Download MHS Student Guide to Organic Chemistry

Honors Chemistry Organic Chemistry Packet
This packet will NOT be graded traditionally.
All Answers are available to you.
Your Teacher is available to you before school, lunch and after school with appointments.
You are expected to keep up with the assigned pages.
Quizzes will be given periodically covering assignments up to the assigned pages that day.
Highlight ALL READINGS showing how molecules are named and made.
The packet will be picked up and graded as follows:
a)
b)
c)
d)
e)
f)
g)
h)
2 points per page.
Any missing or incorrect problems noticed on a page will result in zero points for that page.
All problems marked NR-“no reaction” must have a valid written reason to explain the
problem.
Failure to give a reason for an NR will result in ZERO points for that page.
When grading the packet ,the teacher will grade certain problems but will be looking for
letter b) above.
Follow directions on each page.
Make note of any directions your teacher gives that may change the directions on the pages.
Highlight things the teachers say you MUST KNOW.
Each class period will be divided into the following:
1) Review and discussion of problems assigned the night before.
2) Introduction to new problems.
3) Time to work on new problems.
Page
1
KEEP UP. DO NOT GET BEHIND ON THE ASSIGNED PAGES.
Contents
Organic Families and Functional Groups .................................................................................................... 5
ORGANIC FAMILIES 1 .................................................................................................................................. 6
ORGANIC FAMILIES 2 .................................................................................................................................. 7
Organic nomenclature part (1) ................................................................................................................... 8
ORGANIC NOMENCLATURE Part 2 .............................................................................................................. 9
Organic Nomenclature Part 3 ................................................................................................................... 10
3.4 Naming Alkanes .................................................................................................................................. 11
3.4 Naming Alkanes cont. ......................................................................................................................... 12
3.4 Naming Alkanes cont. ......................................................................................................................... 13
3.4 Naming Alkanes cont. ......................................................................................................................... 14
3.4 Naming Alkanes cont. ......................................................................................................................... 15
3.4 Naming Alkanes cont. ......................................................................................................................... 16
3.4 Practice Problems ............................................................................................................................... 17
Worksheet 3 Organic Nomenclature ........................................................................................................ 18
Identify all the functional groups.............................................................................................................. 19
Nomenclature Examples ........................................................................................................................... 20
Worksheet 4 Organic Nomenclature Part (II) .......................................................................................... 21
Naming Saturaded Hydrocarbons I ........................................................................................................... 22
Naming Saturaded Hydrocarbons II .......................................................................................................... 22
Formula Writing: Saturated Hydrocarbons.............................................................................................. 24
Naming Organic Functional Groups Form WS11.3.2A .............................................................................. 25
3.1 Functional Groups ............................................................................................................................... 26
3.1 Functional Groups ............................................................................................................................... 27
Recognizing Functional Groups................................................................................................................. 28
Recognizing Functional Groups cont. ...................................................................................................... 29
ALKANE NAMING: iso, neo, & cyclo ......................................................................................................... 30
Alkanes ...................................................................................................................................................... 31
Properties of Alkanes ................................................................................................................................ 32
PROPERTIES OF ALKANES
REACTIONS ............................................................................................... 33
Organic Flowsheet .................................................................................................................................... 34
Alcohols and Grignard Reactions ........................................................................................................... 35
Mapping Multistep Synthesis 1 ............................................................................................................... 38
Mapping Multistep Synthesis 2 ............................................................................................................... 39
Page
Organic Chemistry Multistep Synthesis .................................................................................................. 37
2
Organic Synthesis ...................................................................................................................................... 36
Nomenclature Exercise ............................................................................................................................. 40
Haloalkanes ............................................................................................................................................... 41
Haloalkanes cont....................................................................................................................................... 42
Reactions of haloalkanes .......................................................................................................................... 43
Chemistry Worksheet—Prepartions ......................................................................................................... 44
Alkenes...................................................................................................................................................... 45
Naming Alkynes and Dienes ..................................................................................................................... 46
FORMULA WRITING: ALKYNES AND DIENES ............................................................................................. 47
CHEMISTRY ............................................................................................................................................... 48
REACTIONS OF ALKENE AND ALKYNES...................................................................................................... 48
Markownikoff's Rule: ................................................................................................................................ 49
Markownikoff's rule cont.......................................................................................................................... 50
PROPERTIES OF ALKENES I ........................................................................................................................ 51
PROPERTIES OF ALKENES II ....................................................................................................................... 52
PROPERTIES OF ALKENES AND DIENES ..................................................................................................... 53
Organic Chemistry alkanes, alkenes, alkynes ........................................................................................... 54
Chemistry .................................................................................................................................................. 55
Organic Reaction ....................................................................................................................................... 55
Organic Chemistry Show the Predicted Products ................................................................................... 56
Organic Reactions Worksheet .................................................................................................................. 57
Predict Reactants: Complete the following processes ............................................................................ 58
Chemistry Multistep Synthesis ................................................................................................................ 59
ALCOHOLS ................................................................................................................................................. 60
NAMING ALCOHOLS ............................................................................................................................ 61
FORMULA WRITING: ALCOHOLS ..................................................................................................... 62
ORGANIC CHEMISTRY REVIEW – THROUGH ALCOHOLS........................................................................... 63
Br .......................................................................................................................................................... 63
6.
Write Formulas (Expanded as above). .......................................................................................... 63
Cis-2-butene
___________________________________ .......................................................... 63
2-cyclopentyl-3,3-dichloro-1-hexene ___________________________________ .......................... 63
3,3-diamino-1-butyne
__________________________________ .................................................. 63
Alcohol and Oxygen Compounds Reaction Mechanisms ......................................................................... 64
A (down the flowchart) ............................................................................................................................ 64
B (up the flowchart) .................................................................................................................................. 64
Reactions of alcohols ................................................................................................................................ 65
3
+H2O ......................................................................................... 64
Reactions of alcohols cont. ..................................................................................................................... 66
Page
Other Alcohols
PROPERTIES OF ALCOHOLS ....................................................................................................................... 67
Chemistry Preparation of Alcohols ........................................................................................................... 68
Predict Product or Missing Reactant ........................................................................................................ 69
A) ...................................................................................................................................................... 69
F)
G)
C–C–C
CN ................................................................................................. 69
OH
C–C–C
I)
C – C – C ............................................................................................................ 69
OH
C – C – C ......................................................................................................... 69
Do in
O ...................................................................................... 69
Show the steps necessary ......................................................................................................................... 70
Naming Organic Compounds Containing Oxygen..................................................................................... 71
Naming Aldehydes and Ketones ............................................................................................................... 72
PROPERTIES OF ALDEHYDES AND KETONES #1 ........................................................................................ 73
MULTISTEP SYNTHESIS Do the following conversions ...................................................................... 75
ALDEHYDES AND KETONES.............................................................................................................. 76
NAMING ACIDS ..................................................................................................................................... 77
Page
4
FORMULA WRITING: ACIDS ...................................................................................................................... 78
Organic Families and Functional Groups
Family
Functional Group
-
Functional Group
R = carbon group
X = halogen (F, Cl, Br, I)
Example
Alkanes
Carbon, Hydrogen,
and single covalent
bonds only.
Propane
Alkenes
=
|
|
R–C=C–H
Propene
Alkynes

R–CC–H
Propyne
Alkanols
(Alcohols)
-OH
R – OH
Propanol
-O-
R – O – R’
Methyl Ether
||
-C-H
H
|
R–C=O
Alkoxy
Alkanes (Ethers)
Alkanals
(Aldehydes)
Alkanones
(Ketones)
O
||
-C-
Alkanoic Acids
(Carboxylic
Acids)
O
||
-C-OH
Esters
O
||
-C-O-
Propanal
O
R – C – R’
Propanone
O
R – C – OH
O
R – C – O – R’
Propanoic Acid
Methyl
Propanoate
Amines
|
-N-
R’
|
R– N-R”
Aminopropane
Amides
O
|| |
-C-NH
O R’
|| |
R -C-NH
Propanamide
-F fluoro-)
Haloalkanes –Cl (chloro-)
(Alkyl Halides) -Br (bromo-)
-I (iodo-)
R
–
X
(X represents any halogen)
Bromopropane
H H H
|
|
|
H -C – C – C –H
|
|
|
H H H
H H H
|
|
|
C=C–C–H
|
|
H
H
H
|
H–C C–C–H
|
H
H H H
|
|
|
H – C – C – C –OH
|
|
|
H H H
H
H
|
|
H–C–O–C–H
|
|
H
H
H
H
|
|
H–C–C–C=O
|
| |
H H H
H
H
|
|
H–C–C–C–H
| || |
H O H
H
H
|
|
H–C–C–C=O
|
| |
H H OH
H H
H
|
|
|
H–C–C–C–O–C–H
|
| ||
|
H H
O
H
H H H
| | |
H – C – C – C –NH2
| | |
H H H
H H
|
|
H – C – C – C =O
|
|
|
H H NH2
Br H H
| |
|
H - C – C – C- H
|
| |
H H H
Page
5
Aromatic
NAME____________________________DATE_____________________________
CLASS____________________________TEACHER_________________________
ORGANIC FAMILIES 1
Tell which organic family each of the following compounds belongs to. Also, pick out the
functional group(s) in each compound. Write the family on the first line and the functional group(s) on
the second. You may have to draw an expanded structural formula for the compound first.
O
7.
____________________________
____________________________
O
2.
CH3CH2CH2CH2CH2C
________________________
________________________
8.
H
____________________________
____________________________
3.
CH3CH2CH2CH(CH3)CH3
CH3CH2CH2CH2C
9.
CH3CHClCH2CH3
10.
CH2
CHCH2CH2CH3
____________________________
____________________________
CH3CH2CH2CH2CH(NH2)COOH
________________________
________________________
11.
____________________________
____________________________
6.
CH3CH(NH2)CH2CH2CH3
________________________
________________________
OH
____________________________
____________________________
5.
CH3CH2OCH2CH2CH2CH3
________________________
________________________
____________________________
____________________________
O
4.
CH3CH2CCH2CH3
CH
CCH2CH2CH3
________________________
________________________
12.
CH3CHOHCH2CH2CHOHCH3
________________________
________________________
6
CH2OHCH2CH2CH3
Page
1.
ORGANIC FAMILIES 2
Draw an expanded structural formula and a condensed structural formula for any compound that
would belong to each of the families named below.
(to be consistent use propane as the base chain)
1. Alkene
6. Aldehyde
2. Carboxylic acid
7. Alcohol
3. Ketone
8. Amino acid
10. Alkyne.
7
5. Alkane
9. Alkyl halide (haloalkane)
Page
4. Ether
Organic nomenclature part (1)
Chemicals compounds that contain the element Carbon are known as organic compounds. “Organic”
comes from the fact that until the mid 1800’s it was thought that these chemicals could only be derived
from living plant or animal components. In 1828 Friedrich Woher converted the inorganic ammonium
salt of cyanic acid into urea, which is an organic compound. Today hundreds of thousands of new
organic compounds are discovered each year.
With so many new carbon compounds being synthesized by research chemists each year, it
became very important to have a systematic method of naming these compounds. Today most
chemists use what is called the IUPAC system of nomenclature. (IUPAC standards for International
Union of Pure and Applied Chemists). This system gives you the names of the simple organic
compounds and then shows how to combine these names to represent the more complicated
compounds. The simple organic compound are called “hydrocarbons” because they contain only
carbon and hydrogen atoms. The simple groups of hydrocarbons are called the alkanes.
Alkanes consist of straight chains of carbon atoms bonded together. For our purposes today we
will consider derivatives of the first ten alkanes. These compounds are shown below.
#
Name
Carbon
Molecular Structural
Formula Formula
#
Name
Carbon
Molecular Structural
Formula Formula
1
Methane
CH4
CH4
6
Hexane
C6H14
CH3(CH2)4CH3
2
Ethane
C2H6
CH3CH3
7
Heptane
C7H16
CH3(CH2)5CH3
3
Propane
C3H8
CH3CH2CH3
8
Octane
C8H18
CH3(CH2)6CH3
4
Butane
C4H10
CH3CH2CH2CH3
9
Nonane
C9H20
CH3(CH2)7CH3
5
Pentane
C5H12
CH3CH2CH2CH2CH3
10
Decane
C10H22
CH3(CH2)8CH3
*Note: When writing the symbols for organic compounds, chemists usually omit the Hydrogen atoms
from the structural formulas as shown above. Since some of the formulas can get quite complicated
we simply show each Hydrogen as a line extending from the Carbon atoms. The lines between the
Carbon atoms represent bonds that are holding the Carbon’s together.
H
H
C
C
C
C
H
H
H
H
H
can be written as
Often, two or more of the alkanes shown above are joined together to form a compound consisting of
multiple chains. When naming compounds such as this we will name the shortest branch first,
however we will change the ending of the shortest branch to end in –yl, followed by the name of the
longest branch. We must also use a numeral to denote the position of the short branch on the longest
Carbon chain. Study the following examples:
|
|
-C-C| | | | |
| | | | |
-C---C---C----C---C- 2-methylpentane
-C---C----C---C---C3-methylpentane
| | | | |
| | | | |
8
Ex
H
Page
H
H
ORGANIC NOMENCLATURE Part 2
In Part (I) you worked on naming simple organic compounds called alkanes. Some of these alkanes
were found with “side Chains” attached to the main Carbon chain. We will consider naming alkanes
that contain two or more side chains. The rules will be basically the same with only a few
modifications. Below is the chart that you will need to help you with today’s assignment.
# Carbon Name
Molecular Expanded
Formula Structure
Condensed
Structure
1
Methane
CH4
-c-
CH4
2
Ethane
C2H6
-c-c-
CH3CH3
3
Propane
C3H8
-c-c-c-
CH3CH2CH3
4
Butane
C4H10
-c-c-c-c-
CH3CH2CH2CH3
5
Pentane
C5H12
6
Hexane
C6H14
7
Heptane
C7H16
8
Octane
C8H18
-c-c-c-c-c-c-c-c-
CH3(CH2)6CH3
9
Nonane
C9H20
-c-c-c-c-c-c-c-c-c-
CH3(CH2)7CH3
10
Decane
C10H22
-c-c-c-c-c-c-c-
-c-c-c-c-c-c-c-c-c-c-
Numbers for amount of carbons
1 meth
2 eth
3 prop
4 but
5 pent
6 hex
7 hept
8 oct
9 non
10 dec
CH3(CH2)4CH3
CH3(CH2)5CH3
CH3(CH2)8CH3
11
12
13
14
15
16
17
18
19
20
undec
dodec
tridec
tetradec
pentadec
hexadec
heptadec
octadec
nonadec
icos
9
-c-c-c-c-c-c-
CH3CH2CH2CH2CH3
Page
Numbers for how many
of one group there is:
1 mono 9 nona
2 di
10 deca
3 tri
11 undeca
4 tetra
12 dodeca
5 penta
6 hexa
7 hepta
8 oxa
-c-c-c-c-c-
Organic Nomenclature Part 3
In the previous two examples, the numerals 2 and 3 were used to show which carbon in the main chain
had the methyl group attached to it.
WHEN NUMBERING THE LONGEST CARBON CHAIN, ALWAYS BE SURE TO START NUMBERING THE
CHAIN AT THE END CLOSEST TO THE SIDE CHAIN. STUDY THE FOLLOWING EXAMPLES:
| || | ||
-C-C-C-C-C-C| | | | | |
-C|
2-methylhexane
BE CAREFUL WHEN FINDING THE LONGEST CARBON CHAIN FOR NUMBERING PURPOSES. THE LONGEST CHAIN
ISN’T ALWAYS THE HORIZONTAL CHAIN!
WRONG
| | | || |
-C-C-C-C-C-C| | | || |
-C5-methylhexane
|
|| | | |
C-C-C-C-C
|
-C|
-C|
4-ethylpentane
WRONG
RIGHT
| | | | |
C-C-C-C-C|
-C|
-C|
2-ethylpentane
WRONG
| | | | |
C-C-C-C-C|
-C|
-C|
3-methylhexane
RIGHT
EXAMINE THE FOLLOWING EXAMPLES AND THEN TRY TO NAME EACH OF THE COMPOUNDS ON YOUR
WORKSHEET. 1) highlight the main chain 2) circle the subgroups 3) number the chain
| | | | | | | |
| | | |
| | | |
C-C-C-C-C-C-C-C-C-C-C-C-C-C-C-C|
|
|
C-C-C|
|
|
-C-C-CRead
| | and highlight the rules that are|new to you.
|
-C-C-C3 methylpentane
|
| |
5-methylundecane
-C3 methylheptane
| || | | | | |
- C-C-C-C-C-C-C-C| | | | | || |
octane
| | |
C-C-C|
-C|
methylpropane
|
-C|
-C-C- 2-methyl pentane
|
-C| | | | | | |
|
C-C-C-C-C-C- C-C|
|
-C-C|
|
-C3 ethylheptane
| | | | | | |
C-C-C-C-C-C-C|
-C|
2-methylheptane
No numbers
needed because
1-methyl or 3methyl would be
butane
C
/
C
|
C
\
\
C
|
C
/
C
Cyclohexane
(add in H’s)
| | | | | | |
C-C-C-C-C-C-C|
-C|
-C-C-C|
5-methyldecane
|
10
| | | |
C-C-C-C|
-C|
2-methylbutane
Page
|| | | |
C-C-C-C-C-C
|
-C|
2-methylhexane
3.4 Naming Alkanes
Page
11
Directions: Read and HIGHLIGHT the structures to understand the naming/numbering system.
Page
12
3.4 Naming Alkanes cont.
Page
13
3.4 Naming Alkanes cont.
Page
14
3.4 Naming Alkanes cont.
Page
15
3.4 Naming Alkanes cont.
Page
16
3.4 Naming Alkanes CLASSWORK.
3.4 Practice Problems
Page
17
WRITE THE ANSWERS TO THESE PROBLEMS ON A SEPARATE PAGE.
REMEMBER TO “COUNT, HIGHLIGHT, and NUMBER, CIRCLE”
Worksheet 3 Organic Nomenclature
You MUST 1) highlight the longest chain 2) circle the sub group 3) number the longest chain
Name the following molecules:
1.
| | | | |
-C-C-C-C-C| | | | |
-C|
-C|
2.
| | |
-C-C-C| | |
-C|
3.
| | | | | | |
-C-C-C-C-C-C-C| | | | | | |
-C|
-C|
Give the structure for each compound named below. DRAW IN ALL HYDROGENS.
(draw H’s)
6. 5-butylnonane
8. 1-ethylcycloheptane (draw H’s)
18
7. cyclopentane
5. 5-propyldecane
Page
4. 3-methyloctane
Identify all the functional groups
Circle and identify all the functional groups. Use different colors for each type.
Complete the assignment on the other side of this paper.
Piperine (from black pepper)
Cocaine (the coca bush)
Caffeine (coffee and tea)
Ca\\
Pyrethrin (a natural
19
Penicillin G (antibiotic)
Page
Cantharidin (blister beetle)
insecticide)
Nomenclature Examples
In today’s work we will look at naming alkanes that have two or more side chains attached to the main
carbon chain. The same rules apply that we used in Part (1) however we will need to designate all
positions of the side chains with numerals. If two of the attached side chains are attached to the main
chain, the side chains are named in alphabetical order. The side chains are still assigned numerical
positions along the main chain starting with the end closest to the first branch regardless of the
alphabetical nature of the names of the groups. Examine the compounds shown below.
Directions: 1) highlight 2) circle 3) number in order to understand this page.
ι ι ι ι ι ι ι ι
Notice that we started assigning numerals at the left side
C-C-C-C--C-C-C-C
of the main 8 carbon chain. However, we named the ethyl
ι ι ι ι ι ι ι ι
group before the methyl group due to the alphabetical
-C- -Corder of ethyl and methyl
ι
-Cι
5-ethyl-3methyloctane
ι ι ι ι ι ι
C-C-C-C--C-Cι ι ι ι ι ι
-C- -Cι |
2,4-dimethylhexane
-Cι ι ι ι ι ι ι
C-C-C-C--C-C-Cι ι ι ι ι ι ι
-C-
Here we have two groups that are exactly the same
attached to our main 6 carbon hexane chain. We must use
the numerals to denote the position of both of the methyl
groups. The name dimethyl hexane does not supply
adequate information to identify this compound.
In this case we started numbering our main carbon chain
on the right hand side because this was the side closest to
the first side branch. Again, the name dimethyl heptane
would not adequately describe this compound
3,3-dimethylheptane
-Cι ι ι ι ι ι ι ι
C-C-C-C--C-C-C-C
ι ι ι ι ι ι ι ι
-C- -Cι
- C|
5-ethyl-3,3-dimethyl-octane
ι
-Cι ι ι ι ι ι ι ι
C-C-C-C--C-C-C-C
ι ι ι ι ι ι ι ι
-C- -C|
ι
3,3,5-trimethyloctane
Here we begin numbering the 8 carbon chain at the left
which is closest to the first side chains. The dimethyl
groups are NOT alphabetized under “d” but for “m” for
methyl. Alphabetically, the dimethyl comes after the ethyl
and is thus named second.
Here we have three identical methyl groups and thus use
the prefix “tri”. We begin numbering the side chains at the
left which is the closest to the first methyl group.
20
3-ethyl-6methyloctane
|
Here octane is the longest carbon chain. By alphabetical
order we decided to name ethyl before methyl.
Page
ι ι ι ι ι ι ι ι
C-C-C-C--C-C-C-C
ι ι ι ι ι ι ι ι
-C-C|
- C|
Worksheet 4 Organic Nomenclature Part (II)
STUDENT DIRECTIONS: Give the name for each compound shown in the first column and the structure
of each compound named in the second column. Directions: (1)highlight the main chain, 2)circle the
subs, 3)number the chain)
4) name it or draw as appropriate.
Ι
|
3,3 diethylpentane
-C- -Cι ι ι ι ι ι ι
- C- C- C- C- C- C- Cι ι ι ι ι ι ι
ι ι ι ι ι ι ι ι ι ι
- C-C-C-C--C-C-C-C –C-C
ι ι ι ι ι ι ι ι ι ι
- C-C|
ι
-Cι
-Cι
ι
-Cι ι ι ι
- C-C-C-C-ι ι ι ι
-Cι ι ι ι ι ι
-C-C-C-C-C-C –
ι ι ι ι ι ι
2-methyl-5-propylnonane
ι
-Cι ι ι
- C-C-C
ι ι ι
-Cι
ι ι ι ι ι ι ι ι
- C-C-C-C--C-C-C-C –
ι ι ι ι ι ι ι ι
-Cι ι
-C-Cι ι
-Cι
ι ι ι ι ι ι
- C-C-C-C--C-Cι ι ι ι ι ι
-Cι ι ι ι ι
-C-C-C-C-C
| | | | |
-C-
3-ethyl-3-methylhexane
3-ethyl-2-methylhexane
21
2,3,4-trimethylhexane
Page
|
3,3-diethyl-5,5-dipropyldecane
Page
22
Naming Saturaded Hydrocarbons I
Page
23
Naming Saturaded Hydrocarbons II
Formula Writing: Saturated Hydrocarbons
4. 2,3,3-trimethylheptane
2. cyclobutane
5. cis-1,3-diethylcyclopentane
3. 2,2-dimethyl-3-propylhexane
6. 2,2,3,4-tetramethyloctane
7. 2,7-dimethylnonane
10. 3-methyl-4-propylheptane
8. 2,3,3-trimethylpentane
11. 3-ethyl-2-methylpentane
9. 2,4-dimethylhexane
12. 1,2-diethyl-4-methylcycloheptane
Page
1. 2-methylhexane
24
Write expanded structural formulas for the first six compounds and condensed structural
formulas for the last six compounds. Check to be sure that the given name is correct.
Naming Organic Functional Groups Form WS11.3.2A
Page
25
Expand the ones that are not expanded and name the functional groups.
Page
26
3.1 Functional Groups
Page
27
3.1 Functional Groups Practice Problems
Page
28
Recognizing Functional Groups
Page
29
Recognizing Functional Groups cont.
ALKANE NAMING: iso, neo, & cyclo
Examples:
5 isopropylnonane
1 - pentylcyclohexane or
1 - cyclohexylpentane
Pentane
(C5H12)
5 - neobutylnonane
Chain
neopentyl
group
5 - isopropylnonane
Chain
isobutyl
group
NAME THE STRUCTURES
1.)
2.)
name two ways
30
4.)
Page
3.)
Alkanes
I . + CH4 ----->CH3I + H . (unstable)
3.
CH4I ------>CH3I + H .
4.
H . + I . ---->HI
Page
2.
31
Preparation of: Alkanes are generally prepared from the refining of crude oil. Later, we will see that
they can also be obtained from alkenes and alkynes.
Reaction of: There are only two significant reactions of alkanes that we will consider: combustion and
halogenation.
Combustion:
Combustion involves the use of alkanes as fuel. In general, the alkane is mixed with oxygen and
burned producing carbon dioxide and water as the products. When this happens we refer to the process
as complete combustion. If not enough oxygen is present then incomplete combustion occurs producing
carbon monoxide and other complex products. We will always assume complete combustion occurs.
Generally:
flame
Hydrocarbon + x Oxygen -------> y Carbon dioxide + z Water
Examples:
flame
2C2H6 + 7O2 -------> 4CO2 + 6H2O
flame
C11H24 + 17O2 -------> 11CO2 + 12H2O
Halogenation:
Halogenation involves the substitution of an alkane’s hydrogen by an atom of any one of the
halogen atoms (F, Cl, etc). An alkane’s hydrogen is defined as a hydrogen bonded to a carbon atom
which has only single bonds to other carbon atoms or other hydrogens. The process requires ultraviolet
light to occur. The product is a haloalkane with one atom of halogen substituted into the alkane for each
molecule of halogen used. From each molecule of halogen used we also obtain one molecule of the
hydrogen halide (hydrohalogenic acid). This product is formed from the left over halogen atom and the
hydrogen atom removed during the substitution. In this reaction the substitution can occur at any alkane
hydrogen in the molecule so the student is free to choose which hydrogen atom(s) to substitute.
Generally:
Using X to represent any halogen
Alkane + nX2 -------> alkane-Xn + nHX
Examples:
CH4 + Br2 -------> CH3Br + HBr
CH4 + 4Br2 -------> CBr4 + 4HBr
Mechanism of the Substitution Process (Halogenation):
The sequence of steps involved in a chemical process is referred to as the mechanism. In
general, halogenation occurs as a four step process:
1.
The ultraviolet light photon collides with the halogen molecule and separates it into two
very reactive atoms.
2.
The halogen atom collides with an alkane carbon atom and bonds to it.
3.
The carbon atom now has five bonds making it unstable. One bond breaks. If it is the
carbon – halogen bond we return to the start and nothing has happened. If it is the
carbon – hydrogen bond, a substitution of halogen for hydrogen has occurred.
4.
The other halogen atom from step 1 combines with a removed hydrogen forming the
hydrogen halide.
Example:
UV
CH4 + I2 -----> CH3I + HI
Sequence of Steps
1.
I : I + photon UV ------> I + I
Properties of Alkanes
hexane + oxygen ------>
2.
ultraviolet light
2 – methylbutane + chlorine ------------------------>
3.
2,3 – dimethylpentane + dilute sulfuric acid ------>
4.
ultraviolet light
methane + chlorine (4 steps) (4Cl2) ----------------------->
5.
butane + sodium ------>
6.
uv
propane + bromine ------>
7.
3 – ethylpentane (oxidized) ------->
8.
ultraviolet light
ethane + fluorine ---------------------->
Page
1.
32
Write an equation that shows what happens in each of the following reactions. Name all
organic products formed. If no reaction occurs, write N.R. If more than one product is possible, make a
note to that effect. “∆” means “as flame or heat is present”.
PROPERTIES OF ALKANES
REACTIONS
Supply the missing reactant and/or product.
1.
UV
C4H10 + ____________ -------> _________________ + 2HI
2.
___________ + 8O2 -------> 5CO2 + _________________
3.
UV
CH3CH2CH3 + ___________ ------> no reaction
4.
UV
_____________ + 3Cl2 ------> _______________ + _________________
5.)
6.)
____________ + ______________ -------> 3CO2 + 4H2O
UV
_____________ + N2 ------> ___________________
Page
33
7.) ______________ + Cl2 ------> ____________________
Page
34
Organic
Flowsheet
Alcohols and Grignard Reactions
Balanced Reactions using KMnO4
3C3H7OH + 2KMnO4
3CH3COCH3 + 2MnO2 + 2H2O + 2KOH
1o alcohol
Cold
aldehyde
3CH3CH (OH) CH3+ 2KMnO4
3CH3COCH3 + 2MnO2 + 2KOH + 2H2O
2o alcohol
warm
Ketone
3C2H5CHO + 1KMnO4 + 3OHAldehyde
warm
3CH3CH2COOH + 1MnO2 + 1KOH + 1H2O
Carboxylic Acid
Grignard Reactions with Aldehydes and Ketones All reactions of Grignard reagents are like
the carbon dioxide case: the R adds to the C of the carbonyl group and eventually - H to the O.
So from an aldehyde or ketone we can make an alcohol - either primary, secondary or tertiary.
The only difference between these three reactions is the number and nature of the group(s)
attached to the C=O.
Making a primary alcohol from an alkyl bromide and formaldehyde
Making a secondary alcohol from an alkyl bromide and an aldehyde
Making a tertiary alcohol from an alkyl bromide and a ketone
Page
35
Synthetic applications of highly
reactive organometallic reagents such
as alkyllithium (LiR) and Grignard
(RMgX). Sulfoxides (R2SO), for example,
are prepared by treating thionyl
chloride (SOCl2) with a Grignard
reagent.
Organic Synthesis
Organic synthesis is the process of changing an organic substance into a different organic
substance by organic chemical reactions. There are two major groups of organic syntheses that we will
study: single step processes and multistep processes.
Single Step Processes:
A single step process involves the use of only one chemical reaction to change a substance
belonging to a certain family into a new substance belonging to another family. You are already
familiar with many single step processes. You know, for example, that you can treat an alkane with a
halogen in the presence of ultra violet light and change it into a haloalkane. As another example, you
can treat an alkene with water and convert it into an alcohol. In essence, what we do is change a
certain functional group (ie, a double bond) into a different functional group (ie, C-OH).
Multistep Synthesis:
C
C
C
C
KOH
Br2
UV
C
C
Br
In this process, the goal is the same as with single step synthesis: to change a functional group in a
molecule into a different functional group. The difference with multistep synthesis is that it must be
done by a series of several chemical reactions instead of only one reaction. The reason for using a
series of steps is no single step is known for making the desired change. In the above example, the goal
is to change ethane into ethene. The problem is no known reaction will cause the desired change.
However, we do know how to change ethane into bromoethane and we also know how to change
bromoethane into ethene. If we link the two reactions, we can reach our goal.
In the laboratory we would react ethane with bromine in the presence of ultraviolet light, thus
forming bromoethane. We would collect and purify the product bromoethane and then react it with
potassium hydroxide forming the ethene and another product, potassium bromide. The process (ie.
Starting point and goal) is written in a horizontal line and then the individual steps are presented in a
loop below the overall process. To simplify the diagram, the non organic products (ie. Potassium
bromide) are omitted. If they are included, it can be confusing whether they are products from the
previous step or reactants fro the next step. The necessary reactants and conditions (ie. Br2, UV
&KOH) are generally written above or below the arrow(s). Our primary interest is in showing what
changes happen to the original molecule at each step in the process.
Page
36
See the handout “Use of the Organic Flowsheet” for help doing Multistep synthesis problems.
Organic Chemistry
Multistep Synthesis MAPPING
List the sequence of families involved in the following syntheses, include the reactants
necessary to produce the product: (#1 is done for you)
This will be called MAPPING
1. alkane
Alkane X2/uv
haloalkane
alcohol
(give two ways)
KOH alcohol
Or
Alkane X2/uv haloalkane KOH
4. alkene
5. alkyne
6. alkane
trihaloalkane
ketone
ketone
cyanoalkane
cyanoalkane
37
3. haloalkane
alcohol
Page
2. alkyne
alkene H2O/H+catalyst
Multistep Synthesis 1
H
H
C
C
H
H
H
H
C
C
H
H
H
cyanoalkane
H
cyanoalkane
Page
H
H
38
Map 2 ways to this destination. Show reactions and side products.
Mapping Multistep Synthesis 2
1. alkane
alkanone
Alkane 2X2/uv dihaloalkane 2KOH alkyne 2H2O alkanone
2. alkane
3. alkyne
alkanol
alkanol
In problems 4, 5, and 6, write out the multistep synthesis from above using the structures not
the names )
Use Propane as the base molecule. Show all side products.
4. (#1)
C-C-C
5. (#2)
C-C-C
6. (#3)
Page
39
C-C-C
Nomenclature Exercise
H
H C H
H
H C
H
H
C
I
C
H
H
H C H
C
H
H
H C H
H
C
H
H
C H
H
1.
Br
H C
H
H
C
H
H
C
C
H
H
Cl
C
2.
4.
CH3CH(CH3)CH2CHBrCH(CH3)CH3
H
H C H
H
H C
H
H
C
H
C
H
C H
H
H
H
C
C H
H
H
H
C
H
H
C H
H
CH3
H3C
CH
H C H
CH3
CH3
CH
CH2 HC
CH3
Br
3.
5.
6.
(CH3)2CHC(C2H5)3
CH3
CH3
CH2 HC
CH
C
CH2
CH3
H2C
CH2 CH3
CH
Cl
CH2 HC
CH3
40
H3C
Page
CH3 CH2
Haloalkanes
The reaction which characterizes the haloalkane family is that process which
eliminates the halogen atom(s) from the carbon atom of the chain.
The reaction would be represented as follows:
Haloalkane + KOH -----> alcohol + K-X ( X= halogen atom )
The reaction is most easily understood if you remember that there is generally a
difference in electronegativity between the halogen and the carbon atom ( C-Cl
difference is 0.5 ).
The result is that the halogen atom will be slightly negative compared to the
carbon atom. We can take advantage of this difference by adding something positive
to the reaction container. A substance found to be very effective in this process is the
potassium ion in potassium hydroxide (KOH) .
The positive potassium ion attaches to the halogen and helps to pull it off the
carbon chain. When the halogen atom separates from the chain, it will take the bonding
electrons with it ( because of its higher electronegativity ). The remaining carbon chain
now has a positive charge where the halogen atom used to be.
C-C-C-C-C + K+ ------> C-C-C-C-C + KBr
|
Br
This carbon chain ion must now react in such a way that the charge is
neutralized. The particle is then back to the neutral state of a stable molecule.
There are two ways in which this can happen. Which way actually occurs is
governed by the conditions under which the process is conducted.
We will simply assume that you can do whichever process you need to do.
The first possibility for what can happen is that the positive carbon atom can
collide with the negative hydroxide ion used to supply the potassium ion originally. If
this happens, the result is an alcohol.
A specific example would be:
C-C-C-C-C + KOH ------> C-C-C-C-C + KBr
|
|
Br
OH
The second possibility is a little more complicated:
Page
haloalkane + KOH -----> alkene + K-X + H-OH
41
A summary of the second process is:
Haloalkanes cont.
On a carbon chain, the hydrogen atoms are very slightly positive compared to the
carbon atoms. The electrons in the carbon atoms next to the positive carbon atom
which lost the halogen are drawn towards the positive carbon weakening the C-H
bond.
|
|
v
v
C-C—C--C-C
| + |
H
H
e---> <-- eThe hydroxide ion is then able to pull off the hydrogen atom of one of the carbon
atoms marked with the arrows (carbons #2 & #4 ) in the above diagram. The bonding
electrons are left behind on the more electronegative carbon atom. These electrons
can now be used to form a pi bond between the two C atoms giving an alkene product
and water.
|
|
v
v
C—C--C--C--C ------> C-C=C-C-C
|
|
+
H
H
-OH
+ HOH
A specific example would be:
C-C-C-C-C + KOH ------> C=C-C-C-C + KBr + HOH
|
Br
Add this general reaction to your flow sheet now before you forget.
PRODUCTION OF ALKYNES WITH THIS PROCESS:
If a haloalkane has two halogen atoms and two hydrogen atoms next door, it can
undergo the above second possibility twice ( given two KOH ) to form an alkyne
A summary of the this process is:
dihaloalkane + 2 KOH -----> alkyne + 2K-X + 2H-OH
A specific example would be:
Page
Br Br
42
C-C-C-C-C + 2KOH ------> C = C-C-C-C + 2KBr + 2HOH
| |
Reactions of haloalkanes
Name
Period
Supply the missing components or if nothing will happen write N.R. (Double and triple bonds
form towards the center of the molecule. (See first problem)
KOH
1. C-C-C-C
C-C=C-C + KBr + H2O
|
rather than
Br
C-C-C=C
2.
KOH
Cl
5.
Br
|
C-C-C
|
Br
KOH
2KOH
C
|
C-C-C-C + 2KOH
|
I (iodine)
43
4.
C Cl
| |
C-C-C-C
|
C
Page
3.
Chemistry Worksheet—Prepartions
Instructions: Show how to prepare the indicated product using the given reactant.
CH2I2
2. CH3CH2CH2OH
4.
CH2CH3
|
CH3CH2C=CH2
5. butane
6.
Br
|
C-C-C
7.
CH3CH3
CH3CH2CN
H
|
CH3CH2CCH2CH3
|
CH3
2-butanol
Br
|
C-C-C
CH3CH2MgBr
44
3. CH3CH3
CH3CH2CH2Br
Page
1. CH4
Alkenes
Additional Rules:
1.) Functional group is on the
longest chain
2.) Number from end closest
to functional group
Naming Examples:
C
|
C-C-C=C-C-C
|
C
C-C=C-C-C
2 - pentene
or
pent -2- ene
2, 2 - dimethyl -3- hexene
or
2, 2 - dimethyl hex -3- ene
C-C
|
C-C-C-C-C-C=C
|
C-C
6 – ethyl-6 - methyl, -1- octene
or
oct -1- ene
1, 4 - cyclohexadiene
or
cyclohexa -1, -4 diene
NAME THE EXAMPLES ON this SHEET.
Note: It is permissible to leave the hydrogen atoms off of any structures. Just
remember that there are enough hydrogen atoms in the molecule such that every
carbon atom has four (4) bonds.
1.)
2.)
3.)
4 .)
remember the functional group
gets the lowest number
45
6.)
Page
5.)
Page
46
Naming Alkynes and Dienes
FORMULA WRITING: ALKYNES AND DIENES
Write expanded structural formulas for the first six compounds and condensed formulas for the
last four compounds. If geometrical isomers are possible but not specified, write either form. Check to
be sure that the given name is correct.
5.
2,3-diethyl-1,3-hexadiene
5,6-diethyl-1,3-cyclohexadiene
7. 2-methyl-1,3butadiene
3.
2,4-dimethyl-3-ethyl-2,4-hexadiene
8. Acetylene
4.
4,4,5-trimethyl-2-heptyne
9. 2-methylpent-1-ene-3
5,5-dimethyl-1,3-cyclopentadiene
10.
3,3,4,4,-tetramethyl-1,5-hexadiene
47
2.
6.
Page
1. 3-methyl-1-pentyne
CHEMISTRY
REACTIONS OF ALKENE AND ALKYNES
All the reactions of alkenes involve breaking the double bond into a single bond and adding
a new atom to each of the original double-bonded carbons.
Examples: Addition Reactions
AB
\
/
| |
C=C + AB --> -C-C/
\
| |
They are termed AB additions. There is only one product in these reactions. The
family to which this product belongs is determined by the nature of the A & B.
Examples:
1. ADDITION OF H2 (A=H,B=H)
HH
\
/ CATALYST | |
C=C + H2 -------> -C-C- AN ALKANE *
/
\
| |
2. ADDITION OF HBr (HX WHERE X IS ANY HALOGEN) A=H,B=Br
H Br
\
/
| |
C=C + HBr ---> -C-C- AN ALKYL HALIDE *
/
\
| |
3. ADDITION OF X2 (X IS ANY HALOGEN) A=X, B=X
Br Br
\ /
| |
C=C + Br2 ----> -C-C- an alkyl halide *
/ \
| |
Page
5. ADDITION OF HYDROGEN CYANIDE (HCN) H=A, CN=B
H CN
\ /
| |
C=C + HCN ----> -C-C- (a cyanoalkane) *
/
\
| |
48
4. ADDITION OF H2O (HOH) A=H B=OH
H OH
\
/
| |
C=C + H2O ---->-C-C- an alcohol *
/
\
| |
Markownikoff's Rule: With the addition of an AB in which A is an H atom (H-B), the H
goes to the carbon of the double bond which already has the most H atoms.
Examples:
H CH3
H CH3
| |
HBr
| |
H--C=C--CH3 ----> H--C--C--CH3
| |
H Br
Reactions of alkynes are identical to those of alkenes except they can add 2 AB
molecules.
Examples:
1. Addition of H2
-C=C- + H2
H H
H H
catalyst \ /
+ H2
| |
----------> C=C ----------> -C-C/ \
catalyst | |
alkene
H H
alkane
2. Addition of H2O and HBr
-C=C- + H2O
OH
\
/ + HBr
---------> C=C- ---------->
/ \
OH
| |
-C-C| |
Br
3. Addition of 2Br2
-C=C- + Br2
Br Br
Br Br
|
| + Br2
| |
---------> -C = C- --------> C-C
| |
Br Br
Page
49
4. Any two A-B molecules can be added in any combination.
Markownikoff's rule cont
5. If two water molecules are added, the result is unusual. Markownikoff's rule means that both
OH groups will go to the same carbon.( see next page )
H OH
OH
O
H2O
| | H2O
| |
| ||
-C=C- -----> -C=C- ------> --C-C-- ----> -C-C +H2O
| |
| |
| |
OH
(ADD TO FLOW CHART)
(Automatically happens)
This gives us a new reaction of alkynes:
REACTION OF ALKYNES TO PRODUCE KETONES + ALDEHYDES
H OH
O
H+
| |
||
H-C=C-H + 2 H2O ----> H-C-C-H- ---> -C--C--H +H2O
CATALYST | |
H OH
Two oxygens singly bonded to the same carbon makes the carbon too positive so it's
unstable. The molecule rearranges by ejecting one OH group and the H from the other OH
group leaving a double bonded O on the original molecule.
O
H+
||
C-C=C-C + 2 H2O ---> C-C-C-C + H2O ( overall process )
step 1 H2O
H+
step 3
step 2
Page
50
H OH
OH
| |
H2O
|
C-C=C-C ----> C-C-C-C
H+
|
OH
PROPERTIES OF ALKENES I
Write an equation that shows what happens in each of the following reactions. Name all organic products
formed. Use structural formulas (C-C-C or
)
1. propene + bromine 
2. 3-hexene + hydrogen chloride 
12 O2
3. 1-octene (oxidized) 

4. 2-methylpropene + hydrogen cyanide 
5. cyclopentene + chlorine 
15 O2
6. 2,3,3-trimethyl-1-heptene + oxygen 

7. 2,3-dimethyl-2-butene + hydrogen 
Page
51
8. 1,2-dichloro-1-butene + chorine 
PROPERTIES OF ALKENES II
Write an equation that shows what happens in each of the following reactions. Name all organic products
formed.
1. 2,4-dimethyl-2-pentyne + ethyl alcohol 
2. 1,1,2,3,3,3-hexachloro-1-propene + hydrogen chloride 

3. ethylene + ethylene (3 steps)  (NR)
pressure
4. cyclohexene + hydrogen iodide 
5. 2-methyl-3-chloro-4-ethyl-3-heptene + fluorine 
6. 3,5-dichloro-4-methylcyclopentene + hydrogen bromide 

7. 2-methylpropene (polymerized)  (NR)
Page
52
pressure
Name:
Date:
Period:
PROPERTIES OF ALKENES AND DIENES
Write an equation that shows what happens in each of the following reactions. Name all organic products
formed.
1. 1,4-cyclohexadiene + hydrogen bromide (one mole) 
H+
2. 2-butyne + water (2 steps) 
3. 1,3,5-decatriene (completely oxidized) 

4. propyne + bromine (to completion) 
5. 5-methyl-1,3-cyclopentadiene + hydrogen cyanide (one mole) 
6. 1,3-butadiene (polymerized; 2 steps) 
7. 3-hexyne + chlorine (xs) 
OH
-
8. 3-methyl-1-butyne + ethanol 
C-------------C
|
|
C------------C
Page
10.
O
||
C-------C
|
|
C------ C
53
CN
|
9. Hexane
C---C---C---C---C---C
|
CN
Alkane—haloalkane—alkyne—dicyanoalkane
Organic Chemistry alkanes, alkenes, alkynes
Complete the following reactions by supplying the missing reactants or products.
1.
2.
| | | | | |
-C-C-C-C-C=C| | | |
+
C
|
C-C=C-C-C
|
C
H2
H2SO4
catalyst
+
KOH
3.
| | |
C=C-C-C-C| | |
4.
\ /
C
| | ||
-C-C-C + KBr
| | |
+
H2O
HCN
Br2
5.
C-C-C-C-C
C-C=C-C-C
UV
Multistep Synthesis
7.
OH
|
C-C-C-C
CH3CN
Br Br
| |
C-C-C-C
54
CH4
Page
6.
Chemistry
Organic Reaction
Give the steps required to do the following conversions.
O
||
1
.
OH
2.
Br
I
3.
Do the flowing Multistep Synthesis
Use the format presented in class
3. C - C - C
C-C-C
O
||
C-C-C
55
2.
Cl
|
C-C-C
Page
1. C - C - C
OH
|
C-C-C
Organic Chemistry
Show the Predicted Products
Show the predicted Products
(structural formula)
1.
+
2.
Cl2
UV
+ HCN
(1 mole only)
3.
+
2H2O
Show the sequence of step necessary to make the following process happen.
4. C
C-C-C-CBr
|
C-C-C-C-C
C-C-OH
56
C
Page
5. C
Organic Reactions Worksheet
Name
Period
Predict Products (add necessary chemicals)
1.
Br
|
C-C-C-C-C-C
2.
HCl
Br2
3.
C-C-C-C-C
| |
C C
|||
C
|
4.
2H2O
Br
Cl2
UV
5.
6.
CN
|
C-C-C
C8H14
I2
UV
?
no UV
Page
57
7. An unknown chemical is found later to have the formula C5H10. It reacts with I2 only in the presence
of UV. What could its structural formula be?
Predict Reactants: Complete the following processes
8.
+
3HCl
CN
|
|
Br
9.
10.
|
Br
C Br
| |
C--C—C
| |
C Br
O
||
C---C
11.
/
C
\
\
C=O
/
C--C
14.
OH OH
|
|
C—C---C---C---C
C
OH
|
|
C—C---C---C---C
|
C
58
13.
C-C-C
Page
12.
Chemistry
Multistep Synthesis
Show the steps required to go from the reactant to the product.
| | | |
-C-C-C-C| | | |
| |
-C-C| |
3.
|
-C|
-C= C-C--C| |
-C|
4.
Br
| | |
-C—C—C| | |
| | |
|
-C—C--C—C-OH
| | | |
|
O -C| || | |
-C---C—C—C|
| |
-C|
Br
| | |
-C—C—C| | |
59
2.
\ / | |
C=C--C--C/
| |
Page
1.
ALCOHOLS
These contain the -OH group. The general name is alkanol.
CH3CH2OH is ethanol, also called ethyl alcohol. (1-ethanol unnecessary since no confusion of structure
is possible.
A.) CH3CH2CH2CH2OH
__________________________________
B.) CH3CH2CHCH3
|
OH
______2 – butanol or butan – 2 – ol______
C.) CH3 CH3
\
/
CH
|
OH
__________________________________
D.) H H H H H H
| |
|
| |
|
H – C – C – C – C – C – C – CH3
| |
|
| |
|
H H H-C–H H H H
|
H-C-CH3
|
OH
__________________________________
(name by finding the longest chain
containing the -OH group)
E.) Br HO
| | |
– C – C – C – CH3
| | |
COH
4 – bromo – 2 – methyl – 1,3 – butandiol
OH
| |
–C–C–
| |
HO
__________________________________
__________________________________
(commonly called ethylene glycol antifreeze)
60
G.)
OH OH OH OH
| | | |
–C–C–C–C–
| | | |
Page
F.)
NAMING ALCOHOLS
On the lines provided, write the correct name for each of the following compounds. Where appropriate,
indicate whether an alcohol is primary, secondary, or tertiary.
1. CH3CH2CH2CH2OH
______________________________
2. CH3CHOHCH2C(CH3)2CH3
______________________________
3. CH2OHCHOHCH2OH
______________________________
4. (CH3)3COH
______________________________
5. CH3CHClCHOHCH(CH3)C(CH3)3
______________________________
6. CH2ClCH2CH(CH3)C(OH)(C2H5)CH2CH3
Page
61
________________________________
6.
2,3-butandiol
2. 3-chloro-4-methyl-1,2-hexdiol
7.
2-pentanol
3. 1-hydroxyhept-2-yne (hept-2-yne-1-ol)
8.
2,4-dichloro-2-hexanol
4. 2,2-diethylcyclopent-1,4-diol
9.
2-methylhex-3-ene-1-ol
5. 3,4 -dimethyl-2 –ethyl-2- hexanol
10.
3-methyl-2,4-pentanediol
Page
1. sec-butyl alcohol
62
FORMULA WRITING: ALCOHOLS
Write a structural formula for each of the following compounds. Check to be sure that the given name is
correct.
ORGANIC CHEMISTRY REVIEW – THROUGH ALCOHOLS
OH
___________________________________
___________________________________
C–C–C
|
C–C–C–C–C–C–C–C–C
|
C
|
C–C–C
CC–C–C–CC
___________________________________
___________________________________
Br
|
C – C – C – C – C – Br
| |
Br Br
___________________________________
___________________________________
2-cyclopentyl-3,3-dichloro-1-hexene
___________________________________
3,3-diamino-1-butyne
__________________________________
Page
Cis-2-butene
63
6. Write Formulas (Expanded as above).
Alcohol and Oxygen Compounds Reaction Mechanisms
KmnO4
KmnO4
1 alcohol 
aldehyde
——
alkanoic acid
LiAlH4
LiAlH4


A (down the flowchart)

remove H2

B (up the flowchart)

add H2

add H2O and remove H2
remove H2O and add H2


KmnO4 removes H
LiAlH4 adds H
A) Down
OH- - - O
O

Mn
RCH- - -O
O

H
Li+1
H
O- - - - H
OH
O- - H
 H
Al H 
-H2O

COH  R COH  R C- - H


H
H
OH

H  RCH

H
+H2O
2o
OH
O


RCH RCR can’t continue so ends as a ketone (secondary alcohol)

R
3o
OH
O


RCR  RCR can’t start –no reaction (tertiary alcohol)


R
R
64
Other Alcohols
H
Page
B) Up
O
OH- - - O
O
 H2O

 RC  RCOH
Mn O


H
H- - - ---------- - - -O

O
Cold blocks 
RCOH
Reactions of alcohols
A. Oxidation
Alcohols can be oxidized to aldehydes, ketones, and carboxylic acids by KMnO 4(or the ion
Cr2O7-2). The conditions under which the reaction is done determine the results. If everything is
kept cold, an aldehyde is produced from the corresponding primary alcohol and a ketone from
the secondary alcohol. If the reactants are heated, the primary alcohol (or the aldehyde) is
oxidized to the corresponding carboxylic acid. Since an oxygen is double-bonded to its
functional group carbon in the products of this reaction, tertiary alcohols are not oxidized by this
process ( because they have three C-C bonds to the functional group carbon ). KMnO4 is not
reactive enough to break C-C bonds.
Summary:
cold
primary alcohol
--------------> aldehyde
KMnO4
secondary alcohol
--warm------------> ketone
KMnO4
cold or hot
tertiary alcohol --------------> no reaction
KMnO4
warm
primary alcohol
--------------> carboxylic acid
KMnO4
warm
aldehyde
--------------> carboxylic acid
KMnO4
warm/cold
ketone
-------> no reaction
KMnO4
Try these reactions (Cr2O7-2 can be used instead of KMnO4.) :
warm
1. C-C-C-C-C ------->
|
KMnO4
OH
cold
2. C-C-C-OH -------->
KMnO4
Page
hot
-------->
KMnO4
C
OH
|
| cold
4. C-C-C-C-C ------->
| KMnO4
C
65
O
||
3. C-C-C
Reactions of alcohols
5.
cont.
OH
/
C-C
/ \
warm
C C ------->
\ / KMnO4
C-C
B. Dehydration
This reaction is essentially the reverse of the water addition to alkenes we studied earlier.
Concentrated sulfuric acid is used as the dehydrating agent.
H OH
| |
C---C
H2SO4
C=C +H2O
C. Substitution
1. All alcohols can have the OH group replaced by a halogen using the chemical - phosphorous
tri-halide (PBr3, PCl3 etc):
PBr3
C-OH ------> C-Br + PBr2OH
2. This reaction is the reverse of the preparation of alcohols from haloalkanes. Hydrohalogenic
acid or phosphorous trihalide is needed
R-OH + H-X
R-X + H-OH
R-OH + PX3
R-X + PX2-OH
Complete:
PCl3
6. C-C-C-C ------>
|
C-OH
OH
|
PBr3
C--C—C--C -------->
| |
C- C
OH
/
C-C
/ \
PBr3
C C ------->
\ /
C-C
Page
8.
66
7.
PROPERTIES OF ALCOHOLS
Write an equation that shows what happens in each of the following reactions. Name all organic compounds that
are produced. Write NR if no reaction happens. (NOTE: Cr2O7=  KMnO4-)
Cr2O7=
1. 1-butanol
(cold, dilute)
2. 2-methyl-1-pentanol + sodium
3. m-chlorophenol + chlorine
4. 2,2-dimethyl-3-hexanol + hydrogen bromide
2nd degree alcohol
5. ethylalcohol + hydrogenbromide
6.
K MnO4
2-hexanol
(cold, dilute)
7. 3-methyl-1-pentanol + acetic acid
H2SO4 (concentrated)
+
Page
67
8. p-nitrophenol + propanoic acid
Chemistry Preparation of Alcohols
Worksheet
O
1.)
CH3CH2CH2C
H --------->
C
2.)
C
C
C
C
+
__________ -----------> (remember
the Russian)
+
__________ ------------>
C
3.)
C
C
C
C
C
O
4.)
C
5.)
C
OH
C
H2
+ 2H2O ------------> ________________ ------------>
C
Br
C
C
C
C
C
+
KOH ------------>
(dilute)
C
C
6.)
O
7.)
C
C
C
+
+
O2
H2
------------->
Flame
----------->
C
C
C
OH
C
C
C
LiAlH4
------------->
Page
8.)
C
68
O
Predict Product or Missing Reactant
UV
A)
+
3Br2
Light
B)
Combustion
+
C) CC
7CO2 + 7H2O
+
H2O
C
C
+
Br2
HBr
D)
C
E. C - C - C -
C=C
C
Br
|
|
C - C
|
C
Multistep Syntheses
KOH
O
||
C–C–C
F) C – C – C
G)
OH
|
C–C–C–C
CN
|
C–C–C–C
H)
OH
|
C–C–C
Do in
4 steps
O
||
C–C–C
69
I)
C–C–C
| |
C–C
|
CN
Page
C–C–C
| |
C–C
Show the steps necessary to complete the following multistep syntheses. Map and show
reactants
3.) C – C
C–CC–C
O
||
C – C – OH
70
OH
|
2.) C – C – C – C
C – C – OH
Page
1.) C – C
Naming Organic Compounds Containing Oxygen
Naming the alcohols, aldehydes, ketones and carboxylic acids is easily accomplished by simply changing
the ending of the name. To change the ending, simply take the corresponding alkane name and drop the
“e” from the end. Then add the appropriate ending for one of the four families above. See the chart
below:
Family
alcohol
aldehyde
ketone
Carboxylic acid
Formal Name
alkanol
alkanal
alkanone
alkanoic acid
Ending
ol
al
one
oic acid
Example
1-propanol
propanal
2-propanone
propanoic acid
Note that since the aldehyde and carboxylic acid functional groups must be on the end of the longest chain
their locations are automatically at carbon number one and need not be specified.
For complicated molecules the ketone double bonded oxygen can be named as a substituent rather than as
a family functional group. In this case it is called “oxo”. The alcohol group can be name as a “hydroxyl”
substituent.
Examples and sample problems:
C-C-C-C-C-C-C-C-C=O
4-oxononanoic acid
||
|
O
OH
C-C-C-C-C-C=O
hexanal
C-C-C-C-C-C-C-C=O
||
||
O
O
3,6-dioxooctanal
C-C-C-C-C-C-C=O
|
|
OH
OH
___________________________________________
___________________________________________
71
C-C-C-C-C-C-C-C-C
|| |
O Cl
___________________________________________
Page
Try these:
C-C-C-C-C-C-C-C =O
|
|
C C-C
Answers: 4-ethyl-6-methyloctanal, 5-chloro-3-nonanone, 5-hydroxyheptanoic acid
Naming Aldehydes and Ketones
1. CH3CH2CH2CHO
____________________________
9.
=O
2. CH3CH(CH3)CH(CH3)C=O
CH3
____________________________
3. CH2Cl(CHCl)3CHO
____________________________
4.
___________________________
10. CH3CHOHCH2CHClCH2CHO
_______________________________
H3C
=O
CH3
____________________________
5. (CH3)3CC = O
H
____________________________
6.
O
||
CH3CH2CCH2CH3
____________________________
7. (CH3)3 C C =O
C(CH3)3
____________________________
Page
____________________________
72
8. CH2NH2C(CH3)2CH2C = O
|
H
PROPERTIES OF ALDEHYDES AND KETONES #1
Write an equation that shows what happens in each of the following reactions. Name all organic
products formed.
1.
CH3C(CH3)2(CH2)4CHO + HCN -----------> (“AB” addition)
2.
CH3CH(CH3)CH2CHO (mild oxidation) -----acidic------->
3.
CH3CHCl CCH(CH3)2 + H2 ------------>
(CH3)3CC(Cl)2CHO + HBr ------------>
5.
CH3CH(CH3)COCH2CH2CH3 (mild oxidation) ------------>
6.
CH3CHICHICH(CH3)CH2CHO + HOH------------>(refer to alkyne H2O addition)
Page
4.
73
O
CHEMISTRY WORKSHEET: Aldehyde + Ketones #2
1.
Cu
CH3CH2CH2OH ------------>
250OC
OH
2.
KMnO4
CH3CH2CHCH3 ------------>
(________)
O
3.
H2
CH3C H ------------>
+ Catalyst
O
4.
H2O
CH3CCH3 + CH3MgBr ----------->
OH
C
KMnO4
CH2CH3 ----------->
74
CH3
Page
5. CH3
Date:
Period:
MULTISTEP SYNTHESIS Do the following conversions
1. Acid name: _____________________
O
||
C – C – OH
C–C
2. Ketone name: ___________________
O
||
C–C–C
CC–C
3. Aldehyde name: _________________
O
CN
||
|
C–C–C
C–C–C
Page
Reactant name: __________________
O
O
Br Br Br
||
||
| |
|
C – C – C – C – OH
C–C–C–C
|
Br
75
4.
ALDEHYDES AND KETONES
1.) Synthesize pentanoic acid (5 carbons) from 2-bromopentane.
Br
OH
H3C
CH3
2-bromopentane
H3C
O
Page
76
2.) You made two solutions of organic compounds. One is pentanal, the other is 3-hexanone. You
forgot to label them, so you don’t know which is which. Since they smell very similar you can’t tell
them apart by odor. How can you tell them apart?
NAMING ACIDS
On the lines provided, write the correct name for each of the following acids.
1.) CH3CH(CH3)CH2CH2COOH
______________________________
2.) CH3CH(CH3)C(CH3)(C2H5)CH2COOH
______________________________
3.) HOOCCH2CH2CH2COOH
______________________________
4.) CH3CH2CH2CH(NH2)COOH
______________________________
5.) CH(CH3)2C(CH3)2CH2COOH
______________________________
6.) C(Cl)3C = O
|
OH
______________________________
7.) HOOCCH2C(CH3)2CH2COOH
______________________________
8.) CH3CH2CH2CHOHCH2COOH
______________________________
9.) CH3CH=CHCH=CHCH2COOH
Page
77
______________________________
FORMULA WRITING: ACIDS
Write structural formulas for the following acids. Check to be sure that each given name is correct.
3,3,4,6-tetramethyloctanoic acid
2. 2-aminobutanoic acid
7. 2-chloro-3-ethyl-4-methylhexanoic acid
3. 3-methyl-5-phenylpentanoic acid
8. trichloroacetic acid (2 carbons)
/trichloroethanoic acid
4. 3,3-dimethylpentanedioic acid
9. 4-chloro-2,3,3-trimethyl-butanoic acid
5. 3-hydroxyhexanoic acid
10. heptanedioic acid
78
6.
Page
1. formic acid (1 carbon) HCOOH