US2707681A - 8-aminolilolidines and 9-aminojulolidines and their addition salts and developer compositions containing the same - Google Patents

Description

United States Patent 8-AMINOLILOLIDINES AND 9-AMINOJULOLI- DINES AND THEIR ADDITION SALTS AND DEVELOPER COMPOSITIONS CONTAINING THE SAME Maynard S. Raasch, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware N0 Drawing. Application March 7, 1951, Serial No. 214,435

8 Claims. (CI. 95-88) This invention relates to new heterocyclic nitrogen compounds. More particularly it relates to aminolilolidines and aminojulolidines and to photographic developing compositions containing these compounds.

An object of this invention is to provide a new class of heterocyclic nitrogen compounds. provide such compounds which are useful as photographic developing agents. A still further object is to provide such compounds which can be used to form quinoneimine or azomethine images in the cromogenic development of latent silver halide images in place of the conventional N-dialkylaminoaniline developing agents. Still other objects will be apparent from the following description of the invention.

The new heterocyclic nitrogen compounds of this invention include the free bases represented by the general wherein R1 and R2 are hydrogen or alkyl radicals of 1 to 4 carbon atoms and n. is an integer from 2 to 3, and their addition salts with acids, e. g., organic and inorganic non-oxidizing acids having a dissociation constant above 1 10- The 8-aminolilolidine bases of the invention can be represented by the formula:

formula:

- CHzCHr-(LH 4 N R1 10 sort,

9 fibHa HQN 8 wherein R1 and R2 have the same significance as in Formula I.

The above bases can be prepared by reduction of azo compounds of the type R-N=NQ, where R is an aromatic radical and Q represents the lilolidine or julolidine nucleus. The azo compounds are made by coupling lilolidine or julolidine or an alkyl substituted julolidine A further object is to III and the 9-aminojulolidine bases can be represented by the 9 aminojulolidine pared as follows:

2,707,681 Patented May 3, 1955 ice in which the 8 or 9 carbon atom, respectively, is unsubstituted.

The heterocyclic amines of Formula I and their addition salts have been found to be excellent photographic developing agents. They possess an extremely high reducing action on latent silver salt images. They are especially useful as color-coupling developing agents and produce a very large bathochromic shift as compared to p-aminodiethylaniline.

The developer compositions of the invention may be made by admixing the aforedescribed developing agents with the other constituents of a developer composition including alkaline materials, e. g., sodium carbonate, potassium carbonate, sodium hydroxide, lithium hydroxide; preservatives, e. g., lithium, sodium, potassium, and ammonium sulfites and bisulfites, amine salts of sulfurous acids, for example, triethanolamine sulfite, morpholine sulfite, tetramethylamrnonium sulfite, trimethylbenzylammonium sulfite; restrainers, e. g., sodium, potassium, and lithium chlorides, bromides and iodides, ammonium bromide; other ingredients, e. g., emulsion hardeners, for example, potassium aluminum sulfate, chrome alum; buffering salts, e. g., disodium hydrogen phosphate, sodium metaborate, borax. The solutions or compositions may be made in two parts, if desired, which are mixed at the time of use.

The invention will be further illustrated but is not intended to be limited by the following examples in which the parts are by weight.

Example I A solution of 65 parts of sulfanilic acid monohydrate in 300 parts of water containing 21.2 parts of sodium carbonate monohydrate was cooled to 15 C. and treated with 24.5 parts of sodium nitrite in parts of water. The resulting solution was added to a mixture of 300 parts of crushed ice and parts of concentrated hydrochloric acid. After allowing to stand for 20 minutes, the diazonium solution was added to a solution of 59 parts of julolidine (prepared after the manner described in Organic Syntheses 26, 41 (1946)) in 450 parts of acetic acid and parts of water at 5 C. To the reaction mixture was then added parts of sodium acetate in parts of water and the mixture was stored at 4 C. for 16 hours. The crystalline 9-(p-sulfophenylazo)julolidine which has separated was filtered oif and washed successively with dilute acetic acid and water. The yield was 63 parts (51%) of crystals melting at l77179 C.

Sixty (60) parts of this azo compound was charged into an oscillating autoclave with parts of water, 12 parts of ammonium hydroxide and 5 parts of alloy skeleton nickel catalyst and hydrogenated at 15002000 lb./sq. in. hydrogen pressure and 60-75 C. for twov filtrate was concentrated to a small volume and refiltered.

Upon careful addition of a sodium carbonate solution,

monohydrochloride precipitated. After drying, the product was purified by sublimation in vacuo followed by recrystallization from a dioxane/eth-.

anol mixture. 9-aminojulolidine hydrochloride was ob- Analysis.Calculated for CiaHieNz-HCl: C, 64.1; H, 7.62; N, 12.47. Found: C, 63.6; H, 7.61;'N, 12.51.

Example II The 8-methyljulolidine used in this example was pre- Commercial grade 7-methyltetrahydroquinoline was purified by conversion to the N-acetyl derivative ('8. P. 18319l C. at 14 mm.) which was hydrolyzed with hydrochloric acid. The 7-methyltetrahydroquinoline was obtained by treatment of the hydrolysis mixture with sodium hydroxide and distillation, B. P. 264268 C. A mixture of 20 parts of 7-methyltetrahydroquinoline and 29 parts of trimethylene chlorobromide was refluxed for 17 hours. Upon cooling, a salt of 8-methyljulolidine crystallized out. Ether was addedand the salt was filtered off and recry tallized from water (yield, 24 parts). The amine was liberated from the salt by treatment with sodium hydroxide, extraction with ether and distillation, There was thus obtained 14 parts of S-methyljulolidine, B. P. 179-180 C. at 19 mm.

The S-rnethyljulolidine was coupled with diazotizcd sulfanilic acid as described for julolidine in Example I and there was obtained a quantitative yield-of red crystals of Q-sulfophenylazo-S-methyljulolidine.

Twenty-seven (27) parts of :9-sulfophenylazo8-methyljulolidine was added portionwise to a hot mixture of 22 parts of stannous chloride in 60 parts of water. After reduction was complete, 1 part of tartaric acid and 80 parts of potassium hydroxide in 100 parts of water were added. The liberatedamine was extracted with n-butanol and the butanol solution was washed with water. The aminewas then extracted from the butanol with 35 parts of concentrated hydrochloric acid in 50 parts of water. The acid solution was evaporated under reduced pressure, leaving 14 parts of 9-amino-8-methyljulolidine dihydrochloride, which was recrystallized from methanol to give crystals melting at 242-246 C.

Analysis.-Calculated for C13H1aNz-2HCl: N, 10.18. Found: N, 10.10, 10.20.

Example III The lilolidine used in this example was prepared from dihydroindole (King et,al.,,J.Chem. Soc. .1945, 280) and trimethylene chlorobromide as described :by 'Braun et al., Ber. 51, 1219 (1918).

Lilolidine was coupled with diazotizcd sulfanilic acid as described in Example I for julolidine. There was obtained a 29% yield of 8-sulfophenylazolilolidine. This azo compound was reduced with stannous chloride as described in Example II. The S-aminolilolidine was converted to its sulfate by mixing with an equivalent amount of sulfuric acid-in alcohol and crystallized from aqueous acetone. The compound melted at 244-245 C.

Analysis.Calculated for (C11'H14Nz)2-H2SO4: C, 59.17; H, 6.32; N, 12.55. Found: C, 58.4; H, 6.50; N, 12.4.

Example I V The 8,IO-dimethyljulolidine used in this example was prepared as follows:

To 33 parts of 5,7-dimethylquinoline (Borsche and Groth, Ann. 549, 251 (1941)) in 330 parts of absolute ethanol there was added in portions 50 parts of sodium, the mixture being heated during addition of the last half of the sodium. To the cooled mixture there was added 100 parts of water followed by 400 parts of 6 N hydrochloric acid. The mixture was evaporated to dryness, the residue was dissolved in water and the solution was filtered to remove a small amount of tar. The 5,7-dimethyltetrahydroquinoline was liberated with sodium hydroxide, collected with ether, dried and distilled. The yield was 21.5 parts of material boiling at 280-286 C. A mixture of'20 parts-of 5,7-dimethyltetrahydroquinoline and 100 parts of trimethylenechlorobromide was refluxed for 20 hours. The reaction product was steam distilled to remove excess trimethylenechlorobromide. Crystals of dimethyljulolidine hydrohalide crystallized out on cooling the aqueous solutionand were filtered off. The amine remaining in the motherliquor wasliberated with sodium hydroxide, given a crude distillation to remove some tar, converted to the hydrochloride and crystallized from-water. The combined salts were suspended in warm water and treated with sodium hydroxide tov give the free base. The solid 8,10-dimethyljulolidine was filtered off, dried and recrystallized from petroleum ether (yield, 9.4 parts). It melted at 68-69 C.

Analysis.Calculated for C14H19N: N, 6.96. Found: N, 6.89; 7.01.

The 8,10-dimethyljulolidine was coupled with diazotized sulfanilic acid as described in Example I to give a quantitative yield of red crystals of 8,10-dimethyl-9-sulfophenylazojulolidine. This azo compound was reduced with stannous chloride as in Example II. The resulting 8,10-dimethyl-9-aminojulolidine was given a crude distillation under reduced pressure. The amine, which melted at C., was further purified by converting it to its monohydrochloride by evaporating with one equivalent .of hydrochloric acid and recrystallized from water.

While the above examples show the introduction of the amino group into the julolidine or lilolidine nucleus through the use of diazotizcd sulfanilic acid, other diazotized amines can be used such as aniline, anthranilic acid, the naphthylamines, etc. The particular amine employed is not critical since it is eliminated during the subsequent reduction. Other methods of introducing the amino group can also be used, such as nitrosation of the julolidine or lilolidine component and reduction.

For use in development of exposed or latent silver halide images, including color development, the products of this invention may be employed in aqueous solutions containing, for example, 0.0125 mole of the heterocyclic amine (as salt, e. g., hydrochloride or sulfate), 10 grams of sodium sulfite and 25 grams of sodium carbonate per 1000 milliliters of solution. In such an alkaline solution, the amine is liberated from its salt. Other suitable proportions can, of course, be used and other conventional developing ingredients can be employed as described above.

When used to develop photographic films containing immobilized color formers, such as the polyvinyl acetals described in U. S. Patent 2,397,864, the compounds of Examples I, II and III produce rapid development of the entire field, including unexposed areas. They are thus useful as rapid reversal developers for black and white-or color film. If desired, however, these developers can be slowed in speed and made to discriminate between exposed and unexposed silver halide by adding a substantial amount of a restrainer to the solution, such as 6 to 8 grams of potassium bromide per 1000 milliliters.

Developer compositions containing the above aminojulolidines and/or aminolilolidines produce bathochromic shifts as high as 45 millimicrons compared to p-aminodiethylaniline. They are useful in producing new colors and make possible the use of color formers heretofore not suitable for use in color photography because they produced dyes of unsatisfactory spectral characteristics. For example, benzoylacetonitrile produces with p-aminodiethylaniline an orange-red azomethine dye unsuitable for use in 3-color photography, but with the developer of Example I a satisfactory magenta dye is formed. Dialkyllilolidines or julolidines, such as the compound of Example IV, do not couple with color formers as readily as the unsubstituted or monosubstituted compounds because of the hindering effect of the alkyl groups. However, they produce huge spectral shifts. Thus, the product of Example IV produces a spectral shift of :about millimicrons, compared to p-aminodiethylaniline, with pyrazolone color formers, ,e. g., 1-phenyl-3-methyl-5 pyrazolone, 1--psulfophenyl 3 methyl-S-pyrazolonc, and 1 phen yl-3- ethoxy-5-.pyrazolone.

The dyes obtained from pyrazolone color formers and thedevelopers of this invention are unusually :re-

sistant to change by acid.

While the invention has been illustrated with specific reference to E-arninolilolidine, 9-aminojulolidine, 8- methyl-9-aminojulolidine and 8,lO-dirnethyl-9-arninojulolidine, it is generic to heterocyclic amines of Formula I above, and to their addition salts. Other useful compounds which fall within the scope of this invention and can be prepared in manners similar to the above examples are 7 nethyl-S-aminolilolidine, 7-n-butyl-8- aminolilolidine, 7,9-diethyl-8-aminolilolidine, 7,9-di-iso butyl-S-aminolilolidine, 8-n propyl-9-arninojulolidine, 8,l-di-n-butyl-9-aminojulolidine, and the like.

The heterocyclic amines of this invention are preferably handled in the form of their addition salts because of the greater solubility and stability of the latter. The preferred salts are those formed with organic or inorganic non-oxidizing acids having a dissociation constant above l l0 e. g, acetic acid, henzoic acid, oxalic acid, chloroacetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, etc. The more useful salts are those formed with strong mineral acids.

in addition to their use in photographic developing compositions, the amines of this invention are useful as rubber accelerators, antioxidants for gasoline, azo and azomethine dye intermediates, and as intermediates for preparing light-sensitive diazo-type materials.

As many widely diiferent embodiments or" this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.

What is claimed is:

1. The heterocyclic nitrogen compounds taken from the group consisting of the bases having the general formula:

where R1 and R2 are taken from the group consisting 01 hydrogen and alkyl radicals of 1 to 4 carbon atoms and n is an integer from 2 to 3, and their addition salts with non-oxidizing acids having a dissociation constant above 1X10? 2. The heterocyclic nitrogen bases of the formula:

where R1 and R2 are taken from the group consisting of hydrocarbon and alkyl radicals of 1 to 4 carbon atoms. 3. The heterocyclic nitrogen bases of the formula:

N oni HzN JH2 C H2 R2 where R1 and R2 are taken from the group consisting of hydrogen and alkyl radicals of 1 to 4 carbon atoms.

4. T he compound of the formula:

(Fir- EH2 EH2 Ht HQN \C/ 5. The compound of the formula:

CHrCHz-C-Hz 6. An aqueous photographic developing composition comprising a preservative, an alkaline material and a heterocyclic nitrogen compound taken from the group consisting of the bases having the general formula:

where R1 and R2 are taken from the group consisting of hydrogen and alkyl radicals of 1 to 4 carbon atoms and n is an integer from 2 to 3, and their addition salts with non-oxidizing acids having a dissociation constant above 1X10"? 8. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion layer, containing a latent image, with a solution containing a compound selected from the class consisting of ,9-an1inojulolidine and 8-arninolilolidine, for a suflicient time to develop the latent image to a silver image.

References Cited in the file of this patent UNITED STATES PATENTS 2,245,261 Dickey et al June 10, 1941 2,496,958 Reitsema Feb. 7, 1950 2,566,259 Thirtle Aug. 28, 1951 2,566,271 Weissberger Aug. 28, 1951

Claims (1)

1. THE HETEROCYCLIC NITROGEN COMPOUNDS TAKEN FROM THE GROUP CONSISTING OF THE BASES HAVING THE GENERAL FORMULA: WHERE R1 AND R2 ARE TAKEN FROM THE GROUP CONSISTING OF HYDROGEN AND ALKYL RADICALS OF 1 TO 4 CARBON ATOMS AND N IS AN INTEGER FROM 2 TO 3, AND THEIR ADDITION SALTS WITH NON-OXIDIZING ACIDS HAVING A DISSOCIATION CONSTANT ABOVE 1X10-5.