Predict the major product (or products) formed when each of the following reacts with a mixture of concentrated HNO3 and H2SO4. (a) (b) (c) 4-Chlorobenzoic acid (d) 3-Chlorobenzoic acid (e)...

2-Methylnaphthalene can be synthesized from toluene through the following sequence of reactions. Write the structure of each intermediate. 0 Toluene+ AICg A (C11H12O3) mai heaten B (C11H14O2) AICI,...

Provide a mechanism that accounts for the following result. BF,

Show how you might synthesize each of the following starting with a-tetralone (Section 15.9): (a) (b) (c) (d) HO So OH 02 H5

Ring nitration of a dimethylbenzene (a xylene) results in the formation of only one dimethylnitrobenzene. Which dimethylbenzene isomer was the reactant?

When toluene is sulfonated (concentrated H2SO4) at room temperature, predominantly (about 95% of the total) ortho and para substitution occurs. If elevated temperatures (150-200(C) and longer...

Warming piperonal (Section 16.3) with dilute aqueous HCl converts it to a compound with the formula C7H6O3. What is this compound, and what type of reaction is involved?

Consider the reduction of (R)-3-phenyl-2-pentanone by sodium borohydride. After the reduction is complete, the mixture is separated by chromatography into two fractions. These fractions contain...

Compounds W and X are isomers; they have the molecular formula C9H8O. The IR spectrum of each compound shows a strong absorption band near 1715 cm-1. Oxidation of either compound with hot, basic...

Compound B (C8H12O2) shows a strong carbonyl absorption in its IR spectrum. The broadband proton-decoupled 13C NMR spectrum of B has only three signals, at 19 (CH3), 71 (C), and 216 (C). Propose a...

Compound A (C9H18O) forms a phenylhydrazone, but it gives a negative Tollens' test. The IR spectrum of A has a strong band near 1710 cm-1. The broadband proton decoupled 13C NMR spectrum of A is...

One of the important reactions of benzylic alcohols, ethers, and esters is the ease of cleavage of the benzyl-oxygen bond during hydrogenation. This is another example of "hydrogenolysis," the...

Give an IUPAC systematic name for each of the following: (a) (b) (c) (d) (e) ONa Br OH C6Hs OH

Esters can also be synthesized by transesterification In this procedure we shift the equilibrium to the right by allowing the low-boiling alcohol to distill from the reaction mixture. The mechanism...

(a) Write stereochemical formulas for compounds A-F: 1. 2. 3. 4. (b) Which of the last two methods, 3 or 4, would you expect to give a higher yield of F? Why? cis-3-Methylcyclopentanol CoHSO2CIA...

Write a structural formula for each of the following compounds: (a) Octanoic acid (b) Propanamide (c) N, N-Diethylhexanamide (d) 2-Methyl-4-hexenoic acid (e) Butanedioic acid (f) 1, 2-Benzenedioic...

Experiments show that the molecular weight of acetic acid in the vapor state (just above its boiling point) is approximately 120. Explain the discrepancy between this experimental value and the true...

On heating, cis-4-hydroxycyclohexanecarboxylic acid forms a lactone but trans-4-hydroxycyclohexanecarboxylic acid does not. Explain.

What major organic product would you expect to obtain when acetyl chloride reacts with each of the following? (a) H2O (b) BuLi (excess) (c) (d) NH3 (excess) (e) (f) LiAlH(t-BuO)3 (g) NaOH/H2O (h)...

Write structural formulas for the following: (a) Methyl propanoate (b) Ethyl p-nitrobenzoate (c) Dimethyl malonate (d) N, N-Dimethylbenzamide (e) Pentanenitrile (f) Dimethyl phthalate (g) Dipropyl...

Indicate reagents that would accomplish each of following transformations. More than one reaction may be necessary in some cases. (a) (b) (c) (d) (e) (f) OCH HO CI Cl OCH3 NH OH ENH,CI

Which acid of each pair shown here would you expect to be stronger? (a) (b) (c) (d) (e) HO HO 10 HO HO 3 10 F O or OH OH or MeJN OH OH or CF

Give stereochemical formulas for compounds A-Q: (a) (b) (c) (d) (e) (f) (g) p-toluenesultonyl (1)LAIHa (-)-D (GH120) (2) (R)-(-)-2-Butanol pyridine (1) LiAlH4 2 +D (CH120) (R)-(-)-2-Butanol- ga E...

When maleic acid is heated to 200 8C, it loses water and becomes maleic anhydride. Practice Problem 17.8 Fumaric acid, a diastereomer of maleic acid, requires a much higher temperature before it...

How would you use the acetoacetic ester synthesis to prepare the following?

Show how each of the following compounds could be converted to benzoic acid: (a) (b) (c) (d) (e) Benzyl alcohol (f) Benzaldehyde Br

Show how you would prepare each of the following carboxylic acids through a Grignard synthesis: (a) (b) (c) (d) 4-Methylbenzoic acid (e) Hexanoic acid OH OH

Rank the following in order of increasing acidity for the indicated hydrogen atoms (bold) (1 = least acidic; 4 = most acidic). (a) (b) (c) O C OCH3 . CH3 H3C

Write a stepwise mechanism for each of the following reactions. (a) (b) (c) (d) Br Br2, CH CO H + HBr excess la NaoiH O Na t CHl + MeOH MeO CH OH, H,So OCH3

Aldehydes that have no a hydrogen undergo an intermolecular oxidation-reduction called the Cannizzaro reaction when they are treated with concentrated base. An example is the following reaction of...

Additional evidence for the halogenation mechanisms that we just presented comes from the following facts: (a) Optically active 2-methyl-1-phenylbutan-1-one undergoes acid-catalyzed racemization at a...

Starting with p-nitroaniline [Practice Problem 20.10(d)], show how you might synthesize 1, 2, 3-tribromobenzene. In problem 20.10 (a) m-Chloroaniline (b) m-Bromoaniline (c) o-Nitroaniline (d)...

Butter yellow is a dye once used to color margarine. It has since been shown to be carcinogenic, and its use in food is no longer permitted. Outline a synthesis of butter yellow from benzene and N,...

(a) Starting with aniline and assuming that you have 2-aminothiazole available, show how you would synthesize sulfathiazole. (b) How would you convert sulfathiazole to succinylsulfathiazole?...

Show how you might prepare aniline from each of the following compounds: (a) Benzene (b) Bromobenzene (c) Benzamide

Show how you might synthesize each of the following compounds from 1-butanol: (a) Butylamine (free of 28 and 38 amines) (b) Pentylamine (c) Propylamine (d) Butylmethylamine

Show how you might convert aniline into each of the following compounds. (You need not repeat steps carried out in earlier parts of this problem.) (a) Acetanilide (b) N-Phenylphthalimide (c)...

Outline a preparation of benzylamine using the Gabriel synthesis.

Give structures for the products of each of the following reactions: (a) (b) (c) (d) Product of (c) heat (e) (f) (g) Aniline + propanoyl chloride (h) Tetraethylammonium hydroxide heat (i) p-Toluidine...

Using as starting materials 2-chloropropanoic acid, aniline, and 2-naphthol, propose a synthesis of naproanilide, a herbicide used in rice paddies in Asia: Naproanilide

Show how you might utilize the reduction of an amide, oxime, or nitrile to carry out each of the following transformations: (a) (b) (c) (d) NIH NH2 OH NH2

When o-chlorotoluene is subjected to the conditions used in the Dow process (i.e., aqueous NaOH at 350oC at high pressure), the products of the reaction are o-cresol and m-cresol. What does this...

(a) Outline a step-by-step mechanism for the phenylation of acetoacetic ester by bromobenzene and two molar equivalents of sodium amide. (Why are two molar equivalents of NaNH2 necessary?) (b) What...

Rank the following in order of increasing acidity. NO2 CF3 CF3

Complete the following equations: (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) Phenol + NaH (k) Product of (j) + CH3OSO2OCH3 (l) Product of (j) + CH3I (m) Product of (j) + C6H5CH2Cl PhenolBr2 C, CS2...

(a) Show the isoprene units in each of the following terpenes. (b) Classify each as a monoterpene, sesquiterpene, diterpene, and so on. CH Zingiberene (from oil of ginger (from oil of celery)...

(a) Outline a Strecker synthesis of dl-phenylalanine. (b) dl-Methionine can also be synthesized by a Strecker synthesis. The required starting aldehyde can be prepared from acrolein (CH2 == CHCHO)...

Write the structures of other tautomeric forms of adenine, guanine, cytosine, thymine, and uracil.

Basing your answer on reactions that you have seen before, propose a likely mechanism for the condensation reaction in the first step of the preceding uridine synthesis.

(a) What kind of linkage is involved in the acetonide group of the protected nucleoside, and why is it susceptible to mild acid-catalyzed hydrolysis? (b) How might such a protecting group be...

(a) The most stable tautomeric form of guanine is the lactam form (or cyclic amide, see Section 17.8I). This is the form normally present in DNA, and, as we have seen, it pairs specifically with...

Kevlar (C 14 H 10 N 2 O 2 ) is used in various applications from tires to body armor due to its high strength-to-weight ratio. The polymer is produced from the monomers paraphenylene diamine (C 6 H 8...

Use your knowledge of vectors to explain why, even though the C-Cl bond dipole is large, the dipole moment of carbon tetrachloride, CCl4, is zero.

(a) What are the stereochemical relationships among the three conformations of meso-2,3- butanediol (the compound discussed in Sec. 6.7)? (b) Explain why meso-2,3-butanediol is a chiral even though...

Assume that the following compound has the S configuration at its asymmetric carbon. Could this compound be resolved into enantiomers? CHj CH CH2 -CHN: CH CHs

The specific rotation of the R enantiomer of the following alkene is a20D = +76 degree mL g-1 dm-1, and its molecular mass is 146.2. CH HC CHC CH Ph

Apply the principles of this section to solve each of the following problems. Imagine that a certain Mr. D. has been visited by a certain Mr. L. from elsewhere in the universe. Mr. D. and Mr. L. are...

Which one of the following stereoisomers should undergo β-elimination most rapidly with sodium ethoxide in ethanol? Explain your reasoning. CH1 CH3 Br CH3 CH

On the basis of the hybrid orbitals involved in the bonds, arrange the bonds in each of the following sets in order of increasing length. C--C single bond of propan; C--C single bond of propyne; C--C...

(a) Using the principle of microscopic reversibility, give a detailed mechanism for the acid-catalyzed hydrolysis of methyl benzoate (structure in Eq. 20.16, p. 965) to benzoic acid and methanol. (b)...

Give the principal organic product(s) expected when 2- methylpyridine or other compound indicated reacts with each of the following reagents. (a) Diliute aqueous NaOH (b) HNO3, H2SO4, heat; then -OH...

(a) Nitrogen has relatively stable isotopes (half-life greater than 1 second) of mass numbers 13, 14, 15, 16, and 17. (All except 14N and 15N are radioactive.) Calculate how many protons and neutrons...

Write equations for the following acid-base reactions. Label the conjugate acids and bases, and show any resonance stabilization. Predict whether the equilibrium favors the reactants or products. If...

The pKa of ascorbic acid (vitamin C, page 2) is 4.17, showing that it is slightly more acidic than acetic acid (CH3COOH, pKa, 4.74). (a) Show the four different conjugate bases that would be formed...

Draw the hydrogen bonding that takes place between: (a) Two molecules of ethanol. (b) Two molecules of propylamine. (c) A molecule of dimethyl ether and two molecules of water. (d) Two molecules of...

(a) Draw the structure of cis-CH3-CH=CH-CH2CH3 showing the pi bond with its proper geometry. (b) Circle the six coplanar atoms in this compound. (c) Draw the trans isomer, and circle the coplanar...

Give the IUPAC names of the following alkanes. (a) CH3C(CH3)2CH(CH)CH3)CH2CH2CH(CH3)2 (b) (c) (d) (e) (f) (g) (h) CH,CH CHCH CH, CH CH CH,CHCH CH,CHCH CH,CH CH,CH, CH, CH,CH, CH,CH,CH, C(CH,CH),...

(a) Propose a mechanism for the free-radical chlorination of ethane, (b) Calculate ÎHo for each step in this reaction. (c) Calculate the overall value of ÎHo for this reaction. hu CH3...

For each of the compounds described by the following names, 1. Draw a three-dimensional representation. 2. Star each chirality center. 3. Draw any planes of symmetry. 4. Draw any enantiomer. 5. Draw...

(a) Under certain conditions, the reaction of 0.5 M 1-bromobutane with 1.0 M sodium methoxide forms 1-methoxybutane at a rate of 0.05 mol L per second. What would be the rate if 0.1 M 1-bromobutane...

Draw a three-dimensional structure for each compound, and star all asymmetric carbon atoms. Draw the mirror image for each structure, and state whether you have drawn a pair of enantiomers or just...

Choose the member of each pair that will react faster by the SN1 mechanism. (a) 1-bromopropane or 2-bromopropane (b) 2-bromo-2-methylbutane or 2-bromo-3-methylbutane (c) n-propyl bromide or allyl...

A reluctant first-order substrate can be forced to ionize by adding some silver nitrate (one of the few soluble silver salts) to the reaction. Silver ion reacts with the halogen to form a silver...

(a) Optically active 2-bromobutane undergoes racemization on treatment with a solution of KBr. Give a mechanism for this racemization. (b) In contrast, optically active butan-2-ol does not racemize...

(a) Propose a mechanism for the following reaction: (b) Use the bond-dissociation enthalpies given in Table 4-2 (page 143) to calculate the value of (H( for each step shown in your mechanism. (The...

When the following stereoisomer of 2-bromo-1,3-dimethylcyclohexane is treated with sodium methoxide, no E2 reaction is observed. Explain why this compound cannot undergo the E2 reaction in the chair...

Propose mechanisms for the following reactions. (a) (b) CH3 CH2 CH3 CH3 CH CH3 CH3 CH3 CH OEt CH3 EtOH, heat OEt Br

Propose mechanisms for the following reactions. (a) (b) (c) (d) heat cyclopentanol cyclopentene K. OH H SO4 heat pent-2-ene (cis trans) pentan-2-ol pent-1-ene H-SO heat CH3 CH2 CH CH3...

Give a correct name for each compound. (a) (b) (c) (d) (e) (f) CH CH3CH22C CHCH Cl CH,CI

(a) Propose a mechanism for the conversion of cis-hex-3-ene to the epoxide (3,4-epoxyhexane) and the ring-opening reaction to give the glycol, hexane-3,4-diol. In your mechanism, pay particular...

(a) Propose a mechanism for the following reaction. 2 (CH3)2 C = CHCH3 + cat. H+ 2,3,4,4-tetramethylhex-2-ene (b) Show the first three steps (as far as the tetramer) in the polymerization of...

Propose a mechanism for reaction of the first three propylene units in the polymerization of propylene in the presence of a peroxide. ROOR- H2C CHCH high pressure C-C propylene I7 polypropylene

A student adds NBS to a solution of 1-methylcyclohexene and irradiates the mixture with a sunlamp until all the NBS has reacted. After a careful distillation, the product mixture contains two major...

What reaction would acetylene likely undergo if it were kept at 1500 C for too long?

Give IUPAC names for the following compounds. (a) (b) (c) (d) (e) (f) Ph CH3C C CH CH H3C CH3 - (CH3)3C C-CH (CH3)CH2CH3 CH CHC CC-OH CH,CH CH C-C CH

Show how you would convert the following starting materials into the target compound. You may use any additional reagents you need. CH2Br other reagents as needed HC CH

Show how you might synthesize the following compounds, using acetylene and any suitable alkyl halides as your starting materials. If the compound given cannot be synthesized by this method, explain...

Starting from bromobenzene and any other reagents and solvents you need, show how you would synthesize the following compounds. Any of these products may be used as starting materials in subsequent...

Predict the products of the reactions of the following compounds with chromic acid and also with PCC. (a) Cyclohexanol (b) 1-methylcyclohexanol (c) Cyclopentylmethanol (d) Cyclohexanone (e)...

Suggest carbonyl compounds and reducing agents that might be used to form the following alcohols. (a) octan-1-ol (b) 1-cyclohexylpropan-1-ol (c) 1-phenylbutan-1-ol (d) (e) (f) OCH

Classify each reaction as an oxidation, a reduction, or nether. (a) CH3 - CH2OH (b) (c) (d) (e) (f) g) (h) (i) (j) (k) (l) CrOs pyridine CH H2CrO4 CH3CH -- CH3 H3C CH3 CH3---CH3 LiAIH TiCI...

In a 300-MHz spectrometer, the protons in iodomethane absorb at a position 650 Hz downfield from TMS. (a) What is the chemical shift of these protons? (b) What is the chemical shift of the...

An unknown compound (C3H2NCl) shows moderately strong IR absorptions around 1650 cm-1 and 2200 cm-1. Its NMR spectrum consists of two doublets (J = 14 Hz) at 5.9 and 7.1. Propose a structure...

All of the following compounds absorb infrared radiation between 1600 and In each case, 1. Show which bonds absorb in this region. 2. Predict the approximate absorption frequencies. 3. Predict which...

Four infrared spectra are shown, corresponding to four of the following compounds. For each spectrum, determine the structure and explain how the peaks in the spectrum correspond to the structure you...

(a) Show which carbon atoms correspond with which peaks in the 13C NMR spectrum of butan-2-one (Figure 13-45). (b) Draw the proton NMR spectrum you would expect for butan-2-one. How well do the...

An unknown compound has the molecular formula C9H11Br. Its proton NMR spectrum shows the following absorptions: singlet, 7.1, integral 44 mm singlet, 2.3, integral 130 mm singlet, 2.2, integral 67...

A new chemist moved into an industrial lab where work was being done on oxygenated gasoline additives. Among the additives that had been tested, she found an old bottle containing a clear, pleasant...

One of the following compounds is much more stable than the other two. Classify each as aromatic, antiaromatic, or nonaromatic. heptalene azulene pentalene

Draw all the resonance forms of the sigma complex for nitration of bromobenzene at the ortho, meta, and para positions. Point out why the intermediate for meta substitution is less stable than the...