1,3,4-三苯基-4,5-二氢-1H-1,2,4-三氮唑-5-亚基 | 166773-08-6

• 物质功能分类: 有机原料
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 1,3,4-三苯基-4,5-二氢-1H-1,2,4-三氮唑-5-亚基
• 中文别名: 1,3,4-三苯基-4,5-二羟基-1H-1,2,4-噻唑-5-基
• 英文名称: (1,3,4)-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene
• 英文别名: 1,3,4-triphenyl-1,2,4-triazol-5-ylidene；2,4,5-Triphenyl-4H-1,2,4-triazol-2-ium-3-ide
• CAS: 166773-08-6
• 化学式: C₂₀H₁₅N₃
• 分子量: 297.359
• InChiKey: QZHWOLKBXYORRO-UHFFFAOYSA-N

物化性质

• 熔点：
  150 °C
• 沸点：
  428.86°C (rough estimate)
• 密度：
  1.1226 (rough estimate)
• 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)：
  5.1
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  18.6
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 安全说明：
  S24/25
• 储存条件：
  存放于-20°C阴凉干燥处

SDS

Name:	1 3 4-Triphenyl-4 5-dihydro-1H-1 2 4-triazol-5-ylidene Material Safety Data Sheet
Synonym:	None
CAS:	166773-08-6

Section 1 - Chemical Product MSDS Name:1 3 4-Triphenyl-4 5-dihydro-1H-1 2 4-triazol-5-ylidene Material Safety Data Sheet
Synonym:None

---

Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
166773-08-6	1,3,4-Triphenyl-4,5-dihydro-1H-1,2,4-t	100	unlisted

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

---

Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
The toxicological properties of this material have not been fully investigated.Moisture sensitive.
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.

---

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. Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water. 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:
Treat symptomatically and supportively.

---

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.
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:
Vacuum or sweep up material and place into a suitable disposal container. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

---

Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use with adequate ventilation.
Minimize dust generation and accumulation. Avoid breathing dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing.
Keep container tightly closed. Avoid ingestion and inhalation. Do not allow contact with water. Keep from contact with moist air and steam.
Storage:
Store in a tightly closed container. Dark room. Deep freeze (below -20C). Store protected from moisture. Store under argon.

---

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# 166773-08-6: 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.

---

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Crystalline powder
Color: beige
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 150 deg C (dec)
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature: 150 deg C
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C20H15N3
Molecular Weight: 297.13

---

Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not currently available.
Conditions to Avoid:
Dust generation, moisture, excess heat.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Nitrogen oxides, carbon monoxide, carbon dioxide.
Hazardous Polymerization: Has not been reported

---

Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 166773-08-6 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
1,3,4-Triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene - 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
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing Group:
IMO
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing Group:
RID/ADR
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing group:

---

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# 166773-08-6: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 166773-08-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 166773-08-6 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：

  1,3,4-三苯基-4,5-二氢-1H-1,2,4-三氮唑-5-亚基 在 亚硝基苯 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 1,3,4-Triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-one
  参考文献：
  名称：

  Deoxygenation of nitrosoarene by N-heterocyclic carbene (NHC): an elusive Breslow-type intermediate bridging carbene and nitrene

  摘要：

  N-杂环卡宾（NHC）与亚硝基芳烃（ArNO）的相互作用，通过ArNO的脱氧作用形成芳基亚氮化物（ArN）。

  DOI：

  10.1039/d0cc05192f
• 作为产物：
  描述：

  [(5RS)-1,4-bis[2,6-bis(1-methylethyl)phenyl]-4,5-dihydro-3-phenyl-1H-1,2,4-triazol-5-yl]phenylmethanone 在 potassium tert-butylate 、 sodium hydride 、 N,O-双三甲硅基乙酰胺 作用下， 以 氘代四氢呋喃 为溶剂， 生成 1,3,4-三苯基-4,5-二氢-1H-1,2,4-三氮唑-5-亚基
  参考文献：
  名称：

  N-杂环卡宾对醛的Umpolung：Breslow中间体的酮基形式的NMR表征，以及螺-二氧戊环作为催化体系的静止状态

  摘要：

  一个经典的惊喜：NMR光谱法首次以酮基形式（K，高能极小值）表征了三偶氮烯催化的安息香缩合反应的Breslow中间体。由卡宾催化剂和两当量的醛生成的迄今未知的螺二氧戊环S是催化体系的静止状态。

  DOI：

  10.1002/anie.200907275
• 作为试剂：
  描述：

  丙烯酸叔丁酯 、 甲基丙烯腈 在 4-甲氧基苯酚 、 1,3,4-三苯基-4,5-二氢-1H-1,2,4-三氮唑-5-亚基 作用下， 以 1,4-二氧六环 为溶剂， 反应 6.0h， 以48%的产率得到
  参考文献：
  名称：

  N-杂环卡宾催化甲基丙烯酸甲酯/甲基丙烯腈与丙烯酸酯的尾对尾交叉二聚反应

  摘要：

  甲基丙烯酸甲酯 (MMA)/甲基丙烯腈 (MAN) 与丙烯酸酯的尾对尾交叉二聚反应首次通过 N-杂环卡宾有机催化实现，以生产新的双官能化合物，四种 2-甲基己-2-烯二酸酯和三种 5-cyanohex-4-enoates，分离产率中等至良好。高选择性是通过滴加丙烯酸酯实现的，导致稳定的脱氧-布雷斯洛中间体选择性迈克尔加成到丙烯酸酯。

  DOI：

  10.1246/cl.170263

文献信息

• 1,4-Bis-Dipp/Mes-1,2,4-Triazolylidenes: Carbene Catalysts That Efficiently Overcome Steric Hindrance in the Redox Esterification of α- and β-Substituted α,β-Enals
  作者：Veera Reddy Yatham、Wacharee Harnying、Darius Kootz、Jörg-M. Neudörfl、Nils E. Schlörer、Albrecht Berkessel

  DOI：10.1021/jacs.5b11796

  日期：2016.3.2

  2,4-triazolium salts were synthesized and evaluated as (pre)catalysts in the redox esterification of various α- or β-substituted enals. In particular the 1,4-bis-Mes/Dipp-1,2,4-triazolylidenes overcome the above limitations and efficiently catalyze the redox esterification of a whole series of α/β-substituted enals hitherto not amenable to NHC-catalyzed transformations. The synthetic value of 1,4-bis-Mes/Dipp-1

  正如 Scheidt 和 Bode 在 2005 年报道的那样，在醇和 N-杂环卡宾催化剂（例如苯并咪唑亚基或三唑基亚基）的存在下，空间无阻碍的 α,β-烯醛很容易转化为饱和酯。然而，α,β-烯醛底物的α-或β-位上的取代基通常是不能容忍的，因此严重限制了底物光谱。在我们早期的机理研究的基础上，合成了一组 N-Mes- 或 N-Dipp-取代的 1,2,4-三唑鎓盐，并在各种 α- 或 β- 的氧化还原酯化反应中作为（预）催化剂进行了评估。取代的埃纳尔。特别是 1,4-bis-Mes/Dipp-1,2,4-triazolylidenes 克服了上述限制，并有效地催化了一系列 α/β-取代烯醛的氧化还原酯化反应，迄今为止无法进行 NHC 催化转化。
• METHOD FOR MANUFACTURING RUTHENIUM CARBENE COMPLEXES
  申请人：Kadyrov Renat

  公开号：US20110040099A1

  公开（公告）日：2011-02-17

  A method of manufacturing ruthenium carbene complexes and novel aryl alkylidene ruthenium complexes based on the method, the complexes able to used as catalysts in metathesis reactions.

  一种制备钌卡宾配合物和基于该方法的新型芳基烷基亚钌配合物的方法，这些配合物可以用作烯烃交换反应中的催化剂。
• Cooperative N-Heterocyclic Carbene/Brønsted Acid Catalysis for the Tail-to-Tail (Co)dimerization of Methacrylonitrile
  作者：Terumasa Kato、Shin-ichi Matsuoka、Masato Suzuki

  DOI：10.1021/jo500514e

  日期：2014.5.16

  The first tail-to-tail dimerization of methacrylonitrile (MAN) has been realized by the cooperative use of N-heterocyclic carbene (NHC) and Brønsted acid catalysts, producing 2,5-dimethylhex-2-enedinitrile with the E/Z ratio of 24:76. Although the NHC alone was not effective for the catalysis, the addition of alcohols resulted in the significant increase of the dimer yield up to 82% in the presence

  N-杂环卡宾（NHC）和布朗斯台德酸催化剂的联合使用实现了甲基丙烯腈（MAN）的第一个尾到尾二聚反应，用E / Z生产出2,5-二甲基己二烯化的苯腈比例为24:76。尽管仅NHC对催化无效，但是在5mol％NHC存在下，醇的加入导致二聚体产率显着提高至82％。详细的实验研究包括对中间体的ESI-MS分析，化学计量（共）二聚化和氘标记实验，揭示了质子转移，异构化，物质化和限速步骤的机理，使我们能够观察到几种机理差异。在MAN的二聚化和甲基丙烯酸甲酯的二聚化之间。在存在和不存在醇的情况下的化学计量反应表明，在催化循环的后半段中，醇添加剂在促进分子间质子从脱氧-布雷斯洛中间体转移到再生的NHC中发挥作用。此外，已经研究了甲基丙烯酸正丁酯（n -BuMA）。尽管在醇存在下n -BuMA的二聚反应缓慢，但通过合作体系可提高共聚二聚反应的催化活性。
• Tail-to-tail dimerization and Rauhut-Currier reaction of disubstituted Michael acceptors catalyzed by N-heterocyclic carbene
  作者：Shin-ichi Matsuoka、Naoki Awano、Masanori Nakazawa、Masato Suzuki

  DOI：10.1016/j.tetlet.2016.11.031

  日期：2016.12

  The N-heterocyclic carbene (NHC)-catalyzed dimerizations of a variety of disubstituted Michael acceptors have been investigated. In addition to the tail-to-tail dimerization of methacrylates reported previously, the scope of vinylidene substrates expands to γ-methyl-α-methylene-γ-butyrolactone, dimethyl 2-methylenepentanedioate, dimethyl itaconate, methacrylamides, and 2-isopropenylbenzoxazole, none

  已经研究了N-杂环卡宾（NHC）催化的各种双取代Michael受体的二聚反应。除了先前报道的甲基丙烯酸酯的尾到尾二聚以外，亚乙烯基底物的范围还扩大到了γ-甲基-α-亚甲基-γ-丁内酯，2-亚甲基戊二酸二甲酯，衣康酸二甲酯，甲基丙烯酰胺和2-异丙烯基苯并恶唑。其中的一些已被金属催化的对应物二聚化。相反，可能由于β-取代基的空间位阻，诸如丁烯腈，巴豆酸甲酯和2-环己烯-1-酮的亚乙烯基底物不经历二聚化。相反，发现这些的Rauhut-Currier（RC）反应正在进行。
• Proton-Transfer Polymerization by <i>N</i>-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters
  作者：Miao Hong、Xiaoyan Tang、Laura Falivene、Lucia Caporaso、Luigi Cavallo、Eugene Y.-X. Chen

  DOI：10.1021/jacs.5b13019

  日期：2016.2.17

  presents a full account of experimental and theoretical/computational investigations into the N-heterocyclic carbene (NHC)-catalyzed proton-transfer polymerization (HTP) that converts common dimethacrylates (DMAs) containing no protic groups into unsaturated polyesters. This new HTP proceeds through the step-growth propagation cycles via enamine intermediates, consisting of the proposed conjugate addition-proton

  该贡献全面介绍了 N-杂环卡宾 (NHC) 催化的质子转移聚合 (HTP) 的实验和理论/计算研究，该聚合将不含质子基团的常见二甲基丙烯酸酯 (DMA) 转化为不饱和聚酯。这种新的 HTP 通过烯胺中间体通过逐步生长传播循环进行，包括提出的共轭加成 - 质子转移 - NHC 释放基本步骤。本研究考察了单体和催化剂的范围以及整个 HTP 机制中涉及的基本步骤。具有连接两种甲基丙烯酸酯的六种不同类型键的 DMA 已聚合成相应的不饱和聚酯。该系列中最吸引人的不饱和聚酯是基于生物质衍生的二甲基丙烯酸糠酯，表现出独特的自固化能力。四种 MeO 和 Cl 取代的 TPT（1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene）衍生物作为甲醇插入产物，(Rx)TPT(MeO/ H) (R = MeO, Cl; x = 2, 3) 和两种游离卡宾（催化剂），(OMe2)TPT