Thursday, November 28, 2019
The study by Wolfgang Kersten and Jan Koch
Summary of the main issues discussed in the article The study carried out by Wolfgang Kersten and Jan Koch is aimed at analyzing and measuring the relations between business success, quality management, and service quality in German logistics companies. The authors argue that currently these organizations rely on price leadership in order to gain competitive advantage while quality component of their work is not fully emphasized (Kersten Kock 2010, p. 186).Advertising We will write a custom report sample on The study by Wolfgang Kersten and Jan Koch specifically for you for only $16.05 $11/page Learn More In their opinion, quality management can strongly contribute to the success of these companies. The authors discuss several important issues, in particular, the measurement of service quality in logistics companies and its overall effect on the functioning of these enterprises. The authors single out a set of criteria by which the work of logistics ser vices can be evaluated (Kersten Kock 2010, p 188). Secondly, they examine the effects of various quality management techniques like employee development, leadership commitment, or continuous improvement on the quality of logistics services. Finally, the scholars examine the impacts of service quality on business success. From their standpoint, the results derived in the course of the study can be of practical use to quality managers. This paper will present a detailed critique of this research article. Contribution of the article to the understanding of quality management principles The main contribution of this article is that it shows how service quality can be decomposed into several elements or dimensions. On the basis of this classification managers will be able to better apply quality management techniques. It should be noted that Wolfgang Kersten and Jan Koch single out three essential components of quality service: 1) potential, 2) processes, and 3) outcomes (2010, p. 188). To a great extent they rely on the ideas of Avedis Donabedian (1980) who also worked on the assessment of quality. In this case, the term ââ¬Å"potentialâ⬠refers to organizational resources, its qualifications and capabilities (Kersten Kock 2010, p. 188). In turn, such component as process can be explained as the main internal activities of the company, and especially their interactions with their clients. Finally, such element as outcome is primarily related to the lead time, delivery of goods and their conditions (2010, p. 188). To a great extent, this article has helped me better understand the concept of quality when it is applied to service organizations like logistics companies. Furthermore, if it is slightly modified, this classification can be applied to many service companies not only logistics firms. Yet, the most important thing is that these authors establish a set of criteria that enables managers to evaluate the work of service organizations. Wolfgang Kersten and Jan Koch distinguish such standards as reliability of employees, adherence to security regulations, the time required to react to the queries of the customer, responsiveness, delivery correctness, and so forth (2010, p. 194).Advertising Looking for report on business economics? Let's see if we can help you! Get your first paper with 15% OFF Learn More Certainly, the authors relied on the works of other scholars, especially Parasuraman, Zeithaml and Berry who introduced quality measurement tools (1994). On the whole, this article has enabled me to systematize my knowledge of quality evaluation. It is also possible for me to say that this article only emphasized some of the things of which I was aware of. Namely, it has demonstrated that quality should or even must be assessed from customersââ¬â¢ perspective. Each of the criteria identified by Wolfgang Kersten and Jan Koch is closely related to the clients and their perceptions. This research indicates that custo mer focus has to be the main quality management principle if they want to remain competitive and retain customers who are the key to the survival of logistics firms. Overall, with the help of this article I have been able to extend my knowledge of quality management. Most importantly, this study has shown to me this element of performance can be decomposed and evaluated. Hence, this article really increased my understanding of quality management principles. It has been useful from theoretical and practical points of view. The relation between the article and quality theory This study is related to quality theory in several important ways. First of all, this discipline strives to single out various elements of this concept (Pfeifer 2002, p. 12). This is one of the tasks that Wolfgang Kersten and Jan Koch attempt to accomplish. The thing is that such concept as quality is very difficult to decompose into separate elements. Its structure will depend upon the type of organization and it s activities. The study that is being discussed examines quality in a very narrow context, namely, logistics companies. One should bear in mind that quality dimensions vary in different organizations (Basu 2004, p. 5). This study eloquently illustrates this argument. In addition, modern science tries to find ways of measuring or quantifying quality (Pfeifer 2002, p. 12). Similarly these authors also measure quality by numerical means. Certainly, one should also speak about the use of quality management techniques or practical applications of quality theory. One of the purposes of the given study is to measure the effectiveness of such practices or approaches as employee orientation, process management, leadership commitment, or continuous improvement ((Kersten Kock 2010, p 192). Thus, one can say that these scholars work towards one of the most fundamental purposes of quality theory which is the improvement of services or products. These are the main connections between these study and quality theory.Advertising We will write a custom report sample on The study by Wolfgang Kersten and Jan Koch specifically for you for only $16.05 $11/page Learn More The main findings of the study and their applications On the whole, the research conducted by Kersten and Koch has produced several important findings. First, existing quality management do contribute to the improvement of logistics companies. These researches identified a statistically significant relation between each practices and internal processes within the companies and their organizational resources. In other words, their finding indicate that quality management practices facilitate order completion process, reduce reaction time, and prompt workers to comply with safety regulations (Kersen Koch, 2010, p. 196). However, the scholars also point out that these initiatives do not always improve the outcomes such as delivery correctness or condition of goods (2010, p. 196). In par t, these results can be explained by the fact that logistics companies cannot exercise full control over force-majeure circumstances, traffic congestions. Besides, one should take into account that these organizations often cooperate with many subcontractors or third-parties and it is not always possible to monitor their work (Gudehus Kotzab 2009, p. 11). This is one of the reasons why quality management initiatives do not always affect outcomes. The results might have been different if Kersten and Koch focused only on those companies which can closely monitor the work of their subcontractors. Apart from that, Kersten and Koch believe that service quality is conducive to business success (2010, p. 197). However, they do specify how exactly they measure business success. The notion can refer to the profitability of an enterprise, its customer retention rates, or other criteria. This is the main limitation of their research. Additionally, one should keep in mind that the researchers examined only German logistics firms, and at this point it is not known whether these results can be applied to other countries or regions. As Kersten and Koch say an international survey of logistics firms must be carried out to validate the results. At this point, the findings cannot be viewed as definitive. Overall, their findings have many practical implications. First, the tools that they have developed can be used by the managers who work in service organizations. It has to be admitted that these methods cannot be applied to any service companies since they were originally designed for the needs of logistics companies.Advertising Looking for report on business economics? Let's see if we can help you! Get your first paper with 15% OFF Learn More However, practitioners of quality management can benefit from their ideas by decomposing quality into separate categories like potential, processes, and outcomes. Most importantly, with the help of similar assessment tools they can measure the effectiveness of different quality management practices. Still, the primary beneficiaries of this study can be logistics companies. As it has been noted before, these organizations rely on cost leadership, rather than quality leadership. The approach recommended by the authors will enable such companies to better retain customers and reduce their expenses. It is quite possible to assume that this study will soon give rise to further research that will also focus on international companies. References Basu, R, 2004, Implementing quality: a practical guide to tools and techniques : enabling the power of operational excellence. Cengage Learning, NY. Donabedian, A 1980, The Definition of Quality and Approaches to its Assessment, Health Administrat ion Press, Ann Arbor, MI. Gudehus, T Kotzab, H 2009 ââ¬ËComprehensive logisticsââ¬â¢, Springer, NY. Kersten, W Koch, J 2010 ââ¬ËThe effect of quality management on the service quality and business success of logistics service providersââ¬â¢. International Journal of Quality Reliability Management, vol, 27, no, 2, pp 185-200. Parasuraman, A., Zeithaml, V.A. and Berry, L.L. (1994), ââ¬ËReassessment of expectations as a comparison standard in measuring service quality: implications for further researchââ¬â¢, Journal of Marketing, Vol. 58, no. 1, p. 111-124. Pfeifer, T 2002, Quality management, Hanser Verlag, Cincinnati. This report on The study by Wolfgang Kersten and Jan Koch was written and submitted by user Hugo Mccarthy to help you with your own studies. You are free to use it for research and reference purposes in order to write your own paper; however, you must cite it accordingly. You can donate your paper here.
Monday, November 25, 2019
101 Pathos and Visual Rhetoric Professor Ramos Blog
101 Pathos and Visual Rhetoric Four Strategies Quick Write Take a couple minutes and analyze this image. 4 Ways to Persuade with Emotion (Pathos) Four Strategies Concrete Examples Connotative Diction Metaphors and Similes Tone Appeals to pathos target the link between audience members and their values. When we act on our values, we experience emotions like happiness, pride, satisfaction, etc. When we do not, we often feel shame, fear, or anger. The same goes for the actions of people around us: we are often pleased when the actions of people around us align with our values and angry when they donââ¬â¢t. Persuasion: Emotion Handout Visual Rhetoric 1. We live in a Visual Culture We live in a visual culture. We are saturated in images at nearly every moment of our waking lives. For this reason, it is important to develop critical thinking skills that allow us to read images. I challenge you to engage with images actively instead of passively. Take the images apart in order to understand their messages. Accept, reject, or qualify those claims. 2. Visual Media as Texts Learning to read images, deconstruct, and engage with them will make us better readers of texts, and vice versa. Visual materials that accompany written arguments serve several purposes. First, they appeal to the readerââ¬â¢s emotions. While images can be logical, they first appeal to the senses of the reader before they are analyzed more logically. In other words, their immediate impact is more on the viewerââ¬â¢s heart than the mind. Pictures can also serve as visual evidence, establishing proof that something occurred or appeared in a certain way. Pictures can help clarify data with graphs and tables and can also be used to confuse or trick an audience with graphs and tables. Pictures can add humor or satire to an argument. Visual images can be read as text, as such we need to think critically about them. Looking closely we can discern not only what they show but also how and why. Appeals to Emotion Images can be used to instill an emotional response in the audience. Even implied images in text can be very emotionally powerful. A description of blood stained clothes draws certain emotions in a reader. Lawyers know how important visuals can be. They dress their defendants in suits and ties to make them seem more credible. Types of emotional appeals: appeal to pity appeal to fear appeal to self-interest Sexual bandwagon humor celebrity testimonials identity prejudice lifestyle stereotypes patriotic Would you persuade, speak of Interest, not Reason. ââ¬â Benjamin Franklin Intro to Fallacies Logically Fallacious Key Terms Argument: A conclusion together with the premises that support it. Premise: A reason offered as support for another claim. Conclusion: A claim that is supported by a premise. Valid: An argument whose premises genuinely support its conclusion. Unsound: An argument that has at least one false premise. Fallacy: An argument that relies upon faulty reasoning. Booby-trap: An argument that, while not a fallacy itself, might lead an inattentive reader to commit a fallacy. The Internet Encyclopedia of Philosophy Fallacies This is a great resource for further reading on fallacies and how they areà not so simple. The articleà lists 223 of the most common fallacies. I do not expect you to know them all or to never use any. Fallacies are controversial. We appreciate logic and honesty in Western rhetorical thinking and that is at odds with many fallacies. Fallacies are not necessarily wrong, they work very well and are very good at persuading people. Fallacies are considered unethical and so we try to avoid them. They are thought of as flaws in thought, tricks, and sneaky uses of persuasion to convince others. Images as Arguments Images can be used to help us see the argument that the author is intending. They can be used to lower our skepticism, visual proof of something that happened. This is problematic nowadays with the popularity of programs such as Photoshop, where images can be changed or manipulated. Now more than ever, we have to be weary of taking images at face value. We have to critically think about images and their intended effect. Three basic questions we can ask. Who produced the image? Who distributed the image? Who consumed the image? Our textbook suggests a rule for writers. If you think that pictures will help you make the point you are arguing, include them with captions explaining their sources and relevance. I Have a Dream Speech The now famous speech ââ¬Å"I have a Dreamâ⬠by Dr. Martin Luther King was aided by visuals when it was delivered. He is at the Washington Monument, speaking to hundreds of thousands, smiling and waving. Behind him is the Lincoln Memorial. In this Aug. 28, 1963, black-and-white file photo Dr. Martin Luther King Jr., head of the Southern Christian Leadership Conference, addresses marchers during his ââ¬Å"I Have a Dreamâ⬠speech at the Lincoln Memorial in Washington. The 45th anniversary of the iconic leaderââ¬â¢s most memorable speech coincides with the day when another African-American leader, Barack Obama, is scheduled to makes a historic speech of his own, accepting the Democratic Partyââ¬â¢s nomination for president of the United States Aug. 28, 2008, in Denver, Colo. (AP Photo/File) This image shows him speaking with people and some police behind him. The image you choose to use will add meaning to your text. Be careful which images you choose. What does it say if we use his mug shot from one of the many protests he was arrested at? Or this one. Have you ever seen this image of Dr. King? Or this one? Timeââ¬â¢s Man of the Year 1964 The image your choose can help your audience understand your argument. 101 Pathos and Visual Rhetoric Images as Arguments 1937 photo by Margaret Bourke-White ââ¬â Breadline during Louisville Flood. Quick Write Take a couple minutes and analyze this image. Images as Arguments Images can be used to help us see the argument that the author is intending. They can be used to lower our skepticism, visual proof of something that happened. This is problematic nowadays with the popularity of programs such as Photoshop, where images can be changed or manipulated. Now more than ever, we have to be weary of taking images at face value. We have to critically think about images and their intended effect. Three basic questions we can ask. Who produced the image? Who distributed the image? Who consumed the image? Our textbook suggests a rule for writers. If you think that pictures will help you make the point you are arguing, include them with captions explaining their sources and relevance. 4 Ways to Persuade with Emotion (Pathos) Four Strategies Concrete Examples Connotative Diction Metaphors and Similes Tone Appeals to pathos target the link between audience members and their values. When we act on our values, we experience emotions like happiness, pride, satisfaction, etc. When we do not, we often feel shame, fear, or anger. The same goes for the actions of people around us: we are often pleased when the actions of people around us align with our values and angry when they donââ¬â¢t. Persuasion: Emotion Handout Visual Rhetoric 1. We live in a Visual Culture We live in a visual culture. We are saturated in images at nearly every moment of our waking lives. For this reason, it is important to develop critical thinking skills that allow us to read images. I challenge you to engage with images actively instead of passively. Take the images apart in order to understand their messages. Accept, reject, or qualify those claims. 2. Visual Media as Texts Learning to read images, deconstruct, and engage with them will make us better readers of texts, and vice versa. Visual materials that accompany written arguments serve several purposes. First, they appeal to the readerââ¬â¢s emotions. While images can be logical, they first appeal to the senses of the reader before they are analyzed more logically. In other words, their immediate impact is more on the viewerââ¬â¢s heart than the mind. Pictures can also serve as visual evidence, establishing proof that something occurred or appeared in a certain way. Pictures can help clarify data with graphs and tables and can also be used to confuse or trick an audience with graphs and tables. Pictures can add humor or satire to an argument. Visual images can be read as text, as such we need to think critically about them. Looking closely we can discern not only what they show but also how and why. Appeals to Emotion Images can be used to instill an emotional response in the audience. Even implied images in text can be very emotionally powerful. A description of blood stained clothes draws certain emotions in a reader. Lawyers know how important visuals can be. They dress their defendants in suits and ties to make them seem more credible. Types of emotional appeals: appeal to pity appeal to fear appeal to self-interest Sexual bandwagon humor celebrity testimonials identity prejudice lifestyle stereotypes patriotic Would you persuade, speak of Interest, not Reason. ââ¬â Benjamin Franklin Graff ââ¬Å"Hidden Intellectualismâ⬠(369) In the article ââ¬Å"Hidden Intellectualism,â⬠Gerald Graff argues that schools should encourage students to write about subjects that interests them. While passion about a subject does not necessarily mean they will write well about it, they can benefit from reflective and analytical writing about subjects they care about. Nonacademic subjects can be ââ¬Å"more intellectual than school.â⬠What does he mean by intellectual here? Real intellectuals turn any subject, however lightweight it may seem, into grist for their mill through thoughtful questions they bring to it, whereas a dullard will find a way to drain the interest out of the richest subject (265). Do you agree with this statement? Why? Who is his audience? What is his purpose? Give me the student anytime who writes a sharply argued, sociologically acute analysis of an issue inà Sourceà over the student who writes a lifeà less explication ofà Hamletà or Socratesââ¬â¢Ã Apologyà (270).
Thursday, November 21, 2019
Compare Mencius theory of Human Nature as Good with Xunzis Theory of Essay
Compare Mencius theory of Human Nature as Good with Xunzis Theory of Human Nature as Evil - Essay Example He said when people follow their original morality, they show exceptional goodness that has been bestowed on them by nature. According to him people are unhappy when others suffer and would like to save them from such sufferings and that is the side of goodness and he showed the example of all people rushing to save the child, which is about to fall into a well. According to him, the original good nature of man gets hit by disappointments and difficulties like trees on mountain slopes being targeted by horrendous winds and he gives examples of once beautiful, now bedraggled trees of Niu Mountain. "Mencius belonged to one of those philosophical schools and all these schools were competing among themselves for disciples and for the favour of rulers which would bring wealth, power and positionsMencius was therefore, in a position that he had to explain more clearly than Confucius why every man should strive to be a 'superior man'" Hwang (1979, p.205). His arguments are termed as too idealistic, far from reality, far removed from real life happenings and he argues a kind of mysticism beyond comprehension and belief. He is also criticized that all people cannot be endowed with such superfluous goodness as he supposed. Funnily, in spite of criticism, Mencius' theory continued to exist and is quite relevant even today. "Mencius, on the other hand, is more truly a mystic. Not only does he believe that a man can attain oneness with the universe by perfecting his own moral nature, but he has absolute faith in the moral purpose of the universe. His great achievement is that he not only successfully defended the teachings of Confucius against the corrosive influence of new ideas but, in the process, added to Confucianism a depth that it did not possess before," Lau (1970, p.46). He stressed upon ethical predispositions of mind and heart. He argued that any budding evil could be controlled by self-reflection and self-cultivation. His ethical ideal was benevolence humaneness. Xunzi lived towards the end of Warring States Period (453-221 BCE) and along with Mencius and Confucius, was one of the three main architects of Confucius school of Philosophy in China. This period saw great philosophical flowering in China that enveloped almost all spheres of life, society, politics, ruling, warfare, defense etc. He lived in a 'cutthroat' age and it is not surprising that his philosophy is based on human evil. He also felt the need of human education and moral training. "Human nature is evil; what is good is artifice. Now, human nature is as follows. At birth there is fondness for profit in it. Following this, contention and robbery arise, and deference and courtesy are destroyed," Goldin (1999, p.6). Xunzi was directly opposite to Mencius in assuming that human nature starts with evil and not with goodness. His thought clashes with that of Mencius on the fundamentals itself. "But it flatly contradicts the view of Mencius, who taught that man is naturally inclined to goodness and in later centuries, when Mencius' view came to be regarded as the orthodox one, it led to an unhappy clouding of Hsun Tzu's entire system of thought," Watson (1967, p.5). He thought man is prone to evil dispositions, and ethical rules of society are invented to prevent this natural process. His philosophy says that Man is naturally an evil,
Wednesday, November 20, 2019
Artist reaserch and comparison Essay Example | Topics and Well Written Essays - 1250 words
Artist reaserch and comparison - Essay Example Born in 1967, and currently around 43 years of age, Tomma Abts was born in Germany but she currently lives in London, England. In fact, she has been living in London since 1995. She had a tough time during her early days since she had to jobs in telemarketing positions, which is not ââ¬Å"her thing.â⬠However, things have changed and for the past few years, she has been able to finance her living with her painting and art. Tomma Abts is for sure, one of most interesting and fascinating painters of the present times. As mentioned earlier that she never had any formal training. May be that explains why she does not seem to be following any traditional and pre defined rules of painting (Hoptman, Verwoert & Hainley, pp. 32-39). She has a completely different approach as compared to the other painters as if she is challenging the traditional and classical approach to painting. Beginning the painting without any pre defined objective, name, thought or approach for painting, always sticking to small paintings, (she says that all her paintings are 48 x 38 centimeters) and others show that she has some what a rebel inside her (Hoptman, Verwoert & Hainley, pp. 32-39). The upcoming section of this paper would go in the detail of her paintings while comparing it with the painting of Brice Marden. Without any doubts, Brice Marden is one of the biggest names in art industry. Born on October 15, 1938, he joined the Boston University for studying fine and applied arts in the year 1961. Moreover, his biography also shows that he holds a Master of Fine Arts degree from Yale school of arts and architecture in the year 1963. Since then, he deserves the credit of brining up a new chapter in the art history. Although he is somewhat associated with the movement of minimalism in art, which is an old movement but he has taken it to completely different and levels in his own style. This American artist is not only a member of American Academy of art and Architecture but he has
Monday, November 18, 2019
What Factors Influence Gang Behavior Research Paper
What Factors Influence Gang Behavior - Research Paper Example In order to be able to solve this problem, it is important to study the reasons or the root causes of gang behavior with the intention of trying to prevent new gang membership, while at the same time embarking on a mission to dismantle the already existing ones. This paper is a critical evaluation of the factors that influence gang behavior. Factors that Influence.Human beings are born innocent, free of sins and incapable of making any decision. However, as they continue to grow, they are faced with numerous challenges raging from family issues to other environmental factors, which influence their innocent minds either into becoming responsible persons or the worst of criminals in the society. To begin with, parents contribute a significant percentage towards the success or failure of a child in terms of behavior. This is due to the fact that they act as immediate role models and a source of inspiration for their growing children. It is for this reason that Carlie (2002) observes tha t poor parentage is a major contributing factor to gang behavior. For example, if one or both parents are gang members, more often than not, it becomes likely that their children will follow that route. This may be worse in families that are dysfunctional and which are characterized by numerous cases of domestic conflicts and child abuse. The rationale of this assertion is that if a child is subjected to these factors, he will grow up believing that violence is a virtue and unless this mentality is changed through proper guidance and counseling, then, the child would have neither a reason nor the guts to refrain from joining violent organizations. Outside family circles, growing up children and youths are influenced by peer pressure to engage in antisocial behavior, which may include gang membership. Peer pressure refers to the powerful influence that a group of people in the same age group have on each other. In this context, it has been noted that people tend to acquire the behavi ors of other members of their social groups as a way of trying to fit into those groups. This factor has been blamed on other negative behaviors such as alcohol and drug abuse, fornication, among others and gang membership cannot be excluded from this list. According to myelsie.org (2010), ââ¬Å"young people are very susceptible to peer pressure.â⬠One reason for this is that young people always want to identify with friends and when it comes to choosing between friendship and conscience, most of them will definitely choose friendship even if it means that they would have to tolerate and involve themselves in criminal activities. In the US, it is a fact that gang membership is highly prevalent in schools and even if a child comes from a family that is opposed to gang membership and activities, he or she may end up joining the gangs so as not to be rejected or harassed by his or her peers (myelsie.org 2010). Poverty is blamed for numerous atrocities and gang behavior is one of such. Everyone wants to lead a comfortable life, to drive beautiful cars, drink high quality beer or wine, to live in a luxurious home among others. Whereas it is difficult for a normal civilian, especially from poor neighborhoods, to acquire these items, it is highly
Friday, November 15, 2019
Wadsworth-Emmons Cyclopropanation Reaction | Analysis
Wadsworth-Emmons Cyclopropanation Reaction | Analysis Abstract This project aims to look at the development of the Wadsworth-Emmons cyclopropanation reaction and compare it to alternative methods of cyclopropanation in order to understand why it may be used preferentially. Current applications of the WE cyclopropanation reaction are explored to see the efficacy and yield that result. Key of Abbreviations Seen below is a collection of all abbreviations used within this project and their subsequent meaning. à â⬠3: Tertiary Bn: Benzyl group CCR: Corey-Chaykovsky Reagent d.e: DME: Dimethoxyethane e.e: Et: Ethyl group EWG: Electron Withdrawing Group HWE: Horner-Wadsworth-Emmons iPr: isopropyl Me: Methyl NOE: Ph: Phenyl group THF: Tetrahydrofuran WE: Wadsworth-Emmons 1: Introduction Cyclopropaneà [1]à was used as an anaesthetic until it was discovered to be highly reactive and dangerous when combined with oxygen. The reactivity of cyclopropane is mainly due to the high amount of ring strain and the bond strength between the carbons being weaker than normal carbon bonds, allowing the ring to open easily. Cyclopropane structures are often found within compounds in nature (figure 1.)à [2]à that are observed to have medicinal and commercial applications, e.g. degradable insecticides such as the pyrethroid family that are less toxic to other animals in the environmentà [3]à ,à [4]à . Cyclopropanation can also produce a number of hallucinogens and opoid drugs that are most widely used recreationally for there effects on human mental and visual perception, exploiting their psychedelic properties. This type of use has historically been seen within Native American tribes and ancient civilisations. Recently more research shows that they may potentially be useful in therapeutic doses in the treatment of pain, depression, alcoholism and other behavioural problems. An example of this is Codorphone, an analgesic that can be both an agonist and antagonist at ÃŽà ¼-opioid receptors in the body and shows a higher potency than codeine. As a result, efficient synthetic routes that produce high yields have been developed in order to produce synthetic analogues of these natural compounds, with special attention being paid to the cyclopropanation step. Over the years there have been many methods of cyclopropanation, from using zinc carbenoids (Simmons-Smith reactionà [5]à ) to stabilised ylides (Corey-Chaykovsky Reactionà [6]à ), all producing varying ratios of isomers of the product. Often, one enantiomer is the more biologically active molecule, therefore stereoselective reactions are required to obtain high yields of the desired product. The Wadsworth-Emmons cyclopropanation reaction is an example of a reaction that is selective for the generation of the trans-isomer and has advantages over other stereoselective reactions. 1.1: Chemistry of the Cyclopropane Ring Cyclopropane is the smallest of the cycloalkanes that can be formed and consists of three sp3 hybridised carbon atoms bonded to each other to form a triangular ring. Although it is the smallest cycloalkane it is also the most reactive due to the bond angle within the ring. The ideal bond angle for sp3 hybridised carbons is 109.5à ° as it at this angle that orbitals can overlap correctly and form the highest strength carbon-carbon bonds possible. As the propane ring is planar and made up of only three carbon atoms, a bond angle of 109.5à ° is not possible and is reduced to a bond angle of ~60à °. In order to achieve bond angles of 60à ° the sp3 orbitals need to form bent bondsà [8]à where their p-characteristics are increased, causing the carbon-hydrogen bond length to shorten (figure.2). It is this significant difference between the ideal bond angle and the actual bond angle exhibited that causes a high amount of ring strain. Also, the bond angle and the modified overlap of orbitals results in carbon-carbon bonds which are weaker than normal. In figure.3, as the ring size increases from cyclopropane to cyclohexane, the ring strain decreases because the ideal bond angle is reached (when in a planar conformation) and larger rings can assume a non-planar conformation. In comparison to cyclopropane, the most strained and planar ring, cyclohexane has ideal bond angles and can form both chair and boat folded conformations in order to be the least strained ring possible. Further strain in the cyclopropane ring is due to the planar conformation of the molecule, where the two hydrogens present on each carbon atom are in an eclipsed position (figure.4)2. The carbon-hydrogen bonds are locked into this high energy conformation, as the carbon-carbon bonds of the ring are unable to rotate to form a more staggered conformation and reduce torsion strain. The total strain felt by the molecule leads to the ring structure being highly unstable and is ultimately responsible for the high reactivity of cyclopropane. Due to instability, the cyclopropane ring is able to break open very easily and releases a lot of energy in the process. This ring strain causes cyclopropane to release more energy on combustion than a standard strain-free propane chain. 2: Precursors of the Wadsworth Emmons Cyclopropanation Reaction As with most reactions the Wadsworth-Emmons cyclopropanation reaction is simply a different application of an older reaction, the Horner-Wadsworth-Emmons reaction, which has the purpose of forming E- alkenes selectively. This in turn is a derivation of the original Wittig reaction first discovered in 1954 by Georg Wittig in which phosphonium ylides are used in order to form alkenes products from aldehyde or ketone reactants. 2.1: Wittig Reaction The Wittig reaction is very useful in that it will form a carbon-carbon double bond in one site specifically on the desired molecule but the stereoselectivity of the reaction is controlled by the type of phosphonium ylide used. An ylide is a species that carries a positive and a negative charge on adjacent atoms of the molecule, and in this instance it is a phosphorus atom that carries the positive charge. As seen in scheme 12, the negatively charged carbon atom of the ylide acts as a nucleophile towards the carbonyl of the ketone (electrophile) and forms a betaine species. The betaine cyclises into an oxaphosphetane ring which quickly collapses to form a very strong phosphorus-oxygen double bond and results in the production of an alkene and a triphenyl phosphine oxide. When an unstablised ylide is present in the reaction, the kinetic isomer (Z-alkene) is produced preferentially (figure. 5)2 as the intermediate oxaphosphetane ring forms irreversibly. As the stereochemistry of the substituents are locked into a syn-conformation (figure. 7), when elimination of the triphenyl phosphine oxide occurs the alkene formed has its substituents on the same side of the plane. When the negatively charged carbon is adjacent to an electron withdrawing group (EWG), in figure 6 this is represented by the ester substituent, the ylide group becomes more stable as the charge can be dispersed. This leads to the formation of the enolate resonance form and is referred to as a stabilised ylide. Unlike the unstabilised ylide, the oxaphosphetane ring that is formed is now a reversible reaction allowing interconversion between Z-orientation to E-orientation of groups in the ring before an elimination step occurs. Under the right conditions, the interconversion step can become faster than the elimination of phosphine oxide step (collapse of the ring) allowing the reaction to proceed via the thermodynamic product route. The E- isomer is the thermodynamic product as the anti- conformation (Figure.7) of the oxaphosphetane ring has the substituents on opposite sides of the molecule, reducing steric effects and producing a conformation lower in energy. The elimination of the Z-isomer is slower than that of the E-isomer, allowing the oxaphosphetane ring to open and rotation about the carbon-carbon bond to occur to form more of the E-isomer. Although the Wittig reaction works efficiently with simple carbonyl reactants, the more sterically hindered a ketone reactant is, the slower the reaction can become. This does not necessarily have a negative effect on the yield of product but will affect the suitability of the reaction in time sensitive application, e.g. the commercial industry wants a high yield of product with a moderately fast synthetic route in order to keep costs low. 2.2: Horner-Wadsworth-Emmons reaction The Horner-Wadsworth-Emmons reactionà [9]à (scheme 2.) is the preferred method to select for the E-alkenes product and instead of using phosphonium ylides (figure 6.) uses much more nucleophilic phosphonate-stabilized carbanions with an EWG attached, usually in the form of phosphonate esters. Firstly, the phosphonate ester is deprotonated using sodium hydride leading to the generation of an enolate species. This enolate/stabilised carbanion is then reacted with the chosen aldehyde or ketone to give product. As a result of its more nucleophilic nature, similar or better yields are produced and faster rates of reactions for aldehydes and ketones that are more sterically hindered are observed. The stereoselectivity of the reaction for E-alkene can be further increased by modifying the reaction conditions and the substituent groups of the phosphonate ester (figure 8.)à [10]à . The larger the alkyl groups attached to the phosphate and ester functional groups the greater the propor tion of E-isomer obtained. Using the same idea, the larger the substituent group attached to the aldehyde/ketone reagent a more improved E-selectivity is seen, for example a phenyl ring. Increasing the temperature of the reaction to room temperature (23à °C) and changing the solvent from THF to DME will also encourage E-selectivity. Figure 9 shows that the pka of the HWE reagent is lower than that of the Wittig reagent and this is due to the ester EWG on the adjacent carbon to the acidic hydrogen. The EWG helps to stabilise the carbanion that will be formed by the loss of hydrogen making the phosphonate ester a stronger acid than the phosphonium salt, whose conjugate base will be less stabilised. As seen in Scheme 2, along side the E-alkene, there is a water soluble phosphate molecule present in solution. Due to its solubility, the recovery of the pure product from the solution can be done via a simple work up and this is one of the advantages of the HWE reaction over the use of stabilised ylides where a à â⬠3 phosphine oxide is formed. Through Wadsworth and Emmons investigations into the formation of alkenes such as stilbene in 19619, it was reported that the use of phosphonate carbanions was a more cost effective process that led to faster rates of reactions. It also produced very good yields in more mild conditions in comparison to stabilised phosphonium ylides. Phosphonate carbanions have a greater scope in number of different ketone and aldehyde reagents that they can successfully react with. Comparing both methods, when using stabilised ylides the resulting solution will contain a mixture of the isomers and therefore a suitable method is needed in order to separate them. Scheme 2. 2.3: Wadsworth-Emmons Cyclopropanation Similarly to the HWE reaction and keeping in mind the steric effects of large substituents, the reaction uses phosphonate-stabilised carbanions like the phosphonoacetate anion with epoxide and lactone reagents in order to form trans-cyclopropane rings within molecules. As seen in scheme 3à [12]à , the phosphonate carbanion acts as a nucleophile towards the electrophilic carbon of the epoxide resulting in the opening of the strained ring. Due to the negative charge present on the oxygen atom the phosphoryl group undergoes 1, 4 migration on to the oxygen, forming another carbanion. The carbanion can then cyclise leading to the ÃŽà ³-elimination of the phosphono- ÃŽà ³-oxyalkanoate and the closure of the cyclopropane ring. These stabilised phosphonates give a similar yield of trans-cyclopropane to reactions using phosphonium ylides but with faster reaction times and improved diastereoselectivityà [13]à . 3: Other Methods of Cyclopropanation In order to understand how effective the WE cyclopropanation reaction is and its advantages, other methods with slightly different approaches to the same problem can be looked at. 3.1: Simmons-Smith Reaction First developed in 1958, the Simmons-Smith reaction uses the chemistry of carbenes groups, producing cyclopropyl rings from the interaction between alkenes and a carbene derivative, zinc carbenoid. A standard carbene is a neutral species containing a carbon atom with only six valence electrons2 and can be inserted into à Ãâ-bonds and/or à â⠬-bonds of other reagents. Examples of these carbenes are :CH2 and :CCl2, where the whole carbene reagent is incorporated into the final product structure. In cases using reagents like :CCl2, further steps are required to remove the halide atoms if a standard cycloproyl ring is desired. In comparison, the zinc carbenoid is a species capable of forming carbenes but does not react in exactly the same way as them. The zinc carbenoid is formed by the insertion of a zinc atom into a molecule diiodomethane using a copper catalyst, as seen below, and its mechanism of action is compared to that of a singlet carbene where the reaction is concert ed. The carbon structure (-CH2) within the zinc carbenoid is incorporated into the cyclopropyl ring whilst the resulting metal halide is released into solution. This is done via an intermediate complex formed between the alkene, carbene and metal halide so that the carbene is not released on its own. One of the advantages of this method of cyclopropanation is the ease with which the stereochemistry of the product can be controlled. As the reaction is stereospecific, in order to obtain a product with a trans-cyclopropane ring, an alkene with E- stereochemistry can be used as the original stereochemistry will be retained. The rate of reaction of this can be dramatically increased by the presence of allylic alcohols with the same stereochemistry as the alkene, as the zinc atom can coordinate with the oxygen in a transition state to add the carbene to the same face of the molecule. The example below (figure. 10)à [14]à shows that this reaction is extremely effective at producing hig h yields of trans-cyclopropane product. Scheme 4. This reaction exhibits easy control over stereoselectivity and undergoes a relatively simple mechanism, making it easy to understand why this is one of the most popular methods of cyclopropanation. A disadvantage that the WE cyclopropanation reaction does not share is that there will have to be further steps taken in order to remove the product from the solution containing the zinc halide (insoluble) whilst preventing impurities being obtained. Although in some instances the Simmons-Smith reaction has greater stereoselectivity than the WE cyclopropanation reaction with comparable yields. 3.2: Corey-Chaykovsky Reactionà [15]à This reaction uses sulphonium ylides, as opposed to the phosphonium ylides of the Wittig reaction, reacting with enones in order to form cyclopropyl structures in the molecule. Firstly there is the generation in situ of the dimethyloxosulfonium methylide, often called the Corey-Chaykovsky Reagent (CCR), from dimethyl sulfoxide and methyl iodide reacting to give a trimethyl sulfoxonium iodide salt. This salt is then deprotonated using a strong base like sodium hydride resulting in the CCR. In the mechanism of cyclopropanation, the CCR acts as a methylene transfer agent, with the carbanion acting as a nucleophile towards the alkene carbon-carbon double bond of the enone. This 1, 4 addition is followed by cyclisation within the molecule using the new carbon double bond reacting as a nucleophile toward the now electrophilic ylide carbon to form the cyclopropyl structure and a sulfonium cation (Scheme 5). In an attempt to make the reaction stereoselective more substituted sulfonium ylides with specific chirality can be used to encourage the formation of a specific enantiomer as they transfer other substituents to the enone as well as methylene (figure.)à [16]à . Scheme 5. 4: Uses of the Wadsworth-Emmons Cyclopropanation Reaction Though there are only a few specific examples of WE cyclcopropanation in action, a good idea of its efficacy can be obtained. 4.1: Synthesis of Belactosin Aà [17]à (+)-Belactosin A is a naturally occurring antitumor antibacterial compound that acts as an alkylating agent in chemotherapy treatment. As an alkylating agentà [18]à it adds alkyl groups to electronegative groups such as phosphates or the amines found on guanine nucleotide bases, which are present in all cells of the body, although it is used to target mutating cancer cells. Belactosin A specifically stops the cell cycle of cancer cells at the G2/M phase, where normal DNA will have been replicated and the cell undergoes mitosis. In mutated DNA, the areas on the nucleotide bases affected by alkylation form cross bridges with other atoms on the complementary base of the opposite strand of DNA. These bridges prevent the DNA strands from separating at these specific points, stopping steps such as transcription. As a result this prevents the mutated DNA from being copied, cells from dividing into more cancer cells and halts proliferation of these cells through out the body. It affects mutated DNA cells more readily as they undergo cell cycle at a faster and uncontrolled rate and their repair mechanisms are less effective. Armstrong and Scutt reported a good yield of 63% of the cyclopropane intermediate with greater than 95%e.e. By using H1 NMR and NOE they determined that the product obtained was the trans-isomer. 4.2: Synthesis of (R,R)- 2-Methylcyclopropanecarboxylic Acidà [19]à In agriculture and veterinary practices, insecticides like Cyromazine and Pyrethrum Extract4 are formed using the WE cyclopropanation reaction in the synthesis of (+) and (-)-chrysanthemum dicarboxylic acids from anhydro sugarsà [20]à . The pyrethroids are active molecules that prevent normal transmission and excitation along the nerve cells in insects by acting on sodium/potassium channels. This results in immediate death to agricultural pests such as locusts and parasitic insects such as ticks and fleas on household pets. Due to the number of nerve cells and the speed of transmission these insecticides are up to 100 times more effective on insects than humans. Consequently, Pyrethrum extract can be used pharmaceutically without detrimental effects in the treatment of worms and scabies. Using the WE cyclopropanation method to obtain the biologically active enantiomer, Brione and company obtained excellent product yields of ~85-90% with exceptional trans-selectivity (>98%). These results were obtained under the conditions of 150à °C with HexLi/MeTHF solvent. 5: Conclusion Whilst the WE cyclopropanation reaction proves itself to be a useful step in the mechanism of formation of a few interesting biologically active compounds, the fact remains that it is an underused method. This is shown in the small volume of literature that can be obtained specifically for this reaction. As with most reactions the right balance of factors and reaction conditions are needed to get the most efficiency, and excellent yields have proved that the WE cyclopropanation reaction is capable of this in the cases of (R, R)- 2-Methylcyclopropanecarboxylic Acid and Belactosin A. Perhaps one of the reasons it is overlooked as a synthetic route is the presence of better known reactions like the Simmons-Smith reaction, as there are still some small areas that are not fully known e.g the degree of specificity of the reaction. The field of chemistry is one based on the evolution of ideas and continued search for improved yields and rates of reaction, especially in a growing area such a s the synthesis of synthetic analogues of natural compounds. In the same way that the WE cyclopropanation reaction was derived from the Wittig reaction, it could provide as a good basis for future improved methods of cyclopropanation that arise from the modification of its reagents.
Wednesday, November 13, 2019
Relationship of Dreams to Thought, Memory, and Smell :: Sleep Dream
Dreams involve a fundamental integration and spreading of being and experience at the mid-range of feeling between thought and sense. Since dreams [already] involve a fundamental integration and spreading of being and experience at what is the mid-range of feeling between thought and sense, the sense of smell very rarely occurs while dreaming, and the lighting and sound levels are fairly constant (and proper) therein. Memory integrates experience. There is less memory in the dream because experience is already better integrated, and also because experience is less extensive. Dreams improve upon memory and understanding by increasing (or adding to) the integrated extensiveness of being and experience (including thought) in and with time. The sense of relative familiarity involving dream experience is associated with the improvement of understanding and memory therein. Dreams and memory integrate experience, and both add to the extensiveness of experience (including thought) as well, w hile involving a [relative] reduction in the totality of experience. Since the self has extensiveness of being and experience (in and with time) in conjunction with the integrated and natural extensiveness of sensory experience, we spend less time dreaming (and sleeping) than waking. The integrated extensiveness of being and experience go hand in hand. Emotion that is comprehensive and balanced advances consciousness. Dreams are an emotional experience. The comprehensiveness and consistency of both intention and concern are central to our consciousness, life, and growth. (Desire consists of both intention and concern, thereby including interest as well.) The comprehensiveness and consistency of both intention and concern in relation to experience in general is ultimately dependent upon the natural and integrated extensiveness of sensory experience. In keeping with this, consciousness and language involve the ability to represent, form, and experience comprehensive approximations of experience in general, and this includes art and music as well. If the self did not represent, form, and experience a comprehensive approximation of experience in general, we would be incapable of growth and of becoming other than we are. Thought involves a relative reduction in the range and extensiveness of feeling. In keeping with this, dreams make thought more like sensory experience in general. Accordingly, both thought and also the range and extensiveness of feeling are proportionately reduced in the dream. (This reduction in the range and extensiveness of feeling during dreams is consistent with the fact that the experience of smell very rarely occurs therein.
Subscribe to:
Posts (Atom)