Vanillin is an
organic compound
In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. Th ...
with the molecular formula . It is a
phenolic aldehyde. Its
functional groups include
aldehyde
In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl gro ...
,
hydroxyl
In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydrox ...
, and
ether
In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again ...
. It is the primary component of the extract of the
vanilla bean. Synthetic vanillin is now used more often than natural vanilla extract as a
flavoring
A flavoring (or flavouring), also known as flavor (or flavour) or flavorant, is a food additive used to improve the taste or smell of food. It changes the perceptual impression of food as determined primarily by the chemoreceptors of the g ...
in foods, beverages, and pharmaceuticals.
Vanillin and
ethylvanillin are used by the food industry; ethylvanillin is more expensive, but has a stronger
note. It differs from vanillin by having an ethoxy group (−O−CH
2CH
3) instead of a methoxy group (−O−CH
3).
Natural
vanilla extract is a mixture of several hundred different compounds in addition to vanillin. Artificial vanilla flavoring is often a solution of pure vanillin, usually of synthetic origin. Because of the scarcity and expense of natural vanilla extract, synthetic preparation of its predominant component has long been of interest. The first commercial synthesis of vanillin began with the more readily available natural compound
eugenol
Eugenol is an allyl chain-substituted guaiacol, a member of the allylbenzene class of chemical compounds. It is a colorless to pale yellow, aromatic oily liquid extracted from certain essential oils especially from clove, nutmeg, cinnamon, bas ...
(4-allyl-2-methoxyphenol). Today, artificial vanillin is made either from
guaiacol or
lignin.
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, a minor component in the lignin-derived product that is not found in vanillin synthesized from guaiacol.
History
Although it is generally accepted that vanilla was domesticated in
Mesoamerica
Mesoamerica is a historical region and cultural area in southern North America and most of Central America. It extends from approximately central Mexico through Belize, Guatemala, El Salvador, Honduras, Nicaragua, and northern Costa Rica. Wit ...
and subsequently spread to the
Old World in the 16th century, in 2019, researchers published a
paper
Paper is a thin sheet material produced by mechanically or chemically processing cellulose fibres derived from wood, rags, grasses or other vegetable sources in water, draining the water through fine mesh leaving the fibre evenly distribu ...
stating that vanillin residue had been discovered inside jars within a tomb in
Israel
Israel (; he, יִשְׂרָאֵל, ; ar, إِسْرَائِيل, ), officially the State of Israel ( he, מְדִינַת יִשְׂרָאֵל, label=none, translit=Medīnat Yīsrāʾēl; ), is a country in Western Asia. It is situated ...
dating to the 2nd millennium BCE, suggesting the cultivation of an unidentified, Old World-endemic ''
Vanilla'' species in
Canaan
Canaan (; Phoenician: 𐤊𐤍𐤏𐤍 – ; he, כְּנַעַן – , in pausa – ; grc-bib, Χανααν – ;The current scholarly edition of the Greek Old Testament spells the word without any accents, cf. Septuaginta : id est Vetus T ...
since the Middle
Bronze Age
The Bronze Age is a historic period, lasting approximately from 3300 BC to 1200 BC, characterized by the use of bronze, the presence of writing in some areas, and other early features of urban civilization. The Bronze Age is the second pri ...
.
Traces of vanillin were also found in wine jars in
Jerusalem
Jerusalem (; he, יְרוּשָׁלַיִם ; ar, القُدس ) (combining the Biblical and common usage Arabic names); grc, Ἱερουσαλήμ/Ἰεροσόλυμα, Hierousalḗm/Hierosóluma; hy, Երուսաղեմ, Erusałēm. i ...
, which were used by the
Judahite elite before
the city was destroyed in 586 BCE.
Vanilla beans, called ''tlilxochitl,'' were discovered and cultivated as a flavoring for beverages by native Mesoamerican peoples, most famously the Totonacs of modern-day
Veracruz
Veracruz (), formally Veracruz de Ignacio de la Llave (), officially the Free and Sovereign State of Veracruz de Ignacio de la Llave ( es, Estado Libre y Soberano de Veracruz de Ignacio de la Llave), is one of the 31 states which, along with Me ...
, Mexico. Since at least the early 15th century, the
Aztecs used vanilla as a flavoring for
chocolate
Chocolate is a food made from roasted and ground cacao seed kernels that is available as a liquid, solid, or paste, either on its own or as a flavoring agent in other foods. Cacao has been consumed in some form since at least the Olmec ci ...
in drinks called ''xocohotl''.
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
recrystallizing the resulting solids from hot water. 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
glucoside of
isoeugenol found in
pine
A pine is any conifer tree or shrub in the genus ''Pinus'' () of the family (biology), family Pinaceae. ''Pinus'' is the sole genus in the subfamily Pinoideae. The World Flora Online created by the Royal Botanic Gardens, Kew and Missouri Botanic ...
bark. Tiemann and Haarmann founded a company Haarmann and Reimer (now part of
Symrise
Symrise AG is a major producer of flavours and fragrances with sales of €3.154 billion in 2018. Major competitors include Döhler, Firmenich, Givaudan, International Flavors and Fragrances, and Takasago International. Symrise is a member of th ...
) and started the first industrial production of vanillin using their process in
Holzminden
Holzminden (; nds, Holtsminne) is a town in southern Lower Saxony, Germany. It is the capital of the district of Holzminden. It is located on the river Weser, which at this point forms the border with the state of North Rhine-Westphalia.
His ...
, Germany. In 1876,
Karl Reimer synthesized vanillin (2) from guaiacol (1).
By the late 19th century, semisynthetic vanillin derived from the eugenol found in
clove oil
Oil of clove, also known as clove oil, is an essential oil extracted from the clove plant, '' Syzygium aromaticum''. Clove oil is commonly used in aromatherapy and for flavoring food and some medicines. Madagascar and Indonesia are the main produc ...
was commercially available.
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
Thorold, Ontario
Thorold is a city in Ontario, Canada, located on the Niagara Escarpment. It is also the seat of the Regional Municipality of Niagara. The Welland Canal passes through the city, featuring lock 7 and the Twin Flight Locks.
History
The first ...
supplied 60% of the world market for synthetic vanillin.
[ Hocking 1997.] However, subsequent developments in the wood pulp industry have made its lignin wastes less attractive as a raw material for vanillin synthesis. Today, approximately 15% of the world's production of vanillin is still made from lignin wastes,
[ Fache et al 2015] while approximately 85% synthesized in a two-step process from the
petrochemical
Petrochemicals (sometimes abbreviated as petchems) are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewabl ...
precursors guaiacol and
glyoxylic acid.
[ Esposito 1997.]
Beginning in 2000,
Rhodia began marketing biosynthetic vanillin prepared by the action of microorganisms on
ferulic acid extracted from
rice bran. At
USD$700/kg, this product, sold under the trademarked name Rhovanil Natural, is not cost-competitive with petrochemical vanillin, which sells for around US$15/kg. 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 about 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.
It is also found in ''
Leptotes bicolor
''Leptotes bicolor'' is a species of orchid native to Paraguay and southern Brazil. It is the type species of the genus '' Leptotes''.
Its flowers and fruits are used as a substitute for vanilla in milk and ice cream.
It grows in cooler clim ...
'', a species of orchid native to Paraguay and southern Brazil,
and the
Southern Chinese red pine.
At lower concentrations, vanillin contributes to the flavor and aroma profiles of foodstuffs as diverse as
olive oil,
butter
Butter is a dairy product made from the fat and protein components of churned cream. It is a semi-solid emulsion at room temperature, consisting of approximately 80% butterfat. It is used at room temperature as a spread, melted as a condim ...
,
raspberry, and
lychee
Lychee (US: ; UK: ; ''Litchi chinensis''; ) is a Monotypic taxon, monotypic taxon and the sole member in the genus ''Litchi'' in the Sapindus, soapberry family, ''Sapindaceae''.
It is a tropical tree native to Southeast and Southwest China (t ...
fruits.
Aging in
oak barrels
Oak is used in winemaking to vary the color, flavor, tannin profile and texture of wine. It can be introduced in the form of a barrel during the fermentation or aging periods, or as free-floating chips or staves added to wine fermented in a vess ...
imparts vanillin to some
wine
Wine is an alcoholic drink typically made from Fermentation in winemaking, fermented grapes. Yeast in winemaking, Yeast consumes the sugar in the grapes and converts it to ethanol and carbon dioxide, releasing heat in the process. Different ...
s,
vinegar, and
spirits.
In other foods, heat treatment generates vanillin from other compounds. In this way, vanillin contributes to the flavor and aroma of
coffee
Coffee is a drink prepared from roasted coffee beans. Darkly colored, bitter, and slightly acidic, coffee has a stimulating effect on humans, primarily due to its caffeine content. It is the most popular hot drink in the world.
Seeds of ...
,
maple syrup, and
whole-grain products, including corn
tortillas and
oatmeal.
Chemistry
Natural production
Natural vanillin is extracted from the seed pods of ''
Vanilla planifolia
''Vanilla planifolia'' is a species of vanilla orchid. It is native to Mexico and Belize. It is one of the primary sources for vanilla flavouring, due to its high vanillin content. Common names include flat-leaved vanilla, and West Indian van ...
'', a
vining orchid
Orchids are plants that belong to the family Orchidaceae (), a diverse and widespread group of flowering plants with blooms that are often colourful and fragrant.
Along with the Asteraceae, they are one of the two largest families of floweri ...
native to Mexico, but now grown in tropical areas around the globe.
Madagascar
Madagascar (; mg, Madagasikara, ), officially the Republic of Madagascar ( mg, Repoblikan'i Madagasikara, links=no, ; french: République de Madagascar), is an island country in the Indian Ocean, approximately off the coast of East Afric ...
is presently the largest producer of natural vanillin.
As harvested, the green seed pods contain vanillin in the form of its β--
glucoside; the green pods do not have the flavor or odor of vanilla.
[ Walton 2003.]
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
blanched in hot water, to arrest the processes of the living plant tissues. Then, for 1–2 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 dark brown, and
enzyme
Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products ...
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, with its focus on producing a premium product by established methods, rather than on innovations that might alter the product's flavor profile.
Biosynthesis
Although the exact route of vanillin biosynthesis in ''V. planifolia'' is currently unknown, several pathways are proposed for its biosynthesis. Vanillin biosynthesis is generally agreed to be part of the
phenylpropanoid pathway starting with -phenylalanine,
which is deaminated by
phenylalanine ammonia lyase (PAL) to form t-
cinnamic acid. The para position of the ring is then
hydroxylate
In chemistry, hydroxylation can refer to:
*(i) most commonly, hydroxylation describes a chemical process that introduces a hydroxyl group () into an organic compound.
*(ii) the ''degree of hydroxylation'' refers to the number of OH groups in ...
d by the
cytochrome P450
Cytochromes P450 (CYPs) are a superfamily of enzymes containing heme as a cofactor that functions as monooxygenases. In mammals, these proteins oxidize steroids, fatty acids, and xenobiotics, and are important for the clearance of various co ...
enzyme cinnamate 4-hydroxylase (C4H/P450) to create ''p''-
coumaric acid Coumaric acid is a phenolic derivative of cinnamic acid having a hydroxy group
In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. I ...
.
Then, in the proposed ferulate pathway, 4-hydroxycinnamoyl-CoA ligase (4CL) attaches ''p''-coumaric acid to
coenzyme A (CoA) to create ''p''-coumaroyl CoA.
Hydroxycinnamoyl transferase (HCT) then converts ''p''-coumaroyl CoA to 4-coumaroyl
shikimate
Shikimic acid, more commonly known as its anionic form shikimate, is a cyclohexene, a cyclitol and a cyclohexanecarboxylic acid. It is an important biochemical metabolite in plants and microorganisms. Its name comes from the Japanese flower ''shik ...
/
quinate
Quinic acid is a cyclitol, a cyclic polyol, and a cyclohexanecarboxylic acid. It is a colorless solid that can be extracted from plant sources. Quinic acid is implicated in the perceived acidity of coffee.
Occurrence and preparation
The compound i ...
. This subsequently undergoes oxidation by the P450 enzyme coumaroyl ester 3’-hydroxylase (C3’H/P450) to give caffeoyl shikimate/quinate. HCT then exchanges the shikimate/quinate for CoA to create caffeoyl CoA, and 4CL removes CoA to afford caffeic acid. Caffeic acid then undergoes
methylation by caffeic acid O-
methyltransferase
Methyltransferases are a large group of enzymes that all Methylation, methylate their substrates but can be split into several subclasses based on their structural features. The most common class of methyltransferases is class I, all of which co ...
(COMT) to give ferulic acid. Finally, vanillin synthase hydratase/lyase (vp/VAN) catalyzes hydration of the double bond in ferulic acid followed by a retro-aldol elimination to afford vanillin.
Vanillin can also be produced from vanilla glycoside with the additional final step of deglycosylation.
[ In the past ''p''-hydroxybenzaldehyde was speculated to be a precursor for vanillin biosynthesis. However, a 2014 study using radiolabelled ]precursor
Precursor or Precursors may refer to:
* Precursor (religion), a forerunner, predecessor
** The Precursor, John the Baptist
Science and technology
* Precursor (bird), a hypothesized genus of fossil birds that was composed of fossilized parts of u ...
indicated that ''p''-hydroxybenzaldehyde do not synthesise vanillin or vanillin glucoside in the vanilla orchids.
Chemical synthesis
The demand for vanilla flavoring has long exceeded the supply of vanilla beans. , the annual demand for vanillin was 12,000 tons, but only 1,800 tons of natural vanillin were produced. The remainder was produced by chemical synthesis
As a topic of chemistry, chemical synthesis (or combination) is the artificial execution of chemical reactions to obtain one or several products. This occurs by physical and chemical manipulations usually involving one or more reactions. In mod ...
. 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. Later it was synthesized from lignin-containing "brown liquor", a byproduct of the sulfite process for making wood pulp
Pulp is a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops, waste paper, or rags. Mixed with water and other chemical or plant-based additives, pulp is the major raw ...
. Counterintuitively, 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
Petrochemicals (sometimes abbreviated as petchems) are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewabl ...
raw material guaiacol. Several routes exist for synthesizing vanillin from guaiacol.
At present, the most significant of these is the two-step process practiced by Rhodia since the 1970s, in which guaiacol (1) reacts with glyoxylic acid by electrophilic aromatic substitution. The resulting vanillylmandelic acid (2) is then converted by 4-Hydroxy-3-methoxyphenylglyoxylic acid (3) to vanillin (4) by oxidative decarboxylation.
:
Wood-based vanillin
15% of the world's production of vanillin is produced from lignosulfonates, a byproduct from the manufacture of cellulose
Cellulose is an organic compound with the formula , a polysaccharide consisting of a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units. Cellulose is an important structural component of the primary cell wa ...
via the sulfite process. The sole producer of wood-based vanillin is the company Borregaard
Borregaard is a Norwegian company, established in 1889 in the southeastern town of Sarpsborg in Østfold county. Its main products were traditionally pulp and paper. The company later started producing chemicals based on timber as a raw mat ...
located in Sarpsborg
Sarpsborg ( or ), historically Borg, is a city and municipality in Viken county, Norway. The administrative centre of the municipality is the city of Sarpsborg.
Sarpsborg is part of the fifth largest urban area in Norway when paired with neig ...
, Norway
Norway, officially the Kingdom of Norway, is a Nordic countries, Nordic country in Northern Europe, the mainland territory of which comprises the western and northernmost portion of the Scandinavian Peninsula. The remote Arctic island of ...
.
Wood-based vanillin is produced by copper-catalyzed oxidation of the lignin structures in lignosulfonates under alkaline conditions and is claimed by the manufacturing company to be preferred by their customers due to, among other reasons, its much lower carbon footprint than petrochemically synthesized vanillin.
Fermentation
The company Evolva has developed a genetically modified microorganism which can produce vanillin. Because the microbe is a processing aid A processing aid is a substance used in the production of processed food, and which may end up in the finished product, but which is not, by law, required to be disclosed to the consumer as an ingredient.
Ethical concerns
NGOs, journalists, and f ...
, the resulting vanillin would not fall under U.S. GMO labeling requirements, and because the production is nonpetrochemical, food using the ingredient can claim to contain "no artificial ingredients".
Using ferulic acid as an input and a specific non GMO species of ''Amycolatopsis
''Amycolatopsis'' is a genus of high GC-content bacteria within the family Pseudonocardiaceae.
The genus is known for producing many types of antibiotics, including
* Epoxyquinomicin, related to ''Amycolatopsis sulphurea'', are a class of weak ...
'' bacteria, natural vanillin can be produced.
Biochemistry
Several studies have suggested that vanillin can affect the performance of antibiotics
An antibiotic is a type of antimicrobial substance active against bacteria. It is the most important type of antibacterial agent for fighting bacterial infections, and antibiotic medications are widely used in the treatment and preventio ...
in laboratory conditions.
Uses
The largest use of vanillin is as a flavoring, usually in sweet foods. The ice cream
Ice cream is a sweetened frozen food typically eaten as a snack or dessert. It may be made from milk or cream and is flavoured with a sweetener, either sugar or an alternative, and a spice, such as cocoa or vanilla, or with fruit such as ...
and chocolate
Chocolate is a food made from roasted and ground cacao seed kernels that is available as a liquid, solid, or paste, either on its own or as a flavoring agent in other foods. Cacao has been consumed in some form since at least the Olmec ci ...
industries together comprise 75% of the market for vanillin as a flavoring, with smaller amounts being used in confections and baked goods.
Vanillin is also used in the fragrance industry, in perfume
Perfume (, ; french: parfum) is a mixture of fragrant essential oils or aroma compounds (fragrances), fixatives and solvents, usually in liquid form, used to give the human body, animals, food, objects, and living-spaces an agreeable scent ...
s, and to mask unpleasant odors or tastes in medicines, livestock fodder, and cleaning products. It is also used in the flavor industry, as a very important key note for many different flavors, especially creamy profiles such as cream soda.
Additionally, vanillin can be used as a general-purpose stain for visualizing spots on thin-layer chromatography plates. This stain yields a range of colors for these different components.
Vanillin–HCl staining can be used to visualize the localisation of tannins in cells.
Manufacturing
Vanillin has been used as a chemical intermediate in the production of pharmaceuticals, cosmetics
Cosmetics are constituted mixtures of chemical compounds derived from either natural sources, or synthetically created ones. Cosmetics have various purposes. Those designed for personal care and skin care can be used to cleanse or protec ...
, and other fine chemicals. In 1970, more than half the world's vanillin production was used in the synthesis of other chemicals. As of 2016, vanillin uses have expanded to include perfume
Perfume (, ; french: parfum) is a mixture of fragrant essential oils or aroma compounds (fragrances), fixatives and solvents, usually in liquid form, used to give the human body, animals, food, objects, and living-spaces an agreeable scent ...
s, flavoring and aromatic masking in medicines, various consumer and cleaning products, and livestock
Livestock are the domesticated animals raised in an agricultural setting to provide labor and produce diversified products for consumption such as meat, eggs, milk, fur, leather, and wool. The term is sometimes used to refer solely to ani ...
foods.
Adverse effects
Vanillin can trigger migraine headaches in a small fraction of the people who experience migraines.
Some people have allergic reactions to vanilla. They may be allergic to synthetically produced vanilla but not to natural vanilla, or the other way around, or to both.
Vanilla orchid plants can trigger contact dermatitis, especially among people working in the vanilla trade if they come into contact with the plant's sap. An allergic contact dermatitis called vanillism produces swelling and redness, and sometimes other symptoms. The sap of most species of vanilla orchid which exudes from cut stems or where beans are harvested can cause moderate to severe dermatitis if it comes in contact with bare skin. The sap of vanilla orchids contains calcium oxalate crystals, which are thought to be the main causative agent of contact dermatitis in vanilla plantation workers.
A pseudophytodermatitis called vanilla lichen can be caused by tiny mites.
Ecology
''Scolytus multistriatus
''Scolytus multistriatus'', the European elm bark beetle or smaller European elm bark beetle, is a bark beetle species in the genus ''Scolytus''. In Europe, while ''S. multistriatus'' acts as vector of the Dutch elm disease, caused by the Ascomyc ...
'', one of the vectors of the Dutch elm disease
Dutch elm disease (DED) is caused by a member of the sac fungi (Ascomycota) affecting elm trees, and is spread by elm bark beetles. Although believed to be originally native to Asia, the disease was accidentally introduced into America, Europe ...
, uses vanillin as a signal to find a host tree during oviposition.
See also
* Phenolic compounds in wine
* Other positional isomers:
** Isovanillin
Isovanillin is a phenolic aldehyde, an organic compound and isomer of vanillin. It is a selective inhibitor of aldehyde oxidase. It is not a substrate of that enzyme, and is metabolized by aldehyde dehydrogenase into isovanillic acid, which cou ...
** ''ortho''-Vanillin
** 2-Hydroxy-5-methoxybenzaldehyde
** 2-Hydroxy-4-methoxybenzaldehyde
* Benzaldehyde
* Protocatechuic aldehyde
Protocatechuic aldehyde is a phenolic aldehyde, a compound released from cork stoppers into wine.
This molecule can be used as a precursor in the vanillin synthesis by biotransformation by cell cultures of ''Capsicum frutescens'', a type of Chili ...
* Syringaldehyde
References
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Notes
{{Authority control
Flavors
Perfume ingredients
Hydroxybenzaldehydes
Vanilloids
O-methylated natural phenols
Vanilla
Total synthesis