(R)-4-溴-alpha-甲基苄醇 | 76155-78-7

• 物质功能分类: 化学试剂 - 有机试剂 - 芳香醇
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (R)-4-溴-alpha-甲基苄醇
• 中文别名: (R)-4-溴-α-甲基苯甲醇；(R)-4-溴-α-甲基苄醇
• 英文名称: (R)-1-(4-bromophenyl)ethanol
• 英文别名: 1-(4-bromophenyl)ethan-1-ol；(R)-1-(4-bromophenyl)ethan-1-ol；1-(4-bromophenyl)ethanol；(1R)-1-(4-bromophenyl)ethanol
• CAS: 76155-78-7
• 化学式: C₈H₉BrO
• mdl: MFCD06201861
• 分子量: 201.063
• InChiKey: XTDTYSBVMBQIBT-ZCFIWIBFSA-N

物化性质

• 沸点：
  110 °C(Press: 3.0 Torr)
• 密度：
  1.322 g/mL at 25 °C
• 闪点：
  110 °C
• 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：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

安全信息

• 危险品标志：
  Xn
• 安全说明：
  S26,S36/37/39
• 危险类别码：
  R20/21/22,R36/37/38
• WGK Germany：
  3
• 海关编码：
  29062900
• 危险性防范说明：
  P261,P280,P305+P351+P338
• 危险性描述：
  H302+H312+H332,H315,H319,H335
• 储存条件：
  存放于阴凉干燥处。

SDS

Name:	(R)-4-Bromo-alpha-methylbenzyl alcohol 95% (98% e.e.) Material Safety Data Sheet
Synonym:	(R)-1-(4-Bromophenyl)ethano
CAS:	76155-78-7

Section 1 - Chemical Product MSDS Name:(R)-4-Bromo-alpha-methylbenzyl alcohol 95% (98% e.e.) Material Safety Data Sheet
Synonym:(R)-1-(4-Bromophenyl)ethano

---

Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
76155-78-7	(R)-4-Bromo-alpha-methylbenzyl alcohol	95%	unlisted

Hazard Symbols: XI
Risk Phrases: 36/37/38

---

Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Irritating to eyes, respiratory system and skin.
Potential Health Effects
Eye:
Causes eye irritation.
Skin:
Causes skin irritation. May be harmful if absorbed through the skin.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
Causes respiratory tract irritation. May be harmful if inhaled.
Chronic:
Not available.

---

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.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Ingestion:
Get medical aid. Wash mouth out with 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.

---

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.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

---

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.

---

Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Store in a cool, dry place. Store in a tightly closed container.

---

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# 76155-78-7: Personal Protective Equipment Eyes: Not available.
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.

---

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Clear liquid
Color: colorless
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
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:
Molecular Formula: C8H9BrO
Molecular Weight: 201.06

---

Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide, hydrogen bromide.
Hazardous Polymerization: Will not occur.

---

Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 76155-78-7 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(R)-4-Bromo-alpha-methylbenzyl alcohol - Not listed by ACGIH, IARC, or NTP.

---

Section 12 - ECOLOGICAL INFORMATION

---

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

---

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.

---

Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XI
Risk Phrases:
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
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# 76155-78-7: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 76155-78-7 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 76155-78-7 is not listed on the TSCA inventory.
It is for research and development use only.

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

简介

(R)-4-溴-α-甲基苄醇是一种透明无色至淡黄色液体，常见于医药化工领域。它被用于制备光敏材料、醇氧化酶以及标记蛋白质和DNA的分子探针。

用途

作为合成抗肿瘤药物的关键中间体，(R)-4-溴-α-甲基苄醇还广泛应用于制备上述各种功能性化合物。

制备

(R)-4-溴-α-甲基苄醇的合成方法多样。可以通过硼氢化钾催化酮基还原、苯环溴代及溴苄水解制备苄醇的过程来获得，也可从α-甲基苄醇出发，经N-溴代琥珀酰亚胺溴代反应得到目标化合物。文中采用的方法是以α-甲基苄醇为起始物料，通过上述化学反应制备出(R)-4-溴-α-甲基苄醇。

合成过程的化学方程式如下图所示：

反应信息

• 作为反应物：
  描述：

  (R)-4-溴-alpha-甲基苄醇 在 甲醇 、 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 copper(l) iodide 、 potassium carbonate 、 三乙胺 作用下， 反应 37.0h， 生成 (R)-1-(4-ethynylphenyl)ethan-1-ol
  参考文献：
  名称：

  三芳香族截短侧耳素候选抗生素的命中先导鉴定和验证

  摘要：

  在此，我们根据 2020 年报告的三芳香族命中，报告了药物样截短侧耳素缀合物16的命中到先导化合物的鉴定。该先导化合物是命中优化活动中的明确候选者，其中革兰氏阳性抗菌活性，溶解度和 P-gp 亲和力进行了优化。结合物16的体外ADMET 性能经过广泛评估，除了溶解度外，总体上与来法莫林相当。该评估包括 Caco-2 细胞通透性、血浆蛋白结合、hERG 抑制、细胞毒性、微粒体和 CYP3A4 代谢、耐药诱导和时间杀死动力学。 16 种药物的静脉注射药代动力学在小鼠和猪中均被证明是令人满意的；然而，口服生物利用度可能由于溶解度不足而受到限制。在全身感染金黄色葡萄球菌的小鼠中评估了体内功效，其中16 只小鼠的血液菌血症迅速减少。通过我们的综合研究， 16 号先导化合物已成为一种非常有前景且安全的候选抗生素，用于治疗革兰氏阳性细菌感染。

  DOI：

  10.1021/acs.jmedchem.3c02153
• 作为产物：
  描述：

  4-溴苯乙酮 在 sodium tetrahydroborate 、 C₁₁H₁₁BO₅S 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以84%的产率得到(R)-4-溴-alpha-甲基苄醇
  参考文献：
  名称：

  5-羧甲基-2-（4-甲基硫代苯基）-1,3,2-二氧杂硼环烷-4-酮：合成，表征及其在酮的对映选择性还原中的应用

  摘要：

  研究了芳基硼酸与L - O-苯甲酰基-酒石酸与D，L-苹果酸的反应。所获得的（酰氧基）硼烷在溶液中是中等稳定的并且分解以产生硼氧烷。在4-甲基硫代苯基硼酸与D，L-苹果酸的反应中获得了5-羧甲基-2-（4-甲基硫代苯基）-1,3,2-二氧杂硼环烷-4-酮，并通过X射线结构分析对其进行了表征。使用L -（-）-苹果酸提供了光学纯的产物，可用作对映体选择性还原酮的强手性试剂。版权所有©2011 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/aoc.1757

文献信息

• Catalytic enantioselective acyl transfer: the case for 4-PPY with a C-3 carboxamide peptide auxiliary based on synthesis and modelling studies
  作者：Rudy E. Cozett、Gerhard A. Venter、Maheswara Rao Gokada、Roger Hunter

  DOI：10.1039/c6ob01991a

  日期：——

  and evaluated in the kinetic resolution of a small library of chiral benzylic secondary alcohols. A key design element was the incorporation of a tryptophan residue in the peptide side chain for promoting π-stacking between peptide side chain and the pyridinium ring of the N-acyl intermediate, in which modelling was used as a structure-based guiding tool. Together, a catalyst containing a LeuTrp-N-Boc

  已经合成了一系列含有基于肽的侧链的4-吡咯烷二吡啶（4-PPY）C-3羧酰胺，并在手性苄基仲醇小文库的动力学拆分中进行了评估。一个关键的设计元素是在肽侧链中掺入一个色氨酸残基，以促进N-酰基中间体的肽侧链和吡啶鎓环之间的π堆积，其中建模被用作基于结构的指导工具。一起，含有LeuTrp-催化剂Ñ -Boc侧链（催化剂8）经鉴定，实现小号-值高达10，并略有超过10。提出了一种基于建模的过渡状态模型来解释对映选择性的起源。这项研究确立了建模作为对映选择性优化的基于结构的指导工具的有用性，以及为大规模拆分工作开发可扩展的基于肽的DMAP型催化剂的潜力。
• Discovery of Dipeptide-Derived Catalysts for the Enantioselective Addition of Dimethylzinc to Aldehydes
  作者：Seock Yong Kang、Yong Sun Park

  DOI：10.1002/ejoc.201200063

  日期：2012.3

  new class of modular chiral catalysts derived from various amino acid-L-Pro dipeptides was prepared, and the catalysts were tested for their ability to catalyze the enantioselective addition of dimethylzinc to aromatic aldehydes. Dipeptides derived from L-Asp-L-Pro were identified as effective catalysts for the addition at room temperature with up to 97:3 er and 95 % yield.

  制备了一类新的模块化手性催化剂，这些催化剂来源于各种氨基酸-L-Pro 二肽，并测试了催化剂催化二甲基锌对芳香醛的对映选择性加成的能力。源自 L-Asp-L-Pro 的二肽被确定为在室温下添加的有效催化剂，效率高达 97:3，产率为 95%。
• A Simple Biosystem for the High‐Yielding Cascade Conversion of Racemic Alcohols to Enantiopure Amines
  作者：Kaiyuan Tian、Zhi Li

  DOI：10.1002/anie.202009733

  日期：2020.11.23

  intermediate to chiral amine, and isopropylamine to recycle PMP and NAD+ cofactors via the reversed cascade reactions. The concept was proven by using an ambidextrous CpSADH‐W286A engineered from (S)‐enantioselective CpSADH as the first example of evolving ambidextrous ADHs, an enantioselective BmTA, and isopropylamine. A biosystem containing isopropylamine and E. coli (CpSADH‐W286A/BmTA) expressing the two enzymes

  外消旋醇的胺化生产对映体纯胺是药物生产的重要绿色化学反应，需要简单有效的解决方案。在本文中，我们报道了胺化外消旋醇的级联生物转化的发展。该级联反应利用灵巧的醇脱氢酶（ADH）氧化外消旋醇，对映选择性转氨酶（TA）将酮中间体转化为手性胺，异丙基胺通过反向的级联反应再循环PMP和NAD +辅因子。该概念是通过使用（S）设计的灵巧的CpSADH-W286A证明的。）-对映选择性CpSADH作为进化的歧义ADH，对映选择性BmTA和异丙胺的第一个例子。开发了一种包含异丙胺和大肠杆菌（CpSADH-W286A / BmTA）的生物系统来表达这两种酶，用于消旋外消旋醇的胺化反应，以产生八种有用的高价值（S）胺，产率为72-99％，98-99 ％ee，提供了针对此类反应的简单实用的解决方案。
• Asymmetric synthesis of both enantiomers of secondary alcohols by reduction with a single microbe
  作者：Kaoru Nakamura、Keishi Takenaka、Mikio Fujii、Yoshiteru Ida

  DOI：10.1016/s0040-4039(02)00649-4

  日期：2002.5

  Both enantiomers of secondary alcohols were prepared by reduction of the corresponding ketones with a single microbe. Thus, reduction of aromatic ketones with Geotrichum candidum IFO 5767 afforded the corresponding (S)-alcohols in an excellent ee when amberlite™ XAD-7, a hydrophobic polymer, was added to the reaction system and the same microbe afforded (R)-alcohols also in an excellent ee when the

  通过用单个微生物还原相应的酮来制备仲醇的两种对映异构体。因此，还原芳族酮的白地霉IFO 5767，得到相应的（小号）时AMBERLITE™XAD-7，疏水性聚合物，加入到反应体系时，可以得到相同的微生物（ -醇在一个极好EE - [R ）-醇当在有氧条件下进行反应时，在优异的ee中也是如此。
• Designing the “Search Pathway” in the Development of a New Class of Highly Efficient Stereoselective Hydrosilylation Catalysts
  作者：Vincent César、Stéphane Bellemin-Laponnaz、Hubert Wadepohl、Lutz H. Gade

  DOI：10.1002/chem.200500132

  日期：2005.4.22

  coupling of oxazolines and N-heterocyclic carbenes leads to chelating C,N ancillary ligands for asymmetric catalysis that combine both an "anchor" unit and a stereodirecting element. Reacting various N-substituted imidazoles with 2-bromo-4(S)-tert-butyl- and 2-bromo-4(S)-isopropyloxazoline gave the imidazolium precursors of the stereodirecting ancillary ligands. A library of ten different ligand precursors

  恶唑啉和N-杂环卡宾的直接偶联导致螯合C，N辅助配体用于不对称催化，该配体结合了“锚”单元和立体定向元件。使各种N-取代的咪唑与2-溴-4（S）-叔丁基-和2-溴-4（S）-异丙基恶唑啉反应，得到立体定向辅助配体的咪唑前体。通过使用该简单程序，可获得十种不同配体前体的文库（65-97％的收率）。通过与[Rh（mu-OtBu）（nbd）} 2]（nbd =降冰片二烯）反应，在随后的步骤中将这些蛋白配体金属化，由KOtBu和[RhCl（nbd）} 2]原位生成相应的N -杂环卡宾配合物[RhBr（nbd）（恶唑啉基-卡宾）] 4 aj收率良好。两种铑配合物4 d和4 j的X射线衍射研究，建立了扭曲的方金字塔形配位几何结构，其中溴配体占据了顶端位置。发现铑-卡宾键的长度为2.070（4）A（4 d）和2.012（3）A（4 j）。用AgBF 4在二氯甲烷中处理配合物4 aj，得到用于酮的氢化