Download chemistry 232 elementary organic chemistry ii

CHEMISTRY 232
ELEMENTARY ORGANIC CHEMISTRY II
Exam #2 Study Guide
Chapters 1 – 11, 15-17
Functional Groups to Identify/Name using the IUPAC system:
NOTE: This list is not intended to be comprehensive but serves only as an overview of the major topics which will
nd
be assessed on the 2 in-class examination.
Alkanes (Ch. 2)
Alkenes (Ch. 6)
Alkynes (Ch. 7)
Alkyl Halides (Ch. 8)
Alcohols (Ch. 10)
Thiols (Ch. 10)
Ethers (Ch. 11)
Oxiranes (Ch. 11)
Sulfides (Ch. 11)
Organometallics (Ch. 15)
Aldehydes (Ch. 16)
Ketones (Ch. 16)
Carboxylic Acid (Ch. 17)
Reaction Classes for which a Mechanistic Understanding is Required:
NOTE: This list is not intended to be comprehensive but serves only as an overview of the major topics which will
nd
be assessed on the 2 in-class examination.
Electrophilic Addition to Alkenes/Alkynes (Ch. 6 & 7, 11)
Hydrohalogenation (i.e. addition of HCl)
Halogenation (i.e. addition of Br2)
Oxymercuration [addition of Hg(OAc)2]
Hydroboration/Oxidation [addition of BH3 followed by NaOH/H2O2]
Epoxidation (i.e. addition of mCPBA)
Free-Radical Halogenation of Alkanes (Ch. 8)
Free-Radical Formation of organomagnesium (Grignard) reagents (Ch. 15)
Substitution Reactions (Ch. 9 – 11)
via SN2 Reaction Pathway (concerted)
via SN1 Reaction Pathway (step-wise)
Elimination Reactions (Ch. 9 – 11)
via E2 Reaction Pathway (concerted)
via E1 Reaction Pathway (step-wise)
Acid-Base Protonation/Deprotonation Reactions (Ch. 7 & 10)
Protonation/Deprotonation of Alcohols
Deprotonation of Alkynes
Acid-Catalyzed Rearrangements (Ch. 9 & 10)
via SN1 Reaction Pathway (step-wise)
The Pinacol Rearrangement
Nucleophilic Addition to Carbonyl Compounds (Ch. 15, 16, & 17)
Organometallic addition reactions
Addition of alcohols to aldehydes/ketones (acetal/ketal formation)
Addition of amines to aldehydes/ketones (imine formation)
Functional Group Conversions of Which Knowledge is Required
NOTE: This list is not intended to be comprehensive but serves only as an overview of the major topics which will
nd
be assessed on the 2 in-class examination.
Alkene Alkyl Halide
HX (Markovnikov) or HX/Peroxides (antiMarkovnikov)
Alkene Alcohol
Hg(OAc)2, then NaBH4 (Markovnikov) or BH3, then
NaOH/H2O2 (anti-Markovnikov)
Alcohol Alkyl Halide
HX (3° ROH) where X = Cl, Br, or I
ZnX2 / HX (2° or 1° ROH) where X = Cl or Br
SOX2 (2° or 1° ROH) where X = Cl or Br
PX3 (2° or 1° ROH) where X = Cl or Br
TsCl or MsCl with R3N, followed by LiX (where X =
Cl or Br)
Alcohol Alkene
Alkene Epoxide
mCPBA, DMDO, or peracetic acid
H2SO4 or H3PO4 (best for 3° ROH)
TsCl or MsCl with R3N, followed by KOtBu or LDA
(best for 2° or 1° ROH)
Alkene 1,2-Dihalide
1,2-Diol Ketone or Aldehyde
X2 (anti addition product)
catalytic H2SO4 (Pinacol Rearrangement)
Alkene 1,2-Diol
OsO4 or cold KMnO4 (syn addition product)
1,2-Diol α,ω-Dicarbonyl
HIO4
Alkene α,ω-Dicarbonyl
1,2-Diol Epoxide
O3 followed by DMS or Ph3P
OsO4, followed by HIO4
catalytic H2SO4 (3° ROH only)
LiOH / ∆ (2° or 1° ROH only)
Alkene α,ω-diol (via ozonolysis)
Alcohol Ether
O3 followed by NaBH4
Alkyne Alkenyl Halide
HX (Markovnikov) or HX/Peroxides (antiMarkovnikov)
catalytic H2SO4 (symmetrical ethers only)
_
+
R-X, + RO Na (Williamson synthesis)
Alkyne/Alkene Alkane
catalytic Pt/Pd, H2
Alkyne Ketone or Aldehyde
Alkyne/Alkene Alkene (cis only)
Hg(OAc)2, then NaBH4 (Markovnikov) or BH3, then
NaOH/H2O2 (anti-Markovnikov)
Alkyne 1,2-Dihaloalkene
X2 (anti addition product)
Alkane Alkyl Halide
X2 / hν or NXS / hν
Alkyl Halide Alkene
KOtBu or LDA (or other large, hindered base)
catalytic Pd/CaCO3, H2 (Lindlar’s Catalyst)
Aldehyde/Ketone Alcohol
+
LiAlH4/Et2O, then H3O (reduction)
+
NaBH4/CH3OH, then H3O (reduction)
+
RLi, then H3O (C-C bond formation)
+
RMgBr, then H3O (C-C bond formation)
+
RZnX, then H3O (C-C bond formation; only for
aldehydes)
Functional Group Conversions of Which Knowledge is Required
NOTE: This list is not intended to be comprehensive but serves only as an overview of the major topics which will
nd
be assessed on the 2 in-class examination.
Alkyl Halide Alkane
+
LiAlH4/Et2O, then H3O (reduction)
+
R2CuLi, then H3O (C-C bond formation; best for
iodides)
Alkene Cyclopropane
+
IZnCH2I, then H3O (Simmons-Smith)
Aldehyde/Ketone Acetal/Ketal
ROH (xs), catalytic H2SO4 (+ heat for acid)
Acetal/Ketal Aldehyde/Ketone
H2O, catalytic H2SO4
Carboxylic Acid 3° ROH
+
R-Li (xs), then H3O (C-C bond formation)
Carboxylic Acid 1° ROH
+
LiAlH4, then H3O (reduction)
+
Dibal-H (xs) in CH2Cl2, then H3O (reduction)
Acid Chloride Ketone
R2CuLi (xs), THF, then H3O
+
Epoxide Alcohol
+
R-MgBr/Et2O, then H3O (C-C bond formation)
Alkyl Halide Organometal Halide
Mg/Et2O (Grignard Reagent)
Li (2 eq)/Pentane (Organolithium)
Zn/Hexanes (Organozinc)
Organometal Halide Organo Cuprate
CuI/Ether (or THF)