Alpha-甲基苯乙烯 | 622-97-9

• 物质功能分类: 化学试剂 - 有机试剂 - 烯烃（环状与无环状）
• 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: Alpha-甲基苯乙烯
• 中文别名: 4-甲基苯乙烯；2-苯基丙烯；对乙烯甲苯；α-甲基苯乙烯；4-乙烯基甲苯；1-甲基-4-乙烯基苯；对甲基苯乙烯；1-乙烯基-4-甲基苯
• 英文名称: 1-ethenyl-4-methylbenzene
• 英文别名: para-methylstyrene；4-Methylstyrene；1-methyl-4-vinylbenzene；p-methylstyrene；4-vinyltoluene
• CAS: 622-97-9；1319-73-9
• 化学式: C₉H₁₀
• mdl: MFCD00008621
• 分子量: 118.178
• InChiKey: JLBJTVDPSNHSKJ-UHFFFAOYSA-N

物化性质

• 沸点：
  169-172 °C(lit.)
• 密度：
  0.896 g/mL at 20 °C
• 闪点：
  127 °F
• 物理描述：
  P-methylstyrene appears as a clear colorless liquid with an aromatic odor. Usually shipped with an inhibitor such as tert-butyl catechol added May polymerize if contaminated or subjected to heat. If polymerization takes place inside a closed container, the container may rupture violently. Vapors irritate the mucous membranes. Less dense than water and insoluble in water. Hence floats on water. Used in making plastics, especially as a monomer for polyesters.
• 颜色/状态：
  Liquid
• 熔点：
  -34.1 °C
• 溶解度：
  In water, 89 mg/L at 25 °C
• 蒸汽密度：
  Relative vapor density (air = 1): 4.1
• 蒸汽压力：
  1.81 mm Hg at 25 °C
• 稳定性/保质期：
  Stable under recommended storage conditions.
• 自燃温度：
  515 °C.
• 粘度：
  0.0020986 Pa.s (liquid) at 239.02 K
• 燃烧热：
  -4.8229X10+09 J/kmol
• 汽化热：
  6.20X10+07 J/kmol at 25 °C
• 表面张力：
  0.043227 Newtons/m at 239.02 K
• 折光率：
  Index of refraction: 1.5420 at 20 °C/D
• 保留指数：
  980.5;965.9;1000;985;977.5;977.6;977.9;966;980;994;982;978;985

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.111
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

o-乙烯基甲苯、m-乙烯基甲苯和p-乙烯基甲苯通过腹腔注射给大鼠，并通过气相色谱质谱法分析尿液中的酸性代谢物。制备了不同的衍生物，用于识别代谢物的结构。发现了不同类型（11种）的代谢物，尽管不是所有的代谢物都是由每种乙烯基甲苯同分异构体产生的。识别出的代谢物包括：甲基苯乙烯乙二醇、甲基马兰酸、甲基苯基乙二酸、羟基甲基苯乙烯乙二醇、羧基苯乙烯乙二醇、羟基甲基苯基乙二酸、甲基苯甲酰甘氨酸、甲基苯乙酰甘氨酸、乙烯基苯甲酰甘氨酸、甲基苯乙醇的N-乙酰半胱氨酸结合物和甲基苯乙烯乙二醇的葡萄糖苷酸。回收的代谢物（>90%）在最初的24小时内排出。对于所有代谢物的总和，给予剂量与回收代谢物量之间大约呈线性关系。重复每日给药并未导致代谢物排泄的显著增加，也没有明显的酶诱导现象。

o-Vinyltoluene, m-vinyltoluene and p-vinyltoluene were given i.p. to rats and urine was analyzed for acidic metabolites by gas chromatography mass spectrometry. Different derivatives were prepared and used to identify the structure of the metabolites. Different types (11) of metabolites were found, although all metabolites were not produced from each vinyltoluene isomer. The metabolites identified were: methylphenylethylene glycol, methylmandelic acid, methylphenylglyoxylic acid, hydroxymethylphenylethylene glycol, carboxyphenylethylene glycol, hydroxymethylphenylglyoxylic acid, methylbenzoylglycine, methylphenylacetylglycine, vinylbenzoylglycine, N-acetylcysteine conjugate of methylphenylethanol and glucuronide of methylphenylethylene glycol. Metabolites (> 90%) recovered were excreted during the 1st 24 hr. For the sum of all metabolites, there was an approximately linear relation between given dose and recovered amount of metabolites. Repeated daily administration was not followed by any appreciable increase in metabolite excretion and no enzyme induction phenomenon was apparent.

来源:Hazardous Substances Data Bank (HSDB)

代谢

细胞色素P-450在启动苯乙烯衍生物代谢中的作用在Holtzman大鼠肝脏匀浆中进行了研究。六种对位取代的苯乙烯是通过相应的苯乙酮通过硼氢化钠还原到p-溴苯乙烯、p-氯苯乙烯、p-氰基苯乙烯、p-甲基苯乙烯、p-苯基苯乙烯和p-甲氧基苯乙烯而制备的。苯乙烯衍生物与肝脏匀浆一起孵育，并加入还原型烟酰胺腺嘌呤二核苷酸磷酸（NADPH）或一氧化碳（CO）。放射性碳-4-苯基苯乙烯转化为alpha-beta-二醇苯乙烯的转化取决于氧源和在微粒体系统中NADPH的存在以催化底物。对于p-甲基苯乙烯、p-甲氧基苯乙烯和p-苯基苯乙烯，代谢攻击仅限于乙烯基团。所有六种苯乙烯在微粒体底物中给出了类型1的差异结合光谱。通过CO的添加和苯巴比妥的刺激，证实了p-苯基苯乙烯的代谢。取代基没有影响光谱解离常数或酶促环氧化值。作者得出结论，苯乙烯的酶促环氧化对极性取代基的影响不显著，这与早期研究中确定试剂为亲电性的结果不一致。这种差异可能是由于涉及不同种类的细胞色素P-450酶或不同的底物作用模式。

The role of cytochrome-P-450 in initiating the metabolism of styrene derivatives was investigated in Holtzman-rat liver homogenates. Six parasubstituted styrenes were prepared from the corresponding acetophenones by borohydride reduction to p-bromostyrene, p-chlorostyrene, p-cyanostyrene, p-methylstyrene, p-phenylstyrene, and p-methoxystyrene. Styrene derivatives were incubated with liver homogenates with the addition of reduced nicotinamide-adenine-dinucleotide-phosphate (NADPH) or carbon-monoxide (CO). The conversion of tritiated beta-4-phenylstyrene to alpha-beta-diolstyrene depended on an oxygen source and the presence of NADPH in the microsomal system in order to catalyze the substrate. With p-methylstyrene, p-methoxystyrene, and p-phenylstyrene, metabolic attack was confined to the vinyl group. All six styrenes gave a type 1 difference binding spectrum in the microsomal substrate. The metabolism of p-phenylstyrene was confirmed by its inhibition by the addition of CO and by its stimulation and phenobarbital. The substituents did not affect the spectral dissociation constants or the values for enzymatic epoxidation. The authors conclude that the lack of significant polar substituent effects on enzymatic epoxidation of styrenes is not consistent with earlier studies in which it was determined that the reagent is electrophilic. The discrepancy may be due to the involvement of different species of cytochrome-P-450 enzymes or different modes of substrate action.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

鉴定和使用：4-乙烯基甲苯与其他乙烯基甲苯异构体（3-乙烯基甲苯）混合使用，作为生产聚（乙烯基甲苯）的单体。它用作生产聚酯树脂的单体，并与异丁烯共聚以产生合成弹性体。它在涂料工业中用作改性剂，用于干性油和油改性醇酸树脂，用作不饱和聚酯树脂中苯乙烯的替代品，与苯乙烯共聚以增加油漆、涂料和清漆的操作温度范围。人体研究：4-乙烯基甲苯对眼睛、皮肤和呼吸道有刺激性。它还可能对中枢神经系统产生影响。皮肤反复或长期接触可能导致皮炎。4-乙烯基甲苯会使皮肤脱脂，可能导致干燥或开裂。它可能对肝脏和肾脏产生影响，可能导致组织损伤。在一项人体研究中，对苯乙烯相关化合物的接触过敏进行了研究。已知对苯乙烯过敏的患者在先前的研究中进行了斑贴测试，测试了苯乙烯和18种与苯乙烯结构相关的化合物。除了其他物质外，4-乙烯基甲苯也呈阳性反应。在整个人血培养中暴露于4-乙烯基甲苯的人类淋巴细胞中，姐妹染色单体交换的频率显著增加。动物研究：没有可用的数据。

IDENTIFICATION AND USE: 4-Vinyltoluene is used in mixtures with other vinyltoluene isomers (3-vinyltoluene) as monomers for producing poly(vinyltoluene). It is used as a monomer in the production of polyester resins and is co-polymerized with isobutylene to produce synthetic elastomers. It is used in the coatings industry as a modifier for drying oils and oil-modified alkyds, used as a replacement for styrene in unsaturated polyester resins, as a copolymer with styrene to increase the operating temperature range of paints, coatings and varnishes. HUMAN STUDIES: 4-Vinyltoluene is irritating to the eyes, skin and respiratory tract. It may also cause effects on the central nervous system. Repeated or prolonged contact with skin may cause dermatitis. 4-Vinyltoluene defats the skin, which may cause dryness or cracking. It may have effects on the liver and kidneys, which may result in tissue lesions. Contact allergy to styrene related compounds was studied in a human subject. A patient known from previous studies to be sensitive to styrene was patch tested with styrene and 18 compounds structurally related to styrene. Positive results were obtained with 4-vinyltoluene among others. Significant increases in the frequencies of sister chromatid exchange were observed in human lymphocyes exposed in whole blood cultures to 4-vinyltoluene. ANIMAL STUDIES: There are no data available.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 暴露途径

这种物质可以通过吸入和摄入被身体吸收。

The substance can be absorbed into the body by inhalation and by ingestion.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 吸入症状

晕眩。嗜睡。乏力。头痛。喉咙痛。

Dizziness. Drowsiness. Lethargy. Headache. Sore throat.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 皮肤症状

干燥的皮肤。红斑。

Dry skin. Redness.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 眼睛症状

Redness.

Redness.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

安全信息

• 危险等级：
  3.2
• 危险品标志：
  Xn
• 安全说明：
  S26,S36,S62
• 危险类别码：
  R10
• WGK Germany：
  3
• 海关编码：
  29029050
• 危险品运输编号：
  UN 2618 3/PG 3
• 危险类别：
  3
• RTECS号：
  WL5076000
• 包装等级：
  III
• 危险标志：
  GHS02,GHS07,GHS08
• 危险性描述：
  H226,H304,H315,H319,H335
• 危险性防范说明：
  P261,P301 + P310,P305 + P351 + P338,P331

制备方法与用途

概述

α-甲基苯乙烯（简称a-MS或AMS），又称α-甲基苯乙烯或苯基异丙烯，是采用异丙苯法生产苯酚和丙酮时的副产物，通常每吨苯酚会副产0.045吨α-甲基苯乙烯。这种无色液体具有刺激性气味，分子中包含一个苯环以及苯环上的烯基取代基，在受热条件下容易发生聚合反应。

用途

α-甲基苯乙烯虽然作为异丙苯法生产苯酚和丙酮的副产物，但其主要用途包括：

1. 有机合成中间体：α-MS是有机合成的基本原料之一，可用于合成异丙苯、过氧化二异丙苯以及对枯基酚等化合物。
2. 共聚合单体：作为树脂改性剂，α-甲基苯乙烯可以与丙烯腈、甲基丙烯酸甲酯、马来酸酐等进行共聚，从而制造出具有不同特性的共聚树脂。

反应信息

• 作为反应物：
  描述：

  Alpha-甲基苯乙烯 在 Oxone 、 碘 作用下， 以 乙二醇二甲醚 、 水 为溶剂， 反应 2.5h， 以86%的产率得到对甲基苯乙酸
  参考文献：
  名称：

  乙烯基芳烃的无金属催化区域选择性氧化转化：苯乙酸衍生物的温和方法†

  摘要：

  通过使用无毒试剂（例如分子碘和氧杂环丁烷），在温和条件下首次开发了一种新的合成方法，用于从芳族烯烃合成苯乙酸。乙烯基芳烃的这种无金属的催化区域选择性氧化是通过串联的碘官能化/去碘化引起的重排而进行的。

  DOI：

  10.1039/c5ra25296b
• 作为产物：
  描述：

  1-(4-甲基苯基)-1-乙醇 反应 0.25h， 生成 Alpha-甲基苯乙烯
  参考文献：
  名称：

  新分离的曼德假单胞菌 KJLPB5 和 [hmim]Br 的协同混合物，用于在 H2O2 中进行化学选择性 2°芳基醇氧化：通过顺序脱水-氧化 C=C 裂解合成芳基酮或醛

  摘要：

  据报道，曼德假单胞菌 KJLPB5 在离子液体 [hmim]Br（1-己基-3-甲基溴化咪唑鎓）中用 H2O2 氧化芳醇。随着反应条件的轻微改变，所开发的方案导致（i）2°芳醇和脂肪族对应物的化学选择性氧化或（ii）直接将2°芳醇转化为相应的一锅两步顺序转化或两个碳原子较短的芳醛通过氧化裂解途径，从而为无金属氧化提供了一个新的方面。还优化了底物浓度、孵育温度、孵育时间、离子液体类型和离子液体浓度等关键操作参数。 图形摘要

  DOI：

  10.1007/s10562-010-0542-6
• 作为试剂：
  描述：

  3,4-二甲基碘苯 、 methyl 1-ethyl-6-fluoro-4-oxo-7-piperazin-1-yl-1,8-naphthyridine-3-carboxylate 在 4-二甲氨基吡啶 、 Alpha-甲基苯乙烯 、 palladium(II) acetylacetonate 、 tetrabromothiophene S,S-dioxide 作用下， 以 二甲基亚砜 为溶剂， 反应 24.0h， 以60%的产率得到methyl 7-(4-((3,4-dimethylphenyl)sulfonyl)piperazin-1-yl)-1-ethyl-6-fluoro-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carboxylate
  参考文献：
  名称：

  钯催化芳基碘化物和胺之间直接氨基磺酰化反应中SO2替代物的设计和应用

  摘要：

  据报道，一种新的SO 2替代品价格便宜，工作台稳定，并且可以从大宗化学品中分两步进行访问。5分钟内即可实现基本完全的SO 2释放。通过利用两室系统与SO 2替代物组合异位形成SO 2，八个已建立的磺酰化反应顺利进行。此外，我们报告了芳基碘化物和胺之间的第一个直接氨基磺酰化反应。证明了宽泛的官能团耐受性，并且该方法适用于药学上相关的底物，包括杂环底物。

  DOI：

  10.1002/anie.202014111

文献信息

• Highly Regio- and Enantioselective Alkoxycarbonylative Amination of Terminal Allenes Catalyzed by a Spiroketal-Based Diphosphine/Pd(II) Complex
  作者：Jiawang Liu、Zhaobin Han、Xiaoming Wang、Zheng Wang、Kuiling Ding

  DOI：10.1021/jacs.5b07764

  日期：2015.12.16

  An enantioselective alkoxycarbonylation-amination cascade process of terminal allenes with CO, methanol, and arylamines has been developed. It proceeds under mild conditions (room temperature, ambient pressure CO) via oxidative Pd(II) catalysis using an aromatic spiroketal-based diphosphine (SKP) as a chiral ligand and a Cu(II) salt as an oxidant and affords a wide range of α-methylene-β-arylamino

  已经开发了末端丙二烯与 CO、甲醇和芳胺的对映选择性烷氧基羰基化-胺化级联过程。它在温和的条件下（室温，环境压力 CO）通过氧化钯（II）催化，使用芳族螺缩酮基二膦（SKP）作为手性配体和铜（II）盐作为氧化剂，并提供广泛的α-亚甲基-β-芳基氨基酸酯（36 个实例），收率良好，具有出色的对映选择性（高达 96% ee）和高区域选择性（支链/线性 > 92:8）。初步的机理研究表明，该反应可能通过丙二烯的烷氧基羰基钯化和胺化过程进行。该协议的合成效用体现在环庚烯融合手性 β-内酰胺的不对称结构中。
• Alternate Heme Ligation Steers Activity and Selectivity in Engineered Cytochrome P450-Catalyzed Carbene-Transfer Reactions
  作者：Kai Chen、Shuo-Qing Zhang、Oliver F. Brandenberg、Xin Hong、Frances H. Arnold

  DOI：10.1021/jacs.8b09613

  日期：2018.12.5

  platform of engineered cytochrome P450 enzymes to carry out carbene-transfer reactions using a lactone-based carbene precursor. By simply altering the heme-ligating residue, we obtained two enzymes that catalyze olefin cyclopropanation (Ser) or S-H bond insertion (Cys). Both enzymes exhibit high catalytic efficiency and stereoselectivity, thus enabling facile access to structurally diverse spiro[2.4]lactones

  我们报告了工程细胞色素 P450 酶的生物催化平台，以使用基于内酯的卡宾前体进行卡宾转移反应。通过简单地改变血红素连接残基，我们获得了两种催化烯烃环丙烷化 (Ser) 或 SH 键插入 (Cys) 的酶。这两种酶都表现出高催化效率和立体选择性，因此可以轻松获得结构多样化的螺[2.4]内酯和α-硫代-γ-内酯。计算研究揭示了卡宾 SH 插入的机制，并解释了轴向配体如何控制反应性和选择性。这项工作扩展了血红素蛋白的催化库，并提供了有关如何调整这些酶以适应新化学反应的见解。
• <i>C</i>-Alkylation of <i>N</i>-alkylamides with styrenes in air and scale-up using a microwave flow reactor
  作者：Joshua P. Barham、Souma Tamaoki、Hiromichi Egami、Noriyuki Ohneda、Tadashi Okamoto、Hiromichi Odajima、Yoshitaka Hamashima

  DOI：10.1039/c8ob02282h

  日期：——

  N-alkylamides with styrenes is reported, proceeding in ambient air/moisture to give arylbutanamides and pharmaceutically-relevant scaffolds in excellent mass balance. Various amide and styrene derivatives were tolerated, rapidly affording molecular complexity in a single step; thus highlighting the future utility of this transformation in the synthetic chemistry toolbox. Reaction scalability (up to

  Ç的烷基化Ñ -alkylamides与苯乙烯报道，在环境空气中前进/水分，得到arylbutanamides和在良好的质量平衡的药学上相关的支架。可以耐受各种酰胺和苯乙烯衍生物，只需一步即可快速提供分子复杂性。因此，突出了这种转变在合成化学工具箱中的未来实用性。作为使用苯乙烯连续流动的C-烷基化反应的第一个实例，使用微波流反应器证明了反应可扩展性（高达65 gh -1产物）。
• 신규한 셀레늄 고리 화합물 및 이의 제조방법
  申请人：KNU-Industry Cooperation Foundation 강원대학교산학협력단(220040088571) BRN ▼221-82-10213

  公开号：KR102037409B1

  公开（公告）日：2019-10-28

  2개 이상의 질소와 셀레늄이 고리 원소를 이루는 방향족 고리 화합물인 반응물질 1과, 적어도 이중 결합 이상의 결합을 갖는 반응물질 2를 로듐 촉매 반응 하에 반응시키는 단계; 및 상기 반응에 따라 상기 2개 이상의 질소위치에 상기 이중 결합 이상의 결합을 갖는 원소가 고리 원소로 첨가되어 셀레늄 고리 화합물이 합성되는 단계를 포함하며, 상기 반응물질 1 이고, 상기 반응물질 2는 알카인, 알켄, 나이트릴, 다이엔 결합 중 어느 하나를 포함하는 화합물인 것을 특징으로 하는 셀레늄 고리 화합물 합성 방법이 제공된다. (상기 R1, R2는 각각 수소, 할로겐기, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알케닐기, 탄소수 1 내지 10의 알키닐기, 탄소수 6 내지 12의 치환되거나 치환되지 않은 아릴기, 치환되거나 치환되지 않은 탄소수 5 내지 12의 헤테로아릴기 및 탄소수 1 내지 10의 알킬옥시로 이루어진 군으로부터 선택된 어느 하나이며, 상기 R1과 R2는 서로 연결되어 융합고리를 형성될 수 있음)

  2个以上的氮和硒形成环元素的芳香环化合物的反应物质1，至少具有双键以上的键合的反应物质2在铑催化反应下反应的步骤；以及根据所述反应，在所述2个以上的氮位置上，具有双键以上的键合的元素被添加为环元素以合成硒环化合物的步骤，其中所述反应物质1，并且所述反应物质2是包含碱金属，烯烃，腈，二烯键中的任何一种的化合物的硒环化合物合成方法，其特征在于提供。 （其中R1，R2分别为氢，卤素，1到10个碳原子的烷基，1到10个碳原子的烯基，1到10个碳原子的烷基，6到12个被取代或未被取代的芳基，5到12个被取代或未被取代的杂环芳基和1到10个烷氧基中的任何一个，其中R1和R2可以相互连接以形成融合环）
• Synthesis of Unsymmetrically Disubstituted Tetraphenylenes via Carbonyl-Directed C–H Functionalization
  作者：Yanghui Zhang、Shulei Pan、Hang Jiang、Yu Zhang、Dushen Chen

  DOI：10.1055/s-0035-1561862

  日期：——

  strategy for the synthesis of unsymmetrically disubstituted tetraphenylenes from 2-acetylbiphenylene has been developed via ruthenium-catalyzed C–H functionalization. Four reactions, including alkenylation–cyclization, alkenylation, alkylation, and amidation, were achieved. The reactions provide easy access to a variety of unsymmetrically disubstituted tetraphenylene derivatives, which could accelerate research

  已经通过钌催化的 C-H 官能化开发了一种从 2-乙酰联苯合成不对称双取代四苯的新策略。实现了烯基化-环化、烯基化、烷基化和酰胺化四个反应。该反应为获得各种不对称双取代的四亚苯基衍生物提供了便利，可以加速四亚苯基应用的研究。

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