Patent GB-1019451-A (GB)
Title: Improvements in or relating to pesticides
Inventor: PIANKA MAX
IPC: C07D277/72
Filed: 1961-03-22
Abstract: The invention relates to compounds of the formula <FORM:1019451/C2/1> in which X and Y are the same or different and each is an oxygen or sulphur atom, one of the groups R1 and R11 is a nitro group and the other is a branched aliphatic hydrocarbon group of 4-8 carbon atoms or a phenyl, substituted phenyl, cyclohexyl or substituted cyclohexyl group, and R is (a) a saturated or unsaturated aliphatic hydrocarbon residue which may be substituted with one or more of the following substituents, viz., halogen atoms or amino, substituted amino, salted amino, hydroxy, alkoxy, acyl, alkylthio, aryl, alicylic or heterocyclic groups or (b) a phenyl, chlorophenyl, nitrophenyl, tolyl, naphthyl, alicyclic or heterocyclic group.  The compounds may be prepared (1) by reaction of the appropriately substituted phenol with an appropriate haloformic ester, preferably in the presence of an acid-binding agent, e.g. pyridine or dimethylaniline, in an inert organic solvent, e.g. diethyl ether, benzene or tetrahydrofuran, or (2) by reaction of the appropriately substituted phenolate with a haloformic ester in an inert organic solvent, e.g. acetone, the phenolate being preferably formed in situ from the phenol and an alkali-metal compound e.g. an alkali hydroxide, carbonate or bicarbonate, before the haloformic ester is added or (3) by reaction of the appropriately substituted phenol simultaneously with a haloformic ester and an alkali-metal carbonate or bicarbonate (but not hydroxide) in an inert organic solvent, e.g. acetone.  Examples are given of the preparation of the following compounds:-isopropyl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; chloroethyl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; ethoxyethyl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; allyl 2,4-dinitro-6-sec.-butylphenyl carbonate; 21,31-dibromopropyl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; phenyl 2,4-dinitro-6-sec. - butylphenyl carbonate; p - chlorophenyl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; cyclohexyl 2,4 - dinitro - 6 -sec. - butylphenyl carbonate; a  - naphthyl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; ethyl 2,4 - dinitro - 6 - sec. - butylphenyl thiolocarbonate; methyl 2,4 - dinitro - 6 - sec. - butylphenyl thionothiolocarbonate; ethyl 2,4 - dinitro - 6 - sec. - butylphenyl thionocarbonate; a  - tetrahydrofurfuryl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; p - nitrophenyl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; 2 - mercaptobenzthiazolyl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; N,N - diethylaminoethyl 2,4 - dinitro - 6 - tert. - butylphenyl carbonate; b  - ethylthioethyl 2,4 - dinitro - 6 - sec. - butylphenyl carbonate; hydroxyethyl 2,4 - dinitro - 6 - tert. - butylphenyl carbonate; benzoyloxyethyl 2,4-dinitro-6 -tert. - butylphenyl carbonate; benzyl 2,4-dinitro - 6 - tert. - butylphenyl carbonate p - chlorobenzyl - 2,4 - dinitro - 6 - tert. -butylphenyl carbonate; ethyl 2,4 - dinitro - 6 - cyclohexylphenyl carbonate; methyl 2,4-dinitro - 6 - phenylphenyl carbonate; methyl 2,4-dinitro - 6 - phenylphenyl thionolothiocarbonate; ethyl 2,6-dinitro-4-tert.-butylphenyl carbonate. Other examples describe the preparation of isomers or homologues of some of these compounds. The products are useful as pesticides (see Division A5).  The preparation of ethyl 2,4-dinitro-6-sec.-butylphenyl carbonate from ethyl chloroformate and the sodium salt of 2,4-dinitro-6-sec.-butylphenol is disclaimed.ALSO:As components of pesticidal compositions, use is made of compounds of the formula <FORM:1019451/A5-A6/1> in which X and Y are the same or different and each is an oxygen or sulphur atom, one of the groups R1 and R11 is a nitro group and the other is a branched aliphatic hydrocarbon group of 4-8 carbon atoms or a phenyl, substituted phenyl, cyclohexyl or substituted cyclohexyl group, and R is (a) a saturated or unsaturated aliphatic hydrocarbon residue which may be substituted with one or more of the following substituents, viz., halogen atoms or amino, substituted amino, salted amino, hydroxy, alkoxy, acyl, alkylthio, aryl, alicyclic or heterocyclic groups or (b) a phenyl, chlorophenyl, nitrophenyl, tolyl, naphthyl, alicyclic or heterocyclic group (see Division C2).  The products, according to their composition, may have acaricidal, ovicidal, fungicidal and (or) insecticidal properties. They may be prepared in the form of solutions, emulsions, aerosols, dusts, wettable powders, granulates, pellets, pastes or thermal fumigating mixtures.  A wettable powder may comprise the toxicant, synthetic calcium silicate, the calcium salt of sulphite cellulose waste liquor, sodium lauryl sulphate and china clay.  A thermal fumigating composition may comprise the toxicant, potassium chlorate, lactrose and china clay.  Experimental results of the use of some of the compounds are given.  Herbicidal compositions containing ethyl 2, 4-dinitro-6-sec.-butylphenyl carbonate are disclaimed.