Claisen condensation a claisen condensation is a specific type of condensation reaction the condensation of an ester and an enolate contains the cco or cco fu nctional group. O hcoet et ocoet o coet o o et occoet d i et hy l et haned i oat e d i et hy l oxal at e d i et h yl car bonat e et h yl f orm at e et hy l ben zoat e o. What s the different between aldol condensation and claisen. This reaction is essentially an intramolecular form of the claisen condensation. This reaction is named after two of its pioneering investigators rainer ludwig claisen and j. Claisen schmidt condensation mechanism pdf download. The mechanism for carboncarbon bond formation used in the biosynthesis of natural products such as fatty acids and polyketides is a decarboxylating claisen condensation. It is named after rainer ludwig claisen, who first published his work on the reaction in 1887. If the claisen concentration is done between the two esters of a diester, it is called a diekman cyclization. Show the curvedarrow mechanism for the claisen condensation of ethyl ethanoate treated with ethoxide ion. If base is consumed, calculate the ratio of number of molecules. Claisen condensation is a fun reaction used to form a beta keto ester when reacting esters in a strong base.
In this experiment, potassium tertbutoxide and ethyl phenylacetate. The claisen condensation reaction chemistry libretexts. A solventfree claisen condensation reaction for the organic. Claisen condensations between different ester reactants are called crossed claisen reactions.
To suppress this, along with the possible cannizzaro reaction, slow addition of acetaldehyde to benzaldehyde maintained in a mild alkaline medium is suggested. O hcoet et ocoet o coet o o et occoet d i et h y l et h an ed i oat e d i et h y l oxal at e d i et h yl car b o. Aldol condensation is an organic reaction in which an enolate ion reacts with carboxyl compound in order to form a. The presence of an enolate requires the condensation reaction to also have a base, in order to form the enolate. A solventfree claisen condensation reaction for the. The equivalent intermolecular reaction is the claisen condensation. Heres another way to do a mixed, or crossed aldol condensation, this time using a lithium enolate. When the r groups in one molecule are different than those in the other, the reaction is called a crossedaldol reaction. Aldol condensation an overview sciencedirect topics. The claisen condensation reaction is an important reaction in organic chemistry both. The claisen condensation is the ester analogue of the aldol condensation reagents. Crossed claisen condensations between two different esters, each with ahydrogens, give bad mixtures. The aldol reaction, is a remarkable and useful reaction of aldehydes and ketones in which the carbonyl group serves both as an electrophilic reactant and the source of a nucleophilic enol species.
Powerful claisen condensation and claisenaldol tandem reaction of. The general basecatalysed reaction is shown in scheme 1. As the name implies the reaction provides a cyclic compound. The claisen condensation has been widely used as a means of c c bond formation, the reaction having a biological counterpart in the formation of. Patternspatterns r ch2 c oh r ch c r o r r ch2 c c c r o rr 3hydroxyaldehyde or 3hydroxyketone h h. Understanding how the number of equivalents of base used. Claisen condensation reaction and mechanism organic. When the reaction takes place at room temperature, the aldol addition product is produced. The claisen condensation is a carboncarbon bond forming reaction that occurs between two esters or one ester and another carbonyl compound in the presence of a strong base, resulting in a. Claisen condensation organic chemistry video clutch prep.
How to direct a mixed aldol condensation using a lithium enolate. Pdf powerful claisen condensation and claisenaldol tandem. Claisen condensation reaction and mechanism organic chemistry. If ketones or nitriles are used as the donor in this condensation reaction. As the aromatic aldehyde possesses no hydrogens in position. The aldol condensation leads to an aldol product, in which an hydroxyl group is. Feb 23, 2015 a cyclic claisen condensation naome meoh 42. Esters undergo a similar transformation called the claisen condensation. Exam 4 problems ch 22 and 23 enolates and condensations. Understanding how the number of equivalents of base used will. Energy and carbonefficient synthesis of functionalized small molecules in bacteria using nondecarboxylative claisen condensation reactions. Microwavepromoted claisen condensation reaction undergraduate organic chemistry experiment developed and published in j. Schmidt, who independently published on this topic in 1880 and 1881.
So if we took this ketone and this aldohyde and just mixed them together with some base, we would get a mixture of products. Name reactions name reactions and reagents in organic. Claisen condensation an overview sciencedirect topics. The reaction temperature is the factor that determines which product is formed. The cyclization works best with 1,6 and 1,7diesters. The value of the reaction is greatly enhanced if it can be made regioselective. The claisen condensation is an organic reaction used to form a carboncarbon bond between two ester molecules using an alkoxide base in alcohol to make a. A claisen condensation is a specific type of condensation reaction the condensation of an ester and an enolate contains the cco or cco fu nctional group. At the beginning of the experiment, each student obtains an unknown benzaldehyde derivative 4chlorobenzaldehyde, 4bromobenzaldehyde, or 3bromobenzaldehyde to use in the solventfree aldol condensation. The aldol condensation of ethanal is shown in the following equation.
The claisen schmidt condensation is what happens when you have an enolizable aldehyde plus ketone. Ethyl acetate, for example, undergoes a claisen condensation on. For claisen condensation reaction using methyl propanoate, naoch3, is the ideal base. The reaction between an aldehyde or ketone having an. Aldol condensation can occur between two identical or different aldehydes two identical or different ketones an aldehyde and a ketone 10. Exam 4 problems ch 22 and 23 enolates and condensations proton acidity. The reaction starts with the ester in an alkoxidealcohol solution and is worked up with acid to form the neutral. Claisen rearrangement allyl phenyl ethers claisen rearrangement allyl vinyl ethers clemmensen reduction.
Consider the reaction below to answer the following questions. The dieckmann reaction is basically a cyclic claisen ester intramolecular condensation reaction. Claisenschmidt reaction mechanism and problems solving. Claisen condensations are routinely covered in organic textbooks but owing to the long reaction times required to reach equilibrium in solution they are seldom explored in the undergraduate teaching laboratory. You can do this if you use one component with no ahydrogen and if you run the reaction properly. The claisen condensation strictly the condensation of two esters with the concomitant release of one of the constituent alcohol moieties is arguably the most important carboncarbon bondforming reaction in biology, as it is used in the biosynthesis of fatty acids, polyketides, and a large variety of other essential small molecule metabolites.
For claisen condensation reaction using methyl pro. The dieckmann condensation is an organic reaction used to form a carboncarbon bond between two tethered ester groups using an alkoxide base in alcohol to make a cyclic. Exam 4 problems ch 22 and 23 enolates and condensations proton acidity enolate reactions more enolate reactions fill in some reagents enamine reactions more enamine reactions kinetic versus thermodynamic aldol problems claisen problems. One ester group of the starting material must have an.
Acetoacetic ester can be prepared by the claisen self condensation reaction of ethyl acetate. Crossed claisen reactions in which both reactants can serve as donors and acceptors generally give complex mixtures. Carbonyl condensation reactions these are combination reactions. The presence of an enolate requires the condensation reaction. This organic chemistry video tutorial provides the mechanism of the claisen condensation reaction of two identical esters to form a beta keto. Nov 22, 2015 this organic chemistry video tutorial provides the mechanism of the claisen condensation reaction of two identical esters to form a beta keto ester followed by hydrolysis and decarboxylation to. This video shows you the step by step reaction mechanism including why the reaction is reversible only till the final step. Both the aldol reaction and condensation are reversible. The combination of two identical molecules is known as self condensation. The main method for the preparation of keto esters is a reaction known as the claisen condensation. Dieckmann condensation a dieckmann condensation is a specific type. If ketones or nitriles are used as the donor in this condensation reaction, a. What s the different between aldol condensation and. Jun 02, 2016 claisen condensation is a fun reaction used to form a beta keto ester when reacting esters in a strong base.
The product, 3hydroxybutanal, is also known as aldol and gives rise to the name for the whole class of reactions. Energy and carbonefficient synthesis of functionalized. Condensation reaction, any of a class of reactions in which two molecules combine, usually in the presence of a catalyst, with elimination of water or some other simple molecule. Because esters can contain hydrogens they can undergo a condensation reaction similar to the aldol reaction called a claisen. This reaction has been applied to the preparation of chalcone, flavanone, 1,3. Now were going to talk about a very specific type of crossed aldol reaction called the claisen schmidt reaction. Aldol condensation is the reaction of two aldehydes in the presence of a basic catalyst. The claisen condensation between esters containing.
In a fashion similar to the aldol, one ester acts as a nucleophile while a second ester acts as the electrophile. Question 9 a malonic ester synthesis of a carboxylic acid proceeds by alkylation of the enolate of the malonic ester followed by ester hydrolysis and decarboxylation of the. In above reaction, the self aldol condensation of acetaldehyde is a competing reaction. In aldol reactions between two molecules of the same aldehyde are generally quite successful, since the equilibrium lies far to the right, and the yields are very high. However, if one of the ester partners has enolizable. Why is it important to use naoch3 and not naoch2ch3. The aldol condensation leads to an aldol product, in which an hydroxyl group is attached to the beta carbon. Usually, a carbonyl molecule is converted to an enolate anion nucleophile which attacks a second carbonyl molecule in an addition or substitution reaction. An experiment involving the claisen condensation reaction for a firstyear organic chemistry laboratory is presented. Nov 22, 2015 this organic chemistry video tutorial provides the mechanism of the dieckmann condensation reaction. It is named after the german chemist walter dieckmann 18691925. The condensation of an aromatic aldehyde with an aliphatic aldehyde or ketone in the presence of a base or an acid to form an. During the reaction a new carboncarbon bond is formed. Im only going to cover the first reaction sequence he draws since this is going to be a long answer, but the same methods apply each time.
Claisen schmidt condensation mechanism pdf download download. Both reactions use the same quantities of reagents. The alcohol molecule that is formed derives from the alkoxyl group of the ester. Aldol condensation mechanism of aldol condensation, crossed. O hcoet et ocoet o coet o o et occoet d i et h y l et h an ed i oat e d i et h y l oxal at e d i et h yl car b o n at e et h yl f o rm at e et h y l b en zoat e o. Aldol condensation mechanism of aldol condensation.
All claisen rearrangement reactions described to date require temperatures of 100 c if uncatalyzed. Mechanism, references and reaction samples of the claisen schmidt condensation. Claisen condensation reaction mechanism organic chemistry. Crossed claisen condensation crossed reactions can work if one does it carefully and one of the reactants does not have an alpha hydrogen such as. Claisen condensation ester attacking ester claisen, cope and related rearrangements. A nucleophilic substitution reaction, by definition, is a chemical reaction that involves a negatively charged ion viz.
The claisen schmidt reaction the claisen schmidt condensation between acetophenone and benzaldehyde derivatives is an important cc bond forming reaction which allows unsaturated ketone such as chalcones tobe obtained 23. Its easiest if you have the alpha carbon belong to the left carbonyl, so an intramolecule reaction isnt necessary. Sibi lecture 34 dieckmann cyclization the dieckmann cyclization is an intramolecular version of the claisen condensation. Claisenschmidt condensation organic chemistry video. The claisenschmidt reaction is an aldol condensation type, consisting of the synthesis of.
The dieckmann condensation is the intramolecular chemical reaction of diesters with base to give. Organic chemistry university of california riverside. Application of the claisen condensation reaction to 3. However, the application of the claisen condensation reaction to methyl butyrate, isopentyl acetate and benzyl acetate, does not reflect this perception since in the reactions involving isopentyl acetate and benzyl acetate, there were no. They are not useful and will not be accepted as legitimate answers in our class.
Because of this most crossed claisen reactions are usually not performed unless one reactant has no alpha. Aldol problems claisen problems michael addition problems stork enamine problems condensation reactions more condensation reactions even more condensation reactions intramolecular reactions mechanism problems. The claisen condensation is the ester analogue of the aldol condensation. Sep 15, 2010 the condensation of an aromatic aldehyde with an aliphatic aldehyde or ketone in the presence of a base or an acid to form an. The observation that electron withdrawing groups at c1 of the vinyl moiety exert a positive influence on the reaction rate and the yield has led to the development of the following variations.
The claisen condensation is a carboncarbon bond forming reaction that occurs between two. One full equivalent of base must be used in the claisen condensation. In a claisen condensation, the enolate of one ester molecule adds to the carbonyl group of another, resulting in an acyl substitution reaction that forms a bketo ester and an alcohol molecule. Complete guide on claisen schmidt reaction mechanism and problems solving. In the same way that bhydroxyaldehydes and bhydroxyketones are signature structures of the aldol reaction, bketoesters suggest the claisen condensation. The r group of the ester starting material, the alkoxide base, and the alcohol solvent are chosen to be the same to not end up with a mixture of products. The claisen condensation converts 2 molecules of an ester into a. This organic chemistry video tutorial provides a basic introduction into the claisen condensation reaction mechanism which involves the.
194 610 843 1345 1209 793 752 1134 243 385 977 259 968 995 783 247 1471 1500 206 1381 1469 271 1236 576 282 180 1230 1455 1400 9 1189 570 58 2 22 561 387 533 291 357 210 1093 5