Chapter 18: Problem 6
Complete the following transesterification reaction (the stoichiometry is given in the equation).
Chapter 18: Problem 6
Complete the following transesterification reaction (the stoichiometry is given in the equation).
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Get started for freeNicotinic acid, more commonly named niacin, is one of the B vitamins. Show how nicotinic acid can be converted to (a) ethyl nicotinate and then to (b) nicotinamide. Nicotinic acid Ethyl nicotinate Nicotinamide (Niacin)
The following statements are true experimental observations. Explain the reason behind each observation. (a) The reaction of acetic acid with ammonia in water does not give any amide products. (b) The reaction of acetyl chloride with water causes the \(\mathrm{pH}\) to decrease. (c) The hydrolysis of an amide at neutral pH takes seven years at room temperature, while the hydrolysis of an acid chloride takes a few minutes.
In a series of seven steps, (S)-malic acid is converted to the bromoepoxide shown on the right in \(50 \%\) overall yield. This synthesis is enantioselective-of the stereoisomers possible for the bromoepoxide, only one is formed. In thinking about the chemistry of these steps, you will want to review the use of dihydropyran as an - OH protecting group (Section 16.7D) and the use of the \(p\)-toluenesulfonyl chloride to convert the \(-\mathrm{OH}\), a poor leaving group, into a tosylate, a good leaving group (Section 10.5D). (a) Propose structural formulas for intermediates \(\mathrm{A}\) through \(\mathrm{F}\) and specify the configuration at each chiral center. (b) What is the configuration of the chiral center in the bromoepoxide? How do you account for the stereoselectivity of this seven-step conversion?
Procaine (its hydrochloride is marketed as Novocain) was one of the first local anesthetics for infiltration and regional anesthesia. See "Chemical Connections: From Cocaine to Procaine and Beyond." According to the following retrosynthetic scheme, procaine can be synthesized from 4 -aminobenzoic acid, ethylene oxide, and diethylamine as sources of carbon atoms. Provide reagents and experimental conditions to carry out the synthesis of procaine from these three compounds.
A step in a synthesis of \(\mathrm{PGE}_{1}\) (prostaglandin \(\mathrm{E}_{1}\), alprostadil) is the reaction of a trisubstituted cyclohexene with bromine to form a bromolactone. Propose a mechanism for formation of this bromolactone and account for the observed stereochemistry of each substituent on the cyclohexane ring. Alprostadil is used as a 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.
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