The financial support from the National Science Foundation (NSF, grant number 0958901), the Robert Welch Foundation (Welch departmental grant BC-0022 and the Principal Investigator grant BC-1586), and the University of Houston-Clear Lake (FRSF grant) are greatly appreciated.

注意:使用前请咨询所有相关的材料安全数据表（MSDS）。虽然2-aminobenzophenones是无臭，在该反应中产生一些含硫分子。因此，应始终使用通风良好的条件。在温度超过140℃时进行反应时，请使用所有适当安全的做法，因为压力可能会高于5条微波辐射下的记录。当温度被设定在160℃，记录的最高压力为21巴，这几乎是上限微波反应器可以处理。尽管压力没有时，反应在回流下油浴中进行的问题，应始终使用良好的通风。 1.微波小型辐射四苯基喹唑啉的制备<ol><li>反应液的制备<ol><li>兼容的磁性搅拌棒添加至2-5毫升微波反应管中。 </li><li&gt;使用分析天平，称量0.0866克2-氨基二苯酮（黄色粉末），0.0988克硫脲（白水晶，3当量）的入上述反应管中。 注意:2-氨基二苯甲酮和硫脲之间的最佳比例为1:3。 </li><li>将5毫升DMSO到反应管中。 注意:DMSO的量是相当灵活5毫升DMSO中仅有约足以满足体积为根据制造商的指导微波的正确吸收的最小要求。然而，热条件下，需要少得多的溶剂这种规模的反应。 </li><li>密封用含有橡胶隔片入口兼容铝盖的反应管中。 </li><li>大力摇晃管上的涡旋1-2分钟，以溶解反应物。 注意:硫脲可能无法在DMSO在室温下完全溶解，但加热时它会完全溶解。 </li><li>使用微型注射器向撤回5微升反应混合物，以2毫升玻璃小号ampling含0.35毫升的乙酸乙​​酯（EtOAc）为气相色谱/质谱分析（GC / MS）分析在反应开始前管。 </li></ol></li><li>四苯基喹唑啉的形成微波辐射<ol><li>打开微波反应器，将微波反应管中的八个管持有者之一。 </li><li>设置反应通过触摸屏的参数，如管的位置（ 例如，从井1到8），一种类型的管（例如，2-5毫升）中，反应温度（150℃），预搅拌的持续时间（1分），微波的吸收水平（高），搅拌速度（600转），反应时间（5小时）。 </li><li>一旦所有的参数都是正确设置，单击"运行"按钮，机器人就会自动拿起从管夹（或井水）的反应管中，并把它加热孔内。然后，在微波反应器将根据设置先前的参数运行反应。 </li><li>当微波辐射完成后，WAIT直到温度下降到接近30ºC，机器人将拿起反应管，并把它回到原来的持有者。 </li><li>使用微型注射器向撤回5微升反应混合物（透明黄色溶液，没有观察到不溶性物质），并把它添加到含0.35毫升EtOAc中用于GC / MS分析另外2毫升玻璃采样管。 </li><li>作为GC / MS分析表明反应只完成一半，设置相同管子在相同温度下另外5小时微波反应。 注意:反应时间根据起始原料的使用量而不同，反应溶液中的浓度，对2- aminobenzophenones的取代基，以及更重要的是，反应温度。例如，0.3克2-氨基二苯甲酮在3ml DMSO中的反应将在6小时，在160℃下完成的，但两者在微波辐射和热板加热下持续在140℃以上的14小时。此外，还建议监测反应periodically用GC或GC / MS分析。得不到的GC或GC / MS的人应该再使用薄层色谱（TLC）监测反应，尽管它不是最好的工具。 </li></ol></li><li>反应混合物的GC / MS分析<ol><li>确保的GC / MS是正确根据制造商的协议设置。 </li><li>放在自动进样器托盘玻璃取样管。 </li><li>点击屏幕上"GCMS_3"快捷方式启动控制和协调注射器，GC和质谱仪职能的数据采集程序。通过点击"方法"下拉菜单并强调加载适当的方法"加载方法"。所选择的方法包含所有必要的参数为GC和四倍质谱仪分析目标样品。如果不存在这样的方法中，创建一个必要方法。 <ol><li>为一个新的样品，如果修改一些GC参数的以适应特定的样本，突出"编辑EntirE法"通过点击"方法"从下拉菜单，并相应改变它的相关参数。，常常改变GC的参数是初始温度，并保持该温度的持续时间，温度升高的速率，最终温度和持续时间，以保持温度，喷射量，该次注射时，平衡时间之前和之后洗注射针和后运行时间，以及运行后的温度。 </li><li>对于本实验，设置初始的GC温度在70℃（1分钟），在20℃/分钟的温度增加速率，并在250℃（5分钟）的最终温度。使用15分钟的总运行时间。使用2微升的注射体积，用后洗涤针4预洗和4。用纯氦作为在此条件下所使用的载气。 注意:用于GC / MS分析法包含预先设定的参数同时运行的GC和MS仪器。参数FOřGC包括烘箱的起始温度加热GC柱和分钟数保留该温度下，以提高微波炉的温度的速率，烘箱的最终温度和分钟数保留前的最终温度GC分析完成;样品的注入量;载气的分割率;的次数以洗涤针样品被注入之前;和的次数洗针的样品被注入之后; 等等初始温度和最终温度的选择，以及提高温度的速率取决于分析样品的性质。在一般情况下，低沸点的非极性分子在相对低的初始温度进行分析。 </li></ol></li><li>调整质谱仪根据制造商的协议。 <ol><li>一旦选择了一个正在运行的方法，请点击"乐器"的下拉菜单顶部，并突出显示"调谐MSD"。然后另一个窗口出现在数据采集窗口的前面。人们可以选择"调谐MSD"或"其QuickTune"，并单击"确定"按钮，启动质谱仪的调整过程。该"其QuickTune"选项大约需要3分钟即可完成，而"调谐MSD"选项，运行约10分钟。在正常情况下，"其QuickTune"选项是不够好，校准精度达0.1道尔顿质谱仪。在调整过程将测量的峰值69，219和全氟三丁胺（PFTBA），以及作为N 2，O 2量502的相对丰度，H 2 O，CO 2 等 。 注意:质谱仪必须以具有质量的精确测量每隔一天进行校准。调谐是调整参数用于质谱仪能正常工作，如四倍的电压时，真空质量检测器的，背景噪声，标准峰来衡量质谱仪，等。其中可以选择自动调谐或手动调谐模式选择"其QuickTune"或"调谐MSD"选项来校准质谱仪，也就是说，。 </li></ol></li><li>获得GC / MS的数据<ol><li>编辑数据采集序列。点击下拉菜单顶部的"顺序"，以突出"编辑序列"，一个新的窗口弹出，其中关于样本的信息必须填写，如样品（样品，空白，校准，QC的类型等 ），样品瓶（从1到100），样品名称，数据文件的名称，样品的意见等的位置。当所有样品的信息已经被输入，点击"OK"按钮。然后点击下拉菜单顶部的"顺序"，以突出"保存序列为.."，并输入了正确的文件夹序列名。 </li><li>获取的GC / MS的数据。点击下拉菜单顶部的"顺序"，以突出"运行顺序"，选择一个适当的"数据文件目录"保存采集的数据，然后单击"运行序列"按钮开始数据采集过程。 </li></ol></li><li>分析GC / MS的结果 注意:分子可以通过它们从GC柱上洗脱的分钟来表征，即所谓的保留时间。在相同的GC条件（即，上面提到的气相色谱参数），特定分子的保留时间是非常可重复的。该化合物可通过其质谱进一步证实。人们可以很容易识别的化合物在保留时间和质谱条件，并检查化合物的纯度为好。 <ol><li>双击显示器上的"GCMS_3数据分析"的快捷方式，打开了特意从GC / MS机处理采集数据的软件。 </li><li>在数据采集过程中，看到了分析样品的即时结果，单击"文件"，从下拉菜单，highligHT"拍摄快照"来获得样品的同步GC谱。通常情况下，在收购过程完成后，人们会处理数据。在这种情况下，从下拉菜单中单击"文件"突出"加载数据文件"，并选择正确的数据文件，或浏览数据目录，然后双击该数据文件，以显示样品的全光谱GC。一条垂直线出现在哪里鼠标指向GC频谱的窗口内的位置。 </li><li>将鼠标移动到垂直线命中峰的最高点峰值的中心，并双击鼠标右键，弹出样本的质谱，气相色谱光谱窗口下方的新窗口。一个可以通过按住左键放大的质谱，并选择区域放大为质谱的细节。 </li><li>通过双击质谱窗口内的鼠标右键以获得两个新视窗鉴定的化合物。小前窗与"PBM搜索结果:C:数据库 W8N08.L"的名字带来了从最有可能的匹配分析质谱数据库20的分子，并名列20分子在他们的相似之处顺序。大的背窗口包含两个板，其中前面板显示的GC光谱内所分析的峰的原始质谱，和底面板显示从小前窗的列表中所选择的分子的质谱。通常，常见的有机化合物可以通过其质谱与数据库中收集的标准质谱进行比较来确认。虽然新的化合物或在数据库中未收集的分子不能直接确认他们的身份可以通过预期分子量，并与它们的结构可能片段的匹配来获得。 </li><li>由GC上的频谱比较其保留时间识别不同的样品在同一化合物。根据数据acqu相同的条件isition，相同的化合物应显示在GC光谱相同的保留时间。 </li><li>通过点击"色谱"的下拉菜单中，突出无论是"集成"或"AutoIntegrate"，然后选择"百分比报告"分析样品的纯度。 </li><li>打印选择"打印机设置"时，点击"文件"在下拉菜单对应于纵向或横向格式GC光谱内的峰值都GC谱和质谱。此外，通过选择PDF转换直接打印谱成PDF格式。 </li></ol></li></ol></li><li>反应液提取 注意:隔离工艺已在通风柜进行的，与令人不快的气味的含硫分子的少量在该反应中生成的。 <ol><li>与制造商提供的钳打开微波反应管中，将反应混合物转移到125毫升的分液漏斗中。一个DD20毫升的EtOAc此漏斗，接着用10毫升水。 注意:如果该反应溶液在一天在室温下放置，长针形晶体可以取决于溶液中的浓度出现在该溶液中。因此，这是明智在室温下离开大型反应混合物以形成晶体和分离晶体直接的产品，如果时间不是一个因素。 </li><li>摇动分液漏斗大力，漏底水层。然后另外的10毫升的水加入到分液漏斗中，并重复此过程。 </li><li>集中剩余EtOAc溶液降至约1ml由旋转蒸发。 </li></ol></li><li>通过制备TLC -4-苯基喹唑啉的纯化<ol><li>用巴斯德吸管的浓缩EtOAc溶液转移到20×20cm的制备TLC板以这样的方式，在TLC板样品的条纹宽小于1厘米，距离边缘约1厘米。这浸板到GLA含有150mM毫升己烷和EtOAc的分类室（2:1）。观看溶剂前沿接近TLC板的顶部的运动，并取出盘时溶剂前沿从顶部边缘约1厘米。 <ol><li>借鉴薄层板上，以铅笔两条直线装载样品之前标记的地方。另外，浸在玻璃室中的TLC板在这样一种方式，样品的条纹是在底部，但仍高于溶剂水平约2mm。 </li></ol></li><li>在紫外线（UV）光，用铅笔标记与绿色荧光带，刮开对薄层板上显着的波段称量纸（有R F = 0.68，己烷/乙酸乙酯= 2的相对流动性:1）。 注:由于紫外线吸收灵敏度高，可以在平板上观察多弱带。然而，最顶部条带通常对应于含硫分子，如二甲基二硫化物，二甲基三硫化物;其他乐队低于4 - 苯基喹唑啉是visiblÈ但其量是太少进行分离和表征。 </li><li>填充有玻璃棉玻璃吸管，由对角折叠称量纸上，以允许硅胶的粉末落入吸管划伤硅胶粉末转移到吸移管，挖掘吸管对硬表面包装硅胶紧。洗用丙酮（8-15毫升）吸移管到2鼓闪烁瓶中。 </li><li>转移0.35毫升洗脱丙酮溶液来进行GC / MS分析另外2毫升玻璃采样管，并直接干燥在旋转蒸发器中残留的丙酮溶液。把含在真空干燥器进一步干燥纯化的化合物在整个闪烁瓶中。 注意:直到此步骤，该产品是纯化的和可用于进一步表征（例如，核磁共振（NMR）谱）或其他变换。 </li></ol></li></ol> 2. 4-苯基喹唑啉的制备ⅰ通过加热盘N个小规模注意:反应混合物中，反应混合物的萃取物的GC / MS分析的程序，和反应产物的纯化是非常类似于在第1（1.1.1-1.3.4，1.4.1-1.4.3中所述的那些和1.5.1-1.5.5，分别），使大部分的这些步骤将在下面被删去。 <ol><li>反应混合物为热板加热制备<ol><li>权衡0.0240克2-氨基二苯甲酮和0.0280克硫脲到2ml玻璃小瓶中，然后添加0.5毫升DMSO中转移到相同的小瓶中，并用螺旋盖关闭小瓶中。 注意:DMSO中在此条件下所用的量小于在微波辐射下一个小得多。由于该反应的规模小，则不需要磁力搅拌了，所以为将溶液的旋涡搅拌，以溶解反应物。然而，在一个相对大的反应规模，例如，在2-鼓闪烁瓶中或圆底烧瓶中，磁力搅拌仍然是必要的。 </li></ol></li><li>通过加热盘四苯基喹唑啉的制备<ol><li>里面通风柜，把一个加热块上加热板的顶部，并设定温度至160℃。 </li><li>当温度达到160℃，将玻璃小瓶入加热块的孔中的一个。约一个半小时的时间间隔，取出小瓶并用手摇晃2-3秒，并把它回再次好。 6小时后，取出药瓶，并离开它通风柜内冷却下来。 </li><li>转移5μl反应混合物与含0.35毫升EtOAc中另外2毫升玻璃采样管，并提交样品用于GC / MS分析。 </li></ol></li><li>一旦反应完成，对于GC / MS分析制定出产品如第1说明详见第1.1.1-1.3.4，1.4.1-1.4.3细节，1.5.1-1.5.5，分别反应混合物的提取，和产品的纯化。 </li></ol>

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Except for the contents described in patent (pending), the authors have nothing else to disclose.

作为该产品的分子量仅相对于该起始材料（ 见图3和图4）的增加9此洁净反应（如在图2中示出 ）出现在开始非常有趣。这听起来不可能的，因为碳的原子量为12非常有可能的，引进一个碳原子的进入的分子将至少12增加分子量如果未包括在所附的氢原子。因此，反应混淆我们相当多的时间。 在2-氨基二苯甲酮和硫脲之间的反应的一个快速一瞥，可以推断是一个简单的加法氨基-2-氨基二苯甲酮的对连接到硫代羰基的羰基的硫代羰基硫脲，随后加入氨基的内的2-氨基二苯甲酮将形成具有238分子量的结构（ <str翁&gt;图5）。然而，如示于图2中，硫脲迅速分解，因为它不能被后的反应混合物为5小时加热检测;在此条件下，起始材料的约50％仍然存在。如果硫脲是真正的物种与2-氨基二苯甲酮反应，如图5假定，则总是会有起残留在反应溶液中，因为没有更多的硫脲可用来与残留的起始材料反应的材料。因此，这种良好的机制并不代表真正的反应路径，并且也与分子量的从原料到产物的206的197的变化不一致。众所周知，一个偶数分子量表明偶数分子内的氮原子的。因此，该产品要么不具有氮原子的全部或包含偶数个氮原子，最有可能与在这种情况下，两个氮原子的;否则，分子瓦特产物八不能只是增加9。 经过广泛的结构表征，包括1 H NMR，13 C-NMR，和特别是X射线晶体学，很显然，该产品是4-苯基喹唑啉。16但它是如何形成的？计算研究表明，硫化氢和碳化二亚胺可以从硫脲的热分解来形成。17如果碳化二亚胺是与2-氨基二苯甲酮反应，即使硫脲在反应溶液中消失的种类，碳二亚胺将留在溶液中。有了这些知识，可能的是里面2-氨基二苯甲酮最初反应与碳二亚胺的氨基以形成1-（2-苯甲酰基苯基）胍中间体，其中环化以形成4- phenylquinazolin -2（1H） - 亚胺中间体。然而，这样的中间体是不稳定的，可水解成4- phenylquinazolin -2（1H） -酮， 如图6C所示，的条件下加热的电炉。此外，该中间的分解不会导致-4-苯基喹唑啉的形成任一，因为该中间4-苯基喹唑啉的直接转化，需要去除氮原子的。这是不可能的，因为连接到这个氮原子两个键必须打破摆脱NH，一种极不稳定的反应性物质的片段。然而，如果4- phenylquinazolin -2（1H） -亚胺中间体均减少，再与氨的高温下消除会发生非常容易（图7）。然后，必须有其参与了反应，并减少4- phenylquinazolin -2（1H） - 亚胺向4-苯基-1,2-二氢喹唑啉-2-胺的还原试剂。早提到，硫脲的热分解产生硫化氢，与碳二亚胺一起。硫化氢可以用溶剂DMSO中反应，生成有机含硫分子作为还原剂即发挥作用，虽然氢硫化物本身已经在图8中，以及施加作为还原剂18-20最可能的有机还原剂可能是甲硫醇，通过检测二甲基二硫（保留时间= 图 2中3.287分钟作为支持含硫，质谱）和二甲基三硫（保留时间= 图 2中3.691分钟，质谱在图9）。 <img alt="图2" src="/files/ftp_upload/53662/53662fig2highres.jpg" width="700" /> 图2:在微波辐射下于150ºC2-氨基二苯甲酮和硫脲在DMSO之间的反应的GC分析的GC条件为:在70℃（1分钟）的初始温度，以20℃/分钟温度升高速度，最终温度在250℃（5分钟）。总运行时间为15分钟。的注入量为2微升，与4预洗和4后洗NE的edle。 （A）热之前反应混合物应用; （B）在150ºC下加热5小时后的反应混合物（亚胺中间体可观察）; （C）在150ºC加热10小时后，反应混合物。 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53662/53662fig2highres.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图3" src="/files/ftp_upload/53662/53662fig3.jpg" /> 图3:2氨基二苯甲酮（EI模式，四联）的质谱分子式:C 13 H 11 NO，分子量:197典型片段是198，M + +1（9.8％），197:M +（68.6 ％），196，M + -1（100.0％），180:M + -17（NH 3丢失，8.3％），120:M + -77（苯基C 6 H 5丢失，35.9％），105:苯甲酰阳离子（C 6 H 5 CO + &lt;<html> / SUP&gt; 11.4％），92:M +苯甲酰（M + -C 6 H 5 CO，18.0％），77:苯基阳离子（22.4％）。 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53662/53662fig3large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图4" src="/files/ftp_upload/53662/53662fig4.jpg" /> 图4:C 14 H 10 N 2，分子量:206.25 四苯基喹唑啉（EI模式，四联）分子式的质谱 。典型片段是207:M + +（7.2％），206:M +（50.8％），205:M + -1（100.0％），177:M + -1-HCN-1（6.6％），151 :M + -1-C 4 H 4 -H 2（8.9％），129:M + -C 6 H 5（1.6％），102:M + -C 4 H 4 -C 4 H 4（5.3％） 。PG"目标="_空白"&gt;点击此处查看该图的放大版本。 <img alt="图5" src="/files/ftp_upload/53662/53662fig5.jpg" /> 图5:2氨基二苯甲酮和硫脲的反应表观机制， <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53662/53662fig5large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图6" src="/files/ftp_upload/53662/53662fig6highres.jpg" width="700" /> 图6:在160ºC2-氨基二苯甲酮和硫脲在DMSO上热板之间的反应的GC / MS分析 （A）的0.0240克2-氨基二苯甲酮和施加热之前0.0280克在0.5ml DMSO中的硫脲的混合物。 （B）在160ºC6小时加热后反应混合物; （C）质量spectru4 phenylquinazolin-2（1H） -酮副产品为m后的溶液在160ºC加热6小时。 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53662/53662fig6highres.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图7" src="/files/ftp_upload/53662/53662fig7.jpg" /> 图7:从2氨基二苯甲酮和硫脲形成四苯基喹唑啉的真实反应机制， <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53662/53662fig7large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图8" src="/files/ftp_upload/53662/53662fig8.jpg" /> 图8:二甲基二硫质谱（EI模式，四联）分子式:C 2 H 6 S 2，分子量:94.19。典型的片段95.9:M + +2（2.9％），94:M +（62.0％），79:M + -CH 3（100.0％） <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53662/53662fig8large.jpg" target="_blank">点击此处查看该图的放大版本。</a> <img alt="图9" src="/files/ftp_upload/53662/53662fig9.jpg" /> 图9:三硫化二甲酯的质谱（EI模式，四联）分子式:C 2 H 6 S 3，分子量:126.25。典型的片段是128:M + +2（13.7％），126:M +（100.0％），110.9:M + -CH 3（14.6％） <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53662/53662fig9large.jpg" target="_blank">点击此处查看该图的放大版本。</a> 对于这个简单的反应中，关键的步骤是加热温度和之后纯化的控制。由于碳化二亚胺是即用2-氨基二苯甲酮反应的真实物种以形成4- phenylquinazolin -2（1H） - 亚胺中间体，碳二亚胺的从硫脲的热分解形成是非常重要的。早期的研究表明，硫脲开始于140之间和180℃，21这也与硫脲的计算研究是一致的。17然而，当硫脲溶解在像DMSO中极性溶剂的温度分解，它开始在较低温度下分解。该温度已经以具有用于由2-氨基二苯酮的形成4-苯基喹唑啉的一个合理的反应速率约120℃以上观察到的。另一方面，该反应不能在非常高的温度的设置任一。反应温度的上限取决于溶剂的沸点，并可能产生时的温度从硫脲的热分解额外的副产物。例如，已经报道，碳DISulfide是当硫脲在温度之间182和240℃。22还有，微波辐射的条件下，在整个反应体系中被密封在有限的空间的反应管中，温度过高会导致非常高的压力和加热的初级产品潜在的爆炸。因此，建议150和165℃之间的理想的反应温度。而压力可能不是下热回流的问题，高的反应温度将导致需要产生从用DMSO反应的还原剂硫化氢的演变。在这个协议中的另一个关键步骤是产物的纯化。如4-苯基喹唑啉比原料少的极性，在DMSO产物的溶解度小于原料。当反应完成时，如果反应溶液在室温下放置一天或更长的时间出现往往晶体的产物。在这种情况下，晶体可以简单FILTRA泰德并用溶剂洗涤，得到纯产物。另外，反应物的浓度也影响纯化产品的方式。在相同的反应温度下，溶液的浓度越高，则较长时间的反应进行到完成。特别是，当反应溶液过于集中，产品形式的油层和浮在的DMSO溶液顶部。这种情况在对3克2-氨基二苯甲酮和3.5克的硫脲在20ml的微波管中反应以7-8毫升DMSO中。在这种情况下，没有晶体形式，并且产品只能从溶剂通过萃取分离。同时，该产品可与含硫分子例如二甲基二硫化物和二甲基三硫，这将通过柱色谱法除去污染。这是推荐用于大规模反应的纯化过程。 关于该反应中的变形，它可以在不同的极性溶胶进行泄，如N，N-二甲基甲酰胺（DMF）中，在DMSO存在下进行。在这种情况下，DMSO的少量用作试剂，而不是溶剂，用于产生还原剂的目的。在此条件下，除了二甲基亚砜，含硫分子较少存在，使得令人不快的气味可以很好处理。然而，这种修改会减慢总的反应速率。另外，副产物从DMF中始发一个微小的量是通过GC / MS分析引人注目，虽然它可能不会影响整体纯化过程。另一方面，大型的反应可以在回流条件下的圆底烧瓶中进行。因为它是回流的过程中打开，以在通风柜的空气，低挥发性分子，包括二甲基二硫和二甲基三硫化物会从反应体系中发展，从而使较少异味将被检测到。应当指出的是该反应是已重复多次非常可重复的。如果起始队友里亚尔在DMSO中正确地混合，并将该溶液150和165℃之间加热时，它是保证有预期的最终产物，因此，几乎没有故障排除是必要的。然而，反应速率会改变时不同的2-氨基二苯甲酮时，由于取代基作用和位阻效应。 该反应的意义是它的简单性和整洁，除了极少数较小的副产物。 如图 2中所示，几乎没有由2-氨基二苯酮引起的其他副产物可通过GC分析中观察到。虽然一个峰出现在保持时间（即，10.553分钟）除4-苯基喹唑啉更高，例如峰值是很小的，消失随着反应进行至完成。关于该峰光谱研究表明，它是4- phenylquinazolin -2（1H） -亚胺中间体16此外，很便宜的原料，如硫脲在这个反应中使用，而不是其他昂贵REAG，像经济需求测试或乌洛托品溴乙酸乙酯。此外，由2- aminobenzophenones -4- phenylquinazolines制备，该反应可以很容易地扩展，以制备含有喹唑啉脚手架其它芳族稠合的分子，如具有重要的工业应用，染料和颜料perimidines。此外，该反应还可以扩展到2-氨基苯基烷基酮在4位被烷基以制备取代的芳基喹唑啉。但它被限制为仅而不在邻近羰基的碳原子活性α-氢（多个）的那些2-氨基苯基烷基酮，因为如果存在于该α碳原子的活性氢，可发生潜在互变异构以形成烯醇该经历羟醛缩合以形成其他的副产物，而不是喹唑啉衍生物。 对于该反应中，2-氨基二苯甲酮和硫脲之间的最佳比例为1:3。热分解的F计算研究或硫脲表明除了一对硫化氢和碳化二亚胺，氨和硫氰酸的产生，以及，表明不是所有的硫脲将被转换成碳化二亚胺。17因此，需要用于该反应的硫脲中的至少一当量。另一方面，作为小的含硫分子从该反应中生成，这是明智不使用该反应过于硫脲由于副产物含硫-的难闻的气味。 很显然，在DMSO 2-氨基二苯甲酮和硫脲之间的反应是一种独特的互补反应系统，其中，硫脲的热分解产生所需的反应性物质（即，碳二亚胺）耦合与2-氨基二苯甲酮，以形成亚氨基中间体（即，4-苯基喹唑啉-2（1H） - 亚胺），而硫化氢用DMSO反应生成有机含硫分子，其功能作为减少阿让T则减少了中间亚胺。然后，氨的消除由4-苯基-1,2-二氢喹唑啉-2-胺，得到4-苯基喹唑啉。该反应已在其他非质子极性溶剂，如DMF，乙二醇被测试，但反应不象一个在DMSO作为良好。例如，在乙二醇2-氨基二苯甲酮和硫脲之间的反应，得到主要是（5Z，11Z）-6,12 - 二苯基 - 二苯并[b，f]的[1,5] -diazocine，2-氨基二苯甲酮的二聚产物。 16虽然在DMF 2-氨基二苯甲酮和硫脲的反应可以得到4-苯基喹唑啉，该反应并不像一个在DMSO作为干净，如由图 10B中的未知的副产物。显然，这种反应速度比不上一个在DMSO无论是。然而，加入DMSO少量到DMF溶液肯定改善了两个反应速率和减少的副产物（图10D 和图10E的术语反应</strong&gt;的）。此结果清楚地表明DMSO在该反应中的作用，不仅作为溶剂，而且作为试剂以生成还原试剂。因此，这是一个互补的反应体系中。作为一个简单的和干净的反应，使喹唑啉衍生物，所报告的协议可以应用于包含在未来的稠合嘧啶脚手架杂环的制备。含有嘧啶部分许多杂环分子已经在药品以及着色剂被使用。 <img alt="图10" src="/files/ftp_upload/53662/53662fig10.jpg" /> 图10:在DMF中，并在DMF与存在DMSO 2-氨基二苯甲酮和硫脲之间的反应的GC / MS分析 （A）的0.0318克2- aminobeznophenone和0.0382克硫脲在2毫升DMF中之前加热是混合物 。应用; （B）在165ºC下微波我下加热11小时后的DMF溶液rradiation; （C）的0.0663克2-氨基二苯甲酮的，0.0767克硫脲的混合物中，0.5毫升DMSO和5.0毫升DMF中加热之前被施加的;在160ºC加热在微波辐射下6小时后（D）的（C）中的溶液; （E）（C）中，溶液在160ºC加热在微波辐射下18小时后， <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53662/53662fig10large.jpg" target="_blank">请点击此处查看该图的放大版本。</a>

取代的喹唑啉，为一种独特类型的杂环的，已被公知用于多种生物活性，包括除其他抗生素，1抗抑郁，2-抗炎，3,4-抗高血压，3抗疟药，5和抗肿瘤，6 。更重要的是，4-取代的喹唑啉，例如，4-芳基喹唑啉，用抗疟原虫活性7已被确认为表皮生长因子受体（EGFR）酪氨酸激酶抑制剂，8中枢神经系统抑制剂，9和对耐甲氧西林金黄色葡萄球菌抗生素金黄色葡萄球菌和由于它的生物活性广谱的抗万古霉素肠球菌 。10，为取代的喹唑啉的合成方法已经在很大程度上探索。作为一个例子，25个以上的合成方法已被报道用于4- phenylquinazolines制备11代表余丹丹方法包括4- phenylquinazolines由2- aminobenzophenones在三氟化硼醚合物的存在下形成和甲酰胺（BF 3·Et 2 O等）12或甲酸，13或从2- aminobenzophenones与乌洛托品和溴乙酸乙酯反应， 14，或在氧化剂的存在下的醛和乙酸铵进行反应。15 使用湿度敏感的试剂，上述反应不同（例如，BF 3·Et 2 O等）或昂贵的试剂（ 如 ，乌洛托品和溴乙酸乙酯），一个浅显的方法，可以很容易地转换2 aminobenzophenones成二甲基亚砜相应的4-phenylquinazolines（ DMSO）中的硫脲的存在下已探索。关于该反应中广泛机理研究表明它是一个互补的反应，其中的硫脲发生热分解，以形成碳化二亚胺和硫化氢，其中碳二亚胺与2-氨基二苯甲酮反应，形成4- phenylquinazolin -2（1H） - 亚胺中间体，同时使用的DMSO不仅作为溶剂，而且还产生了试剂还原试剂，当它与氢反应含硫硫醚（也由硫脲产生的）。然后，将含硫还原剂减少4- phenylquinazolin -2（1H） - 亚胺中间体，以形成4-苯基-1,2-二氢喹唑啉-2-胺该经过消除氨以形成4-苯基喹唑啉。此反应通常在温度从135-160℃下进行，并且可以通过上热板或在微波辐射下的传统油浴中加热的方法容易地进行。该反应在下面的图1大致示出。 <img alt="图1" src="/files/ftp_upload/53662/53662fig1.jpg" /> 图1:2-氨基二苯甲酮和之间的一般反应硫脲在DMSO。 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53662/53662fig1large.jpg" target="_blank">请点击此处查看该图的放大版本。</a>

<table border="0" cellpadding="0" cellspacing="0" width="811">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">2-Aminobenzophenone</td>
			<td style="width:95px;">Alfa Aesar</td>
			<td style="width:105px;">A12580</td>
			<td style="width:395px;">98% purity, with tiny impurity as seen on Figure 1(A) in the manuscript.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Thiourea</td>
			<td style="width:95px;">Acros</td>
			<td style="width:105px;">138910010</td>
			<td>1 KG package, 99%, extra pure</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Dimethyl Sulfoxide</td>
			<td style="width:95px;">Acros</td>
			<td style="width:105px;">326880010</td>
			<td>Methyl sulfoxide, 99.7+%, Extra Dry, AcroSeal&#174;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">N,N-Dimethylformamide</td>
			<td style="width:95px;">Acros</td>
			<td style="width:105px;">348430010</td>
			<td>N,N-Dimethylformamide, 99.8%, Extra Dry over Molecular Sieve, AcroSeal&#174;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Ethyl Acetate</td>
			<td style="width:95px;">Acros</td>
			<td style="width:105px;">610170040</td>
			<td>Ethyl acetate, used as solvent for GC/MS analysis</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Preparative TLC plate</td>
			<td style="width:95px;">Sigma-Aldrich</td>
			<td style="width:105px;">Z740216 SIGMA</td>
			<td>PTLC (Preparative TLC) Glass Plates from EMD/Merck KGaA</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Rotavapor</td>
			<td style="width:95px;">Buchi</td>
			<td style="width:105px;">Rotavapor R-205</td>
			<td>Use to dry solvent</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Microwave Reactor</td>
			<td style="width:95px;">Biotage</td>
			<td style="width:105px;">Initiator+</td>
			<td>Use to carry out chemical reaction under microwave irradiation</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Hotplate</td>
			<td style="width:95px;">IKA</td>
			<td style="width:105px;">RCT basic</td>
			<td>use to carry out thermal chemical reaction</td>
		</tr>
	</tbody>
</table>

facile preparation of 4-substituted quinazoline derivatives

本文报道，是从在二甲基亚砜（DMSO）的存在下取代的2- aminobenzophenones和硫脲的反应直接制备4-取代的喹唑啉衍生物的一个非常简单的方法。这是一种独特的互补反应系统，其中的硫脲发生热分解而形成的碳二亚胺和硫化氢，其中用2-氨基二苯甲酮前者反应形成4- phenylquinazolin -2（1H） - 亚胺中间体，而硫化氢用DMSO反应，得到甲硫醇或其它含硫分子，其然后用作补充还原剂减少4- phenylquinazolin -2（1H） - 亚胺中间体入4-苯基-1,2-二氢喹唑啉-2-胺。接着，氨从4-苯基-1,2-二氢喹唑啉-2-胺的消除，得到取代的喹唑啉衍生物。该反应通常给出喹唑自2-氨基二苯甲酮所产生的单品衍生物的GC / MS所监测分析，含硫分子例如二甲基二硫化物，二甲基三硫化物等 。反应通常完成在160ºC在小规模4-6小时，但是当在大规模进行的可能持续超过24小时的少量的沿。该反应产物可容易地通过洗涤的方式以水，接着用柱色谱法或薄层色谱法关闭DMSO中。

在反应前反应混合物的GC分析，在微波辐射下反应后5小时，并在150℃微波辐射下反应后10小时在图2中，它清楚地说明了这种整齐反应的过程中提出的。 2-氨基二苯酮和4-苯基喹唑啉的质谱示于图3和图4分别给出。对于与有机化学良好的知识的人可以在图5假定如图2所示氨基二苯甲酮和硫脲之间的反应的表观机制。相比之下，在160ºC上热板在DMSO中反应类似的GC / MS追踪所示在图6中，沿与4- phenylquinazolin -2（1H） -酮副产物的质谱。根据许多实验事实，为4苯基喹唑啉的生成一个完整的解释是所示<strong&gt;图7。二甲基二硫化物（MeSSMe）和二甲基三硫（MeSSSMe）的质谱分别示于图 8和图 9。在DMF中，并在DMF但用DMSO少量2-氨基二苯甲酮和硫脲之间的反应的比较在图10中示出。 上GC / MS分析的基础上，这是很清楚的是原料转化为产品的转化率几乎是定量的（ 图2）。由于起始材料之间的分子量的差异小（例如，2-氨基二苯甲酮，MW = 197，保留时间= 9.673分钟）和取代的喹唑啉衍生物的产物（例如，4-苯基喹唑啉，MW = 206，保留时间= 9.962分），在气相原料和产物的保留时间非常相似，但仍可分离。有超过10个不同的2 aminobenzophenones有蜜蜂Ñ ​​测试用于此反应，并得到类似的结果。16

Watch this Scientific Journal Video about Facile Preparation of 4-Substituted Quinazoline Derivatives at JoVE.com

Facile Preparation of 4-Substituted Quinazoline Derivatives

A protocol for facile preparation of 4-substituted quinazoline derivatives from 2-aminobenzophenones, thiourea and dimethyl sulfoxide is presented.

的4-取代喹唑啉衍生物简便制备

Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted ...

facile-preparation-of-4-substituted-quinazoline-derivatives

Nanyang Technological University

Research

JoVE Journal

Chemistry

11.8K 次观看.  University of Houston-Clear Lake. A protocol for facile preparation of 4-substituted quinazoline derivatives from 2-aminobenzophenones, thiourea and dimethyl sulfoxide is presented.

视频: Facile Preparation of 4-Substituted Quinazoline Derivatives

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order to streamline synthesis by saving steps, time and material compared to conventional methods that require the introduction and removal of activating or directing groups. Therefore, the functionalization of C-H bonds is also attractive for green chemistry. Under oxidative conditions, two C-H bonds or one C-H and one heteroatom-H bond can be transformed to C-C and C-heteroatom bonds, respectively. Often these oxidative coupling reactions require synthetic oxidants, expensive catalysts or high temperatures. Here, we describe a two-step procedure to functionalize indole derivatives, more specifically tetrahydrocarbazoles, by C-H amination using only elemental oxygen as oxidant. The reaction uses the principle of C-H functionalization via Intermediate PeroxideS (CHIPS). In the first step, a hydroperoxide is generated oxidatively using visible light, a photosensitizer and elemental oxygen. In the second step, the N-nucleophile, an aniline, is introduced by Br&#248;nsted-acid catalyzed activation of the hydroperoxide leaving group. The products of the first and second step often precipitate and can be conveniently filtered off. The synthesis of a biologically active compound is shown.

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

A two-step procedure for the synthesis of pharmaceutically active indole-derivatives by C-H functionalization with anilines is described, using photo- and Br&#248;nsted acid catalysis.

通过中级过氧化物的抗病毒四氢咔唑衍生物的合成光化学和酸催化CH官能（筹）

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order ...

科研

化学

Facile and Efficient Preparation of Tri-component Fluorescent Glycopolymers via RAFT-controlled Polymerization

Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and efficient synthesis of well-controlled fluorescent statistical glycopolymers using reversible addition-fragmentation chain-transfer (RAFT)-based polymerization is demonstrated. The synthesis starts with the preparation of &#946;-galactose-containing glycomonomer 2-lactobionamidoethyl methacrylamide obtained by reaction of lactobionolactone and N-(2-aminoethyl) methacrylamide (AEMA). 2-Gluconamidoethyl methacrylamide (GAEMA) is used as a structural analog lacking a terminal &#946;-galactoside. The following RAFT-mediated copolymerization reaction involves three different monomers: N-(2-hydroxyethyl) acrylamide as spacer, AEMA as target for further fluorescence labeling, and the glycomonomers. Tolerant of aqueous systems, the RAFT agent used in the reaction is (4-cyanopentanoic acid)-4-dithiobenzoate. Low dispersities (&#8804;1.32), predictable copolymer compositions, and high reproducibility of the polymerizations were observed among the products. Fluorescent polymers are obtained by modifying the glycopolymers with carboxyfluorescein succinimidyl ester targeting the primary amine functional groups on AEMA. Lectin-binding specificities of the resulting glycopolymers are verified by testing with corresponding agarose beads coated with specific glycoepitope recognizing lectins. Because of the ease of the synthesis, the tight control of the product compositions and the good reproducibility of the reaction, this protocol can be translated towards preparation of other RAFT-based glycopolymers with specific structures and compositions, as desired.

An efficient, three-step synthesis of RAFT-based fluorescent glycopolymers, consisting of glycomonomer preparation, copolymerization, and post-modification, is demonstrated. This protocol can be used to prepare RAFT-based statistical glycopolymers with desired structures.

通过RAFT控制聚合轻便和高效制备三组分荧光Glycopolymers

Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and ...

Facile Preparation of Internally Self-assembled Lipid Particles Stabilized by Carbon Nanotubes

We present a facile method to prepare nanostructured lipid particles stabilized by carbon nanotubes (CNTs). Single-walled (pristine) and multi-walled (functionalized) CNTs are used as stabilizers to produce Pickering type oil-in-water (O/W) emulsions. Lipids namely, Dimodan U and Phytantriol are used as emulsifiers, which in excess water self-assemble into the bicontinuous cubic Pn3m phase. This highly viscous phase is fragmented into smaller particles using a probe ultrasonicator in presence of conventional surfactant stabilizers or CNTs as done here. Initially, the CNTs (powder form) are dispersed in water followed by further ultrasonication with the molten lipid to form the final emulsion. During this process the CNTs get coated with lipid molecules, which in turn are presumed to surround the lipid droplets to form a particulate emulsion that is stable for months. The average size of CNT-stabilized nanostructured lipid particles is in the submicron range, which compares well with the particles stabilized using conventional surfactants. Small angle X-ray scattering data confirms the retention of the original Pn3m cubic phase in the CNT-stabilized lipid dispersions as compared to the pure lipid phase (bulk state). Blue shift and lowering of the intensities in characteristic G and G&#39; bands of CNTs observed in Raman spectroscopy characterize the interaction between CNT surface and lipid molecules. These results suggest that the interactions between the CNTs and lipids are responsible for their mutual stabilization in aqueous solutions. As the concentrations of CNTs employed for stabilization are very low and lipid molecules are able to functionalize the CNTs, the toxicity of CNTs is expected to be insignificant while their biocompatibility is greatly enhanced. Hence the present approach finds a great potential in various biomedical applications, for instance, for developing hybrid nanocarrier systems for the delivery of multiple functional molecules as in combination therapy or polytherapy.

We report on a smart application of carbon nanotubes for kinetic stabilization of lipid particles that contain self-assembled nanostructures in their cores. The preparation of lipid particles requires rather low concentrations of carbon nanotubes permitting their use in biomedical applications such as drug delivery.

内部自组装脂质颗粒的简易制备碳纳米管稳定

We present a facile method to prepare nanostructured lipid particles stabilized by carbon nanotubes (CNTs). Single-walled (pristine) and multi-walled ...

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of trifluoromethoxylated aromatic compounds remains a formidable challenge in organic synthesis. Conventional approaches often suffer from poor substrate scope, or require use of highly toxic, difficult-to-handle, and/or thermally labile reagents. Herein, we report a user-friendly protocol for the synthesis of methyl 4-acetamido-3-(trifluoromethoxy)benzoate using 1-trifluoromethyl-1,2-benziodoxol-3(1H)-one (Togni reagent II). Treating methyl 4-(N-hydroxyacetamido)benzoate (1a) with Togni reagent II in the presence of a catalytic amount of cesium carbonate (Cs2CO3) in chloroform at RT afforded methyl 4-(N-(trifluoromethoxy)acetamido)benzoate (2a). This intermediate was then converted to the final product methyl 4-acetamido-3-(trifluoromethoxy)benzoate (3a) in nitromethane at 120 &#176;C. This procedure is general and can be applied to the synthesis of a broad spectrum of ortho-trifluoromethoxylated aniline derivatives, which could serve as useful synthetic building blocks for the discovery and development of new pharmaceuticals, agrochemicals, and functional materials.

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

An operationally simple procedure for the synthesis of ortho-trifluoromethoxylated aniline derivatives via a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxyacetamide followed by thermally induced intramolecular OCF3-migration is reported.

协议的合成<em&gt;邻</em&gt; -trifluoromethoxylated苯胺类化合物

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of ...

Preparation of Biopolymer Aerogels Using Green Solvents

Although the first reports on aerogels made by Kistler1 in the 1930s dealt with aerogels from both inorganic oxides (silica and others) and biopolymers (gelatin, agar, cellulose), only recently have biomasses been recognized as an abundant source of chemically diverse macromolecules for functional aerogel materials. Biopolymer aerogels (pectin, alginate, chitosan, cellulose, etc.) exhibit both specific inheritable functions of starting biopolymers and distinctive features of aerogels (80-99% porosity and specific surface up to 800 m2/g). This synergy of properties makes biopolymer aerogels promising candidates for a wide gamut of applications such as thermal insulation, tissue engineering and regenerative medicine, drug delivery systems, functional foods, catalysts, adsorbents and sensors. This work demonstrates the use of pressurized carbon dioxide (5 MPa) for the ionic cross linking of amidated pectin into hydrogels. Initially a biopolymer/salt dispersion is prepared in water. Under pressurized CO2 conditions, the pH of the biopolymer solution is lowered to 3 which releases the crosslinking cations from the salt to bind with the biopolymer yielding hydrogels. Solvent exchange to ethanol and further supercritical CO2 drying (10 - 12 MPa) yield aerogels. Obtained aerogels are ultra-porous with low density (as low as 0.02 g/cm3), high specific surface area (350 - 500 m2/g) and pore volume (3 - 7 cm3/g for pore sizes less than 150 nm).

A new way for the production of biopolymer-based aerogels by carbon dioxide (CO2) induced gelation is shown. The technique utilizes pressurized carbon dioxide (5 MPa) for the production of biopolymer hydrogels and supercritical CO2 (12 MPa) to convert gels into aerogels. The only solvents needed besides CO2 are water and ethanol.

生物聚合物气凝胶制备使用绿色溶剂

Although the first reports on aerogels made by Kistler1 in the 1930s dealt with aerogels from both inorganic oxides (silica and others) and biopolymers ...

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

使用Photoredox催化剂蠕虫状胶束的简便合成可见光介导的分散聚合

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

A facile method for the preparation of polycarbodiimide-based secondary structures (e.g., nano-rings, &#34;craters,&#34; fibers, looped fibers, fibrous networks, ribbons, worm-like aggregates, toroidal structures, and spherical particles) is described. These aggregates are morphologically influenced by extensive hydrophobic side chain-side chain interactions of the singular polycarbodiimide strands, as inferred by atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques. Polycarbodiimide-g-polystyrene copolymers (PS-PCDs) were prepared by a combination of synthetic methods, including coordination-insertion polymerization, copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) &#34;click&#34; chemistry, and atom transfer radical polymerization (ATRP). PS-PCDs were found to form specific toroidal architectures at low concentrations in CHCl3. To determine the influence of a more polar solvent medium (i.e., THF and THF/EtOH) on polymer aggregation behavior, a number of representative PS-PCD composites have been tested to show discrete concentration-dependent spherical particles. These fundamental studies are of practical interest to the development of experimental procedures for desirable architectures by directed self-assembly in thin film. These architectures may be exploited as drug carriers, whereas other morphological findings represent certain interest in the area of novel functional materials.

Here, we present a protocol to prepare and visualize secondary structures (e.g., fibers, toroidal architectures, and nano-spheres) derived from helical polycarbodiimides. The morphology characterized by both atomic force microscopy (AFM) and scanning electron microscopy (SEM) was shown to depend on molecular structure, concentration, and the solvent of choice.

从螺旋聚碳化二亚胺共聚物及其三唑衍生物获得自组装形貌

A facile method for the preparation of polycarbodiimide-based secondary structures (e.g., nano-rings, &#34;craters,&#34; fibers, looped fibers, fibrous ...

Facile Preparation of Ultrafine Aluminum Hydroxide Particles with or without Mesoporous MCM-41 in Ambient Environments

An aqueous suspension of nanogibbsite was synthesized via the titration of aluminum aqua acid [Al(H2O)6]3+ with L-arginine to pH 4.6. Since the hydrolysis of aqueous aluminum salts is known to produce a wide array of products with a wide range of size distributions, a variety of state-of-the-art instruments (i.e., 27Al/1H NMR, FTIR, ICP-OES, TEM-EDX, XPS, XRD, and BET) were used to characterize the synthesis products and identification of byproducts. The product, which was comprised of nanoparticles (10-30 nm), was isolated using gel permeation chromatography (GPC) column technique. Fourier transform infrared (FTIR) spectroscopy and powder X-ray diffraction (PXRD) identified the purified material as the gibbsite polymorph of aluminum hydroxide. The addition of inorganic salts (e.g., NaCl) induced electrostatic destabilization of the suspension, thereby agglomerating the nanoparticles to yield Al(OH)3 precipitate with large particle sizes. By utilizing the novel synthetic method described here, Al(OH)3 was partially loaded inside the highly ordered mesoporous framework of MCM-41, with average pore dimensions of 2.7 nm, producing an aluminosilicate material with both octahedral and tetrahedral Al (Oh/Td = 1.4). The total Al content, measured using energy-dispersive X-ray spectrometry (EDX), was 11% w/w with a Si/Al molar ratio of 2.9. A comparison of bulk EDX with surface X-ray photoelectron spectroscopy (XPS) elemental analysis provided insight into the distribution of Al within the aluminosilicate material. Furthermore, a higher ratio of Si/Al was observed on the external surface (3.6) as compared to the bulk (2.9). Approximations of O/Al ratios suggest a higher concentration of Al(O)3 and Al(O)4 groups near the core and external surface, respectively. The newly developed synthesis of Al-MCM-41 yields a relatively high Al content while maintaining the integrity of the ordered silica framework and can be used for applications where hydrated or anhydrous Al2O3 nanoparticles are advantageous.

An ultrafine aluminum hydroxide nanoparticle suspension was prepared via the controlled titration of [Al(H2O)]3+ with L-arginine to pH 4.6 with and without cage-effect confinement within mesoporous channels of MCM-41.

在环境环境中制备具有或不具有介孔MCM-41的超细氢氧化铝颗粒

An aqueous suspension of nanogibbsite was synthesized via the titration of aluminum aqua acid [Al(H2O)6]3+ with L-arginine to pH 4.6. Since the hydrolysis ...

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Direct cross-coupling between two alkenes via vinylic C-H bond activation represents an efficient strategy for the synthesis of butadienes with high atomic and step economy. However, this functionality-directed cross-coupling reaction has not been developed, as there are still limited directing groups in practical use. In particular, a stoichiometric amount of oxidant is usually required, producing a large amount of waste. Due to our interest in novel 1,3-butadiene synthesis, we describe the ruthenium-catalyzed olefination of electron-deficient alkenes using allyl acetate and without external oxidant. The reaction of 2-phenyl acrylamide and allyl acetate was chosen as a model reaction, and the desired diene product was obtained in 80% isolated yield with good stereoselectivity (Z,E/Z,Z = 88:12) under optimal conditions: [Ru(p-cymene) Cl2]2 (3 mol %) and AgSbF6 (20 mol %) in DCE at 110 &#186;C for 16 h. With the optimized catalytic conditions in hand, representative &#945;- and/or &#946;-substituted acrylamides were investigated, and all reacted smoothly, regardless of aliphatic or aromatic groups. Also, differently N-substituted acrylamides have proven to be good substrates. Moreover, we examined the reactivity of different allyl derivatives, suggesting that the chelation of acetate oxygen to the metal is crucial for the catalytic process. Deuterium-labeled experiments were also conducted to investigate the reaction mechanism. Only Z-selective H/D exchanges on acrylamide were observed, indicating a reversible cyclometalation event. In addition, a kinetic isotope effect (KIE) of 3.2 was observed in the intermolecular isotopic study, suggesting that the olefinic C-H metalation step is probably involved in the rate-determining step.

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

The ruthenium-catalyzed olefination of electron-deficient alkenes with allyl acetate is described here. By using aminocarbonyl as a directing group, this external oxidant-free protocol has high efficiency and good stereo- and regioselectivity, opening a novel synthetic route to (Z,E)-butadiene skeletons.

（2<em&gt;ž</em&gt;，4<em&gt;电子</em&gt;） - 通过电子缺陷烯烃与烯丙基乙酸酯的烯化反应制备二烯酰胺

Direct cross-coupling between two alkenes via vinylic C-H bond activation represents an efficient strategy for the synthesis of butadienes with high ...

Preparation and Characterization of C60/Graphene Hybrid Nanostructures

Physical thermal deposition in a high vacuum environment is a clean and controllable method for fabricating novel molecular nanostructures on graphene. We present methods for depositing and passively manipulating C60 molecules on rippled graphene that advance the pursuit of realizing applications involving 1D C60/graphene hybrid structures. The techniques applied in this exposition are geared towards high vacuum systems with preparation areas capable of supporting molecular deposition as well as thermal annealing of the samples. We focus on C60 deposition at low pressure using a homemade Knudsen cell connected to a scanning tunneling microscopy (STM) system. The number of molecules deposited is regulated by controlling the temperature of the Knudsen cell and the deposition time. One-dimensional (1D) C60 chain structures with widths of two to three molecules can be prepared via tuning of the experimental conditions. The surface mobility of the C60 molecules increases with annealing temperature allowing them to move within the periodic potential of the rippled graphene. Using this mechanism, it is possible to control the transition of 1D C60 chain structures to a hexagonal close packed quasi-1D stripe structure.

Preparation and Characterization of C60/Graphene Hybrid Nanostructures

Here we present a protocol for the fabrication of C60/graphene hybrid nanostructures by physical thermal evaporation. Particularly, the proper manipulation of deposition and annealing conditions allow the control over the creation of 1D and quasi 1D C60 structures on rippled graphene.

C 型60/石墨烯混合纳米结构的制备与表征

Physical thermal deposition in a high vacuum environment is a clean and controllable method for fabricating novel molecular nanostructures on graphene. We ...