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Summary

Abstract

Introduction

Protocol

Representative Results

Discussion

Acknowledgements

Materials

References

Chemistry

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source

Published: August 17th, 2018

DOI:

10.3791/58281

1Department of Chemistry and Biochemistry, University of Toledo, 2School of Green Chemistry and Engineering, University of Toledo
* These authors contributed equally

Here we present a protocol for performing reactions in simple reaction vessels under low-to-moderate pressures of CO2. The reactions can be performed in a variety of vessels simply by administering the carbon dioxide in the form of dry ice, without the need for costly or elaborate equipment or set-ups.

Herein is presented a general strategy to perform reactions under mild to moderate CO2 pressures with dry ice. This technique obviates the need for specialized equipment to achieve modest pressures, and can even be used to achieve higher pressures in more specialized equipment and sturdier reaction vessels. At the end of the reaction, the vials can be easily depressurized by opening at room temperature. In the present example CO2 serves as both a putative directing group as well as a way to passivate amine substrates, thereby preventing oxidation during the organometallic reaction. In addition to being easily added, the directing group is also removed under vacuum, obviating the need for extensive purification to remove the directing group. This strategy allows the facile γ-C(sp3)-H arylation of aliphatic amines and has the potential to be applied to a variety of other amine-based reactions.

The use of gaseous compounds in chemical reactions typically requires specialized equipment and procedures1,2. At bench scale, some gases can be added directly from a tank using a high pressure regulator3. An alternative method is to condense the gas under cryogenic conditions4,5. Although useful, these strategies require the use of specialized pressure reactors with valves, which can be cost prohibitive for running numerous reactions in parallel. This can therefore greatly slow the rate at which reaction screening can proceed. ....

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CAUTION: 1) The following protocols have been deemed safe through repeated trials. However, caution should be exercised when sealing vials, throughout the reaction, and especially when opening the reactions, as inhomogeneity in the reaction vials may lead to equipment failure. Vials should be inspected for physical defects prior to use. Vials should be placed behind some form of blast shield or hood sash immediately after sealing to prevent incidents should the vials fail. 2) Although there is little chance for asphyxiat.......

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Following these protocols, it is possible to charge a reaction vial with an appropriate amount of carbon dioxide to achieve chemical reactions that require CO2 atmospheres. The pressure achieved in Step 1 is calculated to be approximately 3 atmospheres (see discussion for determination of this value), although due to partial solvation, the observed pressure is in the vicinity of 2 atmospheres at room temperature, and should be approximately 2.6 atmospheres under the reaction co.......

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Using the van der Waals Equation of State, the approximate pressure of these systems can be calculated45

Eq. 1:          Equation

Under the conditions in Protocol 1, we can assume 26.3 mg of CO2 gives n =5.98 x 10-4 mols

Equation 1b

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The authors wish to acknowledge start-up funding from The University of Toledo, as well as funds from the American Chemical Society's Herman Frasch Foundation in partial support of this work. Mr. Thomas Kina is acknowledged for his assistance with developing a suitable pressure gauge for measuring the reaction pressures. Mr. Steve Modar is thanked for useful discussions.

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Name Company Catalog Number Comments
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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