2-氧代-3-甲基丁酸 | 759-05-7

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 中文名称: 2-氧代-3-甲基丁酸
• 中文别名: 3-甲基-2-氧代丁酸；3-甲基-2-氧丁酸
• 英文名称: 3-methyl-2-ketobutanoic acid
• 英文别名: 3-methyl-2-oxo-butanoic acid；α-ketoisovaleric acid；2-ketoisovaleric acid；α-ketoisovalerate；alpha-ketoisovaleric acid；3-Methyl-2-oxobutanoic acid
• CAS: 759-05-7
• 化学式: C₅H₈O₃
• mdl: MFCD00040427
• 分子量: 116.117
• InChiKey: QHKABHOOEWYVLI-UHFFFAOYSA-N

物化性质

• 熔点：
  31.5℃
• 沸点：
  170.5℃
• 密度：
  0.9968
• 溶解度：
  可溶于苯（微量）、可溶于氯仿、甲醇（微量）
• LogP：
  -0.36
• 物理描述：
  Solid
• 折光率：
  1.436-1.446

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

ADMET

毒理性

• 致癌物分类

对人类无致癌性（未列入国际癌症研究机构IARC清单）。

No indication of carcinogenicity to humans (not listed by IARC).

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

长期高水平的α-酮异戊酸与枫糖尿症有关。

Chronically high levels of alpha-ketoisovaleric acid are associated with Maple Syrup Urine Disease.

来源:Toxin and Toxin Target Database (T3DB)

安全信息

• 海关编码：
  2918300090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  | 温度范围：2-8°C |

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 3-Methyl-2-oxo-butanoic acid
Synonyms:

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Section 2. Hazards identification
Harmful by inhalation, in contact with skin, and if swallowed.

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Section 3. Composition/information on ingredients.
Ingredient name: 3-Methyl-2-oxo-butanoic acid
CAS number: 759-05-7

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Section 4. First aid measures
Skin contact: Immediately wash skin with copious amounts of water for at least 15 minutes while removing
contaminated clothing and shoes. If irritation persists, seek medical attention.
Eye contact: Immediately wash skin with copious amounts of water for at least 15 minutes. Assure adequate
flushing of the eyes by separating the eyelids with fingers. If irritation persists, seek medical
attention.
Inhalation: Remove to fresh air. In severe cases or if symptoms persist, seek medical attention.
Ingestion: Wash out mouth with copious amounts of water for at least 15 minutes. Seek medical attention.

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Section 5. Fire fighting measures
In the event of a fire involving this material, alone or in combination with other materials, use dry
powder or carbon dioxide extinguishers. Protective clothing and self-contained breathing apparatus
should be worn.

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Section 6. Accidental release measures
Personal precautions: Wear suitable personal protective equipment which performs satisfactorily and meets local/state/national
standards.
Respiratory precaution: Wear approved mask/respirator
Hand precaution: Wear suitable gloves/gauntlets
Skin protection: Wear suitable protective clothing
Eye protection: Wear suitable eye protection
Methods for cleaning up: Mix with sand or similar inert absorbent material, sweep up and keep in a tightly closed container
for disposal. See section 12.
Environmental precautions: Do not allow material to enter drains or water courses.

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Section 7. Handling and storage
Handling: This product should be handled only by, or under the close supervision of, those properly qualified
in the handling and use of potentially hazardous chemicals, who should take into account the fire,
health and chemical hazard data given on this sheet.
Store in closed vessels.
Storage:

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Section 8. Exposure Controls / Personal protection
Engineering Controls: Use only in a chemical fume hood.
Personal protective equipment: Wear laboratory clothing, chemical-resistant gloves and safety goggles.
General hydiene measures: Wash thoroughly after handling. Wash contaminated clothing before reuse.

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Section 9. Physical and chemical properties
Appearance: Not specified
Boiling point: No data
No data
Melting point:
Flash point: No data
Density: No data
Molecular formula: C5H8O3
Molecular weight: 116.1

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Section 10. Stability and reactivity
Conditions to avoid: Heat, flames and sparks.
Materials to avoid: Oxidizing agents.
Possible hazardous combustion products: Carbon monoxide.

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Section 11. Toxicological information
No data.

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Section 12. Ecological information
No data.

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Section 13. Disposal consideration
Arrange disposal as special waste, by licensed disposal company, in consultation with local waste
disposal authority, in accordance with national and regional regulations.

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Section 14. Transportation information
Non-harzardous for air and ground transportation.

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Section 15. Regulatory information
No chemicals in this material are subject to the reporting requirements of SARA Title III, Section
302, or have known CAS numbers that exceed the threshold reporting levels established by SARA
Title III, Section 313.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

毒性

GRAS（FEMA）。

使用限量

• 无醇饮料：0.5～10 mg/kg
• 含醇饮料、糖果、糖霜、调味汁、果酱、果冻、汤品：1.0～10.0 mg/kg
• 干酪：0.8～10 mg/kg
• 胶姆糖、硬糖：5～10 mg/kg
• 调味品：1.0～5.0 mg/kg
• 油脂、乳制品：0.5～5.0 mg/kg
• 冷饮：1.2～10.0 mg/kg
• 水果冰品：0.5～3.0 mg/kg
• 凝胶制品、布丁：0.7～5.0 mg/kg
• 代乳品：2.0～10.0 mg/kg
• 速溶咖啡和茶、加工水果：0.1～1.0 mg/kg
• 复水蔬菜：0.6～10 mg/kg
• 加工蔬菜：0.01～1.0 mg/kg
• 代糖品：0.03～5.0 mg/kg
• 调味香料：50～100 mg/kg

生物活性

3-甲基-2-氧丁酸（α-酮异戊酸）是一种神经毒素，由支链氨基酸不完全断裂产生的非正常代谢产物。

靶点

Human Endogenous Metabolite

体外研究

3-甲基-2-氧丁酸（α-酮异戊酸）是大肠杆菌中泛酸的前体。它增强了α-酮异亮氨酸和α-酮β-甲基-n-缬氨酸，但减少了相应的氨基酸，并导致精氨酸早期减少、晚期增加。

体内研究

3-甲基-2-氧丁酸（α-酮异戊酸）通过γ-氨基丁酸能（GABAergic）和谷氨酸能机制在大鼠中引起惊厥。

反应信息

• 作为反应物：
  描述：

  2-氧代-3-甲基丁酸 在 吡啶 、 草酰氯 、 [Ir(cod)2]BARF 、 C₅₀H₄₂N₂OP₂ 、 N,N-二甲基甲酰胺 作用下， 以 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 31.0h， 生成 3-hydroxy-3-isopropyl-4-(N,N-dimethylaminocarbonyl)indolin-2-one
  参考文献：
  名称：

  阳离子Ir / Me-BIPAM催化的α-酮酰胺的不对称分子内直接氢芳基化反应

  摘要：

  α-酮酰胺的不对称分子内直接氢芳基化反应可高产率获得各种类型的旋光3-取代3-羟基2-羟吲哚，具有完全的区域选择性和高对映选择性（84–98％ee）。这是通过使用阳离子铱络合物[Ir（cod）2 ]（BAr F 4）和手性O联双齿亚磷酰胺（R，R）-Me-BIPAM来实现的。

  DOI：

  10.1002/anie.201400147
• 作为产物：
  描述：

  calcium 3-methyl-2-oxobutyrate 在 盐酸 作用下， 以 甲基叔丁基醚 、 水 为溶剂， 反应 0.17h， 生成 2-氧代-3-甲基丁酸
  参考文献：
  名称：

  一种2-(9H-芴-9-甲氧基羰基氨基)-3-甲基-2-丁烯酸的合成方法

  摘要：

  本发明涉及一种2‑(9H‑芴‑9‑甲氧基羰基氨基)‑3‑甲基‑2‑丁烯酸的合成方法。主要解决目前缺少2‑(9H‑芴‑9‑甲氧基羰基氨基)‑3‑甲基‑2‑丁烯酸放大生产方法的技术问题。本发明合成方法包括以下步骤：在冰浴冷却下的甲基叔丁基醚中，3‑甲基‑2‑氧丁酸钙盐用浓盐酸酸化，生成化合物1；在加热回流的甲苯中，化合物1和芴甲氧羰酰胺在对甲苯磺酸的催化作用下，发生脱水缩合反应，生成目标化合物2。作为医药中间体和脱氢氨基酸衍生物，2‑(9H‑芴‑9‑甲氧基羰基氨基)‑3‑甲基‑2‑丁烯酸是被广泛用于合成肽类活性物质和蛋白质工程领域。

  公开号：

  CN112062693A

文献信息

• Total Synthesis of TMC-95A and -B via a New Reaction Leading to <i>Z</i>-Enamides. Some Preliminary Findings as to SAR
  作者：Songnian Lin、Zhi-Qiang Yang、Benjamin H. B. Kwok、Michael Koldobskiy、Craig M. Crews、Samuel J. Danishefsky

  DOI：10.1021/ja049821k

  日期：2004.5.1

  A full account of the total syntheses of proteasome inhibitors TMC-95A and -B is provided. A key feature of the syntheses involved installation of a cis-propenylamide moiety by a thermal rearrangement of an alpha-silylallyl amide. The scope and mechanism of the enamide-forming reaction are discussed. Also provided are some preliminary results from SAR studies. It was found that simplified analogues

  提供了蛋白酶体抑制剂 TMC-95A 和 -B 的全合成的完整说明。合成的一个关键特征涉及通过α-甲硅烷基烯丙基酰胺的热重排安装顺式丙烯酰胺部分。讨论了烯酰胺形成反应的范围和机理。还提供了一些 SAR 研究的初步结果。发现简化的类似物可以保留蛋白酶体抑制的全部效力。
• Syntheses of α-Hydroxyamino Acids from α-Keto Acids
  作者：Afzal Ahmad

  DOI：10.1246/bcsj.47.1819

  日期：1974.7

  A new general method for the synthesis of α-hydroxyamino acids has been developed. Lithium cyanohydridoborate reduces α-keto acid oximes to the corresponding α-hydroxyamino acids and not to the corresponding α-amino acids.

  已经开发了一种新的合成α-羟基氨基酸的通用方法。氰基氢化硼酸锂将 α-酮酸肟还原为相应的 α-羟基氨基酸，而不是相应的 α-氨基酸。
• Dehydrooligopeptides. V. Synthesis of N-carboxy .ALPHA.-dehydroamino acid anhydrides and their transformation to .ALPHA.-dehydroamino acid and dehydrooligopeptide derivatives.
  作者：CHUNGGI SHIN、YASUCHIKA YONEZAWA、TOYOFUMI YAMADA

  DOI：10.1248/cpb.32.3934

  日期：——

  The synthesis of N-carboxy α-dehydroamino acid anhydrides (ΔNCA) from benzyloxycarbonyl-α-dehydroamino acids and the subsequent conversion of these products into new α-dehydroamino acid and dehydrooligopeptide derivatives are described. It was found that the new ΔNCA derivatives were very useful synthons for dehydropeptides. The racemization behavior and configurational determination of all the new dehydrooligopeptides thus obtained are discussed.

  中文翻译如下： 本文描述了从苄氧羰基-α-去氢氨基酸合成N-羧基α-去氢氨基酸酐（ΔNCA），以及后续将这些产物转化为新的α-去氢氨基酸和去氢低聚肽衍生物的过程。研究发现，新的ΔNCA衍生物对于去氢肽的合成非常有用。本文还讨论了所获得的这些新的去氢低聚肽的消旋行为和构型测定。
• Chemoenzymatic Production of Enantiocomplementary 2‐Substituted 3‐Hydroxycarboxylic Acids from <scp>l</scp> ‐α‐Amino Acids
  作者：Mathias Pickl、Roser Marín‐Valls、Jesús Joglar、Jordi Bujons、Pere Clapés

  DOI：10.1002/adsc.202100145

  日期：2021.6.8

  A two-enzyme cascade reaction plus in situ oxidative decarboxylation for the transformation of readily available canonical and non-canonical l-α-amino acids into 2-substituted 3-hydroxycarboxylic acid derivatives is described. The biocatalytic cascade consisted of an oxidative deamination of l-α-amino acids by an l-α-amino acid deaminase from Cosenzaea myxofaciens, rendering 2-oxoacid intermediates

  描述了双酶级联反应加上原位氧化脱羧，用于将容易获得的规范和非规范1 -α-氨基酸转化为2-取代的3-羟基羧酸衍生物。生物催化级联包括通过Cosenzaea myxofaciens的l -α-氨基酸脱氨酶对l -α-氨基酸进行氧化脱氨，产生 2-含氧酸中间体，随后在金属依赖性 ( R)催化下与甲醛发生羟醛加成反应。 )-或( S )-选择性碳连接酶，分别是2-氧代-3-脱氧-1-鼠李酸醛缩酶(YfaU)和酮泛解酸羟甲基转移酶(KPHMT)，提供3-取代的4-羟基-2-含氧酸。通过平衡生物催化剂负载量以及氨基酸和甲醛浓度来优化总体底物转化率，每种对映体产生 36-98% 的羟醛加合物形成和 91-98% ee。随后通过过氧化氢驱动的氧化脱羧进行原位后续化学反应，得到相应的2-取代的3-羟基羧酸衍生物。
• COMPOSITIONS AND METHODS FOR FORMING ARTICLES HAVING SILVER METAL
  申请人：Eastman Kodak Company

  公开号：US20180362547A1

  公开（公告）日：2018-12-20

  Electrically-conductive silver metal can be provided in a thin film or pattern on a substrate from a silver complex having reducing silver ions and represented by: (Ag + ) a (L) b (P) c (I) wherein L represents an α-oxy carboxylate; P represents a 5- or 6-membered N-heteroaromatic compound; a is 1 or 2; b is 1 or 2; and c is 1, 2, 3, or 4, provided that when a is 1, b is 1, and when a is 2, b is 2. The silver complex is mixed in a hydroxy-free, nitrile-containing aprotic solvent with a polymer that is either (i) a hydroxy-containing cellulosic polymer or (ii) a non-cellulosic acrylic polymer having a halo- or hydroxy-containing side chain. The reducible silver ions in the a thermally sensitive thin film or pattern can be thermally converted to electrically-conductive metallic silver under suitable heating conditions to provide a product article that can be used in various devices.

  电导银金属可由含还原银离子的银配合物以薄膜或图案的形式提供在基底上，其由下式表示： (Ag + ) a (L) b (P) c (I) 其中L代表α-氧基羧酸盐；P代表5或6成员的N-杂环化合物；a为1或2；b为1或2；c为1、2、3或4，条件是当a为1时，b为1，当a为2时，b为2。将银配合物与不含羟基、含腈的无质子溶剂中的聚合物混合，该聚合物为(i)含羟基的纤维素聚合物或(ii)具有卤素或含羟基侧链的非纤维素丙烯酸聚合物。在热敏感薄膜或图案中的可还原银离子可以在适当的加热条件下热转换为电导银金属，以提供可用作各种设备的产品物品。