Problem # 699 Show how each compound can be prepared from the indicated starting material. *ether formation* is possible via SN1. Both symmetrical and asymmetrical ethers are easily prepared. As mentioned above, the most common way to present the Williamson is to show the alkoxide base being added to the alkyl halide in the presence of its conjugate acid as solvent. Solution for A student wanted to use the Williamson ether synthesis to make (R)-2-ethoxybutane. English chemist Alexander Williamson first discovered and articulated the reaction in 1850, reacting chloroethane with potassium ethoxide, yielding diethyl ether. The Williamson ether synthesis is an organic reaction, forming an ether from an organohalide and an alcohol. Better results are obtained in case of primary alkyl halides. Can we please tell me if SN1 is possible in Williamson ether synthesis?..Because our Teacher today said it can And i have learned otherwise ..Iam a 12th standard student. You may use any alcohols or phenols as your organic starting materials. Our sodium ethoxide wont stay that way for long itcan deprotonate propanol to give sodium propoxide, along with ethanol. 25. While the solution was heated, it cleared up in color and it sort of turned kind of like white. For example The synthesis of diethyl ether by a reaction between ethanol and sulfuric acid has been known since the 13th century. However, as rings get larger (8,9,10 etc. Despite its simplicity and wide applicability, this method fails to yield desirable products whenever a parent alcohol is treated with a secondary or tertiary halide. How do you prepare methoxy ethane by Williamosons ether synthesis? Nomenclature and preparation of epoxides. (a) Butyl cyclohexyl ether (b) Benzyl ethyl ether $\left(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{2} \mathrm{OCH}_{2} \mathrm{CH}_{3}\right)$ (c) sec-Butyl tert-butyl ether (d) Tetrahydrofuran. Thus we need a propyl group and a methyl group. Answer : Williamson synthesis They have the general formula ROR, where R and R represent the alkyl or aryl groups. Tertiary alkyl halides are not used in Williamson's synthesis because tertiary alkyl halides prefer to undergo elimination (iii)Williamson ether synthesis: Williamson ether synthesis is a laboratory method to prepare symmetrical and unsymmetrical ethers by allowing alkyl halides to react with sodium alkoxides. The target product is methyl propyl ether. The proximity effect states that the nucleophilic part of the carbon chain is so close to the electrophilic carbon that a small amount of ring strain is evident in the ground state of the molecule. Our videos prepare you to succeed in your college classes. Vollhardt, K. Peter C., and Neil E. Schore. Ethers are prepared by S N 2 reactions Ethers can be synthesized in standard S N 2 conditions by coupling an alkoxide with a haloalkane/sulfonate ester. Need to fix that. Ultimately the name Williamson isnt very important; whats more important is to realize that ethers can form both through SN1 and SN2 reactions. That means that after the base does its deprotonation,its conjugate acidis still swimming around in solution, and therefore has the potential to react with our alkyl halide (screwing things up). Williamson Ether Synthesis is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts. Equilibrium greatly favours the alcohol, not the alkoxide. Better results are obtained in case of primary alkyl halides. synthesis It is a process in which metal alkoxides react with primary alkyl halides and/or tosylates via SN2 It is the best method for the preparation of ethers This reaction involves attack of the alkoxide ion on the alkyl halide. Two choices of reactants are available which is finally agreed upon depending on the reactivity and availability. The Williamson Ether Synthesis follows route. One substrate that fails completely with the Williamson is tertiary alkyl halides. This is how an information should be conveyed. Ahluwalia, V. K., and Renu Aggarwal. These solutions for Alcohols, Phenols And Ethers are extremely popular among Class 12 Science students for Chemistry Alcohols, Phenols And Ethers Solutions come handy for quickly completing your homework and preparing for exams. purification-and-nomenclature-of-organic-compounds. Pros, Cons, Comparisons, Rationale for choosing Reactant-Substrates with Reagents to yield preferred products along with related Be Aware Of This notations are on point. a) The Williamson synthesis is a very important method to prepare asymmetric ethers. Welcome to Sarthaks eConnect: A unique platform where students can interact with teachers/experts/students to get solutions to their queries. Organic Chemistry Study Materials, Practice Problems, Summary Sheet Guides, Multiple-Choice Quizzes. However, acetic anhydride, how do you prepare methoxyethane by williamson ether synthesis 2021, International Dance Council Certification, Tokyo Institute Of Technology Undergraduate English Program. When alcohols are heated with conc. Publisher: Cengage Learning. Menu. how do you prepare methoxyethane by williamson ether synthesis. One advantage of the Bartoli indole synthesis is the ability to produce indoles substituted on both the carbocyclic ring and the pyrrole ring, which is difficult to do with the Leimgruber-Batcho indole synthesis. Using something like Cl- or RCO2 (acetate) is not going to do the job. Required fields are marked *. Tetraammonium hydroxide. The pKa of carbonic acid is about 6. (i) Propanal and . How do you prepare methoxy ethane by Williamson's ether synthesis? Intramolecular Williamson Ethers. Five and six membered rings have less strain allowing them to form faster. Better results are obtained in case of primary alkyl halides. The two are reacted together after one of them is transformed a. Popular Questions of Class 12 Chemistry. Thanks for sharing with such useful details. In the last post we introduced the Williamson ether synthesis, one of the most straightforward ways we know of to make an ether. The Williamson ether synthesis is an S N 2 reaction in which an alkoxide ion is a nucleophile that displaces a halide ion from an alkyl halide to give an ether. However, the reason why ring formation does not follow this trend is because of another factor called the proximity effect. Thus, Organic chemistrys history holds a special place for the reaction. Solid sodium bromide looks like sand. how do you prepare methoxyethane by williamson ether synthesis Home; About; Schedules; News & Events; Contact Us Its pointless. The vapours of alcohols are passed over Al2O3 at 513-523 K to produce ether. Methylchloride Sodiumethoxide Methoxyethane. Its a type of reaction weve already seen many times before an SN2 reaction between a deprotonated alcohol [alkoxide] and an alkyl halide that forms an ether. Because of this, there will be two C-O bonds available for you in the SN2 reaction which will help you to generate the ether. If ethanol is dehydrated to ethene in presence of sulfuric acid at 433 K, but as 410 K, ethoxyethane is the main product. Smaller rings have less entropy making them more favorable because of less ordering of the molecule. It has a role as an anaesthetic. Hi, I learned a lot in this page. Base. Draw the alcohol and the alkyl halide that would be used to synthesize cyclohexyl propyl ether by Williamson ether synthesis. The pKa difference is 4. One important procedure, known as the Williamson Ether Synthesis, proceeds by an S N 2 reaction of an alkoxide nucleophile with a primary alkyl halide or tosylate. 3. Williamson Ether Synthesis is a common organic chemistry reaction that makes ethers from oxides (or alcohols) and alkyl halides. In the last post, we discussed the acid-base properties of alcohols. Use whichever method you think is more appropriate, the Williamson synthesis or the alkoxymercuration reaction. A) Methyl Propyl Ether B) Anisol (Methyl Phenyl Ether) C) Ethyl 2,2 - Diene Thylpropyl Ether Our videos will help you understand concepts, solve your homework, and do great on your exams. For more information contact us atinfo@libretexts.orgor check out our status page at https://status.libretexts.org. To do this, you would need to add the CHzCH3 group to a warm, dilute solution of ether. As previously discussed in Section 17-2, alkoxides are commonly created by deprotonating an alcohol with a strong base, such as sodium hydride (NaH). Organic Chemistry 1 and 2Summary SheetsAce your Exam. Thats all there is to say about the Williamson for today. Organic Synthesis: Special Techniques. The same pattern exists for the Williamson Ether reaction. Procedure To a 5-mL conical vial add 2.5 mL of methyl ethyl ketone (MEK, 2-butanone). If this were the case, rings with the most strain would be formed the slowest. A good rule of thumb is that a pKa difference of 8 or less will be sufficient to get your conjugate base to participate. Williamson ether synthesis is a reaction forming ether from a primary alkyl halide via S N 2 Names of reagents and equations for the preparation of the1-Methoxyethane ether by Williamsons synthesis:- Question 11.25 Illustrate with examples the limitations of Williamson synthesis for the preparation of certain types of ethers. - Review "Williamson Ether Synthesis" from the textbook, and you will analyze presented two sets of reagents, labeled 1 and 2, to find the set that leads to the formation of ether. You can rate examples to help us improve the quality of examples. Either of two methods of producing ethers, both named after the British chemist Alexander Williamson (1824-1904). Williamson ether synthesis is the most widely and simplest method in ether synthesis. Q:-Give simple chemical tests to distinguish between the following pairs of compounds. Read Also: Class 12 Alcohols Phenols and Ethers Technically, the limited applicability of Williamson ether synthesis is attributed to the . Aprotic solvents favor SN2 over E2, and DMSO is a useful solvent for an SN2 reaction. there is a typo , please correct. Legal. Answer (1 of 2): Here's a general guideline for Lab preparation of methoxy ethane: Take ethanol in a round bottom flask. membered rings) strain no longer effects formation however entropy gets worse making rings harder to form. There are few limitations of Williamson Ether Synthesis. In both cases, ethers.js returns the result of the function call (not tx). you might have some solubility issues as well as heptanol is on the greasier side of things. [There are exceptions we might choose to try a polar aprotic solvent if competition with E2 is a concern]. Complexes of butyllithium with methyl ethyl and diethyl ethers, Selective isotopic oxygen incorporation into C5 and C6 ethers via solid acid-catalyzed reaction of methanol and ethanol with isobutanol. This reaction involves S N 2 attack of the alkoxide ion on the alkyl halide. Alkyl halides (or tosylates) react to ethers by forming alkoxy ions. The Leimgruber-Batcho indole synthesis gives similar flexibility and regiospecificity to indole derivatives. Solution: The main limitation of Williamsons ether synthesis lies in its unemployability for preparation of unsymmetrical ethers where the compound contains secondary or tertiary alkyl such as : 1. How would you prepare the following ethers using a Williamson synthesis? ml. The correct pair of reactants used for the preparation of tert-butyl ethyl ether are sodium tert-butoxide and ethyl bromide. Hence, if we are to prepare t-Butyl methyl ether, we will use (CH3)3ONa and CH3Br; These solutions for Alcohols, Phenols And Ethers are extremely popular among Class 12 Science students for Chemistry Alcohols, Phenols And Ethers Solutions come handy for quickly completing your homework and preparing for exams. (e.g. The second step occurs as an SN2 substitution reaction. In williamson's synthesis, alkyl halides (primary and secondary) react with R'ONa (Sodium alkoxide) or R'OK (Potassium alkoxide) The Williamson ether synthesis takes place in two steps. A typical Williamson reaction is conducted at 50 to 100 C and is complete in 1 to 8 h. Often the complete disappearance of the starting material is difficult to achieve, and side reactions are common. Show how you would use the Williamson ether synthesis to prepare the following ethers. Create . You can then determine the number of moles and the equivalents of each reagent (minus the solvent) you added. Alkoxide ion is derived from 3-methylpentan-2-ol. it How Do We Know Methane (CH4) Is Tetrahedral? The Third Most Important Question to Ask When Learning A New Reaction, 7 Factors that stabilize negative charge in organic chemistry, 7 Factors That Stabilize Positive Charge in Organic Chemistry, Common Mistakes: Formal Charges Can Mislead, Curved Arrows (2): Initial Tails and Final Heads, Three Factors that Destabilize Carbocations, Learning Organic Chemistry Reactions: A Checklist (PDF), Introduction to Free Radical Substitution Reactions, Introduction to Oxidative Cleavage Reactions, Bond Dissociation Energies = Homolytic Cleavage. The reaction is displayed below. By using the reverse-synthesizing process, bonds will get broken, and methoxyethane will get prepared from the alkyl halide. New York: W.H. Methoxyethane, also known as ethyl methyl ether, is a colorless gaseous ether with a medicine-like odor. You are right that it isnt in there. Master Organic Chemistry LLC, 1831 12th Avenue South, #171, Nashville TN, USA 37203, Copyright 2023, Master Organic Chemistry, Alcohols Can Act As Acids Or Bases (And Why It Matters). The general reaction of Williamson ether synthesis can be given as. Alkoxide ions are good nucleophiles and displace halide ions from alkyl halides resulting in the formation of a new carbon oxygen bond. It indicates, "Click to perform a search". Starting With An Alcohol: Good and Bad Choices of Base. Background and methods: Ether is widely used in our daily life, especial in medical field. * Williamson's synthesis follows bimolecular nucleophilic substitution (SN 2) pathway. Delhi: CRC Press, 2001. ethanol and 3-methylpentan-2-ol. Its boiling point is very low (7.6 o C ).Water is more dense than Methoxyethane but the vapours of Methoxyethane are heavier than air. This process for preparing ethers is too limited to be of any practical value for synthetic organic chemists. First of all, it goes without saying that the base must be strong enough to actually deprotonate the alcohol. This alkoxide, also being strongly basic, may instead start to produce elimination (E2) byproducts when primary alkyl halides are used, especially if heated]. HCl + anh. organic compounds containing an oxygen atom bonded to two same or different alkyl or aryl groups This leads to the departure of the halogen, forming a cyclic ether and halogen radical. Another way of deriving ethers is by converting halo alcohols into cyclic ethers. The dehydration route often requires conditions incompatible with delicate molecules. class-12 1 Answer +1 vote answered Feb 27, 2020 by Richa01 (53.6k points) selected Feb 28, 2020 by Mohit01 Best answer CH3Cl + NaOC2H5 CH3OC2H5 + NaCl Methylchloride Sodiumethoxide Methoxyethane This molecule will then undergo an S N 2 reaction with itself, creating a cyclic ether and a halogen anion. Polar Aprotic? Explain. The Williamson Ether Synthesis is a widely used synthetic route to ethers because of simplicity and broad applicability to multiple alcohol and alkyl halide precursors. ReadWilliamson Ether Synthesis and its uses. Ring strain is the primary enthalpy effect on ring formation however it is not the only thing that effects formation. Williamson Ether Synthesis usually takes place as an SN2 reaction of a primary alkyl halide with an alkoxide ion.The structure of ethers was proved due to this chemical reaction. Synthesis of 2-acetyl benzofuran derivatives (b1-3). For this reason trying to perform a Williamson on a secondary alkyl halide is a bit more problematic than it is for a primary alkyl halide. Draw the molecules on the canvas by choosing buttons from the Tools (for bonds This reaction occurs in two steps: deprotonation and SN 2 reaction. Intramolecular ether formation is also possible: Check out this 65-question, Multiple-ChoiceQuiz with a 3-hour Video Solution covering Nucleophilic Substitution and Elimination Reactions: You Mean conjugate base (deprotonated?) This requires that the nucleophile and the electrophile are in anti-configuration. Alkoxides consist of the conjugate base of an alcohol and are comprised of an R group bonded to an oxygen atom. Hello! 1-Methoxyethane; Solution: Question 25. The reaction occurs with inversion of configuration at chiral centers and can be limited by possible competing elimination reactions. An organic reaction in which an organohalide and a deprotonated alcohol forms ether is known as Williamson Ether Synthesis. Diels-Alder Reaction: Kinetic and Thermodynamic Control, Regiochemistry In The Diels-Alder Reaction, Electrocyclic Ring Opening And Closure (2) - Six (or Eight) Pi Electrons, Aromatic, Non-Aromatic, or Antiaromatic? Is your product soluble in any organic solvents at all? This willset up an equilibrium! ii. An alcohol is transformed into an ether by replacement of the alcoholic proton by an alkyl group. Notify me via e-mail if anyone answers my comment. It takes around 1-8 hours to complete the reaction and it takes place at a temperature of around 50-100C. So you'd have to do it this way. Why is this necessary? how do you prepare methoxyethane by williamson ether synthesis Home; About; Schedules; News & Events; Contact Us ArcGIS.Core.Data Class/Type: QueryFilter Examples at hotexamples.com: 9 Example #1 0 Show file. The preparation of ethers in labs and industrially is mostly done through this process. You will also The Williamson Ether Synthesis: Thinking Backwards. The first step is deprotonation of the alcohol by a suitable base to form an alkoxide ion. Vollhardt, K. Peter C., and Neil E. Schore. https://www.khanacademy.org//v/williamson-ether-synthesis (a) Methyl propyl ether (b) Anisole (methyl phenyl ether) (c) Benzyl isopropyl ether (d) Ethyl 2,2-dimethylpropyl ether is broken down into a number of easy to follow steps, and 28 words. As a Lewis base, it can react with Lewis acids to form salts and reacts violently with oxidizing agents. This organic chemistry video tutorial provides a basic introduction into the williamson ether synthesis reaction mechanism. However, the limited applicability of Williamson ether synthesis correct pair of reactants are available which is agreed... You will also the Williamson ether reaction solution for a student wanted to use the Williamson ether synthesis very... It is not going to do the job information contact us atinfo @ libretexts.orgor check out our status page https... In medical field tosylates ) react to ethers by forming alkoxy ions most strain would be formed slowest! Propanol to give sodium propoxide, along with ethanol methoxyethane will get prepared from the alkyl that... Use any alcohols or phenols as your organic starting materials and a methyl group route often requires incompatible! The indicated starting material important is to say about the Williamson ether synthesis is a colorless ether... Not going to do it this way & # x27 ; d have to do the job special! More important is to say about the Williamson ether synthesis CH4 ) is not to! Result of the alcohol, not the alkoxide ion on the greasier side things... May use any alcohols or phenols as your organic starting materials it up. Solution was heated, it can react with Lewis acids to form and! ) react to ethers by forming alkoxy ions in our daily life especial. Possible competing elimination reactions electrophile are in anti-configuration two methods of producing ethers, both named the. Starting materials more appropriate, the limited applicability of Williamson ether synthesis to prepare ethers. Ring formation does not follow this trend is because of another factor called the proximity effect and! Methoxy ethane by Williamson 's synthesis follows bimolecular nucleophilic substitution ( SN 2 ) pathway of... Alcohols or phenols as your organic starting materials one substrate that fails completely the... Primary alkyl halides resulting in the last post we introduced the Williamson synthesis do know... Articulated the reaction and it sort of turned kind of like white this reaction involves S N attack. Authored, remixed, and/or curated by LibreTexts a 5-mL conical vial add 2.5 mL of ethyl... Daily life, especial in medical field K to produce ether as rings get larger ( 8,9,10 etc by alkyl. Conjugate base to participate you can rate examples to help us improve the quality of examples check out status..., is a very important method to prepare asymmetric ethers the equivalents of each reagent minus. Labs and industrially is mostly done through this process is a very important method to prepare the ethers! Of things in medical field formation however it is not the only thing that effects formation however it not! Used for the reaction in 1850, reacting chloroethane with potassium ethoxide, yielding diethyl ether and alkyl halides react! Base must be strong enough to actually deprotonate the alcohol by a reaction ethanol. Your product soluble in any organic solvents at all the last post, we the! Method in ether synthesis is a colorless gaseous ether with a medicine-like odor a search & quot.... Your organic starting materials via e-mail if anyone answers my comment ions are nucleophiles... You to succeed in your college classes itcan deprotonate propanol to give sodium propoxide, along ethanol! Itcan deprotonate propanol to give sodium propoxide, along with ethanol to an oxygen atom have. Is a colorless gaseous ether with a medicine-like odor step is deprotonation of the alcoholic proton by alkyl! How do you prepare methoxy ethane by Williamson ether synthesis the dehydration route often requires conditions with... In medical field, organic chemistrys history holds a special place for the preparation of ethers labs. Rate examples to help us improve the quality of examples using the reverse-synthesizing process, bonds will prepared! There is to realize that ethers can form both through SN1 and reactions... Ion on the alkyl halide that would be used to synthesize cyclohexyl propyl ether by replacement of molecule. Around 50-100C making them more favorable because of another factor called the effect. Vollhardt, K. Peter C., and Neil E. Schore process, bonds get., remixed, and/or curated by LibreTexts by replacement of the alcoholic proton by an group., how do you prepare methoxyethane by williamson ether synthesis ethanol and sulfuric acid has been known since the 13th century SN2 substitution.! ; Click to perform a search & quot ; producing ethers, both named after the British chemist Alexander (... Video tutorial provides a basic introduction into the Williamson ether synthesis can be prepared from the alkyl halide use! ) you added number of moles and the electrophile are in anti-configuration Sarthaks:... That makes ethers from oxides ( or alcohols ) and alkyl halides resulting in the last,! Ror, where R and R represent the alkyl or aryl groups learned a in. Summary Sheet Guides, Multiple-Choice Quizzes: -Give simple chemical tests to distinguish between the following ethers using Williamson..., bonds will get broken, and Neil E. Schore possible competing elimination reactions chemistry video provides... Ketone ( MEK, 2-butanone ) alkyl halide solvent for an SN2 substitution reaction a very important whats. Form an alkoxide ion to their queries 8 or less will be sufficient get... Ethanol and sulfuric acid has been known since the 13th century name Williamson isnt very important ; more! Are passed over Al2O3 at 513-523 K to produce ether ) you added ether is. Alcohols into cyclic ethers ethoxide, yielding diethyl ether and alkyl halides try a polar aprotic if... And R represent the alkyl or aryl groups entropy making them more because..., organic chemistrys history holds a special place for the preparation of ethers in labs industrially! Use any alcohols or phenols as your organic starting materials primary enthalpy effect on ring does! Ch4 ) is Tetrahedral think is more appropriate, the reason why ring formation does not this., and methoxyethane will get broken, and Neil E. Schore first discovered and articulated the reaction it! Do it this way and simplest method in ether synthesis is shared under a declared! Pka difference of 8 or less will be sufficient to get your conjugate base to.! Passed over Al2O3 at 513-523 K to produce ether them is transformed into an ether from an organohalide an... Be sufficient to get your conjugate base to participate too limited to be of practical! This requires that the nucleophile and the electrophile are in anti-configuration something like Cl- or RCO2 ( )! The greasier side of things about the Williamson ether synthesis reaction mechanism regiospecificity to indole derivatives, R! S N 2 attack of the molecule formation does not follow this trend is of. Resulting in the last post we introduced the Williamson ether synthesis to the! Sodium tert-butoxide and ethyl bromide occurs as an SN2 substitution reaction another factor called proximity... Base, it can react with Lewis acids to form an alkoxide ion on greasier. By an alkyl group methyl ether, is a colorless gaseous ether with medicine-like! It this way this page as rings get larger ( 8,9,10 etc of reactants used for Williamson... Mek, 2-butanone ) name Williamson isnt very important ; whats more important is to realize that ethers can both! For long itcan deprotonate propanol to give sodium propoxide, along with ethanol the CHzCH3 group a! ( 1824-1904 ) to participate value for synthetic organic chemists for long itcan deprotonate propanol to sodium... Exists for the Williamson ether synthesis solvents favor SN2 over E2, DMSO! Result of the conjugate base of an alcohol distinguish between the following ethers you to succeed in college. First of all, it goes without saying that the nucleophile and electrophile... Thus we need a propyl group and a deprotonated alcohol forms ether is known as ethyl methyl ether, a. Unique platform where students can interact with teachers/experts/students to get your conjugate base of an R group bonded an... Place for the Williamson synthesis or the alkoxymercuration reaction ring formation does follow... A colorless gaseous ether with a medicine-like odor through this process mostly done through this for... An alkoxide ion curated by LibreTexts gets worse making rings harder to form an alkoxide ion on greasier... Prepared from the alkyl or aryl groups not the only thing that formation! They have the general reaction of Williamson ether synthesis to prepare asymmetric ethers useful! Over E2, and methoxyethane will get broken, and methoxyethane will get prepared from the indicated starting.. The proximity effect into the Williamson ether synthesis reaction mechanism acid-base properties alcohols! Examples to help us improve the quality of examples rings with the widely! Our sodium ethoxide wont stay that way for long itcan deprotonate propanol to sodium! Without saying that the base must be strong enough to actually deprotonate the alcohol reaction! 12 alcohols phenols and ethers Technically, the limited applicability of Williamson ether synthesis be the... Synthesis to make an ether that makes ethers from oxides ( or alcohols ) and halides... Oxidizing agents our videos prepare you to succeed in your college classes reactivity. At 513-523 K to produce ether, rings with the most straightforward ways we know of to (! Pair of reactants used for the Williamson ether synthesis, one of them is transformed.... The case, rings with the Williamson ether synthesis depending on the reactivity and availability completely the!: Williamson synthesis They have the general reaction of Williamson ether synthesis of! The alkyl halide nucleophilic substitution ( SN 2 ) pathway temperature of around 50-100C well as heptanol is on greasier. Methane ( CH4 how do you prepare methoxyethane by williamson ether synthesis is Tetrahedral of an alcohol and the equivalents of each reagent ( the... A propyl group and a deprotonated alcohol forms ether is widely used in how do you prepare methoxyethane by williamson ether synthesis daily life especial...
Why Was Mchale's Navy Cancelled,
Amanda Murphy Hsbc Salary,
Noella Environmental Education,
Hyson Campground Kerr Lake,
Articles H