CHEMISTRY 102

CHEMISTRY 102
ORGANIC CHEMISTRY SUPPLEMENT A



1. You should be able to define and/or identify the following terms:


	                 Alkanes

     atomic orbital      	position isomers         
     molecular orbital   	IUPAC
     covalent bond       	common name
     sp3 hybrid               	substitutent
     electronegativity        	halogenation
     polarity of molecule     	saturation
     Lewis acid               	combustion
     Lewis base               	mechanism
     structural formula       	substitution
     alkane             	free radical
     skeletal isomers
     
 
                  	Alkenes

     alkene              	glycol
     unsaturated        	elimination reaction
     double bond         	dehydrohalogenation
     sp2 hybrid          	branched alkene
     pi bond             	dehydration
     free rotation       	carbocation
     restricted rotation 	primary
     stereoisomers       	secondary
     geometric isomers   	tertiary
     cis-                	addition reactions
     trans-              	Markovnikov's Rule
     alcohol

          Alkynes and Cyclic Hydrocarbons

     cyclic              	axial
     ring strain         	equatorial
     ring puckering      	steric hindrance
     conformation        	alkyne
     chair form                 alkyne
     boat form           	sp hybrid
    
           Alcohols, Ethers, Phenol

     alcohol             	oxidation
     ether               	aldehyde
     pehnol              	ketone
     hydrogen bonding         	phenoxide ion
     hydrolysis               	acid
     primary             	Ar-
     secondary           	R-




2.   You should be able to draw structural formulas for alkanes,
     alkenes, alkynes, cyclic hydrocarbons, alcohols, ethers and
     phenol when given the IUPAC or common name.

3.   You should be able to give the IUPAC name for any alkane, alkene,
     alkyne cyclic hydrocarbons, alcohols and ethers containing a
     maximum of ten carbons in the longest continuous chain when given
     the structural formula.

4.   You should be able to draw all the structural isomers for an
     alkane when given the IUPAC name or the molecular formula.

5.   You should be able to complete equations for (1) combustion and
     (2) halogenation reactions.

6.   When given reactants and conditions under which a reaction is to
     be run, you should be able to give the structures of the organic
     products for the following types of reactions.

     a)   To form alkenes
          1)   dehydrohalogenation of alkyl halides, RX
          2)   dehydration of alcohols, ROH
     b)   Reactions with alkenes
          3)   addition of hydrogen, H2/cat
          4)   addition of halogens,X2
          5)   addition of hydrogen halides,HX (HCl, HBr, HI)
          6)   addition of water,H2O, H+ (reacts as H+, OH-)
          7)   addition of KMnO4
7.   You should be able to identify primary, secondary and tertiary
     (1) carbons, (2) hydrogens, (3) carbocations, (4) free radicals,
     (5) alcohols.

8.   You should be able to predict the relative stability of primary,
     secondary, and tertiary carbocation.

9.   You should be able to recognize which conformation of
     cyclohexane, boat or chair, is more stable and explain why.

10.  You should be able to draw structural formulas for alkynes when
     given the name or name the compound when given the structure.

11.  You should be able to predict the products of the reaction with
     an alkyne of a) Br2, b) H2, c) HX 

12.  You should be able to explain the unusually high boiling point of
     alcohols and be able to pick the higher boiling of a pair.

13.  You should be able to write equations for the preparation of
     alcohols from a) alkyl halides, b) aldehydes, c) ketones, and
     d) alkenes.

14.  You should be able to write equations for the reaction of
     alcohols with a) sodium, b) hydrogen halides, c) sulfuric acid,
          and d) oxidizing agents. 


              Structural Formulas, Bonding, Alkanes


1.   You may want to review electronegativity in Ch. 10.  H is
     2.1,     C is 2.5, so C-H bonds are not very polar.


2.   You are to know the names of these eight alkyl groups and
     their structures:

     a)   CH3-     methyl

     b)   CH3CH2-     ethyl

     c)   CH3CH2CH2-     n-propyl

     d)   CH3CH-     isopropyl
              
             CH3

     e)   CH3CH2CH2CH2-     n-butyl

     f)   CH3CH2CHCH3      sec-butyl

     g)   CH3CHCH2-     isobutyl
              
             CH3

             CH3
              
     h)   CH3C-    t-butyl
              
             CH3

     Notice the similarity between isopropyl and isobutyl.


3.   Compounds with halogens are called alkyl halides;
     monosubstituted alkyl halides have formulas CnH2n + 1X where X
     is usually Cl or Br but could also be F or I.  The halogens
     are treated as substituents on the C-chain and are named
     ending in o-.  (You are already familiar with chloro, bromo,
          etc.)


                         Alkane Reactions           

1.   Reactions of saturated hydrocarbons:

     Since, in the alkanes, each carbon is bonded to four other
     atoms, the reactions that occur involve substitution or
     oxidation.

     a.   Oxidation:  combustion with O2

          CH4 + 2O2 _____> CO2 + 2H2O
                       

          You should be able to write complete balanced equations
          for combustion.

          Practice:  ______ C4H10  +  ______ O2 _____>
                                                   
     b.   Halogenation:  reaction with Cl2 or Br2/h 

          1)   CH4 + Cl2 ______> CH3Cl + HCl
                          h 

          2)   CH3CH3 + Br2 ______> CH3CH2Br + HBr
                             h 

          These reactions may continue, so that dihalides or
          trihalides, etc., may form.

          CH3Cl + Cl2 ______> CH2Cl2 + HCl
                       h 
                                            Cl
                                             
          3)   CH3CH2CH3  +  Cl2 ______> CH3CHCH3 + CH3CH2CH2Cl
                                   h 
                                        (major product)

          To understand the last reaction, you need to
          distinguish types of carbon:
          
                          Type
                         Symbol
          No. of C atoms
          attached to C
          Type of H
          attached to C
          
          
          Primary
                           1
                          1 C
                           1
          
          
          Secondary
                           2
                         2 C's
                           2
          
          
          Tertiary
                           3
                         3 C's
                           3
          
          
          Quaternary
                           4
                         4 C's
                          none
          
                                                            Cl
     Now look at 3) above again.  One product,          , is
     formed by
                                               CH3CHCH3

     replacement of a 2H; the other (CH3CH2CH2Cl) by replacement
     of a 1 H.

     The ease of replacement of H's is 3 > 2 > 1.



                           PRACTICE SET
        
              Structural Formulas, Bonding, Alkanes

1.   Write condensed structural formulas for all of the isomers
     of

     a.   C6H12               b.   C3H7Br         c.   C4H8Br2

2.   The common names of the following are

          ethyl chloride      CH3-CH2-Cl     or   CH3CH2Cl
          n-propyl chloride   CH3-CH2-CH2-Cl  or  CH3CH2CH2Cl
          isopropyl chloride  CH3-CH-CH3  or  CH3CHCH3
                                                  
                                  Cl             Cl
     Based on these examples, draw structures for

     a.   isobutyl chloride        b.   t-butyl bromide
     c.   n-hexyl chloride         d.   sec-butyl iodide

3.   Identify all of the 2-methylpentane molecules.

     a.     CH3CH2CHCH2CH3
                 
                Cl
     
             CH3
              
     b.     CH3CHCH2CH2CH3
     
                   CH3
                    
     c.     CH3CH2CH2CH
                    
                   CH3
     d.     CH3
           
          CHCH2CH2
                
          CH3  CH3
     
             CH3
              
     e.     CH3CHCH2CH2
                   
                       CH3f.         CH2-CH-CH3
                   
          CH3-CH2 CH3
     
     g.     CH3
           
          CH2          CH2-CH3
           
          CH2-CH2
     
     h.     CH3-CH__CH2
                   
              CH3 CH-CH3
                   
                  CH3
     
     i.           CH3  CH3
                        
               CH3CH2CH___CHCH3
     4.   Name the following:

     a.     CH3CHCH2CH2CHCH3
                      
                  CH3     CH3b.     CH3CHCH2CH3
              
             CH2
              
                  CH3

     5.   Draw a structural formula for the following:
     a.   1-bromo-1,1,2-trichloropropane
     b.   2,7-dimethyloctane
     c.   4-sec-butyldecane


                       PRACTICE SET ANSWERS    

              Structural Formulas, Bonding, Alkanes

1.   a.   C5H12

          (1)  CH3CH2CH2CH2CH3     (2)  CH3CH2CHCH3    (3)     
CH3
                                                                 
                                              CH3           CH3-C-CH3
                                                                 
                                                               
CH3

     Try naming them.  (Good practice!)

     b.   C3H7Br    (1)  CH3CH2CH2Br  and         (2)  CH3CHCH3
                                                           
                                                          Br

     c.   C4H8Br2   (1)  CH3CH2CH2CHBr2           (7)  CH3CHCHBr2
                                                           
                    (2)  CH3CH2CHCH2Br                    CH3
                                
                               Br                 (8)  CH3CHCH2Br
                                                           
                    (3)  CH3CHCH2CH2Br                    CH2Br
                             
                            Br                    (9)     Br
                                                           
                    (4)  BrCH2CH2CH2CH2Br              CH3CCH2Br
                                                           
                    (5)  CH3CH2CBr2CH3                    CH3

                    (6)  CH3CH-CHCH3
                                 
                             Br Br

2.   a.      CH3    isobutyl chloride
              
          CH3CHCH2Cl

     b.       CH3
               
          CH3-C-Br  t-butyl bromide
               
              CH3

     c.   CH3CH2CH2CH2CH2CH2Cl          n-hexyl chloride

     d.   CH3CHCH2CH3    sec-butyl iodide
              
             I

3.   2-methylpentane

     b.        CH3
              
          CH3CHCH2CH2CH3
     
     c.              CH3
                    
          CH3CH2CH2CH
                    
                   CH3
     
     d.     CH3
           
          CHCH2CH2
                 
               CH3  CH3e.        CH3
              
          CH3CHCH2CH2
                   
                  CH3
     
     f.         CH2-CH-CH3
                   
               CH3-CH2 CH3
     
     4.   a.  2,5-dimethylhexane        b.  3-methylpentane 

     c.  5-t-butyl-3-ethyloctane

5.   a.       H  Br      b.      CH3           CH3
                                                
          CH3-C__C-Cl         CH3CHCH2CH2CH2CH2CHCH3        
                  
              Cl Cl           2,7-dimethyloctane

     c.      CH3CH2CHCH3
                    
          CH3CH2CH2CHCH2CH2CH2CH2CH2CH3

          4-sec-butyldecane
                         Alkene Reactions

1.   Preparation of Alkenes:  ( Type?_______________________________)

     "E1".     Dehydrohalogenation (-H, -X):

          1)   Alkyl halides + alcoholic KOH (abbreviated
               KOH/alc):

               CH3CHCH3  +  KOH _______> CH2=CHCH3 + H2O + KCl
                                 alc
                  Cl
                     
          NOTE:      H on a C adjacent to the C holding the
                    halogen      is removed.

          2)   When there is a choice of H's to remove:

               Ease of Removal of H:  3 > 2 > 1


               CH3CH-CHCH3 + KOH _______> CH3CH=C-CH3        
(Eq. 1)
                                   alc           
                  Cl CH3                        CH3
                                         (major product)

     "E2".     Dehydration (-H, -OH)

          1)   Alcohol + H2SO4:

               CH3CHCH3  +  H2SO4   CH2=CHCH3 + H2O
                   
                  OH

          2)   When there is a choice of H's to remove:  use the
               rule above.

               CH3CHCH2CH3 + H2SO4   CH3CH=CHCH3             
(Eq. 2)
                   
                  OH                 (major product)

          Most branched product:  Notice that in Eq. 1 and Eq. 2
          the major product that forms has the most C's attached
          to the C's of the double bond.

          Eq. 1:  minor product              major product
                        *                    *       *
                  CH2=CHCHCH3                CH3CH=C-CH3
                                                    
                        CH3                       *CH3

     * (1 C on C of double bond)       * (3 C's on C's of double
bond)


E.   Reactions of alkenes:  (type?__________________________________)

     Know five addition reactions:

     "A1" HYDROGENATION - add _____ to DB

     Mix alkene + H2 gas + catalyst (_____, _____, _____)

                                             
      C=C      +    H2      Ni  >       -C__C-
                                             
                                         H  H

     _______________                    _______________

     "A2" HALOGENATION - add _______________ to DB

          ROYO in text (easy)

     "A3" Addition of HX to DB (opposite of "E1")

                          
      C=C  +  HX     -C__C-
                          
                      H  X

     There may be two possible products.  For example if, 




                            _____________________________________



     CH3-CH=CH2  +  HBr   


                            _____________________________________

     How to predict which is the major product?

     MARKOVNIKOV'S RULE - In the addition of HX to the DB, the C
     with the most H's gets the H.

     MARK'S RULE __________  __________  __________, __________

     So.... circle the main product above.

     "A4" Addition of HOH to DB

     1.   Must be catalyzed by a strong acid.

     2.   Forms an alcohol, __________, as the product.

     3.   Follows Mark's Rule.

                CH3
                 
          CH3CH=C-CH3 + H2O   H+  >
                               __________________________________
          (Work out the product in your groups.)


"A05" Alkene + KMnO4(aq.)   glycol + MnO2 (type?
____________________)

                                             or
____________________)
                                 OH  OH
                                                  (Remember doing
     CH3CH=CH2 + KMnO4(aq.)   CH3CH__CH2 + MnO2     this in lab?)
                              glycol       brown ppt.

F.   Mechanism of selected addition reactions of alkenes:
     RECALL:  The principle type of alkene reaction is what?

                                      ___________________________

     Mechanism for "A3" above:     Alkene + HX:  (HX = HCl, HBr,
HI)

          1)  CH3CH=CH2 + H+   CH3CHCH3                    STEP 1
                                  +                        (slow)
                               carbocation

          Markovnikov's rule:  H+ goes to the C of the double
          bond that has the most H's.  (or:  "Them that has,
          gits.")

          2)   CH3CHCH3 + X-     CH3CHCH3                  STEP 2
                  +                                        (fast)
                                    X

          [Step 1 is slow (the formation of the carbocation).]


                            
          Carbocations:  (-C + )
                            

          1)   Active intermediates, react quickly.

          2)   Most stable forms first.

          3)   Order of stability of carbocations:  3 > 2 > 1

          4)   Stability of CARCAT determines product.

          5)   Also an intermediate in "Dehydration of Alcohols"
                              - Reaction "E2."


                           PRACTICE SET      

                             Alkenes

1.   Which of the following can be written a stereoisomers (cis-,
     trans-isomers)?
     
     a.     CH3CH=CHCH3
     
     b.     CH3CH=CHCHCl
                   
                  Cl
     
          c.     CH3CH=CBr2d.     ClCH=CHBr
     
     e.     Cl2C=CCl2
     
          f.     (CH3)2C=CHCH3
     
     
2.   Name the stereoisomers drawn in 8. above.



3.   Draw structural formulas for the following:

     a.   1,2-dichloro-3-heptene

     b.   7-chloro-5-isopropyl-2-methyl-3-octene

     c.   3-methyl-3-n-propyl-1-hexene





4.   Complete the following reactions with the major organic
     product.

     a.   CH3CH2CH2CHCH3  +  KOH _______>
                                  alc.
                   Cl

     b.        OH
                
          CH3__C__CH3  +  H2SO4   
                
               CH3

     c.   CH3CH=CHCH3  +  Br2   

     d.   CH3CH2      CH3

                 C=C     +  H2  _______>
                                   Pd
              H       H

     e.   CH3C=CHCH3  +  HCl   
              
             CH3


     f.   CH2=CHCH2CH3  +  H2O _______>
                                H+

     g.   CH3C=CH2  +  KMnO4 _______>
                              H2O
             CH3

     h.        CH3
                
          CH3__C__CH2CH3  +  KOH _______>
                                   alc.
               Cl

     i.   CH3C=CH2  +  HBr   
              
             Cl


5.   Explain and give an example of each of the following:

     a.   dehydrohalogenation

     b.   geometric isomers

     c.   Markovnikov's Rule

     d.   polymer

     e.   pi bond

     f.   sigma bond

     g.   carbocation


                       PRACTICE SET ANSWERS

                             Alkenes

1.   a.     CH3      H               CH3     CH3

               C=C          and         C=C

            H        CH3             H       H


     b.     CH3     H                CH3     CHCl2

               C=C         and          C=C

            H       CHCl2            H       H


     f.     CH3           H

                  C=C         one form only.

            CH3           CH3


2.   a.   CH3CH=CHCH3    2-butene (trans or cis)

     b.   CH3CH=CHCHCl2       1,1-dichloro-2-butene  (trans or
cis)

     f.   (CH3)2C=CHCH3  is really CH3-C=CH-CH3  or 2-methyl-2-butene
                                         
                                       CH3

3.   a.   1,2-dichloro-3-heptene   CH2-CHCH=CHCH2CH2CH3
                                        
                                   Cl  Cl

     b.   7-chloro-5-isopropyl-2-methyl-3-octene

               CH3-CH-CH=CH-CH-CH2-CH-CH3
                                    
                   CH3      CH     Cl

                         CH3  CH3

     d.   3-methyl-3-n-propyl-1-hexene

                 CH3
                  
          CH2=CH-C-CH2CH2CH3
                  
                 CH2CH2CH3

4.   a.   CH3CH2CH-CHCH3  KOH > CH3CH2CH=CHCH3 (major product)
                          alc.
                H  Cl         What is the minor product?


     b.       OH
               
          CH3-C-CH3  conc  > CH2=C-CH3
                     H2SO4        
              CH3                C3

     
     c.   CH3CH=CHCH3 ______>  CH3CH-CHCH3
                      Br2             
                                  Br Br

     d.   CH3CH2        CH3
                              H2
                  C=C               > CH3CH2CH2CH2CH3
                              Pd
              H         H

                                    Cl
                                            *
     e.   CH3C=CHCH3  +  HCl     CH3CCH2CH3
                                     
             CH3                    CH3
                                                   *Markovnikov's
                                                      rule obeyed
                                                    *
     f.   CH2=CHCH2CH3  +  H2O  H+  >   CH3CHCH2CH3
                                            
                                           OH

                                       OH OH
                               H2O         
     g.   CH3C=CH2  +  KMnO4 _____> CH3C__CH2
                                        
             CH3                       CH3

               CH3                   CH3
                                      
     h.   CH3__C__CH2CH3 KOH  > CH3__C  CHCH3
                         alc
               Cl

                                    Br
                                     
     i.   CH3-C=CH2  +  HBr     CH3-C-CH3*
                                     
              Cl                    Cl

6.   a.   dehydrohalogenation means the removal of the elements
          of HCl or HBr from adjacent carbons.

              CH3                  CH3
                                    
          CH3-C-CH-CH3  KOH  > CH3-C  CH-CH3
                        alc
              H Br

     b.   geometric isomers are stereoisomers, or compounds that
          differ only in the arrangement of their atoms in space.

          CH3       H              CH3       CH3

               C=C                      C=C

           H        CH3             H        H

          trans-2-butene           cis-2-butene

     c.   Markovnikov's Rule:  The more positive member of an
          unsymmetrical reagent (the H+) will go to the carbon of
          the double bond that contains the greater number of
          hydrogens.

          CH3-C  CH2  +  HBr      Br
                                   
              CH3             CH3-C__CH3
                                   
                                  CH3

     d.   polymer is a long continuous chain consisting of many
          repeated units.
                              H H   H H    H H
                                              
          CH2  CH2 _______>  -C-C_(_C-C_)__C-C__
                    rad.                 n    
                              H H   H H    H H

          ethylene            polyethylene

     e.   pi bond:  bond formed from the side-by-side overlap of
          both lobes of one p-orbital to both lobes of another p-orbital.

          CH2=CH2




     f.   sigma bond:  bond formed form end-to-end overlap of one
          lobe on one orbital with one lobe on another.  See e.
          above.

     g.   carbocation:  an ionic species containing a positive
          charge on a carbon.
              H
               
          CH3-C+  1
               
                   H    H
          
     CH3-C+  2
          
              CH3    CH3
          
     CH3-C+  3
          
              CH3
                                                         

                      Cycloalkanes, (CnH2n)
                           (aliphatic)

1.   "Aliphatic" hydrocarbons are cyclic alkanes made of rings of
     C; most react pretty much like straight chains.

     a.   Cyclopropane:  CH2__CH2  or

                            CH2

          BA = _______________

     b.   Cyclobutane:   CH2__CH2  or


                         CH2__CH2

          BA = _______________

     c.   Cyclopentane:       CH2            or

                         CH2        CH2

                            CH2__CH2

          BA = _______________

     d.   Cyclohexane:        CH2            or

                         CH2       CH2


                         CH2       CH2

                              CH2


          BA = _______________ (flat) _______________ (puckered)

2.   Ring strain (angle strain):

     a.   Strained rings:  (very reactive)

          cyclopropane        angle:  60    sp3 angle:     109



          cyclobutane         angle:  90    sp3 angle:     109








          Notice the large difference between the bond angle and
          the sp3 angle.  These two rings can undergo reactions
          where they "pop" open.

     b.   Unstrained rings:   (normal reactivity - like 
                               straight-chain alkanes)

          cyclopentane  
          cyclohexane      not planar; puckered.

          Notice that these two do not have angle strain.  They
          "pucker" so their bond angles are 109.5, sp3 hybrid.

     c.   Cyclohexane:

          1)   Found in two major arrangements, called
               conformations:

               BMIG


                                    

               chair form                              boat form

          2)   Stability:  chair > boat      A  axial positions

                                             E  equatorial
positions






          3)   Substituents prefer to go to the less crowded
               equatorial positions.  (Crowding is called steric
               hindrance.)

3.   Reactions:

     a.   Substitution (just like other alkanes)

                                   Cl
               +  Cl2 ______>         +  HCl
                       H 


     b.   Addition:  (only to strained rings)

                    +  H2  _______>  CH3CH2CH3
                             Pt

     c.   Cycloalkenes (just like other alkenes)

                              Br     Br
                 +  Br2   

          CH3
                    +  HCl  



                           PRACTICE SET              

                           Cycloalkanes

1.   Draw structural formulas for the following compounds:

     a.   ethylcyclohexane
     b.   3-isopropylcyclooctene
     c.   cis-1,3-dibromocyclohexane
     d.   trans-1-chloro-2-methyl-cyclobutane

2.   Which conformation of cyclohexane is more stable?  Explain.

3.   What is the bond angle found between 1) sp3, 2) sp2 and 3)
     sp hybrid orbitals?

4.   Draw structural formulas for the following compounds:

     a.   4,4-dichloro-1-pentyne
     b.   6-ethyl-6,7-dimethyl-2-octyne

                       PRACTICE SET ANSWERS

1.   a.   
               H    H
                 C
            H         CH2CH3
              C     C         ethylcyclohexane
            H         H
                                      or        CH2CH3
            H         H
              C     C
            H         H
                 C
               H    H



               H   H
     b.                  CH3       3-isopropylcyclooctane
               C   C      
         H               CHCH3                    CH3
           C           C                           
         H               H         or             CHCH3
                      
         H               H
           C           C
         H               H
               C___C
             H       H
               H   H

     c.        Br     H                 cis-1,3-dibromocyclohexane
                       
               C      C                      or        Br
          H                Br                                    Br
               H      H                                H            
          C                C                                     H 
               H      H     
          H                H
               C      C
                       
               H      H


               Cl
     d.                            trans-chloro-2-methylcyclobutane
               C
          H         H
               H     
          C         C                   or        Cl
               H                                        H
          H         CH3                           H      
               C                                        CH3
                
               H


2.   C6H12, cyclohexane

     H                   H              or           More stable;
                                                    less crowding
     C      H            C                                of H's.
  H                 H       H
          C          
                    C
    H     H                   H
       C              H     C
                             
       H                    H


     chair form


     H              H                            repulsion of H's
                     
     C    H    H    C
  H                    H
           C  C                                   H         H
                                        or
    H      H  H       H
       C          C
                   
       H          H

     boat form3.

                             orbital
                            bond angle


                               sp3
                              109.5


                               sp2
                               120


                                sp
                               180


4.   a.   4,4-dichloro-1-pentyne

             Cl
              
          CH3CCH2CCH
              
             Cl

     b.   6-ethyl-6,7-dimethyl-2-octyne

                         CH2CH3
                          
          CH3-CC-CH2CH2-C____CHCH3
                               
                         CH3  CH3


                       Alcohols and Ethers     

Alcohols:

1.   R-O-H:  have high boiling points for their molecular weights
     because of H-bonding.
                              (CH3__O:
                                       H    :O__CH3)
                                          
                                          H

2.   Reactions:

     a.   With HCl or HBr or HI:

          ROH + HCl ______> RCl + H2O


          CH3CHOH + HI   CH3CHI + H2O
                             
             CH3            CH3

     b.   Organic oxidation:

          Two parts:

          1)   Remove 2 H's, one from C and one from O connected
               to C; make C = O.
                                           O
                                           
          2)   Insert 0 between C and H of CH.

          Example:  These two come off; C=O forms.

          CH3CHOH _________> CH3__C=OPart I only; can't do Part II.
                  K2Cr2O7          
             CH3   or PCC         CH3

          2 ROH              ketone
     ____________________________________________________________

          CH3CH2OH  _________> CH3C=O __________> CH3__C=O
                    K2Cr2O7           K2Cr2O7           
                                  H                    OH

          1 ROH  (Part I)    aldehyde  (Part II)  acid
     ____________________________________________________________

          3 ROH  :  no reaction towards oxidation.

3.   Preparations:

     a.   Alkene hydration:

          CH3CH=CH2 + H2O ______> CH3CHCH3  (major product)
                           H+         
                                     OH

     b.   Reduction of aldehydes or ketones:

          Use H2/cat.; catalyst is usually Pt or Pd.

                  O                    OH
                                            
          1)   CH3CH  +  H2 ______> CH3CH2        <  ald.     1
ROH
                             Pt

                  O                        OH
                                           
          2)   CH3CCH3  +  H2 _______>  CH3CHCH3  <  ket.     2
ROH
                               Pt

     c.   Alkyl halides  +  NaOH/H2O:

          CH3CH2Cl  +  NaOH _______> CH3CH2OH  +  NaCl
                             H2O

          NOTE:  This is a substitution reaction.

          (RX + KOH/alc.   elimination)




                           PRACTICE SET        

                       Alcohols and Ethers

1.   Draw structures for the following compounds:

     a.   2-pentanol
     b.   3-ethyl-3-octanol
     c.   3-bromo-4,4-dimethyl-1-heptanol
     d.   4-phenyl-1-pentanol
     e.   2-methylcyclopentanol ( or 2-methyl-1-cyclopentanol)

2.   Classify the alcohols in 1. above as 1, 2 or 3.

3.   In each pair, pick the higher boiling compound:

     a.   CH3CH2CH2OH  or CH3CH2-O-CH3

     b.        CH2CH2CH3      or        CH3CH2

                                                       OH

4.   Complete the equations with the major organic product:

     a.   CH3CH2CH2Cl  +  NaOH  _______>
                                 H2O

     b.   CH3C  CHCH3 + H2O _______>
                              H+
             CH3

             O
             
     c.   CH3CCH2CH2CH3  +  H2 _______>
                                 pt

                OH
                           K2Cr2O7
     d.   CH3CH2CHCH2CH3  _________>
                             H+

     e.   CH3CH2CH2CH2OH  +  HI   

               CH3
                         K2Cr2O7                  K2Cr2O7
     f.   CH3__C__CH2OH _________>                __________>
                           H+                         H+
               CH3



                       PROBLEM SET ANSWERS    

                       Alcohols and Ethers

1.   a.   CH3CH2CH2CHCH3      2-pentanol
                    
                   OH

                         OH
                          
     b.   CH3CH2CH2CH2CH2C__CH2CH3      3-ethyl-3-octanol
                          
                         CH2CH3

                    CH3
                     
     c.   CH2CH2CH__C__CH2CH2CH3   3-bromo-4,4-dimethyl-1-heptanol
                     
          OH    Br  CH3

     d.   CH3CHCH2CH2CH2OH              4-phenyl-1-pentanol
              




     e.        CH3

                    OH



2.   a.   2        b.  3         c.  1         d.  1         e. 2


3.   a.   CH3CH2CH2OH > CH3CH2-O-CH3 because of H- bonding in the
          alcohol.

     b.   CH3CH2                         CH2CH3because of polarity
                              >
                         OH


4.   a.   CH3CH2CH2Cl  +  Na+/OH- ______> CH3CH2CH2OH
                                  H2O

                                           OH H
                                               
     b.   CH3C=CHCH3  +  H2O ________>  CH3C__CHCH3
                                            
             CH3                           CH3

              O                              OH
                                             
     c.   CH3-C-CH2CH2CH3  +  H2 ______> CH3-C-CH2CH2CH3
                                              
                                             H

                OH                         O
                         K2Cr2O7           
     d.   CH3CH2CHCH2CH3 __________> CH3CH2CCH2CH3
                           H+


     e.   CH3CH2CH2CH2OH  +  HI     CH3CH2CH2CH2I

               CH3                     CH3 O                  CH3
O
                        K2Cr2O7               K2Cr2O7           

     f.   CH3__C__CH2OH _________> CH3-C___CH  _________> CH3-C___COH
                          H+                      H+               
               CH3                     CH3                    CH3

                                     aldehyde                  
acid




                                            

               Alkyl Halides and Petroleum Products              



1.   RX (alkyl halides)  (Omit Grignards)

     These are an important source of starting materials for
     synthesis of other compounds.

     a.   Preparation:  (This is review.)

          1)   Alkanes + X2/h 

               CH3CH2CH3 + Br2 ______> CH3CHCH3  +  HBr
                                H          
                                          Br

          2)   Alkenes + HX (HX = HCl, HBr, HI)

               CH3CH=CH2 + HI   CH3CHCH3
                                    
                                   I

          3)   Alcohol + HX (HX = HCl, HBr, HI)

               CH3CH2CH2OH  +  HBr     CH3CH2CH2Br + H2O

          4)   Alkene + Cl2 or Br2:

               CH3CH=CHCH3 + Cl2   CH2__CH__CH__CH3
                                             
                                        Br  Br

     b.   Reactions:  (This is review too!)

          1)   RX + NaOH/H2O                      (substitution)

               CH3CHCH3  +  NaOH _____> CH3CHCH3
                                 H2O        
                  Br                       OH

          2)   RX + KOH/alc.                      (elimination)

               CH3CHCH3 + KOH ______> CH3CH=CH2
                              alc
                  Br

          3)   RX + RONa

               CH3Cl + CH3ONa     CH3OCH3  +  NaCl
                                  
     (made from:  CH3OH Na)     ether



2.   Environmental impact of alkyl halides:

     a.   Pesticides:

          1)   DDT:      Cl__           __CH__         __Cl
                                           
                                      Cl__C__Cl
                                           
                                          Cl

          Remains in environment about 10-15 yrs.  Stored in fat
          reserves in animals.

          2)   Aldrin:









               Converted to Dieldrin when oxidized here.  Also
               very persistent.

     b.   Herbicides:                        O
                                             
          2,4-D     Cl__           __O__CH2__C__OH

                              Cl

          Toxic to broad leaf plants.

     c.   Gasoline additive:

          EDB (ethylenedibromide)  CH2__CH2
                                         
                                   Br   Br

          Reacts with Pb from Pb(CH2CH3)4 to produce PbBr2 which
          is volatile.

     d.   PCB's:  polychlorinated biphenyls

               Cl   Cl   Cl   Cl

          Cl                       Cl   Toxic; found in
transformers.

               Cl   Cl   Cl   Cl

     e.   Freons:  refrigerant; interferes with ozone layer.

          CCl2F2         Freon-12



            CATEGORIES OF REACTIONS ORGANIC CHEMISTRY


1.   Addition Reactions:

     NOTE:  only one product forms.

                       
     a.   Alkenes, -C=C-

                    CH3CH=CH2  +  HCl     CH3CHCH3
                                              
                       Cl-H                  Cl

                    (Follows Markovnikov's Rule)

                                                       Br Br
                                                           
     b.   Alkynes, -CC-      CH3CH2CCH + 2Br2     CH3C__CH
                                                           
                                                       Br Br

2.   Substitution Reactions:

     NOTE:  two products or more form.

     a.   Alkanes, RH

               CH3CH2CH3  +  Cl2 ______> CH3CHCH3  +  HCl
                                  h          
                                            Cl

     b.   Alcohols, ROH

               CH3CH2CH2OH  + HCl     CH3CH2CH2Cl  +  H2O

     c.   Alkyl Halides, RX

               CH3CHCH2CH3  +  OH- ______> CH3CHCH2CH3  +  Br-
                                    H2O        
                  Br         (NaOH)           OH

3.   Elimination Reactions:

     NOTE:  Double Bonds form

     a.   Alkyl Halides, RX

               CH3CHCH2CH3  +  KOH _________> CH3CH=CHCH3
                                   alcohol
                  Br

               (Ease of abstraction of H:  3 > 2 > 1)

     b.   Alcohols, ROH

                   CH3                     CH3
                                            
               CH3-C-CH3  +  H2SO4     CH3-C=CH2 + H2O
                    
                   OH

4.   Oxidation Reactions:

     NOTE:     Oxidation in organic chemistry means removing H's
               and/or adding O's.

     a.   Primary Alcohols (1 ROH)
                                            O
                                            
               CH3CH2OH  +  KMnO4 _____> CH3COH (acid)
                                     
                                         O                  O
                                            K2Cr2O7        
          CH3CH2OH  +  K2Cr2O7 _____> CH3CH  __________> CH3COH
                                                        
                                    (aldehyde)           (acid)

     b.   Secondary Alcohols (2 ROH)

                               O
                               
          CH3CHCH3        > CH3CCH3  (ketone)
                   KMnO4
             OH      or

                   K2Cr2O7

     c.   Alkenes

               CH3CH=CH2  +  KMnO4 ______> CH3CH-CH2
                                    H2O           
                                              OH OH
                                   (cold)



                          SUPPLEMENT AA

                 TYPES OF FUNCTIONAL GROUPS


NAME		GENERIC FORMULA 	LOOK FOR 	EXAMPLE(S)


1.  Alkane	 CnH2n + 2 or RH	4 atoms 	
						attached 	CH4 methane
					to each C	CH3CH2CH3 propane	

2.  Alkene	CnH2n or RC=C-		 -C=C-		CH2=CH2 ethylene
							CH3CH2CH=CH2 
		                                            1-butene
3.  Alkyne	CnH2n - 2
		or RCC-
   -CC-
HCCH acetylene or
ethyne
CH3CCCH3                                                2-butyne


4.   Cyclo-alkane
CnH2n
                            cycles or
                           rings of C's
cyclohexane

cyclopentane


5.  Alcohol
ROH
-OH group on
alkane
CH3CH2OH   ethanol 
           
   OH
    
CH3CHCH3  2-propanol


6.  Ether
R-O-R
C-O-C single
bonds
CH3CH2-O-CH2CH3 
                                                    diethyl ether
CH3-O-CH2CH2CH3
                                            isopropylmethyl ether


7.  Alkyl     
    halide
RX
                          F, Cl, Br, I
                           on alkane
                      CH3Cl  Chloromethane
                                
                          CH3CHCH2CH3 
                                  
                         Br  2-bromobutane
                                
                                
                          8.  Aromatic
                                  H
                                   
                                  C
                          H         H
                             C     C
                                   
                             C     C
                          H         H
                                  C
                                   
                                  H
                                
                                
                                
                                
                                
                                or
       benzene, C6H6



       CH3  toluene


  

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