Homework - Chapter 14Chem 2320

Name _______________________________

1. Label each alcohol in the the following compounds as primary, secondary, tertiary, enol, or aryl.

a) b)

c) d)

e) f)

OH

OH

OH

OH

OH

OH

OH OH

OH

OH

OH

OH

a) Enols are in equilibrium with their __________________ or ___________________ form.

b) Compounds which contain a C-S-H bonding sequence are called __________________.

c) The alcohol which can cause blindness if ingested is ____________________.

d) An aryl alcohol may also be referred to as a ____________________.

e) An alcohol containing a C=C in any location is referred to as a(n) ______________________ alcohol.

f) The oxygen in an alcohol always has an _________ hybridization.

g) The most common characteristic of thiols is their _________________________________.

h) Isopropanol is often used for __________________________.

i) An aromatic alcohol is one containing a(n) __________________________.

j) The alcohol in alcoholic drinks is called _______________________.

k) An enol must have ______________________________________.

l) Alcohols with _______________________________ or ___________________________ are usually soluble in water.

m) When an alcohol reacts with a base, a(n) __________________ is formed.

n) When an alcohol reacts with an acid, a(n) __________________________ is formed.

2. Fill in the blanks in the following sentences.

3. Match up the following compounds with the spectra shown below. Label ALL important bands!

OH

HOOH

OH

OH

A B C D

HW Ch 14 p 2

HW Ch 14 p 3

4. Match up the following alcohols with the formula C6H14O with the 1H NMR data given below. Sketch each spectrum, and match up the peaks with H's in the structure of the compound you have chosen. Not all compounds will be used!

2-ethyl-1-butanol3,3-dimethyl-1-butanol2-methyl-1-pentanol4-methyl-1-pentanol4-methyl-2-pentanol

a) b)

c) d)

e) f)

a - 0.8 ppm, 3H, tb - 0.9 ppm, 3H, dc - 1.2 ppm, 2H, quintd - 1.6 ppm, 1H, m(8)e - 1.9 ppm, 2H, qf - 2.7 ppm, 1H, bsg - 3.7 ppm, 2H, t

a - 0.9 ppm, 9H, sb - 1.7 ppm, 2H, tc - 2.5 ppm, 1H, bsd - 3.7 ppm, 2H, t

3-methyl-1-pentanol3-methyl-2-pentanol1-hexanol2-hexanol3-hexanol

a - 1.0 ppm, 3H, tb - 1.1 ppm, 3H, dc - 1.2 ppm, 2H, m(6)d - 1.4 ppm, 2H, quinte - 1.6 ppm, 2H, qf - 3.1 ppm, 1H, bsg - 3.7 ppm, 1H, m(6)

a - 0.9 ppm, 6H, db - 1.4 ppm, 2H, qc - 1.6 ppm, 1H, m(9)d - 1.9 ppm, 2H, quinte - 2.2 ppm, 1H, bsf - 3.6 ppm, 2H, t

a - 0.9 ppm, 6H, tb - 1.3 ppm, 4H, quintc - 1.8 ppm, 1H, bsd - 2.2 ppm, 1H, m(7)e - 3.4 ppm, 2H, d

a - 0.9 ppm, 3H, t b - 1.1 ppm, 3H, tc - 1.3 ppm, 2H, m(6)d - 1.8 ppm, 2H, qe - 1.9 ppm, 2H, quintf - 2.1 ppm, 1H, bsg - 3.6 ppm, 1H, quint

HW Ch 14 p 4

5. Circle the compound in each pair which has the higher boiling point, and briefly explain why.

a)

b)

c)

d)

OH OH

O

OH

OHHO FHO

OH

OH

6. Circle the compound in each pair which is more acidic. Then give a brief explanation of why.

a)

b)

c)

d)

OH

OH

OH OH

OHOH

OH OH

OH

OH

OH

SH

OHe)

f)

g)

OH

Cl

OH

OH

OH2

OH

Cl

NaH

OH H2SO4

O H3O+

OH NaOH

SH

OH

NaOH

2 K

OH NaOH

OH

O H2O

OH2 H2O

HW Ch 14 p 5h) rubbing alcoholwater

7. Give all products of the following acid-base reactions. Then indicate whether products or reactants (or neither) are favored by the equilibrium.

a)

d)

e)

f)

+

+

+

+

j)

h)

+

+

i)

j)

b) +

c) +

i) +

g) +

Na

2

HW Ch 14 p 6

8. Draw structures for the following alcohols.

a) b)

c) d)

e) f)

butyl alcohol allyl alcohol

sec-butyl alcohol

tert-butyl alcohol benzyl alcohol

isopropyl alcohol

9. Name the following compounds.

a) b)

c) d)

e) f)

OH

OH

OH

HO

OH

OH

HW Ch 14 p 7

10. Draw structures for the following compounds.

a) dicyclopropylmethanol b) 1-cyclobutyl-4-penten-2-ol

g) h)

i) j)

Cl

OH

OH

OH

OH

OH Br

OH

k) l)OH

HO

OH

OH

c) trans-4-(2-butenyl)-3-isopropyl-1-cyclohexanol d) (S)-1-penten-4-yn-3-ol

e) 3-(3-hydroxypropyl)-1-cyclopentanol f) 3-chloro-4-(1-hydroxyethyl)-2-isopropyl-2-cyclobuten-1-ol

Cl

Br

Cl

OH

OH

OH

OH

OH

OH

OH

OH

HW Ch 14 p 8

11. Give reagents which would convert the following compounds to the alcohol shown.

a)

b)

c)

d)

e)

f)

g)

h)

i)

O

O

OH

OH

HW Ch 14 p 9

12. Indicate whether the following transformations represent an oxidation or reduction and explain why.

a)

b)

c)

d)

e)

f)

OH O

OH

O

H

O

NH2

N

OH

O

O

O

g)

NH2

O

NH2

O

O

h) OH

j)

k)

l)

OH O

H

S

O

S

O

O

N NH

H

O

O

O

O

CH3OH

NaBH4

NaBH4

OH

O

O

O

O

OO

OH

O

H

O

H

O

O

OO

NaBH4

CH3OH

NaBH4

CH3OH

NaBH4

OH

HW Ch 14 p 10

13. Give the products of the following reactions.

a)

b)

c)

d)

e)

f)

g)

h)

i)

j)

1. LiAlH4

2. H3O+

1. LiAlH4

2. H3O+

1. LiAlH4

2. H3O+

1. LiAlH4

2. H3O+

H2, Pd/C

H

O

j)

Raney Ni

HW Ch 14 p 11

Br MgBr OH Li

14. Label the dipole in the following molecules.

MgBr

MgBr

MgI

MgCl

Li

Li

Li

Li

15. Give starting materials and reagents to show how the following organometallic reagents could be formed.

a)

b)

c)

d)

e)

f)

g)

h)

HW Ch 14 p 12

Li

MgBr

O H

OH H

MgCl

Li

MgI

OD D

H3C O H

H

16. Give ALL of the products of the following reactions. Draw arrows to show how the reaction takes place.

a)

b)

c)

d)

e)

Li

Li

MgCl

MgBr

H

O

O

HH

Li

O

O

H

O

OH HH

OH HH

OH HH

OH HH

OH HH

17. Give the products of the following reactions. Draw arrows to show how the reaction occurs.

a)

b)

c)

d)

e)

+

+

+

+

+

HW Ch 14 p 13

O

Cl

MgCl

O

O

MgCl O HO

HO

OH

OH

18. Show the mechanism by which the following products were formed, including all steps, arrows, electron pairs, and formal charges!

a)

b)

c)

2

2. H3O+

1.

2. H3O+

+ MgCl2 + H2O

+ 2 Li+ + 2 H2O

2. H3O++ Mg+2 + Cl- + H2O

H3C Li2 eq

Li

H

O

a)

b

1. CH3MgBr

2. H3O+

1. formaldehyde

2. H3O+

19. Give the final product of the following reactions.

HW Ch 14 p 14

MgClH

O

LiO

c)

d)

2. H3O+

2. H3O+

+

1.

Li

MgCl

Li

Cl

O

MgBr

MgBr

MgBr

O

O

O

O

O

O

O

Cl

O

O

O

MgI

O

O

Li

Li

e)

f)

g)

h)

i)

j)

k)

l)

m)

+

+

+

2. H3O+

2. H3O+

2. H3O+

2

2

+ 22. H3O+

+ 22. H3O+

2. H3O+

2. H3O+

2 +

2. H3O+

1. 2

2. H3O+

HW Ch 14 p 15

20. Show all reagents that would be necessary to perform the following reactions. If more than one arrow is written, it means that there is more than one step.

a)

b)

c)

d)

e)

f)

g)

h)

i)

Br OH

O

O

OH+ CH3OH

O OH

Cl OH

OH

OH

Cl

O OH

OH

O

OH

O

O OH

j)

O O

+ H2O

HW Ch 14 p 16

k)

l)

m)

n)

o)

q)

r)

s)

t)

OH

HO+

ClOH

Br

OH

H H

OO

OHHO

O

O

O

O

OOH

H

O OH

O

HO

HO OH

I2

u)

Br

OH

2 Br

OH

p)

Cl