肉豆蔻酸乙酯 | 127896-07-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 肉豆蔻酸乙酯
• 中文别名: 双(三甲基甲硅烷基)-N-叔-丁基乙酰醛亚胺
• 英文名称: α,α-bis(trimethylsilyl)-tert-butylacetaldehyde imine
• 英文别名: α,α-bis(trimethylsilyl)-N-tert-butylacetaldimine；α,α-bis(trimethylsilyl)-t-butylacetaldimine；N-tert-butyl-2,2-bis(trimethylsilyl)ethanimine
• CAS: 127896-07-5
• 化学式: C₁₂H₂₉NSi₂
• 分子量: 243.54
• InChiKey: WWPDPMRFNPAUIM-UHFFFAOYSA-N

物化性质

• 沸点：
  97-98 °C(Press: 12 Torr)
• 密度：
  0.79±0.1 g/cm3(Predicted)
• 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)：
  4.44
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 安全说明：
  S24/25

SDS

Name:	Bis(trimethylsilyl)-N-tert-butylacetaldimine Material Safety Data Sheet
Synonym:
CAS:	127896-07-5

Section 1 - Chemical Product MSDS Name:Bis(trimethylsilyl)-N-tert-butylacetaldimine Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
127896-07-5	Bis(trimethylsilyl)-N-tert-butylacetal	100	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. May be harmful if absorbed through the skin.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
May cause respiratory tract irritation. May be harmful if inhaled.
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# 127896-07-5: 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: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C12H29NSi2
Molecular Weight: 243.54

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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, oxides of nitrogen, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 127896-07-5 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Bis(trimethylsilyl)-N-tert-butylacetaldimine - 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# 127896-07-5: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 127896-07-5 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 127896-07-5 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：

  糠醛 、 肉豆蔻酸乙酯 在 zinc(II) chloride 、 zinc dibromide 作用下， 生成 反-3-(2-呋喃基)丙烯醛
  参考文献：
  名称：

  A simple and highly stereoselective route to E-.alpha.,.beta.-unsaturated aldehydes

  摘要：

  Zinc bromide mediated reaction of alpha,alpha-bis(trimethylsilyl)-tert-butylacetaldimine (3) with a wide range of aldehydes takes place under mild conditions and affords the corresponding alpha,beta-unsaturated aldehydes in good yields and with very high E stereoselectivity (>98%). This procedure is successfully applied to the preparation of intermediates for retinoid and natural product synthesis.

  DOI：

  10.1021/jo00061a027
• 作为产物：
  描述：

  N-叔丁基乙基亚胺 在 lithium diisopropyl amide 作用下， 反应 27.75h， 生成 肉豆蔻酸乙酯
  参考文献：
  名称：

  A simple and highly stereoselective route to E-.alpha.,.beta.-unsaturated aldehydes

  摘要：

  Zinc bromide mediated reaction of alpha,alpha-bis(trimethylsilyl)-tert-butylacetaldimine (3) with a wide range of aldehydes takes place under mild conditions and affords the corresponding alpha,beta-unsaturated aldehydes in good yields and with very high E stereoselectivity (>98%). This procedure is successfully applied to the preparation of intermediates for retinoid and natural product synthesis.

  DOI：

  10.1021/jo00061a027

文献信息

• Double intramolecular hetero Diels–Alder reactions of α,β-unsaturated hydrazones as 1-azadienes: a new route to 2,2′-bipyridines
  作者：Nicholas Bushby、Christopher J. Moody、David A. Riddick、Ian R. Waldron

  DOI：10.1039/b105409k

  日期：——

  Salicylaldehyde was converted into the O-propynyl- and O-butynyl α,β-unsaturated aldehydes 4 and ketones 6, subsequent reaction of which with N,N-dimethylhydrazine and alkyne homocoupling gave the 1,3-diyne bis(hydrazones) 8, substrates for a double intramolecular hetero Diels–Alder reaction. Similar substrates 11, 15a/15c and 15b/15d were prepared from 2-(N-benzoylamino)cinnamaldehyde, hex-5-ynol and hept-6-ynol

  水杨醛被转化为不饱和的O-丙炔基和O-丁炔基醛类 4和酮类 6，其后的反应与N，N-二甲基肼 和 炔烃均相偶合得到1,3-二炔双（hydr）8，是双分子内杂Diels-Alder反应的底物。类似的基材11，15A / 15C和15B / 15D，从制备2-（N-苯甲酰氨基）肉桂醛， 己-5-炔醇 和 庚-6-炔诺醇分别。加热1,3-二炔基双（α，β-不饱和腙）8a，8c，11和15a导致分子内Diels-Alder双反应，在失去芳香化后产生二甲胺，2,2'-联吡啶21–24。
• A new synthesis of 1-phenylthio- and 1-alkylamino-4-nitrobuta-1,3-dienes
  作者：Noboru Ono、Koji Matsumoto、Takuji Ogawa、Hiroyuki Tani、Hidemitsu Uno

  DOI：10.1039/p19960001905

  日期：——

  A new synthesis of push-pull dienes such as 4-nitro-1-phenylthiopenta-1,3-diene 4 and 1-dialkylamino-4-nitropenta-1,3-diene 5, is described. The X-ray crystal analysis shows that 4-nitro-1-(pyrrolidin-1-yl)penta-1,3-diene 5a is essentially planar in an E,E-configuration with r(C–C)= 1.42(1)Å and r(CC)= 1.35(1) and 1.371(9)Å. Compounds 5 showed a large solvatochromic effects similar to that of merocyanine dyes. Molecule 5a exhibits second harmonic generation (SHG) activity whose efficiency is 2.5 times that of urea (determined by a powder method at 1064 nm). For 5a, the molecular nonlinearity µβ is estimated to be 1200 × 10–48 esu which is calculated from the Pockel coefficient (r33) determined by electrooptic measurements of poled polymers of 5a in poly(methyl methacrylate) at 1300 nm. This value is relatively large for such small conjugated molecules, where donors and acceptors are bridged by only 4π electron systems.

  本文描述了一种新的推拉二烯合成方法，例如4-硝基-1-苯基噻吩五-1,3-二烯4和1-二烷基氨基-4-硝基五-1,3-二烯5。X射线晶体分析显示，4-硝基-1-(吡咯烷-1-基)五-1,3-二烯5a基本为平面E,E构型，r(C–C)=1.42(1)Å，r(CC)=1.35(1)和1.371(9)Å。化合物5表现出与金属氰染料类似的大的溶剂化效应。分子5a表现出二次谐波产生（SHG）活性，其效率是尿素的2.5倍（通过粉末法在1064 nm处测定）。对于5a，分子非线性µβ估计为1200 × 10–48 esu，这是从波克尔系数（r33）计算得出的，该系数是通过在1300 nm处对5a的极化聚合物在聚甲基丙烯酸甲酯中的电光测量确定的。这个值对于这种小的共轭分子来说是相对较大的，其中供体和受体仅通过4π电子系统连接。
• Biomimetic Total Synthesis of (+)-Himbacine
  作者：Kirill Tchabanenko、Robert M. Adlington、Andrew R. Cowley、Jack E. Baldwin

  DOI：10.1021/ol047676+

  日期：2005.2.1

  acid butenolide 14 undergoes N-Boc deprotection and condensation followed by an iminium ion activated intramolecular Diels-Alder cycloaddition to give the (+)-himbacine precursor 11 on reductive work up. Compound 11 was converted into (+)-himbacine in four synthetic steps. [reaction: see text]

  在用三氟乙酸处理时，丁烯内酯14进行N-Boc脱保护和缩合，然后进行亚胺离子活化的分子内Diels-Alder环加成反应，从而在还原反应中得到（+）-半胱氨酸前体11。在四个合成步骤中将化合物11转化为（+）-半胱氨酸。[反应：看文字]
• Studies directed towards the total synthesis of (±)-himbacine
  作者：Govert De Baecke、Pierre J. De Clercq

  DOI：10.1016/0040-4039(95)01520-5

  日期：1995.10

  The synthesis of aldehyde 11a is reported based upon the intramolecular Diels-Alder reaction of triene 10, the butenolide-diene part of which was obtained in one step via the condensation of the enolate derived from the (Z)-enoate ester 5 with 2-acetoxypropanal. Aldehyde 11a possesses the correct stereochemistry of the tricyclic part of himbacine, an important muscarine receptor antagonist.

  根据三烯10的分子内Diels-Alder反应报道了醛11a的合成，三烯10的丁烯内酯-二烯部分是通过将（Z）-烯酸酯5的烯醇与2的缩合反应一步获得的。乙酰氧基丙醛。醛11a具有重要的毒蕈碱受体拮抗剂喜巴因的三环部分的正确立体化学。
• Preparation of (E)-α,β-unsaturated aromatic aldehydes by high stereoselective olefinformylation.
  作者：Marcel Gaudemar、Moncef Bellassoued

  DOI：10.1016/s0040-4039(00)94552-0

  日期：1990.1

  Treatment of acetaldehyde N-ter-butylimine by two equivalents of LDA, followed by trimethylsilyl chloride trapping affords the α,α-disilylated imine ; the latter reacts with aromatic aldehydes producing α,β-ethylenic aldehydes in excellent yields and with very high stereoselectivity in favour of the E isomer.

  用两当量的LDA处理乙醛N-叔丁基亚胺，然后捕集三甲基甲硅烷基氯，得到α，α-二甲硅烷基化的亚胺。后者与芳族醛发生反应，以优异的收率和极高的立体选择性有利于E异构体，生成α，β-烯醛。