the resulting solids from hot water.<ref>[[#gobley1858|Gobley 1858]]</ref> In 1874, the German scientists [[Ferdinand Tiemann]] and [[Wilhelm Haarmann]] deduced its chemical structure, at the same time finding a synthesis for vanillin from [[coniferin]], a [[glycoside]] of [[isoeugenol]] found in [[pine]] bark.<ref>[[#tiemann1874|Tiemann 1874]]</ref> Tiemann and Haarmann founded a company, Haarmann & Reimer (now part of [[Symrise]]) and started the first industrial production of Vanillin using their process in [[Holzminden]] ([[Germany]]). In 1876, [[Karl Reimer]] synthesized vanillin from [[guaiacol]].<ref>[[#reimer1876|Reimer 1876]]</ref> By the late 19th century, semisynthetic vanillin derived from the [[eugenol]] found in [[clove]] oil was commercially available.<ref>According to [[#hocking1997|Hocking 1997]], synthetic vanillin was sold commercially in 1874, the same year Tiemann and Haarmann's original synthesis was published. Haarmann & Reimer, one of the corporate ancestors of the modern flavor and aroma manufacturer [[Symrise]], was in fact established in 1874. However, [[#esposito1997|Esposito 1997]] claims that synthetic vanillin first became available in 1894 when Rhône-Poulenc (since 1998, [[Rhodia (company)|Rhodia]]) entered the vanillin business. If the former claim is correct, the authors of the latter article, being employees of Rhône-Poulenc, may have been unaware of any previous vanillin manufacture.</ref> Synthetic vanillin became significantly more available in the 1930s, when production from [[clove oil]] was supplanted by production from the [[lignin]]-containing waste produced by the [[Sulfite pulping process]] for preparing wood pulp for the [[paper]] industry. By 1981, a single pulp and paper mill in Ontario supplied 60% of the world market for synthetic vanillin.<ref>[[#hocking1997|Hocking 1997]]</ref> However, subsequent developments in the wood pulp industry have made its lignin wastes less attractive as a raw material for vanillin synthesis. While some vanillin is still made from lignin wastes, most synthetic vanillin is today synthesized in a two-step process from the petrochemical precursors [[guaiacol]] and [[glyoxylic acid]].<ref>[[#esposito1997|Esposito 1997]]</ref> Beginning in 2000, [[Rhodia (company)|Rhodia]] began marketing biosynthetic vanillin prepared by the action of microorganisms on [[ferulic acid]] extracted from [[rice bran]]. At $700/kg, this product, sold under the trademarked name Rhovanil Natural, is not cost-competitive with petrochemical vanillin, which sells for around $15/kg.<ref>[[#rouhi2003|Rouhi 2003]]</ref> However, unlike vanillin synthesized from lignin or guaiacol, it can be labeled as a natural flavoring. ==Occurrence== Vanillin is most prominent as the principal flavor and aroma compound in vanilla. Cured vanilla pods contain approximately 2% by dry weight vanillin; on cured pods of high quality, relatively pure vanillin may be visible as a white dust or "frost" on the exterior of the pod. At smaller concentrations, vanillin contributes to the flavor and aroma profiles of foodstuffs as diverse as [[olive oil]],<ref>[[#brenes1999|Brenes 1999]]</ref> [[butter]],<ref>[[#adahchour1999|Adahchour 1999]]</ref> [[raspberry]]<ref>[[#roberts1996|Roberts 1996]]</ref> and [[lychee]]<ref>[[#ong1998|Ong 1998]]</ref> fruits. Aging in [[oak (wine)]] barrels imparts vanillin to some [[wine]]s and [[distilled beverage|spirit]]s.<ref>[[#viriot1993|Viriot 1993]]</ref> In other foods, heat treatment evolves vanillin from other chemicals. In this way, vanillin contributes to the flavor and aroma of [[coffee]],<ref>[[#blank1992|Blank 1992]]</ref> [[maple syrup]],<ref>[[#kermasha1995|Kermasha 1995]]</ref> and [[whole grain]] products including corn [[tortilla]]s<ref>[[#buttery1995|Buttery 1995]]</ref> and [[oatmeal]].<ref>[[#guth1993|Guth 1993]]</ref> ==Production== [[Image:Vanilla fragrans 2.jpg|thumb|left|These green seed pods contain vanillin only in its glycoside form, and lack the characteristic odor of vanilla.]] ===Natural production=== Natural vanillin is extracted from the seed pods of ''[[Vanilla]] planifola'', a [[vine|vining]] [[orchid]] native to [[Mexico]], but now grown in tropical areas around the globe. [[Madagascar]] is presently the largest producer of natural vanillin. As harvested, the green seed pods contain vanillin in the form of its β-D-[[glycoside]]; the green pods do not have the flavor or odor of vanilla.<ref>[[#walton2003|Walton 2003]]</ref> After being harvested, their flavor is developed by a months-long curing process, the details of which vary among vanilla-producing regions, but in broad terms it proceeds as follows: First, the seed pods are [[blanching|blanched]] in hot water, to arrest the processes of the living plant tissues. Then, for 1&ndash;2 weeks, the pods are alternately sunned and sweated: during the day, they are laid out in the sun, and each night, wrapped in cloth and packed in airtight boxes to sweat. During this process, the pods become a dark brown, and [[enzyme]]s in the pod release vanillin as the free molecule. Finally, the pods are dried and further aged for several months, during which time their flavors further develop. Several methods have been described for curing vanilla in days rather than months, although they have not been widely developed in the natural vanilla industry,<ref>[[#dignum2001|Dignum 2001]] reviews several such proposed innovations in vanilla processing, including processes in which the seed pods are chopped, frozen, warmed by a heat source other than the sun, or crushed and treated by various enzymes. Whether or not these procedures produce a product whose taste is comparable to traditionally prepared natural vanilla, many of them are incompatible with the customs of the natural vanilla market, in which the vanilla beans are sold whole, and graded by, among other factors, their length.</ref> with its focus on producing a premium product by established methods, rather than on innovations that might alter the product's flavor profile. Vanillin accounts for about 2% of the dry weight of cured vanilla beans, and is the chief among about 200 other flavor compounds found in vanilla. ===Chemical synthesis=== The demand for vanilla flavoring has long exceeded the supply of vanilla beans. [[As of 2001]], the annual demand for vanillin was 12,000 tons, but only 1800 tons of natural vanillin were produced.<ref>[[#dignum2001|Dignum 2001]]</ref> The remainder was produced by [[chemical synthesis]]. Vanillin was first synthesized from [[eugenol]] (found in oil of [[clove]]) in 1874–75, less than 20 years after it was first identified and isolated. Vanillin was commercially produced from eugenol until the 1920s.<ref>[[#hocking1997|Hocking 1997]]. This chemical process can be conveniently carried out on the laboratory scale using the procedure described by [[#lampman1977|Lampman 1977]].</ref> Later it was synthesized from [[lignin]]-containing "brown liquor", a byproduct of the [[sulfite process]] for making [[wood pulp]].<ref>[[#hocking1997|Hocking 1997]]</ref> Counter-intuitively, even though it uses waste materials, the lignin process is no longer popular because of environmental concerns, and today most vanillin is produced from the [[petrochemical]] raw material [[guaiacol]].<ref>[[#hocking1997|Hocking 1997]]</ref> Several routes exist for synthesizing vanillin from guaiacol.<ref>[[#vanness1983|Van Ness 1983]]</ref> At present, the most significant of these is the two-step process practiced by [[Rhodia (company)|Rhodia]] since the 1970s, in which guaiacol reacts with [[glyoxylic acid]] by [[electrophilic aromatic substitution]]. The resulting vanilmandelic acid is then converted to vanillin by oxidative decarboxylation.<ref>[[#esposito1997|Esposito 1997]]</ref> In October 2007 Mayu Yamamoto of the International Medical Center of Japan won an [[Ignobel|Ig Nobel]] prize for developing a way to extract vanillin from cow dung.<ref>[http://www.japanprobe.com/?p=2875 Japan’s 12th Ig Noble Prize Winner: Mayu Yamamoto & Dung Vanilla : Japan Probe<!-- Bot generated title -->]</ref> ==Uses== The largest single use of vanillin is as a flavoring, usually in [[sweetness|sweet]] foods. The [[ice cream]] and [[chocolate]] industries together comprise 75% of the market for vanillin as a flavoring, with smaller amounts being used in [[confection]]s and [[baked goods]].<ref>[[#fridge2004|FRIDGE 2004]], p. 33</ref> Vanillin is also used in the fragrance industry, in [[perfume]]s, and to mask unpleasant odors or tastes in medicines, livestock [[fodder]], and cleaning products.<ref>[[#esposito1997|Esposito 1997]]</ref> Vanillin has been used as a chemical intermediate in the production of [[pharmaceuticals]] and other [[fine chemicals]]. In 1970, more than half the world's vanillin production was used in the synthesis of other chemicals,<ref>[[#hocking1997|Hocking 1997]]</ref> but as of 2004 this use accounts for only 13% of the market for vanillin.<ref>[[#fridge2004|FRIDGE 2004]], p. 32</ref> Additionally, Vanillin can be used as a general purpose stain for developing [[thin layer chromatography]] (TLC) plates to aid in visualizing components of a reaction mixture. This stain yields a range of colors for these different components. ==References== <div class="references-2column"> *<span id="adahchour1999"> {{cite journal | last = Adahchour | first = Mohamed | coauthors = René J. J. Vreuls, Arnold van der Heijden and Udo A. Th. Brinkman | year = 1999 | title = Trace-level determination of polar flavour compounds in butter by solid-phase extraction and gas chromatography–mass spectrometry | journal = Journal of Chromatography A | volume = 844 | issue = 1-2 | pages = 295–305 | doi = 10.1016/S0021-9673(99)00351-9}}</span> *<span id="blank1992"> {{cite journal | last = Blank | first = Imre | coauthors = Alina Sen, and Werner Grosch | year = 1992 | title = Potent odorants of the roasted powder and brew of Arabica coffee | journal = Zeitschrift für Lebensmittel-Untersuchung und -Forschung A | volume = 195 | issue = 3 | pages = 239–245 | doi = 10.1007/BF01202802}}</span> *<span id="brenes1999"> {{cite journal | last = Brenes | first = Manuel | coauthors = Aranzazu García, Pedro García, José J. Rios, and Antonio Garrido | year = 1999 | title = Phenolic Compounds in Spanish Olive Oils | journal = Journal of Agricultural and Food Chemistry | volume = 47 | issue = 9 | pages = 3535–3540 | doi = 10.1021/jf990009o}}</span> *<span id="buttery1995"> {{cite journal | last = Buttery | first = Ron G. | coauthors = and Louisa C. Ling | year = 1995 | title = Volatile Flavor Components of Corn Tortillas and Related Products | journal = Journal of Agricultural and Food Chemistry | volume = 43 | issue = 7 | pages = 1878–1882 | doi = 10.1021/jf00055a023}}</span> *<span id="dignum2001"> {{cite journal | last = Dignum | first = Mark J. W. | coauthors = Josef Kerlera, and Rob Verpoorte | year = 2001 | title = Vanilla Production: Technological, Chemical, and Biosynthetic Aspects | journal = Food Reviews International | volume = 17 | issue = 2 | pages = 119–120 | doi = 10.1081/FRI-100000269 | url = http://taylorandfrancis.metapress.com/link.asp?id=db9u44c22f9dqt7w | accessdate = 2006-09-09}}</span> *<span id="esposito1997">{{cite encyclopedia | last = Esposito | first = Lawrence J. | coauthors = K. Formanek, G. Kientz, F. Mauger, V. Maureaux, G. Robert, and F. Truchet | title = Vanillin | encyclopedia = Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition | volume = 24 | pages = 812–825 | publisher = John Wiley & Sons | location = New York | date = 1997}}</span> *<span id="fridge2004">{{cite book | author = Fund for Research into Industrial Development, Growth and Equity (FRIDGE) | title = Study into the Establishment of an Aroma and Fragrance Fine Chemicals Value Chain in South Africa, Part Three: Aroma Chemicals Derived from Petrochemical Feedstocks | publisher = National Economic Development and Labor Council | date = 2004 | url = http://www.nedlac.org.za/top.asp?inc=research/fridge/aroma/index.html }}</span> *<span id="gobley1858">{{cite journal | last = Gobley | first = N.-T. | year = 1858 | title = Recherches sur le principe odorant de la vanille | journal = Journal de Pharmacie et de Chimie | volume = 34 | pages = 401–405}}</span> *<span id="guth1993"> {{cite journal | last = Guth | first = Helmut | coauthors = and Werner Grosch | year = 1995 | title = Odorants of extrusion products of oat meal: Changes during storage | journal = Zeitschrift für Lebensmittel-Untersuchung und -Forschung A | volume = 196 | issue = 1 | pages = 22–28 | doi = 10.1007/BF01192979}}</span> *<span id="hocking1997">{{cite journal | last = Hocking | first = Martin B. | year = 1997 | month = September | title = Vanillin: Synthetic Flavoring from Spent Sulfite Liquor | journal = Journal of Chemical Education | volume = 74 | issue = 9 | pages = 1055 | url = http://jchemed.chem.wisc.edu/hs/Journal/Issues/1997/Sep/abs1055.html | format = PDF | accessdate = 2006-09-09}}</span> *<span id="kermasha1995"> {{cite journal | last = Kermasha | first = S. | coauthors = M. Goetghebeur, and J. Dumont | year = 1995 | title = Determination of Phenolic Compound Profiles in Maple Products by High-Performance Liquid Chromatography | journal = Journal of Agricultural and Food Chemistry | volume = 43 | issue = 3 | pages = 708–716 | doi = 10.1021/jf00051a028}}</span> *<span id="lampman1977"> {{cite journal | last = Lampman | first = Gary M. | coauthors = Jennifer Andrews, Wayne Bratz, Otto Hanssen, Kenneth Kelley, Dana Perry, and Anthony Ridgeway | year = 1977 | title = Preparation of vanillin from eugenol and sawdust | journal = Journal of Chemical Education | volume = 54 | issue = 12 | pages = 776–778}}</span> *<span id="ong1998"> {{cite journal | last = Ong | first = Peter K. C. | coauthors = Terry E. Acree | year = 1998 | title = Gas Chromatography/Olfactory Analysis of Lychee (Litchi chinesis Sonn.) | journal = Journal of Agricultural and Food Chemistry | volume = 46 | issue = 6 | pages = 2282–2286 | doi = 10.1021/jf9801318}}</span> *<span id="reimer1876"> {{cite journal | last = Reimer | first = K. | year = 1876 | title = Ueber eine neue Bildungsweise aromatischer Aldehyde | journal = Berichte der deutschen chemischen Gesellschaft | volume = 9 | issue = 1 | pages = 423–424 | doi = 10.1002/cber.187600901134}}</span> *<span id="roberts1996"> {{cite journal | last = Roberts | first = Deborah D. | coauthors = Terry E. Acree | year = 1996 | title = Effects of Heating and Cream Addition on Fresh Raspberry Aroma Using a Retronasal Aroma Simulator and Gas Chromatography Olfactometry | journal = Journal of Agricultural and Food Chemistry | volume = 44 | issue = 12 | pages = 3919–3925 | doi = 10.1021/jf950701t}}</span> *<span id="rouhi2003"> {{cite journal | last = Rouhi | first = A. Maureen | year = 2003 | title = Fine Chemicals Firms Enable Flavor And Fragrance Industry | journal = Chemical and Engineering News | volume = 81 | issue = 28 | pages = 54}}</span> *<span id="tiemann1874"> {{cite journal | last = Tiemann | first = Ferd. | coauthors = Wilh. Haarmann | title = Ueber das Coniferin und seine Umwandlung in das aromatische Princip der Vanille | journal = Berichte der Deutschen Chemischen Gesellschaft | volume = 7 | issue = 1 | pages = 608–623 | doi = 10.1002/cber.187400701193 | year = 1874 }}</span> *<span id="vanness1983">{{cite encyclopedia | last = Van Ness | first = J. H. | title = Vanillin | encyclopedia = Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition | volume = 23 | pages = 704–717 | publisher = John Wiley & Sons | location = New York | date = 1983}}</span> *<span id="viriot1993"> {{cite journal | last = Viriot | first = Carole | coauthors = Augustin Scalbert, Catherine Lapierre, and Michel Moutounet | year = 1993 | title = Ellagitannins and lignins in aging of spirits in oak barrels | journal = Journal of Agricultural and Food Chemistry | volume = 41 | issue = 11 | pages = 1872–1879 | doi = 10.1021/jf00035a013}}</span> *<span id="walton2003">{{cite journal | last = Walton | first = Nicholas J. | coauthors = Melinda J. Mayer, and Arjan Narbad | year = 2003 | month = July | title = Vanillin | journal = Phytochemistry | volume = 63 | issue = 5 | pages = 505–515 | doi = 10.1016/S0031-9422(03)00149-3}}</span> </div> ==Notes== <!-- See [[Wikipedia:Footnotes]] for instructions. --> {{reflist|2}} [[Category:Aldehydes]] [[Category:Phenols]] [[Category:Aromatic compounds]] [[Category:Flavors]] [[Category:perfume ingredients]] [[ar:فانيلين]] [[cs:Vanilin]] [[da:Vanillin]] [[de:Vanillin]] [[es:Vanilina]] [[fr:Vanilline]] [[it:Vanillina]] [[he:ונילין]] [[hu:Vanillin]] [[nl:Vanilline]] [[ja:バニリン]] [[pl:Wanilina]] [[ru:Ванилин]] [[sv:Vanillin]] [[th:วานิลลิน]] [[tr:Vanilin]] [[zh:香草精]]