1,2-dicarba-closo-dodecaborane(12) | 16872-09-6

• 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: 1,2-dicarba-closo-dodecaborane(12)
• 英文别名: 1,2-dicarba-closo-dodecarborane；1,2-dicarbo-closed-dodecaborane；1,2-dicarba-closo-dodecaborane；1,2-dicarba-closododecaborane；closo-1,2-dicarbadodecaborane；1,2-dicarbaclosododecaborane
• CAS: 16872-09-6
• 化学式: C₂H₁₂B₁₀
• 分子量: 144.227
• InChiKey: PPDYBWGWYRHTPJ-UHFFFAOYSA-N

物化性质

• 熔点：
  285-287°C
• 密度：
  0.95
• 溶解度：
  可溶于氯仿（少量）、DMSO（少量）、甲醇（少量）
• 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
• 危险等级：
  4.1
• 危险品标志：
  Xn
• 安全说明：
  S36
• 危险类别码：
  R22
• WGK Germany：
  3
• 海关编码：
  29319090
• 危险品运输编号：
  UN 1325
• RTECS号：
  HS9285000
• 包装等级：
  III
• 危险类别：
  4.1
• 储存条件：
  常温下应密闭避光，并存放在通风干燥处。

SDS

Name:	o-Carborane 99% Material Safety Data Sheet
Synonym:	1,2-Dicarbadodecarborane (12
CAS:	16872-09-6

Section 1 - Chemical Product MSDS Name:o-Carborane 99% Material Safety Data Sheet
Synonym:1,2-Dicarbadodecarborane (12

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
16872-09-6	o-Carborane, 99%	99%	240-897-8

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

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
Ingestion of large amounts may cause gastrointestinal irritation.
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.

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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:
Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Get medical aid if irritation develops or persists.
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.
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 if cough or other symptoms appear.
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 water fog, dry chemical, carbon dioxide, or regular 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.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Wash hands before eating. Use with adequate ventilation. Avoid contact with skin and eyes. Avoid ingestion and inhalation.
Storage:
Store in a cool, dry place. 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 general or local explosion-proof ventilation to keep airborne levels to acceptable levels.
Exposure Limits CAS# 16872-09-6: 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.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Solid
Color: light gray
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: 400 deg C ( 752.00 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature: 400 deg C
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C2H12B10
Molecular Weight: 144.23

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide, oxides of boron, borane.
Hazardous Polymerization: Has not been reported.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 16872-09-6: HS9285000 LD50/LC50:
CAS# 16872-09-6: Inhalation, mouse: LC50 = 170 mg/m3; Oral, mouse: LD50 = 675 mg/kg; Oral, rabbit: LD50 = 1612 mg/kg; Oral, rat: LD50 = 1525 mg/kg.
Carcinogenicity:
o-Carborane, 99% - 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: Not available.
Risk Phrases:
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 16872-09-6: No information available.
Canada
CAS# 16872-09-6 is listed on Canada's NDSL List.
CAS# 16872-09-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 16872-09-6 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

化学性质

邻碳硼烷是一种无色固体，在320°C时熔化而不分解。其分子具有C2v的对称性，是十二氢十二硼酸根的等电子体。当加热至420°C后，它会重新排列形成间位异构体间碳硼烷；而对位异构体则通过加热到600°C以上的温度生成。

它可以被还原形成二价负离子，并与有机锂化合物反应脱去两个质子： [ \text{C}2\text{B}{10}\text{H}{12} + 2\text{BuLi} → \text{Li}2\text{C}2\text{B}{10}\text{H}{10} + 2\text{BuH} ] 生成的锂盐可以与亲电试剂反应。邻碳硼烷的碱降解产生11顶点阴离子碳硼烷，它是巢式二碳杂十一硼烷酸根配合物的前体： [ \text{C}2\text{B}{10}\text{H}{12} + \text{NaOEt} + 2\text{EtOH} → \text{Na}^+\text{C}2\text{B}{9}\text{H}_{12} + \text{H}_2 + \text{B(OEt)}3 ] [ \text{Na}^+\text{C}2\text{B}{9}\text{H}{12} + \text{NaH} → \text{Na}2\text{C}2\text{B}{9}\text{H}{11} + \text{H}2 ] 与环戊二烯负离子类似，这个阴离子（[ \text{C}2\text{B}{9}\text{H}{11}^2- ]）可以形成结构类似的夹心配合物。

用途

邻碳硼烷是一种由两个碳原子和十个硼原子组成的二十面体团簇。当它连接在共轭体系中时，一方面可提供较大的空间位阻，减少不利的分子间相互作用，提高固体发光效率；另一方面作为分子受体产生分子内电荷转移的效果，增加对环境刺激的响应性。

邻碳硼烷是一种具有特殊电子效应和大体积位阻的三维σ-芳香性笼状原子基团，具备良好的化学和热稳定性。基于这些优点，它在有机材料化学、金属有机化学、药物化学、机械力化学以及硼中子捕获疗法等多个领域引起了广泛关注。

由于其分子结构缺电子性，在与绝大多数生色基团连接时表现出较强的吸电子效应，并具有一个非常特殊的C–C键。碳硼烷的C–C键在溶液中可以伸缩旋转，键长随环境变化而变化，从而能够与有机共轭基团（相对于碳硼烷而言通常是电子给体）相互作用，对化合物光学性质产生显著影响。

有趣的是，通过选择性地去除一个碳硼烷的硼顶点，其闭式结构可转换为巢式的阴离子结构[ \text{nido–C}2\text{B}{9}\text{H}_{12}^? ]；该离子结构作为一种优异的水溶性基团，可用于制备具有水溶性的有机荧光分子。

生产方法

美国科学家于1963年首次合成了邻碳硼烷。合成过程涉及两个步骤：首先生成癸硼烷加合物；其次引入乙炔作为两个碳顶点来源。反应方程式为： [ \text{B}{10}\text{H}{14} + 2\text{SEt}2 → \text{B}{10}\text{H}_{12}(\text{SEt}_2)2 + \text{H}2 ] [ \text{B}{10}\text{H}{12}(\text{SEt}_2)_2 + \text{C}_2\text{H}2 → \text{C}2\text{B}{10}\text{H}{12} + 2\text{SEt}_2 + \text{H}_2 ] 使用其他炔烃也可以合成邻碳硼烷及其有机衍生物。

毒性

急性毒性：大鼠经口LD50为9 gm/kg。通常对水体稍微有害，不要将未稀释或大量产品接触地下水、水道或污水系统；未经政府许可勿排入周围环境。

反应信息

• 作为反应物：
  描述：

  1,2-dicarba-closo-dodecaborane(12) 在 正丁基锂 、 碘 作用下， 以 乙醚 为溶剂， 生成 1,2-diiodo-1,2-dicarba-dodecaborane(12)
  参考文献：
  名称：

  二十面体碳硼烷衍生物的强σ孔活化性，可用于定向卤化物识别。

  摘要：

  基于σ空穴相互作用的晶体工程是新兴的实现更高复杂性的新材料的方法。中性无机簇从1,2- dicarba-衍生闭合碳-dodecaborane，与-SeMe，-TeMe和-I部分在两个骨架碳顶点取代的本文中实验证明优秀chalcogen-和卤键供体。特别是，这些新分子与固态中的卤化物阴离子强烈相互作用。卤化物离子被一个或两个供电子基团（配位μ 1 -和μ 2坐标），以将离散的单体或二聚体基序稳定到一维超分子之字形链。至关重要的是，观察到的硫属元素键和卤素键相互作用具有明显的短距离和高方向性。静电势计算进一步证明了碳硼烷衍生物的效率，V s，max与参考有机卤素键供体（如碘五氟苯）相似或什至更高。

  DOI：

  10.1002/anie.202010462
• 作为产物：
  描述：

  3-iodo-o-carborane 在 三苯基膦 、 锌 作用下， 以 吡啶 为溶剂， 生成 1,2-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  The BI activation in o-carborane clusters: their fate towards BH. Easy synthesis of [7,10-C2B10H13]−

  摘要：

  The reaction of 3-I-o-carborane with Cu, Cu/PPh3 [Ni(PPh3)(3)], or [Pd(PPh3)(4)] has been Studied to find the suitability of B-iodine substituted carboranes as sources of new boron-derivatives. In all these reactions a hydrodehalogenation reaction to yield o-carborane has been produced, indicating that B-I activation takes place. It may be considered that B-I adds oxidatively to M, but alternative explanations can be given. Reaction of 3-I-o-carborane with Na/naphthalene also produced o-carborane showing that albeit an oxidative addition is impossible for sodium the same hydrodehalogenation had taken place. The same result was also formed with Mg. Addition of 1,2-dibromoethane to the Mg/o-carborane reaction yielded [7,10-C2B10-H-13](-). Then, the sequence 3-I-o-carborane --> o-carborane [7,10-C2B10H13](-) can be generated with only reducing agents. The synthetic procedure for [7,10-C2B10H13](-) is very simple and produces a 97% yield of [NMe4][7,10-C2B10H13]. Basically, 1,2-C2B10H12 and Mg in excess are refluxed in THF in the presence of I-2 and 1,2-dibromoethane. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)01108-1
• 作为试剂：
  描述：

  硝酸钾-15N 在 1,2-dicarba-closo-dodecaborane(12) 、 三氟甲磺酸 、 六氟异丙醇 作用下， 生成 亚硝酸钾-15N
  参考文献：
  名称：

  B(9)-OH-o-Carboranes：合成、机理和性质探索

  摘要：

  在此，我们通过在三氟甲磺酸 (HOTf) 和六氟异丙醇 (HFIP) 的协助下使用市售的 68% HNO 3氧化邻碳硼烷，提出了一种化学稳健且高效的 B(9)-OH-o-碳硼烷合成路线. 反应效率高，碳硼烷范围广，B(9)/B(8)的选择性高达98:2。这种转化的成功依赖于 HNO 3的强亲电性和氧化性，通过布朗斯台德酸 HOTf 和溶剂 HFIP 的氢键促进。机理研究表明，邻碳硼烷的氧化涉及 HNO 3的初始亲电攻击到邻碳硼烷的最具负电性的 B(9) 处的氢原子。在这种转化中，B-H键的氢原子是亲核位点，不同于亲电取代反应中硼原子是亲核位点。因此，这是邻碳硼烷在温和条件下的氧化还原反应，其中 N(V) → N(III) 和 H(-I) → H(I)。9-OH- o的衍生化-carborane 进一步检查，carboranyl 基团被成功地引入氨基酸、聚乙二醇、生物素、脱氧尿苷和糖类。毫无

  DOI：

  10.1021/jacs.2c13570

文献信息

• Manipulation of Phosphorescence Efficiency of Cyclometalated Iridium Complexes by Substituted<i>o</i>-Carboranes
  作者：Young Hoon Lee、Jihyun Park、Song-Jin Jo、Miyoung Kim、Junseong Lee、Sang Uck Lee、Min Hyung Lee

  DOI：10.1002/chem.201405433

  日期：2015.1.26

  and emission wavelengths of the complexes are almost invariant to the change of 2‐R group, the phosphorescence quantum efficiency varies from highly emissive (ΦPL≈0.80 for R=H, alkyl) to poorly emissive (R=aryl) depending on the 2‐R group and the polarity of the medium. Theoretical studies suggest that 1) the almost nonemissive nature of the 2‐aryl‐substituted complexes is mainly attributable to the

  一系列的[（C ^ N）2的Ir（acac）]的配合物[5-（2-R-CB）PPY} 2的Ir（acac）]的（3 - 3克; ACAC =乙酰，CB = Ö -碳硼烷-1-基，ppy = 2-苯基吡啶; R = H（3 a），Me（3 b），i Pr（3 c），i Bu（3 d），Ph（3 e），CF 3 C 6 H 4（3 f），C 6 F 5（3 g））和各种2-R-取代的o制备了ppy配体苯环中5位的碳酮。X射线衍射研究表明，碳硼烷CC键的长度随着2-R取代基的空间位阻和吸电子作用的增加而增加。尽管复合物的吸收和发射波长几乎不变的2-R基团的变化，磷光量子效率从高发射（可变Φ PL ≈0.80为R = H，烷基）不佳发射（R =芳基），这取决于在2‐R组和介质的极性上 理论研究表明：1）2-芳基取代的配合物几乎没有排斥性，这主要归因于O对S 1激发态的LUMO的巨大贡献。-ca
• Directive effects in the hydroboration of 1-alkenyl derivatives of o-carborane with representative hydroborating agents
  作者：G.W. Kabalka、G. Hondrogiannis

  DOI：10.1016/s0022-328x(96)06695-8

  日期：1997.5

  A series of 1-alkenyl-o-carboranes was hydroborated using representative hydroborating agents with different steric requirements. The steric and electronic effects of the carboranyl group were evaluated by examining the distribution of the isomeric alcohols obtained after oxidation of the intermediate carboranyl-substituted organoboranes.

  一系列的1-链烯基- ö -carboranes使用代表hydroborating剂具有不同的空间要求是硼氢化。通过检查在中间体碳硼烷基取代的有机硼烷的氧化后获得的异构醇的分布，评估了碳硼烷基的空间和电子效应。
• Enantiomerically Pure Bis(phosphanyl)carbaborane(12) Compounds
  作者：Sebastian Bauer、Steffen Tschirschwitz、Peter Lönnecke、René Frank、Barbara Kirchner、Matthew L. Clarke、Evamarie Hey‐Hawkins

  DOI：10.1002/ejic.200900304

  日期：2009.7

  Enantiomerically pure (RP,RP)- and (RP,SP)-1,2-bis[1-adamantyloxy-(–)-menthyloxyphosphanyl]-closo-dicarbaborane(12), 1,2-bis[bis(–)-menthyloxyphosphanyl]-closo-dicarbaborane(12)and 1,2-bis[bis(4-tert-butylphenyloxy)phosphanyl]-closo-dicarbaborane(12) were synthesised by the reaction of dilithiated 1,2-dicarba-closo-dodecaborane(12) with two equivalents of the corresponding chlorophosphite. The phosphonites

  对映体纯 (RP,RP)- 和 (RP,SP)-1,2-双[1-金刚烷氧基-(-)-薄荷氧基膦酰基]-closo-dicarbaborane(12), 1,2-bis[bis(-)-由二锂化的 1,2-二碳-二碳硼烷 (12) 和 1,2-双[双 (4-叔丁基苯氧基) 膦酰基]-邻-二碳硼烷 (12) 反应合成12) 与两当量的相应氯亚磷酸酯。亚膦酸酯对差向异构化、氧气和水稳定。观察到 P…P 空间耦合，3JPP 耦合常数由光谱模拟和 DFT 计算确定。制备了钼和铑的晚期过渡金属配合物来研究双（膦酰基）碳硼烷 (12) 化合物的配位特性。在与各种烯烃的均相催化加氢甲酰化反应中研究了各种铑配合物的催化性能。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Reactivity Studies on 2,3,4,5‐Tetraethyl‐1,6‐diiodo‐2,3,4,5‐tetracarba‐ <i>nido</i> ‐hexaborane(6): Synthesis and Structures of New C ₄ B ₂ <i>nido</i> ‐Carborane Derivatives
  作者：Yong Nie、Hans Pritzkow、Walter Siebert

  DOI：10.1002/ejic.200300938

  日期：2004.6

  6a and 7a are formed as the predominant B6-substituted carborane products. In addition, trace amounts of 1,6-disubstituted species 6b and 7b are also detected. The substitution at the apical B−I group in 2a with an alkynyl group is effected by a Pd0-catalyzed Negishi-type cross-coupling reaction to give compound 8. The reaction of 1 and monolithio-o-carborane affords the C4B2−C2B10 carborane 10, while

  报告了标题化合物 2,3,4,5-四乙基-1,6-diiodo-2,3,4,5-tetracarba-nido-hexaborane(6) (1) 对多种亲核试剂的反应性。当 1 用 RC2Li (R = Ph, tBu, SiMe3, p-tolyl) 和 Ph2PLi 处理时，相应的新 C4B2nido-carborane 衍生物 2a-d 和 3 分别通过在基础 B-I 基团的选择性取代获得，而顶端的 B-I 键保持惰性。1 与 K[(η5-C5H5)Fe(CO)2] 的反应提供了新的物种 4，它包含一个 CpFe(CO)2 片段，σ 键合到 C4B2 簇的基础硼原子上。尝试通过硅胶色谱法分离 4 导致 Fe-B 键断裂并形成化合物 5，其中包含基础 BH 顶点，其可以通过 1 和 LiBEt3H 的反应单独制备。在 1 分别与 PhLi 和 Me3SnLi 的反应中，6a 和 7a
• 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

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