1,1-双(三甲基甲硅烷基氧基)-2-三甲基甲硅烷基乙烯 | 65946-59-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 中文名称: 1,1-双(三甲基甲硅烷基氧基)-2-三甲基甲硅烷基乙烯
• 英文名称: C,O,O-tris(trimethylsilyl)ketene acetal
• 英文别名: Trimethyl-(2-trimethylsilyl-1-trimethylsilyloxyethenoxy)silane
• CAS: 65946-59-0
• 化学式: C₁₁H₂₈O₂Si₃
• mdl: MFCD01632563
• 分子量: 276.599
• InChiKey: LIAZNEMTJSEKDC-UHFFFAOYSA-N

物化性质

• 沸点：
  86 °C10 mm Hg(lit.)
• 密度：
  0.848 g/mL at 25 °C(lit.)
• 闪点：
  106 °F
• 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)：
  5.29
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.818
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险品运输编号：
  UN 1993 3/PG 2
• 储存条件：
  存放于0至6°C的阴凉干燥处。

SDS

Name:	1 1-BIS(TRIMETHYLSILYLOXY)-2-TRIMETHYLSILYLETHENE Material Safety Data Sheet
Synonym:
CAS:	65946-59-0

Section 1 - Chemical Product MSDS Name:1 1-BIS(TRIMETHYLSILYLOXY)-2-TRIMETHYLSILYLETHENE Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
65946-59-0	1,1-BIS(TRIMETHYLSILYLOXY)-2-TRIMETHYL		unlisted

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

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Not available.
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.
Chronic:
Not available.

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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.
Ingestion:
Get medical aid. Wash mouth out with 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.
Extinguishing Media:
Use extinguishing media most appropriate for the surrounding fire.

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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.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Store in a tightly closed container. Keep refrigerated. (Store below 4C/39F.)

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 65946-59-0: Personal Protective Equipment Eyes: Not available.
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: Liquid
Color: colorless
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 available.
Flash Point: 106 deg F ( 41.11 deg C)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula:
Molecular Weight: 276.60

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 65946-59-0 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
1,1-BIS(TRIMETHYLSILYLOXY)-2-TRIMETHYLSILYLETHENE - 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
No information available.
IMO
No information available.
RID/ADR
No information available.

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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# 65946-59-0: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 65946-59-0 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 65946-59-0 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：

  1,1-双(三甲基甲硅烷基氧基)-2-三甲基甲硅烷基乙烯 在 三乙烯二胺 、 三氯化磷 作用下， 反应 3.25h， 生成
  参考文献：
  名称：

  Ko, Y. Y. C. Yeung Lam; Cosquer, P.; Pellon, P., Phosphorus and Sulfur and the Related Elements, 1987, vol. 30, p. 523 - 526

  摘要：

  DOI：
• 作为产物：
  描述：

  三甲基硅乙酸酯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 0.5h， 生成 1,1-双(三甲基甲硅烷基氧基)-2-三甲基甲硅烷基乙烯
  参考文献：
  名称：

  Two-Carbon Homologation of Aldehydes via Silyl Ketene Acetals:  A New Stereoselective Approach to (E)-Alkenoic Acids

  摘要：

  Aldehydes are converted into (E)-alpha,beta-unsaturated carboxylic acids using C,O,O-tris(trimethylsilyl)-ketene acetal 1. This organosilicon reagent is easily generated from trimethylsilyl acetate, LDA, and chlorotrimethylsilane. The effectiveness of the reaction has been explored for a large variety of aldehydes with Lewis acids and fluorides as catalysts.

  DOI：

  10.1021/jo980853y

文献信息

• Transition-metal catalyzed synthesis of δ-hydroxy-γ-lactones from bis(trimethylsilyl) ketene acetals and allylic acetates via γ-unsaturated carboxylic acids. Comments on the formation of α-cyclopropyl carboxylic acids
  作者：Henri Rudler、Paul Harris、Andrée Parlier、Frédéric Cantagrel、Bernard Denise、Moncef Bellassoued、Jacqueline Vaissermann

  DOI：10.1016/s0022-328x(00)00905-0

  日期：2001.4

  Bis(trimethylsilyl)ketene acetals react with allylic acetates in the presence of Pd(0) complexes to give γ-unsaturated carboxylic acids together with α-cyclopropyl carboxylic acids. The unsaturated acids can be converted catalytically to δ-hydroxy-γ-lactones by the H2O2/MTO system (methyltrioxorhenium) and to butenolides by Pd(II) catalyzed intramolecular cyclization reactions. The structure of two

  双（三甲基甲硅烷基）乙烯酮缩醛在Pd（0）配合物的存在下与乙酸烯丙酯反应生成γ-不饱和羧酸与α-环丙基羧酸。H 2 O 2 / MTO系统（甲基三氧or）可将不饱和酸催化转化为δ-羟基-γ-内酯，而Pd（II）催化的分子内环化反应则可将其转化为丁烯化物。这些内酯中的两个的结构已经通过X射线分析确定。将讨论环丙酸的形成机理。
• Stereoselective synthesis of (E)- α, β -unsaturated acids from C,O,O-tri (trimethylsilyl) ketene acetal and aldehydes.
  作者：Moncef Bellassoued、Marcel Gaudemar

  DOI：10.1016/s0040-4039(00)80544-4

  日期：1988.1

  Aldehydes are converted into (E)- α, β -unsaturated carboxylic acids by means of C,O,O-tri(trimethylsilyl) ketene acetal and a catalytic amount of ZnBr2.

  醛借助C，O，O-三（三甲基甲硅烷基）乙烯酮缩醛和催化量的ZnBr 2转化为（E）-α，β-不饱和羧酸。
• Two-carbon homologation of ketones via sily ketene acetals: Synthesis of α,β-unsaturated acids and α-trimethylsilyl δ-ketoacids
  作者：Moncef Bellassoued、Sinda Mouelhi、Pierre Fromentin、Aurélien Gonzalez

  DOI：10.1016/j.jorganchem.2005.01.049

  日期：2005.4

  O-tris(trimethylsilyl)ketene acetal 1 with saturated, cyclic and aromatic ketones 2 proceeds smoothly in the presence of titanium chloride to give (E)-α,β-unsaturated carboxylic acids 3 with fairly good stereoselectivity. With α,β-unsaturated ketones 4, α-trimethylsilyl δ-ketoacids 5 (syn + anti) are obtained according to Michael-type 1,4 addition. These diastereoisomers are separated and the configurations

  C，O，O-三（三甲基甲硅烷基）乙烯酮缩醛1与饱和，环状和芳族酮2的反应在氯化钛存在下平稳进行，得到具有相当好的立体选择性的（E）-α，β-不饱和羧酸3。对于α，β-不饱和酮4，根据迈克尔型1，4加成获得α-三甲基甲硅烷基δ-酮酸5（syn  +  anti）。分离这些非对映异构体，并通过X射线分子分析获得5a的构型。
• Bis(trimethylsilyl)ketene Acetals as C,O-Dinucleophiles: One-Pot Formation of Polycyclic γ- and δ-Lactones from Pyridines and Pyrazines
  作者：Henri Rudler、Bernard Denise、Yiming Xu、Andrée Parlier、Jacqueline Vaissermann

  DOI：10.1002/ejoc.200500162

  日期：2005.9

  interaction with both nitrogen atoms, of polycyclic γ-lactones, a reaction formally reminiscent of the double nucleophilic addition of the same ketene acetals to (arene)tricarbonylchromium complexes. Most of the new structures were assigned through X-ray crystal structure determinations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  双（三甲基甲硅烷基）烯酮缩醛在化学计量量的氯甲酸甲酯存在下与吡啶、喹啉和异喹啉反应，以令人满意的产率得到相应的二氢吡啶-、二氢喹啉-和二氢异喹啉-取代的羧酸。加成反应的区域选择性和非对映选择性以及旋转异构体的存在或不存在都已确定。分离出的酸与过酸反应，通过分子内反应生成 β-羟基-δ-内酯。类似的内酯化也可以直接从氮杂芳族化合物与硅胶、碘或溴的一锅反应中产生。在这些情况下，产生了δ-内酯或β-卤代-δ-内酯。吡嗪在这些转变中的行为是奇特的，由于氯甲酸甲酯本身通过与两个氮原子的相互作用诱导多环γ-内酯的形成，这种反应形式上让人想起相同的烯酮缩醛与（芳烃）三羰基铬配合物的双亲核加成反应。大多数新结构是通过 X 射线晶体结构测定确定的。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• New access to functionalized dichlorophosphines: Synthesis of two coordinated phosphorus heterocycles.
  作者：Pascal Pellon、Jack Hamelin

  DOI：10.1016/s0040-4039(00)85279-x

  日期：1986.1

  An easy access to functionalized dichlorophosphines 2, 4, 5, 7 is described, and these compounds are dehydrochlorinated in situ with DABCO and trapped by a diene or a diazocompound to give phosphabenzenes or diazaphospholes.

  描述了容易获得的官能化二氯膦2、4、5、7，这些化合物用DABCO原位脱氯化氢，并被二烯或重氮化合物截留，得到磷苯或二氮杂磷。