1-(甲氧基甲基)芘 | 91385-15-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 中文名称: 1-(甲氧基甲基)芘
• 英文名称: methyl 1-pyrenylmethyl ether
• 英文别名: methyl 1-prenylmethyl ether；1-methoxy-1-pyrenylmethane；1-(methoxymethyl)pyrene；1-methoxymethylpyrene
• CAS: 91385-15-8
• 化学式: C₁₈H₁₄O
• 分子量: 246.309
• InChiKey: OJCHPCJKMZJQFZ-UHFFFAOYSA-N

物化性质

• 熔点：
  49-50 °C(Solv: methanol (67-56-1))
• 沸点：
  406.1±14.0 °C(Predicted)
• 密度：
  1.224±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(甲氧基甲基)芘 在 四甲基乙二胺 、 叔丁基锂 作用下， 以 苯 为溶剂， -70.0~525.0 ℃ 、9.33 Pa 条件下， 生成 3H-cyclobutapyrene:2,4,7-trinitrofluoren-9-one complex
  参考文献：
  名称：

  Synthesis of peri-Cyclobutarenes by Thermolysis of [Methoxy(trimethylsilyl)methyl]arenes

  摘要：

  [Methoxy(trimethylsilyl)methyl]arenes are readily prepared by reactions of chlorotrimethylsilane with (alpha-methoxy)arenylmethyllithium reagents as obtained from (methoxymethyl)arenes and t-BuLi. The [methoxy(trimethylsilyl)methyl] arenes eliminate methoxytrimethylsilane at 525-675 degrees C/0.05-0.10 mm to yield peri-cyclobutarenes as derived from arenylcarbenes. Of importance is the fact that the initial arenylcarbenes generated insert into adjacent peri C-H bonds and/or isomerize to other arenylcarbenes that insert into their peri C-H bonds to give peri-cyclobutarenes. Thus, flash-vacuum pyrolysis of 1-[methoxy(trimethylsilyl)methyl]naphthalene (13) at 575-675 degrees C/0.05-0.10 mm yields 1H-cyclobuta[de]naphthalene (6, up to 39%) in practical quantities. 2-[Methoxy(trimethylsilyl)methyl]naphthalene (23) also affords 6 as a major thermolysis product. At 510 degrees C/ 0.05-0.10 mm 4-methoxy-1-[methoxy(trimethylsilyl)methyl]naphthalene (29) decomposes to 4-methoxy-1H-cyclobuta[de]naphthalene (31, 46%). Under similar conditions, 2-methoxy-1-[methoxy(trimethylsilyl)methyl]naphthalene (33) converts to 1,2-dihyrdronaphtho[2,1-b]furan (35, 64%) and naphtho[2,1-b]furan (36, 31%), presumably by insertion of 2-methoxy-1-naphthylcarbene (34) into a C-H bond of its o-methoxy group and then dehydrogenation of the resultant dihydrofuran. Further, 1-[methoxy(trimethylsilyl)methyl]-6-methylnaphthalene (39) pyrolyzes (510 degrees C/0.10-0.20 mm) to 6-methyl-1-naphthylcarbene (40), which isomerizes in part to 7-methyl-1-naphthylcarbene (49); carbenes 40 and 49 then undergo peri C-H insertion to give 3-methyl-1H-cyclobuta[de]naphthalene (41) and 2-methyl-1H-cyclobuta[de]naphthalene (42) in an 8:1 ratio and a combined yield of 44%. The pyrolytic method is particularly valuable for preparing higher peri single carbon atom bridged arenes such as 4H-cyclobuta[jk]phenanthrene (53, 65%) and 3H-cyclobuta[cd]pyrene (59, 86%).

  DOI：

  10.1021/jo981104j
• 作为产物：
  描述：

  1-(溴甲基)芘 在 sodium hypochlorite 、 sodium tetrahydroborate 作用下， 以 甲醇 、 水 为溶剂， 反应 20.0h， 生成 1-(甲氧基甲基)芘
  参考文献：
  名称：

  Selenium Blue-α and -β: turning on the fluorescence of a pyrenyl fluorophore via oxidative cleavage of the Se–C bond by reactive oxygen species

  摘要：

  Rapid oxidation of nonfluorescent pyrenyl-CH2SeAr (Ar = o-nitrophenyl) by hypochlorite yielded pyrenyl-CH2Cl and pyrenyl-CH2OH and turns on blue fluorescence, while slow oxidation of pyrenyl-CH2SeAr with excess H2O2 leads to pyrenyl-CHO which emits a bluish-green fluorescence. The homolog, pyrenyl-CH2CH2SeAr' (Ar' = o-nitrophenyl) reacts slower with H2O2 and CIO- giving the same product, vinyl pyrene. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.05.022

文献信息

• Intramolecular fluorescence quenching and exciplex formation in ?-(1-pyrenyl)alkyl para-substituted benzoates
  作者：Jun Kawakami、Michiko Iwamura

  DOI：10.1002/poc.610070107

  日期：1994.1

  40% of the fluorescence is quenched in acetonitrile. PnCl, with slightly negative ΔGET, shows more efficient quenching, but does not show exciplex emission. PnCN, PnCF3 and PnNO2 have ΔGET values between −0·36 and −0·65 eV, and their fluorescence is fairly efficiently quenched. The fluorescence of PnCN is concluded to be strongly quenched by intersystem crossing from the singlet exciplex to the locally

  吸收和发射光谱，荧光量子产率（Φ的测量˚F）和寿命（τ ˚F ω-（1-芘基）的烷基）对位取代的苯甲酸酯P Ñ X（X = H，氯，CF 3，CN，NO 2，n = 1-4）在各种极性的溶剂中进行。在任何这些化合物中均未观察到基态的分子内相互作用。P n CN（n= 2-4）显示在低极性到高极性溶剂中的分子内激基复合物发射。在P1CN的乙酸乙酯溶液中观察到的较长波长处的宽广，无结构的发射归因于“复杂类型”发射，该发射不需要两个生色团的实际重叠。P2CF 3还显示出在中等至高极性溶剂中的激基复合物发射。溶剂既Φ的依赖性˚F和τ ˚F随着的吸电子能力对-sustituents增加。通过电子转移的自由能ΔG ET讨论了电子转移的荧光猝灭和P n X的对位取代基之间的关系。分别由of和对位取代的苯甲酸甲酯在乙腈中的氧化和还原电位获得。P Ñ H，具有正Δ ģ ET，不显示溶剂Φ的依赖性˚F，除了P
• Photoreactivity of 1-Pyrenylmethyl Esters. Dependence on the Structure of the Carboxylic Acid Moieties and the Nature of the Excited States
  作者：Michiko Iwamura、Kazuko Tokuda、Noboru Koga、Hiizu Iwamura

  DOI：10.1246/cl.1987.1729

  日期：1987.9.5

  While the photolysis of 1-pyrenylmethyl phenylacetates in methanol gave the original phenylacetic acids, irradiation of the 1-naphthoate and 9-anthracenecarboxylate leads to the formation of the intramolecular exciplexes that are inert to the photolysis. The Φf and τf values of these esters have been determined.

  虽然 1-芘基甲基苯乙酸酯在甲醇中的光解产生原始苯乙酸，但 1-萘甲酸酯和 9-蒽羧酸酯的辐照导致形成对光解呈惰性的分子内激基复合物。这些酯的 Φf 和 τf 值已经确定。
• New Photochemically Labile Protecting Group for Phosphates
  作者：Toshiaki Furuta、Hiromi Torigai、Tomoko Osawa、Michiko Iwamura

  DOI：10.1246/cl.1993.1179

  日期：1993.7

  New photochemically labile phosphate protecting group was developed. These phosphate esters have high molar extinction coefficient (e340 = 34500 dm3 mol−1 cm−1) and rapidly release parent phosphates upon irradiation ( >300 nm) with high quantum efficiency for disappearance (φdis = 0.22 at 340 nm).

  开发了新的光化学不稳定的磷酸盐保护基团。这些磷酸酯具有高摩尔消光系数 (e340 = 34500 dm3 mol−1 cm−1) 并在辐照后快速释放母体磷酸盐 (>300 nm)，具有高量子效率消失 (φdis = 0.22 at 340 nm)。
• Photoinduced heterolysis of the carbon-oxygen bond in bichromophoric 1-arylmethyloxy-2-pyridones
  作者：Tadamitsu Sakurai、Kanji Kubo、Shunsuke Kojima、Takuya Shoro、Hiroyasu Inoue

  DOI：10.1016/s0040-4039(98)02282-5

  日期：1998.12

  9-anthryl (1a) or a 1-pyrenyl group (1b) in methanol was found to give the heterolytic CO bond cleavage products: 1-hydroxy-2-pyridone and arylmethyl methyl ether, (which predominate for the reaction of 1a), along with 2-pyridone, aryl-substituted methanol and aryl aldehyde derived from the homolysis of the NO bond (that mainly occurs in the photolysis of 1b). Spectroscopic analysis of the ground-state

  发现在甲醇中辐照具有9-蒽基（1a）或1-pyrenyl基团（1b）的标题化合物可得到杂合的CO键裂解产物：1-羟基-2-吡啶酮和芳基甲基甲基醚，（它们主要用于1a）的反应，以及2-吡啶酮，芳基取代的甲醇和芳基醛，其衍生自N = O键均化（主要发生在1b的光解中）。的接地状态，并且激发的单线态行为的光谱分析1揭示了一个非发射分子内激发复合体（其形成速率为在要快得多1A比在图1b）在诱导的CO键heterolysis关键作用。
• 1-Pyrenylmethyl esters, photolabile protecting groups for carboxylic acids
  作者：Michiko Iwamura、Touru Ishikawa、Yukiyoshi Koyama、Keisuke Sakuma、Hiizu Iwamura

  DOI：10.1016/s0040-4039(00)95811-8

  日期：1987.1

  1-Diazomethylpyrenes were prepared and reacted with carboxylic acids to give 1-pyrenylmethyl esters. The fluorescent esters were photolysed at 340 nm in methanol to form the starting acids and the corresponding 1-methoxymethylpyrenes in high yield.

  制备1-重氮甲基吡啶并使其与羧酸反应，得到1-吡啶基甲基酯。荧光酯在340 nm的甲醇中被光解，以高产率形成起始酸和相应的1-甲氧基甲基吡啶。