环(丙氨酰-丙氨酰) | 5845-61-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 环(丙氨酰-丙氨酰)
• 英文名称: cyclo(L-Ala-L-Ala)
• 英文别名: (3S,6S)-3,6-dimethylpiperazine-2,5-dione
• CAS: 5845-61-4
• 化学式: C₆H₁₀N₂O₂
• 分子量: 142.158
• InChiKey: WWISPHBAYBECQZ-IMJSIDKUSA-N

物化性质

• 熔点：
  282-282.5 °C
• 沸点：
  453.0±38.0 °C(Predicted)
• 密度：
  1.081±0.06 g/cm3(Predicted)
• 稳定性/保质期：
  在常温常压下，该物质保持稳定。

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  58.2
• 氢给体数：
  2
• 氢受体数：
  2

安全信息

• 储存条件：
  -15℃下应避光、存于阴凉干燥处并密封保存。

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: Cyclo(-ala-ala)
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: Cyclo(-ala-ala)
CAS number: 5845-61-4

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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: C6H10N2O2
Molecular weight: 142.2

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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, nitrogen oxides.

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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

反应信息

• 作为反应物：
  描述：

  环(丙氨酰-丙氨酰) 在 盐酸 、 sodium chloride 作用下， 以 水 为溶剂， 生成 L-丙氨酸
  参考文献：
  名称：

  K +和Na +对线性和环状二肽水解的相反作用

  摘要：

  钾和钠通常被认为是有机反应的惰性“旁观者”离子。在这里，我们报告了甘氨酸（G）和丙氨酸（A）的七个二肽经酸促进水解的速率常数，以及在K +和Na +存在下这些速率如何不同的意外模式。与相同浓度的NaCl相比，线性二肽在KCl存在下的水解速度要慢12-18％，而在KCl存在下环状二肽的水解速度快5-13％（所有P值<0.025）。我们认为这是一般有机反应（此处为酰胺水解）的首次报道，对于该反应，某些底物在K +存在下反应更快，而另一些在Na +存在下反应更快。。这些结果为生命中普遍选择细胞内钾而不是钠提供了可能的神秘原因。

  DOI：

  10.1016/j.tetlet.2018.04.073
• 作为产物：
  描述：

  L-丙氨酰-L-丙氨酸 在 silica gel 作用下， 以 gas 为溶剂， 190.0~210.0 ℃ 、10.67 Pa 条件下， 以80%的产率得到环(丙氨酰-丙氨酰)
  参考文献：
  名称：

  The Gas-Solid-Phase 2,5-Dioxopiperazine Synthesis. Cyclization of Vaporous Dipeptides on Silica Surface

  摘要：

  “气固相”方法用于在硅胶存在的情况下通过蒸发线性二肽的环化制备对称和非对称的2,5-二氧吡咯烷。

  DOI：

  10.1135/cccc19940461

文献信息

• Enantioselective synthesis of non-proteinogenic amino acids via metallated bis-lactim ethers of 2,5-diketopiperazines
  作者：Ulrich Schöllkopf

  DOI：10.1016/s0040-4020(01)91926-x

  日期：1983.1

  excess = asymmetric induction) of the adduct exceeds 95%. On hydrolysis the adducts are cleaved liberating the chiral auxiliary (used to build up the bis-lactim ether 1) and the target molecules, the optically active amino acid methyl esters of type 8,19,25 or 36. The two amino acid esters are separable either by fractional distillation or (eventually after further hydrolysis to amino acids) by chromatography

  2,5-二酮哌嗪的双-内酯醚1包含一个手性诱导中心，一个酸性CH键和两个易于水解的位点。他们用BuLi反应以得到类型的锂化合物4，15，19或32，其具有前手性的C原子。他们很容易添加亲电试剂（例如烷基化剂或羰基化合物），具有非同寻常的非对映异构性。在许多情况下，加合物的减值（de =非对映异构体过量=不对称诱导）超过95％。水解时，加合物被裂解释放出手性助剂（用于构建双内酰胺醚1）和目标分子，即8型旋光氨基酸甲基酯，19，25或36。两种氨基酸酯可通过分馏或（最终在进一步水解成氨基酸后）通过色谱法分离。讨论了过渡状态模型，该模型可以解释异常高的不对称诱导和诱导构型的可预测性。
• Epimerization of Cyclic Alanyl-Alanine in Basic Solutions
  作者：Toratane Munegumi、Takeshi Fujimoto、Michio Takada、Nozomi Nagashima

  DOI：10.13005/ojc/300103

  日期：2014.3.30

  Alanine anhydrides (Cyclo-(Ala-Ala)) are the simplest dipeptides that have two chiral centers and three diastereomers: Cyclo-(L-Ala-L-Ala), Cyclo-(D-Ala-D-Ala), and Cyclo-(L-Ala-D-Ala).Analysis of the epimerization of these peptides may throw light on the development of homochirality in proteins. We show that the epimerization rate of Cyclo-(L-Ala-L-Ala) and Cyclo-(D-Ala-D-Ala) is higher than that of Cyclo-(L-Ala-D-Ala), while the ring-opening rates of Cyclo-(L-Ala-L-Ala) and Cyclo-(D-Ala-D-Ala) arelower than that of Cyclo-(L-Ala-D-Ala) in basic aqueous solutions. The total reaction resulted in the preferred stability of Cyclo-(L-Ala-L-Ala) and Cyclo-(D-Ala-D-Ala) to Cyclo-(D-Ala-L-Ala).

  丙氨酸酐（环-(丙-丙)）是最简单的二肽，具有两个手性中心和三种非对映异构体：环-(L-丙-L-丙)、环-(D-丙-D-丙)和环-(L-丙-D-丙)。分析这些肽的差向异构化可能有助于揭示蛋白质中同手性的发展。我们表明，环-(L-丙-L-丙)和环-(D-丙-D-丙)的差向异构化速率高于环-(L-丙-D-丙)，而在碱性水溶液中，环-(L-丙-L-丙)和环-(D-丙-D-丙)的环开裂速率低于环-(L-丙-D-丙)。总反应导致了环-(L-丙-L-丙)和环-(D-丙-D-丙)相对于环-(D-丙-L-丙)的优先稳定性。
• Selective hydrogenation of primary amides and cyclic di-peptides under Ru-catalysis
  作者：Murugan Subaramanian、Ganesan Sivakumar、Jessin K. Babu、Ekambaram Balaraman

  DOI：10.1039/d0cc04550k

  日期：——

  A ruthenium(II)-catalyzed selective hydrogenation of challenging primary amides and cyclic di-peptides to their corresponding primary alcohols and amino alcohols, respectively, is reported. The hydrogenation reaction operates under mild and eco-benign conditions and can be scaled-up.

  报道了钌（II）催化的具有挑战性的伯酰胺和环状二肽分别选择性氢化为其相应的伯醇和氨基醇。氢化反应在温和的生态友好条件下进行，并且可以扩大规模。
• Oligomerization of glycine and alanine on metal(II) octacynaomolybdate(IV): role of double metal cyanides in prebiotic chemistry
  作者：Anand Kumar、Kamaluddin

  DOI：10.1007/s00726-012-1320-0

  日期：2012.12

  temperature and time found out. Formation of peptides was observed to start after 7 days at 60 °C. Maximum yield of peptides was found after 35 days at 90 °C. It has been found that zinc(II) octacyanomolybdate(IV) and cobalt(II) were the most effective metal cations present in outer sphere of the MOCMo for the production of high yield of oligomerized products. Surface area of MOCMo seems to play dominating

  使用高效液相色谱（HPLC）和电子喷雾电离质谱（ESI-MS）研究了八价氰钼酸金属盐（IV）（MOCMo）络合物表面上氨基酸（甘氨酸和丙氨酸）的缩合反应。已经合成了一系列MOCMo，并发现了在不同温度和时间下，MOCMo中存在的外球金属离子对甘氨酸和丙氨酸低聚的影响。观察到在60°C下7天后开始形成肽。在90°C下放置35天后，发现多肽的最大产量。已经发现八氰基钼酸锌（II）和钴（II）是MOCMo外球体中最有效的金属阳离子，可用于高产率的低聚产物的生产。MOCMo的表面积似乎是丙氨酸和甘氨酸低聚的主要参数。本研究的结果揭示了MOCMo在化学进化中对生物分子的低聚作用。
• En Route to a Heterogeneous Catalytic Direct Peptide Bond Formation by Zr-Based Metal–Organic Framework Catalysts
  作者：Francisco de Azambuja、Alexandra Loosen、Dragan Conic、Maxime van den Besselaar、Jeremy N. Harvey、Tatjana N. Parac-Vogt

  DOI：10.1021/acscatal.1c01782

  日期：2021.7.2

  assists in lowering the barrier of key proton transfers. The proposed concepts were also used to study the formation of intermolecular peptide bond formation. While intrinsic challenges associated with the catalyst structure and water removal limit a more general intermolecular reaction scope under current conditions, the results suggest that further design of Zr-MOF catalysts could render these materials

  肽键的形成是一个具有挑战性、环境和经济要求高的转变。催化是绕过当前瓶颈的关键。迄今为止，已经开发了许多能够提供合成有用方法的均相催化剂，而多相催化剂仍然主要限于解决肽的益生元形成的研究。这里，Zr 6的催化活性使用二肽环化作为模型反应研究了基于金属 - 有机框架（Zr-MOF）的肽键形成。与以前的催化剂不同，Zr-MOFs 在很大程度上耐受水，并且反应在环境条件下进行。值得注意的是，该催化剂是可回收的，并且不需要用于激活 COOH 基团的添加剂，这是以前方法的常见限制。此外，广泛的反应范围可以容忍具有庞大和路易斯碱性基团的底物。反应机制通过详细的机械和计算研究进行评估，其特征是通过 Zr 中心向胺加成对羧酸根基团进行路易斯酸活化，其中相邻 Zr 位点上的烷氧基配体有助于降低关键质子转移的障碍。所提出的概念还用于研究分子间肽键的形成。虽然与催化剂结构和水去除相关的内在挑战限制了当前条件下更普