مرجع مواد شیمیایی ایران
اطلاعات عمومی وانیلین
  • نام شیمیایی

    • وانیلین

    • Vanillin

  • مترادف ها
    • Methyl vanillin; 4-Hydroxy-3-methoxybenzaldehyde; Vanillic aldehyde

  • CAS
    121-33-5
  • فرمول مولکولی
    C8H8O3
  • جرم مولکولی
    152/15
  • EINECS
    204-465-2
  • ICB Number
    ICB 5336
  • شکل و حالت فیزیکی
    پودر کریستالی سفید
  • نقطه ذوب
    81-83 °C
  • نقطه جوش
    285 °C
  • دانسیته
    1/056 g/cm3
  • فشار بخار
    >0/01 mm Hg ( 25 °C)
  • دانسیته بخار
    5/3 (vs air)
  • دمای نگهداری
    در یخچال
  • حلالیت در آب
    10 g/L (25 ºC)
  • اسیدیته (pka)
    7/781
  • شماره CAS
    121-33-5
  • شماره ثبت تجاری (RBN)
    472792
  • شماره مرک (Merck)
    14,9932
  • NIST Chemistry Reference
  • EPA Substance Registry System
  • مراجع MSDS
  • ارائه دهنده
    زبان
  • انگلیسی
  • Chemical Properties
    • white crystals with vanilla odour

  • General Description
    • White or very slightly yellow needles.

  • Air & Water Reactions
    • Slowly oxidizes on exposure to air. . Slightly water soluble.

  • Reactivity Profile

    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).

  • Synthesis
    • 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%. 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%.

  • Usage
    • 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.

  • Fire Hazard

    Flash point data for Vanillin are not available, however Vanillin is probably combustible.

  • Preparation products

    Sodium hydroxide-->Hydrochloric acid-->Sulfuric acid -->Sodium carbonate-->Chloroform-->Phenol-->N,N-Dimethylaniline-->Hexamethylenetetramine-->Calcium hydroxide -->Chloral-->N-Methylaniline-->o-Anisidine-->SULFUROUS ACID-->Glyoxylic acid-->Guaiacol-->Eugenol-->Benzenesulfonic acid-->LIGNOSULFONIC ACID, CALCIUM SALT-->Safrole-->LIGNIN, ALKALI-->DIMETHYLANILINE-->VANILLA EXTRACT-->Ligninsulfonate

  • Raw materials

    3-Methyl-1-butanol-->(3R,4S)-1-Benzoyl-3-(1-methoxy-1-methylethoxy)-4-phenyl-2-azetidinone-->3-O-Methyldopamine hydrochloride-->3-Iodo-4,5-dimethoxybenzaldehyde-->6-HYDROXY-7-METHOXY-4-PHENYLCOUMARIN-->Curcumin-->Veratraldehyde-->3-Methoxysalicylaldehyde-->3,4,5-Trimethoxybenzaldehyde-->4-BENZYLOXY-3-METHOXYBENZALDEHYDE-->Capsaicin-->Isovanillin-->S-(-)-Carbidopa-->Methyldopa-->1,2,4-Trimethoxybenzene -->Diaveridine-->4-[(2-CHLORO-6-FLUOROBENZYL)OXY]-3-METHOXYBENZALDEHYDE-->Dopamine-->1-(4-HYDROXY-3-METHOXYPHENYL)-2-NITROETHENE-->TERT-BUTYL 4-FORMYL-2-METHOXYPHENYL CARB ONATE, 99-->2,3-Dimethoxybenzaldehyde-->LEMONGRASS OIL, WEST INDIAN TYPE-->2-BROMO-4-FORMYL-6-METHOXYPHENYL ACETATE-->VANILLA EXTRACT-->2,4,5-Trimethoxynitrobenzene -->2,3-DIBROMO-4-HYDROXY-5-METHOXYBENZALDEHYDE-->trans-Ferulic acid-->4-Hydroxy-3-methoxybenzylamine hydrochloride-->5-Bromovanillin-->3,4-Dihydroxybenzoic acid-->4-(2-AMINO-ETHYL)-2-METHOXY-PHENOL -->CITRONELLYL PROPIONATE-->5-Hydroxyvanillin-->B-(3,4-DIMETHOXYPHENYL)-A-CYANOPROPIONALDEHYDE DIMETHYLACETAL-->CITRONELLYL FORMATE

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