IAd | 131042-77-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: IAd
• 英文别名: 1,3-bis(1-adamantyl)-imidazol-2-ylidene；1,3-di(1-adamantyl)imidazol-2-ylidene；1,3-Diadamantylimidazol-2-ylidene；1,3-bis(1-adamantyl)-2H-imidazol-1-ium-2-ide
• CAS: 131042-77-8
• 化学式: C₂₃H₃₂N₂
• 分子量: 336.52
• InChiKey: HPESDZAFNBMVII-UHFFFAOYSA-N

物化性质

• 熔点：
  240-241°C
• 稳定性/保质期：
  遵照规定使用和储存，则不会发生分解。

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  6.2
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 安全说明：
  S9
• 危险类别码：
  R10
• 危险品运输编号：
  UN 1325
• 储存条件：
  存放于阴凉干燥处

SDS

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Section 1: Product Identification
Chemical Name: 1,3-Bis(1-adamantyl)imidazol-2-ylidene, min. 98% ARDUENGO'S CARBENE
CAS Registry Number: 131042-77-8
Formula: C23H32N2
EINECS Number: None
Chemical Family: organic amine
Synonym: 1,3-di-adamantylimidazol-2-ylidene

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 131042-77-8 100% no data no data

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Section 3: Hazards Identification
The product is an irritant to the skin, eyes, mucous membranes and upper respiratory tract. Ingestion of small
Emergency Overview:
amounts are harmful.
Primary Routes of Exposure: Ingestion, inhalation of dust. Eyes and skin.
Eye Contact: Causes moderate irritation of the eyes.
Skin Contact: Causes slight to moderate irritation of the skin.
Inhalation: Dust is irritating to the nose, mucous membranes and respiratory tract.
Ingestion may lead to sleepiness, dizziness, abdominal cramps, vomiting, bloody diarrhea, weakness, and
Ingestion:
convulsions.
Acute Health Affects: Irritating to skin, eyes and respiratory tract.
Chronic Health Affects: No information available on long-term chronic effects.
NTP: No
IARC: No
OSHA: No

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SECTION 4: First Aid Measures
Immediately flush the eyes with copious amounts of water for at least 10-15 minutes. A victim may need
Eye Exposure:
assistance in keeping their eye lids open. Get immediate medical attention.
Wash the affected area with water. Remove contaminated clothes if necessary. Seek medical assistance if
Skin Exposure:
irritation persists.
Remove the victim to fresh air. Closely monitor the victim for signs of respiratory problems, such as difficulty
Inhalation:
in breathing, coughing, wheezing, or pain. In such cases seek immediate medical assistance.
Seek medical attention immediately. Keep the victim calm. Give the victim water (only if conscious). Induce
Ingestion:
vomiting only if directed by medical personnel.

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SECTION 5: Fire Fighting Measures
Flash Point: no data
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: carbon dioxide, foam or dry powder
If this product is involved in a fire, fire fighters should be equipped with a NIOSH approved positive pressure
Special Fire Fighting Procedures:
self- contained breathing apparatus and full protective clothing.
Hazardous Combustion and If involved in a fire this material may emit toxic fumes of nitrogen oxides.
Decomposion Products:
Unusual Fire or Explosion Hazards: Flammable solid. No unusual fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Small spills can be mixed with vermiculite, sodium carbonate or other suitable non combustible adsorbent and
Spill and Leak Procedures:
swept up.

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SECTION 7: Handling and Storage
Handling and Storage: Store cold, in a tightly sealed container under an inert atmosphere of nitrogen or argon.

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SECTION 8: Exposure Controls and Personal Protection
Eye Protection: Always wear approved safety glasses when handling a chemical substance in the laboratory.
Skin Protection: Wear protective clothing and gloves.
Ventilation: Material may form a fine dust. If possible, handle the material in an efficient fume hood.
If ventilation is not available a respirator should be worn. The use of respirators requires a Respirator
Respirator:
Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: Material may form a fine dust. If possible, handle the material in an efficient fume hood.
Additional Protection: No additional protection required.

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SECTION 9: Physical and Chemical Properties
Color and Form: white xtl
Molecular Weight: 336.51
Melting Point: 240-241°C
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: none
Solubility in Water: reactive in water

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SECTION 10: Stability and Reactivity
Stability: air sensitive, moisture sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: exposure to air, halogenated and acidic solvents
Incompatibility: strong oxidizing agents, halogenated solvents and acidic solvents.
Decomposition Products: carbon dioxide, carbon monoxide, nitrogen oxides, and organic fumes.

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SECTION 11: Toxicological Information
RTECS Data: No information available in the RTECS files.
Carcinogenic Effects: No data
Mutagenic Effects: No data
Tetratogenic Effects: No data

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SECTION 12: Ecological Information
Ecological Information: No information available

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SECTION 13: Disposal Considerations
Disposal: Dispose of according to local, state and federal regulations.

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SECTION 14: Transportation
Shipping Name (CFR): Flammable solids, Organic, N.O.S.
Hazard Class (CFR): 4.1
Additional Hazard Class (CFR): NA
Packaging Group (CFR): II
UN ID Number (CFR): UN# 1325
Shipping Name (IATA): Flammable solid, Organic, N.O.S.
Hazard Class (IATA): 4.1
Additional Hazard Class (IATA): NA
Packaging Group (IATA): II
UN ID Number (IATA): UN# 1325

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SECTION 15: Regulatory Information
TSCA: Not listed in the TSCA inventory.
SARA (Title 313): Title compound not listed.
Second Ingredient: None

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  IAd 在 氘代苯 、 C₄₂H₄₈N₆Ru 作用下， 80.0 ℃ 、101.33 kPa 条件下， 反应 48.0h， 以60%的产率得到
  参考文献：
  名称：

  配位不饱和钌 N-杂环卡宾催化剂合成氘标记 N-杂环卡宾的催化方法

  摘要：

  N-杂环卡宾 (NHC)的广泛使用引发了对其氘化分子的探索。然而，获得它们的有效合成方法仍然难以捉摸。我们在这里提出了一种制备氘化 NHC 的催化方法，即使用配位不饱和 Ru NHC 催化剂在 NHC 和氘化苯之间进行催化氢-氘交换反应。该催化系统能够选择性地氘化N 取代基上烷基的 C(sp 3 )–H 键，以及空间位阻的 C(sp 2)–NHCs 的 H 键，如制备 16 个氘标记 NHCs 所证明的，这些 NHCs 在指定位点上的氘化率高于 90%。氘代 IMes 的克级合成表明该催化方法的适用性。机理研究表明，对NHC 上那些 C(sp 3 )-H 键的高区域选择性源于配位不饱和 Ru NHC 物种的环金属化反应的区域选择性。

  DOI：

  10.1021/jacs.1c10071
• 作为产物：
  描述：

  1,3-二(金刚烷-1-基)氯化咪唑 在 sodium hydride 、 二甲基亚砜 作用下， 以 四氢呋喃 为溶剂， 生成 IAd
  参考文献：
  名称：

  稳定的结晶卡宾

  摘要：

  这些合成、结构和表征 du (1,3-bis [1-adamantyl]-2,3-dihydro)-2-carbenoimidazole制备par deprototation du chlorure de (1,3-bis [1-adamantyl]) imidazolium

  DOI：

  10.1021/ja00001a054
• 作为试剂：
  描述：

  反式肉桂醛 、 (三氟甲基)三甲基硅烷 在 IAd 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 trimethyl[[(2E)-3-phenyl-1-(trifluoromethyl)-2-propenyl]oxy]silane
  参考文献：
  名称：

  N-杂环卡宾催化羰基化合物的三氟甲基化。

  摘要：

  [反应：请参见文字]。发现了一种新型的N-杂环卡宾（NHC）催化羰基化合物的三氟甲基化反应。可烯化和不可烯化的醛和α-酮酯在室温下仅以0.5-1 mol％的NHC（1）存在时，可通过TMSCF3进行三氟甲基化反应，从而以高收率提供CF3取代的醇。在NHC催化下，可以实现醛在酮上的选择性三氟甲基化。这些条件温和而简单，并且可以耐受多种功能基团。

  DOI：

  10.1021/ol050568i

文献信息

• Carbene Adducts of Dimethylcadmium
  作者：Anthony J. Arduengo、Jens R. Goerlicha、Fredric Davidson、William J. Marshall

  DOI：10.1515/znb-1999-1102

  日期：1999.11.1

  The first examples of carbene-cadmium complexes are reported from the reactions of a variety of imidazol-2-ylidenes or imidazolin-2-ylidenes with dimethylcadmium. Four new carbene complexes are characterized by NMR spectroscopy (¹H , ¹³C and ¹¹³Cd). The cadmium centers are strongly shifted downfield (100 -150 ppm) by interaction with the carbenes. X-ray structures are reported for three carbene-cadmium 1:1 adducts. The cadmium centers exhibit distorted trigonal-planar geometries in which the carbene ligands have an average 18.2 pm longer bond distance to cadmium compared to the methyl groups. The planes of cadmium coordination are twisted with respect to the plane of the imidazole ring. The more basic imidazolin-2-ylidene is shown to displace imidazol-2-ylidenes from the cadmium center.

  报道了碳-镉配合物的首批实例，这些实例是通过各种咪唑-2-基卡宾或咪唑啉-2-基卡宾与二甲基镉反应而得到的。通过核磁共振光谱（¹H，¹³C和¹¹³Cd）表征了四种新的卡宾配合物。镉中心通过与卡宾的相互作用被强烈地向下场移动（100-150 ppm）。对三种卡宾-镉1:1加合物进行了X射线结构分析。镉中心表现出扭曲的三角平面几何构型，其中卡宾配体与镉的键距平均比甲基基团长18.2 pm。镉配位平面相对于咪唑环的平面扭曲。更碱性的咪唑啉-2-基卡宾被证明可以从镉中心中取代咪唑-2-基卡宾。
• Coordinatively Unsaturated Ruthenium Complexes As Efficient Alkyne–Azide Cycloaddition Catalysts
  作者：Marina Lamberti、George C. Fortman、Albert Poater、Julie Broggi、Alexandra M. Z. Slawin、Luigi Cavallo、Steven P. Nolan

  DOI：10.1021/om2012425

  日期：2012.1.23

  16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azide–alkyne cycloaddition reactions that afford the 1,2,3-triazole products. The scope of the Cp*Ru(PiPr3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were

  在叠氮化物-炔烃环加成反应中研究了通式为Cp * Ru（L）X（其中L =膦或N-杂环卡宾配体； X = Cl或OCH 2 CF 3）的16电子钌配合物的性能。提供1,2,3-三唑产物。研究了Cp * Ru（P i Pr 3）Cl预催化剂的范围，用于末端炔烃，从而以高收率产生新的1,5-二取代的1,2,3-三唑。进行了机理研究，并揭示了许多拟议的中间体。的Cp * Ru（对我镨3）（η 2 -HCCPh）氯观察和表征通过1 H，13 C，和31P NMR在273和213的K.一个罕见的例子之间的温度下Ñ，Ñ -κ 2 -phosphazide复杂中，Cp *茹（κ 2 -我镨3 PN 3 BN）氯，得到充分表征，并且一个单晶X-获得了X射线衍射结构。DFT计算描述了与苯乙炔和/或苄基叠氮化物的催化反应性的完整图谱。
• Steric Properties of <i>N</i> ‐Heterocyclic Carbenes affect the Performance of Electronic Probes
  作者：Christopher Barnett、Marcus L. Cole、Jason B. Harper

  DOI：10.1002/ejic.202100796

  日期：2021.12.21

  Size matters. The impact of the size of the N-substituents of N-heterocyclic carbenes on two common NMR based electronic probes has been investigated, highlighting that care must be taken to ensure the probe gives meaningful information of the ligand properties. That is, make sure you measure what you want.

  尺寸很重要。已经研究了N-杂环卡宾的N-取代基大小对两种常见的基于 NMR 的电子探针的影响，强调必须注意确保探针提供有意义的配体特性信息。也就是说，确保你衡量你想要什么。
• Regioselective Hydrocarbamoylation of 1-Alkenes
  作者：Yosuke Miyazaki、Yuuya Yamada、Yoshiaki Nakao、Tamejiro Hiyama

  DOI：10.1246/cl.2012.298

  日期：2012.3.5

  Nickel/Lewis acid cooperative catalysis derived from [Ni(cod)2], AlEt3, and N-heterocyclic carbene (NHC) effects highly regioselective hydrocarbamoylation of 1-alkenes. Variously substituted formam...

  源自 [Ni(cod)2]、AlEt3 和 N-杂环卡宾 (NHC) 的镍/路易斯酸协同催化作用可对 1-烯烃进行高度区域选择性的烃甲酰化。各种替代形式...
• Steric and Electronic Properties of N-Heterocyclic Carbenes (NHC):  A Detailed Study on Their Interaction with Ni(CO)₄
  作者：Reto Dorta、Edwin D. Stevens、Natalie M. Scott、Chiara Costabile、Luigi Cavallo、Carl D. Hoff、Steven P. Nolan

  DOI：10.1021/ja0438821

  日期：2005.3.1

  experimental findings and show that IAd (6) and I(t)()Bu (7) are more bulky than IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5). Furthermore, a method based on %V(bur) values has been developed for the direct comparison of steric requirements of NHCs and tertiary phosphines. Complexes 8-14, as well as NiCl(C(3)H(5))(I(t)()Bu) (16) and NiBr(C(3)H(5))(I(t)()Bu) (17), have been characterized by X-ray crystallography

  N-杂环卡宾配体 IMes (1)、SIMes (2)、IPr (3)、SIPr (4) 和 ICy (5) 与 Ni(CO)(4) 反应生成饱和三羰基配合物 Ni(CO)( 3)(IMes) (8)、Ni(CO)(3)(SIMes) (9)、Ni(CO)(3)(IPr) (10)、Ni(CO)(3)(SIPr) (11) , 和 Ni(CO)(3)(ICy) (12)，分别。通过记录它们的 nu(CO) 拉伸频率，已将这些配合物的电子特性与通式 Ni(CO)(3)(PR(3)) 的膦类似物进行了比较。虽然所有这些 NHC 都是比叔膦更好的供体，但配体 1-5 之间的供体特性差异非常小。Ni(CO)(2)(IAd) (13) 和 Ni(CO)(2)(I(t)()Bu) (14) 化合物是从 Ni(CO)(4) 的反应中获得的与 IAd (6) 和 I(t)()Bu (7)。配合物 13 和