烯丙基磷酸二甲酯 | 757-54-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 中文名称: 烯丙基磷酸二甲酯
• 中文别名: 烯丙基磷酸二甲酯,TECH
• 英文名称: allylphosphonic acid dimethyl ester
• 英文别名: dimethyl allylphosphonate；3-dimethoxyphosphorylprop-1-ene
• CAS: 757-54-0
• 化学式: C₅H₁₁O₃P
• mdl: MFCD00014951
• 分子量: 150.114
• InChiKey: ZOSQAGGCVFVCNO-UHFFFAOYSA-N

物化性质

• 沸点：
  41-42 °C (0.5 mmHg)
• 密度：
  1.1378 g/cm3(Temp: 0 °C)
• 闪点：
  41-42°C/0.5mm
• 稳定性/保质期：

  常温常压下保持稳定，应避免与氧化物接触。

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 安全说明：
  S24/25
• 储存条件：
  请将容器密封，并存放在干燥、阴凉处。

SDS

Name:	Dimethyl Allylphosphonate 97% Material Safety Data Sheet
Synonym:	None Known
CAS:	757-54-0

Section 1 - Chemical Product MSDS Name:Dimethyl Allylphosphonate 97% Material Safety Data Sheet
Synonym:None Known

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
757-54-0	Dimethyl Allylphosphonate	97%	unlisted

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:
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.

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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:

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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. Vapors may be heavier than air. They can spread along the ground and collect in low or confined areas. Runoff from fire control or dilution water may cause pollution.
Extinguishing Media:
Use extinguishing media most appropriate for the surrounding fire.
Use agent most appropriate to extinguish fire.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. Avoid runoff into storm sewers and ditches which lead to waterways. Clean up spills immediately, observing precautions in the Protective Equipment section. Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use with adequate ventilation. Avoid breathing dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation.
Storage:
Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances.

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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# 757-54-0: 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: Liquid
Color: colorless
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 41-42 deg C @ 0.5 mmHg
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C5H11O3P
Molecular Weight: 150.049

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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, excess heat.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, oxides of phosphorus, irritating and toxic fumes and gases, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 757-54-0 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Dimethyl Allylphosphonate - 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
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# 757-54-0: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 757-54-0 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 757-54-0 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  烯丙基磷酸二甲酯 在 草酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 methyl allylphosphonochloridate
  参考文献：
  名称：

  （E）-丁-2-烯基核苷膦酰胺酸酯的高度聚合合成和抗病毒活性。

  摘要：

  在超声辐射下，通过交叉复分解，用氮试剂指导制备了几种迄今未知的（E）-丁-2-烯基核苷磷酸氨基酰胺类似物（ANP）。通过X射线衍射正式鉴定出两种非对映异构体。这些化合物针对各种DNA和RNA病毒进行了评估。其中，磷酸氨基酰胺胸腺嘧啶类似物19成为对抗水痘带状疱疹病毒（VZV）的最佳前药，野生型和胸苷激酶缺陷型菌株的EC50值分别为0.33和0.39μM，选择性指数≥200μM。这一突破性方法为新的嘌呤和嘧啶（E）-丁-2-烯基磷酸氨基酰胺类似物铺平了道路。

  DOI：

  10.1016/j.ejmech.2018.01.086
• 作为产物：
  描述：

  3-氯丙烯 在 aluminum nickel 三甲氧基磷 作用下， 生成 烯丙基磷酸二甲酯
  参考文献：
  名称：

  Process for the production of (meth)allyl phosphonic acid dialkyl esters

  摘要：

  本发明涉及一种生产烯丙基或甲基烯丙基膦酸二烷基酯的方法，该方法通过在存在价态和/或一价镍化合物或存在价态、一价或二价钴化合物的情况下，将烯丙基氯化物或甲基烯丙基氯化物与三烷基膦酸酯在80℃至160℃的温度下反应而得到。

  公开号：

  US04017564A1

文献信息

• New selectivities from old catalysts. Occlusion of Grubbs’ catalysts in PDMS to change their reactions
  作者：M. Brett Runge、Martin T. Mwangi、Ned B. Bowden

  DOI：10.1016/j.jorganchem.2006.09.022

  日期：2006.12

  dissolved in methylene chloride also react by olefin isomerization with occluded catalysts. Eleven examples of substrates that exhibit dual reactivity by undergoing olefin isomerization with occluded catalysts and olefin metathesis with catalysts dissolved in methylene chloride are reported. Most of these substrates have olefins with allylic phosphine oxides, carbonyls, or ethers. Control experiments demonstrate

  本文介绍了Grubbs第一代和第二代催化剂在聚二甲基硅氧烷（PDMS）的疏水性基质中被吸附时的新选择性。通过用二氯甲烷溶胀，然后在真空下除去溶剂，可将催化剂封闭在毫米大小的PDMS平板中。催化剂均相溶解在PDMS中，但仍保持催化活性。许多通过烯烃复分解反应与自由溶解在二氯甲烷中的Grubbs催化剂反应的底物也通过烯烃异构化与封闭的催化剂反应。报道了通过封闭的催化剂进行烯烃异构化和用溶解在二氯甲烷中的催化剂进行烯烃复分解而表现出双重反应性的底物的十一个实例。这些底物中的大多数具有带有烯丙基氧化膦，羰基或醚的烯烃。对照实验表明，通过催化剂从钌卡宾分解为拟议的氢化钌，溶剂中发生了异构化。通过将封闭的Grubbs的第一代催化剂在90％的MeOH / H中加热至100°C来扩展这项工作在各种烯烃的存在下将2 O转化为用于未官能化烯烃的Grubbs催化剂转化为异构化催化剂。这项工作表明，PDMS中有机
• Radical Transfer Hydroamination with Aminated Cyclohexadienes Using Polarity Reversal Catalysis:  Scope and Limitations
  作者：Joyram Guin、Christian Mück-Lichtenfeld、Stefan Grimme、Armido Studer

  DOI：10.1021/ja0692581

  日期：2007.4.1

  The synthesis of various new 1-aminated-2,5-cyclohexadienes is described. These reagents can be used in radical transfer hydroaminations of unactivated and electron-rich double bonds. With thiols as polarity reversal catalysts good yields are obtained. The radical hydroamination occurs with good to excellent anti-Markovnikov selectivity. Many functional groups such as alcohols, silyl ethers, phosphonates

  描述了各种新的 1-胺化-2,5-环己二烯的合成。这些试剂可用于未活化和富电子双键的自由基转移加氢胺化。使用硫醇作为极性反转催化剂可获得良好的产率。自由基加氢胺化以良好至极好的抗马尔可夫尼科夫选择性发生。许多官能团如醇、甲硅烷基醚、膦酸酯、芳基溴化物、酰亚胺、酰胺以及酸性质子在反应条件下是可以耐受的。DFT 计算提供了对甲硅烷基、烷基和氨基取代的环己二烯基的芳构化以生成相应的 C-、Si-和 N-中心自由基的见解。
• A Practical Route to Cyclobutanols and Fluorocyclobutanes
  作者：Vincent L. Revil‐Baudard、Samir Z. Zard

  DOI：10.1002/hlca.202100106

  日期：2021.9

  1-[(Ethoxycarbonothioyl)sulfanyl]cyclobutyl acetate (xanthate 7) was found to add to electronically unbiased alkenes and to certain heteroarenes. In the latter case, this corresponds to a variant of the Minisci reaction and allows the late-stage modification of biologically active substances. Saponification of the acetate furnishes the corresponding cyclobutanols, which, in the case of the nicotine

  发现 1-[(乙氧基碳硫酰基) 硫烷基] 环丁基乙酸酯 (黄原酸酯7 ) 添加到电子无偏烯烃和某些杂芳烃。在后一种情况下，这对应于Minisci反应的变体，并允许对生物活性物质进行后期修饰。乙酸盐的皂化提供相应的环丁醇，在尼古丁加合物的情况下，可以通过 DAST 的作用将其转化为氟环丁烷。氟环丁基取代的芳烃和杂芳烃越来越多地出现在候选药物中。用 TFA 加热咖啡因的乙酰氧基环丁基衍生物产生环丁烯类似物。最后，O-乙基S-[1-(2,2,2-三氟乙氧基)环丁基]二硫代碳酸酯，在优化黄原酸酯7的合成时意外获得，是一种非常有前途的试剂，用于引入非常罕见的 2,2,2-三氟乙氧基环丁基基序。
• Expedient synthesis and biological evaluation of alkenyl acyclic nucleoside phosphonate prodrugs
  作者：Elisa Pileggi、Michaela Serpi、Graciela Andrei、Dominique Schols、Robert Snoeck、Fabrizio Pertusati

  DOI：10.1016/j.bmc.2018.05.034

  日期：2018.7

  The importance of phosphonoamidate prodrugs (ProTides) of acyclic nucleoside phosphonate (ANPs) is highlighted by the approval of Tenofovir Alafenamide Fumarate for the treatment of HIV and HBV infections. In the present paper we are reporting an expedient, one-pot, two-steps synthesis of allyl phosphonoamidates and diamidates that offers a time saving strategy when compared to literature methods.

  替诺福韦艾拉酚胺富马酸酯获批用于治疗 HIV 和 HBV 感染凸显了无环核苷膦酸酯 (ANPs) 的膦酰胺酸酯前药 (ProTides) 的重要性。在本论文中，我们报告了一种方便的、一锅法、两步合成烯丙基膦酰胺和二酰胺的方法，与文献方法相比，它提供了一种节省时间的策略。报道了这些底物在与烯基官能化胸腺嘧啶和尿嘧啶核碱基的交叉复分解反应中的用途。通过这种方法合成的 ANPs 前药对它们对 DNA 和 RNA 病毒的抗病毒活性进行了评估。预计使用 5,6,7,8-四氢-1-萘基作为芳氧基部分能够在一系列其他无活性的尿嘧啶 ProTides 中赋予抗病毒活性。
• The Shortest Strategy for Generating Phosphonate Prodrugs by Olefin Cross-Metathesis - Application to Acyclonucleoside Phosphonates
  作者：Ugo Pradère、Hervé Clavier、Vincent Roy、Steven P. Nolan、Luigi A. Agrofoglio

  DOI：10.1002/ejoc.201101111

  日期：2011.12

  A short synthetic route to phosphonate prodrugs by olefin cross-metathesis, which uses either (acyloxymethyl) or (hexadecyloxypropyl) allylphosphonate building blocks is described. A study of eight ruthenium catalysts including the Ru–indenylidene catalyst, which bears the N-heterocyclic carbene 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene, was undertaken. This method was applied to

  描述了使用（酰氧基甲基）或（十六烷氧基丙基）烯丙基膦酸酯结构单元的烯烃交叉复分解来合成膦酸酯前药的短路线。对八种钌催化剂的研究，包括 Ru-茚基催化剂，该催化剂带有 N-杂环卡宾 1,3-双（2,6-二异丙基苯基）-4,5-二氢咪唑-2-亚基。该方法用于合成无环核苷膦酸酯前药。这种策略对于药物和医学研究的进一步用途很有吸引力。

表征谱图