甲基环己烷 | 108-87-2

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 环烃
• 分子结构分类: 有机化合物 - 碳氢化合物 - 饱和烃
• 中文名称: 甲基环己烷
• 中文别名: 六氢甲苯；六氢化甲苯；六氢甲苯,环己基甲烷,甲基环已烷；甲基环己胺；环己基甲烷
• 英文名称: Methylcyclohexane
• CAS: 108-87-2
• 化学式: C₇H₁₄
• mdl: MFCD00001497
• 分子量: 98.1882
• InChiKey: UAEPNZWRGJTJPN-UHFFFAOYSA-N

物化性质

• 熔点：
  -126 °C (lit.)
• 沸点：
  101 °C (lit.)
• 密度：
  0.77 g/mL at 25 °C (lit.)
• 蒸气密度：
  3.4 (vs air)
• 闪点：
  25 °F
• 溶解度：
  与丙酮、苯、乙醚、四氯化碳、乙醇混溶，不溶于水。
• 最大波长(λmax)：
  λ: 207 nm Amax: 1.00λ: 221 nm Amax: 0.40λ: 232 nm Amax: 0.15λ: 260 nm Amax: 0.05λ: 300-400 nm Amax: 0.01
• 介电常数：
  2.1（25℃）
• 暴露限值：
  NIOSH REL: TWA 400 ppm (1,600 mg/m3), IDLH 1,200 ppm; OSHA PEL: TWA 500 ppm (2,000 mg/m3); ACGIH TLV: TWA 400 ppm (adopted).
• LogP：
  3.88
• 物理描述：
  Methylcyclohexane appears as a clear colorless liquid with a petroleum-like odor. Flash point 25°F. Less dense than water and insoluble in water. Vapors heavier than air.
• 颜色/状态：
  COLORLESS LIQUID
• 气味：
  Faint, benzene-like odor.
• 蒸汽密度：
  3.39 (air= 1)
• 蒸汽压力：
  46 MM HG @ 25 °C
• 亨利常数：
  0.43 atm-m3/mole
• 大气OH速率常数：
  1.04e-11 cm3/molecule*sec
• 自燃温度：
  482 °F (250 °C)
• 燃烧热：
  4565.3 kJ/mol at 25 °C (liquid)
• 汽化热：
  31.27 kJ/mol at boiling pt; 35.36 kJ/mol at 25 °C
• 电离电位：
  9.85 eV
• 气味阈值：
  630 ug/l
• 折光率：
  INDEX OF REFRACTION: 1.4231 AT 20 °C/D
• 保留指数：
  720.2;715.27;715.65;723.1;719.4;723.05;715;716.67;716.41;716.54;717;716.9;718;721.9;710.4;713.04;714.82;727;727;716;717.1;722.2;737;726;754;717.7;709;715;733.1;750.4;759.7;723.2;724;724.1;724.2;724.4;719;715;724;726;718;726;735;740;735;719;721.4;723.8;726.2;734.6;714;718;722;726;731;735;724;724.4;736;730;744;716;721;721;721;720;730.9;727;739;739;721;717;715;721;726;724;718.9;712.7;716;725;716;724;728;725;715.75;720.5;717;716.7;717;719;729;717;714;714;709;721;729;748;723;725;718;719;726;716.1;727;727;715;716;727;736;721;726;715;715;750;716;717;737
• 稳定性/保质期：

  1. 稳定性：稳定。

  2. 禁配物：强氧化剂、强酸、强碱、卤素。

  3. 聚合危害：不聚合。

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

代谢物在兔子体内是二氧化碳，邻位和对位葡萄糖苷酸结合物。/来自表格/

METABOLITES IN RABBITS WERE CARBON DIOXIDE, ORTHO & PARA GLUCURONIDE CONJUGATES. /FROM TABLE/

来源:Hazardous Substances Data Bank (HSDB)

代谢

以NADPH加强的大鼠肝微粒体能够对甲基环己烷进行羟基化。用苯巴比妥预处理的大鼠的微粒体对甲基环己烷的羟基化速率比对照组快4到5倍；苯巴比妥预处理还导致“类型1”底物结合差异光谱增加了4到5倍。甲基环己烷的羟基化反应不是线性的，这可能是由于反应产物竞争性抑制，因为醇类产物强烈竞争细胞色素p-450上的底物结合位点。

Rat liver microsomes fortified with NADPH were shown to hydroxylate methylcyclohexane. Microsomes prepared from rats pretreated with phenobarbital hydroxylated methylcyclohexane at a 4 to 5 fold greater rate than controls; phenobarbital pretreatment also caused a 4 to 5 fold increase in the "type 1" substrate binding difference spectrum. The hydroxylation reaction of methylcyclohexane was not linear, which was probably due to competitive inhibition by the reaction products since there was strong competition by the alcoholic products for the substrate binding site on cytochrome p-450.

来源:Hazardous Substances Data Bank (HSDB)

代谢

甲基环己烷在Fischer 344雄性大鼠体内的代谢进行了研究。每两天通过口服灌胃给予大鼠0或0.8克/千克的甲基环己烷，持续2周。在给药的前48小时内收集尿液样本。它们被直接分析为代谢物，或者首先用葡萄糖醛酸酶和硫酸酯酶处理。在最后一次给药后的24小时处死大鼠，取出肾脏，切片，并检查其组织病理学变化。经过葡萄糖醛酸酶和硫酸酯酶水解后，在尿液中鉴定的甲基环己烷代谢物包括2(t)-羟基-4(c)-甲基环己醇、2(c)-羟基-4(t)-甲基环己醇、反式-3-甲基环己醇、2(c)-羟基-4(c)-甲基环己醇、反式-4-甲基环己醇和环己基甲醇。其中2(t)-羟基-4(c)-甲基环己醇的含量最多。在没有经过葡萄糖醛酸酶和硫酸酯酶处理的尿液样本中没有检测到代谢物。在肾脏切片中只观察到轻微的肾毒性组织病理学证据。因此，可以得出结论，在大鼠体内，甲基环己烷主要代谢为二羟基代谢物。甲基环己烷的低肾毒性可能是由于环结构上侧链未发生分支。

The metabolism of methylcyclohexane was studied in rats. Male Fischer 344 rats were given 0 or 0.8 g/kg methylcyclohexane by oral gavage every other day for 2 wk. Urine samples were collected during the first 48 hr of dosing. They were analyzed as is for metabolites or treated with glucuronidase and sulfatase first. The rats were killed 24 hr after the last dose, the kidneys were removed, sliced, and examined for histopathological changes. Methylcyclohexane metabolites identified in urine after hydrolysis with glucuronidase and sulfatase were 2(t)-hydroxy-4(c)-methylcyclohexanol 2(c)-hydroxy-4(t)-methylcyclohexanol, trans-3-methylcyclohexanol, 2(c)-hydroxy-4(c)-methylcyclohexanol, trans-4-methylcyclohexanol, and cyclohexylmethanol. 2(t)-hydroxy-4(c)-methylcyclohexanol was found in the largest amount. No metabolites were detected in urine samples not treated with glucuronidase and sulfatase. Only slight histopathological evidence of nephrotoxicity was seen in the kidney slices. It was concluded that methylcyclohexane is metabolized primarily to dihydroxy metabolites in rats. The low nephrotoxicity of methylcyclohexane may be due to the lack of side chain branching on the ring structure.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 暴露途径

该物质可以通过吸入其蒸汽和摄入进入人体。

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

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

毒理性

• 暴露途径

吸入，吞食，皮肤和/或眼睛接触

inhalation, ingestion, skin and/or eye contact

来源:The National Institute for Occupational Safety and Health (NIOSH)

毒理性

• 症状

眼睛、皮肤、鼻子、喉咙刺激；眩晕、嗜睡；在动物中：麻醉

irritation eyes, skin, nose, throat; dizziness, drowsiness; In Animals: narcosis

来源:The National Institute for Occupational Safety and Health (NIOSH)

毒理性

• 吸入症状

晕眩。嗜睡。

Dizziness. Drowsiness.

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

毒理性

• 皮肤症状

干燥的皮肤。

Dry skin.

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

吸收、分配和排泄

甲基环己烷通过吸入被吸收。一小部分被呼出，另一部分在尿液中以原形排出...进入血液的大部分被代谢，并以葡萄糖醛酸或硫酸的共轭物形式在尿液中排出。

METHYLCYCLOHEXANE IS ABSORBED BY INHALATION. A SMALL FRACTION IS EXHALED, ANOTHER FRACTION EXCRETED IN URINE UNCHANGED ... MOST THAT GETS INTO BLOOD IS METABOLIZED AND EXCRETED IN URINE AS CONJUGATES OF GLUCURONIC ACID OR SULFURIC ACID.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

...未在狗尿液中检测到未改变的化合物或其任何代谢物。...在兔子中，只有4-5%的甲基环己烷给药量以葡萄糖醛酸苷形式被排出。

... NEITHER UNCHANGED COMPD NOR ANY OF ITS METABOLITES /WERE FOUND/ IN URINE OF DOG. ... ONLY 4-5% OF THE ADMINISTERED DOSE OF METHYLCYCLOHEXANE IN RABBITS WAS EXCRETED AS GLUCURONIDE CONJUGATES.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

鳟鱼和旗鱼在浓度为0.83-1.85毫克/升的甲基环己烷中暴露七天后的浓缩物，浓缩了150倍。

TROUT & FLAGFISH CONCENTRATED METHYLCYCLOHEXANE 150 FOLD AFTER SEVEN DAY EXPOSURE TO CONCN OF 0.83-1.85 MG/L.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

成年雌性栗鼠口服了2.1-2.4毫摩尔/公斤的(14)C甲基环己烷。总剂量的65%通过尿液排出，15%通过呼出的空气消除（其中10%为未改变的甲基环己烷，5%为二氧化碳），0.5%通过粪便排出，4-5%在给药后60小时仍留在动物体内。总剂量的42%以葡萄糖苷酸形式排出，2%以硫酸盐结合物形式排出。尿液中发现的主要代谢物是反式-4-甲基环己醇的葡萄糖苷酸，约占剂量的15%。尿液中还发现了另外五种甲基环己醇，它们各自以葡萄糖苷酸结合物的形式存在，每种占剂量的0.5-11.5%。没有发现1-甲基环己醇；然而，有少量（1.9%）似乎发生了芳香化生成为苯甲酸，并以马尿酸的形式排出。

... Adult chinchilla doe rabbits /were administered/ an oral dose of 2.1-2.4 mmol/kg (14)C methylcyclohexane. A total of 65% of the dose was excreted in the urine, 15% was eliminated in the expired air (10% as unchanged methylcyclohexane and 5% as carbon dioxide), 0.5% was excreted in the feces, and 4-5% remained in the animals 60 hr after dosing. A total of 42% of this dose was excreted as glucuronides and 2% as sulfate conjugates. The glucuronide of trans-4-methylcyclohexanol was the major urinary metabolite found, and represented approximately 15% of the dose. Five additional methylcyclohexanols were found in the urine as their respective glucuronide conjugates, each representing 0.5-11.5% of dose. No 1-methylcyclohexanol was found; however, a small amount (1.9%) appeared to have aromatized to benzoic acid and was excreted as hippuric acid.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 职业暴露等级：
  A
• 职业暴露限值：
  TWA: 400 ppm (1600 mg/m3)
• TSCA：
  Yes
• 危险等级：
  3
• 立即威胁生命和健康浓度：
  1,200 ppm [10% LEL]
• 危险品标志：
  Xn,F,N
• 安全说明：
  S16,S33,S61,S62,S9
• 危险类别码：
  R67,R38,R11,R51/53,R65
• WGK Germany：
  2
• 海关编码：
  2910200000
• 危险品运输编号：
  UN 2296
• 包装等级：
  II
• 危险标志：
  GHS02,GHS07,GHS08,GHS09
• 危险性描述：
  H225,H304,H315,H336,H410
• 危险性防范说明：
  P210,P301 + P310,P331,P370 + P378,P403 + P235
• 储存条件：
  储存注意事项：应将物品存放在阴凉、通风良好的库房中，远离火源和热源，库温不宜超过37℃。确保容器密封，并与氧化剂分开存放，切忌混合存储。使用防爆型照明和通风设施，并禁止使用可能产生火花的机械设备和工具。储存区域应配备泄漏应急处理设备和合适的收容材料。

SDS

第一部分：化学品名称

制备方法与用途

环保型溶剂——甲基环己烷

甲基环己烷，又称环己基甲烷，是一种无色有机溶剂和萃取剂，部分可替代苯类和酮类。它具有轻微的芳香气味、低毒特性，与皮肤接触可能导致发红及干燥等现象。此溶剂能溶于乙醇、乙醚、苯、丙酮等多种有机溶剂，并不溶于水，广泛应用于涂料、橡胶、清漆用溶剂（例如一些涂改液亦使用甲基环己烷）以及油脂萃取剂等领域。此外，它还可用作油脂萃取剂及有机合成中的溶剂和分析试剂。甲基环己烷也可用于校正温度计的标准物。

应用领域

作为一种环保型涂料，甲基环己烷主要用于油墨、橡胶、涂料、清漆用溶剂以及油脂萃取溶剂等领域；亦可用于有机合成，并作为溶剂及分析试剂。

化学性质

甲基环己烷为无色液体，熔点-126.59℃，沸点100.9℃，相对密度0.7693（20/4℃），折光率1.4231，闪点-3℃。它能与丙酮、苯、乙醚、四氯化碳、乙醇混溶，并不溶于水。

用途

该化合物用作橡胶、涂料、清漆用溶剂以及油脂萃取溶剂；也用于有机合成；作为校正温度计的标准物；并用作溶剂及分析试剂。它还是重要的有机溶剂及萃取剂，广泛应用于橡胶、涂料、油脂等行业。

生产方法

甲基环己烷由甲苯在150℃左右的压力为约11MPa下加氢反应5小时制得。精制时可采用浓硫酸、水、5%氢氧化钠溶液和水依次洗涤，并用脱水剂干燥，最后进行蒸馏。

类别

易燃液体

毒性分级

中毒

急性毒性

口服-大鼠 LD50: >3200毫克/公斤; 口服-小鼠 LD50: 2250 毫克/立方米/24小时

刺激数据

皮肤 - 兔 500 微升/ 24小时 轻度；眼睛 - 兔 100 微升/ 24小时 轻度

爆炸物危险特性

与空气混合可爆

可燃性危险特性

遇明火、高温或氧化剂易燃，燃烧时产生刺激烟雾

储运特性

库房通风低温干燥；与氧化剂和酸类分开存放

灭火剂

干粉、二氧化碳、泡沫、1211灭火剂

职业标准

TWA 1600 毫克/立方米； STEL 2000 毫克/公斤

反应信息

• 作为反应物：
  描述：

  甲基环己烷 在 5%Ni/SiO2 、 氢气 作用下， 300.0 ℃ 、101.33 kPa 条件下， 反应 0.04h， 生成 间甲酚
  参考文献：
  名称：

  Selective conversion of m-cresol to toluene over bimetallic Ni–Fe catalysts

  摘要：

  The catalytic conversion of m-cresol in the presence of H-2 has been investigated on SiO2-supported Ni, Fe, and bimetallic Ni-Fe catalysts at 300 degrees C and atmospheric pressure. Over the monometallic Ni catalyst, the dominant product is 3-methylcyclohexanone while 3-methylcyclohexanol and toluene appear in smaller amounts, even at high conversions. By contrast, on Fe and Ni-Fe bimetallic catalysts, the dominant product is toluene while the hydrogenation products (3-methylcyclohexanone and 3-methylcyclohexanol) are practically negligible in the entire range of conversions.To explain these differences, we have proposed a deoxygenation path that starts with the tautomerization of m-cresol to an unstable ketone intermediate (3-methyl-3,5-cyclohexadienone). The fate of this intermediate is determined by the ability of the catalyst to either hydrogenate the carbonyl group or the ring. The former would mostly occur on Fe and Ni-Fe catalysts that contain an oxophilic metal (Fe), while the latter would occur on Ni, which has a higher affinity for the aromatic ring.Hydrogenation of the carbonyl group produces a very reactive unsaturated alcohol (3-methyl-3,5cyclohexadienol), which can be easily dehydrated to toluene. This would explain the high selectivity of Fe and Ni-Fe to toluene. By contrast, hydrogenation of the ring would result in 3-methylcyclohexanone, which can be further hydrogenated to 3-methylcyclohexanol. On supports that contain acid sites, which are active for dehydration, the formation of toluene would occur via dehydration of the alcohol and sub-sequent dehydrogenation. On the catalysts investigated in this work, dehydration of the corresponding alcohol does not occur, so the only path to toluene is via hydrogenation of the carbonyl of the unstable ketone intermediate.In addition, to the products mentioned above, xylenol is also observed in significant yields, which indicate that transalkylation of m-cresol is another reaction path occurring on these catalysts. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2013.09.029
• 作为产物：
  描述：

  cholesterol 在 三氯化铝 作用下， 生成 甲基环己烷
  参考文献：
  名称：

  Zelinsky, Chemische Berichte, 1927, vol. 60, p. 1797

  摘要：

  DOI：
• 作为试剂：
  描述：

  ethyl 4-methylenehexanoate 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 二甲基硫 、 三乙基硼 、 CpPd(1-phenylallyl) 、 甲基环己烷 、 溶剂黄146 、 三乙胺 、 N,N'-羰基二咪唑 、 potassium hydroxide 、 O,O'-(S)-(1,1'-dinaphthyl-2,2'-diyl)-N,N'-di(R,R)-1-naphthylethylphosphoramidite 、 锌 、 三氯氧磷 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 89.83h， 生成 2-[(1R,12bR)-1-ethyl-3,4,6,7,12,12b-hexahydro-2H-indolo[2,3-a]quinolizin-1-yl]acetonitrile 、 2-((1R,12bS)-1-ethyl-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizin-1-yl)acetonitrile
  参考文献：
  名称：

  不对称烯烃氰酰胺化通过 C-CN 键活化全合成 (+)-Eburnamonine

  摘要：

  我们报道了使用对映选择性烯烃氰酰胺化形成全碳四元立构中心的 (+)-eburnamonine 的全合成。钯、亚磷酰胺配体和路易斯酸结合形成助催化剂，促进氰基甲酰胺的 C-CN 活化，然后进行分子内烯烃氰酰胺化。总体而言，(+)-eburnamonine 的合成由 4-亚甲基己酸和色胺通过 8 个步骤完成，提供了不对称脂肪族连接烯烃氰酰胺化及其在全合成中的应用的例子。

  DOI：

  10.1021/acs.orglett.4c01480

文献信息

• Can Heteroarenes/Arenes Be Hydrogenated Over Catalytic Pd/C Under Ambient Conditions?
  作者：Nao Tanaka、Toyonobu Usuki

  DOI：10.1002/ejoc.202000695

  日期：2020.9.14

  Pd/C‐mediated dearomatic hydrogenation under ambient conditions such as balloon pressure and room temperature can be a powerful tool for constructing alicyclic skeletons. Density functional theory calculations have been performed to confirm the mechanistic aspects and the utility of the established methodology has been demonstrated by donepezil synthesis.

  在诸如气球压力和室温等环境条件下，Pd / C介导的脱芳香族氢化反应可能是构建脂环族骨架的强大工具。已经进行了密度泛函理论计算以确认机理方面，并且通过多奈哌齐合成证明了所建立方法的实用性。
• Highly active iridium(i) complexes for the selective hydrogenation of carbon–carbon multiple bonds
  作者：Linsey S. Bennie、Calum J. Fraser、Stephanie Irvine、William J. Kerr、Shalini Andersson、Göran N. Nilsson

  DOI：10.1039/c1cc14367k

  日期：——

  New iridium(I) complexes, bearing a bulky NHC/phosphine ligand combination, have been established as extremely efficient hydrogenation catalysts that can be used at low catalyst loadings, and are compatible with functional groups which are often sensitive to more routinely employed hydrogenation methods.

  已经建立了带有庞大的NHC /膦配体组合的新型铱（I）配合物，作为可以在低催化剂负载量下使用的极其有效的氢化催化剂，并且与通常对更常用的氢化方法敏感的官能团相容。
• Hydrogenation of arenes, nitroarenes, and alkenes catalyzed by rhodium nanoparticles supported on natural nanozeolite clinoptilolite
  作者：Seyed Meysam Baghbanian、Maryam Farhang、Seyed Mohammad Vahdat、Mahmood Tajbakhsh

  DOI：10.1016/j.molcata.2015.06.029

  日期：2015.10

  Nanozeolite clinoptilolite supported rhodium nanoparticles (Rh/NZ-CP) has been prepared and characterized by a variety of techniques, including XRD, BET, TEM, EDX, ICP-OES and XPS analysis. This nanomaterial contains 2 wt% Rh in the range of 5–20 nm metallic nanoparticles distributed on nanozeolite. The catalytic performance of Rh/NZ-CP was evaluated by the hydrogenation of arenes, nitroarenes, and alkenes under

  纳米沸石斜发沸石负载的铑纳米颗粒（Rh / NZ-CP ）已通过多种技术进行了制备和表征，包括XRD，BET，TEM，EDX，ICP-OES和XPS分析。这种纳米材料包含2 wt％的Rh，分布在5-20 nm范围内的金属纳米颗粒分布在纳米沸石上。Rh / NZ-CP的催化性能通过在中等反应条件下氢化芳烃，硝基芳烃和烯烃来评估。所制备的纳米催化剂可以容易地回收并重复使用多次，而活性和选择性没有显着降低。高催化活性，热稳定性和可重复使用性，简单的回收和生态友好的性质使本催化剂成为独特的催化体系，在绿色化学中特别有吸引力。
• Transition metal nanoparticles stabilized by ammonium salts of hyperbranched polystyrene: effect of metals on catalysis of the biphasic hydrogenation of alkenes and arenes
  作者：Lei Gao、Keisuke Kojima、Hideo Nagashima

  DOI：10.1016/j.tet.2015.04.081

  日期：2015.9

  an excellent stabilizer of ruthenium, rhodium, iridium, palladium, and platinum nanoparticles from 1 to 3 nm in size uniformly dispersed in the polymer matrix. The catalytic performance of the resulting metal-polymer composites, [email protected]3+Cl−, is dependent on the metal. This dependence was investigated by assessing the hydrogenation of alkenes and arenes. The utility of [email protected]3+Cl−

  超支化聚苯乙烯轴承铵盐（HPS-NR 3 +氯- ）表现为钌，铑，铱，钯和铂纳米粒子的大小极好的稳定剂1〜3纳米均匀地分散在聚合物基质中。所得到的金属-聚合物复合材料的催化性能，[电子邮件保护] 3 +氯- ，取决于金属。通过评估烯烃和芳烃的氢化反应研究了这种依赖性。[电子邮件保护] 3 + Cl的实用程序-如在水/有机两相系统可重复使用的催化剂被证明通过检查含有各种官能团的芳族化合物的氢化的由催化[电子邮件保护] 3 +氯- 。
• Alleno-Acetylenic Cage (AAC) Receptors: Chiroptical Switching and Enantioselective Complexation of<i>trans</i>-1,2-Dimethylcyclohexane in a Diaxial Conformation
  作者：Cornelius Gropp、Nils Trapp、François Diederich

  DOI：10.1002/anie.201607681

  日期：2016.11.7

  (AACs) are highly conformation sensitive, the longest wavelength Cotton effect at 304 nm switches from Δϵ=+191 m−1 cm−1 for open (P)4‐AAC⊂acetonitrile to Δϵ=−691 m−1 cm−1 (ΔΔϵ=882 m−1 cm−1) for closed (P)4‐AAC⊂cyclohexane. Complete chiral resolution of (±)‐trans‐1,2‐dimethylcyclohexane was found in the X‐ray structures, with (P)4‐AAC exclusively bound to the (R,R)‐ and (M)4‐AAC to the (S,S)‐guest. Guest

  四个带有OH末端的对映纯1,3-二乙炔基（DEA）被连接在间苯二酚[4]芳烃空洞的边缘上。该系统在由圆形H键阵列封闭的笼形和开放式之间进行构象转换，叔醇基向外延伸。笼型在非极性溶剂中占主导地位，在小极性溶剂中呈开放构象。在溶液和X射线共晶结构中都确认了这两种状态。异炔乙炔笼（AAC）的ECD光谱对构象高度敏感，最长波长在304 nm处的棉花效应从开放的（P）4 -AAC乙腈的Δϵ = + 191  m -1  cm -1切换到Δϵ = −691  m -1 厘米-1（ΔΔ ε = 882 米-1 厘米-1），用于封闭（P）4 -AAC⊂cyclohexane。在X射线结构中发现了（±）-反-1,2-二甲基环己烷的完全手性拆分，其中（P）4- AAC仅与（R，R）-和（M）4- AAC结合（S，S）-访客。客体夹杂物以较高能量的双轴构象发生。

表征谱图