dimethyl azodicarboxylate | 2446-84-6

• 物质功能分类: 化学试剂 - 有机试剂 - 肟
• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: dimethyl azodicarboxylate
• 英文别名: Azodicarboxylic acid dimethyl ester；methyl N-methoxycarbonyliminocarbamate
• CAS: 2446-84-6
• 化学式: C₄H₆N₂O₄
• 分子量: 146.103
• InChiKey: NCBFTYFOPLPRBX-UHFFFAOYSA-N

物化性质

• 熔点：
  10°C
• 沸点：
  84°C 8mm
• 密度：
  0,99 g/cm3
• 闪点：
  23°C

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  77.3
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 安全说明：
  S16,S33,S9
• 危险类别码：
  R36/37/38,R11
• 海关编码：
  2927000090
• 危险品运输编号：
  UN 1993
• 储存条件：
  室温

SDS

Name:	Methyl azodicarboxylate 97% Material Safety Data Sheet
Synonym:	Dimethyl diazenedicarboxylat
CAS:	2446-84-6

Section 1 - Chemical Product MSDS Name:Methyl azodicarboxylate 97% Material Safety Data Sheet
Synonym:Dimethyl diazenedicarboxylat

---

Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
2446-84-6	Methyl azodicarboxylate	97	unlisted

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

---

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.

---

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.
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:

---

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.

---

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. Provide ventilation.

---

Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. 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. Keep refrigerated. (Store below 4C/39F.)

---

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# 2446-84-6: 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.

---

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Clear liquid
Color: clear brown
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: Not available.
Solubility in water: Not available.
Specific Gravity/Density: Not available.
Molecular Formula: C4H6N2O4
Molecular Weight: 146.10

---

Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials, strong oxidants.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Irritating and toxic fumes and gases.
Hazardous Polymerization: Has not been reported.

---

Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 2446-84-6 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Methyl azodicarboxylate - Not listed by ACGIH, IARC, or NTP.

---

Section 12 - ECOLOGICAL INFORMATION

---

Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

---

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.

---

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# 2446-84-6: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 2446-84-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 2446-84-6 is not listed on the TSCA inventory.
It is for research and development use only.

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  dimethyl azodicarboxylate 在 萘 作用下， 生成 草酸二甲酯
  参考文献：
  名称：

  Stolle; Reichert, Journal fur praktische Chemie (Leipzig 1954), 1929, vol. <2> 123, p. 83

  摘要：

  DOI：
• 作为产物：
  描述：

  甲基伸腈基羧酸盐 在 硝酸 作用下， 生成 dimethyl azodicarboxylate
  参考文献：
  名称：

  Diels; Paquin, Chemische Berichte, 1913, vol. 46, p. 2012

  摘要：

  DOI：
• 作为试剂：
  描述：

  咪唑-4-甲酸甲酯 、 4-hydroxy-3,3-dimethyl-3,4-dihydro-2H-naphthalen-1-one 在 dimethyl azodicarboxylate 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 3-(2,2-dimethyl-4-oxo-1,2,3,4-tetrahydronaphthalen-1-yl)-3H-imidazole-4-carboxylic acid methyl ester
  参考文献：
  名称：

  WO2008/76336

  摘要：

  公开号：

文献信息

• Asymmetric Synthesis of Multifunctionalized 2,3-Benzodiazepines by a One-Pot N-heterocyclic Carbene/Chiral Palladium Sequential Catalysis
  作者：Ya-Li Ding、Yun-Long Zhao、Shuang-Shuo Niu、Pei Wu、Ying Cheng

  DOI：10.1021/acs.joc.9b02693

  日期：2020.1.17

  We report the first example of the construction of chiral 2,3-benzodiazepine compounds which are of biologic and pharmaceutical relevance by asymmetric catalysis. Catalyzed by a thiazolium-derived carbene and a palladium-chiral bidentate phosphine complex in sequence, one-pot reaction between 1-(2-(2-nitrovinyl)aryl)allyl esters 1 with azodicarboxylates 2 took place efficiently at ambient temperature

  我们报告了通过不对称催化具有生物和药物相关性的手性2，3-苯并二氮杂化合物手性化合物的构建的第一个例子。依次由噻唑鎓的卡宾和钯-手性双齿膦膦配合物催化，在环境温度下有效地进行了1-（2-（2-硝基乙烯基）芳基）烯丙基酯1与偶氮二羧酸酯2的一锅反应。 -硝基-1-乙烯基-1H-2,3-苯并二氮杂-2,3-二羧酸酯5的收率好至极好，对映体比例最高为95：5。
• Die reaktion von azoestern mit tetraalkyl-tetrazenen-(2)
  作者：F. Effenberger、P. Fischer

  DOI：10.1016/s0040-4020(01)92884-4

  日期：1970.1

  Tetraalkyl-(2)-tetrazenes are attacked by azodicarboxylates at the dialkylamino nitrogen. By intramolecular proton abstraction, the betain 3 first formed is converted into the ylide 4 which then rearranges into 5. Kinetics of the reaction are investigated by UV spectroscopy; a mechanism is proposed.

  四烷基-（2）-四烯在二烷基氨基氮上被偶氮二羧酸盐攻击。通过分子内质子提取，首先形成的甜菜碱3被转化为叶立德4，其然后重排为5。通过紫外光谱研究反应的动力学。提出了一种机制。
• [2 + 3]-Cycloadditions of PhosphonodithioformateS-Methanides with CS, NN, and CC Dipolarophiles
  作者：Grzegorz Mlostoń、Katarzyna Urbaniak、Mihaela Gulea、Serge Masson、Anthony Linden、Heinz Heimgartner

  DOI：10.1002/hlca.200590198

  日期：2005.10

  CH2N2 at − 65° in THF yielded cycloadducts which eliminated N2 between − 40 and − 35° to give the corresponding phosphonodithioformate S-methanides ( =methylenesulfonium (dialkoxyoxidophosphino)(methylthio)methylides) 11 (Scheme 3). These reactive 1,3-dipoles were intercepted by aromatic thioketones to yield 1,3-dithiolanes. Whereas the reaction with thiobenzophenone (12b) led to the sterically more congested

  甲基（dialkoxyphosphinyl）的反应-dithioformates（=甲基dialkoxyphosphinecarbodithioate -1-氧化物）10用CH 2 Ñ 2在- 65℃于THF，得到其中消除Ñcycloadducts 2之间- 40和- 35°，得到相应的phosphonodithioformate小号-甲烷化物（＝亚甲基（（二烷氧基氧化膦基）（甲硫基）甲基化物）11（方案3）。这些反应性1,3-偶极子被芳族硫酮截获，生成1,3-二硫杂环戊烷。而与硫代二苯甲酮（12b）的反应导致空间上更拥挤的异构体15区域选择性地，获得两种区域异构体与9 H-芴-9-硫酮（12a）的混合物。用膦酰基-和磺基二硫代甲酸酯捕获11分别分别导致在空间上受阻较小的1,3-二硫杂环戊酸酯16和18（方案4）。另外，反应性CC偶极亲子例如乙烯四甲腈，马来酸酐和N-苯基马来酰亚胺以及NN
• Intramolecular 1,3-diyl trapping reactions: Total synthesis of the marine natural product (, )Δ9(12)-capnellene
  作者：R.Daniel Little、Gary L. Carroll

  DOI：10.1016/s0040-4039(01)82964-6

  日期：1981.1

  An intramolecular 1,3-diyl trapping reaction is utilized in the key step of a total synthesis of the marine natural product Δ9(12)-capnellene.

  在海洋天然产物Δ9 （12） -capnellene的全合成的关键步骤中，使用了分子内1,3-二基捕获反应。
• 1,3-Diyl trapping reactions. Fundamental investigations with application to the synthesis of linearly fused tricyclopentanoids
  作者：R.Daniel Little、George W. Muller、Manuel G. Venegas、Gary L. Carroll、Ahmed Bukhari、Larry Patton、Keith Stone

  DOI：10.1016/0040-4020(81)80003-8

  日期：1981.1

  no practical effect upon the outcome of the trapping reaction. The intramolecular process is stereospecific with respect to diylophile geometry, and highly stereoselective with respect to the ring junction stereochemistry. Finally, an abortive attempt to synthesize the marine natural product Δ9(12)-capnellene (19) as well as a successful synthesis of the mold metabolite d,l- hirsutene (18) is presented

  比较了分子间和分子内二芳基捕获途径与线性稠合的三环戊烷的关系。另外，检查了与分子内过程有关的几种影响立体选择性的因素，并得出结论，构象而非电子（次级轨道）因素起主要作用。结果表明，位于无环链上的宝石甲基连接了二基和亲二烯基（指32和35，但不包括47）对诱捕反应的结果没有实际影响。分子内过程相对于亲二烯体几何形状是立体定向的，并且对于环结立体化学是高度立体选择性的。最后，提出了合成海洋天然产物Δ9 （12）-capnellene（19）的失败尝试，以及霉菌代谢产物d，l -hirsutene（18）的成功合成。

表征谱图