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Nodal Nomenclature IIЧSpecific Nomenclature for Parent Hydrides Free Radicals Ions and Substituents.

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Nodal Nomenclature 11-Specific Nomenclature for
Parent Hydrides, Free Radicals, Ions, and Substituents””
By Noel Lozac’h and Alan L. Goodson*
Nodal nomenclature is compared with classical organic nomenclature, and the procedure
by which an organic compound is given a nodal name is described. Parent hydride-especially hydrocarbon-names are derived from the names of structure graphs and are modified to incorporate descriptions of heteroatoms, unsaturation, free valences, and ionic
charges. It is also shown how the substitutive method, though not an integral part of the nodal system, may nevertheless be used as a way to simplify the structure graphs without impairing the logic of the nodal system. For this purpose, it is indicated how to use prefixes or
suffixes generally formed according to IUPAC Rules. The r81e of substitution in organic
nodal nomenclature is more restricted than in classical nomenclature because many classical substituents are treated as part of the parent hydrides. The concept of “characteristic
group” is not used in nodal nomenclature for similar reasons, and the term “principal substituent” is preferred to “principal characteristic group”.
1. Preface
The general tendency of classical organic nomenclature,
which is the natural outcome of the historical development
of organic chemistry, is to consider first the chemical nature of the atoms constituting a molecule and then to indicate how these atoms are connected together. Classical systematic organic names generally correspond to a molecular
formula and are sometimes directly derived from this formula (e.g., silane). Nodal nomenclature, on the other
hand, can be compared with a technique used for constructing large buildings. It first creates a framework (i. e.,
a mathematical description of a chemical structure[’]) to
which it adds the detail necessary to complete a usable
chemical name. Just as new techniques made possible the
construction of skyscrapers, so the new concepts of nodal
nomenclature facilitate the description of large chemical
structures.
The preceding paper”] of this series, to which we shall
refer hereafter as Part I, showed how the framework is
created by reducing chemical structures to graphs and then
numbering and naming the graphs. This technique of reducing a problem to a graph and then resolving the problem by manipulating the graph is common in graph the-
graphs. For this purpose, it is practical to use, as far as
possible, prefixes and suffixes having well known chemical
meanings, such as those codified in IUPAC Rules for
Nomenclature of Organic Chemistry[’]. To help the reader
understand how names of parent hydrides are derived
from those of the corresponding graphs, many of the examples in this paper are related to the examples in Part I.
First of all, two important facts should be noted:
1) This paper describes one procedure for using nodal
nomenclature in organic chemistry, but other procedures
such as those involving polynuclear nodes, as in cyclophane nomenclature, can also apply the general method
described in Part I, provided that the principles governing
the choice of nodes are clearly defined.
2) The Rules concerning substituents, ions, and free radicals show how the main principles underlying IUPAC
Rules are applied to parent hydrides named according to
the nodal system. In elaborating these Rules, the Authors
have drawn great benefit from the work accomplished by
the IUPAC Commission on Nomenclature of Organic
Chemistry. However, some of these proposals, although
consistent with the general methods of IUPAC Rules, represent only the Authors’ preference among various possibilities considered by IUPAC.
0ry[3,41.
The names of the chemical structures are obtained by
supplementing the description of the corresponding
graphs, as indicated in Part I, with purely chemical information defining the nature of the atoms and bonds. The
objective of this second paper is therefore to describe how
parent hydrides-generally organic-as well as their derivatives containing free valences, ionic centers, or substituents can be named by modifying the names of the
[*I Prof. N. Lozac’h [‘I
Institut des Sciences de la Matikre et du Rayonnement,
Universite de Caen
F-14032 Caen Cedex (France)
Dr. A. L. Goodson
Chemical Abstracts Service, Columbus, OH 43210 (USA)
[‘I
Author to whom correspondence should be addressed.
[**] Part I (“Nodal Nomenclature-General Principles”) see [2].
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
2. Introduction
It has been argued that the description of the graph, as
given in Part I, leads to long strings of numbers and punctuation marks and accordingly is not practical for common
use. Some explanations are therefore necessary.
Nodal nomenclature provides a unique and sequential
numbering for any graph. The fact that this numbering is
unique avoids, in indexes, the scattering of information for
compounds having the same carbon skeleton. The fact that
it is sequential renders it directly available for construction
of a connection table and for substructure retrievals by
procedures comparable with those used in the DARC and
CAS ONLINE systems. This unique and sequential numbering is intimately connected with the descriptors which
were discussed in Part I[*]. The typographical conventions
0 Verlag Chemie GmbH, 6940 Weinheim, 1984
0570-0833/84/0101-0033 $02.50/0
33
used for the descriptors were adopted to facilitate understanding of the structure under consideration.
Since we claim that nodal nomenclature is of general
use, it is essential for us to show that it works with complicated structures where existing nomenclature rules often
do not provide any clear guidance. One should compare
only what is comparable, and the “simplicity” of nodal
nomenclature should be tested on examples where existing
rules provide clear answers. For this reason, we have chosen, for many examples in this paper, compounds that are
also used as examples in the IUPAC rules[’]. Thus, nodal
nomenclature rules are compared directly with existing
IUPAC rules.
There are two questions which must be borne in mind
during the further development of nodal nomenclature.
The first is the perennial difference in nomenclature requirements between the primary literature and that of an
index.
An essential question for indexing and information retrieval is whether the nomenclature system used leads to a
unique and unambiguous name for any given chemical
structure. IUPAC Rules often provide various possible
names for a substance and, owing to the fundamental inconsistencies of traditional methods, the choice of unique
“official names” often requires that the user define his
own selection rules. On the other hand, nodal nomenclature can define clearly, for indexing and information storage and retrieval purposes, a unique and unambiguous
name for any molecule, provided that the principles governing the choice of nodes and of substituents are clearly
defined.
In the primary literature, an author may name a substance to reflect the nature of the work being described.
Another author may name the same substance differently
because the nature of the work he is describing is different.
Therefore, primary literature requires only that names be
unambiguous, while indexes require not only unambiguous but, as far as possible, unique names. Some flexibility is built into nodal nomenclature so that while unique
names can be derived for indexing purposes, shorter, more
convenient names will also be available for use in the literature.
This leads to the second question that must be borne in
mind. It is generally recognized that existing nomenclature
practices are in need of improvement. When a new nomenclature system is developed and proposed, there is always
the potential for conflict between the needs of the chemist
and the needs of the information retrieval specialist. It is
possible to make minimal (but frequent) changes to existing nomenclature practices and thus retain procedures and
names with which the chemist is familiar and with which
he therefore feels comfortable. The information retrieval
specialist, on the other hand, would prefer a completely
systematic nomenclature system that never needs modification and yields unambiguous names as simple as the
complexity of structures permits. In developing nodal
nomenclature, we are trying to strike a balance between
these two extremes and that is why we show how the substitutive method may be used in nodal nomenclature.
Use of the substitutive method is not essential in nodal
nomenclature but is advisable for two reasons. The first is
34
that removal of substituents simplifies the graph and, accordingly, its name. The second reason is that chemists will
prefer to relate simple substituted structures to the graph
of the unsubstituted one; for example, most chemists will
prefer to relate a chlorohydrocarbon to the graph of the
unsubstituted hydrocarbon. For a similar reason, indexes
require that names of related substances be grouped together. For this purpose a compound commonly named as
“2-chloro-1-butanol” is frequently given the inverted name
“1-butanol, 2-chloro-” in an index. There is no particular
problem for applying this procedure to substitutive nodal
names.
It is important to remember that the following Rules are
modular because of the underlying logic of nodal nomenclature. This means that the various features of a chemical
compound are described successively, in a prescribed order, by prefixes and/or suffixes, and that any new feature
can influence the numbering of the skeleton only if the
preceding features have left a choice.
A parent hydride is named first, and this gives a high
priority to unsaturation for the definition of the numbering. The corresponding Rules are particularly detailed as
they constitute the basis of any nodal name.
Next comes the description of free valences and ionic
centers on skeletal atoms. It should be remarked that any
free valence must belong to a skeletal atom and that the
use of “onia” replacement prefixes, according to IUPAC
Rule B-6.1L5],is not recommended because the neutral parent compound should be completely defined before considering ionic centers.
Last comes the naming of substituents, considered in the
order of seniority: anionic, cationic, neutral. Nodal nomenclature sets relatively stringent limits to the use of substituents (Rule N-10.1) as well as to the r d e of substituents in
name selection. For instance, in nodal nomenclature, no
substituent plays a r6le as important as the “principal
group”[5a1in IUPAC Rules for acyclic compounds. Accordingly, the term “principal substituent” is preferred for
a substituent named by a suffix and having priority for low
locants only over other substituents.
For sake of consistency, exceptional treatment of various characteristic groups is avoided and substitutive prefixes are used more extensively than in IUPAC nomenclature (e.9.. for aldehydes, ketones and nitriles). For the
same reason, radicofunctional names are not used at all
(e.g., for esters and acyl halides). When appropriate prefixes are not available in current nomenclature, groups of
substituents are named with one locant only, such as
“(Mercapto, 0x0)” for [C](O)SH in S-thiocarboxylic acids,
“(Amino, 0x0)’’ for [C](O)NH, in carboxamides, “(Chloro,
0x0)” for [C](O)Cl in acyl chlorides. This procedure has
the advantage that the functional group can be identified
easily, without departing from the general substitutive
method.
3. Glossary
Many terms used in this paper have already been defined in Part I[Za].Some additional definitions are necessary for specific nodal nomenclature.
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
Mononuclear Node:
(see: Node[*”])
Used principally to distinguish
nodes corresponding to single skeletal atoms from polynuclear (contraction) nodes.
Parent
An element whose identity is indicated at the end of the name of a
saturated parent hydride. Other elements, if present, are denoted by replacement prefixes such as oxa or
aza. The parent element is the most,
or one of the most, common in the
skeleton. When the skeleton contains equal numbers of atoms of
more than one element, including
carbon, carbon is preferred as the
parent element. If carbon is not
among the most common elements
of the skeleton, then the parent element is the first cited in Table 3. The
concept of parent element applies to
graphs containing only mononuclear nodes.
In organic nodal nomenclature, the
element hydride obtained through
replacement by hydrogen atoms of
all the atoms or groups considered
as substituents. According to this
definition, while unsaturation endings ( e . g . , ene, yne) are part of the
parent hydride name, suffixes for
principal substituents are not, which
is different from IUPAC Rules concerning principal
characteristic
groups. For this reason, in nodal
nomenclature, the term “parent hydride” is preferred to “parent compound” in order to avoid confusion
with existing IUPAC terminology.
Parent Hydride:
Polynuclear Node:
(see: Contraction
Node‘’“])
Used principally to stress the polyatomic nature of contraction nodes
and to distinguish them from mononuclear nodes.
Principal Substituent: A substituent named as a suffix and
having priority for low locants over
other substituents (see Table 2). The
term “principal substituent” is used
in nodal nomenclature in order to
avoid confusion with the term
“principal characteristic group”,
which has a different use in IUPAC
Rules.
A univalent atom (usually hydroSatellite Atom:
gen) attached to a skeletal atom and
not regarded as part of the structure
graph.
The structure resulting when the
Skeleton:
nodes and lines (or connectivities)
of a structure graph are specified. It
contains neither satellite atoms nor
substituents.
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
Substituent:
An atom or group that replaces a
hydrogen atom of a parent hydride.
The following may be named as substituents in organic nodal nomenclature (see Tables 1 and 2): a) a
heteroatom which may be linked to
hydrogen, or b) a group of heteroatoms which may be associated with
carbon (as exceptions), which may
be linked to hydrogen and which
does not need internal numbering
for defining its structure. Use of
substitution is therefore restricted in
nodal nomenclature. The IUPAC
concept of characteristic group is
not used in nodal nomenclature.
4. General Concepts of
Specific Organic Nodal Nomenclature
For naming purposes, a chemical substance can be regarded either as a neutral parent hydride or as being derived from a neutral parent hydride by introduction of free
valences, ionic charges, or substituents. Use of nodal nomenclature to name a chemical substance proceeds in four
steps:
1) Definition of the Structure Graph;
2) Numbering and Naming of the Structure Graph, according to Part I ;
3) Specification of the Nodes and Lines (i.e., naming the
neutral Parent Hydride according to Rules N-11, N-12
and/or N-13);
4) Addition of Remaining Information, if any.
4.1. Definition of the Structure Graph
The structure graph is defined by 1) removing the atoms
or groups that are to be treated as substituents, 2 ) removing the satellite atoms (generally hydrogen), 3) ignoring
charges, bond values, free valences, and the identity of
skeletal atoms, and 4) defining the nodes as either mononuclear (single atoms) or polynuclear (i.e., contraction
nodes representing, for example, benzene or pyrrole rings).
In this paper we limit ourselves solely to the use of mononuclear nodes.
At this stage, the operation which is most open to discussion is the definition of substituents. As already stated
in the Introduction, use of the substitutive method is not
essential to nodal nomenclature but may be considered advisable by many users. That is why, in the proposed Rules,
two lists of atoms or groups are given which the Authors
believe are advantageously treated as substituents in nodal
nomenclature. However, it should be stressed that these
lists are not limitative and that further development of nodal nomenclature may demonstrate the need to define
larger, but limitative, lists of substituents.
It should also be stressed that this graph-based nomenclature precludes the use of radicofunctional names such
as those generally used for esters. Binary names of this
35
kind are reserved for substances, such as salts, comprising
a loose association of structurally independent chemical
entities.
4.2. Numbering and Naming of the Structure Graph
This step has been described in Part I[21.
4.3. Specification of the Nodes and Lines:
Parent Hydrides
Once the structure graph has been numbered and
named, the graph name is modified to include information
specifying the nodes and lines. For this purpose, the end of
the graph name is changed to indicate the nature of the
parent element. Other elements, if present, are denoted by
replacement prefixes[5b1such as “oxa” and “aza”. Unsaturation is indicated by suffixes: either by the traditional
terms “ene” and “yne” with their usual meaning of double
and triple bond, respectively, or by the new terms “arene”
or “axene” denoting unambiguously the presence of the
maximum number of noncumulative double bonds. A
summary of the Rules indicating how these various features intervene in the choice of the numbering of a substance is given in Rule N-14.2. The resulting name is that
of the parent hydride, for instance a hydrocarbon.
Only when all the nodes of a graph have been defined
and the nature of the lines has been described is hydrogen
formally added to satisfy the valence of each skeletal atom.
This valence is the “normal valence”[5c1unless otherwise
stated”’.
The systematic numbering of structures is a prominent
characteristic of nodal nomenclature which endeavors to
treat the same problem in the same way, without reference
to peculiarities of structure already considered (modularity
principle). This uniformity of treatment contrasts with
some IUPAC Rules. A particularly important example
concerns numbering of heteroatoms in replacement nomenclature. The nodal system retains the method used by
IUPAC[’] for acyclic (Rule C-62.1) and polycyclic structures (Rule B-4.2) but not the method applied to monocycles (Rule B-4.1), which is different.
4.4. Addition of Remaining Information
Once the parent hydride name has been formed, the substance name is derived, if necessary, by addition of the remaining information, such as free valences, ionic charges,
substituents, stereochemistry, and isotopic modifications.
This implies rules for assignment of locants to the diverse
features under consideration.
Application of the modularity principle in nodal nomenclature leads unavoidably to rules rather different from
those of IUPAC nomenclature. This is particularly significant for principal characteristic groups as defined in the
IUPAC Rules. The nodal system treats all unsaturation before considering substituents, even if these are named as
suffixes, while IUPAC Rules do not separate these different issues. For instance, according to Rule C-15.1[’], indicated hydrogen has priority over principal characteristic
36
groups, which, in turn, have priority over multiple bonds.
Apart from this point, the nodal method is rather similar to
the one used by IUPAC for polycyclic systems, where, for
instance, heteroatoms are considered before principal
characteristic groups for assignment of low locants. This is
quite different from the IUPAC practice for acyclic systems, where principal characteristic groups have priority
over heteroatoms, not only for assignment of low locants
(Rule C - 6 2 . 1 9 but also for determining the principal
chain (Rule C-63.1[’]).
The rules proposed in this paper show how it is possible
to deal with free valences, ionic charges and substituents,
but do not consider stereochemistry and isotopic modification, like Sections E and H of the IUPAC Rules[’]. It seems
that there is no particular problem in applying these
IUPAC Rules to nodal names and one can note only that
nodal numbering facilitates their application because each
locant occurs only once.
As for specification of free valences, ionic charges, and
substituents, two different problems have to be solved:
first, the choice of a terminology; second, the definition of
the rules governing the numbering of the substance.
For the first problem, the terminology defined in existing IUPAC Rules[’I is available and only minor decisions.
have to be made. A nonlimiting set of substituent names is
given in Rule N-10, and terms denoting free valences and
ionic charges are recalled in Rule N-14.3.
For the second problem, Rules N-14.3 and N-14.5 indicate how free valences, ionic charges, and substituents can
affect the definitive numbering of a substance.
5. Proposed Rules for Specific Nodal Nomenclature
Rule N-10-Substituents
N-10.1. Substituent groups should not contain an unbranched chain of more than three atoms other than hydrogen and should not need internal numbering. If a hydrogen atom of such a group is substituted with a group
containing the parent element, then the resulting group is
not regarded as a substituent but as a part of the parent hydride. A nonlimiting list of acceptable substituent atoms
and groups cited only as prefixes in nodal nomenclature is
given in Table 1.
N-10.2. Substituents are generally named as prefixes,
but groups susceptible to losing a proton, and the corresponding anionic atoms or groups, are named as suffixes
under the conditions stated in Rule N-14.1. If these conditions are not fulfilled, prefixes are used. A nonlimiting list
of acceptable hydrogen-containing substituents which may
be cited either as prefixes or as suffixes in nodal nomenclature is given in Table 2.
N-10.3. Substitutive prefixes can be derived from the
names of mononuclear hydrides (see Table 3) of elements
having a nonstandard classical valence bonding[’].
Examples (substituents cited in Table 1):
1. -ICI2
2. -I(OHh
3. -SF5
4. -SF2C1
5 . -SC&
Dichloro-h’-iodanyl
Dihydroxy-h3-iodanyl
Pentafluoro-h6-sulfanyl
Chlorodifluoro-h4-sulfanyl
Trichloro-h4-sulfanyl
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
Table 1. Acceptable substituents, which are only cited as prefixes in nodal nomenclature when the parent element is carbon.
Substituent
Prefix
IUPAC Rule [5]
Substituent
Prefix
IUPAC Rule (51
-F
-CI
-ClH
-CIO
Fluoro
Chloro
Chloronio
Chlorosyl
Chloryl
Perchloryl
Bromo
Bromonio
lodo
Iodonio
Dichloroiodo [*I
Iodosyl
Iodyl
Dihydroxyiodo [*I
Ox0
Oxonio
Hydroperoxy
Aminooxy
Cyanato [**I
Thioxo
Sulfonio
Pentafluorothio [*I
Chlorodifluorothio [*]
Chlorothio
c-102.1
c-102.1
c-82.1
C-106.2
C-106.2
C-106.2
c-102.1
C-82.1
c-102.1
c-82.1
C-106.3
C-106.1
C-106.1
C-106.3
C-311.1
c-82.1
C-218.l(b)
C-841.2(d)
C-833.1
(2-532.3
c-82.1
C-621.2
C-621.2
C-621.2
-sc13
Trichlorothio [*I
Sulfinamoyl
Sulfonamoyl
Sulfenamoyl
Thiocyanato [**I
Selenoxo
Selenonio
Selenocyanato [**I
Nitrilo
Diazo
Azido
Iminio
Ammonio
Hydroxyamino
Hydrazino
Nitroso
Nitro
Hydroxyimino
aci- Nitro
Hydrazono
Isocyano [**I
Isocyanato I**]
Isothiocyanato I**]
Isoselenocyanato [**I
C-621.2
C-641.8(b)
C-641.8(b)
C-641.8(b)
‘2-833.1
C-701.1
c-82.1
c-833.1
*
- a 0 2
-a03
-Br
-BrH+
-1
-IH+
-1Cl2
-10
-I02
-I(OH)z
=O
z
-OH
-0OH
-ONHz
-0CN
=S
-SH
-SFS
-SFzCI
-SCI
z
-S(0)NH2
-S(O)zN H2
-SNH2
-SCN
=Se
-SeH
-SeCN
=N
=NZ
-N3
=NH 1
-NH
-NHOH
-NHNHz
-NO
-NOz
=NOH
-N(O)OH
=NNH2
-NC
-NCO
-NCS
-NCSe
z
(2-931.4
C-941.1
C-816.3
C-82.1; C-816.3
C-841.1
C-921.l(b)
C-851.1
C-852.1
C-842.l(b)
C-852.2
C-922.1(b)
(2-833.1
c-833.1
C-833.1
C-833.1
[*] These substituents can also be named according to Rule N-10.3. [**I Exception to the rule according to which, in organic nodal nomenclature, the parent hydride should contain all the carbon atoms present in the molecule. The use of the carbon-containing substituent cyano (-CN), which is generally linked to the parent hydride by a C-C bond, is not recommended.
N-10.4.The prefixes for anionic substituents formed by
loss of a proton from the substituent groups listed in Table
2 are obtained by making the following changes in the
names given in the second column of Table 2:
(la) “-0”to “-onato”;
(lb) ‘‘-0”to “-,to”;
(lc) “Hydroxy” to “Oxido”;
(Id) “Mercapto” to “Sulfido”;
(le) “Hydroseleno” to “Selenido”.
The suffixes for anionic substituents formed by loss of a
proton from the substituent groups listed in Table 2 are obtained by making the following changes in the names given
in the third column of Table 2:
(2a) “-ic acid” to “-ate”;
(2b) “-or’ to “-olate”;
(2c) “-ine” to “4nide”.
Anionic substituents have priority for citation as principal substituents over all other substituents. Among anionic
Table 2. Acceptable Substituents, which can also he cited as suffixes in nodal nomenclature when the parent element is carbon. (In descending order of priority for
citation as principal substituent, cf. Rule N-14.1.)
Substituent
Prefix I**]
suffix I**]
IUPAC Rule (51
-lCl(O)OH
-[Cl(O)SH
-ICl(S)OH
-[Cl(S)SH
-S(0)zOH
-S(O)zSH
-S(O)(S)OH
-S(O)(S)SH
-S(S)zOH
-S(S)$jH
-S(O)OH
-S(O)SH
-S(S)OH
-S(S)SH
-SOH
-Se(O),OH
-Se(O)OH
-SeOH
-OH
-SH
-SeH
-NH2
=NH
[*I
[*I
[*I
-oic acid (2a)
-thio S-acid (2a)
-thio 0-acid (2a)
-dithioic acid (2a)
-sulfonic acid (2a)
-thiosulfonic S-acid (2a)
-thiosulfonic 0-acid (2a)
-dithiosulfonic S-acid (2a)
-dithiosulfonic 0-acid (2a)
-trithiosulfonic acid (2a)
-sulfinic acid (2a)
-thiosulfinic S-acid (2a)
-thiosulfinic 0-acid (2a)
-dithiosulfinic acid (2a)
-sulfenic acid (2a)
-selenonic acid (2a)
-seleninic acid (2a)
-selenenic acid (2a)
-01 (2b)
-thiol (Zb)
-selenol (2b)
-amine (2c)
-imine (2c)
C-11.1; C-401.1
C-541.1
C-541.1
(2-541.1
C-641.4
C-641.3; (2-641.4
C-641.3; C-641.4
C-641.3; C-641.4
C-641.3; (2-641.4
C-641.3
(3641.2
C-641.3; C-641.4
C-641.3; C-641.4
C-641.3
C-641.2
C-701.1
C-701.1
C-701.1
c-201.1; c-201.2; c-202.1
C-511.1
C-701.1
C-811.3; C-11.42
C-815.3(a)
[*I
Sulfo (la)
SH-Thiosulfo (la)
OH-Thiosulfo (la)
SH-Dithiosulfo (la)
OH-Dithiosulfo (la)
Trithiosulfo (la)
Sulfino (Ib)
SH-Thiosulfino (Ib)
OH-Thiosulfino (lb)
Dithiosulfino (Ib)
Sulfeno (lb)
Selenono (Ib)
Selenino (lb)
Seleneno (lb)
Hydroxy (lc)
Mercapto (Id)
Hydroseleno (le)
Amino
Imino
[*I When the parent element is carbon, composite substituents are named as prefixes: for instance, -[C](O)SH is named “(mercapto, 0x0)’’. [**I (la) to (le) and (2a)
to (2c): For naming the anionic substituents derived from these groups, as prefixes or as suffixes, see correspondingly numbered instructions in Rule N-10.4.
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
37
substituents, the priority order is the one adopted for the
corresponding nonionized substituent groups.
Examples (for numbering, refer to Rules N-14.3 and
N-14.5):
Examples :
1. kH3-CH2-&H-CH2-8H,
[5.1 3 ] H e x a c a r b a n e
I
c6 11,
2. ~iH3-SiHz-~iII-SiH2-~iH3 [ 5 . 1 3 ] H e x a s i l a n e
1.
e0,s-t: ~
I
~~~4
- H~--?
6 OSH
SiIIS
I
4 - ( M e r c a p t o , o x o ) [ 4 l t e t r a n e- 1 - s u l f i n a t e
5
1
3. NH2-NH-N-NII-NH2
[5.13]Hexaazane
I
p
2. ~ O ~ S - ~ H ~ ~ H , - & H ~ - & O S Q
4.
4 - S u l f i n a t o [ 4 ] t e t r a n e - 1- t h i o a t e
1 . 5 - B i s ( m e r c a p t o , thioxo)[4. l’lpentane -4 - s u l f o n a t e
4-Sulfonato[4. l’lpentane -1,5 - b i s ( d i t h i o a t e )
5.
Qfy
2 - O x i d o c y c l o [ (0 6 ) l : 7( l ) ] h e p t a n (1- 6 ) a r e n - 7 - o a t e
(For the name of the parent hydride in Example 5 , see Rule
N-12.3.)
Rule N-11-Saturated
2
HA-S-S-;H
[41Tetrasulfane
N-11.2. The systematic names of the higher hydrocarbons are so well known in organic chemistry that the morpheme “carb” can be elided where there is no risk of ambiguity. When a molecule of a saturated hydrocarbon contains less than four carbon atoms, the descriptor is not necessary and the trivial names (i.e., methane, ethane, propane, and cyclopropane) are so firmly entrenched that they
can be used as exceptions instead of the systematic names
(i.e., [llcarbane, [2]dicarbane, [3]tricarbane, and cyclo[03]tricarbane, respectively). However, the systematic
names [4]tetracarbane (or [4]tetrane) and [3.1’ltetracarbane
(or [3. l’ltetrane) are preferred to the trivial butane and isobutane names because use of the descriptor is necessary to
distinguish between the isomers and to define the numbering of the skeleton.
Examples (IUPAC names[’”] are given in parentheses for
comparison) :
a) Saturated acyclic hydrocarbons
Parent Hydrides
[4]Tetrane
(Butane)
N-11.1. Names and bonding numbers for standard
mononuclear element hydrides are given in Table 3.
Higher homologues of these element hydrides are named
by replacing, in the name of the structure graph, the ending “-nodanel’ by the name of the corresponding mononuclear element hydride given in Table 3.
2. ;H,-‘?H-d;H3
[3.12]Tetrane
(I s o b u t a n e )
I
H3
3. ~ H ~ - ( C H Z ) ~ - ( ? H ~
I
3
[GIHexane
(Hexane)
5
4. CH3-CHz-CH-CH2-CH3
[ 5. 13]Hexane
(3-Methylpentane)
I
2 H3
Table 3. Standard bonding numbers (SBN), names for mononuclear element
hydrides and prefixes for elements in replacement nomenclature [Sd].
~
Element
Name
SBN
Fluorine
Chlorine
Bromine
Iodine
Astatine
Oxygen
Sulfur
Selenium
Tellurium
Polonium
Nitrogen
Phosphorus
Arsenic
Antimony
Bismuth
Carbon
Silicon
Germanium
Tin
Lead
Boron
1
1
1
1
1
2
2
2
2
2
3
3
3
3
3
4
4
4
4
4
3
~
Element Hydride
Formula Name
Replacement
Prefix
FH
CIH
BrH
IH
AtH
OH2
SH2
SeH2
TeH2
PoH2
NHJ
PH3
AsHJ
SbH3
BiH3
CHI
SiH4
GeH,
SnH4
PbH4
BH2
Fluora [a]
Chlora [a]
Broma [a]
I d a [a1
Astata [a]
Oxa
Thia
Selena
Tellura
Polona
Aza
Phospha
Arsa
Stiba
Bisma
Carba
Sila
Germa
Stanna
Plumba
Bora
Fluorane [a]
Chlorane [a]
Bromane [a]
Iodane [a]
Astatane [a]
Oxidane [bI
Sulfane
Selane
Tellane
Polane
Azane
Phosphane
Arsane
Stibane
Bismuthane
Carbane [c]
Silane
Germane
Stannane
Plumbane
Borane
[a] These names are needed for bonding numbers other than standard (see
Rules N-10.3 and N-14.1). [b] “Oxidane” is preferred to “oxane” in order to
avoid confusion with Hantzsch-Widman names. [c] For the choice of carbon
as parent element, see particular dispositions of Rules N-11.2 and N-11.3.
38
1
2
7
X
10
5. CH3-CH-( CH2)4-CH-C Il-CHz-CH,
I
5
[*I
I
I
!I
I3
CH3 Cl13
H3
I
4
I
s
6. C H3-( C H2)z-C H-C €I-(C lIz)3-C H3
I
$H3-cH22HZ
?H3-FHz
I
[10.l2l7l8]Tridecane
(2,7.8-Trimethyldecane)
[ 9. 3415]Trideca n e
(5-Methyl-4-propylnonane)
SH3
fH3
7. ~ H ~ - C H ~ - ~ H - C H Z ~ H \&/
- ( : HCH~-$H-CH&H-CHZ-CH~
~
? H3-CH2-(!
I
H - C H2-? H-? Hz’
$H3
I
?‘
$133
Hz-e H - C H z 2H-C Hz-? H3
I
I
$H3
p
3
[ 1 3 .6’6’Z315 191111151171 I 2 3 ] T e t r a t r i a c o n t a n e
(7 , 7 - B i s ( 2 , 4 - d i m e t h y l h e x y l ) - 3 - e t h y l - 5 , 9 , 1 1 - t r i m e t h y l tridecane)
CK~-(CH~)~<HH-(CH
z-dH-(CHz)z<H,
ZI )
$E13-gHZ
[l 2.4631329114118]Tri~o~ane
( 4 - E t h y l - 7-( 1- i s o b u t y l - 2 - methylbuty1)dodecane)
[*] In this and subsequent examples, the morpheme “carb” is elided.
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
b) Saturated cyclic hydrocarbons
<H~Z--?H~
z
,
6 H3-O-NH-C-C
Hz-&(C H2)z-O-CH3
I
1
4.
9.
1
A
10
41
C
14 H2-NH-C
IS
Cyclopropane
16
H3
2,9,12-Trioxa-6-thia-3,15-diaz.a[
10.34341hexadecane
(4- (Methoxymethyl)-4- [(methylamino)methy1]-2,9dioxa-6-thia-3-azadecane)
Cyclo[O6]hexane
(Cyclohexane)
10.
b) Saturated cyclic heteroatomic compounds
1
1-0xacyclopropane
11.
:ml
Bicyclo[04.0’’31tetrane
(Bicycle[ 1.1.O]butane)
H
1-Azacyclopropane
(Aziridine)
”
Bicycle[ 07.1”4]octane
12.
(Bicyclof3.2. lloctane)
4
7.
13.
1- 0 x a - 2 - thiacy clo[ 05 lpent ane
(1,Z-Oxathiolane)
iw’
Tricyclo1012.1‘3703,”]tridecane
(Tricycle[ 5.5.1 .0 3*11] tridecane)
(Perhydo- 2,7-methanocyclopentacyclononene)
4-Thia- 1,Z-diazacyclo[ O61hexane
(l-Thia-3,4-diazinane)
(1-Thia-3,4-diazacyclohexane)
Tricycle[ 08.4’.‘ 5 ’O*‘Olheptadecane
14.
(Dispiro[5.1.7. Zlheptadecane)
N-11.3. Heteroatomic hydrides containing atoms of
more than one element other than hydrogen are named by
replacement nomenclature~sb~q.
Such a structure is first
named as though the skeleton contains only the parent element, i. e. the most common element other than hydrogen.
Atoms of less common elements are then named by means
of the prefixes in Table 3, in the order given, with locants
to indicate their positions. When a skeleton contains equal
numbers of atoms of more than one element, including
carbon, carbon is preferred as the parent element. If carbon is not among the most common elements of the skeleton, the parent element is the first cited in Table 3.
If Part I leaves a choice, lowest locants are assigned first
to heteroatoms as a complete set, then to heteroatoms in
the order of Table 3.
Examples (IUPAC names15b,qare given in parentheses
for comparison):
a) Saturated acyclic heteroatomic compounds
I1
I
1. CH3-( O-CH2-CH,),-O-C
I1
Hz-CH3
2,5,8,11-Tetraoxa[ 13ltridecane
(2,5,8,11-Tetraoxatridecane)
2. &H3-04!H-(CH2)2-6-(CHz)&CH~~H3
I
SH3-p
3.
.es2
2,6,9-Trioxa[ 11.Z3Jtridecane
(3-Ethyl- 2,6,9- trioxaundecane)
6 H3-(C H 2 ) 2 2I H-(C H 2 ) z - h C Hz)z-;HX
?3-%
Hz-? H3
13-Oxa-7-thia- lO-aza[ 12.24]tetradecane
(3- Propyl- 2-oxa- 6 -thia- Y -azaundecane)
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
lo,
11.
@
’,’
7 -Oxabicyclo[ 06.4 ldecane
(1-0xaspirol4.5ldecane)
.@&
8
from:
I1
3-Oxa-11 -azatetracyclo[(06.1’s4)1 : 9(06. l l x 4) J t e t r a d e c a n e
(3- (2-Oxabicyclo[2.2.1 lhept-4 -,yl)1-azabicyclo[2.2. llheptane)
.@+)
8
13
Tetracyclo[(OG. l1j4)l: Y(06.1 ‘24)]tetradecanodane
Rule N-12-Unsaturated Parent Hydrides:
Names Derived from those of Saturated Structures
N-12.1. Double and triple bonds are indicated by the
usual suffixes, i. e., “-enel’, “-diene”, “-yne”, “-diyne”,
“en.. .yne”, etc. In contrast with present usage, the ending
“-ane” of the corresponding saturated structure is maintained in the name of the unsaturated compounds, with elision of the final “e” before the vowels “e” or “y”[*! Locants of two atoms linked by a multiple bond are placed
immediately before the appropriate suffix and are cited in
ascending order, with the second locant enclosed in parentheses. The second locant is omitted when it exceeds the
first by unity. As far as Part 1 and Rule N-11.3 leave a
choice, lowest locants are assigned first to double and triple bonds as a complete set, even though this may, at
times, give “yne” a lower locant than “ene”. When there
remains a choice, lowest locants are assigned to double
bonds.
For the reasons given in Rule N-11.2, the IUPAC systematic names “ethene”, “ethyne”, “propene”, “cyclopropene”, “propadiene” and “propyne” are retained.
39
Examples (IUPAC names are given in parentheses for
comparison):
d) Unsaturated cyclic heteroatomic c o m p o ~ n d s ~ ~ ~ ~
AH
‘KeSH
l-Aza-2-arsacyclo[04]tetran-3-ene
14.
a) Unsaturated acyclic hydrocarbon^[^"]
-
1
I
2
3
I
4
1
4
1
[ 6 . l 3 I H e p t a n - 3 ( 7 ) -e n e
(2-Ethyl- 1-pent ene)
I1
7%
z
3
4. CH3-C H=C-CHz-C H3
I
yH2-$H3
2
1
4
15. Z3JHeptan-2 - e n e
( 3 - Et h y l - 2 - p e n t e n e )
1
6
[GIHexane - 1 , 4 - d i e n e
(1.4-Hexadiene)
5. ~ H ~ = C H - C H , - C H = C H - C H ~
1
’
1
I
4
[ 5 l P e n t a n - 3 - e n - 1- y n e
(3-Penten-1- yne)
6. HC=?-CII=CH-C H3
I
l
l
7 - 0 x a b i c y c l o [ ( 0 6 . 1 1*4 ) 2 :10(4.12)]dodecan-9-ene
(2-(1 , 2 - D i m e t h y l - 1-propcxriyl)7- oxabicyclo[2. 2 . 1 I h e p t a n e )
1
4
4
7 . CH&H-CH=C
1
6
[GIHexane- 1,3 - d i e n - 5 - y n e
(1,3-Hexadien-5-yne)
H-C-CH
b) Unsaturated cyclic hydrocarbon~[~“]
8.
‘0
1-Silacyclo[05lpentan-3-ene
(2,5-Dihydro-lH-silole)
( o r 3,4 - D i d v h y d r o s i l o l a n e )
6
3. C H3-C H2-C -C H2-C H2-C H3
I
’0
[6. l31Heptan- 5- e n e
( 4 - M e t h y l - 1- h e x e n e )
7
2
15.
6
2. CH3-C H2-C H-C H2-C H=C Hz
I
H3
1
(l,Z-Dihydro-l,Z-azarsete)
( o r 3,4-Didehydro-l,Z-azarsetidine)
H2
[GIHexan-2-ene
(2-Hex ene)
1. &H3-CH=CH-(CH2)2-6H3
1
Cyclo[O6]hexanene
(Cyclohexene)
Bicyclo[ ( 0 6.1
) 2 : 1O( 4 . 1 ’) 1-.
dodecanodane
N-12.2. The presence in a more complex hydride of a
part containing the maximum number of noncumulative
double bonds is indicated by the suffix “axene” added to
the name of the saturated hydride, with elision of the latter’s terminal “e”. This procedure is applied when the part
structure contains at least three noncumulative double
bonds.
The position of unsaturation is indicated by locants, preceding the suffix “axene” and describing all the skeletal
atoms present in the part(s) of the structure concerned. A
group of locants such as (1 -6) means that all the atoms
numbered from 1 to 6 inclusively belong to a part of the
compound containing the maximum number of noncumulative double bonds. More than one set of locants may be
associated with the suffix “-axene”.
Examples :
Bicyclo[06.4 ‘ “ ] d e c a n e - 2 , 7 - d i e n e
9.
-
(Spiro[4.5]deca-l,6-diene)
I
10
1.
4
10
6
CH,-CHz-CHz-CH=C 1 I-C-CH=CH-C
II
s
I1
H=CH-C H2-C HZ-CH,
HZ
[13. 1 6 ] T e t r a d e c a n (4 - 1 0 , 1 4 ) a x e n e
10.
@
Bicycle[ 01 1.O ” 5 ] u n d e c a n e - 1 ( 5 ) , 2- d i e n e
(4,5,6,7,8,9-Hexahydro-lH-cyclopentacyclooctene)
Bicyclo[Ol6.2 Ioc t a d e c a n e - 1,3,17 - t r i e n e
(Bicycler 12.2. Zloctadeca- 1(1 6 ),14,17triene) ,
11.
N-12.3. If the aromatic character of the part containing
the maximum number of noncumulative double bonds is
to be stressed, the suffix “axene” can be replaced by “arene”.
Examples :
?,
c) Unsaturated acyclic heteroatomic compounds[5b1
I
4
IJ
14
H3
16
H~=EH-cH~-~-~H~-cH=cH-N=N-cH=cH-~H~-s-~H~-~
H=CH~
1.
1
12.6
H2Cll
1
6
X
9
I1
10
12
15
4-0xa-13-thia-8,9-diaza[1Glhexadecane- 1,6,8,10,15 - p e n t a e n e
( 4 - O x a - 1 3 - t h i a - 8 , 9 - d i a z a - 1 , 6 , 8 ,10,15- h e x a d e c a p e n t a e n e )
@
IICHZ
HzC?
Bicyclo[(010.01’6)2: 1 1 ( 2 ) 4: 1 3 ( 2 ) 7 : 15(2)1hexadwan(1 - l 0 ) a r e n e
I
irCH3
I F 3
1
8
IS
9 1 0
16
13. ~I-13-~-(CH2)4-O-C=C-O-(CH2)~-O-CH3
I
SH3-CH2-O-CHz
I8
I1
I
CH2-O-CHz-CH3
21
..
24
2 , 7 , 1 0 , 1 5 , 1 8, 2 2 - H e x a o x a [ 16 . 4 8 4 9 ] t e t r a c o s a n - 8 -e n e
(8,9-Bis(ethoxymethy1)-2,7,10,15-tetraoxa-8-hexadecene)
40
11- A z a b i c y c l o [ ( 0 6 ) l :7(4)10 :1 1 ( 0 5 ) l p e n t a d e c a n (1- 6 ) a r e n e
Angew. Chem. I n l . Ed. Engl. 23 (1984) 33-46
N-12.4. If there is a choice, the locants of the “axene” or
“arene” suffixes should be as low as possible. All the locants of the atoms belonging to the part with the maximum
number of noncumulative double bonds are then considered as one set notwithstanding the fact that some may be
explicitly cited while others are implicit, such as
3,4,5,6,7,8,9,10 in (2- 11) in the following example.
Example:
Examples:
Bicyclo(O10.0 ‘36]decane-1(6),3-diene
( 1,2,3,4,5,8-Hexahydronaphthalene)
1.
&
16
2.
11
(NOT:(2-10, 13-15 18-21), because 2...10, 11, 13... is lower
than 2... 10, 13, 14 ...)
N-12.5. When a part of a structure contains the maximum number of noncumulative double bonds while other
parts contain either isolated or cumulative double bonds
and/or triple bonds, the corresponding suffixes are cited
in the order: “-axene” (or “-arene”), “-ene”, “-yne”. Locants of cumulative and isolated double bonds are cited together when the “-axene” ending is used.
If there is a choice, lowest possible locants are first assigned to the atoms concerning the “-axenel’ (or “-arene”)
term, as defined in Rule N-12.4; afterwards, if there remains a choice, lowest possible locants are assigned to explicitly cited multiple bonds (double and triple bonds considered together). If there is still a choice, lowest possible
locants are assigned to double bonds. This is the pattern
set by IUPAC Rule A-3.3.
Examples :
Rule N-13-Unsaturated Parent Hydrides:
Names Derived from those of Structures having the
Maximum Number of Noncumulative Double Bonds
(Partly alternative to Rule N-12)
N-13.1. The name of an unsaturated hydride containing
the maximum number of noncumulative double bonds is
obtained by replacing, in the name of the corresponding
saturated hydride, the ending “ane” by the sufjx “axene”.
If the aromatic character of the hydride is to be indicated,
the suffix “arene” is used instead of “axene”.
The presence of at least one hydrogen atom on a skeletal
atom joined to adjacent skeletal atoms by only single
bonds is denoted by “indicated hydrogen”[’’.
Examples:
BicyclolOl 0 . O”6]decarene
(Naphthalene)
2.
14-10
17
( C H 2)3-C =C-CHz-? H3
1
I1
or
T e t r a c yclo[Ol6.1lX50 6,110132171heptadt?cane-l,3,5(17),6(11)-tetraen
T e t racy c lo[ 0 16.1 0 6J1 0 1 3 J 7 1 heptadccan(1-6,11, l 7 ) a x e n e
(5,6,6a.7,8,9,10,11-Octahydro4H-benz[ delanthracene)
12H-Tetracyclo[Ol6 .ll” 0 6211013’17]heptadecarene
(7H-Benz[delanthracene)
Cycle[( 7 ) l : 8(06)11 : 14( 7)licosan(8- 13)aren-4-en-17-yne
10
I
I l l 4
I2
I1
,C H-C H=C=C=C
H-CI1
Tetracyclo[(O6)1: 7(06)9 : 13(06)16: 19(06)]tetracosarene
(NOT.. .(5- 14)axene-1,2,3-triene, since the suffix “-axene”
claims the lowest locants.)
II
I?
I1
1 4 1
2
CH=C H X 3 C - C H=C H
/
\CHq
3. loCH
//
9
8
7
Cyclo[Ol4]tetradecan(1-1 2)axen- 13-yne
20H-16-Oxa- 2,21-diazatetracyclo[(06)1: 7 ( 2 ) 8 : 9(06)12:15(05)17:20(1)7:21(05)]pentacosaxene
6
N-12.6. When, in an “ortho-fused’’ or “ortho- and perifused” polycyclic ring system, the number of double bonds
is equal to, or smaller than, two-thirds of the maximum
number of noncumulative double bonds, the name is
formed from the name of the corresponding saturated ring
system by adding to the ending “ane” the appropriate
“ene”, “axene”, or “arene” suffixes (see Rules N-12.1, N12.2 and N-12.3) and associated locant(s).
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
N-13.2. An unsaturated hydride containing a number of
double bonds less than the maximum number of noncumulative double bonds, but larger than two-thirds of this
number, can be named by adding a prefix “dihydro”, “tetrahydro”, etc., to the name of the corresponding hydride
having the maximum number of noncumulative double
bonds.
Indicated hydrogen has priority over “hydro” prefixes
for assignment of lowest possible locants. For this pur41
pose, a structure with the maximum number of noncumulative double bonds, having the lowest possible locant(s)
for indicated hydrogen(s) is first selected. Only then, are
lowest possible locants assigned to hydro prefixes. This
method implies that, eventually, an indicated hydrogen locant may be higher than a hydro locant (see example 4).
Examples:
2,5-Dihydrobicyclo[ 01 0 . 0 ”61decarene
(1,4-Dihydronaphthalene)
1.
d16
15,16-Dihydro- 14H-tetracyclo[016.1’3506~110’3’’7]heptadecarene
( 5 , 6 - D i h y d r o - 4H-benz[ d e l a n t h r a c e n e )
2.
<I
’I3
3.
4.
17,27-Dihydro- 21H-tetracyclo[ ( 0 6 ) 1 : 7 ( 3 ) 9 : 10(06)13:16(05)17:21(1)4:22(05)24:27(1)]heptacosaxene
(Only 21 H and 27H correspond to canonical structures having the
maximum number of noncumulative double bonds: no 17H structure exists.)
12,13 - D i h y d r o - 8 , 1 4 - d i a z a t r i c y c l o [ ( 0 6 ) 1: 7 ( 0 5 ) 8 : 12(2)4: 14(05)16:19(2)]icosaxene
N-13.3. When a parent hydride corresponds to a loss of
hydrogen from a structure having the maximum number of
noncumulative double bonds, it can be named by adding a
prefix such as “didehydro”, “tetradehydro”, etc., with appropriate locants, to the name of the corresponding hydride having the maximum number of noncumulative double bonds.
It is recommended that the “hydro” and “dehydro” prefixes not be used simultaneously in the same name. Structures for which this circumstance would happen should be
named according to Rule N-12. For assignment of lowest
possible locants, “dehydro” prefixes immediately follow
indicated hydrogen.
Example (to be compared with examples 2 and 3 of Rule
N-12.5):
c H=C H-&=c-c
/
’
CH
‘cH-CH=CH-CH=CH-C
\
NCH
H
-
C H-C H=C =C=C
//
1,2-Didehydrocyclo[Ol4]tetradecaxene
42
H-C H
c\
C\
H
/
C H=CH-C H=C H-C H=C H
N-14.1. The various parts of the name occur in the following order:
a) Substituent prefixes, in alphabetical order;
b) Name of the neutral parent hydride, comprising:
1) Dehydro and hydro prefixes;
2) Indicated hydrogen;
3) Replacement prefixes (“a” prefixes), in the same order as in Table 3;
4) Name of the structure graph in which “nodane” is
replaced by an affix denoting the parent element
(Rule N-11);
5) Endings indicating unsaturation (“-ene”, “-yne”,
“-axene” or “-arene”).
c) EITHER One or several ionic and/or free valence suffix(es), in the order: “-ium”, “-ylium”, “-ide”, suffix for
anionic principal substituent (Rule N-10.4), “-yl”;
OR A suffix denoting a neutral principal substituent
(Rule N-10.2).
Suffixes denoting free valences (“-yl”, “-diyl”, etc.) are
always cited at the end of the name. They preclude the simultaneous presence of a suffix denoting a neutral principal substituent. In nodal nomenclature, these suffixes are
used exclusively for free radicals or for substituents which
do not need internal numbering (e.g., Rule N-10.3 : Dichloro-h3-iodanyl).
Anionic principal substituents defined in Rule N-10.4
may be cited after the other ionic suffixes. If there is more
than one kind of anionic substituent, Rule N-10.4 determines the anionic substituent to be cited as a suffix. Other
anionic substituents are then denoted by the prefix(es)
given in Rule N-10.3.
Only one kind of neutral substituent group can be denoted by a suffix (principal substituent). When there is a
choice, the principal substituent is the first cited in Table 2.
If substituents other than those cited in this table are used,
their order of priority is defined by pertinent IUPAC Rules
such as C-10.4, C-641.2, D-1.31, D-1.32, and D-1.33IS1.
Atoms or groups which cannot be denoted as a substituent by a suffix or a prefix are expressed as part of the
neutral parent hydride.
Examples :
3 - (Hydroxy ,oxo)p r o p a n - 1- y l
1. @CHz-CHz-COOH
@ ~ c H z - c ~ ( ! H - C O o ~ 4-Azacyclo[(O6)1 : 7 ( 1 ) l h e p t a n 2. HzN,
/
4-ium- 7-oate
CHz-CHz
6 0-6k H3
3.
H O z S-~ ? O z H
7-0~0-5-sulfino-8-oxacyclo[ ( 0 6 ) 1:7(3)2: l O ( l ) ] d e c a n ( l - 6 ) aren-10-oic acid
(According to Table 2, (C)OOH is preferred to S 0 3 H as principal
substituent.)
3
H=C H
Rule N-14-Construction of the Name
H
N-14.2. According to Part I[’] and to the preceding
Rules, the numbering of any structure is determined by the
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
following criteria, applied successively until a decision is
reached :
/CH4F2
7’
HC\j@
a) Criteria given in Part I concerning the numbering of the
structure graph;
b) Lowest locants for replacement prefixes considered together (Rule N-11.3);
c) Lowest locants for replacement prefixes considered in
the order of Table 3 (Rule N-11.3).
1,6-Dioxo[6]hexan- 2-eri-4-yne
(2-Hexen-4-ynedial)
l H - C y c l o [ 07jheptaxen- 1 - y l i u m
( 2 , 4 , 6 - C y c l o h e p t a t r i e n - 1- y l i u m )
Depending on whether Rule N-12 or Rule N-13 is used
for indicating unsaturation, locants are then assigned to
unsaturation affixes in one of the two following ways:
(Rule N-l2)-In names derived from those of saturated structures, lowest locants are assigned to:
d,) “-axene” or “-arene” suffixes (Rules N-12.4 and
12.5);
el) Explicitly cited multiple bonds as a complete set,
then double bonds (Rules N-12.1 and 12.5).
(Rule N-l3)-In names derived from those of structures having the maximum number of noncumulative
double bonds, lowest locants are assigned to:
d2) Indicated hydrogen (Rules N-13.1 and N-13.2);
ez) “Hydro” or “dehydro” prefixes (Rules N-13.2 and
N-13.3), it being understood that these two types of
prefixes do not coexist in the same name.
Examples (decisive criteria are indicated within parentheses):
HOHzC,
CH-CHz-CHzOH
HOHzC
[ 4 . 1 ’ 1 ~ e n t a n e - 1 , 4 , 5- t r i o ]
(2-(Hydroxymethyl)-l,4butanediol)
SO~H
3,8-Dihydrobicyclo[OlO.O la6]d e c a r e n e -5,lO-disulfonic a c i d
( 3 , 7 - D i h y d r o n a p h t h a l e n e -1,5disulfonic a c i d )
N-14.3. When Part I and Rule N-14.2 leave a choice for
the numbering of the skeleton of a chemical structure, the
following criteria are applied successively until a decision
is reached, giving the lowest locant to:
Free valences, denoted by the suffix “-yl”;
Anionic skeletal atoms denoted by the suffix “-ide”;
Cationic skeletal atoms denoted by the suffix “-ylium”,
corresponding to the loss of an electron at a free valence position;
Cationic skeletal atoms denoted by the suffix “-ium”,
corresponding to the fixation of a proton;
Anionic substituents named by a suffix (see Rule N10.4) ;
Anionic substituents named by a prefix (see Rule N10.4);
Cationic substituents named by a prefix (see Table 1).
Examples (decisive criteria are indicated within parentheses):
IS
I4
Cyclo[06]hexan-1-en-3-ylium
(2-Cyclohexen-1-ylium) [ a ]
NCH2
CH-CH,
C H2-C OOH
1
1. (a) 6H3-N-CHz-CH2-NH-C
0
B i c y c l 0 [ ( 0 1 0 . 0 ” ~ ):
311(3)2: 1 4 ( 2 ) 8 : 1 6 ( l ) ] h e x a d e c a n ( 1- 1 O ) a r e n e- 13,15,16- t r i o i c a c i d
( 6 - C a r b o x y - 1-(carboxymethyl)-2-naphthalenepropionic
acid)
7
4
3
2. ( a ) bH3<-CH2-CH3
6
H3
2,5 -Diaza[ 61h e x a n - 2-yl
[ 4 ] T et r a n e - 2 , 2 -diyl
D i s o d i u m 4 -sulfonato -7,8- d i a z a - 1 5 H - b i c y c l o [ ( 0 6 ) 1: 7 ( 2 ) 8 : 9 ( 0 6 ) 1 2 : 15(l)]pentadecaxen-l5-oate
( D i s o d i u m 4’- sulfonatoazobenzene-4-carboxylate
o r : D i s o d i u m p-(p-sulfonatopheny1azo)benzoate)
3
4
5
6
1
8
bH3-6-CO-C H2-C 0-O-C H2-CH3
3,5-Dioxo-2,6-dioxa[8]octane
(Ethyl me t h y l maionate)
I
7
1
4
5
6
2-Oxa- 7 -thia[6. Z3]octane
C H - C H2-C H2-C H3 ( 1- Methoxy - 1- ( m e t h y l H 3 3
thio)butane)
CH3-S\
6
HC -CH
6. (el)
CH
Cycloprop-1-en-3-ylium
( 2 - C y c l o p r o p e n - ~ - y l i u m )[*I
Angew. Chem. Int. Ed. EngI. 23 (1984) 33-46
1
1
3
4
6 . ( c ) CH3-CH-CHz-CH3
Q
[4]Tetran- 2-ylium
[*] As in classical organic nomenclature, free radicals with delocalized free
valences, or ions with delocalized charges, can be named by arbitrarily selecting a localized form, e. 9.. 2-cyclohexen-1-ylium (Rule C-83.1 [5]).
When this procedure is used in nodal nomenclature, it is important to
note that the numbering of the neutral parent hydride, including unsaturation, has priority over ionic charges for low locants. This arbitrary numbering may therefore be different from the arbitrary numbering recommended by IUPAC Rules (see examples 6 and 7). Pending publication of
IUPAC Rules on delocalized ions and radicals, no attempt to treat this
subject is made here.
43
5
6
7 . ( c ) &H~-I&H~-CH~-NHZ-CH~
0
8
2,5-Diaza[ 61hexan-5-ium2-ylium
3. ( b )
BraCH3
5 - Bromo - 2 -chlorocyclo( ( 0 6 ) l: i’(l)]heptan(l-G)arene
C1
1
6
8. ( d ) bH3-NH2-C Hz-CH2-NH-CH3
0
2 , 5 -Diaza[ Glhexan- 2 -ium
4 . ( c ) NzC-C Hz-C 0 - C Hz- C I10
5
6
9. (d) dH3-AH,-CH2-CH2-NH-C0-0’
Q
6 - ( Oxido,oxo)- 2,5 -diaza[6]hexan- 2-ium
(Ionic skeletal atoms having priority for low locants over ionic
substituents, it is preferable to use prefixes for the latter.)
CH3C0
Disodium 7 -oxo-6 -sulfidocyclo[ ( 0 6 ) l : 7 (2 ) l o c t a n ( l - 6 ) a r e n e - 3 -
(The principal substituent SO
1
11. ( f )
4
‘0-6 0-? H-C H2-CO-0’
4’
,
J
12.
has the locant 3, not 5.)
Z-Sulfidoi 4 1 t et rane - 1,4 -dioate
4
H2-C 0-Oo 2 -A mmonio[ 4]t et rane - 1,4 dioate
N-14.4. The description of the skeleton is completed before considering the distribution of hydrogen atoms and of
ionic charges. Therefore, a cationic skeletal atom may be
denoted by the suffix “ium” only if it bears at least one hydrogen atom. If this is not the case, the suffix “ylium” is
used, associated with the indication of a nonstandard
bonding number by’ a “h”” symbol[71.
Examples:
6. Conclusion
We have shown that the use of nodal nomenclature
(with its structure graphs, mathematical description of
chemical structures, unique and sequential numbering, and
virtual equivalence of substituents with characteristic
groups) simplifies the naming of chemical substances, particularly organic compounds with complex structures. The
resulting names are not fragmented and are based upon a
single numbering sequence, avoiding the scattering in the
name of substitutive affixes and replacement terms.
The present work giving only rather general suggestions
for adapting the substitutive method to nodal nomenclature, a more extensive and more detailed treatment of
functional groups may deserve a further study. We consider also the extension of nodal nomenclature to other
types of chemical substances such as polynuclear coordination compounds.
The Authors wish to thank members of the IUPAC Commission on Nomenclature of Organic Chemistry for their
comments and, in particular, Prof. D . Hellwinkel for translating this paper into German.
I
$H3
12
+3
,
2,5-Diaza[7 . 1 2151nonan1. CH3-NH-C HZ-CHZ-NH-CHZ-CH~ 2,5 - diium
0
1- Nitrilo- 3,5 -dioxo[ 5 Ipentane
( 4 - F o r m y l - 3 - oxobutanenitrile)
Received: March 7, 1983;
revised: June 22, 1983 [A 480 IE]
German version: Angew. Chem. 96 (1984) 1
6
Note on Part I[21
SH3
N-14.5. When the preceding rules leave a choice for the
numbering of the skeleton of a chemical structure, the following criteria are applied successively until a choice is
made, giving lowest locants to:
a) Neutral principal substituent, denoted by a suffix;
b) Neutral substituents denoted by prefixes, considered
together;
c) Neutral substituents denoted by prefixes, in alphabetical order.
Examples (decisive criteria are indicated within parentheses):
3
4
I4
2. ( a ) HOO~-;H~-CH~-C‘,H~
, *,COOH
HOOZ,
>CH-CHz-CHz-CB
CH<H2
H-$OOH
/?
h00s/’2
H35
[ 10.3518191’2~Hexadecane-l,10,
13,14,16-pentoic acid
( 3- ( 3-Carboxypropyl)- 1 , 1 , 6 , 7 -0ctanetetracarboxy1ic acid)
44
Examination of Rules N-5.3 to N-5.34 inclusive showed
that their selection criteria for numbering and naming assemblies could be simplified and made more exhaustive.
The following Rules, denoted RN-5.3 to RN-5.34 have
therefore been devised in order to replace the preceding
Rules N-5.3 to N-5.34.
This new text reproduces many features of the preceding
one (including note[231),sometimes in a different order, and
does not affect the name of any example in the original paper.
RN-5.3. Numbering of the module seniority graph, i. e . assignment of the module seniority numbers, which determines the order of assignment of the definitive sequential
numbering of the assembly (see Rule N-5.1), begins with
the principal module (see Rule N-4.2) and proceeds successively through each chain of contraction nodes attached
to the principal module. Selection rules for numbering the
module seniority graph differ from those applied to acyclic
graphs (Rule N-1) because module seniority graphs deal
with constituent units (modules) which may greatly differ
in structural complexity. Accordingly, rules for the module
seniority graph take into consideration the nature of the
contraction nodes, while, according to Rule N-1, the nature of the nodes does not affect the numbering of the
graph.
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
RN-5.31. A module seniority graph is considered as
formed by one or more unbranched chain(s) of modules
which are called segments and defined as follows.
RN-5.311. The numbering of a module seniority graph
starts from the (one of the) senior module(s), called the
principal module and continues sequentially according to
the following procedure:
In a chain of modules bound to the principal module,
the main segment is the longest (or one of the longest)
attached to the principal module and is numbered sequentially after the principal module.
Example:
7
G
?-E-E-A-C-B
1
2
1
I
5
6
c) Senior module, at the first difference, when the various
sets of modules are compared, term by term, in order of
decreasing seniority as defined in Rule N-4.2, regardless of the positions of the modules in the chains.
Example :
( B C , not B D )
L)-U-A-$-f(
5
4
,
.
Example:
B
1
A-E-Y-Y
1
2
Other segments of a chain of modules are numbered sequentially, starting always with the (one of the) longest
segment(s) bound to a module already numbered. Segments of equal length are numbered in the increasing
numerical order of their locants of attachment.
RN-5.313. When a module seniority graph contains two
or more modules of highest seniority, i. e. with module seniority descriptor A, the principal module is that senior
module to which is attached the most senior chain of contraction nodes when these chains are compared term by
term, in order of decreasing seniority, this order being determined by the criteria described in Rule RN-5.312.
Examples :
Examples:
1. A-A-B
I
2
1
not
4-A-B
not
A-A-+
1
1
-
1
( s e e Rule RN-5.312a)
,
I
B
I
1. +-E-q-$l
I
2. A-A-A
1
x
7
2
3
l
7
I
G
4
5
4.
4
5
I
7-B~dA-B-B
I
1
2
-
3
D-A-B-A-C
1
6
Example:
B
1
4
5
I
( s e e Rule RN-5.312b)
Any chain of modules, unbranched or branched, bound
to the principal module, is entirely numbered before
numbering another chain (if any) bound to the principle module.
I
6
$-y-A-$-p$-q
not
8
1
1
I
3. C-B-A-4-B-C-D
1
D D
I 1
3 , 4-B-B-C-B-I3
B
I3
D
E
-
(see Rule RN-5.312a)
.
8
I
A-B-B-B~x-E
1
I
J
‘I
B-D-E
2.
2
1
RN-5.312. When two or more chains of modules are attached to the principal module, the order in which these
chains are numbered is decided by the following criteria
considered successively until a decision is reached:
2
J
l
not
U-+-B-A-C
2
4
1
(ABAC, not A H A D ,
5
s e e Rule R N - 5 . 3 1 2 ~ )
RN-5.32. The module graph descriptor consists of quotation marks enclosing: a) an Arabic numeral denoting the
number of modules, including the principal one, in the
first (main) segment to be numbered; b) a period followed
by Arabic numerals denoting the number of modules in
each segment, cited in their order of numbering; c) a superscript locan; for each segment defined under b), denoting the module, in the part of the graph already numbered,
to which the segment is attached.
Examples :
a) Largest number of modules in the entire chain.
Example:
dI
4
1
1
-A-B -C
E -F-G-D
5
iI
2. A-B-B-B-B
2
1
6
1
2
)
4
It5.
z1 211
I
7
7
b) Longest unbranched chain of modules (i. e., longest
main segment).
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
45
RN-5.33. When there remains a choice for the order of
numbering of the chains or for the selection of the principal module, the correct numbering of the module seniority
graph is the one corresponding to the module graph descriptor having the preferred numeral at the first difference: if the first difference corresponds to a segment
length, the preferred numeral is higher; if the first difference appears in a superscript numeral (locant of a module), the preferred numeral is lower.
Examples:
O
I
.
I1
I2
t 1 ~ , ~ 1 ~ 6 1 1
not
I
6
B B
2.
I
1
1
O
V
I
1
I
"
2
1
6
-
3
I
B-B-B-A-A-B-B-B
8
"
5.1'1 3412'"
!l4,123117ll
not
"4.133116"
5. 133' 1'"
not
"5.143117"
4
B
I
9
'" not
6
10
B
4.
5. 23411'
4
3. B-B-B-+-?-B-B
I
I
1
"4.1331"
B
9
€3
8
1
1
2
1
"
4
5
RN-5.34. If the preceding Rules leave a choice for the
numbering, the correct numbering is the one giving the
lowest locant, at the first difference, when modules are
considered in order of decreasing seniority.
Examples:
1.
y.+-BT
l o c a n t s f o r B: 2,5 not 3 , 4
2. C-A-B-B-D-A-C
7
1
2
1
4
5
l o c a n t s f o r B: 2,3
not 3 , 4
l o c a n t s f o r D: 5,6
not 5 , 7
6
6
L)
I
3. A-B-C-B-D
I
46
2
1
2
1
4
5
6
1
6
l o c a n t s f o r B: 2,6
not 2,9
D-B
I
5. A-7-F-B-D
I
l o c a n t s f o r B: 2,4,7
not 2,5,6
I 1 4
I
Received: October 17, 1983 [A 480a IE]
German version: Angew. Chem. 96 (1984) 13
1
B-B
1
B-B-B-B-A-5-B-B-?
1
Y
Rule N-5.35 and following Rules unchanged.
8
D
1. C-B-A-4-B-Y-v
I
1
"
7
C-D-E
I
4. A-B-C-D-E-B
111 For a detailed discussion of mathematical descriptions of chemical structures, see A. L. Goodson, Application of Graph-Based Chemical Nomenclature to Theoretical and Preparative Chemistry - IUPAC International
Symposium on Theoretical Organic Chemistry, Dubrovnik 1982; Croat.
Chem. Acta 56 (1983) 315.
[2] N. Lozac'h, A. L. Goodson, W. H. Powell, Angew. Chem. 91 (1979) 951;
Angew. Chem. I n f . Ed. Engl. 18 (1979) 887; ibid. Section 4.
[3] A. T. Balaban: Chemical Applications of Graph Theory, Academic Press,
London 1976.
[4] A. L. Goodson, J. Chem. hf.Compuf.Sci. 20 (1980) 167; "Nomenclature
of Chemical Compounds", in N. N. Tyutyulkov, D. Bonchev: Graph Theory and its Application in Chemistry, Nauka i Izkutsvo, Sofia, in press.
[S] IUPAC, Nomenclature of Organic Chemistry, Sections A, B, C, D, E, F,
and H,Pergamon Press, Oxford 1979; a) ibid. p. 82 and Section D-0.3; b)
ibid. Section C-0.6; c) ibid. Rule B-1; d) ibid. Rule D-4.11 and Table I, p.
459; ibid. e) Section A; 0 ibid. Section B.
[6] Generalization of replacement nomenclature was proposed in IUPAC
Commission on Nomenclature of Organic Chemistry, Unpublished Studies toward a Structure-Based Substitutive Nomenclature, 1975-1977.
[7] IUPAC Commission on Nomenclature of Organic Chemistry, The Designation of Nonstandard Classical Valence Bonding in Organic Chemistry,
Pure Appl. Chem. 54 (1982) 217.
[8] First proposed by the IUPAC Commission on Nomenclature of Organic
Chemistry Working Party for Section G.
[9] This definition includes the cases covered by Rule A-21.6 [5] but is more
general and applies even when indicated hydrogen is not necessary for
distinguishing isomers. This definition has been adopted by the IUPAC
Commission on Nomenclature of Organic Chemistry in "Revision of the
extended Hantzsch-Widman System of Nomenclature of Heteromonocycles (Recommendations 1982)". Rule RB-1.2, Pure Appl. Chem. 55 (1983)
409.
Angew. Chem. Int. Ed. Engl. 23 (1984) 33-46
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