orgo 2 guide

7/31/2019 Orgo 2 Guide

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ORGO 2 GUIDE

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 thissemester. 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:

H

BrO

NH2

OH

Show the mechanism of the following reaction:

CH3I

B:-

Chapter 13

Draw the complete oxidation sequence of methane (hint, it starts with oxygeninsertion to make methanol) into carbon dioxide and water.

What are the reagents necessary for Swern Oxidation? What is the benefit of thisreagent set?


2/25

Show the mechanism for the following oxidation reaction (use a Bronstead acidbase as necessary):

OH

Cr

O

O

OHHO

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 theyare and identify the functional groups involved:

Cl

CH3OH

B:-

CH3CH2CH2OH

NaH CH3I


3/25

Paying attention to stereochemistry, predict the following intramolecular

reactions:

OH

I

NaH

I

OH

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


4/25

Show the following mechanism (draw out TsOH at least once in yourmechanism) keeping track of the radioactive tracer:

CH3CH3CH218OH

TsOH NaCl (a source of Cl-)

Including stereochemistry predict the product of the following epoxide ringopening reactions:

Cl

OH3C

H

Cl

OH3C

H

NaOCH2CH2CH3

HOCH2CH2CH3

Cat. H2SO4

HOCH2CH2CH3

Why do we put in propanol with propanoxide in the top reaction as the solvent?


5/25

Chapter 14

Predict the product of the following reactions:

MgBr

Cl

OH

O

O

Draw out the following mechanism:O

CH3CH2SH

H-B (cat.)


6/25

Predict the product of the following reactions (assume an acid workup of allreactions):

H

H

O

O

O

O

NaH

LiAlH4

NaBH4

C-Li

Draw the mechanism of the following imine formation reaction:

O

H2N

H-B


7/25

Predict the two organic products of the following reaction:

OO

H2O/H3O+

Predict all possible products from the following reaction (Hints: 1- There is onefor the cis formation and one for the trans formation (therefore stereochemistryis important) 2- One never works with a single molecule 3-No acid is available):

O Br

NaBH4

Which is more reactive, formaldehyde or propanal? Why?

What is the byproduct of all of the reversible nucleophile reactions in thischapter? How does this help increase the reversibility of these reactions?


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Chapter 15

Draw the reaction mechanism to form the acid chloride from the followingstarting material (picking the other reactant):

OH

O

List three ways to make a carboxylic acid:

Perform the following base condition mechanism:

Cl

ONaOH/H2O

Perform the following acidcondition mechanism and circle the importantintermediate:

Cl

OH3O

+/H2O


9/25

Predict the product of the following reaction:

Cl

O

+

O

O

Show the mechanism of the following esterification reaction, and explain why thealcohol doesnt attack directly.

Cl

O

N

OH

This is a bit of an odd reaction, but think logically. Using your knowledge ofChem 210 and 215 predict the product of the following reaction:

O3 Ag2O

NaOH

H3O+


10/25

Predict the product of the following reaction (hint: think intramolecular)

HO

O

O

1) NaBH42) H3O

+

Perform the following mechanism:

O

ONH2CH2CH3

H-B

Because your professors seem to love ita transesterification mechanism!

O

OCH3CH2CH2CH2CH2OH

H-B


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Chapter 16

Find all 5 tautomers of the following compound:

H

H

H

C

C

HH

C

OC

H

H

HO O

Show the following enol formation mechanisms:

O

H 3O

+

/H 2O

NaOH/H 2O


12/25

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:

Br

O O

NaOCH3/CH3OH


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Chapter 17

Form an enol from the following molecule under acid conditions:O

Use that enol with the following aldehyde and show the aldol condensationreaction (show the mechanism):

O

Show the following decarboxylation reaction (draw in the curved arrows):

OH

O

O


14/25

Predict the products of the following retroaldol reaction:OHO Bronstead Base

Carbohydrates

What is the generic structural formula for a carbohydrate?

Draw the Fisher-projection of the simplest carbohydrate, name it. Then show theACID catalyzed mechanism of its tautomerization to its ketose form and namethat:

What size ring is the kinetically favored hemi-acetal of a aldohexose?Thermodynamically favored?


15/25

Show the ACID catalyzed mutorotation of the following molecule:

CH3

OH

N

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 CuSO 4 (which is blue/green)the solution would turn red and a precipitate would form. If you know it, what isthat precipitate?


16/25

Draw the product of the following reactions and predict the number ofstereoisomers present in solution:

O

OH

HO

HO

OH

LiH

CH3CH2CH2Cl

O

OH

HO

HO

OH

HCl

NH2

What is a glycoside?

What is the result of the Tollins test for the following sugar?

O

H3CO

H3CO

H3

CO

OCH3

O

O H

H O

H O

O H

H C l

CH 3C H 2C H 2O H


17/25

Draw an B(1->4) linkage of galactopyranose (the C-4 epimer of glucose) andglucopyranose (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 dont know what it lookslikelook 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 amolecule called?

Draw the titration curve for the amino acid Glu, draw the structure of themolecule at every important point:


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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 Leu Ile Glu Ser GlyPro Asp Val Met

Fill in the following blanks in the protecting group charts:

NH3 H

R

COH

O

NH3 H

R

COCH3

O

NH3 H

R

COCH2Ph

O

NH3 H

R

COC

O


19/25

NH3 H

R

COCH3

O

NH3 H

R

COCH2Ph

O

NH3 H

R

COC

O

R

HH3N

COH

O

R

HH3N

COH

O NH

H

COH

R

O

Ph

O

O

NH

H

COH

R

O

O

O


20/25

NH

H

COH

R

O

Ph

O

O

NH

H

COH

R

O

O

O

H3N H

R

COH

O

If given a choice of one of the following which is the most convenient to use andwhy?

CBzPheAlaOtBu CBzPheAlaOMe BocPheAlaOtBu

Draw the mechanism for removal the methyl ester protecting group from GlyOMe

Draw DCC:

What is the purpose of using DCC?


21/25

Draw the mechanism for the reaction between CBzPhe and AlaOtBu using DCC toform 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 aminoacids is it between?

What is the purpose of enzymes?


22/25

DNA

Draw the mechanism for the reaction between NAD+ and ethanol. What is theproduct?

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 its OH replaced by H in DNA?

Draw the dinucleotide made up of thymine and adenine as it would appear inDNA:

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 toknow, but I wanted to get this done in time for you to start it.


23/25

Naming

Name all of the following molecules using IUPAC naming. If marked with a Talso give their common (trivial name) and IUPAC name. If a name is given, drawthe molecule. Stereochemistry is important if implied by the name or structure.

HO

O

OH

CH3OH

Cl

T:

O

T: HOH2C CH2OH

O

OH

O

Br

OH

O

O

OH

OH

Cl

HO

O

O

OCH3

OCH3


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T:

O

OHHO

O

T: O

OO

HC N

CH3

CH3

O

(2R, 3R)-2,3,4 trihydroxybutanal (give trivial name also)

Propanoyl butanoate m-bromoacetophenone

Tetrahydrofuran Diethylene glycol dimethyl ether (AKA: diglyme)

Benzophenone 2,4-dimethyl-3-oxo-5-phenoxyhexanoic acid

3-cyclohexeneone 2-hydroxypropanamide


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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 dont hesitate to ask questions.E-mail:[email protected]: (248)302-1975
mailto:[email protected]:[email protected]:[email protected]:[email protected]

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