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丙二酸二乙酯
丙二酸乙酯 · 丙二醇二乙酯 · 丙二酸二乙酯 · 胡萝卜酸乙酯 · 二已基丙二酸 · 丙戊酸杂质3 · 丙二酸乙二酯 · 丙二酸二乙脂
标识与物理属性
| CAS No. | 105-53-3 |
|---|---|
| 分子式 | C7H12O4 |
| 平均分子量 | 160.17 g/mol |
| 单同位素质量 | 160.07355886 g/mol |
| SMILES | CCOC(=O)CC(=O)OCC |
| InChIKey | IYXGSMUGOJNHAZ-UHFFFAOYSA-N |
| PubChem CID | 7761 |
| ChEMBL | CHEMBL177114 |
| ChEBI | CHEBI:167785 |
| EC No. | 203-305-9 |
| DTXSID | DTXSID7021863 |
| 中文名 | 丙二酸二乙酯 |
化学与物理性质
| XLogP | 1 |
|---|---|
| 极性表面积 | 52.6 |
| 氢键供体 | 0 |
| 氢键受体 | 4 |
| 可旋转键 | 6 |
| 重原子 | 11 |
| 形式电荷 | 0 |
| 复杂度 | 125 |
| 物质类别 | Other Classes -> Esters, OtherFlammable agents - 2nd degree |
| 化妆品 | Cosmetic ingredients (Diethyl Malonate) -> CIR (Cosmetic Ingredient Review) |
| SpringerMaterials Properties | Boiling point |
| 香料 | Fragrance Ingredient (Diethyl malonate) -> IFRA transparency List |
| LogP（油水分配系数） | log Kow = 0.96 |
| 气味 | Sweet ester odorSlightly aromatic, pleasant odorAroma of ripe fruit, peach, cut grass |
| 味道 | Sweet and fruity taste with apple and pineapple nuances |
| 食品添加剂 | FLAVORING AGENT OR ADJUVANT -> FDA Substance added to food |
| 密度 | 1.0551 g/cu cm at 20 °CDensity (at 20 °C): 1.06 g/cm³Relative density of the vapour/air-mixture at 20 °C (air = 1): 1.001.053-1.0561.055 @ 20°C1.055 g/mL at 25 °C (lit.) |
| 食用香料 | EU Flavoring substances |
| Viscosity | 1.86 centistokes at 25 °C |
| Color/Form | Colorless liquidClear, colorless liquid |
| 熔点 | -51--50 °C (lit.) |
| 沸点 | 199 °C (lit.) |
| 蒸气密度 | 5.52 (vs air) |
| 蒸气压 | 1 mm Hg ( 40 °C) |
| 折射率 | n20/D 1.413(lit.) |
| FEMA | 2375 | DIETHYL MALONATE |
| 闪点 | 212 °F |
| 储存条件 | Store below +30°C. |
| 溶解性 | 20.8g/l (External MSDS)Miscible with ethyl alcohol, ether, chloroform and benzene. Slightly miscible with water. |
| pKa（酸度系数） | 13.5(at 25℃) |
| 形态 | Liquid |
| 颜色 | colourless liquid |
| 香型 | fruity |
| 爆炸极限 | 0.8-12.8%(V) |
| 生物来源 | synthetic |
| 比热容 | Cp(liquid): 1.78 J/(g·K), at 25℃ |
| Merck | 14,3823 |
| JECFA Number | 614 |
| BRN | 774687 |
| 亨利常数 | 3.9×100 mol/(m3Pa) at 25℃, Brockbank (2013) |
| 介电常数 | 7.9(21℃) |
| 稳定性 | Stable. Combustible. Incompatible with strong oxidizing agents, |
| 主要应用 | flavors and fragrances |
| 化妆品成分功效 | PERFUMING |
| 化妆品成分评估 | Diethyl malonate (105-53-3) |
| InChI | 1S/C7H12O4/c1-3-10-6(8)5-7(9)11-4-2/h3-5H2,1-2H3 |
| InChIKey | IYXGSMUGOJNHAZ-UHFFFAOYSA-N |
| SMILES | CCOC(=O)CC(=O)OCC |
| LogP（油水分配系数） | 0.96 at 20℃ |
| CAS 数据库 | 105-53-3(CAS DataBase Reference) |
| NIST化学物质信息 | Propanedioic acid, diethyl ester(105-53-3) |
| EPA化学物质信息 | Diethyl malonate (105-53-3) |
化学性质
无色液体，具有甜的醚气味。 与醇、醚混溶，溶于氯仿、苯等有机溶剂。稍溶于水。20℃时水中溶解度为2.08g/100ml。
安全与法规
| GHS 分类 | This chemical does not meet GHS hazard criteria for 2.7% (69 of 2532) of reports.WarningH319 (96.9%): Causes serious eye irritation [Warning Serious eye damage/eye irritation]P264+P265, P280, P305+P351+P338, and P337+P317 (click each P-code to see the statement)Aggregated GHS information provided per 2532 reports by companies from 18 notifications to the ECHA C&L Inventory. |
|---|---|
| 法规信息 | Chemical: Propanedioic acid, diethyl esterRegulation (EC) No 1831/2003 (amended)Propanedioic acid, 1,3-diethyl ester is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Propanedioic acid, 1,3-diethyl ester are required to report information about their production and use of this chemical to the EPA under the Toxic Substances Control Act (TSCA). (40 eCFR Part 711)Status: Active Update: 06-04-2023 https://echa.europa.eu/registration-dossier/-/registered-dossier/5774Diethyl malonate: Does not have an individual approval but may be used under an appropriate group standardThe New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.) |
| 火灾危害 | Combustible. Gives off irritating or toxic fumes (or gases) in a fire. Heating will cause rise in pressure with risk of bursting. |
| 火灾可能性 | Combustible liquid when exposed to heat or flame. |
| 危害概述 | A slight to moderate eye irritant based on animal studies[eChemPortal: SIDSUNEP] A mild skin irritant based on animal studies[MSDSonline] |
| Chemical Dangers | It reacts with strong oxidants. This generates fire and explosion hazard. |
| NFPA Hazard Classification | 1 - Materials that, under emergency conditions, can cause significant irritation.2 - Materials that must be moderately heated or exposed to relatively high ambient temperatures before ignition can occur. Materials would not under normal conditions form hazardous atmospheres with air, but under high ambient temperatures or under moderate heating could release vapor in sufficient quantities to produce hazardous atmospheres with air.0 - Materials that in themselves are normally stable, even under fire conditions. |
| Hazard Classes and Categories | Eye Irrit. 2A (96.9%)Flammable liquids - Category 4Flammable agents - 2nd degree |
| Explosive Limits and Potential | Explosive limits , vol% in air: 0.8 - 12.8 |
| Skin, Eye, and Respiratory Irritations | Eye irritation in rabbits: moderately irritating.A skin irritant. |
| Critical Temperature and Pressure | Critical temperature: 653 K (estimated)Critical pressure: 2780 kPa (estimated) |
| Hazardous Reactivities and Incompatibilities | Conditions to avoid: Heat, flames and sparks. Incompatible materials: Acids, Bases, Oxidizing agents, Reducing agentscan react with oxidizing materials. |
| 消防 | Use carbon dioxide, dry powder, water spray, foam. In case of fire: keep drums, etc., cool by spraying with water. |
| 急救措施 | Fresh air, rest. Seek medical attention if you feel unwell.Rinse and then wash skin with water and soap.First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.Give one or two glasses of water to drink. Seek medical attention if you feel unwell. |
| 安全储存 | Separated from strong oxidants. Ventilation along the floor. Store in an area without drain or sewer access. |
| 灭火程序 | Water may be used to blanket fire.To fight fire, use water to blanket fire, foam, CO2, dry chemical.Extinguishing media: Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide. Advice for firefighters: Wear self-contained breathing apparatus for firefighting if necessary. Further information: Use water spray to cool unopened containers. |
| 储存条件 | Keep container tightly closed in a dry and well-ventilated place. |
| 清理方法 | ACCIDENTAL RELEASE MEASURESPersonal precautions, protective equipment and emergency procedures: Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Remove all sources of ignition. Beware of vapors accumulating to form explosive concentrations. Vapors can accumulate in low areas. Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided. Methods and materials for containment and cleaning up: Contain spillage, and then collect with an electrically protected vacuum cleaner or by wet-brushing and place in container for disposal according to local regulations. Keep in suitable, closed containers for disposal. |
| 处置方法 | SRP: Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air qualitypotential migration in air, soil or watereffects on animal, aquatic and plant lifeand conformance with environmental and public health regulations. If it is possible or reasonable use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination.Product: This combustible material may be burned in a chemical incinerator equipped with an afterburner and scrubber. Offer surplus and non-recyclable solutions to a licensed disposal company. Contaminated packaging: Dispose of as unused product. |
| 泄漏处置 | Personal protection: filter respirator for organic gases and vapours adapted to the airborne concentration of the substance. Do NOT let this chemical enter the environment. Collect leaking liquid in sealable containers. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations. |
| Preventive Measures | Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands.Avoid inhalation of vapor or mist. Keep away from sources of ignition - No smoking. Take measures to prevent the build up of electrostatic charge.ACCIDENTAL RELEASE MEASURESPersonal precautions, protective equipment and emergency procedures: Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Remove all sources of ignition. Beware of vapors accumulating to form explosive concentrations. Vapors can accumulate in low areas. Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided.Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday.SRP: The scientific literature for the use of contact lenses by industrial workers is inconsistent. The benefits or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place. |
| Eye Prevention | Wear safety goggles. |
| Fire Prevention | NO open flames. |
| Inhalation Risk | Evaporation at 20 °C is negligiblea nuisance-causing concentration of airborne particles can, however, be reached quickly when dispersed. |
| 相互作用 | Because it inhibits dehydrochlorinase activity, diethyl malonate (10-40 ppm) increased the toxicity of DDT (2 ppm) to DDT-resistant mosquitoes Culex fatinans. |
| 生态毒性数值 | EC50Species: Pimephales promelas (Fathead Minnow) age 33 days, length 14 mm, weight 0.036 gConditions: freshwater, flow through, 25.4 °C (23.5-27.7 °C), pH 7.42 (7.35-7.45), hardness 44.0 mg/L CaCO3, alkalinity 45.0 mg/L CaCO3, dissolved oxygen 87.6 mg/L (73.7-102 mg/L)Concentration: 20900 ug/L for 24 hrEffect: behavior, loss of equilibrium /99% purity/Concentration: 15600 ug/L for 48 hrLC50Concentration: 23500 ug/L for 24 hr /99% purity/Concentration: 16600 ug/L for 48 hr /99% purity/For more Ecotoxicity Values (Complete) data for Diethyl malonate (7 total), please visit the HSDB record page. |
| 环境归趋 | TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 10(SRC), determined from a structure estimation method(2), indicates that diethyl malonate is expected to have very high mobility in soil(SRC). Volatilization of diethyl malonate from moist soil surfaces may occur(SRC) given an estimated Henry's Law constant of 2.0X10-6 atm-cu m/mole(SRC), derived from its vapor pressure, 0.19 mm Hg(3), and water solubility, 2.0X10+4 mg/L(4). In chemical stimulant studies simulating chemical warfare agents, diethyl malonate deposited to dry soil and foliar surfaces was rapidly lost through volatilization processes with observed half-lives on soil of about 2 hours (fast) to 5-16 hours (residual material)(4)foliar half-lives ranged from 1 to 242 hours(5). Two screening studies found diethyl malonate to be readily biodegradable(6,7). An 86% of theoretical BOD in two weeks using activated sludge in the Japanese MITI test(6) suggests that biodegradation is an important environmental fate process in soil(SRC).AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 10(SRC), determined from a structure estimation method(2), indicates that diethyl malonate is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(3) based upon an estimated Henry's Law constant of 2.0X10-6 atm-cu m/mole(SRC), derived from its vapor pressure, 0.19 mm Hg(4), and water solubility, 2.0X10+4 mg/L(5). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 23 and 173 days, respectively(SRC). According to a classification scheme(6), an estimated BCF of 3(SRC), from its log Kow of 0.96(7) and a regression-derived equation(2), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Two screening studies found diethyl malonate to be readily biodegradable(8,9). An 86% of theoretical BOD in two weeks using activated sludge in the Japanese MITI test(8) suggests that biodegradation is an important environmental fate process in water(SRC). Diethyl malonate hydrolyzes readily in neutral and alkaline water, but slowly in acidic water(10). Respective hydrolysis half-lives at pH 4, pH7 and pH 9 are <10% after 5 days (50 °C), 137.5 hr (25 °C) and <2.4 hr (50 °C)(10).ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), diethyl malonate, which has a vapor pressure of 0.19 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase diethyl malonate is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC)the half-life for this reaction in air is estimated to be 3.1 days(SRC), calculated from its rate constant of 3.4X10-12 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Diethyl malonate contains chromophores that absorb at wavelengths >290 nm(4) and, therefore, may be susceptible to direct photolysis by sunlight(SRC). |
| 食品调查数值 | Diethyl malonate is reported found in pineapple, bilberry, Cape gooseberry, cognac, malt whiskey, apple brandy, grape brandy port cider, sherry, and red wine, white and strawberry wines. It is used as a flavor additive in alcoholic beverages, baked goods, frozen dairy, gelatins, puddings, hard candy, non-alcoholic beverages and soft candy(1). |
| 毒性概述 | Safe in the present practices of use and concentration. Ingredient, concentration, and use information are available in documents discoverable at https://cir-reports.cir-safety.orgIDENTIFICATION AND USE: Diethyl malonate is used in chemical synthesis. It is also used in food, beverages, and in fragrances. HUMAN STUDIES: A maximization test was reported in 23 volunteers. 4% of the test substance in petrolatum produced no sensitization reactions. Tested at 4% in petrolatum it produced no irritation after a 48-hr closed-patch test on human subjects. ANIMAL STUDIES: Diethyl malonate causes moderate irritation to rabbit's eyes and is non-irritating to rabbit's skin. Application of 0.005 mL of undiluted diethyl malonate to the rabbit cornea caused severe burning. Diethyl malonate fed to rats for 90 days at more than 100 times the equivalent of the human daily dietary intake (averaging 35.93 mg/kg bw per day for males and 41.14 mg/kg bw per day for females) had no adverse effects. The maximum time for inhalation of the concentrated vapor of diethyl malonate by rats without deaths was found to be 8 hr. Mutagenicity test in Salmonella typhimurium TA98, TA 100, TA 1535, TA 1537, TA 1538 was negative with and without activation at concentrations of 8, 40, 200, 1000, 5000 ug/plate 5000 ug/plate (maximal concentration). |
| Average Daily Intake | Diethyl malonate average daily intake = 0.006101 mg/kg/day(1). |
| Signs and Symptoms | Cough.Redness.No acute symptoms expected. |
| Ongoing Test Status | EPA has released the Interactive Chemical Safety for Sustainability (iCSS) Dashboard. The iCSS Dashboard provides an interactive tool to explore rapid, automated (or in vitro high-throughput) chemical screening data generated by the Toxicity Forecaster (ToxCast) project and the federal Toxicity Testing in the 21st century (Tox21) collaboration. /The title compound was tested by ToxCast and/or Tox21 assays/[USEPAICSS Dashboard ApplicationAvailable from, as of August 9, 2018: http://actor.epa.gov/dashboard/] |
| ICSC Environmental Data | The substance is harmful to aquatic organisms. |
| Soil Adsorption/Mobility | Using a structure estimation method based on molecular connectivity indices(1), the Koc of diethyl malonate can be estimated to be 10(SRC). According to a classification scheme(2), this estimated Koc value suggests that diethyl malonate is expected to have very high mobility in soil(SRC). |
| Natural Pollution Sources | Diethyl malonate is reportedly found in pineapple, bilberry, Cape gooseberrys, grapes and strawberries(1). Diethyl malonate is present in guava fruit, melon, concord grape, pineapple, and blackberry(2). The related diester (dimethyl malonate) occurs in pineapple, bananas and blackberries(3). |
| Human Toxicity Excerpts | /HUMAN EXPOSURE STUDIES/ Tested at 4% in petrolatum it produced no irritation after a 48-hr closed-patch test on human subjects./HUMAN EXPOSURE STUDIES/ A maximization test was reported in 23 volunteers. 4% of the test substance in petrolatum produced no sensitization reactions. |
| 水危害等级（WGK） | 1 |
| TSCA 清单状态 | TSCA listed |
| 毒性 | LD50 orally in Rabbit: 15720 mg/kg LD50 dermal Rabbit > 16000 mg/kg |
| RTECS 号 | OO0700000 |
| hazard_note | Irritant |
| 储存类别 | 10 - Combustible liquids |
| 安全说明（S） | 24/25-26 |
| 海关编码 | 29171910 |
| 自燃温度 | 435 °C DIN 51794 |
| 危险品标志 | Xi |
| 危险类别 | Eye Irrit. 2 |
| 危险类别码（R） | 36/37/38-36 |
| 毒害物质数据 | 105-53-3(Hazardous Substances Data) |
用途与应用
概述
丙二酸及其衍生物广泛用于制药、香料、食品添加剂、聚酯等工业，是重要的精细化工原料和中间体。尤其是在医药中间体方面，丙二酸二乙酯广泛用于合成巴比安酸、氨基酸、维生素B1、B2和B6，安眠药物和苯基保泰松等多种药物。
用途
丙二酸二乙酯是制备2-氨基-4，6-二甲氧基嘧啶的重要中间体，可用于制备磺酰脲类除草剂，如苄嘧磺隆、吡嘧磺隆、烟嘧磺隆等，也是医药中用于磺胺药和巴比妥的中间体。它还可用于气相色谱固定液(最高使用温度40℃，溶剂为苯、氯仿、乙醇)来检定氨和钾。此外丙二酸二乙酯也是GB 2760一96规定为允许使用的食用香料，主要用于配制梨、苹果、葡萄、樱桃等水果型香精。
制备与合成方法
生产方法
以氯乙酸为原料，用水溶解后，在<30℃加碳酸钠水溶液至pH=7，氰化钠用水溶解后加入到该氯乙酸钠溶液，于92～95℃氰化反应1h，加入碱液，于100～105℃加热反应1h，进行水解，然后加热除去水分，再加入乙醇和甲苯，滴加少许硫酸，于68～70℃反应3h，进行酯化，然后分层，取酯层进行减压蒸馏即为成品。ClCH2COOH+Na2CO3→ClCH2COONaClCH2COONa+NaCH→NCCH2COONa+NaClNCCH2COONa+NaOH[H2O]→NaOOC-CH2-COONa+NH3
生产方法
丙二酸二乙酯的生产方法主要以氰化酯化法和催化羰基化法，目前工业普遍采用的仍是传统的氰化酯化法。由氯乙酸经中和、氰化、水解、酯化而得。氯乙酸在30℃用碳酸钠中和生成氯乙酸钠，在92-95℃用氰化钠氰化，再用碱水解生成丙二酸钠。丙二酸钠经干燥后在硫酸存在下与乙醇于70-72℃进行酯化。酯化产物经洗涤、蒸馏得成品丙二酸二乙酯。原料消耗定额：氯乙酸（95%）650kg/t、氰化钠（95%）340kg/t、乙醇（95%）910kg/t。国外开发的新工艺主要以催化羰基化法为主，即以氯乙酸酯、一氧化碳、乙醇为原料，在催化剂存在下一步反应合成丙二酸二乙酯。相比之下，催化羰基化法工此外，还有氰乙酸钠法，由氰乙酸与乙醇直接酯化而得。
生产方法
由丙二酸和乙醇在苯介质中共沸、蒸馏、酯化而得。由丙二酸钠与乙醇在硫酸催化下酯化后蒸馏而得。