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外観
無色～ほとんど無色, 澄明の液体
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溶解性
エタノールに極めて溶けやすく、水にほとんど溶けない。
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解説
マロン酸エチル，化学式 CH2(CO2C2H5)2 。マロン酸ジエチル，マロン酸エステルともいわれる。融点－50℃，沸点 199℃の無色の液体。果実様の芳香をもつ。クロロ酢酸ナトリウムとシアン化ナトリウムから得られるシアン酢酸ナトリウムに，エチルアルコールと硫酸を作用させて合成される。メチレン基の水素が反応しやすいので，合成化学上重要な物質であり，染料，医薬，香料など，多くの有機化合物の合成中間原料となる。
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用途
農薬?医薬?香料原料
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用途
医薬品原料、香料原料
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用途
有機合成原料。香料材料。
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説明
Diethyl malonate is a diester derivative of malonic acid, a dicarboxylic acid with two carboxyl groups (-COO-) separated by one methylene group (-CH2-). Diethyl malonate is formed by the replacement of the hydroxyl groups (-OH) of malonic acid with ethoxy groups (-OCH2CH3). The hydrogen atoms on the methylene carbon between the two carboxyl groups make this compound acidic. Because of its unique structure, diethyl malonate is reactive and functions as a reagent for organic synthesis and to make products such as barbiturates, pigments, and agrochemicals. Volatile esters are known to have fruity scents and are often used as fragrances and flavorings. Diethyl malonate is a volatile diester that occurs naturally in fruits such as grapes, strawberries, guava, melon, pineapple, and blackberries.
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化学的特性
Diethyl malonate has a faint, pleasant, aromatic odor.
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天然物の起源
Reported found in pineapple, bilberry, Cape gooseberry, cognac, malt whiskey, apple brandy, grape brandy,
port, cider, sherry and red, white, strawberry and bilberry wines.
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使用
Diethyl Malonate occurs naturally in grapes and strawberries. It is used in the preparation of barbiturates, artificial flavourings, vitamin B1, and vitamin B6 as well as in perfumes.
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製造方法
Reacting chloroacetic acid to cyanoacetic acid using sodium cyanide and subsequent saponification; malonic acid is
finally esterified by azeotropic distillation with ethanol in benzene
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一般的な説明
Diethyl malonate is diethyl ester of malonic acid. Acylation of diethyl malonate using magnesium chloride and triethylamine is reported. K2CO3-catalyzed 1,4-addition reaction of diethyl malonate with various substituted 1,2-allenic ketones yields polyfunctionalized β,γ-unsaturated enones.
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安全性プロファイル
Mildly toxic by
ingestion. A skin irritant. Combustible liquid
when exposed to heat or flame; can react
with oxidizing materials. To fight fire, use
water to blanket fire, foam, CO2, dry
chemical. When heated to decomposition it
emits acrid smoke and irritating fumes. See
also ESTERS.
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代謝
When the ester was fed to chicks at a level of 5% in the diet, 32% of the energy from diethyl malonate was available (Yoshida et al. 1970). Hydrolysis of diethyl malonate would produce ethanol and malonic acid, which is a relatively strong acid and acts as an inhibitor of enzymes, including succinic dehydrogenase (Fassett, 1963). Malonic acid injected into rats or rabbits is excreted largely unchanged, but also causes increased excretion of citric and a-ketoglutaric acids (Krebs, Salvin & Johnson, 1938). Some malonate may be metabolized through the tricarboxylic acid cycle, with decarboxylation to acetate followed by transformation to succinate, which has been detected in rat urine (Lee & Lifson, 1951). Diethyl malonate was hydrolysed by adipose-tissue lipase (Lynn & Perryman, 1960) and to the monoester by α-chymotrypsin (Cohen & Crossely, 1964). It was oxidized in 110 min to the extent of 34% by the homogenized mycelium of urethane-grown Streptomyces nitrifica (Schatz, Trelawny, Schatz & Mohan, 1957).
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純化方法
If too impure (IR, NMR) the ester (250g) is heated on a steam bath for 36hours with absolute EtOH (125mL) and conc H2SO4 (75mL), then fractionally distilled under reduced pressure. Otherwise fractionally distil it under reduced pressure and collect the steady boiling middle fraction. [Beilstein 2 IV 1881.]
