There are 19 problems on 22 pages. Please make sure that …jabjorklund.faculty.noctrl.edu/Organic/Organic 3/review/final_rev1a... · trans-1,3-cyclohexanedicarboxylic acid E-2,5-dimethyl-5-octenoic

1) Give an unambiguous name for the following compounds. Be sure to use cis/trans, E/Z or R/S where appropriate.

a)

b)

CHEMISTRY 222, Spring 2001 Review Problems

There are 19 problems on 22 pages. Please make sure that you have them all.

c)

d)

e)

f)

OH

Cl

cis-3-chlorocyclohexanol

BrOH

4-bromo-2-propyl-1-hexanol

NO2

OH

Br2-bromo-5-nitrophenol

1,(4E)-heptadien-6-yne

3-(1-methylpropyl)-1-heptyne

O1-penten-3-one

Page 1

1) Contd.

g)

h)

i)

j)

k)

l)

2-bromo-4-chlorobenzoic acid

N-propyl-4-methyl-3-octanamine

trans-1,3-cyclohexanedicarboxylic acid

E-2,5-dimethyl-5-octenoic acid

2-bromopropanal

2-bromo-2-methylbutanoyl chloride

Br

CO2H

Cl

NH

CO2H

CO2H

CH2

CH3CH3CH2

H CH2 CH

CO2H

CH3

CH2 C

Br

CH3

O

ClCH3

m)methyl-5-cyanopentanoate

NC CH2 CH2 CH2 CH2 CO2 CH3

CHO

Br

CHEMISTRY 222, Spring 2001 Review_Problems Page 2

––– –––

Increasing acidity

––– –––< <

a)

A CB D

<

2) Rank the following in order of:

C A D B

OH OH OH OH

H3C NC H3CO

––– –––

Increasing rate of reaction in a Diels-Alder reaction

–––< <

b)

A CB

C B A

––– –––

Increasing rate of reaction with an electrophile

––– –––< <

c)

A CB D

<A C B D

NHCOCH3 NH2 OH O–

CHEMISTRY 222, Spring 2001 Review Problems Page 3

O

O

O

O

O

O O

O

OCH3

O

––– ––– ––– –––< <

A CB D

<

g) Increasing acidity

B C A D

––– –––

Increasing rate of hydrolysis

–––<

f)

A CB

<A C B

NHCOCH3 COCl CO2CH3

3) Give the number of enolizable hydrogens for each compound.

–––

O

H

O O OH

––– ––– –––1 1 4 0

Question 2, contd.


Rank the following in order of increasing energy4)

A

•

––– –––

E

–––< <E–––<

B C

D F

–––< < –––B A F D C

5) Draw the HOMO's (π orbitals) for the following systems:

–•


O

N+

N

H

H

N

6) When in a flat configuration, which of the following compounds are:

a) Aromatic? A F

b) Non-aromatic? B C D A B

D E F

c) Antiaromatic? E

C

+

•–+

7) Give the alkyl bromides you would use to make the following ketones using the dithiane synthesis shown.

8) Propose a Wittig synthesis of 3-hexene, using 1-propene as your only source of carbon

OCH

Ph3P+

–OH

PCC

1. BH3.THF

2. –OH, H2O2

HBr

Br 1. PPh3

2. BuLi

ROOR+

9) Give a synthesis of acetonitrile from ethanol

OH

SOCl2

H3C CN

H3C CO2H

Na2Cr2O7/H2SO4

H3C COClNH3

H3C CONH2

POCl3

Ph

O

S S

1. BuLi2. R1-X3. BuLi

4. R2–X5. H3O+

R1-Br =

R2-Br =

Br Ph

Br


CH2 C

O

CH3H CH2 C

O–

CH3 CH2 C

O

CH3

CH2 C

O–

CH3 CH2 C

O

CH3CH2 C

OH

CH3

H3C C

O

CH3

H3C C

+OH

CH2

H

H3C C

OH

CH2

H

H3C C

OH

CH2

b) Of A and B, which will be the major resonance contributor to the structure of the enolate anion?

HO–

H3C C

OH

CH2

c) Draw a detailed (arrow pushing) mechanism for the acid catalyzed conversion of acetone to its enol

A

endothermic

d) Draw a detailed (arrow pushing) mechanism for the reverse reaction.

a) The pKa of acetone is ca. 19, the pKa of water is ca. 16. Is deprotonation of acetone by hydroxide exothermic or endothermic?

H3C C

OH

CH3

H3O+

Review ProblemsCHEMISTRY 222, Spring 2001

10) Keto-enol tautomerism can be catalyzed by base. The mechanism is shown below for the case of acetone.

H3C C

O

CH3

+ H2O

A

+ H2O–

H3C C

O

CH3

A

+

H3O+

B

+

H

–

B

OH2

+

OH2

Page 7

11) Here is an important acid catalyzed reaction which illustrates many of the features of many acid catalyzed reactions. Give a complete arrow pushing mechanism for the reaction.

12) Give a complete arrow pushing mechanism for the following reaction. Be careful indicate if any of the steps are reversible.

H3C OHC

O

CH3CH2OH+H3C OCH2CH3

C

OH3O

+H3O+

H3C OHC

O+H

CH3CH2OHC

OH

OHH3C

O+

CH3CH2 H OH2

C

OH

OHH3C

OCH3CH2

H3O+

C

HOH

OHH3C

OCH3CH2

+C OH3C

OCH3CH2

+H OH2

–OCH3

H2O+

ONa+

CH3OH

–OCH3

H

O–O

O –O

H OCH3O HO

H–OCH3

–O HO

O

heat


a)

b)

c)

d)

e)

13) Give the major organic product for the following reactions. Show stereochemistry where appropriate.

f)

t-Bu

Me KMnO4, boil

t-Bu

HO2C

heat

OH

OH

PCCO

O

H

O

O

OH

OHO

O

O

1. PBr3

2. Mg.THF

3. CH3CHO

OH

HO

4. H3O+

H+

OBr2

O

Br

O

H

H

H

O

NaOEt

heat

Review ProblemsCHEMISTRY 222, Spring 2001 Page 9

g)

h)

i)

j)

k)

13) Contd.

l)

1. Sia2BH/THFH

2. –OH, H2O2CH2CHO

CO2H

1. SOCl2

2. AlCl3

O

NH

O

1. –OH, H2O, heat

2. H3O+ (neutralize) HO NH2

O

Br1. Mg, THF

2. D2O

D

heat/KMnO4

H3O+

CO2H

O


H

O

+ NH3

1. H3O+

2. LiAlH4

H

NH2

m)

13) Contd.

EtO OEt

O O O1. NaOEt/EtOH/heat

2. H3O+/heat

O

OEt

O

+

NaOH, heat

r)

O O

BrNaCN

o)CN

p)CNNC

heat

CN

CN

heatq)

s)

t)


Br2

Br

Br

N2+ –Cl

H3O+ OH

u)

v)

w)

O

H3O+

(CH3)2NH

N

O

H3O+

(CH3)NH2

N

CN

2. H3O+

1. CH3MgBrO13) Contd.


a)

SOCl2

b)

c)

Na, NH3(l)

EtOH

14) Give the reagents/conditions to perform the following transformations. Some will require more than 1 reagent, in which case use the 1. ... and 2. ... notation.

OH Cl

1. Br2/PBr3

2. H2O

OH

O

OH

OBr

d) 1. Hg(OAc)2, EtOH

2. NaBH4

CH3CH2 CH CH2 CH3CH2 CH CH3

OCH2CH3

e)

1.

2. H3O+CH3 C C MgBr

O

CH3 C C

CH3

OH

1. HBr, ROOR

2. NaCNCNx)

h)

i)

j)

k)

l)

m)

14) Contd.

CO2CH3

O

CH2OH

OH

O OHPh

t-Bu

H3C

t-Bu

BrH2C

CNNH2

O

H3CO H3CO

CN


f) Ph C C H Ph CH2 CHO

g)O

MCPBA

LiAlH4

1. Sia2BH.THF

2. –OH, H2O2

1. PhMgBr

2. H3O+

Br2, hν

1. LiAlH4

2. H3O+

HgSO4

H2SO4

heat

CN

15) Show how you would make compounds B from compounds A. Show intermediates, reagents, but do not give arrow pushing mechanisms.

a)

A

1. KMnO4/–OH/heat LiAlH4

HO2CCO2H

2. H3O+

ClOCCOCl

SOCl2H2NOC

CONH2

NH3

NH2H2N B

b)

OH

O

B

A

HC C–

–O

HO

Na2Cr2O7H2SO4 H3O

+

Na+

Br OH

OH

A

B

Br2, hν

K+ –Ot-Bu K+ –Ot-Bu

1. PhMgBr2. H3O+

c)


ONa2Cr2O7

H2SO4

d) A

H3O+

B

CO2H

C

HO

BrMgO

2 CH3MgBr

e) A

H3O+

B

CO2H

O

O––O Li+

Li+2 CH3Li

CN CN

CN

heat

CNO

f) A B

1. BH3.THF

2. –OH, H2O2

15) Contd.


SOCl2

O

Cl

HO

PCC

g)

A B

h)

A B

i)

A B

BrBr

OHPBr3

1. BH3.THF

2. –OH, H2O2

KOH

CN

O

O

Cl

AlCl3

O

OH SOCl2

H3O+

O O

OEtEtO CO2H

O O

OEtEtO

H3O+, heat2. CH3CH2Br

1. NaOH

2. Br

O O

OEtEtO1. NaOH

15) Contd.


15) Contd.

j) BA

F

Br

NO2

HNO3/H2SO4

NO2

Br

N2+ Cl–

BrNH2

Br

Br2/FeBr3H2, Pt NaNO2/HCl

HBF4


k) BA

Br2, hν

O

Cl

OAlCl3 O

CO2H

separateisomers

O

Br

1. Mg.THF2. CO23. H3O+

BA

HNO3H2SO4

H2Pt

NO2 NH2

separateisomers here

NH2

Br

Br

N2+

Br

H3PO2

HONO

Br2

FeBr3

15) Contd.


l)

m) Ph OH

(hint, ethyl acetoacetic ester synthesis)

Ph

O

Ph Br

PBr3

OEt

O ONaOEt

OEt

O O

Ph

H3O+

heatOH

O O

Ph

heat

A B

you must make the ortho-isomer exclusivelywith no contamination from the para-isomer

16) Determine the structure of the compound which has the IR, 13C and proton NMR spectra given below. The molecular formula is C4H8O2. (This is an easy one!!) sa16

O

O


3H

3H

2H

Determine the structure of the compound which has the IR, 13C and proton NMR spectra given below. The molecular formula is C9H10O. (This is easy too!!)

3H triplet

2H quartet

3H multiplet

2H multiplet

O

sa32


18) Draw the structure of the compound which has the IR, 13C and proton nmr spectragiven below. The molecular formula is C4H8O2. If you can not determine the completestructure, write as many molecular fragments as you can.

H3C

O

CH2

O

CH3

This one is just a little bit harder!!

3H3H

2H

sa50


19) Determine the structure of the compound which has the IR, 13C and proton NMR spectra given below. The molecular formula is C9H10O3.

sa53

triplet

triplet

doublet

triplet

triplet

HO2CO

this one is harder!

X

Review ProblemsCHEMISTRY 222, Spring 2--1 Page 22

There are 19 problems on 22 pages. Please make sure that …jabjorklund.faculty.noctrl.edu/Organic/Organic 3/review/final_rev1a... · trans-1,3-cyclohexanedicarboxylic acid E-2,5-dimethyl-5-octenoic

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