4-Hydroxy-3-methoxybenzaldehyde, Vanillic aldehyde
BP, FCC, USP
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Vanillin is the artificial synthesis of the first kind of flavor, synthesized by the German M. Harman, and G-Dr. Twyman in 1874. Usually It 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. It 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 (German patent 3224795). 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 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. It 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. Sales prices range from about USD 1,500 per kg for natural vanilla extract to USD 10-20 per kg for synthetic vanillin.
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.
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. It 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. it is used in medicine. L-DOPA (L-dopa),methyldopa. Also used for nickel, chrome metal plating brightener.
The use of vanillin flavor quality standard reference.
The above information is edited by the chemicalbook Han Ya.
Vanillin has strong and unique vanilla beans, naturally found in vanilla and clove oil, oil, oakmoss, balsam of Peru, and the rest of tolu balsam. Sulfite solution or red pulp softwood lignin sulfonate, under the alkaline conditions, reacted by high-pressure oxidation hydrolysis precipitation to get white to light yellow crystalline powder or acicular crystal. From petroleum ether precipitation can also generate tetragonal crystal. It has Aroma, Bitter sweet. In the air, it is gradually oxidized. In case of light, it generated decomposition. In case of alkali, it generated discoloration. The relative molecular mass is 152.15. The relative density is 1.056. melting point is different form tetragonal crystalline to another, tetragonal crystal is 81 to 83℃. Acicular crystal ranged from 77 to 79℃, the boiling point is 285℃ (in CO2 gas),170℃ (2 x 103Pa),162℃ (1.33 x 103Pa),146 C (0.533 x 103Pa). It can generate sublimation without decomposition. The flash point is162 ℃. Slightly soluble in cold water, soluble in hot water, soluble in ethanol, ethyl ether, propylene Ketone, benzene, chloroform, carbon disulfide, glacial acetic acid, pyridine and volatile oil. Water and FeCl3 generate blue purple solution. For rats, by oral LD 50 1580mg/kg, mice is by percutaneous LD 50 1500mg/kg.
Industrial production method is that eugenol in the presence of potassium hydroxide, produce to ISO eugenol, then reacted with acetic anhydride formation of isoeugenol acetate, followed by oxidation and hydrolysis reaction to produce. It is an important raw material for mixing chocolate, ice cream, chewing gum the pastry and tobacco flavor. It can also be used as cosmetics fragrance coordination agent and a flavor enhancer. It is also the pharmaceutical raw materials of industry.
In recent years, it appeared a new fashion in the commodity of vanillin. Use oil of clove or basil oil provided out of eugenol as raw material, vanillin obtained by isomerization and oxidation, as it can be regarded as a natural equivalent quality, therefore it is called natural vanillin and into the spice market, its price is about 5 times that of the synthetic product.
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. It Accord with FCCIV standard.
General Side Effects
Using of vanillin in large quantity(over 30g a time) could lead to headache, nausea, vomiting, difficulty breathing, and even kidney damage.Don't get too frightened, vanillin isn't one of the most toxic food additives you'll find and in fact usually won't trigger much more than a headache or allergic reaction in sensitive folks. Usually, switching from artificial vanilla extract to pure vanilla extract is all that is needed to avoid issues. Many connoisseurs of the vanilla bean claim vanillin to be an inferior product to pure vanilla extract anyway. If you're making an attempt to eat quality food, you probably won't encounter much vanillin anyway.
Special Groups Precaution
Special groups refer to newborns, children, pregnant and any other applicable vulnerable groups.
There is no evidence that Vanillin could have any negative effects on these vulnerable groups. It should be safe to use Vanillin in food for newborns and pregnant. However, we still recommend consumers to consult professionals before using large quantity of Vanillin for long period in food for newborns or pregnant.
GRAS Affirmation: Yes
Generally recognized as safe(GRAS) is a FDA designation that a specific substance or ingredient is generally considered safe by experts, and so is exempted from the usual Federal Food, Drug, and Cosmetic Act (FFDCA) food additive tolerance requirements. Vanillin is considered safe by FDA according to existing data and granted GRAS status.
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 reacted 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 purity of aroma of the product, so it is very little actual application.
In the fifties of the 20th century, it developed from eugenol preparation of vanitrope synthetic route (U. S. patent 2663741),only then can realize the industrial production.
Catechol flavor chemists,successfully developed by more cheap raw materials of pyrocatechol in the Soviet Union in 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. It also can be used in cosmetics and soap fragrance formula. It 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 flavor. It 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 flavoring test of scented soap, found that soap has 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 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 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. The former Soviet Union and China mainly adopts the method.
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 (German patent 3224795).
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.
The method one: UV absorption Spectrophotometry.
Preparation of Standard solution: taking accurately medicines ginseng than vanillin standard about 100mg, into a 250ml volumetric flask, with constant volume with methanol, mixed. The solution 2.0ml, into a 100 ml volumetric flask, with methanol fixed volume mixing.
The liquid sample preparation: weighed accurately sample of about 100mg, the preparation method and the standard solution preparation are the same.
Operation: Take from the solution into a 1 cm quartz cells. Determine absorbance at the maximum absorption wavelength of about 308 nm. Press type calculation sample vanillin (C8H8O3) content (x) (mg):
C-vanillin in standard solution concentration, g/ml;
Au-The absorbance of sample liquid;
As-The absorbance of standard solution.
Methods two: Accord by gas chromatography (GT-10-4) with non-polar column determination method.
AD is 0~10mg/kg (FAO/WHO, 1994).
LD50 is 1.58g/kg (rat, oral).
MNL is 1g/kg (rat, oral).
GRAS (FDA, 182.602000).
According to the European Union Expert Committee on February 24, reports that high dose can cause headaches, nausea, vomiting, difficulty in breathing, and even damage the liver, kidney, therefore, they are discussing to set lower allowed dose.
FEMA (mg/kg): soft drinks 63; cold 95; candy 200; baking food 220; pudding class 120, chewing gum, 270; chocolate 970; decorating layer 150; margarine 0.20; syrup 330~20000.
According to the provisions of FAO/WHO: The allowable amount is 70mg/kg for fast food, of canned baby foods and cereals (1992).
China is a big country of world vanillin export, the domestic demand was 2350 tons in 2002, accounted for 30% production, 70% of the remaining was for export. In 1988 only exported 2.73 tons, 1700 tons in 1993, 4653 tons in 2002. From 1993 to 2002, China's export volume of vanillin grew at an average annual rate of rate of 12%. In North America, Europe, Southeast Asia and other markets enjoy a good reputation.
In 2012, global vanillin demand is about 17500 tons, which developed countries demand is in equilibrium state, and developing demand of vanillin increased significantly, making the total demand of vanillin still in growth period. The actual total demand of China currently has reached 3000 tons. At present, the per capita amount is still slightly lower than the global per capita use.
Major domestic suppliers of Jiaxing City, China Chemical Co., Ltd. is now the world's largest vanillin professional manufacturer. In 2014, company with an annual output of methyl vanillin is 10000 tons, 2000 tons of ethyl vanillin, which more than 80% of products are for export.
At abroad, there mainly are France Rhodia Inc., Norwegian Bao very company, Ube three vanillin production companies. Among them, Rhodia, France is the world's most famous vanillin production enterprises, annual production capacity is 8000 tons, the distribution device in France and the United States. in addition to the Norwegian company Bao Selig using lignin production of vanillin, domestic and international companies used guaiac wood phenol-aldehyde acid production of vanillin.
1. Used as a flavor, fragrance, pharmaceutical intermediates.
2. It is to obtain the incense powder, bean fragrant spices. Often used in the fragrance foundation with. It 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. It 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. It 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. It 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.
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 acid166kg 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 15min 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%.
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%.
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.
Vanillin can react violently with Br2, HClO4, potassium-tert-butoxide, (tert-chloro-benzene + NaOH),(formic acid + Tl(NO3)3). . Vanillin is an aldehyde. Aldehydes are readily oxidized to give carboxylic acids. Flammable and/or toxic gases are generated by the combination of aldehydes with azo, diazo compounds, dithiocarbamates, nitrides, and strong reducing agents. Aldehydes can react with air to give first peroxo acids, and ultimately carboxylic acids. These autoxidation reactions are activated by light, catalyzed by salts of transition metals, and are autocatalytic (catalyzed by the products of the reaction).
Flash point data for Vanillin are not available, however Vanillin is probably combustible.
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