Chapter 11

Question 1

Oxidation:
______: C-O, C-N, or C-X bonds
______: C-H bonds

Answer 1

form
break

Question 2

Reduction:
______: C-O, C-N, or C-X bonds
______: C-H bonds

Answer 2

break
form

Question 3

_______ results in less bonds to O and more bonds to H

Answer 3

reduction

Question 4

_______ results in more bonds to O and less bonds to H

Answer 4

oxidation

Question 5

What oxidation agents can change an alcohol into a carboxylic acid?

Answer 5

Na2Cr2O7
H2SO4
H2O

or NaOCl, pyridineish ring in excess

Question 6

What happens when you try to oxidize a 3° ROH

Answer 6

inert to oxidation
NO REACTION!

Question 7

NaOCl, pyridinish ring only works for ___ ROH’s

Answer 7

1°

Question 8

NaOCl, HOAc only works for ___ ROH’s

Answer 8

2°

Question 9

Alcohols are very versatile and can act as _______ and _______

Answer 9

nucleophiles
electrophiles

Question 10

What bond is broken when alcohols react as nucleophiles?

Answer 10

O- -H bond

Question 11

What bond is broken when alcohols react as electrophiles?

Answer 11

C- -O bond

Question 12

HCl, ZnCl2 are the _______ reagents

Answer 12

Lucas

Question 13

explain the lucas test and how it reacts with 1°, 2°, 3° alcohols at predictable rates

Answer 13

1°: cloudy in more than 6 mins
2°: cloudy in 1-5 minutes
3°: cloudy in less than 1 min

Question 14

the limitations of hydrohalic acids with alcohols is:
1) poor _______ of alkyl chlorides from primary or secondary alcohols
2) _______ competes with substitution
3) carbocation intermediate may undergo _______
4) limited ability to make alkyl _______ form __

Answer 14

1) yield
2) elimination
3) rearrangement
4) iodides from HI

Question 15

What are the 3 reactions to turn ROH into a better leaving group?

Answer 15

1) Strong acid (HCl or HBr)
2) OTs or OMs
3) turn it into X (special reagents)

Question 16

What are the three special reagents for turning OH into X

Answer 16

1) SOCl2
2) PBr3
3) PI3

Question 17

When using SOCl2, what happens to the stereochemistry of the product?

Answer 17

retention

Question 18

When using PBr3 or PI3, what happens to the stereochemistry of the product?

Answer 18

inversion

Question 19

What is the driving force of SOCl2 reaction?

Answer 19

SO2 (g) leaving

Question 20

Reduction of alcohols must be accomplished in ___ steps
- very rare

Answer 20

2

Question 21

What are the two ways alcohols can be reduced?

Answer 21

1) E1 (H2SO4) then H2, Pt
2) TsCl, pyridine then LiAlH4
2 steps

Question 22

How does a pinacol rearrangement start? and what is the driving force?

Answer 22

Oxygen grabbing a H of H2SO4
Octet rule is the driving force

Question 23

Glycols can be oxidative cleaved by periodic acid (HIO4) to form the corresponding _______ and _______

Answer 23

aldehyde and ketone

Question 24

_______ + _______ + _______ always results in FISCHER esterfication

Answer 24

carboxylic acid + ROH + Acid

Question 25

What is the driving force of Fischer Esterification?

Answer 25

Removal of water

Question 26

_______ + _______ + _______ always results in regular esterfication

Answer 26

acid chloride + ROH + base
- base usually pyridine

Question 27

What is preferred, Fischer esterification or esterification

Answer 27

Esterification

Question 28

What are the three esters of inorganic acid?

Answer 28

1) Sulfate ester
2) Nitrate ester
3) Phosphate ester

Question 29

sulfate ions are good ____: Nuc reacts with sulfate esters to give alkylated products

Answer 29

LG

Question 30

The best-known nitrate ester is “nitroglycerin” = _______

Answer 30

Explosive (Dynomite)

Question 31

Phosphate ester linkages compose the backbone of nucleic acids ______ and ______! they carry the genetic information of the cell

Answer 31

RNA and DNA