Organic Chemistry 2nd Edition solutions

Organic Chemistry 2
In each of the following cases compare the bonds identified in red, and determine which bond you would expect to have the largest bond dissociation energy: (a) (b) Cl F I Br

Organic Chemistry 2
Consider the following reaction: O Br H O + HBr (a) Use Table 6.1 to estimate DH for this reaction. (b) DS of this reaction is positive. Explain. (c) Determine the sign of DG. (d) Is the sign of DG dependent on temperature? (e) Is the magnitude of DG dependent on temperature?

Organic Chemistry 2
For each of the following cases use the information given to determine whether or not the equilibrium will favor products over reactants: (a) A reaction with Keq = 1.2 (b) A reaction with Keq = 0.2 (c) A reaction with a positive DG (d) An exothermic reaction with a positive DS (e) An endothermic reac

Organic Chemistry 2
Which value of DG corresponds with Keq = 1? (a) +1 kJ/mol (b) 0 kJ/mol (c) -1 kJ/mol

Organic Chemistry 2
Which value of DG corresponds with Keq < 1? (a) +1 kJ/mol (b) 0 kJ/mol (c) -1 kJ/mol

Organic Chemistry 2
For each of the following reactions determine whether DS for the reaction (DSsys) will be positive, negative, or approximately zero: (a) HBr Br + (b) Cl + HCl (c) Cl OH H HCl + 2O + (d) (e)

Organic Chemistry 2
Draw an energy diagram of a reaction with the following characteristics: (a) A one-step reaction with a negative DG (b) A one-step reaction with a positive DG (c) A two-step reaction with an overall negative DG, where the intermediate is higher in energy than the reactants and the first transition st

Organic Chemistry 2
Consider the following four energy diagrams: Reaction coordinate A B Reaction coordinate C Reaction coordinate D Reaction coordinate Potential energy Potential energy Potential energy Potential energy (a) Which diagrams correspond with a two-step mechanism? (b) Which diagrams correspond with a one-st

Organic Chemistry 2
Identify all transition states and intermediates on the following energy diagram: Reaction coordinate Potential energ

Organic Chemistry 2
Consider the following reaction: OH Cl OH Cl @ @ + This reaction has been determined to be second order. (a) What is the rate equation for this reaction? (b) How will the rate be affected if the concentration of hydroxide is tripled? (c) How will the rate be affected if the concentration of chloroeth

Organic Chemistry 2
For each of the following reactions identify the arrow-pushing pattern that is being utilized: (a) Cl Cl @ ! + (b) ! ! (c) O O O O O O @ @ (d) O O O OH O H O @ @

Organic Chemistry 2
Rank the three carbocations shown in terms of increasing stability: (a) ! ! ! (b) ! ! !

Organic Chemistry 2
For the following mechanism, identify the sequence of arrowpushing patterns: Cl Al Cl Cl Cl Al Cl Cl Cl Cl Al Cl Cl Cl O Cl O O @ @ ! !

Organic Chemistry 2
For the following mechanism, identify the sequence of arrow-pushing patterns: H O H O N O H N O O H N O O H N O O N O O @ @ @ @ ! ! ! ! ! ! ! !

Organic Chemistry 2
For the following mechanism, identify the sequence of arrow-pushing patterns: SO3 H S O O O H H S O O OH H S O O OH S OH O O H O ! H ! ! + H O H

Organic Chemistry 2
For the following mechanism, identify the sequence of arrow-pushing patterns: NO2 OH OH N O Br O N O O Br HO N O O HO Br N O O HO Br N O O HO Br @ @ @ @ @ @ @ @ @ @ ! ! !

Organic Chemistry 2
For the following mechanism, identify the sequence of arrow-pushing patterns: MeOH OEt O OH OEt O Me H O H O O Et H EtOH H EtOH O O H Et Me H O H Et OH OEt O Me H O Et OEt O H OMe OMe ! ! ! ! ! ! OH

Organic Chemistry 2
For the following mechanism, identify the sequence of arrow-pushing patterns: R OH O H O H R O H O H R O O H H O O Cl R H H Cl Cl @ @ ! !

Organic Chemistry 2
For the following mechanism, identify the sequence of arrow-pushing patterns: R R R R O R H O H H R R R R OH R R R O R Cl Cl O O @ @ @ @ !

Organic Chemistry 2
For the following mechanism, identify the sequence of arrow-pushing patterns: A R H2O O H OR OR R O H OH OR H A A O H OH O H R H A O OR H H O R O OR H R O ! ! ! ! ! !

Organic Chemistry 2
For the following mechanism, identify the sequence of arrow-pushing patterns: H OH N R R H2O N R R A OH N R R A H A O N R R N R R H H H O N R R H O N R H R H A @ ! ! ! ! ! !

Organic Chemistry 2
For the following mechanism, identify the sequence of arrow-pushing patterns: HH N N H H H O H H N N H H O OH H N N H N N H OH H H N N @ @ @ @ @ @

Organic Chemistry 2
Draw curved arrows for each step of the following mechanism: NO2 HO N O S O O H3C O O OH CH3SO3 N O S O O H3C O O OH @ @ @ @ @ ! !

Organic Chemistry 2
Draw curved arrows for each step of the following mechanism: N N + H2O H2O N N H OH N N H OH O O O NH2 NH2 NH2 NH2 NH2 NH2 NH2 NH2 O H N H H OH O N H O O H H N H O N O H N N H H OH N N H H H N N H O O O H H O H H O H H O H H O ! H H H O! H H H O! H H H O! H H H O! ! ! ! ! ! ! !

Organic Chemistry 2
Draw curved arrows for each step of the following mechanism: H H H H H H N H H H N H OH N H H H N H N H O H H H O H H N H OH H N H H H O H O O O O O ! ! ! ! ! !

Organic Chemistry 2
Draw curved arrows for each step of the following mechanism: HO O OH H H H H H2O H HO H OH H H H O H H HO O OH H H H H O H H H HO H O H H H O H H H HO H OH O H O O O O O O O ! ! ! ! ! !

Organic Chemistry 2
Draw curved arrows for each step of the following mechanism: N H H H H HH N H H N H OH H H H N H N H O H H O N H H H N H OH H H H H O O O O O O ! ! ! ! ! !

Organic Chemistry 2
Draw curved arrows for each step of the following mechanism: H2O HO O HO HO OH HO OH H H H H H O H HO O H HO H O H H O O HO H H O O HO H O O O O O O O O O ! ! ! ! ! ! !

Organic Chemistry 2
Predict whether each of the following carbocations will rearrange. If so, draw the expected rearrangement using curved arrows. (a) ! (b) ! (c) ! (d) ! (e) ! (f) + (g) !

Organic Chemistry 2
Consider the following reaction: CH3 C H H H O H3C C H H H O Br Br @ @ + + The following rate equation has been experimentally established for this process: Rate = k[HO-][CH3CH2Br] The energy diagram for this process is shown below: Reaction coordinate C H3C H H Br C CH3 H H HO HO + + Br Potential en

Organic Chemistry 2
Identify whether each of the following factors will affect the rate of a reaction: (a) Keq (b) DG (c) Temperature (d) DH (e) Ea (f) DS

Organic Chemistry 2
1 In the presence of a special type of catalyst, hydrogen gas will add across a triple bond to produce a double bond: H2 Catalyst + The process is exothermic. Do you expect a high temperature to favor products or reactants?

Organic Chemistry 2
Consider the following reaction. Predict whether an increase in temperature will favor reactants or products. Justify your prediction. +

Organic Chemistry 2
When an amine is protonated, the resulting ammonium ion is not electrophilic: An amine An ammonium ion R N R R H R N R R H Cl Cl @ ! + However, when an imine is protonated, the resulting iminium ion is highly electrophilic: An imine An iminium ion N R R R N R H R R Cl H Cl @ ! + Explain this differen

Organic Chemistry 2
Draw the curved arrows that accomplish the following transformation: O Me N N H Cl O Me NN OH O Me N N Cl Cl @ @ @ + +

Organic Chemistry 2
Under basic conditions (catalytic MeO- in MeOH), compound 1 rearranges through the mechanistic sequence shown below to a propellane-type isomer 5 (J. Am. Chem. Soc. 2012, 134, 17877 17880). Note that MeO- is catalytic in that it is consumed in the first step of the mechanism and regenerated in the fi

Organic Chemistry 2
Compound 1 has been prepared and studied to investigate a novel type of intramolecular elimination mechanism (J. Org. Chem. 2007, 72, 793798). The proposed mechanistic pathway for this transformation is presented below. Complete the mechanism by drawing curved arrows consistent with the change in bon

Organic Chemistry 2
Indolizomycin is a potent antibiotic agent produced by a microorganism called SK2-52. Of particular interest is the fact that SK2-52 is a mutant microorganism that was created in a laboratory from two different strains, Streptomyces teryimanensis and Streptomyces grisline, neither of which is antibio

Organic Chemistry 2
The following sequence was utilized in a biosynthetically inspired synthesis of preussomerin, an antifungal agent isolated from a coprophilous (dung-loving) fungus (Org. Lett. 1999, 1, 35): O O O O O O O O O O OH O O O O O O O O O LiOH H H O H @ @ (a) Draw curved arrows for each step of the mechanism

Organic Chemistry 2
This chapter focused on the mechanisms of ionic reactions, which represent the vast majority of the reactions throughout this textbook. In Chapter 17, we will explore another class of reactions, called pericyclic reactions, for which the changes in bonding can be described by electrons moving in a co

Organic Chemistry 2
(+)-Aureol is a natural product that shows selective anticancer activity against certain strains of lung cancer and colon cancer. A key step in the biosynthesis of (+)-aureol (how nature makes the molecule) is believed to involve the conversion of carbocation A to carbocation B (Org. Lett. 2012, 14,

Organic Chemistry 2
Strychnine (6), a notorious poison isolated from the strychnos genus, is commonly used as a pesticide in the treatment of rodent infestations. The sophisticated structure of strychnine, first elucidated in 1946, served as a tantalizing goal for synthetic organic chemists. The first synthesis of stryc

Organic Chemistry 2
There are many examples of carbocation rearrangements that cannot be classified as a methyl shift or hydride shift. For example, consider the following rearrangement that was employed in the synthesis of isocomene, a tricyclic compound isolated from the perennial plant Isocoma wrightii (J. Am. Chem.

Organic Chemistry 2
Compound 1 undergoes a thermal elimination of nitrogen at 250C to form nitrile 4 (Org. Lett. 1999, 1, 537539). One proposed (and subsequently refuted) mechanism for this transformation involves intermediates 2 and 3: N N R1 NH2 R2 N N N R1 N R2 R1 R2 N N H2N C R1 R2 1 4 H H H H 3 2 N N N N N N @ ! (a

Organic Chemistry 2
In the presence of a Lewis acid, compound 1 rearranges, via intermediate 2, to afford compound 3 (Org. Lett. 2005, 7, 515517): O O Ph O O Ph O Ph O 1 2 3 @ ! (a) Draw curved arrows showing how 1 is transformed into 2. Note that the Lewis acid has been left out for simplicity. (b) Draw curved arrows s