Patent GB-597091-A (GB)
Title: Improvements in the production of aryl derivatives of trihalogenoethane
IPC: C07C17/26
Filed: 1944-12-08
Abstract: A wax preparation or furniture cream for the treatment of wood, a staining, varnishing or painting composition, or an oil-bound water paint or distemper, contains a compound having the general formula:- <FORM:0597091/III/1> wherein X represents chlorine or lumine and R1, R2 represent the same or different aryl radicals of the benzene series at least one of which contains fluorine as a nuclear substituent.  In examples, (13) a white spirit solution of a-a-bis-(4-fluoro-phenyl)-b :b :b -trichloroethane is blended with a melt of carnauba and paraffin waxes to obtain an insecticidal wax polish, (14) an insecticidal wood stain is obtained by dissolving the insecticide of (13) in naphtha to which is added a fat soluble dye-stuff, (15) an insecticidal varnish stain is obtained by dissolving the insecticide of (13) in methylated spirits to which is added rosin and button lac and, optionally, adding a spirit dye-stuff, (16) an insecticidal paint is obtained by introducing 1 per cent. of the insecticide of (13) into an oil-bound water paint either by incorporation during grinding of the pigment with the emulsion medium, or by first dissolving it in the oil portion prior to emulsification, (17) an insecticidal distemper is obtained by grinding 1 per cent. of the insecticide of (13) by known methods, with dry distemper ingredients.  Specifications 547,871, 547,874, 566,386, 566,387, 588,205, [all in Group IV], and 590,826 are referred to.ALSO:Aryl derivatives of trihalogenoethane having the general formula either: <FORM:0597091/IV/1> or <FORM:0597091/IV/2> wherein R represents an aryl radical of the benzene series containing fluorine as a nuclear substituent, R1 and R2 represent the same or different aryl radicals of the benzene series at least one of which contains fluorine as a nuclear substituent and X represents chlorine or bromine; are obtained respectively by (1) bringing together substantially two molecular proportions of an aryl compound of the benzene series, nuclearly substituted by fluorine, but containing a replaceable nuclear hydrogen atom and one molecular proportion of chloral or bromal, either in the anhydrous form or in the form of its hydrate or alcoholate, in the presence of sulphuric acid or chlorsulphonic acid as condensing agent; (2) either treating an aryl compound of the benzene series nuclearly substituted by fluorine, but containing a replaceable nuclear hydrogen atom and a trichloromethyl or tribromomethyl aryl carbinol or treating an aryl compound of the benzene series containing a replaceable nuclear hydrogen atom and a trichloromethyl or tribromomethylfluoaryl carbinol, in each method in the presence of sulphuric acid or chlorsulphonic acid as a condensing agent. The products may contain water-solubilizing groups as described in Specification 582,205.  The invention also comprises the production of trichloromethyl-4-fluorophenyl carbinol or tribromomethyl-4-fluorophenyl carbinol by reacting fluorobenzene with chloral or bromal (in the anhydrous form or in the form of the hydrate or alcoholate) in the presence of a Friedel-Craft condensing agent, e.g. aluminium chloride.  In examples, there are obtained, by the use of sulphuric acid as condensing agents: (1) and (2) a  : a -bis-(4-fluorophenyl)-b  : b  : b -trichloroethane by condensing (1) fluorobenzene with chloral, and (2) fluorobenzene with a -p-fluorophenyl-b  : b  : b -trichloroethanol; (3) a  - p - chlorophenyl - a  - p p  - fluorophenyl-b  : b  : b -trichloroethane from a -p-chlorophenyl - b  : b  : b  - trichloroethanol and fluorobenzene; (4) a -p-fluorophenyl-a -p-tolyl-b  : b  : b -trichloroethane from a -p-tolyl-b  : b  : b -trichloroethanol and fluorobenzene; (5) a -p-fluorophenyl - a  - phenyl - b  : b  : b  : trichloro - ethane from a -phenyl-b  : b  : b -trichloroethanol and fluorobenzene; (6) a -p-anisyl-a -p-fluorophenyl -b  : b  : b  - trichloroethane from anisole and a -p-fluorophenyl-b  : b  : b -trichloroethanol; (7) a  : a -bis-(p-fluorophenyl)-b  : b  : b -tribromoethane from fluorobenzene and bromal; (8) a  : a -bis-(o-fluoroanisyl)-b  : b  : b -trichloroethane from o-fluoroanisole and chloral in the presence also of glacial acetic acid; (9) a  : a -bis-(o-chloro-fluorophenyl)-b  : b  : b -trichloroethane from o-chloro-fluorobenzene and chloral.  a  - p - Fluorophenyl - b  : b  : b -trichloroethanol is prepared by condensing chloral with fluorobenzene in the presence of aluminium chloride.  Specifications 547,871, 547,874, 566,386, 566,387 and 590,826, [Group III], also are referred to.ALSO:Plaster is treated or prepared so that there is incorporated therein an insecticidal ingredient consisting of a compound having the general formula: <FORM:0597091/V/1> wherein X represents chlorine or bromine, and R1, R2 represent the same or different aryl radicals of the benzene series at least one of which contains fluorine as a nuclear substituent whereby such insecticidal ingredient becomes a constituent of the plaster.  In an Example (20) a:a-bis (4-fluoro-phenyl)-:b :b :b :-trichloroethane is first ground in an edge runner with twice its weight of plaster of paris until the whole becomes an evenly blended, smooth-flowing powder.  Further plaster of paris and the usual retardants are then added by a suitable known process until the content of the active ingredient corresponds to 5 to 10 per cent. of the whole.  The resulting product can then be used when made up to a paste with water as a "skimming" plaster to render wall or other surfaces insecticidal.  Specifications 547,871, 547,874, 566,386, 566,387, 582,205, and 590,826, [all in Group IV], are referred to.ALSO:An insecticidal composition comprises a compound have the general formula <FORM:0597091/VI/1> wherein X represents chlorine or bromine and R1, R2 represent the same or different aryl radicals of the benzene series, at least one of which contains fluorine as a nuclear substituent, whereby such ingredient becomes a constituent of said materials or articles.  Other ingredients which may or may not have insecticidal or fungicidal properties may be used.  Examples describe: (10) a carbon tetrachloride or trichlorethylene solution of a  : a -bis-(4-fluorophenyl) - b  : b  : b  - trichloroethane; (11) an aqueous emulsion of the insecticide of (10) prepared by dissolving the compound in a mixture of benzene and methyl cyclohexanol adding sulphonated castor oil and ammonia, and diluting with water; (12) a white spirit solution of the insecticide of (10); (18) the insecticide of (10) on ground with china clay and wetting agents; (19) the insecticide of (10) in solution in a spinning oil such as olive oil; (20) a milky solution of the insecticide of (10), stearyl tolyl di-ethyl ammonium etho-sulphate and toluene; (22) a finishing bath containing a solution or emulsion (as in (10) and (11)) of the insecticide and, for example, a resin; (24) sawdust mixed with a suspension of the compound of (10) and with an inert diluent such as china clay, together with a wetting agent and thereafter dried. Specifications 547,871, 547,874, 566,386, 566,387, 582,205 and 590,826, [Group III], are referred to.