1,2-肼二羧酸二乙酯 | 4114-28-7

• 物质功能分类: 有机原料 - 肼或胲的有机衍生物
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 1,2-肼二羧酸二乙酯
• 中文别名: 肼二羧酸二乙酯；叠氮二羧酸二乙酯；1,2-二(乙氧羰基)肼
• 英文名称: diethyl hydrazodicarboxylate
• 英文别名: diethyl hydrazine-1,2-dicarboxylate；Diethyl 1,2-hydrazinedicarboxylate；ethyl N-(ethoxycarbonylamino)carbamate
• CAS: 4114-28-7
• 化学式: C₆H₁₂N₂O₄
• mdl: MFCD00009101
• 分子量: 176.172
• InChiKey: JXMLAPZRDDWRRV-UHFFFAOYSA-N

物化性质

• 熔点：
  131-133 °C(lit.)
• 沸点：
  250 °C(lit.)
• 密度：
  1.3240
• 稳定性/保质期：
  在常温常压下保持稳定

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.666
• 拓扑面积：
  76.7
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 安全说明：
  S22,S24/25
• WGK Germany：
  3
• 海关编码：
  2928000090
• 储存条件：
  请将产品存放在避光、通风且干燥的地方，并密封保存。

SDS

Name:	Sym.-Dicarbethoxyhydrazine 97% Material Safety Data Sheet
Synonym:	None Known
CAS:	4114-28-7

Section 1 - Chemical Product MSDS Name:Sym.-Dicarbethoxyhydrazine 97% Material Safety Data Sheet
Synonym:None Known

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
4114-28-7	Sym.-Dicarbethoxyhydrazine	97%	223-902-8

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:
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.
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. Runoff from fire control or dilution water may cause pollution.
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:
Vacuum or sweep up material and place into a suitable disposal container. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use with adequate ventilation.
Minimize dust generation and accumulation. 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# 4114-28-7: 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: Crystalline powder
Color: white
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 250 deg C @ 760.00mmHg
Freezing/Melting Point: 132 - 134 deg C
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: C6H12N2O4
Molecular Weight: 176.17

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

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 4114-28-7 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Sym.-Dicarbethoxyhydrazine - 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# 4114-28-7: No information available.
Canada
CAS# 4114-28-7 is listed on Canada's NDSL List.
CAS# 4114-28-7 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 4114-28-7 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
白色晶体。熔点为132-134℃，沸点为250℃。

用途
作为有机合成的中间体。

生产方法
将85%水合肼和95%乙醇混合，并冷却至10℃，在搅拌下滴加氯甲酸乙酯和碳酸钠溶液。控制加料速度，确保氯甲酸乙酯过量并先于碳酸钠溶液滴加完毕，同时保持温度在20℃以上。完成加料后继续搅拌反应0.5小时，滤出沉淀，并用清水充分洗涤，在80℃下进行真空干燥，最终得到成品，产率可达81-85%。

反应信息

• 作为反应物：
  描述：

  1,2-肼二羧酸二乙酯 在 肼 作用下， 反应 24.0h， 以55%的产率得到1,2-bis(hydrazinocarbonyl)hydrazine
  参考文献：
  名称：

  Photooxidation mechanism of nitrogen-containing compounds at TiO2/H2O interfaces: an experimental and theoretical examination of hydrazine derivatives

  摘要：

  The photocatalytic oxidation of oxalyldihydrazide, N, N'-bis(hydrazocarbonyl)hydrazide, N, N'-bis(ethoxycarbonyl)hydrazide, malonyldihydrazide, N-malonyl-bis[(N'-ethoxycarbonyl)hydrazide] was examined in aqueous TiO2 dispersions under UV illumination. The photomineralization of nitrogen and carbon atoms in the substrates into N-2 gas, NH4+ (and/or NO3-) ions, and CO2 gas was determined by HPLC and GC analysis. The formation of carboxylic acid intermediates also occurred in the photooxidation process. The photocatalytic mechanism is discussed on the basis of the experimental results, and with molecular orbital (MO) simulation of frontier electron density and point charge. Substrate carbonyl groups readily adsorb on the TiO2 surface, and the bonds between carbonyl group carbon atoms and adjacent hydrate group nitrogen atoms are cleaved predominantly in the initial photooxidation process. The hydrate groups were photoconverted mainly into N-2 gas (in mineralization yields above 70%) and partially to NH4+ ions (below 10%). The formation of NO3- ions was scarcely recognized. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0045-6535(99)00500-7
• 作为产物：
  描述：

  氯甲酸乙酯 在 sodium carbonate 、 肼 作用下， 以 乙醇 、 水 为溶剂， 反应 0.5h， 以79%的产率得到1,2-肼二羧酸二乙酯
  参考文献：
  名称：

  Copper-Catalyzed Cross-Coupling Between (E)-1,2-Diiodoethene and Carbazates: Entry to β-Functionalized N-Alkenylcarbazates

  摘要：

  目的： 这项工作旨在拓宽制备功能化 N-烯基咔嗪酸盐。 背景： 烯基咔嗪酸盐一般通过 Aza-Baylis-Hillman 反应、亲核 酮或炔烃的串联羰基化/酰胺化反应制备。 目标： 这项工作的目的是开发一种制备功能化烯基咔嗪酸盐的方法。 的方法，以解决上述方法中遇到的问题（使用缺电子烯烃 缺电子的烯烃、使用计量单位量的金属、只能制备对称的二咔嗪酸盐）。 方法： 利用铜催化的乙烯基二碘化物与咔唑盐之间的交叉偶联来制备 官能化 N-烯基咔嗪酸盐。 结果： 合成了各种 β-碘乙烯基咔嗪盐，收率高达良好。其中 得率最高。β-碘乙烯基咔嗪酸盐的功能化表明 碘乙烯基咔唑酸盐的官能化表明，通过过渡金属催化，这些分子中的碘乙烯基可以被多种官能团取代。 过渡金属催化的偶联反应。 结论 铜催化的交叉偶联反应能有效地制备功能化的 N- 烷基咔嗪酸盐。

  DOI：

  10.2174/1570180818666210803165347
• 作为试剂：
  描述：

  1-萘甲醇 在 copper(l) iodide 、 1,10-菲罗啉 、 1,2-肼二羧酸二乙酯 、 氧气 、 potassium carbonate 、 三苯基膦 、 copper(l) chloride 、 lithium tert-butoxide 作用下， 以 甲苯 为溶剂， 反应 10.0h， 生成 (E)-1-(2-phenylbut-1-en-1-yl)naphthalene
  参考文献：
  名称：

  由N-甲苯磺酰hydr和醇一锅多步合成三取代烯烃

  摘要：

  摘要 据报道一锅法由N-甲苯磺酰基hydr和醇合成三取代的烯烃。该程序将好氧氧化反应和Wittig反应合二为一，避免了使用对环境有害的氧化剂和中间体的分离。当将醇用作起始原料时，简单的方法使其对于三取代烯烃的合成非常有吸引力。以中等至良好的收率（高达84％）和良好的E-选择性（高达99％）获得了各种三取代的烯烃以及三氟甲基取代的烯烃。 据报道一锅法由N-甲苯磺酰基hydr和醇合成三取代的烯烃。该程序将好氧氧化反应和Wittig反应合二为一，避免了使用对环境有害的氧化剂和中间体的分离。当将醇用作起始原料时，简单的方法使其对于三取代烯烃的合成非常有吸引力。以中等至良好的收率（高达84％）和良好的E-选择性（高达99％）获得了各种三取代的烯烃以及三氟甲基取代的烯烃。

  DOI：

  10.1055/s-0034-1378231

文献信息

• <i>tert-</i> Butyl Iodide Mediated Reductive Fischer Indolization of Conjugated Hydrazones
  作者：Yuta Ito、Masafumi Ueda、Norihiko Takeda、Okiko Miyata

  DOI：10.1002/chem.201504010

  日期：2016.2.18

  available N‐aryl conjugated hydrazones with tert‐butyl iodide has been developed. In this reaction, tert‐butyl iodide is used as anhydrous HI source, and the generated HI acts as a Brønsted acid and a reducing agent. This operationally simple method allows access to various indole derivatives. Furthermore, the procedure can be applied to the synthesis of biologically active compounds.

  已经开发出一种新型的，易于获得的N-芳基共轭与叔丁基碘化物的还原费歇尔吲哚化反应。在该反应中，叔丁基碘化物用作无水HI源，生成的HI用作布朗斯台德酸和还原剂。这种操作简单的方法允许使用各种吲哚衍生物。此外，该方法可以应用于生物活性化合物的合成。
• Sulfonamide derivatives
  申请人：Sankyo Company, Limited

  公开号：US06673804B1

  公开（公告）日：2004-01-06

  A compound of the formula (I) or a pharmacologically acceptable salt, ester or other derivative thereof: R1 is H or NHOH. R2 is H, optionally substituted alkyl, cycloalkyl or a group —AR6. A is an alkylene which may be optionally interrupted by O, —S(O)m— or —N(R9). R6 is a group (II), (III), (IV) X is O, S, —N(R10)—, —C(R11)(R12)—. Y is O, CO, —S(O)n—, —N(R10)—, —C(R11)(R12)—. Each of R7 and R8 is H, alkyl, COOH, optionally substituted alkyl, etc. Each of R9, R10, R11, and R12 is H, alkyl, etc. Each of m and n is 0 to 2. R3 is H, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl. R4 is optionally substituted (hetero)arylene. R5 is optionally substituted alkyl, optionally substituted (hetero)aryl. These compounds have matrixmetalloproteinase—13 inhibitory activity and aglycanase inhibitory activity.

  公式（I）的化合物或其药理学上可接受的盐、酯或其他衍生物： R1为H或NHOH。R2为H，可选择地取代的烷基，环烷基或一种—AR6基团。 A为一种可以选择地被O、—S(O)m—或—N(R9)中断的烷基。R6为一种（II）、（III）、（IV）基团。 X为O、S、—N(R10)—、—C(R11)(R12)—。Y为O、CO、—S(O)n—、—N(R10)—、—C(R11)(R12)—。R7和R8中的每一个为H、烷基、COOH、可选择地取代的烷基等。R9、R10、R11和R12中的每一个为H、烷基等。m和n中的每一个为0到2。R3为H、可选择地取代的烷基、可选择地取代的环烷基、可选择地取代的烯基、可选择地取代的炔基。R4为可选择地取代的（杂）芳基。R5为可选择地取代的烷基、可选择地取代的（杂）芳基。这些化合物具有基质金属蛋白酶-13抑制活性和糖基酶抑制活性。
• [EN] THIOPHENE COMPOUNDS<br/>[FR] COMPOSES DE BENZIMIDAZOLE-1-YL-THIOPHENE UTILISES EN CANCEROTHERAPIE
  申请人：SMITHKLINE BEECHAM CORP

  公开号：WO2004014899A1

  公开（公告）日：2004-02-19

  The present invention provides compounds of formula (I): (I) pharmaceutical compositions containing the same, processes for preparing the same and their use as pharmaceutical agents.

  本发明提供了式(I)的化合物： （I）含有相同化合物的药物组合物，制备该化合物的方法及其作为药物的应用。
• Cu-Catalyzed Aerobic Oxidation of Di-<i>tert</i>-butyl Hydrazodicarboxylate to Di-<i>tert</i>-butyl Azodicarboxylate and Its Application on Dehydrogenation of 1,2,3,4-Tetrahydroquinolines under Mild Conditions
  作者：Dahyeon Jung、Min Hye Kim、Jinho Kim

  DOI：10.1021/acs.orglett.6b03166

  日期：2016.12.16

  developed with homogeneous CuI and di-tert-butyl azodicarboxylate for aerobic dehydrogenation of 1,2,3,4-tetrahydroquinolines under mild conditions. The developed co-catalytic system is consisting of di-tert-butyl azodicarboxylate-mediated dehydrogenation of 1,2,3,4-tetrahydroquinoline and aerobic oxidative regeneration of di-tert-butyl azodicarboxylate from di-tert-butyl hydrazodicarboxylate using molecular

  用均相的CuI和偶氮二甲酸二叔丁酯开发了一种新型的共催化体系，用于在温和条件下对1,2,3,4-四氢喹啉进行好氧脱氢。发达共催化体系是由二-叔丁基偶氮二羧酸酯介导的二- 1,2,3,4-四氢喹啉和好氧氧化再生的脱氢叔丁基偶氮二羧酸酯选自二叔使用分子氧作为丁基hydrazodicarboxylate终端氧化剂。发达的铜和偶氮二羧酸二叔丁酯助催化体系有效地合成了各种喹啉。
• Directed Ortho Metalation Methodology. The <i>N</i>,<i>N</i>-Dialkyl Aryl <i>O</i>-Sulfamate as a New Directed Metalation Group and Cross-Coupling Partner for Grignard Reagents
  作者：Todd K. Macklin、Victor Snieckus

  DOI：10.1021/ol050393c

  日期：2005.6.1

  with a variety of electrophiles constitutes a new general route to substituted aryl O-sulfamates 4a-k. The Kumada-Corriu cross-coupling of O-sulfamates 4e, 4n-s, and 6a with Grignard reagents gives biaryls 9a-m, and the use of 2-halo and boron derivatives 4h, 4i, and 4k for Suzuki-Miyaura cross-coupling and generation of benzynes leads to naphthols 7a and 7b. A relative metalation ranking of the OSONEt(2)

  [反应：参见文本] 3的邻位金属化（RLi / THF / -93摄氏度），然后用各种亲电试剂淬火，构成了取代O-氨基磺酸芳基酯4a-k的新通用路线。O-氨基磺酸盐4e，4n-s和6a与Grignard试剂的Kumada-Corriu交叉偶联可得到联芳基9a-m，而Suzuki-Miyaura交叉使用2-halo和硼衍生物4h，4i和4k。苯并炔的偶合和生成导致萘酚7a和7b。报告了OSONEt（2）的相对金属化等级。

表征谱图