1,1-双(三甲基甲硅烷氧基)-1-丙烯 | 31469-22-4

• 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(三甲基甲硅烷氧基)-1-丙烯
• 英文名称: 1,1-bis(trimethylsilyloxy)prop-1-ene
• 英文别名: 4-ethylidene-2,2,6,6-tetramethyl-3,5-dioxa-2,6-disilaheptane；Trimethyl(1-trimethylsilyloxyprop-1-enoxy)silane
• CAS: 31469-22-4
• 化学式: C₉H₂₂O₂Si₂
• mdl: MFCD01632569
• 分子量: 218.443
• InChiKey: IUFWLBQYLXTUFY-UHFFFAOYSA-N

物化性质

• 沸点：
  60 °C (11 mmHg)
• 闪点：
  25 °C
• 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)：
  4.21
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.777
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xi
• 危险类别码：
  R10,R36/37/38
• 海关编码：
  2931900090
• 储存条件：
  存放于0-6℃阴凉干燥处

SDS

Name:	1 1-Bis(trimethylsilyloxy)-1-propene Material Safety Data Sheet
Synonym:	None Known
CAS:	31469-22-4

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

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
31469-22-4	1,1-Bis(trimethylsilyloxy)-1-propene	100	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: 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. 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 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. Use with adequate ventilation. 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 tightly closed container. Keep refrigerated. (Store below 4C/39F.)

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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# 31469-22-4: 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 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: 60 deg C @ 11.00mmHg
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: C9H22O2Si2
Molecular Weight: 218.44

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not currently 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

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 31469-22-4 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
1,1-Bis(trimethylsilyloxy)-1-propene - 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# 31469-22-4: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 31469-22-4 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 31469-22-4 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：

  1,1-双(三甲基甲硅烷氧基)-1-丙烯 在 SO₃*dioxane 作用下， 生成 trimethylsilyl 1-<(trimethylsiloxy)carbonyl>ethanesulfonate
  参考文献：
  名称：

  Sergeev, V. N.; Baukov, Yu. I., Journal of general chemistry of the USSR, 1983, vol. 53, # 3, p. 619 - 620

  摘要：

  DOI：
• 作为产物：
  描述：

  三甲基氯硅烷 、 丙酸 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 0.67h， 生成 1,1-双(三甲基甲硅烷氧基)-1-丙烯
  参考文献：
  名称：

  通过无痕保护策略钯催化羧酸和仲酰胺的 α-芳基化

  摘要：

  针对钯催化羧酸助剂和仲酰胺与芳基卤化物的 α-芳基化这一长期存在的挑战，提出了一种新颖的无痕保护策略。所提出的两种偶联过程均与各种羧酸和酰胺以及各种含有多种官能团的芳基溴发生，包括碱敏感官能团，如酰基、烷氧基羰基、硝基、氰基，甚至羟基。通过该方法一步制备了5种商品化药物，收率81-96%。低钯负载量药物萘普生和氟比洛芬的克级合成进一步凸显了该方法的实用价值。

  DOI：

  10.1021/jacs.9b03291

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。
• Synthetic Studies toward the Tetrapetalones: Diastereoselective Construction of a Putative Intermediate
  作者：Wen-Ju Bai、Thomas R. R. Pettus

  DOI：10.1021/acs.orglett.7b03500

  日期：2018.2.16

  A strategy toward tetrapetalones was explored including a site-selective ethylenation of the silyl enol ether A to afford a quaternary stereocenter that serves in a stereogenic capacity. Regio- and diastereoselective reactions were observed in conjunction with the oxidative formation of cation B, which included subsequent selective formation of either carbon–oxygen or carbon–carbon bonds at the δ or

  已研究出一种针对四氢萘酮的策略，包括甲硅烷基烯醇醚A的位点选择性乙烯化，以提供具有立体生成能力的四级立体中心。观察到区域和非对映选择性反应与阳离子B的氧化形成有关，其中包括随后在7元环的δ或ζ位选择性形成碳-氧或碳-碳键。使用Stetter反应形成第四环。
• ketene bis(trialkylsilyl) acetals: synthesis, pyrolysis and spectral studies
  作者：C. Ainsworth、Yu-Neng Kuo

  DOI：10.1016/s0022-328x(00)90476-5

  日期：1972.12

  methods are described for the preparation of alkyl, dialkyl, aryl and diaryl ketene bis(trialkylsilyl)acetals. One is by reaction of αmetalated trimethylsilyl carboxylates with trimethylchlorosilane (TMCS) and the otehr is by inteaction of dianions of carboxylic acids and TMCS. The dianion of cyclopropane carboxylic acid and TMCS gave C-silated ester in 90% yield. Pyrolysis of diphenyl ketene bis(trialkylsilyl)

  描述了两种高产率的合成方法，用于制备烷基，二烷基，芳基和二芳基乙烯酮双（三烷基甲硅烷基）缩醛。一种是通过α金属化的三甲基甲硅烷基羧酸盐与三甲基氯硅烷（TMCS）的反应，而另一种是通过羧酸与TMCS的二价阴离子的相互键合。环丙烷羧酸和TMCS的二价阴离子以90％的收率得到C-硅酸酯。交叉实验表明，二苯基乙烯酮双（三烷基甲硅烷基）缩醛热解为二苯基乙烯酮和双（三烷基甲硅烷基）醚在分子间进行。单取代的和二烷基酮烯（三甲基甲硅烷基）缩醛的热解得到了酮烯-酮缩醛的加成产物（III），其在溶剂分解时以高收率提供了β-酮酸。给出了许多化合物的NMR和质谱数据。
• Metal reductions of malonates and oxalates. A covenient decarboxylation route for disubstituted malonates and synthesis of keten acetals
  作者：Yu-Neng Kuo、Francis Chen、C. Ainsworth、Jordan J. Bloomfield

  DOI：10.1039/c29710000136

  日期：——

  Alkali-metal reduction of disubstituted malonates or treatment of esters with base in the presence of trimethylchlorosilane gives high yields of the reactive disubstituted keten alkyl trimethylsilyl acetals, while diethyl oxalate, under similar conditions is reduced to 1,2-diethyl-1,2-bis(trimethylsilyloxy)ethylene.

  二取代丙二酸酯的碱金属还原或在三甲基氯硅烷存在下用碱处理酯类可得到高产率的反应性二取代缩酮烷基三甲基甲硅烷基缩醛，而草酸二乙酯在类似条件下可还原为1,2-二乙基-1,2-双（三甲基甲硅烷氧基）乙烯。
• Catalytic Asymmetric Synthesis of Unprotected β²-Amino Acids
  作者：Chendan Zhu、Francesca Mandrelli、Hui Zhou、Rajat Maji、Benjamin List

  DOI：10.1021/jacs.1c00249

  日期：2021.3.10

  Importantly, both aromatic and aliphatic β2-amino acids can be obtained using this method. Mechanistic studies are consistent with the aminomethylation to proceed via silylium-based asymmetric counteranion-directed catalysis (Si-ACDC) and a transition state to explain the enantioselectivity is suggested on the basis of density functional theory calculation.

  我们在这里报告了一种可扩展的催化一锅法，用于对映体纯和未修饰的 β 2 -氨基酸。新开发的密闭imidodiphosphorimidate（IDPI）催化各种的广泛适用的反应双甲硅烷基烯酮缩醛与甲硅烷基化氨基甲基醚，接着通过水解后处理，得到游离β 2个以高收率，纯度，和对映选择性α-氨基酸。重要的是，使用这种方法可以获得芳香族和脂肪族 β 2氨基酸。机理研究与通过基于甲硅烷基的不对称反阴离子导向催化 (Si-ACDC) 进行的氨甲基化一致，并在密度泛函理论计算的基础上提出了解释对映选择性的过渡态。