(S,S)-(+)-2,5-双(甲氧基甲基)吡咯烷 | 93621-94-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 中文名称: (S,S)-(+)-2,5-双(甲氧基甲基)吡咯烷
• 英文名称: (2S,5S)-2,5-bis(methoxymethyl)pyrrolidine
• 英文别名: (S,S)-2,5-bis(methoxymethyl)pyrrolidine；(2S,5S)-bis(methoxymethyl)pyrrolidine；(S,S)-(+)-Bis(methoxymethyl)pyrrolidine
• CAS: 93621-94-4
• 化学式: C₈H₁₇NO₂
• 分子量: 159.228
• InChiKey: HDXYTIYVVNJFLU-YUMQZZPRSA-N

物化性质

• 沸点：
  110-115 °C(lit.)
• 密度：
  0.971 g/mL at 20 °C(lit.)
• 稳定性/保质期：
  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  30.5
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

• 储存条件：
  存储于阴凉干燥处。

SDS

Name:	(S S)-(+)-2 5-Bis(Methoxymethyl)Pyrrolidine 96% Material Safety Data Sheet
Synonym:	None Known
CAS:	93621-94-4

Section 1 - Chemical Product MSDS Name:(S S)-(+)-2 5-Bis(Methoxymethyl)Pyrrolidine 96% Material Safety Data Sheet
Synonym:None Known

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
93621-94-4	(S,S)-(+)-2,5-Bis(Methoxymethyl)Pyrrol	96%	unlisted

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

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
May cause irritation of the digestive tract. The toxicological properties of this substance have not been fully investigated.
Inhalation:
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: 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. Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:

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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. Vapors may be heavier than air. They can spread along the ground and collect in low or confined areas. Runoff from fire control or dilution water may cause pollution.
Extinguishing Media:
Use agent most appropriate to extinguish fire. Use water spray, dry chemical, carbon dioxide, or appropriate foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. Avoid runoff into storm sewers and ditches which lead to waterways. Clean up spills immediately, observing precautions in the Protective Equipment section. Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation.
Storage:
Keep container closed when not in use. Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances.

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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# 93621-94-4: 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 minimize contact with skin.
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: Clear liquid
Color: clear faint yellow
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: Not available.
Autoignition Temperature: Not applicable.
Flash Point: Not applicable.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C8H17NO2
Molecular Weight: 159.23

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials, excess heat, strong oxidants.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Nitrogen oxides, carbon monoxide, irritating and toxic fumes and gases, carbon dioxide, nitrogen.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 93621-94-4 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(S,S)-(+)-2,5-Bis(Methoxymethyl)Pyrrolidine - 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: Not available.
Risk Phrases:
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 93621-94-4: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 93621-94-4 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 93621-94-4 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：

  (S,S)-(+)-2,5-双(甲氧基甲基)吡咯烷 在 calcium(II) trifluoromethanesulfonate 作用下， 以 氯仿 、 乙腈 为溶剂， 反应 75.0h， 生成 1-[(S)-2-hydroxy-2-phenylethyl]-1-methyl-[(2S,5S)-2,5-bis(methoxymethyl)]pyrrolidinium trifluoromethanesulfonate
  参考文献：
  名称：

  C2-Symmetric Pyrrolidine-Based Chiral Ammonium Salts as a Phase-Transfer Catalyst

  摘要：

  Chiral pyrrolidinium salts having substituents at the alpha, alpha' positions were synthesized to develop a chiral phase-transfer catalyst which have more simplified structure. The catalytic function of these synthesized catalysts was evaluated using asymmetric benzylation of N-(diphenylmethylene)glycine tert-butyl ester, and alpha,alpha'-disubstituded pyrrolidinium salts having an alkyl chain with a hydroxyl group at a chiral center were found to afford moderate enantioselectivity.

  DOI：

  10.3987/com-11-12254
• 作为产物：
  描述：

  (2S,5S)-1-<(S)-1-Phenylethyl>-2,5-bis(methoxymethyl)pyrrolidine 在 palladium dihydroxide 氢气 作用下， 以 甲醇 为溶剂， 以87%的产率得到(S,S)-(+)-2,5-双(甲氧基甲基)吡咯烷
  参考文献：
  名称：

  A Convenient Synthesis of Enantiomeric Pairs of 2,5-Disubstituted Pyrrolidines of C₂-Symmetry

  摘要：

  通过使用 (-)-1-苯基乙胺作为手性辅助剂，从二甲基阳离子-2,5-二溴己二酸酯制备了三种二叠体异构体的 2,5-双(甲氧基羧基)吡咯烷衍生物，并通过结晶和涉及立体选择性水解的色谱分离进行分离。收回顺式异构体并使其异构化为反式异构体。从每种反式异构体出发，通过一种简短的路线合成了具有 C2 对称性的光学活性 2,5-二取代的 [2,5-双(甲氧基甲基)和 2,5-双(甲氧基甲氧基甲基)] 吡咯烷。

  DOI：

  10.1055/s-1993-25852

文献信息

• Substituted pyridines having antiangiogenic activity
  申请人：——

  公开号：US20040014744A1

  公开（公告）日：2004-01-22

  Compounds having the formula 1 are angiogenesis inhibitors. Also disclosed are compositions containing the compounds, methods of making the compounds, and methods of treatment using the compounds.

  具有以下化学式的化合物是抑制血管生成的抑制剂。还公开了含有这些化合物的组合物、制备这些化合物的方法以及使用这些化合物进行治疗的方法。
• Zwitterionic Aza-Claisen Rearrangements Controlled by Pyrrolidine Auxiliaries - Useful Key Steps in Convergent Enantioselective Syntheses
  作者：Nora M. Friedemann、Alice Härter、Sebastian Brandes、Steffen Groß、Dorothea Gerlach、Winfried Münch、Dieter Schollmeyer、Udo Nubbemeyer

  DOI：10.1002/ejoc.201200073

  日期：2012.4

  substituents served as efficient auxiliaries in diastereoselective zwitterionic ketene aza-Claisen rearrangements. Palladium-catalysed N-allylation starting from optically active proline and prolinol derivatives, as well as from (2S,5S)-2,5-dimethoxymethylpyrrolidine, gave various allylamines bearing trisubstituted olefin moieties. Treatment with complex carboxylic acid fluorides in the presence of trimethylaluminium

  手性吡咯烷取代基在非对映选择性两性离子烯酮氮杂-克莱森重排中充当有效助剂。从光学活性脯氨酸和脯氨醇衍生物以及 (2S,5S)-2,5-二甲氧基甲基吡咯烷开始，钯催化的 N-烯丙基化得到各种带有三取代烯烃部分的烯丙胺。在三甲基铝诱导活化乙烯酮加成到氮和随后的 [3,3] σ 重排的情况下，用复合羧酸氟化物处理，得到具有优异简单非对映选择性和高达 11:1 辅助诱导非对映体比率的 γ,δ-不饱和酰胺. 吡咯烷酰胺的裂解是通过碘内酯化实现的，可选择回收辅助吡咯烷。通过合适的酰胺和内酯的 X 射线和 NOEDS 分析确定重排和碘环化的立体化学结果。总的来说，两种对映异构体都可以选择性地获得。以这种方式形成的确定构型的旋光酰胺和内酯应可用作会聚甾体天然和药学上重要的产物合成中的关键中间体。
• Thio-Claisen Rearrangement Used in Preparing Anti-β-Functionalized γ,δ-Unsaturated Amino Acids: Scope and Limitations
  作者：Zhihua Liu、Sukeshi J. Mehta、Kwang-Soo Lee、Bryan Grossman、Hongchang Qu、Xuyuan Gu、Gary S. Nichol、Victor J. Hruby

  DOI：10.1021/jo201753q

  日期：2012.2.3

  of our most recent study using the thio-Claisen rearrangement for the synthesis of anti-β-functionalized γ,δ-unsaturated amino acids. Investigations on scope, limitations, chemoselectivities and stereoselectivities regarding an FeBr3-catalyzed allylation strategy and a thio-enolate dianion formation strategy for asymmetric thio-Claisen rearrangement are documented. An explanation of the chirality crossover

  多功能化氨基酸，尤其是不饱和氨基酸，是肽化学中重要的、要求苛刻的构建模块。在这里，我们总结了我们最近使用硫代-克莱森重排合成抗 β 功能化 γ,δ-不饱和氨基酸的研究。记录了关于 FeBr 3催化烯丙基化策略和不对称硫代-克莱森重排的硫代烯醇二价阴离子形成策略的范围、局限性、化学选择性和立体选择性的研究。提出了对 Eschenmoser-Claisen 重排和 thio-Claisen 重排之间观察到的手性交叉的解释。新型光学活性N α首次制备了具有生物学意义的官能团的保护氨基酸。
• [EN] DUAL NK1/NK3 ANTAGONISTS FOR TREATING SCHIZOPHRENIA<br/>[FR] ANTAGONISTES DOUBLES DES RECEPTEURS NK1/NK3 POUR TRAITER LA SCHIZOPHRENIE
  申请人：HOFFMANN LA ROCHE

  公开号：WO2005002577A1

  公开（公告）日：2005-01-13

  The use of compounds of the general formula wherein the substituents are as described in claim 1 or pharmaceutically active acid-addition salts thereof for the preparation of medicaments for the treatment of schizophrenia.

  使用一般式化合物，其中取代基如权利要求1中所述，或其药用活性酸盐，用于制备治疗精神分裂症的药物。
• Benzylic C–H isocyanation/amine coupling sequence enabling high-throughput synthesis of pharmaceutically relevant ureas
  作者：Sung-Eun Suh、Leah E. Nkulu、Shishi Lin、Shane W. Krska、Shannon S. Stahl

  DOI：10.1039/d1sc02049h

  日期：——

  selectivity and good functional group tolerance, and uses commercially available catalyst components and reagents [CuOAc, 2,2′-bis(oxazoline) ligand, (trimethylsilyl)isocyanate, and N-fluorobenzenesulfonimide]. The isocyanate products may be used without isolation or purification in a subsequent coupling step with primary and secondary amines to afford hundreds of diverse ureas. These results provide

  C(sp 3 )–H 功能化方法为药物化学提供了理想的合成平台；然而，这些方法通常受到实际限制的限制。本研究概述了一种 C(sp 3 )–H 异氰化方案，该方案能够以高通量形式合成多种药学相关的苄基脲。操作简单的 C-H 异氰化方法显示出高位点选择性和良好的官能团耐受性，并使用市售的催化剂组分和试剂 [CuOAc、2,2'-双（恶唑啉）配体、（三甲基甲硅烷基）异氰酸酯和N-氟苯磺酰亚胺]。异氰酸酯产物无需分离或纯化即可用于后续与伯胺和仲胺的偶联步骤，以提供数百种不同的脲。这些结果为在药物发现中实施 C-H 功能化/交叉偶联提供了模板。