1,7-dicarba-closo-dodecaborane(12) | 16986-24-6

• 物质功能分类: 化学试剂 - 有机试剂 - 硼烷
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 各种混合金属/非金属
• 英文名称: 1,7-dicarba-closo-dodecaborane(12)
• 英文别名: 1,7-dicarbora-closo-dodecaborane；1,7-dicarba-closo-dodecaborane；1,7-dicarba-closo-decaborane；1,7-dicarbaclosododecaborane；1,2-dicarbadodecaborane；1,7-dicarbadodecaborane
• CAS: 16986-24-6
• 化学式: C₂H₁₂B₁₀
• 分子量: 144.227
• InChiKey: NHBIWBXUPGPZST-UHFFFAOYSA-N

物化性质

• 熔点：
  272 °C
• 溶解度：
  可溶于氯仿、甲醇（少许）
• 稳定性/保质期：
  常温常压下稳定，避免与氧化物接触。

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

安全信息

• TSCA：
  Y
• 危险品标志：
  Xn
• 安全说明：
  S26,S36/37/39,S37/39
• 危险类别码：
  R22,R36/37/38
• WGK Germany：
  3
• 海关编码：
  29420000
• RTECS号：
  HS9290000
• 储存条件：
  常温密闭避光，存于通风干燥处。

SDS

Name:	M-Carborane Material Safety Data Sheet
Synonym:	1,7-Dicarbadodecaborane; M-Barene; M-Decarborocarborane; M-Dicarbadodecaborane; Neobarene; Neocarborane
CAS:	16986-24-6

Section 1 - Chemical Product MSDS Name:M-Carborane Material Safety Data Sheet
Synonym:1,7-Dicarbadodecaborane; M-Barene; M-Decarborocarborane; M-Dicarbadodecaborane; Neobarene; Neocarborane

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
16986-24-6	M-Carborane	ca 100	241-065-7

Hazard Symbols: XN
Risk Phrases: 22 36/37/38

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Harmful if swallowed. Irritating to eyes, respiratory system and skin.
Potential Health Effects
Eye:
Causes eye irritation.
Skin:
Causes skin irritation.
Ingestion:
May cause gastrointestinal irritation with nausea, vomiting and diarrhea. Can cause nervous system damage. May be harmful if swallowed.
Inhalation:
Causes respiratory tract irritation. The toxicological properties of this substance have not been fully investigated.
Chronic:
Repeated exposure may cause central nervous system damage.

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Section 4 - FIRST AID MEASURES
Eyes: Immediately 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.

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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.
Extinguishing Media:
Use agent most appropriate to extinguish fire. 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:
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.

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Section 7 - HANDLING and STORAGE
Handling:
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. Use with adequate ventilation. Wash clothing before reuse.
Storage:
Store in a tightly closed container. Keep under a nitrogen blanket.
Store in a cool, dry, well-ventilated area away from incompatible substances. 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# 16986-24-6: 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:
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: Powder
Color: white
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 applicable.
Flash Point: Not applicable.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C2H12B10
Molecular Weight: 144.184

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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, dust generation, excess heat, exposure to moist air or water.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide, oxides of boron, borane.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 16986-24-6: HS9290000 LD50/LC50:
CAS# 16986-24-6: Oral, mouse: LD50 = 12 gm/kg; Oral, rat: LD50 = 1410 mg/kg.
Carcinogenicity:
M-Carborane - Not listed by ACGIH, IARC, or NTP.
Other:
See actual entry in RTECS for complete information.

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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: XN
Risk Phrases:
R 22 Harmful if swallowed.
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 37/39 Wear suitable gloves and eye/face
protection.
WGK (Water Danger/Protection)
CAS# 16986-24-6: No information available.
Canada
CAS# 16986-24-6 is listed on Canada's NDSL List.
CAS# 16986-24-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 16986-24-6 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

概述

间碳硼烷C₂B₁₀H₁₂具有二十面体结构，是最早发现并制备的二十面体碳硼烷。随后，研究开发了将邻位衍生物异构化为间位和对位异构体的方法。例如，在高温（600℃）下，通过热管流过的过程，邻-甲基可以重排或异构化为间-甲基。然而，这种在高温下的方法可能导致间碳硼烷蒸气接触空气时燃烧或爆炸，因此对工业操作没有实际应用。

另一种用于使碳硼烷异构化的方法是在较低温度下将大的甲硅烷基团取代的邻氨基甲酸酯热重排为金属异构体。与上述流动方法不同，这种本体异构化在回流温度下容易发生，并且可以使用常规实验室设备进行。

制备

间碳硼烷的制备步骤如下：将配备有机械搅拌器、氮气入口和温度计的500ml三颈烧瓶中加入可得自商标为Dexsil202的碳硼烷-硅氧烷聚合物（10g）和四氢呋喃（100ml）。一次加入氟化钾溶液（1克KF·2H₂O溶于50毫升水中），并同时在冰水浴中搅拌冷却。随后，加入一滴商标为Adogen464的甲基三烷基氯化铵表面活性剂，移除冷却浴，并将两相反应混合物在环境温度下搅拌16小时。

将反应混合物转移至分液漏斗并分离各层。有机层用饱和氯化钠溶液（100ml）洗涤，干燥（使用MgSO₄），并过滤。蒸发溶剂后，得到粘性残余物。通过真空升华产生2.79g（理论值的93%）间碳硼烷。最终产物通过核磁共振和红外光谱以及与真实样品的高效液相保留时间进行分析确认。

反应信息

• 作为反应物：
  描述：

  1,7-dicarba-closo-dodecaborane(12) 以 neat (no solvent) 为溶剂， 以6.5%的产率得到1,12-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  p-Carborane [1,12-Dicarbaclovododecaborane(12)]

  摘要：

  DOI：

  10.1021/ja01065a045
• 作为产物：
  描述：

  1,2-dicarba-closo-dodecaborane(12) 生成 1,7-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  坚持到无法放弃：硼簇中的芳香性在根本性结构变化中幸存下来

  摘要：

  o-C2B10H12 在 400 ºC 加热时异构化为 m-C2B10H12。在 o-C2B10H12 中脱硼是一个相对容易的过程，而在 m-C2B10H12 中则比较困难。这两个实验事实表明 m-C2B10H12 在热力学上比 o-C2B10H12 更稳定。另一方面，人们普遍认为，氯硼烷和碳硼烷是芳香族化合物。在这项工作中，我们将碳硼烷脱硼的困难与稳定性和芳香性联系起来。我们通过结合实验室工作和 DFT 计算来做到这一点。在计算上，我们的结果表明，m-C2B10H12 较高的热力学稳定性与芳香性差异无关，而是与碳硼烷结构中 C 原子的位置有关。还证明了在闭硼烷和碳硼烷中观察到的芳香性也存在于它们的 nido 对应物中，因此，我们得出结论，硼簇中的芳香性在根本的结构变化中仍然存在。此外，夹心金属茂（例如二茂铁）和夹心金属（二碳化物）（例如[Co(C2B9H11)2]-）传统上被认为是相似的

  DOI：

  10.1021/jacs.0c02228
• 作为试剂：
  描述：

  2,2,6,6-四甲基哌啶氧化物 、 N-(tert-Butyl)-N-((1-phenylvinyl)oxy)-3,5-bis(trifluoromethyl)benzamide 在 1,7-dicarba-closo-dodecaborane(12) 作用下， 以60 %的产率得到1-phenyl-2-((2,2,6,6-tetramethylpiperidin-1-yl)oxy)ethan-1-one
  参考文献：
  名称：

  通过氢原子转移对二十面体碳硼烷进行直接 B-H 官能化

  摘要：

  由于在相似的化学环境中存在 10 个惰性 B-H 键，硼顶点处二十面体碳硼烷 (C 2 B 10 H 12 ) 的高效和选择性官能化是一项长期存在的挑战。在此，我们报告了一种新的反应范式，用于通过通过以氮为中心的自由基介导的氢原子转移 (HAT) 策略实现 B-H 均裂。碳硼烷 B-H 键的 HAT 过程和由此产生的以硼为中心的碳硼烷基自由基中间体均已通过实验得到证实。该反应发生在 B-H 键解离能 (BDE) 最低的最富电子的硼顶点处。使用这种策略，在光引发条件下，以无金属和氧化还原中性的方式，已经以令人满意的产率实现了多种碳硼烷衍生化，包括硫醇化、硒化、炔基化、烯基化、氰化和卤化。此外，当前协议的合成效用也通过放大反应和基于碳硼烷的功能分子的构建得到了证明。所以，

  DOI：

  10.1021/jacs.3c01314

文献信息

• Developing nitrosocarborane chemistry
  作者：Samuel L. Powley、Louise Schaefer、Wing. Y. Man、David Ellis、Georgina M. Rosair、Alan J. Welch

  DOI：10.1039/c5dt04831a

  日期：——

  molecule, H-bonded to the acidic C2′H of 10, is “delivered” to the adjacent C2NO unit. The ability of the NO group in nitrosocarboranes to undergo Diels–Alder cycloaddition reactions with cyclic 1,3-dienes was established via the syntheses of [1-(NOC10H14)-1,2-closo-C2B10H11] (14) and [1-(NOC6H8)-2-Ph-1,2-closo-C2B10H10] (15). This strategy was then utilised to prepare derivatives of the elusive dinitroso

  新nitrosocarboranes [1-NO-2-R-1,2-闭合碳-C 2乙10 ħ 10 ] [R = CH 2 Cl（上1），CH 3 OCH 2（2）p -MeC 6 ħ 4（3），SiMe 3（4）和SiMe 2 t Bu（5）]和[1-NO-7-Ph-1,7- closo -C 2 B 10 H 10 ]（6）的合成方法是，使适当的硫代碳烷在乙醚中与NOCl在石油醚中的反应，然后用NaHCO 3水溶液淬灭反应。这些明亮的蓝色化合物在光谱学上进行了表征，在某些情况下，通过使用在衍射仪上从液体样品中原位生长的晶体在晶体学上确定了2和6的结构。在所有情况下，亚硝基键合到碳硼烷作为1E取代基（弯曲C-N-O顺序），并且具有对<几乎没有或没有影响δ 11 B>，加权平均11相对于母体（单取代）碳硼烷的化学位移。单酯和1,1'-二（二亚硝基衍生物米-carborane），化合物7和8分
• Mercuration ofB(9)-substitutedmeta- andortho-carboranes
  作者：A. Ya. Usyatinsky、K. V. Budkina、P. V. Petrovskii、V. I. Bregadze

  DOI：10.1007/bf00698511

  日期：1995.4

  The mercuration of substituted R2C2B10H9X-9 type carboranes (where R=m-H, X= Cl, Br, I, Me; R=o-H, X=Me) was studied. It was found that mercury atoms add to the boron atoms in position 10 ofmeta-carboranes and in position 12 ofortho-carboranes,i.e., to the boron atoms adjacent to the boron atom bonded to the X substituent. Symmetrical (R2C2B10H8X)2Hg type derivatives were obtained. It was shown that

  研究了取代的 R2C2B10H9X-9 型碳硼烷（其中 R=mH，X=Cl、Br、I、Me；R=oH，X=Me）的汞化。发现汞原子加到间碳硼烷的10位和邻位碳硼烷的12位的硼原子上，即加到与与X取代基键合的硼原子相邻的硼原子上。获得了对称的 (R2C2B10H8X)2Hg 型衍生物。结果表明，它们可用作金属转移反应的起始原料。
• Synthesis ofo-andm-carborane derivatives of [2,2]paracyclophane and abnormal Clemmensen reduction of ketones of the [2,2]paracyclophane and carborane series
  作者：L. I. Zakharkin、V. A. Ol'shevskaya、L. E. Vinogradova

  DOI：10.1007/bf02496219

  日期：1997.6

  andm-carboranyl substituents in position 4, separated from the [2,2]paracyclophane system by one or two C atoms (alcohols and ketones) were developed. The Clemmensen reduction of a number of ketones of the [2,2]paracyclophane ando-carbonane series occurs abnormally. The reduction of 1-benzoyl-o-carboranes to the corresponding alcohols by zinc in ethanol in a neutral medium was performed for the first

  开发了合成 [2,2] 对环芳烃衍生物的方法，该衍生物在 4 位含有 o-和 m-碳硼烷基取代基，与 [2,2] 对环芳烃系统通过一或两个碳原子（醇和酮）隔开。[2,2] 对环烷和碳烷系列的许多酮的克莱门森还原异常发生。首次在中性介质中在乙醇中用锌将 1-苯甲酰基-o-碳硼烷还原为相应的醇。
• Transition metal promoted reactions of polyhedral boranes and carboranes
  作者：L. G. Sneddon

  DOI：10.1351/pac198759070837

  日期：1987.1.1

  summarized in the following table: Metal Promoted Reactions Organic Polyhedral Boranes 1. Acetylene Addition Synthesis of Olefins, Synthesis of Alkenyl— Hydrosilylation boranes and —Carboranes 2. Olefin Substitution Arene—Olefin Coupling, Synthesis of Alkenyl— Synthesis of Substituted boranes and —Carboranes Olef ins 3. Cyclo—Addition Synthesis of Alicyclic Synthesis of Two—, Four— Compounds or Higher

  过渡金属催化剂的使用彻底改变了有机化学的合成策略；然而，这些试剂直到最近才被应用于无机领域。我们的工作描述了这些试剂可用于催化或促进涉及多面体硼烷和碳硼烷的各种转化，包括：硼烷-乙炔加成、乙炔-硼烷插入、硼烷-烯烃偶联、脱氢偶联、脱氢缩合和笼-生长反应。讨论了说明这些反应的范围和可能机制的选定实例。引言多面体硼笼化学的主要问题之一是缺乏用于构建更大笼系统的通用合成路线。这种限制既阻碍了这些类型化合物的潜在商业应用，也严重阻碍了该领域的进一步探索性研究。我们的工作试图通过检查过渡金属试剂的使用来解决这个问题，类似于有机和有机金属化学中广泛使用的那些，以诱导多面体硼烷和碳硼烷的高产率选择性转化。过渡金属试剂广泛用于有机化学，以催化或促进各种可能与多面体硼烷化学相似的转化。下表总结了一些反应类型和可能应用的例子： 金属促进反应有机多面体硼烷 1. 烯烃的乙炔加成合成，烯基-氢化硅烷化硼烷和-碳硼烷的合成
• Oxidative Generation of Boron-Centered Radicals in Carboranes
  作者：Harrison A. Mills、Joshua L. Martin、Arnold L. Rheingold、Alexander M. Spokoyny

  DOI：10.1021/jacs.0c00300

  日期：2020.3.11

  dichalcogenides, and N-heterocycles, yielding the corresponding substituted carboranes containing B-O, B-S, B-Se, B-Te, and B-C bonds. Remarkably, this chemistry tolerates various electronic environments, providing access to facile substitution chemistry at both electron-rich and electron-poor B-H vertices in carboranes.

  我们报告了第一次间接观察和使用由改性碳硼酰前体氧化产生的以硼顶点为中心的碳硼酰自由基。这些自由基中间体是通过硼簇笼和外多面体硼基取代基（例如-BF3K、-B(OH)2）之间的BB键的直接氧化形成的。原位生成的自由基物种被证明是与基于氧的自由基、二硫属化物和 N-杂环反应的有效底物，产生含有 BO、BS、B-Se、B-Te 和 BC 键的相应取代碳硼烷。值得注意的是，这种化学能耐受各种电子环境，在碳硼烷中的富电子和缺电子 BH 顶点处提供了简便的取代化学。

表征谱图