Patent GB-1070756-A (GB)
Title: Improvements in or relating to dinitrophenyl carbonates and their use as pesticides
Inventor: PIANKA MAX
IPC: C07C37/18
Filed: 1964-08-07
Abstract: The invention relates to substituted di-nitrophenyl alkyl carbonates of the general formula <FORM:1070756/C2/1> in which R is an alkyl group containing 1 to 6 carbon atoms and R1 is 1-ethyl-n-hexyl or 1-n-propyl-n-pentyl. Compounds claimed per se are 2 - (1 - ethyl - n - hexyl) and 2-(n-propyl-n-pentyl) - 4,6 - dinitrophenyl methyl and ethyl carbonate; n-propyl, isopropyl and n-hexyl 2-(1-ethyl-n-hexyl) 4,6-dinitrophenyl carbonates. The compounds may be prepared by: (1) Reacting a compound of a general formula <FORM:1070756/C2/2> in which Q represents a hydrogen or an alkali metal atom, preferably sodium or potassium, with a haloformic acid ester of the formula (IV)  Z.CO.OR where Z is chlorine, bromine or iodine, preferably chlorine, and R is as above, 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:1070756/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 parent dinitro-alkyl phenols (V), where R1 is as above, may be prepared by dinitration of the corresponding alkylphenols. The latter may be prepared by reacting a o-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 - (1 - ethyl - n - hexyl) - 4,6 - dinitro phenyl ethyl carbonate is prepared by heating 2-(1-ethyl-n-hexyl)-4,6-dinitro phenol, potassium carbonate and acetone and adding thereto ethyl chloroformate.ALSO:Pesticidal compositions comprise as active ingredient one or more compounds of a general formula: <FORM:1070756/A5-A6/1> in which R is an alkyl group containing one to six carbon atoms and R1 represents 1-ethyl-n-hexyl or 1-n-propyl-n-pentyl together with solid or liquid carriers or diluents.  Other pesticides e.g. fungicides, acaricides or insecticides may also be incorporated.  The composition may be in the form of solutions or emulsions, aerosols, pastes, dusts, wettable powders, granulates and pellets and may form thermal fumigating compositions with a solid pyrotechnic component.