(S)-(+)-柠苹酸 | 6236-09-5

• 物质功能分类: 化学试剂 - 有机试剂 - 脂肪酸
• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: (S)-(+)-柠苹酸
• 中文别名: L-(+)-柠苹酸
• 英文名称: (S)-citramalic acid
• 英文别名: S-CMA；(S)-2-Hydroxy-2-methylsuccinic acid；(2S)-2-hydroxy-2-methylbutanedioic acid
• CAS: 6236-09-5
• 化学式: C₅H₈O₅
• 分子量: 148.116
• InChiKey: XFTRTWQBIOMVPK-YFKPBYRVSA-N

物化性质

• 熔点：
  109-111 °C(lit.)
• 沸点：
  188.68°C (rough estimate)
• 密度：
  1.2336 (rough estimate)
• 溶解度：
  甲醇（微溶）、水（微溶）

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  94.8
• 氢给体数：
  3
• 氢受体数：
  5

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26,S36
• 危险类别码：
  R36/37/38

SDS

Name:	(S)-(+)-Citramalic Acid 98+% Material Safety Data Sheet
Synonym:	None known
CAS:	6236-09-5

Section 1 - Chemical Product MSDS Name:(S)-(+)-Citramalic Acid 98+% Material Safety Data Sheet
Synonym:None known

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
6236-09-5	(S)-(+)-Citramalic Acid	98+	228-350-1

Hazard Symbols: None Listed.
Risk Phrases: None Listed.

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
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:
No information found.

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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. 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:

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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.
Extinguishing Media:
Use agent most appropriate to extinguish fire. Use water spray, dry chemical, carbon dioxide, or appropriate foam.

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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. Avoid runoff into storm sewers and ditches which lead to waterways. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. Minimize dust generation and accumulation. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation.
Storage:
Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances.

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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# 6236-09-5: 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:
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements or European Standard EN 149 must be followed whenever workplace conditions warrant respirator use.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Powder
Color: white
Odor: none reported
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 108 - 110 deg C
Autoignition Temperature: Not applicable.
Flash Point: 150 deg C ( 302.00 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature: 150 deg C
Solubility in water: 250 G/L (20C)
Specific Gravity/Density:
Molecular Formula: C5H8O5
Molecular Weight: 148.12

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials, dust generation, excess heat, strong oxidants.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 6236-09-5 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(S)-(+)-Citramalic Acid - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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

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Section 14 - TRANSPORT INFORMATION

IATA
Not regulated as a hazardous material.
IMO
Not regulated as a hazardous material.
RID/ADR
Not regulated as a hazardous material.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: Not available.
Risk Phrases:
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
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# 6236-09-5: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 6236-09-5 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 6236-09-5 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  (S)-(+)-柠苹酸 在 palladium on activated charcoal sodium hydroxide 、 lithium aluminium tetrahydride 、 重铬酸吡啶 、 9-borabicyclo[3.3.1]nonane dimer 、 2Li⁽¹⁺⁾*Cl₄Cu₂^(2-) 、 硫酸 、 氢气 、 双氧水 、 四丁基碘化铵 、 sodium hydride 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 122.17h， 生成 methyl (S)-tetrahydro-2-methyl-5-oxo-2-furanacetate
  参考文献：
  名称：

  真菌颜料，第16部分。（R）-（+）-四氢-2-甲基-5-氧代-2-呋喃乙酸甲酯及其（S）-（-）-正电极的合成，用于绝对值测定的手性参考真菌前蒽醌的立体化学。

  摘要：

  通过香叶醇的不对称环氧化反应合成（R）-和（S）-丁醇化物7和9。（R）-丁醇化物7也由（S）-柠檬酸获得。丁醇化物7和9是用于测定真菌和植物前蒽醌中绝对立体化学的有价值的参考化合物。

  DOI：

  10.1016/s0957-4166(00)86350-8
• 作为产物：
  描述：

  中康酸 在 聚合甲醛 、 四环素 、 paraquat dichloride 作用下， 以 水 为溶剂， 反应 24.0h， 以69.8%的产率得到(S)-(+)-柠苹酸
  参考文献：
  名称：

  通过顺式或反式2-丁烯-1,4-二酸与福尔摩斯氏梭菌的静息细胞立体定向水合制备苹果酸和柠檬酸对映体以及其他羟基琥珀酸衍生物

  摘要：

  （R）-苹果酸，（S）-苹果酸，（R）柠檬酸，（S）-柠檬酸，（2 R，3 S）-2-羟基-3-甲基-琥珀酸和（2 R，3 S）-2通过将水立体定向加成到不同的2-丁烯-1,4-二酸衍生物中，由梭状梭状芽孢杆菌的静止细胞催化，可制备高达25 mmol的规模的3-3-二甲基-2-羟基琥珀酸（方案1）。的（3 - [R）-monodeuterio（[R ）-和（小号） -苹果酸，以及（- [R ）-和（小号）-citramalic苯甲酸用冷冻干燥的细胞中制备的2H 2 O缓冲区。在大多数情况下，产品的立体化学纯度均≥99％。

  DOI：

  10.1016/s0040-4020(01)85678-7
• 作为试剂：
  描述：

  1,1′-nethylenebis(3,3′,4,4′-tetrahydroisoquinoline) 在 盐酸 、 (S)-(+)-柠苹酸 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 反应 0.08h， 生成 (R,R)-1,1'-methylene-bis(1,1',2,2',3,3',4,4'-octahydroisoquinoline) 、 (S,S)-1,1'-methylene-bis(1,1',2,2',3,3',4,4'-octahydroisoquinoline)
  参考文献：
  名称：

  1,1'-亚甲基-双（1,1'，2,2'，3,3'，4,4'-八氢异喹啉）：合成，反应，拆分及在催化对映选择性转化中的应用

  摘要：

  描述了基于1,1'-亚甲基-双（1,1'，2,2'，3,3'，4,4'-八氢异喹啉）骨架的新手性1,3-二胺配体系统的制备。提出了各种单-，二-和桥联的N-烷基衍生物的合成。公开了一种化合物的拆分，其Cu（I）Br X射线晶体学结构以及其在对映选择性亨利和阿尔多反应中的应用的初步结果。

  DOI：

  10.1016/j.tet.2011.04.004

文献信息

• (α-Alkylation of α-heterosubstituted carboxylic acids without racemization
  作者：Dieter Seebach、Reto Naef、Giorgio Calderari

  DOI：10.1016/s0040-4020(01)82417-0

  日期：1984.1

  α-Hydroxy- and α-mercapto-carboxylic acids are condensed with pivalaldehyde to give 2-t-butyl-5-substituted-l,3-dioxolanones or 1,3-oxathiolanones (2); the predominate CK-isomers are separated by crystallization. The cis-disubstituted heterocycles 2 derived from lactic, mandelic and malic acid furnish, after deprotonation with LDA, reaction with electrophiles such as alkyl halides, aldehydes and ketones

  将α-羟基和α-巯基羧酸与新戊醛缩合，生成2-叔丁基-5-取代的-1,3-二氧戊环酮或1,3-氧杂硫杂环戊酮（2）；主要的CK异构体通过结晶分离。的顺式二取代的杂环2从乳酸，扁桃酸和苹果酸配料衍生，用LDA，与亲电子试剂如烷基卤化物，醛和酮，去质子化反应后，水解α-α支链羟基-羧酸（3，6，8，9，10）。这些归因于质子在α-CO位置上的整体置换而保留了构型。旋光羧酸是α-烷基化的，没有消旋作用，也没有使用手性助剂（“手性的自我复制”方案I）。非对映选择性（ds）通常> 95％（表1、2和20-25）。
• <b>Hexafluoroacetone as a Protecting and Activating Reagent: Synthesis of New Types of Fluoro-Substituted α-Amino, α-Hydroxy and α-Mercapto Acids</b>
  作者：Klaus Burger、Sergej Osipov、Torsten Lange、Pavel Tsouker、Jan Spengler、Lothar Hennig、Beate Koksch、Stefan Berger、Salah El-Kousy

  DOI：10.1055/s-2004-829131

  日期：——

  (S)-malic, (S)-citramalic and (S,R)-thiomalic acid, new types of 4,4-difluoro-substituted a-ami- no-, a-hydroxy- and a-mercaptopentanoic acids have been synthe- sized, applying hexafluoroacetone as protecting and activating reagent. The new partially fluorinated a-functionalized carboxylic acids represent interesting monomers for peptide and depsipeptide modification and for rational design and elucidation

  从(S)-天冬氨酸、(S)-苹果酸、(S)-柠苹果酸和(S,R)-硫代苹果酸开始，新型4,4-二氟取代的α-氨基-、α-羟基-和α-巯基戊酸已被合成，使用六氟丙酮作为保护和活化试剂。新的部分氟化的α-官能化羧酸代表了用于肽和缩肽修饰以及合理设计和阐明二级结构的有趣单体。
• A New Method for the Synthesis of (S)-α-Methylisoserine and Its Incorporation into Peptides
  作者：Raul Pires、Klaus Burger

  DOI：10.1055/s-1996-4387

  日期：1996.11

  (S)-(+)-Citramalic acid is converted into isocyanate 4 using hexafluoroacetone as the protecting agent. Isocyanate 4 represents a doubly activated species, which upon reaction with alcohols provides N-protected, carboxyl-activated α-methylisoserine derivatives, perfectly suited for peptide synthesis (5 → 8). Acylation of 4 with N-protected amino acids gives fully protected carboxyl-activated dipeptides. Ring opening with amino acid esters results in the formation of tripeptides (9 → 10).

  (S)-(+)-柠檬酸被转化成异氰酸酯4，使用六氟丙酮作为保护剂。异氰酸酯4是一种双重活化的物质，当其与醇反应时，产生了N-保护、羧基活化的α-甲基异丝氨酸衍生物，非常适合用于多肽合成（5 → 8）。用N-保护的氨基酸对4进行酰化作用，得到完全保护的、羧基活化的二肽。用氨基酸酯进行环开反应，形成了三肽（9 → 10）。
• Efficient stereoconservative syntheses of 4,4-difluoro-2-hydroxybutyric acids from (S)- and (R)-malic and (S)- and (R)-citramalic acid
  作者：Klaus Burger、Torsten Lange、Raul Pires

  DOI：10.1016/s0022-1139(99)00296-1

  日期：2000.3

  A preparative simple stereoconservative synthesis of homochiral 4,4-difluoro-2-hydroxybutyric acid and 4,4-difluoro-2-hydroxy-2-methylbutyric acid using hexafluoroacetone as protecting and activating agent is described.

  描述了使用六氟丙酮作为保护和活化剂的高手性4,4-二氟-2-羟基丁酸和4,4-二氟-2-羟基-2-甲基丁酸的制备简单立体保守性合成。
• <scp>l</scp>-α-Methylhomoisoserine: A New Versatile Building Block for Peptide and Depsipeptide Modification
  作者：Klaus Burger、Gábor Radics、Beate Koksch、Salah M. El-Kousy、Jan Spengler

  DOI：10.1055/s-2003-41477

  日期：——

  An efficient access to l-α-methylhomoisoserine derivatives starting from l -citramalic acid is described. The new compounds are GABA derivatives and represent new, versatile building blocks for peptide and depsipeptide modification.

  报道了一种从L-瓜氨酸酸高效合成L-α-甲基同型丝氨酸衍生物的方法。这些新化合物是γ-氨基丁酸（GABA）衍生物，代表了用于肽和脱肽修饰的新型多功能构建模块。

表征谱图