Predict the major product for each proposed Diels-Alder reaction. Include stereochemistry where appropriate. (a) (b) (c) Ph 0 Ph
Predict the major products of the following reactions: (a) (b) (c) (d) Zn(Hg) HCI, H20 (1) H2NNH (2) KOH, heat (1) N2H4 2) KOH, heat O HCI, H,O
Propose a mechanism for the reaction of benzyl acetate with methylamine. Label the attacking nucleophile and the leaving group, and draw the transition state in which the leaving group leaves.
Show how you would use the Robinson annulation to synthesize the following compounds. (a) (b) (c) H,C Ph CH3
Each of the following reactions has been described in the chemical literature and gives a single organic product in good yield. Identify the product of each reaction. C&Hs I. BH, diglyme 2. H-02, HO...
State whether each of the following elements is a gas, a liquid, or a solid under atmospheric conditions. Also state whether it exists in the elemental form as atoms, as molecules, or as a...
How many signals would be present in the 1H NMR spectrum of each of the cyclopropane derivatives shown below? Consider carefully the geometric environments around each hydrogen. (a) (b) (c) (d) (e)...
A gas at 350 K and 12 atm has a molar volume 12 per cent larger than that calculated from the perfect gas law. Calculate (a) The compression factor under these conditions and (b) The molar volume of...
Propose skeletal structures for compounds that satisfy the following molecular formulas. There is more than one possibility in each case. (a) C5H12 (b) C2H7N (c) C3H6O (d) C4H9Cl
Propose a structure for a compound C4H7N that has the following IR and 1H NMR spectra: 100 80 - 60 40 - 20 - 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm-1) TMS O ppm 10 9. 8. 3. Chemical...
Fill in the reagents a that are missing from the followingscheme: CC -CH CH . H ,
From the following data for liquid nitric acid, determine its heat of vaporization and normal boiling point. Temperature C) Vapor Pressure (mm Hg) 10. 20. 30. 40. 50. 80. 14.4 26.6 47.9 81.3 133 208...
At a particular temperature, Kp = 0.25 for the reaction N2O4(g) 2NO2(g) a. A flask containing only N2O4 at an initial pressure of 4.5 atm is allowed to reach equilibrium. Calculate the equilibrium...
Write a balanced chemical equation for each neutralization reaction in Exercise 4. In exercise 4 a. HBr and Fe(OH)3 b. HNO2 and Al(OH)3 c. HClO3 and Mg(OH)2
Write the half reactions for the electrolysis of the elements listed in Exercise 3.
A diving bell is a container open at the bottom. As the bell descends, the water level inside changes so that the pressure inside equals the pressure outside. Initially, the volume of air is 8.58 m3...
The accompanying photo shows a pipevine swallowtail caterpillar climbing up a twig. (a) As the caterpillar climbs, its potential energy is increasing. What source of energy has been used to effect...
Write bond-line formulas for the following: (a) cis-3-Octene (b) trans-2-Hexene (c) 2,4-Dimethyl-2-pentene (d) trans-1-Chlorobut-2-ene (e) 4,5-Dibromo-1-pentene (f)...
Provide reagents that would accomplish the follwing syntheses. (a) (b) HO Glycerol Epichlorohydrin
Provide retrosynthetic analyses and syntheses for each of the following alcohols, starting with appropriate alkyl or aryl halides. (a) (b) (c) (d) (e) (f) OH (three ways) OH (three ways) (two ways)...
Draw all of the p molecular orbitals for (3E)-1,3,5-hexatriene, order them from lowest to highest in energy, and indicate the number of electrons that would be found in each in the ground state for...
1,3,5-Cycloheptatriene is even less acidic than 1,3,5-heptatriene. Explain how this experimental observation might help to confirm your answer to part (b) of the previous problem.
1-Chloro-3-methyl-2-butene undergoes hydrolysis in a mixture of water and dioxane at a rate that is more than a thousand times that of 1-chloro-2-butene. (a) What factor accounts for the difference...
Show how you might synthesize each of the following compounds starting with either benzyl bromide or allyl bromide: (a) (b) (c) (d) (e) (f) CH5 CN
What products would be obtained when acetophenone reacts under each of the following conditions? (a) (b) (c) (d) (e) (f) (g) Acetophenone HNO H2S04 CBH NHNH2, HA NaBH CH2OH (1) CBHMgBr (2) NHC...
Predict the major product from each of the following reactions. (a) (b) (c) (d) (e) HO OH NH2 HA (cat.) (1) HCN (2) LiAIH4 (3) H2o mCPBA
Give structural formulas for the products that you would expect from the following reactions: (a) (b) (c) (d) KMnO, heat B-Pinene H2. Pt Zingiberene HCi Caryophyllene -Selinene (1) BH3 THF (2 equiv.)...
Propose a structure for the compound A (C6H15O2 N) that is unstable in aqueous acid and has the following NMR spectra: 2.30 (6H, s): 2.45 (2H. d,J Hz); 3.27 (6H, s): 4.50 (1 H. t. 6 Hz) 6 Proton...
Predict the major products of the following substitutions. (a) (b) (c) (d) (e) (f) CH3CH2B(CH3)3CO ethyl bromide potassium tert-butoxide sodium acetylide 1-chlorobutane CH32CHCH2Br + excess NH3 CH...
A bottle of allyl bromide was found to contain a large amount of an impurity. A careful distillation separated the impurity, which has the molecular formula C3H6O.The following 13C NMR spectrum of...
The following spectra are taken from a compound that is an important starting material for organic synthesis. Determine the structure, first by considering each spectrum individually, then by...
In an aqueous solution containing sodium bicarbonate, aniline reacts quickly with bromine to give 2, 4, 6-tribromoaniline. Nitration of aniline requires very strong conditions, however, and the...
Predict the major products of the following reactions. (a) (b) (c) (d) CHO + Ag.o HO CHO + K,Cr,O/H,SO HO CHO + Ag(NHsh OH 0 CHO +KMnO (cold, dilute
The mass spectrum of unknown compound A shows a molecular ion at m/z 116 and prominent peaks at m/z 87 and m/z 101. Its UV spectrum shows no maximum above 200 nm. The IR and NMR spectra of A follow....
Using the data given in Table 10.4, determine which is the stronger acid, acetic or dichloroacetic, and by how much. Table 10.4 The Ionization Constants of Some Acids Name formic acid acetic acid...
Diethyl adipate, when heated with sodium ethoxide, gives the product shown, by an intramolecular Claisen condensation: Write out the steps in a plausible mechanism for the reaction. COCH CH, 1....
How many signals would you expect to find in the 1H NMR spectrum of each of the following compounds? (a) 1-Butanol (b) Butane (c) 1,4-Dibromobutane
Using toluene as the ultimate source of all the carbon atoms, along with any necessary inorganic reagents, show how you could prepare each of the following: (a) Benzoyl chloride (b) Benzoic anhydride...
The ketone shown was prepared in a three-step sequence from ethyl trifluoroacetate. The first step in the sequence involved treating ethyl trifluoroacetate with ammonia to give a compound A. Compound...
The first and second ionization energies of K are 419 kJ/mol and 3052 kJ/mol, and those of Ca are 590 kJ/mol and 1145 kJ/mol, respectively. Compare their values and comment on the differences.
Use Figure 4.5 to answer the following questions about the acid-catalyzed hydration of an alkene: a. How many transition states are there? b. How many intermediates are there? c. Which is more...
What diene and what dienophile should be used to synthesize the following compounds? a. b. c. d. e. f. 0 2 OCH COCH COOH COOH
A compound with molecular formula C4H6O gives the infrared spectrum shown in Figure 13.34. Identify the compound. 3.5 4 5 12 13
Rank each group of compounds in order of increasing boiling point, (a) Cyclohexane, cyclohexanol, chlorocyclohexane; (b) 2,3-dimethyl-2-pentanol, 2-methyl-2-hexanol, 2-heptanol.
Draw the structures of the molecules with the following names. (a) 4,4-Dichloro-trans-2-octene (b) (Z)-4-bromo-2-iodo-2-pentene (c) 5-Methyl.cis-3-hexen-l-ol (d) (R)-l,3-Dichlorocycloheptene (e)...
Calculate S (for the system) when the state of2.00 mol diatomic perfect gas molecules, for which Cp,m = 7/2 R, is changed from 25C and 1.50 atm to 135C and 7.00 atm. How do you rationalize the sign...
The fugacity coefficient of a certain gas at 290 K and 2.1 MPa is 0.68. Calculate the difference of its molar Gibbs energy from that of a perfect gas in the same state.
The vapour pressure of a substance at 20.0DCis 58.0 kPa and its enthalpy of vaporization is 32.7 k] mol-1. Estimate the temperature at which its vapour pressure is 66.0 kPa.
What are the allowed total angular momentum quantum numbers of a composite system in which jl = 5 and j2 = 3?
Calculate the rotational partition function of S0, at 298 K from its rotational constants 2.027 36 cm3, 0.34417 cm3, and 0.293 535 cm3. Above what temperature is the high-temperature approximation...
Draw as many resonance structures as you can for the followingspecies: (b) :NH2 H2N-C=NH2 (c) (a) :0: H --- () HC $H2 (e) H %H
Draw resonance structures of the intermediate carbocations in the bromination of naphthalene, and account for the fact that naphthalene undergoes electrophilic substitution at C1 rather than C2. Br...
The barrier to rotation about the CC bond in bromoethane is 15kJ/mol (3.6kcal/mol). (a) What energy value can you assign to an HBr eclipsing interaction? (b) Construct a quantitative diagram of...
Rank the following substances in order of their expected SN1 reactivity: Br Br H CHCCH CHCH2Br H2C=CHBr
Show how you could use the acetamidomalonate method to prepare the following amino acids: (a) Leucine (b) Tryptophan
The most probable velocity ump is the velocity possessed by the greatest number of gas particles. At a certain temperature, the probability that a gas particle has the most probable velocity is equal...
The gas-phase decomposition 2N2O5 4NO2 + O2 is first order but not unimolecular. A possible mechanism is Apply the steady-state approximation to the concentrations of the intermediates NO3 and NO,...
What monomer(s) must be used to produce the following polymers? a. b. c. d. e. f. Classify these polymers as condensation or addition polymers. Which are copolymers? CH-CH2-CH-CH-CH-CH O-CH2-CH2-C-o...
Combustion of table sugar produces CO2(g) and H2O(l). When 1.46 g of table sugar is combusted in a constant-volume (bomb) calorimeter, 24.00 kJ of heat is liberated. a. Assuming that table sugar is...
Consider 2.00 moles of an ideal gas that is taken from state A (PA = 2.00 atm, VA = 10.0 L) to state B (PB = 1.00 atm, VB = 30.0 L) by two different pathways. These pathways are summarized in the...
Write these numbers in scientific notation by counting the number of places the decimal point is moved. a. 123,456.78 b. 98,490 c. 0.000000445
Determine the mass of each substance. a. IBr3 b. N2O5 c. CCl4
Write a chemical equation that represents (NH4)3PO4(s) dissociating in water.
Write the net ionic equation for each neutralization reaction in Exercise 8. In exercise 8 a. HNO3(aq) + Fe(OH)3(s) ( ? b. H3PO4(aq) + CsOH(aq) ( ?
Predict the products of each acid-base combination listed. Assume that a neutralization reaction occurs. a. HCl and KOH b. H2SO4 and KOH c. H3PO4 and Ni(OH)2
Write a balanced chemical equation for each neutralization reaction in Exercise 3. In exercise 5 a. HCl and KOH b. H2SO4 and KOH c. H3PO4 and Ni(OH)2
Define and relate three units of pressure.
What is the work performed when a gas expands from 0.66 L to 1.33 L against an external pressure of 0.775 atm?
In a calorimeter at constant pressure, 0.10 mol of CH4(g) and 0.20 mol of O2(g) are reacted. CH4(g) + 2O2(g) ( CO2(g) + 2H2O() The reaction warms 750.0 g of H2O by 28.4C. What is H for the reaction...
If the H for C2H4 + H2 ( C2H6 Is 65.6 kJ, what is the H for this reaction? 2C2H4 + 2H2 ( 2C2H6
Determine the enthalpy change of this reaction. Data can be found in Table 7.2. CH2O(g) + O2 ( CO2(g) + H2O()
A 1.88 M solution of NaCl has an initial volume of 34.5 mL. What is the final concentration of the solution if it is diluted to 134 mL?
At 298 K, what concentration of solution is needed to have an osmotic pressure of 1.00 atm?
Calculate the boiling point of an aqueous solution of NaNO3 made by mixing 15.6 g of NaNO3 with 100.0 g of H2O. Assume an ideal van't Hoff factor.
Order these solutions in order of increasing boiling point, assuming an ideal van't Hoff factor for each: 0.10 m C6H12O6, 0.06 m NaCl, 0.4 m Au(NO3)3, and 0.4 m Al2(SO4)3.
Oxidation was once defined as chemically adding oxygen to a substance. Use this reaction to argue that this definition is consistent with the modern definition of oxidation. 2Mg + O2 ( 2MgO
Cr atoms can have a wide range of oxidation numbers. Assign oxidation numbers for the Cr atom in each compound, all of which are known compounds. a. Na2CrO4 b. Na2Cr2O7 c. CrF5 d. CrCl3 e. CrCl2
Match the molecular model with the correct chemical formula: CH3OH, NH3, KCl, H2O. (a) (b) (c) (d)
Sphalerite is a zinc sulfide (ZnS) mineral and an important commercial source of zinc metal. The first step in the processing of the ore consists of heating the sulfide with oxygen to give zinc...
Cyclobutane, C4H8, consisting of molecules in which four carbon atoms form a ring, decomposes, when heated, to give ethylene. C4H8(g) 2C2H4(g) The reaction is first order. In an experiment, the...
Sulfur trioxide, used to manufacture sulfuric acid, is obtained commercially from sulfur dioxide. The equilibrium constant Kc for this reaction is 4.17 Ã 102 at 727oC. What is the direction of...
Formic acid, HCHO2, is a stronger acid than acetic acid, HC2H3O2. Which is the stronger base, formate ion, CHO2, or acetate ion, C2H3O2?
Consider a solution of 0.0010 M HF (K a = 6.8 10 4 ). In solving for the concentrations of species in this solution, could you use the simplifying assumption in which you neglect x in the...
What is the major product when HBr is added to methylpropene?
Natural rubber is an addition polymer of isoprene. Gutta percha is a similar rubber-like material, although its properties are rather different. (It is a hard material at room temperature but softens...
Arrange the following compounds in order of increasing boiling point. Explain your answer in terms of the intermolecular forces in each compound. (a) (b) (c) (d)
Sketch a curve similar to that in Fig. 4.8 showing in general terms the energy changes that arise from rotation about the C2-C3 bond of 2-methylbutane. You need not concern yourself with the actual...
(a) In addition to the 2,2-dimethylpropyl (or neopentyl) group just given, there are seven other five-carbon groups. Draw bond-line formulas for their structures and give each structure its...
Draw bond-line formulas and give IUPAC substitutive names for all of the isomers of (a) C4H9Cl and (b) C5H11Br.
Predict the major product formed when 2-bromobutane is subjected to dehydrobromination using sodium ethoxide in ethanol at 55oC.
How many 1H NMR signals would you expect from each of the following compounds? (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) (k) (l) (m) (n) (o) (p) OH CI
Provide the reagents necessary for the following synthetic transformations. More than one step may be required. (a) (b) (c) (d) (e) (f) OCH3 Br
Provide a retrosynthetic analysis and synthesis for each of the following compounds. Permitted starting materials are phenylmagnesium bromide, oxirane, formaldehyde, and alcohols or esters of four...
Predict the major organic product from each of the following reaction sequences. (a) (b) (c) (d) (e) (f) (1) MeMgBr (excess) (2) NH,CI, H20 (1) Mg (2) H H (3) HyO (1) PBr3 (2) Mg (3) H,o OH OH (1)...
Four benzenoid compounds, all with the formula C7H7Br, gave the following IR peaks in the 680-860-cm-1 region: A, 740 cm-1 (strong) B, 800 cm-1 (very strong) C, 680 cm-1 (strong) and 760 cm-1 (very...
Which of the following molecules would you expect to be aromatic? (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) (k) (l) N+
Provide a detailed mechanism for the following reaction. H,SO + H2O
The lignins are macromolecules that are major components of the many types of wood, where they bind cellulose fibers together in these natural composites. The lignins are built up out of a variety of...
When benzaldehyde reacts with a peroxy acid, the product is benzoic acid. The mechanism for this reaction is analogous to the one just given for the oxidation of acetophenone, and the outcome...
Predict the major organic product from each of the following reactions. (a) (b) (c) (d) (e) (f) (g) HoOH, H.SO, (cat.) H2SO4 (cat.) OH 0 OH H.,SO, (cat.) OH O. (1) H SO, H2O 0 (2)H, H2SO, (cat.) 0 OH...