Nomenclature of an organic compound

Question

Which substituent should be placed first (in case of alphabetisation)?

1. isopropyl-

2. methyl-

I have come across two compounds: 1-methyl-3-methoxy-4-isopropylbenzene and 1-isopropyl-4-methylcyclohexane

So, is “iso” taken care of in case of alphabetisation? And, are there any special criteria for this operation?

Answer 1

(Note that the prefix ‘isopropyl’ is retained for use in general nomenclature but the preferred IUPAC name is ‘propan-2-yl’.)

Simple prefixes (simple substituent groups consisting of just one part that describes an atom, or group of atoms as a unit, for example methyl, methoxy, and isopropyl) are arranged alphabetically disregarding any multiplicative prefixes. Any multiplicative prefixes are inserted later and do not alter the alphabetical order.
For example, ‘1,2-dibromo-’ is considered to begin with ‘b’; ‘isopropyl’ is considered to begin with ‘i’.

On this matter, the current version of Nomenclature of Organic Chemistry – IUPAC Recommendations and Preferred Names 2013 (Blue Book) reads as follows:

P-14.5 ALPHANUMERICAL ORDER

Alphanumerical order has been commonly called ‘alphabetical order’. As these ordering principles do involve ordering both letters and numbers, in a strict sense, it is best called ‘alphanumerical order’ in order to convey the message that both letters and numbers are involved

Alphanumerical order is used to establish the order of citation of detachable substituent prefixes (not the detachable saturation prefixes, hydro and dehydro), and the numbering of a chain, ring, or ring system when a choice is possible.

(…)

P-14.5.1 Simple prefixes (i.e., those describing atoms and unsubstituted substituents) are arranged alphabetically; multiplicative prefixes, if necessary, are then inserted and do not alter the alphabetical order already established.

Therefore, the correct alphanumerical order in your first example corresponds to the name x-isopropyl-y-methoxy-z-methylbenzene.

In your second example, the correct alphanumerical order corresponds to the name x-isopropyl-y-methylcyclohexane.

Furthermore,

P-14.4 NUMBERING

When several structural features appear in cyclic and acyclic compounds, low locants are assigned to them in the following decreasing order of seniority:

(…)

(f) detachable alphabetized prefixes, all considered together in a series of increasing numerical order;

(g) lowest locants for the substituent cited first as a prefix in the name;

(…)

Note that Rule f takes precedence over Rule g.

Therefore, your first example is named as 1-isopropyl-2-methoxy-4-methylbenzene rather than 4-isopropyl-3-methoxy-1-methylbenzene since the locant set ‘1,2,4’ is lower than ‘1,3,4’.

Your second example is named as 1-isopropyl-4-methylcyclohexane rather than 4-isopropyl-1-methylcyclohexane since isopropyl is cited first as a prefix in the name.