Ch. 15 - Reactions To Form Alcohols

Front 1

List 13 different reactions that yield alcohols a product
(1 forms a diol)

Back 1

1. Hydrolysis of Alkyl Halides
2. Acid-Catalyzed Hydration of Alkenes
3. Hydroboration-Oxidation
4. Oxymercuration-Demurcuration
5. Reaction of Grignards (R--MgBr) with Aldehydes or Ketones
6. Reaction of Grignards (R--MgBr) with Esters
7. Reaction of Organolithiums (R--Li) with Aldehydes and Ketones
8. Reduction of Aldehydes and Ketones #1
9. Reduction of Carboxylic Acids
10. Reduction of Esters
11. Reaction of Grignards with Epoxides
12. Hydroxylation of Alkenes to form Diols
13. Reduction of Aldehydes and Ketones #2

Front 2

REAGENTS FOR:

Hydrolysis of Alkyl Halides

Back 2

H2O, Ca(OH)2
------------------------->

Front 3

REAGENTS FOR:

Acid-Catalyzed Hydration of Alkenes

Back 3

H3O+, H2O
------------------------>

Front 4

REAGENTS FOR:

Hydroboration-Oxidation

Back 4

1. B2H6, diglyme
---------------------------->
2. H2O2, HO-

Front 5

REAGENTS FOR:

Oxymercuration-Demurcuration

Back 5

1. Hg(OAc)2, THF, H2O
---------------------------->
2. NaBH4

Front 6

REAGENTS FOR:

Reaction of Grignards (R--MgBr) with Aldehydes or Ketones

Back 6

1. diethyl ether
-------------------------->
2. H3O+ workup

Front 7

REAGENTS FOR:

Reaction of Grignards (R--MgBr) with Esters

Back 7

1. diethyl ether
-------------------------->
2. H3O+ workup

Front 8

REAGENTS FOR:

Reaction of Organolithiums (R--Li) with Aldehydes and Ketones

Back 8

1. diethyl ether
-------------------------->
2. H3O+ workup

Front 9

REAGENTS FOR:

Reduction of Aldehydes and Ketones #1

Back 9

1. NaBH4 or LiAlH4
diethyl ether
---------------------------->
2. H2O

Front 10

REAGENTS FOR:

Reduction of Carboxylic Acids

Back 10

1. LiAlH4, diethyl ether
---------------------------->
2. H2O

Front 11

REAGENTS FOR:

Reduction of Esters

Back 11

1. LiAlH4, diethyl ether
---------------------------->
2. H2O

Front 12

REAGENTS FOR:

Reaction of Grignards with Epoxides

Back 12

1. diethyl ether
--------------------------->
2. H3O+ workup

Front 13

REAGENTS FOR:

Hydroxylation of Alkenes to form Diols

Back 13

(CH3)3COOH, OsO4 (cat)
---------------------------->
tert-butyl alcohol, HO-

Front 14

PROPERTIES OF:

Hydrolysis of Alkyl Halides

Back 14

SN2 pathway
H2O used as nucleophile
HO- can be used, but gives some elimination

Front 15

PROPERTIES OF:

Acid-Catalyzed Hydration of Alkenes

Back 15

'mark' addition

Front 16

PROPERTIES OF:

Hydroboration-Oxidation

Back 16

'anti-mark' addition of OH to alkene
syn
no rearrangement

Front 17

PROPERTIES OF:

Oxymercuration-Demurcuration

Back 17

'mark'
no stereoselectivity (only one isomeric product)

- Overall transformation C=C to H-C-C-OH
- Alternate method for hydrating alkenes to give alcohols

Front 18

PROPERTIES OF:

Reaction of Grignards (R--MgBr) with Aldehydes or Ketones

Back 18

1. forms 1*, 2*, and 3* alcohols

2. nucleophilic carbon of grignard attacks electrophilic carbon of carbonyl group.

3. workup with acid to protonate.

Front 19

PROPERTIES OF:

Reaction of Grignards (R--MgBr) with Esters

Back 19

1. standard grignard pathway that cycles through twice

2. molecule is cleaved at the ether oxygen before 2nd cycle

Front 20

PROPERTIES OF:

Reaction of Organolithiums (R--Li) with Aldehydes and Ketones

Back 20

Standard grignard pathway
2 Eq. of reagents required

Front 21

PRODUCTS OF:

Reduction of Aldehydes and Ketones #1

Back 21

Aldehydes: 1* alcohols
Ketones: 2* alcohols

Front 22

PRODUCTS OF:

Reduction of Carboxylic Acids

Back 22

1* alcohols formed

Front 23

PRODUCTS OF:

Reduction of Esters

Back 23

1* alcohols formed

Front 24

POSSIBLE REAGENTS FOR:

Metal Reduction of Aldehydes and Ketones

Back 24

metal catalyst = Ni,Pd, Pt, or Ru
H2

Front 25

PROPERTIES OF:

Reduction of Aldehydes and Ketones #2

Back 25

syn addition

Front 26

List:
- 3 reactions that form Thiols

Back 26

Thiols:
1. Substitution using an alkanethiolate (analogous to alkoxides)
2. Thiourea Reaction
3. Sulfide-Disulfide Reduction

Front 27

PROPERTIES/PRODUCTS OF:

Substitution using an alkanethiolate

Back 27

Sn2 of 1* and 2* alkyl chlorides
Inversion

Product: thiol

Front 28

REAGENTS FOR:

Thiourea Reaction

Back 28

1. Thiourea (NH2)2CS
2. HO-
3. H3O+

Front 29

REAGENTS/PROPERTIES FOR:
"Sulfide-Disulfide Redox Pair"

- Di/sulfide Reduction
- Thiol Oxidation

Back 29

Oxidation of a dithiol or 2 eq. of regular thiol:
- Product: Disulfide
- Reagents: O2, FeCl

Reduction of disulfide:
- Product: Thiol
- Reagent: (none listed)