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Theme: Alcohols. Phenols. Ethers.

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LECTURE № 6. Theme: Alcohols. Phenols. Ethers. associate. prof. Ye. B. Dmukhalska, assistant. I.I. Medvid. Plane. A lcohols : C lassification , n omenclature . The methods of extraction of monohydroxyl alcohols. - PowerPoint PPT Presentation
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Theme: Alcohols. Phenols. Ethers. LECTURE № 6 associate. prof. Ye. B. Dmukhalska, assistant. I.I. Medvid
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Page 1: Theme: Alcohols. Phenols. Ethers.

Theme: Alcohols.Phenols. Ethers.

LECTURE № 6

associate. prof. Ye. B. Dmukhalska, assistant. I.I. Medvid

Page 2: Theme: Alcohols. Phenols. Ethers.

Plane.Plane.1.1. AAlcoholslcohols: C: Classificationlassification, n, nomenclature.omenclature.

2.2. The methods of extraction of monohydroxyl alcohols.The methods of extraction of monohydroxyl alcohols.

3.3. Monohydric alcohols:Monohydric alcohols: classification, iclassification, isomery, physical, somery, physical, chemical properties of monohydroxyl alcohols.chemical properties of monohydroxyl alcohols.

4.4. Di-, tri- and polyhydroxyl alcohols.Di-, tri- and polyhydroxyl alcohols.

5.5. Thioalcohols.Thioalcohols.

6.6. Ethers (simple ethers).Ethers (simple ethers).

7.7. Enols. Aminoalcohols.Enols. Aminoalcohols.

8.8. The methods of extraction of mononuclear phenolsThe methods of extraction of mononuclear phenols

9.9. Mononuclear phenols: the nomenclature, isomerism, Mononuclear phenols: the nomenclature, isomerism, physical, chemical propertiesphysical, chemical properties

10.10.Di-, tri- and polynuclear phenols: Chemical propertiesDi-, tri- and polynuclear phenols: Chemical properties

11.11.AminophenolsAminophenols

12.12.Aromatic carboxylic acidsAromatic carboxylic acids

Page 3: Theme: Alcohols. Phenols. Ethers.

CClassification of alcoholslassification of alcohols.. All alcohols, а principle, can be divided into All alcohols, а principle, can be divided into two broad categories i.е. aliphatic alcohols two broad categories i.е. aliphatic alcohols and aromatic alcohols. and aromatic alcohols. 1. Aliphatic alcohols. Alcohols in which the 1. Aliphatic alcohols. Alcohols in which the hydroxyl group is linked an aliphatic carbon hydroxyl group is linked an aliphatic carbon chain are called aliphatic alcohols. chain are called aliphatic alcohols.

For example, For example,

Methyl alcohol Ethyl alcohol Isopropyl Methyl alcohol Ethyl alcohol Isopropyl alcohol alcohol

Methanol Ethanol 2-PropanolMethanol Ethanol 2-Propanol

Page 4: Theme: Alcohols. Phenols. Ethers.

2. Aromatic alcohols. Alcohols in which the hydroxyl group is present in the 2. Aromatic alcohols. Alcohols in which the hydroxyl group is present in the side chain of an aromatic hydrocarbon are called aromatic For example.side chain of an aromatic hydrocarbon are called aromatic For example.

phenylmethanol 2-phenylethanolphenylmethanol 2-phenylethanol

(benzyl alcohol) ((benzyl alcohol) (-phenylethyl alcohol)-phenylethyl alcohol)

Alcohols are further classified as Alcohols are further classified as monohydric, dihydric, trihydricmonohydric, dihydric, trihydric and and

роlyhydric according as their molecules contain one, two, threeроlyhydric according as their molecules contain one, two, three, or , or many hydroxyl groups respectively. For ехаmрlе,many hydroxyl groups respectively. For ехаmрlе,

Ethyl alcohol 1,2-Ethanediol 1,2,3-propanetriolEthyl alcohol 1,2-Ethanediol 1,2,3-propanetriol

(Monohydric) (Dihydric) (Trihydric)(Monohydric) (Dihydric) (Trihydric)

Page 5: Theme: Alcohols. Phenols. Ethers.

I.I. Тhe alkyl alcohol systemТhe alkyl alcohol system. In this system of common . In this system of common nomenclature, the name of an alcohol is derived by nomenclature, the name of an alcohol is derived by combining the name of the alkyl group with the word combining the name of the alkyl group with the word alcohol. The names are mitten as two words.alcohol. The names are mitten as two words.

n-butyl alcohol isobutyl alcohol tret-butyl alcoholn-butyl alcohol isobutyl alcohol tret-butyl alcohol

IIII. In this common system. In this common system, the position of an additional , the position of an additional substituent is indicated by use of the Greek alphabet substituent is indicated by use of the Greek alphabet rather than by numbers.rather than by numbers.

-chloroethyl alcohol -chloroethyl alcohol -bromobutyl alcohol-bromobutyl alcohol

Page 6: Theme: Alcohols. Phenols. Ethers.

Any simple radical that has а common name may be used in Any simple radical that has а common name may be used in the alkyl alcohol system, with one important exception. The the alkyl alcohol system, with one important exception. The grouping Сgrouping С66НН55 - has the special name phenyl, but the - has the special name phenyl, but the compound Ccompound C66HH55OH is phenol, not phenyl alcohol. OH is phenol, not phenyl alcohol.

phenolphenol Substituted phenols are named as derivatives of the parent compound Substituted phenols are named as derivatives of the parent compound phenol. The reason for this difference is historical and arose from the fact phenol. The reason for this difference is historical and arose from the fact that phenol and its derivatives have many chemical properties that are that phenol and its derivatives have many chemical properties that are very different from those of alkyl alcohols. However, phenyl substituted very different from those of alkyl alcohols. However, phenyl substituted alkyl alcohols are normal alcohols and often have common names. alkyl alcohols are normal alcohols and often have common names. Examples are:Examples are:

phenylmethanol phenylmethanol 2-phenylethanol2-phenylethanol

(benzyl alcohol)(benzyl alcohol) ((-phenylethyl alcohol)-phenylethyl alcohol)

Page 7: Theme: Alcohols. Phenols. Ethers.

IIIIII. . The carbinol systemThe carbinol system. In this system, the simplest alcohol, . In this system, the simplest alcohol, СНСН33ОН, is called carbinol. More complex alcohols are ОН, is called carbinol. More complex alcohols are named as alkyl substituted carbinols. The names are written named as alkyl substituted carbinols. The names are written as one word.as one word.

butylmethylcarbinol triethylcarbinol phenilcarbinobutylmethylcarbinol triethylcarbinol phenilcarbinoll

The number of carbons attached to the carbinol carbon The number of carbons attached to the carbinol carbon distinguishes primary, secondary, and tertiary carbinols. As in distinguishes primary, secondary, and tertiary carbinols. As in the case of the alkyl halides, this classification is useful the case of the alkyl halides, this classification is useful because the different types of alcohols show important because the different types of alcohols show important differences in reactivity under given conditions. The carbinol differences in reactivity under given conditions. The carbinol system of nomenclature has been falling into disuse in recent system of nomenclature has been falling into disuse in recent years. However, it is found extensively in the older organic years. However, it is found extensively in the older organic chemical literature.chemical literature.

Page 8: Theme: Alcohols. Phenols. Ethers.

Polyhydroxy alcohols: An alcohol in which two Polyhydroxy alcohols: An alcohol in which two hydroxyl groups are present is named as а diol, one hydroxyl groups are present is named as а diol, one containing three hydroxyl groups is named as а triol, containing three hydroxyl groups is named as а triol, and so on. In these names for diols, triols, and so and so on. In these names for diols, triols, and so forth, the final –е of the parent alkane name is forth, the final –е of the parent alkane name is retained for pronunciation reasons.retained for pronunciation reasons.

1,2-Ethanediol 1,2-propanediol 1,2,3-propanetriol1,2-Ethanediol 1,2-propanediol 1,2,3-propanetriol

Page 9: Theme: Alcohols. Phenols. Ethers.

Classification of monohydric alcoholsClassification of monohydric alcohols Monohydroxy alcohols are hydrocarbon derivatives which Monohydroxy alcohols are hydrocarbon derivatives which

contain only one group –OH connected with sp³-hybridizated contain only one group –OH connected with sp³-hybridizated carbon atom. carbon atom.

The general formula of monohydroxy alcohols is:The general formula of monohydroxy alcohols is:

The names of monohydroxy alcohols are the names of the The names of monohydroxy alcohols are the names of the same hydrocarbons with added prefix –ol. same hydrocarbons with added prefix –ol.

Page 10: Theme: Alcohols. Phenols. Ethers.
Page 11: Theme: Alcohols. Phenols. Ethers.

Classification of monohydric alcohols.Classification of monohydric alcohols. As already As already mentioned, alcohols containing one ОН group per molecule mentioned, alcohols containing one ОН group per molecule are called monohydric alcohols. These are further classified are called monohydric alcohols. These are further classified as primary (1'), secondary (2'), and tertiary (3') according as as primary (1'), secondary (2'), and tertiary (3') according as the ОН group is attached to primary, secondary and tertiary the ОН group is attached to primary, secondary and tertiary carbon atoms respectively. For example:carbon atoms respectively. For example:

Ethanol Isopropyl alcohol 2-Methylpropanane-2-ol Ethanol Isopropyl alcohol 2-Methylpropanane-2-ol Primary alcohol Secondary alcohol Tertiary alcoholPrimary alcohol Secondary alcohol Tertiary alcohol

Page 12: Theme: Alcohols. Phenols. Ethers.

Isomery of monohydroxyl alcoholsIsomery of monohydroxyl alcohols

Monohydroxyl alcohols are characterized by structural, Monohydroxyl alcohols are characterized by structural, geometrical and optical isomery. Structural isomery depends geometrical and optical isomery. Structural isomery depends on different structure of carbon chain and different locations on different structure of carbon chain and different locations of –OH group. of –OH group.

For unsaturated monohydroxyl alcohols structural isomery For unsaturated monohydroxyl alcohols structural isomery depends on different locations of double bond too. depends on different locations of double bond too.

H3C CH2 CH2 CH2 OH

butanol-1

H2C CH CH2 CH2 OH

butene-3-ol-1CH CH CH2 OH

butene-2-ol-1

H3C

Page 13: Theme: Alcohols. Phenols. Ethers.

Only unsaturated monohydroxyl alcohols are Only unsaturated monohydroxyl alcohols are characterized by geometrical isomery. characterized by geometrical isomery.

Optical isomery is characteristic for alcohols Optical isomery is characteristic for alcohols which have asymmetric carbon atom in their which have asymmetric carbon atom in their structure. structure.

C C

H3C

H

CH2

H

OH

cys-butene-2-ol-1

C C

H

H3C

CH2

H

OH

trans-butene-2-ol-1

CH2

C

CH3

HOCH3

H*

R-butanol-2

CH2

C

CH3

OH

*

S-butanol-2

H3C

H

Page 14: Theme: Alcohols. Phenols. Ethers.

The methods of extraction of monohydroxyl alcoholsThe methods of extraction of monohydroxyl alcoholsAlcohols can be obtained from many other classes Alcohols can be obtained from many other classes of compounds. Preparations from alkyl halides of compounds. Preparations from alkyl halides and from hydrocarbons will be discussed in this and from hydrocarbons will be discussed in this section. The following important ways of prераring section. The following important ways of prераring alcohols will be discussed later, as reactions of the alcohols will be discussed later, as reactions of the appropriate functional groups.appropriate functional groups.

1.1. Hydrolysis of halogenderivatives of hydrocarbons Hydrolysis of halogenderivatives of hydrocarbons by heating:by heating:

CHCH33−CH−CH22−Cl + NaOH → CH−Cl + NaOH → CH33−CH−CH22−OH + −OH + NaClNaCl

22. Hydrogenation of alkenes. This reaction runs by . Hydrogenation of alkenes. This reaction runs by Markovnikov rule.Markovnikov rule.

H2O CHH3C CH CH2 H3C+ CH3

OH

Page 15: Theme: Alcohols. Phenols. Ethers.

33. Reduction of carbonyl compounds (aldehydes, ketones, . Reduction of carbonyl compounds (aldehydes, ketones, carboxylic acids, complex ethers):carboxylic acids, complex ethers):

C H3C CH2H3CH

O[H], Ni

OH

CH3COH

OLi+AlH4

-

H3C CH2 OH

CH3CO

O

C2H5

[H]H3C CH2 OH

[H], PtC O

H3C

H3C

CH

H3C

H3C

OH

Page 16: Theme: Alcohols. Phenols. Ethers.

11. Alcohols have weak acidic and weak alkaline . Alcohols have weak acidic and weak alkaline properties. They can react with alkaline metals properties. They can react with alkaline metals like acids and form alkoxides:like acids and form alkoxides:

2CH2CH33CHCH22OH + 2Na → 2CHOH + 2Na → 2CH33CHCH22ONa + HONa + H22↑↑

2CH2CH33CHCH22ONa + HONa + H22O ↔ CHO ↔ CH33CHCH22OH + NaOHOH + NaOH

2.2. Alcohols can react with mineral and organic acids Alcohols can react with mineral and organic acids (complex ethers form) like alkalis:(complex ethers form) like alkalis:

CHCH33CHCH22OH + HONOOH + HONO22 ↔ CH ↔ CH33CHCH22ONOONO22 + HOH + HOH

33. Dehydration of alcohols. There are 2 types of dehydration:. Dehydration of alcohols. There are 2 types of dehydration:

a) Dehydration between 2 molecules:a) Dehydration between 2 molecules:

H2O+

H3C CO

O

HOCH2 CH3

HH3C C

O

O

CH2 CH3+

+O HO CH2 CH3HH3C CH2 OH3C CH2 CH2 CH3

Page 17: Theme: Alcohols. Phenols. Ethers.

b) Dehydration in the molecule (intramolecular dehydration):b) Dehydration in the molecule (intramolecular dehydration):

4.4. Reaction with HI, HCl, HBr: Reaction with HI, HCl, HBr:

CHCH33CHCH22OH + HI → CHOH + HI → CH33CHCH22I + HI + H22OO

5. Oxidation5. Oxidation

H2OC C H +

H

OH

H

H

H

CH2 CH2

OHH3C CH2-H2O

H3C CO

HH3C C

O

OH

[O][O]

Page 18: Theme: Alcohols. Phenols. Ethers.

Primary alcohol aldehyde = carboxylic acidPrimary alcohol aldehyde = carboxylic acid

Secondary alcohol = ketoneSecondary alcohol = ketone

Tertiary alcohol = no reactionTertiary alcohol = no reaction

The general reaction for the oxidation of а primary The general reaction for the oxidation of а primary

alcohol isalcohol is

Alcohol Aldehyde Carboxylic acidAlcohol Aldehyde Carboxylic acidIn this equation, the symbol [O] represents the mild oxidizing agent. The In this equation, the symbol [O] represents the mild oxidizing agent. The

immediate product of the oxidation of а primary alcohol is an aldehyde. immediate product of the oxidation of а primary alcohol is an aldehyde. Because aldehydes themselves are readily oxidized by the same Because aldehydes themselves are readily oxidized by the same oxidizing agents that oxidize alcohols, aldehydes are further converted to oxidizing agents that oxidize alcohols, aldehydes are further converted to carboxylic acids. А specific example of а primary alcohol oxidation carboxylic acids. А specific example of а primary alcohol oxidation reaction isreaction is

Page 19: Theme: Alcohols. Phenols. Ethers.

The three classes of alcohols behave differently toward mild The three classes of alcohols behave differently toward mild oxidizing agents. The general reaction for the oxidation of а oxidizing agents. The general reaction for the oxidation of а secondary alcohol issecondary alcohol is

As with primary alcohols, oxidation involves the removal of two As with primary alcohols, oxidation involves the removal of two hydrogen atoms. Unlike aldehydes, ketones are resistant to hydrogen atoms. Unlike aldehydes, ketones are resistant to further oxidation. А specific example of the oxidation of а further oxidation. А specific example of the oxidation of а secondary alcohol issecondary alcohol is

Alcohol Ketone

Page 20: Theme: Alcohols. Phenols. Ethers.

Tertiary alcohols do not undergo oxidation with mild Tertiary alcohols do not undergo oxidation with mild oxidizing agents. This is because they do not have oxidizing agents. This is because they do not have hydrogen on the -ОН-bearing carbon atom.hydrogen on the -ОН-bearing carbon atom.

To determine any alcohol (which contain fragment in To determine any alcohol (which contain fragment in the mixture of compounds it is needed to use iodoform test. the mixture of compounds it is needed to use iodoform test. As the result yellow precipitate forms. As the result yellow precipitate forms.

C OH

CH3

H

+Na+

-

C OH

CH3

R

H

NaOI or NaOH+I2C I

I

I

HR C

O

O

iodoform(yellow

precipitate)

Page 21: Theme: Alcohols. Phenols. Ethers.
Page 22: Theme: Alcohols. Phenols. Ethers.
Page 23: Theme: Alcohols. Phenols. Ethers.
Page 24: Theme: Alcohols. Phenols. Ethers.
Page 25: Theme: Alcohols. Phenols. Ethers.

Di-, tri- and polyhydroxyl alcoholsDi-, tri- and polyhydroxyl alcoholsDihydroxyl alcohols contain two groups –OH in the molecule. Dihydroxyl alcohols contain two groups –OH in the molecule.

They are called diols. There are several types of diols.They are called diols. There are several types of diols.

1. α-diols (groups –OH are situated near neighboring carbon 1. α-diols (groups –OH are situated near neighboring carbon atoms in 1,2-locations);atoms in 1,2-locations);

2. β-diols (groups –OH are situated in 1,3-locations);2. β-diols (groups –OH are situated in 1,3-locations);

3. γ-diols (groups –OH are situated in 1,4-locations) etc.3. γ-diols (groups –OH are situated in 1,4-locations) etc.

R CH CH

CH2R CH

OH OH

R1 R CH CH2

OH

CH R1

OH

OH

CH2 CH R1

OH

1 2

3

Page 26: Theme: Alcohols. Phenols. Ethers.

Trihydroxyl alcohols contain three groups –Trihydroxyl alcohols contain three groups –OH in the molecule. They are called triols. OH in the molecule. They are called triols. The representative is The representative is glycerglycerin:in:

CH2 CH

OH

CH2

OHOH

Page 27: Theme: Alcohols. Phenols. Ethers.

. .

To extract glycerin it is necessary to use next reaction:To extract glycerin it is necessary to use next reaction:

CH2

CH

Cl

Cl

CH2 Cl

KOH

KOH

KOH

CH2

CH

OH

OH

CH2 OH

3KCl++

Page 28: Theme: Alcohols. Phenols. Ethers.

b) Chemical properties of di-, tri- and polihydroxyl alcoholsb) Chemical properties of di-, tri- and polihydroxyl alcohols

1.1. Reaction with alkaline metalsReaction with alkaline metals

22. Reaction with Cu(OH). Reaction with Cu(OH)22

CH2

CH2

OH

OH2Na

CH2

CH2

ONa

OH2Na

CH2

CH2

ONa

ONa

CH2

CH2

ONa

OH

H2

H2+ +2 2

+ +2 2

CH2

CH2

OH

OHCu(OH)2

H2C

H2C

O

OCu

H

O

O

CH2

CH2

H

2H2O+ +2

blue colour

Page 29: Theme: Alcohols. Phenols. Ethers.

33. Reaction with HI, HCl, HBr:. Reaction with HI, HCl, HBr:

44. . Formation of simple and complex ethers (reaction with Formation of simple and complex ethers (reaction with monohydroxy alcohols and organic acids):monohydroxy alcohols and organic acids):

H2O+ +

CH2

CH2

OH

OHHCl

CH2

CH2

Cl

OH

CH2

CH2

OH

OHH2C CH3HO

CH2

CH2

O

OH

CH2 CH3

H2C CH3HO

CH2

CH2

O

OH

CH2 CH3

CH2

CH2

O

O

CH2 CH3

CH2 CH3

H2O

H2O

++

++

incomplete simple ether

complete simple ether

1

Page 30: Theme: Alcohols. Phenols. Ethers.

+

CH2

CH2

OH

OHC CH3HO

CH2

CH2

O

OH

C CH3

+

CH2

CH2

O

OH

C CH3

C CH3HO

CH2

CH2

O

O

C CH3H2O+

C CH3

incomplete complex ether

complete complex ether

OO

H2O+

O

O

O

O

2

5. Reaction with mineral acids:

CH2

CH2

OH

OHHONO2

CH2

CH2

O

OH

NO2

HONO2

CH2

CH2

O

OH

NO2

CH2

CH2

O

O

NO2

NO2

H2O

H2O

+ +

+ +

Page 31: Theme: Alcohols. Phenols. Ethers.

6.6. Oxidation by KMnO Oxidation by KMnO44

77. Dehydration. Dehydration

CH2

CH2

OH

OH

[O] C

C

OH

OH

O

O

H2C

H2C

OH

OH

CH2

CH2

HO

HO

H2C

H2C

O

O

CH2

CH22H2O+

+

dioxane

H2SO4, t

H2O+

CH2CH2 H2C CH2

OH

CH2 CH2

OH CH2

H2SO4, t

O

H2C

Page 32: Theme: Alcohols. Phenols. Ethers.

88. Polycondensation . Polycondensation

9.9. Diols react intramolecularly to form cyclic ethers when a five- Diols react intramolecularly to form cyclic ethers when a five-membered or sixmembered ring can result.membered or sixmembered ring can result.

OHH2C CH2 +HO OHH2C CH2HO OH2C CH2HO OHH2C CH2H2SO4

Page 33: Theme: Alcohols. Phenols. Ethers.

Thioalcohols Thioalcohols Thioalcohols are compounds which contain aliphatic Thioalcohols are compounds which contain aliphatic (CnH(CnH22n+1) and mercaptane (−SH) groups. Thiols are given n+1) and mercaptane (−SH) groups. Thiols are given substitutive IUPAC names by appending the suffix -thiol to substitutive IUPAC names by appending the suffix -thiol to the name of the corresponding alkane, numbering the chain the name of the corresponding alkane, numbering the chain in the direction that gives the lower locant to the carbon that in the direction that gives the lower locant to the carbon that bears the −SH group.bears the −SH group.

The preparation of thiols involves nucleophilic substitution of The preparation of thiols involves nucleophilic substitution of the Sthe SNN22 type on alkylhalides and uses the reagent thiourea type on alkylhalides and uses the reagent thiourea as the source of sulfur. as the source of sulfur.

Page 34: Theme: Alcohols. Phenols. Ethers.

Both steps can be carried out sequentially without isolating the isothiouronium salt.

Page 35: Theme: Alcohols. Phenols. Ethers.

Chemical properties of thiols:Chemical properties of thiols:

1.1. Thiols can react with ions of alkaline and heavy metals (this Thiols can react with ions of alkaline and heavy metals (this property of thiols is used in medicine at the poisoning by property of thiols is used in medicine at the poisoning by heavy metals): heavy metals):

CC22HH55SH + NaOH → CSH + NaOH → C22HH55S−Na+ + HS−Na+ + H22OO

2C2C22HH55SH + Hg²+ → (CSH + Hg²+ → (C22HH55S)S)22Hg + 2H+Hg + 2H+22. They can react with alkenes (peroxides are catalysts):. They can react with alkenes (peroxides are catalysts):

3.3. Reaction with organic acids: Reaction with organic acids:

CH2 CH2H3C S CH3+ CH3H2C CHH SH3C

SHC2H5 H3C CO

OHH3C C

O

S C2H5

H2O++

Page 36: Theme: Alcohols. Phenols. Ethers.

4.4. Oxidation Oxidation

SC2H5 H [O] H S CH3 SC2H5 S CH3 H2O++ +

To prepere thioalcohols it is necessary to use next

reactions:

1. C2H5Cl + NaSH → C2H5SH + NaCl

2. C2H5OH + Na2S → C2H5SH + H2O

Page 37: Theme: Alcohols. Phenols. Ethers.

Ethers (simple ethers)Ethers (simple ethers)The general formula of simple ethers is:The general formula of simple ethers is:

R−O−RR−O−R11

The radicals can be similar or different.The radicals can be similar or different.

Ethers are named, in substitutive IUPAC nomenclature, as Ethers are named, in substitutive IUPAC nomenclature, as alkoxy derivatives of alkanes. Functional class IUPAC names alkoxy derivatives of alkanes. Functional class IUPAC names of ethers are derived by listing the two alkyl groups in the of ethers are derived by listing the two alkyl groups in the general structure RORgeneral structure ROR11 in alphabetical order as separate in alphabetical order as separate words, and then adding the word “ether” at the end. When words, and then adding the word “ether” at the end. When both alkyl groups are the same, the prefix di- precedes the both alkyl groups are the same, the prefix di- precedes the

name of the alkyl group.name of the alkyl group.

Page 38: Theme: Alcohols. Phenols. Ethers.

Physical properties of ethers Physical properties of ethers It is instructive to compare the physical properties of ethers It is instructive to compare the physical properties of ethers with alkanes and alcohols. With respect to boiling point, ethers with alkanes and alcohols. With respect to boiling point, ethers resemble alkanes more than alcohols. With respect to resemble alkanes more than alcohols. With respect to solubility in water the reverse is true; ethers resemble alcohols solubility in water the reverse is true; ethers resemble alcohols more than alkanes.more than alkanes.

In general, the boiling points of alcohols are unusually high In general, the boiling points of alcohols are unusually high because of hydrogen bonding. Attractive forces in the liquid because of hydrogen bonding. Attractive forces in the liquid phases of ethers and alkanes, which lack - OH groups and phases of ethers and alkanes, which lack - OH groups and cannot form intermolecular hydrogen bonds, are much cannot form intermolecular hydrogen bonds, are much weaker, and their boiling points lower. These attractive forces weaker, and their boiling points lower. These attractive forces cause ethers to dissolve in water to approximately the same cause ethers to dissolve in water to approximately the same extent as comparably constituted alcohols. Alkanes cannot extent as comparably constituted alcohols. Alkanes cannot engage in hydrogen bonding to water.engage in hydrogen bonding to water.

Page 39: Theme: Alcohols. Phenols. Ethers.

The methods of extraction of ethers:The methods of extraction of ethers:

1.1. From alkoxides:From alkoxides:

CHCH33CHCH22ONa + CHONa + CH33I → CHI → CH33CHCH22OCHOCH33 + NaI + NaI

22. Dehydration of alcohols (dehydration between 2 . Dehydration of alcohols (dehydration between 2 molecules):molecules):

+O HO CH2 CH3HH3C CH2 OH3C CH2 CH2 CH3

Page 40: Theme: Alcohols. Phenols. Ethers.
Page 41: Theme: Alcohols. Phenols. Ethers.

Chemical properties of ethersChemical properties of ethers1.1. Reaction with concentrated mineral acids (formation of Reaction with concentrated mineral acids (formation of

oxonium salts):oxonium salts):

2.2. A second dangerous property of ethers is the ease with A second dangerous property of ethers is the ease with which they undergo oxidation in air to form explosive which they undergo oxidation in air to form explosive peroxides. Air oxidation of diethyl ether proceeds according peroxides. Air oxidation of diethyl ether proceeds according to the equationto the equation

OH3C CH2 CH3 HONO2OH3C CH2 CH3

H

NO3+

+-

Page 42: Theme: Alcohols. Phenols. Ethers.

The reaction follows a free-radical mechanism and gives a The reaction follows a free-radical mechanism and gives a hydroperoxide, a compound of the type ROOH. hydroperoxide, a compound of the type ROOH. Hydroperoxides tend to be unstable and shock-sensitive. On Hydroperoxides tend to be unstable and shock-sensitive. On standing, they form related peroxidic derivatives, which are standing, they form related peroxidic derivatives, which are also prone to violent decomposition. Air oxidation leads to also prone to violent decomposition. Air oxidation leads to peroxides within a few days if ethers are even briefly peroxides within a few days if ethers are even briefly exposed to atmospheric oxygen. For this reason, one should exposed to atmospheric oxygen. For this reason, one should never use old bottles of dialkyl ethers, and extreme care never use old bottles of dialkyl ethers, and extreme care must be exercised in their disposal.must be exercised in their disposal.

3.3. Reaction with HI Reaction with HI

CHCH33−O−CH−O−CH33 + HI → CH + HI → CH33−OH + CH−OH + CH33II

Page 43: Theme: Alcohols. Phenols. Ethers.

The mechanism for the cleavage of ethers by hydrogen halides, The mechanism for the cleavage of ethers by hydrogen halides, using the reaction of diethyl ether with hydrogen bromide as using the reaction of diethyl ether with hydrogen bromide as an example.an example.

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

Page 44: Theme: Alcohols. Phenols. Ethers.

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

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

Page 45: Theme: Alcohols. Phenols. Ethers.

11. Enols11. Enols Enols (also known as alkenols) are alkenes with a hydroxyl group affixed to Enols (also known as alkenols) are alkenes with a hydroxyl group affixed to

one of the carbon atoms composing the double bond. Enols and carbonyl one of the carbon atoms composing the double bond. Enols and carbonyl compounds (such as ketones and aldehydes) are in fact isomers; this is compounds (such as ketones and aldehydes) are in fact isomers; this is called keto-enol tautomerism:called keto-enol tautomerism:

The enol form is shown above on the left. It is usually The enol form is shown above on the left. It is usually unstable, does not survive long, and changes into the keto unstable, does not survive long, and changes into the keto (ketone) form shown on the right. This is because oxygen is (ketone) form shown on the right. This is because oxygen is more electronegative than carbon and thus forms stronger more electronegative than carbon and thus forms stronger multiple bonds. Hence, a carbon-oxygen (carbonyl) double multiple bonds. Hence, a carbon-oxygen (carbonyl) double bond is more than twice as strong as a carbon-oxygen single bond is more than twice as strong as a carbon-oxygen single bond, but a carbon-carbon double bond is weaker than two bond, but a carbon-carbon double bond is weaker than two carbon-carbon single bonds.carbon-carbon single bonds.

Page 46: Theme: Alcohols. Phenols. Ethers.

The The namename of of eenolnolss systematic nomenclature systematic nomenclature IUPAC IUPAC form the name alkenform the name alkenee to which is added the suffix-ol: to which is added the suffix-ol:

CHCH22=CH-OH CH=CH-OH CH22=CH-CH=CH-CH22-OH-OHethenol, vinyl alcohol Propenol-1(unsaturated alcohol)ethenol, vinyl alcohol Propenol-1(unsaturated alcohol)

HHydration of acetylene as the intermediate substance ydration of acetylene as the intermediate substance is formed vinyl alcohol (is formed vinyl alcohol (eenol), which inol), which isomerizationsomerization in in acetic aldehydeacetic aldehyde..

HH22O,Hg²+,H+O,Hg²+,H+

CC22HH2 2 CHCH22=CH-OH =CH-OH

TThis propertyhis property of enols of enols characterizes the rule characterizes the rule of of Eltekov-ErlenmeyerEltekov-Erlenmeyer. - . - Compounds in which the Compounds in which the hydroxyl group located at carbon atoms that forms hydroxyl group located at carbon atoms that forms a fold communication, unstable and ia fold communication, unstable and isomerizationsomerization of carbonyl compounds - aldehydes and ketonesof carbonyl compounds - aldehydes and ketones

Page 47: Theme: Alcohols. Phenols. Ethers.

AminoalcoholsAminoalcohols

Amino alcohols are organic compounds that Amino alcohols are organic compounds that contain both an amine functional group and contain both an amine functional group and an alcohol functional group.an alcohol functional group.

NHNH22-CH-CH22-CH-CH22-OH N(C-OH N(C22HH55)-CH)-CH22-CH-CH22--OHOH

2-aminoethanol 2-N,N- diethylaminoethanol2-aminoethanol 2-N,N- diethylaminoethanol If the molecule If the molecule of of amino alcohol contains the in its amino alcohol contains the in its

composition two or three hydroxycomposition two or three hydroxyalkylnesalkylnes groups, groups, through through the the combination of nitrogen atom, in this combination of nitrogen atom, in this case, the basis takes the name amcase, the basis takes the name amiinnee. .

OH-CHOH-CH22-CH-CH22-NH-CH-NH-CH22-CH-CH22-OH-OH di (di (ββ-oxyethyl) amine, or di (2-hydroxyethyl) amine -oxyethyl) amine, or di (2-hydroxyethyl) amine

Page 48: Theme: Alcohols. Phenols. Ethers.

The methods of extraction of aminoalcohols The methods of extraction of aminoalcohols

1.1. AAccession of ammonia or amines to the ccession of ammonia or amines to the αα--oxoxyses.yses.

CHCH22-CH-CH2 + 2 + NHNH3 3 NHNH22-CH-CH22-CH-CH22-OH-OH

OO

22. Reduction of nithroarenes.. Reduction of nithroarenes.

CHCH33-CH(NO-CH(NO22)-CH)-CH22-OH + 3H-OH + 3H22 CH CH33-CH(NH-CH(NH33)-CH)-CH22-OH + 2H-OH + 2H22OO

Chemical properties of aminoalcoholsChemical properties of aminoalcohols

Aminoalcohols show properties as alcohols and Aminoalcohols show properties as alcohols and amines. As a basis aminoalcohols form salts with amines. As a basis aminoalcohols form salts with mineral acids. mineral acids.

OH-CHOH-CH22-CH-CH22-NH-NH22 + HCl OH-CH + HCl OH-CH22-CH-CH22-NH-NH33Cl¯Cl¯

Page 49: Theme: Alcohols. Phenols. Ethers.

The nomenclatureThe nomenclature and isomery of mononuclear phenols and isomery of mononuclear phenols

Numbering of the ring begins at the hydroxyl-Numbering of the ring begins at the hydroxyl-substituted carbon and proceeds in the direction that substituted carbon and proceeds in the direction that gives the lower number to the next substituted carbon. gives the lower number to the next substituted carbon. Substituents are cited in alphabetical order.Substituents are cited in alphabetical order.

Page 50: Theme: Alcohols. Phenols. Ethers.

OH NH

CH3

O

C2H5O NH

CH3

O

C2H5O NH2

C

Paracetamol, (N-acetyl-p-aminophenol p-hydroxyacethanilide),

C

Phenacetin (p-еthoxyacethanilide)

Phenetidine (p-ethoxyaniline)

Page 51: Theme: Alcohols. Phenols. Ethers.

The structural isomery of phenols is obtained by The structural isomery of phenols is obtained by different locations of radicals and structural changes different locations of radicals and structural changes of radicals. of radicals.

H2C OHH2CH3C

4-propylphenol

HC OH

H3C

H3C4-isopropylphenol

Page 52: Theme: Alcohols. Phenols. Ethers.

The methods of extraction of monohydric phenolsThe methods of extraction of monohydric phenols

1.Natural sources (from coal tar)1.Natural sources (from coal tar)

2. The synthesis from arenes2. The synthesis from arenes

С6H5-ONa + H2O + CO2 C6H5-OH + NaHCO3

C 6H 5-OH + NaOH C 6H 5-ONa + H 2OPhenolyath

sodium

SO3H

SO3HOH

OH

4NaOH

4000C

+ 2Na2SO3 + 2H2O

Page 53: Theme: Alcohols. Phenols. Ethers.

3. Cumol (isopropyl toluene) synthesis3. Cumol (isopropyl toluene) synthesis

4. The extraction from diazonium salts4. The extraction from diazonium salts

5. The substitution of halogen atom to –OH group5. The substitution of halogen atom to –OH group

NR

N OHR

Cl+ _

+ HOH + N2 + HCl

CH 3 C H

CH3

C 6H 5

CH 3 C

CH3

C 6H 5

O O H CH3 C

O

CH3O2 (OH-)

1300C

.. ..

.. ..

H+

650C

+ C6H5OH

CumolCumol Acetone Phenol

NH2

NH2NH2

OH

OHOH. HCl

. HCl

HCl .

3HOH+ 3NH4Cl

Cl

NO2

NO2

OH

NO2

NO2

NaOH, H2O

-HCl

Page 54: Theme: Alcohols. Phenols. Ethers.
Page 55: Theme: Alcohols. Phenols. Ethers.

Physical properties of phenolsPhysical properties of phenols

Page 56: Theme: Alcohols. Phenols. Ethers.

Substance

lС-О, nm 0,140 0,144

, D 1,53 1,66

, сm-1 1230 1050-1200

O..

..H

H3C CH2 O H

..

..

<

Page 57: Theme: Alcohols. Phenols. Ethers.

18. Chemical properties of mononuclear phenols18. Chemical properties of mononuclear phenols

1. Acidic properties:1. Acidic properties:

CC66HH55−OH + NaOH ↔ C−OH + NaOH ↔ C66HH55−ONa + H−ONa + H22OO

CC66HH55−ONa + H−ONa + H22O ↔ CO ↔ C66HH55−OH + NaOH−OH + NaOH

O HH3C

O H

N O2

N O2

O2N

Picric acid

N

O

O

N

O

O

OO H-

+

-+ H+

Page 58: Theme: Alcohols. Phenols. Ethers.

2. Forming of simple and complex ethers:2. Forming of simple and complex ethers:CC66HH55−ONa + C−ONa + C22HH55−Br ↔ C−Br ↔ C66HH55−O−C−O−C22HH55 + NaBr + NaBr

ethylphenyl etherethylphenyl ether

CC66HH55−ONa + CH−ONa + CH33−COCl ↔ C−COCl ↔ C66HH55−O−CO−CH−O−CO−CH33 + NaCl + NaCl phenylacetate phenylacetate

3. Halogenations. (The reaction that underlies qualitative and 3. Halogenations. (The reaction that underlies qualitative and quantitative analysis of phenol and its derivatives)quantitative analysis of phenol and its derivatives)

OH OH

Br Br

Br

O

Br Br

Br Br

+ 3Br2 -3Br2

+Br2

-HBr

white precipitate yellow precipitate

Page 59: Theme: Alcohols. Phenols. Ethers.

4. Nitrating 4. Nitrating

5. Sulphating5. Sulphating

OH

HNO3 (H2O)

OH

NO2

OH

NO2

2H2O2

++

o-nitrophenol

p-nitrophenol

t=25

OH

SO3H

H2SO4

OH

H2SO4

OH

HO3St=-20 t=+100

o-hydroxybenzylsulphoacid p-hydroxybenzylsulphoacid

Page 60: Theme: Alcohols. Phenols. Ethers.

6. Alkylation and acylation (the catalysts are H6. Alkylation and acylation (the catalysts are H22SOSO44, H, H33POPO44, , BFBF33:: OH

H3C OH

OH

CH3

OH

CH3

2H2O+++ 22

OH

H3C C

O

OH

OH

C

O

CH3

OH

CO

CH3

2H2O2 +++ 2

Page 61: Theme: Alcohols. Phenols. Ethers.

7. Azoaccession7. Azoaccession

8. The synthesis of phenolocarboxylic acids:8. The synthesis of phenolocarboxylic acids:

9. To determine mono-, di-, tri- and polynuclear phenols it is necessary to do 9. To determine mono-, di-, tri- and polynuclear phenols it is necessary to do the the reaction with FeClreaction with FeCl33. As the result of this reaction color complex . As the result of this reaction color complex compounds form. compounds form.

NR

N OH

ROHN NCl

+ _

+ NaOH

-NaCl, -H2O

O

O

O

OH

COONa

OH

COOH

+Na

_

+ C1250C, p

sodium salicylate

HCl

-NaCl

salicylic acid

Fe

OC6H5

OO C6H5C6H5

C6H5 O

H

C6H5O

H

O

H C6H5

6C6H5OH + FeCl3-3HCl

: :

..

Page 62: Theme: Alcohols. Phenols. Ethers.

The coloration of phenols in reaction with FeClThe coloration of phenols in reaction with FeCl33

Name of phenolName of phenol Color products of Color products of reaction with FeClreaction with FeCl

33

pyrocatecholpyrocatechol green colorgreen color

resorcinolresorcinol blue colorblue color

hydroquinonehydroquinone green color green color that turns to that turns to yellow coloryellow color

pyrogallolpyrogallol red colorred color

phloroglucinolphloroglucinol dark dark violet violet colorcolor

Page 63: Theme: Alcohols. Phenols. Ethers.

Oxidation of phenols. Quinones.

Phenols are more easily oxidized than alcohols, and a large Phenols are more easily oxidized than alcohols, and a large number of inorganic oxidizing agents have been used for this number of inorganic oxidizing agents have been used for this purpose. The phenol oxidations that are of the most use to the purpose. The phenol oxidations that are of the most use to the organic chemist are those involving derivatives of 1,2-organic chemist are those involving derivatives of 1,2-benzenediol (pyrocatechol) and 1,4-benzenediol benzenediol (pyrocatechol) and 1,4-benzenediol (hydroquinone). Oxidation of compounds of this type with (hydroquinone). Oxidation of compounds of this type with silver oxide or with chromic acid yields conjugated dicarbonyl silver oxide or with chromic acid yields conjugated dicarbonyl compounds called quinones.compounds called quinones.

Page 64: Theme: Alcohols. Phenols. Ethers.
Page 65: Theme: Alcohols. Phenols. Ethers.
Page 66: Theme: Alcohols. Phenols. Ethers.
Page 67: Theme: Alcohols. Phenols. Ethers.

19. Usage of the chemical properties in the receiving of 19. Usage of the chemical properties in the receiving of medical drugsmedical drugs

А) А) Synthesis of thymolSynthesis of thymol::

CH3

OH

H2SO4

CH3

OH

HSO3 (CH3)2CHOHCH3

OH

HSO3

CH3 CH3CH3

OH

CH3 CH3

H2O

thymol

Page 68: Theme: Alcohols. Phenols. Ethers.

BB) ) Synthesis of paracetamol (pyretic and analgesic means):Synthesis of paracetamol (pyretic and analgesic means):

CC) ) Synthesis of phenethidine and phenacetine (pyretic and anti-Synthesis of phenethidine and phenacetine (pyretic and anti-neuralgic meansneuralgic means))

NO2 NH-OH H2SO4

OH

NH2 (CH3CO)2O

OH

NHCOCH32H2

p-acetylaminophenol,paracetamol

NH2OH

(CH3CO)2O

NH2NaO

C2H5Br

-NaBrNH2C2H5O

NHCOCH3C2H5O

NaOH

phenethidine

phenacetine

Page 69: Theme: Alcohols. Phenols. Ethers.

20. Di-, tri- and polynuclear phenols20. Di-, tri- and polynuclear phenolsO H

O H

O H

O H

O H

O Hnaphthol naphthol pyrocatechol

hydroquinone

O H

O HOH

O H

O HOH

O H

O H

O Hpyrogallol phloroglucinolhydroxyhydroquinone

Page 70: Theme: Alcohols. Phenols. Ethers.

21. Chemical properties of di-, tri- and polynuclear 21. Chemical properties of di-, tri- and polynuclear phenols phenols

Chemical properties of di-, tri- and polynuclear phenols are Chemical properties of di-, tri- and polynuclear phenols are similar to chemical properties of mononuclear phenols. But similar to chemical properties of mononuclear phenols. But they have some peculiarities. they have some peculiarities.

1. Acidic properties of polynuclear phenols are stronger than 1. Acidic properties of polynuclear phenols are stronger than acidic properties of mononuclear phenols. Polynuclear acidic properties of mononuclear phenols. Polynuclear phenols can react with alkaline and heavy metals:phenols can react with alkaline and heavy metals:

OH

OH

(CH3COO)2PbO

O

Pb-2CH3COOH

Page 71: Theme: Alcohols. Phenols. Ethers.

2. Oxidation. polynuclear phenols oxidize more easily 2. Oxidation. polynuclear phenols oxidize more easily than mononuclear phenols.than mononuclear phenols.

OH

OH

Ag2O, ether

O

Opyrocatechol o-benzoquinone

Na2SO4

Page 72: Theme: Alcohols. Phenols. Ethers.

22. The representatives of phenols22. The representatives of phenolsOH

OH

CH3

OH

H3C CHCH3

CH3

OH

O2N NO2

NO2

phenol. Colourless crystals, it has antiseptic properties. It is toxic and can cause combustions. It is used in the manufacture of dyes, medicines.

o-, m- and p-cresols. They are disinfectant compounds and used in veterinary medicine.

thymol. Colourless crystals. It is used in medicine as antiseptic and antihelminthic mean.

picric acid. Yellow crystals. It is used in pharmaceutical analysis.

Page 73: Theme: Alcohols. Phenols. Ethers.

OH

OH

OHHO

α-naphtol. Yellowish crystals. It is used in the manufacture of dyes, medicines.

β-naftol. White powder. It is used in the manufacture of dyes, medicines and in pharmaceutical analysis.

pyrocatechol. Colourless crystals. It can oxidize to brown colour in the open air. It has antiseptic properties. It take part in the synthesis of adrenalin.

resorcinol. Colourless crystals. It is used in the manufacture of dyes. It is antiseptic compound by skin diseases (the ointments contain it).

Page 74: Theme: Alcohols. Phenols. Ethers.

OHHO

OH

OHHO

OH

HO

HO

CH CH2

OHNH CH3

pyrogallol. White crystals. It can oxidize to brown colour in the light. It is used in the manufacture of dyes.

phloroglucinol . Colourless crystals. It is used in pharmaceutical analysis.

adrenalin. Colourless crystals. It is a hormone of catecholamines, it is produced by inner cerebral part of paranephroses. Adrenalin takes part in regulation of carbohydrate metabolism and lipometabolism. It causes narrowing of little blood vasculars, rising of arterial pressure, it can stimulate of heart activity.

Page 75: Theme: Alcohols. Phenols. Ethers.

23. Aminophenols23. Aminophenols

Aminophenols are aromatic compounds that Aminophenols are aromatic compounds that contain phenyl radical, −OH group and contain phenyl radical, −OH group and aminogroup. There are o-, m- and p-aminogroup. There are o-, m- and p-aminophenols.aminophenols.

OH

NH2

OH

NH2

OH

NH2o-aminophenol

m-aminophenolp-aminophenol

Page 76: Theme: Alcohols. Phenols. Ethers.

The methods of extraction of aminophenolsThe methods of extraction of aminophenols 1.1. The reduction of nitrophenols:The reduction of nitrophenols:

2.2. Reaction of dihydroxic phenols with ammonium:Reaction of dihydroxic phenols with ammonium:

3.3. The reduction of nitrobenzene:The reduction of nitrobenzene:

OH

NO23H2

OH

NH2

2H2O+

o-aminophenolo-nitrophenol

+

OH

OHpyrocatechol

NH3t

OH

NH2

H2O+

o-aminophenol

NO2

-H2O

H2

N O

H2

NH OHH2SO4

NH2

HOnitrobenzene nitrozobenzenephenylhydroxylamine p-aminophenol

Page 77: Theme: Alcohols. Phenols. Ethers.

Chemical propertiesChemical properties: aminophenols have properties of : aminophenols have properties of phenols and aromatic amines. phenols and aromatic amines.

The derivatives of aminophenols are medical The derivatives of aminophenols are medical preparations:preparations:

HO NH C CH3

O

p-acetylaminophenol(paracetamol)

O NH C CH3

O

phenacetin

H2CH3C

It is antipyretic, anti-inflammatory mean. It is used for the treatment of headache, toothache, high temperature.

It is antipyretic and antineuralgic mean

Page 78: Theme: Alcohols. Phenols. Ethers.

24. Aromatic carboxylic acids24. Aromatic carboxylic acids

Aromatic carboxylic acids are the derivatives of hydrocarbons Aromatic carboxylic acids are the derivatives of hydrocarbons that contain carboxyl group (-COOH) and benzyl radical. that contain carboxyl group (-COOH) and benzyl radical.

COH

H2CH3C

O

3-ethylbenzoic acid

C

benzoic acid

O

OH

CH3

HNO3 CH3 NO2

[O]O2N COOH

C2H5OH, H2SO4O2N COOCH5

[H]NH2 COOCH5

anesthysine

2 2

Page 79: Theme: Alcohols. Phenols. Ethers.

NH2 COOCH2CH2N(C2H5)2. HCl

novocaine

NH2

COOH

Anthranilic acid

OH

NH2

COONa

Sodium p-aminosalicylate

Page 80: Theme: Alcohols. Phenols. Ethers.

The key compound in the synthesis of aspirin, The key compound in the synthesis of aspirin, salicylic acid, is prepared from phenol by a process salicylic acid, is prepared from phenol by a process discovered in the nineteenth century by the German discovered in the nineteenth century by the German chemist Hermann Kolbe. In the Kolbe synthesis, also chemist Hermann Kolbe. In the Kolbe synthesis, also known as the Kolbe–Schmitt reaction, sodium known as the Kolbe–Schmitt reaction, sodium phenoxide is heated with carbon dioxide under phenoxide is heated with carbon dioxide under pressure, and the reaction mixture is subsequently pressure, and the reaction mixture is subsequently acidified to yield salicylic acid:acidified to yield salicylic acid:

Page 81: Theme: Alcohols. Phenols. Ethers.

OH

COOH

NaHCO3

-CO2, -H2O

OH

COONa POCl3, C 6H5ONa

-NaCl, -NaPO3

OH

OC 6H5

O

CH3OH

(H2SO4)-H2O

OH

COOCH3NH3

OH

NH2

O

(CH3CO)2O

- CH3COOH

O

COOH

CH3

O

NH2

OH

-C 6H5OH

OHO

NH

OH

Salicylic acid

Sodium salicylate

C

Phenylsalicylate, salol

Methylsalicylate

C

Salicylamide

C

Acetylsalicylic acid,aspirin

C

Oxaphenamide

Page 82: Theme: Alcohols. Phenols. Ethers.

Salicylic acid (from the Latin word for the willow tree, Salix, from whose Salicylic acid (from the Latin word for the willow tree, Salix, from whose bark it can be obtained) is a beta hydroxy acid. This colorless crystalline bark it can be obtained) is a beta hydroxy acid. This colorless crystalline organic acid is widely used in organic synthesis and functions as a plant organic acid is widely used in organic synthesis and functions as a plant hormone. It is derived from the metabolism of salicin. In addition to being hormone. It is derived from the metabolism of salicin. In addition to being a compound that is chemically similar to but not identical to the active a compound that is chemically similar to but not identical to the active component of aspirin (acetylsalicylic acid), it is probably best known for component of aspirin (acetylsalicylic acid), it is probably best known for its use in anti-acne treatments. The salts and esters of salicylic acid are its use in anti-acne treatments. The salts and esters of salicylic acid are known as salicylates.known as salicylates.

4-Aminosalicylic acid, commonly known as PAS, is an 4-Aminosalicylic acid, commonly known as PAS, is an antibiotic used to treatment of tuberculosis.antibiotic used to treatment of tuberculosis.

OH

OH

OH

NH2

OH

NH2

COOH

NH3

-H2O

CO2, KOH

PAS

Page 83: Theme: Alcohols. Phenols. Ethers.

The best known aryl ester is O-acetylsalicylic acid, better known as The best known aryl ester is O-acetylsalicylic acid, better known as aspirin. It is prepared by acetylation of the phenolic hydroxyl group of aspirin. It is prepared by acetylation of the phenolic hydroxyl group of salicylic acid:salicylic acid:

Aspirin possesses a number of properties that make it an often-Aspirin possesses a number of properties that make it an often-recommended drug. It is an analgesic, effective in relieving headache recommended drug. It is an analgesic, effective in relieving headache pain. It is also an antiinflammatory agent, providing some relief from pain. It is also an antiinflammatory agent, providing some relief from the swelling associated with arthritis and minor injuries. Aspirin is an the swelling associated with arthritis and minor injuries. Aspirin is an antipyretic compound; that is, it reduces fever. Each year, more than antipyretic compound; that is, it reduces fever. Each year, more than 40 million lb of aspirin is produced in the United States, a rate equal to 40 million lb of aspirin is produced in the United States, a rate equal to 300 tablets per year for every man, woman, and child.300 tablets per year for every man, woman, and child.

Page 84: Theme: Alcohols. Phenols. Ethers.

Thank you for attention!


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