PRODUCTS

VANILLIN

EC / List no.: 204-465-2
CAS no.: 121-33-5
Mol. formula: C8H8O3

Vanillin is an organic compound with the molecular formula C8H8O3.
Vanillin is a phenolic aldehyde.
Its functional groups include aldehyde, hydroxyl, and ether.
Vanillin 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 agent in foods, beverages, and pharmaceuticals.

Vanillin and ethylVanillin are used by the food industry; ethylVanillin is more expensive, but has a stronger note.
Vanillin differs from Vanillin by having an ethoxy group (−O−CH2CH3) instead of a methoxy group (−O−CH3).

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 (4-allyl-2-methoxyphenol).
Today, artificial Vanillin is made either from guaiacol or lignin.

Vanillin crystals extracted from vanilla extract
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 of Vanillin
Vanilla was cultivated as a flavoring by pre-Columbian Mesoamerican people; at the time of their conquest by Hernán Cortés, the Aztecs used it as a flavoring for chocolate.

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 bark.
Tiemann and Haarmann founded a company Haarmann and 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.
By the late 19th century, semisynthetic Vanillin derived from the eugenol found in clove oil 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 supplied 60% of the world market for synthetic Vanillin.
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, while approximately 85% synthesized in a two-step process from the petrochemical precursors guaiacol and glyoxylic acid.

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.

Vanillin is also found in Leptotes bicolor, 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, raspberry, and lychee fruits.

Aging in oak barrels imparts Vanillin to some wines, 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, 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, a 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-glucoside; the green pods do not have the flavor or odor of vanilla.

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 enzymes 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 l-phenylalanine, which is deaminated by phenylalanine ammonia lyase (PAL) to form t-cinnamic acid.
The para position of the ring is then hydroxylated by the cytochrome P450 enzyme cinnamate 4-hydroxylase (C4H/P450) to create p-coumaric acid.
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/quinate.
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 (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 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.
As of 2001, 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.
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.
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 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 reacts with glyoxylic acid by electrophilic aromatic substitution.
The resulting vanillylmandelic acid is then converted by 4-Hydroxy-3-methoxyphenylglyoxylic acid to Vanillin 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 via the sulfite process.
The sole producer of wood-based Vanillin is the company Borregaard located in Sarpsborg, Norway.

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, 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 bacteria, natural Vanillin can be produced.

Biochemistry
Several studies have suggested that Vanillin can affect the performance of antibiotics in laboratory conditions.

Uses of Vanillin
The largest use of Vanillin is as a flavoring, usually in 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 confections and baked goods.

Vanillin is also used in the fragrance industry, in perfumes, and to mask unpleasant odors or tastes in medicines, livestock fodder, and cleaning products.
Vanillin 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.

Vanillin's Manufacturing
Vanillin has been used as a chemical intermediate in the production of pharmaceuticals, cosmetics, 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 perfumes, flavoring and aromatic masking in medicines, various consumer and cleaning products, and livestock foods.

Vanillin is the artificial synthesis of the first kind of flavor, synthesized by the German M. Harman, and G-Dr. Twyman in 1874.
Usually Vanillin is divided into methyl Vanillin and ethyl Vanillin.

1. Methyl Vanillin:
white or slightly yellow crystalline, with vanilla aroma and rich milk fragrance, is the largest varieties of perfume industry, is the main ingredients of universal favorite creamy vanilla flavor.
Its use is very extensive, such as in food, chemical, tobacco industry as spices, flavoring agent or a flavor enhancer, which is the majority in food consumption of drinks, candy, cakes, biscuits, bread and roasted seeds.
There are no relevant reports that Vanillin was harmful to the human body.

2. Ethyl Vanillin:
white to micro yellow needle crystal or crystalline powder, similar to vanilla beans, aroma than methyl Vanillin thicker.
Vanillin is a broad-spectrum flavors, which is one of the world's most important synthetic spice, is an important and indispensable raw material for food additives industry.
The aroma is 3-4 times than the Vanillin, with aromas of vanilla bean aroma and long-lasting fragrance.
Widely used in food, chocolate, ice cream, drinks and cosmetics play aroma and flavour.
Also ethyl Vanillin also is feed additives, electroplating industry of brightening agent, the pharmaceutical industry of intermediates. C. Guaiacol glyoxylate route By using guaiacol and glyoxylic acid as raw material then by condensation, oxidation and decarboxylation made to Vanillin.

This method is mainly composed of French Rhone-Poulenc company research and development, and production in large scale.
The use of glyoxylic acid from maleic acid methyl ester was prepared by two ozone decomposition.
The synthetic route has the advantages of wide material source, less reaction steps, low cost, less three wastes pollution.
Therefore, it is considered to be the most appropriate method.

Vanilla extract
Vanilla is a member of the orchid family, a sprawling conglomeration of some 25,000 different species.
Vanilla is a native of South and Central America and the Caribbean; and the first people to have cultivated it seem to have been the Totonacs of Mexico’s east coast.
The Aztecs acquired vanilla when they conquered the Totonacs in the 15th Century; the Spanish, in turn, got it when they conquered the Aztecs.
Vanilla is a complex blend of flavour and fragrance ingredients extracted from the seed pods of the vanilla orchid, containing at a guess somewhere between 250 and 500 different flavor and fragrance components.
The most important ingredient in this blend is Vanillin.
However, because of the cost and supply chain variability of natural vanilla, most products that want to impart the aroma of vanilla do not in fact use vanilla but rather synthetic Vanillin (99% of all Vanillin consumed worldwide) made primarily from petrochemicals or chemically derived from lignin.

Vanillin is mainly used as a flavouring agent, primarily in foods and beverages such as chocolate and dairy products, but also to mask unpleasant tastes in medicines or livestock fodder.
Vanillin is also an intermediate in the manufacture of certain pharmaceuticals and agrochemicals.
Vanillin and vanilla extracts have an estimated annual total volume of 16,000 metric tonnes, worth some USD 650 million in total.
Natural vanilla extract represents less than 1% by volume, though it is more important in terms of value.
The primary market opportunity is in providing a competitively priced product, with good aroma properties, made from a natural and sustainable source.
Evolva believes such properties will allow fermentation-derived Vanillin to be used in a wide variety of food and other products.
Evolva does not believe that such a product will significantly replace vanilla obtained from the orchid.

Important spices
Vanillin is commonly known as vanilla powder, cloud Nepal with powder, vanilla extract, is extracted from the Rutaceae vanilla bean, is a kind of important spices, is one of synthetic fragrances yield the largest varieties, mixing chocolate, ice cream, chewing gum, pastry and tobacco essence of important raw materials.
Naturally occurring in pods of vanilla planifolia, and clove oil, oakmoss oil, balsam of Peru, tolu balsam storax.
Vanillin has strong and unique vanilla bean aroma, aroma stability, under the high temperature, less volatile.
Vanillin is vulnerable to light, and gradually oxidized in the air, easy to change color at encountering alkali or alkaline material.
Aqueous solution reacts with ferric chloride to produce blue purple solution.
Can be used for many fragrance formulas, but mainly used for edible essence.
Especially widely used in the candy, chocolate, soft drinks, ice cream, wine, and in the smoke flavor.
There is no restrictions imposed on the use of IFRA. But because of easy cause discoloration, we should pay attention to use in white fragrant product.
Vanillin is also an important foundation for edible spices, spices, almost all flavors, most used in food industry.
Food flavors are widely used in bread, butter, cream and brandy etc.
The addition amount of cakes, biscuits is 0.01~0.04%, candy is 0.02~0.08%, which is one of the most the baked food with spices, can be used for chocolate, biscuit, cake, ice cream and Boudin.
Before use, it is dissolved in warm water, the effect is much better.
The highest amount of baked food is 220mg/kg, chocolate is 970mg/kg.
As fixative agent, coordination agent and modifier are widely used in cosmetics, also is the important flavoring agent for food and drink.
Vanillin is used in medicine. L-DOPA (L-dopa), methyldopa.
Also used for nickel, chrome metal plating brightener.

Action and uses:
Flavors: Vanillin is edible flavouring agent, with vanilla bean aroma and strong desire for milk fragrance, is an important and indispensable raw material for food additives industry, widely used in all need to increase milk fragrance flavor flavoring in food, such as cake, cold drinks, chocolate, candy, biscuits, instant noodles, bread and tobacco, flavoring liquor, toothpaste, soap, cosmetics, perfume, ice cream, drinks and cosmetics play aroma and flavour.
Also it can be used for soap, toothpaste, perfume, rubber, plastic, pharmaceutical products.
Vanillin Accord with FCCIV standard.

Vanitrope
Vanitrope has a strong and enduring clove and vanilla aroma, the aroma intensity is from 16 to 25 times of Vanillin.
Vanitrope was early developed. in the twenties of the 20th century.
Early synthetic route is that safrole oil as raw material, the alcohol solution of potassium hydroxide reacts hot pressing enable to open ring, and then used sodium ethyl sulfate to make the hydroxy ethylation, finally in the ethanol solution with sulfuric acid hydrolysis to obtain the vanitrope.
But due to the lack of purity of aroma of the product, it has very little actual application.
In the fifties of the 20th century, it developed from eugenol preparation of vanitrope synthetic route, only then can realize the industrial production.
Catechol flavor chemists,successfully developed cheaper raw materials of pyrocatechol in the Soviet Union in the 1960s.
First with allyl chloride to catechol mono alkylation, and the yield is 75%.
Followed by rearrangement reaction and yield is 35%~38%. then by using ethyl sodium sulfate for single ethylation, yield is 82%.
Finally with potassium hydroxide isomerization will get vanitrope, yield is 84%, after recrystallization of the crude product melting point 85.5 to 86℃.
Vanitrope applied in candy, beverage, ice cream and other food flavoring formulations, the FEMA number is 2922.
Vanillin also can be used in cosmetics and soap fragrance formula. Vanillin not only can used as a spice, but also can be used as a synergistic agent and antioxidant.
Former Soviet Union perfumers hold different views of vanitrope aroma properties.
They added it to the chocolate and other food flavors.
Vanillin is found that the goods are not Vanillin aroma, so that it cannot in the flavor of food as a substitute for Vanillin.
But when used for a flavoring test of scented soap, found that soap has a strong clove and vanilla aroma like it.
The differences with Vanillin and isoeugenol, vanitrope to alkali, light, oxidation is very stable, soap like storage does not change color.
Therefore vanitrope should be used in fragrance formulations, particularly appropriate for fantasy flavor.

Industrial production methods Vanillin
Industrial production of Vanillin has more than 100 years of history, people have studied the ways and methods of many synthetic preparations, but the application in a large-scale industrial production are mainly the following three methods.

A. lignin route
In the papermaking industry, sulfite pulp waste liquid containing wood lignosulfonates as raw material, the alkaline and high temperature and high pressure was hydrolysis dehydration, and then again oxidation.
Canada and the United States mainly adopted the production method of Vanillin.

B. Guaiacol formaldehyde route
Guaiacol is the most important raw material for synthesis of Vanillin, guaiacol, formaldehyde, the nitroso dimethylaniline as raw material of synthetic route, also known as the nitroso process.

C. Guaiacol glyoxylate route
By using guaiacol and glyoxylic acid as raw material then by condensation, oxidation and decarboxylation made to Vanillin.

Chemical property
White needle crystal, with Fragrant smell.
Soluble in water of 125 times, 20 times of ethylene glycol and 2 times of 95% ethanol, insoluble in chloroform.

Vanillin's Uses:
1. Used as a flavor, fragrance, pharmaceutical intermediates.
2. Vanillin is to obtain the incense powder, bean fragrant spices.
Often used in the fragrance foundation with.
Vanillin is widely used in almost all the flavor that doubles as a combination of such as violet, Cymbidium, sunflower, Oriental flavor.
And piperonal, isoeugenol benzyl ether, coumarin, musk and others are set incense, modifier and mixture, can also be used to cover up bad breath.
In edible, smoke flavor as well as wide application, but the amount is larger.
In vanilla bean type, cream, chocolate, too Princess flavor are need to use spices.
3. Vanillin is China's regulations allow the use of edible spices, as a fixative agent, is the preparation of the main raw material of vanilla flavor.
Vanillin can also be directly used in biscuits, cakes, candy, drinks and other food flavoring.
Dosage according to the normal production needs, generally in the chocolate 970mg/kg; 270mg/kg in chewing gum; 220mg/kg in pastry, biscuit; 200mg/kg in candy; 150mg/kg in condiment~95mg/kg in cold drinks.
4. GB 2760 1996 provisions allow the use of edible spices.
Widely used in the preparation of vanilla, chocolate, butter flavor, the amount is up to 25%~30%, or directly used in biscuits, pastries, dosage is 0.1%~0.4%, cold drink is 0.01%~0.3%, candy is 0.2%~0.8%, especially containing dairy products.
5. An important synthetic fragrance, widely used in daily life activities.
Vanillin is used as food, tobacco and wine with a fine wisely.
In the food industry usage amount is large for the preparation of the vanilla, chocolate, butter flavor, the amount is up to 25-30%, directly on a cookie, cake, dosage is 0.1-0.4%, cold is 0.01-0.3%, candy is 0.2-0.8, especially is containing dairy products.
Vanillin is used for chemical analysis, tests for protein nitrogen heterocyclic indene, phloroglucinol and tannic acid.
In the pharmaceutical industry, it is used for production of antihypertensive drug methyldopa, catechols L-dopa medication, and Catalin and diaveridine.

6. Used as a reagent in organic analysis standard.
7. Tests for protein, nitrogen heterocyclic indene, pyrogallol, tannic acid, iron ions.
From benzoic acid in the determination of chloride, spices, organic trace analysis determination of methoxy standard.

Methods of production
1.N N-,dimethylaniline with hydrochloric acid was acidated to salt, with sodium nitrite nitrification out to nitroso-N, N-nitrobine hydrochloride, which with guaiacol and formaldehyde were condensated at 41-43℃.
Then, it with benzene extracted.
The first distillation with benzene, and then the second distillation, water recrystallization, 50℃ drying to obtain the product.
Sulfite pulp waste liquid containing birch cypress structure units of lignin sulfonate, in alkaline conditions oxidation and hydrolysis can be obtained and the raw material consumption (kg/t) guaiacum phenol (98%) in 1460 sodium nitrite 640, N,N-methyl aniline (98%), 974 of hydrochloric acid (30%), 6000 (99%) of 320.
2.The vanilla bean extract.
By theo-aminoanisole by diazonium hydrolysis into guaiacol, in the presence of nitroso dimethylaniline and catalyst, with formaldehyde condensation, or react with chloroform in Catalyzed by potassium hydroxide and after extraction separation, vacuum distillation and crystallization purification.
Also available wood pulp waste liquid, eugenol, guaiacol, safrole were made.
3. Using lignin as raw material
Vanillin can be preparation from paper plant sulfite pulping waste liquor containing lignin. General waste liquid contains solid matter 10%~12%, of which 40%~50% is lignin sulfonic acid calcium.
The waste liquid is concentrated to 40%~50% solid form, adding NaOH of 25% of lignin amount, and heating to 160 to 175 ℃ (about 1.1~1.2 MPa), air oxidation for 2h, the conversion rate is generally up to 8%~11%.
Oxide with benzene extract Vanillin, and water vapor distillation method for the recovery of benzene in the oxide with sodium bisulfite to generate sub hydrogen sulfate salt and impurity separated, and then the decomposition of sulfuric acid to Vanillin. Finally, it is by vacuum distillation and recrystallization to obtain the product.

Use guaiacol as raw materials
Chloral guaiacol method and trichloro acetaldehyde in the presence of sodium carbonate or potassium carbonate, heating to 27℃ was synthesized through the condensation of 3-methoxy-4-hydroxyphenyl trichloro methyl carbinol, not reaction guaiac wood phenol water vapor distillation removed.
In the presence of caustic soda, nitrobenzene as oxidant, heat to 150 ℃ oxidative cleavage of Vanillin was obtained;
Can also be used Cu-CuO-CoCl2 as catalyst and 100℃ in the air oxidation, after reaction with benzene extraction of Vanillin, by vacuum distillation and recrystallization purification so as to obtain the finished product.

Glyoxylic acid method: in glyoxylic acid solution followed by adding guaiacol, sodium hydroxide and sodium carbonate, and at 30 to 33℃ by condensation to 3-methoxy-4-hydroxy phenyl glycollic acid by solvent extraction of guaiacol reaction after adding sodium hydroxide solution, nitrobenzene sulfonic acid and calcium hydroxide in Q presence heated to 100℃ for oxidation and pyrolysis to Vanillin.
Oxidation products were neutralized with two chlorine ethane extraction of Vanillin, crude product by vacuum distillation and recrystallization was finished.

The nitroso process: 30% hydrochloric acid 166kg and water 200kg are added into the reaction kettle, cooled to l0℃, dropping two methyl aniline 61.5kg in 2h the temperature is less than 25%, then continue stirring 20min.
water solution is cooled to 6 ℃ after infusion of sodium nitrite 75kg with 25% water solution, the temperature control and continue to stir 1h.
filter p-nitroso two methyl aniline hydrochloride at 7~10 ℃, adding a quantitative Ethanol and concentrated hydrochloric acid, diluted in solid, the nitroso two methyl aniline.

Guaiacol and p-nitroso two methyl aniline condensation: The 26kg of urotropine dissolved in 34kg water mixture, then add 126kg guaiacol and 63kg ethanol, stored in headtank standby.

The income of the nitroso dimethylaniline dihydrochloride and ethanol mixture of 550Kg will join the reaction kettle, heating to 28℃ after adding metal salt catalyst, and then heated to 35 to 36 ℃ when dropping guaiac wood phenol mixture (3~3.5h), keeping the temperature in 40 to 43 ℃, drop after adding continue to stirring 1h of reaction.
Then add 100kg diluted 40 ℃ water, stirring and 15 min content in liquid condensation of Vanillin should be above 11%.
Use benzene as solvent.
the rotary liquid-liquid extraction column continuous countercurrent extraction the above condensation liquid.
Benzene extraction fluid contains a large number of hydrochloric acid, water washing, and then alkali neutralization to ph=4;
Climbing film evaporator distillation recovery of benzene and water vapor rush steam 1h to remove residual benzene;
decompression steam to water and finally in 120 to 150 ℃ (666.6Pa) rapid steaming out crude Vanillin, freezing point is 70℃ or so.
The crude product was dissolved in 70 ℃ in toluene, filtering after cooling to 18 to 20℃, suction and washing with a small amount of toluene to Vanillin.
Then the second vacuum distillation, from 130 to 140℃ (266.6~399.9Pa) fractions and dissolved in dilute ethanol 60~70 ℃, slowly cooled to 16 to 18 ℃, the crystallization (1H).
Using the centrifuge filter, and use a little dilute ethanol washing. At the end of 50 to 60 ℃, hot air drying 12 h products. According to guaiacol, the yield can reach more than 65%.

P-hydroxyphenylaldehyde method
Use p-hydroxybenzaldehyde as raw materials, through single bromination, methoxylation reaction to preparate Vanillin.
In a 250ml flask, added 16g (0.131mo1) of p-hydroxybenzaldehyde and 90ml solvent.
After the dissolution of the people 6.8mL (0.131mol) bromine and heated to 40~45℃ and reaction for 6h.
Solvent residue and vacuum pumping, boiling water, hot filtering, filtrate cooling crystallization, filtration and drying of white crystalline 3-bromo-4-hydroxy benzaldehyde, the melting point is 123 to 124 ℃, the yield is 90%.

In 250ml flask, join 12g (0.0597mol) of the product, sodium methanol solution of methylmercury 45ml (0.230mol) 28.24%, and 0.2gCuCl, 35mLDMF.
In 115 ℃ reaction for 1.5h and pull the solvent, the residue with 18% hydrochloric acid to pH=4~5, and then hot benzene extraction for 3 times, points to water, benzene layer reduced pressure distillation to benzene, coffee colored liquid.
Which was dissolved in hot dilute alcohol solution, cooling to separate white crystallization, filtering, and drying to obtain the product of Vanillin 8.3g, melting point is 81 to 82 ℃, 99.5% purity yield is 91.1%.

Vanillin's Description
Vanillin is found in many plants, such as the tuber of Rhizoma Gastrodiae (Tian Ma), the whole herb of Equisetum (Mu Zei), Ulva pertusa (Kong Shi Chun), and sugar beets, vanilla beans, Peru balsam, and so on .
Chemical Properties A great variety of vanilla plants bearing the vanilla pods, or siliques, exist.
Those mentioned above are the most important species.
Of special value are those cultivated in Mexico, Madagascar, Java, Tahiti, the Comoro Islands and Réunion.
The cultivation of vanilla beans is very long and laborious.
The plant is a perennial herbaceous vine that grows up to 25 m in height and needs suitable supports in order to grow.
Fecundation of flowers is performed (November to December) by perforating the membrane that separates the pollen from the pistil.
This is an exacting task requiring skilled hand labor.
Natural fecundation occurs when a similar operation is carried out by birds or insects that perforate the membrane in search of food.
After a few months, clusters of hanging pods (siliques) are formed; these start to yellow at the lower tip from August to September.
At this point, the siliques are harvested and undergo special treatment that develops the aroma.
The siliques are placed in straw baskets and dipped into hot water to rupture the inner cell wall.
After a few months, the aroma starts developing. Then the siliques are exuded by intermittent exposure to sunlight (by alternately covering and uncovering the siliques with wool blankets).
When exudation is complete, the siliques are oiled with cocoa oil to avoid chapping during drying and are finally dried to a suitable residual moisture content.
In the final stage of the preparation, the best quality siliques form a vanilla “brine” that crystallizes on the surface of the bean.
Generally, the processing of vanilla bean takes more than a year. The most important commercial qualities are brined vanilla, bastard vanilla and vanilla pompona.
The bean is the only part used.
Vanilla has a sweet, ethereal odor and characteristic flavor.

Chemical Properties
Vanillin has a characteristic, creamy, vanilla-like odor with a very sweet taste.
White, crystalline needles; sweetish smell. Soluble in 125 parts water, in 20 parts glycerol, and in 2 parts 95% alcohol; soluble in chloroform and ether. Combustible.
White or cream, crystalline needles or powder with characteristic vanilla odor and sweet taste.
Vanillin is found in many essential oils and foods but is often not essential for their odor or aroma.
However, it does determine the odor of essential oils and extracts from Vanilla planifolia and Vanilla tahitensis pods, in which it is formed during ripening by enzymatic cleavage of glycosides.
Vanillin is a colorless, crystalline solid (mp 82–83°C) with a typical vanilla odor.
Because it possesses aldehyde and hydroxy substituents, it undergoes many reactions.
Additional reactions are possible due to the reactivity of the aromatic nucleus.
Vanillyl alcohol and 2-methoxy-4-methylphenol are obtained by catalytic hydrogenation;
vanillic acid derivatives are formed after oxidation and protection of the phenolic hydroxy group.
Since Vanillin is a phenol aldehyde, it is stable to autoxidation and does not undergo the Cannizzaro reaction.
Numerous derivatives can be prepared by etherification or esterification of the hydroxy group and by aldol condensation at the aldehyde group.
Several of these derivatives are intermediates, for example, in the synthesis of pharmaceuticals.

Vanillin's Physical properties
Appearance:
white or light yellow needle crystal or crystal powder, with a strong aroma.
The relative density is about 1.060. Solubility:
Vanillin is not only soluble in ethanol, chloroform, ether, carbon disulfide, glacial acetic acid, and pyridine but also in oil, propylene glycol, and hydrogen peroxide in alkaline solution.
Vanillin can slowly oxidize in the air, can be unstable under illumination, and should be stored in a dark condition.
Melting point: the melting point is 81?°C.

Vanillin's Occurrence
Vanillin occurs widely in nature.
Vanillin has been reported in the essential oil of Java citronella (Cymbopogon nardus Rendl.), in benzoin, Peru balsam, clove bud oil and chiefly vanilla pods (Vanilla planifolia, V. tahitensis, V. pompona); more that 40 vanilla varieties are cultivated.
Vanillin is also present in the plants as glucose and Vanillin.

Reported found in:
• guava,
• feyoa fruit,
• many berries,
• asparagus,
• chive,
• cinnamon,
• ginger,
• Scotch spearmint oil,
• nutmeg,
• crisp and rye bread,
• butter,
• milk,
• lean and fatty fish,
• cured pork,
• beer,
• cognac,
• whiskies,
• sherry,
• grape wines,
• rum,
• cocoa,
• coffee,
• tea,
• roast barley,
• popcorn,
• oatmeal,
• cloudberry,
• passion fruit,
• beans,
• tamarind,
• dill herb and seed,
• sake,
• corn oil,
• malt, wort,
• elderberry,
• loquat,
• Bourbon
• Tahiti vanilla
• chicory root.

History of Vanillins
Vanillin is known as one of the first synthetic spices.
In the perfume industry, it is known as vanillic aldehyde.
As early as 1858, French chemist Gby (NicolasTheodore Gobley) obtained pure Vanillin for the first time by the method of rectification.
Due to less production yield of natural Vanillin, it spurred the search for a chemical synthesis method of Vanillin production.
In 1874, German scientist M.?Haarman and coworkers deduced the chemical structure of Vanillin and discovered a new way to produce Vanillin with abietene as the raw material .
In 1965, Chinese scientists found that Vanillin has antiepileptic effect and accomplished a study on the pharmacology and toxicology of Vanillin from edible to officinal.
They also found that Vanillin has certain antibacterial activity, making it a suitable drug formulation for the treatment of skin disease.
Vanillin can be used as intermediate for synthesis of a variety of drugs, such as berberine and antihypertensive drug L-methyldopa, methoxy-pyrimidine, and heart disease drug papaverine .

Uses of Vanillin
Vanillin is a flavorant made from synthetic or artificial vanilla which can be derived from lignin of whey sulfite liquors and is synthetically processed from guaiacol and eugenol.
the related product, ethyl Vanillin, has three and one-half times the flavoring power of Vanillin.
Vanillin also refers to the primary flavor ingredient in vanilla, which is obtained by extraction from the vanilla bean.
Vanillin is used as a substitute for vanilla extract, with application in ice cream, desserts, baked goods, and beverages at 60–220 ppm.
An intermediate and analytical reagent.
Pharmaceutic aid (flavor).
As a flavoring agent in confectionery, beverages, foods and animal feeds.
Fragance and flavor in cosmetics. Reagent for synthesis. Source of L-dopa.
The primary component of Vanilla bean extract.
Labelled Vanillin. Occurs naturally in a wide variety of foods and plants such as orchids; major commercial source of natural Vanillin is from vanilla bean extract.
Synthetically produced in-bulk fro m lignin-based byproduct of paper processes or from guaicol.

Preparation of Vanillin
Commercial Vanillin is obtained by processing waste sulfite liquors or is synthesized from guaiacol.
Preparation by oxidation of isoeugenol is of historical interest only.

1) Preparation from waste sulfite liquors:
The starting material for Vanillin production is the lignin present in sulfite wastes from the cellulose industry.
The concentrated mother liquors are treated with alkali at elevated temperature and pressure in the presence of oxidants.
The Vanillin formed is separated from the by-products, particularly acetovanillone (4-hydroxy-3- methoxyacetophenone), by extraction, distillation, and crystallization.
A large number of patents describe various procedures for the (mainly) continuous hydrolysis and oxidation processes, as well as for the purification steps required to obtain high-grade Vanillin .
Lignin is degraded either with sodium hydroxide or with calcium hydroxide solution and simultaneously oxidized in air in the presence of catalysts.
When the reaction is completed, the solid wastes are removed.
Vanillin is extracted from the acidified solutionwith a solvent (eg, butanol or benzene) and reextractedwith sodium hydrogen sulfite solution.
Reacidification with sulfuric acid followed by vacuum distillation yields technical-grade Vanillin, which must be recrystallized several times to obtain food-grade Vanillin.
Water, to which some ethanol may be added, is used as the solvent in the last crystallization step.

2) Preparation from guaiacol:
Severalmethods can be used to introduce an aldehyde group into an aromatic ring.
Condensation of guaiacol with glyoxylic acid followed by oxidation of the resulting mandelic acid to the corresponding phenylglyoxylic acid and, finally, decarboxylation continues to be a competitive industrial process for Vanillin synthesis.
a. Vanillin from guaiacol and glyoxylic acid:
Currently, guaiacol is synthesized from catechol, which is mainly prepared by acid-catalyzed hydroxylation of phenol with hydrogen peroxide.
In China, a guaiacol prepared from o-nitrochlorobenzene via o-anisidine is also used.
Glyoxylic acid is obtained as a by-product in the synthesis of glyoxal from acetaldehyde and can also be produced by oxidation of glyoxal with nitric acid.
Condensation of guaiacol with glyoxylic acid proceeds smoothly at room temperature and in weakly alkaline media.
A slight excess of guaiacol is maintained to avoid formation of disubstituted products; excess guaiacol is recovered.
The alkaline solution containing 4-hydroxy- 3-methoxymandelic acid is then oxidized in air in the presence of a catalyst until the calculated amount of oxygen is consumed.
Crude Vanillin is obtained by acidification and simultaneous decarboxylation of the (4-hydroxy-3-methoxyphenyl)glyoxylic acid solution.
This process has the advantage that, under the reaction conditions, the glyoxyl radical enters the aromatic guaiacol ring almost exclusively para to the phenolic hydroxy group.
Tedious separation procedures are thus avoided.
B. Vanillin from guaiacol and formaldehyde:
An older process that is still in use consists of the reaction of guaiacolwith formaldehyde or formaldehyde precursors such as urotropine, N,N-dimethyl-aniline, and sodium nitrite .
Production Methods Vanillin occurs naturally in many essential oils and particularly in the pods of Vanilla planifolia and Vanilla tahitensis.
Industrially, Vanillin is prepared from lignin, which is obtained from the sulfite wastes produced during paper manufacture.
Lignin is treated with alkali at elevated temperature and pressure, in the presence of a catalyst, to form a complex mixture of products from which Vanillin is isolated.
Vanillin is then purified by successive recrystallizations.

Vanillin may also be prepared synthetically by condensation, in weak alkali, of a slight excess of guaiacol with glyoxylic acid at room temperature.
The resultant alkaline solution, containing 4- hydroxy-3-methoxymandelic acid is oxidized in air, in the presence of a catalyst, and Vanillin is obtained by acidification and simultaneous decarboxylation.
Vanillin is then purified by successive recrystallizations.

General Description for Vanillin
Certified pharmaceutical secondary standards for application in quality control provide pharma laboratories and manufacturers with a convenient and cost-effective alternative to pharmacopeia primary standards

Pharmaceutical Applications for Vanillin
Vanillin is widely used as a flavor in pharmaceuticals, foods, beverages, and confectionery products, to which it imparts a characteristic taste and odor of natural vanilla.
Vanillin is also used in perfumes, as an analytical reagent and as an intermediate in the synthesis of a number of pharmaceuticals, particularly methyldopa.
Additionally, it has been investigated as a potential therapeutic agent in sickle cell anemia and is claimed to have some antifungal properties.
In food applications, Vanillin has been investigated as a preservative.
As a pharmaceutical excipient, Vanillin is used in tablets, solutions (0.01–0.02% w/v), syrups, and powders to mask the unpleasant taste and odor characteristics of certain formulations, such as caffeine tablets and polythiazide tablets.
Vanillin is similarly used in film coatings to mask the taste and odor of vitamin tablets.
Vanillin has also been investigated as a photostabilizer in furosemide 1% w/v injection, haloperidol 0.5% w/v injection, and thiothixene 0.2% w/v injection.

Vanillin's Clinical Uses
Vanillin tablet has been used in the treatment of epilepsy and has a better therapeutic effect.
Some patients have a minor dizziness response occasionally in the clinic.

Vanillin's Chemical Synthesis
From the waste (liquor) of the wood-pulp industry;
Vanillin is extracted with benzene after saturation of the sulfite waste liquor with CO2.
Vanillin is also derived naturally through fermentation.

Vanillin's Storage Conditions
Vanillin oxidizes slowly in moist air and is affected by light.
Solutions of Vanillin in ethanol decompose rapidly in light to give a yellow-colored, slightly bitter tasting solution of 6,6'-dihydroxy- 5,5'-dimethoxy-1,1'-biphenyl-3,3'-dicarbaldehyde.
Alkaline solutions also decompose rapidly to give a brown-colored solution.
However, solutions stable for several months may be produced by adding sodium metabisulfite 0.2% w/v as an antioxidant.
The bulk material should be stored in a well-closed container, protected from light, in a cool, dry place.

Vanillin is a member of the class of benzaldehydes carrying methoxy and hydroxy substituents at positions 3 and 4 respectively.
Vanillin has a role as a plant metabolite, an anti-inflammatory agent, a flavouring agent, an antioxidant and an anticonvulsant.
Vanillin is a member of phenols, a monomethoxybenzene and a member of benzaldehydes.

Vanillin is a natural product found in Tetracentron sinense, Posidonia oceanica, and other organisms with data available.

Industry Uses
• Odor agents

Consumer Uses
• Air care products
• Cleaning and furnishing care products
• Laundry and dishwashing products
• Personal care products

Household & Commercial/Institutional Products
• Auto Products
• Inside the Home
• Personal Care
• Pet Care

About Vanillin
Helpful information
Vanillin is registered under the REACH Regulation and is manufactured in and / or imported to the European Economic Area, at ≥ 1 000 tonnes per annum.

Vanillin is used by consumers, by professional workers (widespread uses), in formulation or re-packing, at industrial sites and in manufacturing.

Consumer Uses
Vanillin is used in the following products: washing & cleaning products, air care products, polishes and waxes, biocides (eg disinfectants, pest control products), cosmetics and personal care products and perfumes and fragrances. Other release to the environment of Vanillin is likely to occur from: indoor use as processing aid and outdoor use as processing aid.

Article service life
ECHA has no public registered data on the routes by which Vanillin is most likely to be released to the environment. ECHA has no public registered data indicating whether or into which articles the substance might have been processed.

Widespread uses by professional workers
Vanillin is used in the following products: washing & cleaning products and polishes and waxes.
Vanillin is used in the following areas: formulation of mixtures and/or re-packaging.
Other release to the environment of Vanillin is likely to occur from: indoor use (eg machine wash liquids/detergents, automotive care products, paints and coating or adhesives, fragrances and air fresheners).
Formulation or re-packing
Vanillin is used in the following products: cosmetics and personal care products, air care products, biocides (eg disinfectants, pest control products), perfumes and fragrances, pharmaceuticals, polishes and waxes and washing & cleaning products.
Release to the environment of Vanillin can occur from industrial use: formulation of mixtures.
Uses at industrial sites
Vanillin is used in the following products: washing & cleaning products.
Vanillin is used in the following areas: formulation of mixtures and/or re-packaging.
Release to the environment of Vanillin can occur from industrial use: in processing aids at industrial sites.
Other release to the environment of Vanillin is likely to occur from: indoor use as processing aid.
Manufacture
Release to the environment of Vanillin can occur from industrial use: manufacturing of the substance.

General description
Vanillin is the world′s most popular flavor and fragrance compound.
Vanillin may be a potential agent of pharmacological importance and useful for the treatment of major depressive disorder.
Eumelanin-inspired core derived from vanillin has been found to be useful for the synthesis of eumelanin-inspired small molecules and polymer via Sonogashira cross coupling.
Biotechnology-based vanillin synthesis using ferulic acid, eugenol and glucose as substrates and bacteria, fungi and yeasts as microbial production hosts has been reported.
Vanillin, a polar aromatic flavor compound, is present in the extracts of natural and artificial vanilla flavors.

Application
Vanillin is suitable for use in a study to evaluate its sensitizing effect on a tumor necrosis factor-related apoptosis-inducing ligand (TRAIL)-resistant human cervical cancer cell line, HeLa.

IUPAC NAMES:
1-butoxypropan-2-ol
3-hydoxy-4-methoxybenzaldehyde
3-hydroxy-4-methoxybenzaldehyde
3-Methoxy-4-hydroxy benzaldehyde
4-hydroksy-3-metoksybenzaldehyd,
4-Hydroxy-3-methoxy-benzaldehyde
4-hydroxy-3-methoxy-benzaldehyde
4-Hydroxy-3-methoxybenzaldehyd
4-Hydroxy-3-methoxybenzaldehyde
4-hydroxy-3-methoxybenzaldehyde
4-Hydroxy-3-methoxybenzaldehyde
4-hydroxy-3-méthoxybenzaldéhyde
Benzaldehyde, 4-hydroxy-3-methoxy-
Ester
vanilin
vanilla
VANILLIN
Vanillin
Vanillin
Vanillin
Vanillin (4-hydroxy-3-methoxybenzaldehyde)
wanilina

SYNONYMS:
2-Methoxy-4-formylphenol
3-Methoxy-4-hydroxybenzaldehyde (Vanillin)
4-Formyl-2-methoxyphenol
Protocatechualdehyde, methyl-
Vanillin Powder
Vanillin cas:121-33-5
Vanillin NAT
Vanillin 97+%
Vanillin test solution(ChP)
Vanillin sulfuric acid test solution(ChP)
3-метокси-4-гидроксибензальдегид, 3-метокси-4-оксибензальдегид, Vanillin, 3-Methoxy-4-hydroxybenzaldehyde, 4-Formyl-2-methoxyphenol, 4-Hydroxy-3-methoxybenzaldehyde, 4-Hydroxy-m-anisaldehyde, Lioxin, Methoxyprotocatechuic aldehyde, Methylprotocatechuic al
Eugenol EP Impurity H
protocatechualdehyde3-methylether
p-Vanillin
Vanillaldehyde
Vanillin (3-methoxy-4-hydroxy- benzaldehyde)
Zimco
METHYL PROTOCATECHUIC ALDEHYDE
LABOTEST-BB LT00429580
METHOXYPROTOCATECHUIC ALDEHYDE
AURORA 4274
FEMA 3107
3-METHOXY-4-HYDROXYBENZALDEHYDE
4-HYDROXY-3-METHOXYBENZALDEHYDE
AKOS BBS-00003189
OTAVA-BB BB0109160039
Methyl Vanillin (3-Methoxy-4-hydroxybenzaldehyde)
VANILLIN,NF
VANILLIN(USP)(P)
PARA-VANILLIN
VANILLIN CHEM. REIN 100 P. DAB 8
VANILLIN AKA 4-HYDROXY-3-METHOXY BENZALDEHYDE
VANILLIN WITH GC
4-Hydroxy-3-methoxybenzaldehyde（ Vanilline）
Vanillin (contains H2SO4) Ethanol Solution [for TLC Stain]
VANILLIN USP FROM EUGENOL
VANILLIN, NATURAL EX-CLOVE
VANILLIN, NATURAL EX-EUGENOL
VANILLIN, NATURAL EX-TUMERIC
VANILLIN, NATURAL EX-VANILLA
VANILIN extrapure AR,
Vanillin, typically 99%
4-Hydroxy-3-methoxybenzaldehyde, Vanillinum
Rhovanil
VANILLIN, 99%, PURE
Vanillin, AR,99%
Vanilla pods extract
Vanillin ReagentPlus(R), 99%
Vanillin Vetec(TM) reagent grade, 98%
Mettler-Toledo Calibration substance ME 51143093, Vanillin
Eugenol Impurity 8（Eugenol EP Impurity H）
Vanillin (p-Vanillin)
VaniL
Vanillin flavor
VANILLINE
VANILLIC ALDEHYDE
VANILLIN
VANILLA
vanillin
4-Hydroxy-3-methoxybenzaldehyde
121-33-5
Vanillaldehyde
p-Vanillin
Vanillic aldehyde
Vanilla
Vanilline
Benzaldehyde, 4-hydroxy-3-methoxy-
Lioxin
3-Methoxy-4-hydroxybenzaldehyde
Zimco
4-Hydroxy-m-anisaldehyde
2-Methoxy-4-formylphenol
4-Hydroxy-3-methoxy- benzaldehyde
p-Hydroxy-m-methoxybenzaldehyde
Vanilin
4-Formyl-2-methoxyphenol
Methylprotocatechuic aldehyde
Vanillin (natural)
4-Hydroxy-5-methoxybenzadehyde
m-Anisaldehyde, 4-hydroxy-
Protocatechualdehyde, methyl-
Vanillin (NF)
Protocatechualdehyde 3-methyl ether
vaniline
Vanillinum
Vanillin [NF]
m-Methoxy-p-hydroxybenzaldehyde
4-HYDROXY,3-METHOXY-BENZALDEHYDE
4-hydroxy-3-methoxybenzaldehyde (vanillin)
Vanillin [USAN]
Oleoresin vanilla
Vanilla oleoresin
MFCD08702848
CAS-121-33-5
FEMA No. 3107
CCRIS 2687
HSDB 1027
EINECS 204-465-2
BRN 0472792
AI3-00093
Nat.Vanillin
3-methoxy-4-hydroxy-benzaldehyde
Vanillinisobutyrate
oleo-Resins vanilla
V55
Vanillin sodium salt
ACMC-1BURM
oleo-Resins vanilla-bean
Vanillin inclusion complex
Vanillin-[methoxy-13C]
methyl-Protocatechualdehyde
Methylprotcatechuic aldehyde
4-08-00-01763 (Beilstein Handbook Reference)
Vanillin, puriss., 99.5%
Vanillin Melting Point Standard
4-hydroxy 3-methoxybenzaldehydeVanilla oleoresin (vanilla SPP)
3-methoxy-4-hydroxy be nzaldehyde
4-hydroxy-3-methoxy benzaldehyde
3-methoxy-4-hydroxy benzoaldehyde
Vanillin, ReagentPlus(R), 99%
4-hydroxy-3-(methoxy)benzaldehyde
Vanillin, >=97%, FCC, FG
4-hydoxy-3-(methyloxy)benzaldehyde
4-hydoxy-3-(methyloxy)benz aldehyde
Vanillin, tested according to Ph.Eur.
Vanillin, natural, >=97%, FCC, FG
Vanillin 1000 microg/mL in Acetonitrile
Vanillin, JIS special grade, >=98.0%
Vanillin, Vetec(TM) reagent grade, 98%
3-Methoxy-4-hydroxybenzaldehyde (vanillin)
vanillin (3-methoxy-4-hydroxy- benzaldehyde)
4-hydroxy-3-methoxy-Benzaldehyde-5-chlorovanillin
4-hydroxy-3-methoxybenzaldehyde (ACD/Name 4.0)
AC-907/21098004
Q-100102
Vanillin, TraceCERT(R), certified reference material
F2190-0587
Vanillin, European Pharmacopoeia (EP) Reference Standar
1-(AMINOMETHYL)-CYCLOPROPANECARBOXYLICACIDETHYLESTER
Mettler-Toledo Calibration substance ME 51143093, Vanillin
Vanillin, United States Pharmacopeia (USP) Reference Standard
NSC 15351;NSC-15351; NSC15351 pound>>4-Hydroxy-3-methoxybenzaldehyde
Vanillin, Pharmaceutical Secondary Standard; Certified Reference Material
Vanillin Melting Point Standard, United States Pharmacopeia (USP) Reference Standard
Mettler-Toledo Calibration substance ME 51143093, Vanillin, traceable to primary standards (LGC)
Vanillin melting point standard, Pharmaceutical Secondary Standard; Certified Reference Material