Organic Chemistry 6th Edition solutions

Organic Chemistry 6
Which is the stronger acid in each pair? COOH O COOH (a) CH or 3COOH Acetic acid CH3SO3H Methanesulfonic acid (b) or 2-Oxopropanoic acid (Pyruvic acid) Propanoic acid

Organic Chemistry 6
Account for the observation that the following b-ketoacid can be heated for extended periods at temperatures above its melting point without noticeable decarboxylation. O OH O

Organic Chemistry 6
Write the IUPAC name of each compound, showing stereochemistry where relevant: COOH COOH COO2NH4 1 HO COOH COOH COOH OH (a) (b) (c) COOH (d) (e) (f)

Organic Chemistry 6
Draw a structural formula for each compound. (a) Phenylacetic acid (b) 4-Aminobutanoic acid (c) 3- Chloro-4-phenylbutanoic acid (d) Propenoic acid (acrylic acid) (e) (Z)-3-Hexenedioic acid (f) 2- Pentynoic acid (g) Potassium phenylacetate (h) Sodium oxalate (i) 2-Oxocyclohexanecarboxylic acid ( j) 2,

Organic Chemistry 6
Megatomoic acid, the sex attractant of the female black carpet beetle, has the following structure. COOH (a) What is its IUPAC name? (b) State the number of stereoisomers possible for this compound.

Organic Chemistry 6
Draw a structural formula for each salt. (a) Sodium benzoate (b) Lithium acetate (c) Ammonium acetate (d) Disodium adipate (e) Sodium salicylate (f) Calcium butanoate

Organic Chemistry 6
The monopotassium salt of oxalic acid is present in certain leafy vegetables, including rhubarb. Both oxalic acid and its salts are poisonous in high concentrations. Draw the structural formula of monopotassium oxalate.

Organic Chemistry 6
Potassium sorbate is added as a preservative to certain foods to prevent bacteria and molds from causing food spoilage and to extend the foods shelf life. The IUPAC name of potassium sorbate is potassium (2E,4E)-2,4-hexadienoate. Draw a structural formula for potassium sorbate.

Organic Chemistry 6
Zinc 10-undecenoate, the zinc salt of 10-undecenoic acid, is used to treat certain fungal infections, particularly Tinea pedis (athletes foot). Draw a structural formula for this zinc salt.

Organic Chemistry 6
On a cyclohexane ring, an axial carboxyl group has a conformational energy of 5.9 kJ (1.4 kcal)/mol relative to an equatorial carboxyl group. Consider the equilibrium for the alternative chair conformations of trans-1,4-cyclohexanedicarboxylic acid. Draw the less stable chair conformation on the left

Organic Chemistry 6
Arrange the compounds in each set in order of increasing boiling point. (a) CH3(CH2)5COOH CH3(CH2)6CHO CH3(CH2)6CH2OH OH O (b) OH O

Organic Chemistry 6
Acetic acid has a boiling point of 118C, whereas its methyl ester has a boiling point of 57C. Account for the fact that the boiling point of acetic acid is higher than that of its methyl ester, even though acetic acid has a lower molecular weight.

Organic Chemistry 6
Given here are 1 H-NMR and 13C-NMR spectral data for nine compounds. Each compound shows strong absorption between 1720 and 1700 cm21 , and strong, broad absorption over the region 25003300 cm21 . Propose a structural formula for each compound. Refer to Appendices 4, 5, and 6 for spectral correlation

Organic Chemistry 6
Given here are 1 H-NMR and 13C-NMR spectral data for nine compounds. Each compound shows strong absorption between 1720 and 1700 cm21 , and strong, broad absorption over the region 25003300 cm21 . Propose a structural formula for each compound. Refer to Appendices 4, 5, and 6 for spectral correlation

Organic Chemistry 6
Complete each reaction. (a) CH2OH (b) (c) (d) CHO OH HO 1.Cl2, KOH in water/dioxane 2.HCl, H2O K2Cr2O7, H2SO4 H2O, acetone 2.CO2 1.Mg, ether 3.HCl, H2O 1.Ag(NH3)2 1 2.H2O, HCl O Br OCH3

Organic Chemistry 6
Show how to bring about each conversion in good yield. OH (a) (c) (b) OH CH2OH COOH Cl COOH O C6H5 C6H5 COOH

Organic Chemistry 6
Show how to prepare pentanoic acid from each compound. (a) 1-Pentanol (b) Pentanal (c) 1-Pentene (d) 1-Butanol (e) 1-Bromopropane (f) 1-Hexene

Organic Chemistry 6
Draw the structural formula of a compound with the given molecular formula that, on oxidation by potassium dichromate in aqueous sulfuric acid, gives the carboxylic acid or dicarboxylic acid shown. C6H14O OH O oxidation (a) OH HO C6H14O2 O O oxidation (c) C6H12O OH O oxidation

Organic Chemistry 6
Show the reagents and experimental conditions necessary to bring about each conversion in good yield. CH3CH"CHCH3 CH3CH"CHCH2COOH (a) (b) CH3COH CH3CCOOH OH COOH CH3 CH3 CH3 CH3 (d) CH3COH CH3CHCH2COOH CH3 CH3 CH3 (c) CH3COH CH3CHCOOH (e) CH3 CH3 CH3

Organic Chemistry 6
Succinic acid can be synthesized by the following series of reactions from acetylene. Show the reagents and experiential conditions necessary to carry out this synthesis. OH HO OH HO HO OH Acetylene 2-Butyne-1,4-diol 1,4-Butanediol Butanedioic acid (Succinic acid) O O H99999H

Organic Chemistry 6
The reaction of an a-diketone with concentrated sodium or potassium hydroxide to give the salt of an a-hydroxyacid is given the general name benzil-benzilic acid rearrangement. It is illustrated by the conversion of benzil to sodium benzilate and then to benzilic acid. Propose a mechanism for this re

Organic Chemistry 6
Select the stronger acid in each set. (a) Phenol (pKa 9.95) and benzoic acid (pKa 4.19) (b) Lactic acid (Ka 8.4 3 1024 ) and ascorbic acid (Ka 7.9 3 1025 )

Organic Chemistry 6
In each set, assign the acid its appropriate pKa. O (a) (b) (pKa 3.58 and 2.49) (c) CH3CH2COOH and N#CCH2COOH (pKa 4.78 and 2.45) COOH SO3H and and (pKa 4.19 and 0.70) COOH COOH O

Organic Chemistry 6
Low-molecular-weight dicarboxylic acids normally exhibit two different pKa values. Ionization of the fi rst carboxyl group is easier than the second. This effect diminishes with molecular size, and, for adipic acid and longer chain dicarboxylic acids, the two acid ionization constants differ by about

Organic Chemistry 6
Complete the following acid-base reactions. (a) CH2COOH 1 (b) CH3CH"CHCH2COOH 1 NaHCO3 NaOH OCH3 1 NaHCO3 COOH (c) (d) CH3CHCOOH 1 H2NCH2CH2OH OH (e) CH3CH"CHCH2COO2 Na1 1 HCl h (f) CH3CH2CH2CH2Li 1 CH3COOH h (g) CH3CH2CH2CH2MgBr 1 CH3CH2OH

Organic Chemistry 6
The normal pH range for blood plasma is 7.357.45. Under these conditions, would you expect the carboxyl group of lactic acid (pKa 3.08) to exist primarily as a carboxyl group or as a carboxylic anion? Explain.

Organic Chemistry 6
The Ka1 of ascorbic acid is 7.94 3 1025 . Would you expect ascorbic acid dissolved in blood plasma (pH 7.357.45) to exist primarily as ascorbic acid or as ascorbate anion? Explain.

Organic Chemistry 6
Excess ascorbic acid is excreted in the urine, the pH of which is normally in the range 4.88.4. What form of ascorbic acid would you expect to be present in urine of pH 8.4, free ascorbic acid or ascorbate anion? Explain.

Organic Chemistry 6
Give the expected organic product when phenylacetic acid, PhCH2COOH, is treated with each reagent. (a) SOCl2 (b) NaHCO3, H2O (c) NaOH, H2O (d) CH3MgBr (one equivalent) (e) LiAlH4 followed by H2O (f) CH2N2 (g) CH3OH 1 H2SO4 (catalyst)

Organic Chemistry 6
Show how to convert trans-3-phenyl-2-propenoic acid (cinnamic acid) to each compound. (a) (b) (c) O C6H5 OH C6H5 OH C6H5 OH

Organic Chemistry 6
Show how to convert 3-oxobutanoic acid (acetoacetic acid) to each compound. (a) OH (b) (c) (racemic) (racemic) O O OH OH OH OH

Organic Chemistry 6
Complete these examples of Fischer esterifi cation. Assume that the alcohol is present in excess. (a) (c) (b) OH 1 1 O OH HO H1 H1 H1 COOH 1 COOH CH3OH OH O HO O

Organic Chemistry 6
Benzocaine, a topical anesthetic, is prepared by treatment of 4-aminobenzoic acid with ethanol in the presence of an acid catalyst followed by neutralization. Draw a structural formula for benzocaine.

Organic Chemistry 6
Name the carboxylic acid and alcohol from which each ester is derived. (a) (c) (d) (b) OMe O O O O O O EtO O O OEt O

Organic Chemistry 6
When 4-hydroxybutanoic acid is treated with an acid catalyst, it forms a lactone (a cyclic ester). Draw the structural formula of this lactone, and propose a mechanism for its formation

Organic Chemistry 6
Fischer esterifi cation cannot be used to prepare tert-butyl esters. Instead, carboxylic acids are treated with 2-methylpropene in the presence of an acid catalyst to generate them. O 2- Methylpropene A tert-butyl ester (Isobutylene) R OH O R O 1 H1 (a) Why does the Fischer esterifi cation fail for t

Organic Chemistry 6
Draw the product formed on thermal decarboxylation of each compound. C6H5CCH2COOH C6H5CH2CHCOOH CCH3 COOH (a) (b) (c) O O COOH

Organic Chemistry 6
When heated, carboxylic salts in which there is a good leaving group on the carbon beta to the carboxylate group undergo decarboxylation/elimination to give an alkene. O Br O2Na1 1 CO2 1 Na1Br2 (a) heat Br O2Na1 1 CO2 1 Na1Br2 Br (b) heat Br O 5498X_17_ch17_p649-679.indd 676 12/13/10 3:48:59 PM. Prob

Organic Chemistry 6
Show how cyclohexanecarboxylic acid could be synthesized from cyclohexane in good yield. COOH

Organic Chemistry 6
In Section 17.7B, we suggested that the mechanism of Fischer esterifi cation of carboxylic acids is a model for the reactions of functional derivatives of carboxylic acids. One of these reactions is that of an acid chloride with water (Section 18.4A). Suggest a mechanism for this reaction. R9C9Cl 1 H

Organic Chemistry 6
We have studied Fischer esterifi cation, in which a carboxylic acid is reacted with an alcohol in the presence of an acid catalyst to form an ester. Suppose that you start instead with a dicarboxylic acid such as terephthalic acid and a diol such as ethylene glycol. Show how Fischer esterifi cation i

Organic Chemistry 6
Use the roadmap you made for problems 15.19 and 16.72 and update it to contain the reactions in the Key Reactions section of this chapter. Because of their highly specifi c nature, do not use reactions 1, 2, 4, 9, and 10 on your roadmap.

Organic Chemistry 6
Write the products of the following sequences of reactions. Refer to your roadmaps to see how the combined reactions allow you to navigate between the different functional groups. Note that you will need both your old Chapters 611 roadmap and your new Chapters 1517 roadmap for these. (a) 1. Mg, ether

Organic Chemistry 6
Using your roadmaps as a guide, show how to convert propane into propyl propanoate. You must use propane as the source of all carbon atoms in the target molecule. Show all reagents needed and all molecules synthesized along the way. ? Propane Propyl propanoate O O

Organic Chemistry 6
Using your roadmaps as a guide, show how to convert 4-methyl-1-pentene and carbon dioxide into 5- methylhexanoic acid. You must use 4-methyl-1-pentene and carbon dioxide as the source of all carbon atoms in the target molecule. Show all reagents and all molecules synthesized along the way. ? 1 CO2 4-

Organic Chemistry 6
Using your roadmaps as a guide, show how to convert cyclohexane into adipoyl dichloride. Show all reagents and all molecules synthesized along the way. ? Cyclohexane Adipoyl dichloride O O Cl Cl

Organic Chemistry 6
Using your roadmaps as a guide, show how to convert 5-chloro-2-pentanone and carbon dioxide into racemic tetrahydro-6-methyl-2-pyranone. You must use 5-chloro-2-pentanone and carbon dioxide as the source of all carbon atoms in the racemic target molecule. Show all reagents and all molecules synthesiz

Organic Chemistry 6
Diazomethane, CH2N2, is used in the organic chemistry laboratory despite its danger because it produces very high yields and is selective for reaction with carboxylic acids. Write the products of the following reactions. excess CH2N2 CH3OH (a) O O O O H N N OH OH 5498X_17_ch17_p649- 679.indd 678 12/1

Organic Chemistry 6
So far, you have seen a number of reducing agents used in reactions. Functional groups react differently with each of these reagents. With this in mind, complete the following reaction, which is the last step in a synthesis of fexofenadine, a nonsedating antihistamine sold under the trade name of All