Patent GB-526893-A (GB)
Title: Improvements in and relating to dyestuffs for sensitising photographic emulsions
IPC: C09B23/01
Filed: 1939-03-21
Abstract: 526,893. Sensitized photographic emulsions. KENDALL, J. D. March 21, 1939, No. 8986. [Class 98 (ii)] [Also in Group IV] Photographic sensitizing dyes containing a cyclopentadiene grouping are made by condensing a compound of the general formula where Y is an acid radicle, X the remainder of a heterocyclic nucleus, R 1  and R 2  represent hydrogen atoms or hydrocarbon groups or form part of an arylene residue as in indene, R 3  is hydrogen or a hydrocarbon group, x = 0 or 1, and n = 0 or a positive integer, with a quaternary salt of a heterocyclic nitrogen compound containing as a reactive group, in α- or γ-position to the nitrogen atom, a halogen atom, a thioether or selenoether group (including an aryl-, alkyl- or aralkylthioether or -selenoether group) or the group - (CH = CH)n NH 2 , where N is a positive integer (including N-acyl, N-aryl and N-acylaryl substituted groups of this type). The parent cyclopentadiene compounds may be made by the process described in Specification 526,892. As heterocyclic nitrogen compounds are specified thiazoles, thiazolines, oxazoles, oxazolines, selenazoles, selenazolines, pyridines, quinolines, indolenines, diazines, thiodiazoles and quinazolines, including the corresponding' substituted and unsubstituted pelycyclic compounds such as benzthiazoles, naphthathiazoles and anthrathiazoles, and also the diazoles described in Specification 425,609. When n in the general formula is 0, and the heterocyclic compound with which the compound of the general formula is condensed has the same structure as the heterocyclic nucleus of the compound, and the reactive group is a halogen atom or thioether or selenoether group, the products are symmetrical cyanine dyes of the same structure as those described in Specification 431,187 ; in other cases the products are new and include unsymmetrical dyes having two different heterocyclic nuclei each attached directly to the cyclopentadiene grouping, as well as both symmetrical and unsymmetrical dyes in which one or both of the heterocyclic nuclei are linked to the cyclopentadiene grouping by a polymethine chain. In examples (1) 1-methylthiolbenzthiazole is converted into the quaternary salt with methyl-p-toluenesulphonate and condensed with 1 - # - (N - methyldihydrobenzthiazolylidene) - ethylidene indene ; (2) 2- #-acetanilidovinyl- 1:3:3-trimethylindolenium iodide is condensed with indene and the product is condensed with the quaternary salt used in example (1) ; (3) 1-methylthiobenzoxazole is converted into a dyestuff by the process of example (1); (4) 1-#-acetanilidovinyl-benzoxazole methiodide or ethiodide is condensed with 1- #-(N-methyldihydrobenzthiazolylidene)- ethylidene indene ; (5) 1- w-acetanilidovinylbenzthiazole ethiodide is condensed with 1- #- (N - methyldihydrobenzthiazolylidene) - ethylidene indene, (6) 2-#-acetanilidovinyl-1 : 3 : 3- trimethylindolenium iodide is condensed with 1 - # - (N - methyldihydrobenzthiazolylidene)- ethylidine indene; (7) 1-methylthiol benzthiazole methyl-p-toluenesulphonate is condensed with indene and the product is condensed with (a) 2- w-acetanilidovinyl-1 : 3 : 3- trimethylindolenium iodide, (b) 1-methylthiol-α- naphthathiazole methyl-p-toluene sulphonate and(c) 1-methylthiol-benzoxazole methyl-p-toluene sulphonate. Samples have been furnished under Sect. 2 (5) of the products from (a) 1-#-(1<SP>1</SP> : 3<SP>1</SP> : 3<SP>1</SP>- trimethylindolylidene) - ethylidene - cyclopentadiene and 1-methylthiolbenzthiazole methylp-toluenesulphonate, (b) 1-#-( 1<SP>1</SP>-methyldihydroquinolylidene - 4<SP>1</SP>) - ethylidene - indene and 1:3:3 - trimethyl - 2 - # - acetanilidovinyl-indolenium iodide, (c) 1- #-(1<SP>1</SP> : 3<SP>1</SP> : 3<SP>1</SP>- trimethylindolylidene) - butadienyl - indene and 1 - methylthiolbenzthiazole methyl - p - toluenesulphonate, and (d) 1- #-(N-methyldihydrobenzthiazolylidene) - ethylidene - indene and 4-iodoquinoline methiodide.