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CHEM 353. BRIEF REVIEW. OF. ORGANIC REACTIONS. METHODS OF SYNTHESIS FOR THE MAJOR FUNCTIONAL GROUPS OF ORGANIC CHEM. THIS SET OF SLIDES IS STILL UNDER CONSTRUCTION. PLEASE BE PATIENT. ACID HALIDES. SYNTHESIS OF ACID CHLORIDES. thionyl chloride. + SO 2. + HCl.

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slide1

CHEM 353

BRIEF REVIEW

OF

ORGANIC REACTIONS

METHODS OF SYNTHESIS FOR THE MAJOR

FUNCTIONAL GROUPS OF ORGANIC CHEM

slide2

THIS SET OF SLIDES IS STILL

UNDER CONSTRUCTION.

PLEASE BE PATIENT

slide3

ACID

HALIDES

slide4

SYNTHESIS OF ACID CHLORIDES

thionyl chloride

+ SO2

+ HCl

Thionyl chloride is a liquid.

You can do the reaction without a solvent

or sometimes benzene is used.

All of the other acid derivatives can be made

from the acid chloride.

slide6

SYNTHESIS OF ALCOHOLS

H2 Ni

catalytic

hydrogenation

2 atm 40o

ketone or

aldehyde

low reactivity

water and

alcohol solvents

are OK

1. NaBH4

sodium

borohydride

2. H3O+

reduces only aldehydes or ketones

lithium

aluminum

hydride

1. LiAlH4

ether solvent

required

2. H3O+

reduces aldehydes and ketones and

many other polar functional groups

CAUTION:

slide7

SYNTHESIS OF ALCOHOLS - 2

gives low yields,

hydration of

an alkene

oxymercuration

is a better method

H2SO4

Markovnikov rule

oxymer-

curation

1.

2.

Markovnikov

slide8

SYNTHESIS OF ALCOHOLS - 3

H2O

solvolysis

of halides

tertiary, allylic

or benzylic

Grignard

Reaction

H3O+

+

Mg

ether

alkyllithium compounds

react just like the Grignard

Li

Alkyllithium

Compounds

ether or pentane or benzene solvent

slide9

SYNTHESIS OF ALCOHOLS - 4

ether

hydroboration-

oxidation

3

H2O2

NaOH

H3O+

3

anti-Markovnikoff

Grignard +

epoxide

1. RMgX / ether

2. H3O+

SN2

terminal alcohols

slide12

SYNTHESIS OF ALDEHYDES

Sarrett Reagent

primary

alcohol

Jones Reagent does not

stop at the aldehyde and

gives a carboxylic acid.

Other oxidizing agents usually continue to the acid RCOOH.

slide15

SYNTHESIS OF ALKENES

E2

elimination

heat

NaOMe

stereospecific

anti

MeOH

X = Cl, Br, I

Saytzev Rule

strong bases such as NaOH, NaOR required

dehydration

watch for

rearrangements

H2SO4

not

stereospecific

heat

acid-assisted

E1 elimination

Saytzev Rule

strong acids such as H2SO4 and H3PO4 required

slide16

SYNTHESIS OF ALKENES - 2

catalytic

hydrogenation

H2

Lindlar

cis

Lindlar = Pd / BaSO4 / quinoline

syn addition

H2

won’t

stop

Pd

REMEMBER

2X

dissolving metal

reduction

Na/NH3

trans

anti addition

slide17

SYNTHESIS OF ALKENES - 3

Wittig

reaction

R

R

1

benzene

2

+

_

:

+

(C

H

)

P

(

C

H

)

P

C

R

X

R

C

X

6

5

3

6

5

3

2

1

heat

H

H

-

..

Triphenylphosphine

:

O-CH3

halide

..

ether

strong base

R

-

+

..

1

(

C

H

)

P

C

6

5

3

R

ylide

2

Wittig reagent

reaction assembles

the two halves

slide19

C

a

C

O

C

a

O

+

C

O

3

2

C

a

O

+

2

C

C

a

C

+

C

O

2

C

a

(

O

H

)

C

a

C

H

O

+

+

2

2

2

2

H

C

C

H

SYNTHESIS OF ACETYLENES

Acetylene from

limestone

D

calcium oxide

calcium carbonate

D

calcium carbide

lime

acetylene

slide20

SYNTHESIS OF ACETYLENES - 2

alkylation of

acetylene

elimination of dihalides

slide25

SYNTHESIS OF ANHYDRIDES

acid chloride

and sodium

salt

-

+

sodium salt

Section 19.25

acid chloride

anhydride

+ NaCl

slide26

SYNTHESIS OF ANHYDRIDES - 2

dehydration of

carboxylic acids

works for small

symmetric anhydrides

only

slide29

SYNTHESIS OF CARBOXYLIC ACIDS

Jones Reagent

cannot

isolate

primary

alcohol

oxidation continues

Sarrett Reagent will stop

at the aldehyde.

carboxylic acid

oxidation of

an aldehyde

[Ox]

Many oxidizing agents will oxidize aldehydes

including: CrO3, K2Cr2O7, KMnO4, H2O2,

Ag(NH4)OH (Tollen’s).

slide30

SYNTHESIS OF CARBOXYLIC ACIDS - 2

Grignard or

R-Li + CO2

1) CO2

R-MgX

R-COOH

2) H3O+

1) CO2

R-COOH

R-Li

2) H3O+

cleaving double

and triple bonds

(oxidation)

KMnO4

KMnO4

cannot

isolate

oxidation

continues

Alkenes must have

hydrogen on the

double bond.

…..

slide31

SYNTHESIS OF CARBOXYLIC ACIDS - 3

D

hydrolysis

of a nitrile

NaCN

H2O

R-X

R-CN

R-COOH

H2SO4

acetone

NaOH

D

H2O

H3O+

-

+

R-COO Na

hydrolysis of

acid derivatives

H2O

or

or

H2O

H2SO4

or

NaOH

slide32

SYNTHESIS OF CARBOXYLIC ACIDS - 4

oxidation of a

side chain on

an aromatic

ring

KMnO4

or

CrO3/H2SO4

slide34

SYNTHESIS OF EPOXIDES

peracid

cis

cis

stereospecific

via

bromohydrin

cis

anti

addition

stereospecific

overall

cis

slide36

Fischer synthesis

acid chloide or anhydride + alcohol

slide37

GLYCOLS

DIOLS

slide39

SYNTHESIS OF HALIDES

*

#

thionyl chloride

pyridine

inversion of configuration SN2

*

*

+

+

thionyl chloride

ether

retention of configuration

SNi

phosphorous

halides

1o, 2o alcohols

inversion of configuration

SN2

slide40

SYNTHESIS OF HALIDES - 2

watch for rearrangements !

concentrated

acids

the halide

is often

racemized

1o, 2o alcohols proceed by SN2

3o, allylic, benzylic alcohols by SN1

(acid assisted)

slide41

SYNTHESIS OF HALIDES - 3

addition of HX

to alkenes

also HBr, HI

Markovnikov rule

free radical

halogenation

+

hn

rate = 3o H > 2o H > 1o H

usually not a

good laboratory

synthetic method

chain reaction

slide43

oxidation of

alcohols

cleavage of

alkenes

slide44

hydrolysis of imines

don’t forget nitrile + Grignard

don’t forget organocadmium + ester

slide46

NaCN is soluble in acetone,

or DMSO could be used

SN2 displacement

with cyanide

acetone

+

Primary or

secondary

halides

cyanohydrins

slide48

CYCLOHEXENES

Diels-Alder

CYCLOPROPANES

Diazomethane

a-Eliminations

Simmons-Smith