The Reductive Carbonylation of Organic Nitro Compounds

The Reductive Carbonylation of Organic Nitro Compounds Introduction: The development of environmentally more benign and efficient synthetic methods has stimulated the evolution of new strategies and technologies for the synthesis of useful products in a safe, compact, and energy efficient manner. In this respect our preliminary focus to investigate typically efficient and complementary methodology with palladium-catalyzed reductive carbonylation of nitro arenes employing CO gas. CO represents the most important C1 building block molecule to introduce a carbonyl group into parent molecules. In the last fifty years, the reductive carbonylation of organic nitro compounds has been the subject of intense research due to the fact that industrially important chemicals can be obtained in a single step. Among these, the most relevant are isocyanates, ureas and carbamates but also a number of heterocycles and other non-cyclic compounds. Isocyanates are commodity chemicals mostly employed in polyurethane synthesis but also intermediates in the production of carbamates and ureas. Polyurethanes are widely applied in almost every part of modern life in the form of plastic foams, coatings, adhesives, sealants and elastomers and binders. The most widely employed aromatic isocyanates are especially toluenediisocyanate (TDI) and 4,4-methylene diphenyl diisocyanate (MDI) that account for more than seven million metric tons per year. Synthesis of Isocyanetes: Currently, industrial synthesis of isocyanates is carried out with two step reaction process using nitroarenes with very high yield and selectivity. Nitroarenes is usually reduced to corresponding aniline using heterogeneous transition metal catalyst, and subsequently the amine is reacted with phosgene to give corresponding isocyanate along with hydrochloric acid. Phosgene based synthetic route seemed to be effective and well established technology employed. Major drawbacks of the phosgene based synthesis: There are essentially four major drawbacks with the synthesis of MDI and TDI via phosgene route. The first and most prominent observation are its extreme toxicity and flammability of phosgene and isocyanates, which make these chemicals extremely difficult to handle in bulk synthesis. Phosgene was used as a chemical weapon during the World War I, and around million people were injured and got killed by the use of poisonous gases. The second major drawback is the production of corrosive hydrochloric acid, rendering the medium very aggressive with time, thus allowing other side reaction to occur and to result in reactor degradation. The third limiting factor is the dilution of reaction medium as the high dilution is required to avoid recycling and concentration costs. The final drawback is the isolation of pure isocyanate from reaction mixture. The chloride containing side products are difficult-to-remove from the final product leading to detrimental to the further processing of the isocyanate. Considering above drawbacks, any process design incorporating phosgene will get extra costs to ensure a safe environment. Industrial requirements for an alternative isocyanate synthesis: In order to replace the phosgene route, a number of requirements can be made in the ideal scenario. First of all, readily accessible chemicals should be used and second, they should be as harmless as possible. Finally, a one-step synthetic procedure will be the route par excellence. A high overall yield, purity and selectivity, a temperature close to about 25 oC and the absence of over and/or under pressures in the plant should be preserved ideally. In principle, most of the requirements could be met by an efficient catalytic system.The additional requirements such as Turn Over Frequency (TOF) in the order of 104 h-1 or higher, Turn Over Number (TON) in the order of 106 or above and easy recycling of catalyst would be maintained. On this account, the necessity of environmentally acceptable but still economically competitive phosgene-free route to isocyanates synthesis is most demanding in near future. Alternative routes to TDI and MDI: Various synthetic pathways to isocyanates: Reductive carbonylation with Palladium metal catalyzed system has proved to be an effective transition metal catalytic system due to its ability to be oxidized or reduced easily during the reaction and high tendency to form complexes with carbamoyl groups.A palladium strongly prefers the oxidation states 0 and +2, which are separated by a relatively narrow energy gap, making palladium an excellent catalyst for both oxidation and reduction reactions. Secondly, the moderately large van der Waals radius of palladium together with the high number of delectrons (favorable d10 and d8 complexes) means that the organometal is classified as rather â€Å"soft†, with a high tendency for concerted reaction as well as a high affinity to â€Å"soft† and -donors, leading to useful chemoselectivity. Finally, Pd is relatively electronegative, resulting in a rather nonpolar Pd-C bond, suppressing the reactivity towards polar functional groups. In our previous report, nitrobenzene was typically used as a model substrate, and the use of palladium proved to result in the most effective catalytic systems. The carbonylation of nitrobenzene is generally performed in methanol using homogeneous palladium complexes supported by variable bidentate N- or P- donor ligands. Methyl phenyl carbamate (MPC) was synthesized including other side products. Isocyanates and catalysis: Within the vast variety of synthetic strategy for isocyanates, one of the approaches is to catalytically convert a nitro or amine compound to the corresponding isocyanate (see Figure 4). One of the approach using oxidative carbonylation and carboalkoxylation of aniline has been studied with various catalytic systems. However, aniline have to be synthesized by hydrogenation of nitrobenzene, thus considering industrial application, the most attractive strategy would be direct synthesis of isocyanates from nitro compounds which is also thermodynamically favorable. Reactivity of isocyanates and carbamates: Phosphorus and Nitrogen as donor atoms: Both phosphorus and nitrogen ligands of the YR3 (Y = P, N) type (called phosphines and amines respectively) can be described as sp3 hybrids in a (close to) tetrahedral geometry, having a lone pair on the central atom, capable of donating its electron density to an empty (transition) metal d-orbital. Amines are more electronegative than their phosphine analogues, so it could bind strongly with metal centre. However, unlike amines, phosphines can act as a Ï€ acid with their ÏÆ'* orbitals, so they can be involved in Ï€ backbonding (providing the metal has available d-electrons), rendering the overall bond strength larger than would be expected intuitively (see Figure 6). So, the overall bond strength is determined by an interplay of ÏÆ' donation and Ï€ backbonding, the first having an increasing contribution when electropositive/donating substituents are employed, the latter when electronegative/withdrawing substituents are used. In 1990, E. Drent et. al. reported the palladium catalyze reductive carbonylation of nitroarene introducing â€Å"soft-base† ligands like diphosphines in combination with strongly coordinating anions, or â€Å"hard-base† electron-donating ligands such as phenanthroline, combined with non- or weakly-coordinating anions, resulted in relatively active and selective catalytic systems (maximal TOF’s (h-1)/ carbamate selectivities (%) = 150/80 and 1600/98 for diphosphines and phenanthroline respectively). General remarks on P and N based systems: In general, the statement made by Drent already in 1990 that: ‘Pd with chelating â€Å"hard base† electron donating ligands such as phenanthroline, combined with   non or weakly coordinating anions, can result in relatively active and selective catalytic systems.’ Has been generally accepted and indeed thoroughly studied in the past decades by several people. On the other hand, the statement that: ‘Pd with chelating â€Å"soft-base†Ã¢â‚¬â„¢ ligands like diphosphines in combination with strongly   coordinating anions , can result in respectively active and selective catalytic systems.’ Has not yet been the subject of intense academic studies, most likely due to the poor results that were obtained initially, when compared to the N-donor systems. However, in principle, there is no reason why N-donor systems should be superior to P-donor systems, except that phosphine ligands are known to be easily oxidized, thus troubling both the preparation and use of such systems. On the basis of recent observations on chelating N-donor systems like 1,10-phenanthroline with electron donating substituents (R) in combination with Pd(II) and a weakly or non-coordinating anions (Y), comprises the most active systems to date (i.e. [Pd(Rxphen)2][Y]2). Since, 1, 10- phenanthroline (unfettered of substituents ) is relatively cheap and readily available, this ligand ligand is most frequently used. Furthermore, the performed catalyst is more active and selective than its in situ formed analogues and in almost all cases a slight excess of free ligand is added. The addition of a BrOnsted acid (with bulky, non-coordinating anion) as a co catalyst , as well as the addition of a substrate related aniline is known to improve both reactivity and selectivity. The experiment is carried out in inert atmosphere and addition of reactive drying agent is also known to be beneficial. The temperatures are mostly around 120 – 170 oC, and both the concentration of all components a nd the reaction times are differed considerably. Methanol is used as a typical solvent , which is partially consumed to yield the carbamate, but occasionally toluene/methanol or other alcohols are used. Finally, the influence of varying CO pressure results in different reactivity. Most reactions were performed at pCO = 40 – 80 bar, the best results were obtained at pCO = 100 bar, and the elevated pressures are believed to enhance the reactivity even further. The Mechanism The palladium catalyzed reductive carbonylation of nitrobenzene in methanol has been investigated in great extent. All catalytic reactions were performed using both catalyst precursor and pre-formed complex resulted carbamate as well as side products. There are frequently reported (side-) products of this reaction are shown in Figure. : azobenzene(Azo), azoxybenzene (Azoxy), aniline and N.N’-diphenylurea (DPU). Azo and Azoxy are resulted as coupling product of nitrobenzene. Aniline and DPU are hydrogenation products which are indicating the presence of moisture in the reaction mixture as well as methanol could be source of H-atom for hydrogenation reaction. DPU is the carbamate analogue of isocyanate reacting with aniline which is the better nucleophile than methanol. The mechanism of reductive carbonylation of nitro compounds into carbamates has been extensively studied with palladium, (substituted) phenanthroline ligands, MeOH as solvent and an acid cocatalyst. The mechanism proposed by Mooibroek et al. seems to be the most complete as it also explains the formation of all side products Scheme: . The palladium-imido species L2Pd=NPh (C3) and the palladacycle L2PdC(O)N(Ph)OC(O) (C2) were considered as possible carbonylation product-releasing species for both (substituted) phenanthroline and diphosphine ligated catalytic system. The result of catalytic experiments , supported by spectroscopic (ESI-MS and NMR) compound C2 is not the major product- releasing intermediate in reactions performed in the absence of acid. In the absence of acid, Pd-imido complex C3 is the proposed reaction intermediate releasing PhN-containing (Azoxy, MPC, PhNH2) products. On the other hand, in the presence of acid the palladacycle complex C2 becomes the major product-releasing intermediate, resulting the nitrobenzene carbonylation product MPC with high selectivity. Different side products: In all catalytic reactions performed using both catalyst precursor and pre-formed complex resulted carbamate as well as side products. The side product are Conclusion and future prospects: In conclusion, the incentive research output from the last decade facilitated us to understand the catalytic reductive carbonylation reaction of nitroarenes to produce relevant carbamates. The reactivity of PdII compounds supported by 1, 10-phenanthroline (phen) or the bidentate diaryl phosphane has been studied in the reaction of nitrobenzene with CO in methanol. The nitrobenzene reduction chemistry in the Pd/phen/CH3OH/H+ system resulted higher in selectivity but lower in activity wherein Pd/diphospane/CH3OH/H+ system shows higher in activity but lower in selectivity. Based on our continuing interest in reductive carbonylations of nitro-aromatic compounds and considering the importance towards sustainable synthesis of isocyanates, herein our further approach to develop a ultimate catalytic composition of reactants which can produce highly selective product with high yield having tiny or no side-products. However, despite rationalized molecular mechanism developed by Tiddo et. al. f or above catalytic system is still not efficient enough, nor is it exactly clear how the catalyst works. In recent years, Great progress has been made in extending the scope of palladium-catalyzed synthetic organic reactions introducing in-situ reductive carbonylation reaction with CO generated from the solvent molecules. Manirul et. al. have reported polymer anchored ruthenium based catalyst for reductive carbonylation. Raquel et. al. have investigated that gold nanoparticles are efficient in N-carbamoylation of aromatic amines. In this respect, further elucidation of the overall mechanism and research in new directions is urgent requirement to produce effective palladium based reductive carbonylation of nitro-aromatic compounds considering industrial background. Thus, the current research project will address several issues which are envisaged to be worthwhile to explore. Firstly, the modification of ligand system, secondly the designing of catalyst system, thirdly the mechanism, and finally the use of other additives in the catalyst system to be fine-tuned. Modification of ligand system: The active species in the catalytic cycle as Pd(0) are seem to be as stable as possible to prevent inactive metallic Pd(black) formation. Our previous research work were illustrated the sharp observation of the bidentate P or N ligand based Pd-catalyzed system to achieve maximum activity and selectivity. Our further observations are envisaged based on tripodal P and N system to stabilize Pd(0) species as well as Pd(II) species during catalytic transformations. The concept of monolegated active species stabilizing Pd(0) by steric bulk ligand is rationalized to enhance the reactivity. On the basis of the palladium catalyzed coupling reaction of aryl halides system employed with electron rich N-heterocycle carbene ligand which exhibits flexible steric bulk environment, Several factors will be assumed to be execute in these system: 1) electron-rich nature enhances the rate of oxidative addition, 2) the ligands coordinate tightly to the Pd to prevent the formation of Pd black, and 3) thei r steric bulk favors a 12 electron, monocarbene–Pd [L-Pd] species and increases the rate of reductive elimination. Variation in carbamate synthesis: The formation of carbamates in the catalytic system utilizing PdII, phenantroline, acid and various nucleophile has been studied extensively to find an alternative for MeOH as nucleophile. The objective is to yield a carbamate or urea which can be pyrolised at lower temperatures to save energy and prevent degradation of the formed isocyanate. The changing the nucleophile is not straightforward, as the use of another nucleophile as a solvent may be too expensive or not possible (if the nucleophile is a solid), hence use of a solvent may be necessary. Therefore, non –nucleophilic solvents have to be tested in combination with potential nucleophiles in the catalytic synthesis of carbamates and ureas. Despite the use of common known compound used as a nucleophile, still there are broad spectrum of nucleophiles to be tested with various combinations. Isolation of Palladium-imido complex:

The Metamorphosis and Waiting for Godot Analysis | Dark humour in literature

The Metamorphosis and Waiting for Godot Analysis | Dark humour in literature Many writers have significantly utilized dark humor or black humor across various genres and time. Dark humor in Metamorphosis and Waiting For Godot have not only revealed to us through its various moments, ideas and issues that appeal to an audience at that time, but it also revealed to the readers and audience the nature of its characters. Although Vladimir, Estragon, Pozzo and Lucky have been created almost like stock characters, we seem to understand through Samuel Becketts use of dark humor moments of Pathos, meaninglessness and stagnancy in their lives. Franz Kafka on the other hand creates a transformation in his main character, Gregor Samsa, by turning him into a mere insect and watching not only Samsas family but his reading audience react to it. The opening scene of Waiting For Godot is a country road setting with a single tree, and we find Estragon trying to remove his boots with both his hands. After much struggle, he says Nothing to be done as if removing his shoes was such a profound thing to be doing and therefore nothing could be done about his inability to remove his boots. A little later, as through out the play, each of them exchange dialogues that do not correspond or even connect to each other in any way. Estragon: Ah, stop blathering and help me off with this bloody thing Vladimir: handing hand from the top of Eiffel tower, among the first. We were presentable in those days. Now its too late. They wouldnt even let us up. All of these dialogues would have sent the audience into splits but they also resound with the inability of Vladimir and Estragon living a full and meaning life. Another example of black humor in this play is the part where Estragon talks about the Dead Sea and how the very thought of it made him thirsty. This creates a roar of laughter amongst the audience as Estragon talks about the Dead Sea in context to the Gospels. But, the reality is that the water form the Dead Sea will quench no thirst, as it is highly saline. This brings out Estragons naÃÆ' ¯ve character as he talks about the Dead Sea in comparison to the Gospels Estragon: The Dead Sea was pale blue. The very look of it made me thirsty. The entrance of Pozzo and Lucky on stage undoubtedly thrives on dark humor. Lucky is being led by a rope tied to his neck and pozzo says, Lets say no more. Up pig! Every time he falls, he falls asleep. Up hog! Back! Stop! Turn! These staccato instructions, almost army style, seem to evoke a laugh or at least smile amongst the audience or readers. However, the slavish Lucky seems to be put into a demeaning situation, which doesnt fail to catch the audiences attention. The return of Pozzo held by Lucky on a rope seems to create a reverse image of the earlier situation. This image brings a certain satisfaction to the audience, a laugh no doubt, and yet makes the audience aware of how fortune is fickle and can change with such a strong impact. The technique of contrast used by Beckett in Waiting For Godot is another attempt to bring out humor and reveal character. Estragons constant worry of who Godot is and when he will come and Vladimirs attempt to constantly calm his nerves, Vladimir: He said Saturday. I think. Estragon: You think. Pozzos initial arrogance and later his dependence on Lucky while he crawls onto stage are humorous ways of representing the characters. Becketts constant use of repetition of language and actions are humorous but stagnant. This is further intensified when Vladimir and Estragon have nothing to eat but a single carrot and a rotten turnip, Estragon Im hungry Vladimir: Do you want a carrot? Estragon: Is that all there is? Vladimir: I might have some turnips They seem to be holding on to their dignity later in the play when they meet Lucky and Pozzo. They do not show their hunger nor do they ask for food. But the moment Pozzo and Lucky leave the stage, Estragon picks up the eaten chicken bones, trying to get some sustenance out of it, Estragon makes a dart at the bones, picks them up and begins to gnaw on them. All these action and dialogues used by Beckett derive a sense of black humor but reveal to us simultaneously the sterile, meaningless and unfulfilled life of its characters. When Gregor Samsa awoke one morning from troubled dreams he found himself transformed in his bed into a monstrous insect. The very opening lines of The Metamorphosis stated in this casual style does not fail to bring a smile to the readers. For who can wake up and find themselves transformed into an insect and not panic. Strangely, Gregor seems unaffected by this transformation, assuming life would go on with his spindly legs and squeaky voice. Kafka describes Gregor as this thing with a monstrous body and spindly legs. He has legs that dont seem to support him and neither is he aware how to use them. Kafkas humorous description of Gregor Samsa trying to get on those legs and out of the door and back to work, Groping for support, he fell down with a little cry on his numerous legs brings out a roar of laughter as he falls back on his back and cries out in a squeaky voice for help. Gregor gave a start when he heard his voiceà ¢Ã¢â€š ¬Ã‚ ¦ irrepressible, painful squeaky The use of humor here reveals to us the helpless situation Samsa is trapped in and we as readers sympathize with this character. Later on in the book, Kafka describes how Samsas embarrassed father throws an apple at Gregors back and the apple sticks in the insects body It was an apple. Immediately, a second one flew after it. Gregor stood still in fright. Gregors serious wound, from which he suffered for over a month -since no one ventured to remove the apple, it remained in his flesh as a visible reminder. Although this seems visually funny, it draws upon the readers sympathy and empathy with Gregor. From this moment on G regor seems to deteriorate psychologically and physically and dies in a heap of dust, to be swept out and thrown into the trash by the Charwoman. At the end of The Metamorphosis Gregor Samsa is seen for the last time when he hears his sister playing the violin. He sneaks out of his room unaware that his current image not only frightened his family but also the lodgers who had come to stay as paying guests. Gregor attracted by playingà ¢Ã¢â€š ¬Ã‚ ¦Ãƒ ¢Ã¢â€š ¬Ã‚ ¦Ãƒ ¢Ã¢â€š ¬Ã‚ ¦. This episode not only reveals to us almost like children playing Peek-a-boo, a child like humor, but we readers have become pained at such a transformation of Gregor. We have also unmistakably recognized that his family members have transformed too into selfish, heartless human beings who refuse to call the insect their son or brother (in the sisters case): I will not utter my brothers name in front of this monster Thus, through the examination of the two books, Waiting For Godot and The Metamorphosis, it can be concluded that it is through dark humor that the authors have brought out the respective characteristics of the individuals depicted. For example, the blunt Estragon, the clam Vladimir, the dominant Pozzo, the slavish Lucky or the tragic Samsa, all of these characteristics are brought out through the help of dark humor. We have encountered them all through humorous events, descriptions and pictures.

A Comparison of Hard Times and Dulce Et Decorum Est :: comparison compare contrast essays

A Comparison of Hard Times and Dulce Et Decorum Est      Ã‚   It is amazing what we can learn about the different societies by studying the literature prevalent of their times. According to Michel Foucault, "Through language and thought, each period in history develops its own perceptions of the nature of reality (or what it defines as truth) and sets up its own acceptable and unacceptable standards of behavior" which he calls "episteme" (Bressler 242).   Within the text of "Hard Times" Charles Dickens brings the reader an understanding of what was happening to the English society during the Victorian age. As we read this text we can have the opportunity to view the thoughts of the Victorian culture as well as view what happened at that time though our own.    The title of his story brings the reader to an understanding of what is behind the story even before reading the text. It is written in simple language for all to understand, those of the times, and those who read the story in the future. Dickens does not complain of kings who lack morals or knights who seek justice. He does not write of men seeking honor in battle or the absurdity of war. He writes in plain language for the common man to comprehend of a different battle than one might suspect. He speaks of the battle his society faces while going through the growing pains of advancing technology and it's effect on the people of his country. The author speaks of a city called "Coketown" that is being transformed into an industrial conglomeration from what once was a pleasant city of humans living and together to make a better life. When Dickens writes, "It was a town of red brick, or of brick that would have been red if the smoke and ashes had allowed it" he is complainin g of a vanishing beauty that once held this city and it's people in safety (Longman1828).    Dickens goes on to describe the city as having, "a black canal in it, and a river that ran purple with ill-smelling dye" which would bring the reader to consider the possible pollution of the waterway (Longman 1829). It is apparent by reading the comments of Dickens that at the time of writing "Hard Times" was directed at the cities governing body in an attempt at righting the wrongs of technologies effects on the city.

Dunbarton by Robert Lowell Essay example -- Poetry Life Studies Robert

"Dunbarton" by Robert Lowell is one of the poems from his "Life Studies" book. It's a short poem of only two pages but it has very deep meaning. The poem alludes to the poet's relationship with his grandfather. In this essay I will analyze this piece in detail and talk about the author's connection with his grandfather. Robert Lowell prefers the use of free verse for his poems. He doesn't use a specific style for this piece; it is more free styled. He uses poetic language but there is no metered rhythm in the poem. Lowell even said once in an interview: "Prose is in many ways better off than poetry...I thought poetry was getting increasingly stifling. I couldn't get my experiences into tight metrical forms" (J. Myers and D. Wojahn, p. 154). He was also the first poet who wrote about his family to tell the truth about them, and "took the laundry out on the public." In "Life Studies", the author talks about his parents and the family members. Lowell writes about himself as well as his family members in a very critical way, which was unheard of at that time. Though some of the facts are not true and are exaggerated, his poems satirize the family. He does a lot of character description, and he performs it with a great irony. Many metaphors and details make his works very twisted. In a way, he confuses the reader but at the same time, he interchanges that with some sentences that are short, sharp, and very direct. Sometimes, they are even too straightforward: "He was my father. I was his son" (Line 10). He didn't seem to have much love for his father; however, he had a great connection with his grandfather. The poem opens with the following: "My Grandfather found his grandchild's fogbound solitudes sweeter than huma... ...owell is a great poet and writer. Although I do not like reading books that have a depressing mood like Lowell's, I appreciate the work he has done. As I read in one book: "'Life Studies' broke new ground with its despairing yet elegant lucidity" (J. Myers and D. Wojahn, p. 194), I agree with the saying. His poems are very complex, profound, and are even unresolved. It can be discussed unlimited number of times and still have a charming mystery about it. In "Dunbarton", which is a very short piece, Robert Lowell was able to express the great love he had for his grandfather and I think that it takes a great amount of talent to do it with such ease and flow. Works Cited Lowell, Robert. "Life Studies". 1967. Farrar, Straus and Giroux. Myers, J. and D. Wojahn. "A Profile of Twentieth Century American Poetry". 1991. Southern Illinois University Press.

Write Your Response to the First Chapter of Enduring Love by Ian Mcewan

Write your response to the first chapter of â€Å"Enduring Love† â€Å"The beginning is simple to mark. † – The first line of the novel is designed to hook readers and it does. The use of the word â€Å"beginning† begs the question, the beginning of what? Instantly capturing our interests, it also shows the significance of the event as coupled with the word â€Å"simple† it shows complexity surrounding this mysterious, forthcoming event, again capturing our interests, and it shows the narrator has replayed this event a number of times to himself to of found the exact moment where everything began.I believe it is a rather cliche opening to a novel but with McEwan being the author he manages to make it is an effective cliche. McEwan, through the introduction of characters and detail, instantly introduces the subject of class into the novel and so sets the backdrop for the novel. With a bottle of 1987 Daumas Gassac and a name like Clarissa that holds t he connotations of wealth and luxury we are told of the class and lifestyle surrounding who we assume are the main characters. With the narrative voice in chapter one of the novel focusing on thought and detail and not emotion it introduces a rather robotic character in Joe.We get to know him quickly and quite intimately as the novel is written as though he is talking to straight to us. We are shown the absence of feeling in him which is replaced by the almost irrational use of logic he uses. For me, too much emphasis is put on the scientific part of Joe, we are told his mind works in a scientific way and it is made apparent that he is very intelligent but this is drilled into the readers head over and over again until it becomes potentially irritating and monotonous.There is no human being behind the voice, he observes in very close detail everything around him but does not feel a great deal about it. Joe’s need for detail to perhaps eliminate some of the guilt that he feels at this stage of the novel is repeated to the extent that it becomes almost obsessive. The relationship between Joe and Clarissa is intriguing. They are both at opposite ends of a spectrum, with Joe being an unemotional, rational and obsessive scientist it is worlds apart from Clarissa, who is an artist and relies heavily on emotion.Despite being together for seven years, the two are too different to be compatible in a much longer term, they think in different ways and appear to not have a lot of common ground.. In the first chapter the focus is on the balloon accident but when it becomes apparent that this is not the main event in the novel the only other thing we have been given to focus on is the relationship between the pair which is interesting and dare I say it, it makes the reader want to read on.The setting for the opening scene is a blank canvas; the field in which the accident takes place is simple and lets the accident take the forefront of the story. The simplicity give s way for more complex events but the serenity of the scene which is then interrupted by a tragic accident is significant in that it could be a metaphor for the rest of novel. Joe and Clarissa are quite happy together in the beginning and have been for some time but as the story unfolds and Jed, like the balloon, crashes into their relationship, cracks begin to show and disaster strikes.McEwan uses a lot of delay techniques in the first chapter. I find he delays the events to the point of near boredom. Although what he writes is interesting it is repetitive and nauseatingly pretentious. The majority of the chapter is McEwan making his presence felt, the narrative voice changes from being Joe to being McEwan and back to Joe again. There are too many complex paragraphs that have barely any relevance to the novel other than to show how intelligent McEwan is. However despite not particularly enjoying the first chapter of â€Å"Enduring Love†, McEwan achieves his initial objective , to intrigue the reader.

Comaparison of crisis in congo with bangladeshi textile

The videos ‘crisis in Congo' and ‘fault lines' have a tremendous resemblance to Colonialism. The difference being that it is much more indirect and manipulative form in which the exploiter not even takes the responsibility for exploitation. This smarter and indirect approach not only helps them escape when they are questioned about their moral responsibility but also enables them to continue these atrocities without ever being questioned.Walked defines Colonialism as – â€Å"Colonialism is the establishment, exploitation, maintenance, acquisition, and expansion of colonies in one territory by people from another territory. It is a set of unequal relationships between the colonial power and the colony and often between the colonists and the indigenous population. † It also says that colonialism existed from 16th century till mid 20th century. What It actually means Is that from 16th till mid 20th century colonialism existed In a direct and perceivable form.In that sense, the exploitation was honest as the exploiter directly came to another territories and bore the responsibility for exploitation. Also there was a clear line between the exploiter and exploited. But after the outcry in the name of democracy and human rights all over the world and specially in the western countries, the colonialism came out in a much more evolved and concealed way. Due to developed trade channels and the ease of transport and communication the exploitation Is now carried out by capital hungry Mans or capitalist forces and not exclusively by countries.It Is also not about the acquisition of land but direct acquisition of resources without even setting a foot in these resource rich lands. One more difference which is very subtle in nature is that the line between the exploiter and exploited is blurred . This is because of the indirect nature of this exploitation model that not only poor people but even governments are tricked Into thinking that these trade p ractices or so called ‘help' from foreign will provide the much needed employment and development In these underdeveloped nations wherein these practices are Just disguised exploitation model.So by not understanding these unfair advancement of Mans and developed nations ,the native government also becomes their partner in crime. The video ‘Crisis in Congou is about the exploitation of a whole nation by a host of exploiter Rwanda, Uganda, united States Government and the corrupt dictators. The roots of this exploitation are in Rwanda genocide which Is essentially about ethnic differences between the ‘Hut' and â€Å"Tutsis' people but the exploitation Itself has nothing to do with these differences. Interestingly the division of these two ethnic groups was made political during the colonial rule of Germany.This spark of division later escalated into a full scale civil war between these two groups in Rwanda. Some Hut men who fled to Congo during the Civil wars became ‘Genocidal Militant' and hen the Congolese people sought refuge In Rwanda they mixed up with the refugee population and carried out terrorist activities against Rwanda which In their Patriotic Front or RPR government to launch a Revenge attack on Congo refugees where million of peoples were killed Just because the Rwanda government sought few militants hidden in these innocent population.Now starts a whole story of exploitation of Congo. Congo is a resource rich land and all these resources are in heavy demand across various modern industries. If there were to be a fully functional government in Congo the capitalist forces in the developed nations will eave much difficulty accessing these resources so the United States helped install a series of dictators which were easy to manipulate rather than a whole government and thus straightened their interests. The other governments such as UK and France played a similar role but from a different side.They made sure that there is eno ugh supply of arms and ammunition to these combating forces so that Congas political instability and their gains are assured. The native Congolese who were powerful never thought about their own people and chose to support a war which could have easily died in the absence of these catalysts. But soon these capitalist forces realized that the military war is costly to sustain so to further increase their profit margin they employed a much more heinous and lower level of warfare which is now known as ‘Rape War'.They would publicly rape women inferno of their men and communities. They implemented this physiological warfare strategically and systematically across the lands. Since the men were not able to save their women, a deep feeling of helplessness and weakness crept inside the people which made them more easy to control. Now these people would not even think of human rights because they no ore felt human. Result was that there was no one to resist the capitalist forces when t hey are filling up their pockets with the resources.The second video ‘Fault lines' is about Mans like Walter exploiting the human resource of underdeveloped nations. They are also using a similar exploitation scheme in which their direct accountability to exploitation can not be traced. They have made their supply chain so complex that to a distant observer it seems as if Walter clothes are coming from thin air. Reality is they are trying to hide their unfair trade practices through obscurity.In the disguise of a socially and morally responsible organization they are carrying out worst trade practices such as child labor, dangerously insufficient work environment, absence of worker's rights and no accountability whatsoever towards any mishap during production. In order to increase their profit margin they are encouraging a concept called sub-contracting in which a direct supplier who is unable to fulfill his contract will pass a piece of work to some other contractor. These su b-contractor have small unregulated areas which they ignorantly call factories' which in reality is Just a shack in someone's backyard.In case of any accident such as fire accident these places act more like concentration camp wherein people easily get killed unable to get out. The following table depicts a comparison of the two videos in tabular format – Categories Video 1 -Crisis in Congo Video 2 -Fault lines Exploiter forces and Dictators Mans like Walter, Old Navy etc Mass Congolese population Bangladesh workers in textile industry Country of Exploitation Democratic Republic of Congo Bangladesh Exploited for(resources) Mineral such as gold, diamond, tin, copper, cobalt, tungsten etc Cheap Human Resource MethodCataloging military warfare and rape war through political means and otherwise Irresponsible trade practices -Employing a 5-6 layer wide supply chain in production Disguise used Developed nations and UN acting as benevolent mediators were actual perpetrators Walter p osing as ethical and socially responsible organization was implementing unfair trade practices indirectly Catalytic agents Local political elites, dictators and genocidal militants 1st level supplier and loose regulations by Bangladesh government Benefits to exploiter Sustained war translates to political instability which means limitless excess toCongolese resources for outsiders with zero accountability towards local people A long supply chain means no accountability towards any worker as there is no direct connection Results Beastly living conditions to people of Congo , weakening of spirit of people due to rape war and physiological warfare, spiked increase in HIVE positive population, millions of people dead Dangerously insufficient working conditions, inadequate compensation to workers, zero accountability towards workers suffering accidents, child labor, death of workers, financial difficulties to victim's family

Defeat of the Red Army Essay

By looking at what the areas where the Soviets failed during their in Afghanistan, we can further develop our counterinsurgency tactics and doctrine and shape our forces. Mujahideen Defeats of the Red Army An important and remarkable event in history was the Soviet-Afghan War. The Afghans, like their ancestors, battled a hostile, invading force that wanted to dominate their homeland. â€Å"For the first time, Afghanistan would become the center of a modern pan-Arab Jihad (Holy War)† (Hill, 2008). The Afghans were fighting a war of attrition just as their ancestors did during the Anglo-Afghan Wars. The Afghans would find themselves using modern weapons that had the potential of causing a high number casualties and emigration of greater proportions. The difference between the Afghans in the Soviet-Afghan War and the Afghans who fought in the Anglo-Afghan war would be the help and support from outside superpowers. By the end of the Soviet-Afghan War, the Soviet Union was at the point of falling; the Afghans and those who were assisting them were looking at a victory. How could such a powerful country like the Soviet Union be defeated by the Afghans? The Soviet Union lost the Soviet-Afghan War as a result of mistakes and failures that they made. The Soviets failure to seal the border between Pakistan and Afghanistan, failure to stand up and effective Afghan Army and failure to win the hearts and minds of the Afghan people contributed to the defeat of the Red Army. Failure to Disrupt Supply Lines During the initial five years of occupation, the Soviets never mounted a sustained effort to cut off the Mujahideen supply lines that ran from Pakistan’s tribal areas, across the Hindu Kush Mountains, and into Afghanistan (Roy, 1991). Instead, the focus of the Soviets from 1980 to 1982 was to conduct large-scale armored operations in locations that were considered hotbeds of rebel activity. After 1982, the Soviets used aerial assaults to assist in their combat operations to eliminate the support base of the Mujahideen. It was not until 1985 that the Red Army starting making an effort to disrupt the Mujahideen supply lines. The Red Army began using Spetsnaz units, which were the Red army Special Forces units, behind Mujahideen frontlines, to organized surprise attacks against the rebel supply caravans. Once the Spetsnaz had the location of the Mujahideen, they would load into Mi-24 helicopter gunships, sneak behind the Mujahideen positions, and launch attacks. The effectiveness of the raids the Spetsnaz used became apparent in 1986 where there was a decrease in the number of Mujahideen attacks against the Soviets. The attacks against the Soviets decreased because the Mujahideen was not able to get men and equipment that they needed to mount an effective guerrilla campaign. The Soviets leadership was aware of the amount of men and a large amount of equipment that the Mujahideen was moving from Pakistan across into Afghanistan on regular bases, so it’s interesting why they did not make an effort earlier in the war to disrupt the supply lines. The Soviet leadership feared that if they conducted operations that might extend into Pakistan they would draw the United States into a large-scale war that the Soviets did not want. So, conducting operations on the Afghan side of the border against the rebels was an activity that the Soviets could justify without drawing the United States into the war. According to Oliver Roy, the Soviet failure to seal the border with Pakistan was the most significant military mistake in the war against the Mujahideen (Roy, 1991). With an unsealed border, the United States with the help of the help of the Inter-Service Intelligence, ISI, began funneling in weapons to the Mujahideen in the 1980. At the start of 1980, the Central Intelligence Agency began to purchase weapons from several countries to include China, Egypt, Saudi Arabia, and other Arab nations. Once these weapons had been purchased they were shipped to the ISI headquarters located in Peshawar Pakistan. The United States funded some $30 million dollars in 1982, but in 1984, the CIA spent some $250 million purchasing pistols, AK-47s, ammunition, surface to air missiles, and other supplies for the Mujahideen. By 1985, the CIA was spending $500 million dollars on the resistance in Afghanistan. 1985 was the same year the President Ronald Reagan signed the National Security Decision Directive 166. This directive stated that the CIA was to drive out the Soviets from Afghanistan †by all means available† (Crile, 2003, p 363). In 1986, the CIA approved the purchase of heat-seeking missiles and almost 1000 per purchased. The heat-seeking missiles were very effective in downing the Soviets helicopters, but the Mujahideen did not put these missions into use until 1987. Pakistan who was driven by Islamic identity had a vested interest in the outcome of the Soviet-Afghan War and made a great effort to ensure that the Mujahideen was victorious. To ensure victory for the Mujahideen, Pakistan established a network that would transport all of the weapons that had been purchased to the Mujahideen. Once all of the weapons that had been purchased and arrived to the ISI headquarters the ISI would distribute the weapons to the Mujahideen, who would get the weapons and supplies to the soldier in the field. The Mujahideen would use tractors, trucks, camel, mules, and horses that could blend in with the rest of the cross border traffic or they would move on dirt roads that were only accessible by foot over the border into Afghanistan. It is evident that without the help of the Pakistanis, the Mujahideen would not have been able to fight because they could have not been able to supply their soldiers. Throughout the war, the Soviets and the Democratic Republic of Afghanistan, DRA attempted to pressure Pakistan’s President Zia to seal the border between Afghanistan and Pakistan with troops, but this came to no avail. President Zia responds to the request to seal the border was that Pakistan would not do it but that the Red Army and the DRA were more than welcome to do it. Regardless of who would attempt to seal the border it would be an impossible task when you consider the length and mountainous terrain that would have to be covered. In 1985, the Red Army started to disrupt the Mujahideen supply lines by putting thousands of troops on the border with Pakistan. At the same time, The Red Army began a bombing campaign hitting border towns that were sympathetic to the rebels and placing Spetsnaz units along the borders to conduct search and destroy missions from behind Mujahideen front lines. The Red Army began using their gunships to move up and down the border looking for destroying Mujahideen supply caravans. The bombardment used by the Red Army turned a large portion of the border etween Afghanistan and Pakistan to land that no longer could be inhabited. This depopulation effort started to become effective as it made it almost impossible for the Mujahideen supply caravans to move freely. In 1986, the Mujahideen countered the Red Army by using the Stringer missiles to bring down the Red Army Helicopters. To avoid being hit by a Stringer missile the Red Army Pilots had to fly at a higher altitude but the higher alt itude made it difficult for the Red Army to effectively attack the Mujahideen supply lines. Although the terrain along the Afghan and Pakistan border made it difficult to totally seal the border, it would have been possible to disrupt the flow of men and supplies coming into Afghanistan. This was evident by the Red Army between 1985 and 1986. Had the Red Army been willing to take a higher loss of life before 1985, it would have been possible to slow down the Mujahideen’s ability to get weapons into Afghanistan. The inability by the Red Army to establish an effective way to disrupt the Mujahideen supply lines was not the only reason that the PDPA could not survive without the support of the Red Army. The Red Army also failed to build an Afghan National Army that could protect the PDPA against the Mujahideen. Part of the reason why the Red Army could not stand up the Afghan Army was because there were Mujahideen sympathizers in the ranks. This is also part of the reason why the Soviets could not win the hearts and minds of the Afghan people. When the Soviets withdrew from Afghanistan, they left the country without the means to protect its self. Failure to build an Afghan Army As early as 1980, Soviet leadership knew that it was going to be difficult to build up the Afghan Army. This was partially due to the fact that the PDPA regime was unpopular with many Afghan people, and there was also a deep hatred for the Red Army troops. The unwillingness to fight for the Soviet Union and the DRA was reflected by the decrease in the Afghan Army’s ranks. The Afghan Army decreased from 90,000 to 30,000 men from 1980 to 1983 (Schofield, 2003). During the Soviet occupation of Afghanistan, it was common for Afghan soldiers to leave their units with their weapons and ammunition and join the Mujahideen. There is an account in July 1987 where an entire 2,000-man unit defected to the Mujahideen in Kandahar (McMichael, 1991). In addition to the defecting that was happening there were reports of Afghan officers frequently sabotaging Soviet equipment and vehicles. For the Afghans who remained many only fought because of the Soviet troops presences on the frontlines who would not allow them to runaway. As a result of the Afghans people unwillingness to fight for the Soviets and the DRA, the PDPA could only build a small military force, the total that numbers 120,000 to 150,000 fighting men. With its small size and the challenges they had recruiting the Afghans to fight for the PDPA regime, the Afghan Army was ineffective. The Afghan government was also only able to draft sixty-five percent of the personnel it needed to fight the insurgency they faced. Although the Afghan Army did have their share of success, these successes were limited. Mostly because the Mujahideen had sympathizers in the ranks that would provide the rebels with intelligence about upcoming operations that were planned. Since Mujahideen supporters had infiltrated the Afghan Army, Red Army soldier do not care to work closely on operations or share the intelligence they had because of fear that the details on upcoming operations would be shared with the rebels. To make matter worse for both sides, commanding officers of Afghan units would only be informed of upcoming operations one day in advance. On 9 January 1981, a conscription law designed to increase the strength of the DRA Army, was adopted by the Supreme Military Council of Afghanistan. The Afghan Army was given tanks, aircraft, armored personnel carriers, and small arms by the Soviets. Regardless of what had been given to the Afghan Army they were not going to be able to defend the PDPA regime from the rebels by the time the Soviets withdrew from Afghanistan. This is based on the fact that it was going to be hard to recruit soldiers to fight for a socialist an also because many of the soldiers that had been recruited were informant for the Mujahideen. â€Å"The ineffectiveness of the DRA Army was illustrated by two Soviet deserters when they said, â€Å"The Kabul army was not an army, just a mess, with half of the soldiers running away and the other half joining the rebels† (Amstutz, 1986, p. 80). The inability of the Soviets to win over the Afghan population showed to be a tremendous obstacle as the attempt was being made to stand up an effective Afghan military. Had the Soviets convince the Afghan population that the PDPA was worth fighting for; the Soviet’s counterinsurgency plan could have been more effective in getting rid of the Mujahideen. The Soviets inability to win over the hearts and minds of the Afghan people ended up being a big obstacle that led to the Soviet defeat in Afghanistan. Failure to win the Hearts and Minds â€Å"The Soviets needed to convince the Afghan population that it had a stake in the survival of the socialist regime if they were to have a chance of preserving the PDPA government† (Delgado, 2006, p. 27). This would show to be impossible since the Afghan mullahs had declared jihad against the occupying Red Army. Knowing the jihad had been declared against the Red Army, they still launched a program with the intent on winning the hearts and minds of the Afghan people. The Soviets attempt to Sovietize the Afghan people used measures that included revamping the education system and teaching the population a pro-Soviet ideology. Adults and children were taught Marxist terms by Soviet institutions that had been imported into Afghanistan. The Soviets reformed the education system, reinterpreting Afghan history, taking control of the media in order to reeducate adults, and sending children to the Soviet Union in order to be educated. The Soviets goal in all of this was to create a version of Islam that the new Afghanistan would be based off. Building a strong Communist party was part of the Sovietization program. A strong Communist party would be the center of all legitimate political activity for the country. In order to monitor social organizations in Afghanistan, Soviet style government institution were established. A diligent effort had been made by the PDPA to indoctrinate its member, a majority of which joined the party so that they could obtain a job in the state. The task of trying to indoctrinate the member was difficult and many felt that it was irresponsible and corrupt. The DRA was unpopular throughout a large portion of Afghanistan. With this unpopular view of the DRA, there was a need to rewrite history in order to paint the Soviet Union in a more favorable light. This change to history was going to be done in two parts, first was to depict Russia as the essential supporters of Afghan independence, and the second was to minimize the cultural ties the Afghan people had with India, Pakistan, and Iran while emphasizing the ties with the citizens of the Soviet Union. The Soviets strategy in winning the hearts and minds of the Afghan people was not to turn all Afghan into Marxist, but to teach the Afghans that they identified more with the Soviet way of life than with traditional Afghan society and customs (Roy, 1989). The Soviets took total control of the Afghan media and bombarded it with pro-Soviet propaganda. The Soviets desired in all of this was to have the Afghans forget what their history was and replace it with the identity that the Soviets were giving them. The Soviets not only rewrote the history books and took over the media; the Soviets took control of the education system with the goal of molding a new generation of Afghans that would support the PDPA. To accomplish this, teachers who refused to do what was asked were arrested or exiled. â€Å"Fatherland Training Centers† were created around Afghanistan, where Afghan orphans were trained to be Soviet special agents, political organizations for children and teenagers in order to teach them to become faithful Soviet citizens. The Soviets made Russian the official language of all students attending middle school up to college. The Russians were committed to indoctrinating Afghan children. Statics reflects that by 1989, 000 Afghan students were being educated in the Soviets, and another 15,000 students annual would travel to the Soviet Union see the Russian way of life and to take part in short courses and training programs (Roy, 1989). The Soviets used psychological operation to undermine not only the Mujahideen but also the civilian population to resist the Soviet occupation and the PDPA regime. Some of the bigger programs used included massive leaflet drops, propagandistic radio programs, starting conflict between rival tribes that would undermine Mujahideen unity and bribing teachers to use their classroom in order to spread Soviet propaganda. KHAD Intelligence would insert special agents into Mujahideen units and prisons where Mujahideen members were held with the goal of getting information on operations that were being planned and to find out whom the leaders in the resistance were. Regardless of what the Soviets attempted to do in order to win the hearts and minds of the Afghan people they failed. The Afghans remained true to their Islamic identity, culture, and family traditions so it made it impossible for the Soviet Union to convince the Afghans that they were acting in the best interest of the country of Afghanistan by occupying and supporting the PDPA. With a call of jihad being declared against the occupying Red Army, it was going to be impossible for the Soviets to win the hearts and minds. The Afghans viewed the Soviets as an occupying force that were hostile to Islam so no program introduced by the Soviets to win the hearts and minds would be successful. The Soviets made an admirable effort to win over the Afghan people but due to the fact that they were viewed as a foreign occupier took away any possibility that they could convince the Afghan people to support the PDPA government. Winning the hearts and minds of the Afghan people were impossible from the beginning since the Afghan people had such a strong Islamic heritage and tribal culture and that the Soviets were viewed as a foreign occupier, but the Soviets also did not help themselves with their brutal campaign to drive Mujahideen supporters out of Afghanistan as refugees. The effort to rid Afghanistan of Mujahideen supporters left one million Afghan civilians dead and five million displaced (Roy, 1989). The strategy used by the Red Army to rid Afghanistan of Mujahideen supported included artillery strike against Pashtun villages, bombing raids and, the burning of agricultural fields, the killing of livestock through the use mines and artillery, and the contamination of water and food supplies through the use of chemical weapons (McMichael, 1991). The efforts made by the Red Army to deprive the Mujahideen from a portion of its civilian support network was successful, but with the brutal methods that the Soviets used in order to get the objectives done did very little for the chances of winning the hearts and minds of the Afghan people. Conclusion The Soviets lost the Soviet-Afghan War to the Mujahideen do to their own failures and any country could stand to earn a few lessons from the Soviets after their experience in Afghanistan. The first lesson would be the importance of disrupting the Mujahideen supply lines. Although totally securing the border may have been impossible, the Red Army could have focus more of an effort prior to 1985 to slow down the amount of men and supplies that were moving into Afghanistan from Pakistan. Had the Soviets been willing to take more of rest with their Soldiers, the Mujahideen would have never been able to get the supplies they needed into Afghanistan. The second lesson that could be taken from this is that before the Soviets withdrew from Afghanistan they needed to ensure that the Afghan Army was ready to defeat the Mujahideen on their own. Since the Afghan Army was not able to defeat the Mujahideen on their own, everything that the Soviets attempted to achieve in Afghanistan was lost once the Red Army withdrew. The weak Army allowed Afghanistan to fall into a civil war where the Taliban came out victorious. The Soviets should have taken into consideration what they thought the status Afghan Army would be once they withdrew before invading Afghanistan. The third and final lesson is that it was going to be impossible for the Soviets to win the hearts and minds of the Afghan people. Many Afghans viewed the Soviets as invaders, and a jihad had been declared against them. Along with the hatred that the Afghans had for the Soviets the Soviets also countered themselves with brutal military operations against Afghans that were thought to be loyal to the Mujahideen. The Afghan population will refuse to support a regime that is viewed as a foreign occupier, regardless of the sophistication of the occupying country’s effort to win the native hearts and minds†(Delgado, 2006, p. 35). References Crile, G. (2003). Charlie Wilson’s War: The Extraordinary Story of the Largest Covert Operation in History. New York, NY: Delgado, J. A. (2006). Troubling Parallels: An analysis of America ’s Inability to overcome the obstacles that led to the defeat of the Red Army in the Soviet-Afghan War. Athens, OH: The University of Ohio. Hills, C. R. (2006). Beyond Charlie Wilson: The Soviet Afghan War. Atlanta, GA: Atlanta International School. McMichael, S. (1991). Stumbling Bear: Soviet Military Performance in Afghanistan. London, England: Brassey’s. Roy, O. (1989). â€Å"The Sovietization of Afghanistan. † Afghanistan and the Soviet Union. Boulder, Colorado: Westview Press. Roy, O. (1991). The Lessons of the Soviet-Afghan War. London, England: Brassey’s. Schofield, V. (2003). Afghan Frontier. New York, NY: Tauris Parke Paperback.