For each of the following compounds, 1. Give the IUPAC name. 2. Give the common name (if possible). 3. Classify the compound as a methyl, primary, secondary, or tertiary halide. (a) (CH3)2CHCH2Cl (b)...
(a) If a hydrocarbon has nine carbon atoms, three double bonds, and one ring, how many hydrogen atoms must it have? (b) Calculate the number of elements of unsaturation implied by the molecular...
Determine the number of elements of unsaturation in the molecular formula C4H6. Give all nine possible structures having this formula. Remember that A double bond = one element of unsaturation A ring...
Show how you would prepare cyclopentene from each compound. (a) Trans-1, 2-dibromocyclopentane (b) Cyclopentanol (c) Cyclopentyl bromide (d) Cyclopentane (not by dehydrogenation)
Predict the products of the following reactions. When more than one product is expected, predict which will be the major product. (a) (b) (c) (d) OH H2SO4 heat H3PO4 heat BrNaocH, CH CH H,SO4 heat OH
Limonene is one of the compounds that give lemons their tangy odor. Show the structures of the products expected when limonene reacts with an excess of each of these reagents. (a) Borane in...
Show the reagents and intermediates involved in the other order of synthesis of dec-3-yne, by adding the ethyl group first and the hexyl group last.
Write balanced equations for the three preceding reactions?
The following reaction involves a starting material with a double bond and a hydroxyl group, yet its mechanism resembles a pinacol rearrangement. Propose a mechanism, and point out the part of your...
Propose a mechanism for each reaction. (a) (b) (c) (d) OH H2SO heat OCH + CH3OH H20 CH2OH H2So4 heat CH OCH2CH CH CH,CH2OH (a minor product)
(a) The reaction of butan-2-ol with concentrated aqueous HBr goes with partial racemization, giving more inversion than retention of configuration. Propose a mechanism that accounts for racemization...
An inexperienced graduate student was making some 4-hydroxybutanoic acid. He obtained an excellent yield of a different compound, whose 13C NMR spectrum is shown here. (a) Propose a structure for...
The NMR spectrum of toluene (methylbenzene) was shown in Figure 13-11. (a) How many different kinds of protons are there in toluene? (b) Explain why the aromatic region around 7.2 is broad, with...
Propose a complete mechanism for the reaction of cyclopentene oxide with sodium methoxide in methanol.
Give the expected products of the following reactions. Include a protonation step where necessary. (a) 2, 2-dimethyloxirane + isopropylmagnesium bromide (b) Propylene oxide + n-butyllithium (c)...
Show how you might synthesize the following compounds starting with alkyl, alkenyl, or aryl halides containing four carbon atoms or fewer. (a) 3-phenylprop-1-ene (b) 5-methylhex-2-ene c) dec-5-ene
What dienes and dienophiles would react to give the following Diels-Alder products? (a) (b) (c) (d) (e) (f) C-CH CH3O CN C OCH C--OCH, CN CN CH,O CN H O
Azulene is a deep-blue hydrocarbon with resonance energy of 205 kJ mol (49 kcal mol), Azulene has ten pi electrons, so it might be considered as one large aromatic ring. Its electrostatic potential...
The diene lactone shown in part (a) has one electron-donating group (- OR) and one electron-withdrawing group (C = O). This diene lactone is sufficiently electron-rich to serve as the diene in a...
Propose products (if any) and mechanisms for the following ClCl3 reactions: (a) Chlorocyclohexane with benzene (b) Methyl chloride with anisole (c) 3-chloro-2, 2-dimethylbutane with isopropylbenzene
Styrene (vinylbenzene) undergoes electrophilic aromatic substitution much faster than benzene, and the products are found to be primarily ortho- and para-substituted styrenes. Use resonance forms of...
Draw all the resonance forms for the sigma complexes corresponding to bromination of aniline at the ortho, meta, and para positions.
Give the IUPAC name and (if possible) a common name for each compound. (a) (b) (c) (d) OH CH CH CH, C CH,CH Ph CH.-CH-CH,--CHO OCH CHO CH CH
Two structures of the sugar fructose are shown next. The cyclic structure predominates in aqueous solution. (a) Number the carbon atoms in the cyclic structure. What is the functional group at C2 in...
The UV spectrum of an unknown compound shows values of λmax at 225 nm (ε = 10,000) and at 318 nm 1e = 402. The mass spectrum shows a molecular ion at m/z 96 and a prominent...
The alkaloid coniine has been isolated from hemlock and purified. Its molecular formula is C8H17N. Treatment of coniine with excess methyl iodide, followed by silver oxide and heating, gives the pure...
The following drugs are synthesized using the methods in this chapter and in previous chapters. Devise a synthesis for each, starting with any compounds containing no more than six carbon atoms. (a)...
Section 17-12 showed how nucleophilic aromatic substitution can give aryl amines if there is a strong electron-withdrawing group ortho or para to the site of substitution. Consider the following...
Ketones and aldehydes react with primary amines to give imines. They react with secondary amines to give enamines (vinyl amines). (a) For review, propose a mechanism for the following formation of an...
Propose a mechanism for the reaction of benzoic acid with oxalyl chloride. This mechanism begins like the thionyl chloride reaction, to give a reactive mixed anhydride. Nucleophilic acyl substitution...
Show how you would synthesize the following compounds from the appropriate carboxylic acids or acid derivatives. (a) (b) (c) CH,CH,OH CH,CHO CH,OH
Rank the compounds in each set in order of increasing acid strength. (a) CH3CH2COOH CH3CHBrCOOH CH3CBr2COOH (b) CH3CH2CH2CHBrCOOH CH3CH2CHBrCH2COOH CH3CHBrCH2CH2COOH (c) CH CHCOOH CH,CHCOOH CH,CH...
(a) Propose a mechanism for the acid-catalyzed reaction of salicylic acid with acetic anhydride. (b) Explain why a single drop of sulfuric acid dramatically increases the reaction rate.
Suggest the most appropriate reagent for each synthesis, and explain your choice. (a) (b) (c) (d) O-C CH3 COOH COOH COOH CH CH CH2OH C NHPh
Propose a mechanism for the reaction of methyl isocyanate with 1-naphthol to give Sevin insecticide.
Predict the products of the following reactions. (a) Phenol + acetic anhydride (b) Phenol + acetic formic anhydride (c) Aniline + phthalic anhydride (d) Anisole + succinic anhydride and aluminum...
Predict the products of saponification of the following esters. (a) (b) (c) (d) CH CHC-OCH-CH
Propose mechanisms for the following reactions. (a) (b) (c) (d) (e) (f) (g) Does this reaction proceed with retention, inversion, or racemization of the asymmetric carbon atom? Ph-CCI(CH3)2CHOHPhC...
Predict the products of the following reactions. (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) (k) (l) OH CI CH NH2 Ph-C-CI+ NH2 0 + (D LiAIH (2) H20 (2) H,0 -. O (I) excess PhMgBr (2) H,o ( CH Mgl (2)...
Predict the products of aldol condensation, followed by dehydration, of the following ketones and aldehydes. (a) Butyraldehyde (b) Acetophenone (c) Cyclohexanone
1. Rank the following compounds in order of increasing acidity. 2. Indicate which compounds would be more than 99% deprotonated by a solution of sodium ethoxide in ethanol. () (b) () (d) () (f)...
Propose a mechanism for the following reaction. Show the structure of the compound that results from hydrolysis and decarboxylation of the product. CHO + CH2(COOCH2CH3)2 hydrolysis, decarboxylation...
Propose mechanisms for the reactions shown in Problems 22-62 parts (a) and (b) and 22-63 parts (a) and (b). In problem 22-62 (a) (b) In problem 22-63 (a) (b) CH3 TOH CH CH2-C-H CH CH OCH3 CH3OH CH3...
Biochemists studying the structure of collagen (a fibrous protein in connective tissue) found cross-links containing ,-unsaturated aldehydes between protein chains. Show the structures of the side...
The following compounds can be synthesized by aldol condensations, followed by further reactions. (In each case, work backward from the target molecule to an aldol product, and show what compounds...
Propose mechanisms for the following reactions. (a) (b) (c) (d) CHPh OCH3 Ph + Ph COCH OCH OCH OH ) MVK (2) Ho N:
(A true story.) Chemistry lab students added an excess of ethylmagnesium bromide to methyl furoate, expecting the Grignard reagent to add twice and form the tertiary alcohol. After water workup, they...
A reaction involved in the metabolism of sugars is the splitting of fructose-1,6-diphosphate to give glyceraldehyde-3-phosphate and dihydroxyacetone phosphate. In the living system, this retro-aldol...
Give complete mechanisms for the formation of Z-Ala, its activation by ethyl chloroformate, and the coupling with valine.
(a) The isoelectric point (pI) of phenylalanine is pH 5.5. Draw the structure of the major form of phenylalanine at pH values of 1, 5.5, and 11. (b) The isoelectric point of histidine is pH 7.6. Draw...
Give equations to show the reactions of sodium stearate with (a) Ca2+ (b) Mg2+ (c) Fe3+
Several commercial laundry soaps contain water-softening agents, usually sodium carbonate (Na2CO3) or sodium phosphate (Na3PO4 or Na2HPO4). Explain how these water-softening agents allow soaps to be...
Draw a chemical structure for diacetyl (2,3-butanedione), a diketone with the C4H6O2 chemical formula. Diacetyl is used as a flavoring for microwave popcorn, but has been under scrutiny of late as a...
Draw all possible staggered and eclipsed conformations of 1-bromo-2-chloroethane (see the following balland- stick model), using Newman projections. Underneath each structure, draw the corresponding...
Draw the formula for the preferred conformation of a. Cis-1,4-dimethylcyclohexane b. Trans-1-isopropyl-3-methylcyclohexane c. 1,1-diethylcyclopentane d. Ethylcyclohexane
Which will be more stable, cis- or trans-1,4-di-tert-butylcyclohexane? Explain your answer by drawing conformational structures for each compound.
How many monobromination products can be obtained from each of the following polycyclic alkanes? C. b. a. O" CH3 d. CH,CH CH,CH, e.
Write all of the steps in the free-radical chain mechanism for the monochlorination of ethane. What trace by-products would you expect to be formed as a consequence of the chain terminating steps?...
Draw the Fischer projection formulas for the remaining stereoisomers of 2-bromo-3-chlorobutane shown in Figure 5.12. Figure 5.12 mirror irror CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 enantiomers
Which of the following substances contain stereogenic centers? a. 2,2-dibromobutane b. 3-methylcyclopentene c. 1,2-difluoropropane d. 2,3-dimethylheptane e. methylcyclobutane f. 1-deuteriopropanol...
Mature crocodiles secrete from their skin glands the compound with the following structure. This compound is thought to be a communication pheromone for nesting or mating. a. How many stereogenic...
Explain why your answers to parts c, d, and e of Problem 7.38 are consistent with the pKa's of the starting acids and product acids. Problem 7.38 a. b. c. a-O-OH + NaOH Cl + NaOH CH CH CHCH SH+ NaOH
On page 299, "A Word About . . . Green Chemistry and Ibuprofen: A Case Study" showed how efficiently ibuprofen can be prepared on a large scale. Another non steroidal, anti inflammatory drug (NSAID)...
Give an example of each of the following: a. A primary amine b. A cyclic tertiary amine c. A secondary aromatic amine d. A quaternary ammonium salt e. An aryldiazonium salt f. An azo compound g. A...
Complete equations for the following reactions: a. CH3CH2CH2CH2Br + 2 NH3 b. CH3CH2I + 2(CH3CH2)2NH c. (CH3)3N + CH3I d. CH-Br CH,CH,CH2NH2 +
Draw the product of the reaction of nicotinic acid with a. Catalytic sulfuric acid and excess methanol b. LiAlH4, then H3O1 c. H2 (excess) with Pt
Suggest a synthesis of Olestra (see "A Word About Fat Substitutes from Carbohydrates," on page 482) starting from sucrose and lauric acid.
Give the IUPAC names for each of the following compounds: (a) (CH3CH2)2C==CHCH3 (b) (CH3CH2)2C==C(CH2CH3)2 (c) (CH3)3CCH==CCl2 (d) (e) (f) (g) , ,
Write the structure of the major organic product formed in the reaction of 1-pentene with each of the following: (a) Hydrogen chloride (b) Hydrogen bromide (c) Hydrogen bromide in the presence of...
Reaction of 3,3-dimethyl-1-butene with hydrogen iodide yields two compounds A and B, each having the molecular formula C6H13I, in the ratio A:B = 90:10. Compound A, on being heated with potassium...
In 1996, it was determined that the absolute configuration of (-) bromochlorofluoromethane is R. Which of the following is (are) (-)-BrClFCH? Br Br Br
Multifidene is a sperm cell-attracting substance released by the female of a species of brown algae (Cutleria multifida). The constitution of multifidene is (a) How many stereoisomers are represented...
Predict the major organic product of each of the following reactions: (a) Ethyl bromide and potassium cyclohexanolate (b) sec-Butyl bromide solvolysis in methanol (c) sec-Butyl bromide solvolysis in...
Identify the relationship in each of the following pairs. Do the drawings represent constitutional isomers or stereoisomers, or are they just different ways of drawing the same compound? If they are...
Write the organic products of each of the following reactions. If two stereoisomers are formed, show both. Label all stereogenic centers R or S as appropriate. (a) 1-Butene and hydrogen iodide (b)...
Each of the reactions shown involves nucleophilic substitution. The product of reaction (a) is an isomer of the product of reaction (b). What kind of isomer? By what mechanism does nucleophilic...
In each of the following indicate which reaction will occur faster. Explain your reasoning. (a) CH3CH2CH2CH2Br or CH3CH2CH2CH2I with sodium cyanide in dimethyl sulfoxide (b) 1-Chloro-2-methylbutane...
Use frontier orbital analysis to decide whether the dimerization of 1,3-butadiene shown here is allowed or forbidden. 2H2C-CH-CH-CH2- s heat
Using numerical locants and the names in Table 11.1 as a guide, give an acceptable IUPAC name for each of the following compounds: (a) Estragole (principal (b) Diosphenol (used in(c m-Xylidine (used...
Evaluate each of the following processes applied to cyclooctatetraene, and decide whether the species formed is aromatic or not. (a) Addition of one more electron, to give C8H8 (b) Addition of two...
Suggest an efficient synthesis of m-nitrobenzoic acid from toluene.
Using benzene and any necessary organic or inorganic reagents, suggest efficient syntheses of Neopentylbenzene, C6H5CH2C(CH3)3
Infrared spectroscopy is an inherently "faster" method than NMR, and an IR spectrum is a superposition of the spectra of the various conformations, rather than an average of them. When...
Outline practical syntheses of each of the following compounds from alcohols containing no more than four carbon atoms and any necessary organic or inorganic reagents. In many cases the desired...
Give the structure of the expected product of the following reaction: CH2 0 CH3NH2
Which is the stronger acid in each of the following pairs? (a) (b) (c) CH3CH2CO2H CH3CHCO2H CH3CCO2H or CH2 CHCO2H CH3CH2CH CO2H or CH3SCH2CO2H
The compound having the structure shown was heated with dilute sulfuric acid to give a product having the molecular formula C5H12O3 in 63-71% yield. Propose a reasonable structure for this product....
Describe procedures for preparing each of the following compounds, using ethanol as the source of all their carbon atoms. Once you prepare a compound, you need not repeat its synthesis in a...
Show by writing the appropriate sequence of equations how you could carry out each of the following transformations: (a) 1-Butanol to 1-pentanamine (b) tert-Butyl chloride to...
chemistry handbook lists Kb for quinine as 1 10-6. What is pKb for quinine? What are the values of Ka and pKa for the conjugate acid of quinine?
Piperidine, the amine reactant in parts (b) and (c) of the preceding problem, reacts with 1-bromonaphthalene on heating at 230C to give a single product, compound A (C15H17N), as a noncrystallizable...
Suggest a reasonable mechanism for each of the following reactions: (a) (b) (c) (d) I. excess NaNH, NH C,H,Br CH(COOCH,CH)OoCH,CH,) l excess NH 2.,0 CH2CH2CH2CH2COCH2CH3 NaNH Cl COOCH CH CH3 CH3...
Classify the following as qualitative or quantitative statements, giving your reasons. (a) The sun is approximately 93 million mi from Earth. (b) Leonardo da Vinci was a better painter than...
The following procedure was used to determine the volume of a flask. The flask was weighed dry and then filled with water. If the masses of the empty flask and filled flask were 56.12 g and 87.39 g,...
Identify the elements represented by the following symbols and give the number of protons and neutrons in each case a. b. c. d. e. f. 104 47 182 X.
Predict the formula and name of a binary compound formed from the following elements: (a) Na and H, (b) B and O, (c) Na and S, (d) Al and F, (e) F and O,
How many molecules of ethane (C2H6) are present in 0.334 g of C2H6?
The atomic mass of element X is 33.42 amu. A 27.22-g sample of X combines with 84.10 g of another element Y to form a compound XY. Calculate the atomic mass of Y.
Predict the outcome of the reactions represented by the following equations by using the activity series, and balance the equations. (a) Cu(s) + HCl(aq) (b) 12(s) + NaBr(aq)- (c) Mg(s) + CuSO (aq...
Calculate the molarity of each of the following solutions: (a) 29.0 g of ethanol (C2H5OH) in 545 mL of solution, (b) 15.4 g of sucrose (C12H22O11 ) in 74.0 mL of solution, (c) 9.00 g of sodium...