Org 2
Org 2
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2
                            2.1 Alkanes
• IUPAC Conventions
• Alkanes (CnH2n+2 )
• Saturated hydrocarbons.
                                                               3
                         The alkanes
•   1 carbon = ―meth‖
•   2 carbons =―eth‖
•   3carbons = ―prop‖
•   4carbons = ―but‖
•   5 carbons = ―pent‖
•   6 carbons = ―hex‖
•   7 carbons = ―hept‖
•   8 carbons = ―oct‖
•   9 carbons = ―non‖
•   10 carbons = ―dec‖
                                       4
               Common alkyl groups
CH3                     CH3 CH2 CH2 CH2          CH3 CH CH2
      Methyl                Butyl
                                                    CH3
Ethyl (2-Methylpropyl)
                                                     CH3
CH3 CH2 CH2
                         CH3 CH2 CH              CH3 C
    Propyl
                                    CH3              CH3
CH3 CH
                              sec-Butyl              tert-Butyl
      CH3                     (1-Methylpropyl)       (1,1-Dimethylethyl)
      Isopropyl
      (1-Methylethyl)
                                                                           5
                             Cont…
 The name of every organic molecule has 3 parts:
   1. The parent name indicates the number of carbons in the
      longest continuous chain.
   2. The suffix indicates what functional group is present.
   3. The prefix tells us the identity, location, and number of
      substituents attached to the carbon chain.
                                                                  6
                 IUPAC nomenclature of alkanes
                                                 7
                               Cont…
                                                           8
                               Cont…
                                                                      9
                               Cont…
b.    If there are two substituent on the same carbon, give them both
     the same number.
                                                                   10
                               Cont…
Step 4- write the name as a single word
                                                                   11
con
      12
                              Cont…
                                                                13
    Cont…
.
            14
                             Cont…
 Some of the simpler branched-chain alkyl groups also have
   nonsystematic or common names
1.Three –carbon alkyl group;
                                                       15
                    Problems
1. what is the IUPAC name of the following alkane
                                                    16
                                Cont…
A. 3,4-dimethylnonane c. 3-ethyl-4,4-dimethylheptane
B. 2,2-dimethyl-4-propyloctane d. 2,2,4-trimethylpentane
3.Give the IUPAC name for the following hydrocarbon and convert
                                                                  17
                                 Cont…
                                                                 18
                         Cycloalkanes
o Cycloalkanes are alkanes that contain a ring of three or more
  carbons.
o They have the general formula CnH2n , n = 3, 4, 5…..
o Cycloalkanes are named under the IUPAC system by adding
  the prefix cyclo to the name of the unbranched alkane with the
  same number of carbons as the ring.
o The smallest possible ring consists of cyclopropane, C3H6.
                                                                   19
 Cycloalkanes are named by using similar rules, but the prefix
  cyclo- immediately precedes the name of the parent.
                                                            20
Example #1
Example #2
  Example #3
                                    In this example, the ring has four
                                     carbons and the chain has eight.
                                    The chain is the parent and the ring is a
                                     prefix.
             1-cyclobutyloctane.    The ring is a cyclobutyl group on carbon
                                     #1.                                  21
22
                    PROPERTIES OF ALKANES
Physical properties of alkanes
 They are Nonpolar
 Are insoluble in water but soluble in non-polar solvents ( eg.
   diethylether).
 Have lower density than water.
 Have low boiling and melting points.
 Alkanes with 1-4 carbon atoms (methane, propane, butane) are
   gases.
 Alkanes with 5-17 carbon atoms(kerosene, diesel, and jet
   fuels) are Liquids.
                                                              23
                            Cont…
                                                         24
                   Chemical reaction of alkanes
 Alkanes are typically non-reactive. They don’t react with
  acids, bases, active metals, oxidizing agents, reducing agents,
  halogens, etc.
 The following are the most common chemical reaction of
  alkanes.
1) Combustion:
      Alkanes react with oxygen.
      Alkane + O2               CO2 + H2O + heat
      CH4 + 2O2                 CO2 + 2H2O + energy
2)    Halogenation:
 Alkanes react with Halogens.
      CH4 + Cl2 heat or light       CH3Cl      +      HCl
                                       Chloromethane
                                                                    25
                            Preparation of alkanes
                                                                     26
                             Cont…
b) with an active metal and an acid
  I.      R—X + metal/acid  RH
       active metals = Sn, Zn, Fe, etc.
   acid = HCl, etc. (H+)
Examples
                                 +                             +       SnCl2
               CH3CH2CHCH3           Sn/HCl    CH3CH2CH2CH3
Cl
Br
                                                                                  27
•    Alkenes and Alkynes
• Unsaturated
                                                             28
                             Cont…
                                                                 29
                           Cont…
• Step 3: Assign numbers and names to the branching
  substituents, and list the substituents alphabetically.     Use
  commas to separate numbers, and hyphens to separate words
  from numbers.
                                                                30
                  Cont…
Eg.
      1   2 3 4
  CH2=CHCH2CH3    1-butene but-1-ene
                                       31
Cont…
        32
Cont…
        33
Some common name of alkene
                             34
                          Cycloalkenes
                                                                  35
• Alkenes and alkynes are considered to have equal priority
• In the case where each would have the same position number,
  the double bond takes the lower number.
                                                              36
                  Exercise
Write the IUPAC name for each of the following
 unsaturated compounds:
A.   CH3CH2CCCH3
        CH3
B. CH3C=CHCH3
       CH3
C.
                                             37
                 Physical properties of alkenes
                                                                    38
                Chemical Properties of Alkene
                                                         39
                          Cont…
• Hydration;-addition of water to an alkene.
 Hydrohalogenation—Electrophilic Addition of HX
•   Hydrohalogenation is the addition of hydrogen halides HX
    (X = Cl, Br, and I) to alkenes to form alkyl halides.
                                                               40
                           Preparation of Alkenes
1) Dehydrohalogenation;
              H    H                           H       H
                       H       C2H5ONa
          H
              H     Br                         H       H
Mechanism
                                                   H         H
                           H   H
              O                    H
                       H                           H         H
                           H    Br
                  OH
                       85% H3PO4                        +   H 2O
                               o
                        165-170 C
                  H
            CH3
                                            CH2
                        20% H2SO4
     H3 C         OH
                                                        +   H2O
                           85 oC
            CH2                      H3 C         CH3
                                                                   42
                                          Cont…
o Mechanism
                              CH3                                            CH3
                   H 3C              OH                             H3C            OH2
                                              H+
                              CH2                                            CH2
                          H                                             H
-H2O
                                                             Base
                              CH2                                            CH3
                                                         +
                                                    -H
                                          +   H2O                   H
                   H3 C             CH3                                 C          CH3
                                                                        H2
                                                                                         43
                   Physical properties of Alkynes
o The first three members are gases, next eight are liquids and
  the higher alkynes are solids.
o They all are colorless and odorless except acetylene which has
  a garlic odor.
o Their boiling points and melting points show a regular increase
  with the increase in molecular weights.
o Alkynes generally have slightly higher boiling points than the
  corresponding alkenes.
o They are only slightly soluble in water but dissolve readily in
  organic solvent such as benzene, acetone, and ethyl alcohol.
                                                                 44
       Chemical Reaction of Alkynes
1. Addition of Hydrogen (Reduction)
o In the presence of Ni, Pt, or Pd alkynes add up two molecules
  of hydrogen first forming the corresponding alkenes and
  finally alkanes.
                                                             45
                            Cont…
                         H2/Ni2B
                                                 H           H
                                                       97%
                                                  R          R
                       H2, Pd/CaCO3
R               R
                         Quinoline
                                                 H           H
                                                 H
                       (1) Li, C2H5NH2
                         (2) NH4Cl
                                          H
                                                           47
2. Addition of Halogens
o Halogens add to alkynes in two steps forming a dihalide and then
   a tetrahalide
                                   Br                              Br
                                                              Br
              Br2                        Br2
                                                                         Br
             CH2Cl2                      CH2Cl2
1-Butyne
                               Br                             Br
                              (E)-1,2-Dibromo-1-butene   1,1,2,2-tetrabromobutane
                                                                           48
 3. Addition of Halogen Acids
o Hydrogen halides add to alkynes to form alkenyl halides. The
  regioselectivity of addition follows Markovnikov’s rule.
o A proton adds to the carbon that has the greater number of
  hydrogens, and halide adds to the carbon with the fewer
  hydrogens.
 4. Combustion
 Alkynes are burnt in air to form CO2, H2O and heat energy.
                                                               49
    2CH≡CH   + 5O2→   4CO2 + 2 H2O   +   heat energy
5. Alkylation of Terminal Alkynes
                       NaNH2                         CH3Br
  H 3C           H                   H3C                          H3 C         CH3
                        NH3
                        NaNH2                        EtBr
  H3 C            H                  H 3C                         H3 C         Et
                         NH3
                                    CH3                 H3C               H
                                      H
                                                                     +
                           H       C                        H3C
     H3C
                                     C     Br
                               H
                               H3C                                       CH3
                                                                                    50
                        Preparation of alkynes
1. Dehydrohalogenation
          H    H
                          2 eq. NaNH2
     R              R                   R          R
Br Br
                                                         51
                Assignment
1. Discuss about Physical properties, Chemical
  Reactions and Preparations of :-
        A. Alcohol
        B. Ethers
        C. Amines
        D. Aldehydes and ketones
        E. Carboxylic acids and its derivatives
                                              52
                              • Alcohols
• Has an -OH (hydroxyl) group bonded to a tetrahedral carbon
   – methanol, CH3OH, is the simplest alcohol
• Classification of Alcohols
• Depends on the C which has the –OH group attached
CH3 CH2 OH OH OH
                            CH 3 CH CH 3            CH 3 C      CH 3
      ethanol                                              CH 3
                             2-propanol           2-methyl-2-propanol
1o Alcohol—attached to
                         2o Alcohol—attached to
one C                                               3o Alcohol-attached to
                         two Cs                     three Cs
                                                                             53
                      Examples
                                                          54
             Alcohol Nomenclature IUPAC
 1.Find longest carbon chain that contains the -OH group
   (parent chain)
 2.Number chain from end that gives the -OH the lower
   number
 3.Change the ending -e to -ol
 4.Use a number to show the location of the -OH group
     For cyclic alcohols, the carbon with the -OH group is C-1
 5.Name and number substituents and list them in alphabetical
   order
 6. If the same number for the functional group suffix is
obtained in both directions, the chain is numbered in the
direction that gives a substituent the lowest possible number.
                                                            55
                            Examples
                                                            OH
         OH                          OH
    Ethan ol              1-Pro pan ol                2-Prop ano l
(Ethy l alco ho l)      (Prop yl alco ho l)      (Is op ro py l alco ho l)
                                     OH
            OH                                                  OH
  1-Butan ol                2-Bu tano l         2-Meth yl-1-pro pano l
(Bu tyl alco ho l)     (sec-Bu tyl alcoho l)      (Is ob uty l alcoh ol)
OH OH
                                                                             56
Cont…
        57
                Exercise
Write the IUPAC name for each alcohol
           OH                  OH
(a)                    (b)
      OH
(c)                    (d)     OH
                                        58
                              Cont…
     – Alcohols containing more than one hydroxyl groups are
        named as a diol, a triol, and so on
                                                                59
                   Ethers
• Ethers have two alkyl groups bonded to an
  oxygen atom.
                                              60
                             Cont…
• Simple ethers are usually assigned common names. To do so:
      For symmetrical ethers, name the alkyl group and add the
      prefix ―di-‖.
                                                               61
                            Cont…
• More complex ethers are named using the IUPAC system. One
 alkyl group is named as a hydrocarbon chain, and the other is
 named as part of a substituent bonded to that chain:
                                                              62
EXAMPLES
           63
                          2.5 Amines
• Amines are compounds in which one or more of the hydrogen's of
  ammonia have been replaced by alkyl groups.
                                                                64
                          Cont…
• The common name of an amine consists of the names of the
  alkyl groups bonded to N the nitrogen, in alphabetical order,
  followed by ―amine.‖
                                                             65
                            Cont…
                                                       68
                            Cont…
• Their names consist of the names of the alkyl groups in
  alphabetical order, followed
                                                        69
                    2.6 Aldehydes and ketones
                                                               70
                          Cont…
                                                           71
                           Cont…
In ketosis, a pathological condition that can occur in people with
diabetes, the body produces more acetoacetate than can be
metabolized.
                                                             72
                             Aldehyde
                                                                    73
             Cont…
• Examples
                     74
                         Cont…
• If the aldehyde group is attached to a ring, the aldehyde is
  named by adding ―carbaldehyde‖ to the name of the cyclic
  compound.
                                                            75
                              Cont…
If a compound has two functional groups, the one with the lower
priority is indicated by its prefix. The prefix of an aldehyde oxygen
that is part of the parent hydrocarbon is ―oxo.‖
                                                                   76
                            Cont…
• If the compound has both an alkene and an aldehyde functional
  group, the alkene is cited first, with the ―e‖ ending omitted.
                                                                   77
                               ketone
                                                                78
Examples
           79
                          Cont…
Only a few ketones have common names.
                                                           80
                Exercises
• Name the following compounds
                                 81
             2.6 Carboxylic acids and its derivatives
• Carbonyl compounds
                                                                  82
                            Cont…
• Acyl halides, acid anhydrides, esters, and amides are all called
  carboxylic acid derivatives because they differ from a
  carboxylic acid only in the nature of the group that has
  replaced the OH group of the carboxylic acid.
                                                                 83
                         Carboxylic Acids
                                                                 84
                          Cont…
• In systematic nomenclature, the position of a substituent is
  designated by a number.
• The carbonyl carbon of a carboxylic acid is always the C-1
  carbon.
• In common nomenclature, the position of a substituent is
  designated by a lowercase Greek letter, and the carbonyl
  carbon is not given a designation. The carbon adjacent to the
  carbonyl carbon is the α-carbon, the carbon adjacent to the α-
  carbon is the β carbon and so on.
                                                              85
Cont…
        86
                           Cont…
• Carboxylic acids in which a carboxyl group is attached to a ring
  are named by adding ―carboxylic acid‖ to the name of the cyclic
  compound.
                                                               87
                           Acyl Halides
                                                            88
Examples
           89
                        Acid Anhydrides
                                                                90
                              Cont…
• If the two carboxylic acid molecules are different, the anhydride
  is a mixed anhydride. Symmetrical anhydrides are named by
  using the acid name and replacing ―acid‖ with ―anhydride.‖
                                                                91
                           Esters
                                                              92
                           Cont…
Salts of carboxylic acids are named in the same way. The cation
is named first, followed by the name of the acid, again with ―ic
acid‖ replaced by ―ate.‖
                                                               93
                         Cont…
 Cyclic esters are called lactones.
                                       94
                            Amides
• An amide has an NH2, NHR, or NR2 group in place of the OH
  group of a carboxylic acid.
                                                              95
                              Cont…
• If a substituent is bonded to the nitrogen, the name of the
  substituent is stated first (if there is more than one substituent
  bonded to the nitrogen, they are stated alphabetically), followed
  by the name of the amide.
                                                                   96
                               Cont…
• Cyclic amides are called lactams. Their nomenclature is similar to
  that of lactones.
                                                                    97
                       Aromatic compounds
                                                                 98
                                 Cont…
• If the alkyl substituent has six or fewer carbons, the arenes are
    named as alkyl substituted benzene
• If the alkyl substituent has more than six carbons ,the compound is
    named as phenyl-substitued alkane
                                                                   99
                              Cont…
• meta-disubstituted- 1,3
• a para-disubstituted -1,4
                                                               100
                           Cont…
                                                             101
                         Cont…
• The monosubstituted aromatic compounds        can serve as a
  parent name with the particular substituent     CH3 toluene
  assumed to be C1.
102