我们要感谢康宁玻璃流反应器的礼物。

健康警告和试剂规格 
二苯甲酮腙: 可能引起消化道发炎。该物质的毒理学性质尚未得到充分研究。可能引起呼吸道刺激。该物质的毒理学性质尚未得到充分研究。可能引起皮肤刺激和眼部刺激 18 . 
 活性氧化锰 (MnO 2 ): (健康 MSDS 等级为 2) 在皮肤接触, 眼睛接触, 摄入和吸入的情况下有危险 19 。
 二元磷酸钾 (2) PO 4 ): (健康 MSDS 评级为 2) 在皮肤接触, 眼睛接触, 摄入和吸入的情况下危险的 20 。
 二氯甲烷: (健康 MSDS 额定值为 2, 火等级为 1) 非常危险的情况下, 眼睛接触 (刺激性), 摄入, 吸入。皮肤接触时有危险 (刺激性, permeator)。眼睛发炎的特点是发红, 浇水, 发痒 21 . 
 1. Diphenyldiazomethane 的合成: <ol> <li> 在开始综合之前, 请确保所列的所有必需材料以及必要的试剂, 以确保能够进行适当的合成. </li>
	<li> 添加10克 (72 当量) 无水的, 2 PO 4 和31克活化二氧化锰, MnO 2 (3.5 当量) 到250毫升3颈圆底烧瓶 (1), 和磁力搅拌器. </li>
	<li> 将20克苯甲酮腙添加到单独的100毫升2颈圆底烧瓶 (2), 磁力搅拌器, 室温下贮存. </li>
	<li> 添加67毫升的二氯甲烷 (DCM), 并装备两个烧瓶 (1 和 2) 与塞子, 温度计, 和热电偶. </li>
	<li> 将两个烧瓶与惰性气体一起清除15分钟后, 将冰浴应用于 2 PO 4 和 MnO 2 解决方案 (烧瓶 1)。确保解决方案的温度在0和 #176 时保持不变; C 至少 30 min. </li>
	<li> 在30分钟的恒温读数后, 将二苯甲酮腙 (烧瓶 2) 转到包含 "2" PO 4 和 MnO 2 (烧瓶 1) 的烧瓶中。进行24小时的反应, 以达到完成. </li>
</ol> 2。纯化: <ol> <li> 在24小时后, 在反应混合物中加入120毫升戊烷 (深红色紫色溶液). </li>
	<li> 通过中性硅胶 (50-200 和 #181; m) 快速过滤解决方案。重要的是, 该产品的接触时间与二氧化硅做 不 超过5分钟, 是酸敏感的;在更长的接触时间 22 下会发生严重的分解. 
	<ol> <li> 在真空过滤系统或油烟罩真空系统上安装中孔烧结玻璃漏斗进行过滤. </li>
	</ol> </li> <li> 在真空 中将滤液和旋转蒸发器的溶剂移除。由此产生的原油产品是一种 deep-purple 的石油. 
	<ol> <li> 在烧瓶周围用铝箔包住, 以避免光线脱离。是光敏感的. </li>
	</ol> </li> <li> 在用铝箔盖好烧瓶后, 在冷冻库中储存纯净的气体, 密封, 并在惰性气体的气氛下. </li>
	<li> 显示器进行结晶, 通常需要 2-3 天。从冰箱取出烧瓶, 使其达到室温。一个进一步纯化步是必要的。在烧瓶中加入200的乙醇, 过滤然后用旋转蒸发器除去剩余的溶剂。此时, 剩余的大部分杂质应该被去除. 
	<ol> <li> 通过紫外光谱分析产生的深红色紫色晶体。实验测定的摩尔吸收率是 (和 #949;) 94.8, 与文献值匹配. 
		警告: 下面是相关的健康警告和试剂的规格, 以正确和安全地处理执行的反应协议的管理。在处理这些物质时, 要确保在任何时候都有适当的 PPE 和通风罩下的工作环境. 
		 : 长期或重复暴露可能会导致某些敏感个体的过敏反应 23 . 
		 p -硝基苯甲酸: (MSDS 的健康等级为 2) 确保试剂远离热量。远离火源。空集装箱造成火灾风险;将残留物蒸发在通风罩下。研磨所有含有材料的设备。如果摄入, 立即寻求医疗建议, 并显示容器或标签。避免与皮肤和眼睛接触 24 . 
		乙醇, 200 证明: (MSDS 健康等级为 2, 健康等级为 3) 在皮肤接触, 眼睛接触和吸入的情况下危险。乙醇能迅速吸收空气中的水分, 并能与氧化剂 25 强烈反应. 
		甲苯: (MSDS 健康等级为 2, 健康等级为 3) 在皮肤接触 (刺激性), 眼睛接触 (刺激性), 摄入和吸入的情况下危险。皮肤接触时有轻微危险 (permeator)。高度易燃的 26 . 
		 o -二甲苯: (MSDS 的健康等级为 2, 健康等级为 3) 发育致畸作用的可能性, 对雄性生殖系统的发育毒性, 以及摄入肾脏、肝脏、上呼吸道、皮肤、眼睛和中央的毒性神经系统。远离皮肤接触 (刺激性, permeator), 眼睛接触 (刺激性), 或 #160; 摄入和 #160; 吸入 27 . </li>
	</ol> </li> </ol> 3。为连续流准备解决方案: <ol> <li> 用乙醇冲洗100毫升的容积烧瓶. </li>
	<li> 将6个 dram 小瓶放在分析天平上, 并将1942克的内存添加到 dram 瓶中。将无水乙醇 (5 毫升) 添加到小瓶中, 在2到3的增量中, 直到所有的方法都进入解决方案。用吸管将溶液从 6 dram 小瓶转移到清洁的100毫升容积烧瓶中. 
	<ol> <li> 小心地添加乙醇, 直到半月板的最小点与容量烧瓶中的线对齐. </li>
		<li> 加入1毫升的甲苯, 内部标准, 进入烧瓶。容积烧瓶现在可以封顶和储存, 直到两个解决方案和 p 硝基苯甲酸溶液都准备好连续流动反应. </li>
	</ol> </li> </ol> 4。 p 硝基苯甲酸 0.1 M 库存溶液的制备: <ol> <li> 用无水乙醇多次冲洗250毫升容积烧瓶. </li>
	<li> 在分析天平上包装一个 6 dram 小瓶。在 dram 瓶中加入4.1780 克的 p 硝基苯甲酸。加入酸后, 将无水乙醇 (5 毫升) 添加到2至3的小瓶中, 直到所有的 p 硝基苯甲酸进入溶液. 
	<ol> <li> 用吸管将溶液从 6 dram 小瓶转移到清洁的250毫升容积烧瓶中. </li>
		<li> 小心地添加乙醇直到半月板的最小点与容积烧瓶的线对齐. </li>
		<li> 添加1毫升 o -二甲苯, 内部标准, 进入 fl问.容积烧瓶现在可以根据需要进行封顶和储存. </li>
	</ol> </li> </ol> 5。连续流反应器的制备: <ol> <li> 检查传感器是否连接到门户 A 中的 ISCOs 的泵控制器, 以及每个出口管末端的空收集烧杯, 以收集反应解决方案、废料和溶剂. 
	<ol> <li> 设置并检查分类 1 ( p -硝基苯甲酸) 和分类 2 (数据), 如 图 9 所示. </li>
		<li> 设置每个分类泵与自己的控制器, 以独立控制试剂流。这样就可以根据需要独立调整流量. </li>
	</ol> </li> <li> 在单独的烧杯中, 添加400毫升的乙醇。这将被用来冲洗反应堆. 
	<ol> <li> 逆时针旋转入口阀, 直到阀门完全打开 (分别表示为阀 A 和 B)。压力机和 #34; 泵控制器上的恒流和 #34; 然后, #34; A 和 #34;, 表示传感器与分类连接的入口。此操作会提示用户输入所需的流率. </li>
		<li> 输入 #34 的流量; 70 和 #34;, 按下 #34; 输入和 #34;。当准备, 命中和 #34; 填充和 #34; 要与系统通信以70毫升/分钟的速度绘制解决方案. </li>
		<li> 开始通过入口管绘制乙醇溶剂。请注意, 如果流速是在绘制溶剂, ISCOs 的流速应改为-70.000 毫升/分钟。烧瓶中的溶剂水平将开始下降. 
		#8203; 注意: 如果溶剂的体积与控制器上显示的体积不符, 这是完全正常的。空气也会部分地被纳入到系统中. </li>
	</ol> </li> <li> 当分类1和分类2都已完全填满, 并且控制器通过读取和 #34 指示此项时; 已停止和 #34; #34; 停住; 关闭阀门 A 和 B 完全关闭, 完全顺时针转动阀. </li>
	<li> 打开阀门, 其操作方式类似于进气阀, 即通向反应堆的阀门, 通过逆时针旋转。出口阀通过过滤器, 通过 one-way 阀, 并从那里过去的压力释放阀和进入流反应器. </li>
	<li> 此时, 更改流率。在单个运行中建议的最大总流量不应超过30毫升/分钟. 
	<ol> <li> 分别清除每个分类, 以30毫升/分钟的流速运行每一个. </li>
	</ol> </li> <li> 按下和 #34; A 和 #34; 在当前设置为通过系统运行乙醇的分类上。通过输入所需的流量和 #34 来改变流速; 30 和 #34; #34; 进入 #34;, 最后, #34; 奔跑和 #34;。这与系统通信以30毫升/分钟的速率运行. 
	#8203; 注意: 当流动均衡, 溶剂开始流经系统。
	<ol> <li> 监视反应器中的泄漏或堵塞, 并在整个反应器中流动有溶剂。一旦两个 ISCOs 都被清理 2-3 次, 系统现在已经准备好运行这个实验. </li>
	</ol> </li> </ol> 6。设置. 01 M 分类2泵: <ol> <li> 将入口进给100毫升容积烧瓶中。打开进气阀 B (在 图 9 中为 2). </li>
	<li> 将分类设置为70毫升/分钟的流速. 开始绘制解决方案, 直到所有的它被拿起到注射器通过打击和 #34; 灌装和 #34;. </li>
	<li> 注意, 分类中的溶液体积和烧瓶中溶液的原始体积可能稍有不同。空气也被拉进了分类泵. 
	<ol> <li> 如果有剩余的分类, 则在解决方案的摄取量达到最大容量后, 按下 #34; 运行和 #34; 从入口向外推进与烧瓶一起绘制的空气。一旦开始推开, 打击和 #34; 停止和 #34; 然后, #34; 填充和 #34; 开始重新灌装分类. </li>
		<li> 继续重复这些步骤, 直到所有的占用都已占了 (这将被应用到 p 硝基苯甲酸以及). </li>
		<li> 流量约1毫升从泵。分类2泵已准备好运行。溶剂水平是在线的, 并准备开始流经连续流反应器. </li>
	</ol> </li> <li> 关闭入口阀 B, 将髋部阀门顺时针旋转, 直到它不能进一步转动, 然后打开向连续流反应器注入的出口阀, 将阀门逆时针旋转, 直到完全打开。将1毫升的试管和甲苯溶液转化为紫外-可见光分析. </li>
	<li> 将流率设置为1.42 毫升/分钟。不要攻击和 #34; 运行和 #34; 直到 p 硝基苯甲酸分类1已由同一协议设置为3.58 毫升/分钟的流速, 并准备串联运行. </li>
</ol> 7。设置. 1 M p 硝基苯甲酸分类1泵: <ol> <li> 打开分类1泵的入口阀 A, 在进料管的末端有250毫升的 p-硝基苯甲酸的容积烧瓶. 
	<li> 一旦进料管完全浸入容积式烧瓶中, 则将分类设置为70毫升/分钟的流量。再次, 检查控制器上的流量是否在命中和 #34 时读取70.00 毫升/分钟; 重新填充和 #34;. </li>
	<li> 开始绘制解决方案, 直到所有的问题都被注入到注射器中, 然后使用上面列出的相同技术将所有解决方案放入系统中. </li>
	<li> 按顺时针方向关闭入口阀, 直到完全闭合。打开向连续流反应器注入的出口阀门, 将阀门逆时针旋转直到完全打开. </li>
	<li> 将流率设置为3.58 毫升/分钟。总的流量, 包括1.42 毫升/分钟的计算将是5.00 毫升/分钟, 在一个总停留时间在反应器内大约11分钟, 与 10:1 p 硝基苯甲酸的比率. </li>
</ol> 8。用10:1 摩尔当量的 p -硝基苯甲酸和流量来传导反应: <ol> <li> 一旦每个泵都准备好试剂和 #39; s 溶液, 阀门适当地调整, 并且正确的流速被输入了, 命中#34; 在两个水泵上运行和 #34;one-way 阀压力平衡后, 试剂和 #39 的解决方案将开始流入反应堆模块. 
	<ol> <li> 监视流。在模块 1, p -硝基苯甲酸和 #39 的进料进入模块 2, 混合发生在模块3。居住时间大约是11分钟. </li>
		<li> 监视颜色更改 (指示反应进度)。模块2的颜色, 在混合之前, 是强的粉红色。颜色强度降低, 它变得暗淡粉红色在模块3和苍白粉红色的模块4。模块尔后是无色的. </li>
	</ol> </li> </ol> 9。清洗连续流反应器: <ol> <li> 一旦两个运行的管理和 p 硝基苯甲酸完成, 填补一个烧杯与400毫升乙醇。这将用于清洁反应堆和分类泵. </li>
	<li> 逆时针旋转入口阀, 直到阀门完全打开. </li>
	<li> 将流率设置为 70, 按和 #34; 输入和 #34; #34; 填充和 #34; 通过进气管开始绘制乙醇溶剂 (注意, 如果流速是在吸入溶剂, ISCOs 的流速应为70毫升/分). </li>
	<li> 一旦填充了 ISCOs, ISCOs 将自动停止, 控制器将读取和 #34; 汽缸满 #34; #34; 停止 #34;。在这一点上, 关闭阀门完全关闭, 旋转阀顺时针, 直到髋部阀门不能进一步转向. </li>
	<li> 打开与进口阀门相似的出口阀门, 将其逆时针旋转。出口阀通过过滤器, 通过 one-way 阀, 并从那里流过压力释放阀和进入流动反应器. </li>
	<li> 调整流量不超过30毫升/分钟. </li>
	<li> 按 #34; #34; 在当前设置为通过系统运行乙醇的分类上。通过输入所需的流量和 #34 来更改流速; 10 和 #34; 命中和 #34; 输入和 #34;, 然后命中和 #34; 运行和 #34;检查系统, 看有没有泄漏或堵塞, 并有溶剂流经整个系统. 
	注: 一旦两个 ISCOs 已被清洗2次与乙醇, 一旦与公正的空气遵循上述步骤, 系统现在已经准备好运行, 为未来的实验. </li>
</ol>

<ol>
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Definition and contributions to the Imidazide/Tetrazole tautomerism.</a> Chem. Ber. 103, 1900 (1970).</li><li>Baumann, M., Garcia, A. M. R., Baxendale, I. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Flow+synthesis+of+ethyl+isocyanoacetate+enabling+the+telescoped+synthesis+of+1,2,4-triazoles+and+pyrrolo-[1,2-c]+pyrimidines.">Flow synthesis of ethyl isocyanoacetate enabling the telescoped synthesis of 1,2,4-triazoles and pyrrolo-[1,2-c] pyrimidines.</a> Org Biomol Chem. 13 (14), 4231-4239 (2015).</li><li>Baumann, M., Baxendale, I. 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V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Flow+chemistry+syntheses+of+natural+products.">Flow chemistry syntheses of natural products.</a> Chem Soc Rev. 42 (23), 8849-8869 (2013).</li><li>Pirotte, G., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Continuous+Flow+Polymer+Synthesis+toward+Reproducible+Large-Scale+Production+for+Efficient+Bulk+Heterojunction+Organic+Solar+Cells.">Continuous Flow Polymer Synthesis toward Reproducible Large-Scale Production for Efficient Bulk Heterojunction Organic Solar Cells.</a> Chemsuschem. 8 (19), 3228-3233 (2015).</li><li>Kumar, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Continuous-Flow+Synthesis+of+Regioregular+Poly(3-Hexylthiophene):+Ultrafast+Polymerization+with+High+Throughput+and+Low+Polydispersity+Index.">Continuous-Flow Synthesis of Regioregular Poly(3-Hexylthiophene): Ultrafast Polymerization with High Throughput and Low Polydispersity Index.</a> J Flow Chem. 4 (4), 206-210 (2014).</li><li>Helgesen, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Making+Ends+Meet:+Flow+Synthesis+as+the+Answer+to+Reproducible+High-Performance+Conjugated+Polymers+on+the+Scale+that+Roll-to-Roll+Processing+Demands.">Making Ends Meet: Flow Synthesis as the Answer to Reproducible High-Performance Conjugated Polymers on the Scale that Roll-to-Roll Processing Demands.</a> Adv Energy Mater. 5 (9), 1401996 (2015).</li><li>Grenier, F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electroactive+and+Photoactive+Poly[lsoindigo-alt-EDOT]+Synthesized+Using+Direct+(Hetero)Arylation+Polymerization+in+Batch+and+in+Continuous+Flow.">Electroactive and Photoactive Poly[lsoindigo-alt-EDOT] Synthesized Using Direct (Hetero)Arylation Polymerization in Batch and in Continuous Flow.</a> Chem Mater. 27 (6), 2137-2143 (2015).</li><li>Pollet, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Production+of+(S)-1-Benzyl-3-diazo-2-oxopropylcarbamic+Acid+tert-Butyl+Ester,+a+Diazoketone+Pharmaceutical+Intermediate,+Employing+a+Small+Scale+Continuous+Reactor.">Production of (S)-1-Benzyl-3-diazo-2-oxopropylcarbamic Acid tert-Butyl Ester, a Diazoketone Pharmaceutical Intermediate, Employing a Small Scale Continuous Reactor.</a> Ind Eng Chem Res. 48 (15), 7032-7036 (2009).</li><li>Flack, K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Al(OtBu)(3)+as+an+Effective+Catalyst+for+the+Enhancement+of+Meerwein-Ponndorf-Verley+(MPV)+Reductions.">Al(OtBu)(3) as an Effective Catalyst for the Enhancement of Meerwein-Ponndorf-Verley (MPV) Reductions.</a> Org Process Res Dev. 16 (3), 1301-1306 (2012).</li><li>Aponte-Guzman, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Tandem,+Bicatalytic+Continuous+Flow+Cyclopropanation-Homo-Nazarov-Type+Cyclization.">A Tandem, Bicatalytic Continuous Flow Cyclopropanation-Homo-Nazarov-Type Cyclization.</a> Ind Eng Chem Res. 54 (39), 9550-9558 (2015).</li><li>Liotta, C. 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本议定书中的任何作者都没有任何相互竞争的金融利益或利益冲突。

最近, 在化学 (29%) 和工程学 (25%) 的研究领域中, 平均每年大约有1500份关于这个主题的出版物引起了流动化学的关注。许多成功的流程都是在流程中进行的。在许多情况动化学被证明表现出优异的性能 , 以批处理很多应用 , 如准备药学活性成分30,31, 自然产品32, 以及专业, 高价值的化学品, 如高性能的聚合物33,<s...

绿色化学与工程正在为工业的未来方向创造文化变革1,2,3,4。通过 "扩展" 策略, 而不是传统的 "向上扩展"5 , 连续流技术已被确定为利用优异的混合、传热和成本节约的环境和经济优势的工具。,6,7,8,9,10。
虽然制药行业等高价值产品的行业长期青睐批量加工, 但由于经济竞争和商业生产效益的不断增加, 流动技术的优势已变得十分诱人11. 例如, 当扩展批处理过程时, 必须建立和操作先导刻度单位, 以确定精确的热传导和传质机制。这是几乎不可持续的并且从产品的适销对路的专利生活极大地减去。相比之下, 连续流程处理允许扩展的优势, 消除了与生产规模相关的先导工厂阶段和工程-一项重大的财务激励。除了经济影响之外, 连续的技术还能使原子能和能源效率的过程。例如, 增强的混合改善了双相系统的传质, 从而提高了产量、催化剂回收策略和随后的回收计划。此外, 准确地管理反应温度的能力导致反应动力学的精确控制和产品分布12。强化过程控制、产品质量 (产品选择性) 和重现性都对环境和财务观点都有影响力。
流动反应器是可利用的商业与各种各样的大小和设计。此外, 可以很容易地实现对反应器的定制以满足工艺需要。在此, 我们报告在玻璃连续流反应器中进行的实验 (图 1)。由玻璃制成的微结构 (161 毫米 x 131 mm x 8 mm) 的组装与多种化学品和溶剂相兼容, 并且在广泛的温度范围内 (-25–200° c) 和压力 (高达 18 bar) 具有耐腐蚀性。设计了 multi-injection、高性能混合、弹性停留时间、精确传热的显微组织及其布置。所有的显微组织都装有两个射流层 (-25–200° c, 高达 3 bar), 用于在反应层的两侧进行热交换。传热速率与传热面面积成正比, 与体积成反比。因此, 这些微结构促进了最佳的表面积比以改善传热。有两种类型的微结构 (即模块): "混合" 模块和 "线性" 模块 (图 2)。心形 "混合" 模块的设计, 以诱导湍流和最大的混合。相反, 线性模块提供额外的居留时间。
作为概念的证明, 我们选择了羧酸 diphenyldiazomethane 的描述反应13,14,15,16,17。反应方案显示在图 3中。质子从羧酸到 diphenyldiazomethane 的初始转移是缓慢的, 是速率决定的步骤。第二步是快速, 产生反应产物和氮。初步研究了有机羧酸的相对酸度 (质子和质子) 的反应。反应是第一顺序在 diphenyldiazomethane 和一阶在羧酸。
实验中, 这种反应是在大量过量的羧酸 (10 摩尔当量) 的存在下进行的。因此, 这一比率是伪的第一个订单就 diphenyldiazomethane。通过将实验所得的伪一阶速率常数除以羧酸的初始浓度, 即可得到二阶速率常数。初步研究了 diphenyldiazomethane 与苯甲酸 (pKa = 4.2) 的反应。在间歇期, 反应似乎相对缓慢, 在96分钟内达到约90% 的转换。由于反应速率与羧酸的酸度成正比, 我们选择作为反应伙伴的酸性羧酸、 p硝基苯甲酸 (pKa = 3.4) 来缩短反应时间。因此, 在间歇和流中对 diphenyldiazomethane 在无水乙醇中的反应进行了研究 ( 图 4)。下一节将详细介绍结果。
当反应在乙醇中进行时, 可以形成三产品: (i) benzhydryl-4-nitrobenzoate, 这是由p硝基苯甲酸与甲烷氮中间体的反应产生的;(二) 从溶剂、乙醇和甲烷氮反应得到的 benzhydryl 乙醚;和 (iii) 氮。产品分布没有研究, 因为它在文献中有很好的记载;相反, 我们关注的是批量反应的技术转移到连续流13,14,15。实验 diphenyldiazomethane 的消失被监测。反应进行生动的颜色变化, 可以直观地观察到紫外-可见光谱。这是由于 diphenyldiazomethane 是一种强烈的紫色化合物, 而所有其他的反应产物都是无色的。因此, 这种反应可以在定性的基础上进行目视监测, 并定量地遵循紫外光谱 (即 525 nm 的二苯基甲烷吸收消失)。本文首先报告了 diphenyldiazomethane 和p硝基苯甲酸在间歇性乙醇中的反应, 作为时间的函数。然后将反应成功地转移到玻璃流反应器中进行。利用紫外光谱 (分批和流态) 监测 diphenyldiazomethane 的消失, 确定了反应的进展。

<table style="border-collapse:collapse;width:1075pt" width="1433">
	<colgroup>
		<col style="width:189pt" width="252" />
		<col style="width:188pt" width="251" />
		<col style="width:81pt" width="108" />
		<col style="width:617pt" width="822" />
	</colgroup>
	<tbody>
		<tr height="22" style="height:16.5pt">
			<td class="xl16" height="22" style="width:189pt;height:16.5pt" width="252">Thermometer</td>
			<td class="xl17" style="width:188pt" width="251">HB-USA/ Enviro-safe</td>
			<td class="xl17" style="width:81pt" width="108"></td>
			<td class="xl17" style="width:617pt" width="822">Any other instrument scientific company provider works</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Benzophenone hydrazone</td>
			<td class="xl19" style="width:188pt" width="251">Sigma-Aldrich</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Store at 2-8 &#176;C, 96% purity</td>
		</tr>
		<tr height="26" style="height:19.5pt">
			<td class="xl18" height="26" style="width:189pt;height:19.5pt" width="252">Activated MnO2</td>
			<td class="xl19" style="width:188pt" width="251">Fluka</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">&#8805; 90% purity, harmful if inhaled or swallowed. Refer to MSDS for more safety precautions</td>
		</tr>
		<tr height="26" style="height:19.5pt">
			<td class="xl18" height="26" style="width:189pt;height:19.5pt" width="252">Dibasic KH2PO4</td>
			<td class="xl19" style="width:188pt" width="251">Sigma-Aldrich</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Serious eye damage, respiratory irritant. Refer to MSDS for more safety precautions</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Dichloromethane (DCM)</td>
			<td class="xl19" style="width:188pt" width="251">Alfa Aesar</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">&#8805; 99.7% purity, argon packed</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Rotovap</td>
			<td class="xl19" style="width:188pt" width="251">B&#252;chi</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">accessory parts include Welch self-cleaning dry vacuum model 2027, and Neuberger KNP dry ice trap&#160;</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Bump trap</td>
			<td class="xl19" style="width:188pt" width="251">Chemglass</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Any other instrument scientific company provider works&#160;</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Neutral Silica Gel (50-200 mM)</td>
			<td class="xl19" style="width:188pt" width="251">Acros Organic/ Sorbent Technology</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Respiratory irritant if inhaled, refer to MSDS for more safety precautions</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Inert Argon Gas</td>
			<td class="xl19" style="width:188pt" width="251">Airgas</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Always ensure proper regulator is in place before using</td>
		</tr>
		<tr height="43" style="height:32.25pt">
			<td class="xl18" height="43" style="width:189pt;height:32.25pt" width="252">Medium Porosity Sintered Funnel Glass Filter</td>
			<td class="xl19" style="width:188pt" width="251">Sigma-Aldrich</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Any other instrument scientific company provider works</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Aluminum Foil</td>
			<td class="xl19" style="width:188pt" width="251">Reynolds Wrap</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Any other company works. Used to prevent photolytic damage towards DDM</td>
		</tr>
		<tr height="26" style="height:19.5pt">
			<td class="xl20" height="26" style="width:189pt;height:19.5pt" width="252">Para-NO2 benzoic acid</td>
			<td class="xl19" style="width:188pt" width="251">Sigma-Aldrich</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Skin contact irritant, eye irritant, respiratory irritant. Refer to MSDS for more safety precautions</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Pure ethyl alcohol (200 proof)</td>
			<td class="xl19" style="width:188pt" width="251">Sigma-Aldrich</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">&#8805; 99.5% purity, anhydrous. Highly flammable</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Toluene</td>
			<td class="xl19" style="width:188pt" width="251">Sigma-Aldrich</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">&#8805; 99.8% purity, anhydrous. Skin permeator, flammable</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl20" height="22" style="width:189pt;height:16.5pt" width="252">Ortho-xylene</td>
			<td class="xl19" style="width:188pt" width="251">Sigma-Aldrich</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">99% purity, anhydrous. Toxic to organs and CNS. Adhere to specifications dictated within MSDS</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Diphenyl diazo methane</td>
			<td class="xl19" style="width:188pt" width="251">Produced in-house</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Respiratory irritant, refer to MSDS for more safety precautions</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Corning reactor</td>
			<td class="xl19" style="width:188pt" width="251">Corning Proprietary</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Manufactured in 2009. model number MR 09-083-1A</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Stop watch</td>
			<td class="xl19" style="width:188pt" width="251">Traceable Calibration Control Company</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Any other company that provides monitoring with laboratory grade accredidation works</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Analytical balance</td>
			<td class="xl19" style="width:188pt" width="251">Denver Instruments</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Model M-2201, or any analytical balance that has sub-milligram capabilities</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Dram vials</td>
			<td class="xl19" style="width:188pt" width="251">VWR</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">2 dram, 4 dram, and 6 dram vials&#160;</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Micropipettes</td>
			<td class="xl19" style="width:188pt" width="251">Eppendorf</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">2-20 &#956;L and 100-1000 &#956;L micropipettes work</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Glass pipettes</td>
			<td class="xl19" style="width:188pt" width="251">VWR</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Any other instrument scientific company provider works</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">GC-MS</td>
			<td class="xl19" style="width:188pt" width="251">Shimadzu GC</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Software associated: GC Real Time Analysis</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">GC vials</td>
			<td class="xl19" style="width:188pt" width="251">VWR</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Any other providing company works</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Beakers</td>
			<td class="xl19" style="width:188pt" width="251">Pyrex</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">500 mL beakers&#160;</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Syringe pumps</td>
			<td class="xl19" style="width:188pt" width="251">Sigma Aldrich</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Teledyne Isco Model 500D</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Relief valve</td>
			<td class="xl19" style="width:188pt" width="251">Swagelok</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">Spring loaded relieve valve&#160;</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">One-way valves</td>
			<td class="xl19" style="width:188pt" width="251">Nupro&#160;</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">10 psi grade</td>
		</tr>
		<tr height="22" style="height:16.5pt">
			<td class="xl18" height="22" style="width:189pt;height:16.5pt" width="252">Two-way straight valves</td>
			<td class="xl19" style="width:188pt" width="251">HiP</td>
			<td class="xl19" style="width:81pt" width="108"></td>
			<td class="xl19" style="width:617pt" width="822">15,000 psi grade</td>
		</tr>
	</tbody>
</table>

continuous flow chemistry: reaction of diphenyldiazomethane with p-nitrobenzoic acid

连续流技术被确定为它的环境和经济优势的工具, 利用优越的混合, 传热和成本节约通过 "扩展" 战略, 而不是传统的 "扩大"。在此, 我们报告的反应 diphenyldiazomethane 与p硝基苯甲酸在批和流模式。为了有效地将反应从批处理转移到流模式, 必须在批处理过程中首先进行反应。因此, diphenyldiazomethane 的反应首先作为温度、反应时间和浓度的函数来研究, 以获得动力学信息和工艺参数。描述了玻璃流反应器的结构, 并将两类反应模块结合为 "混合" 和 "线性" 显微组织。最后, 在流动反应器中成功地进行了 diphenyldiazomethane 与p硝基苯甲酸的反应, 在11分钟内, diphenyldiazomethane 的转化率高达95%。这一概念反应的证明旨在为科学家们提供洞察力, 以考虑流动技术的竞争力、可持续性和在其研究中的通用性。

间歇反应 Diphenyldiazomethane 根据文献28,29编写。该化合物由石油醚结晶而成: 乙酸乙酯 (100:2) 和紫晶固体, 用 H1核磁共振、熔点和 MS 进行了分析。分析结果与文献资料的结构和报道的价值是一致的。
diphenyldiazomethane (1.0 毫米) 与苯甲酸 (10 毫米) 在无水乙醇中的反?...

Watch this Scientific Journal Video about Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid at JoVE.com

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid

流动化学通过利用优异的混合、传热和成本效益来实现环境和经济优势。在此, 我们提供了一个蓝图, 从分批转移到流程模式的化学过程。采用间歇和流动的方法对 diphenyldiazomethane 的反应进行了研究, 选择了以批和流为依据的p硝基苯甲酸。

连续流动化学: Diphenyldiazomethane 与p硝基苯甲酸的反应

Continuous flow technology has been identified as instrumental for its environmental and economic advantages leveraging superior mixing, heat transfer and ...

continuous-flow-chemistry-reaction-diphenyldiazomethane-with-p

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Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid

Unit 1

Carboxylic Acids

Chemical Kinetics

SCIENTISTS IN ACTION

11.3K 次观看.  Georgia Institute of Technology. 流动化学通过利用优异的混合、传热和成本效益来实现环境和经济优势。在此, 我们提供了一个蓝图, 从分批转移到流程模式的化学过程。采用间歇和流动的方法对 diphenyldiazomethane 的反应进行了研究, 选择了以批和流为依据的p硝基苯甲酸。

视频: Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid

Preparation of Silica Nanoparticles Through Microwave-assisted Acid-catalysis

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle diameters ranging from 30-250 nm by varying the reaction conditions. Through the selection of a microwave compatible solvent, silicic acid precursor, catalyst, and microwave irradiation time, these microwave-assisted methods were capable of overcoming the previously reported shortcomings associated with synthesis of silica nanoparticles using microwave reactors. The siloxane precursor was hydrolyzed using the acid catalyst, HCl. Acetone, a low-tan &#948; solvent, mediates the condensation reactions and has minimal interaction with the electromagnetic field. Condensation reactions begin when the silicic acid precursor couples with the microwave radiation, leading to silica nanoparticle sol formation. The silica nanoparticles were characterized by dynamic light scattering data and scanning electron microscopy, which show the materials&#39; morphology and size to be dependent on the reaction conditions. Microwave-assisted reactions produce silica nanoparticles with roughened textured surfaces that are atypical for silica sols produced by St&#246;ber&#39;s methods, which have smooth surfaces.

Silica nanoparticles were prepared using acid-catalysis of a siloxane precursor and microwave-assisted synthetic techniques resulting in the controlled growth of nanomaterials ranging from 30-250 nm in diameter. The growth dynamics can be controlled by varying the initial silicic acid concentration, time of the reaction, and temperature of reaction.

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle ...

科研

化学

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family of easy accessible, very cheap, and air stable, but highly active and universally applicable C-C cross-coupling catalysts with an excellent functional group tolerance. Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1), the least stable complex within this series towards protons; e.g. in the form of water, allows an eased nanoparticle formation and hence, proved to be the most active Heck catalyst within this series at 100 &#176;C and is a very rare example of an effective and versatile catalyst system that efficiently operates under mild reaction conditions. Rapid and complete catalyst degradation under work-up conditions into phosphonates, piperidinium salts and other, palladium-containing decomposition products assure an easy separation of the coupling products from catalyst and ligands. The facile, cheap, and rapid synthesis of 1,1',1"-(phosphinetriyl)tripiperidine and 1 respectively, the simple and convenient use as well as its excellent catalytic performance in the Heck reaction at 100 &#176;C make 1 to one of the most attractive and greenest Heck catalysts available.
We provide here the visualized protocols for the ligand and catalyst syntheses as well as the reaction protocol for Heck reactions performed at 10 mmol scale at 100 &#176;C and show that this catalyst is suitable for its use in organic syntheses.

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1) is an easy accessible, cheap, and air stable, but highly active Heck catalyst with an excellent functional group tolerance that efficiently operates under mild reaction conditions to give the coupling products in very high yields.

Mizoroki-哎呀交叉偶联反应由二氯{双[1,1&#39;，1&#39;&#39;  - （phosphinetriyl）tripiperidine]}钯催化在温和的反应条件

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family ...

Real-time Monitoring of Reactions Performed Using Continuous-flow Processing: The Preparation of 3-Acetylcoumarin as an Example

By using inline monitoring, it is possible to optimize reactions performed using continuous-flow processing in a simple and rapid way. It is also possible to ensure consistent product quality over time using this technique. We here show how to interface a commercially available flow unit with a Raman spectrometer. The Raman flow cell is placed after the back-pressure regulator, meaning that it can be operated at atmospheric pressure. In addition, the fact that the product stream passes through a length of tubing before entering the flow cell means that the material is at RT. It is important that the spectra are acquired under isothermal conditions since Raman signal intensity is temperature dependent. Having assembled the apparatus, we then show how to monitor a chemical reaction, the piperidine-catalyzed synthesis of 3-acetylcoumarin from salicylaldehyde and ethyl acetoacetate being used as an example. The reaction can be performed over a range of flow rates and temperatures, the in-situ monitoring tool being used to optimize conditions simply and easily.

Real-time monitoring allows for fast optimization of reactions performed using continuous-flow processing. Here the preparation of 3-acetylcoumarin is used as an example. The apparatus for performing in-situ Raman monitoring is described, as are the steps required to optimize the reaction.

反应执行使用连续流处理的实时监控:3  - 乙酰基香豆素的制备为例

By using inline monitoring, it is possible to optimize reactions performed using continuous-flow processing in a simple and rapid way. It is also possible ...

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the material with Au(III) ions. The synthesis method was derived from a sol-gel process used to produce micron-sized monosodium titanate (MST), with several key modifications, including altering reagent concentrations, omitting a particle seed step, and introducing a non-ionic surfactant to facilitate control of particle formation and growth. The resultant nMST material exhibits spherical-shaped particle morphology with a monodisperse distribution of particle diameters in the range from 100 to 150&#160;nm. The nMST material was found to have a Brunauer-Emmett-Teller (BET) surface area of 285 m2g-1, which is more than an order of magnitude higher than the micron-sized MST. The isoelectric point of the nMST measured 3.34 pH units, which is a pH unit lower than that measured for the micron-size MST. The nMST material was found to serve as an effective ion exchanger under weakly acidic conditions for the preparation of an Au(III)-exchange nanotitanate. In addition, the formation of the corresponding peroxotitanate was demonstrated by reaction of the nMST with hydrogen peroxide.

The surfactant mediated sol-gel synthesis of nanosized monosodium titanate is described, along with preparation of the corresponding peroxide modified material. An ion-exchange reaction with Au(III) is also presented.

纳米尺寸钛酸二氢钠的合成和化学反应

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the ...

Post Column Derivatization Using Reaction Flow High Performance Liquid Chromatography Columns

A protocol for the use of reaction flow high performance liquid chromatography columns for methods employing post column derivatization (PCD) is presented. A major difficulty in adapting PCD to modern HPLC systems and columns is the need for large volume reaction coils that enable reagent mixing and then the derivatization reaction to take place. This large post column dead volume leads to band broadening, which results in a loss of observed separation efficiency and indeed detection in sensitivity. In reaction flow post column derivatization (RF-PCD) the derivatization reagent(s) are pumped against the flow of mobile phase into either one or two of the outer ports of the reaction flow column where it is mixed with column effluent inside a frit housed within the column end fitting. This technique allows for more efficient mixing of the column effluent and derivatization reagent(s) meaning that the volume of the reaction loops can be minimized or even eliminated altogether. It has been found that RF-PCD methods perform better than conventional PCD methods in terms of observed separation efficiency and signal to noise ratio. A further advantage of RF-PCD techniques is the ability to monitor effluent coming from the central port in its underivatized state. RF-PCD has currently been trialed on a relatively small range of post column reactions, however, there is currently no reason to suggest that RF-PCD could not be adapted to any existing one or two component (as long as both reagents are added at the same time) post column derivatization reaction.

A protocol for the use of reaction flow high performance liquid chromatography columns for methods employing post column derivatization (PCD) is presented.

柱后衍生用反应流高效液相色谱柱

A protocol for the use of reaction flow high performance liquid chromatography columns for methods employing post column derivatization (PCD) is ...

Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants

We present the synthesis of (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid as an example to demonstrate a method for the synthesis of high purity nonsymmetric dialkylphosphinic acid extractants. Low toxic sodium hypophosphite was chosen as the phosphorus source to react with olefin A (2,3-dimethyl-1-butene) to generate a monoalkylphosphinic acid intermediate. Amantadine was adopted to remove the dialkylphosphinic acid byproduct, as only the monoalkylphosphinic acid can react with amantadine to form an amantadine&#8729;mono-alkylphosphinic acid salt, while the dialkylphosphinic acid cannot react with amantadine due to its large steric hindrance. The purified monoalkylphosphinic acid was then reacted with olefin B (diisobutylene) to yield nonsymmetric dialkylphosphinic acid (NSDAPA). The unreacted monoalkylphosphinic acid can be easily removed by a simple base-acid post-treatment and other organic impurities can be separated out through the precipitation of the cobalt salt. The structure of the (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid was confirmed by 31P NMR, 1H NMR, ESI-MS, and FT-IR. The purity was determined by a potentiometric titration method, and the results indicate that the purity can exceed 96%.

A protocol for the synthesis of high purity nonsymmetric dialkylphosphinic acid extractants is presented, taking (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid as an example.

高纯度对称 Dialkylphosphinic 酸萃取的合成

We present the synthesis of (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid as an example to demonstrate a method for the synthesis of high ...

Combustion Chemistry of Fuels: Quantitative Speciation Data Obtained from an Atmospheric High-temperature Flow Reactor with Coupled Molecular-beam Mass Spectrometer

This manuscript describes a high-temperature flow reactor experiment coupled to the powerful molecular beam mass spectrometry (MBMS) technique. This flexible tool offers a detailed observation of chemical gas-phase kinetics in reacting flows under well-controlled conditions. The vast range of operating conditions available in a laminar flow reactor enables access to extraordinary combustion applications that are typically not achievable by flame experiments. These include rich conditions at high temperatures relevant for gasification processes, the peroxy chemistry governing the low temperature oxidation regime or investigations of complex technical fuels. The presented setup allows measurements of quantitative speciation data for reaction model validation of combustion, gasification and pyrolysis processes, while enabling a systematic general understanding of the reaction chemistry. Validation of kinetic reaction models is generally performed by investigating combustion processes of pure compounds. The flow reactor has been enhanced to be suitable for technical fuels (e.g. multi-component mixtures like Jet A-1) to allow for phenomenological analysis of occurring combustion intermediates like soot precursors or pollutants. The controlled and comparable boundary conditions provided by the experimental design allow for predictions of pollutant formation tendencies. Cold reactants are fed premixed into the reactor that are highly diluted (in around 99 vol% in Ar) in order to suppress self-sustaining combustion reactions. The laminar flowing reactant mixture passes through a known temperature field, while the gas composition is determined at the reactors exhaust as a function of the oven temperature. The flow reactor is operated at atmospheric pressures with temperatures up to 1,800 K. The measurements themselves are performed by decreasing the temperature monotonically at a rate of -200 K/h. With the sensitive MBMS technique, detailed speciation data is acquired and quantified for almost all chemical species in the reactive process, including radical species.

An investigation of the oxidative combustion chemistry of novel biofuels, fuel components, or jet fuels by comparison of quantitative speciation data is presented. The data can be used for kinetic model validation and enables fuel assessment strategies.This manuscript describes the atmospheric high-temperature flow reactor and demonstrates its capabilities.

燃料燃烧化学: 用耦合分子束质谱仪从大气高温流反应器中获得的定量形态数据

This manuscript describes a high-temperature flow reactor experiment coupled to the powerful molecular beam mass spectrometry (MBMS) technique. This ...

Fabricating High-viscosity Droplets using Microfluidic Capillary Device with Phase-inversion Co-flow Structure

The generation of monodisperse droplets with high viscosity has always been a challenge in droplet microfluidics. Here, we demonstrate a phase-inversion co-flow device to generate uniform high-viscosity droplets in a low-viscosity fluid. The microfluidic capillary device has a common co-flow structure with its exit connecting to a wider tube. Elongated droplets of the low-viscosity fluid are first encapsulated by the high-viscosity fluid in the co-flow structure. As the elongated low-viscosity droplets flow through the exit, which is treated to be wetted by the low-viscosity fluid, phase inversion is then induced by the adhesion of the low viscosity droplets to the tip of the exit, which results in the subsequent inverse encapsulation of the high-viscosity fluid. The size of the resultant high-viscosity droplets can be adjusted by changing the flow rate ratio of the low-viscosity fluid to the high-viscosity fluid. We demonstrate several typical examples of the generation of high-viscosity droplets with a viscosity up to 11.9 Pas, such as glycerol, honey, starch, and polymer solution. The method provides a simple and straightforward approach to generate monodisperse high-viscosity droplets, which may be used in a variety of droplet-based applications, such as materials synthesis, drug delivery, cell assay, bioengineering, and food engineering.

A phase-inversion co-flow device is demonstrated to generate monodisperse high-viscosity droplets above 1 Pas, which is difficult to realize in droplet microfluidics.

反相共流微流控毛细管装置制备高粘度水滴的方法

The generation of monodisperse droplets with high viscosity has always been a challenge in droplet microfluidics. Here, we demonstrate a phase-inversion ...

Genetic Encoding of a Non-Canonical Amino Acid for the Generation of Antibody-Drug Conjugates Through a Fast Bioorthogonal Reaction

Antibody-drug conjugates (ADCs) used nowadays in clinical practice are mixtures of antibody molecules linked to a varying number of toxins at different positions. Preclinical studies have shown that the therapeutic index of these traditional ADCs can be improved by the site-specific linkage of toxins. However, current approaches to produce homogeneous ADCs have several limitations, such as low protein expression and slow reaction kinetics. In this protocol we describe how to set up an expression system to incorporate a cyclopropene derivative of lysine (CypK) into antibodies using genetic code expansion. This minimal bioorthogonal handle allows rapid conjugation of tetrazine derivatives through an inverse-demand Diels-Alder cycloaddition. The expression system here reported enables the facile production and purification of trastuzumab bearing CypK in each of the heavy chains. We explain how to link the antibody to the toxin monomethyl auristatin E and characterize the immunoconjugate by hydrophobic interaction chromatography and mass spectrometry. Finally, we describe assays to assess the stability in human serum of the dihydropyridazine linkage resulting from the conjugation and to test the selective cytotoxicity of the ADC for breast cancer cells with high levels of HER2 receptor.

Incorporating a cyclopropene derivative of lysine into antibodies allows the site-specific, rapid and efficient linkage of tetrazine-bearing molecules to generate antibody-drug conjugates.

用快速 Bioorthogonal 反应生成抗体-药物共轭物的非规范氨基酸的遗传编码

Antibody-drug conjugates (ADCs) used nowadays in clinical practice are mixtures of antibody molecules linked to a varying number of toxins at different ...

Extending the Lifespan of Soluble Lead Flow Batteries with a Sodium Acetate Additive

In this report, we present a method for the construction of a soluble lead flow battery (SLFB) with an extended cycle life. By supplying an adequate amount of sodium acetate (NaOAc) to the electrolyte, a cycle life extension of over 50% is demonstrated for SLFBs via long-term galvanostatic charge/discharge experiments. A higher quality of the PbO2 electrodeposit at the positive electrode is quantitatively validated for NaOAc-added electrolyte by throwing index (TI) measurements. Images acquired by scanning electron microscopy (SEM) also exhibit more integrated PbO2 surface morphology when the SLFB is operated with the NaOAc-added electrolyte. This work indicates that electrolyte modification can be a plausible route to economically enable SLFBs for large-scale energy storage.

A protocol for the construction of a soluble lead flow battery with an extended lifespan, in which sodium acetate is supplied in the methanesulfonic electrolyte as an additive, is presented.

用醋酸钠添加剂延长可溶性铅流电池的使用寿命

In this report, we present a method for the construction of a soluble lead flow battery (SLFB) with an extended cycle life. By supplying an adequate ...

连续流动化学: Diphenyldiazomethane 与p硝基苯甲酸的反应

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