bis(phenylsulfonyl)-1,2,5-oxadiazole-2-oxide,the NO donor,was synthesized by etherealization of thiophenol,oxidation,and then cyclization with an overall yield of 70%. This process is simpler and the yield of product ...bis(phenylsulfonyl)-1,2,5-oxadiazole-2-oxide,the NO donor,was synthesized by etherealization of thiophenol,oxidation,and then cyclization with an overall yield of 70%. This process is simpler and the yield of product is higher than that previously reported.展开更多
以丙二腈为原料,采用4个连续反应,得到3-氨基-4-氨基肟基呋咱(Ⅰ),经Sandmeyer反应生成3-氨基-4-酰氯肟基呋咱(Ⅱ),再与3-氯-4-氟苯胺反应得到吲哚胺2,3-双加氧酶抑制剂4-氨基-N-(3-氯-4-氟苯基)-N'-羟基-1,2,5-口恶二唑-3-甲脒(INC...以丙二腈为原料,采用4个连续反应,得到3-氨基-4-氨基肟基呋咱(Ⅰ),经Sandmeyer反应生成3-氨基-4-酰氯肟基呋咱(Ⅱ),再与3-氯-4-氟苯胺反应得到吲哚胺2,3-双加氧酶抑制剂4-氨基-N-(3-氯-4-氟苯基)-N'-羟基-1,2,5-口恶二唑-3-甲脒(INCB024360)。Ⅱ的工艺优化路线:在0℃下,加入化合物Ⅰ2.0 g,浓盐酸6.5 m L,Na NO20.96 g,Cu Cl 2.87 g,水8 m L,反应时间5 h;INCB024360的工艺优化路线:25℃下,加入反应物Ⅱ1.0 g,3-氯-4-氟苯胺1.58 g,三乙胺0.17 m L,无水乙醇25 m L,反应时间5 h。总产率从10.0%提高到43.1%,HPLC纯度为99.6%,其结构经1HMOL/LR,13CMOL/LR,MS表征。展开更多
Benzo[1,2-c;4,5-cʹ]bis[1,2,5]thiadiazole(BBT)has intrinsic diradical character and herein it is used to construct organic near-infrared(NIR)dyes together with the aromatic porphyrin unit.Three BBT-porphyrin hybrid dye...Benzo[1,2-c;4,5-cʹ]bis[1,2,5]thiadiazole(BBT)has intrinsic diradical character and herein it is used to construct organic near-infrared(NIR)dyes together with the aromatic porphyrin unit.Three BBT-porphyrin hybrid dyes 1-3 with different linkage modes are synthesized by Pd-catalyzed Sonogashira crosscoupling between meso-ethynylene porphyrin units and monobromo-/dibromo-BBT,or through unexpected homocoupling between the BBT units.They all possess small open-shell diradical character and display intense NIR absorption in the range of 800-1000 nm.They also exhibit amphoteric redox behavior.BBT-based diradicaloids are thus good candidates for organic NIR dyes.展开更多
The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorpt...The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorption spectroscopy. The quenching mechanism of fluorescence of BSA by FB was considered to be a dynamic quenching procedure. The number of binding sites n and apparent binding constant K were measured by fluorescence quenching method. The results indicate that there is FB molecular binding with BSA, and forming 1 ： 1 complex. The thermodynamic parameters such as △H, △G and △S, etc., were calculated, The results indicate that the binding reaction is mainly entropy-driven and hydrophobic forces play major role in the binding reaction, The distance r between donor （BSA） and acceptor （FB） was obtained according to Forster theory of non-radioactive energy transfer.展开更多
文摘bis(phenylsulfonyl)-1,2,5-oxadiazole-2-oxide,the NO donor,was synthesized by etherealization of thiophenol,oxidation,and then cyclization with an overall yield of 70%. This process is simpler and the yield of product is higher than that previously reported.
文摘以丙二腈为原料,采用4个连续反应,得到3-氨基-4-氨基肟基呋咱(Ⅰ),经Sandmeyer反应生成3-氨基-4-酰氯肟基呋咱(Ⅱ),再与3-氯-4-氟苯胺反应得到吲哚胺2,3-双加氧酶抑制剂4-氨基-N-(3-氯-4-氟苯基)-N'-羟基-1,2,5-口恶二唑-3-甲脒(INCB024360)。Ⅱ的工艺优化路线:在0℃下,加入化合物Ⅰ2.0 g,浓盐酸6.5 m L,Na NO20.96 g,Cu Cl 2.87 g,水8 m L,反应时间5 h;INCB024360的工艺优化路线:25℃下,加入反应物Ⅱ1.0 g,3-氯-4-氟苯胺1.58 g,三乙胺0.17 m L,无水乙醇25 m L,反应时间5 h。总产率从10.0%提高到43.1%,HPLC纯度为99.6%,其结构经1HMOL/LR,13CMOL/LR,MS表征。
基金supported by NRF(NRF-NRFI05-2019-0005)MOE Tier 2 grant(MOE2018-T2-2-094).
文摘Benzo[1,2-c;4,5-cʹ]bis[1,2,5]thiadiazole(BBT)has intrinsic diradical character and herein it is used to construct organic near-infrared(NIR)dyes together with the aromatic porphyrin unit.Three BBT-porphyrin hybrid dyes 1-3 with different linkage modes are synthesized by Pd-catalyzed Sonogashira crosscoupling between meso-ethynylene porphyrin units and monobromo-/dibromo-BBT,or through unexpected homocoupling between the BBT units.They all possess small open-shell diradical character and display intense NIR absorption in the range of 800-1000 nm.They also exhibit amphoteric redox behavior.BBT-based diradicaloids are thus good candidates for organic NIR dyes.
基金Project supported by the National Natural Science Foundation of China （Nos. 30570015, 20373051 ）, the Natural Science Foundation of Hubei Province （Nos. 2006ABA333, 2005ABC002）, and the Science Foundation of Hubei Provincial Educational Department （No. D200528003）, and the Science Research Foundation of Chinese Ministry of Education （No. [2006]8IRT0543）.
文摘The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorption spectroscopy. The quenching mechanism of fluorescence of BSA by FB was considered to be a dynamic quenching procedure. The number of binding sites n and apparent binding constant K were measured by fluorescence quenching method. The results indicate that there is FB molecular binding with BSA, and forming 1 ： 1 complex. The thermodynamic parameters such as △H, △G and △S, etc., were calculated, The results indicate that the binding reaction is mainly entropy-driven and hydrophobic forces play major role in the binding reaction, The distance r between donor （BSA） and acceptor （FB） was obtained according to Forster theory of non-radioactive energy transfer.
