甲基-13C-三苯基碘化膦 | 81826-67-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 甲基-13C-三苯基碘化膦
• 中文别名: 碘化甲基-13C-三苯基磷
• 英文名称: [13C]-methyltriphenylphosphonium iodide
• 英文别名: methyl-¹³C-triphenylphosphonium iodide；(methyl-¹³C)methyltriphenylphosphonium iodide；Methyl-13C-triphenylphosphonium iodide；(113C)methyl(triphenyl)phosphanium;iodide
• CAS: 81826-67-7
• 化学式: C₁₉H₁₈P*I
• 分子量: 405.219
• InChiKey: JNMIXMFEVJHFNY-YTBWXGASSA-M

物化性质

• 熔点：
  186-188 °C(lit.)
• 溶解度：
  溶于二甲基亚砜
• 稳定性/保质期：
  避免使用强氧化剂。

计算性质

• 辛醇/水分配系数(LogP)：
  0.61
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 危险品标志：
  Xi
• 危险标志：
  GHS07
• 危险性描述：
  H315,H319,H335
• 危险性防范说明：
  P261,P305 + P351 + P338
• 储存条件：
  请将贮藏器密封，并将其存放在阴凉、干燥的地方。同时，确保工作环境有良好的通风或排气装置。

SDS

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SECTION 1: Identification of the substance/mixture and of the company/undertaking
Product identifiers
Product name : Methyl-13C-triphenylphosphonium iodide
REACH No. : A registration number is not available for this substance as the substance
or its uses are exempted from registration, the annual tonnage does not
require a registration or the registration is envisaged for a later
registration deadline.
CAS-No. : 81826-67-7
Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances

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SECTION 2: Hazards identification
Classification of the substance or mixture
Classification according to Regulation (EC) No 1272/2008
Skin irritation (Category 2), H315
Eye irritation (Category 2), H319
Specific target organ toxicity - single exposure (Category 3), H335
For the full text of the H-Statements mentioned in this Section, see Section 16.
Classification according to EU Directives 67/548/EEC or 1999/45/EC
Xi Irritant R36/37/38
For the full text of the R-phrases mentioned in this Section, see Section 16.
Label elements
Labelling according Regulation (EC) No 1272/2008
Pictogram
Signal word Warning
Hazard statement(s)
H315 Causes skin irritation.
H319 Causes serious eye irritation.
H335 May cause respiratory irritation.
Precautionary statement(s)
P261 Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray.
P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove
contact lenses, if present and easy to do. Continue rinsing.
Supplemental Hazard none
Statements
Other hazards - none

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SECTION 3: Composition/information on ingredients
Substances
Chemical characterization : Isotopically labeled
Synonyms : 13C Labeled Methyltriphenylphosphonium iodide
Formula : 13CC18H18IP
Molecular Weight : 405,22 g/mol
CAS-No. : 81826-67-7
Hazardous ingredients according to Regulation (EC) No 1272/2008
Component Classification Concentration
Methyl-13C-triphenylphosphonium iodide
CAS-No. 81826-67-7 Skin Irrit. 2; Eye Irrit. 2; STOT <= 100 %
SE 3; H315, H319, H335
Hazardous ingredients according to Directive 1999/45/EC
Component Classification Concentration
Methyl-13C-triphenylphosphonium iodide
CAS-No. 81826-67-7 Xi, R36/37/38 <= 100 %
For the full text of the H-Statements and R-Phrases mentioned in this Section, see Section 16

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SECTION 4: First aid measures
Description of first aid measures
General advice
Consult a physician. Show this safety data sheet to the doctor in attendance.
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.
In case of skin contact
Wash off with soap and plenty of water. Consult a physician.
In case of eye contact
Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.
If swallowed
Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.
Most important symptoms and effects, both acute and delayed
The most important known symptoms and effects are described in the labelling (see section 2.2) and/or in
section 11
Indication of any immediate medical attention and special treatment needed
no data available

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SECTION 5: Firefighting measures
Extinguishing media
Suitable extinguishing media
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
Special hazards arising from the substance or mixture
Carbon oxides, Oxides of phosphorus, Hydrogen iodide
Advice for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Further information
no data available

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SECTION 6: Accidental release measures
Personal precautions, protective equipment and emergency procedures
Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure
adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust.
For personal protection see section 8.
Environmental precautions
Do not let product enter drains.
Methods and materials for containment and cleaning up
Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suitable, closed
containers for disposal.
Reference to other sections
For disposal see section 13.

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SECTION 7: Handling and storage
Precautions for safe handling
Avoid contact with skin and eyes. Avoid formation of dust and aerosols.
Provide appropriate exhaust ventilation at places where dust is formed.
For precautions see section 2.2.
Conditions for safe storage, including any incompatibilities
Store in cool place. Keep container tightly closed in a dry and well-ventilated place.
Store under inert gas. hygroscopic
Specific end use(s)
Apart from the uses mentioned in section 1.2 no other specific uses are stipulated

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SECTION 8: Exposure controls/personal protection
Control parameters
Components with workplace control parameters
Exposure controls
Appropriate engineering controls
Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and
at the end of workday.
Personal protective equipment
Eye/face protection
Safety glasses with side-shields conforming to EN166 Use equipment for eye protection tested
and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique
(without touching glove's outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and
the standard EN 374 derived from it.
Body Protection
impervious clothing, The type of protective equipment must be selected according to the
concentration and amount of the dangerous substance at the specific workplace.
Respiratory protection
For nuisance exposures use type P95 (US) or type P1 (EU EN 143) particle respirator.For higher
level protection use type OV/AG/P99 (US) or type ABEK-P2 (EU EN 143) respirator cartridges.
Use respirators and components tested and approved under appropriate government standards
such as NIOSH (US) or CEN (EU).
Control of environmental exposure
Do not let product enter drains.

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SECTION 9: Physical and chemical properties
Information on basic physical and chemical properties
a) Appearance Form: solid
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing Melting point/range: 186 - 188 °C - lit.
point
f) Initial boiling point and no data available
boiling range
g) Flash point no data available
h) Evapouration rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower no data available
flammability or
explosive limits
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density no data available
n) Water solubility no data available
o) Partition coefficient: n- no data available
octanol/water
p) Auto-ignition no data available
temperature
q) Decomposition no data available
temperature
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available
Other safety information
no data available

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SECTION 10: Stability and reactivity
Reactivity
no data available
Chemical stability
Decomposes on exposure to light.
Stable under recommended storage conditions.
Possibility of hazardous reactions
no data available
Conditions to avoid
no data available
Incompatible materials
Strong oxidizing agents
Hazardous decomposition products
In the event of fire: see section 5

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SECTION 11: Toxicological information
Information on toxicological effects
Acute toxicity
no data available
Skin corrosion/irritation
no data available
Serious eye damage/eye irritation
no data available
Respiratory or skin sensitisation
no data available
Germ cell mutagenicity
no data available
Carcinogenicity
IARC: No component of this product present at levels greater than or equal to 0.1% is identified as
probable, possible or confirmed human carcinogen by IARC.
Reproductive toxicity
no data available
Specific target organ toxicity - single exposure
Inhalation - May cause respiratory irritation.
no data available
Specific target organ toxicity - repeated exposure
no data available
Aspiration hazard
no data available
Additional Information
RTECS: Not available
To the best of our knowledge, the chemical, physical, and toxicological properties have not been
thoroughly investigated.

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SECTION 12: Ecological information
Toxicity
no data available
Persistence and degradability
no data available
Bioaccumulative potential
no data available
Mobility in soil
no data available
Results of PBT and vPvB assessment
PBT/vPvB assessment not available as chemical safety assessment not required/not conducted
Other adverse effects
no data available

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SECTION 13: Disposal considerations
Waste treatment methods
Product
Offer surplus and non-recyclable solutions to a licensed disposal company. Dissolve or mix the material
with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber.
Contaminated packaging
Dispose of as unused product.

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SECTION 14: Transport information
UN number
ADR/RID: - IMDG: - IATA: -
UN proper shipping name
ADR/RID: Not dangerous goods
IMDG: Not dangerous goods
IATA: Not dangerous goods
Transport hazard class(es)
ADR/RID: - IMDG: - IATA: -
Packaging group
ADR/RID: - IMDG: - IATA: -
Environmental hazards
ADR/RID: no IMDG Marine pollutant: no IATA: no
Special precautions for user
no data available

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SECTION 15 - REGULATORY INFORMATION
N/A

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  甲基-13C-三苯基碘化膦 在 potassium tert-butylate 作用下， 以 乙醚 为溶剂， 反应 0.17h， 生成 methylenetriphenylphosphorane-methylene-13C
  参考文献：
  名称：

  不对称膦-亚磷酸酯配体Pd(II)配合物催化丙烯与一氧化碳交替共聚的机理

  摘要：

  负责丙烯与一氧化碳的高度对映选择性不对称共聚的反应步骤，由带有不对称手性双齿膦-亚磷酸酯的阳离子 Pd(II) 配合物催化，(R,S)-BINAPHOS [(R,S)-2-( diphenylphosphino)-1,1'-binaphthalen-2'-yl 1,1'-binaphthalene-2,2'-diyl phosphite = L1]。对催化剂前体 (SP-4-2)- 和 (SP-4-3)-Pd(CH3)Cl(L1) (1a 和 1b) 和 (SP-4-3)-[ Pd(CH3)(CH3CN)(L1)]·X1 (X1 = B{3,5-(CF3)2C6H3}4) (2)，以及与反应步骤相关的配合物，(SP-4-3)-[ Pd(COCH3)(CH3CN)(L1)]·X1 (3), (SP-4-3)- 和 (SP-4-4)-[Pd{CH2CH(CH3)COCH3}(L1)]·X1 (

  DOI：

  10.1021/ja973199x
• 作为产物：
  描述：

  碘甲烷-13C 在 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 72.0h， 生成 甲基-13C-三苯基碘化膦
  参考文献：
  名称：

  高自旋钴 (II) 配合物的 Z-选择性烯烃异构化

  摘要：

  简单的末端烯烃异构化为具有 Z 立体化学的内部异构体的情况很少见，因为通常会形成更稳定的 E 异构体。我们在这里表明，由庞大的 β-二酮亚胺配体支撑的钴 (II) 催化剂具有适当的动力学选择性来催化一些简单的 1-烯烃的异构化，特别是作为稳定性较差的 Z-异构体的 2-烯烃。催化通过“烷基”机制进行，三配位钴 (II) 烷基配合物作为静止状态。如同位素标记实验所示，β-氢化物消除和 [1,2]-插入步骤都很快。立体模型通过在 β-氢化物消除的过渡态钴 (II) 处的方形平面几何结构来解释选择性。该催化剂不仅适用于简单的烯烃，还适用于高烯丙基硅烷、缩酮、和甲硅烷基醚。从与不良底物的反应中分离出钴 (I) 或钴 (II) 产物表明，关键的催化剂分解途径是双分子的，降低催化剂浓度通常会提高选择性。除了潜在有用的选择性转化之外，这些研究还为高自旋钴配合物催化烯烃异构化提供了机理理解，并证明了空间体

  DOI：

  10.1021/ja408238n
• 作为试剂：
  描述：

  (4S,5S,6S)-4-[1,3]Dioxolan-2-ylmethyl-5-formyl-6-((2S,3R,4S,5R,6R)-3,4,5-triacetoxy-6-acetoxymethyl-tetrahydro-pyran-2-yloxy)-5,6-dihydro-4H-pyran-3-carboxylic acid methyl ester 在 硫酸 正丁基锂 、 甲基-13C-三苯基碘化膦 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 11.0h， 生成 (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-(((2S,3R,4S)-4-(2,2-dimethoxyethyl)-5-(methoxycarbonyl)-3-(vinyl-13C)-3,4-dihydro-2H-pyran-2-yl)oxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate
  参考文献：
  名称：

  Tietze, Lutz F.; Henke, Stephan; Remberg, Gerd, Liebigs Annalen der Chemie, 1986, # 8, p. 1413 - 1427

  摘要：

  DOI：

文献信息

• Practical synthesis of d-[1-13C]mannose, l-[1-13C] and l-[6-13C]fucose
  作者：Ken-ichi Sato、Shoji Akai、Hiroki Youda、Masaru Kojima、Mayumi Sakuma、Shu-ichirou Inaba、Kyota Kurosawa

  DOI：10.1016/j.tetlet.2004.11.073

  日期：2005.1

  The chemical synthesis of 13C-labeled mannose and fucose is important for the preparation of molecular probes used in the conformational study of the oligosaccharide portions of glycoproteins. A new method for the synthesis of the title [1-13C]-labeled compounds via the corresponding olefin compounds, which are in turn derived from d-mannitol or l-arabinose by efficient introduction of 13C, by the

  13 C标记的甘露糖和岩藻糖的化学合成对于制备用于糖蛋白寡糖部分构象研究的分子探针非常重要。为标题[1-合成的新方法13 C]标记的化合物通过相应的烯烃化合物，它们是依次从d-甘露醇或通过有效地引入的L-阿拉伯糖来源的13 C，通过Wittig反应使用pH描述了3 P 13 CH 3 I和n- BuLi。引进的13 CH 3我以产生[1- 13 C] -和[6- 13C 1-标记的化合物分别以62％，56％和71％的产率完成。所有甘露糖和岩藻糖质子，从H-1〜H-6，通过使用1 HMQC-TOCSY技术观察：[1- 1分的混合物13 C] -和[6- 13 C]标记的化合物。
• Inserting Porphyrin Quantum Dots in Bottom‐Up Synthesized Graphene Nanoribbons
  作者：Wade Perkins、Felix R. Fischer

  DOI：10.1002/chem.201705252

  日期：2017.12.14

  copolymerization of tetraphenylcyclopentadienone, a precursor for cove graphene nanoribbons (cGNRs), with bifunctional porphyrins yields defined nanostructures comprised of a single cGNR‐porphyrin‐cGNR heterojunction within each ribbon. 13C NMR labeling and high‐resolution mass spectrometry of solubilized polymer intermediates indicates that every porphyrin is covalently linked to two extended segments of

  Diels-Alder共聚四苯基环戊二烯酮（一种海湾石墨烯纳米带（cGNRs）的前体）与双官能卟啉可产生定义的纳米结构，该纳米结构由每个碳带内的单个cGNR-卟啉-cGNR异质结组成。13溶解的聚合物中间体的13 C NMR标记和高分辨率质谱表明，每个卟啉均与cGNR的两个延伸段共价连接。UV / Vis吸收和荧光发射光谱揭示了卟啉与相邻cGNR段之间的强电子相关性，可通过卟啉核的可逆金属化作用来减弱这种相关性。这种通用的自下而上的合成策略可在单个石墨烯纳米带中访问结构明确，功能完善的GNR量子点GNR异质结构。
• Mechanistic Studies of an Antibody-Catalyzed Pericyclic Rearrangement
  作者：Edward M. Driggers、Ho S. Cho、Corey W. Liu、Catherine P. Katzka、Andrew C. Braisted、Helle D. Ulrich、David E. Wemmer、Peter G. Schultz

  DOI：10.1021/ja962933u

  日期：1998.3.1

  We report NMR and kinetic studies of antibody AZ-28, which was generated against the diaryl-substituted cyclohexanol derivative 3 and catalyzes the oxy-Cope rearrangement of the corresponding hexadiene 1 to aldehyde 2 (Braisted, A. C., Schultz, P. G. J. Am. Chem. Soc. 1994, 116, 2211−2212). Conformational studies of free substrate and the antibody−substrate complex using transferred-NOE experiments

  我们报告了抗体 AZ-28 的 NMR 和动力学研究，该抗体是针对二芳基取代的环己醇衍生物 3 产生的，并催化相应的己二烯 1 的 oxy-Cope 重排为醛 2（Braisted, AC, Schultz, PGJ Am. Chem. Soc. 1994, 116, 2211−2212)。使用转移 NOE 实验对游离底物和抗体-底物复合物进行的构象研究表明，抗体以环状构象结合底物，与 3 的椅子状几何形状一致。相反，游离底物在溶液中采用扩展构象。尽管 NMR 显示结合底物的构象限制，但反应的温度依赖性表明抗体主要通过降低 ΔH⧧ 发挥作用，抵消 ΔS⧧ 的降低；ΔH⧧和ΔS⧧的值为15.4±2。分别为 4 kcal/mol 和 -23 ± 8 cal/mol K。测定了底物 23 的二次动力学同位素效应 (kcatH/kcatD) 为 0.61 ± 0.1，其中两个烯丙基 ...
• An α‐Cyclopropanation of Carbonyl Derivatives by Oxidative Umpolung
  作者：Adriano Bauer、Giovanni Di Mauro、Jing Li、Nuno Maulide

  DOI：10.1002/anie.202007439

  日期：2020.10.5

  nucleophiles is often associated with umpolung and cationic mechanisms. Herein, we report a general process converting a range of ketone derivatives into α‐cyclopropanated ketones by oxidative umpolung. Mechanistic investigation and careful characterization of side products revealed that the reaction follows an unexpected pathway and suggests the intermediacy of non‐classical carbocations.

  碘 (III) 试剂对亲核试剂的反应性通常与 umpolung 和阳离子机制有关。在此，我们报告了通过氧化 umpolung 将一系列酮衍生物转化为 α-环丙烷化酮的一般过程。对副产物的机理研究和仔细表征表明，该反应遵循意想不到的途径，并表明非经典碳正离子的中间体。
• Hemisynthesis of 2,3,4-¹³C3-1,4-Androstadien-3,17-dione: A Key Precursor for the Synthesis of ¹³C3-Androstanes and ¹³C3-Estranes
  作者：Clément Berthonneau、Pierrick Nun、Matthieu Rivière、Mickael Pauvert、Fabrice Dénès、Jacques Lebreton

  DOI：10.1021/acs.joc.7b03216

  日期：2018.4.6

  batches of the key intermediate 1 in 42% overall yield. At the final stage, the A-ring was reconstructed through a Wittig reaction with the 1-triphenylphosphoranylidene-13C3-2-propanone 2, followed by an intramolecular condensation assisted by thioacetic acid via a Michael addition/retro-Michael reaction sequence to provide 2,3,4-13C3-1,4-androstadien-3,17-dione.

  在这项贡献中，我们描述了两种简单有效的制备酮醛1的途径，酮醛1是合成13 C3-雄甾烷和13 C3-雌烷的关键中间体。在第一种方法中，目标目标醛1的总产率为40％，是由1,4-雄甾烷3,17-二酮（3 mmol规模）通过两步法进行的，涉及一锅，异常的臭氧分解/硫氧化/ retro-Michael /臭氧分解过程。或者，使用六步序列优化了由4-雄烯酮-3,17-二酮形成的第二条路线，以42％的总收率生产了40 mmol批次的关键中间体1。在最后阶段，通过Wittig反应与1-triphenylphosphoranylidene-13 C3-2-丙酮2，然后通过迈克尔加成反应/复古迈克尔反应序列，在硫代乙酸的协助下进行分子内缩合，得到2,3,4- 13 C3-1,4-androstadien-3,17-dione。