Download Kazzie`s Guide to Orgo 2

Guide to Orgo 2
General Note: Some of these questions have been previously used in examples,
etcetera, but they cover the things that I think are important to know from this
semester. Try to work through them with as few resources as possible, and we
will go through this at the final review.
Chem 210 Stuff
Identify all the chiral centers in this molecule and label them all R/S:
NH2
O
Br
H
OH
Show the mechanism of the following reaction:
CH3I
B:-
Chapter 13
Draw the complete oxidation sequence of methane (hint, it starts with oxygen
insertion to make methanol) into carbon dioxide and water.
What are the reagents necessary for Swern Oxidation? What is the benefit of this
reagent set?
Show the mechanism for the following oxidation reaction (use a Bronstead acid
base as necessary):
O
OH
HO
Cr
OH
O
What color is Cr+6? Cr+3? What does adding Cr+6 to a substance determine?
What is required to oxidize an aldehyde to a carboxylic acid?
Predict the products of the following reactions; say what type of reaction they
are and identify the functional groups involved:
Cl
CH3OH
B:-
NaH
CH3CH2CH2OH
CH3I
Paying attention to stereochemistry, predict the following intramolecular
reactions:
OH
I
NaH
OH
I
NaH
Draw the reactive conformation chair form for the following intramolecular
substitution reaction (initial stereochemistry not shown, show what it has to be)
and predict the product:
HO
Br
Show the following mechanism (draw out TsOH at least once in your
mechanism) keeping track of the radioactive tracer:
NaCl (a source of Cl-)
TsOH
CH3CH3CH218OH
Including stereochemistry predict the product of the following epoxide ring
opening reactions:
O
H3C
NaOCH2CH2CH3
H
HOCH2CH2CH3
Cl
H3C
Cl
O
H
HOCH2CH2CH3
Cat. H2SO4
Why do we put in propanol with propanoxide in the top reaction as the solvent?
Chapter 14
Predict the product of the following reactions:
O
Cl
MgBr
O
OH
Draw out the following mechanism:
O
CH3CH2SH
H-B (cat.)
Predict the product of the following reactions (assume an acid workup of all
reactions):
O
NaBH4
H
O
NaH
O
C-Li
H
O
LiAlH4
Draw the mechanism of the following imine formation reaction:
O
H2N
H-B
Predict the two organic products of the following reaction:
O
O
H2O/H3O+
Predict all possible products from the following reaction (Hints: 1- There is one
for the cis formation and one for the trans formation (therefore stereochemistry
is important) 2- One never works with a single molecule 3-No acid is available):
NaBH4
O
Br
Which is more reactive, formaldehyde or propanal? Why?
What is the byproduct of all of the reversible nucleophile reactions in this
chapter? How does this help increase the reversibility of these reactions?
Chapter 15
Draw the reaction mechanism to form the acid chloride from the following
starting material (picking the other reactant):
O
OH
List three ways to make a carboxylic acid:
Perform the following base condition mechanism:
O
NaOH/H2O
Cl
Perform the following acid condition mechanism and circle the important
intermediate:
O
H3O+/H2O
Cl
Predict the product of the following reaction:
O
O
+
Cl
O
Show the mechanism of the following esterification reaction, and explain why the
alcohol doesn’t attack directly.
O
OH
Cl
N
This is a bit of an odd reaction, but think logically. Using your knowledge of
Chem 210 and 215 predict the product of the following reaction:
Ag2O
O3
H3O+
NaOH
Predict the product of the following reaction (hint: think intramolecular)
O
1) NaBH4
2) H3O+
HO
O
Perform the following mechanism:
O
NH2CH2CH3
O
H-B
Because your professors seem to love it…a transesterification mechanism!
O
CH3CH2CH2CH2CH2OH
O
H-B
Chapter 16
Find all 5 tautomers of the following compound:
O
O
C
C
H
H
C
H
H
H
O
H
H
C
H
Show the following enol formation mechanisms:
H3O+/H2O
O
NaOH/H2O
Predict the product of the following set of proton transfers:
O
O
D2O
Show the mechanism for the following reaction:
O
I
H2O
Show the mechanism of the following reaction:
O
O
NaOCH3/CH3OH
Br
Chapter 17
Form an enol from the following molecule under acid conditions:
O
Use that enol with the following aldehyde and show the aldol condensation
reaction (show the mechanism):
O
Show the following decarboxylation reaction (draw in the curved arrows):
O
OH
O
Predict the products of the following retroaldol reaction:
O
OH
Bronstead Base
Carbohydrates
What is the generic structural formula for a carbohydrate?
Draw the Fisher-projection of the simplest carbohydrate, name it. Then show the
ACID catalyzed mechanism of it’s tautomerization to its ketose form and name
that:
What size ring is the kinetically favored hemi-acetal of a aldohexose?
Thermodynamically favored?
Show the ACID catalyzed mutorotation of the following molecule:
N
OH
CH3
Draw the both products of an ACID catalyzed reaction of B-D Glucopyranose,
circle the major product.
Draw a sugar that if it was added to a solution of CuSO4 (which is blue/green)
the solution would turn red and a precipitate would form. If you know it, what is
that precipitate?
Draw the product of the following reactions and predict the number of
stereoisomers present in solution:
HO
HO
O
CH3CH2CH2Cl
LiH
OH
OH
HO
HO
O
CH3CH2CH2OH
HCl
OH
OH
HO
HO
NH2
O
HCl
OH
OH
What is a glycoside?
What is the result of the Tollins test for the following sugar?
H3CO
H3CO
O
H3CO
OCH3
Draw an B(1->4) linkage of galactopyranose (the C-4 epimer of glucose) and
glucopyranose (this is lactose):
Draw an a(1->4) linkage of two glucopyranose molecules (this is maltose):
What is poly-a-glucose? Poly-b-glucose?
Amino Acids and Proteins
NOTE: I am going to use any amino acid I want, if you don’t know what it looks
like…look it up, it is good to get used to using anything they might throw at you.
Draw the amino acid Gly at physiologic pH (~6.5), what is this form of a
molecule called?
Draw the titration curve for the amino acid Glu, draw the structure of the
molecule at every important point:
Predict the product of the following reaction:
Lys + SOCl2 ->
Draw the tripeptide GlnHisThr at pH 9:
Circle all the amino acids in the following list with hydrophilic sidechains:
Arg
Pro
Leu
Asp
Ile
Val
Glu
Met
Ser
Gly
Fill in the following blanks in the protecting group charts:
O
COCH3
NH3
O
R
COH
NH3
O
H
R
H
COCH2Ph
NH3
H
R
O
COC
NH3
H
R
O
COCH3
NH3
H
R
O
O
COH
COCH2Ph
NH3
H3N
H
H
R
R
O
COC
NH3
H
R
O
O
COH
O
O
COH
H3N
N
H
H
Ph
R
H
R
O
O
COH
O
N
H
H
R
O
O
COH
O
N
H
H
O
Ph
R
COH
H3N
O
H
R
O
COH
O
N
H
H
R
If given a choice of one of the following which is the most convenient to use and
why?
CBzPheAlaOtBu
CBzPheAlaOMe
BocPheAlaOtBu
Draw the mechanism for removal the methyl ester protecting group from GlyOMe
Draw DCC:
What is the purpose of using DCC?
Draw the mechanism for the reaction between CBzPhe and AlaOtBu using DCC to
form CBzPheAlaOtBu:
What is the direction of synthesis of a protein in a machine? In nature?
What is the base material amino acids are connected to in solid state synthesis?
What is the primary structure of a protein? Secondary? Tertiary? Quaternary?
What is the most common kind of crosslinkage in protein structure? What amino
acids is it between?
What is the purpose of enzymes?
DNA
Draw the mechanism for the reaction between NAD+ and ethanol. What is the
product?
Which direction does a DNA chain grow in?
How many H-bonds hold together Guanine and Cytosine?
Which base appears in RNA but not DNA?
Which carbon has it’s OH replaced by H in DNA?
Draw the dinucleotide made up of thymine and adenine as it would appear in
DNA:
What is PG-Cl (draw it)? What is it used for in DNA synthesis?
NOTE: Due to lack of notes on this section there is more you probably need to
know, but I wanted to get this done in time for you to start it.
Naming
Name all of the following molecules using IUPAC naming. If marked with a “T”
also give their common (trivial name) and IUPAC name. If a name is given, draw
the molecule. Stereochemistry is important if implied by the name or structure.
O
OH
Cl
OH
CH3
HO
O
O
T:
T: HOH2C
CH2OH
O
OH
O
O
OH
OH
HO
O
Br
O
OCH3
OCH3
OH
Cl
O
O
T:
O
HO
OH
O
HC
O
T:
O
CH3
N
CH3
(2R, 3R)-2,3,4 trihydroxybutanal (give trivial name also)
Propanoyl butanoate
Tetrahydrofuran
Benzophenone
3-cyclohexeneone
m-bromoacetophenone
Diethylene glycol dimethyl ether (AKA: diglyme)
2,4-dimethyl-3-oxo-5-phenoxyhexanoic acid
2-hydroxypropanamide
Isopentylbromide
m,m-Diaminodiphenylmethane (I use this)
n-hexylmagnesiumbromide
p-toluene sulfonic acid
Methanoic acid (also give trivial name)
2,4-dimethylcyclohexanecarboxylic acid
Potassium benzoate
ethyl propanoate
2,4-dihydroxyhexanoylchloride
3-methylhexanenitrile
(9Z) Sodium octadec-9-enoate
Good luck all and don’t hesitate to ask questions.
E-mail: [email protected]
Cell: (248)302-1975