ガロイルアルコール 化學(xué)特性,用途語,生産方法
種類
沒食子酸は主に研究開発用試薬製品や、産業(yè)用化成品として販売されています。研究開発用試薬は、有機(jī)合成原料や生物化學(xué)実験などの分野で用いられる物質(zhì)です。
容量の種類には10 g , 250g , 1kgなどがあります。常溫保存可能な試薬として扱われます。また、沒食子酸は一水和物が安定に存在することから、一水和物も試薬製品として販売されている物質(zhì)です。
産業(yè)用化成品としては、一般工業(yè)用途、電子材料や食品添加物などの用途で販売されています。15kgや25kgなど工場(chǎng)での汎用性が高い大容量での提供が一般的です。
定義
本品は、次の化學(xué)式で表される有機(jī)酸である。
性質(zhì)
図2. 沒食子酸の脫炭酸反応
沒食子酸は、水に溶けると、アルカリ性水溶液となる物質(zhì)です。沒食子酸のアルカリ性水溶液は、還元力が強(qiáng)く、空気中の酸素によって容易に酸化されます。また、沒食子酸の接觸水素化還元では、芳香環(huán)が還元されてシクロヘキサン環(huán)誘導(dǎo)體を與えます。?
沒食子酸を加熱すると、脫炭酸によってカルボキシル基が除去されます。この反応の生成物がピロガロールです。ピロガロールは、焦性沒食子酸という別名を持ち、有機(jī)合成試薬、寫真の現(xiàn)像液、毛織物の媒染剤、染料の成分などとして活用されている物質(zhì)です。
沒食子酸は吸濕性があることから、一水和物が安定に存在します。沒食子酸一水和物は、1分子の結(jié)晶水を含んでいますが、融點(diǎn)に達(dá)すると分解し、ピロガロールとが生成されます。
解説
沒食子酸は，芳香族ヒドロキシカルボン酸の一つ。「もっしょくしさん」ともいわれる。別名はピロガロール-5-カルボン酸、3,4,5-トリヒドロキシ安息香酸。分子式C7H6O5、分子量188.1。無水物は融點(diǎn)235～240 ℃ で，融解と同時(shí)にピロガロールと二酸化炭素に分解する．熱水，エタノール，アセトンに易溶．アルカリ性水溶液は還元力が強(qiáng)く，空気中からすみやかに酸素を吸収する．植物の葉、莖、根、および沒食子、五倍子(ごばいし)の蟲こぶなどに遊離の狀態(tài)またはタンニンの構(gòu)成成分として分布している。 沒食子?茶?五倍子や広く植物の根?莖?葉?果実などに含まれ、タンニンを加水分解して得られる無色針狀の結(jié)晶。渋味?収斂(しゅうれん)性があり、還元性が強(qiáng)い。醫(yī)薬のほかインク?染料?寫真現(xiàn)像剤などに用いられる。ぼっしょくしさん。沒食子はブナ科植物の若芽のモッショクシバチによる蟲こぶから、五倍子はウルシ科植物ヌルデの若芽や葉のアブラムシによる蟲こぶから得られ、乾物として漢方薬などに使われている。タンニンを加水分解して得られる無色の柱狀結(jié)晶で、1分子の結(jié)晶水を含むが120℃付近で結(jié)晶水を失う。融點(diǎn)（258～265℃）において分解し、ピロガロールと二酸化炭素になる（図）。水によく溶け、鉄(Ⅲ)塩水溶液を加えると青黒色の沈殿を生ずる。強(qiáng)力な還元?jiǎng)垽扦ⅳ搿％骏螗衰螭卧?、青インキの製造に使われるほか、寫真現(xiàn)像剤、染料の原料、止血?jiǎng)垽趣筏皮斡猛兢猡猡?。［廣田 穰 2016年2月17日］[參照項(xiàng)目] | タンニン | ヒドロキシカルボン酸 | ピロガロール 
"沒食子酸の反応〔図〕
小學(xué)館 日本大百科全書(ニッポニカ) ）
用途
油脂の酸化防止剤、インキ原料
化粧品の成分用途
収れん剤
合成
沒食子酸の生合成
沒食子酸は、五倍子 (ヌルデの蟲こぶ) 、沒食子 (中近東のブナ?カシワの蟲こぶ) 、マンサク科の植物ハマメリス、茶の葉、オークの樹皮など、多くの植物に含まれている物質(zhì)です。加水分解性タンニンの基本骨格を成しています。
自然界における生合成では、まずシキミ酸デヒドロゲナーゼの働きによって、3-デヒドロシキミ酸から3,5-ジデヒドロシキミ酸が合成されます。沒食子酸は、この中間體物質(zhì)の芳香環(huán)化によって合成されている物質(zhì)です。
説明
Gallic acid is a trihydroxybenzoic acid, a type of phenolic acid, a type of organic acid, also known as 3,4,5- trihydroxy benzoic acid, found in gallnuts, sumac, witch hazel, tea leaves, oak bark, and other plants. The chemical formula is C
6H
2(OH)
3COOH. Gallic acid is found both free and as part of hydrolyzable tannins.
Salts and esters of gallic acid are termed 'gallates'. Despite its name, it does not contain gallium.
Gallic acid is commonly used in the pharmaceutical industry. It is used as a standard for determining the phenol content of various analytes by the Folin - Ciocalteau assay; results are reported in gallic acid equivalents. Gallic acid can also be used as a starting material in the synthesis of the psychedelic alkaloid mescaline.
Gallic acid seems to have anti-fungal and antiviral properties. Gallic acid acts as an antioxidant and helps to protect human cells against oxidative damage. Gallic acid was found to show cytotoxicity against cancer cells, without harming healthy cells. Gallic acid is used as a remote astringent in cases of internal haemorrhage. Gallic acid is also used to treat albuminuria and diabetes. Some ointments to treat psoriasis and external haemorrhoids contain gallic acid.
化學(xué)的特性
Gallic acid, also known as trihydroxybenzoic acid, is a colorless crystalline needles or prisms that is obtained from nutgall tannins. It is soluble in hot water, ether, ethanol, acetone and glycerin, insoluble in cold water, insoluble in benzene and chloroform and has a melting point of 235 to 240 °C (decomposition). When heated to 100-120°C, crystal water will be lost, and when heated above 200°C, carbon dioxide will be lost to generate pyrogallic acid (ie, pyrogallol). It is used in photography, tanning, ink manufacture and pharmaceuticals.
天然物の起源
Gallic acid is found in a number of land plants. It is also found in the aquatic plant Myriophyllum spicatum and shows an allelopathic effect on the growth of the blue-green alga Microcystis aeruginosa.
In food Areca nut
Bearberry (Arctostaphylos sp)
Bergenia sp
Blackberry
Hot chocolate
Juglans regia (Common walnut)
Mango in peels and leaves
Phyllanthus emblica (Indian gooseberry) in fruits
Raspberry
Syzygium aromaticum (clove)
Vinegar
wine
Witch hazel (Hamamelis virginiana)
White tea.
來歴
Gallic acid is an important component of iron gall ink, the standard European writing and drawing ink from the 12 th to 19th century with a history extending to the Roman empire and the Dead Sea Scrolls. Pliny the Elder (23-79 AD) describes his experiments with it and writes that it was used to produce dyes. Galls (also known as oak apples) from oak trees were crushed and mixed with water, producing tannic acid (a macromolecular complex containing gallic acid). It could then be mixed with green vitriol (ferrous sulfate) — obtained by allowing sulfate - saturated water from a spring or mine drainage to evaporate — and gum arabic from acacia trees; this combination of ingredients produced the ink.
Gallic acid was one of the substances used by Angelo Mai (1782–1854), among other early investigators of palimpsests, to clear the top layer of text off and reveal hidden manuscripts underneath. Mai was the first to employ it, but did so "with a heavy hand", often rendering manuscripts too damaged for subsequent study by other researchers.
Early photographers, including Joseph Bancroft Reade (1801– 1870) and William Fox Talbot (1800 – 1877), used gallic acid for developing latent images in calotypes. It has also been used as a coating agent in zincography.
使用
gallic acid is a potential bleaching agent and anti-oxidant, it is also astringent and potentially anti-microbial and anti-fungal. Scientists are finding that gallic acid may serve as a skin-lightening agent by inhibiting the action of the tyrosinase and peroxidase enzymes. Some studies indicate that it is more effective than hydroquinone when combined with the proper ingredients. It is also incorporated into anti-aging formulations for its ability to prevent mucopolysaccaride deterioration. It is a constituent of witch hazel and oak bark, among many other plants; however, it is generally obtained from nutgalls for commercial purposes.
調(diào)製方法
Gallic acid, a component of many tanning agents is an endogenous product in plants. The acid occurs free or bound to tannin [1401-55-4] (e.g., in divi-divi, oak bark, gallnuts, pomegranate roots, sumac, and tea). The acid is produced from tannin-rich aqueous gallnut extracts by acidic or alkaline hydrolysis. It is also obtained by using the enzyme tannase [9025-71- 2] or molds (Penicillium glaucum, Aspergillus niger) to cleave tannin by fermentation. Both the metabolism of gallic acid and its impact on plant growth enzymes have been studied.
定義
ChEBI: Gallic acid is a trihydroxybenzoic acid in which the hydroxy groups are at positions 3, 4, and 5. It has a role as an astringent, a cyclooxygenase 2 inhibitor, a plant metabolite, an antioxidant, an antineoplastic agent, a human xenobiotic metabolite, an EC 1.13.11.33 (arachidonate 15-lipoxygenase) inhibitor, an apoptosis inducer and a geroprotector. It is a conjugate acid of a gallate.
一般的な説明
Gallic acid is a phenol that has been found in C. sinensis and has diverse biological activities. It scavenges DPPH and hydroxyl radicals in cell-free assays (IC50s = 9.4 and 191 μM, respectively). Gallic acid (1-100 μM) reverses abscisic acid-induced inhibition of hypocotyl growth in A. caudatus seedlings. In vivo, gallic acid (21.8 g/kg) inhibits morpholine- and sodium nitrite-induced adenocarcinoma formation in mice. It also inhibits passive cutaneous anaphylaxis in mice when administered at a dose of 50 mg/kg.
空気と水の反応
Sparingly water soluble
反応プロフィール
Phenols, such as Gallic acid, do not behave as organic alcohols, as one might guess from the presence of a hydroxyl (-OH) group in their structure. Instead, they react as weak organic acids. Phenols and cresols are much weaker as acids than common carboxylic acids (phenol has Ka = 1.3 x 10^[-10]). These materials are incompatible with strong reducing substances such as hydrides, nitrides, alkali metals, and sulfides. Flammable gas (H2) is often generated, and the heat of the reaction may ignite the gas. Heat is also generated by the acid-base reaction between phenols and bases. Such heating may initiate polymerization of the organic compound. Phenols are sulfonated very readily (for example, by concentrated sulfuric acid at room temperature). The reactions generate heat. Phenols are also nitrated very rapidly, even by dilute nitric acid.
健康ハザード
Inhalation of dust may irritate nose and throat. Contact with eyes or skin causes irritation.
火災(zāi)危険
Flash point data for Gallic acid are not available. Gallic acid is probably combustible.
使用用途
沒食子酸は、還元力が非常に高い物質(zhì)です。そのため、食品や化粧品、飼料等の酸化防止剤として用いられており、アルカリ性水溶液は、還元?jiǎng)?、寫真の現(xiàn)像剤に使われています。
その他の用途は、タンニンの原料や青インキの製造や、染料の原料などです。また、培養(yǎng)工學(xué)用試薬や植物生長(zhǎng)制御試薬、生長(zhǎng)阻害剤などに利用されることもあります。
沒食子酸は、多くの誘導(dǎo)體が合成されており、さまざまな分野で活用されている物質(zhì)です。例えば、沒食子酸プロピル、沒食子酸イソアミルなどのエステルは、油脂?バターの酸化防止剤にも使用されます。
カテキンの一種、エピガロカテキンガラートも沒食子酸のエステルです。これらの誘導(dǎo)體の一部は、工業(yè)薬品や電子材料製造薬品などにも応用されており、醫(yī)薬品分野においては、収斂剤や喀血のとして用いられています。
副作用
It is a weak carbonic anhydrase inhibitor.
代謝
Biosynthesis Chemical structure of 3,5- didehydro shikimate Gallic acid is formed from 3-dehydro shikimate by the action of the enzyme shikimate dehydro genase to produce 3,5-didehydro shikimate. This latter compound tautomerizes to form the redox equivalent gallic acid, where the equilibrium lies essentially entirely toward gallic acid because of the coincidently occurring aromatization.
Degradation Gallate dioxygenase is an enzyme found in Pseudomonas putida that catalyzes the reaction :
gallate + O
2 → (1E)-4-oxobut-1-ene-1,2,4-tri carboxylate.
Gallate decarboxylase is another enzyme in the degradation of gallic acid.
Conjugation Gallate 1-beta-glucosyltransferase is an enzyme that uses UDPglucose and gallate, whereas its two products are UDP and 1-galloylbeta- D-glucose.
純化方法
Crystallise gallic from water. The tri-O-acetyl derivative has m 172o (from MeOH), and the anilide has m 207o(from EtOH). [Beilstein 10 H 470, 10 IV 1993.]
參考文獻(xiàn)
Plant polyphenols (vegetable tannins): gallic acid metabolism. DOI:
10.1039/NP9941100041Biotechnology of Food and Feed Additives DOI:
10.1007/978-3-662-43761-2Purification of Laboratory Chemicals DOI:
10.5860/choice.50-6768Gallic acid: a versatile antioxidant with promising therapeutic and industrial applications DOI:
10.1039/C5RA01911GAntioxidant properties and total phenolics content of green and black tea under different brewing conditions DOI:
10.1007/S002170050406Comparative study of eight well‐known polyphenolic antioxidants DOI:
10.1211/0022357021693Antagonistic Action of Phenolic Compounds on Abscisic Acid-Induced Inhibition of Hypocotyl Growth DOI:
10.1093/JXB/31.6.1651
ガロイルアルコール 上流と下流の製品情報(bào)
原材料
準(zhǔn)備製品
沒食子酸メチル
ink
2,3,4-トリヒドロキシベンズアルデヒド
沒食子酸エチル
1,2,3-トリメトキシベンゼン
3,4,5-トリエトキシ安息香酸
2,3,4-トリメトキシベンズアルデヒド
3,4,5-トリメトキシ安息香酸
プロシアニジンB1
3,5-ジヒドロキシ-4-メトキシ安息香酸メチル
5-(ブロモメチル)-1,2,3-トリメトキシベンゼン
沒食子酸n-オクチル
3,4-ジメトキシ-5-ヒドロキシ安息香酸メチル
ガレイン
C.I. Mordant Violet 35 (8CI)
1,2,3-トリヒドロキシ-9,10-アントラセンジオン
Mordant Violet 55