Classify the following amines as primary, secondary, or tertiary: (a) (b) (c) (d) (e) (f) H IN NH2 HN

Write structural formulas for each of the following: (a) Three ethers with the formula C4H10O. (b) Three primary alcohols with the formula C4H8O. (c) A secondary alcohol with the formula C3H6O. (d) A...

Predict the key IR absorption bands whose presence would allow each compound in pairs (a), (c), (d), (e), (g), and (i) from Problem 2.46 to be distinguished from each other. In problems 2.46 (a) (c)...

Indicate the direction of the important bond moments in each of the following compounds (neglect C-H bonds). You should also give the direction of the net dipole moment for the molecule. If there is...

Write structures for all compounds with molecular formula C4H6O that would not be expected to exhibit infrared absorption in the 3200-3550-cm-1 and 1620-1780-cm-1 regions.

The IR spectrum of propanoic acid (Fig. 2.17) indicates that the absorption for the O-H stretch of the carboxylic acid functional group is due to a hydrogen-bonded form. Draw the structure of two...

When two substituents are on the same side of a ring skeleton, they are said to be cis, and when on opposite sides, trans (analogous to use of those terms with 1,2-disubstituted alkene isomers)....

Which would you expect to be the stronger acid? Explain your reasoning in each instance. (a) CH2ClCO2H or CHCl2CO2H (b) CCl3CO2H or CHCl2CO2H (c) CH2FCO2H or CH2BrCO2H (d) CH2FCO2H or CH2FCH2CO2H

Write equations for the acid-base reaction that would occur when each of the following compounds or solutions are mixed. In each case label the stronger acid and stronger base, and the weaker acid...

Acid HA has pKa = 20; acid HB has pKa = 10. (a) Which is the stronger acid? (b) Will an acid-base reaction with an equilibrium lying to the right take place if Na+A- s added to HB? Explain your...

Use the curved-arrow notation to write the reaction that would take place between dimethylamine (CH3)2NH and boron trifluoride. Identify the Lewis acid, Lewis base, nucleophile, and electrophile and...

First, complete and balance each of the equations below. Then, choosing among ethanol, hexane, and liquid ammonia, state which (there may be more than one) might be suitable solvents for each of...

Dimethylformamide (DMF), HCON(CH3)2, is an example of a polar aprotic solvent, aprotic meaning it has no hydrogen atoms attached to highly electronegative atoms. (a) Draw its dash structural formula,...

(a) Write the two conformations of cis-1-tert-butyl-2-methylcyclohexane. (b) Which conformer has the lowest potential energy?

Show the reactions involved for hydrogenation of all the alkenes and alkynes that would yield 2-methylbutane.

As noted in Table 3.1, the pKa of acetone, CH3COCH3, is 19.2. In Table 3.1 (a) Draw the bond-line formula of acetone and of any other contributing resonance form. (b) Predict and draw the structure...

Using the pKa values of analogous compounds in Table 3.1, predict which would be the stronger base. (a) (b) (c) (d) or (CHa),Cor O: HO or

(a) What is the index of hydrogen deficiency of 2-hexene? (b) Of methylcyclopentane? (c) Does the index of hydrogen deficiency reveal anything about the location of the double bond in the chain? (d)...

Zingiberene, a fragrant compound isolated from ginger, has the molecular formula C15H24 and is known not to contain any triple bonds. (a) What is the index of hydrogen deficiency of zingiberene? (b)...

Show by a calculation (using the formula Go = -RT ln Keq) that a free-energy difference of 7.6 kJ mol-1 between the axial and equatorial forms of methylcyclohexane at 25oC (with the equatorial form...

An alkane with the formula C6H14 can be prepared by hydrogenation of either of only two precursor alkenes having the formula C6H12. Write the structure of this alkane, give its IUPAC name, and show...

Rank the following compounds in order of increasing stability based on relative ring strain.

Write the structures of two chair conformations of 1-tert-butyl-1-methylcyclohexane. Which conformation is more stable? Explain your answer.

Write the two chair conformations of each of the following and in each part designate which conformation would be the more stable: (a) cis-1-tert-butyl-3-methylcyclohexane, (b)...

Specify the missing compounds and/or reagents in each of the following syntheses: (a) Trans-5-Methly-2-hexene 2-methlhexane (b) (c) Chemical reactions rarely yield products in such initially pure...

Write three-dimensional formulas for all of the stereoisomers of each of the following compounds. Label pairs of enantiomers and label meso compounds. (a) (b) (c) (d) (e) (f) CI Cl OH OH Cl Cl OH CI...

Albuterol, shown here, is a commonly prescribed asthma medication. For either enantiomer of albuterol, draw a three-dimensional formula using dashes and wedges for bonds that are not in the plane of...

(a) An aqueous solution of pure stereoisomer X of concentration 0.10 g mL-1 had an observed rotation of -300 in a 1.0-dm tube at 589.6 nm (the sodium D line) and 25oC. What do you calculate its [a]D...

Starting with (S)-2-bromobutane, outline syntheses of each of the following compounds: (a) (b) (c) (d) (R)-CH3CHCH2CH3 OCH2CH3 (R)-CH3CHCH2CH3 CCH3 (R)-CH3CHCH2CH3 SH (R)-CH3CHCH2CH3 SCH3

Acid-catalyzed dehydration of neopentyl alcohol, (CH3)3CCH2OH, yields 2-methyl-2- butene as the major product. Outline a mechanism showing all steps in its formation.

Using the (E)-(Z) designation [and in parts (e) and (f) the (R)-(S) designation as well] give IUPAC names for each of the following: (a) (b) (c) (d) (e) (f) Br CC Cl CH2CH2CH3 CI Br - CH2CH3 - CHs CI...

Your goal is to synthesize 4, 4-dimethyl-2-pentyne. You have a choice of beginning with any of the following reagents: Assume that you also have available sodium amide and liquid ammonia. Outline the...

When the deuterium-labeled compound shown at right is subjected to dehydrohalogenation using sodium ethoxide in ethanol, the only alkene product is 3-methylcyclohexene. (The product contains no...

Squalene, an important intermediate in the biosynthesis of steroids, has the molecular formula C30H50 and has no triple bonds. (a) What is the index of hydrogen deficiency of squalene? (b) Squalene...

How many stereoisomers are possible for 4-methyl-2-hexene, and how many fractions would you obtain if you distilled the mixture?

(a) Partial dehydrohalogenation of either (1R, 2R)-1,2-dibromo-1,2-diphenylethane or (1S, 2S)-1,2-dibromo-1,2-diphenylethane enantiomers (or a race mate of the two) produces...

(a) Using reactions studied in this chapter, show steps by which this alkyne could be converted to the seven-membered ring homolog of the product obtained in Problem 7.44(b). (b) Could the homologous...

Specify the alkene needed for synthesis of each of the following alkylboranes by hydroboration: (a) (b) (c) (d) Show the stereochemistry involved in the hydroboration of 1-methylcyclohexene.

Treating a hindered alkene such as 2-methyl-2-butene with BH3: THF leads to the for- mation of a dialkylborane instead of a trialkylborane. When 2 mol of 2-methyl-2-butene is added to 1 mol of BH3,...

Alkenes are more reactive than alkynes toward addition of electrophilic reagents (i.e., Br2, Cl2, or HCl). Yet when alkynes are treated with one molar equivalent of these same electrophilic reagents,...

(a) Write a mechanism for the following reaction. (b) What general conditions would you use to ensure a good yield of the product? (c) What general conditions would you use to carry out the reverse...

What is the dihedral angle and expected coupling constant between the labeled protons in each of the following molecules? (a) (b) Ho

Explain how you could distinguish between the following two compounds using NMR coupling constants. (These compounds are derived from glucose, by a reaction we shall study in Chapters 16 and 22.) A B...

Explain in detail how you would distinguish between the following sets of compounds using the indicated method of spectroscopy. (a) 1H NMR (b) 13C and 1H NMR (c) 13C NMR CH3 CH3 CH3 H3C

Using the method of Section 9.8A, determine the number of expected signals for the following compounds. (a) (b) (c) CH3

Deduce the structure of the compound that gives the following 1H, 13C, and IR spectra (Figs. 9.51-9.53). Assign all aspects of the 1H, and 13C spectra to the structure you propose. Use letters to...

Peroxides are often used to initiate radical chain reactions such as in the following radical halogenation. (a) Using bond dissociation energies in Table 10.1, explain why peroxides are especially...

Draw mechanism arrows to show electron movements in the Bergman cycloaromatization reaction that leads to the diradical believed responsible for the DNA-cleaving action of the antitumor agent...

In the radical chlorination of 2,2-dimethylhexane, chlorine substitution occurs much more rapidly at C5 than it does at a typical secondary carbon (e.g., C2 in butane). Consider the mechanism of...

Write a mechanism for the following reaction. (PhCO2)2, heat + CO

The halogen atom of an alkyl halide can be replaced by the hydrogen atom bonded to tin in tributyltin hydride (Bu3SnH). The process, called dehalogenation, is a radical reaction, and it can be...

Write structures for products X, Y, A, and B, showing stereochemistry. (a) (b) SO C NaOH (SN2) Pyridine (R)-2-Butanol LiCI Pyridine OH

What is wrong with the use of such names as "isopropanol" and "tert-butanol"?

Suggest an experiment using an isotopically labeled alcohol that would prove that the formation of an alkyl sulfonate does not cause cleavage at the C-O bond of the alcohol.

If one were to try to draw the simplest Lewis structure for molecular oxygen, the result might be the following However, it is known from the properties of molecular oxygen and experiments that O2...

(a) What percentages of 1-chloropropane and 2-chloropropane would you expect to obtain from the chlorination of propane if 1( and 2( hydrogen atoms were equally reactive? (b) What percentages of...

Propose mechanisms for the following reactions. (a) (b) cat. H.SO Br C3 cat. H.,SO OH

Provide a mechanism for the following reaction. HCI CI

Provide a mechanistic explanation for the following observation. MeONa MeOH MeO

When sodium ethoxide reacts with 1-(chloromethyl)oxirane (also called epichlorohy drin), labeled with 14C as shown by the asterisk in I, the major product is II. Provide a mechanistic explanation for...

Propose structures for each of the following products derived from oxirane (ethylene oxide): (a) (b) (c) (d) (e) Methyl Cellosolve cat. HA, CH1002 EtOH Ethyl Cellosolve H2O

Write structural formulas for each of the following: (a) (Z)-But-2-en-1-ol (b) (R)-Butane-1,2,4-triol (c) (1R,2R)-Cyclopentane-1,2-diol (d) 1-Ethylcyclobutanol (e) 2-Chlorohex-3-yn-1-ol (f)...

Considering A-L to represent the major products formed in each of the following reactions, provide a structure for each of A through L. If more than one product can reasonably be conceived from a...

Write structures for the products that would be formed under the conditions in Problem 11.34 if cyclopentanol had been used as the starting material. If more than one product can reasonably be...

Predict the major products of the following reactions: (a) (b) (c) cat. H2SO H,O (2) H202. NaOH (1) Hg(OAc), H2O/THF (2) NaBH4, NaOH

Provide the reagents necessary for the following syntheses. More than one step may be required. (a) (b) (c) (d) (e) (f) HO HO Br OH HO HO CI OH

Write structures for compounds A-J showing stereochemistry where appropriate. (a) What is the stereochemical relationship between A and C? (b) (c) What is the stereochemical relationship between H...

Reaction of an alcohol with thionyl chloride in the presence of a tertiary amine (e.g., pyridine) affords replacement of the OH group by Cl with inversion of configuration (Section 11.9). However, if...

Write a mechanism for the following reaction. Include formal charges and curved arrows to show the movement of electrons in all steps. MgBr OH (excess) HO 12) NH,CI, H,C

Which oxidizing or reducing agent would you use to carry out the following transformations? (a) (b) (c) (d) (e) OCH3 OCH3 OCH3 HHO HHO

Write a retrosynthetic analysis and then synthetic reactions that could be used to prepare racemic Meparfynol, a mild hypnotic (sleep-inducing compound), starting with compounds of four carbon atoms...

Predict the organic product from each of the following oxidation and reduction reactions. (a) (b) (c) (d) (e) HO HCrO4 OH HO OH 1) LAH (2) aq. H2SO4 NaBH4

(a) Although we have described the hydrogenation of an alkene as an addition reaction, organic chemists often refer to it as a "reduction." Use the method described in Section 12.2A for assigning...

Predict the major organic product from each of the following reactions. (a) (b) (c) (d) (1) CH MgBr (2) HO (1) MgBr (2) NH,CI, H20 MgBr (1 equiv.) O (1) o (2) H,O (1) CH,CHLi (excess) (2) NH,CI, H2O O

Write a retrosynthetic analysis and synthesis for the following transformation. OH Br HO HO

Consider the allylic bromination of cyclohexene labeled at C3 with 13C. Neglecting stereoisomers, what products would you expect from this reaction? NBS, ROOR heat (-13C-labeled position)

Diels-Alder reactions also take place with triple-bonded (acetylenic) dienophiles. Which diene and which dienophile would you use to prepare the following? CO2Me CO2Me

What oxidation product would result from each of the following reactions? (a) (b) (c) (1) DMSO, (COC)2. -60 C (2) Et,N OH (1) DMSO, (COCI2,-60 C (2) EtyN (1) DMSO, (COC)2 2 equiv., -60 C (2) EtN...

If we were to write a chemical equation for the reaction of (2E,4E )-hexa-2,4-diene and methyl propenoate we might write it as shown below. (a) Explain why we can predict that the endo and exo...

Provide the reagents needed to synthesize 1,3-butadiene starting from (a) 1,4-Dibromobutane (b) (c) (d) (e) (f) (g) HO Cl CI

(a) Draw resonance structures for the carbocation that could be formed from (E)-2-butenyl trifluoromethanesulfonate. (b) One of the resonance structures for this carbocation should be a more...

Write the important resonance structures for each of the following: (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) CH2 CH-Br NO2

Treating either 1-chloro-3-methyl-2-butene or 3-chloro-3-methyl-1-butene with Ag2O in water gives (in addition to AgCl) the following mixture of alcohol products. (a) Write a mechanism that accounts...

Rank the following dienes in order of increasing reactivity in a Diels-Alder reaction (1 = least reactive, 4 = most reactive). Briefly explain your ranking.

Draw the structure of the product from the following reaction (formed during a synthesis of one of the endiandric acids by K. C. Nicolaou): MeO2C osi(t-Bu)Phe toluene, 110C

(a) Which other compounds in Section 13.5 are conjugated dienes? (b) Which other compounds are isolated dienes? (c) Which compound is an isolated enyne?

Propose structures for D, E, and F. C n peakoer0 D UV:max 230 nm H2. Pt IR: 3300 cm1, sharp UV: max 230 nm IR: -3300 cm, sharp UV: max 200 nm

Predict the products of the following reactions. (a) (b) HCI DCI (D-2H)

Provide a name for each of the following compounds. (a) (b) (c) (d) OH CI

The rings below are joined by a double bond that undergoes cis-trans isomerization much more readily than the bond of a typical alkene. Provide an explanation.

Although Hückel's rule (Section 14.7) strictly applies only to monocyclic compounds, it does appear to have application to certain bicyclic compounds, if one assumes use of resonance...

A compound (N) with the molecular formula C9H10O reacts with osmium tetroxide. The 1H NMR spectrum of N is shown in Fig. 14.31 and the IR spectrum of N is shown in Fig. 14.32. Propose a structure for...

The IR and 1H NMR spectra of compound Y (C9H12O) are given in Fig. 14.34. Propose a structure for Y.

The final product of this sequence, D, is an orange, crystalline solid melting at 174(C and having molecular weight 186: In its 1H and 13C NMR spectra, product D shows only one kind of hydrogen and...

When 1,3,5-cycloheptatriene reacts with one molar equivalent of bromine at 0 8C, it undergoes 1,6 addition. (a) Write the structure of this product.

In 1967 R. Breslow (of Columbia University) and co-workers showed that adding SbCl5 to a solution of 3-chlorocyclopropene in CH2Cl2 caused the precipitation of a white solid with the composition C3H3...

Write mechanisms for the reactions whereby HBr adds to 1-phenylpropene (a) in the presence of peroxides and (b) in the absence of peroxides. In each case account for the regiochemistry of the...

One ring of phenyl benzoate undergoes electrophilic aromatic substitution much more readily than the other. (a) Which one is it? (b) Explain your answer.

The addition of a hydrogen halide (hydrogen bromide or hydrogen chloride) to 1-phenyl 1,3-butadiene produces (only) 1-phenyl- 3-halo-1-butene. (a) Write a mechanism that accounts for the formation of...

Many polycyclic aromatic compounds have been synthesized by a cyclization reaction known as the Bradsher reaction or aromatic cyclodehydration. This method can be illustrated by the following...