Then, place the flask in the second ice water bath for 10 minutes. In the past few decades, the ubiquity of the alderdiels reaction da between cyclopentadiene cp and maleic anhydride ma in the undergraduate curriculum left very little room for the improvement of this reaction. Anthracenemaleic anhydride dielsalder adduct c18h12o3. Introduction conjugated dienes undergo a cycloaddition reaction with multiple bonds to form unsaturated sixmembered rings. Exoselectivity in dielsalder reactions of maleic anhydride. In fulfilling objective 2, above, you must recognize that the diels alder reaction is stereospecific. The formed maleic acid would undergo diels alder reaction but leads to a product which would not be crystallized under the experiment conditions.
I know ligroin can be used as a solvent and it is also nonpolar, though ethyl acetate is also a solvent and nonpolar in this experiment. Infrared spectra of reactants and product of the dielsalder reaction of cyclopentadiene with maleic anhydride to form endonorbornene. Regio and stereoselective dielsalder additions of maleic. Regioselective and asymmetric dielsalder reaction of 1 and 2substituted cyclopentadienes catalyzed by a bronsted acid activated chiral oxazaborolidine. Dielsalder and melting point the purpose of this lab is to introduce the concept of the melting point of an organic compound as a rst step in chemical identi cation of that compound and assessing its purit. Ir spectra dielsalder reaction houston community college. We already know that cyclopentadiene is a good diene because of its inherent scis conformation. The diacid obtained has been incorporated into polyester. A diels alder reaction of cyclopentadiene with maleic anhydride experiment was conducted in lab.
The diels alder reaction of anthracene with maleic anhydride organic chemistry with vernier 3 8. Click the structures and reaction arrows in sequence to view the 3d models and animations respectively. Stereochemistry of the dielsalder reaction master organic. The dielsalder reactions of cyclopentadiene with maleic anhydride and with some other dienophile models in which the co bonds were.
Alder reaction between cyclopentadiene and maleic anhydride the diels. Preparation of cisnorbornene5,6endodicarboxylic anhydride. Wait at least 15 minutes for the flask to warm to room temperature. The diels alder reaction consists in an addition of a compound containing a double or triple bond usually activated by additional unsaturation in the alpha, betaposition to the 1,4positions of. Jan 23, 2016 i saw in books that reaction between dicyclopentadiene and maleic acid result in dicyclopentadienemaleat ester.
It was first described by otto diels and kurt alder in 1928, for which work they were awarded the nobel prize in chemistry in 1950. In a dielsalder reaction with cyclopentadiene and maleic. Dione 1 was converted to the requisite diene by enolization using two successive silylations with tmscl. A particularly rapid diels alder reaction takes place between cyclopentadiene and maleic anhydride. Synthesis of cyclopentadiene derivatives by retrodielsalder. Request pdf origin of the endo selectivity in the diels. The ratio of endo to exo products is strongly dependent on the activity of the alumina. Finally, note reaction b in the reading shows 1,3 cyclopentadiene reacting with another molecule of 1,3 cyclopentadiene. Unconventional exo selectivity in thermal normalelectron. Oct 12, 2016 the dielsalder reaction is a useful tool for generating functionalized chiral molecules through the concerted cycloaddition of dienes and dienophiles leading to sixmembered rings. In organic chemistry, the dielsalder reaction is a chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile also spelled dieneophile, to form a substituted cyclohexene derivative.
The released butadiene from the retro diels alder reaction will react with the dienophile to form an adduct, cis4cyclohexene1,2dicarboxylic anhydride. Reaction of 1,3cyclopentadiene with maleic anhydride, forming endonorbornenecis5,6carboxylic anhydride. Solventfree diels alder reactions of in situ generated cyclopentadiene. For example if the dienophile is maleic anhydride, it must be kept away from water as it will react with water to form maleic acid. The dielsalder reaction of anthracene with maleic anhydride. Select the major product of this reaction from the list of structures available. The adducts of furan with fumaric acid, diethyl fumarate and diethyl maleate are.
It is very possible that cyclopentadiene can dimerize. Organic chemistry ii lab diels alder reaction purpose. For the diels alder reaction we performed in the lab, we used maleic anhydride and cyclopentadiene to form the product cisnorbornene5, 6endodicarboxylic anhydride. If it is heated above degrees, the fumaric acid starts to decompose and form maleic acid, maleic anhydride, carbon monoxide and carbon dioxide. Show the reaction between maleic anhydride and water. The reaction provides optically active azatetracycles in good yields with high diastereo and enantioselectivities under mild reaction conditions. Cyclopentadiene belongs to the class of organic compounds known as cycloalkenes. A dielsalder reaction was the key step in amos smiths synthesis of furaquinocin c. After 30 minutes, let the reaction flask warm to room temperature. Characteristics of the dielsalder reaction chemistry. Explain why when the solvent is a mixture of ethyl acetate and hexane in a 1. The dielsalder reaction of cyclopentadiene and methyl acrylate has been run on. Thus activation by strongly lewis acidic cupric tetrafluoroborate was required to allow for the reaction to take place.
Regio and stereoselective thermal diels alder reaction of methyl. Although the two reactions are highly similar with regard to their preference for endo and exo steroisomers, notable differences were experimentally observed and explained on the basis of calculated reactionfree energies and transitionstate barriers. When the same compound acts as both diene and dienophile in a diels alder reaction to couple it is a dimerization. The rate at which a diels alder reaction takes place depends on electronic as well as steric factors. Cyclopentadiene, furan, and maleic anhydride were each built and their equilibrium geometry calculated using hartreefock 321g calculations. The cyclopentadiene undergoes dimerization at 25 o c to produce dicyclopentadiene, using the diels alder reaction, where one cyclopentadiene molecule is the diene and the other cyclopentadiene molecule is the dienophile. In order for a dielsalder reaction to occur, the diene molecule must. Cyclopentadiene and fumaric acid undergo a diels alder cycloaddition reaction under mild conditions. The simplest dielsalder reaction is the reaction of 1,3butadiene and ethylene to yield cyclohexene figure 1.
The exo adduct was also found to epimerize slowly to the endo adduct by a mechanism involving the retrodielsalder reaction of the exo adduct. Dielsalder addition of maleic anhydride for determination of the configuration of eleostearic acids, observed a higher reactivity of the alltrans. Take the two dienophiles maleic acid and fumaric acid for example. The purpose of this experiment was to demonstrate the formation of sixmembered rings by cycloaddition, also known as a dielsalder reaction. In some cases, isomerized cyclopentadienes 14 were also observed beside to 12.
You should notice that both of them have three double bonds. Origin of the endo selectivity in the dielsalder reaction between. It was used for work in 1928, on the reaction between maleic anhydride and 1,3butadiene, for which otto paul hermann diels and kurt alder were awarded the nobel prize in 1950. Cracking of dicyclopentadiene performed by your instructor, see figure l 2.
Furthermore, melting point analysis yielded the following values for the diels alder product and the hydrolysis product respectively. You may have to use an ice bath to prevent the reaction from going too fast. It is the prototypical example of a pericyclic reaction with a concerted mechanism. The dielsalder reaction of cyclopentadiene and methyl. The reaction of cyclopentadiene and butenone for example is 700 times. Jul 12, 2005 the stereoselectivity of the reaction of furan 1 with maleic anhydride 2 and maleimide 3 was studied experimentally and theoretically. To print or download this file, click the link below.
Dielsalder reaction of cyclopentadiene with maleic anhydride johnson, chad philip. Pdf dielsalder reaction between cyclopentadiene and maleic. The endoadduct was isolated and the structure established by its spectral properties and conversion into known compounds. Diels alder reactions with conjugated triene fatty acid esters full paper scheme 2. As most of the cyclopentadiene derivatives are not stable enough at reaction condition. The reactants in the dielsalder reaction are a 1,3diene and an alkene called the dienophile. Diarylprolinol silyl ether as catalyst of an exo selective, enantioselective dielsalder reaction. Apr 22, 2020 in fulfilling objective 2, above, you must recognize that the diels alder reaction is stereospecific.
Cyclopentadiene and maleic acid undergo a diels alder cycloaddition reaction under mild conditions. Major product of maleic acid reaction with cyclopentadiene. Molecular modelling all calculations were performed using the program spartan 02 for windows, from wavefunction. In this experiment, you will synthesize cisnorbornene2,3endodicarboxylic anhydride, commonly called carbic anhydride, from cyclopentadiene and maleic anhydride.
Alder reaction consists in an addition of a compound containing a double or triple bond usually activated by additional unsaturation in the alpha, beta. Diels alder reaction of cyclopentadiene and maleic anhydride. Fumaric acid with cyclopentadiene gives only one product. The dielsalder reaction is a well known example of cycloaddition chemistry. Experiment 5 cisnorbronene5,6endodicarboxyiic acid by diels aider reaction part a. The diels alder reaction of anthracene with maleic anhydride the diels alder reaction is a member of a class of reactions called cycloadditions. Dielsalder reaction of furan with some dienophiles. Diels alder reactions 2 the reaction is even more favorable when the diene is fixed in the scis form as in the case of cyclopentadiene see figure 2. Also, in two patents the diels alder reaction is mentioned in connection with water 4. These hydrocarbons have reacted with maleic anhydride and fumaric acid to yield anhydride and diacid adducts of the diels alder type. And although it may seem tempting to believe that maleic anhydride can do that too, it is in an strans conformation, which isnt favorable in the diels alder reaction, so i would only choose the cyclopentadiene dimerization as a plausible side product.
Maleic anhydride and the diels alder adducts are intense skin irritants. Introducing complex nmr mixtures at the undergraduate level. It is formed by diels alder reaction from two cyclopentadiene molecules and exists in. In this case both the diene and dienophile have stereochemistry.
Heat of addition of cyclopentadiene to maleic anhydride. Synthesis of cisnorbornene5,6endodicaroboxylic anhydride introduction. An experimental and theoretical study of stereoselectivity. Learn vocabulary, terms, and more with flashcards, games, and other study tools.
To mitigate isomerization of the substituted cyclopentadiene via 1,5hydride shift, it was found necessary to keep this intermediate below 0 c until the dielsalder could take place. A dielsalder reaction of cyclopentadiene with maleic. Give structures for the major diels alder product of the following reactions. In this experiment, 3sulfolene will be heated in the presence of the dienophile maleic anhydride. David huertas, melinda florscher, veljko dragojlovic.
The dielsalder cycloaddition with bromoquinone was followed by a spontaneous dehydrohalogenation to reform the aromatic ring. Considering a diels alder reaction with cyclopentadiene and. European journal of organic chemistry 2016, 2016 25, 42754278. Results and discussion when combining the reagents, a cloudy mixture was produced and problems arose in the attempt to completely dissolve the mixture. Also, in two patents the dielsalder reaction is mentioned in connection with water 4. Diels alder reaction of cyclopentadiene and maleic. Diels alder reaction of furan with some dienophiles.
The presence of the alcohol group indicates that the diels alder product did indeed undergo a hydrolytic reaction to form the carboxylic acid. Origin of the endo selectivity in the diels alder reaction between cyclopentadiene and maleic anhydride. In organic chemistry, the dielsalder reaction is a chemical reaction between a conjugated. This reaction has a great synthetic importance and was discovered by two german chemists, otto diels and kurt alder, who received the 1950 nobel prize. The diels alder reaction paulo sgarbi the diels alder reaction of cyclopentadiene and maleic anhydride is a classic at langaras organic chemistry course. And they said this is and ene reaction but i couldnt understand how this reaction is subset of ene reaction and how ester group is made. Pdf the structures of cyclopentadiene, maleic anhydride, their endo and exo adducts and the transition states leading to them were optimized. Direct evaluation of secondary orbital interactions in the. Reaction mechanism the scheme below depicts the concerted mechanism of the dielsalder reaction of cyclopentadiene and maleic anhydride to form cisnorbornene5,6endodicarboxylic anhydride. In conventional terminology, this is a 1,4addition of a diene and a dienophile. Methylcyclopentadiene, diels alder reaction, complex mixtures, nuclear magnetic resonance analysis. Inverse electrondemand diels alder methylcellulose. Use of the information, documents and data from the echa website is subject to the terms and conditions of this legal notice, and subject to other binding limitations provided for under applicable law, the information, documents and data made available on the echa website may be reproduced, distributed andor used, totally or in part, for noncommercial purposes provided that echa is. Lewis acid catalysis also enables dielsalder reactions to proceed at low.
In a cycloaddition reaction, a 1,3diene reacts with an alkene, or dienophile, to produce a sixmembered ring. Analysis of a simple nmr spectrum is fairly easy and straight forward for undergraduate students but analyzing a fairly complex nmr can be very daunting and requires a methodical approach. Csun chemistry and biochemistry department 2nd semester organic chemistry lab dielsalder reaction stereoselective synthesis of cis4. The purpose of this experiment was to synthesize, isolate and characterize the diels alder adduct 9,10dihydroanthracene9,10. The reaction of furan and maleic acid was carried out in several solvents. These authors noticed a change in endoexo selectivity when comparing the reaction in water with that in ether. It is through this reaction that maleic anhydride converted to many pesticides and pharmaceuticals. Alder reaction between norbornene and methylphenyltetrazine to form rapidly gelling diels alder puzzles. Diels alder reaction an overview sciencedirect topics. A new chiral bronsted acidcatalyzed azadielsalder reaction of cyclic cacylimines with cyclopentadiene has been developed. Reaction of 1,3 cyclopentadiene with maleic anhydride, forming endonorbornenecis5,6carboxylic anhydride.
These are compounds containing a nonaromatic closed ring of carbon atoms in which at least 2 atoms are connected by a double bond. Cyclopentadiene and maleic anhydride were reacted together to form cisnorbornene5,6endodicarboxylic anhydride. Substituent effects in the diels alder reactions of butadienes, cyclopentadienes, furans and pyroles with maleic anhydride. This work uses the ubiquitous diels alder reaction of methylcyclopentadiene and maleic anhydride to introduce students to an nmr spectrum that consist of inseparable mixtures of isomers and their analysis. Cyclopentadiene is a colorless liquid with an irritating, terpenelike odor.
Asymmetric bronsted acidcatalyzed azadielsalder reaction. O a cooh cooh cooh ooh ooh ooh previous check answer nextexit hint. The chemical abstract service registry number casrn is 77736. The purpose of this experiment was to demonstrate the formation of sixmembered rings by cycloaddition, also known as a diels alder reaction.
But i was wondering why we added ligroin to the maleic anhydride and ethyl acetate. Dielsalder reaction between cyclopentadiene and maleic. Maleic anhydride is a classic substrate for diels alder reactions. Dielsalder reaction the laboratory procedure used was written by dr. The main goal of this experiment is to perform a diels alder reaction between 2,3dimethyl1,3butadiene and maleic anhydride, identify the product and hydrolyze to form the dicarboxylic acid. Infrared spectra of reactants and product of the diels alder reaction of cyclopentadiene with maleic anhydride to form endonorbornene cis5,6carboxylic anhydride. The purpose of this experiment was to synthesize, isolate and characterize the dielsalder adduct 9,10dihydroanthracene9,10. Introducing complex nmr mixtures at the undergraduate. The reaction is exothermic, so you may have to cool the solution in an ice bath before adding the cold. Dielsalder reaction of cyclopentadiene with maleic anhydride. The purpose of this experiment is to carry out a diels alder reaction of 1,3butadiene and maleic anhydride to produce 4cyclohexenecis1,2dicarboxylic anhydride. Diels alder reaction of cyclopentadiene with maleic anhydride johnson, chad philip. In this experiment a diels alder reaction was used to form the products. This type of reaction is named in honor of the german scientists, otto diels and kurt alder, who.