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Pyrrolo(2,1-A)Isoquinoline Dyes

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Pyrrolo(2,1-A)Isoquinoline Dyes Europaisches Patentamt ||||||| |||||| ||| ||||| ||||| ||||| ||| ||||| ||||| ||||| ||||| |||||| |||| |||| ||| (1 9) Qjl) European Patent Office Office euroDeen des brevets (11) EP 0 780 443 A2 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int. CI.6: C09B 57/00, C07D 471/04 25.06.1997 Bulletin 1997/26 // G1 B7/24j G03C1/83 , (21) Application number: 96119155.8 (C07D471/04, 221 :00, 209:00) (22) Date of filing: 29.11.1996 (84) Designated Contracting States: (72) Inventor: Cuny, Gregory D. DE FR GB IT Saint Paul, Minnesota 551 33-3427 (US) (30) Priority: 21.12.1995 US 576502 (74) Representative: Allaix, Roberto, Dr. et al Imation S.p.A., (71 ) Applicant: MINNESOTA MINING AND Intellectual Property Department, MANUFACTURING COMPANY Viale Martiri della Liberta, 57 St. Paul, Minnesota 551 33-3427 (US) 1 701 6 Ferrania (Savona) (IT) (54) Pyrrolo(2,1-a)isoquinoline dyes (57) A series of novel pyrrolo[2,1-a]isoquinoline dyes has been prepared using readily available starting materials via a simple synthetic pathway. These dyes have narrow absorption bands in the range of 500-900 nm. Those that absorb in the near-infrared region (700- 1 400 nm) lack significant absorption in the 300-400 nm ultraviolet region of the spectrum; this is an advantage for use in an applications such as imaging setting film. In addition, the greater thermal and chemical stability of these dyes in comparison to their indolizine analogues should be valuable in many applications. CM < CO o CO o Q_ LU Printed by Rank Xerox (UK) Business Services 2.14.8/3.4 EP 0 780 443 A2 Description FIELD OF INVENTION 5 This invention relates to novel dyes having narrow absorption bands in the visible or near-infrared region of the spectrum. These dyes are useful in applications requiring dyes to suppress halation or to convert light-to-heat. BACKGROUND 10 Single-mode laser diodes and diode-pumped lasers, both emitting radiation in the near-infrared region of the elec- tromagnetic spectrum, are now commercially available. These laser sources have made possible the development of compact, efficient, and relatively inexpensive recording devices. Rapid growth in a broad range of fields, including opti- cal recording, thermal writing displays, laser printers, laser filters and infrared photography, has resulted. This growth has created a demand for media that contains near-infrared absorbing materials to support these technologies. 15 It is well known that black body absorbers can be used to absorb near-infrared radiation. These highly colored absorbers include both dyes and pigments (e.g., carbon black) that absorb strongly throughout the visible and near- infrared spectrum. Although such highly colored materials have been used in black and white imaging systems, their use is often prohibited in color imaging systems that require color purity in the resulting image; the highly colored absorber frequently contaminates the colored image. Dyes that strongly absorb in the near-infrared without significantly 20 absorbing in the visible spectrum are currently the best choice for maintaining color purity in color imaging systems. Although a variety of near-infrared absorbing dyes is known in the literature, most of these dyes are not commer- cially available due to lack of readily available starting materials, lack of simple synthetic pathways, or lack of both. Often a suitable dye for an application is either not available or prohibitively expensive; this precludes development of the application. For example, near-infrared absorbing dyes having narrow absorption bands are often sought for uses such 25 as suppression of halation in infrared film and conversion of light-to-heat in laser imaging systems. These uses require an infrared dye lacking visible absorption to maintain color purity in the resulting image. The lack of commercially avail- able dyes meeting these requirements has limited the development of these technologies. There is a need for new dyes having narrow absorption bands in the near-infrared that can be prepared by simple synthetic pathways from readily available starting materials. 30 SUMMARY A series of novel pyrrolo[2,1-a]isoquinoline dyes has been prepared using readily available starting materials via a simple synthetic pathway. These dyes have narrow absorption bands in the range of 500-900 nm. Those that absorb in 35 the near-infrared region (700-1400 nm) lack significant absorption in the 300-400 nm ultraviolet region of the spectrum. This is an advantage for use in applications such as imaging setting film. In addition, the greater thermal and chemical stability of these dyes in comparison to their indolizine analogues should be valuable in many applications; cyanine dyes containing the pyrrolo[2,1-a]isoquinoline moiety have shorter bridging units than indolizine dye analogues with comparable absorption maxima, and shorter bridging units are known to result in increased stability for cyanine dyes. 40 Dyes of the present invention have a central pyrrolo[2, 1 -a]isoquinoline nucleus of the formula: 45 50 wherein Ar is a phenyl group; R1 is an alkyl, alkaryl, aralkyl or aryl group; and Z represents the group of atoms that includes either a positively charged nitrogen atom (N+), a carbonyl group (C=0), or a nitrile group (CN) and completes a conjugate chain between the nitrogen atom of the pyrrolo[2, 1 -ajisoquinoline nucleus and the positively charged nitro- 55 gen atom, carbonyl group, or nitrile group contained in Z. In one embodiment, dyes of the present invention have a central nucleus of the formula: 2 EP 0 780 443 A2 I wherein Ar is a phenyl group; R1 is an alkyl, alkaryl, aralkyl or aryl group; and X is selected from the bridging groups consisting of: and -(-CH=CH^-CH= wherein n is 0, 1 or 2 and Q" is an anion. In still another embodiment, dyes of the present invention have a central nucleus of the formula: II wherein Ar is a phenyl or subsituted phenyl group; R1 is an alkyl, alkaryl, aralkyl or aryl group; and Y is selected from the group consisting of: EP 0 780 443 A2 wherein each R2 is independently an alkyl group having from 1 to 8 carbon atoms and Q" is an anion. When the term "group" is used in defining a chemical species or component, it is understood that placing conven- tional substituents on that group is contemplated by the invention. For example, the term "alkyl group" covers not only unsubstituted alkyl such as methyl, ethyl, hexyl, cyclohexyl, isooctyl and the like, but also includes hydroxyethyl, omega- chlorohexyl, 2-ethoxy-dodecyl and the like. When the term "alkyl" or "alkyl moiety" is used, no substitution is included within the use of that term. Similarly, when a general structure is referred to as a compound having the "central nucleus" of a given formula, any substitution which alters neither the bond structure of the formula nor the shown atoms within that structure is included. For example, where a polymethine chain is shown between two defined heterocyclic nuclei, the chain may be rigidized by a cyclic group, and substituent groups may be placed on the chain, but the conjugation of the chain may not be altered, and the atoms shown in the heterocyclic nuclei may not be replaced. The description of a formula as a "general formula" does not specifically allow for such broader substitution on the structure. Other aspects, advantages, and benefits of the present invention are apparent from the detailed description, the examples and the claims. DETAILED DESCRIPTION OF INVENTION A class of dyes of the present invention has a central nucleus of the formula: Z wherein Z is selected from the group consisting of EP 0 780 443 A2 O wherein Ar is a phenyl or subsituted phenyl group; R1 is an alkyl, alkaryl, aralkyl or aryl group; each R2 is independently an alkyl group having from 1 to 8 carbon atoms; Q" is an anion, preferably one selected from the group consisting of CI" , Br", I", F", CI04", PF6", HSO4", HCO3", SbF6", AsF6", R,S03", (R,S02)3C", (R,S02)2HC", and (R,S02)2N" wherein R, rep- resents a perfluoroalkyl group or two Rf groups taken together represent the necessary atoms to form a five- or six- membered perfluorinated ring; and X is selected from the bridging groups consisting of: I wherein Ar is a phenyl or subsituted phenyl group; R1 is an alkyl, alkaryl, aralkyl or aryl group and X is selected from the bridging group consisting of: EP 0 780 443 A2 wherein n is 0, 1 or 2 and Q" is an anion, preferably one selected from the group consisting of CI", Br", I", F", CI04", PF6" , HS04", HCO3", SbF6", AsF6", R,S03", (RfS02)3C", (RfS02)2HC", and (RfS02)2N" wherein Rf represents a perfluoro- alkyl group or two Rf groups taken together represent the necessary atoms to form a five- or six-membered perfluori- nated ring. Preferred dyes having a nucleus of Formula I include those having the formula: wherein X is as defined above and R is methyl or phenyl. In another embodiment, dyes of the present invention have a central nucleus of the formula: II wherein Ar is a phenyl or subsituted phenyl group; R1 is an alkyl, alkaryl, aralkyl or aryl group; and Y is selected from the group consisting of: EP 0 780 443 A2 wherein each R2 is independently an alkyl group having from 1 to 8 carbon atoms and Q" is an anion, preferably one selected from the group consisting of CI", Br", I", F", CI04", PF6", HS04", HC03", SbF6", AsF6", R,S03", (R,S02)3C", (RfS02)2HC", and (RfSC^N" wherein Rf represents a perfluoroalkyl group or two Rf groups taken together represent the necessary atoms to form a five- or six-membered perf luorinated ring.
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