バニリン 化学特性,用途語,生産方法
外観
白色〜わずかにうすい黄色, 結晶〜結晶性粉末
定義
本品は、次の化学式で表される芳香族アルデヒドである。
溶解性
エタノール及びエーテルに溶けやすく、水にやや溶けにくい。
解説
4-hydroxy-3-methoxybenzaldehyde．C8H8O3(152.15)．バニラ豆(ラン科)から抽出されたのでこの名称がある．そのほか，安息香，ペルーバルサム，ちょうじ油などのなかにも存在する．工業的には，亜硫酸パルプ廃液中のリグニンスルホン酸を酸化する方法が用いられている．
"ほかの合成法としては，オイゲノールやサフロールから得られるプロトカテクアルデヒドをメチル化する方法がある．バニリンはバニラ特有の甘いかおりをもつ白色の結晶．融点81～82 ℃，沸点285 ℃，170 ℃(2.0 kPa)．水への溶解度1 g L－1(15 ℃)．エタノールに易溶，水に難溶．香料として広い用途をもち，とくにアイスクリーム，チョコレート，キャンデー，あるいはエッセンス，タバコなど，さまざまな食品やし好品にフレーバーとして添加される．LD50 2000 mg/kg(ラット，経口)．[CAS 121-33-5]
森北出版「化学辞典（第2版）
用途
香料
用途
有機合成原料, 香料, 脱臭剤。
化粧品の成分用途
酸化防止剤、香料、香味剤
効能
着香料
説明
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 .
化学的特性
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.
物理的性質
Appearance: white or light yellow needle crystal or crystal powder, with a strong
aroma. The relative density is about 1.060. Solubility: It 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. It 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.
天然物の起源
Vanillin occurs widely in nature; it 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 and Tahiti vanilla and chicory root.
来歴
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 co-workers 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 .
使用
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.
定義
ChEBI: A member of the class of benzaldehydes carrying methoxy and hydroxy substituents at positions 3 and 4 respectively.
適応症
It can be used to treat various types of epilepsy and attention deficit hyperactivity
disorder and vertigo.
調製方法
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.
一般的な説明
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
空気と水の反応
Slowly oxidizes on exposure to air. . Slightly water soluble.
反応プロフィール
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).
火災危険
Flash point data for Vanillin are not available, however Vanillin is probably combustible.
応用例（製薬）
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. It 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. It 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.
臨床応用
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.
安全性プロファイル
Moderately toxic by
ingestion, intraperitoneal, subcutaneous, and
intravenous routes. Experimental
reproductive effects. Human mutation data
reported. Can react violently with Br2,
HClO4, potassium-tert-butoxide, tert-
chlorobenzene + NaOH, formic acid +
thallium nitrate. When heated to
decomposition it emits acrid smoke and
irritating fumes. See also ALDEHYDES.
安全性
There have been few reports of adverse reactions to vanillin,
although it has been speculated that cross-sensitization with other
structurally similar molecules, such as benzoic acid, may occur.
Adverse reactions that have been reported include contact
dermatitis and bronchospasm caused by hypersensitivity.
The WHO has allocated an estimated acceptable daily intake for
vanillin of up to 10 mg/kg body-weight.
LD50 (guinea pig, IP): 1.19 g/kg
LD50 (guinea pig, oral): 1.4 g/kg
LD50 (mouse, IP): 0.48 g/kg
LD50 (rat, IP): 1.16 g/kg
LD50 (rat, oral): 1.58 g/kg
LD50 (rat, SC): 1.5 g/kg
代謝
Early observers noted conversion of vanillin to vanillic acid which was excreted mainly as the free acid, a conjugated ethereal sulphate or glucurovanillic acid (Preusse, 1880). In man, vanillin is broken down by the liver to vanillic acid which is excreted in the urine. Human liver homogenates readily convert vanillin to vanillic acid in vitro (Dirscherl & Brisse, 1966). Endogenous vanillic acid production and excretion in man from body catecholamines amounts to <0.5 mg/day, compared with the normal contribution from dietary sources of about 9 mg/day (Dirscherl & Wirtzfeldt, 1964).
貯蔵
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.
純化方法
Crystallise vanillin from water or aqueous EtOH, or by distillation in vacuo.[Beilstein 8 IV 1763.]
不和合性
Incompatible with acetone, forming a brightly colored compound. A compound practically insoluble in ethanol is formed
with glycerin.
規制状況(Regulatory Status)
GRAS listed. Included in the FDA Inactive Ingredients Database
(oral solutions, suspensions, syrups, and tablets). Included in nonparenteral medicines licensed in the UK. Included in the
Canadian List of Acceptable Non-medicinal Ingredients.
バニリン 上流と下流の製品情報
原材料
準備製品
B-(3,4-DIMETHOXYPHENYL)-A-CYANOPROPIONALDEHYDE DIMETHYLACETAL
2,4,5-Trimethoxynitrobenzene
4-フェニル-6-ヒドロキシ-7-メトキシ-2H-1-ベンゾピラン-2-オン
イソバニリン
ぎ酸3,7-ジメチル-6-オクテニル
5-ブロモバニリン
ジアベリジン
4-[(2-クロロ-6-フルオロベンジル)オキシ]-3-メトキシベンズアルデヒド
TERT-BUTYL 4-FORMYL-2-METHOXYPHENYL CARB ONATE, 99
3,4-ジヒドロキシ安息香酸
trans-フェルラ酸
3-メトキシ-4-(ベンジルオキシ)ベンズアルデヒド
3,4‐ジメトキシ‐5‐ヨードベンズアルデヒド
酪酸
酢酸2-ブロモ-4-ホルミル-6-メトキシフェニル
3,4,5-トリメトキシベンズアルデヒド
2-(3-メトキシ-4-ヒドロキシフェニル)エチルアミン
クルクミン
1,2,4-トリメトキシベンゼン
メチルドーパ
3,7-ジメチル-6-オクテン-1-オールプロパノアート
4,5-ジヒドロキシ-3-メトキシベンズアルデヒド
(S)-2-ヒドラジノ-2-メチル-3-(3,4-ジヒドロキシフェニル)プロパン酸
カプサイシン
2-メトキシ-4-(2-ニトロエテニル)フェノール
2,3-ジメトキシベンズアルデヒド
4-ヒドロキシ-3-メトキシベンジルアミン·塩酸塩
バニラエッセンス
3,4-ジメトキシベンズアルデヒド
o-バニリン
2,3-ジブロモ-4-ヒドロキシ-5-メトキシベンズアルデヒド
3,4-ジヒドロキシフェニルエチルアミン
3-メチル-1-ブタノール
レモングラス葉油
3-O-メチルドーパミン塩酸塩