百里香酚杂质 | 3077-71-2

• 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: 百里香酚杂质
• 英文名称: 8-hydroperoxy-p-cymene
• 英文别名: p-Cymolhydroperoxid；1-(2-hydroperoxypropan-2-yl)-4-methylbenzene
• CAS: 3077-71-2
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: YCCHNFGPIFYNTF-UHFFFAOYSA-N

物化性质

• 保留指数：
  1321

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 海关编码：
  2909600000

反应信息

• 作为反应物：
  描述：

  百里香酚杂质 在 氧气 作用下， 100.0 ℃ 、3.5 MPa 条件下， 反应 18.0h， 生成 对甲基苯乙酮
  参考文献：
  名称：

  用氧对苯二甲基氧化合成对苯二甲酸：实现生物聚对苯二甲酸乙二酯的更可持续生产

  摘要：

  由生物质合成对苯二甲酸仍然是一项尚未解决的挑战。在这项研究中，我们在Mn-Fe混合氧化物非均相催化剂上将对苯甲基异丙基苯（由可生物降解的萜烯，柠檬烯或桉树醇合成）选择性氧化为对苯二甲酸。评价了各种工艺参数（氧化剂，温度，反应时间，催化剂量，氧气压力）对对苯二甲酸选择性的影响，并阐明了一些机理方面。报道了在O 2存在下空前的生物基对苯二甲酸合成（产率为51％）。

  DOI：

  10.1002/cssc.201600718
• 作为产物：
  描述：

  三甲基苯甲醇 在 硫酸 、 双氧水 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以23%的产率得到百里香酚杂质
  参考文献：
  名称：

  对甲基苯乙酮通过叔烷氧基自由基中间体从柠檬醛形成的机理。

  摘要：

  这项研究的目的是阐明酸性水溶液条件下由柠檬醛形成的强力除臭剂对甲基苯乙酮的形成机理。将含有10 mg / L柠檬醛的酸性水溶液（pH 3.0）在40摄氏度下保存2周。在储存的柠檬醛溶液中检测到的化合物中，首次发现4-（2-羟基-2-丙基）苯甲醛是柠檬醛的降解产物。当将抗氧化剂添加到柠檬醛溶液中时，对甲基苯乙酮和4-（2-羟基-2-丙基）苯甲醛的形成行为相同。此外，这两种化合物都是由Fe（2+）诱导的8-氢过氧-对-异丙基分解而形成的，这是在储存的柠檬醛溶液中鉴定出的另一种化合物。这些结果表明，对-甲基苯乙酮和4-（2-羟基-2-丙基）苯甲醛可以通过相同的自由基中间体[p-CH3C6H4C（CH3）2O *]形成，该中间体可以从OO键的8均质化获得。 -氢过氧-对异丙苯。另一方面，在酸性水溶液条件下，在没有Fe 2+的情况下降解8-氢过氧-对-甲基苯甲基不会产生对甲基苯乙酮和4-（2-羟基-2-丙基）苯甲醛，而在没有Fe

  DOI：

  10.1021/jf035517j

文献信息

• Catalytic activity of iron-substituted polyoxotungstates in the oxidation of aromatic compounds with hydrogen peroxide
  作者：Ana C. Estrada、Mário M. Q. Simões、Isabel C. M. S. Santos、M. Graça P. M. S. Neves、José A. S. Cavaleiro、Ana M. V. Cavaleiro

  DOI：10.1007/s00706-010-0370-9

  日期：2010.11

  corresponding acetophenone and hydroperoxide. In order to understand the reaction pathways, the oxidation of several products and presumed intermediates was also carried out in the presence of TBA4[PW11Fe(H2O)O39]·2H2O. Under the conditions used, the oxidation of styrene and styrene derivatives gave rise mainly to carbon–carbon double-bond cleavage, affording the corresponding products in very high yields

  摘要通式Keggin型polyoxotungstates的四丁基铵（TBA）盐[ X w ^ 11的Fe III（H 2 O）O- 39 ] ñ - ，其中X  = P，B或Si，被评价为在氧化催化剂中，下H 3 O 2在CH 3中的乙苯，枯烯，对-甲基苯甲基和仲丁基苯的温和条件CN在80°C。以系统的方式研究了各种因素的影响，例如底物/催化剂的摩尔比，氧化剂的添加量或反应时间。通常，该系统表现出中等转化率，对相应的苯乙酮和氢过氧化物具有良好的选择性。为了理解反应途径，还在TBA 4 [PW 11 Fe（H 2 O）O 39 ]·2H 2的存在下对几种产物和假定的中间体进行了氧化。O.在所用条件下，苯乙烯和苯乙烯衍生物的氧化主要引起碳-碳双键裂解，从而以非常高的收率（81-87％）提供相应的产物。提出了可能的反应途径。 图形概要
• The PANDAS Subgroup: Recognition and Treatment
  作者：Susan E. Swedo、Marjorie Garvey、Lisa Snider、Charlotte Hamilton、Henrietta L. Leonard

  DOI：10.1017/s1092852900021799

  日期：2001.11

  A subgroup of patients with childhood-onset obsessive-compulsive disorder (OCD) has been identified who share a common clinical course characterized by dramatic symptom exacerbations following Group A beta-hemolytic streptococcal (GABHS) infections. The term PANDAS has been applied to the subgroup, to indicate the postulated etiology of their symptoms: Pediatric Autoimmune Neuropsychiatric Disorders Associated with Streptococcal infections. Five clinical characteristics define the PANDAS subgroup: presence of OCD and/or tic disorder, prepubertal symptom onset, sudden onset or abrupt exacerbations (sawtooth course), association with neurological abnormalities (presence of adventitious movements or motoric hyperactivity during exacerbations), and temporal association between symptom exacerbations and GABHS infections. Post-streptococcal symptom exacerbations are typically quite dramatic, with patients reporting that their symptoms “…came on overnight” or “…appeared all of a sudden a few days after I had a sore throat.” The post-streptococcal inflammatory nature of the neuropsychiatric symptoms provides novel opportunities for treatment and prevention, including immunomodulatory therapies such as therapeutic plasma exchange (TPE) and intravenous immunoglobulin (IVIG). A recently completed placebo-controlled trial revealed that both IVIG and TPE were effective in reducing neuropsychiatric symptom severity (40% to 55% reductions, respectively) for a group of severely ill children with OCD and/or tic disorders. Further research is required to determine why the treatments are helpful, as well as to ascertain whether or not antibiotic prophylaxis can help prevent post-streptococcal symptom exacerbations.

  摘要 在儿童期发病的强迫症（OCD）患者中发现了一个亚群，他们具有共同的临床病程，其特点是在感染 A 组β-溶血性链球菌（GABHS）后症状急剧加重。PANDAS 一词已用于该亚群，以表明其症状的假定病因：与链球菌感染相关的小儿自身免疫性神经精神障碍。PANDAS 亚组有五个临床特征：存在强迫症和/或抽搐症、青春期前发病、突然发病或突然加重（锯齿状病程）、与神经系统异常有关（加重时出现临近运动或运动亢进）以及症状加重与 GABHS 感染在时间上有关。链球菌感染后的症状加重通常相当剧烈，患者会说他们的症状"......一夜之间就出现了 "或"......在我喉咙痛几天后突然出现"。链球菌感染后神经精神症状的炎症性质为治疗和预防提供了新的机会，包括治疗性血浆置换（TPE）和静脉注射免疫球蛋白（IVIG）等免疫调节疗法。最近完成的一项安慰剂对照试验显示，对于一组患有强迫症和/或抽搐症的重症儿童，静脉注射免疫球蛋白和治疗性血浆置换疗法都能有效减轻神经精神症状的严重程度（分别减轻 40% 至 55%）。还需要进一步的研究来确定为什么这些治疗方法有帮助，以及抗生素预防是否有助于预防链球菌感染后症状加重。
• Efficient and selective oxidation of tertiary benzylic C H bonds with O2 catalyzed by metalloporphyrins under mild and solvent-free conditions
  作者：Hai-Min Shen、Meng-Yun Hu、Lei Liu、Bei Qi、Hong-Liang Ye、Yuan-Bin She

  DOI：10.1016/j.apcata.2020.117599

  日期：2020.6

  The direct and efficient oxidation of tertiary benzylic CH bonds to alcohols with O2 was accomplished in the presence of metalloporphyrins as catalysts under solvent-free and additive-free conditions. Based on effective inhibition on the unselective autoxidation and deep oxidation, systematical investigation on the effects of porphyrin ligands and metal centers, and apparent kinetics study, the oxidation

  叔苄基C H键直接有效地氧化为具有O 2的醇在无溶剂和无添加剂的条件下，在金属卟啉作为催化剂的存在下完成。基于对非选择性自氧化和深度氧化的有效抑制作用，对卟啉配体和金属中心的影响的系统研究以及表观动力学研究，使用卟啉锰（II）（T（2,3,6-triCl）PPMn的氧化系统）以更大的取代基作为催化剂，被认为是最有前途和最有效的方法。对于典型的底物，枯烯的转化率可高达57.6％，对醇的选择性为70.5％，在相似的条件下，两者均高于当前文献。T（2,3,6-triCl）PPMn的优越性主要归因于其较大的取代基可防止金属卟啉氧化降解，
• Cerium (IV) ammonium nitrate catalyzed photochemical autoxidation of alkylbenzenes
  作者：E. Baciocchi、T. Del Giacco、C. Rol、G.V. Sebastiani

  DOI：10.1016/s0040-4039(00)98296-0

  日期：1985.1

  The autoxidation of alkylbenzenes can be promoted photochemically in the presence of catalytic amounts of cerim (IV) ammonium nitrate (CAN) under very mild conditions, the efficiency of the process being significantly increased by added acids. It is suggested that the reaction is promoted by NO3, radicals formed in the light induced decomposition of CAN and that Ce(III) may be reoxidized to Ce(IV)

  在非常温和的条件下，在催化量的铈（IV）硝酸铵（CAN）的存在下，可以光化学方式促进烷基苯的自氧化。通过添加酸，可以显着提高该方法的效率。提示该反应由NO 3促进，在光诱导的CAN分解中形成自由基，并且Ce（III）可能被苄基过氧自由基再氧化为Ce（IV）。
• Separation of primary and tertiary cymene hydroperoxides
  申请人：HERCULES POWDER CO LTD

  公开号：US02779797A1

  公开（公告）日：1957-01-29

  A process of separating primary and tertiary cymene hydroperoxides from a mixture thereof comprises contacting the mixture with an aqueous alkali metal solution of concentration in the range of 0.1 to 20 per cent w./v. to form an alkaline solution containing primary and tertiary hydroperoxide in which solution the ratio of primary to tertiary is greater than in the mixture subjected to the process, fractionally extracting the alkaline solution with an organic solvent for the hydroperoxides boiling below about 70 DEG C. at 20 mm. Hg pressure, stable to alkali metal hydroxide solutions of the strength employed, having a solubility of less than 5 per cent in water at about 30 DEG C. and a dielectric constant greater than three to form a solution of tertiary cymene hydroperoxide in said organic solvent and volatilizing said organic solvent to recover the tertiary hydroperoxide. The alkaline solution of primary hydroperoxide may be extracted with a water-insoluble organic solvent as defined above to form a solution of primary hydroxide in said organic solvent and an alkaline solution substantially free from hydroperoxides which may be recycled to the step of contacting the initial mixture of hydroperoxides and the tertiary and primary hydroperoxides may be recovered from their solutions by volatilization of the organic solvents. The cymene hydroperoxides employed may be made from individual or mixed o-, m- and p-cymenes, especially m- and p-cymene hydroperoxides which are more readily produced by oxidation in the liquid phase at elevated temperatures with elementary oxygen and the oxidation mixture may be recycled to the oxidation stage after extraction with aqueous alkali metal hydroxide solution. The oxidation mixture may be concentrated by distillation before extraction. The alkali metal hydroxides mentioned are sodium and potassium hydroxides. Solvents mentioned include chlorinates, hydrocarbons such as methylene chloride, chloroform and ethylene chloride, ethers such as diethyl, diisopropyl and ethyl isopropyl ethers, ketones such as methyl propyl, methyl isopropyl and methyl isobutyl ketones and cyclohexanone, and alcohols such as butanols and pentanols. The process may be carried out with countercurrent extraction equipment, the mixture of hydroperoxides being to the centre, alkali metal hydroxide solution to the top and organic solvent to the bottom. At the top a mixture of tertiary hydroperoxide and neutral components such as cymene and methyl acetophenone may be removed in the organic solvent and at the bottom an alkali metal solution of primary cymene hydroperoxide. The tertiary cymene hydroperoxide may be further extracted with alkali metal hydroxide to separate neutral products in a second extractor and may be again extracted with an organic solvent of the kind defined above. In examples: p-cymene is oxidized with air at elevated temperature in the presence of aqueous sodium carbonate and the mixture of products is contacted with aqueous sodium hydroxide in counter-current. The extracted mixture is recycled to the oxidation process and the aqueous alkali extract is extracted in countercurrent with isopropyl ether. On evaporation of the isopropyl ether extract tertiary p-cymenehydroperoxide is obtained. The aqueous alkali extract is then contacted with methyl isobutyl ketone in countercurrent and p-cymene hydroperoxide is obtained on evaporation of the methyl isobutyl ketone extract. The organic solvents are extracted with aqueous alkali solution and employed in further extraction (1); a mixture of p-cymene oxidation products similar to that employed in Example (1) is distilled under reduced pressure to remove p-cymene and the hydroperoxide concentrate fed to the centre stage of an extraction column and treated with countercurrent streams of aqueous sodium hydroxide and isopropyl ether. Tertiary p-cymene hydroperoxide is obtained on evaporation of the isopropyl ether solution and p-cymene hydroperoxide is obtained by evaporating a methyl isobutyl ketone solution obtained by countercurrent extraction of the alkali extract with methyl isobutyl ketone (2). Similar results are obtained when m-cymene is employed in a process similar to (1).

  将一种从混合物中分离主要和三级环甲基苯过氧化物的过程包括将混合物与浓度在0.1至20％w./v.范围内的水溶性碱金属溶液接触，以形成含有主要和三级过氧化物的碱性溶液，在该溶液中，主要过氧化物与三级过氧化物的比例大于经过该过程的混合物中的比例，用于沸点约为70摄氏度，20毫米汞柱压力下稳定于所使用的碱金属氢氧化物溶液，其在约30摄氏度时在水中的溶解度小于5％且介电常数大于3的有机溶剂分级萃取碱性溶液，以形成含有三级环甲基苯过氧化物的有机溶剂溶液，并挥发有机溶剂以回收三级过氧化物。主要过氧化物的碱性溶液可用上述定义的不溶于水的有机溶剂提取，以形成含有主要氢氧化物的有机溶剂溶液和几乎不含过氧化物的碱性溶液，后者可循环使用于接触最初的过氧化物混合物的步骤，并且可以通过挥发有机溶剂从其溶液中回收三级和主要过氧化物。使用的环甲基苯过氧化物可以由独立或混合的o-、m-和p-环甲基苯制备，特别是通过在液相中在高温下与元氧气氧化而更容易产生的m-和p-环甲基苯过氧化物，氧化混合物可以在提取后与水溶性碱金属氢氧化物溶液循环使用之后再循环使用于氧化阶段。氧化混合物可以在提取之前通过蒸馏浓缩。提到的碱金属氢氧化物是钠和钾氢氧化物。提到的溶剂包括氯化物，碳氢化合物如二氯甲烷，氯仿和氯乙烷，醚类如乙基，二异丙基和乙基异丙基醚，酮类如甲基丙基，甲基异丙基和甲基异丁基酮和环己酮，以及醇类如丁醇和戊醇。该过程可以使用逆流萃取设备进行，过氧化物混合物位于中间，碱金属氢氧化物溶液位于顶部，有机溶剂位于底部。在顶部，可以用有机溶剂去除三级过氧化物和诸如环甲基苯和甲基苯乙酮等中性组分的混合物，在底部是含有主要环甲基苯过氧化物的碱金属溶液。三级环甲基苯过氧化物可以进一步与碱金属氢氧化物提取以分离中性产物在第二萃取器中，然后再用上述类型的有机溶剂再次提取。在示例中：p-环甲基苯在高温下与空气氧化，在水碳酸钠存在下，产物混合物与水氢氧化钠逆流接触。提取的混合物循环使用于氧化过程，水碱提取物与异丙基醚逆流提取。蒸发异丙基醚提取物得到三级p-环甲基苯过氧化物。然后，水碱提取物与甲基异丁基酮逆流接触，蒸发甲基异丁基酮提取物得到p-环甲基苯过氧化物。有机溶剂用水碱溶液提取并用于进一步提取（1）；与示例（1）中使用的类似的p-环甲基苯氧化产物混合物在减压下蒸馏以去除p-环甲基苯，将过氧化物浓缩物送入萃取柱的中间阶段，并与水碱和异丙基醚的逆流流进行处理。蒸发异丙基醚溶液得到三级p-环甲基苯过氧化物，通过蒸发甲基异丁基酮提取物得到p-环甲基苯过氧化物，该提取物是通过与甲基异丁基酮逆流提取碱提取物而得到的。当使用m-环甲基苯进行类似于（1）的过程时，可以获得类似的结果。