Abstract the objective of this experiment was to crack dicyclopentadiene to create two molecules of cyclopentadiene, and then perform a diels alder reaction by reacting the diene with maleic anhydride, the dienophile, to create cisnorbornene5,6endodicarboxylic anhydride. Diels alder reaction of cyclopentadiene with maleic anhydride to form cisnorbornene 5,6endo dicarboxylic acid anhydride miaya conyers organic chemistry lab 14505 2017 february abstract cis norbornene5,6endodicarboxylic anhydride was prepared in 83. Synthesis of cyclopentadiene derivatives by retrodielsalder reaction of. The transition state for this process is none other than the green point reached earlier. In the second step, the remaining components of the original c5 fraction. Most predominantly, dcpd molecules are formed and the product is further purified by vacuum distillation. Raise the temperature of the heating mantle slowly until cyclopentadiene monomer collects slowly dropwise in the receiving flask. A copy of the current dow msds for this product should be kept on. Write my paper on dielsalder reaction of maleic anhydride. It cannot be stored at room temperature because it spontaneously undergoes a dielsalder reaction with itself that forms the bridged dimer dicyclopentadiene.
And although it may seem tempting to believe that maleic anhydride can do that too, it is in an strans conformation, which isnt favorable. Dicyclopentadiene, abbreviated dcpd, is a chemical compound with formula c10h12. Also, when cooling a piece of equipment that contains the hot bottoms from the distillation or. In petrochemistry, petroleum geology and organic chemistry, cracking is the process whereby complex organic molecules such as kerogens or longchain hydrocarbons are broken down into simpler molecules such as light hydrocarbons, by the breaking of carboncarbon bonds in the precursors. Dicyclopentadiene, abbreviated dcpd, is a chemical compound with formula c 10 h 12. I saw in books that reaction between dicyclopentadiene and maleic acid result in dicyclopentadienemaleat ester. Cyclopentadiene is an organic compound with the formula c5h6.
Dielsalder reactions of neat reactive dienes and dienophiles are frequently vigorous and have a limited preparative. Abstract the conversion and stereoselectivity of transformation to endo and exo norbornene derivatives was determined in the dielsalder reaction of cyclopentadiene with alkyl acrylates. This dimer can be restored by heating to give the monomer. The epoxidation of dimers obtained from dielsalder. A microwave induced reaction of dicyclopentadiene 1 was used to rapidly and.
The dielsalder reaction is essentially a cycloaddition reaction cycloaddition reaction is one example of a. It is not available commercially as the monomer, due to the rapid formation of dicyclopentadiene. Solventfree dielsalder reactions were carried out by heating a mixture of a volatile diene, such as 1,3butadiene, isoprene, or 2,3dimethyl1,3butadiene, and a dienophile, such as methyl vinyl. This reaction has a great synthetic importance and was discovered by two german chemists, otto diels and kurt alder, who. In conventional terminology, this is a 1,4addition of a diene and a dienophile. At the boiling point of dicyclopentadiene, equilibration with the monomer is. The dielsalder reaction is a particularly useful method for the synthesis of compounds with cyclic structure. Experimental procedure part a cracking of dicyclopentadiene part b diels alder from pcb 4531 at university of south florida. Dielsalder reaction of cyclopentadiene and maleic anhydride savion. Solventfree dielsalder reactions of in situ generated. Cracking of dicyclopentadiene before the beginning of lab the cyclopentadiene was prepared by a lab technician by cracking it. Cyclopentadiene is a useful diene in diels alder reactions as well as a precursor to metallocenes in organometallic chemistry. Preparation of cyclopentadiene from its dimer journal of.
And 180 dc is a bit much, id just stay under the boiling point of the dimer. A reactive antibody platform for onestep production of antibodydrug conjugates through a dielsalder reaction with maleimide. It is very possible that cyclopentadiene can dimerize. Procedure place dicyclopentadiene 30 cm3 and a few antibumping granules in a 100 cm3 roundbottom flask and set up the apparatus for distillation, with the receiving flask in an icebath. The reaction provides optically active azatetracycles in good. And they said this is and ene reaction but i couldnt understand how. Synthesis of an imidazolidinone organocatalyst and its application in a dielsalder cycloaddition. In this process, the diels alder reaction is the key step to produce a suitable hdf precursor. The diels alder reaction is one of the most important methods for formation of sixmembered rings. Dcpd is a highly reactive intermediate product originated from high temperature cracking of petroleum fractions. The majority of syntheses proceed with the formation of a mixture of isomers. Dicyclopentadiene is coproduced with ethylene from the c5 fraction in the steam cracking of naphtha and gas oils.
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. Immobilized cyclopentadiene in the diels alderretrodiels. Pdf dielsalder reaction of cyclopentadiene and alkyl. A solventfree dielsalder reaction was carried out by heating a mixture of dicyclopentadiene. Dielsalder reactions in the presence of a minimal amount of water.
When pure cyclopentadiene is stored it also undergoes a dielsalder cycloaddition reaction and forms dicyclopentadiene. In a dielsalder reaction with cyclopentadiene and maleic. I remember adding some iron powder was supposed to speed up the retrodielsalder reaction, i guess by lowering the effective. Dicyclopentadiene should never be distilled to dryness since there is danger of explosion if peroxides are present. After learning about the reaction, i was able to complete a diels alder reaction in organic lab. At room temperature, this cyclic diene dimerizes over the course of hours to give. Dielsalder reactions of neat reactive dienes and dienophiles are.
At room temperature, it is a clear light yellow color liquid with an acrid odor. Microwave induced preparations of incipient and solvent stabilized. The dielsalder is unlike other organic reactions in that it doesnt involve any nucleophiles, leaving groups, or radicals, so there. A detailed study of the general application of immobilized cyclopentadiene in the diels alderretrodiels alder synthetic strategy has not yet been undertaken.
When pure cyclopentadiene is stored it also undergoes a dielsalder. Except where noted, spectra from this collection were measured on dispersive instruments, often in carefully selected solvents, and hence may differ in detail from measurements on ftir instruments. In this case 2 was used for dielsalder reactions at ambient temperature. In the case of solid reaction products, solidification of the reaction mixture. In the dielsalder reaction of cyclopentadiene and maleicanhydride what are the two side reactions of cyclopenadiene and maleic anhydride not including the endo and exo major products. Experiment 14 the dielsalder cycloaddition reaction pg.
Dielsalder and melting point chem217labsfall07 openstax cnx. Jul 19, 2011 the dielsalder is a stereospecific reaction, because the stereochemistry of the dienophile is maintained in the cyclohexene product. The distillation temperature should not exceed 65 oc. Fock calculations for the prediction of substituent effects.
Synthesis of cyclopentadiene derivatives by retrodielsalder. Dielsalder reaction is reversible by cracking dicyclopentadiene using slow distillation and keeping the cyclopentadiene cold. Dielsalder reaction of cyclopentadiene with maleic anhydride to form cisnorbornene 5,6endo dicarboxylic acid anhydride miaya conyers organic chemistry lab 14505 2017 february abstract cis. An uncontrolled cracking of dcpd reverse diels alder reaction with. Monomer and dimer are close enough in boiling point that a sloppy job will deliver a lot of dimer to the collection pot, which is a real pain to remove from many diels alder product mixtures. Please let a resonable explanation pertaining to diels alder reactions.
The c9c10 fraction formally contains all kinds of diels alder adducts because the various c5 diolefin molecules form dimers during the process steps of the ethylene manufacturing process. Learn vocabulary, terms, and more with flashcards, games, and other study tools. When i read your heading i said to myself its a reverse diels. Alder reactions of cyclopentadiene and 9,10dimethylanthracene with cyanoalkenes. Solventfree diels alder reactions were carried out by heating a mixture of a volatile diene, such as 1,3butadiene, isoprene, or 2,3dimethyl1,3butadiene, and a dienophile, such as methyl vinyl. The reaction is strongly exothermic hazardous chemicals desk reference, p. Cyclopentadiene is obtained by cracking of dicyclopentadiene 27 moffett, r. Synthesis of an imidazolidinone organocatalyst and its application in a diels alder cycloaddition. Sep 14, 2001 cyclopentadiene and dicyclopentadiene, which occur as byproducts in the steam cracking process in ethylene plants, are the major ingredients in the production of hydrocarbon resins, unsaturated polyester resins, elastomers, pesticides, flame retardants and a host of specialty chemicals. Consecutive retro diels alder reactions played an important role in these synthetic pathways. In order to be of any use, the dimer must be cracked and distilled. In this case 2 was used for diels alder reactions at ambient temperature. The dielsalder reaction solely refers to the above reaction, but by altering the diene and dienophile, the final product can be altered to something the chemist desires. Kinetic and thermodynamic control in the dielsalder reaction.
Nov 20, 20 the diels alder reaction solely refers to the above reaction, but by altering the diene and dienophile, the final product can be altered to something the chemist desires. Identification of the substancemixture and of the companyundertaking. Only two of these aldehydes 3 and 4 were reactive and. Dielsalder reaction of cyclopentadiene with maleic anhydride. Aldrich 454338 page 1 of 7 sigmaaldrich material safety data sheet version 4. It will dissolve in water and evaporates quickly from water and soil surfaces. Microwave induced preparations of incipient and solvent. Cracking apparatus the dielsalder reaction of cyclopentadiene with maleic anhydride. This new compound must be separated before the desired compound can be used.
Diels alder reactions of cyclopentadiene brainmass. Usually it is obtained by cracking of dicyclopentadiene and is used. The performance of density functional theory and hartree. A solventfree dielsalder reaction was carried out by heating a mixture of dicyclopentadiene and a dienophile. What kind of reaction does the cracking of dicyclopentadiene represent. The largest consumption of dicyclopentadiene is linked to the production of resins. However, this dielsalder reaction is reversible by cracking dicyclopentadiene using slow distillation and keeping the. In this lab we will be studying the reaction of cyclopentadiene with maleic anhydride. Color improvement of petroleum resin some components coloring petroleum resin in thermal cracked higher fractions.
At room temperature, this cyclic diene dimerizes over the course of hours to give dicyclopentadiene via a diels alder reaction. In the case of the weighted squares sum all products. Kinetics of the thermal decompositions of exo and endodicyclopentadiene. Above 150 c, dicyclopentadiene undergoes a retrodielsalder reaction at. The c9c10 fraction formally contains all kinds of diels alder adducts because the various c5 diolefin molecules form dimers during the process steps of the ethylene. Synthesis of cyclopentadiene derivatives by retrodiels.
The dielsalder reaction that you will be performing between cyclopentadiene and maleic anhydride occurs rapidly at room temperature. This colorless liquid has a strong and unpleasant odor. Ab initio study of dielsalder reactions of cyclopentadiene. Cracking apparatus the dielsalder reaction of cyclopentadiene with maleic anhydride the dielsalder reaction that you will be. Color improvement of petroleum resin some components coloring petroleum resin in thermalcracked higher fractions. Give balanced equations for both retro diels alder reaction and the diels alder reaction that you plan to do in this lab. Its name is anthracenemaleic anhydride diels alder adduct amp version. It is unstable under ordinary conditions and, at room temperature, dimerizes into dicyclopentadiene. In the cracking of dicyclopentadiene, why is it ne.
Dielsalder reactions between cyclopentadiene cp and butadiene bd give a variety of dimers such as 4vinylcyclohexene vch, 5vinyl2norbornene vnb, cis3a, 4, 7, 7atetrahydroindene. The friedrichs condenser is for refluxing dicyclopentadiene bp 170 c. Cyclopentadiene and dicyclopentadiene cheung major. This method now precludes the previous arduous thermal cracking of 1 along with. Sigmaaldrich offers a number of dicyclopentadiene products. The largest consumption of dicyclopentadiene is linked to the production of resins including unsaturated polyester resins, petroleum resins, terpolymers, polynorbornenes, and other cyclic olefin polymers.
However, this diels alder reaction is reversible by cracking dicyclopentadiene using slow distillation and keeping the cyclopentadiene cold. At the boiling point of dicyclopentadiene, equilibration with the monomer is rapid. A microwave induced reaction of dicyclopentadiene 1 was used to rapidly and conveniently generate cyclopentadiene 2 which is stabilized in a polar solvent for subsequent use. The apparatus for the cracking of dicyclopentadiene to cyclopentadiene will be set up in the hood and will be used to prepare all of the cyclopentadiene needed for the dielsalder reaction and for the preparation of ferrocene. Apr 17, 2014 the dielsalder reaction is categorized as a pericyclic reaction, which involves the overlap of spatial orbitals as well as the hybridization and delocalization of the molecules. This reaction is reversible at elevated temperatures, so the most convenient way to obtain cyclopentadiene is to distill the commercially available dimer. Journal of chemical education 2016, 93 9, 16261630. Dielsalder reactions chemical and biomolecular engineering. At the boiling point of dicyclopentadiene, equilibration with the.
Monomer and dimer are close enough in boiling point that a sloppy job will deliver a lot of dimer to the collection pot, which is a real pain to remove from. Its kept at 50 c to let the cyclopentadiene bp 40 c pass without condensing. Dicyclopentadiene is coproduced in large quantities in the steam cracking of. This week youll be creating a product via the dielsalder reaction. The journal of physical chemistry a 2006, 110 4, 12161224. It can be prepared via the dielsalder addition of dcpd with cpd, hydrogenation, and. Dicyclopentadiene, abbreviated dcpd, is a chemical compound with formula c 10h12. To aid in product isolation, the entire reaction will be carried out in the craig tube. In the first step, cyclopentadiene is dimerized to give dicyclopentadiene by heat soaking the entire c5 fraction, either at normal pressure and 30 100 deg c over 5 24 hr or at elevated pressure and 140 150 deg c.
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