二溴乙腈 | 3252-43-5

• 物质功能分类: 化学试剂 - 有机试剂 - 氰化物/腈
• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 二溴乙腈
• 中文别名: 3-乙酰氧基-5-溴-4-氯吲哚
• 英文名称: dibromoacetonitrile
• 英文别名: DBAN；2,2-dibromoacetonitrile
• CAS: 3252-43-5
• 化学式: C₂HBr₂N
• 分子量: 198.845
• InChiKey: NDSBDLSWTGLNQA-UHFFFAOYSA-N

物化性质

• 沸点：
  67-69 °C (24 mmHg)
• 密度：
  2.29
• 闪点：
  37°C
• 溶解度：
  氯仿（可溶）、甲醇（微溶）
• 物理描述：
  Dibromoacetonitrile is a clear amber oily liquid. (NTP, 1992)
• 颜色/状态：
  Liquid
• 蒸汽压力：
  3.01X10-1 mm Hg at 25 °C (est)
• 分解：
  When heated to decomposition it emits very toxic fumes of /Nitrogen oxides/, /Hydrogen Bromide/ and /Cyanide/.
• 折光率：
  Index of refraction = 1.5393 at 20 °C/D
• 保留指数：
  853.3;863.1;857;860;861
• 稳定性/保质期：
  在常温常压下，该物质是稳定的，其密度为2.296克/毫升（25/4℃）。

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

ADMET

代谢

当大鼠口服卤乙腈（HAN）时，它们被代谢成氰化物，并作为硫氰酸盐通过尿液排出。硫氰酸盐排出的程度是氯乙腈（CAN）大于溴氯乙腈（BCAN）大于二氯乙腈（DCAN）大于二溴乙腈（DBAN）远大于三氯乙腈（TCAN）。

When administered orally to rats, the haloacetonitriles (HAN) were metabolized to cyanide and excreted in the urine as thiocyanate. The extent of thiocyanate excretion was chloroacetonitrile (CAN) greater than bromochloroacetonitrile (BCAN) greater than dichloroacetonitrile (DCAN) greater than dibromoacetonitrile (DBAN) much greater than trichloroacetonitrile (TCAN).

来源:Hazardous Substances Data Bank (HSDB)

代谢

大约8%的单次口服剂量（每千克体重149毫克）的二溴乙腈在大鼠体内24小时内以硫氰酸盐的形式通过尿液排出，这是由释放的氰化物通过罗丹酶代谢产生的产物。

Approximately 8% of a single oral dose of 149 mg/kg bw of dibromoacetonitrile to rats was excreted in urine within 24 hr as thiocyanate, the product of released cyanide metabolized by rhodanese.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

评估：没有关于二溴乙腈致癌性的相关流行病学数据。在实验动物中，关于二溴乙腈致癌性的证据不足。总体评估：二溴乙腈的致癌性无法分类为对人类的致癌物（第3组）。

Evaluation: No epidemiological data relevant to the carcinogenicity of dibromoacetonitrile were available. There is inadequate evidence in experimental animals for the carcinogenicity of dibromoacetonitrile. Overall evaluation: Dibromoacetonitrile is not classifiable as to its carcinogenicity to humans (Group 3).

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

国际癌症研究机构致癌物：二溴乙腈

IARC Carcinogenic Agent:Dibromoacetonitrile

来源:International Agency for Research on Cancer (IARC)

毒理性

• 致癌物分类

国际癌症研究机构（IARC）致癌物分类：2B组：可能对人类致癌

IARC Carcinogenic Classes:Group 2B: Possibly carcinogenic to humans

来源:International Agency for Research on Cancer (IARC)

毒理性

• 致癌物分类

国际癌症研究机构专论集：第52卷（1991年）氯化饮用水；氯化副产物；其他一些卤化化合物；钴和钴化合物 第71卷（1999年）对一些有机化学品、联胺和过氧化氢（第1部分、第2部分、第3部分）的再评估 第101卷（2012年）工业和消费品、食品和饮用水中存在的一些化学品

IARC Monographs:Volume 52: (1991) Chlorinated Drinking-water; Chlorination By-products; Some Other Halogenated Compounds; Cobalt and Cobalt Compounds Volume 71: (1999) Re-evaluation of Some Organic Chemicals, Hydrazine and Hydrogen Peroxide (Part 1, Part 2, Part 3) Volume 101: (2012) Some Chemicals Present in Industrial and Consumer Products, Food and Drinking-water

来源:International Agency for Research on Cancer (IARC)

毒理性

• 副作用

其他毒物 - 化学性窒息物 催泪剂（ lacrimator） - 刺激眼睛并引起流泪的物质。 国际癌症研究机构（IARC）致癌物 - 3类：国际癌症研究机构无法分类的化学品。

Other Poison - Chemical Asphyxiant Lacrimator (Lachrymator) - A substance that irritates the eyes and induces the flow of tears. IARC Carcinogen - Class 3: Chemicals are not classifiable by the International Agency for Research on Cancer.

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

吸收、分配和排泄

大约8%的单次口服剂量（每千克体重149毫克）的二溴乙腈在大鼠体内24小时内以硫氰酸盐的形式通过尿液排出，这是由释放的氰化物通过罗丹酶代谢产生的产物。

Approximately 8% of a single oral dose of 149 mg/kg bw of dibromoacetonitrile to rats was excreted in urine within 24 hr as thiocyanate, the product of released cyanide metabolized by rhodanese.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• TSCA：
  T
• 危险等级：
  3
• 危险品标志：
  Xn,T
• 安全说明：
  S26,S36/37
• 危险类别码：
  R20/21/22
• WGK Germany：
  3
• 海关编码：
  2926909090
• RTECS号：
  AL8450000
• 包装等级：
  III
• 危险类别：
  3
• 危险品运输编号：
  3275
• 危险性防范说明：
  P280,P301+P310,P305+P351+P338,P261
• 危险性描述：
  H301,H319,H351,H410
• 储存条件：
  存储条件：20℃，避光，通风干燥处

SDS

Name:	Dibromoacetonitrile 99% Material Safety Data Sheet
Synonym:
CAS:	3252-43-5

Section 1 - Chemical Product MSDS Name:Dibromoacetonitrile 99% Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
3252-43-5	Dibromoacetonitrile	99	221-843-2

Hazard Symbols: T
Risk Phrases: 23/24 33

---

Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Toxic by inhalation and in contact with skin. Danger of cummulative effects.
Potential Health Effects
The toxicological properties of this material have not been investigated. Use appropriate procedures to prevent opportunities for direct contact with the skin or eyes and to prevent inhalation.

---

Section 4 - FIRST AID MEASURES
Eyes: Not available.
Skin:
Not available.
Ingestion:
Not available.
Inhalation:
Not available.
Notes to Physician:
Treat symptomatically and supportively.

---

Section 5 - FIRE FIGHTING MEASURES
General Information:
Not available.
Extinguishing Media:
Not available.
Autoignition Temperature: Not available.
Flash Point: Not available.
NFPA Rating: Not published.
Explosion Limits, Lower: Not available.
Upper: Not available.

---

Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Not available.

---

Section 7 - HANDLING and STORAGE
Handling:
Not available.
Storage:
Not available.

---

Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Personal Protective Equipment Eyes: Not available.
Skin:
Not available.
Clothing:
Not available.
Respirators:
Not available.

---

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Not available.
Appearance: clear colorless to yellow
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Vapor Density: Not available.
Evaporation Rate: Not available.
Viscosity: Not available.
Boiling Point: 67.0 - 69.0 deg C @ 24.00mm Hg
Freezing/Melting Point: 0 deg C
Decomposition Temperature: Not available.
Solubility: Not available.
Specific Gravity/Density: 2.2960g/cm3
Molecular Formula: C2HBr2N
Molecular Weight: 198.84

---

Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Not available.
Incompatibilities with Other Materials:
Not available.
Hazardous Decomposition Products:
Not available.
Hazardous Polymerization: Not available.

---

Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 3252-43-5: AL8450000 LD50/LC50:
CAS# 3252-43-5: Oral, mouse: LD50 = 289 mg/kg; Oral, rat: LD50 = 245 mg/kg.
Carcinogenicity:
Dibromoacetonitrile - IARC: Group 3 carcinogen See actual entry in RTECS for complete information.

---

Section 12 - ECOLOGICAL INFORMATION
For further information, contact Fisher Scientific.

---

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

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Section 14 - TRANSPORT INFORMATION

CDG/CPL
IMO
Shipping Name: CYANIDE SOLUTION, N.O.S.
Hazard Class: 6.1
UN Number: 1935
Packing Group: I
IATA
Shipping Name: CYANIDE SOLUTION, N.O.S.
Hazard Class: 6.1
UN Number: 1935
Packing Group: I
RID/ADR
Shipping Name: CYANIDE SOLUTION, N.O.S.
Dangerous Goods Code: 6.1(41A)
UN Number: 1935
Canadian TDG
No information available.

---

Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: T
Risk Phrases:
R 23/24 Toxic by inhalation and in contact with
skin.
R 33 Danger of cummulative effects.
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 3252-43-5:
Canada
CAS# 3252-43-5 is listed on Canada's DSL/NDSL List.
WHMIS: Not available.
CAS# 3252-43-5 is not listed on Canada's Ingredient Disclosure List.
Exposure Limits
US FEDERAL
TSCA
CAS# 3252-43-5 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

制备方法：

1. 制法：在2L烧杯中加入氰基乙酸(2)63.8g（0.75mol），再加650mL水，搅拌溶解。冷却后，在搅拌下以较快的速度加入N-溴代丁二酰亚胺(NBS)276g（1.5mol），约需6min加完，注意不要让生成的二氧化碳溢出反应液。加完后将烧杯置于冰浴中冷却2h，然后抽滤析出的琥珀酰亚胺结晶，并用二氯甲烷洗5～6次，每次50mL。分出水层中的二溴乙腈粗品，水层再用上述洗涤琥珀酰亚胺后的二氯甲烷提取2次，与粗品合并，依次用5%的氢氧化钠、水洗涤，并通过无水硫酸钠干燥。回收二氯甲烷后，进行减压蒸馏，收集70～72℃/2.7kPa的馏分，得到化合物(1)112～119g，收率75%～87%。

合成制备方法：

1. 制法：同样地，在2L烧杯中加入氰基乙酸(2)63.8g（0.75mol），再加650mL水，搅拌溶解。冷却后，在搅拌下以较快的速度加入N-溴代丁二酰亚胺(NBS)276g（1.5mol），约需6min加完，注意不要让生成的二氧化碳溢出反应液。加完后将烧杯置于冰浴中冷却2h，然后抽滤析出的琥珀酰亚胺结晶，并用二氯甲烷洗5～6次，每次50mL。分出水层中的二溴乙腈粗品，水层再用上述洗涤琥珀酰亚胺后的二氯甲烷提取2次，与粗品合并，依次用5%的氢氧化钠、水洗涤，并通过无水硫酸钠干燥。回收二氯甲烷后，进行减压蒸馏，收集70～72℃/2.7kPa的馏分，得到化合物(1)112～119g，收率75%～87%。

用途简介： 目前暂无相关用途信息。

反应信息

• 作为反应物：
  描述：

  二溴乙腈 以 various solvent(s) 为溶剂， 生成 cyanocarbene
  参考文献：
  名称：

  Quasi-linearity in HCCN: effects of the v2 fundamental

  摘要：

  The high resolution infrared spectrum of the quasi-linear molecule HCCN in the region of its nu(2) CCN antisymmetric stretching fundamental has been observed. Six separate vibrational bands have been positively identified and rotationally analyzed. The lower states of these transitions belong to the ground state and the first and second excited states of the HCC bending mode (nu(5) in linear molecule notation), nu(5)(+/-1) and 2 nu(5)(+/-2). Multiple occurrences of transitions originating from each of these lower levels combined with the presence of partially resolved fine structure splitting in some bands and its absence in others suggest a strong coupling of the nu(2) mode with otherwise ''dark'' vibrational states. Fermi resonance between nu(2) and a combination level, such as nu(3) + (nu(4) + nu(5))(0+), provides such an intensity borrowing mechanism.

  DOI：

  10.1016/0022-2860(94)08512-g
• 作为产物：
  描述：

  azidoacetylene 在 溴 作用下， 以 二氯甲烷-D2 为溶剂， 以95%的产率得到二溴乙腈
  参考文献：
  名称：

  叠氮乙炔在气相、固体基质和溶液中的光化学和热分解

  摘要：

  在气相、固体氩基质和溶液中研究了极易爆炸且不稳定的 1-叠氮炔母体化合物 HCCN3（叠氮乙炔）的分解。在气相中，这种叠氮化物在室温下快速分解，在 0.8 毫巴的初始压力 (p0) 下，半衰期 (t1/2) 为 20 分钟。衰变 (p0 = 1.0 mbar) 在 O2 气氛中显着增加，t1/2 为 3 分钟，其中 HC(O)CN 被确定为氰卡宾中间体 HCCN 的捕集产物。在溶液中的叠氮化物分解过程中也发现了这种卡宾被溶剂分子（CH2Cl2 和 CHCl3）捕获的产物，而与溴溶液形成二溴乙腈的反应被解释为是通过炔烃本身的亲核攻击发生的。

  DOI：

  10.1002/ejoc.201402153

文献信息

• Halonitriles, their preparation and use to make halopyridines
  申请人：The Dow Chemical Company

  公开号：US04562009A1

  公开（公告）日：1985-12-31

  Novel halonitriles, e.g., 2,4-dichloro-2-fluoro-5,5-dimethoxy-4-methylpentanenitrile, method of preparation and use to make halopyridines, some of which are novel, e.g., 2-chloro-3-fluoro-5-methylpyridine. These compounds are intermediates in the preparation of pharmaceutical and agricultural products.

  新型卤代腈化合物，例如2,4-二氯-2-氟-5,5-二甲氧基-4-甲基戊腈，其制备方法及用于制备卤代吡啶，其中一些是新型的，例如2-氯-3-氟-5-甲基吡啶。这些化合物是制备药物和农业产品的中间体。
• Cobalt‐Catalyzed 1,4‐Aryl Migration/Desulfonylation Cascade: Synthesis of α‐Aryl Amides
  作者：Nicolas Gillaizeau‐Simonian、Etienne Barde、Amandine Guérinot、Janine Cossy

  DOI：10.1002/chem.202005129

  日期：2021.2.24

  A cobalt‐catalyzed 1,4‐aryl migration/disulfonylation cascade applied to α‐bromo N‐sulfonyl amides was developed. The reaction was highly chemoselective, allowing the preparation of α‐aryl amides possessing a variety of functional groups. The method was used as the key step to synthesize an alkaloid, (±)‐deoxyeseroline. Mechanistic investigations suggest a radical process.

  开发了应用于α-溴代N-磺酰基酰胺的钴催化的1,4-芳基迁移/二磺酰化级联反应。该反应具有高度的化学选择性，可以制备具有各种官能团的α-芳基酰胺。该方法被用作合成生物碱（±）-脱氧羟脯氨酸的关键步骤。机械研究表明这是一个激进的过程。
• Nitrogenous macrocyclic compounds
  申请人：Isis Pharmaceuticals, Inc.

  公开号：US06107482A1

  公开（公告）日：2000-08-22

  Novel macrocyclic compounds are constructed to include large cyclic structures that are interrupted by at least one ring system. Each interrupting ring system includes two bridgehead atoms. Bridgehead atoms are bonded to one or more bridges that interconnect one or more ring systems thereby forming a large cyclic structure. Located in each bridge are two or more nitrogenous moieties that are derivatized with chemical functional groups. The ring systems can include further nitrogenous moieties, either as ring atoms or on pendant groups attached to the ring. These can also be derivatized with chemical functional groups. The totality of the chemical functional groups imparts certain conformational and other properties to the macrocyclic compounds. In accordance with certain embodiments of the invention, libraries of such macrocyclic compounds are prepared utilizing permutations and combinations of the chemical functional groups and the nitrogenous moieties to build complexity into the library.

  新型大环化合物被构建成包含至少一个环系统打断的大环结构。每个打断的环系统包括两个桥头原子。桥头原子与一个或多个桥连接，连接一个或多个环系统，从而形成一个大环结构。每个桥中都含有两个或更多的氮基团，这些氮基团经过化学官能团衍生。环系统可以包括进一步的氮基团，可以是环原子，也可以是连接到环上的侧链基团。这些也可以经过化学官能团衍生。化学官能团的总体赋予大环化合物特定的构象和其他性质。根据发明的某些实施例，利用化学官能团和氮基团的排列组合制备这种大环化合物的文库，以在文库中构建复杂性。
• 一种具有抗氧化作用的环丁烯酮类化合物及其制备方法
  申请人：河南湾流生物科技有限公司

  公开号：CN109879854A

  公开（公告）日：2019-06-14

  本发明公开了一种具有抗氧化作用的环丁烯酮类化合物及其制备方法，属于功能有机分子的合成技术领域。本发明的技术方案要点为：该环丁烯酮类化合物具有结构本发明通过高效的竞争性[2+2]环加成反应得到了结构新型的环丁烯酮类化合物，并通过DPPH法进行抗氧化检测发现目标化合物具有良好的抗氧化作用，进而该化合物有望能够应用到聚烯烃材料合成等领域，作为抑制聚烯烃材料发生氧化降解的氧化剂。
• Reaction of α-halo organoindium reagents with carbonyl compounds and electron-deficient alkenes
  作者：Shuki Araki、Tsunehisa Hirashita、Ken Shimizu、Takahiro Ikeda、Yasuo Butsugan

  DOI：10.1016/0040-4020(96)00002-6

  日期：1996.2

  with indium metal, and their reactions with carbonyl compounds and electron-deficient alkenes were examined. The reactions of simple 1,1-diiodoalkanes with indium metal gave no defined products but benzal iodide gave stilbene in a moderate yield. α-Halo organoindium reagents drived from α,α-dibromo carbonyl compounds gave oxiranes and cyclopropanes upon the reactions with aldehydes and alkenes, respectively

  从宝石-二卤代化合物与铟金属的反应中原位制备了多种α-卤代有机铟试剂，并研究了它们与羰基化合物和缺电子烯烃的反应。简单的1，1-二碘代烷烃与铟金属的反应未得到确定的产物，但碘代苯碘化物以中等收率得到了1,2-二苯乙烯。由α，α-二溴羰基化合物驱动的α-卤代有机铟试剂在与醛和烯烃反应后分别生成环氧乙烷和环丙烷。3，3-二氯丙烯在金属铟的存在下与醛反应，生成相应的氯醇和/或均烯丙基醇，这取决于所用的二氯丙烯和醛的结构。

表征谱图