9-(methoxymethyl)phenanthrene | 57741-37-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 9-(methoxymethyl)phenanthrene
• 英文别名: 9-Methoxymethylphenanthren
• CAS: 57741-37-4
• 化学式: C₁₆H₁₄O
• 分子量: 222.287
• InChiKey: XILYADAUCYRKMF-UHFFFAOYSA-N

物化性质

• 熔点：
  69-70 °C(Solv: methanol (67-56-1))
• 沸点：
  373.9±11.0 °C(Predicted)
• 密度：
  1.129±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 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：

  9-(methoxymethyl)phenanthrene 在 四甲基乙二胺 、 叔丁基锂 作用下， -70.0~590.0 ℃ 、13.33 Pa 条件下， 生成 4H-cyclobutaphenanthrene
  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：

  9-Brom-10-methoxymethylphenanthren 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 9-(methoxymethyl)phenanthrene
  参考文献：
  名称：

  Chuah,T.S. et al., Australian Journal of Chemistry, 1977, vol. 30, p. 1769 - 1774

  摘要：

  DOI：

文献信息

• Generation of Organic Cations from Group 14 Organometallic Compounds via Photoinduced Electron Transfer in the Presence of Cu(II) Salt
  作者：Kazuhiko Mizuno、Masahiro Yasueda、Yoshio Otsuji

  DOI：10.1246/cl.1988.229

  日期：1988.2.5

  Irradiations of acetonitrile-alcohol (3 : 1) solutions of arylmethyl silanes, germane, or stannanes in the presence of Cu(BF4)2 gave alkyl arylmethyl ethers in good yields via arylmethyl cations. The efficiency of this photoreaction increased in the order of Si- < Ge- < Sn-compounds.

  在Cu(BF4)2 存在下，芳甲基硅烷、锗烷或锡烷的乙腈-醇(3:1)溶液的辐照通过芳甲基阳离子以良好的产率得到烷基芳甲基醚。这种光反应的效率以 Si- < Ge- < Sn-化合物的顺序增加。
• Formation of a bicyclo[4.1.0]heptatriene by intramolecular addition of a carbene to a carbon-carbon triple bond
  作者：John P. Mykytka、W. M. Jones

  DOI：10.1021/ja00853a059

  日期：1975.10
• CHUAH T. S.; CRAIG J. T.; HALTON B.; HARRISON S. A. R.; OFFICER D. L., AUSTRAL. J. CHEM., 1977, 30, NO 8, 1769-1774
  作者：CHUAH T. S.、 CRAIG J. T.、 HALTON B.、 HARRISON S. A. R.、 OFFICER D. L.

  DOI：——

  日期：——
• MIZUNO, KAZUHIKO;YASUEDA, MASAHIRO;OTSUJI, YOSHIO, CHEM. LETT.,(1988) N 2, 229-232
  作者：MIZUNO, KAZUHIKO、YASUEDA, MASAHIRO、OTSUJI, YOSHIO

  DOI：——

  日期：——
• Synthesis of <i>peri</i>-Cyclobutarenes by Thermolysis of [Methoxy(trimethylsilyl)methyl]arenes
  作者：Thomas A. Engler、Harold Shechter

  DOI：10.1021/jo981104j

  日期：1999.6.1

  [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%).