CH3 CO₂Et Hagemann's ester The compound known as Hagemann's ester is prepared by treatment of a mixture of formaldehyde and ethyl acetoacetate with base, followed by acid-catalyzed decarboxylation. The reaction involves the following steps: 1. Deprotonation of ethyl acetoacetate to form enolate ion 1; 2. Reaction of the enolate ion with formaldehyde to form tetrahedral intermediate 2; 3. Protonation and dehydration to form unsaturated intermediate 3; 4. Michael reaction between a second ethyl acetoacetate enolate and the unsaturated intermediate to form enolate ion 4; 5. Proton transfer to form enolate ion 5; 6. Internal aldol cyclization to form cyclohexenone 6; 7. Acid-catalyzed ester hydrolysis to form carboxylic acid 7; 8. Decarboxylation to form the final product. Write out the mechanism on a sheet of paper and then draw the structure of enolate ion 4.

Quinapril (trade name Accupril) is used to treat high blood pressure andcongestive heart failure. One step in the synthesis of quinapril involvesreaction of the racemic alkyl bromide A with a single enantiomer of theamino ester B. Given the structure of quinapril, which one of these two products isneeded to synthesize the drug?

Treatment of ethyl acetoacetate with NaOEt (2 equiv) and BrCH2CH2Br forms compound X. This reaction is the first step in the synthesis of illudin-S, an antitumor substance isolated from the jack-o'-lantern, a poisonous, saffron-colored mushroom. What is the structure of X?

Prostaglandins are a class of eicosanoids, fatty acid derivatives involved in a variety of important phenomena, including fever, inflammation, and pain. The first step in prostaglandin synthesis involves the conversion of the 20-carbon fatty acid arachidonic acid to PGG2 by the enzyme prostaglandin endoperoxide synthase, or cyclooxy: Ibuprofen is one of several inhibitors of cyclooxogenase used therapeutically. Arachidonic acid 20₂ 0.5 1.0 1.5 2.5 3.5 cyclooxrygenase PGG₂ JOH محمد The following kinetic data were obtained for the enzyme cyclooxygenase in the absence of any inhibitor (1), and in the presence of ibuprofen (2) at a concentration of 48 [arachidonic acid] (uM) (1) v(uM/min) (2) v(uM/min) 23.5 32.2 36.9 41.8 44.0 16.67 25.25 30.49 37.04 38.91 Ibuprofen A. Plot the data in standard Michaelis-Menten form as well as in double-reciprocal form. B. Determine Vmax and Km for the enzyme. C. Based on this limited data set, what type of inhibition does ibuprofen likely exhibit?…

From each pair of compounds, choose the one with the indicated property and explain your choice. a) is racemized when placed in basic solution: (R)-4-methyl-2-hexanone or (R)-3-methyl-2-hexanone b) forms an enamine when treated with a ketone: diethylmethylamine or diethylamine

What is the product formed by hydrolysis of the following lactone with acid? А. ос B. H3O+ ОН с. OH D. будося OH ОН

Aziridines are heterocycles that contain an N atom in a three-membered ring. Like epoxides, aziridines are strained and reactive because the 60° bond angles of the three-membered ring deviate greatly from the theoretical tetrahedral bond angle. One step in the synthesis of the drug oseltamivir (trade name Tamiflu, Section 3.2) involves the conversion of amine X to diamine Y, a reaction that occurs by way of an intermediate aziridine. Draw a stepwise mechanism for the conversion of X to Y. Indicate the structure of the aziridine intermediate, and explain the trans stereochemistry of the two amines in Y.

Draw the carbonyl and amine product

A step in a synthesis of PGE1 (prostanglandin E1, alprostadil) is reaction of a trisubstituted cyclohexene with bromine to form a bromolactone. Alprostadil is used as temporary therapy for infants born with congenital heart defects that restrict pulmonary blood flow. It brings about dilation of the ductus arteriosus, which in turn increases blood flow in the lungs and blood oxygenation. Propose a mechanism for formation of This bromolactone, and account for the observed stereochemistry of each substituent on the cyclohexane ring.

Rank the following compounds in order of increasing basicity and explain the order you chose.