4-哌啶苯羧酸甲酯 | 10338-58-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 中文名称: 4-哌啶苯羧酸甲酯
• 英文名称: methyl 4-(piperidin-1-yl)benzoate
• 英文别名: methyl 4-(1-piperidinyl)benzoate；methyl 4-piperidin-1-ylbenzoate
• CAS: 10338-58-6
• 化学式: C₁₃H₁₇NO₂
• mdl: MFCD08444024
• 分子量: 219.283
• InChiKey: DGHBETAWIXVCFO-UHFFFAOYSA-N

物化性质

• 熔点：
  94-96°C
• 沸点：
  354.7±25.0 °C(Predicted)
• 密度：
  1.098±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.461
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 危险等级：
  IRRITANT
• 危险品标志：
  Xi
• 海关编码：
  2933399090

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: Methyl 4-piperidinobenzenecarboxylate
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: Methyl 4-piperidinobenzenecarboxylate
CAS number: 10338-58-6

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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: C13H17NO2
Molecular weight: 219.3

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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：

  4-哌啶苯羧酸甲酯 在 sodium cyanide 、 硝基甲烷 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 水 为溶剂， 反应 3.0h， 以76%的产率得到methyl 3-nitro-4-(piperidin-1-yl)benzoate
  参考文献：
  名称：

  PIFA促进的C（sp 2）–H或C（sp 3）–H的溶剂控制的选择性功能化：通过CH 3 NO 2的C–N键裂解，硝化或在水中加氧进行硝化

  摘要：

  描述了由[双（三氟乙酰氧基）碘]苯（PIFA）介导的新型硝化作用（通过C（sp 3）–N破坏/ C（sp 2）–N与CH 3 NO 2形成）。的NO 2从CH转印3 NO 2到基板的芳族基团是可能的溶剂，的NaX，和氧化剂的仔细选择。此外，溶剂控制的C（SP 2）-H官能化可转移到一个α-C（SP 3）-H官能的α-C（SP的（氰化或氧合）3）-H的环胺。

  DOI：

  10.1021/acs.orglett.9b00751
• 作为产物：
  描述：

  4-碘苯甲酸甲酯 在 potassium fluoride 、 对甲苯磺酸一水合物 、 间氯过氧苯甲酸 作用下， 以 水 、 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 24.58h， 生成 4-哌啶苯羧酸甲酯
  参考文献：
  名称：

  芳胺的无金属合成：超越亲核芳香取代

  摘要：

  描述了一种温和且无金属的C-N偶联方法，该方法使用二芳基碘鎓盐亲电试剂和脂肪族仲胺亲核试剂。该反应导致碘鎓部分直接ipso取代，主要使用不对称的芳基（TMP）碘鎓盐。此外，可以容纳目前对经典的无金属方法构成挑战的芳烃取代基和取代形式，并且此处使用的脂环族胺亲核试剂在其他当代的无金属CN偶联反应中是前所未有的。

  DOI：

  10.1002/anie.201610086

文献信息

• Silver-catalyzed intermolecular amination of fluoroarenes
  作者：Yu Wang、Chenlong Wei、Ruyun Tang、Haosheng Zhan、Jing Lin、Zhenhua Liu、Weihua Tao、Zhongxue Fang

  DOI：10.1039/c8ob01749b

  日期：——

  A novel highly selective Ag-catalyzed intermolecular amination of fluoroarenes has been developed. This transformation starts from readily available 4-carbonyl fluorobenzene and NaN3 or other nitrogen-source, via amination followed by C–F bond cleavage, thus affording the desired 4-carbonyl arylamine products under mild conditions. The reaction is accelerated using a small amount of water. This pathway

  已经开发了新颖的高选择性的Ag催化的氟代芳烃的分子间胺化。这种转变从容易获得的4-羰基氟苯和NaN 3或其他氮源开始，通过胺化，然后进行CF键断裂，从而在温和的条件下提供所需的4-羰基芳胺产品。用少量水促进反应。该途径不同于先前报道的自由基胺化反应。
• Chan–Evans–Lam Amination of Boronic Acid Pinacol (BPin) Esters: Overcoming the Aryl Amine Problem
  作者：Julien C. Vantourout、Robert P. Law、Albert Isidro-Llobet、Stephen J. Atkinson、Allan J. B. Watson

  DOI：10.1021/acs.joc.6b00466

  日期：2016.5.6

  The Chan–Evans–Lam reaction is a valuable C–N bond forming process. However, aryl boronic acid pinacol (BPin) ester reagents can be difficult coupling partners that often deliver low yields, in particular in reactions with aryl amines. Herein, we report effective reaction conditions for the Chan–Evans–Lam amination of aryl BPin with alkyl and aryl amines. A mixed MeCN/EtOH solvent system was found

  Chan–Evans–Lam反应是有价值的C–N键形成过程。但是，芳基硼酸频哪醇（BPin）酯试剂可能很难成为偶合剂，常常导致收率低，特别是在与芳基胺反应时。在此，我们报告了烷基-芳基胺与芳基BPin的Chan-Evans-Lam胺化反应的有效反应条件。发现混合的MeCN / EtOH溶剂系统可以使用芳基胺形成有效的C–N键，而烷基胺的偶联则不需要EtOH。
• Synthesis of β-Methylsulfonylated N-Heterocycles from Saturated Cyclic Amines with the Insertion of Sulfur Dioxide
  作者：Yan He、Jintao Yang、Qimeng Liu、Xinying Zhang、Xuesen Fan

  DOI：10.1021/acs.joc.0c02368

  日期：2020.12.4

  An efficient synthesis of β-methylsulfonylated N-heterocycles via FeCl3-catalyzed C(sp3)–H dehydrogenation and C(sp2)–H methylsulfonylation of inactivated cyclic amines with the promotion and participation of inorganic sodium metabisulfite and dicumyl peroxide (DCP) has been developed. Notably, bifunctional DCP acted not only as an oxidant to promote the dehydrogenation but also as a methyl radical

  FeCl 3催化的灭活环胺的C（sp 3）-H脱氢和C（sp 2）-H甲基磺酰化，并通过无机亚硫酸氢钠和过氧化二枯基的促进和参与，有效合成β-甲基磺酰化N-杂环。） 已经被开发出来。明显地，双官能DCP不仅充当促进脱氢的氧化剂，而且充当参与砜形成的甲基。通过该方案，以简便的一锅法获得了许多β-甲基磺酰化的四氢吡啶，四氢氮杂和吡咯。
• Solvent-Regulated Coupling of 2-Alkynylbenzaldehydes with Cyclic Amines: Selective Synthesis of Fused N-Heterocycles and Functionalized Naphthalene Derivatives
  作者：Yan He、Zhi Zheng、Qimeng Liu、Xinying Zhang、Xuesen Fan

  DOI：10.1021/acs.orglett.0c03442

  日期：2020.11.20

  synthesis of 1,2,3,4-tetrahydrobenzo[g]quinoline derivatives through PdCl2-catalyzed, TBHP-promoted, and toluene-mediated dehydrogenation/[4+2] cycloaddition of saturated cyclic amines with 2-alkynylbenzaldehydes was developed. On the contrary, when the reaction medium was changed from toluene to DMSO/H2O, another class of important compounds, naphthyl chain amines, formed via a dehydrogenation–intermolecular

  通过PdCl 2催化，TBHP促进和甲苯介导的饱和环胺的脱氢/ [4 + 2]与2-炔基苯甲醛的环加成反应，成功合成了1,2,3,4-四氢苯并[ g ]喹啉衍生物。相反，当反应介质从甲苯变为DMSO / H 2 O时，通过脱氢-分子间缩合-C-N键裂解-分子间缩合途径形成的另一类重要化合物萘链胺选择性好。
• General Paradigm in Photoredox Nickel‐Catalyzed Cross‐Coupling Allows for Light‐Free Access to Reactivity
  作者：Rui Sun、Yangzhong Qin、Daniel G. Nocera

  DOI：10.1002/anie.201916398

  日期：2020.6.8

  Self‐sustained NiI/III cycles are established as a potentially general paradigm in photoredox Ni‐catalyzed carbon–heteroatom cross‐coupling reactions through a strategy that allows us to recapitulate photoredox‐like reactivity in the absence of light across a wide range of substrates in the amination, etherification, and esterification of aryl bromides, the latter of which has remained, hitherto, elusive

  自我维持的Ni I / III循环被确立为光氧化还原Ni催化的碳-杂原子交叉偶联反应中的潜在一般范式，其策略是使我们能够在没有光的情况下在各种各样的底物上重现类似光氧化还原的反应性。在芳基溴化物的胺化，醚化和酯化反应中，迄今为止，后者在热镍催化下仍然难以捉摸。此外，在没有光照的情况下酯化的可及性尤其显着，因为先前在光氧化还原条件下对该转化进行的机理研究一致地调用了能量转移介导的途径。