Color Photographic Recording Material

2.8 g of 3-(p-aminophenyl)-phosphonic acid diethyl ester (manufactured according to JACS, 81, 3026, [1959]) and 2.7 g of benzoylacetic acid methyl ester are warmed with 70 mg of sodium ethylate in 15 ml of absolute xylene isomer mixture to 125.degree. C. for 31/2hours and the methyl alcohol formed is distilled off. After recrystallisation from ethyl acetate and acetone/ether, 0.9 g of pure coupling agent of the formula (101) of Table I is obtained in the form of a white powder of melting point 99.degree.- 101.degree. C.

The compounds of the formulae (102), (103), (113), (114), (115), (116), (117), (119), (124 ) and (125) of Table I are manufactured analogously.

10.4 g of 3-bromo-propane-phosphonic acid diethyl ester (manufactured in a known manner by heating 1,3 -dibromopropane with triethyl phosphite and distilling off the ethyl bromide formed) and 15.2 g of N-methyl-3-nitroaniline in 50 ml of methyl ethyl ketone are warmed with 13 g of N-ethyl-diisopropylamine for 20 hours under reflux. After separating the reaction mixture on a chromatography column (silica gel; chloroform as the eluant), 9.9 g of pure 3-(N-methyl-N-3'-nitro-phenylamino) propane-phosphonic acid diethyl ester are obtained in the form of an orange-coloured oil.

9.9 g of this intermediate product, in 100 ml of ethanol, are hydrogenated with 0.5 g of palladium on active charcoal at room temperature and normal pressure in the usual manner, until the absorption of hydrogen has ceased.

After separating off the catalyst, distilling off the ethanol and treating the residue with 2 N sodium hydroxide solution and chloroform, 5.4 g of 3-(N-methyl-N-3'-amino-phenylamino) propane-phosphonic acid diethyl ester are obtained as a light brown oil.

The condensation with benzoylacetic acid methyl ester is carried out as indicated in Example 1.

The compound of the formula (104) is obtained in the form of a light brown resin, in a yield of 32%.

25.9 g of bromoacetic acid 3-nitrophenylamide and 37.5 g of tributyl phosphite in 150 ml of pure xylene isomer mixture are stirred under nitrogen for 30 minutes at 130.degree. C. The residue obtained after distilling off the xylene and the excess tributyl phosphite at 1 mm Hg gives, after recrystallisation from chloroform/hexane, 29.5 g of pure 3-nitro-phenylcarbamoyl-methane-phosphonic acid dibutyl ester of melting point 80.degree.- 81.degree. C. in the form of fine white needles.

Reduction of the nitro group according to Example 2 and condensation with pivaloylacetic acid ethyl ester analogously to Example 1 gives, in good yield, the coupling agent of the formula (105 ) in the form of a colourless, highly viscous oil.

The compounds of the formulae (106) and (109) are obtained analogously.

83 g of 3-nitrobenzoyl chloride in 150 ml of acetonitrile are added dropwise to a solution of 105 g of 2-aminopropane-2-phosphonic acid diethyl ester and 45 g of triethylamine in 300 ml of acetonitrile at 0.degree. C., with good stirring. After completion of the addition, the mixture is stirred for a further 3 hours at 0.degree. C.; it is then filtered and the solvent is distilled off in vacuo. The residue is purified by extraction by shaking with ether and aqueous 2 normal sodium carbonate solution. 99 g of 2-(3'-nitrobenzamido)propane-2-phosphonic acid diethyl ester of melting point 95.degree.-96.degree. C. are obtained. This product is reduced with hydrogen as indicated in Example 2.

A solution of 5.6 g of 3-nitrobenzoyl chloride in 30 ml of acetonitrile is added dropwise to a mixture of 10.4 g of the amino compound obtained above and 3 g of triethylamine in 100 ml of acetonitrile at 0.degree. C., with good stirring. Thereafter, the mixture is stirred for a further hour at 0.degree. C. and after distilling off the acetonitrile, the residue is dissolved in chloroform and purified by successive extraction by shaking with 2 N hydrochloric acid, water and 2 N ammonia.

11.5 g of 2-[3'-(3"-nitrobenzamido)benzamido] propane- 2-phosphonic acid diethyl ester of melting point 120.degree.- 121.degree. C. are obtained.

After reduction of the nitro group and subsequent condensation with benzoylacetic acid methyl ester according to Example 1, the coupling agent of the formula (107) is obtained in good yield as a yellowish powder of melting point 93.degree. - 95.degree. C. The compounds of the formulae (126 ), (136 ), (137) and (143 ) are manufactured analogously, employing the anilines from Example 1 in place of 2-(3'-aminobenzamido) propane-2phosphonic acid diethyl ester.

If 2-(3'-aminobenzamido)propane-2-phosphonic acid diethyl ester is condensed directly with benzoylacetic acid methyl ester, analogously to Example 1, the compound of the formula (108) is obtained in excellent yield, in the form of a white powder of melting point 158.degree. - 160.degree. C.

The compounds of the formulae (110), (111), (118), (127), (128), (131), (133), (134), (135), (139) and (140) are manufactured analogously.

1.34 g of 3-amino-benzoylacetic acid 2'-methoxy-5'-methyl-phenylamide, prepared by condensation of 3-nitro-benzoylacetic acid methyl ester with 2-methoxy-5-methylaniline and subsequent reduction of the nitro group, and 1.6 g of the acid chloride from Example 15, in 15 ml of N-methylpyrrolidone, are stirred for 3 hours at room temperature. After evaporation under 1 mm Hg and purification by column chromatography (silica gel), 1.5 g of the compound (112) are obtained in the form of a light yellow resin. The compounds (120) and (121) are prepared analogously.

3.4 g of the amino compound prepared according to Example 15, 2.1 g of benzoylacetic acid methyl ester and 0.1 ml of sym.-collidine in 30 ml of p-xylene are warmed for one and a half hours to 140.degree. C. and the methanol formed is distilled off. After purification through a chromatography column, the compound of the formula (122) is obtained in the form of a light yellow resin.

The compound of the formula (123 ) is obtained analogously.

41.9 g of t-butane-phosphonic acid dichloride are dissolved in 300 ml of acetonitrile and a suspension of 33 g of sodium phenolate in 150 ml of acetonitrile is added at -15.degree. C. in such a way that the temperature does not exceed -12.degree. C. After completion of the addition, the temperature is allowed to rise slowly to 20.degree. C. and after 3 hours a suspension of 46 g of sodium 4-nitrophenolate in 150 ml of acetonitrile is added and the mixture is warmed to 60.degree. C. for 2 hours. After distilling off the solvent, the residue is hydrogenated in isopropanol with palladium on charcoal as the catalyst (1 atmosphere). After purifying the crude product by extraction with ether and of the ether extract with hexane, 30 g of t-butanephosphonic acid 4-aminophenyl-(phenyl) ester of melting point 105.degree. C. are obtained. Condensation with benzoylacetic acid methyl ester in accordance with the method indicated in Example 6 gives the compound of the formula (129), of melting point 148.degree. C., in excellent yield.

The compound of the formula (130) is prepared analogously.

31 g of diisoamyl phosphite are slowly added dropwise at 80.degree. C. to a suspension of 3.1 g of sodium in 150 ml of absolute toluene. After completion of the reaction, the suspension thus obtained is slowly added to a solution of 30 g of 3-phenyl-propyl bromide at 80.degree. C., whilst stirring well. After 3 hours, the reaction mixture is centrifuged, the supernatant solution is evaporated and the residue is distilled under a vacuum of 0.2 mm Hg. At 158.degree. C., 18 g of pure 3-phenylpropane-phosphonic acid diisoamyl ester pass over. After nitration and reduction (compare Example 1 ), 15.5 g of 3-(4'-aminophenyl)-propane-phosphonic acid diisoamyl ester are obtained.

The condensation with 4-chloro-benzoylacetic acid methyl ester in accordance with the method indicated in Example 6 gives the coupling agent of the formula (132), of melting point 116.degree. C., in good yield.

20 g of n-butanephosphonic acid n-butyl ester chloride are added dropwise to a suspension of 14.3 g of sodium 3-nitrophenolate in 170 ml toluene at 20.degree. C. After 4 hours, the mixture is filtered, the filtrate is evaporated and the residue is distilled in vacuo at 0.1 mm Hg. 16 g of n-butanephosphonic acid n-butyl-(3-nitrophenyl) ester are obtained. After reduction with hydrogen and palladium on charcoal, in isopropanol, at 1 atmosphere pressure, 13.8 g of n-butanephosphonic acid n-butyl-(3-aminophenyl) ester are obtained.

A solution of 16 g of 4-nitrophenylacetyl chloride in 30 ml of benzene is added dropwise to a solution of 11.5 g of n-butanephosphonic acid n-butyl-(3-aminophenyl) ester and 6 g of triethylamine in 50 ml of benzene at 20.degree. C. After 40 hours, the mixture is filtered and the filtrate is purified by extraction by shaking with potassium bicarbonate solution and hydrochloric acid. 9.3 g of n-butanephosphonic acid n-butyl-[3-(4'-nitrophenyl-acetamido)phenyl] ester are obtained. This is reduced as indicated in Example 7 . After the condensation with 2-chlorobenzoylacetic acid ethyl ester in accordance with the method indicated in Example 6, a crude product is obtained, from which the pure product of the formula (138 ) is obtained by purification by column chromatography.

29 g of n-butanephosphonic acid n-butyl ester chloride are added dropwise to a solution of 20 g of 3-nitroaniline and 14.1 g of triethylamine in 300 ml of acetonitrile at 0.degree. C. After 20 hours the mixture is evaporated, the residue is suspended in 300 ml of ether, the mixture is acidified with hydrochloric acid in ether and filtered, and the filtrate is evaporated. 33 g of n-butanephosphonic acid n-butyl ester 3-nitroanilide are obtained in the form of a yellow oil.

After reduction with hydrogen and acylation with 2-chloro-5-nitro-benzoyl chloride in chloroform/triethylamine, and purification by column chromatography, 7 g of n-butane-phosphonic acid n-butyl ester-3-(2'-chloro-5'-nitro-benzamido)-anilide are obtained. 4.7 g of this compound are dissolved in 50 ml of glacial acetic acid at 20.degree. C. 1.25 g of iron powder, 0.2 ml of water and a little iron-(II) sulphate are added thereto. The reaction mixture is warmed to 55.degree. C. whilst stirring well and is kept at this temperature for 3 hours. After evaporation in vacuo, the residue is partitioned between 80 ml of 1 normal sodium carbonate solution and 300 ml of chloroform. The chloroform phase on evaporation gives 5.5 g of n-butanephosphonic acid n-butyl ester-3-(2'-chloro-5'-amino-benzamido)-anilide. After condensation with benzoylacetic acid methyl ester in accordance with Example 6 and purification of the crude product by column chromatography, the compound of the formula (141) is obtained in the form of a dark yellow resin.

A solution of 15 g of 4-nitro-benzoyl chloride in 100 ml of acetonitrile is added dropwise to a solution of 20 g of .alpha.-hydroxy-propanephosphonic acid dibutyl ester and 8 g of pyridine in 20 ml of acetonitrile at 0.degree. C. After 16 hours the mixture is filtered, the filtrate is evaporated and the residue is extracted with 200 ml of diethyl ether. After evaporation, and purification by column chromatography, 13 g of pure .alpha.-(4-nitro-benzoyloxy)-propanephosphonic acid dibutyl ester are obtained. This is reduced with hydrogen as indicated in Example 2. 12.5 g of .alpha.-(4-amino-benzoyl-oxy)-propanephosphonic acid dibutyl ester are obtained. After condensation with o-methoxybenzoylacetic acid methyl ester according to Example 6, and purification by column chromatography, the compound of the formula (142 ) is obtained in the form of a yellow resin.

A solution of 10.3 g of 4-chloro-3-nitro-benzoyl chloride in 40 ml of acetonitrile is added dropwise to a solution of 15 g of 5-amino-1,3,3-trimethyl-cyclo-hexanephosphonic acid diisopropyl ester and 5 g of triethylamine in 250 ml of acetonitrile at -5.degree. C. After 2 hours, the temperature is allowed to rise to 20.degree. C. and the mixture is stirred for a further 17 hours at this temperature. It is then stirred for a further 4 hours, at 50.degree. C. After evaporation, the residue is partitioned between 300 ml of chloroform and 50 ml of water and the chloroform phase is successively extracted by shaking with 2 N hydrochloric acid and 2 N sodium carbonate solution. After distilling off the chloroform and recrystallising from ethyl acetate, 14.1 g of 5-(3'-chloro-4'-nitro-benzamido)-1,3,3-trimethylcyclohexanephosphonic acid diisopropyl ester of melting point 174.degree. C. are obtained.

11.2 g of this product, in a solution of 1.5 g of sodium and 3.3 g of phenol in 200 ml of isopropanol, are allowed to react for 40 hours at 50.degree. C. After distilling off the isopropanol, the residue is dissolved in chloroform and the chloroform phase is washed with water until neutral. After distilling off the chloroform, 11.7 g of 5-(3'-phenoxy-4'-nitro-benzamido)- 1,3,3-trimethyl-cyclohexane-phosphonic acid diisopropyl ester are obtained in the form of a reddish-yellow oil.

This is reduced in isopropanol by means of hydrogen, as indicated in Example 2. 7.7 g of 5-(3'-phenoxy-4'-amino-benzamido)- 1,3,3-trimethyl-cyclohexane-phosphonic acid diisopropyl ester are obtained in the form of a dark brown oil.

After condensation with 4-chlorobenzylacetic acid methyl ester in accordance with Example 6 and purification by column chromatography, the compound of the formula (144) is obtained in the form of a light yellow resin.

A solution of 5.5 g of 3-nitro-benzoyl chloride in 25 ml of acetonitrile is added dropwise to a solution of 11.4 g of 4-amino-benzenephosphonic acid di-n-hexyl ester and 3.7 g of triethylamine in 100 ml of acetonitrile at 0.degree. C. After one and a half hours, the mixture is allowed to warm up to 20.degree. C. and is stirred for a further hour at this temperature.

After distilling off the acetonitrile, the residue is extracted with 200 ml of benzene, the benzene phase is successively washed with 50 ml of 2 N sodium carbonate solution, 50 ml of 2 N hydrochloric acid and 50 ml of water and the benzene is distilled off apart from a small residue. After completion of crystallisation, the product is filtered off and recrystallised from diethyl ether. 6.1 g of 4-(3'-nitrobenzamido)-benzenephosphonic acid di-n-hexyl ester of melting point 98.degree. C. are obtained. After reduction with hydrogen and condensation with 4-chlorobenzoylacetic acid methyl ester in accordance with the method indicated in Example 6, the coupling agent of the formula (145) is obtained in good yield.

0.3 g of sulphuryl chloride is added dropwise at 20.degree. C. to a solution of 0.8 g of the compound of the formula (130) and 0.14 g of anhydrous sodium acetate in 8 ml of glacial acetic acid. After 50 minutes, the mixture is poured into 70 ml of ice water and the product is filtered off and recrystallised from ethyl acetate. 0.4 g of the compound (146), of melting point 128.degree. C., is obtained.

The compound of the formula (117) is prepared analogously.

The compounds of the formulae which follow are prepared according to methods which are in themselves known, from the corresponding 4-equivalent coupling agents (the corresponding compounds with hydrogen in the position marked with , in place of the substituents drawn). With regard to methods of manufacture, compare DT-OS or DT-AS 1,236,332, 2,043,271, 1,547,672 or 1,187,477. Next to the formula, the absorption maximum in nm is specified in each case (see footnote to Table I). ##STR23##

1.5 g of m-hydroxybenzoic acid methyl ester, 2.6 g of 3-bromopropane-phosphonic acid diethyl ester prepared in the usual manner from 1,3-dibromopropane and triethyl phosphite and 0.7 g of anhydrous potassium carbonate in 20 ml of ethyl methyl ketone are heated to the boil under reflux for 36 hours. The potassium bromide which has separated out is filtered off and the filtrate is evaporated to dryness, whereupon 2.9 g of ester of the formula ##STR70## are obtained in the form of a yellowish oil.

Saponification of 30 g of this ester in ethanolic sodium hydroxide solution at 55.degree. C. gives 25 g of acid of the formula ##STR71## in the form of a yellowish oil.

5 g of the carboxylic acid thus obtained, on reaction with thionyl chloride in the usual manner, give 5 g of the acid chloride of the formula ##STR72## as a yellowish oil.

0.4 g of 1(2',4',6'trichlorophenyl)-3(4"aminobenzamido) 5-pyrazolone obtained in a known manner is dissolved in 5 ml of N-methyl-5-pyrrolidone and this solution is added to 0.4 g of acid chloride of the above formula. The reaction mixture is stirred for 1 hour at room temperature and poured into a mixture of 25 ml of water and 1.2 ml of 30% strength sodium hydroxide solution, the whole is stirred for 15 minutes and filtered, and 40 ml of water and 5 ml of 36% strength hydrochloric acid are added to the filtrate.

The product which has precipitated is filtered off, washed with water until neutral and dried, and 0.6 g of coupling agent of the formula (201) is obtained in the form of a light beige powder of melting point 120.degree. C.

The remaining compounds of Table II are prepared analogously. ##STR73## Abs. max in Formula[nm]*) (see No. R.sub.11 R.sub.12 footnote, Table I) (201) ##STR74## ##STR75## 432 + 542 (202) ##STR76## ##STR77## 434 + 535 (203) ##STR78## ##STR79## 434 + 539 (204) ##STR80## ##STR81## 434 + 534 (205) ##STR82## ##STR83## 434 + 542 (206) ##STR84## ##STR85## 434 + 542 (207) ##STR86## ##STR87## 434 + 540 (208) ##STR88## ##STR89## 434 + 546 (209) ##STR90## ##STR91## 436 + 540 (210) ##STR92## ##STR93## 434 + 543 (211) ##STR94## ##STR95## 434 + 543 (212) ##STR96## ##STR97## 434 + 544 (213) ##STR98## ##STR99## 434 + 537 (214) ##STR100## ##STR101## 432 + 540 (215) ##STR102## ##STR103## 434 + 540 (216) ##STR104## ##STR105## 432 + 546 (217) ##STR106## ##STR107## 435 + 538 (218) ##STR108## ##STR109## 436 + 542 (219) ##STR110## ##STR111## 436 + 542 (220) ##STR112## ##STR113## 434 + 544 (221) ##STR114## ##STR115## 436 + 538 (222) ##STR116## ##STR117## 434 + 544 (223) ##STR118## ##STR119## 440 + 534 (224) ##STR120## ##STR121## 440 + 534 (225) ##STR122## ##STR123## 440 + 532 (226) ##STR124## ##STR125## 439 + 534 (227) ##STR126## ##STR127## 438 + 532 (228) ##STR128## ##STR129## 438 + 533 (229) ##STR130## ##STR131## 440 + 532 (230) ##STR132## ##STR133## 434 + 544 (231) ##STR134## ##STR135## 434 + 545 (232) ##STR136## ##STR137## 434 + 541 (233) ##STR138## ##STR139## 441 + 530 (234) ##STR140## ##STR141## 434 + 540 (235) ##STR142## ##STR143## 440 + 532 (236) ##STR144## ##STR145## 436 + 541 (237) ##STR146## ##STR147## 432 + 536 (238) ##STR148## ##STR149## 440 + 530 (239) ##STR150## ##STR151## 440 + 532 (240) ##STR152## ##STR153## 434 + 544 (241) ##STR154## ##STR155## 434 + 541 (242) ##STR156## ##STR157## 436 + 542 (243) ##STR158## ##STR159## 434 + 544 (244) ##STR160## ##STR161## 434 + 542 (245) ##STR162## ##STR163## 434 + 542 (246) ##STR164## ##STR165## 440 + 532 (247) ##STR166## ##STR167## 436 + 540 (248) ##STR168## ##STR169## 436 + 541 (249) ##STR170## ##STR171## 442 + 532 (250) ##STR172## ##STR173## 434 + 537 (251) ##STR174## ##STR175## 436 + 540 (252) ##STR176## ##STR177## 440 + 532 (253) ##STR178## ##STR179## 440 + 540 (254) ##STR180## ##STR181## 438 + 540 (255) ##STR182## ##STR183## 438 + 536 (256) ##STR184## ##STR185## 438 + 534 (257) ##STR186## ##STR187## 430 + 537 (258) ##STR188## ##STR189## 550 + 580 (259) ##STR190## ##STR191## 548 + 583 (260) ##STR192## ##STR193## 440 + 535 (261) ##STR194## ##STR195## 440 + 535 (262) ##STR196## ##STR197## 440 + 536 (263) ##STR198## ##STR199## 440 + 534 (264) ##STR200## ##STR201## 440 + 536 (265) ##STR202## ##STR203## 436 + 537 (266) ##STR204## ##STR205## 436 + 540 (267) ##STR206## ##STR207## 436 + 536 (268) ##STR208## ##STR209## 438 + 540 (269) ##STR210## ##STR211## 438 + 540 (270) ##STR212## ##STR213## 438 + 544 (271) ##STR214## ##STR215## 440 + 532 (272) ##STR216## ##STR217## 438 + 540 (273) ##STR218## ##STR219## 430 + 547 (274) ##STR220## ##STR221## 430 + 546 (275) ##STR222## ##STR223## 440 + 538 (276) ##STR224## ##STR225## 440 +

Bromination of the compound of the formula (245) according to US-PS 3,006,759 gives the compound of the formula ##STR226## Absorption maximum 434 + 542 nm.

14.2 g of sodium m-nitrophenolate and 22.8 g of 3-bromopropylphosphonic acid diethyl ester in 200 ml of methyl ethyl ketone are stirred for 6 hours at 110.degree. C. The mixture is cooled to room temperature, the sodium bromide which has separated out is filtered off, the solvent is distilled off and the residue is fractionated in a high vacuum.

21.0 g of nitro compound of the formula ##STR227## are obtained as a yellow oil of boiling point (0.3 mm Hg) 180.degree.- 185.degree. C.

Catalytic reduction of 43.0 g of the nitro compound at room temperature under normal pressure gives 36.5 g of amino compound of the formula ##STR228## as a light yellow oil.

4.0 of 1-ethoxy-1-amino-acrylic acid ethyl ester hydrochloride are dissolved in 23 ml of methanol and this solution is added to 5.8 g of amine of the above formula. The mixture is stirred for 24 hours at room temperature and evaporated to dryness, the residue is extracted with 50 ml of benzene and the extract is concentrated. The residue consists of 8.5 g of red-brown oil of the formula ##STR229## 4.4 g of this compound and 1.1 g of phenylhydrazine in 10 ml of ethanol are stirred for 18 hours at room temperature. The mixture is filtered and the residue is concentrated and caused to crystallise by trituration with diethyl ether. Recrystallisation from benzene and from acetone gives 0.5 g of pure coupling agent of the formula (401) (Table III) as a light yellow powder of melting point 148.degree. -150.degree. C.

The compounds of the formulae (402) and (410) to (413) are prepared analogously.

6.8 g of 3-methoxy-3-(2',4',6'-trichlorophenylhydrazino)-acrylic acid ethyl ester and 5.7 g of compound of the formula ##STR230## in 5 ml of glacial acetic acid are stirred for 3 hours at 100.degree. C. under nitrogen. 50 ml of ethanol are added, the mixture is cooled to 0.degree. C. and the product which has crystallised out is filtered off.

After recrystallisation from ethanol, 1.7 g of coupling agent of the formula (403) are obtained as a yellow powder of melting point 162.degree. -164.degree. C.

The compounds of the formulae (404) to (409) are prepared analogously.

The compounds of the formulae (414) to (424) and (427) to (430) are prepared analogously to Example 15. The compounds (408) and (409) are prepared analogously to Example 17.

26.9 g (0.14 mol) of trimethoxypropionic acid ethyl ester (prepared according to DT-OS 2,042,920 ) are dissolved in 100 ml of absolute methanol, 7 ml of glacial acetic acid are added and the mixture is heated to the boil. 23.4 g (0.12 mol) of 3-nitro-2,4,6-trimethylphenylhydrazine (prepared according to DT-OS 2,156,913) are introduced in portions into the mixture over the course of 10 minutes. The mixture is stirred for a further 10 minutes at the boil and is allowed to cool whilst stirring. The orange crystals which have precipitated are filtered off, washed with a little methanol and dried (18 hours in vacuo at 50.degree. C.). 14.4 g of .beta.-methoxy-.beta.-(3-nitro-2,4,6-trimethylphenylhydrazino)-acrylic acid ethyl ester of melting point 82.degree. - 83.degree. C. are obtained.

16.3 g (0.05 mol) of this compound are well mixed with 6.95 g (0.054 mol) of p-chloroaniline and the mixture is stirred with 10.1 ml of glacial acetic acid. The mixture is warmed to 50.degree. C. for 4 hours and 50 ml of absolute methanol are then added. The whole is allowed to cool whilst stirring and the crystals are filtered off and rinsed with a little methanol. After drying in vacuo at 70.degree. C., 11.9 g of the pyrazolone, of melting point 263.degree. - 265.degree. C, are obtained. 1-(3-Amino-2,4,6-trimethylphenyl)-3-(4-chloroanilino)-5 -pyrazolone.

7.5 g (0.02 mol) of the above nitropyrazolone are dissolved in 70 ml of DMF and 15 ml of glacial acetic acid and 6 ml of H.sub.2 O are added. The mixture is warmed to 40.degree. C. under a N.sub.2 atmosphere and 20 g of Fe powder are introduced. The reaction is allowed to take place for 8 hours at 40.degree. C., 40 ml of methanol are added, and the mixture is filtered. The filtrate is poured into 700 ml of H.sub.2 O and the product which has precipitated is filtered off. The filter residue is dissolved in 60 ml of hot methanol and allowed to crystallise. After filtering off the crystals, and drying them at 70.degree. C. in vacuo, 5.7 g of the above aminopyrazolone, of melting point 236.degree. -237.degree. C., are obtained.

0.72 g (0.002 mol) of the above aminopyrazolone are dissolved in 10 ml of glacial acetic acid and the solution is mixed with 210 mg of anhydrous sodium acetate. A solution of 0.73 g (0.0022 mol) of the acid chloride of the formula ##STR231## (prepared according to Example 15) in 2.5 ml of glacial acetic acid is allowed to run in at 45.degree. -50.degree. C. The reaction is allowed to take place for 2 hours at this temperature, the reaction mixture is poured into 100 ml of ice water and the product is filtered off and washed thoroughly with H.sub.2 O. The crude product is taken up in chloroform and precipitated with petroleum ether. After addition of a little H.sub.2 O, the product solidifies. It is filtered off and dried in vacuo at 50.degree. C. Yield: 200 mg. Melting point: 132.degree. -138.degree. C.

This coupling agent is prepared analogously to Example 20. However, instead of the acid chloride used in Example 20, the acid chloride of the formula ##STR232## prepared analogously to Example 15 is employed.

A product of melting point 117.degree. -127.degree. C. is obtained. ##STR233## Formula Abs.max.*) No. R.sub.13 R.sub.14 in[nm] (401) ##STR234## ##STR235## 429 + 524 (402) ##STR236## ##STR237## 430 + 534 (403) ##STR238## ##STR239## 424 + 526 (404) ##STR240## ##STR241## 425 + 530 (405) ##STR242## ##STR243## 428 + 526 (406) ##STR244## ##STR245## 426 + 530 (407) ##STR246## ##STR247## 429 + 527 (408) ##STR248## ##STR249## 426 + 530 (409) ##STR250## ##STR251## 426 + 330 (410) ##STR252## ##STR253## 438 + 532 (411) ##STR254## ##STR255## 428 + 532 (412) ##STR256## ##STR257## 430 + 528 (413) ##STR258## ##STR259## 428 + 533 (414) ##STR260## ##STR261## 430 + 530 (415) ##STR262## ##STR263## 426 + 532 (416) ##STR264## ##STR265## 426 + 528 (417) ##STR266## ##STR267## 428 + 528 (418) ##STR268## ##STR269## 430 + 530 (419) ##STR270## ##STR271## 427 + 532 (420) ##STR272## ##STR273## 428 + 529 (421) ##STR274## ##STR275## 430 + 528 (422) ##STR276## ##STR277## 426 + 530 (423) ##STR278## ##STR279## 430 + 530 (424) ##STR280## ##STR281## 427 + 532 (425) ##STR282## ##STR283## 430 + 530 ##STR284## (426) ##STR285## ##STR286## 430 + 528 ##STR287## (427) ##STR288## ##STR289## 431 + 538 (428) ##STR290## ##STR291## 430 + 537 (429) ##STR292## ##STR293## 430 + 538 (430) ##STR294## ##STR295## 430 +

2.6 g of 1-hydroxy-2-naphthoic acid phenyl ester and 2.9 g of 3-(m-aminophenyl)-propoxy-phosphonic acid diethyl ester are warmed to 130.degree. - 140.degree. C. over the course of 4 hours. The phenol split off is distilled off in vacuo and the crude product is purified by column chromatography on silica. 1.5 g of pure coupling agent of the formula (601) of Table IV are obtained in the form of a white powder of melting point 104.degree. - 107.degree. C.

The compound of the formula (602) is prepared analogously. Melting point 79.degree. -81.degree. C.

3.1 g of 3,5-di[3'-di-n-butoxy-phospho)-propoxy] benzoic acid chloride and 1.0 g of 2-amino-4,6-dichloro-5-methyl-phenol (prepared according to DOS 2,216,804) in 20 ml of N-methyl-pyrrolidone are stirred for 3 hours at room temperature. The reaction mixture is poured into 100 ml of water and the emulsion is then extracted with 150 ml of ether. The organic phase is washed until neutral, dried and concentrated. The crude product is purified by column chromatography on silica. 1.0 g of light brown oil of the formula (701) ##STR299## is obtained. The cyan dyestuff prepared therefrom according to Use Example I has an absorption maximum of 662 nm.

0.3 mmol of coupling agent of the formula (215) is dissolved in 2.0 ml of tricresyl phosphate/methylene chloride (3:7). The methylene chloride is evaporated off, 6.0 ml of an 8% strength aqueous solution of sodium isopropylnaphthalene-sulphonate, 20.0 ml of 6% strength gelatine solution and 3.4 ml of water are added and the mixture is adjusted to pH 6.5 and emulsified for 5 minutes by means of an ultrasonic apparatus with an output of 100 watt.

5.0 ml of coupling agent emulsion freshly treated with ultrasonics, 3.3 ml of silver bromide emulsion of pH 6.5, containing 1.4% of silver and 6.0% of gelatine, 2.0 ml of 1% strength aqueous solution of the hardener of the formula ##STR300## and 1.7 ml of water are mixed with one another and cast at 40.degree. C. on a substrated glass plate of size 13.times. 18 cm. After solidifying at 10.degree. C., the plate is dried in a drying cabinet with circulating air at 32.degree. C.

A strip cut to 4.0 cm .times. 6.5 cm is exposed to 500 Lux/cm.sup.2 under a step wedge for 2 seconds and is subsequently treated at 24.degree. C. as follows:

The processing solutions have the following composition:

A clear, sharp magenta wedge with an absorption maximum at 540 nm and a subsidiary maximum at 434 nm is obtained.

Analogous results are obtained on using the remaining coupling agents listed in Tables I to IV.

The strip obtained, and exposed, according to Example I is developed for 6 minutes at 24.degree. C. by means of the developer solution specified below and is rinsed with water at the same temperature.

It is then uniformly exposed to white light and colour-developed as stated in Example I. The strip thus treated gives a clear magenta wedge corresponding to a colour reversal material.

Analogous results are obtained on using the remaining coupling agents listed in Tables I to IV or on using the coupling agent of the formula (701).

The casting solution obtained according to Example I using an emulsion which is sensitive to green and the coupling agent of the formula (215) is cast on an opaque white acetate film provided with an adhesive layer. On top of this is cast an emulsion sensitive to red, which has been prepared analogously and contains the coupling agent of the formula (701), and finally an emulsion prepared analogously which contains the coupling agent of the formula (105).

The material is exposed through a colour-negative film and developed in accordance with the instructions given in Example I, whereby a clear colour copy is obtained.

A solution of 25 mg of the coupling agent of the formula (222) in 1 ml of methylene chloride is emulsified by means of ultrasonics in a mixture consisting of 1.6 ml of 6% strength gelatine solution, 2.0 ml of distilled water and 1.0 ml of an 8% strength aqueous solution of sodium diisobutylnaphthalene sulphonate.

After adjusting the pH value to 6.5, 1.0 ml of a 1% strength aqueous solution of the hardener from Example I and 1.6 ml of a silver bromide emulsion containing 1.4% of silver are added and the mixture thus obtained is spread by means of a glass rod on a substrated glass plate of size 13.times. 18 cm. After drying at room temperature, the material is exposed, and developed, as described in Example I. A colour wedge with a maximum density of 1.00 is obtained.

25 mg of the coupling agent of the formula (218) and 50 mg of a copolymer consisting of 50 parts of styrene and 50 parts of ethyl acrylate are dissolved in 1.2 ml of methylene chloride and this solution is dispersed, and cast with an emulsion, as described in Example IV. After drying, the material is exposed, and developed, as described in Example I. A colour wedge of maximum density 0.78 is obtained.