Patent GB-1070755-A (GB)
Title: Improvements in or relating to 2,6-dinitro-4-alkylphenols and carbonates thereof
Inventor: PIANKA MAX
IPC: C07C37/18
Filed: 1964-08-07
Abstract: The invention relates to substituted dinitro phenyl alkyl carbonates of the general formula <FORM:1070755/C2/1> in which R is an alkyl group and R1 and R2 are n-alkyl groups containing from 2 to 5 carbon atoms each and together containing a total of 6 to 10 carbon atoms. Many compounds are claimed per se.  The compounds may be prepared by: (1)  Reacting a compound of the general formula <FORM:1070755/C2/2> in which Q represents a hydrogen or an alkali metal atom, preferably sodium or potassum with a haloformic acid ester of the formula (IV) Z.CO.OR where Z is chlorine, bromine or iodine, preferably chlorine, and R has the above-defined meaning, the reaction being effected in the presence of an acid binding agent, e.g. an alkali metal carbonate, an alkali metal bicarbonate or a tertiary amine (e.g. pyridine), where Q represents a hydrogen atom, preferably in solution in an inert organic solvent, e.g. a ketone such as acetone.  The phenoxide of Formula (III) (where Q is an alkali metal) may be performed, or, preferably may be formed in situ in an inert organic solvent prior to introduction of the haloformic acid ester by reaction of the parent phenol <FORM:1070755/C2/3> with a suitable alkali metal compound, e.g. the hydroxide, carbonate or bi-carbonate. (2)  The simultaneous reaction of the parent phenol (V) with a haloformic acid ester (IV) in an inert organic solvent (e.g. a ketone such as acetone) in the presence of an alkali metal carbonate or alkali metal bicarbonate, preferably an alkali metal carbonate.  The haloformic acid esters (IV) may be prepared by reaction of a compound of the formula ROH with a compound of the formula COZ2 preferably in the presence of aluminium chloride as catalyst and where required in the presence of an acid binding agent.  The invention also relates to the parent dinitro-alkyl phenols: <FORM:1070755/C2/4> in which R3 is a 1-n-propyl-n-butyl, 1-ethyl-n-pentyl, 1-n-butyl-pentyl, 1-n-propyl-n-hexyl, 1-n-butyl-n-hexyl, or 1-n-pentyl-n-hexyl group. Examples of compounds claimed per se are those in which R3 is 1-n-propyl-n-butyl, 1-ethyl-n-pentyl, 1-n-pentyl-n-hexyl.  The compounds may be prepared by dinitration of the corresponding alkylphenols which may be prepared by reacting a p-hydroxybenzoketone with an appropriate alkylmagnesium halide, to yield a tertiary carbinol, dehydration of the carbinol, followed by catalytic hydrogenation of the resultant olefine, e.g. using palladium/charcoal in ethanol.  Dehydration may occur spontaneously during heating or may be effected by the use of an acid catalyst, e.g. potassium hydrogen sulphate, p-toluene sulphonic acid or sulphuric acid.  In an example, 2,6-di-nitro-4-(1-ethyl hexyl) phenyl ethyl carbonate is prepared by heating 2,6-di-nitro-4-(1-ethyl hexyl) phenol, carbonate and acetone and adding ethyl chloro formate.ALSO:Pesticidal compositions comprise as active ingredient one or more compounds of the general formula:  <FORM:1070755/A5-A6/1> in which R is an alkyl group and R1 and R2 are n-alkyl groups containing from 2 to 5 carbon atoms each and together containing a total of 6 to 10 carbon atoms together with a solid or liquid diluent.  Other pesticides, e.g. fungicides, acaricides or insecticides may also be incorporated.  The composition may be in the form of solutions, emulsions, aerosols, pastes, dusts, wettable powders, granulates and pellets and may form thermal fumigating compositions with a solid pyrotechnic component.