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Deadline for CH310N POW 1: Jan 31 3:00 PM

1) For the following structures, label the equivalent protons with the "a, b, c"lettering system.

COOH

O CH3

O

Asprin (salicylic acid)

O

a

b

c

d

e

f

a

b

CH3CH2

O

CH2

CH3

a

b

c

d

e

a

a

b

b

c

c

NH

O

a

bc

d

2) Assign the splitting pattern to each type of protons in these structures.Use the following abbreviations: s= singlet; d=doublet; t=triplet;q=quartet; 5 or more peaks: multiplet. If there is coupling from differentsets of protons, then both couplings must be identified. E.G. doublet oftriplets: d of t or t of d.

CH3CH2

O

CH2

H2C

CH3

triplet

triplettripletquartet

triplet of quartets (12 peaks)

H3C

H2C

O

C

CH3

O

triplet

quartet

singlet

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Deadline for CH310N POW 2: Feb 7 3:00 PM

Cl

CH2

H2C

CH2

ClCl H

C

H2C

CH3

Cl

1) The NMRs of three isomers of dichloropropane are shown below. Matcheach compound with it's NMR and provide an interpretation of eachspectrum. (i.e. draw the structure on the NMR and label protons, with theirsplitting.)

H3C

C

CH3

Cl Cl

0123PPM

H3C

C

CH3

Cl Cl

a a

a, singlet

01234PPM

2

4 Cl

CH2

H2C

CH2

Cl

a, tripleta, triplet

a

b, pentet

b

0123456PPM

3

2

1

Cl HC

H2C

CH3

Cl

a

a, triplet

b

b, d of qc, triplet

c

8 peaks

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1) Grignard reagents: Provide the products for the following reactions.(structure-n-a-box). If there is stereo- or regiochemistry in the products, you mustindicate it with the appropriate drawings, such as wedge and dashed bonds.

O

H1) CH3CH2MgBr

2) H3O+

OH

CH2CH3

O

CH2

H3C

1) CH3CH2MgBr

2) H3O+H

OH

CH2

H3C

H

CH2CH3

O1) PhMgBr

2) H3O+

OH

Ph

a)

b)

c)

2) Grignard reagents: Provide the reagents for the following reactions. If morethan one step is required (e.g. acid) you must show it.

O

CH3

OH

CH3

1) PhMgBr

2) H3O+a)

b)

c)

CH3

O

CH3

OH1) CH3CH2CH2MgBr

2) H3O+

MgBr

OOH

1)

2) H3O+

d)

MgBr1) CH2O (formaldehyde)

2) H3O+OH


Multi-step synthesis: Provide products for the following sequence of reactions. Draweach product in the box (structure-n-a-box) provided and indicate stereochemistry, if any isinvolved. (Hint: ref er to Rxn Summary handout)

Br2

h

BrKOtBu

HOtBu

O

ArCO3H

CH2Cl2

MgBr

1)

2) H3O+OH

Ph

Must show correctstereochemistryMust show correct stereochemistry

A)

H3C

CH3

CHCl3

tBuO-K+

B)

Br2

CuLi

H3C CH3

Cl Cl

2) Provide the product(s) for the following reactions or sequence of reactions. If anystereochemistry is involved, clearly indicate (draw) it in the structure. (Hint: ref er to RxnSummary handout)

HH

Br(H3CCH2CH2)2CuLi

Must show correctstereochemistry

Must show correct stereochemistry

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Multi-step synthesis: Provide products for the following sequence of reactions. Draweach product in the box provided and indicate stereochemistry, if any is involved. (Hint:refer to Rxn Summary handout)

Br

OH

H

O

H

1) Mg

2) H2CO3) H3O

+

(OEt)2P

OO

OCH3

C4H9 H

O

OCH3

OH

Ph

1)

2) H3O+

MgBr

O

Ph

H2CrO4

1)

2) H3O+

PCC

Must show correctstereochemistry

Mechanism: Provide a mechanism for the following transformation. Show all importantflows of electrons, charges and intermediates. Where indicated, (in the structure-n-a- box)-draw the intermediates.

OH

O

CH3OH

H3O+ (cat)

OCH3

O

OH

O H+

H5C3 OH

O

H

H5C3 OH

O

H

HO CH3 HO CH3

H5C3 OH

O

H

O

H3C HH5C3 OH2

O

H

O

H3C

H2O

O

O

CH3

Protonated Crotonic Acid-Show both resonance structures

Show theintramolecularproton transfer

Show the loss ofwater and theformation of thecarbonyl

H2O

Show the attackby methanol

Crotonic Acid

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Deadline for CH310N POW 6: Mar 7 3:00 PMMechanism: Provide a mechanism for the following transformation. Show all importantflows of electrons, charges and intermediates. Where indicated, (in the structure-n-a- box)-draw the intermediates.

OCH3

O H+

H3C OCH3

O H

Show the nucleophilic attackby piperidine

Show the loss ofmethanol and theformation of theamide

Protonate the ester

HN

H3C OCH3

O

N

O

+ CH3OH+

TsOH (cat)

heat

HN

piperidine

H3C

OCH3

OH

Tetrahedral intermediate withN-protonated

N H

H3C

OCH3

O

Tetrahedral intermediate withO-protonated

N H

H

Intramolecular protontransfer

N

O

+ CH3OH

O3S

Multi-step synthesis: Provide products for the following sequence of reactions. Providethe reagents (boxes) or intermediates (rounded boxes). Indicate stereochemistry, if any isinvolved. (Hint: refer to Rxn Summary handout)

CH3O

OH

CH3O

OH

O

H2CrO4

CH3O

Cl

O

CH3O

OCuLi

2

CH3O

OH

CH3O

O

O

O

CH3Cl

SOCl2 orSO2Cl2

1) LiAlH4

2) H3O+

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Deadline for CH310N POW 7: Mar 21 3:00 PM

A)

B)

C)

O

CH3

Retrosynthesis: Each of the following -unsaturated ketones can be produced from analdol condensation-dehydration reaction. Provide the starting material(s) for thepreparation of each compound.

O OO

H

H3C

O

CH3

O

H

O

CH3

CHO

O

CH3

Multi-step synthesis: Provide products or the reagents for the following sequence ofreactions. Draw each product or reagent in the box provided.

OCH3

O O1) NaOCH3

2)Br OCH3

O O

O

1) NaOCH3

2) CH3CH2Br

CO2CH3O

1) NaOH (aq)2) HCl (aq)

3) heat

OH

1) CH3CH2CH2MgBr

2) H3O+

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Deadline for CH310N POW 8: Mar 28 3:00 PM

2,6-Diketones can be cyclized to form cyclohexenones, through aseries of equilibrating intermediates. Propose a mechanism for the example below.Show all important flows of electrons, charges and intermediates. Where indicated,(in the structure boxes)- draw the intermediates.

CH2

O

NaOH (aq)

HO

Intramolecular Aldol

Formation of an enolate

O

H3C CH3

O O

CH3

H

O

CH2

O

H2O

CH3

O

HO

-alkoxy-ketone

O

CH3

O

H

H OHContinue on next page

Box #3

OH

-hydroxy-ketone-alkoxy-ketone

Protontransf er

Dehydration

Final Product

O

CH3

O

H

H OH

O

CH3

OH

H

OH2O

This is the same box #3:

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Deadline for CH310N POW 9: Apr 4 3:00 PM

Mechanism: Methyl vinyl ketone will undergo 1,4 addition when treated with HBr (in ether).Show the mechanism for the reaction following the steps below.

O HBr

ether, 0o

O

Br

O

OH

H Br

Br

OH O

BrBr

protonate MVK

show the addition of Br toprotonated MVK

show the product of the addition-(this is the 1,4 addition product)

OH

CO2CH3

O

CO2CH3

O

CO2CH3

O

COCH3O

O

COCH3O

This structureexplains theacidity

Draw thephenoxideion first

Resonance: Phenols are more acidic than aliphatic alcohols. For p-Carbomethoxyphenol, draw the resonance structures of the phenoxide anion, which showthe reason for the enhanced acidity.

O

CO2CH3

NaOH

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A)

B)

NO2

1) Cl2; FeCl3

2) H2; Ni

C)

ClCOCH2CH3

AlCl3

CH(CH3)2CH(CH3)2

CH3

H2CrO4

or KMnO4

ClCOOH

Cl

O

Reactions: Provide the reagents for the following transformations. If more than onestep is required, then label the steps 1); 2); etc.

H3C

NH2

H3C

Cl

Mechanism: Provide the stepwise mechanism for the following Friedel-Crafts alkylation.Show all important flows of electrons, charges and intermediates. Follow the instructions foreach of the stages.

AlCl3

Cl CH3

CH3

Show the generation of the electrophile:

H3C

H2C

CH2

Cl AlCl3 H3C CH2AlCl4

HH

H3C CH3

H

Show the carbon-carbon bond formation (the rate determining step):

H

H3C CH3

H

H

CH(CH3)2

H

CH(CH3)2

H

CH(CH3)2

H

CH(CH3)2

CH(CH3)2

Draw the family of resonance structures:

AlCl3

Show the last step-the loss of the proton:

must show the rearrangement

Cl

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Reactions: Provide the products for the following multi-step synthesis. You mustshow the correct regioisomer for any of the electrophilic substitution reactions.

H2SO4

H2/ Ni

HNO3

NO2

Cl

NH2

Cl

Br

Cl

NO2

AlCl3

Cl2

1) HONO

2) CuBr

Resonance: Using resonance sturctures, predict the relative basicity of the twoaniline derivatives below. (i.e. is the compound more or less basic than aniline itself?).

NH2

NO2

NH2

NO2

NH2NH2

N

OO

N

OO

Thisstructureexplainsthedecreasedbasicity

NH2

OCH3

NH2

OCH3

NH2

OCH3

NH2

OCH3

This structureexplains theincreasedbasicity

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Diels-Alder Reactions: Draw the structures of the products between the following dienesand dienophiles. Be sure to clearly indicate both regio and stereochemistry.

OCH3

+

OCH3

OCH3

+

OCH3

OCH3

+

OCH3

CH3

CH3CH3

CH3

+ O

O

O

O

O

O

H

H

OCH3

OCH3

OCH3

CH3

CH3

CH3

Cl

Cl

+

+

+

H3C

CH3

CH3

These are enantiomers, butboth are the endo product

These are entiomers and thetrans dienophile results inendo-exo orientation.

ClCl

ClClCl

Cl

One product is formed-theendo adduct-note: the mirrorimage isomer is the samecompound.

Diels-Alder Reactions-Bicyclic Products: Draw the structures of the products betweenthe following dienes and dienophiles. Be sure to clearly indicate both regio andstereochemistry.

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Deadline for CH310N POW 13: May 2 3:00 PM

Carbohydrates: Draw the products of each reaction below. Each of these reactions areanalogous to other reactions of aldehydes, ketones or alcohols.

CHO

OHH

HHO

HHO

OHH

CH2OH

D-galactose

CH2OH

OHH

HHO

HHO

OHH

CH2OH

COOH

OHH

HHO

HHO

OHH

COOH

NaBH4

in H2O

Galactitolmeso; optically inactive

HNO3; heat

Galactaric Acidmeso; optically inactive

1

CHO

OHH

HHO

HHO

OHH

CH2OH

CH2OH

OHH

HHO

HHO

OHH

CH2OH

Galactitolmeso; optically inactive

H2/Pt

PhNH2

HC

OHH

HHO

HHO

OHH

CH2OH

NPh

Shiff Base of Galactose

Ag(NH3)2+

COOH

OHH

HHO

HHO

OHH

COOHGalactaric Acidmeso; optically inactive

2

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