乙酰基环已烯 | 932-66-1

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 环烃
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 乙酰基环已烯
• 中文别名: 1-乙酰基-1-环己烯；1-乙酰环己烯
• 英文名称: 1-cyclohexenyl methyl ketone
• 英文别名: 1-Acetyl-1-cyclohexene；1-acetylcyclohexene；1-(cyclohexen-1-yl)ethanone
• CAS: 932-66-1
• 化学式: C₈H₁₂O
• 分子量: 124.183
• InChiKey: LTYLUDGDHUEBGX-UHFFFAOYSA-N

物化性质

• 熔点：
  73 °C
• 沸点：
  201-202 °C(lit.)
• 密度：
  0.966 g/mL at 25 °C(lit.)
• 闪点：
  150 °F
• LogP：
  1.648 (est)
• 保留指数：
  931
• 稳定性/保质期：
  1. 在常温常压下稳定，应避免与强碱和氧化物接触。 2. 主要存在于烟气中。

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 安全说明：
  S24/25
• WGK Germany：
  3
• 海关编码：
  2914299000
• 危险性防范说明：
  P210,P280,P370+P378,P403+P235,P501
• 危险性描述：
  H227,H302
• 储存条件：
  请将容器密封保存，并储存在阴凉、干燥的地方。

SDS

Name:	1-Acetyl-1-cyclohexene 97% Material Safety Data Sheet
Synonym:	None
CAS:	932-66-1

Section 1 - Chemical Product MSDS Name:1-Acetyl-1-cyclohexene 97% Material Safety Data Sheet
Synonym:None

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
932-66-1	1-Acetyl-1-cyclohexene	97	213-256-5

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 gastrointestinal irritation with nausea, vomiting and diarrhea. The toxicological properties of this substance have not been fully investigated.
Inhalation:
May cause respiratory tract irritation. No information available.
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: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid immediately.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Ingestion:
Do not induce vomiting. If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give anything by mouth to an unconscious person. Get medical aid.
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. Combustible liquid and vapor.
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. Clean up spills immediately, observing precautions in the Protective Equipment section.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Wash hands before eating. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. Avoid contact with skin and eyes. Avoid ingestion and inhalation. Keep away from heat and flame.
Storage:
Keep away from sources of ignition. 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 general or local explosion-proof ventilation to keep airborne levels to acceptable levels.
Exposure Limits CAS# 932-66-1: 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 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: Liquid
Color: clear very slight yellow
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 201 - 202 deg C @ 760.00mm Hg
Freezing/Melting Point: 73 deg C
Autoignition Temperature: Not available.
Flash Point: 65 deg C ( 149.00 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density: .9660g/cm3
Molecular Formula: C6H9COCH3
Molecular Weight: 124.18

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Ignition sources.
Incompatibilities with Other Materials:
Strong oxidizing agents, strong bases.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide.
Hazardous Polymerization: Has not been reported.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 932-66-1 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
1-Acetyl-1-cyclohexene - 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.
WGK (Water Danger/Protection)
CAS# 932-66-1: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 932-66-1 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 932-66-1 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

制备方法与用途

化学性质： 这是一种无色液体。其熔点为73℃，沸点在201-202℃（2.67kPa）之间，密度为0.966，折光率为1.49，闪点为65℃。

用途： 主要用于有机合成。

生产方法： 通过1-乙炔基环己醇在五氧化二磷存在下发生重排而制得。

反应信息

• 作为反应物：
  描述：

  乙酰基环已烯 在 C₃₂H₁₂BF₂₄^(1-)*C₃₄H₃₇IrN₂PS⁽¹⁺⁾ 、 氢气 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、2.0 MPa 条件下， 生成 乙酰基环己烷
  参考文献：
  名称：

  构象自由与限制对不对称氢化反应速率的影响：铱催化二烯酮的区域和对映选择性单氢化

  摘要：

  研究发现，不饱和羰基的构象对于铱催化氢化反应的反应性极其重要。这种反应性差异用于二烯的新型区域选择性氢化，其中(s)-顺式构型烯烃优先被氢化。在铱催化的烯烃加氢中，区域歧视推翻了取代模式中的传统反应顺序。

  DOI：

  10.1002/chem.202303406
• 作为产物：
  描述：

  2-乙酰基环己酮 在 四(三苯基膦)钯 三乙胺 、 lithium bromide 作用下， 以 四氢呋喃 、 乙二醇二甲醚 为溶剂， 反应 48.0h， 生成 乙酰基环已烯
  参考文献：
  名称：

  Palladium-catalyzed cross-coupling of .beta.-(methanesulfonyl)oxyenones with organostannanes

  摘要：

  beta-(Methanesulfonyl)oxy enones, derived from 1,3-diones, cross-couple with vinylstannanes in 50-80% yields when a substoichiometric amount of Pd(PPh3)4 and stoichiometric lithium bromide are used. Phenyltributylstannane affords low yields of cross-coupled product. Tetrabutyltin, tributyltin hydride, and ethynyltributyltin do not couple under the reaction conditions. The reaction is proposed to involve in situ formation of the beta-bromo enone, oxidative addition to the Pd(0) catalyst, transmetalation, and reductive elimination to afford cross-coupled products. The analogous enol phosphates undergo coupling in low yields, the major product resulting from regeneration of the 1,3-dione.

  DOI：

  10.1021/jo00004a028
• 作为试剂：
  描述：

  N-Chlorourethan 在 乙酰基环已烯 作用下， 以 二氯甲烷 为溶剂， 以11%的产率得到4-(1'-甲基-1'-硝基乙基)甲苯
  参考文献：
  名称：

  Lessard, Jean; Mondon, Martine; Touchard, Daniel, Canadian Journal of Chemistry, 1981, vol. 59, p. 431 - 450

  摘要：

  DOI：

文献信息

• Fe(0)-Mediated Synthesis of Tri- and Tetra-Substituted Olefins from Carbonyls:  An Environmentally Friendly Alternative to Cr(II)
  作者：J. R. Falck、Romain Bejot、Deb K. Barma、Anish Bandyopadhyay、Suju Joseph、Charles Mioskowski

  DOI：10.1021/jo061445u

  日期：2006.10.1

  carbonyls by activated polyhalides. In many instances, Fe(0) was equivalent or superior to Cr(II). Notably, Fe(0), but not Cr(II), proved compatible with a wide range of functionality, inter alia, unprotected phenol, aryl nitro, carboxylic acid, and alkyl nitrile. A surprising reversal of stereoselectivity for aldehydes versus ketones was observed using both metals. The resultant α-halo-α,β-unsaturated or α

  研究了Fe（0）作为Cr（II）的一种经济高效，环保的替代品，用于活化多卤化物对羰基进行烯化。在许多情况下，Fe（0）等于或优于Cr（II）。值得注意的是，事实证明，Fe（0）而不是Cr（II）与广泛的官能度兼容，尤其是与未保护的苯酚，芳基硝基，羧酸和烷基腈。使用两种金属均观察到醛相对于酮的立体选择性出乎意料的逆转。所得的α-卤代-α，β-不饱和或α，β-不饱和的羧酸，酯和腈是许多目标化合物中常见的结构元素，也是制备其他官能团的关键中间体。
• Highly chemoselective palladium-catalyzed conjugate reduction of .alpha.,.beta.-unsaturated carbonyl compounds with silicon hydrides and zinc chloride cocatalyst
  作者：Ehud. Keinan、Noam. Greenspoon

  DOI：10.1021/ja00283a029

  日期：1986.11

  experiments and 'H NMR studies, a catalytic cycle is postulated in which the first step involves reversible coordination of the palladium complex to the electron-deficient olefin and oxidative addition of silicon hydride to form a hydridopalladium olefin complex. Migratory insertion of hydride into the coordinated olefin produces an intermediate palladium enolate which, via reductive elimination, collapses back

  由可溶性钯催化剂、氢化硅烷和氯化锌组成的三组分体系能够有效地共轭还原α、不饱和酮和醛。最佳条件组包括二苯基硅烷作为最有效的氢化物供体，任何可溶于 0 或 I1 氧化态的钯配合物，当它被膦配体稳定时，以及作为最佳路易斯酸助催化剂的 ZnCl。该反应对于范围广泛的不饱和酮和醛非常普遍，并且对于这些迈克尔受体具有高度选择性，因为在这些条件下α，-不饱和羧酸衍生物的还原非常缓慢。当双氘代二苯基硅烷用于还原不饱和酮时，氘在底物的受阻较少的面上立体选择性地引入，并在 8 位上以区域选择性的方式引入。相反，当在痕量 D2O 存在下进行还原时，氘掺入发生在 a 位。在掺入氘的实验和 1 H NMR 研究的基础上，假定催化循环，其中第一步涉及钯配合物与缺电子烯烃的可逆配位和氢化硅的氧化加成以形成氢化钯烯烃配合物。氢化物迁移插入配位的烯烃产生中间体烯醇钯，通过还原消除，它塌缩回 Pd(0) 络合物和甲硅烷基烯
• Mild Chemoenzymatic Oxidation of Allylic <i>sec</i>-Alcohols. Application to Biocatalytic Stereoselective Redox Isomerizations
  作者：Lía Martínez-Montero、Vicente Gotor、Vicente Gotor-Fernández、Iván Lavandera

  DOI：10.1021/acscatal.7b03293

  日期：2018.3.2

  β-unsaturated ketones. Afterward, these compounds react with different commercially available ene-reductases to afford the corresponding saturated ketones. Remarkably, in the case of trisubstituted alkenes, the bioreduction reaction occurred with high stereoselectivity. Overall, a bienzymatic one-pot two-step sequential strategy has been described with respect to the synthesis of saturated ketones starting

  在温和的反应条件下，在水性介质中设计催化氧化方法，并使用分子氧作为最终电子受体，是传统氧化转化的合适替代方法。如果在同一分子内存在其他可氧化的官能团（如烯丙醇的情况），则这些方法尤为重要。本文我们应用漆酶组成的简单化学酶促系统从云芝和2,2,6,6-四甲基自由基（TEMPO），以氧化一系列外消旋烯丙基的秒-醇转化为相应的α，β-不饱和酮。然后，这些化合物与不同的市售烯还原酶反应，得到相应的饱和酮。显着地，在三取代的烯烃的情况下，生物还原反应以高的立体选择性发生。总的来说，关于从外消旋烯丙基醇开始的饱和酮的合成，已经描述了双酶一锅两步顺序策略，因此类似于先前在文献中报道的这些衍生物的金属催化的氧化还原异构化。
• Copper-Mediated Cross-Dehydrogenative Coupling of 2-Methylpyridine and 8-Methylquinoline with Methyl Ketones and Benzamides
  作者：Gadde Sathish Kumar、Joshua William Boyle、Ciputra Tejo、Philip Wai Hong Chan

  DOI：10.1002/asia.201501096

  日期：2016.2

  synthetic method to prepare (E)‐(pyridin‐2‐yl)enones and (E)‐(quinolin‐8‐yl)enones that relies on the respective copper(I)‐catalyzed formal cross‐dehydrogenative coupling (CDC) reaction of 2‐methylpyridine and 8‐methylquinoline with methyl ketones has been discovered. The mechanism was delineated to follow a pathway involving oxidation of the N‐heterocycle to its corresponding aldehyde adduct prior

  合成方法（E）-（吡啶-2-基）烯酮和（E）-（喹啉-8-基）烯酮依赖于各自的铜（I）催化的正式交叉脱氢偶联（CDC）反应发现了2-甲基吡啶和8-甲基喹啉与甲基酮的混合物。机理被描述为遵循在与甲基酮反应之前将N-杂环氧化成其相应的醛加合物的途径。铜介导的CDC策略在反应性上的多功能性和与底物有关的差异以其在合成N-（喹啉-8-基甲基）酰胺和N中的应用为例-（喹啉-8-甲基）苯胺加成物，将交叉偶联伙伴转换为苯甲酰胺或苯胺衍生物。
• <scp>Regio‐Divergent</scp> C—H Alkynylation with Janus Directing Strategy <i>via</i> Ir( <scp>III</scp> ) Catalysis
  作者：Xianwei Li、Guangxin Liang、Zhang‐Jie Shi

  DOI：10.1002/cjoc.202000204

  日期：2020.9

  Directing strategy has been extensively exploited to maintain activity and selectivity for the rapid access to functionalized molecules and pharmaceutical targets. However, ‘one‐to‐one’ activation model was usually achieved through traditional directing strategy. Herein, we achieved ‘one‐to‐two’ activation model by slight modification of simple and practical ketoxime and amide functionality. With judicious

  指导策略已得到广泛利用，以保持活性和选择性，以快速获得功能化分子和药物靶标。但是，“一对一”激活模型通常是通过传统的指导策略来实现的。在这里，我们通过对简单而实用的酮肟和酰胺功能进行一些修改，实现了“一对二”激活模型。通过明智地选择导向基团，实现了Csp 3 -H和Csp 2 -H键的炔基化反应，更重要的是，实现了脱氢的Csp 3 -H炔基化，从而实现了药物在区域上的分散后期修饰。

表征谱图