Summary of IUPAC Nomenclature of Organic Compounds

Introduction The purpose of the IUPAC system of nomenclature is to establish an international standard of naming compounds to facilitate communication. The goal of the system is to give each structure a unique and unambiguous name, and to correlate each name with a unique and unambiguous structure. I. Fundamental Principle IUPAC nomenclature is based on naming a molecule's longest chain of carbons connected by single bonds, whether in a continuous chain or in a ring. All deviations, either multiple bonds or atoms other than carbon and hydrogen, are indicated by prefixes or suffixes according to a specific set of priorities. II. Alkanes and Cycloalkanes Alkanes are the family of saturated hydrocarbons, that is, molecules containing carbon and hydrogen connected by single bonds only. These molecules can be in continuous chains (called linear or acyclic), or in rings (called cyclic or alicyclic). The names of alkanes and cycloalkanes are the root names of organic compounds. Beginning with the five-carbon alkane, the number of carbons in the chain is indicated by the Greek or Latin prefix. Rings are designated by the prefix "cyclo". (In the geometrical symbols for rings, each apex represents a carbon with the number of hydrogens required to fill its valence.) C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 CH4 CH3CH3 CH3CH2CH3 CH3[CH2]2CH3 CH3[CH2]3CH3 CH3[CH2]4CH3 CH3[CH2]5CH3 CH3[CH2]6CH3 CH3[CH2]7CH3 CH3[CH2]8CH3 CH3[CH2]9CH3 methane ethane propane butane pentane hexane heptane octane nonane decane undecane H C H cyclopropane H C C H H cyclobutane cyclopentane H C12 C13 C14 C20 C21 C22 C23 C30 C31 C40 C50 CH3[CH2]10CH3 CH3[CH2]11CH3 CH3[CH2]12CH3 CH3[CH2]18CH3 CH3[CH2]19CH3 CH3[CH2]20CH3 CH3[CH2]21CH3 CH3[CH2]28CH3 CH3[CH2]29CH3 CH3[CH2]38CH3 CH3[CH2]48CH3 dodecane tridecane tetradecane icosane henicosane docosane tricosane triacontane hentriacontane tetracontane pentacontane

cyclohexane

cycloheptane

cyclooctane

The IUPAC system of nomenclature is undergoing many changes, most notably in the placement of position numbers. The new system places the position number close to the functional group designation; however, you should be able to use and recognize names in either the old or the new style. Ask your instructor which system to use. 1

Summary of IUPAC Nomenclature, continued III. Nomenclature of Molecules Containing Substituents and Functional Groups A. Priorities of Substituents and Functional Groups LISTED HERE FROM HIGHEST TO LOWEST PRIORITY, except that the substituents within Group C have equivalent priority. Group AFunctional Groups Named By Prefix Or Suffix Functional Group Carboxylic Acid Aldehyde Ketone Alcohol Amine Structure O R R R C OH O C H O C R Prefix carboxyoxo(formyl) oxohydroxyaminoSuffix -oic acid (-carboxylic acid) -al (carbaldehyde) -one -ol -amine

R O H R N

Group BFunctional Groups Named By Suffix Only Functional Group Alkene Alkyne Structure C C C C Prefix --------------Suffix -ene -yne

Group CSubstituent Groups Named By Prefix Only Substituent Structure Prefix Suffix Alkyl (see next page) Alkoxy Halogen R R O F Cl Br I alkylalkoxyfluorochlorobromoiodo-------------------------------------------

Miscellaneous substituents and their prefixes NO2 nitro CH CH2 vinyl 2 CH2CH allyl CH2 phenyl

Summary of IUPAC Nomenclature, continued Common alkyl groupsreplace "ane" ending of alkane name with "yl". Alternate names for complex substituents are given in brackets. CH3 methyl CH2CH3 ethyl CH3 CH CH3 isopropyl [1-methylethyl] CH3 CH CH3 isobutyl [2-methylpropyl] CH3 CH CH2CH3 sec-butyl [1-methylpropyl] CH3 C CH3 CH3 t-butyl or tert-butyl [1,1-dimethylethyl]

CH2CH2CH3 propyl (n-propyl) CH2CH2CH2CH3 butyl (n-butyl)

CH2

B. Naming Substituted Alkanes and CycloalkanesGroup C Substituents Only Organic compounds containing substituents from Group C are named following this sequence of steps, as indicated on the examples below: Step 1. Find the longest continuous carbon chain. Determine the root name for this parent chain. In cyclic compounds, the ring is usually considered the parent chain, unless it is attached to a longer chain of carbons; indicate a ring with the prefix "cyclo" before the root name. (When there are two longest chains of equal length, use the chain with the greater number of substituents.) Step 2. Number the chain in the direction such that the position number of the first substituent is the smaller number. If the first substituents have the same number, then number so that the second substituent has the smaller number, etc. Step 3. Determine the name and position number of each substituent. (A substituent on a nitrogen is designated with an "N" instead of a number; see Section III.D.1. below.) Step 4. Indicate the number of identical groups by the prefixes di, tri, tetra, etc. Step 5. Place the position numbers and names of the substituent groups, in alphabetical order, before the root name. In alphabetizing, ignore prefixes like sec-, tert-, di, tri, etc., but include iso and cyclo. Always include a position number for each substituent, regardless of redundancies.
6 1 2 3 7 8 5 6 7 1

CH3 CH2CH2CH3 C 4 CH 5 CH2CH3 CH3 CH

CH2CH2CH3
4

CH3

CH

CH

CH

CH

2 CHCH3

Cl Br CH3 3-bromo-2-chloro-5-ethyl-4,4-dimethyloctane H3C CHCH2CH3

CH3 F CH3 3-fluoro-4-isopropyl-2-methylheptane

NO2

1-sec-butyl-3-nitrocyclohexane (numbering determined by the alphabetical order of substituents, "b" comes before "n") 3

Summary of IUPAC Nomenclature, continued C. Naming Molecules Containing Functional Groups from Group BSuffix Only 1. AlkenesFollow the same steps as for alkanes, except: a. Number the chain of carbons that includes the C=C so that the C=C has the lower position number, since it has a higher priority than any substituents; b. Change "ane" to "ene" and assign a position number to the first carbon of the C=C; place the position number just before the name of functional group(s); c. Designate geometrical isomers with a cis,trans or E,Z prefix. CH3 F
4 CH

H C

F
1C

5 2 3 4

C H

CH2

C H

CH2

1 2 3

CH3 4,4-difluoro-3-methylbut-1-ene

CH3 1,1-difluoro-2-methylbuta-1,3-diene

5-methylcyclopenta1,3-diene

Special case: When the chain cannot include an alkene, a substituent name is used. See Section V.A.2.a.
1 2 3

C H

CH2

3-vinylcyclohex-1-ene

2. AlkynesFollow the same steps as for alkanes, except: a. Number the chain of carbons that includes the CtC so that the alkyne has the lower position number; b. Change "ane" to "yne" and assign a position number to the first carbon of the CtC; place the position number just before the name of functional group(s). Note: The Group B functional groups (alkene and alkyne) are considered to have equal priority: in a molecule with both an ene and an yne, whichever is closer to the end of the chain determines the direction of numbering. In the case where each would have the same position number, the alkene takes the lower number. In the name, "ene" comes before "yne" because of alphabetization. F
4 CH 3

H C

CH

HC

CH3 4,4-difluoro-3-methylbut-1-yne

H2 C C CH3 HC C C C CH2 H H H pent-3-en-1-yne pent-1-en-4-yne ("yne" closer to end of ("ene" and "yne" have equal priority unless they have the same position number, when chain) "ene" takes the lower number) C

(Notes: 1. An "e" is dropped if the letter following it is a vowel: "pent-3-en-1-yne" , not "pent-3ene-1-yne". 2. An "a" is added if inclusion of di, tri, etc., would put two consonants together: "buta-1,3-diene", not "but-1,3-diene".) D. Naming Molecules Containing Functional Groups from Group APrefix or Suffix In naming molecules containing one or more of the functional groups in Group A, the group of highest priority is indicated by suffix; the others are indicated by prefix, with priority equivalent to any other substituents. The table in Section III.A. defines the priorities; they are discussed on the following pages in order of increasing priority. 4

Summary of IUPAC Nomenclature, continued Now that the functional groups and substituents from Groups A, B, and C have been described, a modified set of steps for naming organic compounds can be applied to all simple structures: Step 1. Find the highest priority functional group. Determine and name the longest continuous carbon chain that includes this group. Step 2. Number the chain so that the highest priority functional group is assigned the lower number. (The number "1" is often omitted when there is no confusion about where the group must be. Aldehydes and carboxylic acids must be at the first carbon of a chain, so a "1" is rarely used with those functional groups.) Step 3. If the carbon chain includes multiple bonds (Group B), replace "ane" with "ene" for an alkene or "yne" for an alkyne. Designate the position of the multiple bond with the number of the first carbon of the multiple bond. Step 4. If the molecule includes Group A functional groups, replace the last "e" with the suffix of the highest priority functional group, and include its position number just before the name of the highest priority functional group. Step 5. Indicate all Group C substituents, and Group A functional groups of lower priority, with a prefix. Place the prefixes, with appropriate position numbers, in alphabetical order before the root name. 1. Amines: prefix: amino-; suffix: -aminesubstituents on nitrogen denoted by "N" CH3O NH2 CH3CH2 CH2CH3 N CH CH CH NH
3 2 2 2

3-methoxycyclohexan-1-amine ("1" is optional in this case) 2. Alcohols: prefix: hydroxy-; suffix: -ol OH CH3CH2 ethanol OH H3C C C CH2 H H but-3-en-2-ol

propan-1-amine

C CHCH3 H N,N-diethylbut-3-en-2-amine OH

H2C

NH2 2-aminocyclobutan-1-ol ("1" is optional in this case) H3C O CH3 C N CH2 C CH2 CH3

3. Ketones: prefix: oxo-; suffix: -one (pronounced "own") O O CH3 CH C CH3 cyclohex-3-en-1-one ("1" is optional in this case)

OH 3-hydroxybutan-2-one

4-amino-N,N-dimethylpent-4-en-2-one

4. Aldehydes: prefix: oxo-, or formyl- (O=CH-); suffix: -al (abbreviation: CHO) An aldehyde can only be on carbon 1, so the "1" is generally omitted from the name. O HCH methanal; formaldehyde CH3 O CH OH H2C O O O

ethanal; acetaldehyde

C C CH H H 4-hydroxybut-2-enal 5

CH3CCH2CH2CH 4-oxopentanal

Summary of IUPAC Nomenclature, continued Special case: When the chain cannot include the carbon of the aldehyde, the suffix "carbaldehyde" is used: O 3 2
4 5 6 1

CH

cyclohexanecarbaldehyde

5. Carboxylic Acids: prefix: carboxy-; suffix: -oic acid (abbreviation: COOH) A carboxylic acid can only be on carbon 1, so the "1" is generally omitted from the name. (Note: Chemists traditionally use, and IUPAC accepts, the names "formic acid" and "acetic acid" in place of "methanoic acid" and "ethanoic acid".) O HC OH methanoic acid; formic acid O CH3C OH ethanoic acid; acetic acid O CH2 CH COH NH2 2-amino-3-phenylpropanoic acid O HC O C CH3 C COOH

CH3 2,2-dimethyl-3,4dioxobutanoic acid

Special case: When the chain numbering cannot include the carbon of the carboxylic acid, the suffix "carboxylic acid" is used: CHO
3 2 1 4

2-formyl-4-oxocyclohexanecarboxylic acid ("formyl" is used to indicate an aldehyde as COOH a substituent when its carbon cannot be in the chain numbering)

E. Naming Carboxylic Acid Derivatives The six common groups derived from carboxylic acids are, in decreasing priority after carboxylic acids: salts, anhydrides, esters, acyl halides, amides, and nitriles. 1. Salts of Carboxylic Acids Salts are named with cation first, followed by the anion name of the carboxylic acid, where "ic acid" is replaced by "ate" : acetic acid becomes acetate butanoic acid becomes butanoate cyclohexanebarboxylic acid becomes cyclohexanecarboxylate NH2 CH3 CHCOO Li+ ClCH2COO Na+ sodium chloroacetate ammonium 2-methoxycyclobutanecarboxylate CH3O COO NH4

lithium 2-aminopropanoate

2. Anhydrides: "oic acid" is replaced by "oic anhydride" O O O R C OH alkanoic acid R C O C R alkanoic anhydride

O O

benzoic anhydride 6

Summary of IUPAC Nomenclature, continued 3. Esters Esters are named as "organic salts" that is, the alkyl name comes first, followed by the name of the carboxylate anion. (common abbreviation: COOR) carboxylate O R C O R "alkanoate" "alkyl" "alkyl alkanoate" O H2C C C O C H H vinyl prop-2-enoate CH2 methyl 3-hydroxycyclopentanecarboxylate O Cl butanoyl chloride O NH2 butanamide H3C alkyl O C O CH2CH3 O HO C OCH3 CH2COO cyclohexyl 2-phenylacetate O Cl benzoyl chloride O NH2 benzamide H3C CH3 O C CH3 isopropyl 2,2-dimethylpropanoate C O CH3 CHCH3

ethyl acetate

4. Acyl Halides: "oic acid" is replaced by "oyl halide" O O R C OH alkanoic acid R C Cl alkanoyl chloride

5. Amides: "oic acid" is replaced by "amide" O R C OH alkanoic acid O R C NH2 alkanamide

Amides are notable for their role in biochemistry, i.e., the special amide bond between two amino acids is called a peptide bond.

6. Nitriles: "oic acid" is replaced by "enitrile" O R C OH alkanoic acid R C N alkanenitrile

C N butanenitrile

C N benzonitrile
(common spelling differs from IUPAC)

IV. Nomenclature of Aromatic Compounds "Aromatic" compounds are those derived from benzene and similar ring systems. As with aliphatic nomenclature described above, the process is: determining the root name of the parent ring; determining priority, name, and position number of substituents; and assembling the name in alphabetical order. Functional group priorities are the same in aliphatic and aromatic nomenclature. See p. 2 for the list of priorities. A. Common Parent Ring Systems
7 8

()
1 2 3 5 4

()

7 6

2 3

or
6

benzene

10

naphthalene 7

anthracene

Summary of IUPAC Nomenclature, continued B. Monosubstituted Benzenes 1. Most substituents keep their designation, followed by the word "benzene": Cl NO2 CH2CH3

chlorobenzene

nitrobenzene

ethylbenzene

2. Some common substituents change the root name of the ring. IUPAC accepts these as root names, listed here in decreasing priority (same as Group A, p. 2): COOH SO3H CHO OH NH2 OCH3 CH3

benzoic acid

benzenebenzaldehyde sulfonic acid

phenol

aniline

anisole

toluene

C. Disubstituted Benzenes 1. Designation of substitutiononly three possibilities: X X Y Y common: IUPAC: ortho1,2(o-) meta1,3(m-)

Y para1,4-

(p-)

2. Naming disubstituted benzenesPriorities from Group A, p. 2, determine root name and substituents COOH Br Br OCH3 NH2 p-dibromobenzene 1,4-dibromobenzene m-aminobenzoic acid 3-aminobenzoic acid CHO o-methoxybenzaldehyde 2-methoxybenzaldehyde CH3 m-methylphenol 3-methylphenol HO

D. Polysubstituted Benzenesmust use numbers to indicate substituent position CH3 Cl HN CH3 Cl NO2 2,4,6-trinitrotoluene (TNT) 8 NH2 ethyl 4-amino-3-hydroxybenzoate O2N NO2 OH COOCH2CH3

3,4-dichloro-N-methylaniline

Summary of IUPAC Nomenclature, continued E. Aromatic Ketones A special group of aromatic compounds are ketones where the carbonyl is attached to at least one benzene ring. Such compounds are named as "phenones", the prefix depending on the size and nature of the group on the other side of the carbonyl. These are the common examples: O C CH3 acetophenone O C CH2CH2CH3 butyrophenone O C CH2CH3 propiophenone O C benzophenone

In a companion document entitled Special Topics of IUPAC Nomenclature, three more advanced topics are discussed: 1. Nomenclature of Bicyclic Compounds 2. Replacement Nomenclature of Heteroatoms 3. Stereochemical Designations (R and S, E and Z, the Cahn-Ingold-Prelog system)

revised June 2004 9