Atkins odds and Ends

1. 1
• A large portion of the materials on
plagiarism on the University of Wisconsin
Oshkosh's Writing Center Web site was
revealed in February to have been taken
verbatim from Purdue University's Web
page on plagiarism.

2. Nomenclature of Ethers,
Aldehydes, Ketones,
Carboxylic Acids, and
Esters

3. 3
Ethers and Their Relatives
• An ether has two organic groups (alkyl, aryl, or vinyl)
bonded to the same oxygen atom, R–O–R
• Diethyl ether is used industrially as a solvent
• Tetrahydrofuran (THF) is a solvent that is a cyclic ether
• Thiols (R–S–H) and sulfides (R–S–R) are sulfur (for
oxygen) analogs of alcohols and ethers

4. 4
Naming Ethers
• Simple ethers are named by identifying the two organic
substituents and adding the word ether

5. 5
Naming Ethers, continued
•If other functional groups are present, the ether part is
considered an alkoxy substituent

6. 6
18.9 Crown Ethers
• Large rings consisting repeating (-OCH2CH2-) or similar
units
• Named as x-crown-y
– x is the total number of atoms in the ring
– y is the number of oxygen atoms
– 18-crown-6 ether: 18-membered ring
containing 6 oxygens atoms
• Central cavity is electronegative and attracts cations

7. 7
18-Crown-6

8. 8
Uses of Crown Ethers
• Complexes between crown ethers and ionic salts are
soluble in nonpolar organic solvents
• Creates reagents that are free of water that have useful
properties
• Inorganic salts dissolve in organic solvents leaving the
anion unassociated, enhancing reactivity

9. 9
18.10 Thiols and Sulfides
• Thiols (RSH), are sulfur analogs of alcohols
– Named with the suffix -thiol
– SH group is called “mercapto group”
(“capturer of mercury”)

10. 10
Sulfides
• Sulfides (RSR), are sulfur analogs of ethers
– Named by rules used for ethers, with
sulfide in place of ether for simple
compounds and alkylthio in place of alkoxy

11. 11
Aldehydes and Ketones
• Aldehydes and ketones are characterized by the the
carbonyl functional group (C=O)
• The compounds occur widely in nature as intermediates
in metabolism and biosynthesis
• They are also common as chemicals, as solvents,
monomers, adhesives, agrichemicals and
pharmaceuticals

12. 12
Naming Aldehydes and Ketones
• Aldehydes are named by replacing the terminal -e of the
corresponding alkane name with –al
• The parent chain must contain the CHO group
– The CHO carbon is numbered as C1
• If the CHO group is attached to a ring, use the suffix
See Table 19.1 for common names

13. 13
Common Name of Some Simple Aldehydes
Formula Common Name Systematic Name
HCHO Formaldehye Methanal
CH3CHO Acetaldehyde Ethanal
CH3CH2CHO Propionaldehyde Propanal
CH3CH2CH2CHO Butyraldehyde Butanal
CH3CH2CH2CH2CHO Valeraldehyde Pentanal
H2C=CHCHO Acrolein Propenal
PhCHO Benzaldehyde Benzenecarbaldehyde

14. 14
Naming Ketones
• Replace the terminal -e of the alkane name with –one
• Parent chain is the longest one that contains the ketone
group
– Numbering begins at the end nearer the
carbonyl carbon

15. 15
Ketones with Common Names
• IUPAC retains well-used but unsystematic names for a
few ketones

16. 16
Ketones and Aldehydes as Substituents
• The R–C=O as a substituent is an acyl group is used
with the suffix -yl from the root of the carboxylic acid
– CH3CO: acetyl; CHO: formyl; C6H5CO:
benzoyl
• The prefix oxo- is used if other functional groups are
present and the doubly bonded oxygen is labeled as a
substituent on a parent chain

17. 17
The Importance of Carboxylic Acids
(RCO2H or RCOOH)
• Starting materials for acyl derivatives (esters, amides,
and acid chlorides)
• Abundant in nature from oxidation of aldehydes and
alcohols in metabolism
– Acetic acid, CH3CO2H, - vinegar
– Butanoic acid, CH3CH2CH2CO2H (rancid
butter)
– Long-chain aliphatic acids from the
breakdown of fats

18. 18
20.1 Naming Carboxylic Acids and
Nitriles
• Carboxylic Acids, RCO2H
• If derived from open-chain alkanes, replace the terminal
-e of the alkane name with -oic acid
• The carboxyl carbon atom is C1

19. 19
Alternative Names
• Compounds with CO2H bonded to a ring are named
using the suffix -carboxylic acid
• The CO2H carbon is not itself numbered in this system
• Use common names for formic acid (HCOOH) and acetic
acid (CH3COOH) – see Table 20.1

20. 20
Common Names
Systematic Name Common Name
O
HCOH methanoic acid formic acid
O
CH3COH
ethanoic acid acetic acid
O
CH3(CH2)16COH octadecanoic acid stearic acid
– common names are based on natural
origin rather than structure

21. 21
More Common Names
Systematic Name Common Name
2-hydroxypropanoic
acid
lactic acid
(Z)-9-octadecenoic
acid
oleic acid
O
CH3CHCOH
OH O
(CH2)7COH
C C
H H
CH3(CH2)7

22. 22

23. 23
Common Diacids
C
O OH
C
O OH
C
O OH
CH2
C
O OH
C
O OH
CH2
CH2
C
O OH
C
O OH
CH2
CH2
CH2
C
O OH
C
O OH
CH2
CH2
CH2
CH2
C
O OH
Oxalic Malonic Succinic Glutaric Adipic

24. 24
Nitriles, RCN
• Closely related to carboxylic acids named by adding -
nitrile as a suffix to the alkane name, with the nitrile
carbon numbered C1
• Complex nitriles are named as derivatives of carboxylic
acids.
– Replace -ic acid or -oic acid ending with -
onitrile
R C N RCN
or

25. 25

26. 26
Naming Esters, RCO2R
• Name R’ and then, after a space, the carboxylic acid
(RCOOH), with the “-ic acid” ending replaced by “-ate”