Patent GB-327702-A (GB)
Abstract: 327,702. Johnson, J. Y., (I. G. Farbenindustrie Akt.-Ges.). Oct. 29, 1928. Samples furnished. Iodinated organic compounds capable of being vatted are prepared by treating such compounds in a strong oxygen-containing mineral acid capable of dissolving the compound in at least small amounts and not splitting off halogen, with iodine or iodinating agents such as the solts of hydriodic acid, sulphur iodide or iodine chloride. The most suitable oxygen-containing mineral acids are, oleum and sulphuric acid, and perchloric, periodic and phosphoric acids may also be used; these acids are used alone or in admixture, and preferably in a highly concentrated form. Halogenating catalysts such as sulphur, phosphorus, antimony, iron, and the amalgams of metals known as halogen carriers, for example, copper amalgam, may be present. This iodination process is applicable to such compounds as anthraquinone, anthanthrone, pyranthrone, dibenzanthrone, ms-benzdianthrone, ms-naphthodianthrone, allo-ms-naphthodianthrone, msanthradianthrone, indigo, thioindigo, vattable pyrazolanthrones, acridones and thioacridones and isomers and derivatives of these substances such as halogen, nitro and amino derivatives. The process may also be applied to substances which do not themselves contain groups rendering the substance vattable but which are transformed during the iodination into vattable compounds by the action of the oxygen-containing mineral acid. Two such substances are 1.1<1>-dinaphthyl-8.8<1>- dicarboxylic acid and perylene. Further condensation of the iodinated organic vattable compound may result by the halogenation process; examples of this are carbazolization of iodinated 1.1<1>- dianthridides, acridone ring formation of iodinated 2<1>.1-dianthraquinonylamine-2-carboxylic acid (or ester), and the preparation of an iodinated ms-anthradianthrone from allo-ms-naphthodianthrone. The reacting temperature depends on the nature of the compound to be iodinated, the kind and concentration of the acid diluent, and on the amount of iodine to be introduced into the molecule; the temperature is kept as low as possible if it is desired to avoid the above sidereactions or sulphonation &c. When using iodine chloride or iodine bromide as halogenating agent a further halogen besides iodine may be introduced into the molecule. Generally the use of 1 to 2 atoms of iodine is sufficient to introduce 1 atom into the molecule. The following substances are prepared in examples, shades of dyestuffs being bracketed :-(1) monoiodoanthanthrone (orange) and diiodoanthanthrone (bluered); (2) bromoiodoanthanthrone (red) either from the bromoanthanthrone prepared from the monamino derivative (Specification 323,750) by diazotization and a Sandmeyer replacement, or from the bromo derivative obtained by bromination of anthanthrone in oleum with the calculated amount of bromine, or by the use of bromo-iodide on the parent material; (3) chloriodoanthanthrone (orange-red) from the monochloranthanthrone obtained from the monamino derivative by diazotization and a Sandmeyer replacement, or from bromoiodoanthanthrone (orange-red) from the chlorbromanthanthrone obtained by chlorination and then bromination of the parent material in sulphuric acid monohydrate; these anthanthrones containing different halogens and having a halogen content equivalent to a dihalogen derivative are particularly valuable dyes; (5) iodopyranthrone (reddish-orange); (6) dibromoiodopyranthrone (red-orange) from the dibromo derivative prepared by brominating pyranthrone in chlorsulphonic acid in presence of sulphur; (7) iododibenzanthrone (blue-violet); (8) dibromoiododibenzanthrone (navy) from the dibromo derivative obtained by brominating dibenzanthrone in chlorsulphonic acid in presence of antimony; (9) iodoisodibenzanthrone (violet); (10) bromoiodo- 4.5.8.9-dibenzpyrene-3-10-quinone (blue-red) from the monobromo derivative obtained by condensation of 2-(p-bromobenzoyl)benzanthrone with aluminium chloride; (11) chloriodo-4.5.8.9-dibenzpyrene-3-10-quinone (red) from the corresponding monochloro derivative; (12) iodoanthraquinone; iodo derivatives of methyl-, halogen- and aminoanthraquinones are also referred to; (13) iodo- 1.2.5.6-diphthaloylacridine (red-orange); (14) iodo- or-dihydro-1.2.1<1>.2<1>-anthraquinoneazine (greenishblue); (15) iodobenzanthronepyrazolanthrone (navy-blue) from the product of alkaline condensation of Bz.1.N-benzanthronylpyrazolanthrone; (16) iodo-ms-anthradianthrone (yellow-orange) either from the parent material or from allo-msnaphthodianthrone; (17) bromoiodo-ms-anthradianthrone (orange) from allo-ms-naphthodianthrone by using bromoiodide; (18) iodoperylenediquinone (grey) either from perylene itself or from the quinone obtainable by oxidation of perylene in aqueous suspension with chromic acid; (19) iodo-4.4<1>-dimethyl-6.6<1>-dichlorthioindigo (red-violet) and a similar product containing more chlorine by the use of iodine chloride as halogenating agent. Specifications 278,100, 303,184, and 327,756 are referred to. One of the Provisional Specifications also refers to the use of potassium or sodium iodide as halogenating agent.