2,3-dimethyl-2,3-di-p-tolyl-butane | 734-17-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,3-dimethyl-2,3-di-p-tolyl-butane
• 英文别名: 8,8'-bi-p-cymene；2,3-Dimethyl-2,3-di-p-tolyl-butan；Benzene, 1,1'-(1,1,2,2-tetramethyl-1,2-ethanediyl)bis[4-methyl-；1-[2,3-dimethyl-3-(4-methylphenyl)butan-2-yl]-4-methylbenzene
• CAS: 734-17-8
• 化学式: C₂₀H₂₆
• 分子量: 266.426
• InChiKey: DTVHTGANUBTKPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2,3-dimethyl-2,3-di-p-tolyl-butane 在 二氧化氮 作用下， 反应 2.0h， 以85%的产率得到1-甲基-4-(1-甲基乙烯基)苯
  参考文献：
  名称：

  Thermal and Photochemical Nitration of Aromatic Hydrocarbons with Nitrogen Dioxide

  摘要：

  Aromatic hydrocarbons (ArH) are readily nitrated by nitrogen dioxide (NO2) in dichloromethane at room temperature and below (in the dark). The red colors, transiently observed, arise from the metastable precursor complex [ArH, NO+]NO3-, which is formed in the prior disproportionation of nitrogen dioxide induced by the aromatic donor (eq 7). The deliberate irradiation of the diagnostic (red) charge-transfer absorption band (h nu(CT)) of [ArH, NO+] NO3- at low temperatures results directly in aromatic nitration, even at -78 degrees C, where the thermal nitration is too slow to compete. The mechanism of the photochemical (charge-transfer) nitration is established by time-resolved laser spectroscopy to proceed via the aromatic cation radical (ArH.+) formed spontaneously upon the charge-transfer excitation of [ArH, NO+]NO3- in Scheme 1. The related thermal activation of [ArH, NO+]NO3- derives from the adiabatic electron transfer that produces the same radical pair [ArH.+ NO.] as the reactive intermediate in Scheme 3. The close relationship between the thermal/photochemical nitrations with nitrogen dioxide and those conventionally carried out with nitric acid (in the presence of nitrous acid) is delineated by Scheme 4.

  DOI：

  10.1021/jo00091a018
• 作为产物：
  描述：

  2-methyl-2-(4-methylphenyl)propionaldehyde 以 正戊烷 为溶剂， 生成 2,3-dimethyl-2,3-di-p-tolyl-butane
  参考文献：
  名称：

  光化学反应。第63篇[1]。α-芳基醛的光脱羰

  摘要：

  醛的紫外线照射6 - 11在排他地在脱羰基的主要产品脱气的解决方案的结果34，35和37 - 40，以及少量的2,3-二苯基2,3二甲基丁烷36从苯基醛6和7。在三-的存在Ñ -butylstannane，锡烷氢竞速赛的掺入，对具体底物的限制，并在分子内氘转移7 35和11 40。对于苯醛6和苯甲醛，脱羰基的量子产率为Φ〜0.4-1.0。9，和0.02 8.哈米特Φ与共振常数（相关性[R ）为6（X = H，p -CH 3，OCH 3）和（CF 3）中，用ω米+为值元取代的异构体是与拟议的将α-裂解为仅具有中等自由基特征的相关自由基对作为主要的光化学步骤相一致。

  DOI：

  10.1002/hlca.19710540312

文献信息

• Dicyanobenzene sensitized carbon-carbon bond cleavage in methoxybicumenes. Products and mechanistic studies
  作者：Przemyslaw Maslak、William H. Chapman

  DOI：10.1016/s0040-4020(01)88366-6

  日期：1990.1

  Radical cations of p-methoxy-p-X-bicumenes generated by ET to excited-state dicyanobenzene undergo rapid irreversible C-C bond scission giving cumyl cations and radicals. The photoefficiency of the process (Φ = 0.13 for X = MeO, Φ< 0.005 for X = CN) and the fate of the radicals produced depends strongly on substitution.

  由ET生成的对甲氧基-pX-双碳二烯的自由基阳离子到激发态的二氰基苯经历快速不可逆的CC键断裂，产生枯基阳离子和自由基。该过程的光效率（对于X = MeO，Φ= 0.13；对于对于X = CN，Φ<0.005）和产生的自由基的命运在很大程度上取决于取代。
• Electron-transfer processes
  作者：Claudio Giordano、Aldo Belli、Attilio Citterio、Francesco Minisci

  DOI：10.1016/0040-4020(80)88052-5

  日期：1980.1

  A new synthesis of γ-lactones by peroxydisulfate oxidation of isopropylbenzenes is described. Evidence concerning the free-radical mechanism is reported; the intermediate formation of alkyl and benzyl radicals is evidenced by trapping them with quinoxaline. The role of the iron catalyst is discussed.

  描述了一种通过异丙基苯的过氧二硫酸盐氧化合成γ-内酯的新方法。报告了有关自由基机制的证据；烷基和苄基的中间形成可以通过用喹喔啉捕获来证明。讨论了铁催化剂的作用。
• Extent of charge transfer in the photoreduction of phenyl ketones by alkylbenzenes
  作者：Peter J. Wagner、Royal J. Truman、Alan E. Puchalski、Ronald. Wake

  DOI：10.1021/ja00284a041

  日期：1986.11

  Rate constants for triplet-state reaction of various ring-substituted benzophenones (BPs), acetophenones (APs), and ..cap alpha..,..cap alpha..,..cap alpha..-trifluoroacetophenones (TFAs) with toluene and p-xylene have been determined by a combination of flash kinetics, steady-state quenching, and quantum yield measurements. The relative amounts of primary and tertiary radicals formed by reaction of

  各种环取代二苯甲酮 (BPs)、苯乙酮 (APs) 和 ..cap alpha..,..cap alpha..,..cap alpha..-三氟苯乙酮 (TFA) 与甲苯的三重态反应的速率常数和对二甲苯是通过闪光动力学、稳态猝灭和量子产率测量的组合来确定的。还测量了由相同酮与对伞花烃反应形成的伯基和叔基的相对量。对于所有三种类型的酮，速率常数与三线态酮还原电位密切相关。用甲苯-d/sub 8/ 和对二甲苯-d/sub 10/ 观察到的动力学同位素效应的大小随着酮变得更容易还原而减小。所有酮三联体主要通过电荷转移机制与烷基苯反应，随着酮变得更难还原，速率决定步骤从络合变为氢转移。反应性最低的 AP 三联体也可能通过简单的氢原子提取产生显着的反应。那些具有 n,..pi..* 最低三联体的酮（所有 BPs 和一些 APs）与对伞花烃反应，得到与叔丁氧基显示的 0.40 值相差不超过 2 倍的伯/叔自由基比率自由基；那些具有
• Hydrogen abstraction from the isomeric cymenes
  作者：A. Sulpizio、M. Mella、A. Albini

  DOI：10.1016/s0040-4020(01)89216-4

  日期：1989.1

  obtained from the ortho isomer), with minimal ring nitration. The formation of bibenzyls on irradiation with t-butyl peroxide of the same substrates is also studied. The mechanisms of the reactions with the NO•3 radical, a good electron acceptor, and with the alkoxy radical are contrasted and compared with photochemical hydrogen abstraction by nπ* and, respectively, ππ* excited states.

  在邻，间和对伞花烃存在下辐照硝酸铈（IV）铵会产生攻击甲基的产物（硝酸盐-这些硝酸盐的分离产率为55-69％-硝基衍生物和醛）以及在异丙基上（苯乙酮，不是从邻位异构体获得的），且环硝化作用极小。还研究了在相同的底物上用叔丁基过氧化物辐照形成联苄。对比了与NO • 3自由基（一种良好的电子受体）和与烷氧基的反应机理，并分别通过nπ*和ππ*激发态与光化学氢提取进行了比较。
• Effects of oral and transdermal 17β-estradiol with cyclical oral norethindrone acetate on insulin sensitivity, secretion, and elimination in postmenopausal women
  作者：Christopher P. Spencer、Ian F. Godsland、Alison J. Cooper、David Ross、Malcolm I. Whitehead、John C. Stevenson

  DOI：10.1053/meta.2000.6238

  日期：2000.6

  Few studies have examined the effects of 17 beta-estradiol on parameters of insulin and glucose metabolism. We studied 42 healthy, untreated postmenopausal women seeking relief from menopausal symptoms. They were randomized to receive either oral 17 beta-estradiol 2 mg daily combined with sequential oral norethindrone acetate (NETA) 1 mg daily from days 12 to 22, or transdermal 17 beta-estradiol 0.05 mg daily combined with sequential oral NETA 1 mg daily from days 17 to 28. Intravenous glucose tolerance tests (IVGTTs) were performed at baseline and after 48 weeks (estrogen-alone phase) and 48 weeks (combined phase) of completed therapy. Mathematical modeling analysis of plasma glucose, insulin, and C-peptide concentration profiles provided measures of insulin resistance, secretion, and elimination. Both types of therapy were associated with a decrease in fasting insulin and glucose levels. Insulin sensitivity was increased by oral estradiol during the estrogen-alone phase but was reversed by the addition of NETA. Transdermal estradiol did not affect insulin sensitivity. Hepatic insulin uptake and insulin secretion were increased with both types of treatment. The oral regimen of estradiol therapy was favorable to both insulin elimination and sensitivity. Transdermal estradiol therapy had relatively few effects on insulin metabolism. Copyright (C) 2000 by W.B. Saunders Company.