2,2’-联吡啶-4,4’-二甲酸乙酯 | 1762-42-1

• 物质功能分类: 医药中间体 - 杂环化合物 - 吡啶类化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 中文名称: 2,2’-联吡啶-4,4’-二甲酸乙酯
• 中文别名: 2,2'-联吡啶-4,4'-二甲酸乙酯
• 英文名称: 4,4'-bis(ethoxycarbonyl)-2,2'-bipyridine
• 英文别名: diethyl [2,2'-bipyridine]-4,4'-dicarboxylate；ethyl 2-(4-ethoxycarbonylpyridin-2-yl)pyridine-4-carboxylate
• CAS: 1762-42-1
• 化学式: C₁₆H₁₆N₂O₄
• 分子量: 300.314
• InChiKey: CTXJVXIVHPUFIP-UHFFFAOYSA-N

物化性质

• 熔点：
  160-161 °C(Solv: ethanol (64-17-5))
• 沸点：
  460.6±45.0 °C(Predicted)
• 密度：
  1.201±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  78.4
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 海关编码：
  2933399090
• 危险性防范说明：
  P302+P352,P305+P351+P338
• 危险性描述：
  H315,H319,H335
• 储存条件：
  存储条件：2-8℃，干燥，密封。

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 4,4’-Bis(ethoxycarbonly)-2,2’-bipyridine
Synonyms:

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Section 2. Hazards identification
Harmful by inhalation, in contact with skin, and if swallowed.

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Section 3. Composition/information on ingredients.
Ingredient name: 4,4’-Bis(ethoxycarbonly)-2,2’-bipyridine
CAS number: 1762-42-1

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Section 4. First aid measures
Skin contact: Immediately wash skin with copious amounts of water for at least 15 minutes while removing
contaminated clothing and shoes. If irritation persists, seek medical attention.
Eye contact: Immediately wash skin with copious amounts of water for at least 15 minutes. Assure adequate
flushing of the eyes by separating the eyelids with fingers. If irritation persists, seek medical
attention.
Inhalation: Remove to fresh air. In severe cases or if symptoms persist, seek medical attention.
Ingestion: Wash out mouth with copious amounts of water for at least 15 minutes. Seek medical attention.

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Section 5. Fire fighting measures
In the event of a fire involving this material, alone or in combination with other materials, use dry
powder or carbon dioxide extinguishers. Protective clothing and self-contained breathing apparatus
should be worn.

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Section 6. Accidental release measures
Personal precautions: Wear suitable personal protective equipment which performs satisfactorily and meets local/state/national
standards.
Respiratory precaution: Wear approved mask/respirator
Hand precaution: Wear suitable gloves/gauntlets
Skin protection: Wear suitable protective clothing
Eye protection: Wear suitable eye protection
Methods for cleaning up: Mix with sand or similar inert absorbent material, sweep up and keep in a tightly closed container
for disposal. See section 12.
Environmental precautions: Do not allow material to enter drains or water courses.

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Section 7. Handling and storage
Handling: This product should be handled only by, or under the close supervision of, those properly qualified
in the handling and use of potentially hazardous chemicals, who should take into account the fire,
health and chemical hazard data given on this sheet.
Store in closed vessels.
Storage:

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Section 8. Exposure Controls / Personal protection
Engineering Controls: Use only in a chemical fume hood.
Personal protective equipment: Wear laboratory clothing, chemical-resistant gloves and safety goggles.
General hydiene measures: Wash thoroughly after handling. Wash contaminated clothing before reuse.

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Section 9. Physical and chemical properties
Appearance: Not specified
Boiling point: No data
No data
Melting point:
Flash point: No data
Density: No data
Molecular formula: C16H16N2O4
Molecular weight: 300.3

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Section 10. Stability and reactivity
Conditions to avoid: Heat, flames and sparks.
Materials to avoid: Oxidizing agents.
Possible hazardous combustion products: Carbon monoxide, nitrogen oxides.

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Section 11. Toxicological information
No data.

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Section 12. Ecological information
No data.

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Section 13. Disposal consideration
Arrange disposal as special waste, by licensed disposal company, in consultation with local waste
disposal authority, in accordance with national and regional regulations.

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Section 14. Transportation information
Non-harzardous for air and ground transportation.

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Section 15. Regulatory information
No chemicals in this material are subject to the reporting requirements of SARA Title III, Section
302, or have known CAS numbers that exceed the threshold reporting levels established by SARA
Title III, Section 313.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  2,2’-联吡啶-4,4’-二甲酸乙酯 在 过氧乙酸 作用下， 以 溶剂黄146 为溶剂， 反应 72.0h， 以95%的产率得到4,4'-bis(ethoxycarbonyl)-2,2'-bipyridine N,N'-dioxide
  参考文献：
  名称：

  Functionalized tetradentate ligands for Ru-sensitized solar cells

  摘要：

  Syntheses of 6,6'-bis(1-H-benzirnidazol-2-yl)-4,4'-bis(methoxycarbonyl)-2,2'-bipyridine and a series of new quaterpyridines as functionalized tetradentate ligands is described. A molecular engineering was developed allowing different solubilities, pi -systems or grafting modes. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00801-8
• 作为产物：
  描述：

  2,2'-联吡啶-4,4'-二甲酸 在 氯化亚砜 、 三乙胺 作用下， 反应 17.0h， 生成 2,2’-联吡啶-4,4’-二甲酸乙酯
  参考文献：
  名称：

  [Cp * Rh（取代的联吡啶）]配合物对NADH再生的结构与催化活性之间的相关性

  摘要：

  一系列水溶性半三明治[Cp * Rh III（N ^ N）Cl] +（Cp * =五甲基环戊二烯，N ^ N取代的2,2'-联吡啶）配合物，在2周围含给电子取代基合成了2'-联吡啶基配体，并充分表征了烟酰胺辅酶（NAD +）的区域选择性还原。详细研究了取代基的位置效应对催化剂的结构，电化学和催化性能的影响。取代的联吡啶Cp * Rh III配合物的催化效率与其氧化还原电位成反比。5,5'-取代的联吡啶Cp * Rh III还原电位最低的复合物，能最有效地再生NADH，周转频率为1100 h –1。关于中间体生成的详细动力学研究为这种催化循环提供了有价值的机理见解，并有助于指导相应催化剂的未来设计策略。

  DOI：

  10.1021/acs.inorgchem.6b02474
• 作为试剂：
  描述：

  对羟基联苯 在 三氟甲磺酸三甲基硅酯 、 bis(acetoxy)iodylbenzene 、 2,2’-联吡啶-4,4’-二甲酸乙酯 作用下， 以 氘代氯仿 为溶剂， 反应 0.25h， 以59%的产率得到4-苯基-1,2-苯醌
  参考文献：
  名称：

  缺电子酚脱芳构化为邻醌：双齿氮连接碘 (V) 试剂。

  摘要：

  尽管其用途广泛，邻醌的合成仍然是一个重大挑战，特别是获得缺电子衍生物仍然是一个未解决的问题。这里报道了第一个通过酚类直接氧化合成缺电子邻醌的通用方法。该反应是通过一种新型双齿氮连接碘 (V) 试剂实现的，这是一类以前未开发的化合物，我们将其称为 Bi( N )-HVI。该反应非常普遍，并且对于邻位异构体和对位异构体具有优异的区域选择性。对邻醌产物的官能化进行了检查，从而实现了儿茶酚的简单一锅合成，以及多种杂原子亲核试剂的掺入。该方法代表了 Bi( N )-HVI的首次合成应用，并展示了它们作为进一步开发高反应性、高度可调的 I(V) 试剂的平台的潜力。

  DOI：

  10.1002/anie.201909868

文献信息

• Synthesis and Characterization of a Series of Bis-homoleptic Cycloruthenates with Terdentate Ligands as a Family of Panchromatic Dyes
  作者：Thomas W. Rees、JinFeng Liao、Alessandro Sinopoli、Louise Male、Giuseppe Calogero、Basile F.E. Curchod、Etienne Baranoff

  DOI：10.1021/acs.inorgchem.7b01412

  日期：2017.8.21

  A series of six homoleptic bis-cyclometalated ruthenium complexes, Ru(N^N^C)2, is reported where N^N^C is a 6-(2,4-difluoro-3-R3-phenyl)-4-R2-4′-R1-2,2′-bipyridine with R3 = −H or −CF3 and R2 and R1 = −COOEt or −CF3. An effective synthesis of the ligands and the complexes is described. The UV–visible absorption studies demonstrate that these complexes are panchromatic dyes absorbing up to 900 nm. Importantly

  报道了一系列六个均一的双环金属化钌络合物Ru（N ^ N ^ C）2，其中N ^ N ^ C是6-（2,4-二氟-3-R 3-苯基）-4- R 2 -4'-R 1 -2,2'-联吡啶，其中R 3 = -H或-CF 3且R 2和R 1 = -COOEt或-CF 3。描述了配体和配合物的有效合成。紫外可见吸收研究表明，这些络合物是吸收高达900 nm的全色染料。重要的是，吸收的开始仅取决于金属化苯基上的取代，而整个光谱的吸收强度是苯基和联吡啶部分上的取代基的函数。在电化学中观察到相同的趋势，因为氧化还原间隙仅取决于金属化苯基上的取代，而氧化和还原电势是苯基和联吡啶部分上的取代基的函数。用作染料敏化太阳能电池敏化剂的初步测试表明，染料上的锚定基团数量对器件效率有重要影响。
• Dehydrogenative Synthesis of 2,2′‐Bipyridyls through Regioselective Pyridine Dimerization
  作者：Shuya Yamada、Takeshi Kaneda、Philip Steib、Kei Murakami、Kenichiro Itami

  DOI：10.1002/anie.201814701

  日期：2019.6.17

  reactions. The most streamlined approach for the synthesis of 2,2′‐bipyridyls is the dehydrogenative dimerization of unfunctionalized pyridine. Herein, we report on the palladium‐catalyzed dehydrogenative synthesis of 2,2′‐bipyridyl derivatives. The Pd catalysis effectively works with an AgI salt as the oxidant in the presence of pivalic acid. A variety of pyridines regioselectively react at the C2‐positions

  2,2'-联吡啶已被用作金属催化反应中必不可少的配体。合成2,2'-联吡啶的最简化方法是未官能化吡啶的脱氢二聚作用。在这里，我们报道了钯催化的2,2'-联吡啶衍生物的脱氢合成。在新戊酸存在下，Pd催化有效地以Ag I盐为氧化剂。多种吡啶在C2位置发生区域选择性反应。这种二聚方法适用于具有挑战性的底物，例如空间受阻的3-取代的吡啶，其中吡啶在C2位上发生区域选择性反应。该反应使简明的合成3,3'-di取代-2,2'-联吡啶作为一种不发达的配体。
• Molecularly Engineered Ru(II) Sensitizers Compatible with Cobalt(II/III) Redox Mediators for Dye-Sensitized Solar Cells
  作者：Kuan-Lin Wu、Aron J. Huckaba、John N. Clifford、Ya-Wen Yang、Aswani Yella、Emilio Palomares、Michael Grätzel、Yun Chi、Mohammad Khaja Nazeeruddin

  DOI：10.1021/acs.inorgchem.6b00427

  日期：2016.8.1

  Thiocyanate-free isoquinazolylpyrazolate Ru(II) complexes were synthesized and applied as sensitizers in dye-sensitized solar cells (DSCs). Unlike most other successful Ru sensitizers, Co-based electrolytes were used, and resulting record efficiency of 9.53% was obtained under simulated sunlight with an intensity of 100 mW cm–2. Specifically, dye 51-57dht.1 and an electrolyte based on Co(phen)3 led

  合成了无硫氰酸盐的异喹唑基吡唑啉化物Ru（II）配合物，并将其用作染料敏化太阳能电池（DSC）中的敏化剂。与大多数其他成功的Ru敏化剂不同，使用了Co基电解质，在模拟的日光强度为100 mW cm –2的情况下，记录效率为9.53％。具体来说，染料51-57dht.1和基于Co（phen）3的电解质导致J SC的测量值为13.89 mA cm –2，V OC900 mV的FF和0.762的FF产生9.53％的效率。器件性能的改善是通过在异喹啉亚基上包含2-己基噻吩单元，以及延长吡唑酸酯螯合基团上的全氟烷基链来实现的，这在使用Co基电解质时起到了增加光吸收和降低重组效果的作用。如本研究所示，带有空间要求的配体的Ru（II）敏化剂可以成功地利用重要的Co电解质和高性能。
• Synthesis of Asymmetrically Substituted Terpyridines by Palladium‐Catalyzed Direct CH Arylation of Pyridine <i>N</i> ‐Oxides
  作者：Sasa Duric、Fanni D. Sypaseuth、Santina Hoof、Emma Svensson、C. Christoph Tzschucke

  DOI：10.1002/chem.201302118

  日期：2013.12.16

  The synthesis of asymmetrically substituted 2,2′:6′,2′′‐terpyridines is reported. First, palladium‐catalyzed CH arylation of pyridine N‐oxides with substituted bromopyridines gave 2,2′‐bipyridine N‐oxides, which were further arylated in a second step to form 2,2′:6′,2′′‐terpyridine N‐oxides. Yields of up to 77 % were obtained with N‐oxides bearing an electron‐withdrawing ethoxycarbonyl substituent

  报道了不对称取代的2,2'：6'，2''-叔吡啶的合成。首先，钯催化的C ^  ħ吡啶芳基化Ñ -oxides与取代的溴吡啶，得到2,2'-联吡啶Ñ -oxides，其中在第二步骤中进一步芳基化以形成2,2'：6'，2'' -特吡啶N-氧化物。使用在4位带有吸电子乙氧基羰基取代基的N氧化物，收率高达77％。带有P（t Bu）3或P（邻甲苯基）3的Pd（OAc）2被用作催化剂。衍生自Pd（OAc）2的环金属配合物这些膦也有效。以K 3 PO 4为碱比K 2 CO 3可获得更好的结果。随后用H 2和Pd / C作为催化剂进行脱氧，得到了接近定量收率的不对称取代的2,2'：6'，2''-吡啶。与已知的交叉偶联方法相比，该反应序列显着减少了所需的步骤数，因此可以方便且可扩展地使用取代的吡啶。
• Bathochromic Shifts in Rhenium Carbonyl Dyes Induced through Destabilization of Occupied Orbitals
  作者：Daniel A. Kurtz、Kelsey R. Brereton、Kevin P. Ruoff、Hui Min Tang、Greg A. N. Felton、Alexander J. M. Miller、Jillian L. Dempsey

  DOI：10.1021/acs.inorgchem.8b00360

  日期：2018.5.7

  A series of rhenium diimine carbonyl complexes was prepared and characterized in order to examine the influence of axial ligands on electronic structure. Systematic substitution of the axial carbonyl and acetonitrile ligands of [Re(deeb)(CO)3(NCCH3)]+ (deeb = 4,4′-diethylester-2,2′-bipyridine) with trimethylphosphine and chloride, respectively, gives rise to red-shifted absorbance features. These bathochromic

  制备了一系列of二亚胺羰基配合物并进行了表征，以研究轴向配体对电子结构的影响。[Re（deeb）（CO）3（NCCH 3）] +（deeb = 4,4'-diethylester-2,2'- bipyridine）的轴向羰基和乙腈配体分别被三甲基膦和氯化物系统取代出现红移的吸光度特征。这些红移是由于参与金属到配体的电荷转移跃迁的占据的d轨道不稳定而引起的。时变密度泛函理论确定了每个跃迁中涉及的轨道，并为配体取代引起的轨道能量变化提供了支持。