Patent GB-473424-A (GB)
Title: Improvements in the manufacture and production of esters of high molecular weight
Filed: 1936-03-12
Abstract: Esters of the general formula (R.COO)n--X, where R is a radicle of high molecular weight with a straight or branched alkyl group having at least six carbon atoms or a hydroaromatic radicle also having at least six carbon atoms, n is a whole number, and X is the radicle of a cyclic compound having at least four condensed isocyclic nuclei with or without heterocyclic nuclei, are manufactured by reacting cyclic compounds having at least four condensed isocyclic nuclei with or without heterocyclic nuclei and containing at least one hydroxyl group, or compounds yielding such substances under suitable reaction conditions, with esterifying derivatives, e.g. halides or anhydrides, of carboxylic acids R.COOH, where R is a radicle as defined above, e.g. a cyclohexyl radicle, the radicle of a hydronaphthalene or of a hydroanthracene, which radicles may be attached to the carboxylic group by an open carbon chain, or a straight or branched alkyl group with more than six carbon atoms, e.g. heptyl, nonyl, undecyl, heptadecyl or heptadecenyl, or the radicle of a compound of the terpene series or similar hydroaromatic compound, e.g. a bornyl, camphene, camphane, naphthenyl or abietinyl radicle.  The cyclic hydroxy compounds may belong to the pyrene, chrysene, perylene, benzperylene, triphenylene, benzanthrene and benzanthrone series, and are obtainable by sulphonating the corresponding compounds free from hydroxy groups and fusing the sulphonic acids with caustic alkali. There may alternatively be employed compounds which under suitable reaction conditions, e.g. in the presence of reducing agents, behave as hydroxyl compounds, particularly compounds having cyclic-combined carbonyl groups. The reaction may be effected by heating the initial materials, generally in the presence of solvents or diluents, e.g. hydrocarbons, or secondary or tertiary amines, in many cases preferably in a closed vessel, if desired while pressing in inert gases.  The products are suitable for colouring or rendering fluorescent artificial resins, hydrocarbons, paraffin waxes, oils, waxes, fats, mineral oils, rubber and other natural and synthetic plastic masses, and also lacquers, e.g. nitrocellulose lacquers, or for the preparation of other dyestuffs.  In examples: (1) Bz2-hydroxydibenzanthrone is stirred with stearic acid chloride and pyridine; (2) Bz2 : Bz2<1>-dihydroxydibenzanthrone is heated with stearic acid chloride, pyridine and chlorobenzene; the stearic acid chloride may be replaced by oleic acid chloride or the halides of the acids of palm kernel oil or naphthenic acids; (3) Bz2 : Bz2<1> : Bz3 p  - trihydroxydibenzanthrone is stirred with stearic acid chloride and pyridine, with or without heating; (4) the same reaction materials are heated in the presence of o-dichlorobenzene; Bz2 : Bz2<1> : Bz3 : Bz3<1>-tetrahydroxydibenzanthrone may be similarly treated; (5) Bz3 - amino - Bz2 : Bz2<1> - dihydroxydibenzanthrone is heated with stearic acid chloride and pyridine; (6) the same reaction materials are heated in the presence of trichlorobenzene; Bz3 : Bz3<1> - diamino - Bz2 : Bz2<1> - dihydroxydibenzanthrone may be similarly treated; (7) Bz2 : Bz2<1> : Bz3 - trihydroxybenzanthrone is dissolved in sulphuric acid and heated with paraformaldehyde, and the product is heated with stearic acid chloride in the presence of pyridine; (8) Bz3 - hydroxydibenzanthrone-Bz2 : Bz2<1>-quinone (obtainable by oxidizing Bz2 : Bz2<1> : Bz3 - trihydroxydibenzanthrone with sodium nitrite in the presence of dilute sulphuric acid) is stirred with stearic acid chloride and pyridine; (9) Bz2 : Bz2<1>-dihydroxyisodibenzanthrone is heated with lauric acid chloride and pyridine; (10) dihydroxyperylenetetracarboxylic acid diimide (obtainable by alkali fusion of hydroxynaphthalene-1 : 8-dicarboxylic acid diimide) is heated with oleic acid chloride and pyridine; compounds in which the imido hydrogen is replaced may be similarly treated; (11) Bz2 : Bz2<1>-dihydroxydibenzanthrone is heated with stearic acid chloride, pyridine and zinc dust; (12) stearic acid chloride is added to a vat prepared from dibenzanthrone and alkaline hydrosulphite solution; (13) dibenzanthrone is heated with stearic acid chloride (which reduces the keto groups of the dibenzanthrone and esterifies the resulting hydroxy groups) in the presence of trichlorobenzene; isodibenzanthrone may be similarly treated; (14) as in (13) but using half the quantity of stearic acid chloride; the reaction may also be effected at lower temperatures, e.g. in boiling chlorobenzene; the benzanthrone may be replaced by its derivatives, e.g. 6-methyl-, 2-chloro- or Bz1-bromobenzanthrone; (15) benzanthronepyrazolanthrone (cf. example 1 of German Specification 490,723) is heated with stearic acid chloride, pyridine and zinc dust; (16) pyranthrone is heated with stearic acid chloride, pyridine, trichlorobenzene and zinc dust. Specifications 393,966, 442,860, and 461,885 are referred to.  Samples have been furnished under Sect. 2 (5) of products prepared as follows: (A) thionyl chloride is added to a heated mixture of Bz2 : Bz2<1> - dihydroxydibenzanthrone, hexahydrobenzoic acid and pyridine; (B) Bz2 : Bz2<1>-dihydroxydibenzanthrone is heated with stearic anhydride, pyridine and chlorobenzene.  Reference has been directed by the Comptroller to Specification 393,966.ALSO:Rubber is coloured or rendered fluorescent by the addition of esters of the general formula (R.COO)n-X, where R is a radicle of high molecular weight with a straight or branched alkyl group having at least six carbon atoms or a hydroaromatic radicle also having at least six carbon atoms, n is a whole number, and X is the radicle of a cyclic compound having at least four condensed isocyclic nuclei with or without heterocyclic nuclei.  Reference has been directed by the Comptroller to Specification 393,966, [Group IV].