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Ethers and Epoxides Thiols and Sulfides

This document discusses ethers and epoxides. It begins by defining ethers as compounds containing an oxygen atom bonded to two alkyl, aryl, or vinyl groups. Ethers are named using common or IUPAC nomenclature based on the alkyl groups. Ethers have lower boiling points than alcohols due to an inability to form hydrogen bonds. Crown ethers form especially strong attractions to metal ions and are used to solubilize ions in organic solvents. Ethers can be prepared through dehydration of alcohols, Williamson ether synthesis, or oxymercuration-demercuration. Epoxides are cyclic ethers that can be named indicating the location of oxygen or using ox

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33 views

Ethers and Epoxides Thiols and Sulfides

This document discusses ethers and epoxides. It begins by defining ethers as compounds containing an oxygen atom bonded to two alkyl, aryl, or vinyl groups. Ethers are named using common or IUPAC nomenclature based on the alkyl groups. Ethers have lower boiling points than alcohols due to an inability to form hydrogen bonds. Crown ethers form especially strong attractions to metal ions and are used to solubilize ions in organic solvents. Ethers can be prepared through dehydration of alcohols, Williamson ether synthesis, or oxymercuration-demercuration. Epoxides are cyclic ethers that can be named indicating the location of oxygen or using ox

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Nguyệt Bình
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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Chapter 14

Ethers and Epoxides; Thiols and Sulfides


14.1 Introduction to Ethers
• An ether group includes an oxygen atom that is bonded
to TWO –R groups

• -R groups can be alkyl, aryl, or vinyl groups


• Would the compound below be considered an ether?
O

O
14.1 Introduction to Ethers
• Compounds containing ether groups are quite common
14.2 Naming Ethers
• Common names are used frequently
1. Name each –R group
2. Arrange them alphabetically
3. End with the word, “ether”
14.2 Naming Ethers
• IUPAC systematic names are often used as well
1. Make the larger of the –R groups the parent chain
2. Name the smaller of the –R groups as an alkoxy substituent

• Practice with SkillBuilder 14.1


14.3 Structure and Properties of Ethers
• The bond angle in ethers is very similar to that found in
water and in alcohols

• Is the oxygen atom in an ether sp3, sp2, or sp hybridized?

• How do the –R groups affect the bond angle?


14.3 Structure and Properties of Ethers
• In chapter 13, we learned that due to H-bonding,
alcohols have relatively high boiling points

• What is the maximum number of H-bonds an alcohol


can have?
• Draw an H-bond between an ether and an alcohol
• What is the maximum number of H-bonds an ether can
have?
• In chapter 13, we learned that due to H-bonding,
alcohols have relatively high boiling points

• Would you expect the boiling point of an ether to be


elevated similar to alcohols?
• WHY or WHY not?
• Explain the boiling point trends below using all relevant
intermolecular attractions
– Trend 1

– Trend 2
• Ethers are often used by organic chemists as solvents
– Relatively low boiling points allow them to be evaporated
after the reaction is complete
– Their dipole moment allows them to stabilize charged or
partially charged transition states. HOW?

– They are NOT protic. WHY is that an advantage for a solvent


in many reactions?
• Metal atoms with a full or partial positive charge can be
stabilized by ether solvents
• Ethers are generally used as the solvent in the Grignard
reaction

• Give another reason why an ether makes a good solvent


in this reaction
14.4 Crown Ethers
• Crown ethers have been shown to form especially
strong attractions to metal atoms. WHY?

• Note how many carbon atoms separate the oxygens


• Why are they called CROWN ethers?
• Explain the numbers found in their names
• The size of the metal must match the size of the crown
to form a strong attraction
• 18-crown-6 fits a K+ ion just right
• Normally metal ions are not soluble in low polarity
solvents. WHY?
• The crown ether – metal complex should dissolve nicely
in low polarity solvents. WHY?
• Imagine how a crown ether
could be used to aid reactions
between ion (especially anions)
and low polarity organic
substrates
• The F- ion below is ready to react because the K+ ion is
sequestered by the crown ether

• Without the crown ether, the solubility of KF in benzene


is miniscule
• Generally, F- ion is not used as a nucleophile, because it
is strongly solvated by polar solvents
• Such solvation greatly reduces its nucleophilic strength
• In the presence of the crown ether, it is soluble enough
in a nonpolar solvent that it can readily attack an
electrophile
• Smaller crown ethers bind smaller cations

• Practice with conceptual checkpoint 14.4


14.5 Preparation of Ethers
• Diethyl ether is prepared industrially by the acid-
catalyzed dehydration of ethanol

• How is it a dehydration?
• Can this method be used
to make asymmetrical
ethers?
• The Williamson ether synthesis is a viable approach for
many unsymmetrical ethers

• What happens to the halide?


• The Williamson ether synthesis is a viable approach for
many asymmetrical ethers

• The alkoxide that forms in step 1 is also a strong base


• Are elimination products likely for methyl, primary,
secondary, or tertiary alkyl halides?
• Use the Williamson ether approach to prepare MTBE

• Consider a retrosynthetic disconnect on the t-butyl side


• It is better to make your retrosynthetic disconnect on
the methyl side. WHY?
• Practice with SkillBuilder 14.2
14.5 Preparation of Ethers
• Use the Williamson ether approach to synthesize the
following molecule

O
• Recall from section 9.5 that oxymercuration-
demercuration can be used to synthesize alcohols

• Is the addition Markovnikov or anti-Markovnikov?


14.5 Preparation of Ethers
• Similarly, alkoxymercuration-demercuration can be used
to synthesize ethers

• Is the addition Markovnikov or anti-Markovnikov?

• Practice conceptual checkpoints 14.8–14.10


14.6 Reactions of Ethers
• As we mentioned earlier, because they are aprotic,
ethers are generally unreactive
• However, ethers can react under the right conditions
• Consider the ether below

O
• Where are the most reactive sites?
• Is it most likely to react as an acid, base, nucleophile,
electrophile, etc.?
• Ethers can undergo acid-promoted cleavage
• Draw a complete mechanism and predict the products
for the following acid-promoted cleavage
• To promote cleavage, HI and HBr are generally effective
• HCl is less effective, and HF does not cause significant
cleavage
• Explain the trend above considering the relative strength
of the halide nucleophiles

• Why is the cleavage considered acid-promoted rather


than acid-catalyzed?

• Practice with conceptual checkpoint 14.11


• Predict products for the reaction below, and draw a
complete mechanism

HBr

O
14.6 Reactions of Ethers
• Recall from section 11.9 that ethers can undergo
autooxidation

• Hydroperoxides can be explosive, so laboratory samples


of ether must be frequently tested for the presence of
hydroperoxides before they are used
• The autooxidation occurs through a free radical
mechanism – see next few slides
Mechanism
• Recall that the net reaction is the sum of the
propagation steps
14.7 Naming Epoxides
• For cyclic ethers, the size of the ring determines the
parent name of the molecule

• Oxiranes are also known as epoxides


• Which cyclic ether system do you think is most reactive?
14.7 Naming Epoxides
• An epoxide can have up to 4 –R groups

• Although they are unstable, epoxides are found


commonly in nature
• There are two methods for naming epoxides
1. The oxygen is treated as a side group, and two numbers are
given as its locants

2. Oxirane is used as the parent name


14.7 Naming Epoxides
• Name the molecules below by both methods if possible
O

O
O

O
• Practice conceptual checkpoints 14.12 and 14.13
14.8 Preparation of Epoxides
• Recall from section 9.9 that epoxides can be formed
when an alkene is treated with a peroxy acid

• MCPBA and peroxyacetic acid are most commonly used


• Recall that the process is stereospecific
• Epoxides can also be formed from halohydrins
• What is a halohydrin?
• How are halohydrins formed from alkenes?
• When a Halohydrin is treated with NaOH, a ring-closing
reaction can occur

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