2,5-二氧代二环[2.2.2]辛烷-1,4-二甲酸二乙酯 | 843-59-4

• 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: 2,5-二氧代二环[2.2.2]辛烷-1,4-二甲酸二乙酯
• 中文别名: 1,1-双(4-羟苯基)环己烷；1,1'-双(4-羟基苯基)环己烷；1,1-二(4-羟基苯基)环己烷
• 英文名称: diethyl 2,5-dioxobicyclo[2.2.2]octane-1,4-dicarboxylate
• 英文别名: 2,5-Dioxo-bicyclo<2.2.2>octan-1,4-dicarbonsaeure-diethylester
• CAS: 843-59-4
• 化学式: C₁₄H₁₈O₆
• mdl: MFCD00213759
• 分子量: 282.293
• InChiKey: ZRMZQKZRZQCGJV-UHFFFAOYSA-N

物化性质

• 熔点：
  111 °C
• 沸点：
  393.0±42.0 °C(Predicted)
• 密度：
  1.320±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.714
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 危险品标志：
  Xi
• 海关编码：
  2918300090
• 安全说明：
  S24/25
• 危险性防范说明：
  P261,P280,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H332,H335
• 储存条件：
  室温且干燥

SDS

Name:	Diethyl 2 5-dioxobicyclo[2.2.2]octane-1 4-dicarboxylate 97% Material Safety Data Sheet
Synonym:
CAS:	843-59-4

Section 1 - Chemical Product MSDS Name:Diethyl 2 5-dioxobicyclo[2.2.2]octane-1 4-dicarboxylate 97% Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
843-59-4	Diethyl 2,5-dioxobicyclo[2.2.2]octane-	97%	unlisted

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

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Not available.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation. May be harmful if absorbed through the skin.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
May cause respiratory tract irritation. May be harmful if inhaled.
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.
Notes to Physician:
Treat symptomatically and supportively.

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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:
Vacuum or sweep up material and place into a suitable disposal 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# 843-59-4: 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: Solid
Color: cream
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 108 - 110 deg C
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C14H18O6
Molecular Weight: 282

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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.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide, acrid smoke and fumes.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 843-59-4 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Diethyl 2,5-dioxobicyclo[2.2.2]octane-1,4-dicarboxylate - 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: Not available.
Risk Phrases:
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 843-59-4: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 843-59-4 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 843-59-4 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：

  2,5-二氧代二环[2.2.2]辛烷-1,4-二甲酸二乙酯 在 吡啶 、 盐酸 、 lithium aluminium tetrahydride 、 镍 作用下， 以 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 氯仿 、 水 为溶剂， 反应 64.0h， 生成 4-<(Dimethylamino)methyl>-N,N,N-trimethylbicyclo<2.2.2>octane-1-methanaminium Trifluoromethanesulfonate
  参考文献：
  名称：

  Synthesis, characterization, and chemistry of bridgehead-functionalized bicyclo[2.2.2]octanes: reactions at neopentyl sites

  摘要：

  DOI：

  10.1021/jo00178a018
• 作为产物：
  描述：

  丁二酸二乙酯 在 sodium hydride 作用下， 以 乙二醇二甲醚 、 叔丁醇 为溶剂， 反应 38.0h， 生成 2,5-二氧代二环[2.2.2]辛烷-1,4-二甲酸二乙酯
  参考文献：
  名称：

  一种合成4-羧甲基环己烷羧酸的新方法

  摘要：

  本发明涉及化合物的合成方法。合成4‑羧甲基环己烷羧酸的新方法，第一步丁二酰丁二酸二乙酯的合成：以氢化钠、叔丁醇和丁二酸二乙酯为原料制得丁二酰丁二酸二乙酯；第二步中间体I的合成：以氢化钠、丁二酰丁二酸二乙酯和1，2‑二溴乙烷为原料制得得中间体I；第三步产品1和2的合成：在反应釜中加入中间体I、氢氧化钾、乙醇和水，回流反应得到中间体I的钾盐；另取反应器中加入上述钾盐、氢氧化钾、水合肼，乙二醇，升温回流反应，得到固体4‑羧甲基环己烷羧酸产品1，母液中大部分为产品2。本发明合成路线设计合理、简短，反应条件温合，易于操作，原料易得成本低，制得产品选择性好，产品分离容易，兼具高收率和高纯度的优点。

  公开号：

  CN101768074B

文献信息

• [EN] MODULATORS OF THE INTEGRATED STRESS PATHWAY<br/>[FR] MODULATEURS DE LA VOIE DE RÉPONSE INTÉGRÉE AU STRESS
  申请人：CALICO LIFE SCIENCES LLC

  公开号：WO2019090069A1

  公开（公告）日：2019-05-09

  Provided herein are compounds, compositions, and methods useful for the modulation of elF2B, for modulating the integrated stress response (ISR) and for treating related diseases; disorders and conditions.

  本文提供了用于调节elF2B、调节综合应激反应（ISR）以及治疗相关疾病、疾病和症状的化合物、组合物和方法。
• Total Synthesis of (+)-Daphmanidin E
  作者：Matthias E. Weiss、Erick M. Carreira

  DOI：10.1002/anie.201104681

  日期：2011.11.25

  From ring to ring: The first total synthesis of (+)‐daphmanidin E features rapid access to an enantiomerically pure bicyclo[2.2.2]octadione and elaboration around its periphery through the implementation of two Claisen rearrangements, the use of a copper/peptide complex for reagent‐controlled stereoselective conjugate addition, a diastereoselective hydroboration, and a cobalt‐catalyzed alkyl‐Heck cyclization

  从一个环到另一个环：（+）-daphmanidin E的第一个全合成具有快速获得对映体纯的双环[2.2.2]辛二酮并通过实施两个克莱森重排（使用铜/肽）围绕其外围进行修饰的功能。用于试剂控制的立体选择性共轭物加成，非对映选择性硼氢化和钴催化的烷基-Heck环化反应的复合物。
• A Practical and Cost-Effective Method for the Synthesis of Bicyclo[2.2.2]octane-1,4-dicarboxylic Acid
  作者：Arnaud Martel、Nicolas Le Marquer、Mathieu Laurent

  DOI：10.1055/s-0034-1380432

  日期：——

  the use of large amounts of Raney nickel to a solid-phase process, both the safety and cost are improved notably. A short and efficient synthesis of bicyclo[2.2.2]octane-1,4-dicarboxylic acid involving the formation of a semicarbazone is developed, and a reproducible protocol for the reduction of this semicarbazone is described. The use of microwaves significantly shortens the duration of the sequence

  摘要 开发了一种短而有效的涉及形成半卡巴zone的双环[2.2.2]辛烷-1,4-二羧酸的合成方法，并描述了还原该半卡巴zone的可再现方案。与先前描述的合成方法相比，微波的使用显着缩短了到二酸的序列的持续时间。另外，通过从大量阮内镍的使用转向固相工艺，安全性和成本均得到显着提高。 开发了一种短而有效的涉及形成半卡巴zone的双环[2.2.2]辛烷-1,4-二羧酸的合成方法，并描述了还原该半卡巴zone的可再现方案。与先前描述的合成方法相比，微波的使用显着缩短了到二酸的序列的持续时间。另外，通过从大量阮内镍的使用转向固相工艺，安全性和成本均得到显着提高。
• Unexpectedly Similar Charge Transfer Rates through Benzo-Annulated Bicyclo[2.2.2]octanes
  作者：Randall H. Goldsmith、Josh Vura-Weis、Amy M. Scott、Sachin Borkar、Ayusman Sen、Mark A. Ratner、Michael R. Wasielewski

  DOI：10.1021/ja8004623

  日期：2008.6.18

  A 4-(pyrrolidin-1-yl)phenyl electron donor and 10-cyanoanthracen-9-yl electron acceptor are attached via alkyne linkages to the bridgehead carbon atoms of bicyclo[2.2.2]octane and all three benzo-annulated bicyclo[2.2.2]octanes. The sigma-system of bicyclo[2.2.2]octane provides a scaffold having nearly constant bridge geometry on which to append multiple, weakly interacting benzo pi-bridges, so that

  4-(吡咯烷-1-基)苯基电子供体和10-氰基蒽-9-基电子受体通过炔键连接到双环[2.2.2]辛烷和所有三个苯并环化双环[2.2的桥头碳原子.2]辛烷。双环 [2.2.2] 辛烷的 sigma 系统提供了一个具有几乎恒定桥几何形状的支架，在该支架上可以附加多个弱相互作用的苯并 pi 桥，因此递增数量的 pi 桥对电子转移速率的影响可以被研究。令人惊讶的是，通过甲苯中的瞬态吸收光谱法测量的光致电荷转移率显示增加桥 pi 系统的数量没有任何好处，这表明通过 sigma 系统的主要传输。更令人惊讶的是，由于苯并环化，sigma 系统经历的杂交的显着变化似乎也对电荷转移速率没有影响。自然键轨道分析适用于 sigma 和 pi 通信路径。在 2-甲基四氢呋喃 (MTHF) 中获得的瞬态吸收光谱表明，苯并环化分子之间存在微小差异，这归因于溶剂化的变化。将 MTHF 溶液冷却至玻璃态后，所有电荷转移速
• Design, Synthesis, Radiolabeling, and in Vitro and in Vivo Evaluation of Bridgehead Iodinated Analogues of <i>N</i>-{2-[4-(2-Methoxyphenyl)piperazin-1-yl]ethyl}-<i>N</i>-(pyridin-2-yl)cyclohexanecarboxamide (WAY-100635) as Potential SPECT Ligands for the 5-HT_1A Receptor
  作者：Rana Al Hussainy、Joost Verbeek、Dion van der Born、Anton H. Braker、Josée E. Leysen、Remco J. Knol、Jan Booij、J. (Koos) D. M. Herscheid

  DOI：10.1021/jm1009956

  日期：2011.5.26

  Here we describe the design, synthesis, and pharmacological profile of 5-HT1A receptor ligands related to 1 (WAY-100635). The cyclohexyl moiety in 1 and its O-desmethylated analogue 3 were replaced by the bridgehead iodinated bridge-fused rings: adamantyl, cubyl, bicyclo[2.2.2]octyl, or bicyclo[2.2.1]heptyl. All analogues displayed a (sub)nanomolar affinity for the 5-HT1A receptor in vitro. Compounds

  在这里，我们描述与1（WAY-100635）相关的5-HT 1A受体配体的设计，合成和药理学特征。在环己基部分1和其O形脱甲基类似物3是由桥头碘化桥接稠环替代：金刚烷基，cubyl，双环[2.2.2]辛基，或二环[2.2.1]庚基。在体外，所有类似物均对5-HT 1A受体表现出（亚）纳摩尔亲和力。化合物6b和7b似乎对该受体具有比其他相关受体更高的选择性，并且可以很容易地用放射性碘123碘化。在人肝细胞中，[ 123 I] 6b表现出较低的酰胺水解倾向和稳定的碳碘键。[ 123 I] 6b和[ 123 I] 7b在大鼠中的生物分布表明，碳碘键在体内也很稳定。不幸的是，两种放射性配体的脑摄取和特异性均显着低于母体分子1。总之，设计的示踪剂不适用于SPECT成像。