1-(4-tolyl)-1-azacyclotetradecane-2,14-dione | 307493-18-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: 1-(4-tolyl)-1-azacyclotetradecane-2,14-dione
• 英文别名: 1-(4-Methylphenyl)-azacyclotetradecane-2,14-dione
• CAS: 307493-18-1
• 化学式: C₂₀H₂₉NO₂
• 分子量: 315.456
• InChiKey: JYXLPHCSNGSXTI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(4-tolyl)-1-azacyclotetradecane-2,14-dione 以 乙腈 为溶剂， 反应 16.5h， 以74%的产率得到18-methyl-2-azabicyclo[14.4.0]icosa-1(16),17,19-triene-3,15-dione
  参考文献：
  名称：

  大环N-苯基酰亚胺光化学扩环成环芳烃

  摘要：

  Allylic N-phenyl imides containing 12- and 14-membered rings, such as compounds 3 and 12, are easily synthesized by ring enlargement from cycloalkanones and phenyl isocyanates. Irradiation of 3 and 12 in EtOH and MeCN, with high- and low-pressure Hg lamps,led, via the photo-Fries rearrangement, to the same primary products: the orthocyclophane 8 and the paracyclophane 9 from 3 (Scheme 2), and the corresponding compounds 13 and 14 from 12 (Scheme 3). Besides the primary photorearrangement products, secondary products, the aminocyclophanes 10 and 11, or 15 and 16, respectively, were also formed. The total yields of the four products were very high when the N-phenyl imides were irradiated in MeCN with a low-pressure Hg lamp: 97 and 93%, respectively If the pam-position in 3 or 12 is blocked by a Me group, the para-photo-Fries rearrangement is prevented. In this case, only one primary photoproduct is formed: the corresponding orthocyclophane (17 or 23, resp.). The most remarkable result was observed on irradiation of the 12-membered N-(4-tolyl) imide 5 in MeCN (low-pressure lamp). It reacted nearly quantitatively to give only two products: 15-methyl-1-aza[12]orthocyclophane-2,12-dione (=16-methyl-2-azabicyclo[12.4.0]octadeca-1(14),15,17-triene-3,13-dione; 17) in 80% yield and 17-amino-14-methyl [11]metacyclophane-1, 11-dione (= 17-amino-15-methylbicyclo[11.3.1]heptadeca-1(17),13,15-triene-2,12-dione; 19) in 16% yield (Scheme 5).

  DOI：

  10.1002/1522-2675(20000809)83:8<1809::aid-hlca1809>3.0.co;2-l
• 作为产物：
  描述：

  2-Oxocyclododecan-1-carbonsaeure-allylester 在 四(三苯基膦)钯 、 甲酸 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 1-(4-tolyl)-1-azacyclotetradecane-2,14-dione
  参考文献：
  名称：

  大环N-苯基酰亚胺光化学扩环成环芳烃

  摘要：

  Allylic N-phenyl imides containing 12- and 14-membered rings, such as compounds 3 and 12, are easily synthesized by ring enlargement from cycloalkanones and phenyl isocyanates. Irradiation of 3 and 12 in EtOH and MeCN, with high- and low-pressure Hg lamps,led, via the photo-Fries rearrangement, to the same primary products: the orthocyclophane 8 and the paracyclophane 9 from 3 (Scheme 2), and the corresponding compounds 13 and 14 from 12 (Scheme 3). Besides the primary photorearrangement products, secondary products, the aminocyclophanes 10 and 11, or 15 and 16, respectively, were also formed. The total yields of the four products were very high when the N-phenyl imides were irradiated in MeCN with a low-pressure Hg lamp: 97 and 93%, respectively If the pam-position in 3 or 12 is blocked by a Me group, the para-photo-Fries rearrangement is prevented. In this case, only one primary photoproduct is formed: the corresponding orthocyclophane (17 or 23, resp.). The most remarkable result was observed on irradiation of the 12-membered N-(4-tolyl) imide 5 in MeCN (low-pressure lamp). It reacted nearly quantitatively to give only two products: 15-methyl-1-aza[12]orthocyclophane-2,12-dione (=16-methyl-2-azabicyclo[12.4.0]octadeca-1(14),15,17-triene-3,13-dione; 17) in 80% yield and 17-amino-14-methyl [11]metacyclophane-1, 11-dione (= 17-amino-15-methylbicyclo[11.3.1]heptadeca-1(17),13,15-triene-2,12-dione; 19) in 16% yield (Scheme 5).

  DOI：

  10.1002/1522-2675(20000809)83:8<1809::aid-hlca1809>3.0.co;2-l

文献信息

• Photochemical Ring Enlargement of MacrocyclicN-Phenyl Imides into Cyclophanes
  作者：Jörg A. Heerklotz、Changchun Fu、Anthony Linden、Manfred Hesse

  DOI：10.1002/1522-2675(20000809)83:8<1809::aid-hlca1809>3.0.co;2-l

  日期：2000.8.9

  Allylic N-phenyl imides containing 12- and 14-membered rings, such as compounds 3 and 12, are easily synthesized by ring enlargement from cycloalkanones and phenyl isocyanates. Irradiation of 3 and 12 in EtOH and MeCN, with high- and low-pressure Hg lamps,led, via the photo-Fries rearrangement, to the same primary products: the orthocyclophane 8 and the paracyclophane 9 from 3 (Scheme 2), and the corresponding compounds 13 and 14 from 12 (Scheme 3). Besides the primary photorearrangement products, secondary products, the aminocyclophanes 10 and 11, or 15 and 16, respectively, were also formed. The total yields of the four products were very high when the N-phenyl imides were irradiated in MeCN with a low-pressure Hg lamp: 97 and 93%, respectively If the pam-position in 3 or 12 is blocked by a Me group, the para-photo-Fries rearrangement is prevented. In this case, only one primary photoproduct is formed: the corresponding orthocyclophane (17 or 23, resp.). The most remarkable result was observed on irradiation of the 12-membered N-(4-tolyl) imide 5 in MeCN (low-pressure lamp). It reacted nearly quantitatively to give only two products: 15-methyl-1-aza[12]orthocyclophane-2,12-dione (=16-methyl-2-azabicyclo[12.4.0]octadeca-1(14),15,17-triene-3,13-dione; 17) in 80% yield and 17-amino-14-methyl [11]metacyclophane-1, 11-dione (= 17-amino-15-methylbicyclo[11.3.1]heptadeca-1(17),13,15-triene-2,12-dione; 19) in 16% yield (Scheme 5).