Patent GB-190922714-A (GB)
Title: The Manufacture of Halogen Derivatives of the Indigo Series and of Intermediate Products.
Inventor: JOHNSON JAMES YATE
IPC: C09B7/04
Filed: 1909-10-05
Granted: 1910-09-08
Abstract: 22,714. Johnson, J. Y., [Badische Anilin & Soda Fabrik]. Oct. 5. Indigo dyes.-Salts of halogenated dehydroindigo bodies are obtained by treating with a halogenizing-agent salts of dehydroindigo bodies (except the sulphites and bisulphites), or the free dehydroindigo bases or indigo dyes, including homologues and derivatives of indigo, or indigoid dyes such as indirubin, in the presence or not of a salt capable of fixing halogen hydride, and a solvent or diluent. Di-, tri-, and tetra-halogendehydroindigo salts, or mixed halogenized bodies, are thus obtained. In the production of mixed halogenized bodies, bromine, if used before chlorine, may be employed in smaller amounts than the theoretical amount, as the bromide formed is decomposed by the chlorine ; or the bromine may te employed entirely in the form of bromide. Halogen carriers such as sulphur chloride, or chlorine iodide, may be used. The halogenized dehydroindigo salts are converted into the halogenized indigo dyes or leuco compounds thereof by reducing-agents. According to examples :-di- and tri-bromdehydroindigo acetate are obtained by treating indigo with bromine in presence of sodium acetate and glacial acetic acid ; tetrabromdehydroindigo acetate is obtained similarly in presence of tetrachloride ; mono-, di-, tri- or tetra-chlordehydroindigo acetate is obtained similarly by the use of chlorine, and dibrom-mono- or -di-chlordehydroindigo acetate from dibromindigo ; di- and tri-bromdehydroindigo benzoate are obtained by treating indigo with bromine in the presence of carbon tetrachloride, sodium benzoate, and benzoic acid ; dibromdehydroindigo acetate is obtained by brominating dehydroindigo acetate in the presence of acetic acid and sodium acetate ; brom- or chlor-dehydroindirubin acetate is obtained similarly from indirubin ; tribrommonochlordehydroindigo acetate is obtained by treating indigo in the presence of sodium acetate and acetic acid, first with bromine and then with chlorine ; tetrachlordehydroindigo acetate is obtained from dehydroindigo and chlorine in the presence of carbon tetrachloride and sodium acetate ; chlordehydroindigo acetates are obtained by treating dehydroindigo acetate with chlorine in the presence of acetic acid, acetic anhydride, trichlorbenzene, nitrobenzene, or carbon tetrachloride, and chlorbrom derivatives similarly from dibromdehydroindigo acetate; tri- and tetrachlordehydroindigo hydrochlorides are obtained by chlorinating dehydroindigo or indigo in nitrobenzene ; chlororomdehydroindigo hydrochlorides are obtained by treating 5 : 5<1>-dibromindigo with chlorine in the presence of acetic acid or anhydride, and chlor derivatives similarly from 4 : 4<1> or 6 : 6<1>- dichlorindigo ; trichlordehydroindigo hydrochloride is obtained by treating indigo with chlorine in the presence of acetyl chloride, or phosphorus oxychlorine ; a chlordehydroindigo hydrochloride is obtained by treating indigo with sulphuryl chloride in the presence of carbon tetrachloride. The above-described salts are converted into the corresponding halogenized indigo bodies by reduction ; the 5 :7 : 5<1>-tribrom-7<1>-chlorindigo thus obtained is stated to be new. Specification 16,377/09 is referred to.