3-(甲基硒基)-L-丙氨酸 | 26046-90-2

• 物质功能分类: 生物化工 - 氨基酸及其衍生物 - 丙氨酸类衍生物
• 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: 3-(甲基硒基)-L-丙氨酸
• 中文别名: L-硒甲基硒代半胱氨酸；甲基硒代半胱氨酸；3-甲基硒代-L-丙氨酸；3-甲基硒代-L-D-Α-氨基羧酸
• 英文名称: L-methylselenocysteine
• 英文别名: methylselenocysteine；Se-methyl-L-selenocysteine；Se-(methyl)selenocysteine；L-Se-methylselenocysteine；Se-methyl selenocystein；Se‑(methyl)‑selenocysteine；L-selenomethyl selenocysteine；MSC；(2R)-2-azaniumyl-3-methylselanylpropanoate
• CAS: 26046-90-2
• 化学式: C₄H₉NO₂Se
• 分子量: 182.081
• InChiKey: XDSSPSLGNGIIHP-VKHMYHEASA-N

物化性质

• 熔点：
  177 °C(dec.)
• 沸点：
  314.1±37.0 °C(Predicted)
• 溶解度：
  DMSO（少许）、水（少许）
• LogP：
  -0.043 (est)
• 物理描述：
  Solid

计算性质

• 辛醇/水分配系数(LogP)：
  -0.43
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  63.3
• 氢给体数：
  2
• 氢受体数：
  3

安全信息

• 危险品标志：
  T,N
• 安全说明：
  S20/21,S28,S45,S60,S61
• 危险类别码：
  R50/53,R23/25,R33
• WGK Germany：
  3
• 海关编码：
  2922499990
• 危险品运输编号：
  UN 3283
• 包装等级：
  III
• 危险类别：
  6.1
• 危险性防范说明：
  P501,P273,P260,P270,P271,P264,P391,P314,P301+P310+P330,P304+P340+P311,P403+P233,P405
• 危险性描述：
  H301+H331,H373,H410
• 储存条件：
  -20℃

SDS

Name:	SE-Methylseleno-L-Cysteine Material Safety Data Sheet
Synonym:	2-Amino-3-Methylselanyl Propionic Acid; 3-(Methylseleno)-L-Alanine
CAS:	26046-90-2

Section 1 - Chemical Product MSDS Name:SE-Methylseleno-L-Cysteine Material Safety Data Sheet
Synonym:2-Amino-3-Methylselanyl Propionic Acid; 3-(Methylseleno)-L-Alanine

---

Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
26046-90-2	SE-Methylseleno-L-Cysteine	ca. 100%	unlisted

Hazard Symbols: T
Risk Phrases: 23/25 33

---

Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Toxic by inhalation and if swallowed. Danger of cumulative effects.The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
May cause irritation of the digestive tract. The toxicological properties of this substance have not been fully investigated.
Inhalation:
May cause respiratory tract irritation. The toxicological properties of this substance have not been fully investigated.
Chronic:
Effects may be delayed.

---

Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid. Get medical aid immediately. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:
Treat symptomatically and supportively.

---

Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Containers may explode when heated. Non-combustible, substance itself does not burn but may decompose upon heating to produce irritating, corrosive and/or toxic fumes. Runoff from fire control or dilution water may cause pollution.
Extinguishing Media:
Use water spray to cool fire-exposed containers. Do NOT get water inside containers. For small fires, use dry chemical, carbon dioxide, or water spray. For large fires, use water spray, fog or regular foam.

---

Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

---

Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use only in a well-ventilated area.
Minimize dust generation and accumulation. Do not breathe dust, vapor, mist, or gas. Do not get in eyes, on skin, or on clothing.
Keep container tightly closed. Do not ingest or inhale. Use only in a chemical fume hood. Discard contaminated shoes.
Storage:
Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances.

---

Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 26046-90-2: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

---

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Solid
Color: white
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: Not available.
Autoignition Temperature: Not applicable.
Flash Point: Not applicable.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density: Not available.
Molecular Formula: C4H9NO2Se
Molecular Weight: 182.0285

---

Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable at room temperature in closed containers under normal storage and handling conditions.
Conditions to Avoid:
Incompatible materials, dust generation, excess heat, strong oxidants.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, oxides of nitrogen, irritating and toxic fumes and gases, carbon dioxide, selenium/selenium oxides.
Hazardous Polymerization: Has not been reported

---

Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 26046-90-2 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
SE-Methylseleno-L-Cysteine - Not listed by ACGIH, IARC, or NTP.

---

Section 12 - ECOLOGICAL INFORMATION

---

Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

---

Section 14 - TRANSPORT INFORMATION

IATA
Shipping Name: SELENIUM COMPOUND, N.O.S.
Hazard Class: 6.1
UN Number: 3283
Packing Group: III
IMO
Shipping Name: SELENIUM COMPOUND, N.O.S.
Hazard Class: 6.1
UN Number: 3283
Packing Group: III
RID/ADR
Shipping Name: SELENIUM COMPOUND, N.O.S.
Hazard Class: 6.1
UN Number: 3283
Packing group: III

---

Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: T
Risk Phrases:
R 23/25 Toxic by inhalation and if swallowed.
R 33 Danger of cumulative effects.
Safety Phrases:
S 20/21 When using do not eat, drink or smoke.
S 28A After contact with skin, wash immediately with
plenty of water.
S 37 Wear suitable gloves.
S 45 In case of accident or if you feel unwell, seek
medical advice immediately (show the label where
possible).
WGK (Water Danger/Protection)
CAS# 26046-90-2: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 26046-90-2 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 26046-90-2 is not listed on the TSCA inventory.
It is for research and development use only.

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

应用

3-(甲基硒基)-L-丙氨酸又叫L-硒代半胱氨酸的硒甲基化衍生物，常用作硒营养强化剂。它广泛存在于黄芪、大蒜、洋葱和椰菜等植物以及富硒酵母中，具有明确的化学结构、较小的毒性、较高的生物利用率及良好的补硒效果。此外，3-(甲基硒基)-L-丙氨酸不仅对多种肿瘤（如乳腺癌、前列腺癌、肝癌等）有预防作用，还对癌症治疗有一定的辅助作用，具有广阔的前景。

2002年，美国FDA认定硒-甲基硒代半胱氨酸为最新一代硒源类饮食补充剂；2009年，我国卫生部批准3-(甲基硒基)-L-丙氨酸为新型营养强化剂（食品添加剂新品种2009年第11号公告）。

用途

2-氨基-3-甲基硒基丙酸是DMBA诱导的乳腺肿瘤的抑制剂。

生物活性

Se-Methylselenocysteine 是甲基硒的前体，具有强大的癌症化学预防活性和抗氧化活性。它还具有口服生物活性，能诱导细胞凋亡（apoptosis）。

优点

L-硒代半胱氨酸的硒甲基化衍生物——3-(甲基硒基)-L-丙氨酸广泛存在于多种植物及富硒酵母中，具备明确的化学结构、较小的毒性、较高的生物利用率和良好的补硒效果。

体外研究

Se-Methylselenocysteine (100-400 μM; 3 days) 在SKOV-3细胞中诱导凋亡。Se-Methylselenocysteine（100-400 μM; 3 days）通过 caspase-3 介导的机制诱导 SKOV-3 细胞凋亡。

琼脂糖凝胶电泳分析

细胞系：	SKOV-3 细胞
浓度：	100, 200, 400 μM
培养时间：	3天
结果：	导致 Sub-G1 相位显著增加，这种变化在 SeMSC 浓度和培养时间依赖性方面均有表现。

蛋白印迹分析

细胞系：	SKOV-3 细胞
浓度：	100, 200, 400 μM
培养时间：	3天
结果：	导致 32 kDa 形式的 procaspase-3 表达下降。

体内研究

Se-Methylselenocysteine (0.2 mg/mouse; p.o.; 每日给药14天) 在裸鼠（携有人 FaDu 和 A253 头颈部移植瘤）中增强了顺铂和环磷酰胺的抗肿瘤活性。Alzheimer's 病小鼠通过饮用水每天给予 Se-Methylselenocysteine 10个月，Se-Methylselenocysteine 减轻了氧化应激和神经炎症；它调节多种金属离子的分布和水平；通过抑制其前体蛋白 APP 和 β-分泌酶（BACE1）表达来减少β淀粉样肽（Aβ）生成，并通过促进蛋白质磷酸化酶 2A（PP2A）活性来减轻 tau 超磷酸化和神经纤维缠结（NFT）的形成，从而保护突触蛋白和神经元活动，最终改善 Alzheimer's 模型小鼠的空间学习和记忆障碍。

动物模型：	女性无胸腺裸鼠（携带人 A253 和 FaDu 腺癌移植瘤）
用量：	0.2 mg/只
给药方式：	p.o.; 每日给药14天，其中7天在 Cyclophosphamide 或顺铂前进行。

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  硒代-L-半胱氨酸	L-selenocysteine	10236-58-5	C3H7NO2Se	168.054

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  3-(甲基硒)丙氨酸	Se-methylselenocysteine	——	C4H9NO2Se	182.081

反应信息

• 作为反应物：
  描述：

  3-(甲基硒基)-L-丙氨酸 在 苯甲醛 溶剂黄146 作用下， 反应 2.58h， 以92%的产率得到3-(甲基硒)丙氨酸
  参考文献：
  名称：

  Manufacturing processes for Se-methyl-L-selenocysteine

  摘要：

  方便的方法被描述用于从氯丙氨酸衍生物合成L-甲硒蛋氨酸。该过程很容易扩展到其他硒替代氨基酸。DL-甲硒蛋氨酸可以通过苯甲醛催化的L-甲硒蛋氨酸消旋得到。

  公开号：

  US06794537B1
• 作为产物：
  描述：

  N-(tetr-butoxycarbonyl)-L-Se-methylselenocysteine 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 以100%的产率得到3-(甲基硒基)-L-丙氨酸
  参考文献：
  名称：

  A method of using synthetic L-SE-Methylselenocysteine as a nutriceutical and a method of its synthesis

  摘要：

  描述了一种合成和使用L-Se-甲硒氨酸作为一种营养保健品，基于L-Se-甲硒氨酸对正常细胞比L-硒蛋氨酸毒性较小的知识。合成过程包括将N-(叔丁氧羰基)-L-丝氨酸与二烷基重氮二羧酸酯和三烷基膦、三芳基膦和磷酸酯中的至少一种混合，形成包含N-(叔丁氧羰基)-L-丝氨酸β-内酯的第一混合物。甲硒醇或其盐与N-(叔丁氧羰基)-L-丝氨酸β-内酯混合，形成包含N-(叔丁氧羰基)-Se-甲硒氨酸的第二混合物。将N-(叔丁氧羰基)-Se-甲硒氨酸中的叔丁氧羰基团去除，形成L-Se-甲硒氨酸。这种合成显著改善了这种天然存在的稀有有机硒形式的可制造性、制造效率和实用性。例如，以这种方式形成的L-Se-甲硒氨酸可用作一种营养保健品，添加到人类或动物的饮食中，以达到各种有益目的，例如预防或减少患癌症的风险。

  公开号：

  EP1205471A1

文献信息

• 一种制备光学纯L型硒-甲基硒代半胱氨酸的 方法
  申请人：济源希健生物医药科技发展有限公司

  公开号：CN108947881B

  公开（公告）日：2020-10-27

  本发明涉及氨基酸药物制备方法，具体涉及一种制备光学纯L型硒‑甲基硒代半胱氨酸的方法。本发明将N‑乙酰基‑3‑氯‑L‑丝氨酸甲酯和甲硒醇盐混合，得到N‑乙酰基‑3‑甲硒基‑L‑丝氨酸甲酯，然后与盐酸溶液混合，进行水解反应，得到硒‑甲基硒代半胱氨酸，将硒‑甲基硒代半胱氨酸溶解于水中，然后加入溶剂A，混合均匀；加入活性炭脱色，过滤，收集滤液；在滤液中加入溶剂B，混合均匀，然后冷却并放置1h以上，收集晶体，得到光学纯L型硒‑甲基硒代半胱氨酸；本发明具有工艺简单、产品光学纯度高、绿色、环保等特点，适合大规模工业化生产。
• <i>Allium</i> Chemistry:  Synthesis, Natural Occurrence, Biological Activity, and Chemistry of <i>Se</i>-Alk(en)ylselenocysteines and Their γ-Glutamyl Derivatives and Oxidation Products
  作者：Eric Block、Marc Birringer、Weiqin Jiang、Tsukasa Nakahodo、Henry J. Thompson、Paul J. Toscano、Horst Uzar、Xing Zhang、Zongjian Zhu

  DOI：10.1021/jf001097b

  日期：2001.1.1

  selenocystine (4). Oxidation of 6d gives 2-[(E,Z)-1-propenylseleno]propanal (36). These oxidations occur by way of selenoxides, detected by chromatographic and spectroscopic methods. The natural occurrence of many of the Se-alk(en)ylselenocysteines and their gamma-glutamyl derivatives and oxidation products is discussed. Three homologues of the potent cancer chemoprevention agents 6a and 6c, namely

  据报道合成了γ-谷氨酰基Se-甲基硒代半胱氨酸（Sa），硒代羊毛硫氨酸（16），Se-1-丙烯基硒代半胱氨酸（Gd），Se-2-甲基-2-丙烯基-L-硒代半胱氨酸（6e）和Se-2-丙炔基-L-硒代半胱氨酸（6f）。8a和Se-甲基硒代半胱氨酸（Ga）的氧化得到甲烷硒酸（24）（通过X射线晶体学表征）和二甲基二硒化物（25）。Se-2-丙烯基-L-硒代半胱氨酸（6c）的氧化得到烯丙醇和3-硒代丙氨酸（22）。化合物22也会在16和硒代胱氨酸（4）氧化时形成。6d的氧化得到2-[（（E，Z）-1-丙烯基硒基]丙醛（36）。这些氧化通过亚硒酸盐发生，通过色谱法和光谱法检测。讨论了许多Se-alk（en）ylselenocysteines和它们的gamma-谷氨酰基衍生物和氧化产物的自然发生。使用两种鼠类乳腺上皮细胞系评估了三种有效的癌症化学预防剂6a和6c的同系物，即6d-f对细胞生长，细胞凋
• Novel Dipeptides incorporating selenoamino acids with enhanced bioavailability- Synthesis, pharmaceutical and cosmeceutical applications thereof
  申请人：Majeed Muhammed

  公开号：US20080026017A1

  公开（公告）日：2008-01-31

  Disclosed is a novel synthetic method for isomeric peptides through an appropriate linkage of L-selenomethionine or Se-Methyl-L-selenocysteine with L-glutamic acid. The novel synthetic method produces isomeric peptides of L-selenomethionine or Se-Methyl-L-selenocysteine that exhibit (i) enhanced water solubility; (ii) enhanced rate of dissolution in water; (iii) enhanced bioavailability; (iv) excellent vascular endothelial growth factor promoting activity; (v) excellent anti-5-alpha-reductase activity; (vi) capabilities to prevent/reduce “hair fall” and promote “hair growth”, thereby maintaining a perfect homeostasis for “hair care”. Cosmeceutical and pharmaceutical compositions comprising the isomeric peptides obtained through an appropriate linkage of L-selenomethionine or Se-Methyl-L-selenocysteine with L-glutamic acid are also disclosed. Other dipeptides with several other amino acids and uses thereof are also disclosed.

  揭示了一种新颖的合成方法，通过将L-硒代蛋氨酸或Se-甲基-L-硒蛋氨酸与L-谷氨酸适当连接，制备L-硒代蛋氨酸或Se-甲基-L-硒蛋氨酸的同分异构肽。这种新颖的合成方法产生的同分异构肽具有以下特点：(i)增强的水溶性；(ii)在水中溶解速度增强；(iii)增强的生物利用度；(iv)出色的血管内皮生长因子促进活性；(v)出色的抗5α-还原酶活性；(vi)具有预防/减少“脱发”和促进“头发生长”的能力，从而维持“头发护理”的完美稳态。还揭示了包括通过将L-硒代蛋氨酸或Se-甲基-L-硒蛋氨酸与L-谷氨酸适当连接获得的同分异构肽的化妆品和药用组合物。还揭示了包括其他多种氨基酸的二肽及其用途。
• Efficient Assembly of Iminodicarboxamides by a “Truly” Four-Component Reaction
  作者：Kareem Khoury、Mantosh K. Sinha、Tadamichi Nagashima、Eberhardt Herdtweck、Alexander Dömling

  DOI：10.1002/anie.201205366

  日期：2012.10.8

  Mix and match: Similar to a galaxy consisting of millions of stars, a multicomponent reaction (MCR) system can result in millions of compounds. The MCR of α‐amino acids, oxo components, isocyanides, and amines leads to numerous and diverse compounds, thus having enormous potential for drug discovery or catalyst screening.

  混合搭配：类似于由数百万颗恒星组成的星系，多组分反应 (MCR) 系统可以产生数百万种化合物。α-氨基酸、含氧组分、异氰化物和胺的 MCR 导致产生大量不同的化合物，因此在药物发现或催化剂筛选方面具有巨大的潜力。
• Synthesis of Novel Se-Substituted Selenocysteine Derivatives as Potential Kidney Selective Prodrugs of Biologically Active Selenol Compounds:  Evaluation of Kinetics of β-Elimination Reactions in Rat Renal Cytosol
  作者：Ioanna Andreadou、Wiro M. P. B. Menge、Jan N. M. Commandeur、Eduard A. Worthington、Nico P. E. Vermeulen

  DOI：10.1021/jm950750x

  日期：1996.1.1

  Eighteen Se-substituted selenocysteine derivatives were synthesized as potential kidney selective prodrugs which can be activated by renal cysteine conjugate beta-lyase to selenium-containing chemoprotectants or antitumor agents. Selenocysteine derivatives with aliphatic and benzylic Se-substituents were synthesized by reducing selenocystine to selenocysteine followed by a reaction with the corresponding

  合成了十八种硒取代的硒代半胱氨酸衍生物，作为潜在的肾脏选择性前药，可以通过肾脏半胱氨酸共轭β-裂解酶将其激活为含硒的化学保护剂或抗肿瘤剂。通过将硒代半胱氨酸还原为硒代半胱氨酸，然后与相应的烷基和苄基卤化物反应，可以合成具有脂肪族和苄基硒取代基的硒代半胱氨酸衍生物。通过β-氯丙氨酸与取代的苯硒醇化合物反应合成具有芳香族Se取代基的硒代半胱氨酸衍生物，后者是通过用NaBH4还原取代的二苯二硒化物而形成的。研究了大鼠肾脏细胞溶胶中硒代半胱氨酸缀合物的β-消除反应的酶动力学参数（表观Km和Vmax）。结果表明，硒取代的L-硒代半胱氨酸结合物是肾半胱氨酸结合物β-裂合酶的极好底物，如表观Km低和Vmax值高所表明的。苄基取代的Se-共轭物似乎比苯基和烷基取代的Se-共轭物是更好的底物。相应的L-半胱氨酸S-缀合物太差，无法获得合适的酶动力学。最近，提出了通过肾脏半胱氨酸缀合物β-裂合酶局部激活半胱氨