Patent GB-812177-A (GB)
Title: Improvements in and relating to esters
IPC: C07D215/26
Filed: 1956-06-15
Abstract: The invention comprises carbonic acid esters of the formula: <FORM:0812177/IV (b)/1> (wherein R is hydrogen or methyl, R1 is alkyl of at most 4 carbon atoms or phenyl, which radicals may be halogen substituted, and R2 is alkyl, alkenyl, cycloalkyl, aryl or aralkyl in which radicals any chain or ring methylene group can be replaced by O or S and which radicals may be substituted by halogen atoms or nitro groups), and their preparation by reacting the appropriate 2-R-5-acyl-8-hydroxy-quinoline or a salt thereof, e.g. the potassium salt, with an ester Hal-CO-OR2 (wherein Hal is chlorine or bromine), an acid binding agent being present if the free hydroxy compounds is used.  The reaction is advantageously performed in an inert anhydrous organic solvent, e.g. a benzene hydrocarbon.  Examples describe the preparation of ethyl-[5-aceto-quinolyl - (8)] - carbonate and (4 - chlorophenyl) - [5 - aceto - quinolyl - (8)] - carbonate by the process of the invention and it is stated that compounds in which R, R1 and R2 have the following values can be produced similarly: (1) R being H and R1 methyl, R2 is methyl, n-propyl, isopropyl, isobutyl, sec-butyl, n-amyl, n-hexyl, 2-ethyl-hexyl, n-dodecyl, b -chloro-ethyl, b -methoxy-ethyl, b -ethoxy-ethyl, b  - n - butoxy - ethyl, b  - n - hexyloxy - ethyl, b -phenoxy-ethyl and b -benzyloxy-ethyl, allyl, cyclohexyl, tetrahydrofurfuryl, 2 : 2 - dimethyl - 1 : 3 - dioxolanylmethyl, phenyl, 2-chlorophenyl, 2 : 4- and 3 : 4-dichlorophenyl, o-and p-cresyl, 4-(a  : a -dimethylg  : g -dimethyl-butyl)-, phenyl, 2-methoxy- and 4-nitro-phenyl, benzyl, 4-chlorobenzyl, b -(2-chlorophenoxy)-ethyl and b -phenylmercapto-ethyl; (2) R being H and R2 methyl, R1 is n-propyl, isobutyl, chloromethyl, phenyl and 2-chlorophenyl; (3) R is H, R1 is isobutyl and R2 is phenyl; (4) R is H, R1 is phenyl and R2 is b -phenylmercapto-ethyl; (5) R and R1 being methyl, R2 is ethyl, phenyl, 2-methoxy- and 4-nitro-phenyl, 4-chlorobenzyl and b -phenylmercaptoethyl; and (6) R and R2 are methyl and R1 is phenyl. The use of 5-propionyl- and 5-isobutyryl-8-hydroxyquinolines, 5-propionyl-, 5-butyryl-, 5-isovaleryl and 5-(21-chloro-benzoyl)-8-hydroxy-quinaldines and the chloroformic acid esters of n-butyl-, isoamyl-, methallyl-, methylcyclohexyl-, ethoxyethoxyethyl-, methylmercapto-ethyl-, 4-chlorophenoxyethyl-, and 2-nitro- and 4 - nitro - phenyl - mercaptoethyl - alcohols, 4 - (t - butyl) - phenol, glycide and acetone glycerin in addition to starting materials giving the above specific products is also referred to. 5-Isobutyryl-, 5-chloracetyl- and 5-(21-chlorobenzoyl) - 8 - hydroxyquinolines and 5 - acetyl-, 5-propionyl-, 5-butyryl-, 5-isovaleryl-, 5-benzoyl-and 5 - (21 - chloro - benzoyl) - 8 - hydroxyquinaldines are prepared by condensing 8-hydroxyquinoline or 8-hydroxyquinaldine with the appropriate acid chloride in presence of aluminium chloride.ALSO:Fungicidal and bacteriostatic seed dressings contain a compound of the formula <FORM:0812177/I/1> (wherein R is hydrogen or methyl, R1 is an alkyl radical having at most 4 carbon atoms or phenyl, which radicals may be halogen substituted, and R2 is alkyl, cycloalkyl, aryl or aralkyl in which radicals any chain or ring methylene group can be replaced by O or S and which radicals may be substituted by halogen atoms or nitro groups) mixed, if desired, with a carrier such as talc, kaolin, bole, bentonite, chalk or limestone.  A fungicidal dry seed dressing comprising ethyl-[5-aceto-quinolyl-(8)]-carbonate, is described.  The dressings may be dispersed in water containing, if desired, a dispersing agent or emulsifier.  The dressings may be dissolved in an organic solvent such as trichloroethylene or petroleum.  The organic solvent may contain acetone or a higher ketone. Alternatively, the dressings may be dissolved or dispersed in liquids which are gaseous at normal pressures, e.g. difluorodichloromethane or fluorotrichloromethane, so that they can be distributed as smokes or mists.ALSO:Fungicidal and disinfectant compositions contain a compound of the formula: <FORM:0812177/VI/1> (wherein R is hydrogen or methyl, R1 is alkyl of at most 4 carbon atoms or phenyl, which radicals may be halogen substituted, and R2 is alkyl, alkenyl, cycloalkyl, aryl or aralkyl in which radicals any chain or ring methylene group can be replaced by O or S and which radicals may be substituted by halogen atoms or nitro groups) in a finely-distributable form combined with a suitable carrier.  The compositions may also contain distributing/dispersing agents.  Suitable carriers are talc, kaolin, bole, bentonite and chalk and suitable dispersing agents for the preparation of aqueous dispersions are sulphite waste liquor and the sodium salt of dibutyl naphthalene sulphonic acid. Suitable emulsifying agents for the preparation of aqueous emulsions are quaternary ammonium compounds, soap, soft soap, salts of aliphatic sulphuric acid monoesters or aliphatic-aromatic sulphonic acids and higher molecular ethylene oxide condensation products.  Suitable organic solvents are chlorinated hydrocarbons, medium petroleum fractions, ketones and liquefied gases such as difluorodichloromethane and fluorotrichloromethane.  Examples describe the preparation of the following compositions: (1) ethyl-[5-aceto-quinolyl-(8)]-carbonate and talc with or without an adhesive agent; (2) methyl-[5-aceto-quinolyl-(8)]-carbonate, kaolin or chalk, wetting agent, e.g. sulphite waste liquor, and water; (3) allyl - [5 - aceto - quinolyl - (8)] - carbonate, xylene and ethylene oxide condensation products of alkyl phenols; (4) n-hexyl-[5-aceto-quinolyl - (8)] - carbonate, xylene and a polyethylene oxide esterified with ricinoleic acid; (5) p - cresyl - [5 - aceto - quinolyl - (8)] - carbonate, a protective colloid, e.g. dried sulphite waste liquor, an adhesive agent, a pulverulent carrier, e.g. koalin, champagne chalk or bentonite, water and, optionally, a wetting agent; and (6) 41 - chlorophenyl - [5 - aceto - quinolyl - (8)]-carbonate, liquid sulphite waste liquor and water.