Last Name: UTEID: First Name: SCORE: KEY 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 CH 3 O Asprin (salicylic acid) O a b c d e f a b CH 3 C H 2 O C H 2 CH 3 a b c d e a a b b c c N H O a b c d
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Last Name:
UTEID:
First Name:
SCORE: KEY
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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Deadline for CH310N POW 3: Feb 14 3:00 PM
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
Deadline for CH310N POW 4: Feb 21 3:00 PM
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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Deadline for CH310N POW 5: Feb 28 3:00 PM
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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Deadline for CH310N POW 10: Apr 11 3:00 PM
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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Deadline for CH310N POW 11: Apr 18 3:00 PM
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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Deadline for CH310N POW 12: Apr 25 3:00 PM
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.