Patent GB-868787-A (GB)
Title: Light-sensitive silver halide emulsions containing fog-inhibiting agents
IPC: C07D471/04
Filed: 1957-10-21
Abstract: Compounds are described having the general formula:  <FORM:0868787/IV (b)/1> wherein D completes a quinoline nucleus and Q is -N= or -CR= (R being H, OH or substituted or unsubstituted alkyl or aryl), and, when Q is -CR=, quaternary alkyl salts of such compounds.  The quinoline ring completed by D may carry methyl, ethyl, chloro, bromo, hydroxyl, methoxy, ethoxy or amino substituents. Compounds wherein Q is -CR= and R is H or an alkyl group of 1-3 carbon atoms are prepared by condensing a compound of the formula:  <FORM:0868787/IV (b)/2> with an ortho ester RC(OR2)3 where R2 is methyl or ethyl, by refluxing, e.g. in xylene and removing the alcohol formed with a fractionating column until the theoretical amount (3 mols.) has been removed.  Thus 2-hydrazinoquinoline is refluxed with ethyl orthoformate to give 2,3,9b-triazabenz[g]indene.  The 1-methyl- and 1-ethyl-2,3,9b-triazabenz[g]indenes are similarly prepared. Compounds wherein Q is -CR= and R is an alkyl group of 3 or more carbon atoms or a substituted alkyl group, e.g. an alkyl group substituted by a chlorine atom or a carboxy group, and including b -carboxymethyl and g -hydroxypropyl, are prepared by refluxing a compound of Formula II with an acid RCOOH to give an acyl hydrazine, and refluxing this with phenol to effect ring closure.  By this method, 1-isopropyl-2,3,9b-triazabenz[g]indene is prepared.  By using less than 1 mol. of a dicarboxylic acid to 1 mol. of Compound II in this method, a symmetrical bis(azabenzindene)alkane such as 1,8-bis(2,3,9b-triazabenz[g]indene-1-yl)octane is prepared. Compounds where Q is -CR= and R is o-hydroxyaryl, are prepared by refluxing an o-hydroxyaryl acid ester with a hydrazine of Formula II, e.g. in 1,2,4,-trichlorobenzene, and distilling off the water formed.  By this method 1-(2-hydroxyphenyl)-, 1-(2-hydroxy-5-sulphophenyl)-, 1-(1-hydroxy-4-sulpho-2-naphthyl)- or 1-(1- hydroxy-2- naphthyl)-2,3,9btriazabenz[g]indene is prepared.  Compounds wherein Q is -CR= and R is -OH are prepared by refluxing a hydrazine of Formula II with an arylisocyanate in trichlorobenzene. 1-Hydroxy2,3,9b-triazabenz[g]indene (or the corresponding keto form) is prepared by this method.  Compounds where Q is -CR= and R is aryl or substituted aryl are prepared by condensing a compound of formula: <FORM:0868787/IV (b)/3> with a compound RCONHNH2 in phenol, and preferably in the presence of sodium phenoxide. 1-Phenyl-2,3,9b-triazabenz[g]indene is so prepared.  Compounds wherein Q is -N= are prepared by dissolving a hydrazine of Formula II in aqueous acetic acid, cooling and adding sodium nitrite. 1,2,3,9b-Tetrazabenz [g]indene is prepared in this manner. Alternatively, a compound of Formula VII such as 2-chloroquinoline may be refluxed with sodium azide in aqueous ethanol to give a 1,2,3,9b-tetrazabenz[g]indene.  The quaternary alkyl salts of compounds of Formula I wherein Q is -CH= can be prepared by heating the compound with an alkyl salt such as methyl-p-toluene sulphonate or methyl or ethyl sulphate.  Specifications 742,219, 742,220, 742,221, 742,224, 782,311, 805,824 and 868,786 are referred to.