4-(2,6-di-tert-butyl-4-methylphenoxy)-2,6-di-tert-butyl-4-methyl-2,5-cyclohexadien-1-one | 2179-51-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4-(2,6-di-tert-butyl-4-methylphenoxy)-2,6-di-tert-butyl-4-methyl-2,5-cyclohexadien-1-one
• 英文别名: 2,6-di-tert-butyl-4-(2,6-di-tert-butyl-4-methylphenoxy)-4-methyl-2-5-cyclohexadienone；4-Phenoxy-2,5-cyclohexadien-1-one；4-(2,6-Di-tert-butyl-4-methyl-phenoxy)-2,6-di-tert-butyl-4-methyl-cyclohexa-2,5-dien-1-on；2,6-Ditert-butyl-4-(2,6-ditert-butyl-4-methylphenoxy)-4-methylcyclohexa-2,5-dien-1-one
• CAS: 2179-51-3
• 化学式: C₃₀H₄₆O₂
• 分子量: 438.694
• InChiKey: ZBPMNALBJHSLMT-UHFFFAOYSA-N

物化性质

• 熔点：
  85-90 °C
• 沸点：
  506.7±50.0 °C(Predicted)
• 密度：
  0.962±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.6
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(2,6-di-tert-butyl-4-methylphenoxy)-2,6-di-tert-butyl-4-methyl-2,5-cyclohexadien-1-one 在 三乙胺 作用下， 以 正己烷 、 乙腈 为溶剂， 生成 四叔丁基联苯酚
  参考文献：
  名称：

  The reaction of the 2,6-di-tert-butyl-4-methylphenoxy radical with phenols

  摘要：

  Dimer 3 dissociates in solution to give the phenoxy radical 4. When solid 3 is dissolved in a solution of phenol 11a, radical 4 dehydrogenates the phenol to afford phenol 5 and phenoxy radical 12. Radical 12 couples with more 4 to afford principally bis(cyclohexadienone) 16a and a minor amount of the dimeric bis(cyclohexadienone) 13. The preferential formation of 16a over 13 is explained as the result of a solvent-cage reaction. Compounds 13 and 16a are isomerized in the presence of silica gel or triethylamine to 4,4'-dihydroxybiphenyl 14 and phenolic dienone 17a, respectively. Compound 13 is relatively stable in hexane at 30-degrees-C, while 16a slowly dissociates under these conditions to afford parent radicals 4 and 12. If 11a is present, radical 4 either recombines with 12 or dehydrogenates the phenol. Two radicals of 12 generated by the dissociation of 16a and the subsequent dehydrogenation of 11a couple to give 13. Therefore, dissolving 3 in hexane containing excess 11a and keeping the resulting solution at 30-degrees-C results in the preferential formation of 13. Dissolving 3 in triethylamine containing phenols 11 or 21 similarly affords dienones 17 or 23. The yields of these dienones increase with increasing electron-donating capability of the substituent on the phenol ring.

  DOI：

  10.1021/jo00003a006
• 作为产物：
  描述：

  2,6-二叔丁基-4-甲基苯酚 在 氢氧化钾 、 碘 作用下， 以 甲醇 为溶剂， 以93%的产率得到4-(2,6-di-tert-butyl-4-methylphenoxy)-2,6-di-tert-butyl-4-methyl-2,5-cyclohexadien-1-one
  参考文献：
  名称：

  Oxidation of phenols with iodine in alkaline methanol

  摘要：

  DOI：

  10.1021/jo00191a002

文献信息

• Biotransformation of butylated hydroxytoluene (BHT) to BHT-quinone methide in rats.
  作者：KAZUO TAJIMA、KENJI YAMAMOTO、TAMIO MIZUTANI

  DOI：10.1248/cpb.29.3738

  日期：——

  2, 6-Di-tert-butyl-4-methylene-2, 5-cyclohexadien-1-one (BHT-quinone methide, BHT-QM) was detected in the bile of rats given butylated hydroxytoluene (BHT). The biliary excretion of BHT-QM during 24 h after administration of BHT, 3, 5-di-tert-butyl-4-hydroxybenzyl alcohol (BHT-alcohol), or 2, 6-di-tert-butyl-4-hydroxy-4-methyl-2, 5-cyclohexadien-1-one (4-hydroxy-BHT) was determined by high-performance liquid chromatography. BHT-alcohol gave about 7 times as much BHT-QM as did BHT, but no BHT-QM was detected after administration of 4-hydroxy-BHT. This result suggests that the transformation of BHT to BHT-QM proceeds mainly through BHT-alcohol. Although 1, 2-bis (3, 5-di-tert-butyl-4-hydroxyphenyl) ethane (BHT-dimer) has been reported as a biliary metabolite of BHT in rats, most of the BHT-dimer seems to be formed artificially by dimerization of BHT-QM during the isolation process.

  2,6-二叔丁基-4-亚甲基-2,5-环己二烯-1-酮(BHT-醌甲基化物，BHT-QM)在大鼠给予丁基羟基甲苯(BHT)后的胆汁中被检测到。通过高效液相色谱法测定了在给予BHT、3,5-二叔丁基-4-羟基苄醇(BHT-醇)或2,6-二叔丁基-4-羟基-4-甲基-2,5-环己二烯-1-酮(4-羟基-BHT)后24小时内BHT-QM的胆汁排泄。BHT-醇产生的BHT-QM大约是BHT的7倍，但在给予4-羟基-BHT后未检测到BHT-QM。这一结果表明，BHT向BHT-QM的转化主要通过BHT-醇进行。尽管有报道称1,2-双(3,5-二叔丁基-4-羟基苯基)乙烷(BHT-二聚体)是大鼠胆汁中BHT的代谢物，但大部分BHT-二聚体似乎是在分离过程中通过BHT-QM的二聚化人为形成的。
• Kinetic electron spin resonance spectroscopy of complex reaction systems
  作者：Daniel Rüegge、Hanns Fischer

  DOI：10.1039/f19888403187

  日期：——

  Kinetic electron spin resonance spectroscopy with intermittent radical generation has been used to obtain the rate constants of various simultaneous reactions in systems containing 2,6-di-t-butylphenoxyl or 2,6-di-t-butyl-4-methylphenoxyl radicals, the latter terminating reversibly. The radicals were generated in various solvents by photolysis of di-t-butyl peroxide in presence of the parent phenols

  具有间歇性基团生成的动力学电子自旋共振光谱已用于获得包含2,6-二叔丁基苯氧基或2,6-二叔丁基-4-甲基苯氧基的体系中各种同时反应的速率常数。后者可逆地终止。在母体酚的存在下，通过过氧化二叔丁基过氧化物在各种溶剂中生成自由基。提出了一种反应系统的数据分析程序，该系统还涉及不能通过esr检测到的物种。结果表明，苯氧基自由基的自终止速率常数比扩散控制的预期值低两个数量级。这通常归因于叔丁基的庞大位阻，但大多数溶剂的活化能与这种解释相矛盾。
• Identification and determination of glutathione and glucuronide conjugates formed from butylated hydroxytoluene in rats.
  作者：KAZUO TAJIMA、KENJI YAMAMOTO、TAMIO MIZUTANI

  DOI：10.1248/cpb.31.3671

  日期：——

  Rats which had received butylated hydroxytoluene (BHT) excreted S- (3, 5-di-tert-butyl-4-hydroxybenzyl) glutathione (BHT-glutathione) and 3, 5-di-tert-butylhydroquinone (BHQ) glucuronide in the bile. After being separated by high-performance liquid chromatography, the glutathione conjugate was identified by 13C-nuclear magnetic resonance and field desorption mass spectrometry ; the glucuronide was identified by gas chromatography-mass spectrometry. The structures of BHT-glutathione and BHQ glucuronide were further confirmed by comparison with synthetic samples. The excretion rates of BHT-glutathione and BHQ glucuronide in rat bile were 3.5 and 1.6%, respectively, of the dose in 24h after intraperitoneal administration of BHT at a dose of 400 mg/kg. The occurrence of BHT-glutathione suggests that 2, 6-di-tert-butyl-4-methylene-2, 5-cyclohexadienone, a toxic metabolite of BHT, is detoxified by glutathione conjugation.

  摄入丁基羟基甲苯（BHT）的大鼠在胆汁中排出 S-（3，5-二叔丁基-4-羟基苄基）谷胱甘肽（BHT-谷胱甘肽）和 3，5-二叔丁基对苯二酚（BHQ）葡萄糖醛酸。经高效液相色谱分离后，谷胱甘肽共轭物通过 13C 核磁共振和场解吸附质谱法进行鉴定；葡萄糖醛酸通过气相色谱-质谱法进行鉴定。通过与合成样品进行比较，进一步确认了 BHT-谷胱甘肽和 BHQ 葡萄糖醛酸苷的结构。大鼠腹腔注射 400 毫克/千克剂量的 BHT 后，24 小时内 BHT-谷胱甘肽和 BHQ 葡萄糖醛酸苷在胆汁中的排泄率分别为剂量的 3.5% 和 1.6%。出现 BHT-谷胱甘肽表明，BHT 的毒性代谢物 2，6-二叔丁基-4-亚甲基-2，5-环己二烯酮可通过谷胱甘肽共轭作用解毒。
• OMURA, KENJI, J. ORG. CHEM., 56,(1991) N, C. 921-926
  作者：OMURA, KENJI

  DOI：——

  日期：——
• OMURA, KANJI, J. ORG. CHEM., 1984, 49, N 17, 3046-3050
  作者：OMURA, KANJI

  DOI：——

  日期：——