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Theme: Alcohols.Phenols. Ethers.
LECTURE № 6
associate. prof. Ye. B. Dmukhalska, assistant. I.I. Medvid
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
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
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)
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
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)
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.
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
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.
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
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
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
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
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
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
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]
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
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
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)
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
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
. .
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++
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
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
+
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
+ +
+ +
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
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
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.
Both steps can be carried out sequentially without isolating the isothiouronium salt.
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++
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
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.
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.
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
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+
+-
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
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.
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 .
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.
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
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
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¯
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.
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)
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
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
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
Physical properties of phenolsPhysical properties of phenols
Substance
lС-О, nm 0,140 0,144
, D 1,53 1,66
, сm-1 1230 1050-1200
O..
..H
H3C CH2 O H
..
..
<
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+
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
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
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
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
: :
..
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
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.
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
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
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
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
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
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.
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).
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.
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
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
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
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
NH2 COOCH2CH2N(C2H5)2. HCl
novocaine
NH2
COOH
Anthranilic acid
OH
NH2
COONa
Sodium p-aminosalicylate
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:
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
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
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.
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