dimethyl (9H-xanthene-9-ylidene)malonate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: dimethyl (9H-xanthene-9-ylidene)malonate
• 英文别名: dimethyl (9-xanthenylidene)malonate；Dimethyl 2-xanthen-9-ylidenepropanedioate
• 化学式: C₁₈H₁₄O₅
• 分子量: 310.306
• InChiKey: BGFVNUPPASSCLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl (9H-xanthene-9-ylidene)malonate 在 甲醇 、 potassium hydroxide 作用下， 以87%的产率得到9-Xanthenylidenessigsaeuremethylester
  参考文献：
  名称：

  锰（III）基氧化性1,2-自由基重排合成二苯并[ b，f ]氧杂环丁烷

  摘要：

  用Mn（OAc）3氧化2-（9 H-黄嘌呤基）丙二酸单烷基酯1可获得高产率的9-或10-二苯并[ b，f ]氧苯哌酸酯2。除了（1-甲氧基黄蒽基）丙二酸酯1（R 1＝ Me，R 2＝ 1-MeO）的情况以外，该反应以高区域选择性进行，其给出两种区域异构体。提出形成2的方法必须包括1,2-芳基自由基重排，然后进行氧化脱羧。

  DOI：

  10.1021/jo9002773
• 作为产物：
  描述：

  dimethyl ester of 9-dicarboxymethylxanthene 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 苯 为溶剂， 反应 5.0h， 以91%的产率得到dimethyl (9H-xanthene-9-ylidene)malonate
  参考文献：
  名称：

  锰（III）基氧化性1,2-自由基重排合成二苯并[ b，f ]氧杂环丁烷

  摘要：

  用Mn（OAc）3氧化2-（9 H-黄嘌呤基）丙二酸单烷基酯1可获得高产率的9-或10-二苯并[ b，f ]氧苯哌酸酯2。除了（1-甲氧基黄蒽基）丙二酸酯1（R 1＝ Me，R 2＝ 1-MeO）的情况以外，该反应以高区域选择性进行，其给出两种区域异构体。提出形成2的方法必须包括1,2-芳基自由基重排，然后进行氧化脱羧。

  DOI：

  10.1021/jo9002773

文献信息

• Carbenoid Reactions of Dimethyl Diazomalonate with Aromatic Thioketones and 1,3-Thiazole-5(4<i>H</i>)-thiones
  作者：Grzegorz Mlostón、Heinz Heimgartner

  DOI：10.1002/hlca.19960790704

  日期：1996.10.30

  even after warming to 50°. After addition of catalytic amounts of Rh2(OAc)4, a smooth reaction under N2 evolution afforded a mixture of thiiranedicarboxylate 5 and (diphenylmethylidene)malonate 6 (Scheme 2). A reaction mechanism via an intermediate ‘thiocarbonyl ylide’ 7, formed by the addition of the carbenoid species 8 to the S-atom of 2a, is plausible. Similar reactions were carried out with 9H-xanthene-9-thione

  重氮丙二酸二甲酯（4）和硫代二苯甲酮（2a）即使在升温至50°后也不会在甲苯中反应。在添加催化量的Rh 2（OAc）4之后，在N 2放出下的平稳反应提供了噻吩二羧酸酯5和（二苯基亚甲基）丙二酸酯6的混合物（方案2）。通过中间类“硫代羰基叶立德” 7的反应机理是合理的，该中间体是通过向2a的S原子中添加类胡萝卜素8而形成的。用9 H -an吨-9-硫酮（2b），9 H-噻吨蒽-9-硫酮（2c，方案4）和1，3-噻唑-5（4H）-硫酮18（方案6）。在2b和2c的情况下，分别获得了螺环的1，3-二硫杂环戊基四羧酸酯14a和14b作为第三产物。方案5中提出了形成它们的反应机理：从中间体硫杂噻烷12到类胡萝卜素的S-转移产生硫代xomalonate 15，其与1，3-偶极环加成有“硫代羰基内酯” 16。另一种选择是通过将卡宾加成至15形成“硫代羰基内酯” 17，然后分别与2b和2c进行1,3-偶极环加成。
• Method of quenching singlet and triplet excited states of photodegradable pigments, such as porphyrin compounds, particularly protoporphyrin IX, with conjugated fused tricyclic compounds having electron withdrawing groups, to reduce generation of singlet oxygen
  申请人：Hallstar Innovations Corp.

  公开号：US10632096B2

  公开（公告）日：2020-04-28

  A method of quenching excited state energy from a photodegradable pigment that has been excited by absorption of light having a wavelength in the wavelength range of 290-800 nm, comprising reacting a pigment with a conjugated fused tricyclic compound having electron withdrawing groups of Formula (II) or a salt thereof: wherein: A is selected from the group consisting of O, S, C═O, C═S, B1, B2, D1 and D2 are each independently selected from the group consisting of F, Cl, Br, I, CF3, CC13, NR33+, NO2, CN, C(═O)R4, C(═O)OR′, SO2R5, aryl, and —C═CHR6; each m independently is 0, 1, 2, 3, or 4; a is 0 or 1; each R′ is independently selected from the group consisting of LI, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl; R2 is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; each R3 is independently selected from the group consisting of H and C1-C6 alkyl; each R4 is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl; each R5 is independently selected from the group consisting of H, O, OH, NH2, and Cl; and each R6 is-independently selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl.

  一种淬灭光降解颜料激发态能量的方法，该颜料通过吸收波长在 290-800 纳米范围内的光而激发，该方法包括使颜料与具有式 (II) 或其盐类电子萃取基团的共轭熔融三环化合物反应： 其中： A 选自 O、S、C═O、C═S 所组成的组、 B1、B2、D1 和 D2 各自独立地选自由 F、Cl、Br、I、CF3、CC13、NR33+、NO2、CN、C(═O)R4、C(═O)OR′、SO2R5、芳基和-C═CHR6 组成的组； 每个 m 独立地为 0、1、2、3 或 4； a 是 0 或 1； 每个 R′独立地选自由 LI、烷基、烯基、炔基、环烷基、环烯基和芳基组成的组； R2 选自由 H、烷基、环烷基、烯基、炔基和芳基组成的组； 每个 R3 独立选自由 H 和 C1-C6 烷基组成的组 每个 R4 独立地选自由 H、烷基、烯基、炔基、环烷基、环烯基和芳基组成的组； 每个 R5 独立地选自由 H、O、OH、NH2 和 Cl 组成的组；以及 每个 R6 独立地选自由烷基、烯基、炔基、环烷基、环烯基和芳基组成的组。
• Manganese(III)-mediated carbon-carbon bond formation in the reaction of xanthenes with active methylene compounds
  作者：Hiroshi Nishino、Hironori Kamachi、Harumi Baba、Kazu Kurosawa

  DOI：10.1021/jo00039a010

  日期：1992.6

  Oxidation of xanthenes with manganese(III) acetate in the presence of active methylene compounds such as 1,3-dicarbonyl compounds, malononitrile derivatives, acetone, and nitromethane selectively gives 9-substituted xanthene derivatives in good yields. A similar oxidation of thioxanthene also yields 2-(9-thioxanthenyl)-1,3-dicarbonyl compounds in 57-91% yields. The obtained 2-(9-xanthenyl)-1,3-dicarbonyl compounds are readily converted to 2-(9-xanthenylidene)-1,3-dicarbonyl derivatives using manganese(III) complexes or 2,3-dichloro-5, 6-dicyano-1,4-benzoquinone. The mechanisms for the formation of 9-substituted xanthenes are discussed on the basis of the reaction of intermediates, the electron-donating substituent effect on the xanthene ring system, effect of additives, and comparison with a reaction of radical-trapping reagents.
• METHOD OF QUENCHING SINGLET AND TRIPLET EXCITED STATES OF PIGMENTS, SUCH AS PORPHYRIN COMPOUNDS, PARTICULARLY PROTOPORPHYRIN IX, WITH CONJUGATED FUSED TRICYCLIC COMPOUNDS HAVE ELECTRON WITHDRAWING GROUPS, TO REDUCE GENERATION OF REACTIVE OXYGEN SPECIES, PARTICULARLY SINGLET OXYGEN
  申请人：HALLSTAR INNOVATIONS CORP.

  公开号：US20150164852A1

  公开（公告）日：2015-06-18

  A method of quenching excited state energy from a pigment that has been excited by absorption of light having a wavelength in the wavelength range of 290-800 nm, comprising reacting a pigment with a conjugated fused tricyclic compound having electron withdrawing groups: of Formula (II) or a salt thereof: wherein: A is selected from the group consisting of O, S, C═O, C═S, and B 1 , B 2 , D 1 , and D 2 are each independently selected from the group consisting of F, Cl, Br, I, CF 3 , CCl 3 , NR 3 3 + , NO 2 , CN, C(═O)R 4 , C(═O)OR 1 , SO 2 R 5 , aryl, and —C═CHR 6 ; each m independently is 0, 1, 2, 3, or 4; n is 0 or 1; each R 1 is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl; R 2 is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; each R 3 is independently selected from the group consisting of H and C 1 -C 6 alkyl; each R 4 is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl; each R 5 is independently selected from the group consisting of H, O − , OH, NH 2 , and Cl; and, each R 6 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl.
• US9867800B2
  申请人：——

  公开号：US9867800B2

  公开（公告）日：2018-01-16