Reaction review. Without consulting the Reaction Road Map on p. 721, suggest a reagent to convert benzene into each of the following compounds. C(CH3)3 NO2 CH3 CH,CH; SO,H Br (e) (f) (h)

The rate of nitration of (chloromethyl)benzene, shown below is 0.71 relative to the rate of nitration of benzene (=1). The (chloromethyl)nitrobenzene product mixture that results contains 32% ortho,...

Specify whether you expect the benzene rings in the following compounds to be activated or deactivated. NO2 OH (a) (b) 'NO2 CH3 COOH NH2 SO-H HO C(CH3)3 (d) (e) (f) 'NO2 H3

Rank the compounds in each of the following groups in order of decreasing reactivity toward electrophilic aromatic substitution. Explain your answers. CH3 () (b) H; H3

Write the structure(s) of the major product(s) that you expect from each of the following electrophilic aromatic substitutions. (a) Nitration of methylbenzene (toluene); (b) sulfonation of...

Draw appropriate resonance forms to explain the activating ortho, para-directing character of the phenyl substituent in biphenyl Biphenyl

(a) When a mixture containing one mole each of the three dimethylbenzenes (o-, m-, and p-xylene) is treated with one mole of chlorine in the presence of a Lewis acid catalyst, one of the three...

Describe the experimental conditions that would be best suited for the efficient synthesis of each of the following compounds from the corresponding nonhalogenated ketone. (a) (b) (c) Br O CH;CHCCH3

Formulate a mechanism for the acid-catalyzed hydrolysis of the pyrrolidine enamine of cyclohexanone (shown in the margin). + H,O H+ 'N' H

When 2-methylcyclopentanone is treated with the bulky base triphenylmethyllithium under the two sets of conditions shown, the two possible enolates are generated in differing ratios. Why is this so?...

Name or draw the structure of each of the following compounds. (a) (b) (c) (d) (e) (f) (e) (Z )-2-Acetyl-2-butenal (f) trans-3-Chlorocyclobutanecarbaldehyde (CH3),CHCCH(CH;)2

For each of the following molecules, propose two methods of synthesis from the different precursor molecules indicated. (a) CH 3 CH=CHCH 2 CH(CH 3 ) 2 from (1) an aldehyde and (2) a different...

Give the product(s) of reaction of hexanal with each of the following reagents. (a) HOCH 2 CH 2 OH, H + (b) LiAlH 4 , then H + , H 2 O (c) NH 2 OH, H + (d) NH 2 NH 2 , KOH, heat (e) (CH 3 ) 2 CHCH 2...

When 1,4- and 1,5-dicarboxylic acids, such as butanedioic (succinic) acid (Section 19-8), are treated with SOCl2 or PBr3 in attempted preparations of the diacyl halides, the corresponding cyclic...

Reaction review II. Without consulting the Reaction Road Map on p. 915, suggest reagents to convert hexanoic acid into each of the following compounds: (a) 1-hexanol; (b) hexanoic anhydride; (c)...

(a) Write a mechanism for the esterification of propanoic acid with 18 O-labeled ethanol. Show clearly the fate of the 18 O label. (b) Acid-catalyzed hydrolysis of an unlabeled ester with 18...

Interpret the labeled peaks in the mass spectrum of 2-methylhexanoic acid (MS-H). 74 100 MS CH;CH,CH,CH,CHCOOH 50 CH3 87 45 130 20 40 60 80 100 120 140 160 mlz MS-H Relative abundance

Give the product of reaction of cyclopentanecarboxylic acid with each of the reagents in Problem 40. Data From problem 40 (a) SOCl2 (b) PBr3 (c) CH3CH2COBr 1 pyridine (d) (CH3)2CHOH 1 HCl (e) (f)...

When methyl ketones are treated with a halogen in the presence of base, the three hydrogen atoms on the methyl carbon are replaced to give a CX 3 -substituted ketone. This product is not stable under...

Show how the Hell-Volhard-Zelinsky reaction might be used in the synthesis of each of the following compounds, beginning in each case with a simple monocarboxylic acid. Write detailed mechanisms for...

The Hell-Volhard-Zelinsky reaction produces only bromocarboxylic acids. However, modifi ed procedures have been developed to convert acyl chlorides into a-chloro- and a-bromoacyl chlorides by...

Propose a short synthesis of 2-butynoic acid, CH3CqCCO2H, starting from propyne.

What is the IUPAC name of the compound shown? (a) (E )-3-Methyl-2-hexenoic acid (b) (Z )-3-Methyl-2-hexenoic acid (c) (E )-3-Methyl-3-hexenoic acid (d) (Z )-3-Methyl-3-hexenoic acid H;C CO.H C=C...

Illustrate by means of appropriate structures (including all relevant resonance forms) the initial species formed by (a) breaking the weakest C H bond in 1-butene; (b) treating 4-methylcyclohexene...

Rank primary, secondary, tertiary, and allylic radicals in order of decreasing stability. Do the same for the corresponding carbocations. Do the results indicate something about the relative ability...

Formulate a mechanism for the formation of acetamide, from methyl acetate and ammonia. CH;CNH2

Show how you might synthesize chlorpheniramine, a powerful antihistamine used in several decongestants, from each of carboxylic acids A and B. Use a different carboxylic amide in each synthesis. N-...

Give the structure of the product of the fi rst of the following reactions, and then propose a scheme that will ultimately convert it into the methyl-substituted ketone at the end of the scheme. This...

Give structures that correspond to each of the following names. (a) N,N-Dimethyl-3-cyclohexenamine; (b) N-ethyl-2-phenylethylamine; (c) 2-aminoethanol; (d) m-chloroaniline.

Give the structures of all possible nitrogen-containing organic products that might be expected to form on reaction of chloroethane with ammonia.

Suggest the best syntheses that you can for the following amines, beginning each with any organic compounds that do not contain nitrogen. (a) Butanamine; (b) N-methylbutanamine; (c)...

Give the expected product(s) of each of the following reactions. (a) (b) H;C NH2 CH NaNO,, HCI, H,O

2-Aminobenzoic (anthranilic) acid is prepared from 1,2-benzenedicarboxylic anhydride (phthalic anhydride) by using the two reactions shown here. Explain these processes mechanistically. 1. NaOH, Br,...

Upon completing a synthetic procedure, every chemist is faced with the job of cleaning glassware. Because the compounds present may be dangerous in some way or have unpleasant properties, a little...

Spectroscopic data for two carboxylic acid derivatives are given in NMR-A and NMR-B. Identify these compounds, which may contain C, H, O, N, Cl, and Br but no other elements. (a) 1 H NMR: spectrum A...

One of the following four amines is tertiary. Which one? (a) Propanamine; (b) N-methylethanamine; (c) N,N-dimethylmethanamine; (d) N-methylpropanamine.

Identify the best conditions for the following transformation: (a) H 2 , metal catalyst; (b) excess CH 3 I, K 2 CO 3 ; (c) Br 2 , NaOH, H 2 O; (d) LiAlH 4 , ether; (e) CH 2 N 2 , ether. CH;CH,CNH,...

Give the expected major product(s) of each of the following reactions. (a) (b) CH,CH3 CI.(1 equivalent), hv

Formulate a mechanism for the reaction described in Problem 35(b). Problem 35(b) (b) NBS (1 equivalent), hv

The inversion of nitrogen requires a change of hybridization. (a) What is the approximate energy difference between pyramidal nitrogen (sp 3 hybridized) and trigonal planar nitrogen (sp 2 hybridized)...

Tropinone (Problem 48) was first synthesized by Sir Robert Robinson, in 1917, by the following reaction. Show a mechanism for this transformation. Problem 48 H3C H H3C H,C + CH;NH, + C=0 H,C. H;C H

Propose syntheses of each of the following compounds, beginning in each case with ethylbenzene. (a) (1-Chloroethyl)benzene; (b) 2-phenylpropanoic acid; (c) 2-phenylethanol; (d)...

Predict the order of relative stability of the three benzylic cations derived from chloromethylbenzene (benzyl chloride), 1-(chloromethyl)-4-methoxybenzene (4-methoxybenzyl chloride), and...

By drawing appropriate resonance structures, illustrate why halogen atom attachment at the para position of phenylmethyl (benzyl) radical is unfavored compared with attachment at the benzylic...

Triphenylmethyl radical, (C 6 H 5 ) 3 C, is stable at room temperature in dilute solution in an inert solvent, and salts of triphenylmethyl cation, (C 6 H 5 ) 3 C + , can be isolated as stable...

Illustrate a method for achieving the transformation shown in the margin, using combinations of reactions presented in Sections 21-8 and 21-9. Section 21-8 Section 21-9 Hofmann Elimination of...

Tertiary amines add readily as nucleophiles to carbonyl compounds, but, lacking a hydrogen on nitrogen, they cannot deprotonate to give a stable product. Instead, their addition gives an intermediate...

Tertiary amines undergo reversible conjugate addition to a,b-unsaturated ketones (see Chapter 18). This process is the basis for the Baylis-Hillman reaction, which is catalyzed by tertiary amines,...

Reductive amination of excess formaldehyde with a primary amine leads to the formation of a dimethylated tertiary amine as the product (see the following example). Propose an explanation. NABH,CN,...

From the following information, deduce the structure of coniine, a toxic amine found in poison hemlock, which, deservedly, has a very bad reputation. IR: 3330 cm -1 . 1 H NMR: = 0.91 (t, J = 7 Hz, 3...

Pethidine, the active ingredient in the narcotic analgesic Demerol, was subjected to two successive exhaustive methylations with Hofmann eliminations, and then ozonolysis, with the following results:...

Skytanthine is a monoterpene alkaloid with the following properties. Analysis: C 11 H 21 N. 1 H NMR: two CH 3 doublets (J = 7 Hz) at = 1.20 and 1.33 ppm; one CH 3 singlet at = 2.32 ppm; other...

Many alkaloids are synthesized in nature from a precursor molecule called norlaudanosoline, which in turn appears to be derived from the condensation of amine A with aldehyde B. Formulate a mechanism...

Quaternary ammonium salts catalyze reactions between species dissolved in two immiscible phases, a phenomenon called phase-transfer catalysis. For example, heating a mixture of 1-chlorooctane...

Which of the following formulas best represents diazomethane? (a) (b) (c) (d) (e) CH,=N=N:

The specific enthalpy of liquid n-hexane at 1 atm varies linearly with temperature and equals 25.8 kJ/kg at 30C and 129.8 kJ/kg at 50C. (a) Determine the equation that relates H(kJ/kg) to T(C) and...

-Dicarbonyl compounds condense with aldehydes and ketones that do not undergo self-aldol reaction. The products are ,-unsaturated dicarbonyl compounds, and the process goes by the colorful name of...

Some of the most important building blocks for synthesis are very simple molecules. Although cyclopentanone and cyclohexanone are readily available commercially, an understanding of how they can be...

When acid A (margin) is heated to 230C, CO 2 and H 2 O are evolved and a new compound is formed. Which one? (a) (b) HO 2 CCH 2 CH 2 CH 2 CH 3 (c) (d) CH 3 CH 2 CH(CO 2 H) 2 (e) CO,H HO,C(CH2),CH CO,H

A radioactive isotope has a half-life of 56.6 days. What fraction of the isotope remains after 449 days? a. 3.2 10 6 b. 1.00 c. 0.92 d. 4.1 10 3 e. 0.83

The penicillins are a class of antibiotics containing two heterocyclic rings that interfere with the construction of cell walls by bacteria (Chemical Highlight 20-2). The interference results from...

Propose reasonable mechanisms for the following transformations. (a) (b) (c) 1. SnCl, (a Lewis acid), CH,CI, 2. H', . H,OH

Chelidonic acid, a 4-oxacyclohexanone (common name, g-pyrone), is found in a number of plants and is synthesized from acetone and diethyl ethanedioate. Formulate a mechanism for this transformation.

Write balanced equations for each of the following nuclear reactions: (a) 238 92 U(n, ) 239 92 U, (b) 14 7 N(p, ) 11 6 C, (c) 18 8 O(n, ) 19 9 F

A solution prepared by mixing 10 mL of a 0.10 M solution of the R enantiomer and 30 mL of a 0.10 M solution of the S enantiomer was found to have an observed specific rotation of +480. What is the...

Write the structure and give the IUPAC name for an alkane with formula C 6 H 14 that has only primary and secondary carbon atoms.

Give the (R,S ) designation for each compound given as an answer to Practice Problem 5.29. Practice Problem 5.29 (a) 1-Bromo-2-chlorocyclohexane (c) 1-Bromo-4-chlorocyclohexane (b)...

What is the index of hydrogen deficiency for (a) C 7 H 10 O 2 (b) C 5 H 4 N 4 ?

How many signals would you expect to obtain in the 1 H NMR spectrum of undecadeuteriocyclohexane at room temperature?

The 1 H NMR spectrum of cyclooctatetraene consists of a single line located at 5.78. What does the location of this signal suggest about electron delocalization in cyclooctatetraene?

Compound E has the spectral features given below. What is its structure? MS (m/z): M 202 IR (cm -1 ): 30303080, 2150 (very weak), 1600, 1490, 760, and 690 1 H NMR (): narrow multiplet centered at...

A gas turbine power plant receives a shipment of hydrocarbon fuel whose composition is uncertain but may be represented by the expression C x H y . The fuel is burned with excess air. An analysis of...

A fuel cell is an electrochemical device that reacts hydrogen with oxygen from the air to produce water and DC electricity. A proposed application is replacement of the gasoline-fueled internal...

Where would you expect to find the labeled oxygen if you carried out an acid-catalyzed hydrolysis of methyl benzoate in 18 O-labeled water? Write a detailed mechanism to support your answer.

Write detailed mechanisms for the acidic and basic hydrolysis of propanamide.

(a) What products would you expect to be formed when each of the amines in the preceding problem reacts with benzenesulfonyl chloride and excess aqueous potassium hydroxide? (b) What would you...

Give the structures of 4-isopropyloctane and 5-tert-butyldecane.

Propose a mechanism for each cyanohydrin synthesis just shown.

Propose mechanisms for the three imine-forming reactions just shown.

Show how C3 of fructose can epimerize under basic conditions.

Is gentiobiose a reducing sugar? Does it mutarotate? Explain your reasoning.

Which of the sugars mentioned in Problems 23-59, 23-60, and 23-61 are reducing sugars? Which ones would undergo mutarotation?

The latent heat of fusion for water is 33.5 10 4 J/kg, while the latent heat of vaporization is 22.6 10 5 J/kg. What mass m of water must be frozen in order to release the amount of heat that 1.00...

The equilibrium 2NO(g) + Cl 2 (g) 2NOCl(g) is established at 500K. An equilibrium mixture of the three gases has partial pressures of 0.095 atm, 0.171 atm, and 0.28 atm for NO, Cl 2 , and NOCl,...

A gaseous fuel containing methane and ethane is burned with excess air. The fuel enters the furnace at 25C and 1 atm, and the air enters at 200C and 1 atm. The stack gas leaves the furnace at 800C...

Which of the following compounds is likely to be more soluble in water: C 4 H 9 OH or C 4 H 9 SH? Explain.

A sample of air at 21C has a relative humidity of 55%. At what temperature will water begin to condense as dew?

(a) If 3 and 4 are enantiomers, what are 1 and 4? (b) What are 2 and 3, and 2 and 4? (c) Would you expect 1 and 3 to have the same melting point? (d) The same boiling point? (e) The same vapor...

Classify each of the following organic halides as primary, secondary, tertiary, alkenyl, or aryl. a. b. c. d. e. Br

An evaporator has R-410a at 20C and quality 20% flowing in, with the exit flow being saturated vapor at 20C. Knowing that there is no work, find the specific heat transfer.

A flow of 5 kg/s water at 100 kPa, 20C should be delivered as steam at 1000 kPa, 350C to some application. We have a heat source at constant 500C. If the process should be reversible, how much heat...

Chapter 9 covered a synthesis of alkynes by a double dehydrohalogenation of dihalides. A student tried to convert trans-2,5-dimethylhex-3-ene to 2,5-dimethylhex-3-yne by adding bromine across the...

Draw structures of the following derivatives. (a) The 2,4-dinitrophenylhydrazone of benzaldehyde (b) The semicarbazone of cyclobutanone (c) Cyclopropanone oxime (d) The ethylene acetal of hexan-3-one...

Propose mechanisms for the following reactions. a. b. c. d. e. f. CH,OH, H* CH;O OCH3 Ph-C-H Ph

Show how you would accomplish the following syntheses efficiently (you may use any necessary reagents). (a) Trans-l-bromobut-2-ene trans-pent-3-enoic acid (two ways) (b) Hex-3-ene , propanoic acid...

Two of the methods for converting alkyl halides to carboxylic acids are covered in Sections 20-8B and 20-8C. One is formation of a Grignard reagent followed by addition of carbon dioxide and then...

(A true story) The manager of an organic chemistry stockroom prepared unknowns for a Ketones and Aldehydes experiment by placing two drops of the liquid unknowns in test tubes and storing the test...

The relative acidities of carboxylic acids (and, by inference, the stabilities of their carboxylate ions) have been used to compare the electron-donating and electron-withdrawing properties of...

Explain the following. a. Ammonia is a gas at room temperature. b. The melting points of sodium chloride and iodine are very different. c. Metals generally are good conductors of electricity. d....

a. Define the terms: proton, neutron and electron. b. An atom X has a proton number of 19 and relative atomic mass of 39. (i) How many electrons, protons and neutrons are there in an atom of X? (ii)...