US2727062A - Storage stable 4, 6-diamino metanilic acids - Google Patents
Storage stable 4, 6-diamino metanilic acids Download PDFInfo
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- US2727062A US2727062A US432601A US43260154A US2727062A US 2727062 A US2727062 A US 2727062A US 432601 A US432601 A US 432601A US 43260154 A US43260154 A US 43260154A US 2727062 A US2727062 A US 2727062A
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- diamino
- metanilic
- storage stable
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- 239000002253 acid Substances 0.000 title claims description 14
- 150000007513 acids Chemical class 0.000 title description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims 1
- -1 alkali metal sulfite Chemical class 0.000 description 40
- 239000000047 product Substances 0.000 description 19
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical class NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 235000010265 sodium sulphite Nutrition 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 6
- 229940001584 sodium metabisulfite Drugs 0.000 description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000004181 carboxyalkyl group Chemical group 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical class NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000008121 dextrose Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WRUZLCLJULHLEY-UHFFFAOYSA-N N-(p-hydroxyphenyl)glycine Chemical compound OC(=O)CNC1=CC=C(O)C=C1 WRUZLCLJULHLEY-UHFFFAOYSA-N 0.000 description 1
- 229910017711 NHRa Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005111 carboxyalkoxy group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical group O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 101150009274 nhr-1 gene Proteins 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001047 purple dye Substances 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 229940044609 sulfur dioxide Drugs 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/46—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
Definitions
- the presentinvention pertains to storage stable azine developers and more particularly to the stabilization of 4,6-diamino metanilic'acid developers by crystallizing the same from an aqueous solution containing an alkali metal sulfite on the one hand and an alkali metal bisulfite on the other hand.
- the azine process as contemplated by the aforementioned patents has many attributes to recommend it.
- the dye images obtained are much more stable, particularly to acid fumes than are the dye images obtained from quinoneimines and azomethines.
- 4,6-diamino metanilic acids which are storage stable in the dry state and which are obtained by crystallization from an aqueous solution containing an alkali metal sulfite and an alkali metal bisulfite, and the use of the same as azine developers, constitute the purposes and objects of the present invention.
- R is hydrogen or alkyl, i. e., methyl, ethyl, propyl, butyl, amyl or the like and R1 is an aliphatic radical such as alkyl as above, carboxy alkyl, such as carboxy methyl, carboxy ethyl, and the like; hydroxy alkyl, such as hydroxy ethyl, hydroxy propyl, and the like; aryl such as phenyl, toluyl and the like; carboxy alkyl aryl, such as carboxy methyl phenyl, carboxy ethyl phenyl, and the like, carboxy alkoxy aryl, such as carboxy methoxy phenyl, carboxy ethoxy phenyl; hydroxy alkyl aryl, such as hydroxy methyl phenyl, hydroxy ethyl phenyl, and the like; and hydroxy alkoXy aryl, such as hydroxy
- Examples of such developers are 2-phenylamino-4-(B- hydroxyethylamino)-6-phenylamino metanilic acid; 4,6- dimethylamino metanilic acid; 4,6-diphenylamino metanilic acid; 4,6-di(,B-hydroxyethylamino)metanilic acid; 4- (B-hydroxyethylamino) '6 (4 carboxymethoxyphenylamino)metanilic acid; 4-(o-rnethoxyphenylamino)-6-(pmethoxyphenylamino)metanilic acid and the like.
- the storage stable crystalline products referred to above are readily made from the 4,6-diamino metanilic acids by dissolving the latter in a hot aqueous solution containing alkali metal sulfite on'the one hand, such as potassium suliite, sodium sulfite and the like, and an alkali metal bisulfite on the other hand, such as sodium metabisulfite, potassium metabisulfite and the like, cooling the solution and filtering the needle-like crystals which are formed.
- alkali metal sulfite on'the one hand, such as potassium suliite, sodium sulfite and the like
- an alkali metal bisulfite such as sodium metabisulfite, potassium metabisulfite and the like
- crystals may be purified by washing with a solution of an alkali metal sulfite and bisulfite in water, followed by further washing with a low boiling organic solvent, such as isopropanol or mixtures thereof with methanol or ethanol.
- a low boiling organic solvent such as isopropanol or mixtures thereof with methanol or ethanol.
- the product is then dried, either in a stream of air or in vacuum.
- more than one mol of the bisulfite should be used per mol of the 4,6-diamino metanilic acid.
- an excess-of the alkali metal sulfiteup to a saturated solution thereof is recommended for best results.
- the storage stable products are utilized in the formulation of photographic developers in the same manner as.
- the de- Example I 2300 parts of water and 150 parts by volume of concentrated ammonium hydroxide are heated to 85 95 C. in an open container equipped for agitation. 600 parts of sodium hydrosulfite are gradually introduced in small portions while insuring that each portion dissolves before the next succeeding addition. When a solution has been obtained, 152 parts of the potassium salt of 2-phenylamino-4(e-hydroxyethylamino) 5 nitrobenzenesulfonic acid are cautiously introduced in small portions. Concentrated ammonium hydroxide is also added at intervals to maintain the pH of the solution between 7 and 8.
- aceticacid is-added to reduce the pH to from 5 to '6 (Acetic acid should be added until the solution assumes a distinct amber or brown color.)
- the reaction mixture is now decolorized, filtered and the filtrate treated with concentrated hydrochloric acid to efiect crystallization of the product.
- the suspension is cooled and filtered and the, collected solid thoroughly washed with a cold, concentrated solution of sulfur-dioxide in distilled water.
- the yield is approximately 83 parts of what'appears to be the addition product of 4-(B-hydroxyethylamino)-- phenylamino metanilicacid.
- Example III parts of 4,6-diphenylamino metanilic acid (prepared according to the procedure of U. S. P. 2,486,440) were dissolved in a solution of 110 parts of sodium sulfite and 80 parts of sodium metabisulfite in 700 parts of hot water. The resutling solution was allowed 'to cool slowly.
- the crystalline solid was collected by filtration and thoroughly washed with a cold solution of parts of sodium metabisulfite in 350 parts of water. It was then further washed with isopropanol and dried.
- the white crystalline product thus obtained is the bisulfite addition product of 4,6-diphenylamino metanilic acid and is extremely stable to oxidation under normal storage conditions.
- Example I The procedure is the same as in Example I], excepting that there is used an equivalent amount of -4',6-di(p-hydroxyethylamino metanilic acid.
- A'photo'graphic silver halide emulsion is exposed and developed in a black and white developer.
- the residual silver halide is re-exposedand developed in a developer of the following composition: g Sodium carbonate (monohydrate) parts Potassium br do 2 Water to make 1000 parts.
- the film after development is bleached with a ferricyanide bleach and fixed in an acid hardening fixer.
- a positive azine dye image completely free from stain is thus obtained.
- R1 is selected from the class consisting of hydrogen and aliphatic radicals
- R2 is selected from the class consisting of hydrogen, alkyl and aromatic radicals
- R3 is selected from the class consisting of aromatic radicals, a ring carbon atom of which is directly linked to the nitrogen atom and aliphatic radicals, a carbon atom of which is directly linked to the nitrogen atom, said carbon atom being substituted by at least two hydrogen atoms
- Y is selected from the class consisting of hydrogen, sulfo and carboxy.
- the storage stable compound which results from crystallizing 4,6-diphenylamino metanilic acid from an aqueous solution containing sodium sulfite and sodium bisulfite.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent fiice 2,727,062 Patented Dec. 13, 1955 STORAGE STABLE 4,6-DIAM1NO NIETANILIC ACIDS Vsevolod Tulagin, Binghamton, N. Y., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application May 26, 1954, Serial .No. 432,601
5 Claims. (Cl. 260-509) The presentinvention pertains to storage stable azine developers and more particularly to the stabilization of 4,6-diamino metanilic'acid developers by crystallizing the same from an aqueous solution containing an alkali metal sulfite on the one hand and an alkali metal bisulfite on the other hand.
Schmidt and Tulagin, in their U. S. P. 2,486,440 granted November 1, 1949, and Gunther, in his U. S. P. 2,570,116 granted October 2, I951, disclose that the development of light sensitive photographic material in color, wherein the color is imparted by an azine dye, is best effected by the utilization, asthe color developer, of 2,4- diamino anilines. It is emphasized in both these patents that the most 'e'fiectivedevelopers within this general category are those containing a sulfo group meta to the primary amino group, to wit, the metanilic acid derivatives.
The azine process as contemplated by the aforementioned patents has many attributes to recommend it. For example, the dye images obtained are much more stable, particularly to acid fumes than are the dye images obtained from quinoneimines and azomethines. However, the commercial exploitation and acceptance of this method'have been, to a great extent, retarded by the fact that the 2,4-diamino anilines are very unstable products and deteriorate rapidly on storage.
It has been possible for several years to prepare the azine developers in 'a high state of purity. It has not been possible, however, Ito stabilize these developers or to preserve them during storage despite the great amount of work contributed to 'thisproflblem. Thus, after as little as six monthsstorage in the dry state, the developers become a deep purple. A serious consequence of this transformation resides in the staining of the .highlight or transparent portions of the azine film by the purple dyes so obtained. As a result, the azinematerials 'displaya pink toe or a pink highlight. The matter is further aggravated by the fact that the degradation of the developer is not of a limited nature but progresses indefinitely until the developer finally becomes completely useless even when carefully stored in the dried state.
It has been suggested that stability be imparted to the developers by the employment of known preservatives and, to this end, there have been used-dextrose, hydroxylamine, p-hydroxyphenyl glycine and Rongalite, among others. It was found that even it some of these agents tended to effect stabilizatiomatthe same time they injected some other problem which srend'ered their use intolerable. For example, :dextrose, pehydroxyphenyl glycine and Rongalite decrease the development potential. Hydroxylamine, conversely, causes-a'serious loss in color rendition by augmenting proximity development.
The particular problem involved was recognized and discussed in-Guntlrer s U. S.-P. 2,656,272 granted October 20, 1953. Gunther-was aware of the ineffectiveness of preserving agents and sought to solve the difliculty by employing sodium 'metaborate as "the sole alkali for the developer. While the Gunther method permitted the realization of some stability, it was far from optimum and this is self-evident from a consideration of paragraph 1, column 6 of the patent.
Because of the seriousness of the developer instability and my recognition that the tactics previously followed had not yielded the result desired, I proposed to investigate the possibility of stabilizing the developer by chemically converting the same. I found that the 4,6-diamino metanilic acids readily formed crystals in aqueous solutions contaning an alkali metal sulfite and an alkali bisulfite, and that surprisingly such crystals when in the dry condition were remarkably storage stable. Such crystals, for instance, could be stored for prolonged periods of time prior to use, and when incorporated in the developer solution reverted to the 4,6-diamino metanilic acid structure without loss of developing power.
4,6-diamino metanilic acids which are storage stable in the dry state and which are obtained by crystallization from an aqueous solution containing an alkali metal sulfite and an alkali metal bisulfite, and the use of the same as azine developers, constitute the purposes and objects of the present invention.
The 4,6-diarnino metanilic acids contemplated herein are those described in the aforementioned U. S. Patents 2,486,440 and 2,570,116. These compounds may be typified by the following structural formula:
NRR
HOaS
Y NHR1 1km wherein R is hydrogen or alkyl, i. e., methyl, ethyl, propyl, butyl, amyl or the like and R1 is an aliphatic radical such as alkyl as above, carboxy alkyl, such as carboxy methyl, carboxy ethyl, and the like; hydroxy alkyl, such as hydroxy ethyl, hydroxy propyl, and the like; aryl such as phenyl, toluyl and the like; carboxy alkyl aryl, such as carboxy methyl phenyl, carboxy ethyl phenyl, and the like, carboxy alkoxy aryl, such as carboxy methoxy phenyl, carboxy ethoxy phenyl; hydroxy alkyl aryl, such as hydroxy methyl phenyl, hydroxy ethyl phenyl, and the like; and hydroxy alkoXy aryl, such as hydroxy methoxy phenyl, hydroxy ethoXy phenyl and the .like; R2 is an alkyl group substituted by a'hydrophilic group such as carboxy alkyl, such as carboxy methyl, carboxy ethyl and the like; hydroxy alkyl, such as hydroxy ethyl, hydroxy propyl and the like; sulfo alkyl such as sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl and the like, and Y is hydrogen, alkyl as above, sulfo or carboxy.
Examples of such developers are 2-phenylamino-4-(B- hydroxyethylamino)-6-phenylamino metanilic acid; 4,6- dimethylamino metanilic acid; 4,6-diphenylamino metanilic acid; 4,6-di(,B-hydroxyethylamino)metanilic acid; 4- (B-hydroxyethylamino) '6 (4 carboxymethoxyphenylamino)metanilic acid; 4-(o-rnethoxyphenylamino)-6-(pmethoxyphenylamino)metanilic acid and the like.
The storage stable crystalline products referred to above are readily made from the 4,6-diamino metanilic acids by dissolving the latter in a hot aqueous solution containing alkali metal sulfite on'the one hand, such as potassium suliite, sodium sulfite and the like, and an alkali metal bisulfite on the other hand, such as sodium metabisulfite, potassium metabisulfite and the like, cooling the solution and filtering the needle-like crystals which are formed. These crystals may be purified by washing with a solution of an alkali metal sulfite and bisulfite in water, followed by further washing with a low boiling organic solvent, such as isopropanol or mixtures thereof with methanol or ethanol. The product is then dried, either in a stream of air or in vacuum. Preferably, to insure a good yield of such needle-like products, more than one mol of the bisulfite should be used per mol of the 4,6-diamino metanilic acid. Similarly, an excess-of the alkali metal sulfiteup to a saturated solution thereof is recommended for best results. e
The particular structure of the storage stable crystalline products is not known, nor has the same been ascertained, although efiorts to resolve the structure have been attempted. Ithas-been found, as previously stated, that the storage stable products hereof precipitate as needles, whereas the 4,6-diamino metanilic acids are isolated in the form of plates. It is also known that the products hereof have extraordinary stability in the dry state as compared to the 4,6-diamino metanilic acids per se. it is my conviction, drawn from this phenomena, that the products are bisulfite addition products. It is to be pointed out, in this connection, that both 1,3-diamino benzene and 1,2-diamino benzene add three mols of sodium bisulfite to form non-aromatic addition complexes of the following constitution:
SOsNa and The azine developers, although they are triamines, possess both of the above structures and would, therefore, be expected to give non-aromatic alkali metal bisulfite addition complexes. The much higher resistance to oxidation exhibited by these addition complexes would then be completely explained by the fact that the aromatic structure has been destroyed. Thus, it is pertinent to observe that such compounds as ethylenediamine, ethanolamine and other purely aliphatic diamines and triamines are highly resistant to oxidation. It would, therefore, appear that the new compounds hereof are bisulfite addition products Whose resistance to oxidation is traceable to the conversion of the aromatic form of the 4,6-diamino metanilic acids into an aliphatic form. However, analyses have not definitely established that such addition products are formed and, hence, I consider it preferable to characterize the products by their mode of formation.
The storage stable products are utilized in the formulation of photographic developers in the same manner as.
Thus, the de- Example I 2300 parts of water and 150 parts by volume of concentrated ammonium hydroxide are heated to 85 95 C. in an open container equipped for agitation. 600 parts of sodium hydrosulfite are gradually introduced in small portions while insuring that each portion dissolves before the next succeeding addition. When a solution has been obtained, 152 parts of the potassium salt of 2-phenylamino-4(e-hydroxyethylamino) 5 nitrobenzenesulfonic acid are cautiously introduced in small portions. Concentrated ammonium hydroxide is also added at intervals to maintain the pH of the solution between 7 and 8. When reduction is complete, aceticacid is-added to reduce the pH to from 5 to '6 (Acetic acid should be added until the solution assumes a distinct amber or brown color.) The reaction mixture is now decolorized, filtered and the filtrate treated with concentrated hydrochloric acid to efiect crystallization of the product. The suspension is cooled and filtered and the, collected solid thoroughly washed with a cold, concentrated solution of sulfur-dioxide in distilled water.
700 parts of hot water (distilled), 100' parts of sodium sulfite (anhydrous) and 50 parts of sodium metabisulfite are run into a containerand the solution heated to boiling. The cake obtained by the previous reduction of. the
2-phenylamino-4-(fi-hydroxyethylamino) 5 nitrobenzenesulfonic acid is now introduced. (This cake is pale yellow in color and not pink.) After the components have dissolved, the boiling solution is treated with 150 parts of sodium metabisulfite. When asolution has been obtained, it is set aside to cool slowly without disturbance.
After 5 to 20 hours, the mixture is filtered. The collected crystalline solid is washed with several portions of a solution containing 100 parts of sodium metabisulfite and 50 parts of sodium sulfite in 350 parts of water. The solid is then washed withtwo portions-of isopropanol and one of methanol and dried either in a stream of air in a vacuum. v I
The yield is approximately 83 parts of what'appears to be the addition product of 4-(B-hydroxyethylamino)-- phenylamino metanilicacid.
Exajriple II V The procedure is the same as in Example I, excepting. that there is used 150 parts of the potassium salt of-2,4.-
climetnylamino-S-nitrobenzenesulfonic acid in lieu of the potassium salt of 2-phenylamino-4-(fl-hydroxyethylamino)-5-nitrobenzenesulfonic acid.
Example III parts of 4,6-diphenylamino metanilic acid (prepared according to the procedure of U. S. P. 2,486,440) were dissolved in a solution of 110 parts of sodium sulfite and 80 parts of sodium metabisulfite in 700 parts of hot water. The resutling solution was allowed 'to cool slowly.
The crystalline solid was collected by filtration and thoroughly washed with a cold solution of parts of sodium metabisulfite in 350 parts of water. It was then further washed with isopropanol and dried.
The white crystalline product thus obtained: is the bisulfite addition product of 4,6-diphenylamino metanilic acid and is extremely stable to oxidation under normal storage conditions.
Example I The procedure is the same as in Example I], excepting that there is used an equivalent amount of -4',6-di(p-hydroxyethylamino metanilic acid.
p Example V I.
A'photo'graphic silver halide emulsion is exposed and developed in a black and white developer. The residual silver halide is re-exposedand developed in a developer of the following composition: g Sodium carbonate (monohydrate) parts Potassium br do 2 Water to make 1000 parts.
The film after development is bleached with a ferricyanide bleach and fixed in an acid hardening fixer. A positive azine dye image completely free from stain is thus obtained.
Various modifications of the invention will occur to operators in this field. Thus, it is self-evident that the procedure outlined above may be utilized for the stabilization of any of the 4,6-diamino metanilic acids described in U. S. Patents 2,486,440 and 2,570,116. I, therefore, do not intend to be limited in the patent granted except as necessitated by the appended claims.
I claim:
1. The storage stable products which result from crystallizing a 4,6-diamino metanilic acid from an aqueous solution containing an alkali metal sulfite and an alkali metal bisulfite.
2. The storage stable produ :ts which result from crystallizing, from an aqueous solution containing an alkali metal sulfite and an alkali metal bisulfite, compounds of the following formula:
llqR Rz HOaS NHRa
wherein R1 is selected from the class consisting of hydrogen and aliphatic radicals, R2 is selected from the class consisting of hydrogen, alkyl and aromatic radicals, R3 is selected from the class consisting of aromatic radicals, a ring carbon atom of which is directly linked to the nitrogen atom and aliphatic radicals, a carbon atom of which is directly linked to the nitrogen atom, said carbon atom being substituted by at least two hydrogen atoms, and Y is selected from the class consisting of hydrogen, sulfo and carboxy.
3. The storage stable product which results from the crystallization of 4-(B-hydroxyethylamino)-6-phenylamino metanilic acid from an aqueous solution containing sodium sulfite and sodium bisulfite.
4. The storage stable compound which results from the crystallization of 4,6-dimethylamino metanilic acid from an aqueous solution containing sodium sulfite and sodium bisulfite.
5. The storage stable compound which results from crystallizing 4,6-diphenylamino metanilic acid from an aqueous solution containing sodium sulfite and sodium bisulfite.
References Cited in the file of this patent UNITED STATES PATENTS 1,938,022 Huismann Dec. 5,1933 2,592,363 Weissberger Apr. 8, 1952 2,603,657 Vinton July 15,1952 2,611,785 Gunther Sept. 23,1952 2,656,272 Gunther Oct. 20, 1953
Claims (1)
1. THE STORAGE OF PRODUCTS WHICH RESULTS FROM CRYSTALLIZING A 4,6-DIAMINO METALLIC ACID FROM AN AQUEOUS SOLUTION CONTAINING AN ALKALI SULFITE AND AN ALKALI METAL DISULFITE.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US432601A US2727062A (en) | 1954-05-26 | 1954-05-26 | Storage stable 4, 6-diamino metanilic acids |
| US464871A US2728669A (en) | 1954-05-26 | 1954-10-26 | Photographic developer containing storage stable 4,6-diamino metanilic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US432601A US2727062A (en) | 1954-05-26 | 1954-05-26 | Storage stable 4, 6-diamino metanilic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2727062A true US2727062A (en) | 1955-12-13 |
Family
ID=23716829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US432601A Expired - Lifetime US2727062A (en) | 1954-05-26 | 1954-05-26 | Storage stable 4, 6-diamino metanilic acids |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2727062A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3790381A (en) * | 1971-09-24 | 1974-02-05 | Minnesota Mining & Mfg | Alkaline photographic developer concentrate |
| US5041631A (en) * | 1989-09-20 | 1991-08-20 | Basf Aktiengesellschaft | Process for the preparation of 2-alkylamino-4-aminobenzenesulfonic acids |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1938022A (en) * | 1930-02-27 | 1933-12-05 | Ig Farbenindustrie Ag | Tanning agent |
| US2592363A (en) * | 1947-05-23 | 1952-04-08 | Eastman Kodak Co | P-phenylenediamine developer containing nu-alkylacetamido ethyl substituent |
| US2603657A (en) * | 1951-05-05 | 1952-07-15 | Du Pont | N-alkyl-n-(sulfophenylthio) alkylaminoanilines |
| US2611785A (en) * | 1952-09-23 | N-substituted x | ||
| US2656272A (en) * | 1950-11-30 | 1953-10-20 | Gen Aniline & Film Corp | Stabilized azine photographic developers containing sodium metaborate as the sole alkali |
-
1954
- 1954-05-26 US US432601A patent/US2727062A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2611785A (en) * | 1952-09-23 | N-substituted x | ||
| US1938022A (en) * | 1930-02-27 | 1933-12-05 | Ig Farbenindustrie Ag | Tanning agent |
| US2592363A (en) * | 1947-05-23 | 1952-04-08 | Eastman Kodak Co | P-phenylenediamine developer containing nu-alkylacetamido ethyl substituent |
| US2656272A (en) * | 1950-11-30 | 1953-10-20 | Gen Aniline & Film Corp | Stabilized azine photographic developers containing sodium metaborate as the sole alkali |
| US2603657A (en) * | 1951-05-05 | 1952-07-15 | Du Pont | N-alkyl-n-(sulfophenylthio) alkylaminoanilines |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3790381A (en) * | 1971-09-24 | 1974-02-05 | Minnesota Mining & Mfg | Alkaline photographic developer concentrate |
| US5041631A (en) * | 1989-09-20 | 1991-08-20 | Basf Aktiengesellschaft | Process for the preparation of 2-alkylamino-4-aminobenzenesulfonic acids |
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