US3733335A

US3733335A - Indazolone magenta couplers

Info

Publication number: US3733335A
Application number: US00104510A
Authority: US
Inventors: B Anderson
Original assignee: Ilford Ltd
Current assignee: Ilford Imaging UK Ltd
Priority date: 1970-01-07
Filing date: 1971-01-06
Publication date: 1973-05-15
Anticipated expiration: 1990-05-15
Also published as: CH557046A; GB1285432A; BE761237A; DE2100538A1

Abstract

THIS APPLICATION DESCRIBES AN INDAZOLONE MAGNETA COUPLER OF THE FORMULA:

3-(O=),Q-2,3-DIHYDRO-1H-INDAZOLE

WHERE Q IS EITHER A GROUP -NH-R WHEREIN R IS AN ACYL GROUP CONTAINING A NITROGEN ATOM TO WHICH THERE IS ATTACHED EITHER DIRECTLY OR VIA A PHENYL GROUP AN ALKYL RESIDUE OF AT LEAST 10 CARBON ATOMS, TOGETHER WITH A FREE CARBOXYLIC ACID GROUP OR A GROUP WHICH CAN LIBERATE A FREE CARBOXYLIC ACID GROUP OR Q IS A GROUP -N<(T) WHEREIN T IS AN ACYL GROUP WHICH IS ATTACHED TO THE NITROGEN ATOM BY A CYCLIC IMIDE LINKAGE, THE GROUP T CONTAINING AN ALKYL RESIDUE OF AT LEAST 10 CARBON ATOMS, THE RING TO WHICH Q IS ATTACHED OPTIONALLY CONTAINING OTHER SUBSTITUENTS.

Description

United States Patent US. Cl. 260310 A 1 Claim ABSTRACT OF THE DISCLOSURE This application describes an indazolone magenta coupler of the tformula:

where Q is either a group -NH--R wherein R is an acyl group containing a nitrogen atom to which there is attached either directly or via a phenyl group an alkyl residue of at least carbon atoms, together with a free carboxylic acid group or a group which can liberate a free carboxylic acid group or Q is a group -N (T) wherein T is an acyl group which is attached to the nitrogen atom by a cyclic imide linkage, the group T containing an alkyl residue of at least 10 carbon atoms, the ring to which Q is attached optionally containing other substituents.

This invention relates to new indazolone magenta colour couplers Olf use in colour photographic material.

Indazolone magenta colour couplers have been known for a number of years but have not in fact been used to any great extent in colour photographic material because most of the known indazolone colour couplers are converted in part into a yellow product when they come into contact with an oxidising medium such as the bleach bath for the removal of the silver image during the processing of colour photographic material. Thus in addition to the magenta image dye a yellow product is also formed in the non image areas. It is possible to prevent the occurrence of this yellow reversal image by treating the colour developed layer with a bath containing formaldehyde before the silver is removed by bleaching. This however adds another step to the processing sequence and, further, sometimes causes unwanted side effects.

It is an object of the present invention to provide a new class of indazolone magenta colour couplers which have a reduced tendency to give a yellow product when they come into contact with an oxidising solution.

According to the present invention there is provided an indazolone coupler of the General Formula I:

Q, NH (1..

where Q is either a group --NH-R wherein R is an acyl group containing a nitrogen atom to which there is attached either directly or via a phenyl group, an alkyl residue of at least 10 carbon atoms, and containing a free carboxylic acid group or a group which can liberate a free carboxylic acid group, or Q is a group -N (T) wherein T is an acyl group which is attached to the nitrogen atom by a cyclic imide linkage, the group T con- 3,733,335 Patented May 15,, 1973 "ice taining an alkyl residue of at least 10 carbon atoms, the ring to which Q is attached optionally containing other substituents.

-Particularly suitable acyl groups containing an alkyl residue of at least 10 carbon atoms and at least one carboxylic acid or a group which can liberate a free carboxylic acid group are those derived from the acylating agents described in British Pats. Nos. 830,482, 858,564, 944,838, 997,500, 1,004,075, 1,039,452 and in British patent application No. 20,003/ 69 and which contain an alkyl group of at least 10 carbon atoms.

The following are suitable acylating agents:

Stearoylamino succinic anhydride Lauroylamino succinic anhydride N-n-octadecylacetylamino succinic anhydride N-n-octadecyl-iso-butyrylamino succinic anhydride N-p-n-dodecylphenylacetylamino succinic anhydride N-p-n-dodecylphenyl-iso-butyrylaminosuccinic anhydride 4-(4-dodecylphenylaminocarbonyl) phthalic anhydride 4-(n-octadecylaminocarbonyl) phthalic anhydride 4-chlorocarbonylN-n-octadecylphthalimide 4-chlorocarbonyl-N-n-dodecylphthalimide 4-chlorocarbonyl-N-n-tetradecylphthalimide 4-chlorocarbonyl-n-hexadecylphthalimide 4-chlorocarbonyl-N-(4-n-dodecylphenyl)phthalimide a- (N-n-octadecylsuccinimido) acetyl chloride or [N(4-n-dodecylphenyl)succinimido]acetyl chloride N-(4-dodecylphenyl)pyromellitic mono-imide mono-anhydride N-n-octadecylpyromellitic mono-imide mono-anhydride The colour couplers of this invention contain as a solubilising group a free carboxylic acid group or a group which can liberate a free carboxylic acid group when acted on by aqueous alkali. For example the compounds of Examples 5, 6 and -8 which follow each contain a five membered cyclic inside ring and the colour couplers of Examples 2, 4, 7 and 9 which follow contain two such rings. These imide rings may be converted to the amic acid having a free carboxylic acid group by treatment with aqueous alkali'in the presence Olf a solvent such as a lower alcohol, for example n-propanol followed by acidification. The colour couplers of this invention are usually incorporated in a colloid silver halide emuslion by means of their alkali solubilising groups, i.e. as the salts of the amic acid. The behaviour of the imide rings may be shown thus:

When mixed with the silver halide emulsion the exact state of the free carboxylic acid group will be determined by the particular colour coupler structure and pH of the mixture.

A compound of Formula I may be prepared by the reaction of a compound of the Formula II:

The ring-numbering of the indazolone colour couplers of the present invention is as follows:

II o Such indazolone colour couplers which are unsubstituted in the l, 2 or 3 position couple with oxidised colour developer to give magenta mesoionic dyes.

Since indazolones are readily acylated in the l, 2 or 3 position and because of the different coupling behaviour of these derivatives it is necessary in the preparation of the acylamino indazolones of the present invention to minimise acylation occurring in the heterocyclic ring. Thus in the preparation of a compound of Formula I as hereinbefore set forth it is preferred that the compound of Formula II is treated with an equimolar quantity of acylating agent at a temperature preferably not greater than 65 C.

Alternatively a readily hydrolysable group, for example, an acetyl group, may be employed to protect the coupling ring of the indazolone compound before treatment with a long chain acylating agent. Subsequently the protecting group is removed by a short alkaline hydrolysis, e.g.

\ Acetic anhydride NH O'COCHa ll 0 N0 N partial NH 2 N hydrolysis N/ (E0 CH3 OCH;

/Reductlon l/ long chain acylating agent N H,

Therefore according to another embodiment of this aspect of the present invention there is provided a process fo h p p r tion 9 ea insiazqlq s o our cou ler of th above Formula I which comprises the reaction of a compound of General Formula V:

with an acylating agent as hereinbefore defined, followed by an alkaline hydrolysis to remove the l-acetyl group.

The colour coupler which comprises the l-acetyl group, i.e. the compound formed after acylation and before the final alkaline hydrolysis may be isolated and stored as such. The final hydrolysis may be conducted during the preparation of the colour coupler solution for coating because the initial step prior to coating is to dissolve the colour coupler in aqueous alkali.

Preferably the colour couplers of Formula I are incorporated in a silver halide photographic emulsion by dissolving them in aqueous alkali and most preferably in the presence of a water miscible alcohol as well, and adding this solution to the silver halide photographic emulsion.

The invention includes not only the new indazolone colour couplers and the methods for their preparation but also colour photographic material having a silver halide photographic emulsion layer which comprises a compound of Formula I.

The following examples will serve to illustrate the invention. All the parts are quoted by weight.

EXAMPLE I 6-[3-carboxy-3-(N-n-octadecylisobutyramido)-propionamido-] -3 -indazolone o I! 0 01: :41 \NH tonmonooN-ononzooun c 0011 NH Method l.-A mixture of 2.22 parts of 6-arnino-indadazolone dihydrochloride and 5.0 parts of pyridine was warmed until an oil formed and parts of glacial acetic acid added to obtain a complete solution. 4.37 parts of vn-octadecylisobutyrylamino succinic anhydride (the preparation of which is described in Example 25 of specification No. 830,797) was then added and the mixture stirred at 5060 C. for 2 hours and allowed to stand overnight to crystallise. The colourless precipitate was filtered off, washed well with ethyl acetate and dried at C. The 5.0 parts of 6-[3-carboxy-3-(N-n-octadecylisobutyrylamido)-propionamido]-3-indazol0ne were obtained as a solid melting at 197-199" C. On analysis the compound was found to contain 67.8% of carbon, 9.3% of hydrogen and 9.6% nitrogen. (C H N O requires 67.6% of carbon, 9.2% of hydrogen and 9.5% of nitrogen.)

Method 2.A mixture of 9.0 parts of l-acetyl-6-[3- carboxy 3 (N n-octadecylisobutylramido)-propionamido]-3-indazolone, 22 parts of 2 N potassium hydroxide solution, 50 parts n-propanol and 20 ml. water was heated to the boil, held at the reflux for 1 minute and acidified with acetic acid to obtain a colourless precipitate. The solid was collected by filtration, washed with water and dried at 60 C. The product was boiled with 250 parts of methanol, cooled and filtered. The 6-[3-carboxy-3-(N- n-octadecylisobutyramido)-propionamido] 3-indazolone so obtained melted at l97199 C. and when mixed with the product obtained by method 1 the melti g P t howed 119 depression.

The 1 acetyl-6-[3-carboxy-3-(N-n-octadecylisobutyramido)-propionamido]-3-indazolone was prepared as follows:

A mixture of 9.5 parts of l-acetyl-6-aminoindazolone and 250 parts of glacial acetic acid was heated until a complete solution was obtained. After cooling to 60 C., 21.75 parts of N-n-octadecylisobutyrylamino succinic anhydride was added, the mixture stirred at 50 C. for 2 hours, and allowed to cool to crystallise. The colourless product was recrystallised from 250 parts of methanol. The 19.1 parts of 1-acetyl-6-[3-carboxy-3-(N-n-octadecylisobutyramido)-propionamido] 3 indazolone were obtained as a solid melting at 201-203" C. On analysis the compound was found to contain 66.5% of carbon, 8.9% of hydrogen and 9.0% of nitrogen. (C 'H N4O requires 66.9% of carbon, 8.9% of hydrogen and 8.9% of nitro- 'gen.)

The l-acetyl-6-aminoinrlazolone used here was prepared from 6-nitro indazolone by acetylation to 1:3-diacetyl-6-nitroindazolone, followed by partial hydrolysis to 1-acetyl-6-nitroindazolone and finally reduction by hydrogenation.

A photographic layer containing the colour coupler just prepared was obtained in the following manner:

A mixture of 1.17 parts of the coupler, 2.0 parts of 2 N potassium hydroxide solution and 5 parts of n-propyl alcohol was warmed to dissolve. The solution so obtained was diluted with 25 parts of distilled water and added to 72 parts of a green sensitised gelatino silver halide emulsion containing silver halide equivalent to 1.9 parts of silver and 7.5 parts of gelatin. After addition of wetting agent and hardening agent the mixture is made to a total of 250 parts with distilled water and coated onto a paper base. When the photographic material so obtained was exposed to green light and developed in a colour developer containing 4 amino-N-ethyl-N-B-hydroxyethylaniline sulphate, bleached and fixed, a bright magenta image dye was obtained.

EXAMPLE II 1-acetyl-6- [6- (4-dodecylphenyl -1,3,5 ,7 -tetraoxohexahydrobenzo 1,2-c;4,5-c' dipyrrol-Z-yl] -3-indazolone E E E A mixture of 1.91 parts of 1-acetyl-G-aminoindazolone, 4.61 parts of N-(4 dodecylphenyl)pyromellitic monoanhydride, which is described in Example I of British patent specification No. 1,004,075, and 50 parts of glacial acetic acid were heated under reflux for 2 hours. The yellow solid which precipitated during the course of the reaction was filtered from the hot mixture, washed with ethyl acetate and dried at 60 C. The 5.8 parts of 1-acetyl-6-[6- (4-dodecylphenyl)-1,3,5,7-tetroxohexahydrobenzo (1,2-c; 4,5-c)dipyrrol-2-yl]-3-indazolone was obtained as a yellow solid melting above 300 C. On analysis the compound was found to contain 70.0% of carbon, 5.8% of hydrogen and 8.8% of nitrogen. (C31H33N406 requires 70.0% of carbon, 6.0% of hydrogen and 8.8% of nitrogen.)

EXAMPLE III l-acetyl-S- [3-carboxy-3- (N-n-octadecylisobutyramido) propionarnido]-3-indazoline is a'l til) (CHshCHCON-CHCHzCONH -C\ A mixture of 1.91 parts of 1-acetyl-S-aminoindazolone, and 50 parts of glacial acetic acid was heated to dissolve, cooled to 60 C. and 4.37 parts of N-n-octadecylisobutyrylamino succinic anhydride was added. The whole was stirred at 60 C. for 2 hours. After cooling the colourless precipitate was collected by filtration and recrystallised from 30 parts of methanol. The 1.3 parts of 1-acetyl-5-[3- carboxy-3- (N-n-octadecylisobutyramido propionamido] 3-indazolone were obtained as a colourless solid melting at 198201 C. On analysis the compound was found to contain 67.0% of carbon, 8.9% of hydrogen and 8.5% of nitrogen. (C H N O requires 66.9% of carbon, 8.9% of hydrogen and 8.9% of nitrogen.)

A photographic layer containing the colour coupler derived from the above compound was prepared as follows:

A mixture of 1.3 parts of the above compound, 3.0 parts of 2 N potassium hydroxide and 5 parts of n-propyl alcohol was heated at the reflux for 1 minute to hydrolyse the acetyl group from the 1-position, diluted with 25 parts of distilled water and completed as in Example I.

EXAMPLE IV l-acetyl-6-[6-(3-dodecyloxyphenyl)-1,3,5,7-tetraoxohexahydrobenzo(l,2-c; 4,5-c) dipyrrol-Z-yl]-3-indazolone 0 II c (312E250 /c o og\ \NH N c 0 oo (300753 In place of the 4.61 parts of N-(4-dodecylphenyl)pyromellitic mono-imide mono-anhydride used in Example H, there were used 4.76 parts of N-(3-dodecyloxyphenyl) pyromellitic mono-imide mono-anhydride. The 5.6 parts of 1-acetal-6-[6-(3 dodecyloxyphenyl) 1,3,5,7 tetraoxohexahydrobenzo (1,2-c; 4,5-c)dipyrrol-2-yl]-3-indazolone were obtained as a yellow solid melting above 300 C. On analysis the compound was found to contain 68.4% of carbon, 6.0% of hydrogen and 8.4% of nitrogen. (C37H38N407 requires 68.3% of carbon, 5.8% of hydrogen and 8.6% of nitrogen.)

The N-( 3 dodecyloxyphenyl)pyromellitic mono-imide mono-anhydride used in this example was made by the method described in Example I of British patent specification No. 1,004,075 for N-( l-dodecylphenyl)pyromellitic mono-imide mono-anhydride.

A photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example HI using 1.32 parts of compound and 4.0 parts of 2 N potassium hydroxide solution.

EXAMPLE V 1-acety1-6-[4-(3-dodecyloxyphenylcarbamoyl) phthalimido] -3-indazolone NH /N OOCHa 012E253) A mixture of 1.91 parts of 1-acetyl-6-aminoindazolone, 4.51 parts of 4-(3-dodecyloxyphenylarninocarbonyl) phthalic anhydride, obtained by the method described in our co-pending application No. 20,003/69, 50 parts of glacial acetic acid was heated under reflux for 2 hours. The yellow precipitate formed was filtered from the hot reaction mixture, washed with ethanol and dried at 60 C. The 4.3 parts of 1-acetyl-6-[4-(3-dodecyloxycarbamoyl)phthalimido]-3-indazolone were obtained as a solid melting at 248-250 C. On analysis the compound was found to contain 69.4% of carbon, 6.4% of hydrogen and 8.7% of nitrogen. (C H N O requires 69.8% of carbon, 6.6% of hydrogen and 8.9% of nitrogen.)

A photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example III using 1.28 parts of compound and 3.0 parts of 2 N potassium hydroxide solution.

EXAMPLE VI 1-acetyl-6- [4-dodecylphenylcarbamoyl) phthalimido]- 3-indazolone I \N/ CHH Q-NHOC c 0 ('JOCHB In place of the 4.51 parts of 4-(3-dodecyloxyphenylaminocarbonyl)phthalic anhydride used in Example V, there were used 5.35 parts of 4-(4-dodecylphenylaminocarbonyl) phthalic anhydride, which was described in Example 1 of British patent specification No. 1,039,452. The 5.2 parts of 1-acetyl-6-[4-(4-dodecylphenylcarbamoyl) phthalimido]-3-imdazolone were obtained as a yellow solid melting at 272274 C.

A photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example III using 1.24 parts of compound and 3.0 parts of 2 N potassium hydroxide solution.

EXAMPLE VII 1-acetyl-5-[6-(3-dodecyloxyphenyl)-1,3,'5,7-tetraoxohexahydrobenzo(-l,2-c; 4,5-c)dipyrrol-2-yl]-3-indazolone u u o COCHQ A mixture of 1.91 parts of 1-acetyl-S-aminoindazolone, 4.76 parts of N-(3-dodecyloxyphenyl)pyromellitic monoimide mono-anhydride and 50 parts of glacial acetic acid was heated under reflux for 2 hours. The precipitate was filtered from the hot mixture and washed with ethyl acetate. The 4.4 parts of l-acetyl-S-[6-(3-dodecyloxyphenyl)- 1, 3,5 ,7-tetraoxohydrobenzo 1,2-c; 4,5-c' dipyrrol-Z-yl] -3- indazolone were obtained as a solid melting above 300 C. On analysis the compound was found to contain 68.0% of carbon, 5.9% of hydrogen and 8.5% of nitrogen. (C37H38N4O7 requires 68.3% of carbon, 5.8% of hydrogen and 8.6 of nitrogen).

A photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example III using 1.28 parts of compound and 4.0 parts of 2 N potassium hydroxide solution.

EXAMPLE VIII l-acetyl-S- [4- 3-dodecyloxyphenylcarbamoyl) phthalimido] -3-indazolone o 0N Q-NHO 0G0 N/ can boon A mixture of 1.91 parts of 1-acetyl-5-aminoindazolone, 4.51 parts of 4 (3 dodecyloxyphenylaminocarbonyl) phthalic anhydride and 50 parts of glacial acetic acid was heated under reflux for 2 hours. After cooling the precipitate was collected by filtration and washed with ethyl acetate. The 3.4 parts of 1 acetyl-S-[4-(3-dodecyloxyphenylcarbamoyl)phthalimido] 3 indazolone were obtained as a solid melting at 272-274 C.

A photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example III using 1.28 parts of the compound and 3.0 parts of 2 N potassium hydroxide solution.

EXAMPLE IX a1-acetyl-5-[6-(4-dodecylphenyl)-1,3,5,7-tetrahexahydrobenzo(1,2-c;4,5-c')dipyrrol-2-yl]-3-indazolone EXAMPLE X 7-bromo-5- [3-carboxy-3-(N-n-octadecylisobutyramido) propionamido] -3-indazolone o CnHaI y; (CHahCHC ONCHCHaCONH OOH NH I NH Br A mixture of 3.02 parts of 5-amino-7-bromoindazolone dihydrochloride and 5.0 parts of pyridine was warmed until and oil formed and 50 parts of glacial acetic acid added to give a suspension. N-n-octadecyl-isobutrylamino succinic anhydride (4.37 parts) was then added and the mixture stirred at 50-60 C. for 2 hours. The solution obtained was allowed to stand overnight to allow crystallisation to take place. The colourless precipitate was filtered off, washed with ethanol and dried at C. The 7 bromo-S-[3-carboxy-3-(N-n-octadecylisobutyramido) propionamide]-3-indazolone (2.3 parts) was obtained as a solid melting at 182 C.

A photographic layer containing 1.33 parts of the above coupler, prepared by the method of Example I gave a bright magenta dye image.

EXAMPLE XI 7- [3 -carboxy-3 (N-n-octadecylisobutyramido) propionamido]-3 -indazolone (CH2):CHCONOHCH2CONH COOH A mixture of 1.49 parts of 7-amino indazolone and 35 parts of glacial acetic acid was warmed to dissolved and 4.37 parts of N-n-octadecylisobutyrylamino succinic anhydried then added. The mixture was stirred at 45-50 C. for 2 hours. The solution so obtained was poured into water and the product, which separated as a sticky solid, was isolated and stirred with methanol to solidify. The solid was filtered off, washed with methanol and dried at 60 C. The 7-[3-carboxy-3-(N-n-octadecylisobutyramido) propionamido]-3-indazolone (3.35 parts) was obtained as a solid melting at 182-184" C.

A photographic layer containing the above coupler was produced by the method of Example I.

I claim as my invention:

1. An indazolone magneta coupler of the formula:

wherein Q is (CH3)2CHC ON-CHCH2COHN References Cited UNITED STATES PATENTS 12/1968 Nordmann et a1. 260310 C OTHER REFERENCES Noller, Chemistry of Organic Compounds, 2nd ed., 20 p. 246, Philadelphia, Saunders, 1958, QD253N6S.

NATALIE TROUSOF, Primary Examiner US. Cl. X.R.