Organic Chemistry Study Sheets - Pacific Lutheran University

Organic Chemistry Study Sheets
For T.W.G. Solomons Organic Chemistry, 6th Ed.

Prepared By Craig B. Fryhle
Pacific Lutheran University

Section	Goals
1.1, 1.2	Note the pervasive relevance of organic chemistry to life and society.
1.3	Understand molecular and empirical formulas. Know valences for C, H, N, O, halogens, S. Learn bonding arrangements for the above elements. Understand constitutional isomers and connectivity.
1.4	Know octet rule and ramifications thereof. Understand ionic and covalent bonds and electronegativity trends.
1.5	Be able to draw proper Lewis structures for neutral and ionic species. Note exceptions to the octet rule.
1.7	Be able to calculate formal charge on any atom and determine overall ionic charge.
1.8	Understand essential principles of resonance and be able to draw resonance structures for simple structures where resonance is possible.
1.9	Know the meaning of endothermic, exothermic and enthalpy as applied to energy changes in chemical reactions.
1.10	Understand wave characteristics (phase interactions) leading to reinforcement , and interference. Accept the general relevance of wave properties to atomic structure.
1.11	Understand interpretation of the square of the wave function (psi**2) as indicating a region of space where probability of finding an electron is high. Learn the three dimensional shapes and orientations of s and p orbitals derived from wave functions. Be able to draw proper valence electron configurations for C, N, O, and halogens.
1.12	Understand the derivation of a specific number of molecular orbitals from combinations of a given number of atomic orbitals.
1.13, 1.14, 1.15	Be able to apply electron configurations and the principle of orbital hybridization to predict the structure of sp3, sp2, and sp hybridized atoms.
1.16	Use this section to unify your understanding of quantum mechanics concepts discussed earlier.
1.17	Be able to use the VSEPR model to predict tetrahedral, trigonal planar, and linear molecular geometries for various examples.
1.18, 1.19	Be able to apply the principles of electronegativity and bond polarization for prediction of the overall polarity or lack thereof in any given molecule.
1.20	Gain unquestionable proficiency in representing organic molecules in their dash, condensed, bond- line, and three-dimensional (dash-wedge) structural formulas.

Section	Goals
2.2	Understand the structural meaning of the terms hydrocarbon, alkanes, alkenes, alkynes, saturated, and unsaturated. Gain a 3-D sense of the structure of alkanes based on their hybridization and bonding.
2.3	Understand the 3-D arrangement of atoms that are part of an alkene double bond.
2.4	Understand the origin of sp2 hybridization through electron promotion and hybridization. Know unequivocally the orbital structure of an sp2 hybridized atom and the orbital representation of a * (pi) bond with a sigma bond framework. Understand the ramifications of restricted rotation about pi bonds and the potential for cis-trans isomerism, as compared to free rotation about * (sigma) bonds.
2.5	Understand the 3-D arrangement of atoms that are part of an alkyne triple bond.
2.6	Understand the origin of sp orbitals through hybridization and know the orbital structure of an sp hybridized atom. Understand the overlap of adjacent p orbitals from sp hybridized carbon atoms leading to the orthogonal relationship of the two * bonds in an alkyne.
2.7	Know the structural meaning of the names and shorthand representations for the phenyl and benzyl aromatic groups.
2.8	Understand what alkyl groups are. Know the names and be able to draw structures for all alkyl ("R") groups of three carbons or fewer. Understand the notion of a functional group.
2.9	Be able to write the general structures of 1o (primary), 2o (secondary), and 3o (tertiary) alkyl halides (using R groups) and identify real examples of each type.
2.10	Be able to write the general structures of 1o (primary), 2o (secondary), and 3o (tertiary) alcohols (using R groups) and identify examples of each type in a real molecule.
2.11	Be able to write the general structure of an ether and identify the ether functional group in real examples.
2.12	Be able to write the general structures of 1o (primary), 2o (secondary), and 3o (tertiary) amines (using R groups) and identify examples of each type in a real molecule.
2.13	Know the 3-D structure and hybridization of the carbonyl group. Be able to write the general structures of aldehydes and ketones and identify both functional groups in real examples.
2.14	Be able to write the general structures of carboxylic acids, amides, and esters and identify these functional groups in real examples.
2.15	Know the dash and all condensed structural formula representations for the above functional groups and be able to draw every one from memory. Not the summary inside the front cover and in Table 2.2.
2.16, 2.16 A-F	Know the various types of intermolecular forces that are possible and understand their influence on physical properties (such as mp, bp and solubility) for a given molecule.

Section	Goals
3.1	Note the general changes in structure accompanying substitution, addition, elimination, and rearrangement reactions.
3.1A	Understand the concept of a mechanism as a stepwise description of events in a chemical reaction.
3.1B	Understand that cleavage of a bond to a carbon could conceivably occur by in three ways: homolytically (to forma free radical), or heterolytically with the carbon either keeping or losing both electrons of the bond (to form a carbanion or carbocation, resp.) Understand the general meaning of heterolytic and homolytic bond cleavage.
3.2A	Review concepts of Bronsted-Lowry Acids and Bases.
3.2B	Understand Lewis acids and bases as generally applicable to acid base theory. Be able to classify compounds as Lewis acids or bases, especially with regard to examples involving organic compounds.
3.3	Know the general structure of a carbocation and carbanion, Learn the basic definition/character of nucleophiles and electrophiles.
3.4	Understand the precise use of the double-barbed curved arrow and be able to draw them appropriately and with accurate meaning.
3.5	Understand the mathematical derivation of Ka and pKa. Know the significance of both Ka and pKa regarding acid (and conjugate base) strength. Be able to write the conjugate base or conjugate acid from any acid or base, respectively, and the corresponding acid or base from the respective conjugate .
3.6	Be able to use Ka or pKa values to predict the direction of an acid-base reaction.
3.7	Understand the influences of bond strength (to the acidic hydrogen), electronegativity, hybridization, and inductive effects on acidity.
3.9	Know the relative acidities of carboxylic acids and alcohols.
3.10	Recognize the ability of protic solvents to solvate the anions formed upon ionization of an acid.
3.11	Understand the capacity of organic compounds containing oxygen to act as bases and engage in proton transfer reactions.
3.12	Note the format and stepwise detail in this example of a mechanism.
3.13	Understand the need for solvents other than water when bases stronger than hydroxide ion are used (understand the leveling effect of water in these cases). Begin to recognize some exceptionally strong bases (e.g. NaNH2, NaH, and alkyllithium reagents (RLi).
3.14	Understand the ability to introduce deuterium and tritium by acid-base reactions.
3.15	Review the highlights listed in this section and those noted above.

Section	Goals
4.1	Recognize petroleum as the primary natural source of alkanes and aromatic hydrocarbons. Know the general formulas for an alkane and cycloalkane.
4.2	Be ever cognizant of the general three-dimensional structure of alkanes, based on the appropriate hybridization state of carbon, regardless of the type of formula presented. Understand the structural meanings as pertains to alkanes of the designations "straight-chain" (or unbranched) and branched. Recall that constitutional isomers have different physical properties.
4.5, 4.3A-F	Learn the IUPAC names of alkanes through C20. Learn all the alkyl group names from C1 through C5. Be able to apply the IUPAC rules for naming branched chain alkanes. Learn the names of branched alkyl groups through C5. including the meaning of prefixes iso-, sec-, tert-. Be able to classify hydrogens as 1^o,2^o, or 3^o. Be able to name alkyl halides and alcohols using the IUPAC system.
4.4	Be able to name monocyclic alkanes (section 4.4A). Read section 4.4B for interest.
4.5	Recognize the trends in mp and bp among hydrocarbon homologs. Know the general density and solubility properties of alkanes and cycloalkanes, as compared to water.
4.6	Be able to perform conformational analyses on simple alkanes using Newman projections to draw the various conformation. Recognize a given conformation as being staggered or eclipsed.
4.7	Understand the significance of torsional strain regarding conformational anyalysis. Recognize a given conformation as being anti or gauche, as well as staggered and eclipsed.
4.8	Know the relative order of stability for cycloalkanes from cyclohexane to cyclopropane. Disregard heats of combustion (section 4.8B) unless interested in further explanation.
4.9	Understand the influence of angle and torsional strain on the overall ring strain in cyclopropane and cyclobutane, as compared to cyclopentane and cyclohexane.
4.10	Be able to recognize and draw clearly the boat and chair conformations of cyclohexane, especially the chair, showing correct 3-D perspective. Be able to draw a Newman projection for cyclohexane, viewed along any pair of C-C bonds.
4.11	Learn to identify the axial and equatorial positions on the chair conformation of cyclohexane. Be able to draw cyclohexane so that axial and equatorial positions of substituents are absolutely unambiguous. Understand the origin of 1,3-diaxial interactions and the basis for the relatively greater stability of chair conformations with substituents in equitorial orientations. Lean to depict a chair-chair conformational ring flip with accurate drawings showing the changes in axial and equitorial orientations of groups.
4.12	Understand the possibility for cis and trans stereoisomers in disubstituted cycloalkanes. Be able to draw both the unrealistic "flat" ring structures (e.g. pp.159 and 160) and realistic chair conformational structures for disubstituted cyclohexanes (e.g. pp. 161 and 162). Correctly place cis or trans groups in axial or equitorial orientations, depending on the preferred, lowest energy conformation for the chair.
4.14	Recognize the relatively inert character of alkanes, aside from combustion.
4.15	Learn the reagents, reaction conditions, types of starting materials required and products formed for the reactions presented for the synthesis of alkanes in sections 4.15A-C: i) hydrogenation of alkenes,ii) reduction of alkyl halides, and iii) the use of lithium dialkylcuprates. Be able to write examples of each reaction using R groups for generalized reactants and products. Be able to translate an understanding of the general reactions to use of the reaction conditions with specific molecules to form the corresponding products.
4.16	Begin to understand the notion and use of retrosynthetic analysis. Be able to envision specific and logical retrosyntheetic disconnections and precursor intermediates when planning the synthesis of a given molecule. Be able to evaluate the merits of vaious synthetic routes to a given molecule.<
4.17	Note the biological role of some relatively simple hydrocarbons.
4.18	Review the topics listed here and highlights of chapter four noted above.

Section	Goals
5.1	Know the definitions of constitutional isomers, stereoisomers, enantiomers, and diastereomers, and their relationship to each other. Be able to classify the specific type of isomeric relationship between any one compound and another.
5.2	Be able to identify tetrahedral and trigonal stereocenters in molecules. Be able to identify a compound as being chiral or achiral by testing for superposability on its mirror image. Work on visualizing molecules in three dimensions, especially regions involving stereocenters. Do this by making models and drawing dash-wedge structures of models, and by making models of drawn structures. Understand the importance of mirror planes for determining whether an enantiomer to a given molecule can exist. Understand the effect of interchanging the position of any two groups at a tetrahedral stereocenter.
5.3	Note the profound importance of chirality in natural products and biologically active molecules.
5.5	Be able to use the mirror plane test for chirality.
5.6	In general, be able to assign the R or S configuration to any tetrahedral stereocenter by correctly determing the relative priorities of groups bonded to the stereocenter and determining the direction of priority rotation. Specifically, be able to apply the priority rules to any type of attached group, including those with multiple bonds. Develop expert facility at visualizing the direction of rotation of the attached groups at a tetrahedral stereocenter, according to their priorities and with a mind's eye view from inside the "inverted umbrella" of the tetrahedron.
5.7	Understand the definition of optical activity as the rotation of plane polarized light by chiral molecules. Know that optical activity is measured using instruments called polarimeters. Recognize that no obvious correlation exists between the sign of rotation (+ or -) for an optically active molecule and the R or S configuration of enantiomers. Understand that an optical rotation measurement can be standardized for use as a physical constant for a given optically active substance by calculating what is known as the specific rotation, through taking into account sample characteristics such as concentration, etc.
5.8	Understanding the meaning of the term racemic mixture (or racemic form, or racemate). Have an intuitive understanding of the origin of optically activity and why there is no optical activity in a racemic mixture.
5.9	Understand that a racemic mixture results when a chiral molecule is formed by a chemical reaction between achiral starting materials and achiral reagents. Consider how an optically active product might result from using either chiral starting materials or chiral reagents.
5.10	Not the importance of chirality in drug design and manufacture.
5.11	Understand the ramifications of having more than one stereocenter in a molecule ("n" stereocenters) with regard to the total number of isomers possible (2n), how many enantiomer pairs are possible (2n- 1) and how many diastereomers could exist (2n-1). Understand the relationship between diastereomers with regard to physical constants. Be able to identify meso compounds. Be able to use the R,S system to name compounds with more than one stereocenter.
5.12	Understand how to draw and interpret Fischer projection formulas, while recognizing the advantages and pitfalls of their use.
5.13	Understand how stereoisomerism applies to cyclic molecules and be able to recognize cases where planes of symmetry may influence the existence or number of stereoisomers in cyclic compounds.
5.14	Understand how the R,S configuration of a stereocenter may or not be affected by the breaking and forming of bonds to the stereocenter (according to the priorities of the new and old groups), and also how the R,S configuration of a stereocenter may or not be affected by the breaking of bonds not directly attached to the stereocenter (according to how a group's priority might change through remote alteration). Understand the process of relating configurations between molecules by use of reactions with known stereochemical outcome.
5.15	Understand the principle behind methods for the separation of enantiomers, i.e. that reversible conversion of a pair of enantiomers into diastereomeric species results in materials of differing physical properties, which after separation could be used to regenerate each original enantiomer in isolated form.
5.18	Review the the concepts discussed therein, as well as the above topics.

Section	Goals
6.1	Know the general structural characteristics of an alkyl halide, re: bond polarity, geometry, etc. Be able to readily identify an alkyl halide as 1o (primary), 2o (secondary), or 3o (tertiary). Be able to recognize vinylic and aryl halides (significant because vinylic and aryl halides do not react by the mechanisms in Chapter 6).
6.3	Be able to write the general reaction for a nucleophilic substitution reaction and identify the nucleophile, substrate (e.g. alkyl halide), and leaving group.
6.4	Gain thorough understanding of what a nucleophile is and be able to recognize the nucleophilic participant in a reaction. Be able to recall specific examples of nucleophiles. Understand the general character of nucleophiles, such that you could identify potentially nucleophilic species in a reaction. For specific examples where the nucleophilic atom bears a hydrogen (e.g. HOH, ROH), understand the reason for a proton transfer step after the substitution).
6.5	Understand the general nature of a leaving group as being the species that departs with a pair of electrons during a nucleophilic substitution reaction. Learn to recognize the leaving group in substrates for nucleophilic substitution. Recognize that the better a leaving group is able to accomodate (stabilize) the electron pair it takes with it, the better the leaving group will be.
6.7	Read for general understanding.
6.8	Understand that in SN2 reactions both the nucleophile and alkyl halide substrate are involved in the rate determining step.
6.8	As one of the most important sections in the entire book, have emblazened upon one's memory the general aspects of the SN2 reaction depicted on page 233. Pay special attention to the site of nucleophic attack (backside with respect to the leaving group), the structure of the transition state (involving concerted bond forming to the nucleophile and bond breaking to the leaving group), and the configuration of the product as compared to the substrate (inversion of the tetrahedral center).
6.9	Be able to draw a generic free energy diagram for an SN2 reaction, labeling the transition state, and showing the overall free energy change for the reaction (Go), whether it be endergonic or exergonic. Understand the influence of the magnitude of the energy of activation (G*) on the rate of reaction. Understand the influence of temperature on reaction rates.
6.10	Further cement in place an understanding of SN2 reaction as occuring by backside attack of the nucleophile with inversion of configuration and simultaneous bond forming and breaking. Understand the ramifications of inversion for SN2 reactions taking place at stereocenters. Be able to draw from memory and in three-dimensions a generic mechanism for an SN2 reaction, including, of course, the transition state.
6.11	Know that SN1 reactions are unimolecular in the rate determining step.
6.12	Ingrain the sequence of steps involved in any general SN1 reaction (see p. 242 for a specific example): 1) departure of the leaving group (with the pair of electrons that bonded the LG to the substrate), 2) concomitant formation of a carbocation at the carbon that lost the LG, and 3) attack of the nucleophile on the carbocation. Understand that there may be proton transfer steps necessary, depending on the nature of the nucleophile and leaving group, but consider the above three stages the essential components of every SN1 reaction.
6.13	Cement an understanding of the orbital/3D structure of a carbocation, especially the planar nature of the sp2 carbon and the vacant p orbital. Know the general trend in relative carbocation stability.
6.14A	Understand how the stereochemical outcome of an SN1 reaction (racemization) follows from the planar structure of the intermediate carbocation (allowing both frontside and backside attack by the nucleophile). Be able to draw from memory and in three dimensions where appropriate the stepwise mechanism for a generic SN1 reaction, as outlined in the three steps of section 6.12.
6.14B	Recognize solvents as potential nucleophiles in SN1 reactions and understand the concomitant proton transfer steps that are required.
6.15	Be able to list and discuss the four most important factors affecting rates of SN1 and SN2 reactions.
6.15A	Know how structure affects the rate of SN1 and SN2 reactions, i.e. steric hindrance for SN2 and relative carbocation stability for SN1.
6.15B	Be able to assess the relative strength of a nucleophile, based on it's charge or lack thereof, and relative basicity. Understand the effect of concentration on the rate of SN2 reactions.
6.15C	Understand why polar aprotic solvents facilitate SN2 reactions. Understand the structural difference between polar and aprotic solvents and be able togive examples of each. <
6.15D	Understand the ionizing ability of polar protic solvents and their tendency to increase the rate of SN1 reactions. Recognize that while water is a good ionizing solvent, many organic compounds are not soluble in water, and therefor other organic solvents such as methanol and alcohol are frequently mixed with water to assist in solvation of the organic reactants.
6.15E	Learn some of the common leaving groups and recognize the common ability among them to stabilize/accomodate the pair of electrons taken with them when they act as leaving groups. Understand the inverse relationship of base strength to leaving group ability.
6.16	Be able to prepare compounds with a variety of functional groups by transformation or incorporation of functional groups using SN2 reactions on suitable substrates. Recall the unreactivity of vinyl and aryl halides in SN1 and SN2 reactions.
6.17	Be able to draw from memory a generic example of a dehydrohalogenation reaction. Be able to recognize hydrogens (-hydrogens) eligible for removal by a base, and the position of the double bond that will form upon departure of the leaving group (from the -carbon).
6.17B	Know the common bases used for dehydrohalogenation (also called 1,2-elimination).
6.18	Ingrain in memory the general mechanism of an E2 reaction (in three dimensions), including the transition state, as depicted on page 263).
6.19	Understand the mechanism of an E1 reaction, recognizing the possibility for elimination of any *- hydrogen from a carbocation intermediate, in addition to the possiblity for an SN1 substitution.
6.20	Understand the combined influence of factors such as base/nucleophile strength and substrate structure (steric hindrance) with regard to competition between SN2 and E2 reactions. With regard to SN1 and E1 reactions, recognize the inherent difficulty in directing a tertiary substrate toward substitution. If substitution is desired, attempt to use a 2o or 1o substrate. If elimination is desired use a strong base.
6.21	Be able to prepare for yourself from memory a comparison of all factors influencing whether each substrate type will undergo an SN1, SN2, E1, or E2 reaction.

Section	Goals
7.2	Be able to correctly apply the IUPAC nomenclature rules to the naming of any alkene or cycloalkene. Be able to recognize vinyl and allyl groups by their respective substructures. Be able to apply the (E) and (Z) system for designating alkene diastereomers (as a preferable alternative to cis and trans designations).
7.3	Be able to correctly name any alkyne using the IUPAC system. Be able to recognize terminal alkynes and the weak acidity of their terminal hydrogen.
7.5	Review the conditions and characteristics of the catalytic hydrogenation of alkenes.
7.6	Understand the function of the metal catalyst in catalytic hydrogenation and the necessary stereochemistry resulting from hydrogen addition (syn) by catalytic hydrogenation.
7.7	Know reagents and reaction conditions for i) the exhaustive hydrogenation of an alkyne (to form an alkane by addition of two molar equivalents of hydrogen), ii) partial hydrogenation of an alkyne (to form an alkene by one molar equivalent of hydrogen), and iii) conditions that will lead, as desired, to specifically syn or anti addition of hydrogen to produce Z or E alkenes, respectively.
7.8	Be able to utilize the Index of Hydrogen Deficiency as a clue to structure based on the molecular formula. Include consideration of the "Optional Material" section.
7.9C	Know the relative order of alkene stabilities, although the thermodynamic evidence for such will be de-emphasized.
7.10	Understand intuitively the relative stability of cycloalkenes as a function of ring size.
7.11	Gain acquaintance with the three elimination reactions presented here for synthesis of alkenes.
7.12	Review the essential E2 mech. Understand that if alkene synthesis is desired, conditions favoring an E2 mechanism should be chosen. Be able to describe reaction conditions favoring an E2 mechanism.
7.12A	Understand how a given elimination reaction might proceed to give more than one product. Be able to identify all hydrogens eligible for removal in an elimination reaction. Be able to predict the Zaitsev (more stable alkene) product from a given reaction.
7.12B	Know conditions that could be used to favor elimination to form a less substituted alkene.
7.12C	Be able to draw from memory the antiperiplanar transition state for an E2 reaction. Be able to analyze and predict the products from elimination reactions involving cyclohexane substrates.
7.13	Know conditions for preparation of alkenes by dehydration of alcohols. Understand the effect on ease of dehydration with respect to alcohol structure, and the potential for carbocation rearrangements (see sections 7.13A, 7.14, and 7.15).
7.13A	Be able to draw from memory a stepwise mechanism for acid-catalyzed alcohol dehydration. Recognize this reaction as an E1 process.
7.14	Recall the trend of carbocation stability and understand its influence on ease of alcohol dehydration.
7.15	Be able to recognize the potential for and predict molecular rearrangements in a given substrate as a function of carbocation stability. Be able to draw correct detailed curly arrow mechanisms for both hydride and alkanide (alkyl) migrations, showing the initial carbocation and the carbocation resulting after rearrangement.
7.16	Be able to use debromination of a vicinal dibromide for synthesis of an alkene.
7.17	Review all methods for alkene synthesis, paying attention to substrate types and typical reactions conditions for each, and the form of products favored. Be able to specify reaction conditions leading to alkenes from alkyl halides, alcohols, and dibromides. Be able to specify reaction conditions that would give either a more or less substituted alkene, depending on the reagents and specific substrate structure. Be able to draw the general reaction (using R groups) for any of these reactions.
7.18	Know reaction conditions and substrate types suitable for synthesis of alkynes.
7.19	Recognize the acidity of terminal alkynes and know conditions (use of the appropriate base) for forming an alkynide anion.
7.20	Be able to utilize alkynide anions (starting with the corresponding alkyne) for SN2 reactions to from new carbon-carbon bonds. Recognize the limitation of only being able to use 1o alkyl halide substrates (otherwise E2 occurs).

Section	Goals
8.1	Recall the 3-D orbital structure of alkenes and the pi bond. Understand how a pi bond can be a source of electron density for reaction with electrophiles. Have a general understanding of electrophiles as Lewis acids and know relevant examples. Be able to draw a generalized alkene addition reaction using a generic E-Nu reagent.
8.2	Be able to write a general reaction for the addition of a hydrogen halide to an alkene. Recognize that addition of hydrogen halides to alkenes constitutes a method for synthesis of alkyl halides. Understand the theoretical basis for the most general statement of Markovnikov's rule. Be able to apply it in the addition of any E-Nu reagent to an alkene. Understand the meaning of the term regioselective. Note that carbocation rearrangements are possible. Note that for HBr an exception to Markovnikov addition is possible (Section 8.2D). That is, know the consequences with respect to regiochemistry of using peroxides during addition of HBr to an alkene (anti-Markovnikov addition). Consider the mechanism, although it is OK to wait until Chapter 9 for thorough understanding.
8.3	Know the stereochemical outcome of addition to alkenes when a carbocation is involved and understand the theoretical basis (the nature of the carbocation intermediate). Also recognize the possibility for carbocation rearrangements (see section 7.15).
8.4	Understand the addition of cold sulfuric acid to alkenes within the context of the general mechanism for addition of E-Nu reagents to alkenes.
8.5	Know the acid-catalyzed hydration of alkenes and be able to draw a detailed mechanism for this reaction. Note the regiochemistry of acid-catalyzed hydration. Understand hydration of alkenes within the context of equilibrium reactions and its converse reaction (dehydration of alcohols). Recognize alkene hydration as a method for the synthesis of alcohols.
8.6	Be able to write a three-dimensional mechanism for halogen (Br2, Cl2) addition to an alkene.
8.7	Understand the stereochemical consequences in the mechanism for halogen addition to E and Z alkenes. Be able to determine the stereochemical form of the products based on the structure of the starting alkene. Understand what is meant when a reaction is stereospecific.
8.8	Know how halohydrins are prepared and understand the mechanism for their synthesis as a variation on the theme of halogen addition to alkenes with participation of a nucleophilic solvent.
8.9	Know how to prepare 1,2-diols from alkenes using OsO4 . Recognize the stereospecific aspect of this reaction (syn hydroxylation). Knowledge of cold KMnO4 as a reagent for syn hydroxylation is not essential.
8.10	Know the oxidative cleavage reactions of alkenes using either hot KMnO4 or ozone (O3), including conditions and the specific form of products obtained (aldehydes. ketones, carboxylic acids). Be able to think retrosynthetically with regard to what reaction conditions could be used to prepare a given compound.
8.11	Use Figure 8.5 as a review and summary of alkene addition reaction conditions, regiochemistry, and stereochemistry. Organize your knowledge of addition reactions of alkenes according to 1) which functional groups can be prepared by each reaction, and 2) the stereochemical and/or regiochemical outcome of each. Begin to consider how various addition reactions could be applied to synthesis of compounds with the type of functional groups resulting from addition to alkenes. Also note how cleavage reactions can be used for synthesis of various functional groups.
8.12	Know the addition reactions of halogens to alkynes, noting that reaction with either one or two molar equivalents of reagent are possible with an alkyne (as compared with an alkene).
8.13	Note the regioselectivity of addition of one or two molar equivalents of a hydrogen halide to an alkyne.
8.14	Note that carboxylic acids can be prepared by oxidative cleavage of alkynes.
8.15	Use Figure 8.6 to place in perspective the addition reactions of alkynes by comparing and contrasting the various outcomes with respect to product functional group and reaction stereochemistry and/or regiochemistry.
8.16	Place all of the reactions in this chapter (and from previous chapters) within the context of being able to use them to synthesize molecules by a series of reactions. Practice retrosynthetic analysis by looking for functional groups and carbon-carbon bond disconnections that you now know how to prepare by various reactions. That is, consider how reactions can be used to form carbon-carbon bonds, interconvert functional groups, and control stereochemistry and/or stereochemistry. Note how the stereochemistry and regiochemistry of each reaction must be considered in the planning of any synthesis.
8.17	Omit this section except for the following : 1) concentrated sulfuric acid as a test for alcohols, alkenes and alkynes by their solubility, 2) Br2 as a test for alkenes and alkynes by discharge of the orange color of Br2, and 3) use of alcoholic silver nitrate or sodium iodide in acetone to test for specific aspects of alkyl halide structure.

Section	Goals
9.1	Understand the difference between heterolytic and homolytic bond cleavage with regard to respective formation of ionic and free radical reaction intermediates. Be able to use single-barbed arrows to clearly show single electron movements in reactions of radicals. Know the common ways of producing radicals. Recognize the importance of radicals in industry and biological processes.
9.2	Be able to calculate the overall enthalpy change (Delta H, or heat of reaction) for bond forming and/or bond breaking steps, given the bond dissociation energies (DH) for each pertinent species. Know whether to apply a positive or negative mathematical sign to each bond dissociation energy used in an enthalpy calculation. Know the relative order of alkyl radical stability (3 > 2 > 1).
9.3	With regard to free radical halogenation of alkanes, recognize the possibility for both multiple halogen substitution and the formation of constitutional isomers. Note that use of an excess of alkane with respect to the halogen can lead to primarily mono-substitution (although without selectivity for chlorination). Recognize the importance of symmetry in determining the number of possible products. Know the relative reactivites of chlorine and bromine, i.e. that chlorine is more reactive but less selective whereas bromine is less reactive but more selective.
9.4	Know, as a simple example to be extended later (section 9.7), the chain reaction mechanism for free radical halogenation of methane, including the chain initiating, chain propagating, and possible chain terminating steps. Understand that the sum of the chain propagating steps is equivalent to the overall reaction equation.
9.5	Know how to calculate the overall Delta H for a reaction by summing the H for the chain propagation steps. Omit sections 9.5A and 9.5B unless interested.
9.6	Take as the major points from this section that 1) radical chlorination and bromination are energetically feasible, 2) radical fluorination is very exergonic (so much so as to be impractical outside of industrial laboratories), 3) radical iodination is energetically unfavorable and therefore not feasible.
9.7	Recognize that chlorination is relatively non-selective regarding the position of substitution, typically leading to multiple products. Consider free radical bromination as a synthetically useful reaction due to its relative selectivity as compared to chlorination. Disregard (or read if interested) the accompanying explanation invoking transition state theory.
9.8, 9.9	Know the hybridization of a carbon free radical and be able to draw a three dimensional dash-wedge structure for a carbon free radical intermediate. Understand the ramifications of this structure with regard to radical reactions that involve or produce a stereocenter. Be able to predict whether a free radical reaction will lead to stereoisomers, and if so, whether enantiomers or diastereomers would be formed.
9.10	Recognize the relevance of radical chain reactions in combustion, autoxidation (air oxidation), and reactions of halogen radicals with ozone. Consider the example of hydroperoxide formation shown by autoxidation of a polyunsaturated fat.

Chapter 1 Chapter 2 Chapter 3 Chapter 4 Chapter 5 Chapter 6
Chapter 7 Chapter 8 Chapter 9 Chapter 10 Chapter 11 Chapter 12
Chapter 13 Chapter14 Chapter 15 Chapter 16 Chapter 17 Chapter 18
Chapter 19 Chapter20 Chapter 21 Chapter 22 Chapter 23 Chapter 24

Follow this link back to the Organic Chemistry (Chem 331) Syllabus.

Copyright 1995, 1996 Craig B. Fryhle

Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet
Chapter 1 - Solomons 6/E

Read all of chapter 1 for understanding and general information. Emphasize the sections noted below and develop abilities directed toward meeting the specific goals outlined.

Section Goals
1.1, 1.2 Note the pervasive relevance of organic chemistry to life and society.
1.3 Understand molecular and empirical formulas. Know valences for C, H, N, O, halogens, S. Learn bonding arrangements for the above elements. Understand constitutional isomers and connectivity.
1.4 Know octet rule and ramifications thereof. Understand ionic and covalent bonds and electronegativity trends.
1.5 Be able to draw proper Lewis structures for neutral and ionic species. Note exceptions to the octet rule.
1.7 Be able to calculate formal charge on any atom and determine overall ionic charge.
1.8 Understand essential principles of resonance and be able to draw resonance structures for simple structures where resonance is possible.
1.9 Know the meaning of endothermic, exothermic and enthalpy as applied to energy changes in chemical reactions.
1.10 Understand wave characteristics (phase interactions) leading to reinforcement , and interference. Accept the general relevance of wave properties to atomic structure.
1.11 Understand interpretation of the square of the wave function (psi**2) as indicating a region of space where probability of finding an electron is high. Learn the three dimensional shapes and orientations of s and p orbitals derived from wave functions. Be able to draw proper valence electron configurations for C, N, O, and halogens.
1.12 Understand the derivation of a specific number of molecular orbitals from combinations of a given number of atomic orbitals.
1.13, 1.14, 1.15 Be able to apply electron configurations and the principle of orbital hybridization to predict the structure of sp3, sp2, and sp hybridized atoms.
1.16 Use this section to unify your understanding of quantum mechanics concepts discussed earlier.
1.17 Be able to use the VSEPR model to predict tetrahedral, trigonal planar, and linear molecular geometries for various examples.
1.18, 1.19 Be able to apply the principles of electronegativity and bond polarization for prediction of the overall polarity or lack thereof in any given molecule.
1.20 Gain unquestionable proficiency in representing organic molecules in their dash, condensed, bond- line, and three-dimensional (dash-wedge) structural formulas.

Assigned Problems: 1, 2bcde, 3, 4, 8cdef, 9, 10, 11, 12, 14, 16, 21abcd, 22ad, 23, 24, 26, 27abdfhi, 28abcd, 30, 33, 34
331ss1.doc rev 8/95
Copyright 1995, Craig B. Fryhle
Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet
Chapter 2 - Solomons 6/E

Read all of Chapter 2 for understanding and general information. Emphasize the sections noted below and develop abilities directed toward meeting the specific goals outlined.

Section Goals
2.2 Understand the structural meaning of the terms hydrocarbon, alkanes, alkenes, alkynes, saturated, and unsaturated. Gain a 3-D sense of the structure of alkanes based on their hybridization and bonding.
2.3 Understand the 3-D arrangement of atoms that are part of an alkene double bond.
2.4 Understand the origin of sp2 hybridization through electron promotion and hybridization. Know unequivocally the orbital structure of an sp2 hybridized atom and the orbital representation of a * (pi) bond with a sigma bond framework. Understand the ramifications of restricted rotation about pi bonds and the potential for cis-trans isomerism, as compared to free rotation about * (sigma) bonds.
2.5 Understand the 3-D arrangement of atoms that are part of an alkyne triple bond.
2.6 Understand the origin of sp orbitals through hybridization and know the orbital structure of an sp hybridized atom. Understand the overlap of adjacent p orbitals from sp hybridized carbon atoms leading to the orthogonal relationship of the two * bonds in an alkyne.
2.7 Know the structural meaning of the names and shorthand representations for the phenyl and benzyl aromatic groups.
2.8 Understand what alkyl groups are. Know the names and be able to draw structures for all alkyl ("R") groups of three carbons or fewer. Understand the notion of a functional group.
2.9 Be able to write the general structures of 1o (primary), 2o (secondary), and 3o (tertiary) alkyl halides (using R groups) and identify real examples of each type.
2.10 Be able to write the general structures of 1o (primary), 2o (secondary), and 3o (tertiary) alcohols (using R groups) and identify examples of each type in a real molecule.
2.11 Be able to write the general structure of an ether and identify the ether functional group in real examples.
2.12 Be able to write the general structures of 1o (primary), 2o (secondary), and 3o (tertiary) amines (using R groups) and identify examples of each type in a real molecule.
2.13 Know the 3-D structure and hybridization of the carbonyl group. Be able to write the general structures of aldehydes and ketones and identify both functional groups in real examples.
2.14 Be able to write the general structures of carboxylic acids, amides, and esters and identify these functional groups in real examples.
2.15 Know the dash and all condensed structural formula representations for the above functional groups and be able to draw every one from memory. Not the summary inside the front cover and in Table 2.2.
2.16, 2.16 A-F Know the various types of intermolecular forces that are possible and understand their influence on physical properties (such as mp, bp and solubility) for a given molecule.

Assigned Problems: 1, 2, 3, 4, 5, 6, 7, 8acde, 9acdf, 10, 11, 12, 14, 15, 16, 18, 19ace, 20abce, 21(odd), 22(odd), 23
331ss2.doc rev 8/95
Copyright 1995, Craig B. Fryhle
Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet

Chapter 3 - Solomons 6/E

Read all of Chapter 3 for understanding and general information. Emphasize the sections noted below and develop abilities directed toward meeting the specific goals outlined.

Section Goals
3.1 Note the general changes in structure accompanying substitution, addition, elimination, and rearrangement reactions.
3.1A Understand the concept of a mechanism as a stepwise description of events in a chemical reaction.
3.1B Understand that cleavage of a bond to a carbon could conceivably occur by in three ways: homolytically (to forma free radical), or heterolytically with the carbon either keeping or losing both electrons of the bond (to form a carbanion or carbocation, resp.) Understand the general meaning of heterolytic and homolytic bond cleavage.
3.2A Review concepts of Bronsted-Lowry Acids and Bases.
3.2B Understand Lewis acids and bases as generally applicable to acid base theory. Be able to classify compounds as Lewis acids or bases, especially with regard to examples involving organic compounds.
3.3 Know the general structure of a carbocation and carbanion, Learn the basic definition/character of nucleophiles and electrophiles.
3.4 Understand the precise use of the double-barbed curved arrow and be able to draw them appropriately and with accurate meaning.
3.5 Understand the mathematical derivation of Ka and pKa. Know the significance of both Ka and pKa regarding acid (and conjugate base) strength. Be able to write the conjugate base or conjugate acid from any acid or base, respectively, and the corresponding acid or base from the respective conjugate .
3.6 Be able to use Ka or pKa values to predict the direction of an acid-base reaction.
3.7 Understand the influences of bond strength (to the acidic hydrogen), electronegativity, hybridization, and inductive effects on acidity.
3.9 Know the relative acidities of carboxylic acids and alcohols.
3.10 Recognize the ability of protic solvents to solvate the anions formed upon ionization of an acid.
3.11 Understand the capacity of organic compounds containing oxygen to act as bases and engage in proton transfer reactions.
3.12 Note the format and stepwise detail in this example of a mechanism.
3.13 Understand the need for solvents other than water when bases stronger than hydroxide ion are used (understand the leveling effect of water in these cases). Begin to recognize some exceptionally strong bases (e.g. NaNH2, NaH, and alkyllithium reagents (RLi).
3.14 Understand the ability to introduce deuterium and tritium by acid-base reactions.
3.15 Review the highlights listed in this section and those noted above.

Assigned Problems: 1ac, 2, 3, 5, 7, 8, 10, 11acd, 12, 13abef, 15, 16, 17, 18, 19, 20, 22, 24, 25abde, 29bc, 32, 33
331ss3.doc rev 8/95
Copyright 1995, Craig B. Fryhle
Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet
Chapter 4 - Solomons 6/E

Read all of Chapter 4 for understanding and general information. Emphasize the sections noted below and develop abilities directed toward meeting the specific goals outlined.

Section Goals
4.1 Recognize petroleum as the primary natural source of alkanes and aromatic hydrocarbons.
Know the general formulas for an alkane and cycloalkane.
4.2 Be ever cognizant of the general three-dimensional structure of alkanes, based on the appropriate hybridization state of carbon, regardless of the type of formula presented.
Understand the structural meanings as pertains to alkanes of the designations "straight-chain" (or unbranched) and branched. Recall that constitutional isomers have different physical properties.
4.5, 4.3A-F Learn the IUPAC names of alkanes through C20. Learn all the alkyl group names from C1 through C5. Be able to apply the IUPAC rules for naming branched chain alkanes. Learn the names of branched alkyl groups through C5. including the meaning of prefixes iso-, sec-, tert-. Be able to classify hydrogens as 1^o,2^o, or 3^o. Be able to name alkyl halides and alcohols using the IUPAC system.
4.4 Be able to name monocyclic alkanes (section 4.4A). Read section 4.4B for interest.
4.5 Recognize the trends in mp and bp among hydrocarbon homologs. Know the general density and solubility properties of alkanes and cycloalkanes, as compared to water.
4.6 Be able to perform conformational analyses on simple alkanes using Newman projections to draw the various conformation. Recognize a given conformation as being staggered or eclipsed.
4.7 Understand the significance of torsional strain regarding conformational anyalysis. Recognize a given conformation as being anti or gauche, as well as staggered and eclipsed.
4.8 Know the relative order of stability for cycloalkanes from cyclohexane to cyclopropane.
Disregard heats of combustion (section 4.8B) unless interested in further explanation.
4.9 Understand the influence of angle and torsional strain on the overall ring strain in cyclopropane and cyclobutane, as compared to cyclopentane and cyclohexane.
4.10 Be able to recognize and draw clearly the boat and chair conformations of cyclohexane, especially the chair, showing correct 3-D perspective. Be able to draw a Newman projection for cyclohexane, viewed along any pair of C-C bonds.
4.11 Learn to identify the axial and equatorial positions on the chair conformation of cyclohexane. Be able to draw cyclohexane so that axial and equatorial positions of substituents are absolutely unambiguous. Understand the origin of 1,3-diaxial interactions and the basis for the relatively greater stability of chair conformations with substituents in equitorial orientations.
Lean to depict a chair-chair conformational ring flip with accurate drawings showing the changes in axial and equitorial orientations of groups.
4.12 Understand the possibility for cis and trans stereoisomers in disubstituted cycloalkanes. Be able to draw both the unrealistic "flat" ring structures (e.g. pp.159 and 160) and realistic chair conformational structures for disubstituted cyclohexanes (e.g. pp. 161 and 162). Correctly place cis or trans groups in axial or equitorial orientations, depending on the preferred, lowest energy conformation for the chair.
4.14 Recognize the relatively inert character of alkanes, aside from combustion.
4.15 Learn the reagents, reaction conditions, types of starting materials required and products formed for the reactions presented for the synthesis of alkanes in sections 4.15A-C:
i) hydrogenation of alkenes,ii) reduction of alkyl halides, and iii) the use of lithium dialkylcuprates. Be able to write examples of each reaction using R groups for generalized reactants and products. Be able to translate an understanding of the general reactions to use of the reaction conditions with specific molecules to form the corresponding products.
4.16 Begin to understand the notion and use of retrosynthetic analysis. Be able to envision specific and logical retrosyntheetic disconnections and precursor intermediates when planning the synthesis of a given molecule. Be able to evaluate the merits of vaious synthetic routes to a given molecule.<
4.17 Note the biological role of some relatively simple hydrocarbons.
4.18 Review the topics listed here and highlights of chapter four noted above.
Assigned Problems: 1, 3b, 4a, 5ac, 6be, 7, 9, 10, 11, 12, 13, 14ac, 16, 18bdef, 20ab, 23, 27, 32, 35, 37af

331ss4.doc rev 8/95
Copyright 1995, Craig B. Fryhle
Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet
Chapter 5 - Solomons 6/E

Read all of Chapter 5 for understanding and general information. Emphasize the sections noted below and develop abilities directed toward meeting the specific goals outlined.

Section Goals
5.1 Know the definitions of constitutional isomers, stereoisomers, enantiomers, and diastereomers, and their relationship to each other. Be able to classify the specific type of isomeric relationship between any one compound and another.
5.2 Be able to identify tetrahedral and trigonal stereocenters in molecules. Be able to identify a compound as being chiral or achiral by testing for superposability on its mirror image. Work on visualizing molecules in three dimensions, especially regions involving stereocenters. Do this by making models and drawing dash-wedge structures of models, and by making models of drawn structures. Understand the importance of mirror planes for determining whether an enantiomer to a given molecule can exist. Understand the effect of interchanging the position of any two groups at a tetrahedral stereocenter.
5.3 Note the profound importance of chirality in natural products and biologically active molecules.
5.5 Be able to use the mirror plane test for chirality.
5.6 In general, be able to assign the R or S configuration to any tetrahedral stereocenter by correctly determing the relative priorities of groups bonded to the stereocenter and determining the direction of priority rotation. Specifically, be able to apply the priority rules to any type of attached group, including those with multiple bonds. Develop expert facility at visualizing the direction of rotation of the attached groups at a tetrahedral stereocenter, according to their priorities and with a mind's eye view from inside the "inverted umbrella" of the tetrahedron.
5.7 Understand the definition of optical activity as the rotation of plane polarized light by chiral molecules. Know that optical activity is measured using instruments called polarimeters. Recognize that no obvious correlation exists between the sign of rotation (+ or -) for an optically active molecule and the R or S configuration of enantiomers. Understand that an optical rotation measurement can be standardized for use as a physical constant for a given optically active substance by calculating what is known as the specific rotation, through taking into account sample characteristics such as concentration, etc.
5.8 Understanding the meaning of the term racemic mixture (or racemic form, or racemate). Have an intuitive understanding of the origin of optically activity and why there is no optical activity in a racemic mixture.
5.9 Understand that a racemic mixture results when a chiral molecule is formed by a chemical reaction between achiral starting materials and achiral reagents. Consider how an optically active product might result from using either chiral starting materials or chiral reagents.
5.10 Not the importance of chirality in drug design and manufacture.
5.11 Understand the ramifications of having more than one stereocenter in a molecule ("n" stereocenters) with regard to the total number of isomers possible (2n), how many enantiomer pairs are possible (2n- 1) and how many diastereomers could exist (2n-1). Understand the relationship between diastereomers with regard to physical constants. Be able to identify meso compounds. Be able to use the R,S system to name compounds with more than one stereocenter.
5.12 Understand how to draw and interpret Fischer projection formulas, while recognizing the advantages and pitfalls of their use.
5.13 Understand how stereoisomerism applies to cyclic molecules and be able to recognize cases where planes of symmetry may influence the existence or number of stereoisomers in cyclic compounds.
5.14 Understand how the R,S configuration of a stereocenter may or not be affected by the breaking and forming of bonds to the stereocenter (according to the priorities of the new and old groups), and also how the R,S configuration of a stereocenter may or not be affected by the breaking of bonds not directly attached to the stereocenter (according to how a group's priority might change through remote alteration). Understand the process of relating configurations between molecules by use of reactions with known stereochemical outcome.
5.15 Understand the principle behind methods for the separation of enantiomers, i.e. that reversible conversion of a pair of enantiomers into diastereomeric species results in materials of differing physical properties, which after separation could be used to regenerate each original enantiomer in isolated form.
5.18 Review the the concepts discussed therein, as well as the above topics.

Assigned Problems: 2, 3, 4, 5, 8, 9, 10, 11, 12, 13, 14, 16, 17, 19, 20adf, 21, 22(for 20ad), 23, 26, 27, 30abcd, 35a-j,nop, 38, 39, 40

331ss5.doc rev 8/95
Copyright 1995, Craig B. Fryhle
Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet
Chapter 6 - Solomons 6/E

Read all of Chapter 6 for understanding and general information. Emphasize the sections noted below and develop abilities directed toward meeting the specific goals outlined.

Section Goals
6.1 Know the general structural characteristics of an alkyl halide, re: bond polarity, geometry, etc. Be able to readily identify an alkyl halide as 1o (primary), 2o (secondary), or 3o (tertiary). Be able to recognize vinylic and aryl halides (significant because vinylic and aryl halides do not react by the mechanisms in Chapter 6).
6.3 Be able to write the general reaction for a nucleophilic substitution reaction and identify the nucleophile, substrate (e.g. alkyl halide), and leaving group.
6.4 Gain thorough understanding of what a nucleophile is and be able to recognize the nucleophilic participant in a reaction. Be able to recall specific examples of nucleophiles. Understand the general character of nucleophiles, such that you could identify potentially nucleophilic species in a reaction. For specific examples where the nucleophilic atom bears a hydrogen (e.g. HOH, ROH), understand the reason for a proton transfer step after the substitution).
6.5 Understand the general nature of a leaving group as being the species that departs with a pair of electrons during a nucleophilic substitution reaction. Learn to recognize the leaving group in substrates for nucleophilic substitution. Recognize that the better a leaving group is able to accomodate (stabilize) the electron pair it takes with it, the better the leaving group will be.
6.7 Read for general understanding.
6.8 Understand that in SN2 reactions both the nucleophile and alkyl halide substrate are involved in the rate determining step.
6.8 As one of the most important sections in the entire book, have emblazened upon one's memory the general aspects of the SN2 reaction depicted on page 233. Pay special attention to the site of nucleophic attack (backside with respect to the leaving group), the structure of the transition state (involving concerted bond forming to the nucleophile and bond breaking to the leaving group), and the configuration of the product as compared to the substrate (inversion of the tetrahedral center).
6.9 Be able to draw a generic free energy diagram for an SN2 reaction, labeling the transition state, and showing the overall free energy change for the reaction (*Go), whether it be endergonic or exergonic. Understand the influence of the magnitude of the energy of activation (*G*) on the rate of reaction. Understand the influence of temperature on reaction rates.
6.10 Further cement in place an understanding of SN2 reaction as occuring by backside attack of the nucleophile with inversion of configuration and simultaneous bond forming and breaking. Understand the ramifications of inversion for SN2 reactions taking place at stereocenters. Be able to draw from memory and in three-dimensions a generic mechanism for an SN2 reaction, including, of course, the transition state.
6.11 Know that SN1 reactions are unimolecular in the rate determining step.
6.12 Ingrain the sequence of steps involved in any general SN1 reaction (see p. 242 for a specific example): 1) departure of the leaving group (with the pair of electrons that bonded the LG to the substrate), 2) concomitant formation of a carbocation at the carbon that lost the LG, and 3) attack of the nucleophile on the carbocation. Understand that there may be proton transfer steps necessary, depending on the nature of the nucleophile and leaving group, but consider the above three stages the essential components of every SN1 reaction.
6.13 Cement an understanding of the orbital/3D structure of a carbocation, especially the planar nature of the sp2 carbon and the vacant p orbital. Know the general trend in relative carbocation stability.
6.14A Understand how the stereochemical outcome of an SN1 reaction (racemization) follows from the planar structure of the intermediate carbocation (allowing both frontside and backside attack by the nucleophile). Be able to draw from memory and in three dimensions where appropriate the stepwise mechanism for a generic SN1 reaction, as outlined in the three steps of section 6.12.
6.14B Recognize solvents as potential nucleophiles in SN1 reactions and understand the concomitant proton transfer steps that are required.
6.15 Be able to list and discuss the four most important factors affecting rates of SN1 and SN2 reactions.
6.15A Know how structure affects the rate of SN1 and SN2 reactions, i.e. steric hindrance for SN2 and relative carbocation stability for SN1.
6.15B Be able to assess the relative strength of a nucleophile, based on it's charge or lack thereof, and relative basicity. Understand the effect of concentration on the rate of SN2 reactions.
6.15C Understand why polar aprotic solvents facilitate SN2 reactions. Understand the structural difference between polar and aprotic solvents and be able togive examples of each. <
6.15D Understand the ionizing ability of polar protic solvents and their tendency to increase the rate of SN1 reactions. Recognize that while water is a good ionizing solvent, many organic compounds are not soluble in water, and therefor other organic solvents such as methanol and alcohol are frequently mixed with water to assist in solvation of the organic reactants.
6.15E Learn some of the common leaving groups and recognize the common ability among them to stabilize/accomodate the pair of electrons taken with them when they act as leaving groups. Understand the inverse relationship of base strength to leaving group ability.
6.16 Be able to prepare compounds with a variety of functional groups by transformation or incorporation of functional groups using SN2 reactions on suitable substrates. Recall the unreactivity of vinyl and aryl halides in SN1 and SN2 reactions.
6.17 Be able to draw from memory a generic example of a dehydrohalogenation reaction. Be able to recognize hydrogens (*-hydrogens) eligible for removal by a base, and the position of the double bond that will form upon departure of the leaving group (from the *-carbon).
6.17B Know the common bases used for dehydrohalogenation (also called 1,2-elimination).
6.18 Ingrain in memory the general mechanism of an E2 reaction (in three dimensions), including the transition state, as depicted on page 263).
6.19 Understand the mechanism of an E1 reaction, recognizing the possibility for elimination of any *- hydrogen from a carbocation intermediate, in addition to the possiblity for an SN1 substitution.
6.20 Understand the combined influence of factors such as base/nucleophile strength and substrate structure (steric hindrance) with regard to competition between SN2 and E2 reactions. With regard to SN1 and E1 reactions, recognize the inherent difficulty in directing a tertiary substrate toward substitution. If substitution is desired, attempt to use a 2o or 1o substrate. If elimination is desired use a strong base.
6.21 Be able to prepare for yourself from memory a comparison of all factors influencing whether each substrate type will undergo an SN1, SN2, E1, or E2 reaction.

Assigned Problems: 1abde, 2, 3, 4, 5, 7, 8, 9, 12, 13, 14, 16abe, 17, 18, 19, 20, 21, 25, 26, 27, 29, 32, 33, 35, 38

331ss6.doc rev 8/95

Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet
Chapter 7 - Solomons 6/E

Read all of Chapter 7 for understanding and general information. Emphasize the sections noted below and develop abilities directed toward meeting the specific goals outlined.

Section Goals
7.2 Be able to correctly apply the IUPAC nomenclature rules to the naming of any alkene or cycloalkene. Be able to recognize vinyl and allyl groups by their respective substructures. Be able to apply the (E) and (Z) system for designating alkene diastereomers (as a preferable alternative to cis and trans designations).
7.3 Be able to correctly name any alkyne using the IUPAC system. Be able to recognize terminal alkynes and the weak acidity of their terminal hydrogen.
7.5 Review the conditions and characteristics of the catalytic hydrogenation of alkenes.
7.6 Understand the function of the metal catalyst in catalytic hydrogenation and the necessary stereochemistry resulting from hydrogen addition (syn) by catalytic hydrogenation.
7.7 Know reagents and reaction conditions for i) the exhaustive hydrogenation of an alkyne (to form an alkane by addition of two molar equivalents of hydrogen), ii) partial hydrogenation of an alkyne (to form an alkene by one molar equivalent of hydrogen), and iii) conditions that will lead, as desired, to specifically syn or anti addition of hydrogen to produce Z or E alkenes, respectively.
7.8 Be able to utilize the Index of Hydrogen Deficiency as a clue to structure based on the molecular formula. Include consideration of the "Optional Material" section.
7.9C Know the relative order of alkene stabilities, although the thermodynamic evidence for such will be de-emphasized.
7.10 Understand intuitively the relative stability of cycloalkenes as a function of ring size.
7.11 Gain acquaintance with the three elimination reactions presented here for synthesis of alkenes.
7.12 Review the essential E2 mech. Understand that if alkene synthesis is desired, conditions favoring an E2 mechanism should be chosen. Be able to describe reaction conditions favoring an E2 mechanism.
7.12A Understand how a given elimination reaction might proceed to give more than one product. Be able to identify all hydrogens eligible for removal in an elimination reaction. Be able to predict the Zaitsev (more stable alkene) product from a given reaction.
7.12B Know conditions that could be used to favor elimination to form a less substituted alkene.
7.12C Be able to draw from memory the antiperiplanar transition state for an E2 reaction. Be able to analyze and predict the products from elimination reactions involving cyclohexane substrates.
7.13 Know conditions for preparation of alkenes by dehydration of alcohols. Understand the effect on ease of dehydration with respect to alcohol structure, and the potential for carbocation rearrangements (see sections 7.13A, 7.14, and 7.15).
7.13A Be able to draw from memory a stepwise mechanism for acid-catalyzed alcohol dehydration. Recognize this reaction as an E1 process.
7.14 Recall the trend of carbocation stability and understand its influence on ease of alcohol dehydration.
7.15 Be able to recognize the potential for and predict molecular rearrangements in a given substrate as a function of carbocation stability. Be able to draw correct detailed curly arrow mechanisms for both hydride and alkanide (alkyl) migrations, showing the initial carbocation and the carbocation resulting after rearrangement.
7.16 Be able to use debromination of a vicinal dibromide for synthesis of an alkene.
7.17 Review all methods for alkene synthesis, paying attention to substrate types and typical reactions conditions for each, and the form of products favored. Be able to specify reaction conditions leading to alkenes from alkyl halides, alcohols, and dibromides. Be able to specify reaction conditions that would give either a more or less substituted alkene, depending on the reagents and specific substrate structure. Be able to draw the general reaction (using R groups) for any of these reactions.
7.18 Know reaction conditions and substrate types suitable for synthesis of alkynes.
7.19 Recognize the acidity of terminal alkynes and know conditions (use of the appropriate base) for forming an alkynide anion.
7.20 Be able to utilize alkynide anions (starting with the corresponding alkyne) for SN2 reactions to from new carbon-carbon bonds. Recognize the limitation of only being able to use 1o alkyl halide substrates (otherwise E2 occurs).

Assigned Problems: 1a-e, 2bdfj, 3ace, 5, 6, 10, 11, 13, 14, 15, 16, 18, 19, 20, 22cegkl, 23 24acd, 25, 27acde, 29, 33, 34, 35, 36, 37, 38, 41, 43, 46, 49
331ss7.doc rev 10/95

Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet
Chapter 8 - Solomons 6/E

Read all of Chapter 8 for understanding and general information. Emphasize the sections noted below and develop abilities directed toward meeting the specific goals outlined.

Section Goals
8.1 Recall the 3-D orbital structure of alkenes and the pi bond. Understand how a pi bond can be a source of electron density for reaction with electrophiles. Have a general understanding of electrophiles as Lewis acids and know relevant examples. Be able to draw a generalized alkene addition reaction using a generic E-Nu reagent.
8.2 Be able to write a general reaction for the addition of a hydrogen halide to an alkene. Recognize that addition of hydrogen halides to alkenes constitutes a method for synthesis of alkyl halides. Understand the theoretical basis for the most general statement of Markovnikov's rule. Be able to apply it in the addition of any E-Nu reagent to an alkene. Understand the meaning of the term regioselective. Note that carbocation rearrangements are possible. Note that for HBr an exception to Markovnikov addition is possible (Section 8.2D). That is, know the consequences with respect to regiochemistry of using peroxides during addition of HBr to an alkene (anti-Markovnikov addition). Consider the mechanism, although it is OK to wait until Chapter 9 for thorough understanding.
8.3 Know the stereochemical outcome of addition to alkenes when a carbocation is involved and understand the theoretical basis (the nature of the carbocation intermediate). Also recognize the possibility for carbocation rearrangements (see section 7.15).
8.4 Understand the addition of cold sulfuric acid to alkenes within the context of the general mechanism for addition of E-Nu reagents to alkenes.
8.5 Know the acid-catalyzed hydration of alkenes and be able to draw a detailed mechanism for this reaction. Note the regiochemistry of acid-catalyzed hydration. Understand hydration of alkenes within the context of equilibrium reactions and its converse reaction (dehydration of alcohols). Recognize alkene hydration as a method for the synthesis of alcohols.
8.6 Be able to write a three-dimensional mechanism for halogen (Br2, Cl2) addition to an alkene.
8.7 Understand the stereochemical consequences in the mechanism for halogen addition to E and Z alkenes. Be able to determine the stereochemical form of the products based on the structure of the starting alkene. Understand what is meant when a reaction is stereospecific.
8.8 Know how halohydrins are prepared and understand the mechanism for their synthesis as a variation on the theme of halogen addition to alkenes with participation of a nucleophilic solvent.
8.9 Know how to prepare 1,2-diols from alkenes using OsO4 . Recognize the stereospecific aspect of this reaction (syn hydroxylation). Knowledge of cold KMnO4 as a reagent for syn hydroxylation is not essential.
8.10 Know the oxidative cleavage reactions of alkenes using either hot KMnO4 or ozone (O3), including conditions and the specific form of products obtained (aldehydes. ketones, carboxylic acids). Be able to think retrosynthetically with regard to what reaction conditions could be used to prepare a given compound.
8.11 Use Figure 8.5 as a review and summary of alkene addition reaction conditions, regiochemistry, and stereochemistry. Organize your knowledge of addition reactions of alkenes according to 1) which functional groups can be prepared by each reaction, and 2) the stereochemical and/or regiochemical outcome of each. Begin to consider how various addition reactions could be applied to synthesis of compounds with the type of functional groups resulting from addition to alkenes. Also note how cleavage reactions can be used for synthesis of various functional groups.
8.12 Know the addition reactions of halogens to alkynes, noting that reaction with either one or two molar equivalents of reagent are possible with an alkyne (as compared with an alkene).
8.13 Note the regioselectivity of addition of one or two molar equivalents of a hydrogen halide to an alkyne.
8.14 Note that carboxylic acids can be prepared by oxidative cleavage of alkynes.
8.15 Use Figure 8.6 to place in perspective the addition reactions of alkynes by comparing and contrasting the various outcomes with respect to product functional group and reaction stereochemistry and/or regiochemistry.
8.16 Place all of the reactions in this chapter (and from previous chapters) within the context of being able to use them to synthesize molecules by a series of reactions. Practice retrosynthetic analysis by looking for functional groups and carbon-carbon bond disconnections that you now know how to prepare by various reactions. That is, consider how reactions can be used to form carbon-carbon bonds, interconvert functional groups, and control stereochemistry and/or stereochemistry. Note how the stereochemistry and regiochemistry of each reaction must be considered in the planning of any synthesis.
8.17 Omit this section except for the following : 1) concentrated sulfuric acid as a test for alcohols, alkenes and alkynes by their solubility, 2) Br2 as a test for alkenes and alkynes by discharge of the orange color of Br2, and 3) use of alcoholic silver nitrate or sodium iodide in acetone to test for specific aspects of alkyl halide structure.

Assigned Problems: 2, 3, 6, 7, 8, 9, 10, 11, 12, 13, 14, 17, 18abfghijklmn, 19abfghijklmn, 20a-g, 21a-ehlm, 22abde, 23, 24, 25, 26, 33, 35, 36ac, 37, 38, 42, 43, 44, 45
331ss8.doc rev 10/95

Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet
Chapter 9 - Solomons 6/E

Read all of Chapter 9 for understanding and general information. Emphasize the sections noted below and develop abilities directed toward meeting the specific goals outlined.

Section Goals
9.1 Understand the difference between heterolytic and homolytic bond cleavage with regard to respective formation of ionic and free radical reaction intermediates. Be able to use single-barbed arrows to clearly show single electron movements in reactions of radicals. Know the common ways of producing radicals. Recognize the importance of radicals in industry and biological processes.
9.2 Be able to calculate the overall enthalpy change (Delta H, or heat of reaction) for bond forming and/or bond breaking steps, given the bond dissociation energies (DH) for each pertinent species. Know whether to apply a positive or negative mathematical sign to each bond dissociation energy used in an enthalpy calculation. Know the relative order of alkyl radical stability (3 > 2 > 1).
9.3 With regard to free radical halogenation of alkanes, recognize the possibility for both multiple halogen substitution and the formation of constitutional isomers. Note that use of an excess of alkane with respect to the halogen can lead to primarily mono-substitution (although without selectivity for chlorination). Recognize the importance of symmetry in determining the number of possible products. Know the relative reactivites of chlorine and bromine, i.e. that chlorine is more reactive but less selective whereas bromine is less reactive but more selective.
9.4 Know, as a simple example to be extended later (section 9.7), the chain reaction mechanism for free radical halogenation of methane, including the chain initiating, chain propagating, and possible chain terminating steps. Understand that the sum of the chain propagating steps is equivalent to the overall reaction equation.
9.5 Know how to calculate the overall Delta H for a reaction by summing the H for the chain propagation steps. Omit sections 9.5A and 9.5B unless interested.
9.6 Take as the major points from this section that 1) radical chlorination and bromination are energetically feasible, 2) radical fluorination is very exergonic (so much so as to be impractical outside of industrial laboratories), 3) radical iodination is energetically unfavorable and therefore not feasible.
9.7 Recognize that chlorination is relatively non-selective regarding the position of substitution, typically leading to multiple products. Consider free radical bromination as a synthetically useful reaction due to its relative selectivity as compared to chlorination. Disregard (or read if interested) the accompanying explanation invoking transition state theory.
9.8, 9.9 Know the hybridization of a carbon free radical and be able to draw a three dimensional dash-wedge structure for a carbon free radical intermediate. Understand the ramifications of this structure with regard to radical reactions that involve or produce a stereocenter. Be able to predict whether a free radical reaction will lead to stereoisomers, and if so, whether enantiomers or diastereomers would be formed.
9.10 Recognize the relevance of radical chain reactions in combustion, autoxidation (air oxidation), and reactions of halogen radicals with ozone. Consider the example of hydroperoxide formation shown by autoxidation of a polyunsaturated fat.

Assigned Problems 1d,g, 3, 5, 6, 7, 8, 12, 14, 15a,b, 17, 18, 23, 26
331ss9.doc

Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||
Organic Chemistry Study Sheet
Chapter 10 - Solomons 6/E

Read all of Chapter 10 for understanding and general information. Although there are many new reagents and reactions in this chapter, there is little new regarding general mechanisms and reaction types. Attempt to place each new reaction within the context of a general mechanistic class you have already learned, i.e. addition reactions of alkenes (oxymercuration-demurcuration, hydroboration-oxidation, epoxide synthesis), nucleophilic substitution (tosylates, mesylates, alkyl halide and ether synthesis from alcohols, and epoxide ring opening), and general acid-base principles.

Section Goals
10.1 Be able to name alcohols by the IUPAC system. Be able to name ethers using common radicofunctional names for simple ethers or IUPAC substitutive names for more complicated ethers. Be able to distinguish a phenol from an alcohol, and recognize benzyl and allyl alcohols/ethers. Be able to write the general formula (using R groups) for an alcohol or ether.
10.2 Understand the general differences in terms of intermolecular forces between alcohols and ethers.
10.3 Read for general information and appreciation of practical applications for some alcohols and ethers.
10.4 Recall and review alcohol synthesis by hydration of alkenes. Recall the limitations of this method (carbocation rearrangements, etc.).
10.5 Be able to synthesize an alcohol using the oxymercuration-demurcuration protocol. Know its benefits (lack of molecular rearrangements) and regiochemistry (Markovnikov). Recognize the potential for ether synthesis by simply making the solvent nucleophile an alcohol instead of water (solovomercuration-demurcuration).
10.6, 10.7 Know the reaction conditions for the hydroboration-oxidation sequence for synthesis of alcohols [1) BH3THF, 2) H2O2,OH-]. Know the stereochemistry for the overall addition of the hydrogen and hydroxyl group (syn) and the regiochemistry (anti-Markonvikov). Recognize hydroboration-oxidation as a synthetic compliment to oxymercuration-demurcuration with respect to regiochemistry. Omit section 10.7B.
10.8 Recall the essential properties of alcohols: the alcohol oxygen is moderately nucleophilic and weakly basic, the alcohol hydroxy group is a poor leaving group unless first protonated or converted into a leaving group by formation of some type of sulfonate ester (e.g. a tosylate, mesylate, triflate).
10.9 Recall that alcohols are weakly acidic and can form strong alkoxide bases/nucleophiles upon deprotonation by a stronger base (e.g. NaH) or alkaline earth metal (Na or K).
10.10 Know the reaction conditions for forming tosylates and mesylates and the structures of the products, including those written with the Ts or Ms abbreviation. Disregard the mechanism of formation unless interested.
10.11 Know that alkyl sulfonates can be used as an indirect method for accomplishing SN2 nucleophilic substition of the hydroxyl group in an alcohol (initial conversion of the alcohol to an alkyl sulfonate leaving group followed by SN2 substitution by the desired nucleophile).
10.12 Note that alkyl phosphates are one of nature's most important leaving groups in biochemical reactions.
10.13 This is a preliminary introduction to sections 10.14 and 10.15.
10.14 Recognize that alcohols can be converted to alkyl halides by reaction with the appropriate HX. Understand the mechanism as simply applications of acid-base reactions followed by nucleophilic substitution.
10.15 Know PBr3 and SOCl2 as the preferred reagents for conversion of 1o and 2o alcohols to alkyl bromides and chlorides, respectively. Note mechanisms only if interested.
10.16 Recognize the intermolecular dehydration of alcohols as a method for synthesis of symmetrical ethers. Understand the mechanism as simply applications of acid-base and nucleophilic substitution reaction mechanisms. Know how to accomplish a Williamson ether synthesis (10.16B) and recognize it's limitations according to the requirement that it be an SN2 reaction. Omit sections 10.16C and D.
10.17 Understand the reactions of ethers with acids as protonation to form a leaving group followed by nucleophilic substitution to form the respective products.
10.18 Know the general structure of an epoxide and the reagents used for their formation from alkenes (peroxy carboxylic acids, i.e. RCOOOH or RCO3H). Know the stereochemistry of oxygen addition (syn, by default, with retention of the original alkene geometry).
10.19 Understand the principles of acidic or basic ring-opening of epoxides, and know the mechanistic/regiochemical implications of each (e.g. regiochemistry of attack by nucleophile).
10.20 Recognize epoxidation followed by hydrolysis (acidic or basic) as a means for anti-hydroxylation of alkenes.
10.21 Use this section to tie together the various reactions and their stereochemical and regiochemical ramifications. Consider how each reaction could be used in synthesis problems. Catagorize reactions according to the types of functional groups each one allows you to form, the functional groups required in the starting materials, and the stereochemical/regiochemical control each reaction may exhibit.
10.22 Omit this section, except for noting the biochemical significance of crown ether antibiotics (10.22B).

Section	Goals
10.1	Be able to name alcohols by the IUPAC system. Be able to name ethers using common radicofunctional names for simple ethers or IUPAC substitutive names for more complicated ethers. Be able to distinguish a phenol from an alcohol, and recognize benzyl and allyl alcohols/ethers. Be able to write the general formula (using R groups) for an alcohol or ether.
10.2	Understand the general differences in terms of intermolecular forces between alcohols and ethers.
10.3	Read for general information and appreciation of practical applications for some alcohols and ethers.
10.4	Recall and review alcohol synthesis by hydration of alkenes. Recall the limitations of this method (carbocation rearrangements, etc.).
10.5	Be able to synthesize an alcohol using the oxymercuration-demurcuration protocol. Know its benefits (lack of molecular rearrangements) and regiochemistry (Markovnikov). Recognize the potential for ether synthesis by simply making the solvent nucleophile an alcohol instead of water (solovomercuration-demurcuration).
10.6, 10.7	Know the reaction conditions for the hydroboration-oxidation sequence for synthesis of alcohols [1) BH3THF, 2) H2O2,OH-]. Know the stereochemistry for the overall addition of the hydrogen and hydroxyl group (syn) and the regiochemistry (anti-Markonvikov). Recognize hydroboration-oxidation as a synthetic compliment to oxymercuration-demurcuration with respect to regiochemistry. Omit section 10.7B.
10.8	Recall the essential properties of alcohols: the alcohol oxygen is moderately nucleophilic and weakly basic, the alcohol hydroxy group is a poor leaving group unless first protonated or converted into a leaving group by formation of some type of sulfonate ester (e.g. a tosylate, mesylate, triflate).
10.9	Recall that alcohols are weakly acidic and can form strong alkoxide bases/nucleophiles upon deprotonation by a stronger base (e.g. NaH) or alkaline earth metal (Na or K).
10.10	Know the reaction conditions for forming tosylates and mesylates and the structures of the products, including those written with the Ts or Ms abbreviation. Disregard the mechanism of formation unless interested.
10.11	Know that alkyl sulfonates can be used as an indirect method for accomplishing SN2 nucleophilic substition of the hydroxyl group in an alcohol (initial conversion of the alcohol to an alkyl sulfonate leaving group followed by SN2 substitution by the desired nucleophile).
10.12	Note that alkyl phosphates are one of nature's most important leaving groups in biochemical reactions.
10.13	This is a preliminary introduction to sections 10.14 and 10.15.
10.14	Recognize that alcohols can be converted to alkyl halides by reaction with the appropriate HX. Understand the mechanism as simply applications of acid-base reactions followed by nucleophilic substitution.
10.15	Know PBr3 and SOCl2 as the preferred reagents for conversion of 1o and 2o alcohols to alkyl bromides and chlorides, respectively. Note mechanisms only if interested.
10.16	Recognize the intermolecular dehydration of alcohols as a method for synthesis of symmetrical ethers. Understand the mechanism as simply applications of acid-base and nucleophilic substitution reaction mechanisms. Know how to accomplish a Williamson ether synthesis (10.16B) and recognize it's limitations according to the requirement that it be an SN2 reaction. Omit sections 10.16C and D.
10.17	Understand the reactions of ethers with acids as protonation to form a leaving group followed by nucleophilic substitution to form the respective products.
10.18	Know the general structure of an epoxide and the reagents used for their formation from alkenes (peroxy carboxylic acids, i.e. RCOOOH or RCO3H). Know the stereochemistry of oxygen addition (syn, by default, with retention of the original alkene geometry).
10.19	Understand the principles of acidic or basic ring-opening of epoxides, and know the mechanistic/regiochemical implications of each (e.g. regiochemistry of attack by nucleophile).
10.20	Recognize epoxidation followed by hydrolysis (acidic or basic) as a means for anti-hydroxylation of alkenes.
10.21	Use this section to tie together the various reactions and their stereochemical and regiochemical ramifications. Consider how each reaction could be used in synthesis problems. Catagorize reactions according to the types of functional groups each one allows you to form, the functional groups required in the starting materials, and the stereochemical/regiochemical control each reaction may exhibit.
10.22	Omit this section, except for noting the biochemical significance of crown ether antibiotics (10.22B).

Assigned Problems: 2, 3, 4, 5, 6b 7, 10ace, 12, 15, 16, 17, 18, 20, 22, 25, 26, 28, 31, 32abegh, 33, 34, 35acd, 36, 38, 39, 40, 42, 43, 44, 45ad, 46ac, 47

331ss10.doc 11/16/95

Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||

Organic Chemistry Study Sheet

Chapter 11 - Solomons 6/E

Read all of Chapter 11 for understanding and general information. This chapter is largely devoted to methods for the interconversion of functional groups by oxidation and reduction and the formation of carbon-carbon bonds by reactions of organometallic reagents. Work toward expanding your synthetic repertoire and developing your retrosynthetic analysis skills.

Section Goals
11.1 Know the structure of the carbonyl group with respect to hybridization, bond angles, and C==O polarity. Note the general reaction for nucleophilic addition to carbonyl groups. Especially relevant to this chapter is the nucleophilic addition of hydride and organometallic carbanion reagents.
11.2 Know the general definitions of oxidation and reduction as applied to organic compounds (with regard to hydrogen and oxygen content). Know the relative order of oxidation state when comparing alcohols, aldehydes and ketones, carboxylic acids, and esters.
11.3 Be able to draw the structure of each respective product resulting from lithium aluminum hydride (LiAlH4, or LAH) reduction of any aldehyde, ketone, carboxylic acid or ester. Recognize the lesser reducing power of sodium borohydride (NaBH4) as compared to LiAlH4. Know the functional groups that can be reduced by NaBH4 and be able to draw structures for the resulting products.
11.4 Know how to prepare an aldehyde from a 1o alcohol using PCC (pyridinium chlorochromate). Know how to prepare a carboxylic acid from a 1o alcohol using basic KMnO4 followed by acidification. Know how to prepare a ketone from a 2o alcohol using H2CrO4 (chromic acid). Recognize that 3o alcohols cannot be oxidized. Read sections 11.4D and E for interest only.
11.5 Understand the general polarity of carbon-metal bonds and the potential for the carbon to be strongly nucleophilic or basic in an organometallic compound.
11.6 Recall the synthesis of organolithium (RLi) compounds and know how to prepare organomagnesium compounds (RMgX, Grignard reagents).
11.7 Know the products that result when organolithium and organomagnesium compounds react with a) compounds containing acidic (even relatively weakly acidic) hydrogens, b) epoxides, and c) carbonyl compounds. Understand these reactions as being due to either the strongly basic or powerfully nucleophilic nature of the RLi and RMgX reagents. Note that neither RLi nor RMgX reagents can be used for SN1 and SN2 nucleophilic substitution reactions because they would primarily cause E2 elimination by their strongly basic character.
11.8 Know how to synthesize 1o, 2o, or 3o alcohols from the appropriate aldehyde or ketone by a Grignard reaction. Note, as an aside, the reaction of two molar equivalents of a Grignard reagent with an ester.
11.8A Study the retrosynthetic and synthetic methodologies that become possible using Grignard reactions and other reactions in your repertoire. Practice synthesis and retrosynthetic analysis on a variety of target molecules. Become versatile with functional group interconversions and C-C bond forming reactions.
11.8B, C and D Understand that limitations exist for the use of Grignard and organolithium reagents when other functional groups are present in a molecule that would react competitively or instead of reaction in the desired way (11.8B). Note the parallel reactivity of RLi and Grignard reagents (11.8C). Note that sodium alkynides also undergo addition reactions to carbonyl groups of aldehydes and ketones (11.8D).

Section	Goals
11.1	Know the structure of the carbonyl group with respect to hybridization, bond angles, and C==O polarity. Note the general reaction for nucleophilic addition to carbonyl groups. Especially relevant to this chapter is the nucleophilic addition of hydride and organometallic carbanion reagents.
11.2	Know the general definitions of oxidation and reduction as applied to organic compounds (with regard to hydrogen and oxygen content). Know the relative order of oxidation state when comparing alcohols, aldehydes and ketones, carboxylic acids, and esters.
11.3	Be able to draw the structure of each respective product resulting from lithium aluminum hydride (LiAlH4, or LAH) reduction of any aldehyde, ketone, carboxylic acid or ester. Recognize the lesser reducing power of sodium borohydride (NaBH4) as compared to LiAlH4. Know the functional groups that can be reduced by NaBH4 and be able to draw structures for the resulting products.
11.4	Know how to prepare an aldehyde from a 1o alcohol using PCC (pyridinium chlorochromate). Know how to prepare a carboxylic acid from a 1o alcohol using basic KMnO4 followed by acidification. Know how to prepare a ketone from a 2o alcohol using H2CrO4 (chromic acid). Recognize that 3o alcohols cannot be oxidized. Read sections 11.4D and E for interest only.
11.5	Understand the general polarity of carbon-metal bonds and the potential for the carbon to be strongly nucleophilic or basic in an organometallic compound.
11.6	Recall the synthesis of organolithium (RLi) compounds and know how to prepare organomagnesium compounds (RMgX, Grignard reagents).
11.7	Know the products that result when organolithium and organomagnesium compounds react with a) compounds containing acidic (even relatively weakly acidic) hydrogens, b) epoxides, and c) carbonyl compounds. Understand these reactions as being due to either the strongly basic or powerfully nucleophilic nature of the RLi and RMgX reagents. Note that neither RLi nor RMgX reagents can be used for SN1 and SN2 nucleophilic substitution reactions because they would primarily cause E2 elimination by their strongly basic character.
11.8	Know how to synthesize 1o, 2o, or 3o alcohols from the appropriate aldehyde or ketone by a Grignard reaction. Note, as an aside, the reaction of two molar equivalents of a Grignard reagent with an ester.
11.8A	Study the retrosynthetic and synthetic methodologies that become possible using Grignard reactions and other reactions in your repertoire. Practice synthesis and retrosynthetic analysis on a variety of target molecules. Become versatile with functional group interconversions and C-C bond forming reactions.
11.8B, C and D	Understand that limitations exist for the use of Grignard and organolithium reagents when other functional groups are present in a molecule that would react competitively or instead of reaction in the desired way (11.8B). Note the parallel reactivity of RLi and Grignard reagents (11.8C). Note that sodium alkynides also undergo addition reactions to carbonyl groups of aldehydes and ketones (11.8D).

Assigned Problems: 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 24

331ss11.doc rev 11/95

Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||

Organic Chemistry Study Sheet

Chapter 12 - Solomons 6/E

The Study Sheet for Chapter 12 is not available at present.

Top || 1 || 2 || 3 || 4 || 5 || 6 || 7 || 8 || 9 || 10 || 11 || 12 || 13 ||

Organic Chemistry Study Sheet

Chapter 13 - Solomons 6/E

Study the sections of Chapter 13 noted below. Note that this Study Sheet only covers selected portions of Chapter 13 (UV-Vis is omitted). Develop abilities directed toward meeting the specific goals outlined.

Section Goals
13.1 Understand the general properties of waves (wavelength, frequency, units used in describing waves). Gain a general appreciation for wavelength and the relative energy of various regions of the electromagnetic spectrum.
13.3 Understand that atoms and groups of atoms vibrate about the covalent bonds that connect them. Molecular vibrations can be thought of as balls (atoms) connected by springs (bonds) oscillating at frequencies in the infrared region specific to the types of bonds and atoms involved. Begin to use IR spectra for functional group identification (assuming a frequency chart is provided, e.g. Table 13.2).
13.3A Recognize 3000 cm-1 as the "dividing line between sp2 (3200-3000 cm-1) and sp3 (3000-2800 cm-1) carbon-hydrogen stretches. Be able to use an IR spectrum to infer the presence or absence in a molecule of these respective types of C-H bonds.
13.3B Be able to use IR spectra to infer the presence or absence of various functional groups (with the aid of a frequency table like Table 13.2). Understand this use as probably the most important application of IR spectroscopy in structure elucidation.
13.4 Read for background and general understanding of the basis for nuclear magnetic resonance (NMR).
13.4A Understand the meaning of "chemical shift", the reason for differences in chemical shift from one nuclear environment to another, and the use of the terms "upfield" and "downfield". Understand interpretation of chemical shift with respect to number of peaks in an NMR spectrum and the number of different types of hydrogens in a molecule.
13.4B Understand the interpretation of integral curves, i.e. the correspondence of peak area with the number of hydrogens producing a given signal.
13.4C Know what is meant by "signal splitting" (the interpretation of which will be explained in later sections).
13.5 Read for general understanding.
13.6 Recognize that nuclei can be shielded or deshielded from the applied magnetic field in an NMR spectrometer by the influence of electron density and circulating electrons near a given nucleus. As a result, the position of peaks for nuclei in various environments fall in predictable chemical shift regions. (see Table 13.3)
13.7 Be able to use Table 13.3 for predicting the chemical shifts of hydrogens in molecules. Know that TMS is the reference standard (with a chemical shift of zero) for the chemical shift scale.
13.8 Be able to identify chemically equivalent (and therefore chemical shift equivalent, or homotopic) nuclei in NMR spectra. Know what enantiopic and diastereotopic hydrogens are.
13.9 Using the n+1 rule for signal splitting, be able to predict the number of peaks in an NMR spectrum for a given set of hydrogens, bearing in mind the relevance of chemically equivalent (homotopic), enantiotopic, and diastereotopic hydrogens. Be able to work backwards from spin-spin splitting patterns in a spectrum to determine how many hydrogens are neighboring the hydrogens giving rise to the signal being interpreted. Understand the reciprocity of coupling constants.
13.10 Know that spin-spin splitting is usually not observed between hydrogens on O and N atoms (e.g. alcohols, amines, and carboxylic acids) and the hydrogens on carbon atoms adjacent to these groups, due to chemical exchange by virtue of their acidity.
13.11A-E Be able to interpret carbon-13 (13C) NMR spectra (elucidate a structure) using chemical shift and DEPT information (with a chemical shift table). Be able to predict a 13C NMR spectrum for a compound with a given structure.

Section	Goals
13.1	Understand the general properties of waves (wavelength, frequency, units used in describing waves). Gain a general appreciation for wavelength and the relative energy of various regions of the electromagnetic spectrum.
13.3	Understand that atoms and groups of atoms vibrate about the covalent bonds that connect them. Molecular vibrations can be thought of as balls (atoms) connected by springs (bonds) oscillating at frequencies in the infrared region specific to the types of bonds and atoms involved. Begin to use IR spectra for functional group identification (assuming a frequency chart is provided, e.g. Table 13.2).
13.3A	Recognize 3000 cm-1 as the "dividing line between sp2 (3200-3000 cm-1) and sp3 (3000-2800 cm-1) carbon-hydrogen stretches. Be able to use an IR spectrum to infer the presence or absence in a molecule of these respective types of C-H bonds.
13.3B	Be able to use IR spectra to infer the presence or absence of various functional groups (with the aid of a frequency table like Table 13.2). Understand this use as probably the most important application of IR spectroscopy in structure elucidation.
13.4	Read for background and general understanding of the basis for nuclear magnetic resonance (NMR).
13.4A	Understand the meaning of "chemical shift", the reason for differences in chemical shift from one nuclear environment to another, and the use of the terms "upfield" and "downfield". Understand interpretation of chemical shift with respect to number of peaks in an NMR spectrum and the number of different types of hydrogens in a molecule.
13.4B	Understand the interpretation of integral curves, i.e. the correspondence of peak area with the number of hydrogens producing a given signal.
13.4C	Know what is meant by "signal splitting" (the interpretation of which will be explained in later sections).
13.5	Read for general understanding.
13.6	Recognize that nuclei can be shielded or deshielded from the applied magnetic field in an NMR spectrometer by the influence of electron density and circulating electrons near a given nucleus. As a result, the position of peaks for nuclei in various environments fall in predictable chemical shift regions. (see Table 13.3)
13.7	Be able to use Table 13.3 for predicting the chemical shifts of hydrogens in molecules. Know that TMS is the reference standard (with a chemical shift of zero) for the chemical shift scale.
13.8	Be able to identify chemically equivalent (and therefore chemical shift equivalent, or homotopic) nuclei in NMR spectra. Know what enantiopic and diastereotopic hydrogens are.
13.9	Using the n+1 rule for signal splitting, be able to predict the number of peaks in an NMR spectrum for a given set of hydrogens, bearing in mind the relevance of chemically equivalent (homotopic), enantiotopic, and diastereotopic hydrogens. Be able to work backwards from spin-spin splitting patterns in a spectrum to determine how many hydrogens are neighboring the hydrogens giving rise to the signal being interpreted. Understand the reciprocity of coupling constants.
13.10	Know that spin-spin splitting is usually not observed between hydrogens on O and N atoms (e.g. alcohols, amines, and carboxylic acids) and the hydrogens on carbon atoms adjacent to these groups, due to chemical exchange by virtue of their acidity.
13.11A-E	Be able to interpret carbon-13 (13C) NMR spectra (elucidate a structure) using chemical shift and DEPT information (with a chemical shift table). Be able to predict a 13C NMR spectrum for a compound with a given structure.

Assigned Problems: 3, 4, 5, 6abcdfghj, 7, 8, 9, 10, 11(extra), 13, a4a-eghil, 16, 18, 20, 21, 22, 23

331ss13.doc rev 11/95

Chapter 1	Chapter 2	Chapter 3	Chapter 4	Chapter 5	Chapter 6
Chapter 7	Chapter 8	Chapter 9	Chapter 10	Chapter 11	Chapter 12
Chapter 13	Chapter14	Chapter 15	Chapter 16	Chapter 17	Chapter 18
Chapter 19	Chapter20	Chapter 21	Chapter 22	Chapter 23	Chapter 24

Organic Chemistry Study Sheets For T.W.G. Solomons Organic Chemistry, 6th Ed.

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet Chapter 3 - Solomons 6/E

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheet

Organic Chemistry Study Sheets
For T.W.G. Solomons Organic Chemistry, 6th Ed.

Organic Chemistry Study Sheet

Chapter 3 - Solomons 6/E