六甲基磷酰三胺-d18 | 51219-90-0

• 物质功能分类: 有机原料 - 氨基化合物
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 中文名称: 六甲基磷酰三胺-d18
• 英文名称: hexamethylphosphoric triamide-D18
• 英文别名: hexakis-trideuteriomethyl-phosphamide；Tris(di(2H3)methylamido)phosphorus；Octadecadeuterio-hexamethyl-phosphoramide；N-bis[bis(trideuteriomethyl)amino]phosphoryl-1,1,1-trideuterio-N-(trideuteriomethyl)methanamine
• CAS: 51219-90-0
• 化学式: C₆H₁₈N₃OP
• 分子量: 197.059
• InChiKey: GNOIPBMMFNIUFM-NBDUPMGQSA-N

物化性质

• 密度：
  1.03

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  26.8
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险品标志：
  Xi
• 危险类别码：
  R45,R46
• 安全说明：
  S45,S53

SDS

Name:	Hexamethylphosphoramide-d18 99.8 atom% d Material Safety Data Sheet
Synonym:
CAS:	51219-90-0

Section 1 - Chemical Product MSDS Name:Hexamethylphosphoramide-d18 99.8 atom% d Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
51219-90-0	Hexamethylphosphoramide-d18	99.8	257-063-4

Hazard Symbols: T
Risk Phrases: 36/37/38 45 46

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Irritating to eyes, respiratory system and skin. May cause cancer.
May cause heritable genetic damage.Hygroscopic (absorbs moisture from the air).
Potential Health Effects
Eye:
Causes eye irritation. May cause chemical conjunctivitis.
Skin:
Causes skin irritation.
Ingestion:
May cause gastrointestinal irritation with nausea, vomiting and diarrhea.
Inhalation:
Causes respiratory tract irritation. Can produce delayed pulmonary edema.
Chronic:
Effects may be delayed. Chronic exposure may cause lung damage. May cause kidney damage. Possible risk of irreversible effects.

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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:
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.
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. 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. 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:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. 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. Remove contaminated clothing and wash before reuse. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation. Use with adequate ventilation.
Storage:
Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances. Store protected from moisture.

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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# 51219-90-0: 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:
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
Odor: None reported.
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: C6D18N3OP
Molecular Weight: 197.31

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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, exposure to moist air or water.
Incompatibilities with Other Materials:
Moisture, strong oxidizing agents.
Hazardous Decomposition Products:
Nitrogen oxides, phosphine, carbon monoxide, irritating and toxic fumes and gases, carbon dioxide, nitrogen.
Hazardous Polymerization: Has not been reported.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 51219-90-0 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Hexamethylphosphoramide-d18 - 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
Shipping Name: TOXIC LIQUID, ORGANIC, N.O.S.*
Hazard Class: 6.1
UN Number: 2810
Packing Group: II
IMO
Shipping Name: TOXIC LIQUID, ORGANIC, N.O.S.
Hazard Class: 6.1
UN Number: 2810
Packing Group: II
RID/ADR
Shipping Name: TOXIC LIQUID, ORGANIC, N.O.S.
Hazard Class: 6.1
UN Number: 2810
Packing group: II

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: T
Risk Phrases:
R 45 May cause cancer.
R 46 May cause heritable genetic damage.
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
S 53 Avoid exposure - obtain special instructions
before use.
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# 51219-90-0: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 51219-90-0 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 51219-90-0 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：

  3,4-二氢-1H-苯并吡喃 、 六甲基磷酰三胺-d18 在 叔丁基锂 作用下， 以 氘代四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  打破叔丁基锂接触离子对：锂化反应中替代选择性的途径

  摘要：

  通过NMR和DFT方法详细研究了路易斯碱性磷酰胺对叔丁基锂聚集结构的影响。据确定，六甲基磷酰胺 (HMPA) 可以改变t- BuLi 的平衡，以包含三重离子对 ( t -Bu–Li– t -Bu) - /HMPA 4 Li + ，它充当高反应性分离离子的储存库对t -Bu – /HMPA 4 Li + 。由于该离子对中锂原子的价态已饱和，路易斯酸度显着降低；反过来，碱度被最大化，这使得氧杂环内的典型定向效应被覆盖，并且远程 sp 3 C-H 键被去质子化。此外，利用这些新获得的锂聚集态开发了一种简单的γ-锂化和苯并二氢吡喃杂环与各种烷基卤化物亲电子试剂的捕获方案，收率良好。

  DOI：

  10.1021/jacs.2c13047
• 作为产物：
  描述：

  二甲基-D6-胺盐酸盐 在 三乙胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 16.5h， 以90%的产率得到六甲基磷酰三胺-d18
  参考文献：
  名称：

  一种氘代六甲基磷酰三胺-D18的合成方法

  摘要：

  本发明提供了一种氘代六甲基磷酰三胺‑D18的合成方法，所述的方法包括如下步骤：在三乙胺的存在下，将氘代二甲胺盐酸盐和三氯氧磷进行取代反应，制得氘代六甲基磷酰三胺‑D18；所述的反应中，反应溶剂为二氯甲烷，反应温度为室温，反应时间为16小时。本发明具有如下技术效果：本发明首次使用一种市售的氘代二甲胺盐酸盐替代氘代二甲胺气体，与三氯氧磷反应制得氘代六甲基磷酰三胺‑D18。

  公开号：

  CN111303206B

文献信息

• The Second Cyclopropannulene:  Cycloprop-[8]annulene
  作者：Matthew K. Kiesewetter、Richard C. Reiter、Cheryl D. Stevenson

  DOI：10.1021/ja044278t

  日期：2005.2.1

  monobromo[8]annulene (C8H7Br) with potassium tert-butoxide in hexamethylphosphoramide (HMPA) and following with exposure to potassium metal led to the formation of the anion radical of an HMPA-[6.1.0]bicyclononatetraene condensation product, in which two HMPA fragments are geminal and attached to the number 9 carbon. When the reaction sequence is carried out in THF, the dianion of cycloprop[8]annulene is predominantly

  将 CH2Cl2 和一溴 [8] 环烯 (C8H7Br) 的混合物与叔丁醇钾在六甲基磷酰胺 (HMPA) 中反应（在 0 摄氏度），然后暴露于金属钾，形成 HMPA-[ 6.1.0]bicyclononatetraene 缩合产物，其中两个 HMPA 片段是成对的并连接到数字 9 碳。当反应序列在 THF 中进行时，主要形成环丙 [8] 环烯的二价阴离子。中性环丙 [8] 环烯可以通过四氢呋喃溶液的 I2 氧化来分离。核磁共振分析表明，八元环几乎是平面的，三元环更像是二亚甲基环丙烷而不是环丙烯。更多，
• Zwitterion Radicals and Anion Radicals from Electron Transfer and Solvent Condensation with the Fingerprint Developing Agent Ninhydrin
  作者：Tyler D. Schertz、Richard C. Reiter、Cheryl D. Stevenson

  DOI：10.1021/jo0102720

  日期：2001.11.1

  solution electron affinity to extract an electron from the solvent (HMPA) to produce the indantrione anion radical. In liquid NH(3), the presence of trace amounts of amide ion causes the spontaneous formation of an anion radical condensation product, wherein the no. 2 carbon (originally a carbonyl carbon) becomes substituted with -NH(2) and -OH groups. In HMPA, the indantrione anion radical spontaneously

  茚三酮（指纹显影剂）在液氨和六甲基磷酰胺（HMPA）中自发脱水形成茚满三酮，其具有足够大的溶液电子亲和力，可从溶剂（HMPA）中提取电子以产生茚满三酮阴离子自由基。在液态NH（3）中，痕量酰胺离子的存在会导致阴离子自由基缩合产物的自发形成，2个碳原子（最初是羰基碳原子）被-NH（2）和-OH基团取代。在HMPA中，茚满三酮阴离子基团与HMPA自发形成缩合产物，从而产生各种两性离子基团。2个碳直接连接到HMPA的氮上。两性离子顺磁性缩合产物的形成机理类似于茚三酮与氨基酸反应生成Ruhemann紫，这是指纹显影中的对比产物。由茚三酮和含氮溶剂形成的阴离子和两性离子自由基缩合产物可能代表了一系列类似的聚酮-溶剂反应的例子。
• Reduction of an Hexamethylphosphoramide Degradation Product: A Diazabutadiene
  作者：Brad D. Rose、Steven J. Peters、Richard C. Reiter、Cheryl D. Stevenson

  DOI：10.1021/ol901798s

  日期：2009.10.15

  Alkali metal over-reduction of an electron acceptor in the presence of a hydrogen atom donor, In hexamethylphosphoramide (HMPA), results in a radical that is not simply the anion radical of the acceptor. This new species exhibits an enigmatic EPR pattern. Using N-15 and H-2 labeling studies, the "HMPA degradation product" was found to be the anion radical of N,N'-dimethyl-1,4-diazabutadiene. DFT calculations support this assignment and a mechanism for its formation.
• 一种氘代六甲基磷酰三胺-D18的合成方法
  申请人：南京昊绿生物科技有限公司

  公开号：CN111303206B

  公开（公告）日：2022-09-20

  本发明提供了一种氘代六甲基磷酰三胺‑D18的合成方法，所述的方法包括如下步骤：在三乙胺的存在下，将氘代二甲胺盐酸盐和三氯氧磷进行取代反应，制得氘代六甲基磷酰三胺‑D18；所述的反应中，反应溶剂为二氯甲烷，反应温度为室温，反应时间为16小时。本发明具有如下技术效果：本发明首次使用一种市售的氘代二甲胺盐酸盐替代氘代二甲胺气体，与三氯氧磷反应制得氘代六甲基磷酰三胺‑D18。
• Breaking the <i>tert</i>-Butyllithium Contact Ion Pair: A Gateway to Alternate Selectivity in Lithiation Reactions
  作者：Michael P. Crockett、Jeanette Piña、Achyut Ranjan Gogoi、Remy F. Lalisse、Andrew V. Nguyen、Osvaldo Gutierrez、Andy A. Thomas

  DOI：10.1021/jacs.2c13047

  日期：2023.5.17

  by NMR and DFT methods. It was determined that hexamethylphosphoramide (HMPA) can shift the equilibrium of t-BuLi to include the triple ion pair (t-Bu–Li–t-Bu)−/HMPA4Li+ which serves as a reservoir for the highly reactive separated ion pair t-Bu–/HMPA4Li+. Because the Li-atom’s valences are saturated in this ion pair, the Lewis acidity is significantly decreased; in turn, the basicity is maximized

  通过NMR和DFT方法详细研究了路易斯碱性磷酰胺对叔丁基锂聚集结构的影响。据确定，六甲基磷酰胺 (HMPA) 可以改变t- BuLi 的平衡，以包含三重离子对 ( t -Bu–Li– t -Bu) - /HMPA 4 Li + ，它充当高反应性分离离子的储存库对t -Bu – /HMPA 4 Li + 。由于该离子对中锂原子的价态已饱和，路易斯酸度显着降低；反过来，碱度被最大化，这使得氧杂环内的典型定向效应被覆盖，并且远程 sp 3 C-H 键被去质子化。此外，利用这些新获得的锂聚集态开发了一种简单的γ-锂化和苯并二氢吡喃杂环与各种烷基卤化物亲电子试剂的捕获方案，收率良好。