降冰片烯 | 498-66-8

• 物质功能分类: 化学试剂 - 有机试剂 - 胺盐（铵盐）
• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 中文名称: 降冰片烯
• 中文别名: 降莰烯
• 英文名称: norborn-2-ene
• 英文别名: bicyclo[2.2.1]hept-2-ene；bicyclo(2.2.1)heptene；norbornylene；norbornen；norbornene；2-norbornene；NBE
• CAS: 498-66-8
• 化学式: C₇H₁₀
• 分子量: 94.1564
• InChiKey: JFNLZVQOOSMTJK-UHFFFAOYSA-N

物化性质

• 熔点：
  44-46 °C (lit.)
• 沸点：
  96 °C (lit.)
• 密度：
  0.955
• 闪点：
  5 °F
• 溶解度：
  可溶于氯仿、乙酸乙酯（微量）、甲醇（微量）
• 暴露限值：
  ACGIH: TWA 20 ppmOSHA: Ceiling 300 ppm; TWA 200 ppmNIOSH: IDLH 500 ppm; TWA 100 ppm(375 mg/m3); STEL 150 ppm(560 mg/m3)
• LogP：
  4.101 at 25℃
• 蒸汽压力：
  39.19 mmHg
• 大气OH速率常数：
  4.93e-11 cm3/molecule*sec
• 保留指数：
  726;731;726;731;699;727
• 稳定性/保质期：
  按规格使用和贮存，不会发生分解，避免与氧化物接触。

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

毒理性

• 毒性数据

LC50 (大鼠) > 26,590 毫克/立方米/4小时

LC50 (rat) > 26,590 mg/m3/4hr

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

安全信息

• TSCA：
  Yes
• 危险等级：
  4.1
• 危险品标志：
  F
• 安全说明：
  S16,S29,S33,S9
• 危险类别码：
  R11
• WGK Germany：
  1
• 海关编码：
  29021990
• 危险品运输编号：
  UN 1325 4.1/PG 2
• 危险类别：
  4.1
• RTECS号：
  RB7900000
• 包装等级：
  II
• 危险标志：
  GHS02,GHS07,GHS09
• 危险性描述：
  H228,H319,H411
• 危险性防范说明：
  P210,P273,P305 + P351 + P338
• 储存条件：
  本品应远离火源，并在通风良好的地方密封保存。

SDS

Name:	Norbornylene stabilized 99% Material Safety Data Sheet
Synonym:	Bicyclo[2.2.1]-2-heptene; Norbornene; Norbornylene; Bicyclo[2.2.1]hept-2-ene
CAS:	498-66-8

Section 1 - Chemical Product MSDS Name:Norbornylene stabilized 99% Material Safety Data Sheet
Synonym:Bicyclo[2.2.1]-2-heptene; Norbornene; Norbornylene; Bicyclo[2.2.1]hept-2-ene

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
498-66-8	Norbornylene	99	207-866-0

Hazard Symbols: F
Risk Phrases: 11

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Highly flammable.Extremely flammable.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
May cause irritation of the digestive tract.
Inhalation:
May cause respiratory tract irritation. May be harmful if inhaled.
Chronic:
No information found.

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Section 4 - FIRST AID MEASURES
Eyes: In case of contact, immediately flush eyes with plenty of water for at least 15 minutes. Get medical aid.
Skin:
In case of contact, flush skin with plenty of water. Remove contaminated clothing and shoes. Get medical aid if irritation develops and persists. Wash clothing before reuse.
Ingestion:
If swallowed, do not induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. Get medical aid.
Inhalation:
If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:
Treat symptomatically and supportively.

---

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. Vapors can travel to a source of ignition and flash back. Flammable solid.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical 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. Remove all sources of ignition. Provide ventilation. Use only non-sparking tools and equipment.

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Section 7 - HANDLING and STORAGE
Handling:
Use spark-proof tools and explosion proof equipment. Avoid breathing dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing. Take precautionary measures against static discharges. Use only with adequate ventilation. Keep away from heat, sparks and flame.
Storage:
Keep away from sources of ignition. Store in a tightly closed container. Refrigerator/flammables.

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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# 498-66-8: Russia: 3 mg/m3 TWA Personal Protective Equipment Eyes: Wear chemical splash goggles.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear a chemical apron.
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.

---

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Solid
Color: white
Odor: pungent sour
pH: Not available.
Vapor Pressure: 39.2 mm Hg @ 25 deg C
Viscosity: Not available.
Boiling Point: 96 deg C @ 760 mm Hg
Freezing/Melting Point: 42 - 46 deg C
Autoignition Temperature: Not available.
Flash Point: -15 deg C ( 5.00 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: practically insoluble
Specific Gravity/Density:
Molecular Formula: C7H10
Molecular Weight: 94.15

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
No information found.
Conditions to Avoid:
High temperatures, ignition sources, confined spaces.
Incompatibilities with Other Materials:
Strong oxidizing agents, strong acids.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide.
Hazardous Polymerization: May occur.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 498-66-8: RB7900000 LD50/LC50:
CAS# 498-66-8: Oral, mouse: LD50 = 13000 mg/kg; Oral, rat: LD50 = 11300 mg/kg; Skin, rabbit: LD50 = >5 mL/kg.
Carcinogenicity:
Norbornylene - Not listed by ACGIH, IARC, or NTP.
Other:
See actual entry in RTECS for complete information.

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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: FLAMMABLE SOLID, ORGANIC, N.O.S.*
Hazard Class: 4.1
UN Number: 1325
Packing Group: II
IMO
Shipping Name: FLAMMABLE SOLID, ORGANIC, N.O.S.
Hazard Class: 4.1
UN Number: 1325
Packing Group: II
RID/ADR
Shipping Name: FLAMMABLE SOLID, ORGANIC, N.O.S.
Hazard Class: 4.1
UN Number: 1325
Packing group: II

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: F
Risk Phrases:
R 11 Highly flammable.
Safety Phrases:
S 9 Keep container in a well-ventilated place.
S 16 Keep away from sources of ignition - No
smoking.
S 33 Take precautionary measures against static
discharges.
WGK (Water Danger/Protection)
CAS# 498-66-8: No information available.
Canada
CAS# 498-66-8 is listed on Canada's NDSL List.
CAS# 498-66-8 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 498-66-8 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

简介

降冰片烯（NB）常温下为白色透明结晶，易升华。它主要用于合成环烯烃共聚物（COC）。COC具有低密度、低吸湿性、高透明性、高耐热性、高折光指数以及优良的加工性能等优势，在工业界受到高度关注。

应用

降冰片烯是一种重要的共聚单体，可与乙烯、丙烯和苯乙烯等α-烯烃在Ziegler-Natta或茂金属催化剂的作用下通过非开环聚合反应制备环烯烃共聚物。这种材料兼具低密度、低吸湿性、高透明性、高耐热性和优良的加工性能，近年来在工业界和学术界引起了高度重视，并在光学、电子、医药包装等领域展现出广泛的应用前景。

制备

一种降冰片烯的生产方法采用两个串联的第一釜式反应器和第二釜式反应器。具体步骤如下：

1. 将配制好的双环戊二烯（DCPD）、溶剂甲基异丁基酮（MIBK）以及阻聚剂对叔丁基邻苯二酚（TBC）溶液，通过泵从第一釜式反应器的底部连续送入。开启搅拌后通入所需比例的乙烯气体，使乙烯溶解在溶剂中；其中乙烯与双环戊二烯（DCPD）的摩尔比为10～50:1，溶剂甲基异丁基酮（MIBK）与双环戊二烯（DCPD）的重量比为0.5～2.0:1，阻聚剂对叔丁基邻苯二酚（TBC）加入量为双环戊二烯（DCPD）质量的0.003％。反应温度控制在170～190℃之间，并通过乙烯压缩机持续补充反应消耗的乙烯以维持系统压力为7～11MPa，物料在第一釜式反应器中的停留时间为10～120分钟，在此期间连续排出至第二釜式反应器。

2. 在第二釜式反应器中，继续控制反应温度为200～220℃，持续补充反应消耗的乙烯，使系统压力维持在7～10MPa之间，物料停留时间为10～80分钟。反应后的液体通过设置在反应器侧面的出料口连续排出至精制系统进行溶剂甲基异丁基酮（MIBK）回收和降冰片烯（NB）产品的精制。循环使用的溶剂可以多次利用。精制后得到的降冰片烯（NB）纯度可达99.9%以上。

反应信息

• 作为反应物：
  描述：

  降冰片烯 在 吡啶 、 sodium amalgam 、 氘氧化钠 、 mercury(II) diacetate 作用下， 反应 87.0h， 生成 <3-exo-²H1>bicyclo<2.2.1>heptan-2-exo-yl toluene-p-sulphonate
  参考文献：
  名称：

  Stereochemistry of base-promoted 1,2-elimination from exo-2-bicyclo[2.2.1]heptyl tosylate and chloride

  摘要：

  Elimination reactions of exo-2-bicyclo[2.2.1]heptyl tosylate and chloride and their exo-3-deuterated analogues are studied in base-solvent systems that induce clean bimolecular 1,2-eliminations. The relative propensities for competitive syn-exo and anti-endo-H elimination modes are assessed from nonkinetically determined deuterium isotope effects and the deuterium content in the bicyclo[2.2.1]hept-2-ene formed from the deuterated substrates. The competition between syn-exo and anti-endo-H elimination is influenced by base association, which stabilizes the syn elimination transition state. Potential steric hindrance by oversized dissociated bases has no effect on the elimination stereochemistry.

  DOI：

  10.1021/jo00001a041
• 作为产物：
  描述：

  2,5-降冰片二烯 在 (S)-1(1-naphthyloxy)-2,3-O,N-bis(diphenylphosphino)-2-hydroxy-3-cyclohexylaminopropanerhodium (1,5-cyclooctadiene)tetrafluoroborate 氢气 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、101.32 kPa 条件下， 生成 降冰片烯
  参考文献：
  名称：

  催化前体中不对称还原前手性烯烃的二烯烃配体加氢的动力学研究[1]

  摘要：

  通过[Rh（L）（PP *）] A类型的手性铑（I）配合物（L = COD，[（Z，Z）-cycloocta-1,5-diene]或NBD（norborna-2; 5 -二烯），PP * =手性bisphosphane形成7元螯合环，A =阴离子等BF 4 - ）往往与所造成的催化剂的部分遮挡的诱导期相关联。NBD配合物的氢化速度快于相应的COD配合物。COD / NBD混合物的催化加氢和米氏常数的确定表明，COD配合物在氢下的稳态浓度高于NBD配合物。但是，在氩气下，NBD配合物占主导地位，因为与COD配合物相比，NBD配合物具有更高的热力学稳定性。31 P-NMR谱。通过UV / Vis光谱法证明了在氢化条件下，热力学确定的COD与NBD配合物浓度之比的完全逆转。

  DOI：

  10.1002/cber.19961290117
• 作为试剂：
  描述：

  4-碘苯甲酸甲酯 、 3,5-双三氟甲基苄基溴 在 降冰片烯 、 三(2-呋喃基)膦 、 palladium diacetate 、 caesium carbonate 作用下， 以 四氢呋喃 、 异丙醇 、 甲苯 为溶剂， 以47 %的产率得到
  参考文献：
  名称：

  由钯/降冰片烯催化实现的内部功能化树枝状大分子的模块化合成平台

  摘要：

  内部功能化树枝状大分子的合成通常是繁琐且劳动密集型的，这一直是阻碍其实际应用的关键因素。在这里，我们重新审视了这一长期存在的挑战，并设计了一个模块化聚合平台，通过原位功能化策略合成具有全碳主链的多功能树枝，最多可达四代。通过钯/降冰片烯协同催化，在树枝状大分子生长过程中可以将不同的官能团引入到每一代树枝状大分子中，从而方便系统地比较它们的性能。这种多功能平台的实用性进一步体现在树枝状分子作为有机凝胶和聚集诱导发射材料的内部功能化依赖性特性中。

  DOI：

  10.1021/jacs.4c06090

文献信息

• Catalytic Azido‐Hydrazination of Alkenes Enabled by Visible Light: Mechanistic Studies and Synthetic Applications
  作者：Peng Wang、Yunxuan Luo、Songsong Zhu、Dengfu Lu、Yuefa Gong

  DOI：10.1002/adsc.201901041

  日期：2019.12.17

  visible‐light‐enabled catalytic intermolecular azido‐hydrazination method for unactivated alkenes is developed via an orderly radical addition sequence. This transformation features metal‐free and redox‐neutral conditions and is applicable to a wide range of alkenes with commercially available reagents. Mechanistic and kinetic studies reveal that the efficient generation of azide radical enabled by fluorenone

  通过有序的自由基加成顺序，开发出了一种可在可见光下催化的未活化烯烃分子间叠氮酰肼化方法。这种转变具有无金属和氧化还原中性的条件，适用于使用市售试剂的多种烯烃。力学和动力学研究表明，芴酮在可见光下有效生成叠氮化物自由基对于该方法至关重要。通过该反应制备的β-叠氮基烷基肼可方便地衍生为有价值的合成构件，并且其中一种产品已成功用于（±）-依鲁替尼的全合成，用于治疗B细胞癌。
• Development of the Copper-Catalyzed Olefin Aziridination Reaction
  作者：David A. Evans、Mark T. Bilodeau、Margaret M. Faul

  DOI：10.1021/ja00086a007

  日期：1994.4

  Soluble Cu(1) and Cu(I1) triflate and perchlorate salts are efficient catalysts for the aziridination of olefins employing (N-@-tolylsulfonyl)imino)phenyliodinane, PhI=NTs, as the nitrene precursor. Electron-rich as well as electron-deficient olefins undergo aziridination with this reagent in 55-958 yields, at temperatures ranging from -20 OC to +25 OC. The catalyzed nitrogen atom-transfer reaction

  可溶性 Cu(1) 和 Cu(I1) 三氟甲磺酸盐和高氯酸盐是使用（N-@-甲苯磺酰基）亚氨基）苯基碘烷（PhI=NTs）作为氮烯前体的烯烃氮丙啶化反应的有效催化剂。在 -20 OC 至 +25 OC 的温度范围内，富电子和缺电子烯烃与该试剂发生氮丙啶化反应，产率为 55-958。还开发了催化氮原子转移反应生成烯醇硅烷和甲硅烷基乙烯酮缩醛，以提供 α-氨基酮的简便合成。发现其他金属配合物在催化反应方面效果较差，而 PhI=NTs 被证明优于其他亚氨基供体作为氮烯前体。在极性非质子溶剂如 MeCN 和 MeNO 2 中反应速率和产率提高。对顺式和反式双取代烯烃的氮丙啶化反应的立体定向性进行了评估，发现它依赖于催化剂和底物。单和双取代烯烃对之间的分子间竞争实验表明，反应的烯烃选择性曲线与所用铜催化剂的氧化态无关。得出的结论是，在所用条件下，这些反应是通过 2+ 催化剂氧化态进行的。
• Structure−Activity Relationships of Potent, Selective Inhibitors of Neuronal Nitric Oxide Synthase Based on the 6-Phenyl-2-aminopyridine Structure
  作者：John A. Lowe、Weimin Qian、Susan E. Drozda、Robert A. Volkmann、Deane Nason、Robert B. Nelson、Charles Nolan、Dane Liston、Karen Ward、Steve Faraci、Kim Verdries、Pat Seymour、Michael Majchrzak、Anabella Villalobos、W. Frost White

  DOI：10.1021/jm030519g

  日期：2004.3.1

  The synthesis and structure-activity relationships of a series of 6-phenyl-2-aminopyridines that potently and selectively inhibit the neuronal isoform of nitric oxide synthase (nNOS) are described. Compound 14bi from this series exhibits potent in vivo activity in harmaline-induced cGMP formation in rat cerebellum, a functional model of nNOS inhibition, and in the PCP-induced hypermotility model in

  描述了一系列6-苯基-2-氨基吡啶的合成和结构-活性关系，这些6-苯基-2-氨基吡啶有效和选择性地抑制一氧化氮合酶（nNOS）的神经元亚型。来自该系列的化合物14bi在大鼠小脑中由harmaline诱导的cGMP形成，nNOS抑制的功能模型以及在PCP诱导的高运动性模型中表现出强大的体内活性。这些结果表明，14bi可能是用于评估nNOS抑制剂在中枢神经系统中潜在治疗应用的有用试剂。
• Nitrogen-enriched porous carbon supported Pd-nanoparticles as an efficient catalyst for the transfer hydrogenation of alkenes
  作者：Jie Li、Xin Zhou、Ning-Zhao Shang、Cheng Feng、Shu-Tao Gao、Chun Wang

  DOI：10.1039/c8nj03656j

  日期：——

  g-C3N4 as a nitrogen source and a self-sacrificial template. The prepared Pd@NPC exhibited superior catalytic activity and chemoselectivity for the catalytic transfer hydrogenation of alkenes under mild conditions with formic acid as a hydrogen donor. Moreover, the catalyst displays high structure stability, and can be reused for five runs without any significant decrease of its catalytic activity and

  将超细钯纳米颗粒固定在富氮多孔碳纳米片（NPC）上，该碳纳米片是用gC 3 N 4作为氮源和自牺牲模板制备的。所制得的Pd @ NPC在温和条件下，以甲酸为氢供体，对烯烃进行催化转移加氢显示出优异的催化活性和化学选择性。而且，该催化剂显示出高的结构稳定性，并且可以重复使用五次而不会显着降低其催化活性和明显的Pd浸出。这项工作提供了一种简便可行的方法来制造富氮碳纳米片，并构造高级钯负载的多相催化剂以实现高催化活性。
• Tetrahydroxydiboron-Mediated Palladium-Catalyzed Transfer Hydrogenation and Deuteriation of Alkenes and Alkynes Using Water as the Stoichiometric H or D Atom Donor
  作者：Steven P. Cummings、Thanh-Ngoc Le、Gilberto E. Fernandez、Lorenzo G. Quiambao、Benjamin J. Stokes

  DOI：10.1021/jacs.6b02132

  日期：2016.5.18

  There are few examples of catalytic transfer hydrogenations of simple alkenes and alkynes that use water as a stoichiometric H or D atom donor. We have found that diboron reagents efficiently mediate the transfer of H or D atoms from water directly onto unsaturated C-C bonds using a palladium catalyst. This reaction is conducted on a broad variety of alkenes and alkynes at ambient temperature, and boric

  使用水作为化学计量的 H 或 D 原子供体的简单烯烃和炔烃的催化转移氢化的例子很少。我们发现二硼试剂使用钯催化剂有效地介导了 H 或 D 原子从水中直接转移到不饱和 CC 键上。该反应在环境温度下对多种烯烃和炔烃进行，硼酸是唯一的副产物。机理实验表明，该反应是通过从水中的氢原子转移生成 Pd 氢化物中间体而实现的。重要的是，还实现了从化学计量的 D2O 中完全掺入氘。

表征谱图