2-氰基-3-甲基丁烯酸乙酯 | 759-58-0

• 物质功能分类: 化学试剂 - 有机试剂 - 氰化物/腈
• 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: 2-氰基-3-甲基丁烯酸乙酯
• 中文别名: 2-氰基-3-甲基巴豆酸乙酯
• 英文名称: ethyl isopropylidenecyanoacetate
• 英文别名: ethyl 2-cyano-3-methylbut-2-enoate；ethyl 2-cyano-3-methyl-2-butenoate；Ethyl 2-cyano-3-methylcrotonate
• CAS: 759-58-0
• 化学式: C₈H₁₁NO₂
• 分子量: 153.181
• InChiKey: PZMDAADKKAXROL-UHFFFAOYSA-N

物化性质

• 熔点：
  ca 20℃
• 沸点：
  98-99 °C/1 mmHg (lit.)
• 密度：
  1.014 g/mL at 25 °C (lit.)
• 闪点：
  224 °F
• 稳定性/保质期：
  在常温常压下保持稳定，应避免与氧化物接触。

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 危险等级：
  6.1
• 危险品标志：
  Xn
• 安全说明：
  S26,S37,S39
• 危险类别码：
  R20/21/22
• WGK Germany：
  3
• 海关编码：
  2926909090
• 危险品运输编号：
  UN 3276
• 包装等级：
  III
• 危险类别：
  6.1
• 储存条件：
  将容器密封后，放入一个紧密封装的储存器中，并储存在阴凉、干燥的地方。

SDS

Name:	Ethyl 2-cyano-3-methyl-2-butenoate 98% Material Safety Data Sheet
Synonym:
CAS:	759-58-0

Section 1 - Chemical Product MSDS Name:Ethyl 2-cyano-3-methyl-2-butenoate 98% Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
759-58-0	Ethyl 2-cyano-3-methyl-2-butenoate	98%	unlisted

Hazard Symbols: XI
Risk Phrases: 36/37/38

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Irritating to eyes, respiratory system and skin.
Potential Health Effects
Eye:
Causes eye irritation.
Skin:
Causes skin irritation.
Ingestion:
May cause irritation of the digestive tract. The toxicological properties of this substance have not been fully investigated.
Inhalation:
Causes respiratory tract irritation. The toxicological properties of this substance have not been fully investigated.
Chronic:
Not available.

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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.
Ingestion:
Get medical aid. Wash mouth out with 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.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Store in a cool, dry place. Store in a tightly closed container.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 759-58-0: Personal Protective Equipment Eyes: Not available.
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.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Clear liquid
Color: colorless to slightly yellow
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 120 - 122 deg C @ 2
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: 107 deg C ( 224.60 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: immiscible with water
Specific Gravity/Density: 1.0140g/cm3
Molecular Formula: C8H11NO2
Molecular Weight: 153.0825

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Strong oxidizing agents, strong bases.
Hazardous Decomposition Products:
Carbon monoxide, oxides of nitrogen, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 759-58-0 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Ethyl 2-cyano-3-methyl-2-butenoate - 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
No information available.
IMO
No information available.
RID/ADR
No information available.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XI
Risk Phrases:
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 37/39 Wear suitable gloves and eye/face
protection.
WGK (Water Danger/Protection)
CAS# 759-58-0: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 759-58-0 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 759-58-0 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：

  2-氰基-3-甲基丁烯酸乙酯 在 甲基碘化镁 、 乙醚 作用下， 生成 3,3-二甲基丁腈
  参考文献：
  名称：

  Birch, Journal of the Chemical Society, 1949, p. 2721

  摘要：

  DOI：
• 作为产物：
  描述：

  氰乙酸乙酯 、 丙酮 在 lithium bromide 作用下， 反应 18.0h， 以66%的产率得到2-氰基-3-甲基丁烯酸乙酯
  参考文献：
  名称：

  （±）-（Z）-和（±）-（E）-9-（溴亚甲基）-1,5,5-三甲基螺[5.5] undeca-1,7-dien-3-one和（± ）-Majusculone

  摘要：

  香米草倍半萜类化合物（Z）-9-（溴亚甲基）-1,5,5-三甲基螺[5.5] undeca-1,7-二烯-3-酮及其15- E表基的新的全合成已于2007年完成。 13个步骤。在我们的序列中，Diels-Alder反应和随后的加合物还原烷基化被用作关键策略，以创建具有合适功能性的A环和季螺中心，以接近B环。此外，还可以通过两步轻松地从高级中间体完全合成去甲香豆素天然产物（±）-大丁烯酮。 变体-倍半萜-大枣-总合成-Diels-Alder反应

  DOI：

  10.1055/s-0030-1258412

文献信息

• β‐Aryl Nitrile Construction<i>via</i>Palladium‐Catalyzed Decarboxylative Benzylation of α‐Cyano Aliphatic Carboxylate Salts
  作者：Rui Shang、Zheng Huang、Xiao Xiao、Xi Lu、Yao Fu、Lei Liu

  DOI：10.1002/adsc.201200383

  日期：2012.9.17

  The palladium‐catalyzed decarboxylative benzylation of α‐cyano aliphatic carboxylate salts with benzyl electrophiles was discovered. This reaction exhibits good functional group compatibility and proceeds under relatively mild conditions. A diverse range of quaternary, tertiary and secondary β‐aryl nitriles can be conveniently prepared by this method.

  发现了α-氰基脂肪族羧酸盐与苄基亲电试剂的钯催化脱羧苄基化反应。该反应表现出良好的官能团相容性，并且在相对温和的条件下进行。通过这种方法可以方便地制备各种范围的季，叔和仲β-芳基腈。
• Flash preparation of carbenoids: A different performance of cyanogen bromide
  作者：Mohammad Hedayati、Nader Pesyan

  DOI：10.13005/ojc/300477

  日期：2014.12.31

  Cyanogen halides are known substances for the cyanating reaction. There are a few evidences for bromination reaction too. On the other hand carbenes are known as very important substances due to their remarkable reactions. Unfortunately carbenes at room temperature are very unstable and there is not a simple method for preparation of them. In most cases the isolation is not possible. We have reported a new reliable and fast preparation method of almost stable carbenoids. The mechanism of the formation has been discussed.

  氰化卤是众所周知的用于氰化反应的物质，也有一些证据表明它们可用于溴化反应。另一方面，由于其显著的反应性，卡宾被认为是非常重要的物质。不幸的是，卡宾在室温下极不稳定，并且没有简单的方法来制备它们。在大多数情况下，它们的分离是不可能的。我们报道了一种新的可靠且快速的制备几乎稳定的卡宾类似物的方法，并讨论了其形成的机制。
• Transition metal polyhydrides-catalyzed addition of activated nitriles to aldehydes and ketones via Knoevenagel condensation
  作者：Yingrui Lin、Xianchao Zhu、Min Xiang

  DOI：10.1016/0022-328x(93)80087-r

  日期：1993.4

  Transition metal polyhydrides and dihydrogen complexes catalyze Knoevenagel addition of cyanoacetate to aldehydes and ketones under neutral and mild conditions, the adducts undergo dehydration to give substituted (E)-2-cyano-α,β-unsaturated esters exclusively.

  在中性和温和条件下，过渡金属多羟基化合物和二氢配合物催化氰基乙酸的氰基乙酸加成到醛和酮上，加合物脱水后仅得到取代的（E）-2-氰基-α，β-不饱和酯。
• Bifunctional Acid-Base Ionic Liquid Organocatalysts with a Controlled Distance Between Acid and Base Sites
  作者：Mercedes Boronat、Maria J. Climent、Avelino Corma、Sara Iborra、Raquel Montón、Maria J. Sabater

  DOI：10.1002/chem.200901519

  日期：2010.1.25

  Bifunctional acid–base ionic liquid organocatalysts with different distances between the two sites have been synthesised, and their activity for the Knoevenagel condensation has been tested. As has been found to be the case with enzymes, the distance between the acidic and basic sites determines the activity of the bifunctional organocatalyst, and at the optimal distance the reaction rate increases

  合成了在两个位置之间具有不同距离的双官能酸基离子液体有机催化剂，并测试了它们在Knoevenagel缩合反应中的活性。如发现酶的情况一样，酸性和碱性位点之间的距离决定了双功能有机催化剂的活性，并且在最佳距离下，反应速率相对于纯酸性或碱性对应物增加了两个数量级。有机催化剂。通过DFT计算研究丙二腈与苯甲醛之间的Knoevenagel缩合反应机理，使实验结果合理化。已经发现它包括两个连续的步骤。第一的，C键形成反应。计算和动力学研究表明，当改变酸性和碱性位点之间的距离时，速率控制步骤将发生逆转，这直接关系到反应速率。
• Synthesis of nitrocyclopropanedicarboxylic acid derivatives by addition of α-bromonitroalkanes to methylidene malonic, methylidene cyanoacetic or maleic acid derivatives
  作者：G. V. Kryshtal、G. M. Zhdankina、A. S. Shashkov、S. G. Zlotin

  DOI：10.1007/s11172-011-0348-8

  日期：2011.11

  A potassium carbonate promoted addition of 2-bromonitroalkanes to methylidenemalonic and methylidenecyanoacetic acid derivatives and N-benzylmaleimide leads to the functionalized nitrocyclopropanes. In the case of less active olefins, it is reasonable to use the phase-transfer catalyst Bu4NPF6 (10 mol.%), whereas in the case of N-benzylmaleimide, to carry out the process in the ionic liquid [bmim]BF4.

  以碳酸钾促进2-溴硝基烷与亚甲基丙二酸酯及亚甲基氰基乙酸酯衍生物以及N-苄基马来酰亚胺的加成反应，可制得官能化的硝基环丙烷。对于活性较低的烯烃，使用相转移催化剂Bu4NPF6（10 mol.%）是合理的；而对于N-苄基马来酰亚胺，则应在离子液体[bmim]BF4中进行反应。

表征谱图