(S)-2-(2-溴苯基)-4-叔丁基-4,5-二氢噁唑 | 154701-60-7

• 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: (S)-2-(2-溴苯基)-4-叔丁基-4,5-二氢噁唑
• 中文别名: (S)-2-(2-溴苯基)-4-(叔丁基)-4,5-二氢恶唑；(S)-2-(2-溴苯基)-4-叔丁基-4,5-二氢恶唑
• 英文名称: (S)-2-(2-bromophenyl)-4-(tert-butyl)-4,5-dihydrooxazole
• 英文别名: (4S)-2-(2-bromophenyl)-4-tert-butyl-4,5-dihydro-1,3-oxazole
• CAS: 154701-60-7
• 化学式: C₁₃H₁₆BrNO
• 分子量: 282.18
• InChiKey: NJQJYOLYDOCZGX-LLVKDONJSA-N

物化性质

• 熔点：
  47-48 °C
• 沸点：
  345.1±25.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2934999090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  存储条件：2-8°C，密封保存，并保持干燥。

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: (S)-2-(2-Bromophenyl)-4-t-butyl-4,5-dihydrooxazole
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: (S)-2-(2-Bromophenyl)-4-t-butyl-4,5-dihydrooxazole
CAS number: 154701-60-7

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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: C13H16BrNO
Molecular weight: 282.2

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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, hydrogen bromide.

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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：

  (S)-2-(2-溴苯基)-4-叔丁基-4,5-二氢噁唑 在 正丁基锂 、 sulfur 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.0h， 以61%的产率得到(4S)-4,5-dihydro-2-(2'-mercaptophenyl)-4-tert-butyloxazole
  参考文献：
  名称：

  手性巯基芳基-恶唑啉作为对映选择性铜催化格氏试剂与烯酮的1,4-加成中的配体

  摘要：

  已经合成了一系列手性对映体纯的巯基芳基-恶唑啉。衍生自这些配体的硫醇铜（I）络合物被证明是格氏试剂向环状烯酮1,4-加成的有效催化剂。对映选择性按顺序依次增加：环戊烯酮（16-37％ee）<环己烯酮（60-72％ee）<环庚烯酮（83-87％ee）。

  DOI：

  10.1016/s0040-4020(01)89379-0
• 作为产物：
  描述：

  L-叔亮氨酸 在 sodium tetrahydroborate 、 碘 、 sodium carbonate 、 甲基磺酰氯 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 33.75h， 生成 (S)-2-(2-溴苯基)-4-叔丁基-4,5-二氢噁唑
  参考文献：
  名称：

  Kraut, Michael R.; Mohr, Justin T.; Stoltz, Brian M., Organic Syntheses, 2009, vol. 86, p. 181 - 193

  摘要：

  DOI：

文献信息

• Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies
  作者：Douglas C. Behenna、Justin T. Mohr、Nathaniel H. Sherden、Smaranda C. Marinescu、Andrew M. Harned、Kousuke Tani、Masaki Seto、Sandy Ma、Zoltán Novák、Michael R. Krout、Ryan M. McFadden、Jennifer L. Roizen、John A. Enquist、David E. White、Samantha R. Levine、Krastina V. Petrova、Akihiko Iwashita、Scott C. Virgil、Brian M. Stoltz

  DOI：10.1002/chem.201003383

  日期：2011.12.9

  functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target‐directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner‐sphere mechanism involving binding of the prochiral

  在钯配合物与各种膦恶唑啉 (PHOX) 配体的存在下，通过不稳定的前手性烯醇化亲核试剂对烯丙基和炔丙基亲电子试剂进行新颖的对映选择性烷基化来获得 α-季酮。三类烯醇化物前体获得了优异的产率和高对映体过量：烯醇碳酸酯、烯醇硅烷和外消旋 β-酮酯。这些底物类别中的每一种在产率和对映选择性方面都具有几乎相同的效率。报道了催化剂的发现和开发、反应条件的优化、反应范围的探索以及在靶向合成中的应用。实验观察表明，这些烷基化反应通过一种不寻常的内球机制发生，涉及前手性烯醇化亲核试剂直接与钯中心结合。
• Preparation of Chiral Allenes through Pd-Catalyzed Intermolecular Hydroamination of Conjugated Enynes: Enantioselective Synthesis Enabled by Catalyst Design
  作者：Nathan J. Adamson、Haleh Jeddi、Steven J. Malcolmson

  DOI：10.1021/jacs.9b02637

  日期：2019.5.29

  surrogate to afford primary amines in a two-step/one-pot process. Examination of chiral catalysts revealed a high degree of reversibility in the C-N bond formation that negatively impacted enantioselectivity. Consequently, an electron-poor ferrocenyl-PHOX ligand was developed to enable efficient and enantioselective enyne hydroamination.

  在这项研究中，我们确定共轭烯炔在 Pd 催化下进行选择性 1,4-加氢胺化，以提供带有侧链烯丙基胺的手性丙二烯。在非对映选择性反应中，DPEphos 作为 Pd 的配体，几种伯胺和仲脂肪胺和芳基取代的胺与各种单取代和双取代的烯炔偶联。二苯甲酮亚胺作为氨替代物，在两步/一锅法中提供伯胺。手性催化剂的检查揭示了 CN 键形成的高度可逆性，这对对映选择性产生了负面影响。因此，开发了一种缺电子的二茂铁基-PHOX 配体，以实现高效和对映选择性的烯炔加氢胺化。
• Chiral Amido-Oxazolinate Zinc Complexes for Asymmetric Alternating Copolymerization of CO₂ and Cyclohexene Oxide
  作者：Srinivas Abbina、Guodong Du

  DOI：10.1021/om3006992

  日期：2012.11.12

  PhCO, R2 = (S)-iPr) exists as an amide oxygen-bridged dimer in the solid state with zinc in a distorted tetrahedral geometry. These complexes are viable initiators for alternating copolymerization of carbon dioxide (CO2) and cyclohexene oxide (CHO), yielding poly(cyclohexene carbonate) (PCHC) with good to high carbonate linkage and moderate molecular weights and PDI values, depending on the substituents

  一系列手性锌络合物的合成和表征（大号1A -米）ZNN（森达3）2（2A -米用）Ç 1 -对称酰氨基oxazolinate配体（HL 1A -米= 2-（2'--R已经描述了1 NH）苯基-4-R 2-恶唑啉。单晶X射线晶体学研究证实2a（R 1 = 2,6-二甲基苯基，R 2 =（S）-i Pr）和2d（R 1＝ 2，6-二甲基苯基，R 2＝（R）-i Bu）是三配位的单核络合物，并且2k（R 1＝ PhCO，R 2＝（S）-i Pr）作为酰胺氧桥存在。固态的二聚体，以及扭曲的四面体几何形状的锌。这些配合物是用于二氧化碳（CO 2）和环己烯氧化物（CHO）交替共聚，产生具有良好或高碳酸酯键以及适中分子量和PDI值的聚（环己烯碳酸酯）（PCHC）的可行引发剂，具体取决于取代基。产生的PCHCs通常全同立构，含有高达72％米通过-centered四分2H（R 1 = 2,6-二异丙基，R 2
• A Facile and Modular Synthesis of Phosphinooxazoline Ligands
  作者：Kousuke Tani、Douglas C. Behenna、Ryan M. McFadden、Brian M. Stoltz

  DOI：10.1021/ol070884s

  日期：2007.6.1

  iodide catalyzed phosphine/aryl halide coupling procedure of Buchwald et al. provides modular, robust, and scaleable access to phosphinooxazoline (PHOX) ligands. The advantages of this method are highlighted by the convenient synthesis of PHOX ligands with varied steric and electronic properties, which would be challenging to synthesize by other protocols.

  Buchwald等人的碘化铜（I）催化的膦/芳基卤化物偶联过程。提供了对膦氧恶唑啉（PHOX）配体的模块化，稳定且可扩展的访问方式。这种方法的优点是可以方便地合成具有变化的空间和电子特性的PHOX配体，这对其他方法很难合成。
• The synthesis of phosphine oxide-linked bis(oxazoline) ligands and their application in asymmetric allylic alkylation
  作者：Yu Jin、Da-Ming Du

  DOI：10.1016/j.tet.2012.02.078

  日期：2012.5

  The phosphine oxide-linked bis(oxazoline) ligands were designed and synthesized in two ways. One is the coupling of Grignard reagent derived from 2-(2-bromophenyl)oxazoline with phenylphosphonic dichloride, another route is the condensation of bis(2-formylphenyl)(phenyl)phosphine oxide with chiral amino alcohols followed by NBS oxidation. These new bis(oxazoline) ligands were applied in Pd-catalyzed

  设计和合成氧化膦连接的双（恶唑啉）配体。一种是衍生自2-（2-溴苯基）恶唑啉的格氏试剂与苯基二氯膦偶联，另一种途径是将双（2-甲酰基苯基）（苯基）膦氧化物与手性氨基醇缩合，然后进行NBS氧化。这些新的双（恶唑啉）配体用于钯催化的不对称烯丙基烷基化反应中，并用二苯基取代的配体（高达95％ee）获得了良好的收率和对映选择性。