Reaction involve? What is ether? Application?

Introduction
Acid cleavage Ask question

Match autoxidation

Empowering

Reaction of ether

Enhancing
crossword

Epoxide True of false

conclusion

END

FACTS

Ether was discovered in 1275 by Spanish chemist Raymundus Lullius and named it as sweet vitriol. Later, in 1730, a German scientist W.G. Frobenius changed the name of sweet vitriol to ether

DO YOU KNOW??
Chemical formula of ETHER is (CHCH)2O

Ether boiling points are roughly comparable to hydrocarbons of the same molecular weight

BACK

REACTION OF EHTER INVOLVED

ACID CLEAVAGE

AUTOXIDATION

EPOXIDE

BACK

WHAT ARE USES OF ETHER

Chemical Application -used as powerful non-polar solvents for both industrial applications and for chemical reactions.Petroleum ether (Naptha) is often used in an industrial setting due to its low cost while either diethyl ether or tetrahydrofuran is commonly used is a chemical laboratory setting

Medical application - Ether was used as a general anesthetic/analgesic for surgeries. Its use replaced chloroform which was extremely toxic.Dimethyl ether is used as a refrigerant. Whenever we applied ether it will produce colder so that the body tissue may freeze thats why it is used in surgeries in which the patient doesnt feel any pain.

Automotive application -Ether is sprayed into the air intake to start a stubborn engine. It may also be added to the fuel in race cars for extra power.

BACK

Acid Cleavage of Ethers

Ethers are generally unreactive to most species.

Some od E1s alkene product, as always will be mixed in if SN1 occurs.

With strong acid, ethers undergo a cleavage through a process begun by protonation of the ether oxygen. HI and HBr are often used.

The products separate in either an SN1 or SN2 style process, determined by the shape of the ether, the halide anion serving as nucleophile.

Do you know it reaction??

Acid-catalyzed cleavage of ethers:

What is X? Can you tell me

I think X is bromine (Br) or iodine (I)

ITS CHARACTERISTIC

SN1?

Cleavage requires high temperatures and concentrated acids

acid?

Order of acid reactivity: HI > HBr > HCl

Cleavage involves nucleophilic attack by the halide ion on the protonated ether, with the weak base (good leaving group) R'-OH being displaced

The reaction of the protonated ether with the halide ion can be either SN1 or SN2 and depends on the ether structure and reaction conditions

Primary alkyl groups (R, not R') undergo SN2 substitution

Tertiary R groups undergo SN1 substitution

Overall Reaction:

CH3CH2OCH2CH3
Diethyl ether
Mechanism:

HBr
Hydrogen bromide

heat

2CH3CH2Br
Ethyl bromide

H2 O
Water

Step 1 : Proton transfer to the oxygen of the ether to give a dialkyloxonium ion

CH3CH2 :O: CH3CH2

.. + H - Br : ..

fast

CH3CH2 CH3CH2

:O-H

.. _ : Br : ..
Bromide ion

Diethyloxotonium ion

Step 2 : Nucleophilic attack of the halide anion on carbon of the dialkyloxonium ion. This step gives one molecule of an alkyl halide and one molecule of an alcohol

CH3CH2 .._ :Br: .. CH3CH2

slow

:O -H

.. CH3CH2Br : ..

.. CH3CH2 OH ..

Step 3 and 4 : These two steps do not involve an ether at all. They correspond to those in which an alcohol is converted to an alkyl halide.

.. CH3CH2OH ..

.. H - Br : ..

fast

H H

.._

slow

..

CH3CH2 O :

: Br : ..

CH3CH2Br + H2O:

Hopefully you understand this mechanism. Good luck

EXAMPLE

Excess HCl

CH3CH2OCH3
H2O2, heat

CH3CH2-Cl

CH3-Cl

H2 O

OCH2CH3

Br
Excess HBr H2O2, heat

CH3CH2Br

+ H2 0

QUESTIONS 1. If the excess HBr is used, what would the products of the reaction be?

2. is the mechanism shown below SN1 or SN2?

ANSWERS

1. Two molecules of alkyl halides since ROH + HBr -> RBr. 2. SN2 type since there is no carbocation intermediate formed

Do you understand??

Alkyl ethers are cleaved by the strong acids HI or HBr in a nucleophilic substitution reaction similar to that of alcohols.

Protonation of the ethereal oxygen creates a good leaving group, a neutral alcohol molecule.

Refresh back.

The halide ion, bromide or iodide are both good nucleophiles.

Depending on the structure of the alkyl groups, the reaction can be SN1 or SN2 like.

BACK

AUTOXIDATION

Do you know ??

Ethers are good solvents partly because they are not reactive

AUTOXIDATION..what is it ??

Autoxidation is any oxidation that occurs in open air or in the presence of oxygen and /or UV radiation and forms peroxides and hydroperoxides.

It can be considered to be a slow, flameless combustion of materials by reaction with oxygen.

Certain types are particularly prone to autoxidation, including unsaturated compounds that have allylic hydrogens or benzylic hydrogens that converted to hydroperoxides by autoxidation

H O W I T S M E C H A N I S M O C C U R ? ?

Autoxidation is a free radical chain process

It easy right!!

Involve three stages: chain initiation, propagation, and termination

Initiation process -some event causes free radicals to be formed. initiation occurs by a process that is not well understood but is thought to be the spontaneous reaction of oxygen with a material with a readily abstractable hydrogen.

Once free radicals are formed, they react in a chain to convert the material to a hydroperoxide. The chain is ended by termination reactions in which free radicals collide and combine their odd electrons to form a new bond.

Chain initiation
ENERGY

R00H + RH

RO. + HO + R.

H-abstraction

RO. + RH
Chain propagation

R. + ROH

ATTENTION !!
hydroperoxides and dialkyl peroxides highly explosive. Precautions: Do not distill to dryness. Store in full bottles with tight caps. REACTION STEP

R. + O
ROO + RH

fast

ROO.
ROOH + R.

H-abstraction

Chain termination

2ROO .

2RO . + O

ROH + QO + O

REMINDER !!!

EXAMPLE

USES OF AUTOXIDATION

process of enormous economic impact, since all foods, plastics, gasolines, oils, rubber and other materials that must be exposed to air undergo continuous destructive reactions of this type

Autoxidations in industry
All plastics and rubber and most processed foods contain antioxidants to protect them against the attack of oxygen.

In the chemical industry many chemicals are produced by autoxidation:

In the cumene process phenol and acetone are made from benzene and propylene Autoxidation of cyclohexane yields cyclohexanol and cyclohexanone p-xylene is oxidized to terephthalic acid Ethylbenzene is oxidized to ethylbenzene hydroperoxide, an epoxidizing agent in the propylene oxide/styrene process POSM.

VERY GOOD !!

Autoxidation in food

It known that fats become rancid, when kept at low temperatures. The compounds found in wine, including polyphenols, polysaccharides, and proteins, can undergo autoxidation during the ageing process. Simple polyphenols can lead to the formation of Btype procyanidins in wines or in model solutions. Browning color change characteristic of this process also observed in carrot puree.

BACK

WHAT IS EPOXIDE??

Three membered ring ether is called an oxirane (root ir from tri for 3-membered; prefix ox for oxygen; ane for saturated)

Also called epoxides

The COC bond angle for an epoxide must be 60, a considerable deviation from the tetrahedral bond angle of 109.5. Thus, epoxides have angle strain, making them much more reactive than other ethers.

EXAMPLE

O O 1,2-Epoxycyclohexane 2-Methyl-2,3-epoxybutane

Reactions of Epoxides

Reactions of Epoxides (neutral or basic media)

STEPS INVOLVES
step 1 : the nucleophile attacks an electron-deficient carbon, thus cleaving the CO bond and relieving the strain of the threemembered ring.

Step 2: the alkoxide is protonated with water to generate a neutral product with two functional groups on adjacent atoms.

Common nucleophiles that open the epoxide ring include OH, OR, CN, SR and NH3. With the strong nucleophiles, the reaction occurs by an SN2 mechanism

EXAMPLE

Reactions of Epoxides (acid media):

Acids HZ that contain a nucleophile Z also open epoxide rings by a two-step sequence.

HCl, HBr and HI, as well as H2O and ROH in the presence of acid, all open an epoxide ring in this manner.

LET SEE THIS.

Reactions of Epoxides (base vs acid):

BACK

QUESTION

1.

The reaction occurs readily with strong atom.

and with acids like HZ, where Z is a nucleophilic

Answer : nucleophiles 2. Reaction of epoxide involve reaction of in _______ and reaction of in

Answer : acid medium , base medium 3. Epoxides do contain a ________with two polar bonds.

Answer : strained three-membered ring 4. Three membered ring ether is called an oxirane . It also called ________

Answer : Epoxides

Enter to see the answer

BACK

Can you match this??

HALIDE ION

SN2 SUBSTITUTION

PRIMARY ALKYL GROUP

CH3CH2CH3

TERTIARY ALKYL GROUP

IODINE, BROMINE

HYDROCARBON

SN1 SUBSTITUTION

Enter to see the answer

BACK

CROSSWORD

IODINE

BROMINE

EPOXIDE

AUTOXIDATION

ETHER

X H E P R O X D E J E N G J K A H O J R Y

C I D C K E A V A G E A C A J S A U K Y M

V D N L Y O R O J J A I V B I D L P L V O

B F B N R P A N U U W L Y U H E I R B N R

N L L C R O I I Y J A R I B R H D E C R T

M O Q X Z A D N A I N A M A D J E W Z D S

P K W S E D A Q Z Q U N V K U Y I Q S I E

O J M Y W H R R N O I T A D I X O T U A W

L H I U Q Y T F L M W S D J K U N O Q L F

H I N N A O U D K N A A F H L I Y R E K K

T Y A I L H K A J O A Z F G P O T T V Y A

Q S Z Y C V B N M W E R T Y U I W O C L J

A O X Y G E N F E A Q E B A K M N X X P T

C X C T I T P G D B W Y T E R L B I Z E B

I W L U E H I H A C R I H F P G H D A R E

D Z E C R E O U C Y T T O D S O J T W O H

S Q A P B R O M I N E I T A D I X I E X A

R G V U P M O C D B E D U A A K A I R I M

U B A T H L N U C L E O P H I L I C D D S

T R G H O I Z X L P U P L N O U L L E E I

A O I A M D E S E R Y E A O D Y R A T I R

M M M N U E G T A I I B T R I I I E H H A

K I A K K I K Q V T E V E K N O H V A T K

I N N O A O K C A K M G H A E P T A N W N

O K U O I N Q W G D F G I H J K E G O O A

P C H Y D R O P E R O X I D E O L E B L K

X L I A H N A B H H Y D R O F A S U T S A

A O A S E L E C T H U P E Q W J O G T E R

HALIDE ION NUCLEOPHILIC

HYDROPEROXIDE

DIALKYL PEROXIDE

ACID CLEAVAGE

OXYGEN

Enter please

BACK

Activity
Write true or false for this questions
1. 2. Ethers are generally unreactive to most species. Ethers react with HNa CO bonds are cleaved and two alkyl halides are formed as products. Cleavage requires high temperatures and concentrated Epoxides are four-membered ring cyclic ethers with two polar bonds. The reaction occurs readily with strong nucleophiles and with acids like HZ, where Z is a nucleophilic atom. Epoxides can be named in three different waysAs epoxyalkanes, oxiranes, or alkene oxides.

3. 4. 5.

ANSWER

6.

1.TRUE 2.FALSE 3.TRUE 4.FALSE 5.TRUE 6.TRUE

Enter to see the answer

BACK

CONCLUSION

Ether has three reaction that are acid cleavage, autoxidation and epoxide reaction.

In acid cleavage, the products separate in either an SN1 or SN2 style process. Autoxidation is a free radical chain process that involve three stage (chain initiation, propagation, and termination). While, epoxide is special type of ehter. it also called oxirane that has three membered ring ether.

BACK