苯偶酰腙 | 5344-88-7

• 物质功能分类: 化学试剂 - 有机试剂 - 腙
• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 中文名称: 苯偶酰腙
• 中文别名: 苯偶酰一腙
• 英文名称: benzil monohydrazone
• 英文别名: 2-hydrazono-1,2-diphenylethanone；benzil hydrazone；2-Hydrazinylidene-1,2-diphenylethanone
• CAS: 5344-88-7
• 化学式: C₁₄H₁₂N₂O
• mdl: MFCD00007625
• 分子量: 224.262
• InChiKey: CDQPGWNBSOSEMZ-UHFFFAOYSA-N

物化性质

• 熔点：
  150-152 °C(lit.)
• 沸点：
  365.66°C (rough estimate)
• 密度：
  1.1117 (rough estimate)
• 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)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

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

SDS

Name:	Benzil monohydrazone 98% Material Safety Data Sheet
Synonym:
CAS:	5344-88-7

Section 1 - Chemical Product MSDS Name:Benzil monohydrazone 98% Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
5344-88-7	Benzil monohydrazone	98.0	226-292-1

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 immediately.
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 immediately. 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.
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:
Clean up spills immediately, observing precautions in the Protective Equipment section. Sweep up or absorb material, then place into a suitable clean, dry, closed container for disposal. Avoid generating dusty conditions. Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. Minimize dust generation and accumulation. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation.
Storage:
Keep container closed when not in use. 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# 5344-88-7: 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:
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: Solid
Color: very slightly yellow
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 150.00 - 152.00 deg C
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: C14H12N2O
Molecular Weight: 224.26

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials, dust generation, strong oxidants.
Incompatibilities with Other Materials:
Strong 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# 5344-88-7 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Benzil monohydrazone - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION
Other No information available.

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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.
S 28A After contact with skin, wash immediately with
plenty of water.
S 37 Wear suitable gloves.
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# 5344-88-7: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 5344-88-7 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 5344-88-7 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

制备方法与用途

用于经氧化汞处理制备二苯乙烯酮的前体。

反应信息

• 作为反应物：
  描述：

  苯偶酰腙 在 氨 、 sodium acetate 、 potassium iodide 作用下， 以 甲醇 为溶剂， 反应 2.0h， 生成 2,2-联苯基乙酰胺
  参考文献：
  名称：

  卤化物离子存在下苯腙的阳极氧化

  摘要：

  苄基腙在含有卤离子源（如 KI 和 KBr）的 MeOH 中进行电解氧化。结果表明，反应产物取决于电解质和取代基。在 KI 存在下，得到苯甲酰基苯基重氮甲烷，而在 KBr 存在下，得到苯甲基二甲基缩醛。

  DOI：

  10.1246/bcsj.75.2059
• 作为产物：
  描述：

  联苯甲酰 在 一水合肼 、 溶剂黄146 作用下， 以 甲醇 、 水 为溶剂， 以87%的产率得到苯偶酰腙
  参考文献：
  名称：

  腙电合成稳定的重氮化合物

  摘要：

  以高达 99% 的收率从腙进行了重氮化合物的电化学合成。该方法被阐述为一种有用的合成方法，并在各种重氮化合物（24 个例子）上进行了证明。除了表现出与常用的苛刻和有毒化学氧化剂相匹配的效率外，该反应实际上易于建立，需要温和的条件，并且电子效率高（3 F/mol）。

  DOI：

  10.1021/acs.orglett.2c01803

文献信息

• Purported Synthesis of 3,4,7,8-Tetraphenyl-1,2,5,6-tetraazocine from Benzil and Hydrazine: Competing Cyclization and Carbon–Carbon σ-Bond Scission
  作者：John J. Eisch、Tsz Y. Chan、John N. Gitua

  DOI：10.1002/ejoc.200700848

  日期：2008.1

  derivative was detected. The following products were unambiguously formed from the heating of molten benzil monohydrazone (%): benzil (10), benzaldehyde (10), benzamide (22), benzyl phenyl ketone (19), benzil bis(ketazine) (11), 3,4,5,6-tetraphenylpyridazine (9), benzil benzaldehyde azine (10), and, after column chromatography, 2,4,5-triphenylimidazole (2). This last component had a melting point and the

  3,4,7,8-四苯基-1,2,5,6-tetraazocine 可以通过两摩尔苄基单腙或苄基和苄基二腙的等摩尔混合物的热缩合制备的说法已被彻底重新研究。当在潮湿空气中进行这种热解时，既没有检测到要求保护的 3,4,7,8-四苯基-1,2,5,6-四氮杂辛，也没有检测到前面提到的异构四氮杂戊烯衍生物。加热熔融的苄基一腙（%）明确形成以下产物：苄基（10）、苯甲醛（10）、苯甲酰胺（22）、苄基苯基酮（19）、苄基双（酮嗪）（11）、3、 4,5,6-四苯基哒嗪 (9)、苄基苯甲醛吖嗪 (10) 和柱色谱后的 2,4,5-三苯基咪唑 (2)。这最后一个组分具有熔点和紫外光下的荧光特性，最初的研究人员将其归因于错误地假定为 3,4,7,8-四苯基-1,2,5,6-tetraazocine。因此，关于合成这种新型四氮杂辛环或什至合成先行的异构两性离子四氮杂戊烯的原始权利要求现已被否定。2,4,5
• Reaction of Hydrazones with Methoxy(tosyloxy)iodobenzene (MTIB): Tosylate Formation under Oxidative Conditions
  作者：Christopher Ramsden、Helen Rose

  DOI：10.1055/s-1997-702

  日期：——

  Treatment of aromatic hydrazones 1 containing electron-withdrawing, reduction sensitive substituents with MTIB gives the corresponding tosylates 2 in high yield. When the tosylate is particularly reactive the thermodynamically more stable methyl ether 3 is isolated. Analogous reactions with DAIB give acetates 4 in high yield. Dialkyl hydrazones give olefinic products (e.g. 7 and 8). (+)-Camphor hydrazone 1k with either MTIB or DAIB gives both camphene 12 (major product) and tricyclene 11 (minor product) suggesting that a carbene pathway accounts for some of the material formed in these oxidations.

  含有吸电子、还原敏感取代基的芳香腙1与MTIB反应，可高效地得到相应的甲苯磺酸酯2。当甲苯磺酸酯具有特别高的反应活性时，则会分离得到热力学上更稳定的方式形成的甲醚3。类似地，与DAIB反应可高效地得到乙酸酯4。二烷基腙则生成烯烃产物（例如7和8）。(+)-樟脑腙1k与MTIB或DAIB反应，会同时生成荻烯12（主要产物）和三环烯11（次要产物），表明在这些氧化反应中，卡宾路径可能用于形成一部分反应产物。
• Phototropic Products from the Reactions of Aril Monoazines with Bases
  作者：Peter Yates、E. M. Levi、B. L. Shapiro

  DOI：10.1139/v74-494

  日期：1974.10.1

  monoazine. Analogous phototropic products are formed on reaction of p-anisil monoazine and p-tolil monoazine with sodium methoxide. Reduction of the azines to the phototropic products may occur by cleavage to α-keto imine anions followed by their dimerization; such a pathway can also account for the formation of the cleavage products. Alternatively, reduction may proceed by hydride or electron transfer;

  用甲醇钠处理苄基单嗪得到 5-甲氧基-1,2,5-三苯基-3,4-二氮杂-2,4-戊二烯-1-酮 (2), 5-苯甲酰基-4,5-二氢-3 ,4,5-triphenylpyrazol-4-ol (3) 和简单的裂解产物。化合物3水解为3,4,5-三苯基吡唑和苯甲酸。它是向光性的，在暴露于阳光下时可逆地转化为红色产物，该产物很容易自氧化为苄基单嗪。对苯甲醚单嗪和对甲苯基单嗪与甲醇钠反应会形成类似的光致产物。通过裂解为 α-酮亚胺阴离子，然后将它们二聚化，可以将吖嗪还原为光致产物；这种途径也可以解释裂解产物的形成。或者，可以通过氢化物或电子转移进行还原；通过观察到用叔丁醇钾处理对甲苯里单嗪也得到相应的光致产物，确定了氢化物转移不一定涉及。它是提议...
• Alkyl Halide-Free Heteroatom Alkylation and Epoxidation Facilitated by a Recyclable Polymer-Supported Oxidant for the In-Flow Preparation of Diazo Compounds
  作者：Simon M. Nicolle、Christopher J. Hayes、Christopher J. Moody

  DOI：10.1002/chem.201500118

  日期：2015.3.16

  simple ketones via diazo compounds, including diazo‐amides and ‐phosphonates, using a recyclable reagent in‐flow, are transient but versatile electrophiles for heteroatom alkylation reactions and for epoxide formation. The method produces no organic waste, with the only by‐products being water, KI and nitrogen, without the attendant hazards of isolation of intermediate diazo compounds.

  高活性金属卡宾，是通过简单的酮类通过重氮化合物（包括重氮酰胺和膦酸酯）通过重氮化合物（使用可循环利用的试剂流入）生成的，是一种瞬态但通用的亲电子试剂，可用于杂原子烷基化反应和环氧化物的形成。该方法不产生有机废物，唯一的副产品是水，KI和氮气，并且没有分离中间体重氮化合物的伴随危险。
• Reactions of 2-Diazo-1,2-Diphenylethanone and Diphenyldiazomethane with Ketohydrazones
  作者：Girija Shankar Singh、Surendra Bahadur Singh、Kailash Nath Mehrotra

  DOI：10.1246/bcsj.57.1667

  日期：1984.6

  The reactions of 2-diazo-1,2-diphenylethanone (1) with ketohydrazones (3a–c) in equimolecular ratio yield (diphenylacetyl)hydrazones (4a–c) of the corresponding benzophenones which on further treatment with 1 in equimolecular ratio leads to 1-diphenylacetylazo-1,1,3,3-tetraaryl-2-propanones (5a–c). The product 5a is also obtained in the reaction of 1 with benzophenone hydrazone (3a) in 2 : 1 molecular

  2-重氮-1,2-二苯乙酮 (1) 与酮腙 (3a-c) 以等分子比的反应产生相应二苯甲酮的 (二苯乙酰) 腙 (4a-c)，进一步用等分子比的 1 处理导致1-二苯基乙酰偶氮-1,1,3,3-四芳基-2-丙酮 (5a–c)。产物5a也在1与二苯甲酮腙(3a)以2:1的分子比反应中获得。1 以及二苯基重氮甲烷 (2) 与酮腙 (3) 的双 (乙酰丙酮) 铜 (II) 催化反应得到酮 (6)。讨论了产物形成的机理途径。

表征谱图