organic chemistry - What is the numbering of substituted benzene derivatives according to IUPAC nomenclature?

According to the lowest locant rule shouldn't the numbering of the compound 1 start from the carbon at the 4th position, thus giving the IUPAC name as 1,2-dimethyl-4-hydroxybenzene?

For compound 2 they could have prioritized the functional group, but they have prioritized the lowest locant rule instead.

Answer

There are several criteria for the numbering of locants. The most important simplified criteria for the numbering for substituted benzene compounds are:

1. lower locants for the principal characteristic groups, which are expressed as a suffix or implied by the name of the functional parent compound (If there is a choice, the principal characteristic groups are assigned in accordance with the order of seniority of classes of compounds.)


2. lower locants for prefixes


3. lower locants for substituents cited first as a prefix in the name

The corresponding actual wording of the nomenclature rules (taken from Nomenclature of Organic Chemistry – IUPAC Recommendations and Preferred Names 2013 (Blue Book)) reads as follows:

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:

(…)

(c) principal characteristic groups and free valences (suffixes);

(…)

(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;

(…)

The first compound given in the question has the functional parent compound phenol. The name ‘phenol’ implies the presence of the characteristic group $\ce{-OH}$. Since there are no other characteristic groups and low locants are assigned first to the principal characteristic group, the locant ‘1’ is assigned to the substituent group $\ce{-OH}$. Therefore, the systematic name for this compound is 3,4-dimethylphenol.

The second compound given in the question does not have any principal characteristic group – neither expressed as a suffix nor implied by the name of a functional parent compound. Therefore, low locants are assigned to the prefixes ‘chloro’, ‘methyl’, and ‘nitro’, all considered together as a set in a series of increasing numerical order. Thus, the systematic name for this compound is 2-chloro-1-methyl-4-nitrobenzene and neither ‘1-chloro-2-methyl-5-nitrobenzene’ nor ‘3-chloro-4-methyl-1-nitrobenzene’ since the locant set ‘1,2,4’ is lower than ‘1,2,5’ or ‘1,3,4’.