Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic halides
Reexamination Certificate
1998-12-31
2001-01-09
Raymond, Richard L. (Department: 1611)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic halides
C562S846000, C548S196000
Reexamination Certificate
active
06172260
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to carbamyl chlorides of aninoarylcarbonyl compounds useful as intermediates for the preparation of photographic high dye-yield couplers, and to methods of making and using the intermediates to prepare photographic couplers.
BACKGROUND OF THE INVENTION
It has been known in the art to employ a releasable dye as the coupling-off group to provide a so-called ‘high dye-yield’ coupler. Such a coupler reacts with oxidized color developer to form one dye and in doing so releases a second dye. The net results are formation of two dyes with two equivalents of silver. It enables the reduction of the amount of coupler, silver, and other materials in the film layers. It also enables thinner layers which in turn reduces the amount of light scatter to improve sharpness in underlying layers. Thinner layers can also reduce the level of unwanted absorption, which can further enhance the image quality in underlying layers. The benefits of the high dye-yield couplers are thus particularly advantageous if they are placed in the uppermost layers, i.e., the blue sensitive layers, of multilayer films.
Useful high dye-yield couplers have been disclosed by J. Mooberry and S. Singer in U.S. Pat. No. 4,840,884. Mooberry, et al. have later disclosed improved high dye-yield couplers with methine dye chromophores in U.S. Pat. No. 5,457,004. The latter patent teaches the advantages of using methine dyes. Compared to couplers releasing analogous azo dyes, the couplers releasing methine dyes provide much higher extinction and superior photographic properties such as hue, Dmax, and low unwanted absorption by the coupler.
One of the obstacles in manufacturing high dye-yield couplers is difficulty of synthesis. These couplers require a fair number of synthetic steps, some of which proceed only in modest yield and are difficult to adapt to large-scale manufacture. The synthesis outlined in U.S. Pat. No. 5,457,004, for instance, involves a hooking up reaction between a hydroxy group in the coupler-timing group piece and the methine dye carbamyl chloride. The hooking up reaction proceeds in reasonable yield in case (a) where a timing group (T)
m
is present and the alkyl group on the nitrogen atom of the dye molecule is straight chain alkyl. When the N-alkyl group of the requisite dye carbamyl [chromophol-N(—R)—C(═O)—Cl] is branched or bulky, the reaction with the hydroxy group in coupler-timing group component is sluggish and yields of desired product are poor due to undesired side reactions. Fairly strong organic bases must be used to effect the attachment of coupler and dye components, but the desired product and starting components are easily destroyed by the base if the desired reaction is not rapid. In the case (b) where the timing group is absent (m=0), the methine dye is attached directly to the coupling site via the linking group (usually acyloxy). This requires the coupler synthesis unit to be COUP-OH (hydroxyl group attached at the coupling site) in order to react with the methine dye carbamyl chloride. Hydroxy couplers also react with the methine dye carbamyl chloride to give the desired HDY coupler in reasonable yield only when the R group is small, i.e., methyl. As the R group becomes larger and steric demands are greater, the reaction proceeds progressively poorer or not at all. In the comparative example herein (Example 2) where R=ethyl, this reaction proceeds in a modest 31% yield. Generally, as the R group increases in size the desired reaction slows down because of steric effects, but undesired reactions such as aerial oxidation of COUP-OH and reactions which decompose the dye chromophore do not necessarily decrease in rate. A competing reaction corresponding to addition of COUP-OH to the carbon-carbon double bond of the methine dye chromophore to yield dihydrofurans is particularly troublesome and prevails in the case where R is larger than ethyl, particularly in cases where R is branched alkyl. It is desirable to be able to make the desired coupler without incurring a large degree of undesired side reactions.
Preparation of straight chain alkyl aminoaryl aldeh′,des is described in U.S. Pat. Nos. 5,447,819 and 5,457,004. Other methods are available. However, carbamyl chlorides of aminoarylcarbonyl compounds are not known in the literature.
It is therefore a problem to be solved to provide carbamyl chlorides of aminoarylcarbonyl compounds, a method of making them, and a method of using them in the preparation of high dye-yield couplers.
SUMMARY OF THE INVENTION
In one aspect the invention relates to a carbamyl chloride of an aminoarylcarbonyl compound having the structural Formula I:
wherein:
R is an alkyl, alkenyl, or aryl group;
A is an aryl (including heteroaryl) ring group;
each R′ is independently an alkyl group which may form a ring with Z or Z′;
p is 0, 1, 2, or 3;
each Z, Z′, and Y is independently hydrogen or a substituent; and
n is 0, 1, or 2.
In another aspect the invention provides a method of making the intermediates of Formula I, comprising the steps of:
(a) blocking the carbonyl function of an aminoarylcarbonyl compound via Schiff base formation with a hindered alkyl amine;
(b) making a carbamyl chloride of the blocked aminoarylcarbonyl compound by phosgenation; and
(c) deblocking the carbamyl chloride of the blocked aminoarylcarbonyl via acid hydrolysis to regenerate the carbonyl function and give the desired carbamyl chloride of an aminoarylcarbonyl compound having formula I.
In yet another aspect the invention provides a method of using the intermediates of Formula I in the preparation of high dye-yield couplers.
The compound and methods of the invention allow the preparation of the high dye-yield couplers in much higher yields than heretofore possible.
DETAILED DESCRIPTION OF THE INVENTION
In one aspect this invention relates to intermediates useful for the preparation of high dye-yield couplers having the structural Formula I as described in the Summary of the Invention. In another aspect, this invention relates to a process for using the intermediates of Formula I in the preparation of high dye yield couplers, to make a coupler of Formula II:
the method comprising the steps of:
(a) reacting the carbamyl chloride compound of Formula I with a coupler piece of Formula III
to form a carbamate link between the coupler piece and the aminoaiylcarbonyl compound,
wherein
COUP is a photographic coupler residue bonded at the coupling position to T or X and capable of coupling with oxidized color developer to form a first dye;
T is a timing group;
m is an integer from 0 to 2; and
X is O, S, or N(R
12
) where R
1
is hydrogen or alkyl; and
(b) conducting a condensation reaction between the carbon3l portion of the coupler-timing group-aminoarylcarbonyl product of part (a) with a portion of methine dye of Formula IV as below having an active methylene group:
wherein
E is an electron withdrawing group;
X′ is O, S, or N(R
2
) where R
2
is hydrogen or alkyl;
G is N or C(R
3
) where R
3
is hydrogen or a substituent; and
R″ is a substituent linked to the heterocycle by a carbon or nitrogen atom of the substituent, provided that R″ and R
3
may be linked to form a ring to give a high dye-yield coupler having Formula II:
Examples of useful COUP groups are:
A free bond from the coupling site in the above formulae indicates a position to which the coupling release group or coupling-off group is linked. In the above formulae, when R
1a
or R
1b
contains a ballast or antidiffusing group, it is selected so that the total number of carbon atoms is from 8 to 32 and preferably from 10 to 22.
R
1a
represents an aliphatic- or alicyclic-hydrocarbon group, an aryl group, an alkoxyl group, or a heterocyclic group, and each R
1b
independently represents an aryl group or a heterocyclic group.
The aliphatic- or alicyclic hydrocarbon group represented by R
1a
preferably has at most 22 carbon atoms, may be substituted or unsubstituted, and aliphatic hydrocarbon may be straight or b
Hoke David
Kim Chang-Kyu
Mooberry Jared B.
Seifert James J.
Eastman Kodak Company
Kluegel Arthur E.
Raymond Richard L.
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