Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1999-04-07
2001-06-05
Oswecki, Jane (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C548S181000, C548S206000, C548S250000, C548S254000, C548S360500, C548S379100, C548S379400, C548S510000, C548S511000, C548S530000, C548S540000, C548S110000, C548S114000, C560S027000, C560S028000, C560S034000, C560S100000, C562S467000, C562S475000, C564S084000, C564S102000, C564S155000, C564S158000, C564S161000, C564S173000, C564S174000, C564S182000, C564S184000, C564S186000, C564S190000, C564S191000, C564S192000, C564S200000, C564S211000, C564S214000, C564S218000, C564S223000, C564S442000, C564S443000, C568S
Reexamination Certificate
active
06242609
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a method for manufacturing color couplers used in a silver halide color photographic light-sensitive material by using ammonium trihalide as a halogenation agent, and specifically to a method for manufacturing color couplers with small amounts of by-products and in high yield.
BACKGROUND OF THE INVENTION
In a silver halide color photographic light-sensitive material, an organic compound termed color coupler is used to form a color image. Said silver halide color photographic light-sensitive material contains at least three kinds of silver halide emulsions being photosensitive to blue light, green light and red light, and contains at least three kinds of couplers each corresponding to the three primary colors of light. When said silver halide color photographic light-sensitive material is exposed to light and then processed in developing solution containing a color developing agent, it forms the three colors of yellow, magenta and cyan, which are produced by reaction of an oxidized color developer generated in response to the amount of exposure with three kinds of couplers. By blending pixels of these three colors, all colors in the visible spectrum can be produced.
In these color couplers, in cases where a carbon atom of the couplers reacting with the oxidized color developing agent (this carbon atom being called a coupling-positioned carbon atom) is not substituted by any substituent (active methylene), four silver atoms are theoretically required to form one molecule of dye. On the other hand, in cases where the coupling-positioned carbon atom is substituted by an anionic eliminating group, it is known that two silver atoms are required to form one molecule of dye. The former is termed a four-equivalent coupler, and the latter is termed a two-equivalent coupler. Said two-equivalent coupler generally exhibits high coupling reactivity and is used in many color photographic materials because smaller amount of silver halide is required to obtain the same density of dye, compared to the four-equivalent coupler.
Cited as eliminating groups of the two-equivalent coupler, are a halogen atom, an alkoxy group, a phenoxy group, an alkylthio group, a phenylthio group and a nitrogen-containing heterocyclic group, etc., and combined usage of the two-equivalent couplers containing various eliminating groups is employed in current color photographic light-sensitive materials. Specifically couplers in which the coupling-positioned carbon atom is substituted by a halogen atom, such as a chlorine atom and a bromine atom, etc., is not only useful as a final coupler but also useful as an intermediate to introduce an eliminating group other than the halogen atom to the coupling-positioned carbon atom of the coupler by nucleophilic substitution reaction. For this reason, in manufacturing photographic color couplers, the halogenation reaction process is considered to be very critical.
Various methods for introducing the halogen atom to the photographic color coupler and its intermediate are known. For example, as described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as JP-A) Nos. 60-55343, 61-57536, it is known that chlorine gas and sulfuryl chloride are reacted in a halogen type solvent. However, the above mentioned method exhibits problems such as, toxicity of the chlorine gas, sulfurous acid gas and hydrogen chloride gas generated in course of reaction being dispersed into the air, production of by-products caused by acidification in the course of the reaction, and corrosion of the reaction vessel.
With respect to a halagenation agent to overcome these problems, disclosed in JP-A 60-98434 is N-chlorosuccinimide as a chlorination agent for a photographic color coupler. In this case, it is possible to prevent the generation of the sulfurous acid gas and hydrogen chloride gas which is a problem in using sulfuryl chloride, etc., but there have been other problems such as the necessity to remove resultant succinimide after reaction and the high cost of N-chlorosuccinimide.
Further, dihalohydantoin has been recently disclosed for an use to synthesize the photographic color coupler and its intermediate in JP-A Nos., 7-304776, 8-301830, 8-310999, 9-59197 and 9-59250, etc. However, this agent is not sufficiently acceptable in reaction yield, side reaction and cost of the agent. Therefore, more improvement is sought.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a method for manufacturing a halogenated compound useful as a color coupler used in a silver halide color photographic light-sensitive material and its intermediate in high reaction yields, with low side reaction rate and low cost.
DETAILED DESCRIPTION OF THE INVENTION
Above object of the invention could be attained by the following method:
In this invention, when an ammonium trihalide as a halogenation agent was reacted with a color coupler having an active methylene, it was found that a hydrogen atom of the active methylene of said color coupler was substituted by a halogen atom such as a chlorine atom and bromine atom, etc. in high reaction yield compared to a conventional known halogenation agent, and with this halogenation agent, an advantage that an amount of by-products was very little was found. As the ammonium trihalide used in the invention, a compound represented by the following Formula (A) is preferably used.
Wherein R
11
, R
12
, R
13
and R
14
each represent a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group and an aralkyl group, and R
11
, R
12
, R
13
and R
14
may be the same with each other or different. R
11
, R
12
, R
13
and R
14
are each preferably a hydrogen atom, a straight chain or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, a phenyl group and a benzyl group, and more preferable said alkyl group is one having 1 to 16 carbon atoms. X represents a halogen atom and preferable one is a chlorine atom or a bromine atom. Specifically preferable one is a chlorine atom.
Exemplified ammonium trihalides mentioned above used in the invention are shown below, but are not limited thereto.
The above mentioned ammonium trihalide represented by the Formula (A) used in the invention is synthesized by using an inexpensive ammonium halide as a starting raw material.
For example, ammonium trichloride can be synthesized employing a method described in T. Schlama, K. Gabriel, V. Gouverneur and C. Mioskowski, Angew. Chem. Int. Ed. Engl., 36, 2342 (1997), and ammonium tribromide can be syhthesized employing a method described in S. Kajigaeshi, T. Kakinami, M. Moriwaki, S. Fujisaki and T. Okamoto, Bull. Chem. Soc. Jpn., 62, 439 (1989), etc.
Color couplers used in the silver halide photographic light-sensitive material obtained according to the manufacturing method of the invention are compounds characterized in that they have a halogen-substituted active methylene in their molecules which can cause coupling reaction with an oxidized color developing agent resulting in forming dyes for color images.
With regard to the exemplified couplers, one can refer to the disclosure on pages 353-362, fourth edition of “The theory of the photographic process” edited by T. H. James and published by Macmillan Co. in New York in 1977, and on pages 204-222, “Shashin Kogaku no Kiso, Ginen Shashin hen” (Basic Photographic Technology, Silver Halide Photography Compilation) edited by The Society of Photographic Science and Technology of Japan
The manufacturing method of the invention is effective in halogenation reaction of the compound other than the compound containing the active methylene group described in the above mentioned references and can be used in halogenating a hydrogen atom of a nitrogen-containing five or six membered aromatic compound ring.
Among the color couplers used in the silver halide photographic light-sensitive material obtained according to the manufacturing method of the invention, a 3-substituted-3-oxo-2-halopropionic acid amide compound represented by the above mentioned Form
Bierman Jordan B.
Bierman, Muserlian and Lucas
Konica Corporation
Oswecki Jane
LandOfFree
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