氘代三氟乙酸 | 599-00-8

• 物质功能分类: 化学试剂 - 氘代试剂
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 氘代三氟乙酸
• 中文别名: 三氟乙酸-d1；三氯乙酸-d；氘代三氟乙酸-d1；氘代-三氟乙酸
• 英文名称: trifluoroacetic acid-d₁
• 英文别名: trifluoroacetic acid-d；TFA-d；TFA-d1；d-TFA；deuterated trifluoroacetic acid；d₁-trifluoroacetic acid；deuteriotrifluoroacetic acid；trifluoroacetic acid-OD；deuterio 2,2,2-trifluoroacetate
• CAS: 599-00-8
• 化学式: C₂HF₃O₂
• 分子量: 115.016
• InChiKey: DTQVDTLACAAQTR-DYCDLGHISA-N

物化性质

• 熔点：
  -15 °C
• 沸点：
  75 °C(lit.)
• 密度：
  1.493 g/mL at 25 °C(lit.)
• 闪点：
  72°C
• 溶解度：
  可溶于氯仿、甲醇（微量）
• 稳定性/保质期：
  性质与稳定性：在常温常压下，该物质不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  5

ADMET

毒理性

• 副作用

职业性肝毒素 - 第二性肝毒素：在职业环境中的毒性效应潜力是基于人类摄入或动物实验的中毒案例。 皮肤毒素 - 皮肤烧伤。 毒性肺炎 - 由于吸入金属烟雾或有毒气体和蒸气引起的肺部炎症。

Occupational hepatotoxin - Secondary hepatotoxins: the potential for toxic effect in the occupational setting is based on cases of poisoning by human ingestion or animal experimentation. Dermatotoxin - Skin burns. Toxic Pneumonitis - Inflammation of the lungs induced by inhalation of metal fumes or toxic gases and vapors.

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

安全信息

• TSCA：
  Yes
• 危险等级：
  8
• 危险品标志：
  C
• 安全说明：
  S26,S27,S28,S45,S61,S9
• 危险类别码：
  R35,R52/53,R20
• WGK Germany：
  3
• 海关编码：
  28459000
• 危险品运输编号：
  UN 2699 8/PG 1
• 危险标志：
  GHS05,GHS07
• 危险性描述：
  H314,H332
• 危险性防范说明：
  P280,P305 + P351 + P338,P310
• 储存条件：
  贮存：将密器密封后，存放于密封的主藏器中，并置于阴凉、干燥处。

SDS

Name:	Trifluoroacetic Acid-D 99.5 Atom% D Material Safety Data Sheet
Synonym:	TFA-
CAS:	599-00-8

Section 1 - Chemical Product MSDS Name:Trifluoroacetic Acid-D 99.5 Atom% D Material Safety Data Sheet
Synonym:TFA-

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
599-00-8	Trifluoroacetic Acid-D	99.5	209-961-2

Hazard Symbols: C
Risk Phrases: 35 20

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Causes severe burns. Harmful by inhalation.Corrosive.
Potential Health Effects
Eye:
Causes eye burns. May cause chemical conjunctivitis and corneal damage.
Skin:
Causes skin burns. May be absorbed through the skin. May cause skin rash (in milder cases), and cold and clammy skin with cyanosis or pale color.
Ingestion:
May cause severe and permanent damage to the digestive tract. Causes gastrointestinal tract burns. May cause perforation of the digestive tract. The toxicological properties of this substance have not been fully investigated. Ingestion of large amounts of fluoride may cause salivation, nausea, vomiting, abdominal pain, fever, labored breathing. Exposure to fluoride compounds can result in systemic toxic effects on the heart, liver, and kidneys. It may also deplete calcium levels in the body leading to hypocalcemia and death.
Fluoride can reduce calcium levels leading to fatal hypocalcemia.
May cause systemic effects.
Inhalation:
Causes chemical burns to the respiratory tract. The toxicological properties of this substance have not been fully investigated.
Aspiration may lead to pulmonary edema. May cause systemic effects.
Chronic:
Chronic inhalation and ingestion may cause chronic fluoride poisoning (fluorosis) characterized by weight loss, weakness, anemia, brittle bones, and stiff joints. Effects may be delayed.
Chronic exposure to fluoride compounds may cause systemic toxicity.

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Section 4 - FIRST AID MEASURES
Eyes: Get medical aid immediately. Do NOT allow victim to rub eyes or keep eyes closed. Extensive irrigation with water is required (at least 30 minutes).
Skin:
Get medical aid immediately. Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse. Destroy contaminated shoes.
Ingestion:
Do not induce vomiting. If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give anything by mouth to an unconscious person. Get medical aid immediately.
Inhalation:
Get medical aid immediately. Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Do NOT use mouth-to-mouth resuscitation. If breathing has ceased apply artificial respiration using oxygen and a suitable mechanical device such as a bag and a mask.
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. Can burn in a fire, releasing toxic vapors. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Use water spray to keep fire-exposed containers cool. Containers may explode in the heat of a fire. Vapors may be heavier than air. They can spread along the ground and collect in low or confined areas.
Extinguishing Media:
Use agent most appropriate to extinguish fire. Do NOT get water inside containers. Cool containers with flooding quantities of water until well after fire is out. 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:
Avoid runoff into storm sewers and ditches which lead to waterways.
Clean up spills immediately, observing precautions in the Protective Equipment section. Absorb spill using an absorbent, non-combustible material such as earth, sand, or vermiculite. Do not use combustible materials such as sawdust. Provide ventilation. Do not get water inside containers.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use with adequate ventilation. Do not breathe dust, vapor, mist, or gas. Do not get in eyes, on skin, or on clothing. Keep container tightly closed. Avoid ingestion and inhalation. Discard contaminated shoes.
Storage:
Keep container closed when not in use. Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances. Corrosives area.

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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 process enclosure, local exhaust ventilation, or other engineering controls to control airborne levels.
Exposure Limits CAS# 599-00-8: 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:
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements or European Standard EN 149 must be followed whenever workplace conditions warrant respirator use.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Liquid
Color: clear colorless to faint yellow
Odor: acetic odor
pH: acidic
Vapor Pressure: 4.0 mm Hg @ 0C
Viscosity: Not available.
Boiling Point: 75 deg C
Freezing/Melting Point: -15 deg C
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: Moderately Soluble.
Specific Gravity/Density: 1.493
Molecular Formula: C2DF3O2
Molecular Weight: 115.008

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable at room temperature in closed containers under normal storage and handling conditions.
Conditions to Avoid:
Incompatible materials, ignition sources, acids, strong oxidants, bases.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide, fluoride fumes, hydrogen fluoride gas.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 599-00-8 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Trifluoroacetic Acid-D - 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: C
Risk Phrases:
R 20 Harmful by inhalation.
R 35 Causes severe burns.
Safety Phrases:
S 28A After contact with skin, wash immediately with
plenty of water.
S 37 Wear suitable gloves.
S 45 In case of accident or if you feel unwell, seek
medical advice immediately (show the label where
possible).
WGK (Water Danger/Protection)
CAS# 599-00-8: No information available.
Canada
CAS# 599-00-8 is listed on Canada's NDSL List.
CAS# 599-00-8 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 599-00-8 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

简介

氘代三氟乙酸又称三氟乙酸-d，简称TFAA-d，是一种适用于常规核磁共振（NMR）分析的三氟乙酸（TFAA）的氘代同位素化合物。

用途

氘代三氟乙酸是一种多功能试剂，在有机化合物（包括精细化学品）合成中具有广泛应用。此外，它还可作为有机反应催化剂以及聚合物和染料生产中的溶剂。在各种工业产品的制备过程中，尤其是可生物降解塑料的制造中，也发挥着重要作用。作为氘代同位素化合物，它可用于合成NMR溶剂混合物，以研究高分子量聚酯（如聚乙醇酸(PG)和聚对苯二甲酸乙二醇酯(PET)）的NMR谱。

反应信息

• 作为反应物：
  描述：

  氘代三氟乙酸 在 [η⁵-CpFe(CO)(N,N-bis(2-mercaptoethyl)-1,5-diazacycloheptane)Ni]⁺ 、 tert-butylammonium hexafluorophosphate(V) 作用下， 以 乙腈 为溶剂， 生成 氘
  参考文献：
  名称：

  Hemilabile桥接硫醇盐作为仿生H2生产电催化剂中的质子穿梭

  摘要：

  合成类似物和计算辅助的结构-功能分析已被用于探索受 [NiFe]-氢化酶活性位点启发的电催化剂中控制质子-电子和质子-氢化物偶联的特征。衍生自二硫醇络合物 MN2S2（N2S2 = 双巯基乙烷二氮杂环庚烷；M = Ni 或 Fe（NO））与 (η5-C5H5)Fe(CO)+（Fe' 组分）或 (η5-C5H5) 的聚集的双金属配合物Fe(CO)2+、Fe"，分别生成 Ni-Fe'+、Fe-Fe'+、Ni-Fe"+ 和 Fe-Fe"+，Ni-Fe'+ 和 Fe-Fe' + 被确定为在三氟乙酸存在下生产 H2 的活性电催化剂。电化学势和 H2 生成的相关性与预测机制中的计算参数一致，该机制描述了电子和质子的添加顺序、氧化还原活性非无害 NO 配体在电子吸收中的作用、Fe'-S 键的必要性断裂（或金属二硫醇配体的半化能力）和氢化物-质子偶联途径。尽管氧化还原活性 {Fe(NO)}7 部分可以接受

  DOI：

  10.1021/jacs.6b06461
• 作为产物：
  描述：

  三氟乙酸酐 在 重水 作用下， 生成 氘代三氟乙酸
  参考文献：
  名称：

  4,8-脱水-2,3-二脱氧-d-半乳糖和-d-葡萄糖-非-3-烯丙基二甲基乙缩醛的合成及其作为1H-nmr光谱测定质子化过程的新探针的应用糖苷水解酶

  摘要：

  摘要通过多步合成法制备了标题非蔗糖衍生物2（d-galacto）和4-（d-葡萄糖）。仅通过来自大肠杆菌的相应酶β-d-半乳糖苷酶，来自生咖啡豆的α-d-半乳糖苷酶和来自甜杏仁的β-d-葡萄糖苷酶，α-d才将水加至这两种化合物的烯醇双键中。 -酵母中的葡萄糖苷酶。在D 2 O中进行2的酶促水合以分析加成反应的空间过程，得到2,3-二脱氧-α-d-半乳糖-（3- 2 H）-壬基-4-纤维素二甲基乙缩醛（5） ，当水解时，提供了以螺烷16和17为主要产物（85％）和稠环系统18和19为次要成分（15％）的平衡混合物。酶促水合产物的硼氢化物还原得到两种差向异构体14和15的可分离混合物，可在酸性甲醇中于62°转化8小时，分别转化为20和22。刚性的双环系统允许轻松地将单氘C-3上的构型指定为（S），从而可以确定酶催化起始步骤的空间过程，即底物中烯醇双键的氘化用过的。

  DOI：

  10.1016/0008-6215(91)84092-s
• 作为试剂：
  描述：

  2,5-bis(2-(hex-1-yn-1-yl)phenyl)-3-methylthiophene 在 氘代三氟乙酸 、 platinum(II) chloride 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  通过 Pt(II) 催化的一锅扩环和 6-内环化反应合成噻喃稠合多环芳香族化合物

  摘要：

  通过一锅扩环和6-内环化反应，由含2,5-二(1-en-3-炔基)噻吩前体直接合成了一系列噻喃稠合多环芳烃(PAH)。反应监测和密度函数理论计算表明扩环反应发生在6-内环化之前。此外，噻喃稠合 PAH 的吸收曲线表明，环戊二烯环戊二烯环一侧的 π 共轭延伸在延长有效共轭长度方面起主导作用，而延伸对另一侧的影响则占主导地位。边可以忽略不计。此外，所有噻喃稠合的多环芳烃均表现出卤色特性。添加三氟甲磺酸后，可以发现这些噻喃稠合多环芳烃的荧光“关闭-开启”开关。因此，这项工作不仅为一锅扩环和6-内环化反应提供了一种新的合成方法，而且扩大了噻喃稠合PAHs的多样性。

  DOI：

  10.1021/acs.joc.4c00446

文献信息

• Reactions of a dinuclear tungsten complex containing an O-co-ordinated bridging ketene with various heterocumulenes
  作者：Luxti J. J. Wang、Sen-Jen You、Shou-Ling Huang、Yu-Lee Yang、Ying-Chih Lin、Gene-Hsiang Lee、Shie-Ming Peng

  DOI：10.1039/a901823i

  日期：——

  Treatment of the dinuclear O-co-ordinated ketene complex W2Cp2(CO)5(µ-η1∶η2-CH2CO) (Cp = η5-C5H5) with PhCH2NCS afforded the dark red bridging thioketene complex W2Cp2(CO)5(µ-η3-SCCH2). Reaction of the latter with HBF4 gave the stable cationic product [W2Cp2(CO)5(µ-SCMe3)]BF4 by addition of a proton to the terminal carbon of the thioketene group. In the reaction of W2Cp2(CO)5(µ-η1∶η2-CH2CO) with CS2 cleavage

  双核O形协调烯酮复杂W的处理2的Cp 2（CO）5（μ-η 1 :η 2 -CH 2 CO）（CP =η 5 -C 5 H ^ 5）用的PhCH 2个NCS，得到暗红桥接硫代双烯酮复杂w ^ 2的Cp 2（CO）5（μ-η 3 -SC CH 2）。后者与HBF 4的反应得到稳定的阳离子产物[W 2 Cp 2（CO）5（µ-SCMe 3）] BF 4通过在硫代烯基的末端碳上加一个质子。在W的反应2的Cp 2（CO）5（μ-η 1 :η 2 -CH 2 CO）与CS 2一个CS键的断裂是伴随着将所得硫原子插入钨酰基键，得到W 2 Cp 2（CO）5（CS）（µ-CH 2 COS）。在CP'类似物（CP'=η 5 -C 5 H ^ 4 Me）中还制备。三硫代碳酸酯S C（SCH 2）2与W 2 Cp的反应2（CO） 5（μ-η 1 :η 2 -CH 2得到卡宾络合物W公司） 2的Cp 2（CO）
• Reaction of Cp*(CO)₂ReRe(CO)₂Cp* with Alkynes Produces Dimetallacyclopentenones Cp*(CO)₂Re(μ-η¹,η³-CRCR‘CO)Re(CO)Cp* Which React with Acid To Form Cationic Bridging Vinyl Complexes
  作者：Charles P. Casey、Ronald S. Cariño、Hiroyuki Sakaba

  DOI：10.1021/om960658e

  日期：1997.2.1

  η3-(CO2CH3)CC(CH3)CO]Re(CO)Cp* (10). At low temperature, the η2-propyne complex Cp*(CO)2Re(μ-CO)Re(CO)(HC⋮CCH3)Cp* (12) and Cp*(CO)2Re[μ-η1,η3-C(CH3)CHCO]Re(CO)Cp* (11) were observed as intermediates in the formation of Cp*(CO)2Re[μ-η1,η3-CHC(CH3)CO]Re(CO)Cp* (5). Protonation of dimetallacyclopentenone 2 with CF3CO2H produced [Cp*(CO)2Re(μ-η1,η2-CHCH2)Re(CO)2Cp*]+CF3CO2- (14), a species with a bridging

  Cp *（CO）2 Re Re（CO）2 Cp *（1）与末端炔烃HC⋮CR（R = H，CH 3，C 6 H 5，C（CH 3）CH 2，OCH 2 CH 3）反应以产生dimetallacyclopentenones的Cp *（CO）2的Re（μ-η 1，η 3 -CH CRCO）的Re（CO）的Cp *（4 - 8）。1与具有一个酯取代基的炔烃的反应也产生了双金属环戊烯酮。的反应1与HC⋮CCO 2我得到的Cp *（CO）2重新[μ-η 1，η 3 -CH C（CO 2 CH 3）CO]的Re（CO）的Cp *（9），并用CH 3 Ç⋮CCO 2我得到的Cp *（CO）2再[μ-η 1，η 3 - （CO 2 CH 3）C C（CH 3）CO]的Re（CO）的Cp *（10）。在低温时，η 2 -propyne复杂的Cp *（CO）2的Re（μ-CO）的Re（CO）（HC⋮CCH 3）的Cp
• Synthesis of protonated carboxylato and trifluoromethanesulfonato derivatives of vanadium(II) by redox reactions on bis(mesitylene)vanadium(0)
  作者：Fausto Calderazzo、Giuseppe E. De Benedetto、Serena Detti、Guido Pampaloni

  DOI：10.1039/a702462b

  日期：——

  Bis(mesitylene)vanadium(0), V(mes) 2 , underwent a two-electron redox process in heptane with CF 3 SO 3 H affording the vanadium(II) derivative [V(CF 3 SO 3 ) 2 (CF 3 SO 3 H)], an example of a co-ordination compound containing both the acid and its conjugated base in its composition. The vanadium(0) complex and CF 3 CO 2 H gave a product resulting from a one-electron transfer process, namely [V(mes) 2 ][CF 3 CO 2 ]. This compound, which dissolves unchanged in neat CF 3 CO 2 H–(CF 3 CO) 2 O, evolves to the vanadium(II) derivative [H(thf) n ][V(CF 3 CO 2 ) 3 ] (thf = tetrahydrofuran) by addition of tetrahydrofuran. Deprotonation of the vanadium(II) complexes occurs in the presence of thf or heterocyclic nitrogen bases to form the ionic derivatives [HB][VA 3 ], B = thf or a heterocyclic nitrogen base; A = CF 3 SO 3 or CF 3 CO 2 . The trifluoroacetato derivative [H(thf) n ][V(CF 3 CO 2 ) 3 ] undergoes methylation with CH 2 N 2 to the vanadium(II) ester adduct [V(CF 3 CO 2 ) 2 (CF 3 CO 2 CH 3 )], and is oxidized to the vanadium(III) trifluoroacetato derivatives [V(CF 3 CO 2 ) 3 ] and [V(CF 3 CO 2 ) 2 C 14 H 8 O 2 ] by benzoyl peroxide (or dioxygen) and 9,10-phenanthrenedione, respectively.

  双(均三甲苯)钒(0), V(mes)2, 在庚烷中经历了一个两电子的氧化还原过程，与CF3SO3H反应生成了钒(II)衍生物 [V(CF3SO3)2(CF3SO3H)]，这是一个在其组成中同时含有酸及其共轭碱的配位化合物实例。钒(0)配合物与CF3CO2H通过单电子转移过程生成了产物 [V(mes)2][CF3CO2]。该化合物在纯净的CF3CO2H-(CF3CO)2O中溶解不变，通过加入四氢呋喃转变为钒(II)衍生物 [H(thf)n][V(CF3CO2)3] (thf = 四氢呋喃)。在存在四氢呋喃或杂环氮碱的情况下，钒(II)配合物发生去质子化，形成离子衍生物 [HB][VA3]，其中B = 四氢呋喃或杂环氮碱；A = CF3SO3 或 CF3CO2。三氟乙酸钒(II)衍生物 [H(thf)n][V(CF3CO2)3] 经CH2N2甲基化得到钒(II)酯加合物 [V(CF3CO2)2(CF3CO2CH3)]，并可通过苯甲酰过氧化物（或氧气）和9,10-菲醌分别氧化为钒(III)三氟乙酸盐衍生物 [V(CF3CO2)3] 和 [V(CF3CO2)2C14H8O2]。
• Palladium-Catalyzed Regioselective C–H Functionalization of Arenes Substituted by Two <i>N</i>-Heterocycles and Application in Late-Stage Functionalization
  作者：Da-Wei Yin、Gang Liu

  DOI：10.1021/acs.joc.8b00322

  日期：2018.4.6

  Pd-catalyzed regioselective C–H activation method that is used for C–H deuteration, carbonylation, halogenation, and oxidation of arene substrates substituted by two N-heterocycles. When conducted in acetic acid (AcOH), these reactions occur at the five-membered palladacycle sites, whereas they switch to the six-membered palladacycle sites in trifluoroacetic acid (TFA). This controllable regioselective C–H

  本文报道了一种钯催化的区域选择性C–H活化方法，用于C–H氘代，羰基化，卤化和氧化被两个N-杂环取代的芳烃底物。当在乙酸（AcOH）中进行时，这些反应发生在五元的Palladacycle位置，而它们切换到三氟乙酸（TFA）中的六元的Palladacycle位置。这种可控的区域选择性C–H激活被用于生物活性分子的后期功能化。一项机理研究表明，区域选择性是通过布朗斯台德酸-刘易斯碱相互作用和电子效应（在TFA中）以及palladacycle中间体的不同动力学稳定性（在AcOH中）实现的。
• 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。