Organolithium compounds are useful but hazardous reagents that require careful handling. They are corrosive, flammable, and some are pyrophoric. With proper planning, protective equipment, and techniques to minimize air/moisture exposure, organolithium compounds can be used safely in the laboratory. Key safety practices include conducting experiments in well-ventilated hoods, removing combustibles from work areas, and using inert gas delivery systems.
This PPT is usefull for aspirants of JEE-IIT, CSIR-NET and UPSC exams in CHEMISTRY section. It is also usefull for grduates and Post graduates students of Indian Universities.
- Organometallic compounds contain a carbon-metal bond and are important organic reagents, such as Grignard reagents (RMgX).
- Organometallic compounds provide a source of nucleophilic carbon that can react with electrophilic carbons to form new carbon-carbon bonds, allowing synthesis of complex molecules from simple starting materials.
- Common reactions involve organolithium (RLi) and Grignard (RMgX) reagents adding to the carbonyl groups in aldehydes, ketones, and esters to form alcohols.
This document provides an introduction to organometallic compounds and reagents. It discusses that organometallic compounds contain carbon-metal bonds and some important examples. Organometallic reagents of magnesium, lithium, and copper are important for stoichiometric and industrial reactions. The document also summarizes key reactions of organolithium, Grignard, and organocopper reagents that involve nucleophilic addition or substitution. Finally, it recognizes three great contributors to the field of organometallic chemistry.
Ppt on Organometallic Compounds-Zamir ShekhZAMIR SHEKH
The document discusses various types of organometallic compounds, including their definitions, nomenclature, properties, structures, and reactions. It describes organolithium, organomagnesium, organozinc, organocopper, and other organometallic compounds. It also discusses their applications in synthesis such as additions, displacements, conjugate additions, cyclopropanation, and opening of epoxides.
Organozinc reagents play an important role in C-C bond formation through various reactions. They are synthesized through methods such as insertion of zinc metal into alkyl halides, functional group exchange, and transmetallation. Key reactions involving organozinc reagents include the Reformatsky reaction, Simmons-Smith reaction, Negishi coupling, Fukuyama coupling, and Barbier reaction. Organozincates, which involve sodium or lithium zincates, also participate in C-C bond forming reactions.
This document discusses various types of organometallic compounds. It defines organometallic chemistry as the study of compounds with a carbon-metal bond. Key types discussed include organolithium, organomagnesium (Grignard reagents), organozinc, and organocopper compounds. The document also summarizes several important reactions of these compounds, such as addition reactions, cross-coupling reactions, and cyclopropanation.
This presentation discusses the reactions of organolithium compounds. Organolithium compounds undergo several reactions including: reaction with carbon dioxide to form ketones; reaction with oxygen to form hydroperoxides; reaction with esters and alkyl cyanides to form ketones; and electrophilic displacement reactions with organic halides. Electrophilic displacement, or metal-halogen exchange, is an important reaction as it allows for the synthesis of reactive organolithium compounds like vinyl lithium and phenyl lithium which can be used as precursors in organic synthesis.
This PPT is usefull for aspirants of JEE-IIT, CSIR-NET and UPSC exams in CHEMISTRY section. It is also usefull for grduates and Post graduates students of Indian Universities.
- Organometallic compounds contain a carbon-metal bond and are important organic reagents, such as Grignard reagents (RMgX).
- Organometallic compounds provide a source of nucleophilic carbon that can react with electrophilic carbons to form new carbon-carbon bonds, allowing synthesis of complex molecules from simple starting materials.
- Common reactions involve organolithium (RLi) and Grignard (RMgX) reagents adding to the carbonyl groups in aldehydes, ketones, and esters to form alcohols.
This document provides an introduction to organometallic compounds and reagents. It discusses that organometallic compounds contain carbon-metal bonds and some important examples. Organometallic reagents of magnesium, lithium, and copper are important for stoichiometric and industrial reactions. The document also summarizes key reactions of organolithium, Grignard, and organocopper reagents that involve nucleophilic addition or substitution. Finally, it recognizes three great contributors to the field of organometallic chemistry.
Ppt on Organometallic Compounds-Zamir ShekhZAMIR SHEKH
The document discusses various types of organometallic compounds, including their definitions, nomenclature, properties, structures, and reactions. It describes organolithium, organomagnesium, organozinc, organocopper, and other organometallic compounds. It also discusses their applications in synthesis such as additions, displacements, conjugate additions, cyclopropanation, and opening of epoxides.
Organozinc reagents play an important role in C-C bond formation through various reactions. They are synthesized through methods such as insertion of zinc metal into alkyl halides, functional group exchange, and transmetallation. Key reactions involving organozinc reagents include the Reformatsky reaction, Simmons-Smith reaction, Negishi coupling, Fukuyama coupling, and Barbier reaction. Organozincates, which involve sodium or lithium zincates, also participate in C-C bond forming reactions.
This document discusses various types of organometallic compounds. It defines organometallic chemistry as the study of compounds with a carbon-metal bond. Key types discussed include organolithium, organomagnesium (Grignard reagents), organozinc, and organocopper compounds. The document also summarizes several important reactions of these compounds, such as addition reactions, cross-coupling reactions, and cyclopropanation.
This presentation discusses the reactions of organolithium compounds. Organolithium compounds undergo several reactions including: reaction with carbon dioxide to form ketones; reaction with oxygen to form hydroperoxides; reaction with esters and alkyl cyanides to form ketones; and electrophilic displacement reactions with organic halides. Electrophilic displacement, or metal-halogen exchange, is an important reaction as it allows for the synthesis of reactive organolithium compounds like vinyl lithium and phenyl lithium which can be used as precursors in organic synthesis.
1) Organozinc compounds are less reactive than organolithium and organomagnesium compounds due to their more covalent C-Zn bond, allowing preparation of functionalized derivatives.
2) Organozinc compounds are commonly prepared by reacting primary or secondary halides with zinc metal or Rieke zinc under inert atmosphere due to their sensitivity to oxidation.
3) Organozinc reagents are useful in organic syntheses such as Reformatsky reactions, Simmons-Smith cyclopropanation reactions, and cross-coupling reactions like Negishi and Fukuyama couplings.
This document provides an overview of organometallic compounds, focusing on organolithium, organomagnesium, organozinc, and organocopper compounds. It defines organometallic chemistry as the study of chemical compounds containing carbon-metal bonds. Key applications of these compounds include forming new carbon-carbon bonds through nucleophilic addition reactions and serving as precursors for other organometallic reagents. The document discusses the structures, properties, preparations and reactions of various organometallic compounds.
This document presents information on organomercury compounds. It introduces organomercury compounds and notes that the Hg-C bond is typically stable but sensitive to light. It discusses the structure, preparation, reactions and examples of important organomercury compounds like methylmercury and dimethyl mercury. The preparation methods covered include the direct reaction of hydrocarbons with mercury salts and the use of sodium amalgam. Key reactions discussed are the Heck reaction and oxymercuration-demercuration reactions. Applications mentioned include use as fungicides, catalysts, and in medicines.
Gilman reagent, also known as organocopper reagents, are prepared by reacting organomagnesium, organolithium, or organozinc reagents with copper(I) salts. Gilman reagents react with a variety of electrophiles including acid chlorides, aldehydes, ketones, epoxides, and alkyl halides. Some common reactions of Gilman reagents are: 1) reactions with acid chlorides to form ketones, 2) coupling reactions between two different alkyl halides to form C-C bonds, and 3) conjugate addition reactions of the organocopper reagent to unsaturated carbonyl compounds like enones. Gilman reagents offer advantages over Grignard reagents for
Gilman's reagent is a lithium and copper (diorganocopper) compound that can be prepared by adding copper(I) iodide to methyllithium at -78°C. Gilman's reagent is useful for replacing halide groups with organic groups through SN2 reactions. Some applications include 1) 1,4-addition to conjugated enones due to the soft nucleophilicity of the reagent, 2) alkyl cross-coupling reactions with organic halides, and 3) addition to acid chlorides to form ketones.
This document provides an overview of catalysis by organometallic compounds. It discusses that organometallic compounds are widely used as homogeneous catalysts in industrial processes and research. Nobel Prizes have been awarded for discoveries in organometallic chemistry and homogeneous catalysis. Examples of important organometallic catalysts discussed include Wilkinson's catalyst, Noyori's catalyst for asymmetric hydrogenation, and Ziegler-Natta catalysts for polymerization of olefins. The mechanisms of homogeneous hydrogenation and different types of catalysis such as homogeneous versus heterogeneous are also summarized.
Mechanistic aspects of C-C cross coupling reactionRashmi Gaur
The document discusses palladium-catalyzed cross-coupling reactions, which were awarded the 2010 Nobel Prize in Chemistry. It summarizes the key reactions including Suzuki, Negishi, Stille, Sonogashira, and Heck reactions. These reactions involve the coupling of organic electrophiles and nucleophiles through oxidative addition, transmetallation, migratory insertion, and reductive elimination steps using a palladium catalyst. The document also discusses the mechanisms and factors influencing these important C-C bond forming reactions.
This document summarizes key aspects of palladium-catalyzed cross-coupling reactions, with a focus on the Heck reaction and its mechanisms and applications. The Heck reaction involves the coupling of alkenyl or aryl halides with alkenes, catalyzed by palladium. The mechanism proceeds through oxidative addition, transmetalation, and reductive elimination steps. The document discusses factors that determine regioselectivity and provides examples of the Heck reaction in total syntheses of natural products like dehydrotubifoline, capnellene, and taxol. It also describes domino and intramolecular Heck reactions and summarizes the related Stille coupling reaction.
Organolithium compounds react through several mechanisms. They form hydrocarbons when reacted with compounds containing active hydrogens like water, alcohols, and amines. Organolithium compounds also undergo 1,2-addition with α, β-unsaturated carbonyl compounds, while Grignard reagents give 1,4 products due to steric hindrance. When reacted with carboxylic acids, organolithium compounds form hydrocarbons in the first step and ketones in the second step. Additionally, organolithium compounds can polymerize with alkenes to form long chain alkanes under high pressure and low temperature.
The Sonogashira cross-coupling reaction forms carbon-carbon bonds between a terminal alkyne and an aryl or vinyl halide using a palladium catalyst. It was developed in 1975 and offers milder conditions than previous coupling reactions, such as room temperature. The reaction employs both a palladium and copper catalyst, with the copper activating the alkyne. It has become a highly useful reaction for carbon-carbon bond formation and has applications in pharmaceuticals, natural products, and organic materials synthesis.
The Suzuki reaction is an organic reaction where an organoboron compound reacts with an organohalide compound to form a carbon-carbon bond. It is catalyzed by palladium and involves three main steps - oxidative addition, transmetalation, and reductive elimination. The Suzuki reaction is widely used in chemical synthesis due to its mild reaction conditions, tolerance of functional groups, and ability to form C-C bonds under aqueous conditions.
Organocatalysis uses small organic molecules rather than metals to catalyze chemical reactions. Thiourea organocatalysis specifically uses thiourea derivatives to accelerate reactions through hydrogen bonding interactions. Primary amine thiourea catalysts have many advantages including being inexpensive, non-toxic, stable, and able to catalyze reactions with high enantioselectivity. The document provides procedures for synthesizing a primary amine thiourea catalyst through Boc protection of an amino acid, formation of an amide bond with benzyl amine, Boc deprotection, and conversion to an isothiocyanate derivative.
TRANSITION METAL CATALYSIS , THE DIFFERENT METALS OF TRANSITION USED AS CATALYTIC REAGENT WITH ITS PROPERTIES , THEIR CHARGE TRANSFER ITS REACTION INCLUDING COPPER, PALLADIUM FOLLWED BY HECKMAN, ULLMAN COUPLING REACTION, GILLMAN REACTION, HECK REACTION
The document discusses organic reactions and reaction mechanisms. It defines nucleophiles and electrophiles, and provides examples of each. It then summarizes several common types of organic reactions including addition reactions, substitution reactions, elimination reactions, and aromatic substitutions. The mechanisms and examples of nucleophilic addition, electrophilic addition, nucleophilic substitution, and electrophilic aromatic substitutions like nitration, sulfonation, and halogenation are described in detail.
1) Elimination reactions occur when two atoms or groups are removed from two adjacent carbon atoms of a substrate molecule to form a multiple bond.
2) Elimination occurs when a nucleophile attacks a hydrogen instead of a carbon.
3) In an E1 elimination reaction, the leaving group leaves in the rate-determining unimolecular step, and the proton is removed in a separate second step.
This document discusses retrosynthetic analysis approaches for aromatic compounds. It covers aromatic electrophilic and nucleophilic substitution reactions, including addition of cationic synthons, Friedel-Crafts alkylation and acylation, and substitution of diazonium salts. It also discusses aromatic side chain transformations through functional group interconversion and nucleophilic aromatic substitution of halides.
The Diels-Alder reaction is a [4+2] cycloaddition between a conjugated diene and a substituted alkene (dienophile) to form a cyclohexene ring. It was discovered in 1928 by Otto Diels and Kurt Alder. The reaction proceeds in a single, concerted step through a transition state and can be accelerated by heating or using catalysts. It is useful for synthesizing 6-membered rings in a stereoselective and stereospecific manner. Lewis acids are commonly used to catalyze the reaction by activating the dienophile. Chiral dienes and dienophiles, as well as chiral Lewis acids, allow for asymmetric Diels-A
The document discusses recent advances in 1,3-dipolar cycloadditions. It begins by introducing the [3+2] 1,3-dipolar cycloaddition reaction which combines a dipolarophile and 1,3-dipole to form a five-membered heterocycle. This reaction is widely used in natural product and pharmaceutical synthesis. It then describes different types of dipolarophiles and 1,3-dipoles that can be used. The reaction mechanisms, classification based on frontier molecular orbitals, effect of Lewis acids, and methods for asymmetric variants are also covered. Recent literature examples of this reaction in natural product synthesis and regioselectivity/stereoselectivity are summarized.
Princeton University has rigorous lab safety training requirements for all individuals working in its over 600 laboratories. The training includes a 3-hour classroom session covering topics like health hazards, emergency procedures, and risk assessment. Undergraduate science majors must complete this training, as well as additional in-lab training, to ensure they are prepared to work independently in future research projects. Graduate students also receive mandatory safety training tailored to their programs. The goal is for all laboratory workers to have a strong base of safety knowledge no matter their role at the university.
This document summarizes Steven G. Oberg's presentation about integrating environmental health and safety programs into university research and teaching. It describes how the University of Nevada, Reno transformed their program from being in chronic violation in 1995 to achieving full regulatory compliance in 2005 by taking an integrated, enterprise-wide approach. This involved attracting quality EH&S staff aligned with the university mission, integrating EH&S staff within departments and academic processes, and integrating EH&S management within the university structure through advisory committees and information sharing. The results were improved lab safety, regulatory compliance, and receiving the 2005 ACS-CHAS Lab Safety Program award.
1) Organozinc compounds are less reactive than organolithium and organomagnesium compounds due to their more covalent C-Zn bond, allowing preparation of functionalized derivatives.
2) Organozinc compounds are commonly prepared by reacting primary or secondary halides with zinc metal or Rieke zinc under inert atmosphere due to their sensitivity to oxidation.
3) Organozinc reagents are useful in organic syntheses such as Reformatsky reactions, Simmons-Smith cyclopropanation reactions, and cross-coupling reactions like Negishi and Fukuyama couplings.
This document provides an overview of organometallic compounds, focusing on organolithium, organomagnesium, organozinc, and organocopper compounds. It defines organometallic chemistry as the study of chemical compounds containing carbon-metal bonds. Key applications of these compounds include forming new carbon-carbon bonds through nucleophilic addition reactions and serving as precursors for other organometallic reagents. The document discusses the structures, properties, preparations and reactions of various organometallic compounds.
This document presents information on organomercury compounds. It introduces organomercury compounds and notes that the Hg-C bond is typically stable but sensitive to light. It discusses the structure, preparation, reactions and examples of important organomercury compounds like methylmercury and dimethyl mercury. The preparation methods covered include the direct reaction of hydrocarbons with mercury salts and the use of sodium amalgam. Key reactions discussed are the Heck reaction and oxymercuration-demercuration reactions. Applications mentioned include use as fungicides, catalysts, and in medicines.
Gilman reagent, also known as organocopper reagents, are prepared by reacting organomagnesium, organolithium, or organozinc reagents with copper(I) salts. Gilman reagents react with a variety of electrophiles including acid chlorides, aldehydes, ketones, epoxides, and alkyl halides. Some common reactions of Gilman reagents are: 1) reactions with acid chlorides to form ketones, 2) coupling reactions between two different alkyl halides to form C-C bonds, and 3) conjugate addition reactions of the organocopper reagent to unsaturated carbonyl compounds like enones. Gilman reagents offer advantages over Grignard reagents for
Gilman's reagent is a lithium and copper (diorganocopper) compound that can be prepared by adding copper(I) iodide to methyllithium at -78°C. Gilman's reagent is useful for replacing halide groups with organic groups through SN2 reactions. Some applications include 1) 1,4-addition to conjugated enones due to the soft nucleophilicity of the reagent, 2) alkyl cross-coupling reactions with organic halides, and 3) addition to acid chlorides to form ketones.
This document provides an overview of catalysis by organometallic compounds. It discusses that organometallic compounds are widely used as homogeneous catalysts in industrial processes and research. Nobel Prizes have been awarded for discoveries in organometallic chemistry and homogeneous catalysis. Examples of important organometallic catalysts discussed include Wilkinson's catalyst, Noyori's catalyst for asymmetric hydrogenation, and Ziegler-Natta catalysts for polymerization of olefins. The mechanisms of homogeneous hydrogenation and different types of catalysis such as homogeneous versus heterogeneous are also summarized.
Mechanistic aspects of C-C cross coupling reactionRashmi Gaur
The document discusses palladium-catalyzed cross-coupling reactions, which were awarded the 2010 Nobel Prize in Chemistry. It summarizes the key reactions including Suzuki, Negishi, Stille, Sonogashira, and Heck reactions. These reactions involve the coupling of organic electrophiles and nucleophiles through oxidative addition, transmetallation, migratory insertion, and reductive elimination steps using a palladium catalyst. The document also discusses the mechanisms and factors influencing these important C-C bond forming reactions.
This document summarizes key aspects of palladium-catalyzed cross-coupling reactions, with a focus on the Heck reaction and its mechanisms and applications. The Heck reaction involves the coupling of alkenyl or aryl halides with alkenes, catalyzed by palladium. The mechanism proceeds through oxidative addition, transmetalation, and reductive elimination steps. The document discusses factors that determine regioselectivity and provides examples of the Heck reaction in total syntheses of natural products like dehydrotubifoline, capnellene, and taxol. It also describes domino and intramolecular Heck reactions and summarizes the related Stille coupling reaction.
Organolithium compounds react through several mechanisms. They form hydrocarbons when reacted with compounds containing active hydrogens like water, alcohols, and amines. Organolithium compounds also undergo 1,2-addition with α, β-unsaturated carbonyl compounds, while Grignard reagents give 1,4 products due to steric hindrance. When reacted with carboxylic acids, organolithium compounds form hydrocarbons in the first step and ketones in the second step. Additionally, organolithium compounds can polymerize with alkenes to form long chain alkanes under high pressure and low temperature.
The Sonogashira cross-coupling reaction forms carbon-carbon bonds between a terminal alkyne and an aryl or vinyl halide using a palladium catalyst. It was developed in 1975 and offers milder conditions than previous coupling reactions, such as room temperature. The reaction employs both a palladium and copper catalyst, with the copper activating the alkyne. It has become a highly useful reaction for carbon-carbon bond formation and has applications in pharmaceuticals, natural products, and organic materials synthesis.
The Suzuki reaction is an organic reaction where an organoboron compound reacts with an organohalide compound to form a carbon-carbon bond. It is catalyzed by palladium and involves three main steps - oxidative addition, transmetalation, and reductive elimination. The Suzuki reaction is widely used in chemical synthesis due to its mild reaction conditions, tolerance of functional groups, and ability to form C-C bonds under aqueous conditions.
Organocatalysis uses small organic molecules rather than metals to catalyze chemical reactions. Thiourea organocatalysis specifically uses thiourea derivatives to accelerate reactions through hydrogen bonding interactions. Primary amine thiourea catalysts have many advantages including being inexpensive, non-toxic, stable, and able to catalyze reactions with high enantioselectivity. The document provides procedures for synthesizing a primary amine thiourea catalyst through Boc protection of an amino acid, formation of an amide bond with benzyl amine, Boc deprotection, and conversion to an isothiocyanate derivative.
TRANSITION METAL CATALYSIS , THE DIFFERENT METALS OF TRANSITION USED AS CATALYTIC REAGENT WITH ITS PROPERTIES , THEIR CHARGE TRANSFER ITS REACTION INCLUDING COPPER, PALLADIUM FOLLWED BY HECKMAN, ULLMAN COUPLING REACTION, GILLMAN REACTION, HECK REACTION
The document discusses organic reactions and reaction mechanisms. It defines nucleophiles and electrophiles, and provides examples of each. It then summarizes several common types of organic reactions including addition reactions, substitution reactions, elimination reactions, and aromatic substitutions. The mechanisms and examples of nucleophilic addition, electrophilic addition, nucleophilic substitution, and electrophilic aromatic substitutions like nitration, sulfonation, and halogenation are described in detail.
1) Elimination reactions occur when two atoms or groups are removed from two adjacent carbon atoms of a substrate molecule to form a multiple bond.
2) Elimination occurs when a nucleophile attacks a hydrogen instead of a carbon.
3) In an E1 elimination reaction, the leaving group leaves in the rate-determining unimolecular step, and the proton is removed in a separate second step.
This document discusses retrosynthetic analysis approaches for aromatic compounds. It covers aromatic electrophilic and nucleophilic substitution reactions, including addition of cationic synthons, Friedel-Crafts alkylation and acylation, and substitution of diazonium salts. It also discusses aromatic side chain transformations through functional group interconversion and nucleophilic aromatic substitution of halides.
The Diels-Alder reaction is a [4+2] cycloaddition between a conjugated diene and a substituted alkene (dienophile) to form a cyclohexene ring. It was discovered in 1928 by Otto Diels and Kurt Alder. The reaction proceeds in a single, concerted step through a transition state and can be accelerated by heating or using catalysts. It is useful for synthesizing 6-membered rings in a stereoselective and stereospecific manner. Lewis acids are commonly used to catalyze the reaction by activating the dienophile. Chiral dienes and dienophiles, as well as chiral Lewis acids, allow for asymmetric Diels-A
The document discusses recent advances in 1,3-dipolar cycloadditions. It begins by introducing the [3+2] 1,3-dipolar cycloaddition reaction which combines a dipolarophile and 1,3-dipole to form a five-membered heterocycle. This reaction is widely used in natural product and pharmaceutical synthesis. It then describes different types of dipolarophiles and 1,3-dipoles that can be used. The reaction mechanisms, classification based on frontier molecular orbitals, effect of Lewis acids, and methods for asymmetric variants are also covered. Recent literature examples of this reaction in natural product synthesis and regioselectivity/stereoselectivity are summarized.
Princeton University has rigorous lab safety training requirements for all individuals working in its over 600 laboratories. The training includes a 3-hour classroom session covering topics like health hazards, emergency procedures, and risk assessment. Undergraduate science majors must complete this training, as well as additional in-lab training, to ensure they are prepared to work independently in future research projects. Graduate students also receive mandatory safety training tailored to their programs. The goal is for all laboratory workers to have a strong base of safety knowledge no matter their role at the university.
This document summarizes Steven G. Oberg's presentation about integrating environmental health and safety programs into university research and teaching. It describes how the University of Nevada, Reno transformed their program from being in chronic violation in 1995 to achieving full regulatory compliance in 2005 by taking an integrated, enterprise-wide approach. This involved attracting quality EH&S staff aligned with the university mission, integrating EH&S staff within departments and academic processes, and integrating EH&S management within the university structure through advisory committees and information sharing. The results were improved lab safety, regulatory compliance, and receiving the 2005 ACS-CHAS Lab Safety Program award.
The document discusses systemic toxicity that can result from skin exposures to chemicals. It describes how both the penetration of chemicals through skin and their toxic potency determine cutaneous toxicity. Several case reports are presented of specific chemicals like pesticides, acids, mercury, and hexachlorophene that have caused mortality through skin exposures alone or in combination with inhalation. The document also discusses chemicals like solvents, metals, and nicotine that can cause morbidity through skin absorption. In summary, while skin provides protection from absorption, some chemicals are able to cause lethal or harmful systemic effects when exposure occurs through the skin.
This document discusses the development and use of chemical safety levels (CSLs) for laboratory risk assessment. It argues that CSLs could help address evolving challenges in laboratory safety by providing a framework to assess risk based on chemical hazards and select appropriate controls. The document outlines stakeholders in laboratory risk assessment and factors to consider when selecting a CSL level. It proposes conceptual CSL levels from 1 to 4 based on fire, corrosivity, reactivity and toxicity hazards and matching controls. Next steps include completing a risk assessment tool and guidance documents for implementing CSLs.
Debbie M. Decker has over 15 years of experience in health and safety roles. She began her career at Explosive Technology, Inc. working with high explosives. She then worked at California State University, Sacramento focusing on chemical and laboratory safety, hazardous waste management, and training. Debbie is currently the Chemical Hygiene Officer at the University of California, Davis where she works on various projects and provides support and guidance on environmental health and safety matters. In her presentation, Debbie reflects on her diverse career path and experiences, emphasizing that no experience is without value and that she has learned to accept uncertainty in her day-to-day responsibilities.
The document outlines the ACS Committee on Professional Training's (CPT) guidelines for safety education in undergraduate chemistry programs. It discusses (1) safety considerations in the ACS guidelines, including adequate facilities, resources, and training students in safe practices; (2) how CPT assesses safety through infrastructure reviews and program self-reports; and (3) the challenges CPT faces in an advisory/consultative role without investigative or enforcement powers.
The document outlines ways that environmental companies can help colleges and universities improve their chemical waste management programs. It suggests identifying schools with needs, offering expertise in regulations and technologies, providing management assistance through training and procedures, conducting chemical inventories, and helping with transportation if permitted. The goal is to be good neighbors while gaining experience for staff.
The document discusses a new Chemical Hazard Use Authorization (CHUA) online application that will allow principal investigators to register high hazard chemicals and obtain Hazard Control Plans. The CHUA aims to provide predictable and effective management of high-risk materials through cooperative management between campus entities, promotion of active safety management, rigorous oversight and accountability, and tools to help safely manage high-risk activities.
The National Institute for Occupational Safety and Health (NIOSH) is the U.S. agency responsible for conducting research to prevent work-related injury and illness. NIOSH provides resources for safe nanotechnology including guidance documents, a nanoparticle information library, reference materials, training, and recommendations for further research needs such as developing methods to detect nanomaterials and characterize their properties. NIOSH also conducts field research at organizations working with nanomaterials to assess exposures, practices, and make recommendations to update their guidance.
This document discusses the challenges and solutions for research operations at a premier aerospace and defense company that works with high-risk energetic materials. It outlines the organizational structure, business challenges including budget constraints, and technical challenges of working with explosives and propellants. Solutions discussed include organizational checks and balances between research and operations, implementing hazard recognition and risk management processes, taking a lifecycle approach with operational discipline, using tracking tools, and ensuring leadership engagement. Recent successes highlighted effective planning and preparation, establishing new processes safely, and growing business lines.
This document proposes integrating a variety of learning methods into safety training based on adult learning principles. It describes a systems approach to conceptualizing the many interrelated factors that influence lab safety. An example training program is outlined that uses a hands-on format addressing the key aspects of recognizing hazards, assessing risks, managing hazards, and preparing for emergencies (the RAMP model). References are provided on systems analysis concepts and specific safety training resources.
The document discusses strategies for balancing laboratory building performance across four types of capital: natural, human, built, and social. It outlines approaches within each type of capital such as facility design and optimization for built capital. For human capital it discusses education and incentives. Social capital strategies include communication, leadership, and policies. The document emphasizes that institutions are complex systems and achieving change requires understanding the relationships between dynamic parts and emerging behaviors.
Ventilation in laboratory buildings accounts for a large portion of campus energy usage, between 4-8 times more than other campus buildings. Laboratory ventilation rates are typically designed between 6-10 air changes per hour for safety reasons, but these high rates significantly increase energy costs. There are opportunities to reduce ventilation rates through better laboratory practices like keeping fume hood sashes low. Electricity usage is also high in laboratories due to numerous instruments and equipment. Regulations around waste disposal and air emissions further increase operating costs of laboratory buildings. However, safety and sustainability considerations do not have to compete - they can be aligned through coordinated efforts between safety, sustainability, and laboratory professionals and staff.
Yale University has transformed its former pharmaceutical campus into a research hub known as Yale West Campus. The 136-acre campus contains over 1.6 million square feet of research labs, administrative offices, and specialty storage facilities. Yale aims to establish interdisciplinary institutes that bring together faculty from across the university to work on challenges in health, environment and energy. The director of research technology discusses challenges in integrating the new campus, developing its identity and vision, and planning state-of-the-art research facilities. Several case studies highlight how old buildings have been repurposed and new centers designed to foster collaboration among researchers.
The document outlines an agenda for a presentation on building better laboratories. The presentation will discuss project roles and definitions, and provide examples of thinking like a user, including engaging maintenance staff in design, cleanliness perceptions, means and methods, BIM value, hoteling concepts, commissioning integration, and always seeking new solutions. The purpose is to explain key concepts for a successful lab project from a builder's perspective and identify what end users and facility managers should know and expect.
This document provides a history of process safety and loss prevention within the American Institute of Chemical Engineers (AIChE) from the early 1900s to present day. It discusses how safety has always been an integral part of chemical engineering. It outlines key events that shaped the field, such as the formation of early safety groups within AIChE in the 1950s in response to ammonia plant incidents. It also describes the establishment of influential organizations like the Center for Chemical Process Safety and their impact promoting process safety guidelines and research. The document illustrates how the field of process safety has grown and evolved over the past century to address new challenges through continued collaboration within the chemical engineering community.
This document discusses reproductive toxins and their impacts in the workplace. It defines terms like teratogens, mutagens, and fetal toxins. It also provides statistics on reproductive issues like infertility, miscarriages, birth defects, and discusses the magnitude of these problems. The document encourages measures to decrease potential exposures to reproductive hazards for male and female laboratory workers and poses questions for discussion.
This document provides a history of occupational exposure levels (OELs) and their development over time. It discusses early figures who studied occupational illnesses and diseases. Some of the earliest attempts to establish OELs occurred in the 1880s-1930s and were based on animal studies. Dust exposure limits were also established beginning in the early 1900s. Modern OEL development began in the late 1930s with organizations like ACGIH publishing recommended values. Throughout the 20th century, various government agencies and laws influenced OEL adoption and regulation in different countries.
This document describes research into direct aldol reactions mediated by dimethylzinc. Three aromatic aldol products were synthesized and their NMR data reported. Racemic aldol products were produced using either dialkylzinc/dialcohol or magnesium bromide/DIPEA. Successful asymmetric and autocatalytic aldol reactions were also achieved using chiral catalysts. The products of some aldol reactions were found to facilitate their own formation and the reaction between other substrates, demonstrating autocatalytic properties. Further study of this autocatalytic process is warranted.
Ionic liquids are excellent substitutes for traditional organic solvents in many typical organic reactions, often producing higher selectivity as well as higher yields, and enhancing the reaction rate.
Additionally, they can serve as catalyst immobilization for the easy recycling of homogeneous catalysts without need for special functionalization, and have been successfully employed as electrolytes in electrochemistry. "Tailor-made" solvents (optimization of the ionic liquid's characteristics) can be achieved through a broad choice of anion and cation combinations. Ionic liquids are attractive solvents as they are non-volatile, non-flammable, have a high thermal stability and are relatively inexpensive to manufacture. They usually exist as liquids well below room temperature up to a temperature as high as 200oC.
The key point about ionic liquids is that they are liquid salts, which means they consist of a salt that exists in the liquid phase. They are not simply salts dissolved in liquid. Usually one or both of the ions is particularly large and the cation has a low degree of symmetry, these factors result in ionic liquids having a reduced lattice energy and hence lower melting points.Many ionic liquids have even been developed for specific synthetic problems. For this reason, ionic liquids have been termed "designer solvents".
to overcome the problem of easily fire catching to fabrics
it will reduce the wealth loss and causing material saving as well as it will cause healthy environment without sudden damage due to fire
chemicals treated are chlorine bromine , and also the bad effects of flame retardants
This document summarizes the characterization of various hydrophilic and hydrophobic room temperature ionic liquids containing the imidazolium cation. The key findings are:
1) The choice of anion determines the water miscibility of the ionic liquid and has the largest effect on properties such as density, viscosity, and surface tension. Hydrophilic anions like chloride and iodide produce water-miscible liquids while more hydrophobic anions like PF6 and N(SO2CF3)2 produce water-immiscible liquids.
2) Increasing the alkyl chain length of the cation from butyl to hexyl to octyl increases the hydrophobicity of the ionic liquid and leads to higher viscos
Effect of Hindered Phenol Stabilizers on the Oxygen Induction Time (OIT) Test...Philip Jacoby
This paper examines the use of the OIT test in predicting the stability of polyolefins and adhesives to thermal oxidative degradation, and the effect of antioxidant type and concentration on the OIT results
This document discusses various methods for depolymerizing polypropylene to reduce its molecular weight. It begins by providing background on how polypropylene is traditionally produced and some limitations of high molecular weight polypropylene for certain applications. It then reviews four main types of depolymerization methods - oxidative, thermal, radiation-based, and chemical - and discusses how each works and its effects. Specifically, it explores using heat, oxygen, ozone, radiation like x-rays, or free radicals to initiate depolymerization reactions that break polymer chains through scission or other reactions to reduce molecular weight and improve processability. The document aims to provide an overview of depolymerization techniques and their impact on polypropylene
History, Classification, Uses of organic chemistryAnm Sharif
Organic chemistry is the study of carbon-based compounds found in living things. The first organic chemist, Berzelius, believed organic compounds could only come from living organisms, but Wöhler discovered the organic compound urea could be synthesized from inorganic precursors, disproving this idea of vitalism. Organic compounds make up the basic building blocks of life like carbohydrates, lipids, proteins, and nucleic acids and have a wide variety of uses from medicines to plastics.
1) The document discusses the synthesis of ultrahigh molecular weight polyethylene (UHMWPE) using traditional Ziegler-Natta catalyst systems.
2) Different catalyst batches were prepared with varying amounts of trivalent titanium (16-32%) and used to polymerize ethylene under various conditions.
3) Process parameters like ethylene pressure, temperature, and hydrogen pressure can be tuned to control the properties of the resulting UHMWPE, including molecular weight, bulk density, and particle size distribution. Fine-tuning these conditions allows for consistent, high-quality UHMWPE production.
This document provides information about several synthetic reagents and their applications:
- Aluminum isopropoxide is used in reductions and oxidations. Diazomethane methylates carboxylic acids and forms cyclopropanes from alkenes. Osmium tetroxide dihydroxylates alkenes and stains polymers. Triphenylphosphine is used in Mitsunobu, Appel, and Staudinger reactions. N-Bromosuccinimide brominates alkenes, allylic/benzylic positions, and carbonyls. Diazopropane and diethyl azodicarboxylate form cyclopropanes and assist Mitsunobu reactions.
— Processes based on immobilized enzymes have been studied extensively in the last few decades and today are also applied to the safeguard of environmental parameters. In this work, zeolite composite flat membranes with different chemical composition, transition metal, and microporous structures were prepared using in situ and secondary growth crystallization synthesis methods in/on stainless steel porous disks. All zeolite materials were been used in catalase adsorption to analyze the zeolite behavior andthe effect of chemical composition and structure on interaction with the enzyme. This study shows that the electrostatic type of interaction seems to be of the utmost importance in influencing immobilization, while the zeolite Brönsted acidity of the support is the subordinate parameter, which differentiates the adsorption performances of different zeolite structures (that distinct for chemical composition of the framework). Moreover, it permits to conclude that transition metal-containing membranes adsorb a higher percentage of the enzyme with respect to no-exchanged membranes and that, for all materials synthesized, the amount of catalase adsorbed onto the zeolite crystals and membranes increases with the temperature.
Hybrid Polymer Electrolytes for Use in Secondary Lithium Ion Batteries-V2-LBAnisha Joenathan
This document summarizes research into improving the properties of hybrid polymer electrolytes for use in lithium ion batteries. The researcher added ionic liquids and varied the molecular weight of polyethylene glycol (PEG) to enhance ionic conductivity and lithium ion transference numbers. Scanning transmission electron microscopy, differential scanning calorimetry, and conductivity measurements were used to characterize the hybrid polymer electrolytes. The addition of ionic liquids, specifically 1-butyl-3-methylimidazolium trifluoromethanosulfonate, increased conductivity by over two orders of magnitude. 400 Da PEG achieved the highest conductivity. Replacement of the lithium salt with sodium resulted in similar conductivity, showing potential for sodium ion batteries.
The document discusses biodegradable polymers and their classification. It covers the history of biodegradable polymers and defines biodegradation. Biodegradable polymers are classified into categories including those derived from biomass, microorganisms, biotechnology, and petrochemical products. The mechanisms of biodegradation and various types of biodegradable polymers like photolytic, peroxidisable, and hydro-biodegradable polymers are also explained. Agricultural applications of biodegradable mulch films are highlighted.
Catalysis Science & Technology covers both the science of catalysis and catalysis technology, including applications addressing global issues. The journal publishes research in the applied, fundamental, experimental and computational areas of catalysis. Contributions are made by the homogeneous, heterogeneous and biocatalysis communities.
The document discusses unexpected results from treating MgCl2-supported polypropylene catalysts containing organometallic complexes with additional TiCl4. Adding TiCl4 at a level equal to the existing Ti increased catalyst activity by 70-95% and decreased the polymer melt flow rate by 50%, suggesting a two-component catalyst system. The author proposes the TiCl4 treatment replaces the organometallic complex and frees it to take an external role while restoring the original MgCl2/TiCl4 catalyst. This two-component system provides roughly equal contributions to activity from each component but differing effects on polymer properties like extractables. The author also suggests these complexes could be converted to single-site catalysts using reactive
Here is a draft statement of teaching philosophy based on the provided prompt:
My teaching philosophy is grounded in the belief that effective teaching is as much about learning as it is about imparting knowledge. As Tagore eloquently stated, a teacher must keep their own flame of learning burning in order to light that flame within students. It is through active engagement with course material, ongoing reflection and improvement, and a genuine curiosity about each student's learning process that I strive to create an enriching educational experience.
My goal in the classroom is not only to convey information, but also to inspire students to think critically and develop a lifelong passion for learning. I aim to foster a collaborative environment where students feel empowered to explore ideas, respectfully
This document discusses the synthesis of poly(lactic acid) (PLA) biomaterials. There are two main synthetic methods - direct polycondensation and ring-opening polymerization of lactide monomers. Direct polycondensation includes solution and melt polycondensation, but yields PLA with low molecular weight. Ring-opening polymerization using metal catalysts is more common and can produce high molecular weight PLA, but the metal catalysts require removal. Recent research focuses on developing non-toxic catalysts and new polymerization conditions.
CHE235L4Spring2017.pdf
FW
(g/mol)
mp (
o
C) bp (
o
C) mmol mass (g)
density
(g/mL)
volume
(mL)
N/A
N/A
bismuth(III) nitrate pentahydrate N/A N/A N/A N/A
sodium chloride, saturated (brine) N/A N/A N/A N/A N/A
ethyl acetate N/A N/A
cis -1,2-cyclohexanediol N/A N/A N/A
trans -1,2-cyclohexanediol, (±) N/A N/A N/A
Prelab 4: Green Lewis Acid-Catalyzed Hydrolysis of Cyclohexene Oxide
Name:
Reaction equation:
Note: For those reagents that are in solution, the FW, mmol, and mass columns refer to the solute in the
solution.
Limiting reagent:
Reagent Table
water
Theoretical yield:
Chemical
cyclohexene oxide
EXPERIMENT #4
GREEN LEWIS ACID-CATALYZED HYDROLYSIS OF CYCLOHEXENE OXIDE
Introduction:
Epoxides are three-membered ethers. They are special because unlike most ethers, they can react
with nucleophiles to form a new bond between carbon and the nucleophile and break a bond
between that carbon and oxygen. This ring-opening reaction makes epoxides versatile functional
groups for organic synthesis. (In fact epoxide is the functional group that makes epoxy resins
possible.)
Scheme 1. Ring opening of an epoxide in the presence of a nucleophile.
Ring-opening of the epoxide can occur under basic or acidic conditions. Under basic conditions,
the reaction is similar to an SN2 reaction so that the nucleophile attacks the less substituted carbon
of an unsymmetrical epoxide by backside attack. Sodium ethoxide reacts with this epoxide in the
following reaction.
Scheme 2. Ring opening of an unsymmetrical epoxide under basic conditions.
Under acidic conditions, the reaction is more complicated. It is similar to an SN2 reaction because
the nucleophile reacts by backside attack. However, because there is partial positive charge on the
Reference Material:
MAHHS Chapter 1: Safety in the Laboratory
MAHHS Chapter 2: Protecting the Environment
MAHHS Chapter 3: Laboratory Notebooks and Prelaboratory Information
MAHHS Chapter 4: Laboratory Glassware
MAHHS Chapter 5: Measurements and Transferring Reagents
MAHHS Chapter 10: Filtration
MAHHS Chapter 11: Extraction
MAHHS Chapter 12: Drying Organic Liquids and Recovering Reaction Products
MAHHS Chapter 17: Thin-Layer Chromatography, especially section 17.8
MAHHS Chapter 20: Infrared Spectroscopy
Klein Chapter 14: Ethers and Epoxides; Thiols and Sulfides
three atoms of the epoxide ring, the nucleophile attacks where the partial positive charge is more
stabilized, the more substituted carbon of an unsymmetrical epoxide. Ethanol in the presence of
sulfuric acid reacts with this epoxide in the following reaction.
Scheme 3. Ring opening of an unsymmetrical epoxide under acidic conditions.
While sulfuric acid is an inexpensive acid catalyst, it is difficult to handle. It is very corrosive and
can cause severe burns. In addition, it is viscous, which makes it difficult to handle on the scale of
the reactions perfor ...
Green chemistry, Its Applications and BenefitsAmit Amola
Green chemistry is the design of chemical products and processes to reduce or eliminate the use and generation of hazardous substances. It was formally established 15 years ago by the EPA in response to pollution regulations. The key principles of green chemistry developed by Anastas and Warner include preventing waste through inherently safer design of synthesis processes and products. Examples show how green chemistry has led to replacement of hazardous chemicals like phosgene and solvents like benzene with safer alternatives like solid-state synthesis routes and ionic liquids.
A new generation of cable grade poly(vinyl chloride) containing heavy metal f...Ali I. Al-Mosawi
Many additives are used to improve the performance of cables in terms of increasing their flame retardancy, thermal stability, thermal conductivity, and other characteristics. Unfortunately, most of these additives contain heavy metals. Therefore, the main objective of this study is to introduce a material representing a new generation of environmentally friendly heavy metal-free stabilizers for cable grade poly(vinyl chloride) that can compete with traditional materials in terms of performance and distinctive properties. This unique additive is Oxydtron, a synthetic silicate or simply nanocement. The tests performed are rheological properties represented by a capillary rheometry analysis, limiting oxygen index, and volume resistivity. The most significant improvement in Bagley correction measurements was 14.61%; 18.13%; and 27.20% more than poly(vinyl chloride) basic formulation when using 5wt.% Oxydtron at 160°C, 170°C, and 180°C, respectively. Also, the mean increases in relaxation time were 3.200 times, 8.825 times, and 12.458 times more than poly(vinyl chloride) basic formulation with 1wt.%, 3wt.%, and 5wt.% of Oxydtron, respectively. Furthermore, the Oxydtron lowered the value of the accompanying thermal gradient of the L.O.I test, reducing the heat-affected zone. The best result was with the extrusion processing method due to the uniformity of the processing conditions. However, the thermal gradient analysis showed residual heat stress in the test samples after cutting the burning layer and re-testing the samples again; this causes them to burn faster. This situation requires caution for designs that are exposed to high temperatures without burning. The optimum improvement in volume resistivity value was 14.71% and 38.24% more than poly(vinyl chloride) basic formulation after adding 5wt.% and 7wt.% of Oxydtron, respectively.
The document summarizes a study on the degradation of the synthetic polymer Nylon 6 through composting. Nylon 6 sheets were submerged in a semi-natural composting environment for 3 months. Analysis found a 10% reduction in weight and 13% reduction in thickness of the Nylon 6 sheets. Fourier transform spectroscopy and thermo gravimetric analysis indicated weakening of the amide bonds in the polymer and degradation through composting conditions. The study confirms that composting can actively degrade synthetic Nylon 6 polymer.
The document summarizes the role and activities of the Director of Research Technology (DoRT) at Yale University. It discusses how DoRT supports research by managing shared research instrumentation, facilitating relationships with faculty and vendors, assisting with facilities planning, and providing other services. It also gives examples of DoRT's work, such as acquiring and inventorying lab equipment from a new research campus and providing a 5-stage process for integrating new faculty into the research environment at Yale within 1 year.
The document summarizes OSHA's Hazard Communication Standard 1910.1200. It outlines the purpose and definitions of key terms to ensure chemical hazards are evaluated and communicated. It describes requirements for written hazard programs, labels, safety data sheets, and employee training. It provides details on hazard classification and the changes made to harmonize with the global standard including new definitions, pictograms, and safety data sheet format.
The document describes a technique called Lab-HIRA (Hazard Identification and Risk Analysis) for identifying and assessing hazards associated with chemical synthesis in a research laboratory. Lab-HIRA involves identifying hazards using data on the physical, chemical and health properties of reactants and reactions. Once hazards are identified, appropriate risk minimization measures can be implemented. The document provides examples of how Lab-HIRA classifies hazard data and identifies hazardous characteristics and reaction types.
Using transparency to increase awareness of chemical hazardsDIv CHAS
This document summarizes a study on how to make chemical hazard information on the internet more useful for researchers and workers at universities. It tested the relevance, compatibility, and accessibility of various chemical safety websites using ratings from students and laboratory staff. Websites from the Agency for Toxic Substances and Disease Registry (ATSDR), New Jersey Right to Know program, and International Chemical Safety Cards were rated most highly. The study found that for chemical safety sites to be useful, they need relevant and easily accessible content, as well as high search engine rankings like on Google.
Chemistry involves exposure to hazardous chemicals, but exposure can be managed by keeping it below recognized limits and informing workers of risks. While universities produce chemists for industry, government, and academia, textbooks often omit teaching students how to safely handle concentrated acids/bases and toxic chemicals. This misses opportunities to explain dilution, hazard assessments, risk evaluations, and safe waste disposal. Instructors should introduce concepts like hazard, risk management, and chemical substitution to help students respect chemical risks and safely handle hazardous materials as future professionals.
This document discusses lessons learned from designing an interactive safety training course. It covers how people learn, including the difference between working and long-term memory. It also presents models for instructional design, like the ROPES model of review, overview, presentation, exercise and summary. Specific techniques are discussed like varying activities every 20 minutes and interacting every 8 minutes. The document concludes by outlining the implementation of safety lessons for different chemistry courses.
This document summarizes a presentation on challenges and solutions for research operations at Oak Ridge National Laboratory. It discusses defining an operations philosophy focused on directly supporting research. It also addresses developing a team approach with expertise at all levels, from subject matter experts to local support staff. Finally, it outlines taking a plan-based approach to focus areas to continuously improve operations while keeping research progressing efficiently.
The document discusses the role of managing the interface between research organizations and teams involved in designing, constructing, and moving facilities. It focuses on minimizing research downtime by having a research representative embedded throughout the process to facilitate efficient planning, communication, and timely resolution of conflicts. The role involves listening to researcher needs, balancing those with flexibility, and negotiating communication between all parties.
This document discusses fire codes and chemical limits for scientific facilities. It provides examples of how infrastructure affects maximum allowable quantities of hazardous materials. Specifically, it compares a 1950s facility with one constructed in 1999. The older facility had inadequate fire barriers and a single chemical control area, limiting it to lower quantities. The newer facility has proper fire barriers and 10 separate chemical control areas, allowing storage of much greater amounts divided among the areas. The document emphasizes that chemical storage limits depend on the occupancy classification, safety features of the building, and requirements of the building and fire codes.
Developing effective safety training for a changing audienceDIv CHAS
The document discusses developing effective safety training for a changing audience. It notes that effective training incorporates visual, auditory, and kinesthetic learning modalities and encourages active learning. Examples of training methods discussed include instructor-led training using objectives, worksheets, and demonstrations, as well as online or computer-based training using video, audio, and interactivity. The goal is to develop training that meets different learning needs and engages learners through problem-based scenarios.
Using transparency to increase awareness of chemical hazards.pptxDIv CHAS
This document summarizes a study on how to make chemical hazard information on the internet more useful for researchers and workers. The study tested how 35 participants rated the relevance, compatibility and accessibility of various chemical safety websites in responding to hypothetical chemical exposure scenarios. Websites from government agencies like ATSDR and NIOSH rated highly according to these criteria. The findings suggest that for chemical safety information online to be truly useful, sites need relevant and easy-to-understand content as well as high searchability in engines like Google.
This document discusses efforts to improve chemical safety culture at Texas Tech University's Department of Chemistry and Biochemistry following a laboratory explosion in 2010. It provides background on Texas Tech University and the chemistry department. It then outlines the response to the explosion, which included reorganizing safety committees, requiring safety training and personal protective equipment, and increasing regulatory oversight of laboratories. It describes additional changes made by the chemistry department such as implementing peer safety reviews, developing incident reporting processes, and emphasizing safety in graduate education and faculty evaluations. Finally, it discusses lessons learned about the challenges of ensuring chemical safety culture.
Safety culture and academic laboratory accidentsDIv CHAS
The document summarizes Miriam Weil's research on safety culture in academic laboratories. It details accidents that occurred at UCLA, Northwestern, and Dartmouth and how each institution addressed laboratory safety after the incidents. Weil conducted interviews and literature reviews to analyze the key elements of safety culture. Her research identified management commitment to safety, communication of safety information, and trust as the three most critical values of an effective safety culture.
This document describes a hazard identification and risk analysis (Lab-HIRA) technique for chemical research laboratories. The Lab-HIRA technique involves identifying hazards of planned chemical syntheses using data on reactants, reactions, and experimental conditions. This includes assigning hazard indices to discrete property values and characteristic hazards. Once hazards are identified, appropriate risk minimization measures can be implemented. The document provides examples of applying the Lab-HIRA technique to sample chemical properties, characteristics, reaction types, and conditions.
Chemistry involves exposure to hazardous chemicals, but exposure can be managed by keeping it below recognized limits and informing workers of risks. While universities produce chemists for industry, government, and academia, textbooks often omit teaching students how to safely handle concentrated acids/bases and toxic chemicals. This misses opportunities to explain dilution, hazard assessments, risk evaluations, and safe waste disposal. Instructors should introduce concepts like hazard, risk management, and chemical substitution to help students respect chemical risks and safely work with hazardous materials as future chemists.
This document discusses the installation of fire suppression systems in gloveboxes and summarizes the research done to evaluate options. An automatic clean agent fire extinguisher was selected that is self-contained, compact, and activates based on temperature. Computational modeling and experiments were used to validate the reliability and performance of the extinguisher under different conditions. The extinguisher was certified to extinguish Class A, B, and C fires and presents the most reliable option, especially in seismic events.
Ralph Stuart discusses rethinking laboratory ventilation traditions to balance safety and sustainability. Key points include:
1. Laboratory ventilation aims to control temperature, fire hazards, odors, toxicity, dust, and humidity, often through excessive air changes.
2. Fume hoods, while important for safety, can use as much energy as 3.5 houses each. Variable air volume hoods and occupancy sensors can reduce this impact.
3. Studies show 6 air changes per hour may adequately control chemical hazards in many labs, offering energy savings over the traditional standard of 8 changes. Proper chemical storage and local exhaust also improve safety.
The document summarizes renovation plans for the Chemistry Department at the National University of Singapore. It describes the existing facilities and plans to consolidate space and research areas through renovating existing buildings and constructing new buildings by 20XX. The first renovation involved converting a synthesis teaching lab, which required redesigning the lab layout, ventilation, and addressing issues like humidity control. Future plans include renovating entire labs and teaching labs on tighter schedules while managing utility considerations.
This document summarizes research on laboratory safety culture in academic chemistry laboratories. It discusses how safety culture has evolved to mean an organization's commitment to safety as demonstrated through its policies, communication, and employee involvement. The document reports on two surveys conducted by the Division of Chemical Health and Safety: one of chemistry departments nationwide and one of its membership. The surveys found general acceptance of safety responsibilities but missing elements of a fully developed safety management system in many departments. The document also reviews other relevant literature on measuring safety culture and case studies of implementing safety programs at institutions.
The National Library of Medicine has developed several tools to provide first responders and medical professionals with information for responding to chemical, biological, radiological, and nuclear incidents. Two such tools are CHEMM (Chemical Hazards Emergency Medical Management) and REMM (Radiation Emergency Medical Management). CHEMM provides medical guidelines for treating exposures to toxic chemicals and includes the CHEMM-IST diagnostic tool. REMM provides clinical guidance for mass casualty radiation events. Both tools are available online and via mobile applications. The NLM aims to keep the content up-to-date and expand to additional hazard types based on user needs and available resources.
Epistemic Interaction - tuning interfaces to provide information for AI supportAlan Dix
Paper presented at SYNERGY workshop at AVI 2024, Genoa, Italy. 3rd June 2024
https://alandix.com/academic/papers/synergy2024-epistemic/
As machine learning integrates deeper into human-computer interactions, the concept of epistemic interaction emerges, aiming to refine these interactions to enhance system adaptability. This approach encourages minor, intentional adjustments in user behaviour to enrich the data available for system learning. This paper introduces epistemic interaction within the context of human-system communication, illustrating how deliberate interaction design can improve system understanding and adaptation. Through concrete examples, we demonstrate the potential of epistemic interaction to significantly advance human-computer interaction by leveraging intuitive human communication strategies to inform system design and functionality, offering a novel pathway for enriching user-system engagements.
LF Energy Webinar: Electrical Grid Modelling and Simulation Through PowSyBl -...DanBrown980551
Do you want to learn how to model and simulate an electrical network from scratch in under an hour?
Then welcome to this PowSyBl workshop, hosted by Rte, the French Transmission System Operator (TSO)!
During the webinar, you will discover the PowSyBl ecosystem as well as handle and study an electrical network through an interactive Python notebook.
PowSyBl is an open source project hosted by LF Energy, which offers a comprehensive set of features for electrical grid modelling and simulation. Among other advanced features, PowSyBl provides:
- A fully editable and extendable library for grid component modelling;
- Visualization tools to display your network;
- Grid simulation tools, such as power flows, security analyses (with or without remedial actions) and sensitivity analyses;
The framework is mostly written in Java, with a Python binding so that Python developers can access PowSyBl functionalities as well.
What you will learn during the webinar:
- For beginners: discover PowSyBl's functionalities through a quick general presentation and the notebook, without needing any expert coding skills;
- For advanced developers: master the skills to efficiently apply PowSyBl functionalities to your real-world scenarios.
Maruthi Prithivirajan, Head of ASEAN & IN Solution Architecture, Neo4j
Get an inside look at the latest Neo4j innovations that enable relationship-driven intelligence at scale. Learn more about the newest cloud integrations and product enhancements that make Neo4j an essential choice for developers building apps with interconnected data and generative AI.
Alt. GDG Cloud Southlake #33: Boule & Rebala: Effective AppSec in SDLC using ...James Anderson
Effective Application Security in Software Delivery lifecycle using Deployment Firewall and DBOM
The modern software delivery process (or the CI/CD process) includes many tools, distributed teams, open-source code, and cloud platforms. Constant focus on speed to release software to market, along with the traditional slow and manual security checks has caused gaps in continuous security as an important piece in the software supply chain. Today organizations feel more susceptible to external and internal cyber threats due to the vast attack surface in their applications supply chain and the lack of end-to-end governance and risk management.
The software team must secure its software delivery process to avoid vulnerability and security breaches. This needs to be achieved with existing tool chains and without extensive rework of the delivery processes. This talk will present strategies and techniques for providing visibility into the true risk of the existing vulnerabilities, preventing the introduction of security issues in the software, resolving vulnerabilities in production environments quickly, and capturing the deployment bill of materials (DBOM).
Speakers:
Bob Boule
Robert Boule is a technology enthusiast with PASSION for technology and making things work along with a knack for helping others understand how things work. He comes with around 20 years of solution engineering experience in application security, software continuous delivery, and SaaS platforms. He is known for his dynamic presentations in CI/CD and application security integrated in software delivery lifecycle.
Gopinath Rebala
Gopinath Rebala is the CTO of OpsMx, where he has overall responsibility for the machine learning and data processing architectures for Secure Software Delivery. Gopi also has a strong connection with our customers, leading design and architecture for strategic implementations. Gopi is a frequent speaker and well-known leader in continuous delivery and integrating security into software delivery.
Why You Should Replace Windows 11 with Nitrux Linux 3.5.0 for enhanced perfor...SOFTTECHHUB
The choice of an operating system plays a pivotal role in shaping our computing experience. For decades, Microsoft's Windows has dominated the market, offering a familiar and widely adopted platform for personal and professional use. However, as technological advancements continue to push the boundaries of innovation, alternative operating systems have emerged, challenging the status quo and offering users a fresh perspective on computing.
One such alternative that has garnered significant attention and acclaim is Nitrux Linux 3.5.0, a sleek, powerful, and user-friendly Linux distribution that promises to redefine the way we interact with our devices. With its focus on performance, security, and customization, Nitrux Linux presents a compelling case for those seeking to break free from the constraints of proprietary software and embrace the freedom and flexibility of open-source computing.
UiPath Test Automation using UiPath Test Suite series, part 6DianaGray10
Welcome to UiPath Test Automation using UiPath Test Suite series part 6. In this session, we will cover Test Automation with generative AI and Open AI.
UiPath Test Automation with generative AI and Open AI webinar offers an in-depth exploration of leveraging cutting-edge technologies for test automation within the UiPath platform. Attendees will delve into the integration of generative AI, a test automation solution, with Open AI advanced natural language processing capabilities.
Throughout the session, participants will discover how this synergy empowers testers to automate repetitive tasks, enhance testing accuracy, and expedite the software testing life cycle. Topics covered include the seamless integration process, practical use cases, and the benefits of harnessing AI-driven automation for UiPath testing initiatives. By attending this webinar, testers, and automation professionals can gain valuable insights into harnessing the power of AI to optimize their test automation workflows within the UiPath ecosystem, ultimately driving efficiency and quality in software development processes.
What will you get from this session?
1. Insights into integrating generative AI.
2. Understanding how this integration enhances test automation within the UiPath platform
3. Practical demonstrations
4. Exploration of real-world use cases illustrating the benefits of AI-driven test automation for UiPath
Topics covered:
What is generative AI
Test Automation with generative AI and Open AI.
UiPath integration with generative AI
Speaker:
Deepak Rai, Automation Practice Lead, Boundaryless Group and UiPath MVP
UiPath Test Automation using UiPath Test Suite series, part 5DianaGray10
Welcome to UiPath Test Automation using UiPath Test Suite series part 5. In this session, we will cover CI/CD with devops.
Topics covered:
CI/CD with in UiPath
End-to-end overview of CI/CD pipeline with Azure devops
Speaker:
Lyndsey Byblow, Test Suite Sales Engineer @ UiPath, Inc.
Unlock the Future of Search with MongoDB Atlas_ Vector Search Unleashed.pdfMalak Abu Hammad
Discover how MongoDB Atlas and vector search technology can revolutionize your application's search capabilities. This comprehensive presentation covers:
* What is Vector Search?
* Importance and benefits of vector search
* Practical use cases across various industries
* Step-by-step implementation guide
* Live demos with code snippets
* Enhancing LLM capabilities with vector search
* Best practices and optimization strategies
Perfect for developers, AI enthusiasts, and tech leaders. Learn how to leverage MongoDB Atlas to deliver highly relevant, context-aware search results, transforming your data retrieval process. Stay ahead in tech innovation and maximize the potential of your applications.
#MongoDB #VectorSearch #AI #SemanticSearch #TechInnovation #DataScience #LLM #MachineLearning #SearchTechnology
Generative AI Deep Dive: Advancing from Proof of Concept to ProductionAggregage
Join Maher Hanafi, VP of Engineering at Betterworks, in this new session where he'll share a practical framework to transform Gen AI prototypes into impactful products! He'll delve into the complexities of data collection and management, model selection and optimization, and ensuring security, scalability, and responsible use.
In the rapidly evolving landscape of technologies, XML continues to play a vital role in structuring, storing, and transporting data across diverse systems. The recent advancements in artificial intelligence (AI) present new methodologies for enhancing XML development workflows, introducing efficiency, automation, and intelligent capabilities. This presentation will outline the scope and perspective of utilizing AI in XML development. The potential benefits and the possible pitfalls will be highlighted, providing a balanced view of the subject.
We will explore the capabilities of AI in understanding XML markup languages and autonomously creating structured XML content. Additionally, we will examine the capacity of AI to enrich plain text with appropriate XML markup. Practical examples and methodological guidelines will be provided to elucidate how AI can be effectively prompted to interpret and generate accurate XML markup.
Further emphasis will be placed on the role of AI in developing XSLT, or schemas such as XSD and Schematron. We will address the techniques and strategies adopted to create prompts for generating code, explaining code, or refactoring the code, and the results achieved.
The discussion will extend to how AI can be used to transform XML content. In particular, the focus will be on the use of AI XPath extension functions in XSLT, Schematron, Schematron Quick Fixes, or for XML content refactoring.
The presentation aims to deliver a comprehensive overview of AI usage in XML development, providing attendees with the necessary knowledge to make informed decisions. Whether you’re at the early stages of adopting AI or considering integrating it in advanced XML development, this presentation will cover all levels of expertise.
By highlighting the potential advantages and challenges of integrating AI with XML development tools and languages, the presentation seeks to inspire thoughtful conversation around the future of XML development. We’ll not only delve into the technical aspects of AI-powered XML development but also discuss practical implications and possible future directions.
Pushing the limits of ePRTC: 100ns holdover for 100 daysAdtran
At WSTS 2024, Alon Stern explored the topic of parametric holdover and explained how recent research findings can be implemented in real-world PNT networks to achieve 100 nanoseconds of accuracy for up to 100 days.
Climate Impact of Software Testing at Nordic Testing DaysKari Kakkonen
My slides at Nordic Testing Days 6.6.2024
Climate impact / sustainability of software testing discussed on the talk. ICT and testing must carry their part of global responsibility to help with the climat warming. We can minimize the carbon footprint but we can also have a carbon handprint, a positive impact on the climate. Quality characteristics can be added with sustainability, and then measured continuously. Test environments can be used less, and in smaller scale and on demand. Test techniques can be used in optimizing or minimizing number of tests. Test automation can be used to speed up testing.
A tale of scale & speed: How the US Navy is enabling software delivery from l...sonjaschweigert1
Rapid and secure feature delivery is a goal across every application team and every branch of the DoD. The Navy’s DevSecOps platform, Party Barge, has achieved:
- Reduction in onboarding time from 5 weeks to 1 day
- Improved developer experience and productivity through actionable findings and reduction of false positives
- Maintenance of superior security standards and inherent policy enforcement with Authorization to Operate (ATO)
Development teams can ship efficiently and ensure applications are cyber ready for Navy Authorizing Officials (AOs). In this webinar, Sigma Defense and Anchore will give attendees a look behind the scenes and demo secure pipeline automation and security artifacts that speed up application ATO and time to production.
We will cover:
- How to remove silos in DevSecOps
- How to build efficient development pipeline roles and component templates
- How to deliver security artifacts that matter for ATO’s (SBOMs, vulnerability reports, and policy evidence)
- How to streamline operations with automated policy checks on container images
GraphSummit Singapore | The Future of Agility: Supercharging Digital Transfor...Neo4j
Leonard Jayamohan, Partner & Generative AI Lead, Deloitte
This keynote will reveal how Deloitte leverages Neo4j’s graph power for groundbreaking digital twin solutions, achieving a staggering 100x performance boost. Discover the essential role knowledge graphs play in successful generative AI implementations. Plus, get an exclusive look at an innovative Neo4j + Generative AI solution Deloitte is developing in-house.
1. 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: jim_schwindeman@fmc.com. 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 Chemical Engineering 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
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 is primarily impacted recommendations for handling and lithium nitride (Li3N). Further, this
by the storage temperature. Higher storage of the speci®c organolithium reaction is catalyzed by moisture.
temperature accelerates the decompo- compound of interest. The glassware employed in the reac-
sition. The lithium hydride that is pro- The ®rst consideration in planning tion must be free of moisture and
duced in the decomposition of the experiment is locationÐwhere to oxygen before introducing the organo-
alkyllithium compounds and lithium conduct the experiment. To minimize lithium compound. There are several
dialkylamides precipitates from the personnel exposure, it is highly advi- techniques routinely employed to dry
and inert a reaction apparatus. One
technique is to assemble the glassware
in the hood, attach the inert gas line,
Figure 1. Thermal decomposition of n-butyllithium. evacuate the apparatus with a vacuum
Chemical Health & Safety, May/June 2002 7
3. source, heat the apparatus with a heat mended ®re extinguisher is a Class B in a metal bowl. This serves as a catch
gun for several minutes, isolate the ®re extinguisher.15 It is imperative pan for the organolithium solution in
vacuum, then re®ll the apparatus with NOT to use ®re extinguishers that con- the event either breaks. In addition, the
the inert gas. This vacuum/inert gas tain water, carbon dioxide or haloge- metal bowl surrounding the reaction
cycle should be repeated several times. nated hydrocarbons for organolithium vessel can be employed to hold the
A popular alternative is to assemble ®res. Alkyllithiums react violently with cooling medium for a cryogenic reac-
the glassware in the hood, attach the these three classes of extinguishing tion. This cooling medium should be
inert gas line, start the ¯ow of the gas, agents. The use of these improper
heat the apparatus with a heat gun for extinguishers will exacerbate, rather There are two basic
several minutes and then let it cool to than mitigate, the ®re scenario.
room temperature in a stream of the techniques for the
inert gas. One additional technique for
glassware drying/inerting is to place LABORATORY SET-UP
transfer of organoli-
the individual glassware pieces in an A typical organolithium reaction appa- thium solutions in the
oven to dry. The glassware should ratus, out®tted for cannula transfer, is
remain in the oven for at least several illustrated schematically in Figure 3. laboratory, the syringe
hours at 1208C, assembled hot in the
hood, and allowed to cool to room
The reactor is equipped with a
mechanical stirrer, a pressure-equaliz-
technique and the
temperature in a stream of inert gas. ing addition funnel equipped with a cannula technique.
Alternatively, the glassware can be septum, and a Claisen adapter ®tted
removed from the oven, placed in a with a thermometer to measure inter- an inert hydrocarbon solvent, such as
desiccator to cool to room tempera- nal temperature and a dry ice conden- hexane or heptane, mixed with solid
ture, assembled in the hood then ser. The inert gas line is attached to the carbon dioxide, ``dry ice.'' The more
purged with the inert gas. outlet of the condenser, which is con- traditional cooling bath solvents, acet-
The proper personal protective nected via a ``T'' ®tting to a bubbler one or 2-propanol, react vigorously
equipment (PPE) for handling organo- ®lled with mineral oil. This bubbler16 with organolithium solutions and
lithium compounds should also be monitors the positive ¯ow of inert gas should be avoided. Similarly, a water
secured prior to experimentation. To through the system and prevents the condenser should not be used, due to
protect the eyes from the corrosivity of in¯ow of air into the reactor in the potential for leaks, which could enter
organolithium compounds, eye protec- event of partial vacuum. A second inert the reaction vessel.
tion in the form of safety glasses or gas line is employed for the reagent
goggles should always be worn. Addi- bottle of organolithium. The mineral
tional eye protection, provided by a oil bubbler on this side has a clamp on TRANSFER TECHNIQUES
face shield, is recommended in experi- the outlet to facilitate transfer via the There are two basic techniques for the
ments where higher volumes of orga- cannula. The reaction vessel and the transfer of organolithium solutions in
nolithium reagents (greater than 1 L) organolithium should each be placed the laboratory, the syringe technique
are employed. The ¯ammability and
pyrophoricity hazards are mitigated
by the use of a ¯ame-resistant lab coat
or coveralls.12 Proper glove selection
will provide protection for hands
potentially exposed to the corrosive
nature of the organolithium com-
pounds and the organic solvents in
which they are formulated. Gloves
made of Viton1 afford the best overall
protection; however, they are expen-
sive.13 Nitrile gloves offer a good com-
promise between chemical protection
and affordability.14 Proper footwear,
leather, closed-toe shoes, protect the
feet from spills.
In the event of a spill, another
important element to protection of
personnel and equipment is a ®re
extinguisher. It is important to secure
the appropriate ®re extinguisher for
organolithium reagents prior to initia-
tion of the experiment. The recom- Figure 3. Laboratory apparatus for cannula transfer.
8 Chemical Health & Safety, May/June 2002
4. and the cannula technique. The two down on the syringe plunger. The solid bottle. The other tip of the cannula is
techniques are very similar. The syr- cap is replaced on the sample bottle inserted into the septum in the addi-
inge technique is preferred when rela- and it is returned to the refrigerator. tion funnel. The tip of the cannula is
tively small volumes of organolithium The amount of the organolithium dis- lowered into the liquid of the organo-
solutions are required (less than pensed can be calculated by noting the lithium solution. The clamp on the exit
50 mL). The transfer of larger volumes ®nal volume in the addition funnel. A of the mineral oil bubbler attached to
is most easily accomplished with the more accurate technique for determin- the reagent bottle is slowly closed. This
cannula technique. The laboratory ing the amount of organolithium trans- causes pressure to build in the reagent
apparatus for a cannula transfer is illu- ferred is by weight. This is bottle and the organolithium solution
strated in Figure 3.17 accomplished by weighing the sample will transfer to the addition funnel.
bottle before and after the reagent has Inert gas pressure should never exceed
Syringe Technique been dispensed. It is advisable to clean 5 psi (0.3 bar). When the desired
Clutter and combustibles are removed the syringe soon after the transfer is volume has been transferred, the
from the hood where the reaction will complete, to minimize the chance of clamp on the bubbler is released and
be conducted. The reaction apparatus the plunger sticking and ``freezing'' in the tip of the cannula is raised above
is dried, purged with an inert gas and the barrel. For pyrophoric solutions, the liquid level in the bottle. This latter
assembled in the hood using one of the any residue in the syringe should be action will prevent siphoning of the
techniques detailed previously. The diluted to less than 5 wt.% with an organolithium solution. Let any excess
reaction ¯ask is placed in a metal bowl. inert solvent, such as heptane. This organolithium solution drain back into
The bottle of the organolithium com- rinse solution can then be quenched the reagent bottle by gravity. The can-
pound is removed from the refrigerator by slowly mixing with an equal volume nula is removed from the reagent bottle
and is clamped in the hood in a metal of cold water. and then from the addition funnel. The
bowl. This minimizes the chance of a solid cap is replaced on the sample
spill if the bottle is accidentally Cannula Technique bottle and it is returned to the refrig-
bumped during the transfer. It is Clutter and combustibles are removed erator. The amount of the organo-
recommended that the syringe be at from the hood where the reaction will lithium dispensed can be calculated
least twice the volume of the organo- be conducted. The reaction apparatus by noting the ®nal volume in the addi-
lithium to be dispensed. The syringe is dried, purged with an inert gas and tion funnel. A more accurate technique
that will be employed in transfer must assembled in the hood using one of the for determining the amount of organo-
also be dried before it is employed. The techniques detailed previously. The lithium transferred is by weight. This is
syringe should be dried in an oven for reaction ¯ask is placed in a metal bowl. accomplished by weighing the sample
at least 2 hr at 1208C, placed in a The bottle of the organolithium com- bottle before and after the reagent has
desiccator to cool to ambient tempera- pound is removed from the refrigerator been dispensed. It is advisable to clean
ture, then purged with a stream of inert and is clamped in the hood in a metal the cannula soon after the transfer is
gas. Don all the recommended PPE. If bowl. This minimizes the chance of a complete, to minimize the chance of
the reagent bottle for the organo- spill if the bottle is accidentally cannula plugging. For pyrophoric solu-
lithium compound was shipped with bumped during the transfer. The can- tions, any residue in the cannula
a solid cap from the supplier, it should nula is a long syringe needle with a should be diluted to less than 5 wt.%
be replaced with a cap with a septum. sharpened tip at each end. The cannula with an inert solvent, such as heptane.
The inert gas ¯ow is started on the that will be employed in transfer must This rinse solution can then be
reagent line. A standard syringe needle also be dried before it is employed. The quenched by slowly mixing with an
is inserted into the end of the inert gas cannula should be dried in an oven for equal volume of cold water.
line. The tip of this needle is then at least 2 hr at 1208C, placed in a
inserted into the septum of the reagent desiccator to cool to ambient tempera-
bottle. Observe the inert gas ¯ow at the ture, then purged with a stream of inert DISPOSAL OF ORGANOLITHIUM
bubbler and adjust the ¯ow accord- gas. Don all the recommended PPE. If COMPOUNDS
ingly. The syringe is then employed the reagent bottle for the organo- Small residues of organolithium com-
to withdraw the required amount of lithium compound was shipped with pounds can be safely quenched in a
organolithium from the sample bottle. a solid cap from the supplier, it should hood. Pyrophoric materials should be
Care must be taken not to withdraw be replaced with a cap with a septum. diluted to less than 5 wt.% with an
the organolithium solution faster than The inert gas ¯ow is started on the inert solvent, such as heptane. This
the inert gas ¯ow can re®ll the void. reagent line. A standard syringe needle solution should then be added slowly
This would allow air to enter the inert is inserted into the end of the inert gas (via an addition funnel) to well-stirred
gas line and possibly contaminate the line. The tip of this needle is then solution 2 M of 2-propanol in heptane.
organolithium solution. The tip of the inserted into the septum of the sample Monitor the temperature of this
syringe needle is then inserted into the bottle. Observe the inert gas ¯ow at the quench solution with an internal ther-
septum of the addition funnel. The bubbler and adjust the ¯ow accord- mometer. Maintain the temperature at
organolithium solution is then dis- ingly. One tip of the cannula is then 508C or below by controlling the feed
pensed into the funnel by pushing inserted into the septum of the reagent rate of the organolithium solution or
Chemical Health & Safety, May/June 2002 9
5. by application of an external cooling ane, a liquid with a boiling point of corrosive, ¯ammable and in certain
bath of dry ice/heptane. The resultant 678C. A similar reaction with n-butyl- cases, pyrophoric. However, these
solution of lithium isopropoxide in lithium would afford butane (boiling hazards can be minimized. The experi-
heptane can then be disposed of as point ˆ À0:58C) as the co-product. n- ment should be carefully planned prior
¯ammable, hazardous waste. Contain- Hexane is much easier to contain than to its execution to minimize hazards to
ers of organolithium reagents that have butane, particularly on an industrial personnel and the physical plant.
developed signi®cant quantities of scale. Another innovation is the com- Proper PPE to mitigate the hazards
solids should be discarded. These lar- mercial availability of preformed solu- of organolithium compounds should
ger volumes of organolithium reagents tions of lithium diisopropylamide be secured and worn at all times. All
that are no longer needed should be (LDA). These formulations of LDA are equipment that is employed for the
sent out for disposal as a lab pack. non-pyrophoric.7 In addition, when experiment must be free of moisture.
This minimizes laboratory personnel the preformed solution of LDA is An inert atmosphere of nitrogen or
exposure to the hazards of quenching employed, the experimenter does not argon is also critical in minimizing
large volumes of organolithium com- have to handle pyrophoric n-butyl- the hazards of organolithium com-
pounds and their decomposition lithium traditionally employed. A pounds. Solutions of organolithium
products. further advantage of the preformed compounds can be safely transferred
LDA formulation is that again, the from the storage bottles to the reaction
experimenter does not have to deal ¯ask with either a syringe or a cannula.
NEW DEVELOPMENTS with the emission of the co-product With the utilization of these basic tech-
Several innovative organolithium com- butane. A third innovation is the newly niques, organolithium compounds can
pounds and formulations have recently commercialized formulation of t-butyl- be safely handled in the laboratory.
been commercialized. These innova- lithium in heptane.18 While this new When properly handled, organoli-
tions have improved safety character- formulation is still pyrophoric, it is thiums provide unique properties that
istics over the older, more traditional much safer to handle than the tradi- allow for precise control of a molecular
organolithium reagents. The ®rst is tional pentane formulation of t-butyl- architecture, while also demonstrating
33 wt.% n-hexyllithium in hexanes. lithium.19 This is due to the much enhanced nucleophilicity, stability, and
This 2.5 M solution of n-hexyllithium higher ¯ash point of heptane (Fp ˆ excellent solubility in organic solvents.
has similar reactivity to the analogous À18C) versus pentane (Fp ˆ À49 C). With proper care and attention, orga-
nolithiums can be safely and effectively
utilized in both laboratory and physical
Several innovative CONCLUSIONS plant environments.
organolithium Organolithium compounds are extre-
mely useful reagents in organic synth-
compounds and Acknowledgements
formulations have Organolithium The authors would like to thank
Doug Sutton for his practical sugges-
recently been com- compounds are tions on transfer techniques.
mercialized. These extremely useful
innovations have reagents in organic References
improved safety synthesis and as
1. Wake®eld, B. J. The Chemistry of
Organolithium Compounds; Perga-
characteristics over initiators in anionic
mon: Oxford, 1974;
Wake®eld, B. J. Organolithium Meth-
the older, more tradi- polymerizations. ods, Academic Press: London, 1988;
Brandsma, L.; Verkruijsse, H. Pre-
tional organolithium These reagents are parative Polar Organometallic Chem-
reagents. corrosive, ¯ammable
istry I; Springer-Verlag: Berlin, 1987;
Brandsma, L. Preparative Polar Orga-
nometallic Chemistry II; Springer-
concentration of n-butyllithium in and in certain cases, Verlag: Berlin, 1990;
Stowell, J. C. Carbanions in Organic
typical applications. Furthermore, it
exhibits two signi®cant safety advan-
pyrophoric. However, Synthesis; Wiley: New York, NY,
tages over n-butyllithium.First, this for- these hazards can be 1979. (For the application of or-
ganolithium reagents in organic
mulation of n-hexyllithium in hexanes
tested as non-pyrophoric, even at con- minimized. synthesis.)
2. Hsieh, H. L.; Quirk, R. P. Anionic
centrations up to 85 wt.%.7 The second Polymerization; Marcel Dekker: New
advantage is that in deprotonation esis and as initiators in anionic York, NY, 1996. (For an excellent
experiments, the co-product is n-hex- polymerizations. These reagents are overview of anionic polymerization.)
10 Chemical Health Safety, May/June 2002
6. 3. Stanetty, P.; Mihovilovic, M. D. J. Org. 8. Wake®eld, B. J. Organolithium Meth- 13. One pair of Viton1 gloves, size 9, is
Chem., 1997, 62, 1514. (For example, ods; Academic Press: London, 1988, listed in the 2000±2001 Aldrich catalog
the half-life of n-butyllithium in THF p. 12. for $57.60.
at 208C is 1.78 hr. The half-lives of 9. Totter, F.; Rittmeyer, P. Organometal- 14. One pair of nitrile gloves, size L, is
various alkyllithiums in ethereal sol- lics in Synthesis: A Manual; Schlosser, listed in the 2000±2001 Aldrich cata-
vents as a function of temperature.). M., Ed.; Wiley: Chichester, 1994, log for $7.20.
4. Malpass, D. B.; Fannin, L. W.; Ligi, J. J. pp. 171±2. 15. Ansul1 Purple K is one popular choice
Kirk-Othmer Encyclopedia of Chemi- 10. Kamienski, C. W.; McDonald, D. P.; for a Class B ®re extinguisher.
cal Technology, 3rd ed.; Grayson, M., Stark, M. W. Kirk-Othmer Encyclope- 16. A number of bubbler designs are
Ed.; Wiley: New York, NY, 1981, Vol. dia of Chemical Technology, 4th ed.; commercially available from labora-
16, pp. 557±8. Kroschwitz, J. I., Ed.; Wiley: New tory glassware suppliers. A versatile
5. March, J. Advanced Organic Chemistry, York, NY, 1995, Vol. 15, pp. 453±4. bubbler design is Chemglass catalog
5th ed.; Wiley: New York, NY, 2001, 11. Kamienski, C. W. Lithium Link, 1994 number AF-0513-20.
p. 330. (Winter). (For an excellent review of 17. Butyllithium: Guidelines for Safe
6. Pyrophoric is derived from the Greek the various methods of analysis of Handling, a brochure available at no
word pyrophoros, which is a combina- organolithium compounds.) charge from FMC Lithium. (For a
tion of pyr (®re) and pherein (to bear), 12. One brand of ¯ame resistant fabric is more extensive discussion of these
in Webster's New World Dictionary of Nomex1. A variety of clothing styles, transfer techniques.)
American English, 3rd College ed.; including lab coats, coveralls, shirts 18. Commercially available from FMC
Prentice Hall: New York, NY, 1994, and pants, is commercially available. Lithium, 449 N. Cox Road, Gastonia,
p. 1096. Flame-resistant clothing is available NC 28054.
7. The of®cial test for pyrophoricity is from a number of laboratory supply 19. Bailey, B.; Longstaff, S. Lithium Link,
detailed in the Department of Trans- vendors, including Aldrich, Fisher and 2000 (Fall). (For an excellent review of
portation (DOT) regulations (49 CFR VWR. t-butyllithium chemistry.)
173, Appendix E).
Chemical Health Safety, May/June 2002 11