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Acenaphthylene 反应生成 香豆素
参考文献:有氧条件下香豆素和异香豆素二聚体的循环转化性能:Uv-A 光引发的意外行为
标题:有氧条件下香豆素和异香豆素二聚体的循环转化性能:Uv-A 光引发的意外行为
摘要:香豆素类单体的光化学 [2+2]-环加成是光形成和光裂解反应的教科书范例.单体和二聚体的电子共轭长度完全不同,这导致 Uv-A 和 Uv-C 中几乎完全分离的 Uv/vis 吸收带.通过选择适当的波长,此功能可实现单体和二聚体形式之间的选择性光控制转换.一些应用基于这种在可见光范围内没有吸收的可逆光连接剂.但是对于这种应用,香豆素家族中哪种分子是最好的呢在这项研究中,我们比较了十二种香豆素型环丁烷二聚体的光化学裂解行为.特别地,研究了异构体结构和取代模式的影响.鉴定了两种具有意外高量子产率的环丁烷裂解二聚体.这种行为是通过环丁烷部分的不同环应变来解释的.框架的供电子替代物,例如具有甲氧基功能(+m 效应),导致氧化电位降低,使二聚体对氧化二聚体分裂敏感.这一结果使香豆素不合格,例如通过醚键连接到聚合物主链上,通常在 7 位,因为它们在有氧环境中的不稳定性和副反应.甲基化二聚体(+i 效应
DOI:10.1039/d1Cp01919H

专利信息

专利号:US-2021107859-A1
优先权日:2018-04-06
标题 :A process for the synthesis of carbon labeled organic compounds
发明人：AUDISIO DAVIDE; CANTAT THIBAULT; DESTRO GIANLUCA
权利人:COMMISSARIAT ENERGIE ATOMIQUE
摘要:A process for the synthesis of a carbon labeled organic compound containing a carbon labeled carboxyl group is described. A method of using carbon labeled organic compounds containing a carbon labeled carboxyl group according to the present disclosure; a process for manufacturing labeled pharmaceuticals and agrochemicals comprising synthesis of carbon labeled organic compounds containing a carbon labeled carboxyl group according to the present disclosure; and a process for producing tracers comprising synthesis of carbon labeled organic compounds containing a carbon labeled carboxyl group according to the present disclosure are also described.

专利号:US-11542269-B2
优先权日:2018-01-03
标 题:Prins reaction and compounds useful in the synthesis of halichondrin macrolides and analogs thereof
发明人：CHOI HYEONG-WOOK; FANG FRANCIS G
权利人:EISAI R&D MAN CO LTD
摘要:The invention provides methods utilizing Prins reaction in the preparation of compounds that may be useful as intermediates in the synthesis of halichondrin macrolides and analogs thereof. The invention also provides compounds that may be useful as intermediates in the synthesis of a halichondrin macrolides and methods for preparing the same.

专利号:US-10913749-B2
优先权日:2015-05-07
标 题 :Macrocyclization reactions and intermediates and other fragments useful in the synthesis of halichondrin macrolides
发明人：FANG FRANCIS G; KIM DAE-SHIK; CHOI HYEONG-WOOK; CHASE CHARLES E
权利人:EISAI R&D MAN CO LTD
摘要:The invention provides methods for the synthesis of a halichondrin macrolides through a macrocyclization strategy. The macrocyclization strategy of the present invention involves subjecting a non-macrocyclic intermediate to a carbon-carbon bond-forming reaction (e.g., an olefination reaction (e.g., Horner-Wadsworth-Emmons olefination), catalytic Ring-Closing Olefin Metathesis, or Nozaki-Hiyama-Kishi reaction) to afford a macrocyclic macrolide. The invention also provides compounds useful as intermediates in the synthesis of a halichondrin macrolides and methods for preparing the same.

专利号:US-11136335-B2
优先权日:2016-06-30
标题:Prins reaction and intermediates useful in the synthesis of halichondrin macrolides and analogs thereof
发明人：CHASE CHARLES E; CHOI HYEONG-WOOK; ENDO ATSUSHI; FANG FRANCIS G; KIM DAE-SHIK
权利人:EISAI R&D MAN CO LTD
摘要:The invention provides methods for the synthesis of a halichondrin macrolides or analogs thereof through a cyclization reaction strategy. The strategy of the present invention involves subjecting an intermediate to Prins reaction conditions to afford a macrolide. The invention also provides compounds useful as intermediates in the synthesis of a halichondrin macrolides or analogs thereof and methods for preparing the same.

专利号:US-5756770-A
优先权日:1987-12-31
标题:Synthesis of stable, water-soluble chemiluminescent 1,2-dioxetanes and intermediates therefor
发明人：BRONSTEIN IRENA Y; EDWARDS BROOKS
权利人:TROPIX INC
摘要:A novel synthesis of 1,2-dioxetane phosphate alkali metal salts and novel intermediates employed in this synthesis are disclosed. A hydroxyaryl enol ether alkali metal salt having the formula: ##STR1## wherein T can be an unsubstituted or substituted adamant-2'-ylidene group, R 3 can be a methyl group, Y can be a phenyl group and M + can be a sodium cation, is reacted with a phosphorohalidate to give the corresponding enol ether ethylene phosphate, which is then reacted with an alkali metal cyanide to give the corresponding enol ether cyanoethyl phosphate diester alkali metal salt intermediate. Singlet oxygen addition to this enol ether cyanoethyl phosphate diester alkali metal salt intermediate to give the corresponding 1,2-dioxetane cyanoethyl phosphate diester alkali metal salt, followed by β-elimination of the cyanoethyl group using an alkali metal hydroxide or the like, gives the corresponding 1,2-dioxetane phosphate alkali metal salt.

专利号:EP-0629195-B1
优先权日:1992-03-05
标 题 :Synthesis of stable, water-soluble chemiluminescent 1,2-dioxetanes and intermediates therefor
发明人：BRONSTEIN IRENA Y; EDWARDS BROOKS
权利人:TROPIX INC
摘要:A novel synthesis of 1,2-dioxetane phosphate alkali metal salts and novel intermediates employed in this synthesis are disclosed. A hydroxyaryl enol ether alkali metal salt having formula (1), wherein T can be an unsubstituted or substituted adamant-2'-ylidene group, R<3> can be a methyl group, Y can be a phenyl group and M<+> can be a sodium cation, is reacted with a phosphorohalidate to give the corresponding enol ether ethylene phosphate, which is then reacted with an alkali metal cyanide to give the corresponding enol ether cyanoethyl phosphate diester alkali metal salt intermediate. Singlet oxygen addition to this enol ether cyanoethyl phosphate diester alkali metal salt intermediate to give the corresponding 1,2-dioxetane cyanoethyl phosphate diester alkali metal salt, followed by beta -elimination of the cyanoethyl group using an alkali metal hydroxide or the like, gives the corresponding 1,2-dioxetane phosphate alkali metal salt.