Burgess and Martin Dehydrating Reagents

Burgess and Martin Dehydrating Reagents An understanding of synthetically useful dehydrating reagents for the reduction of hydroxyl groups, various functional group interconversions and other synthetically useful operations. Oday Alrifai Dehydration of alcohols has been a synthetically useful strategy in order to attain olefins in high yields through the treatment of secondary, tertiary and homoallylic alcohols. Martin sulfurane and Burgess dehydrating reagents have been useful because of their mild and selective properties on alcohol containing species. [1] Both reagents have made a significant contribution in industrial and academic applications, aiding in the synthesis of natural products and drugs. The Burgess Reagent, known as Methyl-N-(triethylammoniumsulphonyl)carbamate (Figure 1), is an interesting reagent assisting formations of 5-membered heterocycles, initially derived from the acyclic precursor by dehydrative treatment. [1] It was first discovered by Edward Meredith Burgess in 1968, but was not given much attention until Peter Wipf proposed the idea of heterocyclic formation. Further research on this reagent, such as the preparation of isocyanides and nitrile oxides from formamides and nitroalkanes, respe ctively, have been investigated. [1] Figure 1. Structure of Methyl-N-(triethylammoniumsulphonyl)carbamate, also known as Burgess’s dehydrating reagent. [1] Similar to the Burgess reagent, Martin reagent (or Martin sulfurane) is another dehydrating reagent possessing high reactivity to allow the production of alkenes, with diphenyl sulfoxide and a alcohol as minor products, occurring fast (approximately one hour) and at below room temperatures. [2] It was James C. Martin who discovered this stable, moisture sensitive sulfurane, also known as bis(ÃŽ ±,ÃŽ ±-bis[trifluoromethyl]benzyloxy)diphenyl sulfur (Figure 2), in 1971. [2][3] Similar to the Burgess reagent, the mechanistic action may be similar, via E1 and/or E2 (or cis) elimination, in order for the treatment of secondary and primary alcohols, respectively. [3] Also similar, cyclic heteroatoms have been more favorable in synthesis, due to carbenium ion rearrangement, via alcoholic dehydration. [3] Figure 2. Structure of bis(ÃŽ ±,ÃŽ ±-bis[trifluoromethyl]benzyloxy)diphenyl sulfur, also known as Martin’s sulfurane or Martin’s dehydrating reagent. [10] Preparation of the Burgess reagent requires the incorporation of two commercially available chemicals, chlorosulfonyl isocyanate (CSI) and trieethylamine (TEA), and ceases in two steps. Figure 3 illustrates the treatment of CSI with anhydrous methanol and dry benzene at temperatures ranging from 25-30 °C, for approximately half-hour. This fairly quick reaction gives good yields (88-92%) of methyl (chlorosulfonyl) carbamate (MCC) which exists as white crystals when filtered and washed with hexanes. The generated MCC is then treated with a solution of TEA in anhydrous benzene, at temperatures ranging from 10-15 °C, over the course of one hour. The generated salt, Methyl-N-(triethylammoniumsulphonyl)carbamate, precipitates into colorless needles (84-86% yield). [1] Figure 3. Preparation of the inner salt (Burgess reagent) from two commercially available compounds, trieethylamine and chlorosulfonyl isocyanate. A special type of elimination reaction is believed to occur during the period the Burgess reagent is operational. The simultaneous elimination of two vicinal substituents, forming an alkene framework from an alkane, is the route of an intramolecular (Ei) mechanism or a syn elimination. The mechanistic action taken by the Burgess reagent, illustrated in Figure 4, will first produce a sulfamate ester by the attack of the sulfonyl group as well as the rapid displacement of the TEA group, by oxygen’s lone pair in methanol (pka=15.5). [1][4] By heating the sulfamate ester, pyrolysis is initiated, the ÃŽ ±-carbon is ionized and bears an ion that rapidly transfers the ÃŽ ²-hydrogen from the cationic to the anionic state. [1] Figure 4. Mechanism illustrating treatment of Burgess reagent with ethanol, allowing the extraction of the ÃŽ ²-hydrogen and formation of the olefin. In general, the extraction of the proton and the expulsion of the leaving group will generate the expected olefin, shown in Figure 5. The production of the olefin depends on the geometry of the molecule, therefore the hydrogen must be present in the syn conformation to the leaving group (TEA) in order for the reaction to proceed. In addition, the leaving group has nucleophilic properties that will allow the proton to be extracted readily in low polarity solvents. It also should bear multiple proton acceptor sites to permit favorable proton capture. [1] It is possible however that the cis elimination not be observed due to carbonium ion stability, which is stabilized by substituents, and/or a more stable configuration by means of rearrangement. [1] Figure 5. Example of a syn elimination, where the proton adjacent to the carbon bearing the reagent is removed and the deuterium remains a substituent with the olefin formation. Pertaining to Figure 5, the type of alcohol group (secondary, tertiary and homoallylic), the configuration and the environment are the main factors that affect the process of the reaction. The dehydration of a secondary or tertiary alcohol, in an aprotic solvent, follows Saytzef’s rule to form a more thermodynamically stable alkene, versus the kinetic product. Oppositely, primary alcohols (Figure 5i) will not yield the expected olefins; rather carbamates via an SN2 pathway as they are energetically more favorable. Steric hindrance is another important factor when treating with the Burgess Reagent.[1] Such an example holds true in primary sulfamate esters where intramolecular rearrangement occurs when temperatures increase due to the restrictions on bimolecular displacement (Figure 5ii). Depending on the conditions of the reaction, such as solvent polarity and temperature, allylic alcohols can either undergo elimination or SN1 rearrangement (Figure 5iii), with more favorable ap proaches of SN1 reactions providing greater than 90% yields. The same is applicable for tertiary alcohols where they can be subjected to rearrangement even though, under normal conditions, undergo dehydration. [1] Figure 6. Examples illustrating i) primary alcohols will not undergo olefin formation, rather producing a carbamate via SN2, ii) sterically hindered compounds can proceed with the formation of a thermodynamic product (Saytzef’s rule) and iii) allylic alcohol dehydration via elimination or SN1. [1] Functional group interconversions (FGI) can aid in many useful syntheses to design versatile compounds. With the assistance of Burgess’s reagent, high yields have been obtained through the transformation of formamides to isocyanides, nitrile oxides from nitroalkanes and nitriles from primary amides, for example. To stimulate the formation of nitriles from primary amides, the Burgess reagent is often employed instead of other reagents. [1] The problem arises when particular reagents come in contact with certain functional groups, requiring protecting groups or alternative multi-step syntheses to carry out the production. Burgess reagent is employed due to its chemoselective properties and its ability to form the intermediate in a fast(er) manner. As a result of this quick reaction, the product is kinetically more favored. [1] Figure 7 illustrates the interconversion of an amide to allow the Burgess reagent to proceed with dehydrative activities, thus yielding isocyanide with re arrangement. Figure 7. To allow dehydration of the alcohol, an amide undergoes interconversion to allow the Burgess reagent to proceed, forming isocyanide. Knowing the environment the alcohol group is in and how its configuration can be altered, the synthesis of natural products in industry, by usage of this reagent, has been of great synthetic value. For example, dihydrooxazoles are important heterocyclic-containing intermediates used in the synthesis of many biologically active natural products. Initially, these compounds have required an extensive multi-step synthesis for their preparation and previous attempts to cyclize have provided low product yields (25%) and an abundance of recovered starting material. [5] Wipf and Miller investigated more efficient protocols that would obtain better yields of the ÃŽ ²-sulfonate derivatives (Figure 8) of threonine and serine via a more selective intramolecular substitution. Treating the hydroxyl amino acid precursors, threonine and serine, with the reagent allowed the production of dihydrooxazoles because of their high reactivity to stimulate intramolecular cyclization. [5] Unlike other reagent s removing hydroxyl substituents, Burgess reagent allows stereospecific production of dihydrooxazoles without the formation of minor products like azirdine or ÃŽ ²-lactam. [5] Figure 8. Formation of the olefin, via dehydration, and proceeding with intramolecular cyclization to form the 5-membered ring. A paper by Rigby et al. investigated phenanthridone alkaloids originating from the narciclasine family and their anti-tumor properties. The synthesis of (+)-lycoricidine involved the use of the Burgess reagent in order to selectively deprotect the hydroxyl group and to promote cis elimination. [1][6] When dehydrated into an olefin, the compound can exhibit antimitotic activity, which in turn can elicit cytotoxic activities involved in the inhibition of plant growth and regulation, for example. [7] Chida et al. reported that synthetic (+)-lycoricidine exhibited strong cytotoxic activity against P-388 lymphocytic leukemia, suggesting stereochemistry was a responsible and an important component for the elevated cytotoxicity. [7] Other synthetically useful examples of products that are of value are medicinal drugs such as Efrotomycin, which is a new class of antibiotics eliciting anti-bacterial properties that act on gram-positive bacteria, [8] and Pravastatin, which is involved in the management of atherosclerosis and is a regulator of blood lipid levels. [9] Burgess reagent is either involved in the final step in order to form the olefin or participates in a one or two-step synthesis for the production of the precursor. Other uses of the Burgess reagent have been investigated by Canadian researchers at Brock University by designing thermally stable versions of the Burgess reagent with an objective to improve reactivity on epoxides, diols and vinyl oxiranes in comparison to the original reagent. [17] They tested the reactivity of the Burgess reagent with oxiranes, both in cyclic and acyclic conformations, providing low yields of sulfamidates. Also, epoxidation reactions, which required two equivalents of the Burgess reagent, provided cis-sulfamidates at low yields. [17] Since yields were not above their expected 40%, new derivatives created by Metcalf et al. allowed for anion or cation stability in the zwitterion. They tested thermal stability by monitoring the decomposition, in THF-d8 at 50 °C, of four new versions of the Burgess reagent showing stability and reactivity of the original reagent can be improved by inductive components of the zwitterion. [17] The inductive effects depress the nucleop hilicity of the carbamate anion, reducing formation of the sulfamidates and favouring diamine formation. This allows for the Burgess reagent to be synthetically useful in work other than dehydrative operations. [17] Figure 9 illustrates the conversion of a styrene diol to the diamine compound by treating with the modified Burgess reagent 1. Figure 9. Treatment of the modified Burgess reagent 1 with styrene diol, yielding a diamine compound to demonstrate other uses for this reagent. Martin sulfurane not only participates in dehydrative reactions but also in several other synthetically useful reactions, such as the production of sulfinimines, epoxidation reactions, cleavage of amides and oxidation. [12] Preparation of the diphenylsulfur compound incorporates commercially available 2-phenyl-2-propanol, using potassium hydroxide as the deprotonating agent, bromine and diphenylsulfide. [12] Stereospecificity of a molecule, as a reactant or product, is important in order to carry out biological functions. Under certain conditions, such as varying solvent polarities and reaction temperatures, Martin sulfurane induces stereospecific dehydration that allows for the formation of certain isomers. (E)-isomerism in certain products exists because of trans-E2 eliminations, whereas the (Z)-isomer is more favored due to the attachment of the sulfurane in the antiperiplanar conformation for the E2 elimination. [2] The mechanistic action first involves the exchange of the alkoxy ligand on either side the sulfurane, producing an alkoxysulfonium ion as a result of ionization and then proceeding through E1 or E2 elimination. [12] Illustrated in Figure 10, using tertiary-butyl alcohol as an example, Arhart and Martin suggest that all alcohols used in their experimental appeared to exchange rapidly with the alkoxy ligands of the Martin reagent. The cause of this is not definite but it wa s proposed that a dissociative mechanism was carried out. [10][11] Figure 10. The proposed mechanism illustrating the production of the expected olefin by means of dehydration when Martin sulfurane is used. Similar to the Burgess reagent, dehydration of secondary and tertiary alcohols yield the expected olefin but treatment of primary alcohols, such as ethanol and neopentyl alcohols with Martin reagent, favors the formation of unsymmetrical ethers due to the absence of structural features that aid in the elevation of ÃŽ ²-proton acidity. [10][11] Wensley et al. reported that treatment of a secondary alcohol with Martin sulfurane can lead to the production of a ketone by oxidation, in addition to the predicted olefin containing compound during the synthesis of their natural product containing a spiroketal enol ether. They proposed that the intermediate, containing the alkoxysulfonium ion, had proceeded forward via two possible routes, one of which was the deprotontation of the ÃŽ ²-proton allowing the olefin (or enol ether) formation and/or the other resulting in oxidation through intermolecular deprotonation by the excess –ORf (Rf = C6H5C(CF3)2 . [13] A paper written by Moslin and Jamison investigated the synthesis of (+)-acutiphycin, a natural metabolite found in blue-green algae, exhibiting effective antineoplastic activity against Lewis lung carcinoma and a potent cytotoxic agent against KB and N1H/3T3 cell lines. [14] The synthesis of (+)-acutiphycin underwent intermolecular condensation, through application of the Reformatsky reaction, affording a ÃŽ ²-hydroxy ketone followed by dehydration with the Martin sulfurane. [14] Prior to treatment with Martin sulfurane, samarium (II) iodide (SmI2 or Kagan’s reagent) was used to carry out the intramolecular Reformatsky reaction. [14] SmI2 has its limitations when intermolecular rearrangements occur because of side reaction formation and and oxidative dimerization of the enolate by the samarium therefore when coupled with Martin sulfurane, a 2-step sequence was carried forward to overcome sterically hindered structures (Figure 11). [12][14] Figure 11. Neurodegenerative disorders such as Parkinson’s disease and Alzheimers are caused by the degradation of the nerve growth factor (NGF) in the neurotrophin family of proteins. Therapeutic potential of NGFs have been extensively studied for the prevention, slow progression and even the reversal of these disorders. [15][16] Trzoss et al. have investigated other therapeutic strategies by synthetically mimicking neurotrophins in order to allow their biosynthesis. [16] The enantioselective synthesis of (-)-jiadifenin was carried forward with the assistance of Martin sulfurane. Trzoss et al. were unsuccessful when trying to eliminate the secondary alcohol via Barton-McCombie deoxygenation as well as mesylation and treatment with a variety of bases in order to obtain the desired alkene. When treated with Martin sulfurane, the olefin was obtained and was selectively hydrogenated, obtaining a 72% yield in two steps. [16] Geng and Danishefsky recently synthesized the macrolide aigiolamycin D, via Diels-Alder, using disiloxydiene and a 14-membered dienophile also known as the ynolide (or dienophile).[18] Having two or more of the same functional groups within a system can be difficult when trying to selectively treat one of the targets. Protecting groups are important in unsymmetrical synthesis, in comparison with symmetrical molecules which are chemically equivalent and protecting either side (with functional groups) is simple. Greg and Danishefsky proceeded to protect the diol group to allow the loner –OH unit to participate in the upcoming sequences. The loner –OH was protected via a silyl ether to allow the deprotection of the pivaloyl ester and formation of the –OH group. This –OH group can then be treated with Martin sulfurane, in methylene chloride solution, to form the resulting olefin and then deprotection (or conversion) of the dioxylane to the diol. [18] REFERENCES Khapli, S.; Dey, S.; Mal, D. J. Indian Inst. Sci. 2001, 81, 461-476. Li, J.J; Corey, E.J. Name Reactions of Functional Group Transformations. 2007 (Wiley) Meth-Cohn, R.K. Synthesis: Carbon with No Attached Heteroatoms. 2003 (Elsevier) Ballinger, P.; Long, F.A. J. Am. Chem. Soc. 1960, 82, 795-798. Wipf, P.; Miller, C.P. Tetrahedron Letters. 1992, 33, 907-910. Rigby, J.H.; Maharoof, U.S.M.; Mateo, M.E. J. Am. Chem. Soc. 2000, 122, 6224-6228. Chida, N.; Ohtsuka, M.; Ogawa, S. J. Org. Chem. 1993, 58, 4441-4447. Dolle, R.E.; Nicolaou, K.C. J. Am. Chem. Soc. 1985, 107, 1691-1694. Daniewski, A.; Wovkulich, P.M.; UskokoviĆ¡. J. Org. Chem. 1992, 57, 7133-7139. Arhart, R.J.; Martin, J.C. J. Am. Chem. Soc. 1972, 94, 5003-5010 Li, J.J. Name Reactions. 2014 (Springer) Pooppanal, S.S. Synlett. 2009, 5, 850-851. Wensley, A. M.; Hardy, A.O.; Gonsalves, K.M.; Koviach, J.L. Tetrahedron Letters. 2007, 48, 2431-2434. Moslin, R.M.; Jamison, T.F. J. Am. Chem. Soc. 2006, 128, 15106-15107. Price, R.D.; Milne, S.A.; Sharkey, J.; Matsuoka. Pharmacology Therapeutics. 2007, 115, 292-306. Trzoss, L.; Xu, J.; Lacoske, M.H.; Mobley, W.C.; Theodorakis, E.A. Org. Lett. 2011, 13, 4554-4557. Metcalf, T.A.; Simionescu, R; Hudlicky, T. J. Org. Chem. 2010, 75, 3447-3450. Geng, X.; Danishefsky, S.J. Org. Letters. 2004, 6, 413-416.

Gulliver’s Travels Essay

Ten days after returning from his previous voyage, Gulliver is confronted by Captain William Robinson to work as his journey to the West Indies. The doubled salary is cause enough for Gulliver to accept the invitation and sets sail two month after the invitation. Upon arriving in Tonquin, Gulliver is appointed Captain of a sloop (a small sailboat with one mast and two sails) and ordered to transport goods; he is shortly captured by pirates. He earns his crews freedom but his attitude lands him on a small boat with limited food. He soon finds a few isles and decides to stay in the cave of a seemingly barren island—except for a few shrub patches. After some keen observation, Gulliver notices something strange obstructing the sunlight and deduces it must be a floating island. He tries to be noticed but the inhabitants seem to give little regard for his shouting. Eventually, the floating mass draws near and from it, descends a seat that Gulliver is instructed to mount. He is then drawn up into the Island. Gulliver is welcome by many people, whom he noticed to be very strange. Their eyes look in different directions and their heads do not sit level upon their heads. In addition, he takes note of their attires, which are covered with â€Å"celestial bodies and musical instruments. † People also have a servant who follows them and carries a â€Å"flapper. † This is essentially a mace, but with a soft sac on the end. The servant’s use it to slap their masters’ mouth or ear with the intent of alerting them that it is their turn to speak or listen while in conversation. After meeting with the King, Gulliver is appointed a language tutor. Shortly after his first lesson, Gulliver notices the island to move over villages, during which, subjects collect monies from the people below. In addition, he learns that the people value mathematics and music above all. (Because of this, their language is primarily based on the sciences stated previously. ) Their skill sets are limited to these two disciplines, as well as astrology. There are also in constant fear of an apocalyptic demise, resulting from an ever incumbent meteor. After a months stay, Gulliver is learned enough to speak to the King. Gulliver is now informed by the Prince, (one of the few free thinking individuals) of the dimensions and working of the Island. He is most intrigued by the motion of the Island and how it manages to stay afloat. It is explained to him that the most experienced astronomers figured that by mounting and manipulating a great magnet in the center of their island, they are able to float and move in any direction at will. However, the island is only able to move over a specific area on earth because of the specific magnetic forces required to maintain their desired altitude. Gulliver also learns how the Island is able to rule over the inhabitants of the land below. This is done mainly through varying degrees of punishments. Essentially, Laputa uses its size and position to, block out the sun, bombard the villagers, or, simply crush the village by means of ‘dropping’ the island. Gulliver then learns of a rebellious village, with capabilities to ‘capture’ the island and kill the King. In order to maintain peace and save himself, the King has granted freedom to these people. From that instance, the King and his family are restricted from leaving the Isle. Gulliver’s boredom leads him to want to leave the Island. He approaches a lord who seems to be genuinely intelligent and curious. (An oddity on Laputa) The lord lacks musical talent and is therefore regarded as unintelligent by the inhabitants. With the help of this lord, Gulliver proceeds in petitioning the King to leave Laputa. The King accepts and proceeds in leaving Gulliver with a friend of Laputa in a place called Balnibarbi. The man whom he is left with goes by the Lord Munodi. He is of high rank and possesses great wealth. The Lord proceeds to take Gulliver around the city of Lagado. It is of great surprise to Gulliver that the city is in shambles, the people are poorly dressed, and the ground is barren. They then proceed to the lord’s estate and it is evident of the stark contrast between the city and the estate. It is well built, well managed, and has fertile vineyards, as well as cornfields, fountains and meadows. The villagers do not have high esteem for this estate and do not strive to exemplify it—rather the opposite. Gulliver is then informed that, after a visit to Laputa by some if the city’s inhabitants, they decided to construct the Academy of Laguda. The sole purpose of this Academy is to develop new agricultural and architectural techniques. The new techniques are very flawed and extremely outlandish and have left the city in its current in its current state. The techniques are supported by so many mindless individual that they allowed for the destruction of the mill. Gulliver is very curious to the details of the projects that the Academy is working, so much so, that he decides to visit. Gulliver is allowed to visit the Academy. He takes careful note of the ongoing projects. First he sees a man attempting to use cucumbers as sun storage devices. He then witnesses a scientist attempting to turn feces into food. Another researcher attempts to turn ice in gunpowder and is fully invested into the idea of the â€Å"malleability of fire. † Gulliver travels throughout the Academy and witnesses many more experiments. There are blind paint mixers who are under the impression that they can smell color. There is even a scientist who is under the impression that his random word generator is capable of writing books on any topic. A linguist is under the impression that speaking is a waste of life and every breath used to speak brings people closer to death. He proposed everyone be mute and simply act out the message they wish to convey. Lastly, Gulliver witnesses a professor attempt to teach mathematics by writing equations onto wafers and feeding them to his students. Part III: Chapter 6 Gulliver is still at the academy and proceeds to visit professors who are dealing with politics and government. They propose that taxation of women be based upon their physical attributes and relative beauty. Other claims that to uncover conspiracies, they should search through the feces of the citizens. They even propose kicking and pinching the politicians to make them ‘less forgetful. ’ After witnessing the propositions and experiments of many, Gulliver concludes that there is nothing here that he could benefit from and wishes to leave. Gulliver wishes to travel to Luggnagg but cannot find a vassal to take him. Not wanting to stay in Lagado any longer, he decided to travel to Glubbdubdrib. He is able to deduce that the Isle is inhabited by people capable of doing magic. Upon his arrival, Gulliver requests an audience with the King—he is granted his wish. Gulliver then witnesses people simply disappearing and reappearing and ghosts serving food. He is initially surprised and startled by these events but becomes accustomed to them. He even goes so far to request the King to appease his personal requests. The King willfully satisfies Gulliver’s requests to speak the dead. He speaks to many prominent historical figures such as: Hannibal, Caesar, Pompey, Brutus, Junius, Socrates, Epaminondas, Cato, and Sir Thomas More. He converses with them and learns that history is not as it seems and that often, it is glorified in order to cover up the embarrassing truth.   Still in the company of the King, Gulliver continues to talk to the reincarnations of prominent historical figures. He observes how Homer and Aristotle carry themselves and even goes as far to point out their mistakes; mistakes that they accept without any aggression toward Gulliver for doing so. He then proceeds to interrogate the more modern rulers and is disappointed to learn that they have not been honest with their subjects as they should have. He also calls upon simple ‘less developed’ English ancestors, whom he finds remarkable large and of good stature. He concludes that the Nobles have diminished the physical strength that the English were once blessed with. Part III: Chapter 9 Gulliver returns to Luggnagg in disguise. He only wished to return to his beloved mother country—the Kingdom of England. His shipmates confess to the officials that a stranger is aboard, resulting in his capture, interrogation and confinement. The King has heard of Gulliver’s adventures and wishes to speak to him. Gulliver is then informed that, all of the Kings visitors are required to lick the floor as they enter the Kings room. Because Gulliver was a guest, the floor was cleaned very well, but on occasion, it is sprinkled with poison to kill the Kings enemies. Because of his vast knowledge of foreign places, the King grows to favor Gulliver and treats him very well. Gulliver is ‘invited’ to stay for an additional three months—he is obedient.   While in the company of the Luggnaggs’, Gulliver is told of an immortal people. These people are marked by a spot on their forehead and are called the Struldbrugs. Gulliver fantasizes how he would live his life if he were immortal. He concludes that he would study all arts and sciences and learn to acquire riches. Gulliver ponders the topic even further and postulates that he would ‘reasonably expect’ to be the â€Å"wealthiest man in the kingdom. † After being exposed to these individuals, he learns that they live forever, but are not young forever. This is a tragic flaw and the government actually considers them dead after the age of eighty. He also learns that they grow to be saddened and to live a life with neither joy, nor love. All of their marriages eventually become dissolved and they despise all mortals, most likely out of envy. As he learned of these people and about their true state, Gulliver regretted wishing that he could be immortal. Part III: Chapter 11 After spending ample time in Luggnagg, Gulliver is eventually allowed to leave. He is finally able to find a vassal to take him to Japan, with hopes of continuing on to England. Upon arrival, Gulliver had again; found himself in an uncomfortable situation. He eventually finds a Dutch ship travelling to England. The captain agrees to take him, as long as Gulliver provides works as a surgeon for half the usual rate. By blending in as a Dutchman, Gulliver is able to satisfy the Emperors requirements. He is then excused from the ritual stomping of the cross. They are now free and continue to Amsterdam, from where Gulliver is able to find passage to England. Upon arrival he goes immediately home to his healthy family.

Late Imperial Russia Essay

How was Russia set up to be the nation it is today? Introduction: ‘Imperial Russia’ all started in the 17th century where a man named Tsar Ivan IV the terrible’ battled and defeated the Mongols which were the previous rulers of Russia. He appointed himself the emperor of Russia and his heirs would carry on his principles and his way of ruling throughout the century’s to build a strong nation. The Tsars of the Romanov dynasty would carry on ruling till the last reign in 1890-1917 which was held by Tsar Nicholas II son of Tsar Alexander Ill, it was his and is father’s reign which changed Russia from having its own system (tsarism) to become a nation with a fair government Just like the European nations of their time. At first glance the Tsar’s were thought to be grateful to Russia e. g. ictory over the swedes which transformed Muscovy into a great power of Europe and Alexander II the liberator ended serfdom and restored the government of Russia after losing the Crimean war. However there were many situations, problems in governments and people that caused Russia to change from having Tsarism to having an official government such as parliament. Tsar & Tsarism: The system of Tsarism was governed through three organisations: Firstly there was the imperial council, which were a group of advisers to the Tsar. Secondly there was the Cabinet of Ministers, which ran the government departments of the Tsar. Thirdly there was the Senate, which were the supervisors of the law. All three of these governmental bodies were ranked under the Tsar so every organisation they run, laws they make or suggestions, the final word or decision has to be from the current Tsar ruler, e. g. To quote Reaction and Revolution ‘They were appointed, not elected nd they did not govern’. This is because their roles are basically to give advice because whatever they say has to go through the Tsar. The Tsar which caused most problems were as I mentioned above Nicholas II and Alexander Ill because of what they tried to do to the Russian empire as well as what they didn’t try to do, unlike their reforming heirs, they didn’t fight for Russia or change for Russia, they only did what they did to benefit them, not the rest of Russia. By the time of Nicholas’s reign Russia stretched a distance of 5000 miles from west to east and 2000 miles from outh to north, this of course made ruling Russia even more difficult because one family couldn’t possibly enforce their system on their own unless they had an actual government like other European countries of their time. Even though the sheer size of Russia gave it a well-known powerful image that it’s a nation of strength, it didn’t prove that because parts of the landscape are either unreachable, uninhabitable or just not worth the time to build upon. Considering these facts Tsar Nicholas II wasn’t indeed that powerful as well as the Tsarism system which soon lead to changing into communist government ruled by the Bolsheviks in 1917. Overall the system of Tsarism is the system the Tsar family ran to rule the nation of Russia, this involved only them having command and if any governmental bodies have any ideas to change/improve Russia they could only advise it as only the Tsars nad control. How did the geography of Russia compare to other nations in Europe and effect the Tsar: As IVe mentioned above, Russia consists a land mass of 16,093,440 Kilometres Squared which makes it 2 and a half times bigger than the USA and a whole lot harder to rule, this is because Russia of this time is being ruled by one family which nly cause poverty, social segregation and a failed work force, if you compare it to the USA of its time its doing far better than Russia because the USA is a democracy unlike Russia which is a socialist nation. The differences are that the USA vote and elect, they have different ‘Parties’ which have different Jobs to run the country when Russia is run by one family which tries to do everything and when they do make laws or enforce something, it only rewards them not the nation. The advantage the Tsars had is that the size of Russia made them seem untouchable which explains the lack f countries invading or taking over Russia, this is the only way that the geography of Russia affects it positively, IVe mentioned how it affects Russia negatively e. . bad landscape, too much to rule over, cannot handle to control such a large area. Ruling Russia back then was difficult even with the Trans-Siberian Railway, sure it provided a way to cross the 5000 miles from west to east but it still caused neglect to places like Vladivostok and Irkutsk because they aren’t at all near the capitals such as Moscow and St Petersburg. How did the people of Russia effect the Tsar and what did they do to respond to the ays of the tsar: The people of Russia were so constricted because of Tsarism it caused many problems, one of the catalysts to the problems was that it was a criminal offence to go against the Tsar or Tsarism, therefore if anyone decided they wanted to reform the tsarism system they had to go through the Tsar themselves and of course if it goes against their wishes they’ll say no and arrest the person responsible. There has been Reforming Tsars which improved transport, improved efficiency of the army, re-built cities so they could change Russia for the better, but ventually it was all done for nothing because whenever an heir gained the throne from a reformed Tsar they always went back to the strict ways. This did effect the nation greatly but not as much until the last Tsar ever: Nicholas II, he was meant to carry on the rulings his tatner made to help build Russia into a stronger nation e. g. mproving standard of living, education, employment etc. but he decided to go back to the old socialist ways that caused poverty, distrust of the nation and weakening the barrier between a fair command and compete domination of the people of Russia. People didn’t Just stand around been ruled or told off by the tsars, there have been a few moments where theyVe risen up, worked together to eradicate the current Tsar leader or went underground to discuss what differences they could make on their own without the permission of the Tsar. For example since free speech’ was a common myth in the reigns of Tsar, various people most likely in political activist groups decided to go to extremism. They thought the only way they could get their word out or make a change is through threats or by force, for example in 1881 Tsar Alexander II was blown up by a bomb thrown from the ‘Peoples Will’ hich were a terrorist group, they went this far because they didn’t want to be plagued by the Tsar or Tsarism anymore. However other people of the nation went down low and created societies or non-activist groups which wouldn’t allow the Tsar’s to see how theyre changing Russia in a non-obvious fashion, but eventually after they started to plan a revolution the Tsar caught on and decided to infiltrate them with their own secret police known as the Okhrama. They were issued to perform raids, arrests, imprisonments and infiltrations to stop the ‘secret’ societies so the Tsar could carry on running the government. The only thing that was good that the Tsar provided to the people was an Orthodox Church in every city (ST. Petersburg & Moscow), the people encouraged this because the church was a part of Russian culture and because it didn’t rely on any foreign influence or governmental body. Of course the Church supported the tsarist system throughout the century’s right up to the 19th century where it became well opposed to political/governmental change which caused it to so low in growth, unlike the industrial part of Russia. Consider the fact the only 0. 5% of Russia is the Tsar and their advisors, 12% is military and the last 3. 9% is the public, the public consist of merchants, factory workers and owners, land owners and mainly peasants. This causes issues because of course the Tsar allow the chance that people can buy/own/sell land, but it comes with a price, considering most workers soon save up to buy a farm land but then it comes with a mortgage thus causing them to be in debt and nearly as poor as the peasants. This effected the economy massively because by these statistics 80% of the population were peasants, and they knew peasants were illiterate and have a lack of skills, this portion of the opulation was the catalyst to everything the people did in response to what the Tsar did to Russia. This made the Tsar lower the ranks of the army so they could be filled with ‘conscription’ (the forcing of large numbers of peasants to Join the armed services), these were often called the ‘Dark Masses’. The problems caused by botn Tsarism and the People ot Russia : The issues that were caused by the Tsar effect Russia more frequently and at a higher scale after Alexander the seconds reign, this is because he was the first reforming Tsar for a while and what he did was for the better interest of the nation not himself; People tarted noticing his reforms in 1861 when he emancipated the Serfs, he restored Russia’s governing structure after the loss in the Crimean war and he set up a network of elected councils in the rural areas which were called ‘Zemstvos’, even though it seemed with these elected bodies that anyone could vote, that wasn’t the case because of strict voting regulations only the land owners not the peasants could take part in the voting. Alexander II has obviously made a difference to his nation because of this evidence, but it still did solve the problem that there might be a hance that the next Tsar could ignore his reformative ways and crea te discipline, poverty and all the other problems again like other Tsars before him. He also feared that since he’s doing all of this, he’s not committing to his Tsar duties, so near the end of his reign he goes back to the old ways which doesn’t affect much but leads to his assassination in 188111880. His successor ‘Alexander Ill’ caused all sorts of problems, problems so bad that everyone in the nation felt oppressed during his whole reign, after he was replaced by Nicholas II things got even worse because he didn’t like the eforming that alexander II did, so he carried on the repressive policies of his predecessor, which made Alexander the seconds reformation worth nothing, this of course angered the intelligent, richer and educated class of Russia known as the intelligentsia. The army of Russia was weakened by Nicholas II because he decided to lower ranks in the military so that even peasants could Join, this made becoming a high ranking officer easier therefore more of a chance to affect the tsarism system that Nicholas II has moulded. This weakened the force or strength of the military reatly, so much that the people created their own group called the ‘Militia’ which basically had their own form of Justice against criminals. If the military was going downhill so was the Tsar because Just about 50% of their expenditure was funding the army which was only able to produce a million and nalt me, which does sound powerful but most of which were peasants and land owners. People of Russia had less specific reasons of why the army, or their nation is so bad, they thought that the Tsar civil service was corrupt and the evidence to show it was that it’s the nation hose tried and tried again to reform itself but always goes back and corrupts itself again. Many citizens accused the Tsar of ‘sucking the blood of the people’ which refers to the fact that they control them, they corrupt them and they use them. Overall many people of Russia either appreciated the reformation to be on par with other nations or hating the reformation, the people which wanted the reformation were known as the Westerners’ because they wanted Russia to adopt aspects of European nations so they won’t live in horrendous conditions e. g. destroyed towns/ cities because of wars. Or have economic problems e. g. iving in poverty. The people who wanted Russia to stay the same were known as ‘Slavophiles’ they wanted to preserve the best aspects of Russia, yes solve the problems but not via adopting features of other European nations. Conclusion: The system of Tsarism is the system the Tsar family ran to rule the nation of Russia, this involved only them having command and if any governmental bodies have any ideas to change/improve Russia they could only advise it as only the Tsars had control. The geography of Russia effects its government greatly because it made them seem stronger when actually the tsar couldn’t possibly control the whole of Russia, also because of the vast landscape they couldn’t industrialise as fast as other nations could therefore putting them at a disadvantage as a nation. The people of Russia lived in poverty because of the strict rulings of the tsar, that the tsar couldn’t control all of them, they were in debt if they paid for land, even if theyre factory workers everyone couldn’t possibly benefit the whole nation. Because of the constant change of reforming tsars to cruel tsars the people of Russia didn’t know what to do and what they can do, which lead to assassinations, societies being created and being invaded by military or police.

Defining Literature Essay - 928 Words

The definition of literature has been discussed and argued over time and there is no precise answer to be given. Any reader or author can define literature as whatever they wish it to be defined as. This is more of an opinion of how one views certain pieces of work or writings and whether or not they feel that is actually literature or not. Literature is any type of creative writing such as fiction or poetry, for example. Literature is also any form of body of written works of language, which could be from the English era or even as far back as the Shakespearean or Elizabethan era. It is also work from a specific period or culture defining key elements or somehow relating to and/or expressing how it is exactly from that time. The†¦show more content†¦In her poem, Dylan in lines 4 and 5, she writes, Her hair was a halo of warm light / and color dripped off her tongue (23). The reader can interpret just from those two lines the creativity and imagination not only in tha t one poem, but also in all poetry. The description of hair being a halo of warm light allows the reader to use his or her own imagination to perceive that image in whichever way they would like. Creative writing can be determined by many other things not only image or structure of how the poem is set into stanzas, but what is left up to the reader for interpretation. Jewel writes in Cautious in lines 23-29, an open vessel / whose function it was / to be filled / until my consciousness / could return and / spit out / the bad seeds (18). After reading these lines the reader can be left with different feelings and emotions that vary from disgust or simplicity. This is just another example of how poetry is creative writing. According to the American Heritage Dictionary, literature is defined as being the body of written works of a language, period, or culture. 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