(3R-CIS)-7A-甲基-3-苯基四水吡啶-[2,1-B]唑-5(6H)-酮 | 137869-70-6

• 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: (3R-CIS)-7A-甲基-3-苯基四水吡啶-[2,1-B]唑-5(6H)-酮
• 中文别名: (3R-cis)-7a-甲基-3-苯基四水吡啶-[2,1-b]噁唑-5(6H)-酮
• 英文名称: trans-(3R,7aS)-7a-methyl-3-phenyl-tetrahydro-pyrrolo[2,1-b]oxazol-5-one
• 英文别名: (3R,7aS)-7a-methyl-3-phenyl-tetrahydro-pyrrolo[2,1-b]oxazol-5-one；(3R,7aS)-7a-methyl-3-phenyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one；(3R,7aS)-7a-methyl-3-phenyl-2,3,6,7-tetrahydropyrrolo[2,1-b][1,3]oxazol-5-one
• CAS: 137869-70-6
• 化学式: C₁₃H₁₅NO₂
• 分子量: 217.268
• InChiKey: JVEHIYMWPAQEIR-AAEUAGOBSA-N

物化性质

• 熔点：
  125 °C
• 沸点：
  357.82°C (rough estimate)
• 密度：
  1.0960 (rough estimate)
• 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)：
  1.3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xn
• 安全说明：
  S36/37
• 危险类别码：
  R20/21/22
• 储存条件：
  存放于阴凉干燥处。

SDS

Name:	(3R-cis)-7a-Methyl-3-phenyltetrahydropyrrolo-[2 1-b]oxazol-5(6H)-one Material Safety Data Sheet
Synonym:	None Known
CAS:	137869-70-6

Section 1 - Chemical Product MSDS Name:(3R-cis)-7a-Methyl-3-phenyltetrahydropyrrolo-[2 1-b]oxazol-5(6H)-one Material Safety Data Sheet
Synonym:None Known

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
137869-70-6	(3R-cis)-7a-Methyl-3-phenyltetrahydrop	97%	unlisted

Hazard Symbols: XN
Risk Phrases: 20/21/22

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Harmful by inhalation, in contact with skin and if swallowed.The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation. Harmful if absorbed through the skin.
Ingestion:
Harmful if swallowed. May cause irritation of the digestive tract.
The toxicological properties of this substance have not been fully investigated.
Inhalation:
Harmful if inhaled. 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: In case of contact, immediately flush eyes with plenty of water for at least 15 minutes. Get medical aid.
Skin:
In case of contact, flush skin with plenty of water. Remove contaminated clothing and shoes. Get medical aid if irritation develops and persists. Wash clothing before reuse.
Ingestion:
If swallowed, do not induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. Get medical aid.
Inhalation:
If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
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. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.
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. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use with adequate ventilation.
Minimize dust generation and accumulation. Avoid breathing dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing.
Keep container tightly closed. Avoid ingestion and inhalation.
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:
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# 137869-70-6: 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:
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: white to off-white
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 130 - 131 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: C13H15NO2
Molecular Weight: 217.1105

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Light, dust generation.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, oxides of nitrogen, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 137869-70-6 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(3R-cis)-7a-Methyl-3-phenyltetrahydropyrrolo-[2,1-b]oxazol-5(6H)-one - 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: XN
Risk Phrases:
R 20/21/22 Harmful by inhalation, in contact with
skin and if swallowed.
Safety Phrases:
S 36/37 Wear suitable protective clothing and
gloves.
WGK (Water Danger/Protection)
CAS# 137869-70-6: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 137869-70-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 137869-70-6 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：

  (3R-CIS)-7A-甲基-3-苯基四水吡啶-[2,1-B]唑-5(6H)-酮 在 氨 、 四氯化钛 、 lithium 、 potassium hydride 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 (R)-2-Allyl-2-methyl-5-oxo-pyrrolidine-1-carboxylic acid benzyl ester
  参考文献：
  名称：

  Asymmetric synthesis of .gamma.,.gamma.-dialkyl-.gamma.-aminobutyric acid analogs and 2,2-disubstituted pyrrolidines. Control of stereochemistry in aminal ring opening by varying the extent of allylic 1,3 strain

  摘要：

  DOI：

  10.1021/ja00026a026
• 作为产物：
  描述：

  2-甲基呋喃 在 氧气 、 rose bengal 、 三氟乙酸 作用下， 以 甲醇 为溶剂， 反应 5.13h， 生成 (3R-CIS)-7A-甲基-3-苯基四水吡啶-[2,1-B]唑-5(6H)-酮
  参考文献：
  名称：

  呋喃对迈耶斯双环内酰胺的多功能合成：单重态氧引发的反应级联

  摘要：

  所有在一个：迈尔斯双环的内酰胺以高收率合成从使用涉及一锅单线-氧-引发的反应级联中的新的和有效的方法呋喃（参见方案; TFA =三氟乙酸）。该方法具有由于容易获得了广泛范围呋喃与各种取代基中的广泛的合成潜力。

  DOI：

  10.1002/anie.201204419

文献信息

• Water-based conditions for the microscale parallel synthesis of bicyclic lactams
  作者：Sandra Malaquin、Mouhamad Jida、Justin Courtin、Guillaume Laconde、Nicolas Willand、Benoit Deprez、Rebecca Deprez-Poulain

  DOI：10.1016/j.tetlet.2012.11.082

  日期：2013.2

  a mixture of ethanol and water yields the expected lactams, we exemplified the reaction and procedure with the preparation of a library of 80 members. Our synthesis scheme is validated for synthesis scales from 1 to 100 mg. Therefore, it can be used both to produce rapidly test samples for HTS as well as to prepare intermediates for the synthesis of more elaborated nature-inspired compounds.

  我们报告了有效的小型化条件，以准备用于筛选的双环内酰胺阵列。溶剂的性质通常是反应性的重要因素。在小的合成规模下，当需要自动移液装置时，溶剂的物理性质（例如表面张力和蒸气压）也变得非常重要。在证明试剂在水中或乙醇和水的混合物中完全蒸发会产生预期的内酰胺后，我们以制备80个成员的文库为例，说明了反应和过程。我们的合成方案经验证可用于1到100 mg的合成规模。因此，它既可用于生产HTS的快速测试样品，又可用于制备中间体，用于合成更多复杂的，受自然界启发的化合物。
• Unsaturation of ketones, nitriles and lactams with methyl phenylsulfinate
  作者：James E. Resek、A.I. Meyers

  DOI：10.1016/0040-4039(95)01461-p

  日期：1995.9

  An improved synthesis of methyl phenylsulfinate 2 by treatment of diphenyl disulfide with bromine in the presence of methanol has been developed. Use of this reagent in the preparation of α,β-unsaturated ketones, nitriles and lactams is described.

  已经开发了通过在甲醇存在下用溴处理二苯基二硫化物来改进苯基亚磺酸甲酯2的合成。描述了该试剂在制备α，β-不饱和酮，腈和内酰胺中的用途。
• Solvent-free microwave-assisted Meyers’ lactamization
  作者：Mouhamad Jida、Rebecca Deprez-Poulain、Sandra Malaquin、Pascal Roussel、Francine Agbossou-Niedercorn、Benoit Deprez、Guillaume Laconde

  DOI：10.1039/b924111f

  日期：——

  Microwave solvent-free conditions developed for Meyers’ lactamization, a typical bielectrophile-binucleophile reaction that produces quaternary centers in a stereoselective manner, give access to Meyers’ chiral lactams in good yield and high diastereoselectivity in short times.

  所开发的无需溶剂的微波条件下，Meyers内酰胺化反应得以实现，这是一种典型的双亲电-双亲核反应，能够以立体选择性的方式生成季碳中心。这种方法能够在短时间内以高产率和高对映选择性地获得Meyers手性内酰胺。
• Meyers’ bicyclic lactam formation under mild and highly stereoselective conditions
  作者：Maël Penhoat、Stephane Leleu、Georges Dupas、Cyril Papamicaël、Francis Marsais、Vincent Levacher

  DOI：10.1016/j.tetlet.2005.09.154

  日期：2005.11

  New and mild conditions to prepare chiral bicyclic lactams in high yields and high diastereoselectivities are reported herein. This approach based on the activation of the carboxylic acid by means of Mukaiyama’s reagent is an excellent alternative to Meyers’ dehydrating conditions and provide the main advantage to work at lower temperature (40 °C). Higher diastereoselectivity was obtained with 5,7-bicyclic

  本文报道了以高产率和高非对映选择性制备手性双环内酰胺的新的温和条件。这种基于Mukaiyama试剂对羧酸进行活化的方法是Meyers脱水条件的极佳替代方法，并提供了在较低温度（40°C）下工作的主要优势。用5,7-双环内酰胺获得更高的非对映选择性（标准脱水条件下，de = 82％，而不是44％）。
• Enantiospecific Formal Total Synthesis of (+)-Fawcettimine
  作者：Michael E. Jung、Jonah J. Chang

  DOI：10.1021/ol1009762

  日期：2010.7.2

  cyclopropyl diester 27 generated the hydrindanone 28 with complete stereocontrol. Thermal decarbomethoxylation of 28 gave the monoester 29, a key intermediate in Heathcock’s synthesis, thereby completing a formal total synthesis of (+)-fawcettimine 1. The analogous cyclization of 33, the diastereomer of 27, afforded the diastereomeric diester 34, thereby demonstrating that the cyclization process is diastereospecific

  甲硅烷基烯醇醚对活化的环丙基二酯27的非对映特异性攻击产生了具有完全立体控制的氢化丹酮28。28的热脱碳甲氧基化作用使单酯29成为希思考克合成中的关键中间体，从而完成了（+）-fawcettimine 1的正式全合成。33的非对映异构体的类似环化为27，得到非对映二酯34，从而证明环化过程是非对映特异性的。