Organic Chemistry I

Exam Four Study Guide

CHAPTER TWELVE
Section Concept/Skill
Practice
Problems
12.1
12.3
Use provided Mass Spectroscopy information (spectra and correlating data) to
deduce the molecular weight, formula and maybe even structure of an unknown
molecule
Identify/interpret the base peak and parent peak in a given spectrum
Apply the nitrogen rule
Consider isotopic abundance for various elements
Memorize: chlorine (3:1); bromine (1:1); sulfur (25:1)
Recognize common fragments/fragmenting patterns
Memorize: minus 15 for methyl fragment
Memorize: minus 29 for ethyl fragment
Memorize: minus 18 for loss of water from alcohol (dehydration)
Cleavage to form allylic (from alkene) or benzylic (from aromatic)
carbocations frequently occurs
Alcohols also undergo alpha cleavage
2, 3ab, 16, 18,
19, 21, 23,
26bc, 39
12.6
12.8
Use provided Infrared Spectroscopy information (spectra and correlating data)
to identify functional groups present in a given (unknown) molecule
Memorize Table 12.1 and Figure 12.15
7, 8, 27, 30,
31, 32, 34, 41,
42, 43

CHAPTER THIRTEEN

Section Concept/Skill
Practice
Problems
13.5,
13.8,
13.10
Predict the number of 1H AND their relative integrations for a given molecule
Identify the molecule that best matches an NMR spectrum based on number of
signals and integration information
18, 25, 34, 36
13.3,
13.9
Use tables of chemical shift to determine information about the specific
environment(s) of carbon or hydrogen atoms in a given molecule
35
13.11 Predict
1
H NMR splitting patterns for given organic molecules
Use splitting information to elucidate a molecular structure
19, 21, 24, 38, 39
Big
Picture
Use your understanding of NMR concepts (number & integration of peaks,
chemical shift, splitting patterns) to interpret NMR spectra and solve for
structures.
43, 44, 45
CHAPTER TEN
Section Concept/Skill
Practice
Problems
10.1
(6.4)
Use IUPAC nomenclature conventions for naming alkyl halides (even those
containing double or triple bonds)
Be familiar with the common convention for naming simple alkyl halides, e.g.
butyl bromide (rather than 1-bromobutane)
Review the nucleophilicity/electrophilicity of alkyl halides
1, 2, 17
10.3
(7.7, 7.8,
8.2)
Review hydrohalogenation and halogenation of alkenes 20a
10.2
10.4
Radical Halogenation of Alkane
Recall mechanism for radical halogen substitution of an alkane, including the
initiation, propagation and termination steps (sections 3.5 and 6.3)
Describe lack of selectivity for mono-chlorination reactions when more than one
type of hydrogen is present on an alkane
This reaction works best in the case of alkyl bromides due to lack of selectivity or
reactivity for other alkyl halides
Compare relative stabilities of alkyl radicals (p. 349/351)
Allylic Bromination (via Radical Mechanism) with N-bromosuccinimide (NBS)
Predict the products of, identify and/or describe allylic bromination of alkenes,
with emphasis on:
The reagents needed: NBS, light
Why NBS is used as a bromine source, rather than Br
2
or Br
-

Describe (and draw) resonance-stabilization of a allylic radical
5, 6, 7,
20cf, 21c,
22, 23, 25,
30, 32
10.5 Conversion of Tertiary Alcohols into Alkyl Halides
Predict the product of, identify, and/or describe this reaction
Describe and/or draw a full mechanism for this substitution (SN1) reaction, with
emphasis on the:
Reagents/conditions needed: HX
Carbocation intermediate
Stereochemistry (all stereoisomers are possible, although some may be
slightly more favored see pages 387/388)
Conversion of Primary and Secondary Alcohols into Alkyl Halides
Predict the product of, identify, and/or describe this reaction involving:
thionyl chloride (SOCl2)
phosphorus tribromide (PBr3)
Describe SN2 substitution reaction attributes of these specific reaction
8, 21abd,
34, 39
10.6 Conversion of Alkyl Halides to Alkylmagnesium Halides (Grignard Reagents)
Predict the product of, identify, and/or describe this reaction, with emphasis on:
Reagents/conditions needed: Mg & ether
Its synthetic versatility
(R = 1, 2, and 3 alkyl, vinyl and aryl groups; Halide = Cl, Br, and I)
Reactivity with H
2
O to form alkane and Mg(OH)Br
We will do much more exciting reactions (than forming alkanes) with
Grignard reagents in 2
nd
semester (see Chapter 17)
9, 10, 21e,
36
CHAPTER TEN
Section Concept/Skill Practice
Problems
10.7 Alkyl Halides in Organometallic Coupling Reactions
Predict the product of, identify, and/or describe each step in this multi-step
reaction, with emphasis on:
Reagents/conditions and product:
1) alkyl halide + Li alkyl lithium
2) alkyl lithium + CuI lithium dialkyl copper
3) lithium dialkyl copper + alkylhalide longer alkane
Its synthetic versatility related to Step Three
(Alkyl = 1, 2, and 3 alkyl, alkenyl and aryl groups; Halide = Cl, Br, and I)
11, 20be,
21fg, 34,
39
10.8 Recognize reactions that involve formation of C-H bonds or cleavage of C-O,
C-N, or C-X bonds as reduction reactions
Recognize reactions that involve formation of C-O, C-N, or C-X bonds or
cleavage of C-H bonds as oxidation reactions
26, 28

CHAPTER ELEVEN
Section Concept/Skill Practice
Problems
11.2
11.3
SN2 Substitution Reactions
Predict the products of, identify, and/or describe an SN2 Reaction
Describe and/or draw a mechanism for this reaction, with emphasis on the:
Relationship between the reactions second-order kinetics and the rate-
determining step involving a pentavalent-carbon transition state
Stereochemistry inversion between reactant and product
Describe how the following factors influence the rate and yield of an S
N
2
reaction (listed in order of importance for S
N
2 reaction):
Subtrate (Starting Material)
(Favored for methyl > 1 > 2 group due to steric considerations)
Nucleophile
(Stronger nucleophiles enhance reaction see Table 11.1)
Solvent (Good S
N
2 solvents: acetone, ethers, DMSO, DMF, CH
3
CN)
(Polar aprotic solvents enhance reaction; Protic solvents significantly interfere)
Leaving Group
(Leaving group stability influences reaction; Least important factor for S
N
2)
2, 5, 27, 28,
29, 32, 42, 44
11.4
11.5
SN1 Substitution Reactions
Predict the products of, identify, and/or describe an SN1 Reaction
Describe and/or draw a mechanism for this reaction, with emphasis on the:
Relationship between the reactions first-order kinetics and the rate-
determining step to generate a carbocation intermediate
Stereochemistry (all stereoisomers are possible, although some may be
more favored)
Describe how the following factors influence the rate and yield of an S
N
2
reaction (listed in order of importance for an S
N
1 reaction):
Subtrate (Starting Material)
(Favored for 3 > 2 ~ allylic ~ benzylic group due to carbocation stability)
Leaving Group
(Leaving group stability influences reaction)
Solvent (Good SN1 solvents: contain OH or NH)
(Increased polarity enhances reaction; Protic solvents desirable)
Nucleophile
(Nucleophile strength does not influence; Least important factor for S
N
1)
8, 11, 12, 30,
41, 58
FYI about SN1 and SN2
Aryl and vynilic groups will not react via either mechanism
Primary allylic and benzylic groups will react via either mechanism



Section Concept/Skill Practice
Problems
11.7
11.10
Elimination Reactions
Predict the products of, identify, and/or describe an elimination reaction from an
alkyl halide
Apply Zaitsevs rule to predict all products from an asymmetric halide
Describe and/or draw a mechanism for an E1 reaction, with emphasis on the:
Relationship between the reactions first-order kinetics and the rate-
determining step (identical to first step of S
N
1)
Potential for rearrangement due to carbocation intermediate
Describe and/or draw a mechanism for an E2 reaction, with emphasis on the:
Relationship between the reactions second-order kinetics and the
rate-determining step
Requirement for periplanar geometry in transition state (which would be
trans diaxial groups on cyclohexane)
15, 16, 19
Big
Picture
Put yourself into situations where you have to decide which type of
mechanism (or mixture of mechanisms) will prevail for a given set of reagents
and reaction conditions
13, 31, 36, 38,
40