(-)-Alpha-氧化蒎烯 | 19894-99-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: (-)-Alpha-氧化蒎烯
• 中文别名: L-alpha-(-)-环氧蒎烷；(-)-α-氧化蒎烯；氧化蒎烯
• 英文名称: (1R,2R,4S,6R)-2,7,7-trimethyl-3-oxatricyclo[4.1.1.0.^2,4]octane
• 英文别名: α-pinene oxide；2,3-epoxypinane；(1R-(1alpha,2beta,4beta,6alpha))-2,2,7-Trimethyl-3-oxatricyclo(4.1.1.02,4)octane；(1R,2R,4S,6R)-2,7,7-trimethyl-3-oxatricyclo[4.1.1.02,4]octane
• CAS: 19894-99-6
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: NQFUSWIGRKFAHK-BDNRQGISSA-N

物化性质

• 沸点：
  192°C
• 密度：
  0.9600
• 稳定性/保质期：
  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S16,S26,S37/39
• 危险类别码：
  R10,R41,R37/38
• 储存条件：
  存于阴凉干燥处。

SDS

Name:	(-)-alpha-Pinene oxide 95% Material Safety Data Sheet
Synonym:	3-Oxatricyclo[4.1.1.02,4]octane, 2,7,7-trimethyl-, (1R,2R,4S,6R)-; 3-Oxatricyclo[4.1.1.02,4]octane, 2,7,7-trimethyl-, [1R-(1alpha,2beta,4beta,6alpha)]-; Pinane, 2,3-epoxy-, (1R,2R,3S,5R)-(-)-
CAS:	19894-99-6

Section 1 - Chemical Product MSDS Name:(-)-alpha-Pinene oxide 95% Material Safety Data Sheet
Synonym:3-Oxatricyclo[4.1.1.02,4]octane, 2,7,7-trimethyl-, (1R,2R,4S,6R)-; 3-Oxatricyclo[4.1.1.02,4]octane, 2,7,7-trimethyl-, [1R-(1alpha,2beta,4beta,6alpha)]-; Pinane, 2,3-epoxy-, (1R,2R,3S,5R)-(-)-

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
19894-99-6	(-)-alpha-Pinene oxide	95	243-411-2

Hazard Symbols: XI
Risk Phrases: 10 37/38 41

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Flammable. Irritating to respiratory system and skin. Risk of serious damage to eyes.
Potential Health Effects
Eye:
Causes severe eye irritation and possible burns.
Skin:
Causes skin irritation.
Ingestion:
May cause gastrointestinal irritation with nausea, vomiting and diarrhea. The toxicological properties of this substance have not been fully investigated. Ingestion of large amounts may cause central nervous depression.
Inhalation:
Causes respiratory tract irritation.
Chronic:
Effects may be delayed.

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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:
Get medical aid immediately. Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Do NOT use mouth-to-mouth resuscitation.
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. Use water spray to keep fire-exposed containers cool. Flammable liquid and vapor. Vapors may be heavier than air. They can spread along the ground and collect in low or confined areas. Containers may explode when heated. Runoff from fire control or dilution water may cause pollution.
Extinguishing Media:
In case of fire, use water, dry chemical, chemical foam, or alcohol-resistant foam. Use water spray to cool fire-exposed containers. Use agent most appropriate to extinguish fire.

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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. Avoid runoff into storm sewers and ditches which lead to waterways. Clean up spills immediately, observing precautions in the Protective Equipment section. Remove all sources of ignition. Use a spark-proof tool. Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use only in a well-ventilated area. Avoid contact with eyes, skin, and clothing. Empty containers retain product residue, (liquid and/or vapor), and can be dangerous. Keep container tightly closed. Keep away from heat, sparks and flame. Avoid ingestion and inhalation. Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames.
Storage:
Keep away from sources of ignition. 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# 19894-99-6: CAS# 72936-74-4: Personal Protective Equipment Eyes: Wear chemical splash goggles.
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: Liquid
Color: clear, colorless
Odor: camphor
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 192 deg C
Freezing/Melting Point: Not available.
Autoignition Temperature: Not applicable.
Flash Point: 55 deg C ( 131.00 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: Negligible.
Specific Gravity/Density: .9640g/cm3
Molecular Formula: C10H16O
Molecular Weight: 152.24

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Ignition sources, excess heat.
Incompatibilities with Other Materials:
Oxidizing agents, strong acids, strong bases.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 19894-99-6 unlisted.
CAS# 72936-74-4 unlisted.
LD50/LC50:
Not available.
Not available.
Carcinogenicity:
(-)-alpha-Pinene oxide - Not listed by ACGIH, IARC, or NTP.
Epoxypinene - 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
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing group:

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XI
Risk Phrases:
R 10 Flammable.
R 37/38 Irritating to respiratory system and skin.
R 41 Risk of serious damage to eyes.
Safety Phrases:
S 16 Keep away from sources of ignition - No
smoking.
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 37/39 Wear suitable gloves and eye/face
protection.
WGK (Water Danger/Protection)
CAS# 19894-99-6: No information available.
CAS# 72936-74-4: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 19894-99-6 is not listed on Canada's Ingredient Disclosure List.
CAS# 72936-74-4 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 19894-99-6 is not listed on the TSCA inventory.
It is for research and development use only.
CAS# 72936-74-4 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

反应信息

• 作为反应物：
  描述：

  (-)-Alpha-氧化蒎烯 在 水 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 32.0h， 生成 2-methyl-5-(propan-2-ylidene)cyclohex-2-enol
  参考文献：
  名称：

  热水促进的烯丙醇和苄醇的SN1溶剂化反应

  摘要：

  在研究环氧化合物在水中的水解过程中，我们发现（-）-α- pine烯氧化物在20°C的水解产生对映体纯的反式（-）-sobrerol，而在回流加热的水中同样的反应出乎意料地产生的外消旋混合物的反式-和顺-sobrerol（反式/顺式= 6:4）。我们详细研究了这种显着差异，发现与室温或高温水相比行为截然不同的热水可以促进烯丙醇的S N 1溶剂分解反应，从而引起反式的外消旋化。-（-）-sobrerol。进一步研究了反应温度，有机助溶剂的添加以及溶质浓度对反式-（-）-sobrerol外消旋速率的影响，以了解热水在反应中的作用。有人提出热水的催化作用是由于其温和的酸性特征，热活化，高电离能和有机反应物更好的溶解性。进一步的研究表明，其他手性烯丙基/苄基醇的消旋作用可以在热水中有效地进行。

  DOI：

  10.1002/chem.201202886
• 作为产物：
  描述：

  (-)-α-蒎烯 在 Fe(bpmen)(OTf)2 、 双氧水 、 溶剂黄146 作用下， 以 乙腈 为溶剂， 以50%的产率得到(-)-Alpha-氧化蒎烯
  参考文献：
  名称：

  C，CH和CH 2氧化反应中的非血红素铁催化。Fe（bpmen）（OTf）2催化萜类化合物的氧化转化

  摘要：

  在非血液催化剂5a的存在下用过氧化氢氧化萜烯，得到环氧化物的混合物，其组成取决于每种情况下使用的氧化方案。对于萜类烯酮，由于在该系列中存在的双键上的电子密度的逐渐失活，获得的混合物从α-紫罗兰酮23的纯环氧化演变成大马士革28的纯烯丙基氧化。 双环和三环萜类化合物的氧化提供了从环氧化到烯烃降解，亚甲基和亚甲基活化产物的氧化产物。可能最吸引人的结果是由三环醚45合成马格努斯内酯46，收率为88％，转化率为100％。

  DOI：

  10.1016/j.tet.2013.02.013

文献信息

• An Effective Synthesis of Acid-Sensitive Epoxides via Oxidation of Terpenes and Styrenes Using Hydrogen Peroxide under Organic Solvent-Free Conditions
  作者：Kazuhiko Sato、Yoshihiro Kon、Houjin Hachiya、Yutaka Ono、Tomohiro Matsumoto

  DOI：10.1055/s-0030-1258467

  日期：2011.4

  An efficient epoxidation process for various terpenes and styrenes using a hydrogen peroxide-tungsten catalytic system with organic solvent- and halide-free conditions was developed. In the presence of the catalytic system, Na2WO4, PhP(O)(OH)2, and [Me(n-C8H17)3N]HSO4, and under weak acidic conditions, hydrogen peroxide successfully epoxidized α-pinene to α-pinene oxide in 95% selectivity at 91% conversion

  开发了一种在无有机溶剂和无卤化物条件下使用过氧化氢-钨催化体系对各种萜烯和苯乙烯进行高效环氧化的方法。在催化体系Na 2 WO 4，PhP（O）（OH）2和[Me（n -C 8 H 17）3 N] HSO 4的存在下，在弱酸性条件下，过氧化氢成功地环氧化了α -pine烯至α-pine烯氧化物的转化率为95％，转化率为91％，而先前公布的利用NH 2 CH 2 P（O）（OH）2作为促进剂的条件没有提供环氧化物。 氧化-催化-环氧化物-萜类化合物-苯乙烯
• 3-Methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol: the Importance of Functional Groups for Antiparkinsonian Activity
  作者：Oleg Ardashov、Alla Pavlova、Dina Korchagina、Konstantin Volcho、Tat’ yana Tolstikova、Nariman Salakhutdinov

  DOI：10.2174/1573406411309050013

  日期：2013.6.1

  Compounds with different sets of three of the four functional groups of (1R,2R,6S)-3-methyl-6-(prop-1-en-2- yl)cyclohex-3-ene-1,2-diol 1 possessing high antiparkinsonian activity were synthesized. The synthesized compounds were tested for the antiparkinsonian activity in vivo on a mouse model with MPTP neurotoxin. A pronounced antiparkinsonian effect of 1 can only be achieved if it contains all the

  具有（1R，2R，6S）-3-甲基-6-（prop-1-en-2-yl）cyclohex-3-ene-1,2-diol 1的四个官能团中的三个的不同集合的化合物合成了高抗帕金森病活性。在具有MPTP神经毒素的小鼠模型上测试了合成的化合物的体内抗帕金森病活性。只有包含所有四个官能团（两个羟基和两个双键），才能实现显着的1的抗帕金森效应。刺激动物的探索活性不需要2-羟基或3,4-双键。
• Selective epoxidation of monoterpenes with methyltrioxorhenium and H2O2
  作者：Aída L.P. de Villa、Dirk E. De Vos、Consuelo C. de Montes、Pierre A. Jacobs

  DOI：10.1016/s0040-4039(98)01853-x

  日期：1998.11

  terpenes such as α-pinene with H2O2 with minimal rearrangement of the epoxide. Pyridine is also critical to suppress isomerisation of the olefin substrate (in case of nerol, geraniol). The reaction can be directed towards selective single or double epoxidation, or in one step towards the rearranged product (e.g. from linalool to the ring-closure product linalool oxide).

  在吡啶作为助催化剂的存在下，CH 3 ReO 3以最小的环氧基重排催化H 2 O 2对萜烯（如α-pine烯）的环氧化。吡啶对于抑制烯烃底物的异构化也是至关重要的（如果是神经醇，香叶醇）。该反应可以针对选择性的单或双环氧化，或在一步中针对重排的产物（例如从芳樟醇到闭环产物芳樟醇氧化物）。
• Substrate-Induced Diastereoselectivity in the Dimethyldioxirane Epoxidation of Simple Alkenes and Dienes
  作者：Amalia Asouti、Lazaros P. Hadjiarapoglou

  DOI：10.1055/s-2001-18751

  日期：——

  Various alkenes and dienes, such as (R)- or (S)-limonene 2, 2-carene 6, 3-carene 8, (R)-α-pinene 10, (S)-α-pinene 12, and endo-dicyclopentadiene 14 were transformed into the corresponding mono- and bis-epoxides by epoxidation with dimethyldioxirane (as an acetone solution). The selectivity observed in these epoxidations is explained by the assumption of hydrogen bonding between bridge protons and the dioxirane.

  各种烯烃和二烯烃，例如（R）-或（S）-柠檬烯2、2-蒈烯6、3-蒈烯8、（R）-α-蒎烯10、（S）-α-蒎烯12以及endo-二环戊二烯14，通过二甲基二氧杂环丙烷（以丙酮溶液形式）的环氧化反应，被转化为相应的单环氧和双环氧化合物。在这些环氧化过程中观察到的选择性可以通过桥连质子与二氧杂环丙烷之间氢键的假设来解释。
• Unique Salt Effect on Highly Selective Synthesis of Acid-Labile Terpene and Styrene Oxides with a Tungsten/H2O2 Catalytic System under Acidic Aqueous Conditions
  作者：Yoshihiro Kon、Kazuhiko Sato、Houjin Hachiya、Yutaka Ono、Kiyoshi Takumi、Naoki Sasagawa、Yoichiro Ezaki

  DOI：10.1055/s-0031-1290948

  日期：2012.6

  styrene oxides are effectively synthesized in high yields with good selectivities using tungsten-catalyzed hydrogen peroxide epoxidation in the presence of Na2SO4. The salt effect is thought to originate with the addition of a saturated amount of Na2SO4 to aqueous H2O2; this addition strongly inhibited the undesired hydrolysis of the acid-labile epoxy products, despite the biphasic conditions of substrate

  摘要 在Na 2 SO 4的存在下，使用钨催化的过氧化氢环氧化，可以高产率，高选择性地有效合成酸不稳定的环氧化物，例如萜烯和氧化苯乙烯。盐的作用被认为是由于在H 2 O 2水溶液中加入了饱和的Na 2 SO 4引起的。尽管底物为油相且H 2 O 2为酸性水相的双相条件，但这种添加强烈地抑制了酸不稳定的环氧产物的不希望的水解。 在Na 2 SO 4的存在下，使用钨催化的过氧化氢环氧化，可以高产率，高选择性地有效合成酸不稳定的环氧化物，例如萜烯和氧化苯乙烯。盐的作用被认为是由于在H 2 O 2水溶液中加入了饱和的Na 2 SO 4引起的。尽管底物为油相且H 2 O 2为酸性水相的双相条件，但这种添加强烈地抑制了酸不稳定的环氧产物的不希望的水解。