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Summary
Abstract
Introduction
Protocol
Results
Discussion
Disclosures
Acknowledgements
Materials
References
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Chemistry

用干冰作为固体 CO2源实现密封容器中的适度压力

Published: August 17, 2018
doi:
10.3791/58281
, , ,
1Department of Chemistry and Biochemistry,University of Toledo, 2School of Green Chemistry and Engineering,University of Toledo

Summary

在这里, 我们提出了一个协议, 以执行反应的简单反应容器在低到中等压力的 CO2。这种反应可以通过在各种容器中进行, 只需以干冰的形式管理二氧化碳, 而不需要昂贵的或精密的设备或装置。

Abstract

本文提出了在轻度至中度 CO2压力下, 用干冰进行反应的一般策略。这种技术省却了需要专门的设备来达到适度的压力, 甚至可以用来在更专业的设备和更坚固的反应容器中获得更高的压力。在反应结束时, 瓶子可以很容易地减压在室温下打开。在本例子 CO2担当两个假定的指挥的小组并且方式到钝化胺基体, 从而防止氧化在有机金属反应期间。除了容易添加, 指导组也被排除在真空下, 不需要广泛的净化, 以消除指导组。这一策略允许简便的γ C (sp3) H arylation 脂肪胺, 并有可能被应用于各种其他胺基反应。

Introduction

气体化合物在化学反应中的使用通常需要专门的设备和程序1,2。在工作台刻度上, 某些气体可以直接从油箱中添加, 使用高压调节器3。另一种方法是在低温条件下冷凝气体4,5。虽然有用, 这些战略需要使用专门的压力反应堆与阀门, 这可能是成本高昂的运行许多反应并行。因此, 这可以大大减慢反应筛查的速度。因此, 化学家们发现使用其他方法来介绍这些化合物是可取的。氨可以添加到反应使用不同的羧酸铵盐, 利用弱平衡, 这些盐和自由氨6。转移氢化是烯烃、羰基和硝基基团还原反应的重要策略, 它绕过了以甲酸铵或肼等化合物为 H27的载体的易燃氢气的使用。另一种对这一地区感兴趣的气体是一氧化碳8 -co 可以通过从金属羰基络合物9,10的解放原位产生, 也可以由脱羰产生。来源如合成和芳基11,12,13或氯仿14,15。

在这方面没有取得重大进展的一种气体是二氧化碳16。其中一个原因是, 涉及 CO2的许多转换也需要高温和压力, 因此自动降级到专门的反应堆17,18。然而, 最近开发更多反应性催化剂的努力促进了在 CO219、20、21、22的大气压下运行许多这些反应。我们最近发现了一种反应, 其中二氧化碳可以用来调解γ C (sp3) –H arylation 脂肪胺23。这一战略预计将结合静态指导组方法的好处, 包括酰胺24,25,26,27,28, 磺胺类药物29,30,31,32, thiocarbonyl33,34, 或腙35基指挥小组 (化学鲁棒性), 以容易瞬变指挥小组(减少的步经济)36, 37,38,39。

尽管反应可能发生在 CO2的大气压下, 但对筛查反应的 Schlenk 的需要却是缓慢的。此外, 增加的压力轻微导致改善反应的收益率, 但不能轻易实现使用 Schlenk 线。因此, 我们寻求一种替代战略, 随后确定干冰可以很容易地用作 CO2的固体来源, 可以添加到各种反应容器中, 引入必要量的二氧化碳, 以达到适度压力 (图 1)。虽然在合成中未充分利用, 类似的策略是相当常见的一种方法来生成液体 CO2用于色谱和萃取应用40,41,42,43, 44。利用这一策略, 我们的小组能够快速地筛查大量的反应, 而在2-20 大气压之间获得适度 CO2压力的能力对于提高反应的产量至关重要。在这些条件下, 主要 (1°) 和二次 (2°) 胺可以 arylated 与电子丰富和电子可怜的芳卤化物。

Protocol

警告: 1) 通过反复试验, 下列议定书被认为是安全的。然而, 当密封瓶, 在整个反应, 特别是当打开反应时应谨慎, 因为反应瓶的不均匀性可能导致设备故障。在使用前, 应检查瓶子的物理缺陷。瓶子应该被放置在某种形式的爆炸盾或罩窗扇后, 立即密封, 以防止事故, 如果瓶子失败。2) 虽然几乎没有机会窒息由于少量 CO2使用, 反应应该被设置并且打开在一个通风良好的区域或在通风罩。3) 干冰…

Representative Results

遵循这些协议, 有可能向反应瓶收取适量的二氧化碳, 以实现化学反应, 需要 CO2大气。在步骤1中实现的压力计算为大约3大气压 (参见讨论确定这个值), 虽然由于部分溶剂化, 观察到的压力在室温附近2大气压, 应大约2.6 大气在反应条件之下。因此, 在步骤1中的条件下, 2-甲基-4-苯基丁胺可以获得69% 的产量 (图 2)。通过升华 CO2 (步骤 2) 首?…

Discussion

利用范德华状态方程, 可以计算出这些系统的近似压强45 。

情商 1:Equation

在协议1的条件下, 我们可以假设26.3 毫克的 CO2给n = 5.98 x 10-4 mols

Equation 1b

粗略估计, 这表明在1号议定书中, 反?…

Disclosures

The authors have nothing to disclose.

Acknowledgements

作者希望承认托莱多大学开办的资金, 以及美国化学学会赫尔曼 Frasch 基金会的资金, 部分支持这项工作。托马斯爱上先生得到了他的帮助, 他开发了一个合适的压力表来测量反应压力。史蒂夫. Modar 先生对有用的讨论表示感谢。

Materials

7.5 mL Sample Vial with Screw Cap (Thermoset) Qorpak GLC-00984 Can be reused.
40 mL Sample Vial with Screw Cap (Thermoset) Qorpak GLC-01039 Can be reused.
Pressure Tube, #15 Thread, 7" Long, 25.4 mm O.D. Ace Glass 8648-06 Can be reused.
Pie-Block for 2 Dram Vials ChemGlass CG-1991-P14 Can be reused.
Pie-Block for 10 Dram Vials ChemGlass CG-1991-P12 Can be reused.
3.2 mm PTFE Disposable Stir Bars Fisher 14-513-93 Can be reused.
C-MAG HS 7 Control Hotplate IKA 20002695
Analytical Weighing Balance Sartorius QUINTIX2241S
Double-Ended Micro-Tapered Spatula Fisher Scientific 21-401-10
Hei-VAP Advantage – Hand Lift Model with G5 Dry Ice Condenser Rotary Evaporator Heidolph 561-01500-00
Bump Trap 14/20 Joint ChemGlass CG-1322-01
tert-Amyl amine Alfa Aesar B24639-14 Used as received.
2-Methyl-N-(3-methylbenzyl)butan-2-amine N/A N/A Prepared from reductive amination of tert-amyl amine and 3-tolualdehyde in the presence of sodium borohydride in methanol.
Palladium Acetate Chem-Impex International, Inc. 4898 Used as received.
Silver Trifluoroacetate Oakwood Chemicals 007271 Used as received.
Phenyl Iodide Oakwood Chemicals 003461 Used as received.
Acetic Acid Fisher Chemical A38 Used as received.
1,1,1,3,3,3-Hexafluoroisopropanol Oakwood Chemicals 003409 Used as received.
Deionized Water Obtained from in-house deionized water system.
Dry Ice Carbonic Enterprises Dry Ice Inc. Non-food grade dry ice.
Concentrated Hydrochloric Acid Fisher Chemical A144SI Diluted to a 1.2 M solution prior to use.
Diethyl Ether, Certified Fisher Chemical E138 Used as received.
Hexanes, Certified ACS Fisher Chemical H292 Used as received.
Saturated Ammonium Hydroxide Fisher Chemical A669 Used as received.
Dichloromethane Fisher Chemical D37 Used as received.
Sodium Sulfate, Anhydrous Oakwood Chemicals 044702 Used as received.
250 mL Separatory Funnel Prepared in-house by staff glassblower.
100 mL Round Bottom Flask Prepared in-house by staff glassblower.
Scientific Disposable Funnel Caplugs 2085136030
Borosilicate Glass Scintillation Vials, 20 mL Fisher Scientific 03-337-15
5 mm O.D. Thin Walled Precision NMR Tubes Wilmad 666000575
Chloroform-d Cambridge Isotope Laboratories, Inc. DLM-7 Used as received.
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Dry IceCO2 AtmosphereSynthetic Organic ChemistryCarbon DioxideSolid CO2 SourceModerate PressuresSealed VesselsCH ArylationCH CapitulationEpoxidesSyntha CarbonatesPalladium AcetateSilver TrifluoroacetatePhenyl IodideTert-amylamineAcetic AcidDeionized WaterPTFE CapRoom TemperatureElevated Temperature
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Kapoor, M., Chand-Thakuri, P., Maxwell, J. M., Young, M. C. Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source. J. Vis. Exp. (138), e58281, doi:10.3791/58281 (2018).
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