CHEM 233 Reading List Klein 3rd ed PDF

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1 Learning Objectives and Reading List for Klein 3 rd edition Notes o Review topics are bolded o This list is subject to minor changes throughout the term. This is a guideline, not a contract. Reaction learning objective legend: (R) Be able to predict the product/use in synthesis (M) Be able to predict the product/use in synthesis AND draw the mechanism Learning objectives Chemical Bonding • Describe chemical bonding in terms of valence bond theory & hybrid atomic orbitals (sigma and pi bonds)

•

Identify and visualize molecular geometry of chemical species using VSEPR (the location of nuclei, bonding electrons, and lone pairs of electrons)

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Explain why compounds are polar or nonpolar based on geometry and bond polarity

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Recognize resonance and draw resonance structures of chemical species

• • •

Define aromaticity Determine whether a chemical species is aromatic Describe the reduced reactivity/increased stability of aromatic compounds NOTE: Things are either ‘aromatic’ or ‘not aromatic’. In the answer key, think of anti-aromatic = not aromatic Last Updated: 9/2/19 11:37 AM

Sections

Skillbuilders

Problems

1.6, 1.7, 1.9

1.6, 1.7

1.1-1.12, 1.18-1.19, 1.201.24, 1.34, 1.35, 1.38, 1.42 1.46, 1.47, 1.49-1.51, 1.541.56, 1.58 1.63-1.67, 1.741.75, 1.78, 1.80, 2.1-2.3

1.10

1.8

1.25-1.28, 1.39-1.41, 1.50, 1.55, 1.56, 1.58, 1.59, 1.6869, 1.71-73, 1.74ac, 1.75, 2.43

1.5, 1.11

1.5, 1.9

1.15, 1.29-1.32, 1.36, 1.37, 1.40, 1.43, 1.45, 1.48, 1.57, 1.61, 1.62, 2.10, 4.62

2.7-2.13

2.6-2.10

2.12- 2.33 2.21-2.38, 2.41, 2.47, 2.52-2.53, 2.56-2.57, 2.59-2.74, 2.77-2.78, 2.812.84 (hard)

17.1, 17.3 17.5 17.4

17.3

17.7-17.8, 17.10-17.15, 17.26-17.30, 17.32-17.34, 17.40, 17.48-17.49, 17.56 (hard), 17.57, 17.62, 17.67

Representing organic structures • Use a variety of molecular representations (molecular formulae, Lewis, condensed, bond-line, three dimensional representation with wedges/dashes, orbital overlap – like Figure 1.33 on page 22) o Identify when atoms with a complete or incomplete octet will have particular formal charges/lone pairs •

Identify functional groups in chemical species as a group of atoms/bonds that possess a predictable chemical behaviour (alkyl halide, alkene, alkyne, alcohol, ether, thiol, sulfide, arene, ketone, aldehyde, imine, carboxylic acid, acyl halide, anhydride, ester, amide, amine, ketal, hemiketal, acetal, hemiacetal)

•

Identify and use the terms primary, secondary, and tertiary related to functional groups (e.g. primary alcohol) and carbocations (e.g. secondary carbocation)

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Name simple alkyl halides, alkenes, alkynes, alcohols, aldehydes, ketones, esters, carboxylic acids, amides, and thiols (you do not need to know any common names, just simple IUPAC nomenclature)

Last Updated: 9/2/19 11:37 AM

1.2, 1.3, 2.1-2.2, 2.6

1.1-1.3

1.4, 2.4, 2.5

1.4

2 2.1-2.11, 2.34-2.39, 2.422.46, 2.48-2.51, 2.54-2.55, 2.58, 2.79-2.80 1.13-1.14, 1.77, 1.79 2.122.19, 2.40, 2.44, 2.53

2.3

7.2, 13.1

4.1-4.2 (Omit bicyclic naming) 7.2, 7.7, 9.2, 12.1, 13.11, 19.2, 20.2, 20.6

4.1-4.2, 9.1, 12.1, 19.1

Naming Q’s: 4.1-4.10, 4.36a-I, 4.40ab, 4.48, 4.61, 7.12-7.13, 7.47, 7.48adgh, 9.1-9.4, 9.329.33, 9.55, 12.1ab, 12.2, 12.27ab, 12.28-12.29, 13.113.3, 13.26, 13.28, 19.119.4, 19.43, 19.44abcdei, 20.1bef, 20.2a, 20.3, 20.12abdfhi, 20.13bcd

3 Stereochemistry • Define the following stereochemical terms: o Constitutional/structural isomers o Conformational isomers/conformers o Stereoisomers o Enantiomers o Diastereomers

• • • • • • • •

o o o o o

Classify the relationship between pairs of molecules Draw isomers of a given compound Determine R and S designation at a chirality centre Describe the factors that influence alkane and cycloalkane conformer stability (torsional, steric, and angle strain) Define the descriptors used to describe conformations of alkanes and cycloalkanes (chair, boat, eclipsed, staggered) Classify alkenes as cis/trans and E/Z Work with different representations of organic compounds (Fischer, Newman, wedge/dash perspective diagrams, sawhorse) Describe the biological consequence(s) of stereoisomerism

Intermolecular forces o Define and describe hydrogen bonding, London dispersion forces, and dipole-dipole forces • Identify the predominant intermolecular forces in a chemical species or mixture (for compounds that include the important functional groups in this course: hydrocarbons, alkyl halides, alcohols, amines, ethers, thiols, sulfides, carbonyls) • Rank boiling/melting points and compare solubility with respect to intermolecular forces acting in a substance/mixture • Identify the hydrogen bonds between nucleic acids (DNA) and amino acids in proteins

Last Updated: 9/2/19 11:37 AM

5.1-5.8

5.1-5.3, 5.7-5.8

Meso compound Stereogenic centre (stereocentre) Chirality centre Optical activity Chiral/achiral

5.1-5.10, 5.19-5.39, 5.445.48, 5.50-5.53, 5.55, 5.57-5.70, 5.71a, 5.725.80

5.6

4.7-4.15

4.8-13, 5.9

8.4 4.6

8.2 4.7

4.19-4.35, 4.37-4.38, 4.414.43, 4.45-4.47, 4.494.60, 4.63-4.64a, 4.654.68, 4.70-4.72, 4.744.76(hard) 4.16-4.18

See 5.3, pg 188, 5.4, pg 191-192 and 5.11, pg 215216for examples 1.11-1.12

1.12, 24.10, 25.7

1.9-1.10

1.31-1.34, 1.38, 1.40, 1.43, 1.61-1.64, 1.52-1.53, 1.60, 1.65, 1.76, 4.69

4 Fundamentals of chemical reactions & Introduction to Mechanisms • Describe what equilibrium constants represent (K eq) and what their relative sizes mean for a particular reaction • Correctly use electron-movement arrow convention (nucleophile to electrophile) to show how chemical reactions occur • Define, identify, and compare nucleophiles, electrophiles, and leaving groups • Draw/interpret simple reaction coordinate diagrams (transition states, intermediates) • Classify reaction types as substitution, elimination, addition, rearrangement, or proton transfer Organic acidity/basicity • Describe what acid constants represent (e.g. K a, pKa) and what their relative sizes mean for a particular acid/base reaction (i.e. a compound with larger K a is more acidic than one with a lower K a) • Define strong and weak acids/bases (Arrhenius, Brønsted-Lowry, Lewis acid/base theories) • Draw conjugate bases and acids of chemical species • Predict chemical behaviour of a conjugate base (or acid) using what you know about the nature of its acid (or base) (e.g. strong acids have weak conjugate bases) • Rationalize acidity and basicity by determining relative stability of ions and molecules using size, electronegativity, hybridization, induction (electron withdrawal and donation), and resonance • Predict how changes in a reaction mixture shift the equilibrium (Le Chatelier’s principle) • Describe how aromaticity impacts acidity/basicity & use this to rank acids and bases according to strength • Know pK a values for strong mineral acids, hydronium ion, carboxylic acids, phenols, ammonium/alkylammonium ions, water, primary alcohols, aldehydes/ketones, esters, terminal alkynes, amines, alkenes, alkanes • Determine the structure of an amino acid at a particular pH when given its pK a Last Updated: 9/2/19 11:37 AM

6.1-6.10, 6.12

6.1-6.5

6.1-6.10, 6.11b-e, 6.126.16, 6.19-6.27ac, 6.296.40, 6.42-6.51, 6.536.56, 6.58(hard), 6.59(hard)

3.1-3.5, 3.7-3.9, 12.2 21.1

3.1-3.12, 12.2, 21.1

3.1-3.63, 3.66-3.73(hard), 12.4-12.6, 12.30-12.31, 12.52

9.3

9.2

9.5-9.6, 9.35, 9.38, 21.4721.50, 21.54

17.5

17.15, 17.37, 17.39, 17.47

See page 98 for a list of pKa values (also, see handout on Connect)

20.5-20.9, 20.35-20.36

20.3,25.2

25.1

25.4-25.6, 25.40, 25.4725. 48

5 Bimolecular Reaction Mechansims (S N 2 and E2) • SN 2 (Substrates: alkyl halides and alkyl tosylates; Nucleophiles: hydroxide, alkoxides, halogen ions, sulfide ions, thiols, acetylide ions, enolates of carbonyls and dicarbonyls, carboxylates, azides and nitriles) (M)

7.1-7.5, 9.10, 13.5(ignore pg 566), 13.6(to pg 567 bottom), 13.10-13.12(omit pg 584, until “sulfides”), 21.1(pgs 958-962)

7.1-7.2, 9.5, 13.2, 13.4, 21.1

•

E2 (Substrates: alkyl halides, alkyl tosylates) (M)

7.6-7.8 (OMIT pg 295-top of 297, follow instructions in class for Zaitsev’s Rule)

7.3-7.5

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Conversion of alcohols to alkyl halides with SOCl 2 or PBr3 (R) Conversion of alcohols to tosylates with p-TsCl (R)

7.12, 12.9

12.6

•

Identify the nucleophile, electrophile, and leaving group in a methylation involving S-adenosylmethionine (“SAM”)

7.5, pg 287

Unimolecular Reactions (SN1 and E1) • SN 1 (Substrates: alkyl halides, alkyl tosylates, alcohols, ethers; Nucleophiles: water, alcohol, hydrogen sulfide, halogen ions) (M) • E1 (Substrates: alcohols, ethers) (M) • Rank carbocations and carbanions in terms of stability • Describe the differences in S N1 and SN 2 reactions (intermediates/transition states, kinetics, catalyst, nucleophile and substrate) Last Updated: 9/2/19 11:37 AM

7.2-7.9, 7.11, 7.15-7.18, 7.20-7.26, 7.50-7.66, 7.68, 7.72, 7.74-7.81, 7.84, 7.89-7.90, 7.92, 7.94-7.95- 7.102(hard), 7.104(hard), 7.105(hard), 7.106 9.27-9.28, 9.36f, 9.45, 9.56, 9.58, 9.61, 9.68(hard), 9.69(hard), 13.5-13.6, 13.16bce, 13.1713.20, 13.21b, 13.27, 13.30, 13.34ab, 13.35, 13.38bcdef, 13.39-13.40, 13.46, 13.51efmors, 13.69-13.71a, 13.75(hard), 21.4-21.7,

12.4bd, 12.7b, 12.17-12.19, 12.31-12.32abgi, 12.38, 12.51f 7.10

7.9

7.6, 6.28, 7.27-7.33, 7.34acd, 7.37-7.43ab, 7.70acd, 7.71, 7.73, 7.83, 7.85, 7.88, 7.91, 7.103

6 Combining Bi- and Unimolecular Concepts • Describe differences in E1 and E2 reactions (intermediates/transition states, kinetics, catalyst, base and substrate) • Describe differences in S N 1 and SN 2 reactions (intermediates/transition states, kinetics, catalyst, base and substrate) • Determine whether SN 1/SN 2/E1/E2 will occur with a particular starting material and reagents • Determine starting materials that may be used to synthesize a compound (Retrosynthesis)

7.11 (follow and use in class charts and/or explanations)

7.7

7.13

7.8

8.1-8.4, IGNORE AntiMarkovnikov additions

8.1, 8.3, 8.10

8.1acde, 8.2a, 8.3-8.5, 8.8, 8.10-8.11, 8.35begh, 8.41, 8.44ac, 8.51, 8.55, 8.57b, 8.61, 8.64, 8.68b, 8.70b, 8.71, 8.79, 8.92, 8.95,

26.8, see page 1210

26.4

26.25-26.28, 26.37, 26.48, 26.49, 26.55ab

7.44-7.46, 7.86-7.87, 12.55

NOTE: A CHEM 233 specific answer key for Ch:7 will be available on Connect which is consistent with in class rules.

Electrophilic addition (alkenes) • Hydrohalogenation (M) • Acid-catalyzed hydration (M)

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Identify the nucleophile, electrophile, and leaving group in a terpene biosynthesis

Last Updated: 9/2/19 11:37 AM

7 Reduction and oxidation reactions • Catalytic hydrogenation of alkenes and alkynes (R) • Reduction of alkynes with H 2/Lindlar’s catalyst and Na or Li/NH 3 (R)

8.8 (OMIT pg 370-373) 9.5

8.5

8.18-8.19,8.48, 8.67, 8.73 9.9a, 9.10-9.12, 9.439.44, 9.46, 9.52bc, 9.559.56, 9.58, 9.75, 9.77

•

Reduction of aldehydes and ketones with NaBH 4 and LiAlH4 (M)

12.4, 19.9

12.4

12.11-12.12, 12.36, 12.37b, 12.42, 12.43c, 12.44ef, 12.45c, 12.49, 12.58, 12.61, 12.64, 12.70, 19.28, 19.87

• •

Oxidation of alcohols and aldehydes with H 2CrO4 and PCC (R) Describe how NADH acts as a biological reducing agent

12.10(OMIT 535-536) 12.11

12.7

12.20, 12.32e, 12.34ab, 12.44abcd, 12.51bh, 12.68, 19.5ab

• •

Define reduction and oxidation in an organic chemistry context Classify reactions as reduction, oxidation, or neither

Follow instructions given during class regarding assigning oxidation states.

Last Updated: 9/2/19 11:37 AM

12.9-12.10

8 Nucleophilic addition (aldehydes and ketones) • Equilibrium paths of carbonyls in water (keto-enol tautomerization in acid and base (M) • Addition of water in acid and base (M)

• • • • • • • • • •

Addition of alcohols, acid-catalyzed (M) Addition of ammonia and primary amines, acid-catalyzed (M) Classify chemical species as hemiacetal, acetal, hemiketal, and ketal, and imine functional groups Rank the stability of aldehydes/ketones, hemiacetals/hemiketals, and acetals/ketals Hydrolysis of hemiacetals, acetals, hemiketals, and ketals, and imines (M) Reductive amination (H 2, Pd/C + imine) (R) Explain why an acid catalyst improves the reaction rate of weak nucleophile addition Use ketal/acetal protecting groups in synthesis Aldol condensation, base-catalyzed ONLY (M) Retroaldol, base-catalyzed ONLY (M)

Last Updated: 9/2/19 11:37 AM

9.7(middle page 417-418), 9.3 21.1(to end of pg 957)

9.16-9.17, 9.39, 9.44b, 9.62, 9.66, 9.71, 9.76, 21.51-21.52, 21.55-21.56, 21.59-21.60, 21.70, 21.98

19.1-19.5 19.6 (to end of pg 864)

19.1-19.2 19.3

Combination of all learning outcomes below line

19.7

19.5

21.3

21.2-21.4

19.7-19.9, 19.10ac, 19.1119.14, 19.15acd, 19.1619.18, 19.40g, 19.41, 19.49, 19.54abcefgl, 19.55-19.56, 19.58-19.59, 19.61bcd, 19.63, 19.65, 19.67b, 19.68, 19.7019.71, 19.76abc, 19.8319.84, 19.92-19.93 Aldol Questions

21.14-21.23, 21.57-21.58, 21.61-21.63, 21.66, 21.71, 21.74c, 21.75, 21.77bc, 21.78a, 21.81-21.82, 21.87, 21.95, 21.97, 21.99(hard), 21.114

9 Carbohydrates • Define carbohydrate • Classify carbohydrates by a variety of features: o Number of carbons (triose, tetrose, pentose, hexose, heptose) o Functional group (aldose, ketose) o D, L o Number of sugar units (monosaccharide, disaccharide, oligosaccharide, polysaccharide) o Pyranose, furanose o Disaccharide and polysaccharide linkages using numbering of linking carbons, alpha/beta relationship in branched and linear structures o Reducing, non-reducing • Determine stereochemical relationships between carbohydrates (enantiomers, diastereomers, epimers, α & β anomers) • Draw the structure of glucose (this is the only carbohydrate structure you need to know) • Hemiacetal/hemiketal formation to form pyranoses and furanoses (M) • Acetal/ketal formation (glycosidic bond formation) (M) • Hydrolysis to hemiacetals/hemiketals and to open chain carbonyl form (M) • Redox: Tollens’ reagent (Ag(NH3 )2+ in H 2O), HNO3 , and NaBH4 (R) • Carbohydrates acylation (Ac 2O, pyridine) (M) and alkylation (Ag 2O, alkyl halide) (R) • Conversion between ketoses and aldoses (tautomerization) (M) • Recognize when mutarotation is possible and use this concept in consideration of the structure, reactivity, and optical rotation of carbohydrates in solution

Last Updated: 9/2/19 11:37 AM

24.1-24.4 24.1-24.11, 24.27, 24.4224.49, 24.51-24.53, 24.6224.63, 24.82, 24.8424.85-24.86

24.75

24.7-24.8

24.4-24.5 24.12-24.22, 24.50, 24.5424.56, 24.60 24.5

24.1-24.3

24.6

OMIT: Oxidation of monosaccharides (pg 1124-1125). OMIT: KilianiFischer Synthesis and Wohl Degradation (middle pg 1126- top 1128)

24.23-24.30, 24.41acd, 24.57, 24.61, 24.67-24.71, 24.72bcd, 24.73-24.74, 24.76-24.80, 24.87

10 Nucleophilic acyl substitution (carboxylic acids, acid chlorides, acid anhydrides, esters, amides (M) • Direct conversion of carboxylic acids to acyl chlorides (R), anhydrides (M), esters (M) • Direct conversion of acyl halides to carboxylic acids (M), anhydrides (M), esters (M), amides (M) • Direct conversion of anhydrides to carboxylic acids (M), esters (M), amides (M) • Direct conversion of esters to carboxylic acids (M), amides (M) • Amide hydrolysis (M) • Rationalize the relative reactivity of carboxylic acid derivatives • Reduction of carboxylic acids & esters with LiAlH4 (M) • Claisen condensation (M) NOTE: While not explicitly listed in some cases, students are responsible for interconverting acid halides, acid anhydrides, esters and amides to carboxylic acids, and into eachother.

20.1-20.3 20.8-20.10(OMIT: bottom pg 920-end 921) See pg 918-bottom 919, pg 923 See middle pg 923

Combination of all learning outcomes

20.1-20.2

20.10-20.12 (OMIT: DIBAH & Grignard) 20.12(OMIT: top pg 934) 20.7 20.5 21.4 OMIT: Mechanism 20.2

20.1acd, 20.2b, 20.4, 20.10ad, 20.12c, 20.1420.15, 20.16aef, 20.17, 20.19-20.20, 20.21a, 20.22acde, 20.23-20.26, 20.30abcdfgh, 20.3720.40, 20.41a, 20.44abcdef, 20.45, 20.46abcdfgh, 20.47, 20.48abcd, 20.49ace, 20.52-20.53, 20.56, 20.57ab, 20.58, 20.61abcd, 20.62-20.67, 20.69g, 20.72, 20.7820.79, 20.83-20.84, 20.86 (hard), 20.8720.89, 20.92(hard), 20.93(hard) Claisen Reactions

21.24-21.28 Decarboxylation (M) • Malonic ester/acetoacetic ester synthesis (M) • Amidomalonate synthesis to synthesize amino acids (M)

Last Updated: 9/2/19 11:37 AM

22.5 25.3

22.5, 6 25.2

22.35-43, 78-79 25.14-16, 57-58, 59c, 60b, 84-86, 89

11 Integration objectives • Predict the products and draw mechanisms of intramolecular reactions • Explain experimental results of chemical reactions (e.g. yield, rate, reactions that do not work) • Rank and/or rationalize reaction equilibrium position and/or rate based on the following concepts: acidity, basicity, nucleophilicity, electrophilicity, sterics, stability, and equilibria • Justify mechanistic steps using proper chemical terminology for both familiar and unfamiliar reactions (e.g. identify the nucleophile and electrophile in each step) • Provide the product(s) when given the starting material(s) and reagent(s); provide the missing starting material(s) when given reagent(s) and product(s) in a chemical equation; provide the missing reagent(s) when given the starting material(s) and product(s) • Solve multi-step synthesis problems using reactions learned in the course • Apply chemistry concepts to metabolic processes (e.g. glycolysis, citric acid cycle, etc.) and identify reactions in biosynthetic routes (e.g. fatty acid biosynthesis). To do this, you do not need to have memorized these pathways!!!

Last Updated: 9/2/19 11:37 AM...