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


1
Alcohols. Phenols. Ethers.
Prepared by ass. Medvid I.I., ass. Burmas N. I.
2
  • Outline
  • 1. Classification of alcohols.
  • 2. Nomenclature of alcohols.
  • 3. Classification of monohydric alcohols
  • 4. Isomery of monohydroxyl alcohols
  • 5. Physical properties of monohydroxyl alcohols
  • 6. The methods of extraction of monohydroxyl
    alcohols
  • 7. Chemical properties of monohydroxyl alcohols
  • 8. Di-, tri- and polyhydroxyl alcohols
  • 9. Thioalcohols
  • 10. Ethers (simple ethers)
  • 11. Enols
  • 12. Aminoalcohols
  • 13. Some of the alcohols

3
  • 14. Mononuclear phenols
  • 15. The nomenclature and isomery of mononuclear
    phenols
  • 16. The methods of extraction of mononuclear
    phenols
  • 17. Physical properties of phenols
  • 18. Chemical properties of mononuclear phenols
  • 19. Usage of the chemical properties in the
    receiving of medical drugs
  • 20. Di-, tri- and polynuclear phenols
  • 21. Chemical properties of di-, tri- and
    polynuclear phenols
  • 22. The representatives of phenols
  • 23. Aminophenols
  • 24. Aromatic carboxylic acids

4
  • 1. Classification of alcohols.
  • All alcohols, ? principle, can be divided into
    two broad categories i.?. aliphatic alcohols and
    aromatic alcohols.
  • 1. Aliphatic alcohols. Alcohols in which the
    hydroxyl group is linked an aliphatic carbon
    chain are called aliphatic alcohols.
  • For example,
  • Methyl alcohol Ethyl alcohol
    Isopropyl alcohol
  • Methanol Ethanol
    2-Propanol

5
  • 2. Aromatic alcohols. Alcohols in which the
    hydroxyl group is present in the side chain of an
    aromatic hydrocarbon are called aromatic For
    example.
  • phenylmethanol
    2-phenylethanol
  • (benzyl alcohol)
    (?-phenylethyl alcohol)
  • Alcohols are further classified as monohydric,
    dihydric, trihydric and ??lyhidric according as
    their molecules contain one, two, three, or many
    hydroxyl groups respectively. For ???m?l?,
  • Ethyl alcohol 1,2-Ethanediol
    1,2,3-propanetriol
  • (Monohydric) (Dihydric)
    (Trihydric)

6
  • 2. Nomenclature of alcohols.
  • As with most other classes of organic compounds,
    alcohols can be named in several ways. Common
    names are useful only for the simpler members of
    ? class. However, common names are widely used in
    colloquial conversation and in the scientific
    literature. In order to communicate freely, the
    student must know common names. Since the
    systematic IUPAC names are often used for
    indexing the scientific literature, the student
    must be thoroughly familiar with systematic names
    in order to retrieve data from the literature.

7
  • ?he alkyl alcohol system. In this system of
    common nomenclature, the name of an alcohol is
    derived by combining the name of the alkyl group
    with the word alcohol. The names are mitten as
    two words.
  • n-butyl alcohol isobutyl
    alcohol t-butyl alcohol
  • II. In this common system, the position of an
    additional substituent is indicated by use of the
    Greek alphabet rather than by numbers.
  • ?-chloroethyl alcohol
    ?-bromobutyl alcohol

8
  • This use of the Greek alphabet is widespread in
    organic chemistry and it is important to learn
    the first few letters, at least through delta.
    Many of the letters, small and capital, have
    evolved standard meanings in the mathematical and
    physical sciences (for example, the number ?). In
    organic chemistry, the lower case letters are
    used more frequently than the capital letters.
  • The last letter of the Greek alphabet is omega,
    ?. Correspondingly, this letter is used to refer
    to difunctional compounds when the secondary
    substituent is on the end carbon of the chain.
  • Br(CH2)nOH ?-bromo alcohols

9
  • Any simple radical that has ? common name may be
    used in the alkyl alcohol system, with one
    important exception. The grouping ?6?5 - has the
    special name phenyl, but the compound C6H5OH is
    phenol, not phenyl alcohol.
  • phenol
  • Substituted phenols are named as derivatives of
    the parent compound phenol. The reason for this
    difference is historical and arose from the fact
    that phenol and its derivatives have many
    chemical properties that are very different from
    those of alkyl alcohols. However, phenyl
    substituted alkyl alcohols are normal alcohols
    and often have common names. Examples are
  • phenylmethanol
    2-phenylethanol
  • (benzyl alcohol)
    (?-phenylethyl alcohol)

10
  • III. The carbinol system. In this system, the
    simplest alcohol, ??3??, is called carbinol. More
    complex alcohols are named as alkyl substituted
    carbinols. The names are written as one word.
  • ethylmethylcarbinol triethylcarbinol
    methylphenilcarbinol
  • The number of carbons attached to the carbinol
    carbon distinguishes primary, secondary, and
    tertiary carbinols. As in the case of the alkyl
    halides, this classification is useful because
    the different types of alcohols show important
    differences in reactivity under given conditions.
    The carbinol system of nomenclature has been
    falling into disuse in recent years. However, it
    is found extensively in the older organic
    chemical literature.

11
  • IUPAC rules for naming alcohols that contain ?
    single hydroxyl group follow.
  • Rule 1 Name the longest carbon' chain to which
    the hydroxyl group is attached. The chain
    name is obtained by dropping the final -? from
    the alkane name and adding the suffix -ol.
    alkanols.
  • ??3?? - methanol ??3??2?? -
    ethanol
  • Rule 2 Number the chain starting at the end
    nearest the hydroxyl group, and use the
    appropriate number to indicate the position of
    the - ?? group. (In numbering of the longest
    carbon chain, the hydroxyl group has priority
    over double an triple bonds, as well as over
    alkyl, cycloalkyl, and halogen substituents.)
  • Rule 3 Name and locate any other substituents
    present.
  • Rule 4 In alcohols where the - ?? group is
    attached to ? carbon atom in ? ring, the
    hydroxyl group is assumed to be on carbon 1.
  • In the naming of alcohols with unsaturated
    carbon chains, two endings are needed one for
    the double or triple bond and one for the
    hydroxyl group. The -ol suffix always comes last
    in the name that is, unsaturated alcohols are
    named as alkenols or alkynols.

12
  • Polyhydroxy alcohols alcohols that possess
    more than one hydroxyl group - can be names with
    only ? slight modification of the preceding IUPAC
    rules. An alcohol in which two hydroxyl groups
    are present is named as ? diol, one containing
    three hydroxyl groups is named as ? triol, and so
    on. In these names for diols, triols, and so
    forth, the final ? of the parent alkane name is
    retained for pronunciation reasons.
  • 1,2-Ethanediol 1,2-propanediol
    1,2,3-propanetriol

13
  • 3. Classification of monohydric alcohols
    Monohydroxy alcohols are hydrocarbon derivatives
    which contain only one group OH connected with
    sp³-hybridizated carbon atom.
  • The general formula of monohydroxy alcohols is
  • The names of monohydroxy alcohols are the names
    of the same hydrocarbons with added prefix ol.





14



15
  • Classification of monohydric alcohols. As
    already mentioned, alcohols containing one ??
    group per molecule are called monohydric
    alcohols. These are further classified as primary
    (1'), secondary (2'), and tertiary (3') according
    as the ?? group is attached to primary, secondary
    and tertiary carbon atoms respectively. For
    example
  • Ethanol Isopropyl
    alcohol 2-Methylpropanane-2-ol
    Primary alcohol Secondary alcohol
    Tertiary alcohol

16
  • 4. Isomery of monohydroxyl alcohols
  • Monohydroxyl alcohols are characterized by
    structural, geometrical and optical isomery.
    Structural isomery depends on different structure
    of carbon chain and different locations of OH
    group.
  • For unsaturated monohydroxyl alcohols structural
    isomery depends on different locations of double
    bond too.

17
  • Only unsaturated monohydroxyl alcohols are
    characterized by geometrical isomery.
  • Optical isomery is characteristic for alcohols
    which have asymmetric carbon atom in their
    structure.

18
  • 5. Physical properties of monohydroxyl alcohols
  • Saturated alcohols are colourless liquids and
    crystal solids with peculiar smell. The smallest
    representatives of homological row have smell of
    alcohol, but higher representatives have good
    smell. The lower alcohols e liquids with
    characteristic odors and sharp tastes. One
    striking feature is their relatively high boiling
    points. The ?? group is roughly equivalent to ?
    methyl group in approximate size and
    polarization, but alcohols have much higher
    boiling points than the corresponding
    hydrocarbons for example, compare ethanol (mol.
    wt. 46, b.?.78.50) and propane (mol. wt. 44, b.?.
    - 420). The abnormally high boiling points of
    alcohols are the result of ? special type of
    dipolar association in the liquid phase. Both the
    ? - ? and the ? - ? bonds are polar because of
    the different electronegativities of carbon,
    oxygen, and hydrogen. These polar bonds
    contribute to the substantial dipole moments.

19
  • However, the dipole moments of alcohols are no
    greater than those of corresponding chlorides.
  • ??3??, ? 1.71 D ??3?l, ?
    194 D
  • ??3??3??, ? 1.70 D ??3??2?l, ?
    2.04 D
  • For alcohols the negative end of the dipole is
    out at the oxygen lone pairs, and the positive
    end is close to the small hydrogen. For hydrogen
    atoms bonded to electronegative elements
    dipole-dipole interaction is uniquely important
    and is called ? hydrogen bond. This proximity of
    approach is shown by bond distance data. The O
    ? bond length in alcohols is 0.96 ?. The hydrogen
    bonded ?. . .O distance is 2.07 ?, about twice as
    large. In fact, this distance is sufficiently
    small that some hydrogen bonds may have ?
    significant amount of covalent or shared electron
    character.

20
  • Methanol and ethanol are reasonably good
    solvents for salt-like compounds. Because they
    are also good solvents for organic compounds,
    they are used frequently for organic reactions
    such as SN2 displacement reactions.
  • The ?? group of alcohols can participate in the
    hydrogen bond network of water. The lower
    alcohols are completely soluble in water. As the
    hydrocarbon chain gets larger, the compound
    begins to look more like an alkane, and more of
    the hydrogen bonds in water must be broken to
    make room for the hydrocarbon chain. Since the
    hydrogen bonds that are lost are not completely
    compensated by bonding to the alcohol ??,
    solubility decreases as the hydrocarbon chain
    gets larger. ? rough point of division is four
    carbons to one oxygen. Above this ratio, alcohols
    tend to have little solubility in water. This
    guideline is only approximate because the shape
    of the hydrocarbon portion is also important.
    t-Butyl alcohol is much more soluble than ?-butyl
    alcohol because the t-butyl group is more compact
    and requires less room or broken water hydrogen
    bonds in an aqueous solution. ? similar
    phenomenon is seen with the branched pentyl
    alcohols.

21
  • 6. The methods of extraction of monohydroxyl
    alcohols
  • Alcohols can be obtained from many other classes
    of compounds. Preparations from alkyl halides and
    from hydrocarbons will be discussed in this
    section. The following important ways of
    pr???ring alcohols will be discussed later, as
    reactions of the appropriate functional groups.
  • Hydrolysis of halogenderivatives of hydrocarbons
    by heating
  • CH3-CH2-Cl NaOH ? CH3-CH2-OH NaCl
  • 2. Hydrogenation of alkenes. This reaction runs
    by Markovnikov rule.

22
  • 3. Reduction of carbonyl compounds (aldehydes,
    ketones, carboxylic acids, complex ethers)

23
  • 7. Chemical properties of monohydroxyl alcohols
  • Alcohols are classified as primary (1'),
    secondary (2'), or tertiary (3'), depending on
    the number of carbon atoms bonded to the carbon
    atom that bears the hydroxyl group. ? primary
    alcohol is an alcohol in which the
    hydroxyl-bearing carbon atom is attached to only
    one other carbon atom. ? secondary alcohol is an
    alcohol in which the hydroxyl-bearing carbon atom
    is attached to two other carbon atoms. ? tertiary
    alcohol is an alcohol in which the
    hydroxyl-bearing carbon atom is attached to three
    other carbon atoms. Chemical reactions of
    alcohols often depend on alcohol class (1', 2',
    or 3').
  • In general, alcohols (1', 2', and 3') are very
    flammable substances that, when burned, produce
    carbon dioxide and water. Additional important
    reactions of alcohols besides combustion include
  • 1. Intramolecular dehydration to produce alkenes
  • 2. Intermolecular dehydration to produce an ether
  • 3. Oxidation to produce aldehydes, ketones, and
    carboxylic acids
  • 4. Substitution reactions to produce alkyl halides

24
  • 1. Alcohols have weak acidic and weak alkaline
    properties. They can react with alkaline metals
    like acids and form alkoxides
  • 2CH3CH2OH 2Na ? 2CH3CH2ONa H2?
  • 2CH3CH2ONa H2O ? CH3CH2OH NaOH
  • 2. Alcohols can react with mineral and organic
    acids (complex ethers form) like alkalis
  • CH3CH2OH HONO2 ? CH3CH2ONO2 HOH
  • 3. Dehydration of alcohols. There are 2 types of
    dehydration
  • a) Dehydration between 2 molecules

25
  • b) Dehydration in the molecule (intramolecular
    dehydration)
  • 4. Reaction with HI, HCl, HBr
  • CH3CH2OH HI ? CH3CH2I H2O
  • 5. Oxidation

26
  • Primary and secondary alcohols readily undergo
    oxidation in the presence of mild oxidizing
    agents to produce compounds that contain ? carbon
    oxygen double bond (aldehydes, ketones, and
    carboxylic acids). ? number of different
    oxidizing agents can be used for the oxidation,
    including potassium permanganate (??nO4),
    potassium dichromate (?2?r2?7), and chromic acid
    (H2CrO4). The net effect of the action of ? mild
    oxidizing agent on ? primary or secondary alcohol
    is the removal of two hydrogen atoms from the
    alcohol. One hydrogen comes from the - ?? group,
    the other from the carbon atom to which the -??
    group is attached. This ? removal generates ?
    carbon oxygen double bond. The two "removed"
    hydrogen atoms combine with oxygen supplied by
    the oxidizing agent to give H2O.

27
  • Primary alcohol aldehyde carboxylic acid
  • Secondary alcohol ketone
  • Tertiary alcohol no reaction
  • The general reaction for the oxidation of ?
    primary alcohol is
  • Alcohol Aldehyde
    Carboxylic acid
  • In this equation, the symbol O represents the
    mild oxidizing agent. The immediate product of
    the oxidation of ? primary alcohol is an
    aldehyde. Because aldehydes themselves are
    readily oxidized by the same oxidizing agents
    that oxidize alcohols, aldehydes are further
    converted to carboxylic acids. ? specific example
    of ? primary alcohol oxidation reaction is

28
  • The three classes of alcohols behave
    differently toward mild oxidizing agents. The
    general reaction for the oxidation of ? secondary
    alcohol is
  • As with primary alcohols, oxidation involves
    the removal of two hydrogen atoms. Unlike
    aldehydes, ketones are resistant to further
    oxidation. ? specific example of the oxidation of
    ? secondary alcohol is

Alcohol Ketone
29
  • Tertiary alcohols do not undergo oxidation with
    mild oxidizing agents. This is because they do
    not have hydrogen on the -??-bearing carbon atom.
  • To determine any alcohol (which contain
    fragment in the mixture of compounds
    it is needed to use iodoform test. As the result
    yellow precipitate forms.

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  • 8. Di-, tri- and polyhydroxyl alcohols
  • Dihydroxyl alcohols contain two groups OH in
    the molecule. They are called diols. There are
    several types of diols.
  • 1. a-diols (groups OH are situated near
    neighboring carbon atoms in 1,2-locations)
  • 2. ß-diols (groups OH are situated in
    1,3-locations)
  • 3. ?-diols (groups OH are situated in
    1,4-locations) etc.

35
  • Trihydroxyl alcohols contain three groups OH in
    the molecule. They are called triols. The
    representative is glycerine

36
  • preparation of di-, tri- and polyhydroxyl
    alcohols
  • 1. Much of the chemistry of diolscompounds that
    bear two hydroxyl groupsis analogous to that of
    alcohols. Diols may be prepared, for example,
    from compounds that contain two carbonyl groups,
    using the same reducing agents employed in the
    preparation of alcohols. The following example
    shows the conversion of a dialdehyde to a diol by
    catalytic hydrogenation. Alternatively, the same
    transformation can be achieved by reduction with
    sodium borohydride or lithium aluminum hydride.

37
  • 2. Since osmium tetraoxide is regenerated in this
    step, alkenes can be converted to vicinal diols
    using only catalytic amounts of osmium
    tetraoxide, which is both toxic and expensive.
    The entire process is performed in a single
    operation by simply allowing a solution of the
    alkene and tert-butyl hydroperoxide in tert-butyl
    alcohol containing a small amount of osmium
    tetraoxide and base to stand for several hours.

38
  • Overall, the reaction leads to addition of two
    hydroxyl groups to the double bond and is
    referred to as hydroxylation. Both oxygens of the
    diol come from osmium tetraoxide via the cyclic
    osmate ester. The reaction of OsO4 with the
    alkene is a syn addition, and the conversion of
    the cyclic osmate to the diol involves cleavage
    of the bonds between oxygen and osmium. Thus,
    both hydroxyl groups of the diol become attached
    to the same face of the double bond syn
    hydroxylation of the alkene is observed.
  • 3. To extract glycerine it is necessary to use
    next reaction

39
  • b) Chemical properties of di-, tri- and
    polihydroxyl alcohols
  • Reaction with alkaline metals
  • 2. Reaction with Cu(OH)2

40
  • 3. Reaction with HI, HCl, HBr
  • 4. Formation of simple and complex ethers
    (reaction with monohydroxy alcohols and organic
    acids)

41
5. Reaction with mineral acids
42
  • 6. Oxidation by KMnO4
  • 7. Dehydration

43
  • 8. Polycondensation
  • 9. Diols react intramolecularly to form cyclic
    ethers when a five-membered or sixmembered ring
    can result.

44
  • 9. Thioalcohols
  • Thioalcohols are compounds which contain
    aliphatic (CnH2n1) and mercaptane (-SH) groups.
    Thiols are given substitutive IUPAC names by
    appending the suffix -thiol to the name of the
    corresponding alkane, numbering the chain in the
    direction that gives the lower locant to the
    carbon that bears the -SH group.
  • The preparation of thiols involves nucleophilic
    substitution of the SN2 type on alkylhalides and
    uses the reagent thiourea as the source of
    sulfur. Reaction of the alkyl halide with
    thiourea gives a compound known as an
    isothiouronium salt in the first step. Hydrolysis
    of the isothiouronium salt in base gives the
    desired thiol (along with urea)

45
Both steps can be carried out sequentially
without isolating the isothiouronium salt.
46
  • To extract thioalcohols it is necessary to use
    next reactions
  • 1. C2H5Cl NaSH ? C2H5SH NaCl
  • 2. C2H5OH Na2S ? C2H5SH H2O
  • Physical properties of thiols
  • When one encounters a thiol for the first
    time, especially a low-molecular-weight thiol,
    its most obvious property is its foul odor.
    Ethanethiol is added to natural gas so that leaks
    can be detected without special equipmentyour
    nose is so sensitive that it can detect less than
    one part of ethanethiol in 10,000,000,000 parts
    of air! The odor of thiols weakens with the
    number of carbons, because both the volatility
    and the sulfur content decrease. 1-Dodecanethiol,
    for example, has only a faint odor. The S-H bond
    is less polar than the O-H bond, and hydrogen
    bonding in thiols is much weaker than that of
    alcohols. Thus, methanethiol (CH3SH) is a gas at
    room temperature (bp 6C), and methanol (CH3OH)
    is a liquid (bp 65C).

47
  • Chemical properties of thiols
  • Thiols can react with ions of alkaline and heavy
    metals (this property of thiols is used in
    medicine at the poisoning by heavy metals)
  • C2H5SH NaOH ? C2H5S-Na H2O
  • 2C2H5SH Hg² ? (C2H5S)2Hg 2H
  • 2. They can react with alkenes (peroxides are
    catalysts)
  • 3. Reaction with organic acids

48
  • 4. Oxidation

49
  • 10. Ethers (simple ethers)
  • The general formula of simple ethers is
  • R-O-R1
  • The radicals can be similar or different.
  • Ethers are named, in substitutive IUPAC
    nomenclature, as alkoxy derivatives of alkanes.
    Functional class IUPAC names of ethers are
    derived by listing the two alkyl groups in the
    general structure ROR1 in alphabetical order as
    separate words, and then adding the word ether
    at the end. When both alkyl groups are the same,
    the prefix di- precedes the name of the alkyl
    group.

50
  • Physical properties of ethers
  • It is instructive to compare the physical
    properties of ethers with alkanes and alcohols.
    With respect to boiling point, ethers resemble
    alkanes more than alcohols. With respect to
    solubility in water the reverse is true ethers
    resemble alcohols more than alkanes.
  • In general, the boiling points of alcohols are
    unusually high because of hydrogen bonding .
    Attractive forces in the liquid phases of ethers
    and alkanes, which lack - OH groups and cannot
    form intermolecular hydrogen bonds, are much
    weaker, and their boiling points lower. These
    attractive forces cause ethers to dissolve in
    water to approximately the same extent as
    comparably constituted alcohols. Alkanes cannot
    engage in hydrogen bonding to water.

51
  • The methods of extraction of ethers
  • From alkoxides
  • CH3CH2ONa CH3I ? CH3CH2OCH3 NaI
  • 2. Dehydration of alcohols (dehydration between 2
    molecules)

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  • Chemical properties of ethers
  • Reaction with concentrated mineral acids
    (formation of oxonium salts)
  • A second dangerous property of ethers is the ease
    with which they undergo oxidation in air to form
    explosive peroxides. Air oxidation of diethyl
    ether proceeds according to the equation

54
  • The reaction follows a free-radical mechanism
    and gives a hydroperoxide, a compound of the type
    ROOH. Hydroperoxides tend to be unstable and
    shock-sensitive. On standing, they form related
    peroxidic derivatives, which are also prone to
    violent decomposition. Air oxidation leads to
    peroxides within a few days if ethers are even
    briefly exposed to atmospheric oxygen. For this
    reason, one should never use old bottles of
    dialkyl ethers, and extreme care must be
    exercised in their disposal.
  • 3. Reaction with HI
  • CH3-O-CH3 HI ? CH3-OH CH3I

55
  • The mechanism for the cleavage of ethers by
    hydrogen halides, using the reaction of diethyl
    ether with hydrogen bromide as an example.
  • Step 1 Proton transfer to the oxygen of the
    ether to give a dialkyloxonium ion.

56
  • Step 2 Nucleophilic attack of the halide anion
    on carbon of the dialkyloxonium ion. This step
    gives one molecule of an alkyl halide and one
    molecule of an alcohol.
  • Step 3 and Step 4 These two steps do not involve
    an ether at all. They correspond to those in
    which an alcohol is converted to an alkyl
    halide .

57
  • 11. Enols
  • 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 compounds (such as ketones and
    aldehydes) are in fact isomers this is called
    keto-enol tautomerism
  • The enol form is shown above on the left. It is
    usually unstable, does not survive long, and
    changes into the keto (ketone) form shown on the
    right. This is because oxygen is more
    electronegative than carbon and thus forms
    stronger multiple bonds. Hence, a carbon-oxygen
    (carbonyl) double bond is more than twice as
    strong as a carbon-oxygen single bond, but a
    carbon-carbon double bond is weaker than two
    carbon-carbon single bonds.

58
  • The name of enols systematic nomenclature IUPAC
    form the name alkene to which is added the
    suffix-ol
  • CH2CH-OH CH2CH-CH2-OH
  • ethenol, vinyl alcohol
    Propenol-1(unsaturated alcohol)
  • Hydration of acetylene as the intermediate
    substance is formed vinyl alcohol (enol), which
    isomerization in acetic aldehyde.
  • H2O,Hg²,H
  • C2H2 CH2CH-OH
  • This property of enols characterizes the rule of
    Eltekov-Erlenmeyer. - Compounds in which the
    hydroxyl group located at carbon atoms that forms
    a fold communication, unstable and isomerization
    of carbonyl compounds - aldehydes and ketones

59
  • Unlike enols, and their simples and composites
    esters are stable. They do not contain the
    rolling of the hydrogen atom and under normal
    conditions do not form carbonyl compounds. Yes,
    there are esters of vinyl alcohols, such as vinyl
    acetate, a which produce the reaction of acetic
    acid to join acetylene.
  • CH3-COOH C2H2 CH3-C(O)-O-CHCH2

60
  • 12. Aminoalcohols
  • Amino alcohols are organic compounds that
    contain both an amine functional group and an
    alcohol functional group.
  • NH2-CH2-CH2-OH N(C2H5)-CH2-CH2-OH
  • 2-aminoethanol 2-N,N-
    diethylaminoethanol
  • If the molecule of amino alcohol contains the
    in its composition two or three hydroxyalkylnes
    groups, through the combination of nitrogen atom,
    in this case, the basis takes the name amine.
  • OH-CH2-CH2-NH-CH2-CH2-OH
  • di (ß-oxyethyl) amine, or di
    (2-hydroxyethyl) amine

61
  • The methods of extraction of aminoalcohols
  • Accession of ammonia or amines to the a-oxyses.
  • CH2-CH2 NH3 NH2-CH2-CH2-OH
  • O
  • 2. Reduction of nithroarenes.
  • CH3-CH(NO2)-CH2-OH 3H2
    CH3-CH(NH3)-CH2-OH 2H2O
  • Chemical properties of aminoalcohols
  • Aminoalcohols show properties as alcohols and
    amines. As a basis aminoalcohols form salts with
    mineral acids.
  • OH-CH2-CH2-NH2 HCl OH-CH2-CH2-NH3Cl

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  • Ethanolamine, also called 2-aminoethanol or
    monoethanolamine (often abbreviated as ETA or
    MEA), is an organic chemical compound that is
    both a primary amine (due to an amino group in
    its molecule) and a primary alcohol (due to a
    hydroxyl group). Like other amines,
    monoethanolamine acts as a weak base.
  • Monoethanolamine is produced by reacting
    ethylene oxide with aqueous ammonia the reaction
    also produces diethanolamine and triethanolamine.
    The ratio of the products can be controlled by
    changing the stoichiometry of the reactants.

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  • 13. Some of the
    alcohols
  • Methyl alcohol (Methanol). Methyl alcohol, with
    one carbon atom and one ?? group, is the
    simplest alcohol. This colorless liquid is ? good
    fuel for internal combustion engines. Since 1965
    all racing cars at the Indianapolis Speedway have
    been fueled with methyl alcohol. (Methyl alcohol
    fires are easier to put out than gasoline fires,
    because water mixes with and dilutes methyl
    alcohol.) Methyl alcohol also has excellent
    solvent properties, and it is the solvent of
    choice for paints, shellacs, and varnishes.
    Methyl alcohol is sometimes called wood alcohol,
    terminology that draws attention to an early
    method for its preparation the heating of wood
    to ? high temperature in the absence of air.
    Today, almost all methyl alcohol is produced via
    the reaction between H2 and ??. Drinking methyl
    alcohol is dangerous. Within the human body,
    methyl alcohol is oxidized by the liver enzyme
    alcohol dehydrogenase to the toxic metabolites
    formaldehyde and formic acid. Formaldehyde is
    toxic to the eyes and can cause blindness
    (temporary or permanent). Formic acid causes
    acidosis. Ingesting as little as 1 oz (30 ml.) of
    methyl alcohol can cause optic nerve damage.

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  • Ethyl alcohol (Ethanol), the two-carbon
    monohydroxy alcohol, is the alcohol present in
    alcoholic beverages and is commonly referred to
    as simply alcohol or drinking alcohol. Like
    methyl alcohol, ethyl alcohol is oxidized in the
    human body by the liver enzyme alcohol
    dehydrogenase. Acetaldehyde, the first oxidation
    product, is largely responsible for the symptoms
    of hangover. The odors of both acetaldehyde and
    acetic acid are detected on the breath of someone
    who has consumed ? large amount of alcohol. Ethyl
    alcohol oxidation products are less toxic than
    these of methyl alcohol. Long-term excessive use
    of ethyl alcohol may cause undesirable effects
    such as cirrhosis of the liver, loss of memory,
    and strong physiological addiction. Links have
    also been established between certain birth
    defects and the ingestion of ethyl alcohol by
    women during pregnancy (fetal alcohol syndrome).
    Ethyl alcohol can be produced by yeast
    fermentation of sugars found in plant extracts.
    The synthesis of ethyl alcohol in this manner,
    from grains such as corn, rice, and barley, is
    the reason why ethyl alcohol is often called
    grain alcohol. Denatured alcohol is ethyl alcohol
    that has been rendered unfit to drink by the
    addition of small amounts of toxic substances
    (denaturing agents). Almost all of the ethyl
    alcohol used for industrial purposes is denatured
    alcohol. Most ethyl alcohol used in industry is
    prepared from ethene via ? hydration reaction The
    reaction produces ? product that is 95 alcohol
    and 5 water. In applications where water does
    interfere with use, the mixture is treated with ?
    dehydrating agent to produce 100 ethyl alcohol.
    Such alcohol, with all traces of water removed,
    is called absolute alcohol.

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  • Isopropyl alcohol (2-propanol) is one of two
    three-carbon monohydroxy alcohols the other is
    propyl alcohol. ? 70 isopropyl alcohol 30
    water solution marketed as rubbing alcohol.
    Isopropyl alcohol's rapid evaporation rate
    creates ? dramatic cooling effect when it is
    applied to the skin, hence its use for alcohol
    rubs to combat high body temperature. Isopropyl
    alcohol has ? bitter taste. Its toxicity is twice
    that of ethyl alcohol but causes few fatalities
    because it often induces vomiting and thus doesn'
    t stay down long enough to kill you. In the body
    it is oxidized to acetone. Large amounts, about
    150 mL, of ingested isopropyl alcohol can be
    fatal death occurs from paralysis of the central
    nervous system.

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  • Ethylene glycol (1,2-ethanediol) and propylene
    glycol (1,2-propanediol) are the two simplest
    alcohols possessing two ?? groups. Besides
    being diols, they are also classified as glycols.
    ? glycol is ? diol in which the two - ?? groups
    are on adjacent carbon atoms. Both of these
    glycols are colorless, odorless, high-boiling
    liquids that are completely miscible with water.
    Their major uses are as the main ingredient in
    automobile "year-round" antifreeze and airplane
    "de-icers" and as ? starting material for the
    manufacture of polyester fibers. Ethylene glycol
    is extremely toxic when ingested. In the body,
    liver enzymes oxidize it to oxalic acid. Oxalic
    acid, as ? calcium salt, crystallizes in the
    kidneys, which leads to renal problems. On the
    other hand, propylene glycol is essentially
    nontoxic and has been used as ? solvent for
    drugs. Like ethylene glycol, it is oxidized by
    liver enzymes however, pyruvic acid, its
    oxidation product, is ? compound normally found
    in the human body, being an intermediate in
    carbohydrate metabolism.
  • Glycerol (1,2,3-propanetriol) is ? clear, thick
    liquid that has the consistency of honey. Its
    molecular structure involves three ?? groups on
    three different carbon atoms.

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  • 14. Mononuclear phenols
  • Phenols are compounds that have a hydroxyl group
    bonded directly to a benzene or benzenoid ring.
    The parent compound of this group, C6H5OH, called
    simply phenol, is an important industrial
    chemical. Many of the properties of phenols are
    analogous to those of alcohols, but this
    similarity is something of an oversimplification.
    Like arylamines, phenols are difunctional
    compounds the hydroxyl group and the aromatic
    ring interact strongly, affecting each others
    reactivity. This interaction leads to some novel
    and useful properties of phenols.

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  • 15. The nomenclature and isomery of mononuclear
    phenols
  • Numbering of the ring begins at the
    hydroxyl-substituted carbon and proceeds in the
    direction that gives the lower number to the next
    substituted carbon. Substituents are cited in
    alphabetical order.

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

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  • 16. The methods of extraction of monohydric
    phenols
  • 1.Natural sources (from coal tar)
  • 2. The synthesis from arenes

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  • 3. Cumol (isopropyl toluene) synthesis
  • 4. The extraction from diazonium salts
  • 5. The substitution of halogen atom to OH group

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  • 17. Physical properties of phenols
  • All phenols have peculiar smell. They are
    colorless compounds but oxygen from the air can
    cause brown colour of phenols (oxidation). They
    solve in water badly. The physical properties of
    phenols are strongly influenced by the hydroxyl
    group, which permits phenols to form hydrogen
    bonds with other phenol molecules and with water
    . Thus, phenols have higher melting points and
    boiling points and are more soluble in water than
    arenes and aryl halides of comparable molecular
    weight. Table 24.1 compares phenol, toluene, and
    fluorobenzene with regard to these physical
    properties. Some ortho-substituted phenols, such
    as o-nitrophenol, have significantly lower
    boiling points than those of the meta and
    para-isomers. This is because the intramolecular
    hydrogen bond that forms between the hydroxyl
    group and the substituent partially compensates
    for the energy required to go from the liquid
    state to the vapor. Electron delocalization in
    phenoxide is represented by resonance among the
    structures

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  • 18. Chemical properties of mononuclear phenols
  • 1. Acidic properties
  • C6H5-OH NaOH ? C6H5-ONa H2O
  • C6H5-ONa H2O ? C6H5-OH NaOH

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  • 2. Forming of simple and complex ethers
  • C6H5-ONa C2H5-Br ? C6H5-O-C2H5 NaBr
  • ethylphenyl ether
  • C6H5-ONa CH3-COCl ? C6H5-O-CO-CH3 NaCl
    phenylacetate
  • 3. Halogenations. (The reaction that underlies
    qualitative and quantitative analysis of phenol
    and its derivatives)

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  • 4. Nitrating
  • 5. Sulphating

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  • 6. Alkylation and acylation (the catalysts are
    H2SO4, H3PO4, BF3

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  • 7. Azoaccession
  • 8. The synthesis of phenolocarboxylic acids
  • 9. To determine mono-, di-, tri- and polynuclear
    phenols it is necessary to do the reaction with
    FeCl3. As the result of this reaction color
    complex compounds form.

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  • The coloration of phenols in reaction with FeCl3

Name of phenol Color products of reaction with FeCl3
pyrocatechol green color
resorcinol blue color
hydroquinone green color that turns to yellow color
pyrogallol red color
phloroglucinol dark violet color
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  • 10. Oxidation of phenols. Quinones.
  • Phenols are more easily oxidized than
    alcohols, and a large number of inorganic
    oxidizing agents have been used for this purpose.
    The phenol oxidations that are of the most use to
    the organic chemist are those involving
    derivatives of 1,2-benzenediol (pyrocatechol) and
    1,4-benzenediol (hydroquinone). Oxidation of
    compounds of this type with silver oxide or with
    chromic acid yields conjugated dicarbonyl
    compounds called quinones.

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  • Quinones are compounds having a fully conjugated
    cyclic dione structure, such as that of
    benzoquinones, derived from aromatic compounds by
    conversion of an even number of CH groups into
    C(O) groups with any necessary rearrangement
    of double bonds (polycyclic and heterocyclic
    analogues are included). Benzoquinone, sometimes
    referred to simply as "quinone", is either of the
    two isomers of cyclohexadienedione. These
    compounds have the molecular formula C6H4O2.
    Orthobenzoquinone is the 1,2-dione, whereas
    parabenzoquinone is the 1,4-dione.
    Orthobenzoquinone is the oxidized form of
    catechol (1,2-dihydroxybenzene), while
    parabenzoquinone is the oxidized form of
    hydroquinone. An acidic potassium iodide solution
    reduces a solution of benzoquinone to
    hydroquinone, which is oxidized back with a
    solution of silver nitrate.

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  • 19. Usage of the chemical properties in the
    receiving of medical drugs
  • ?) Synthesis of thymol

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  • B) Synthesis of paracetamol (pyretic and
    analgesic means)
  • C) Synthesis of phenethidine and phenacetine
    (pyretic and anti-neuralgic means)

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  • 20. Di-, tri- and polynuclear phenols

O
H
O
H
O
H
O
H
O
H
O
H
O
H
O
H
pyrogallol
O
H
phloroglucinol
hydroxyhydroquinone
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  • 21. Chemical properties of di-, tri- and
    polynuclear phenols
  • Chemical properties of di-, tri- and polynuclear
    phenols are similar to chemical properties of
    mononuclear phenols. But they have some
    peculiarities.
  • 1. Acidic properties of polynuclear phenols
    are stronger than acidic properties of
    mononuclear phenols. Polynuclear phenols can
    react with alkaline and heavy metals

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

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  • 22. The representatives of phenols

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.
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a-naphtol. Yellowish crystals. It is used in the
manufacture of dyes, medicines.
ß-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).
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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.
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  • 23. Aminophenols
  • Aminophenols are aromatic compounds that contain
    phenyl radical, -OH group and aminogroup. There
    are o-, m- and p-aminophenols.

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  • The methods of extraction of aminophenols
  • The reduction of nitrophenols
  • Reaction of dihydroxic phenols with ammonium
  • The reduction of nitrobenzene

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  • Chemical properties aminophenols have properties
    of phenols and aromatic amines.
  • The derivatives of aminophenols are medical
    preparations

It is antipyretic, anti-inflammatory mean. It is
used for the treatment of headache, toothache,
high temperature.
It is antipyretic and antineuralgic mean
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  • 24. Aromatic carboxylic acids
  • Aromatic carboxylic acids are the derivatives of
    hydrocarbons that contain carboxyl group (-COOH)
    and benzyl radical.

2
2
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  • The key compound in the synthesis of aspirin,
    salicylic acid, is prepared from phenol by a
    process discovered in the nineteenth century by
    the German chemist Hermann Kolbe. In the Kolbe
    synthesis, also known as the KolbeSchmitt
    reaction, sodium phenoxide is heated with carbon
    dioxide under pressure, and the reaction mixture
    is subsequently acidified to yield salicylic acid

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  • 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 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 a compound that is
    chemically similar to but not identical to the
    active 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 known as salicylates.
  • 4-Aminosalicylic acid, commonly known as PAS,
    is an antibiotic used to treatment of
    tuberculosis.

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  • The best known aryl ester is O-acetylsalicylic
    acid, better known as aspirin. It is prepared by
    acetylation of the phenolic hydroxyl group of
    salicylic acid
  • Aspirin possesses a number of properties that
    make it an often-recommended drug. It is an
    analgesic, effective in relieving headache pain.
    It is also an antiinflammatory agent, providing
    some relief from the swelling associated with
    arthritis and minor injuries. Aspirin is an
    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
    300 tablets per year for every man, woman, and
    child.

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