(’±)-2-苯基环庚酮 | 14996-78-2

• 物质功能分类: 生物 - 生化试剂盒
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (’±)-2-苯基环庚酮
• 中文别名: ('±)-2-苯基环庚酮；(+/-)-2-苯基环庚酮
• 英文名称: 2-phenylcycloheptanone
• 英文别名: 2-phenylcycloheptan-1-one
• CAS: 14996-78-2
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: PVHNKILPLXXDDZ-UHFFFAOYSA-N

物化性质

• 熔点：
  21-23 °C
• 沸点：
  136-138 °C (4 mmHg)
• 密度：
  1.038 g/mL at 25 °C(lit.)
• 闪点：
  113 °C
• 稳定性/保质期：
  遵照规定使用和储存，则不会发生分解。

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 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
• 海关编码：
  2914399090

SDS

Name:	(+/-)-2-Phenylcycloheptanone 99% Material Safety Data Sheet
Synonym:	None
CAS:	14996-78-2

Section 1 - Chemical Product MSDS Name:(+/-)-2-Phenylcycloheptanone 99% Material Safety Data Sheet
Synonym:None

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
14996-78-2	(+/-)-2-Phenylcycloheptanone	99%	239-083-5

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 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:
Avoid runoff into storm sewers and ditches which lead to waterways.
Clean up spills immediately, observing precautions in the Protective Equipment section. Sweep up or absorb material, then place into a suitable clean, dry, closed container for disposal. Avoid generating dusty conditions. Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use with adequate ventilation. 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# 14996-78-2: 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:
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: Liquid above room te
Color: moist yellow cyrstals - pale yellow
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 136 - 138 deg C @ 4.00mm Hg
Freezing/Melting Point: 21 - 23 deg C
Autoignition Temperature: Not available.
Flash Point: > 110 deg C (> 230.00 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density: 1.038
Molecular Formula: C13H16O
Molecular Weight: 188.27

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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, excess heat.
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# 14996-78-2 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(+/-)-2-Phenylcycloheptanone - 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# 14996-78-2: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 14996-78-2 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 14996-78-2 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

生产方法

1. 制法：

   • N-苄基氨基甲酸乙酯（3）的制备： 在装有搅拌器、两个滴液漏斗的12L反应瓶中，加入苄基胺（2）1Kg（9.3mol）、500mL冰水以及1.5kg碎冰，并将体系置于冰水浴冷却。在搅拌下缓慢滴加氯甲酸乙酯525g（4.83mol），保持温度在10～15℃，约1～1.5小时加完。随后加入500mL水和1Kg碎冰，再继续滴加氯甲酸乙酯525g（4.83mol）。与此同时，从另一滴液漏斗中以相同速度滴加由氢氧化钠400g溶于1.3L水中配成的溶液。反应温度保持在10～15℃，共约2.5～3小时加完后继续搅拌30分钟。过滤、冷水洗涤并空气中干燥，得到白色固体（3）1.6kg，收率为96%，熔点45～47℃。

   • N-亚硝基-N-苄基氨基甲酸乙酯（4）的制备： 在装有温度计、2L滴液漏斗和通气导管的12L反应瓶中，加入化合物（3）360g（2mol）、2L乙醚以及由1.2kg亚硝酸钠（17.4mol）溶解于2L水中的溶液。无需搅拌，将体系置于水浴冷至20℃。随后滴加由1L浓硝酸和1L水配成的硝酸水溶液，此时水层会变为持久绿色。保持此温度继续滴加，约5小时完成，期间温度维持在20～25℃。滴完后继续反应30分钟。分出乙醚层，并用10%碳酸钾溶液洗涤至无二氧化碳气体逸出。使用无水碳酸钾干燥并以水浴温度低于50℃减压蒸除乙醚，得到浅橙色油状液体（4）400～415g，收率为95%～99%。

   • 2-苯基环庚酮（1）的制备： 在装有搅拌器、回流冷凝器和滴液漏斗的反应瓶中，加入新蒸馏的环己酮392g（4mol）、粉碎的碳酸钾30g以及400mL无水甲醇。在搅拌下缓慢滴加化合物（4）415g（2mol），确保反应液温度维持在25℃，约1.5小时滴完。将黑红色混合物室温放置直至无氮气释放为止（约24～28小时）。过滤出固体物质，并通过蒸汽浴减压蒸馏除去低沸点组分，剩余物进行分馏。收集到的产物为纯度41%～47%、折射率n²⁰ 1.5395～1.5398的无色针状结晶体，熔点为21～23℃。

   [1]

反应信息

• 作为反应物：
  描述：

  (’±)-2-苯基环庚酮 在 玫红酸 、 水 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 乙腈 为溶剂， 反应 48.0h， 以37%的产率得到6-苄酰基己酸
  参考文献：
  名称：

  可见光驱动、铜催化的环烷酮需氧氧化裂解

  摘要：

  已经提出了一种可见光驱动的、铜催化的环烷酮有氧氧化裂解。具有不同环大小和各种α-取代基的各种环烷酮反应良好，以中等至良好的产率得到远端酮酸或二羧酸。

  DOI：

  10.1021/acs.joc.1c00708
• 作为产物：
  描述：

  苯甲醛腙 在 草酰氯 、 二甲基亚砜 、 三乙胺 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 1.75h， 生成 (’±)-2-苯基环庚酮
  参考文献：
  名称：

  An Enantioselective Synthesis of 2-Aryl Cycloalkanones by Sc-Catalyzed Carbon Insertion

  摘要：

  Current methods for asymmetric alpha-arylation require blocking groups to prevent reaction at the alpha'-carbon, basic conditions that promote racemization, or multistep synthesis. This work records the first catalytic enantioselective examples of the diazoalkane-carbonyl homologation reaction. Medium ring 2-aryl ketones are prepared in one step in up to 98:2 er and 99% yield from the unsubstituted lower homologue by Sc-catalyzed aryldiazomethyl insertion with simple bis- and tris(oxazoline) ligands.

  DOI：

  10.1021/ol200402m

文献信息

• GaCl₃-Catalyzed Skeletal Rearrangement of α,α,α-Trisubstituted Aldehydes
  作者：Masayuki Oshita、Takao Okazaki、Kouichi Ohe、Naoto Chatani

  DOI：10.1021/ol047640h

  日期：2005.1.1

  [Reaction: see text] GaCl3 is found to be a superior catalyst for the skeletal rearrangement of alpha,alpha,alpha-trisubstituted aldehydes to ketones. The rearrangement can proceed smoothly in the presence of a catalytic amount of GaCl3, and even substrates having no heteroatoms alpha to the carbonyl group or without steric strains can be used. Double activation of a carbonyl group by two molecules

  [反应：见正文]发现GaCl3是α，α，α-三取代醛向酮的骨架重排的优良催化剂。在催化量的GaCl 3的存在下，重排可以顺利进行，甚至可以使用不具有羰基α杂原子或没有空间应变的底物。在实验数据和DFT研究的基础上，通过两个GaCl3分子对羰基的双重活化得到了支持。
• An activated catalyst RhH(PPh3)4-dppe- Me2S2 for α-methylthiolaton of α-phenyl ketones
  作者：Mieko Arisawa、Fumihiko Toriyama、Masahiko Yamaguchi

  DOI：10.1002/hc.20650

  日期：——

  In the presence of catalytic amounts of RhH(PPh3)4, 1,2-bis(diphenylphosphino)ethane (dppe), and dimethyl disulfide, cyclic and acyclic α-phenyl ketones reacted with p-cyano-α-methylthioa- cetophenone giving α-methylthio-α-phenylketones. The activated catalyst containing dimethyl disulfide was effective for the α-methylthiolation reaction of these less reactive substrates. © 2010 Wiley Periodicals

  在催化量的 RhH(PPh3)4、1,2-双(二苯基膦)乙烷 (dppe) 和二甲基二硫化物存在下，环状和非环状 α-苯基酮与对氰基-α-甲硫基苯乙酮反应生成 α -甲硫基-α-苯基酮。含有二甲基二硫化物的活化催化剂对这些反应性较低的底物的 α-甲基硫醇化反应是有效的。© 2010 Wiley Periodicals, Inc. 杂原子化学 22:18–23, 2011; 在 wileyonlinelibrary.com 上在线查看这篇文章。DOI 10.1002/hc.20650
• Method for the Direct Enantioselective Synthesis of Chiral Primary α-Amino Ketones by Catalytic α-Amination
  作者：Yixin Han、E. J. Corey

  DOI：10.1021/acs.orglett.8b03733

  日期：2019.1.4

  A useful catalytic enantioselective approach has been developed for the synthesis of chiral ketamine analogs using Rh(II)-catalyzed amination of triisopropylsilyl enol ethers to form α-amino ketones with O-(4-nitrophenyl)hydroxylamine as nitrogen donor in 81–91% ee.

  已开发出一种有用的催化对映选择性方法，用于合成手性氯胺酮类似物，该化合物使用Rh（II）催化的三异丙基甲硅烷基烯醇醚的胺化反应，以O-（4-硝基苯基）羟胺为氮供体，形成α-氨基酮，占81-91％ ee。
• Oxidation of Nonactivated Anilines to Generate <i>N</i>-Aryl Nitrenoids
  作者：Tianning Deng、Wrickban Mazumdar、Russell L. Ford、Navendu Jana、Ragda Izar、Donald J. Wink、Tom G. Driver

  DOI：10.1021/jacs.9b13599

  日期：2020.3.4

  and selective C-NAr and C-C bond formation to yield spirocyclic- or bicyclic 3H-indoles or benzazepinones. Our experiments demonstrate the breadth of these oxidative processes, uncover underlying fundamental elements that control selectivity and demonstrate how the distinct reactivi-ty patterns embedded in N-aryl nitrenoid reactive intermediates can enable access to functionalized 3H-indoles or benzazepinones

  已开发出 2-取代苯胺的低温无保护基氧化以生成亲电 N-芳基氮烯中间体，该中间体可以参与 C-NAr 键的形成以构建功能化的 N-杂环。将 2-取代苯胺暴露于 PIFA 和三氟乙酸或 10 mol% 的 Sc(OTf)3 会触发类氮烯类化合物的形成，然后形成生产性和选择性的 C-NAr 和 CC 键，以产生螺环或双环 3H-吲哚或苯并氮杂酮。我们的实验证明了这些氧化过程的广度，揭示了控制选择性的潜在基本要素，并证明了嵌入在 N-芳基氮烯类反应中间体中的独特反应模式如何能够获得功能化的 3H-吲哚或苯并氮杂酮。
• I(III)-Catalyzed Oxidative Cyclization–Migration Tandem Reactions of Unactivated Anilines
  作者：Tianning Deng、Emily Shi、Elana Thomas、Tom G. Driver

  DOI：10.1021/acs.orglett.0c03497

  日期：2020.11.20

  An I(III)-catalyzed oxidative cyclization–migration tandem reaction using Selectfluor as the oxidant was developed that converts unactivated anilines into 3H-indoles is reported herein. The reaction requires as little as 1 mol % of the iodocatalyst and is mild, tolerating pyridine and thiophene functional groups, and the dependence of the diastereoselectivity of the process on the identity of the iodoarene

  本文报道了使用 Selectfluor 作为氧化剂的 I(III) 催化氧化环化-迁移串联反应，将未活化的苯胺转化为 3 H-吲哚。该反应只需要 1 mol% 的碘催化剂，并且是温和的，可耐受吡啶和噻吩官能团，并且该过程的非对映选择性依赖于碘芳烃或碘代烷烃预催化剂的特性表明该催化剂存在于立体化学反应中。确定 C-N 键形成步骤。