1,1-双(三甲基甲硅烷基氧基)-1,3-丁二烯 | 87121-06-0

• 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)-1,3-丁二烯
• 英文名称: 1,1-bis(trimethylsilyloxy)-buta-1,3-diene
• 英文别名: ketene bis(trimethylsilyl)acetal of crotonic acid；1,1-Bis(trimethylsilyloxy)-1,3-butadiene；trimethyl(1-trimethylsilyloxybuta-1,3-dienoxy)silane
• CAS: 87121-06-0
• 化学式: C₁₀H₂₂O₂Si₂
• mdl: MFCD01632567
• 分子量: 230.454
• InChiKey: KRDZQGWHCOOABR-UHFFFAOYSA-N

物化性质

• 沸点：
  80 °C (11 mmHg)
• 密度：
  0.888 (estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  4.39
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2931900090
• 安全说明：
  S24/25

SDS

Name:	1 1-Bis(trimethylsilyloxy)-1 3-butadiene Material Safety Data Sheet
Synonym:	None
CAS:	87121-06-0

Section 1 - Chemical Product MSDS Name:1 1-Bis(trimethylsilyloxy)-1 3-butadiene Material Safety Data Sheet
Synonym:None

---

Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
87121-06-0	1,1-Bis(trimethylsilyloxy)-1,3-butadie	100	unlisted

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

---

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.

---

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:

---

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.

---

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.

---

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.)

---

Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 87121-06-0: Personal Protective Equipment Eyes: Wear chemical splash goggles.
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.

---

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: 80 deg C @ 11 mm Hg
Freezing/Melting Point: Not available.
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: C10H22O2Si2
Molecular Weight: 230.45

---

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

---

Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 87121-06-0 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
1,1-Bis(trimethylsilyloxy)-1,3-butadiene - Not listed by ACGIH, IARC, or NTP.

---

Section 12 - ECOLOGICAL INFORMATION

---

Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

---

Section 14 - TRANSPORT INFORMATION

IATA
No information available.
IMO
No information available.
RID/ADR
No information available.

---

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# 87121-06-0: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 87121-06-0 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 87121-06-0 is not listed on the TSCA inventory.
It is for research and development use only.

---

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)-1,3-丁二烯 在 fluorine 作用下， 以 一氟三氯甲烷 为溶剂， 以75%的产率得到(E)-4-fluorobut-2-enoic acid
  参考文献：
  名称：

  关于三甲基甲硅烷基化合物直接氟化的机理

  摘要：

  为了阐明甲硅烷基化合物的氟化机理，已经对许多化合物进行了氟化。取决于所使用的底物，涉及的途径可以是加成消除，循环或逐步的。

  DOI：

  10.1016/s0022-1139(00)80219-5
• 作为产物：
  描述：

  三甲基氯硅烷 、 三甲基甲硅烷基丁-3-烯酸酯 在 lithium diisopropyl amide 作用下， 生成 1,1-双(三甲基甲硅烷基氧基)-1,3-丁二烯
  参考文献：
  名称：

  Silylcetenes acetals issus d'acides α,β-ethyleniques: Preparations et applications en synthese

  摘要：

  DOI：

  10.1016/s0022-328x(00)99191-5

文献信息

• 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)
• Double nucleophilic addition of bis(trimethylsilyl)ketene acetals to carbon–carbon double bonds of pyrazines: formation of polycyclic γ-lactones
  作者：Henri Rudler、Bernard Denise、Yiming Xu、Jacqueline Vaissermann

  DOI：10.1016/j.tetlet.2005.03.131

  日期：2005.5

  The double activation of pyrazines upon their interaction with methyl chloroformate leading in the presence of bis(TMS)ketene acetals to polycyclic N-containing γ-lactones parallels the interaction of the same ketene acetals with metal-activated aromatics. The fundamental role of the two oxygen–silicon bonds is outlined. This result broadens the scope of application of these ketene acetals as potential

  吡嗪与氯甲酸甲酯相互作用时的双活化导致双（TMS）乙烯酮缩醛在双环含N的γ-内酯的存在下与相同的乙烯酮缩醛与金属活化的芳族化合物的相互作用平行。概述了两个氧-硅键的基本作用。该结果拓宽了这些烯酮缩醛作为潜在的1，3-二亲核试剂的应用范围。
• A Convenient Synthesis of Aminoacids by ZnBr₂ Promoted Reaction of Ketene <i>bis</i>(Trimethylsilyl) Acetals with Aldimines
  作者：M. Mladenova、M. Bellassoued

  DOI：10.1080/00397919308009832

  日期：1993.3

  Abstract The ZnBr2 promoted addition of ketene bis(trimethylsilyl) acetals to aromatic aldimines affords β-arylaminoacids in good to excellent yields. Under the same reaction conditions vinylic ketene bis(trimethylsilyl) acetals give exclusively or mainly δ - phenylaminoacids.

  摘要 ZnBr2 促进乙烯酮双（三甲基甲硅烷基）缩醛与芳族醛亚胺的加成，以良好至极好的收率提供 β-芳基氨基酸。在相同的反应条件下，乙烯基烯酮双(三甲基甲硅烷基)缩醛仅或主要产生δ-苯基氨基酸。
• Total synthesis of queen substance of honeybee using an organosilicon route
  作者：Moncef Bellassoued、Assieh Majidi

  DOI：10.1016/0040-4039(91)80490-w

  日期：1991.12

  O-Silylated enolates are used as the key intermediates in the total synthesis of queen substance. The synthesis proceeds in 7 steps and affords the desired pheromone with very high stereoselectivity and 34% overall yield.

  O-甲硅烷基化的烯酸酯被用作皇后物质全合成中的关键中间体。合成以7个步骤进行，并以非常高的立体选择性和34％的总收率提供了所需的信息素。
• Bis(triméthylsiloxy)-1,1 butadiène-1,3 et triméthylsilyl-4 butène-2 oate de triméthylsilyle: préparations et réactions avec le benzaldéhyde
  作者：M. Bellassoued、R. Ennigrou、M. Gaudemar

  DOI：10.1016/0022-328x(88)80497-2

  日期：1988.1

  The preparations of 4-trimethylsilyl-2-butenoate trimethylsilyl ester and 1,1- bis(trimethylsiloxy)-1,3-butadiene are described. The latter silyl derivative reacts with benzaldehyde in the presence of ZnBr2 in THF to give exclusively γ-substituted product (E configuration) in high yield. The fluoride ion catalyzed reaction affords predominantly α-alkylated compounds.

  描述了4-三甲基甲硅烷基-2-丁烯酸酯三甲基甲硅烷基酯和1，1-双（三甲基甲硅烷氧基）-1，3-丁二烯的制备。后者的甲硅烷基衍生物在ZnBr 2存在的条件下与苯甲醛在THF中反应，以高收率仅得到γ-取代的产物（E构型）。氟离子催化的反应主要得到α-烷基化的化合物。