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Safe Handling of Organolithium Compounds in the Laboratory

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Safe Handling of Organolithium Compounds in the Laboratory FEATURE Safe handling of organolithium compounds in the laboratory Organolithium compounds are extremely useful reagents in organic synthesis and as initiators in anionic polymerizations. These reagents are corrosive, flammable, and in certain cases, pyrophoric. Careful planning prior to execution of the experiment will minimize hazards to personnel and the physical plant. The proper personal protective equipment (PPE) for handling organolithium compounds will be identified. Procedures to minimize contact with air and moisture will be presented. Solutions of organolithium compounds can be safely transferred from the storage bottles to the reaction flask with either a syringe or a cannula. With the utilization of these basic techniques, organolithium compounds can be safely handled in the laboratory. By James A. Schwindeman, oxides (typi®ed by lithium t-butoxide). various classes of organolithium com- Chris J. Woltermann, and These organolithium compounds have pounds, with pKa from 15.2 (lithium Robert J. Letchford found wide utility as reagents for methoxide) to 53 (t-butyllithium).5 organic synthesis in a variety of appli- Fourth, organolithium reagents demon- cations. For example, they can be strate enhanced nucleophilicity com- INTRODUCTION employed as strong bases (alkyl- pared to the corresponding organo- When properly handled, organo- lithiums, aryllithiums, lithium amides magnesium compound. Finally, they lithiums provide unique properties and lithium alkoxides), nucleophiles are convenient, as a variety of organo- that allow for more precise control (alkyllithium and aryllithium com- lithium compounds from all four cate- and greater performance features. pounds) and reagents for metal±halo- gories are commercially available. With proper care and attention, orga- gen exchange (alkyllithium and arylli- Thus, the experimentalist can select nolithiums can be safely and effectively thium compounds).1 Alkyllithium com- and purchase the appropriate reagent utilized in both laboratory and physi- pounds have also found extensive needed for the desired transformation. cal plant environments, while being application as initiators for anionic the effective choice for many synthesis polymerization. The unique properties applications. Organolithium com- of the carbon±lithium bond in poly- HAZARDS OF ORGANOLITHIUM pounds fall into four broad categories: merization processes allow the precise COMPOUNDS alkyllithiums (exempli®ed by n-butyl- control of the polymer's molecular Organolithium compounds, which lithium), aryllithiums (such as phenyl- architecture.2 exhibit outstanding performance in a lithium), lithium amides (for example, variety of applications, are highly reac- lithium diisopropylamide and lithium tive materials. There are three princi- hexamethyldisilazide) and lithium alk- CHARACTERISTICS OF pal hazards associated with these ORGANOLITHIUM COMPOUNDS compounds: corrosivity, ¯ammability James A. Schwindeman received his Several characteristics of organo- and, in certain instances, pyrophori- B.S. degree in Chemistry from Miami lithium compounds have enhanced city. The inherent corrosive nature of University and his Ph.D. in Organic their utilization in the laboratory. First, all four classes of organolithiums can Chemistry from the Ohio State organolithium compounds exhibit cause chemical and thermal burns University, has over 10 years experience excellent solubility in organic solvents. upon operator exposure. The organo- in the synthesis of organometallic As an example, n-butyllithium is avail- lithium compounds themselves are compounds at FMC Lithium. able commercially as a solution in hex- ¯ammable. Typically, they are supplied E-mail: [email protected]. anes from 1.5 M (15 wt.%) to 10 M in an organic solvent, which exacer- Chris J. Woltermann received his B.S. in (85 wt.%). One caveat is that alkyl- bates the ¯ammability. Pyrophoricity6 Chemistry from the University of lithium compounds do react with ethe- is de®ned as the property of a material Dayton in 1990 and his Ph.D. in real solvents.3 Second, in contrast to to spontaneously ignite on exposure to Organic Chemistry from the Ohio State alkylorganometallics derived from air, oxygen or moisture. In particular, University in 1996. other alkali metals, alkyllithium com- all formulations of n-butyllithium, s- Robert J. Letchford received his B.S. pounds have enhanced stability.4 The butyllithium and t-butyllithium are pyr- degree in ChemicalEngineering from alkyllithium compounds exhibit suf®- ophoric, as determined by the of®cial Youngstown State University and a cient stability to be prepared, stored Department of Transportation (DOT) M.S. degree in Polymer Chemistry from and transported. Third, a wide range protocol.7 Before any laboratory work the University of Akron. of base strength is available from the with an organolithium is conducted, 6 ß Division of Chemical Health and Safety of the American Chemical Society 1074-9098/02/$22.00 Elsevier Science Inc.All rights reserved. PII S1074-9098(02)00295-2 appropriate planning should be con- ducted to safeguard personnel and property against these hazards. There are a number of factors that in¯uence the pyrophoric nature of the alkyllithium compound. For the same concentration of alkyllithium, the pyr- ophoricity increases in the order n- butyllithium<s-butyllithium < t-butyl- Figure 2. Thermal decomposition of lithium diisopropylamide. lithium. For a given alkyllithium, the pyrophoricity also increases as the solution as very ®ne particles. This sable to conduct the experiment in an concentration of the alkyllithium ®nely divided lithium hydride is pyro- ef®cient fume hood. The fume hood increases in the formulation. The sol- phoric. To maximize the shelf-life of should be free of clutter. The hood vent in the formulation also in¯uences these materials, it is recommended that should not be used as a storage area pyrophoricity. The lower the ¯ash they be stored in an explosion-proof for out of service equipment and sup- point of the solvent the greater the refrigerator at <108C. Further, since plies. Less clutter makes it easier to pyrophoricity. Pyrophoricity is also the assay of these reagents can decline clean up a spill or extinguish a ®re in impacted by environmental factors in with storage, it is good practice to ver- the event of a release of an organo- the laboratory. Higher relative humid- ify the assay prior to utilization in an lithium. The fume hood will also sweep ity and higher ambient temperature experiment.11 fumes away more effectively with less result in greater pyrophoricity.8 clutter present. Combustible materials, The stability of two classes of orga- such as solvents, ¯ammable chemicals nolithium compounds must also be PLANNING THE EXPERIMENT (reagents or samples), paper or cloth considered. Alkyllithium compounds In spite of these hazards, the reactivity should be removed from the hood undergo thermal decomposition via of organolithium compounds has been prior to the experiment. These are all loss of lithium hydride, with formation successfully harnessed. Indeed, with potential fuel sources that can contri- of the corresponding alkene. The proper planning on the part of the bute to a ®re in the event of spill of an decomposition of n-butyllithium is il- experimenter, organolithium com- organolithium. The fume hood must be lustrated in Figure 1. pounds can be safely handled in the equipped with a source of inert gas, Several factors in¯uence the rate laboratory. These same techniques can such as nitrogen or argon. A delivery of this decomposition. The thermal also be employed in large-scale appli- system to distribute the inert gas to the stability of alkyllithiums increases cations, from kilo laboratory up to reactor, such as manifold or plastic in the series s-butyllithium < n- commercial-scale production. Proper lines, and a bubbler system are also butyllithium < t-butyllithium, at the precautions must be taken against required. The delivery system will be same concentration.9 For a given alkyl- the principle hazards of organolithium described in more detail in the next lithium, the stability increases with compounds: corrosivity, ¯ammability section. Equipment is also required decreasing concentration in the formu- and in certain instances, pyrophoricity. to dry the glassware prior to the experi- lation.9 A lower storage temperature There are a number of circumstances ment. lowers the decomposition rate. The that must be avoided in dealing with Nitrogen or argon can be employed presence of alkoxide impurities, gen- organolithium compounds in the labo- as the inert gas in reactions that erated from admission of adventious ratory: personnel exposure, air, oxygen, employ organolithium reagents. Typi- oxygen, accelerates the rate of decom- moisture, water, heat, clutter, source of cally, nitrogen is available in several position.10 Lithium dialkylamides also ignition (spark) and fuel. Prior to the grades from the supplier. Select the undergo decomposition via loss of commencement of an experiment that grade with the lowest moisture and lithium hydride, to afford the corre- utilizes an organolithium, it is strongly oxygen content. Argon must be utilized sponding imine. The decomposition recommended to consult the Material in reactions where lithium metal is a of lithium diisopropylamide is illu- Safety Data Sheet (MSDS) supplied by reactant. Nitrogen reacts exothermi- strated in Figure 2. The rate of this the vendor. The MSDS will contain cally with lithium metal to afford decomposition
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