Nitrogen containing Nitrogen containing compounds. compounds.

Nitrocompounds. Nitrocompounds. Amines.Amines. DiaDiazo- and azocompoundszo- and azocompounds..

Prepared by ass. Medvid I.I., Prepared by ass. Medvid I.I., ass. Burmas N.I.ass. Burmas N.I.

OutlineOutline1.1. Nitroderivates of hydrocarbons.Nitroderivates of hydrocarbons.2.2. The methods of extraction of nitroalkanes.The methods of extraction of nitroalkanes.3.3. Chemical properties of nitroalkanes.Chemical properties of nitroalkanes.4.4. The aromatic nitrocompounds. The aromatic nitrocompounds. 5.5. Amines. Amines. 6.6. Isomery of amines.Isomery of amines.7.7. Structure and bonding of amines.Structure and bonding of amines.8.8. Physical propertiesPhysical properties of amines.of amines.9.9. The methods of extraction of amines.The methods of extraction of amines.10.10. Chemical properties of amines.Chemical properties of amines.11.11. Synthetically useful transformations involving aryl diazonium ions.Synthetically useful transformations involving aryl diazonium ions.12.12. The medico-biological importance of amines.The medico-biological importance of amines.13.13. Aminoalcohols.Aminoalcohols.14.14. The methods of extraction of aminoalcohols.The methods of extraction of aminoalcohols.15.15. Chemical properties of aminoalcohols.Chemical properties of aminoalcohols.16.16. Arylamines.Arylamines.17.17. The methods of extraction of aromatic amines.The methods of extraction of aromatic amines.18.18. Physical properties of aromatic aminesPhysical properties of aromatic amines19.19. Comparative structure of aromatic and aliphatic aminesComparative structure of aromatic and aliphatic amines20.20. SulphanilicSulphanilic acidacid21.21. The synthesis of streptocideThe synthesis of streptocide22.22. Sulphanylamidic preparationsSulphanylamidic preparations 23.23. Medicinal preparations (derivates of p-aminobenzoic acid (pABA).Medicinal preparations (derivates of p-aminobenzoic acid (pABA). 24.24. DiazocompoundsDiazocompounds25.25. The methods of extraction of aromatic diazocompoundsThe methods of extraction of aromatic diazocompounds 26.26. Chemical properties aromatic diazocompounds Chemical properties aromatic diazocompounds 27.27. AzocompoundsAzocompounds28.28. The methods of extraction of aromatic azocompounds.The methods of extraction of aromatic azocompounds.29.29. Chemical properties of aromatic azocompoundsChemical properties of aromatic azocompounds30.30. Physical bases of theory of colourationPhysical bases of theory of colouration31.31. Azo-dyes.Azo-dyes.

1. Nitroderivates of hydrocarbons1. Nitroderivates of hydrocarbons

Nitrocompounds are the derivatives of hydrocarbons which Nitrocompounds are the derivatives of hydrocarbons which contain one or several groups –NO2 in their molecule. contain one or several groups –NO2 in their molecule. Nitroalkanes are poisonous colourless or yellowish liquids Nitroalkanes are poisonous colourless or yellowish liquids with good smell. They are not dissoluble in water but are with good smell. They are not dissoluble in water but are dissoluble in organic solvents. The names of nitrocompound dissoluble in organic solvents. The names of nitrocompound are formed by adding prefix are formed by adding prefix nitro-nitro- to the names of to the names of hydrocarbons. hydrocarbons. The isomery of nitrocompound is specified by different The isomery of nitrocompound is specified by different structure of carbon chain and different location of group –NOstructure of carbon chain and different location of group –NO22 in the in the molecule.molecule.

H3C CH

NO2

CH2 CH3

2-nitrobutane

H3C CH

NO2

CH CH3

CH32-methyl-3-nitrobutane

NO2

nitrobenzene

NO2H3C

3-nitrotoluene

CH2 NO2

phenylnitromethane

CH2 CH2 NO2

1-nitro-2-phenylethane

2. The methods of extraction of nitroalkanes2. The methods of extraction of nitroalkanes

1. Nitration of alkanes1. Nitration of alkanes

CHCH33−CH−CH33 + HNO + HNO33 → CH → CH33−CH−CH22−NO−NO22 + H + H22OO

2. The reaction of halogenalkanes with salts of 2. The reaction of halogenalkanes with salts of HNOHNO22

CHCH33−CH−CH22−I + NaNO−I + NaNO22 → CH → CH33−CH−CH22−NO−NO22 + NaI + NaI

3. Oxidation of amines3. Oxidation of amines

C

CH3

CH3

NH2

H3C3[O]

C

CH3

CH3

NO2

H3C H2O+

2-methylpropanamine 2-methyl-2-nitropropane

3.Chemical properties of nitroalkanes3.Chemical properties of nitroalkanesChemical properties of nitroalkanes are specified by the presence of Chemical properties of nitroalkanes are specified by the presence of

group –NOgroup –NO22 in the structure of the molecule. in the structure of the molecule.

1.1. Reaction with HNOReaction with HNO22

2.2. Reaction with aldehydes and ketonesReaction with aldehydes and ketones

3. Reduction of nitroalkanes. In the result of this reaction 3. Reduction of nitroalkanes. In the result of this reaction amines form (catalyst is SnClamines form (catalyst is SnCl22))

CHCH33−CH−CH22−NO−NO22 + 3H + 3H22 → CH → CH33−CH−CH22−NH−NH2 2 + 2H+ 2H22OO

CH

H

H3C NO2 HNO2 C

N

H3C NO2

OH

H2O+ +

CH2

NO2

H2CH3C C CH3H

OC

NO2

H2CH3C CH

OH

CH3

H-H2O

+ C

NO2

H2CH3C CH

CH3

4.The aromatic nitrocompounds4.The aromatic nitrocompounds

The simplest aromatic nitro compound, having the molecular The simplest aromatic nitro compound, having the molecular formula Cformula C66HH55NONO22..

NitrobenzeneNitrobenzene, also known as , also known as nitrobenzolnitrobenzol or or oil of oil of mirbanemirbane, is an organic compound with the chemical formula , is an organic compound with the chemical formula CC66HH55NONO22. Nitrobenzene is a water-insoluble oil which . Nitrobenzene is a water-insoluble oil which exhibits a pale yellow to yellow-brown coloration in liquid exhibits a pale yellow to yellow-brown coloration in liquid form (at room temperature and pressure) with an almond-form (at room temperature and pressure) with an almond-like odor. When frozen, it appears as a greenish-yellow like odor. When frozen, it appears as a greenish-yellow crystal. Although occasionally used as a flavoring or crystal. Although occasionally used as a flavoring or perfume additive, nitrobenzene is highly toxic in large perfume additive, nitrobenzene is highly toxic in large quantities and is mainly produced as a precursor to aniline. quantities and is mainly produced as a precursor to aniline. In the laboratory, it is occasionally used as a solvent, In the laboratory, it is occasionally used as a solvent, especially for electrophilic reagents.especially for electrophilic reagents.

PProperties of nitrobenzeneroperties of nitrobenzene::

1. Production1. ProductionNitrobenzene is prepared by nitration of benzene with a mixture of Nitrobenzene is prepared by nitration of benzene with a mixture of concentrated sulfuric acid, water, and nitric acid, called "mixed acid." Its concentrated sulfuric acid, water, and nitric acid, called "mixed acid." Its production is one of the most dangerous processes conducted in the production is one of the most dangerous processes conducted in the chemical industry because of the exothermicity of the reaction (chemical industry because of the exothermicity of the reaction (ΔΔH = H = −117 kJ/mol).−117 kJ/mol).

There were four producers of nitrobenzene in the United States in 1991. There were four producers of nitrobenzene in the United States in 1991. 2. Mechanism of nitration2. Mechanism of nitration

The reaction pathway entails formation of an adduct between the Lewis The reaction pathway entails formation of an adduct between the Lewis acidic nitronium ion, NOacidic nitronium ion, NO22+, and benzene. The nitronium ion is +, and benzene. The nitronium ion is generated in situ via the reaction of nitric acid and an acidic dehydration generated in situ via the reaction of nitric acid and an acidic dehydration agent, typically sulfuric acid:agent, typically sulfuric acid:

HNOHNO33 + H+ NO⇌ + H+ NO⇌ 22+ + H+ + H22OO

Zinin’s reaction:

3. Uses3. UsesApproximately 95% of nitrobenzene is consumed in the Approximately 95% of nitrobenzene is consumed in the production of aniline.production of aniline.

4. Specialized applications4. Specialized applicationsMore specialized applications include the use of More specialized applications include the use of nitrobenzene as a precursor to rubber chemicals, nitrobenzene as a precursor to rubber chemicals, pesticides, dyes, explosives, and pharmaceuticals. pesticides, dyes, explosives, and pharmaceuticals. Nitrobenzene is also used in shoe and floor polishes, Nitrobenzene is also used in shoe and floor polishes, leather dressings, paint solvents, and other materials to leather dressings, paint solvents, and other materials to mask unpleasant odors. Redistilled, as oil of mirbane, mask unpleasant odors. Redistilled, as oil of mirbane, nitrobenzene has been used as an inexpensive perfume for nitrobenzene has been used as an inexpensive perfume for soaps. A significant merchant market for nitrobenzene is its soaps. A significant merchant market for nitrobenzene is its use in the production of the analgesic paracetamol (also use in the production of the analgesic paracetamol (also known as acetaminophen) (Mannsville 1991). Nitrobenzene known as acetaminophen) (Mannsville 1991). Nitrobenzene is also used in Kerr cells, as it has an unusually large Kerr is also used in Kerr cells, as it has an unusually large Kerr constant.constant.

5. Organic reactions5. Organic reactionsAside from its conversion to aniline, nitrobenzene is readily Aside from its conversion to aniline, nitrobenzene is readily converted to related derivatives such as azobenzene, converted to related derivatives such as azobenzene, nitrosobenzene, and phenylhydroxylamine. The nitro- group nitrosobenzene, and phenylhydroxylamine. The nitro- group is deactivating, thus substitution tends to occur at the is deactivating, thus substitution tends to occur at the metameta--position.position.

6. Safety6. SafetyNitrobenzene is highly toxic (TLV 5 mg/m3) and readily Nitrobenzene is highly toxic (TLV 5 mg/m3) and readily absorbed through the skin.absorbed through the skin.Although nitrobenzene is not currently known to be a Although nitrobenzene is not currently known to be a carcinogen, prolonged exposure may cause serious carcinogen, prolonged exposure may cause serious damage to the central nervous system, impair vision, cause damage to the central nervous system, impair vision, cause liver or kidney damage, anemia and lung irritation. Inhalation liver or kidney damage, anemia and lung irritation. Inhalation of fumes may induce headache, nausea, fatigue, dizziness, of fumes may induce headache, nausea, fatigue, dizziness, cyanosis, weakness in the arms and legs, and in rare cases cyanosis, weakness in the arms and legs, and in rare cases may be fatal. The oil is readily absorbed through the skin may be fatal. The oil is readily absorbed through the skin and may increase heart rate, cause convulsions or rarely and may increase heart rate, cause convulsions or rarely death. Ingestion may similarly cause headaches, dizziness, death. Ingestion may similarly cause headaches, dizziness, nausea, vomiting and gastrointestinal irritation.nausea, vomiting and gastrointestinal irritation.

5. Amines5. AminesAmines are the derivatives of ammonium. In its molecules atoms of Amines are the derivatives of ammonium. In its molecules atoms of hydrogen (1,2 or 3) are substituted to atoms of hydrocarbon radicals.hydrogen (1,2 or 3) are substituted to atoms of hydrocarbon radicals.

The names of amines are formed by adding suffix The names of amines are formed by adding suffix -amine-amine to the names of to the names of hydrocarbon radical. hydrocarbon radical.

R NH2

N HR1

RN

R2

RR1

primary amine secondary amine tertiary amine

H3C NH2methylamine

H3C CH

propanamine-2

CH3

NH2

H3C NH

N-methylethanamine

CH2 CH3

H3C N

N-ethyl-N-methylpropanamine-1

CH2 CH2

CH2

CH3

CH3

1 2 3

NH

diphenylamine

N

triphenylamine

6. Isomery of amines6. Isomery of amines Isomery of amines is specified by different structure of Isomery of amines is specified by different structure of hydrocarbon radicals, different location of aminogroup and hydrocarbon radicals, different location of aminogroup and methamery. Methamery is a phenomenon when amines methamery. Methamery is a phenomenon when amines have the same molecular formula but can be primary, have the same molecular formula but can be primary, secondary or tertiary.secondary or tertiary.

H2N CH2CH2CH3 H3C NH CH2CH3 H3C N

CH3

CH3n-propylamine ethylmehylamine trimethylamine

Aniline Aniline is the parent IUPAC name for amino-substituted derivatives of is the parent IUPAC name for amino-substituted derivatives of benzene. Substituted derivatives of aniline are numbered beginning at benzene. Substituted derivatives of aniline are numbered beginning at the carbon that bears the amino group. Substituents are listed in the carbon that bears the amino group. Substituents are listed in alphabetical order, and the direction of numbering is governed by the alphabetical order, and the direction of numbering is governed by the usual “first point of difference” rule.usual “first point of difference” rule.

Arylamines may also be named as Arylamines may also be named as arenamines. arenamines. Thus, Thus, benzenamine benzenamine is is an alternative, but rarely used, name for aniline. Compounds with two an alternative, but rarely used, name for aniline. Compounds with two amino groups are named by adding the suffix amino groups are named by adding the suffix -diamine -diamine toto

the name of the corresponding alkane or arene. The final the name of the corresponding alkane or arene. The final -e -e of the of the parent hydrocarbon is retained.parent hydrocarbon is retained.

Amino groups rank rather low in seniority when the parent compound is Amino groups rank rather low in seniority when the parent compound is identified for naming purposes. Hydroxyl groups and carbonyl groups identified for naming purposes. Hydroxyl groups and carbonyl groups outrank amino groups. In these cases, the amino group is named as a outrank amino groups. In these cases, the amino group is named as a substituent.substituent.

Secondary and tertiary amines are named as Secondary and tertiary amines are named as NN-substituted derivatives of -substituted derivatives of primary amines. The parent primary amine is taken to be the one with the primary amines. The parent primary amine is taken to be the one with the longest carbon chain. The prefix longest carbon chain. The prefix N- N- is added as a locant to identify is added as a locant to identify substituents on the amino nitrogen as substituents on the amino nitrogen as needed. needed.

7. Structure and bonding of amines7. Structure and bonding of amines

Alkylamines: Alkylamines: As shown in Figure.1 methylamine, like As shown in Figure.1 methylamine, like ammonia, has a pyramidal arrangement of bonds to ammonia, has a pyramidal arrangement of bonds to nitrogen. Its Hnitrogen. Its H--NN--H angles (106°) are slightly smaller thanH angles (106°) are slightly smaller thanthe tetrahedral value of 109.5°, whereas the Cthe tetrahedral value of 109.5°, whereas the C--NN--H angle H angle (112°) is slightly larger. The C(112°) is slightly larger. The C--N bond distance of 147 pm N bond distance of 147 pm lies between typical Clies between typical C--C bond distances in alkanesC bond distances in alkanes(153 pm) and C(153 pm) and C--O bond distances in alcohols (143 pm). An O bond distances in alcohols (143 pm). An orbital hybridization description of bonding in methylamine orbital hybridization description of bonding in methylamine is shown in Figure. 2. Nitrogen and carbon are both is shown in Figure. 2. Nitrogen and carbon are both spsp3-3-hybridized and are joined by a σ bond.hybridized and are joined by a σ bond.

Figure.1 MethylamineFigure.1 Methylamine

Arylamines: Arylamines: Aniline, like alkylamines, has a pyramidal arrangement Aniline, like alkylamines, has a pyramidal arrangement of bonds around nitrogen, but its pyramid is somewhat shallower. One of bonds around nitrogen, but its pyramid is somewhat shallower. One measure of the extent of this flattening is given by the angle between measure of the extent of this flattening is given by the angle between the carbon–nitrogen bond and the bisector of the the carbon–nitrogen bond and the bisector of the HH--NN--H angle. H angle.

For For spsp3-hybridized nitrogen, this angle (not the same as the C3-hybridized nitrogen, this angle (not the same as the C--NN--H H bond angle) is 125°, and the measured angles in simple alkylamines bond angle) is 125°, and the measured angles in simple alkylamines are close to that. The corresponding angle for are close to that. The corresponding angle for spsp2 hybridization at 2 hybridization at nitrogen with a planar arrangement of bonds, as in amides, for nitrogen with a planar arrangement of bonds, as in amides, for example, is 180°. The measured value for this angle in aniline is example, is 180°. The measured value for this angle in aniline is 142.5°, suggesting a hybridization somewhat closer to 142.5°, suggesting a hybridization somewhat closer to spsp3 than to 3 than to spsp2.2.

Figure.2Figure.2

The corresponding resonance description shows The corresponding resonance description shows the delocalization of the nitrogen lone-pair the delocalization of the nitrogen lone-pair electrons in terms of contributions from dipolar electrons in terms of contributions from dipolar structures.structures.

8.Physical properties8.Physical properties of aminesof aminesWe have often seen that the polar nature of a substance can affect We have often seen that the polar nature of a substance can affect physical properties such as boiling point. This is true for amines, which physical properties such as boiling point. This is true for amines, which are more polar than alkanes but less polar than alcohols. For similarly are more polar than alkanes but less polar than alcohols. For similarly constituted compounds, alkylamines have boiling points higher than those constituted compounds, alkylamines have boiling points higher than those of alkanes but lower than those of alcohols.of alkanes but lower than those of alcohols.

Dipole–dipole interactions, especially hydrogen bonding, are present in Dipole–dipole interactions, especially hydrogen bonding, are present in amines but absent in alkanes. The less polar nature of amines as amines but absent in alkanes. The less polar nature of amines as compared with alcohols, however, makes these intermolecular forces compared with alcohols, however, makes these intermolecular forces weaker in amines than in alcohols. Among isomeric amines, primary weaker in amines than in alcohols. Among isomeric amines, primary amines have the highest boiling points, and tertiary amines have the highest boiling points, and tertiary amines the lowest.amines the lowest.

Primary and secondary amines can participate in Primary and secondary amines can participate in intermolecular hydrogen bonding, but tertiary intermolecular hydrogen bonding, but tertiary amines cannot. Amines that have fewer than six amines cannot. Amines that have fewer than six or seven carbon atoms are soluble in water. All or seven carbon atoms are soluble in water. All amines, even tertiary amines, can act as proton amines, even tertiary amines, can act as proton acceptors in hydrogen bonding to water acceptors in hydrogen bonding to water molecules. The simplest arylamine, aniline, is a molecules. The simplest arylamine, aniline, is a liquid at room temperature and has a boilingliquid at room temperature and has a boilingpoint of 184°C. Almost all other arylamines have point of 184°C. Almost all other arylamines have higher boiling points. Aniline is only slightly higher boiling points. Aniline is only slightly soluble in water (3 g/100 mL). Substituted soluble in water (3 g/100 mL). Substituted derivatives of aniline tend to be even derivatives of aniline tend to be even less water-less water-soluble.soluble.

9. The methods of extraction of amines9. The methods of extraction of amines

Hoffman reaction: Hoffman reaction: NHNH33

NHNH33 + CH + CH33I → [CHI → [CH33NHNH33+]I− ↔ CH+]I− ↔ CH33NHNH22 + NH + NH44I I NHNH33

CHCH33NHNH22 + CH + CH33I → [(CHI → [(CH33))22NHNH22+]I− ↔ (CH+]I− ↔ (CH33))22NH + NHNH + NH44I I NHNH33

(CH(CH33))22NH + CHNH + CH33I → [(CHI → [(CH33))33NH+]I− ↔ (CHNH+]I− ↔ (CH33))33N + NHN + NH44II NHNH33

(CH(CH33))33N + CHN + CH33I → [(CHI → [(CH33))44N+]I−N+]I−

Gabriele synthesis: Gabriele synthesis: C

C

O

O

N-K+

C

C

O

O

N C2H5

Cl C2H5

2H2O

C

C

O

O

OH

OH

C

C

O

O

N C2H5

C2H5 NH2

KCl+ +

potassium phtalimide N-ethylphtalimide

N-ethylphtalimide

+ +

phtalic acid

ethylamine

10. Chemical properties of amines10. Chemical properties of amines

Nitrosation of arylamines

We learned in the preceding section that different reactions are observed when the various classes of alkylamines—primary, secondary, and tertiary—react with nitrosating agents.

Primary arylamines, like primary alkylamines, form diazonium ion Primary arylamines, like primary alkylamines, form diazonium ion salts on nitrosation. Aryl diazonium ions are considerably more salts on nitrosation. Aryl diazonium ions are considerably more stable than their alkyl counterparts. Whereas alkyl diazonium ions stable than their alkyl counterparts. Whereas alkyl diazonium ions decompose under the conditions of their formation, aryl diazonium decompose under the conditions of their formation, aryl diazonium salts are stable enough to be stored in aqueous solution at 0–5°C salts are stable enough to be stored in aqueous solution at 0–5°C for reasonable periods of time. Loss of nitrogen from an aryl for reasonable periods of time. Loss of nitrogen from an aryl diazonium ion generates an unstable aryl cation and is much slower diazonium ion generates an unstable aryl cation and is much slower than loss of nitrogen from an alkyl diazonium ion.than loss of nitrogen from an alkyl diazonium ion.

Reaction with acids:Reaction with acids:

CHCH33CHCH22NHNH22 + HCl → [CH + HCl → [CH33CHCH22NHNH33]+Cl−]+Cl−

Reaction with halogenalkanes:Reaction with halogenalkanes:

CHCH33CHCH22NHNH22 + CH + CH33−I → [CH−I → [CH33CHCH22NHNH33]+I− → CH]+I− → CH33CHCH22NHCHNHCH33 + HI + HI

Reaction with functional derivatives of carboxylic acids. In the result of Reaction with functional derivatives of carboxylic acids. In the result of these reactions amides form.these reactions amides form.

Reaction with HNOReaction with HNO22

Isonitrylic reactionIsonitrylic reaction

+ HClH3C CH2 NH2 +H3C C Cl

O

H3C CH2 NH C CH3

O

+ H2OHO N+H3C CH2 NH2 OHCl

-2H2OH3C CH2 N N Cl-

H3C CH2 OH N2 HCl+ +

H3C CH2 NH2 CHCl3 3KOHC2H5OH

H3C CH2 N C 3KCl 3H2O+

++ + +-

Oxidation

C2H5NH2 + O3 → C2H5NO2 + H2O

11. Synthetically useful transformations involving aryl 11. Synthetically useful transformations involving aryl diazonium ionsdiazonium ions

12.The medico-biological importance of amines12.The medico-biological importance of amines MethylamineMethylamine CH CH33NHNH22. It is a gas with the smell of . It is a gas with the smell of

ammonium. Methylamine is used in the production of ammonium. Methylamine is used in the production of medicines, dyes, insecticides and fungicides. medicines, dyes, insecticides and fungicides.

PutrescinPutrescin NH NH22CHCH22CHCH22CHCH22CHCH22NHNH22 (tetramethylendiamine). It is crystal solid. It is formed (tetramethylendiamine). It is crystal solid. It is formed in the process of rotting of corpses. In the human in the process of rotting of corpses. In the human organism it is used for synthesis of biologically active organism it is used for synthesis of biologically active polyamines which take part in the biosynthesis of DNA polyamines which take part in the biosynthesis of DNA and RNA.and RNA.

CadaverineCadaverine NH NH22CHCH22CHCH22CHCH22CHCH22CHCH22NHNH22 (pentamethylendiamine). It is liquid. It is formed in the (pentamethylendiamine). It is liquid. It is formed in the process of rotting of corpses like putrescin.process of rotting of corpses like putrescin.

AnilineAniline C C66HH55NHNH22. It is colourless liquid with peculiar . It is colourless liquid with peculiar smell. It is poisonous. It is used in the process of smell. It is poisonous. It is used in the process of synthesis of dyes, medicines, plastic materials.synthesis of dyes, medicines, plastic materials.

Phenamine Phenamine CC66HH55CHCH22CH(NHCH(NH22)CH)CH33 (1- (1-phenylpropanamine-phenylpropanamine-22). It is white crystal solid. It is ). It is white crystal solid. It is used as stimulator of CNS.used as stimulator of CNS.

13. Aminoalcohols13. Aminoalcohols

Aminoalcohols are the derivatives of hydrocarbons which contain Aminoalcohols are the derivatives of hydrocarbons which contain aminogroup in their molecule. For aminoalcohols it is used the aminogroup in their molecule. For aminoalcohols it is used the nomenclature according to which the location of aminogroup is nomenclature according to which the location of aminogroup is denoted by number or Greek letter. denoted by number or Greek letter.

Isomery of aminoalcohols is similar to isomery of Isomery of aminoalcohols is similar to isomery of disubstituted hydrocarbons. disubstituted hydrocarbons.

H2C CH2 OH

NH2

H2C CH2 OH

NH CH32-aminoethanol or β-aminoethyl alkohol 2-N-methylaminoethanol

14. The methods of extraction of aminoalcohols:

1.1. Joining of ammonium or amines to α-oxidesJoining of ammonium or amines to α-oxides

2.2. Reduction of nitroalcoholsReduction of nitroalcohols

3.3. Reaction of halogenalcohols with ammonium or Reaction of halogenalcohols with ammonium or aminesamines

H2C CH2

O

+ NH3 H2C CH2 OH

NH22-aminoethanol

HC CH2 OH

NO2

H3C3H2 HC CH2 OH

NH2

H3C H2O+

+ HCl

H2C CH2 OH

NH2C CH2 OH

Cl

H3CNH

H3CCH3

CH3

+

2-N,N-dimethylaminoethanol

15. Chemical properties of aminoalcohols Chemical properties of aminoalcohols are specified by are specified by the presence of –OH and aminogroups in the structure the presence of –OH and aminogroups in the structure of its molecules. Aminoalcohols have basic reaction. of its molecules. Aminoalcohols have basic reaction.

1. Reaction with acids:1. Reaction with acids:

2.Reaction with SOCl2.Reaction with SOCl22::

H2C CH2 OH

NH2

HCl H2C CH2 OH

NH3Cl

+

+ -

H2C CH2 OH

NH2

H2SO4H2C CH2

N

H

H2O+

H2CNH

H2C

HO

HO

2SOCl2

H2CNH

H2C

Cl

Cl

2SO2 2HCl+ + +

16. Arylamines Arylamines are the derivatives of ammonium. In its molecule one, two or three hydrogen atoms are substituted to aromatic radicals. The names of arylamines depend on the presence of aromatic radicals and their locations.

NH

diphenylamine

Arylamines: Aniline, like alkylamines, has a pyramidal arrangement of bonds around nitrogen, but its pyramid is somewhat shallower. One measure of the extent of this flattening is given by the angle between the carbon–nitrogen bond and the bisector of the H-N-H angle.

For sp³-hybridized nitrogen, this angle (not the same as the C-N-H bond angle) is 125°, and the measured angles in simple alkylamines are close to that. The corresponding angle for sp² hybridization at nitrogen with a planar arrangement of bonds, as in amides, for example, is 180°. The measured value for this angle in aniline is 142.5°, suggesting a hybridization somewhat closer to sp³ than to sp². The structure of aniline reflects a compromise between two modes of binding the nitrogen lone pair (Figure 22.3).

FIGURE 22.3 Electrostatic potential maps of the aniline in which the geometry at nitrogen is (a) nonplanar and (b) planar.

The electrons are more strongly attracted to nitrogen when they are in an orbital with some s character—an sp³-hybridized orbital, for example— than when they are in a p orbital. On the other hand, delocalization of these electrons into the aromatic π system is better achieved if they occupy a p orbital. A p orbital of nitrogen is better aligned for overlap with the p orbitals of the benzene ring to forman extended π system than is an sp³-hybridized orbital. As a result of these two opposing forces, nitrogen adopts an orbital hybridization that is between sp³ and sp². The corresponding resonance description shows the delocalization of the nitrogen lone-pair electrons in terms of contributions from dipolar structures. In the nonplanar geometry, the unshared pair occupies an sp³ hybrid orbital of nitrogen. The region of highest electron density in (a) is associated with nitrogen. In the planar geometry, nitrogen is sp²-hybridized and the electron pair is delocalized between a p orbital of nitrogen and the π system of the ring. The region of highest electron density in (b) encompasses both the ring and nitrogen.

The actual structure combines features of both; nitrogen adopts a hybridization state between sp³ and sp².

The orbital and resonance models for bonding in arylamines are simply alternative ways of describing the same phenomenon. Delocalization of the nitrogen lone pair decreases the electron density at nitrogen while increasing it in the π system of the aromatic ring. We’ve already seen one chemical consequence of this in the high level of reactivity of aniline in electrophilic aromatic substitution reaction. Other ways in which electron delocalization affects the properties of arylamines are described in later sections of this chapter.

The derivatives of toluene are called toluidines:

NH2

CH3

NH2

CH3

NH2

CH3

CH2 NH2 NH CH3

о-Толуїдин м-Толуїдин п-Толуїдин Бензиламін N-Метиланілінo-toluidine m-toluidine p-toluidine benzylamine N-methylaniline

17. The methods of extraction of aromatic amines

I. Recovery of nitroarenes (Zinin reaction)

C6H5-NO2 + 2Fe + 4H2O C6H5-NH2 + 2Fe(OH)3

HCl

С6H5-NO2 + 3(NH4)2S C6H5-NH2 + 2H2O + 6NH3 + 3S

C6 H5 -NO2 C6 H5 -N=O C6 H5 -NH- OH C6 H5 -NH2

2 H, pH= 7 2H 2H

-H2 O -H2 O

Nitrozo-benzene

N-Phenylhydroxilaniline

II. Reaction of halogenarenes with ammonium and amines.

C6H5-Cl + 2NH3 C6H5-NH2

2000C, 0,6-1,0 МПа

-NH4Cl

Cl NH2

NH

+ Cu, t, p

+ HClCu, t, p

III. Alkylation of primary aromatic amines

NH2NH

CH3

NCH3

CH3

+ CH3Cl- HCl

CH3Cl

- HCl

CH3Cl

- HCl

18. Physical properties of aromatic aminesAromatic amines are colourless liquids or solids with peculiar smell. They can be oxidized by open air very easily. Aromatic amines are very toxic compounds. Hydrogen bonding significantly influences the properties of primary and secondary amines. Thus the boiling point of amines is higher than those of the corresponding phosphines, but generally lower than those of the corresponding alcohols. Thus methylamine and ethylamine are gases under standard conditions, whereas the corresponding methyl alcohol and ethyl alcohols are liquids. Gaseous amines possess a characteristic ammonia smell, liquid amines have a distinctive "fishy" smell. Also reflecting their ability to form hydrogen bonds, most aliphatic amines display some solubility in water. Solubility decreases with the increase in the number of carbon atoms. Aliphatic amines display significant solubility in organic solvents, especially polar organic solvents. Primary amines react with ketones such as acetone, and most amines are incompatible with chloroform and carbon tetrachloride. The aromatic amines, such as aniline, have their lone pair electrons conjugated into the benzene ring, thus their tendency to engage in hydrogen bonding is diminished. Their boiling points are high and their solubility in water low

4.Comparative structure of aromatic and aliphatic amines.

NH2СН3 СН2

....NH2

D 1,53 3,19

lC-N, нм 0,127 0,147

: NH2

:NH2

0,00

0,00

19. Chemical properties of aromatic amines 1. Reaction with acids

2. Alkylation

NH2 NH3+ HCl .. +

Cl

I CH2

NH2

HI+ CH3

NH

+

CH2 CH3

N-ethylaniline

3. Acylation (reaction with halogenanhydrides or anhydrides of carbon acids). In the result of this reaction acylderivatives are formed.

Acylderivatives are used as antipyretic means.

NH2 NH CH3

O

+ (CH3CO)2O

C

+ CH3COOH

OH NH CH3

O

C2H5O NH CH3

O

C C

парацетамол фенацетин paracetomol phenacethine

4. Qualitative reaction to primary aminogroup

The peculiar smell of C6H5CN is felt in the result of this reaction.

5. Reaction with HNO2. If primary, secondary and tertiary arylamines react with HNO2 different products can form.

a) primary arylamines

NH2 N

+ CHCl3 + 3KOHC2H5OH

C+

+ 3KCl + 3H2O

NH2

HNO2HCl

N N

Cl- 2H2O

+

+ +

b) secondary arylamines

c) tertiary arylamines

NH

diphenylamine

HNO2 N

NO

H2O+ +

N-nitrozodiphenylamine

6. Reaction with aromatic aldehyds - formation azomethans

(Schiff bases) - quality response.

7. Halogenation (white precipitate forms).

N-benzylidenaniline

NH2

3Br2H2O

NH2

BrBr

Br

3HBr++

8.Nitration reaction - reaction of transmitting, making protection of amino groups.

NH2 NH-COCH3 NH-COCH3

NO2

NH-COCH3

NO2NH2

NO2

NH2

NO2

(CH3CO)2O

- CH3COOH

HO-NO2

+

H2O, H+

- CH3COOH +

9. Oxidation

NH2

HNO3(concentrated)

NH2

NO2

H2OH2SO4(concentrated), t

+ +

NH2

O2

NH

O

H2O++

hinoniminhinonimin

NH2 NO

+ [O]H2SO5

NH2 NO2

+ [O]CF3COOOH

nitrozobenzene

nitrobenzene

10. Reaction with H2SO4

The product of this reaction is called sulphanilic acid.

N H 2 N H 3

N H - S O 3H

H

N H 2

S O 3H

conc. H 2 SO 4 HSO4t

t t

-H 2 O

-H 2 O

20. Sulphanilic acidSulphanilic acid has acidic (-SO3H) and alkaline (-

NH2) centers in its molecule. Sulphanilic acid is quite active acid. It easily forms salts with alkalis. But it does not react with mineral acids. Although it has alkaline (-NH2) group it does not have alkaline properties.

Sulphanilic acid is widely used in production of some medicines and dyes. It is the structural part of a large group of medicines which have antibacterial action. They are called sulphanylamides. The basic compound of all sulphanylamides is streptocide. It is amide of sulphanilic acid:

SO2NH2H2N

21. The synthesis of streptocideThe synthesis of streptocide consists of 4 stages:

1. Acylation

acetanilide 2. Sulphochloration

HNC

CH3

O

HOSO2Cl

HNC

CH3

O

SO2Cl

H2O+ +

p-chlorsulfonilacetanilidep-chlorsulfonilacetanilide

3. Amidation

4. Hydrolysis

HNC

CH3

O

SO2Cl

NH3

HNC

CH3

O

SO2NH2

HCl+ +

p-sulfamoilacetanilidep-sulfamoilacetanilide

HNC

CH3

O

SO2NH2

H2O

SO2NH2

NH2

CH3COOH++

streptocide

Streptocide has amphoteric properties:

NH2

SO2NH2

NH3

SO2NH2

NH2

SO2NH Nа

HCl

+

ClNаOH

+

22.Sulphanylamidic preparations Sulfanilamide is a molecule containing the sulfonamide functional group attached to an aniline. Sulfanilamide is a sulfonamide antibiotic. The sulfonamides are synthetic bacteriostatic antibiotics with a wide spectrum against most gram-positive and many gram-negative organisms. However, many strains of an individual species may be resistant. Sulfonamides inhibit multiplication of bacteria by acting as competitive inhibitors of p-aminobenzoic acid in the folic acid metabolism cycle. Bacterial sensitivity is the same for the various sulfonamides, and resistance to one sulfonamide indicates resistance to all. Most sulfonamides are readily absorbed orally. However, parenteral administration is difficult, since the soluble sulfonamide salts are highly alkaline and irritating to the tissues. The sulfonamides are widely distributed throughout all tissues. High levels are achieved in pleural, peritoneal, synovial, and ocular fluids. Although these drugs are no longer used to treat meningitis, CSF levels are high in meningeal infections. Their antibacterial action is inhibited by pus. Mechanism of action: Sulfanilamide is a competitive inhibitor of bacterial para-aminobenzoic acid (PABA), a substrate of the enzyme dihydropteroate synthetase. The inhibited reaction is necessary in these organisms for the synthesis of folic acid. Indication: For the treatment of vulvovaginitis caused by Candida albicans

Sulphanylamidic preparations. All sulphanylamidic

medicines contain the next fragment:

Albucyde (sulphacyl) – is an antibacterial mean, is a part of eye-drops.

Urosulphane – is an antibacterial mean by infection of urinal canals.

Norsulphazol – is used by pneumonia, meningitis, staphylococcal and streptococcal sepsis, infectious diseases.

Bucarbane – is a hypoglycemic mean.

NH2

O2SNH

CH3

O

NH2

O2SNH

NH2

O

S

N

NH2

O2SNH

NH2

O2SNH

NH

C4H9

O

C

Альбуцил,сульфацил

C

Уросульфан Норсульфазол

C

БукарбанAlbucyde Urosulphane Norsulphazol Bucarbane(sulphacyl)

23. Medicinal preparations (derivates of p-aminobenzoic

acid (pABA). NH2

COOC2H5

NH2

COO-CH2-CH2-N(C2H5)2

NH

COOH

CH3 CH3Анестезин Прокаїн (новокаїн) гідрохлорид

HCl.

Мефенамінова кислотаAnaesthesine procaine (novocaine) hydrochloride mefenaminic acid

Anaesthesine – is used as an 5-10% ointment or powder by wounds, urticaria or skin diseases which are characterized by itching.Procaine (novocaine) hydrochloride – is a local anaesthetic. Mefenaminic acid – is an anaesthetic substance, antiinflamed and antipyretic mean, is used by parodontosis.

4-Aminobenzoic acid (also known as para-aminobenzoic acid or PABA) is an organic compound with the molecular formula C7H7NO2. PABA is a white crystalline substance that is only slightly soluble in water. It consists of a benzene ring substituted with an amino group and a carboxyl group. PABA is an essential nutrient for some bacteria and is sometimes called Vitamin Bx. In humans, PABA is normally made by E. coli in the colon and therefore PABA from food is not normally essential to human health. PABA is therefore not officially classified as a vitamin. PABA is an intermediate in bacterial synthesis of folate. Although humans lack the ability to synthesize folate from PABA, that is also normally done by E. coli. PABA is sometimes marketed as an essential nutrient for use whenever normal PABA synthesis by intestinal bacteria is insufficient.

Medical use of 4-Aminobenzoic acid (also known as para-aminobenzoic acid or PABA)

The potassium salt is used as a drug against fibrotic skin disorders, such as Peyronie's disease, under the trade name Potaba. PABA is also occasionally used in pill form by sufferers of Irritable bowel syndrome to treat its associated gastrointestinal symptoms, and in nutritional epidemiological studies to assess the completeness of 24-hour urine collection for the determination of urinary sodium, potassium, or nitrogen levels.

24. DiazocompoundsDiazocompounds are organic compounds that contain NN-group which is connected with hydrocarbon radical and radical of mineral acid. The general formula of diazocompounds is:RN2X, where R – is a hydrocarbon radical X – is a radical of mineral acid (Cl−, Br−, NO3−, SO4H−, OH−, CN−, SO3H−, SH−.There are aliphatic and aromatic diazocompounds. But aromatic diazocompounds are more important for production of dyes and medicines, in pharmaceutical analysis. The general formula of aromatic diazocompounds is ArN2X, where Ar – is an aromatic radical X – is a radical of mineral acid (Cl−, Br−, NO3−, SO4H−, OH−, CN−, SO3H−, SH−.

In acid medium aromatic diazocompounds have ionic structure and they are called salts of diazonium (Ar–N+≡NX−). In neutral medium aromatic diazocompounds have covalent structure (Ar–N=N–X). In alkaline medium aromatic diazocompounds are diazotates.

N N OHАr - N Cl+ NаOH

Аr - N+

Аr - N = N - OHNаOH

Аr - N = N - O Nа+

кисле середовище

лужне середовищенейтральне середовище

арилдіазогідроксид арилдіазотат натрію

N N OHАr - N Cl+ NаOH

Аr - N+

Аr - N = N - OHNаOH

Аr - N = N - O Nа+

кисле середовище

лужне середовищенейтральне середовище

арилдіазогідроксид арилдіазотат натрію

acid medium neutral medium

alkaline medium

The systematic (IUPAC) name of aromatic diazocompounds is obtained by adding the suffix “-diazo-”or “-dizonium-” (in the case of salts of diazonium). For example:

Physical properties salts of diazonium Salts of diazonium are colorless crystalline substance,

easily soluble in water. They are unstable on heating and mechanical actions of explosion.That why decomposed in reactions usually use them freshly prepared aqueous solutions

Cl N = N - CN CH3 N N

С6H5 - N = N - OH С6H5 - N = N - O Nа+

бензолдіазогідроксид бензолдіазотат натрію

4-хлорбензолдіазоціанід 4-метилбензолдіазоній хлорид

+ benzenediazohydroxide sodium benzenediazotate

Cl N = N - CN CH3 N N

С6H5 - N = N - OH С6H5 - N = N - O Nа+

бензолдіазогідроксид бензолдіазотат натрію

4-хлорбензолдіазоціанід 4-метилбензолдіазоній хлорид

Cl+

4-chlorobenzenedizocyanide 4-methylbenzenediazonium chloride

25. The methods of extraction of aromatic diazocompounds

1. Reaction of diazotation

2. Reaction of aromatic amines with alkylnitrites

NC6H5 - NH2 + C2H5 -O-N=O + HCl С6H5 - N +

Cl + C2H5OH + H2O

NH2

R

N

R

NNаNO2, HCl excess Cl+

+ NаCl + H2O

Reaction mechanism of diazotationof diazotation :

HO - N=O + H H-O-N=O N = O + H2O+

H

+

+

C6H5 - NH2 + N=O +

C6H5 - N - N=O

H

H+

-H+

C6H5 - N - N=O..

H

NС6H5 - N = N - OH

benzendiazohydroxide

С6H5 - N +

Cl + H2O

26. Chemical properties of aromatic diazocompounds

I. Reaction with extraction of N2

NС6H5 - N +

Cl

CuCl, t C6H5Cl + N2SO2, CuCl, tC6H5SO2Cl + N2

CuBr, tC6H5Br + N2 + KCl

KCN, CuCN, tC6H5CN + N2 + KCl

CH2=CH -X + MeАn

C6H5 -CH2 - CH - X

Аn

+KBr

II. Reaction without extraction of N2 :

a) Formation of diazoderivativesC6H5–N≡N–Cl + 2NaOH → C6H5–N=N–ONa + NaCl + H2O

C6H5–N≡N–Cl + CH3–NH2 → C6H5–N=N–NH–CH3 + HCl

C6H5–N≡N–Cl + NaCN → C6H5–N=N–CN + NaCl

b) Reduction (catalysts are SnCl2 and HCl) [H]

C6H5–N≡N–Cl + 2SnCl2 + 4HCl → C6H5–NH– NH2∙HCl + 2SnCl4

c) Reaction of azojoining

III. Reactions of substitutionC6H5–N≡N–Cl + HOH → C6H5OH + N2 + HCl

C6H5–N≡N–Cl + KI → C6H5I + N2 + KCl

C6H5–N≡N–Cl + H3PO2 + HOH → C6H6 + N2 + HCl + H3PO3

+H+

NH2NN

Cl

HCl+N N NH2

4- aminoazobenzene4- aminoazobenzene

27.Azocompounds Azocompounds are organic compounds that contain -N=N-group which

is connected with 2 hydrocarbon radicals.

There are aliphatic and aromatic azocompounds.

Physical properties of azocompounds

Azocompounds are crystalline substances, colored in yellow, orange, red, blue and other colors. This feature allows you to use many of them as a means of chemotherapeutic means

N=N

OH

NH2

OH

N=N

4-amino-2-hydroxiazobenzene

1

2 3

41/

2/3/

4/

1 2

3

45

6

7

8

benzene-2-hydroxiazonaphtalene

28.The methods of extraction of aromatic azocompounds.

1. Formation of diazoderivatives

C6H5–N≡N–Cl + 2NaOH → C6H5–N=N–ONa + NaCl + H2O

C6H5–N≡N–Cl + CH3–NH2 → C6H5–N=N–NH–CH3 + HCl

C6H5–N≡N–Cl + NaCN → C6H5–N=N–CN + NaCl

2. Reduction nitroarenes in alkaline medium (reaction with Zn + NaOH) .

[H]

C6H5–NO2 ↔ C6H5–N=N–C6H5azobenzene

29. Chemical properties of aromatic azocompounds:

Chemical properties are specified by group –N=N–:

1.Reaction with mineral acids:C6H5–N=N–C6H5 + HCl ↔ C6H5–N+H=N–C6H5 + Cl¯

2. Oxidation (reaction with peroxiacids) [O]

C6H5–N=N–C6H5 ↔ C6H5–N+O ¯ =N–C6H5

3.Reduction (reaction with Zn + NaOH) [2H]

C6H5–N=N–C6H5 ↔ C6H5–NH–NH–C6H5

30. Physical bases of theory of colouration.The theory of colouration studies the dependence of colour of organic compounds on the structure of molecules. The colour of any compound is specified its ability to absorb electromagnetic radiation. Color or colour (see spelling differences) is the visual perceptual property corresponding in humans to the categories called red, yellow, blue and others. Color derives from the spectrum of light (distribution of light energy versus wavelength) interacting in the eye with the spectral sensitivities of the light receptors. Color categories and physical specifications of color are also associated with objects, materials, light sources, etc., based on their physical properties such as light absorption, reflection, or emission spectra.

Structural fragments of molecule which cause the certain colour are called chromophores. The main chromophores are the next groups:

–N=N––NO2

–N=OIn the structure of molecule there are groups which can amplify the colour of compound. They are called auxochromes. They are the next groups:

1)–OH 2) –NH2

3) –NHR 4) –NR2

5)–OR 6) –SH

The colors of the visible light spectrum

colorwavelength

intervalfrequency interval

red ~ 700–635 nm ~ 430–480 THz

orange ~ 635–590 nm ~ 480–510 THz

yellow ~ 590–560 nm ~ 510–540 THz

green ~ 560–490 nm ~ 540–610 THz

blue ~ 490–450 nm ~ 610–670 THz

violet ~ 450–400 nm ~ 670–750 THz

Color, wavelength, frequency and energy of light

Color λ/nm ν/1014 Hzνb/104 cm−1

E/eVE/kJ mol−1

Infrared >1000 <3.00 <1.00 <1.24 <120

Red 700 4.28 1.43 1.77 171

Orange 620 4.84 1.61 2.00 193

Yellow 580 5.17 1.72 2.14 206

Green 530 5.66 1.89 2.34 226

Blue 470 6.38 2.13 2.64 254

Violet 420 7.14 2.38 2.95 285

Near ultraviolet

300 10.0 3.33 4.15 400

Far ultraviolet

<200 >15.0 >5.00 >6.20 >598

In the 1969 study Basic Color Terms: Their Universality and Evolution, Brent Berlin and Paul Kay describe a pattern in naming "basic" colors (like "red" but not "red-orange" or "dark red" or "blood red", which are "shades" of red). All languages that have two "basic" color names distinguish dark/cool colors from bright/warm colors. The next colors to be distinguished are usually red and then yellow or green. All languages with six "basic" colors include black, white, red, green, blue and yellow. The pattern holds up to a set of twelve: black, grey, white, pink, red, orange, yellow, green, blue, purple, brown, and azure (distinct from blue in Russian and Italian but not English).

31.Azo dyesAzo dyes are dyes with -N=N- azo structure as a chromophore.

Methyl orange is a pH indicator frequently used in titrations. It is often chosen to be used in titrations because of its clear colour change. Because it changes colour at the pH of a mid-strength acid, it is usually used in titrations for acids. Unlike a universal indicator, methyl orange does not have a full spectrum of colour change, but has a sharper end point.

NSO3Na N N

CH3

CH3

methylorange

N N N

CH3

CH3

methylred

C

O

OH

In a solution becoming less acidic, methyl orange moves from red to orange and finally to yellow with the reverse occurring for a solution increasing in acidity. It should be noted that the entire colour change occurs in acidic conditions.

In an acid it is reddish and in alkali it is yellow.

Methyl red, also called C.I. Acid Red 2, is an indicator dye that turns red in acidic solutions. It is an azo-dye, and is a dark red crystalline powder. Methyl red is a pH indicator; it is red in pH under 4.4, yellow in pH over 6.2, and orange in between, with a pKa of approximately 5.

Preparation of methyl red

As an azo dye, methyl red may be prepared by diazotization of anthranilic acid, followed by reaction with dimethylaniline:

Methyl yellow, or C.I. 11020, is a chemical compound which may be used as a pH indicator.

In aqueous solution at low pH, methyl yellow appears red. Between pH 2.9 and 4.0, methyl yellow undergoes a transition, to become yellow above pH 4.0. Additional indicators are listed in the article on pH indicators. As "butter yellow" the agent had been used as a food additive before its toxicity was recognized.

Thank you for attention!