Organic Chemistry 2nd Edition solutions

Organic Chemistry 2
Rank each set of compounds in order of increasing acidity: COOH O2N COOH H3C COOH O COOH Br COOH O (a) OH Br O OH O Br OH O (b) Br

Organic Chemistry 2
Malonic acid has two acidic protons: OH O HO O Malonic acid The pKa of the first proton (pK1) is measured to be 2.8, while the pKa of the second proton (pK2) is measured to be 5.7. (a) Explain why the first proton is more acidic than acetic acid (pKa=4.76). (b) Explain why the second proton is less a

Organic Chemistry 2
Identify a systematic (IUPAC) name for each of the following compounds: OH O (a) NH2 O (b) Cl O (c) Note: Most of the Problems are available within , an online teaching and learning solution. O O (d) (e) CH3(CH2)4CO2H (f) CH3(CH2)3COCl (g) CH3(CH2)4CONH2

Organic Chemistry 2
Identify the common name for each of the following compounds: O O O (a) OH O (b) H OH O (c) HO OH O O (d

Organic Chemistry 2
Draw the structures of eight different carboxylic acids with molecular formula C6H12O2. Then, provide a systematic name for each compound and identify which three isomers exhibit chirality centers.

Organic Chemistry 2
Draw and name all constitutionally isomeric acid chlorides with molecular formula C4H7ClO. Then provide a systematic name for each isomer.

Organic Chemistry 2
Identify the reagents you would use to convert pentanoic acid into each of the following compounds: (a) 1-Pentanol (b) 1-Pentene (c) Hexanoic acid

Organic Chemistry 2
Identify the reagents you would use to convert each of the following compounds into pentanoic acid: (a) 1-Pentene (b) 1-Bromobutane

Organic Chemistry 2
Careful measurements reveal that para-methoxybenzoic acid is less acidic than benzoic acid, while meta-methoxybenzoic acid is more acidic than benzoic acid. Explain these observations.

Organic Chemistry 2
Predict the major product(s) formed when hexanoyl chloride is treated with each of the following reagents: (a) CH3CH2NH2 (excess) (b) LAH (excess), followed by H2O (c) CH3CH2OH, pyridine (d) H2O, pyridine (e) C6H5CO2Na (f) NH3 (excess) (g) Et2CuLi (h) EtMgBr (excess), followed by H2O

Organic Chemistry 2
Predict the major product(s) formed when cyclopentanecarboxylic acid is treated with each of the following reagents: (a) SOCl2 (b) LAH (excess), followed by H2O (c) NaOH (d) [H+], EtOH

Organic Chemistry 2
Predict the major product(s) for each of the following reactions: OH O 1) xs LAH (a) 2) H2O ? OH O 1) SOCl2 2) xs (CH3) (b) 2NH ? NH2 O SOCl2 (c) ? OMe O 1) H3O+ 2) CH3COCl, (d) pyridine ? OMe O 1) DIBAH (e) 2) H2O ? OH O O O (f) ? N H Cl O (g) Pyridine ? O O 1) xs LAH 2) H2O ? (h) N O H3O+ (i) Heat

Organic Chemistry 2
Identify the carboxylic acid and the alcohol that are necessary in order to make each of the following compounds via a Fischer esterification: O O (a) O O (b) (c) CH3CH2CO2C(CH3)3

Organic Chemistry 2
Determine the structures of compounds A through F: OH D A E F B C 2) H2O 1) LiAl(OR)3H [H+] EtOH Na2Cr2O7 H2SO4, H2O SOCl2 xs NH3

Organic Chemistry 2
Identify the reagents you would use to convert 1-bromopentane into each of the following compounds: (a) Pentanoic acid (b) Hexanoic acid (c) Pentanoyl chloride (d) Hexanamide (e) Pentanamide (f) Ethyl hexanoate

Organic Chemistry 2
Starting with benzene and using any other reagents of your choice, show how you would prepare each of the following compounds: OH (a) N O (b) OH (c) O N O H (d)

Organic Chemistry 2
Propose an efficient synthesis for each of the following transformations: Br O O (a) OH O (b) Br N O (c) Br O (d)

Organic Chemistry 2
When methyl benzoate bears a substituent at the para position, the rate of hydrolysis of the ester group depends on the nature of the substituent at the para position. Apparently, a methoxy substituent renders the ester less reactive, while a nitro substituent renders the ester more reactive. Explain

Organic Chemistry 2
Identify the reagents necessary to accomplish each of the following transformations: OH O Cl O O O O OR O NH2 O O H

Organic Chemistry 2
DEET is the active ingredient in many insect repellants, such as OFFTM. Starting with meta- bromotoluene and using any other reagents of your choice, devise an efficient synthesis for DEET. N O N,N-Diethyl-m-toluamide (DEET) Br m-Bromotoluene

Organic Chemistry 2
Predict the products that are formed when diphenyl carbonate is treated with excess methyl magnesium bromide. O O O 1) Excess MeMgBr 2) H3O+

Organic Chemistry 2
When acetic acid is treated with isotopically labeled water ( 18O, shown in red) in the presence of a catalytic amount of acid, it is observed that the isotopic label becomes incorporated at both possible positions of acetic acid. Draw a mechanism that accounts for this observation. OH O OH O OH O [H

Organic Chemistry 2
Phosgene is highly toxic and was used as a chemical weapon in World War I. It is also a synthetic precursor used in the production of many plastics. (a) When vapors of phosgene are inhaled, the compound rapidly reacts with any nucleophilic sites present (OH groups, NH2 groups, etc.), producing HCl ga

Organic Chemistry 2
Fluphenazine is an antipsychotic drug that is administered as an ester prodrug via intramuscular injection: S N N N O CF3 O Fluphenazine decanoate The hydrophobic tail of the ester is deliberately designed to enable a slow release of the prodrug into the bloodstream, where the prodrug is rapidly hydr

Organic Chemistry 2
Benzyl acetate is a pleasant-smelling ester found in the essential oil of jasmine flowers and is used in many perfume formulations. Starting with benzene and using any other reagents of your choice, design an efficient synthesis for benzyl acetate.

Organic Chemistry 2
Aspartame (below) is an artificial sweetener used in diet soft drinks and is marketed under many trade names, including Equal and Nutrasweet. In the body, aspartame is hydrolyzed to produce methanol, aspartic acid, and phenylalanine. The production of phenylalanine poses a health risk to infants born

Organic Chemistry 2
Draw a plausible mechanism for each of the following transformations: Cl O O O Pyridine OH (a) O O HO O OH 1) NaOH 2) H3O+ (b) O O OH OH (c) O 1) NaOH 2) H3O+ Cl O Cl O N O N O H H (d) H2N NH2 Excess pyridine O O OH OH 1) Excess EtMgBr 2) H2O (e)

Organic Chemistry 2
Ethyl trichloroacetate is significantly more reactive toward hydrolysis than ethyl acetate. Explain this observation.

Organic Chemistry 2
Draw the structure of the diol that is produced when the following carbonate is heated under aqueous acidic conditions: O O O H3O+ Heat

Organic Chemistry 2
Pivampicillin is a penicillin prodrug: Pivampicillin N O N S O 2 HNH O O O O The prodrug ester group (in red) enables a more rapid delivery of the prodrug to the bloodstream, where the ester group is subsequently hydrolyzed by enzymes, releasing the active drug. (a) Draw the structure of the active d

Organic Chemistry 2
Dexon (below) is a polyester that is spun into fibers and used for surgical stitches that dissolve over time, eliminating the need for a follow-up procedure to remove the stitches. The ester groups are slowly hydrolyzed by enzymes present in the body, and in this way, the stitches are dissolved over

Organic Chemistry 2
Draw the structure of the polymer produced when the following two monomers are allowed to react with each other: Cl Cl O O HO OH

Organic Chemistry 2
Identify what monomers you would use to produce the following polymer: N O N H H O O O N H N H

Organic Chemistry 2
meta-Hydroxybenzoyl chloride is not a stable compound, and it polymerizes upon preparation. Show a mechanism for the polymerization of this hypothetical compound.

Organic Chemistry 2
Propose an efficient synthesis for each of the following transformations: OH O OO (a) NH2 O N (b) O N O (c) OMe O H SS (d) COOH O O (e) OH (f) OH O O O O O (g)

Organic Chemistry 2
Starting with benzene and using any other reagents of your choice, devise a synthesis for acetaminophen: Acetaminophen (Tylenol) N HO O H

Organic Chemistry 2
Draw a plausible mechanism for the following transformation: OH O O O O O HO H3O+

Organic Chemistry 2
A carboxylic acid with molecular formula C5H10O2 is treated with thionyl chloride to give compound A. Compound A has only one signal in its 1 H NMR spectrum. Draw the structure of the product that is formed when compound A is treated with excess ammonia.

Organic Chemistry 2
A compound with molecular formula C10H10O4 exhibits only two signals in its 1 H NMR spectrum: a singlet at 4.0 (I = 3H) and a singlet at 8.1 (I = 2H). Identify the structure of this compound.

Organic Chemistry 2
Describe how you could use IR spectroscopy to distinguish between ethyl acetate and butyric acid.

Organic Chemistry 2
Describe how you could use NMR spectroscopy to distinguish between benzoyl chloride and para- chlorobenzaldehyde.

Organic Chemistry 2
A compound with molecular formula C8H8O3 exhibits the following IR, 1 H NMR, and 13C NMR spectra. Deduce the structure of this compound. Proton NMR Carbon NMR 1 2 2 3 180 160 140 120 100 80 60 40 20 0 12 11 10 9 8 7 6 5 3 4 Chemical Shift (ppm) Chemical Shift (ppm) 172.8 167.9 118.3 64.1 139.4 128.0

Organic Chemistry 2
Propose a mechanism for the following transformation, and explain how you could use an isotopic labeling experiment to verify your proposed mechanism: O O HO R HO O O [H2SO4] R

Organic Chemistry 2
N-Acetylazoles undergo hydrolysis more readily than regular amides. Suggest a reason for the enhanced reactivity of N-acetylazoles toward nucleophilic acyl substitution:

Organic Chemistry 2
Dimethylformamide (DMF) is a common solvent: Dimethylformamide H N CH3 CH3 O (a) The 1 H NMR spectrum of DMF exhibits three signals. Upon treatment with excess LAH followed by water, DMF is converted into a new compound that exhibits only one signal in its 1 H NMR spectrum. Explain. (b) Based on your

Organic Chemistry 2
Olefin metathesis (2005 Nobel Prize) using the Grubbs catalyst has emerged as one of the most important tools for the organic chemist (e.g., 2 to 3). Metathesis substrate 2 can be prepared from 1 in three steps, shown below (Org. Lett. 2000, 2, 791794). Show the product of each synthetic step. Ph OH

Organic Chemistry 2
Aminotetralins are a class of compounds currently being studied for their promise as antidepressant drugs. The following conversion was employed during a mechanistic study associated with a synthetic route for preparing aminotetralin drugs (J. Org. Chem. 2012, 77, 55035514). Propose a three-step synt

Organic Chemistry 2
Steroidal derivatives are important pharmacologically and biologically, and they continue to be a popular backbone in the search for new biologically active steroid hormone analogues. Propose a possible three-step synthesis for the conversion of steroid 1 to steroid 2, an intermediate in the synthesi

Organic Chemistry 2
Allylic bromide 2 was recently used as a key fragment in progress toward the total synthesis of an analogue of amphidinolide N, a potent cytotoxic agent isolated from the marine organism Amphidinium sp. (Org. Biomol. Chem. 2006, 4, 21192157). Propose an efficient synthesis of bromide 2 from carboxyli

Organic Chemistry 2
Compound 3 (below) was used as an intermediate in a recently reported synthesis of the g-secretase inhibitor BMS-708163 (Tetrahedron Lett. 2010, 51, 65426544). Compound 3 was made from compound 1 via the two-step process shown below. (a) Compound 1 cannot be directly converted into compound 3 upon tr

Organic Chemistry 2
The m- and p-substituted methyl benzoates listed in the table below were treated with NaOH in dioxane and water. The rate constants of saponification, k, are also listed in the table (J. Am. Chem. Soc. 1961, 83, 42144216). Provide structural explanations for the trend observed in the rate constants b

Organic Chemistry 2
Prostaglandins (Section 26.7) are a group of structurally related compounds that function as biochemical regulators and exhibit a wide array of activity, including the regulation of blood pressure, blood clotting, gastric secretions, inflammation, kidney function, and reproductive systems. The follow

Organic Chemistry 2
The following two-step rearrangement was the cornerstone of the first stereoselective total synthesis of quadrone, a biologically active natural product isolated from an Aspergillus fungus (J. Org. Chem. 1984, 49, 40944095). Propose a plausible mechanism for this transformation. 1) NaH 2) H2SO2 CO2H

Organic Chemistry 2
During recent studies to determine the absolute stereochemistry of a bromohydrin, the investigators observed an unexpected skeletal rearrangement (Tetrahedron Lett. 2008, 49, 68536855). Provide a plausible mechanism for the formation of epoxide 2 from bromohydrin 1. O O H H Br HO NaH O O H H O 1 2

Organic Chemistry 2
During a recent total synthesis of englerin A, a potent cytotoxic natural product isolated from the stem bark of a Tanzanian plant, the investigators observed the following (unusual) base-catalyzed ring contraction (Angew. Chem. Int. Ed. 2009, 48, 91059108). Propose a plausible mechanism for this tra