紫苏醇 | 536-59-4

• 物质功能分类: 化学试剂 - 有机试剂 - 脂肪醇
• 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: 紫苏醇
• 中文别名: 4-(1-甲基乙烯基)-1-环己烯-1-甲醇；1-羟甲基-4-异丙烯基-1-环己烯；L-紫苏醇；芥子醇
• 英文名称: perillol
• 英文别名: Perillyl alcohol；perilla alcohol；p-mentha-1,8-dien-7-ol；perrilyl alcohol；4-(1-methylethenyl)-1-cyclohexene-1-methanol；Isocarveol；(4-prop-1-en-2-ylcyclohexen-1-yl)methanol
• CAS: 536-59-4
• 化学式: C₁₀H₁₆O
• mdl: MFCD00001567
• 分子量: 152.236
• InChiKey: NDTYTMIUWGWIMO-UHFFFAOYSA-N

物化性质

• 熔点：
  271-272 °C
• 沸点：
  119-121 °C11 mm Hg(lit.)
• 密度：
  0.96 g/mL at 25 °C(lit.)
• 闪点：
  >230 °F
• 溶解度：
  Very slightly soluble in water, soluble in alcohol and oils
• LogP：
  3.170
• 物理描述：
  Solid
• 折光率：
  1.495-1.505
• 保留指数：
  1287;1274;1278;1290;1295;1275;1276;1279;1277;1281;1288;1267;1274;1275;1285;1284;1300;1275;1276;1283.1;1301;1277;1284;1275;1276;1286;1287;1280;1286;1287;1281
• 稳定性/保质期：

  存在于主流烟气中。

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

ADMET

代谢

Limonen-10-ol 已知的人类代谢物包括 (2S,3S,4S,5R)-3,4,5-三羟基-6-[(4-丙烯基-2-环己烯基)甲氧基]氧杂环己烷-2-羧酸。

Limonen-10-ol has known human metabolites that include (2S,3S,4S,5R)-3,4,5-trihydroxy-6-[(4-prop-1-en-2-ylcyclohexen-1-yl)methoxy]oxane-2-carboxylic acid.

来源:NORMAN Suspect List Exchange

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26,S39
• 危险类别码：
  R36/37/38,R41,R37/38
• WGK Germany：
  3
• 海关编码：
  2906199090
• RTECS号：
  OS8395000
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H315,H319,H335
• 储存条件：
  | 室温 |

SDS

Name:	L(-)-Perillyl Alcohol 85% Material Safety Data Sheet
Synonym:	Dihydrocuminyl Alcohol; 4-Isopropenyl-Cyclohex-1-Ene-1-Methanol; Perilla Alcohol
CAS:	536-59-4

Section 1 - Chemical Product MSDS Name:L(-)-Perillyl Alcohol 85% Material Safety Data Sheet
Synonym:Dihydrocuminyl Alcohol; 4-Isopropenyl-Cyclohex-1-Ene-1-Methanol; Perilla Alcohol

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
536-59-4	L(-)-Perillyl Alcohol	85	208-639-9

Hazard Symbols: XI
Risk Phrases: 36/38

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Irritating to eyes and skin.
Potential Health Effects
Eye:
Causes eye irritation. May cause chemical conjunctivitis.
Skin:
Causes skin irritation.
Ingestion:
May cause gastrointestinal irritation with nausea, vomiting and diarrhea.
Inhalation:
May cause respiratory tract irritation. Can produce delayed pulmonary edema.
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 immediately.
Skin:
Get medical aid immediately. Immediately 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:
Treat symptomatically and supportively.

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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. Vapors may be heavier than air. They can spread along the ground and collect in low or confined areas. 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:
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. Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation. Use with adequate ventilation.
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 process enclosure, local exhaust ventilation, or other engineering controls to control airborne levels.
Exposure Limits CAS# 536-59-4: 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 minimize contact with skin.
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: Liquid
Color: clear, colorless
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 119 - 121 deg C @ 11.00mmHg
Freezing/Melting Point: Not available.
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: .9600g/cm3
Molecular Formula: C10H16O
Molecular Weight: 152.24

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

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 536-59-4: OS8395000 LD50/LC50:
CAS# 536-59-4: Draize test, rabbit, skin: 500 mg/24H Severe; Oral, rat: LD50 = 2100 mg/kg; Skin, rabbit: LD50 = >5 gm/kg.
Carcinogenicity:
L(-)-Perillyl Alcohol - 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: Not regulated.
Hazard Class:
UN Number:
Packing Group:
IMO
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing Group:
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 36/38 Irritating to eyes and skin.
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 536-59-4: No information available.
Canada
CAS# 536-59-4 is listed on Canada's DSL List.
CAS# 536-59-4 is listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 536-59-4 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

概述

紫苏醇，学名为4-异丙烯基-1-环己烯甲醇，是一种具有类似芳樟醇和松油醇气味的稠粘油液。它存在于姜草油、青柠檬油、拉文定油及留兰香等精油中。由于其芳香味道，常被用作食用香精和添加剂的调配剂。

紫苏醇作为一种治疗及预防癌症的单萜类药物，在肿瘤如卵巢肿瘤、食道癌、乳腺癌等的治疗方面表现出显著的效果。此信息由ChemicalBook的张茜编辑整理。

理化性质

紫苏醇为一种粘稠油状液体，带有似芳樟醇和松油醇的气味。其沸点在118～121℃（11×133.322Pa）之间，相对密度0.9690，折光率1.4996，[α]D-7°。该物质性质稳定、耐热耐酸且不易挥发。

合成方法

紫苏醇天然存在于柑桔、樱桃、薄荷、香柠檬、姜草及多种植物中，是植物甲醛和戊酸代谢途径产生的单萜化合物。原则上，可通过从天然植物精油中分离获得，如Row等采用有机溶剂或超临界CO2萃取提取紫苏醇。

尽管紫苏醇存在于多种天然植物精油中，但由于其含量低、分离难度大而成本高昂，因此化学合成显得尤为重要。常见的合成方法包括：

1. 苧烯氧化法：柠檬油、甜橙油等天然精油的主要成分——苧烯，在适当的条件下可经氧化转化为紫苏醇。
2. β-蒎烯直接氧化法：该方法通过在含有氯化亚铜和苯甲酸铜的乙腈中使用过氧化二苯甲酰，获得主要产物反式香芹醇及少量紫苏醇。南京林业大学程芝等人采用四乙酸铅作为催化剂，取得了较好的结果。
3. 2,10-环氧蒎烷的酸催化异构化：通过环氧化反应生成2,10-环氧蒎烷，在酸催化下进行异构化反应，最终制得紫苏醇。此方法是利用松节油中丰富β-蒎烯的有效途径。

应用领域

1. 紫苏醇可用作单体香料，用于仿制柑橘、香草及水果型的食用香精，食品赋香剂和酱油防腐剂。
2. 作为有机合成的重要中间体，紫苏醇是合成紫苏醛、紫苏葶等的关键化合物。
3. 合成植物生产调节剂、农用杀虫剂和昆虫拒食剂。
4. 紫苏醇具有独特的药用效果，可用于器官移植，降低同种异体移植物的排斥作用。
5. 作为一种治疗及预防癌症的单萜类药物，紫苏醇表现出广谱、高效且低毒的抗癌特性。

生物活性

Perillyl alcohol 是一种从薰衣草、薄荷和樱桃等植物精油中分离出的单萜化合物。它能够在不影响正常细胞的情况下诱导肿瘤细胞凋亡（apoptosis）。

Human Endogenous Metabolite	——

反应信息

• 作为反应物：
  描述：

  紫苏醇 在 5 weight% palladium(0) nanoparticles supported on mesoporous natural phosphate 作用下， 以 neat (no solvent) 为溶剂， 反应 24.0h， 以91%的产率得到4-异丙基苯甲醇
  参考文献：
  名称：

  介孔天然磷酸盐上负载的新型钯纳米颗粒：从天然萜烯制备芳烃的催化能力

  摘要：

  使用湿法浸渍法制备了不同比例负载在介孔天然磷酸盐（Pd @ NP）上的钯纳米粒子。通过IR，XRD，CV，SEM，EDX，XRF，TEM和BET分析对所制备的催化剂进行表征。钯纳米颗粒的还原和制备提供了10.88nm的微晶尺寸。在以雪松油为模型底物的α-，β-和γ-喜马al林混合物的无溶剂脱氢芳构化过程中，研究了合成催化剂的性能。为了实现有效和选择性的催化，研究了各种萜烯如柠檬烯，柠檬烯酮，香芹酮，香芹酚和紫苏醇的催化脱氢芳构化。Pd @ NP催化剂在萜烯脱氢芳构化反应中具有很高的催化活性，选择性和可回收性。

  DOI：

  10.1002/aoc.5917
• 作为产物：
  描述：

  2-methylene-5-(1-methylethenyl)cyclohexanol 在 ammonium metavanadate 作用下， 反应 8.0h， 生成 紫苏醇
  参考文献：
  名称：

  Process for making perillyl alcohol

  摘要：

  揭示了一种制备过氧蒎醇的方法。该方法包括在100°C至220°C的温度范围内，在第5族金属催化剂的存在下使含有反式异香叶醇的起始物异构化，以产生过氧蒎醇。我们惊讶地发现，可以直接将反式异香叶醇异构化为过氧蒎醇，而反式异香叶醇可以从商业上可获得的顺式和反式LMO混合物中选择性地产生。当在惰性气氛和/或酚类抗氧化剂的存在下进行异构化时，过氧蒎醇的产量得到提高。在高沸点醇的存在下进行异构化或在高沸点醇的存在下从反应混合物中蒸馏过氧蒎醇产品，可以提高产量并最大限度地利用催化剂。所得的蒸馏残渣含有回收的第5族金属催化剂，对催化额外的反式异香叶醇异构化具有价值。

  公开号：

  US07851660B1

文献信息

• Uncommon overoxidative catalytic activity in a new halo‐tolerant alcohol dehydrogenase
  作者：Martina L. Contente、Noemi Fiore、Pietro Cannazza、David Roura Padrosa、Francesco Molinari、Louise Gourlay、Francesca Paradisi

  DOI：10.1002/cctc.202001112

  日期：2020.11.19

  useful enzymes employed as biocatalysts, especially for the selective oxidation of primary and secondary alcohols, and for the reduction of carbonyl moieties. A new alcohol dehydrogenase (HeADH‐II) has been identified from the genome of the halo‐adapted bacterium Halomonas elongata, which proved stable in the presence of polar organic solvents and salt exposure. Unusual for this class of enzymes, HeADH‐II

  醇脱氢酶（ADH）是用作生物催化剂的通用且有用的酶，特别是用于伯醇和仲醇的选择性氧化以及羰基部分的还原。一种新的醇脱氢酶（HeADH-II）已经从基因组中确定的卤代适于细菌盐单胞菌泡桐，其在极性有机溶剂及盐曝光的存在证明是稳定的。对于这类酶而言，HeADH-II不常见，它缺乏对映异构体，并且能够氧化醇和醛，从而使伯醇直接过氧化为羧酸。HeADH-II与戊糖乳杆菌（LpNOX），以提高工艺产量并允许回收辅因子。伯醇的酶促氧化还与中间醛与羟胺的原位缩合配对以制备相应的醛肟，尤其要注意perillartine（一种强力的甜味剂），其酶促合成是从天然来源开始的，可得到同样的天然产物。
• Hydroheteroarylation of Unactivated Alkenes Using <i>N</i>-Methoxyheteroarenium Salts
  作者：Xiaoshen Ma、Hester Dang、John A. Rose、Paul Rablen、Seth B. Herzon

  DOI：10.1021/jacs.7b02388

  日期：2017.4.26

  reductive coupling of unactivated alkenes with N-methoxy pyridazinium, imidazolium, quinolinium, and isoquinolinium salts under hydrogen atom transfer (HAT) conditions, and an expanded scope for the coupling of alkenes with N-methoxy pyridinium salts. N-Methoxy pyridazinium, imidazolium, quinolinium, and isoquinolinium salts are accessible in 1-2 steps from the commercial arenes or arene N-oxides (25-99%)

  我们报告了在氢原子转移 (HAT) 条件下未活化的烯烃与 N-甲氧基哒嗪鎓、咪唑鎓、喹啉鎓和异喹啉鎓盐的首次还原偶联，并扩大了烯烃与 N-甲氧基吡啶鎓盐的偶联范围。N-甲氧基哒嗪鎓、咪唑鎓、喹啉鎓和异喹啉鎓盐可通过 1-2 个步骤从商业芳烃或芳烃 N-氧化物 (25-99%) 中获得。N-甲氧基咪唑鎓盐可通过三个步骤从商业胺（50-85%）中获得。总共制备了 36 种带有给电子、吸电子、烷基、芳基、卤素和卤代烷基取代基的离散甲氧基杂芳鎓盐（数种为数克），并与 38 种不同的烯烃偶联。转变在环境温度和中性条件下进行，专门提供单烷基化产物，并形成单一的烯烃加成区域异构体。将仲和叔自由基加成到吡啶鎓盐中的制备性有用和互补位点选择性已被记录：较硬的仲自由基有利于 C-2 加成 (2->10:1)，而较软的叔自由基有利于与 C-4 的键形成 (4.7 -> 29:1）。具有 1,2-二取代和 2,2-二取代烯烃的二烯仅在后者
• Organoselenium-Catalyzed Regioselective C−H Pyridination of 1,3-Dienes and Alkenes
  作者：Lihao Liao、Ruizhi Guo、Xiaodan Zhao

  DOI：10.1002/anie.201610657

  日期：2017.3.13

  organoselenium‐catalyzed regioselective C−H pyridination of 1,3‐dienes to form pyridinium salts has been developed. This method was also successfully applied to direct C−H pyridination of alkenes. Fluoropyridinium reagents, or initially loaded pyridine derivatives, acted as pyridine sources in the pyridination reactions. The obtained pyridinium salts could be further converted under different conditions

  已开发出一种有效的方法，用于有机硒催化的1,3-二烯的区域H吡啶氧化反应生成吡啶鎓盐。该方法也成功地应用于烯烃的直接CH吡啶化反应。氟吡啶鎓试剂或最初加载的吡啶衍生物在吡啶化反应中充当吡啶源。所获得的吡啶鎓盐可以在不同条件下进一步转化。这项工作是1，3-二烯催化C–2直接C–H官能化的第一个例子，也是有机硒催化的C–H吡啶化的第一种情况。
• Selective Oxidation of Activated Alcohols by Supported Gold Nanoparticles under an Atmospheric Pressure of O₂ : Batch and Continuous-Flow Studies
  作者：Pascal D. Giorgi、Nelli Elizarov、Sylvain Antoniotti

  DOI：10.1002/cctc.201700179

  日期：2017.5.23

  scalable protocol for gold nanoparticle‐catalyzed oxidation of benzylic and allylic alcohols under O2, we have used commercially available gold nanoparticles supported on alumina to selectively oxidize a large range of activated alcohols to the corresponding carbonyl compounds in good yields (68–99 %) and with excellent selectivity (ca. 100 %). The true heterogeneous nature of the catalysis by gold was

  为了寻找一种简单，温和且可扩展的方案，在O 2下金纳米颗粒催化苄基和烯丙基醇的氧化，我们使用了负载在氧化铝上的市售金纳米颗粒将多种活化醇选择性氧化为相应的羰基化合物收率高（68–99％），选择性极好（约100％）。证明了金催化的真正多相性质，使我们能够通过使用管中管技术将该协议进一步应用于连续流反应器中，该技术由于反应介质的氧合作用提高而获得了更高的收率。
• Deoxygenation of allylic alcohols to terminal olefins via stannylation/destannylation
  作者：Yoshio Ueno、Hiroshi Sano、Makoto Okawara

  DOI：10.1016/s0040-4039(00)77832-4

  日期：1980.1

  Deoxygenation of allylic alcohols to terminal olefins was performed via three steps; 1) [3,3]-sigmatropic rearrangement of O-allylxanthates, 2) the successive stannolysis with tributyltin hydride yielding allylic stannanes, and 3) final protolysis of allylic stannanes to terminal olefins.

  烯丙基醇的脱氧反应通过三个步骤进行；1）O-烯丙基黄原酸酯的[3,3]-σ重排，2）用氢化三丁基锡进行连续锡锡酸酯化，生成烯丙基锡烷，和3）最终将烯丙基锡烷酮分解为末端烯烃。

表征谱图