www.JCE.DivCHED.org Vol. 83 No. 11 November 2006 Journal of Chemical Education 1633
Textbooks used for teaching undergraduate courses pro- vide basic rules and examples for naming monofunctional compounds. However, students of more advanced organic chemistry courses and graduate students dealing with more complex molecules need a set of additional rules and guide- lines to identify polyfunctional compounds. The following summary of general principles may also be useful to instruc- tors. The formation of the systematic name for an organic compound involves several steps, to be taken as far as they are applicable in the following order (15). Step 1 Determine the principal functional group in the com- pound. When a compound contains more than one group in Table 1, the principal group is that which has the highest precedence. This principal group will be cited as a suffix; all other groups are cited as prefixes. Step 2 Determine the parent hydrocarbon (principal chain or parent ring system): (a) If the principal group occurs in a chain, the principal chain is selected as (i) the chain containing the functional group of the highest seniority as the parent. (ii) If more than one such a choice is possible, select the chain with the maximum number of multiple bonds. (iii) If (i) and (ii) together are not definitive, then choose the chain with maximum length. (iv) If two chains of the same length are possible, choose the one with maximum number of substituents. 2-(butan-1-yl)-4-methylhexanal O H The parent chain here contains six carbon atoms. The IUPAC Rules for Naming Organic Molecules W Stanislaw Skonieczny Department of Chemistry, University of Toronto, Toronto, Ontario, M5S 3H6, Canada; sskoniec@chem.utoronto.ca e c n e d e c e r P f o r e d r O g n i s a e r c e D e h T . 1 e l b a T s p u o r G l a n o i t c n u F r o j a M e h t r o f a l a n o i t c n u F p u o r G t s e h g i H f i x i f f u S e c n e d e c e r P r e w o L f i x i f e r P e c n e d e c e r P H O O ) C ( - b d i c a c i o - - - - H O O C - d i c a c i l y x o b r a c - - y x o b r a c O S - 2 H O d i c a c i n o f l u s - - o f l u s - ) O ( C O ) O ( C - e d i r d y h n a c i o - - - - R O O ) C ( - b e t a o - l y k l a - o x o - y x o k l a R O O C - e t a l y x o b r a c l y k l a - - - l a H O ) C ( - b e d i l a h l y o - - o x o - o l a h l a H O C - e d i l a h l y n o b r a c - - l y n o b r a c o l a h H N O ) C ( - 2 b e d i m a - - o x o - o n i m a H N O C - 2 e d i m a x o b r a c - - l y n o b r a c o n i m a ) C ( - N b e l i r t i n - - - - C - N e l i r t i n o b r a c - - o n a y c O H ) C ( - b l a - - o x o O H C - e d y h e d l a b r a c - - l y m r o f ) C ( > O e n o - - o x o H O - l o - c - y x o r d y h H S - l o i h t - - l y n a f l u s d H N - 2 ) e n i m a - ( e n a z a - d ) - o n i m a ( - l y n a z a e H N > ) e n i m i - ( e n a z a - d ) - o n i m i ( - e n e d i l y n a z a e C > < C e n e - * C - - C e n y - * * R O - , R - , X - * * * - y x o k l a , - l y k l a , - o l a h O N - , r A - 2 , * * * - o r t i n , - l y r a N - , O N - 3 , * * * - o d i z a , - o s o r t i n N 2 R S - , * * * ( , - o z a i d R l y n a f l u s - ) a n o m m o c f o r e b m u n a r o f s e m a n l a i v i r t l a n o i t i d a r t d n a c i t a m e t s y S e h t n i d e t s i l s p u o r g l a n o i t c n u f e h t f o t s o m g n i t n e s e r p e r s d n u o p m o c . l a i r e t a M l a t n e m e l p l p u S e h t n i n e v i g e r a e l b a t b a s e t a n g i s e d ) C ( t o n s e o d t i ( e d i r d y h t n e r a p e h t f o e m a n e h t n i d e d u l c n i m o t a n o b r a c . ) x i f e r p a r o x i f f u s a y b d e t a n g i s e d p u o r g a o t g n o l e b c e h t g n o m A e r a m e h t g n o m A . e l b a t p e c c a e r a s e m a n l a i v i r t e m o s , s l o n e h p l a n o i t i s o p r i e h t d n a , l o r h t n a n e h p - 1 , l o r h t n a - 1 , l o h t h p a n - 1 , l o n e h p l l i t s e r a d i c a c i r c i p d n a , l o m y h t , l o s e r c s a h c u s , s r e h t O . s r e m o s i y b m e h t e m a n o t t s e b s i t i t u b , d e t u t i t s b u s n u n e h w C A P U I y b d e t p e c c a . e r u t a l c n e m o n c i t a m e t s y s d x i f e r p e h t , s n o i t a d n e m m o c e r 8 9 9 1 e h t n I . y l s u o i v e r p d e s u s a w h c i h w , ' - o t p a c r e m ' o t d e r r e f e r p s i ' - l y n a f l u s ' e t u b , e n i m i d n a e n i m a - o t e v i t a n r e t l a n a s a e n a z a - s d n e m m o c e r C A P U I e c n e r e f e r , s e u g o l a t a c , s k o o b - t x e t l l A . e g a s u h c u m e e s o t t e y s a h s i h t e n i m i - d n a ) - o n i m a ( e n i m a - e s u l l i t s e r u t a r e t i l c i f i t n e i c s d n a , s k o o b , r e v e w o H . x i f f u s a s a d e s u s y a w l A * . e l b a t p e c c a e r a h c i h w , ) - o n i m i ( s i x i f f u s e h t , e l u c e l o m e h t n i t n e s e r p s i p u o r g y t i r o i r p r e h g i h a f i y t i r o i r p r e h g i h e h t f o x i f f u s e h t y b d e w o l l o f s i t i d n a - n e - o t d e g n a h c p u o r g y t i r o i r p r e h g i h a f i , r e v e w o H . x i f f u s a s a d e s u s y a w l A * * . p u o r g d e w o l l o f s i t i d n a - n y - o t d e g n a h c s i x i f f u s e h t , e l u c e l o m e h t n i t n e s e r p s i . x i f e r p a s a d e s u s y a w l A * * * . p u o r g y t i r o i r p r e h g i h e h t f o x i f f u s e h t y b In the Classroom 1634 Journal of Chemical Education Vol. 83 No. 11 November 2006 www.JCE.DivCHED.org (b) If the principal functional group occurs in a cyclic sys- tem, that system forms the parent. 2-(octan-1-yl)cyclohexanol OH Step 3 Name the parent structure and the principal group(s). Give the parent the same name as if it were an alkane, but replace -ane with the suffix characteristic of the functional group of the highest priority (Table 1). Note: Multiple un- saturation in hydrocarbons is indicated by the numerical pre- fixes di-, tri-, etc. In such cases, however, the ending -ane of the parent alkane is replaced with -adiene, -atriene, etc. leav- ing the a in the root alkane whenever the first letter of the suffix is a consonant to make the name easier to pronounce. Thus we get alkadienes, alkatriens, alkadiynes, etc. Step 4 Complete the numbering. (a) Number the carbon atoms consecutively from the end of the chain nearer the functional group of the high- est priority. 4,5-dimethylhexan-3-one 1 2 3 5 4 6 O (b) If the same number for the functional group of highest pri- ority is obtained in both directions, the correct IUPAC name is the one that contains the lowest substituent number. 2,4-dimethylhex-3-ene 1 2 3 5 4 6 First substituent has number 2. If we numbered the chain from the other side, the first substituent would have num- ber 3. (c) If first substituents occur at an equal distance from each end of the chain, number from the end nearer a second sub- stituent. If still the same, continue until first point of dif- ference. (E)-2,3,5-trimethylhex-3-ene 1 2 3 5 4 6 (d) If numbering from either side gives the same set of locants, number from the end with the substituent that comes first in alphabetical order. (e) In monosubstituted cycloalkanes and benzene derivatives, the carbon to which the substituent is bonded is always number 1. If there is only one substituent, the locant 1 is omitted. However, it is necessary in polysubstituted com- pounds.
(f ) In polysubstituted cyclic compounds, the starting point and the direction of numbering are chosen to give lowest lo- cant to the following factors (if present), considered suc- cessively in the order listed below until a decision is reached. (i) The principal functional group named as suffix is always given lowest possible number. When the numbering is pre- determined by the nature of the parent hydrocarbon, as in polycyclic hydrocarbons and heterocyclic compounds, low- est locants are still the rule.
Note: When one heteroatom is present in the ring, the lo- cant 1 is attributed to the heteroatom. If two or more kinds of heteroatom occur in the same ring, the number- ing starts from the heteroatom cited first in the following descending order: O, S, Se, N, P, As, Sb, Si, Ge, Sn, Pb, B, and Hg. Other heteroatoms get other lowest possible locants.
1,2-oxathiolane 1 5 4 2 3 O S
1,3,5-triazine 1 2 3 5 6 4 N N N In the Classroom www.JCE.DivCHED.org Vol. 83 No. 11 November 2006 Journal of Chemical Education 1635 (ii) Lowest locant for multiple bonds in cyclic compounds.
Note: In naming cycloalkenes, the double bond is located between C1 and C2, and the 1 is usually omitted in the name. The ring is numbered clockwise or counterclockwise to give the first substituent the lower number. However, when a higher seniority functional group is present, the car- bon bonded to such a group becomes C1 and then mul- tiple bonds are considered for lowest possible locants. (iii) Lowest locant for a first substituent (or first point of dif- ference).
(iv) If the same numbers will result from numbering in either direction, give the lowest locant for that substituent which is cited first.
Step 5 Name alkyl groups, halides, and other substituents and determine their position on the chain by the numbering es- tablished by step 4. Step 6 Assign the stereochemistry to chiral carbon atoms (ste- reocenters) and the double bond(s): (a) Disubstituted alkenes may be named in two ways: (i) using terms cis- and trans- or (ii) using terms (E) or (Z ). Note: Use of (EZ) stereodescriptors is preferred. However, the cistrans terms are still accepted.
(b) Tri- and tetra-substituted alkenes may only be named us- ing the (EZ ) system. (c) Disubstituted cycloalkanes may be named using the terms cistrans or (RS ). (d) Chiral carbon atoms are assigned (R) or (S) configuration. (S)-5-methylhexan-3-ol H OH (e) When both (RS) and (EZ) stereodescriptors are present, they are placed in parentheses followed by a hyphen; each stereodescriptor is immediately preceded by the lower or less primed locant and they are arranged in numerical order.
In the Classroom 1636 Journal of Chemical Education Vol. 83 No. 11 November 2006 www.JCE.DivCHED.org Figure 1. Some examples of IUPAC names for commonly known compounds Step 7 Compounds with multiple double and triple bonds have the following suffixes: -adiene, -adiyne, -atriene, -atetraene, and so on. Specify the location of each multiple bond by a locant placed between -a and -diene, -diyne, -triene, etc. Step 8 Compounds with both double bonds and triple bonds are called enynes. Start the numbering of compounds with both double and triple bonds from the end nearer the first multiple bond, regardless of type. When a double bond is the same distance from one end as a triple bond from the other end, assign the double bond the lower number.
Step 9 Write the complete name of the compound as a single word with the correct locants for all substituents, which are listed in alphabetical order. The stereochemistry is indicated by placing the appropriate prefix within parentheses followed by a hyphen in front of the name. The prefixes di-, tri-, tetra-, etc. do not alter the alphabetical ordering of substituents. (a) The numbers indicating the locations of substituents are separated by commas. (b) The letters and numbers are joined by hyphens. N OH NH 2 CH 3 NH 2 NH 2 OH O OCH 3 O O IUPAC: Trivial (retained): azabenzene pyridine IUPAC: Trivial (retained): phenylazane benzenamine aniline IUPAC: Trivial (retained): benzenecarboxylic acid benzoic acid methyl benzenecarboxylate methyl benzoate 1-phenylpropan-1-one propiophenone 2-methylphenylazane 2-methylbenzenamine o-toluidine naphthalen-2-ylazane naphthalen-2-amine 2-naphthylamine 1,2-dehydrobenzene benzyne benzenol phenol In the Classroom www.JCE.DivCHED.org Vol. 83 No. 11 November 2006 Journal of Chemical Education 1637 Step 10 A complex substituent is named by applying the above steps just as if the substituent were a compound itself. We begin numbering at the point of attachment to the parent hydrocarbon and we give this substituent the suffix -yl and put its name in parentheses when the name of the complete compound is given. Note: There are many traditional names accepted by IUPAC and retained because of their wide use in organic, biochemi- cal, and polymer nomenclature. A few examples are given here: toluene, styrene, phenol, aniline, acetone, acetylene, acetic acid, benzoic acid, and phthalic acid (Figure 1). A list of such compounds can be found on the Web (6). Other names are retained for referring to unsubstituted compounds only. Compounds derived from them by substi- tution must be named systematically. For example, the names butanoic acid (systematic) and butyric acid (retained) are both approved by IUPAC for the unsubstituted acid. However, BrCH 2 CH 2 CH 2 COOH must be named systematically as 4- bromobutanoic acid. Some other examples of such names re- tained for unsubstituted compounds only include lactic acid, toluidine, anisole, glycerol, propionic acid, isoprene, cumene, pinacol, and many others. W Supplemental Material Examples of names of organic compounds, seniority of chains in naming, seniority of ring systems in naming, and the HantzschWidman sytem of naming are available in this issue of JCE Online. Note 1. The extended HantzschWidman system used to name het- erocycles is presented in the Supplemental Material. W Literature Cited 1. Fox, R. B.; Powell, W. H. Nomenclature of Organic Compounds, Principles and Practice, 2nd ed.; Oxford University Press: Ox- ford, 2001. 2. Hellwinkel, D. Systematic Nomenclature of Organic Chemistry, A Directory to Comprehension and Application of its Basic Prin- ciples; Springer: Berlin, New York, London, 2001. 3. Leigh, G. J.; Favre, H. A.; Metanomski, W. V. Principles of Chemical Nomenclature, A Guide to IUPAC Recommendations; Blackwell Science: Oxford, 1998. 4. Panico, R.; Powell, W. H.; Richer, J.C. A Guide to IUPAC Nomenclature of Organic Compounds, Recommendations 1993; Blackwell Science: Oxford, 1993. 5. Rigaudy, J.; Klesney, S. P. Nomenclature of Organic Chemistry, Sections A, B, C, D, E, F, and H; Pergamon Press: Oxford, 1979. 6. Trivial and Semisystematic Names Retained for Naming Or- ganic Ccompounds. http://www.acdlabs.com/iupac/nomencla- ture/93/r93_671.htm (accessed Jul 2006).