US 2566259 A
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Patented Aug. 28, 1951 8-ALKYL SULFONAMIDOETHYL-N-SUBSTI- TUTED SATURATED HETEROCYCLIC DE- VELOPERS John R. Thirtle and Arnold Weissberger, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application September 25, 1948, Serial No. 51,316
This invention relates to photographic developers and more particularly to saturated heterocyclic developers containing a p-alkylsulfonamidoethyl group on the nitrogen atom of the heterocyclic ring.
It is known that photographicdevelopers of the p-phenylene diamine type are valuable compounds for producing fine-grain black and white photographic images and also that these compounds, especially when they contain alkyl substituents on one of the nitrogen atoms are useful as developers in producing colored photographic images. A serious disadvantage of the p-phenylene diamine developers is that they are highly allergenic, that is, they are poisonous to the human skin and are therefore somewhat dangerous to use.
The allergenic properties of the p-phenylene diamine developers may be overcome by substituting a sulfonamide group or an amino sulfonyl group in the alkyl group on the nitrogen atom of p-phenylene'diamine as described in Weissberger U. S. Patent 2,193,015, granted March 12, 1940. These substituted p-phenylene diamine developers, however, are sometimes too low in developing strength (or reduction potential) so that it is difiicult to obtain with them black and white or dye images of sufliciently high density and contrast.
It is therefore an object of the present invention to provide a new class of photographic developing agents. A further object is to provide developing agents which produce coupled dye images having the desired characteristics.
These objects are accomplished by the present invention by the use as developing agents of compounds having the following general formula:
where X represents CH2-- or a single chemical bond, Y represents hydrogen or a methylgroup and R represents a lower alkyl group. By lower alkyl group, we mean a methyl, ethyl or propyl group.
4 Claims. (CI. 95-88) Compounds of this class which may be used according to our invention are as follows:
5-amino'1- B-methylsulfonamidoethyl 2,3-dihydroindole The specific compounds illustrated above were prepared as follows:
' p-Methylsulfonamidoethyl bromide The J-bromoethylamine hydrobromide (Heilbron I (1943), p. 294) (513 g.; 2.5 moles) was dissolved in 250 cc. of Water in a 3-1. B-necked flask equipped with a stirrer, thermometer and two dropping funnels. Through the latter were added 343.8 g. (3.0 moles) of methane sulfonyl chloride and 220 g. of sodium hydroxide in 800 cc. of water keeping the temperature at 0-5 and the pH slightly on the alkaline side.
The reaction mixture was stirred for one hour longer, then it was made acid to Congo red by adding 6.5 cc. of concentrated hydrochloric acid. The crystals were collected at 0 on an Lil-cm. Biichner funnel and washed quickly with 200 cc. of cold Water. two 500-cc. portions of ether and the moist crystals were taken up in 2 l. of ether. The ether layers were combined, dried over anhydrous so- The filtrate was extracted with 3 dium sulfate and cooled to 20. When crystallization started, the mixture was diluted with 2 l. of petroleum ether (B. P. 30-35).
After chilling at 5 for one-half hour, the crystals were collected on a Biichner funnel and dried in air overnight. The yield was 371 g. (73.5%) of glistening white plates melting at 47-49".
1- (e-Methylsulfonamidoethyl) -1,2,3,4-tetrahydroquinoline A mixture of 51 g. (0.384 mole) of l,2,3,4-tetrahydroquinoline, 77.5 g. (0.384 mole) of ft-methylsulfonamidoethyl bromide, 35.4 g. (0.422 mole) of sodium bicarbonate,.65 cc.'of water and 180 .cc. of 95% alcohol was heated on a steam bath at reflux in a l-l. round-bottomed flask for 16 hours.
The reaction mixture was concentrated under a vacuum on the steam bath untilall of the alcohol and some of the water had been removed. The residue was partitioned between 50 cc of water and 200 cc. of ether. The aqueous layer was extracted with two 25-00. portions of ether and the combined ether solutions were dried over sodium sulfate. The ether was removed on a steam bath, finally at 6 mm. for one-half hour. The residue weighed 91.4 g. (93.7%), crystallized on standing and melted at 45-48.
1101 NH2 NaNOz Onwm c1 c1 CH2 NaOCOCH N201 CH2 I 01 N famic acid was added. After 5 minutes longer the diazonium solution was poured with stirring into a solution of 56.1 g. (0.221 mole) of l-(fl-methylsulfonamidoethyl) -1,2,3,4-tetrahydroquinoline in 60 cc. of concentrated hydrochloric acid and 100 cc. of water at 5. Four successive 100-g. portions ,of anhydrous sodium acetate were added. The thick tarry precipitate was worked with a 4 stirring rod for a few minutes and then chilled in the ice bath for 1 hours.
The liquid phase was decanted and the residue was stirred mechanically with 1500 cc. of ethanol while heating on the steam bath for 15 minutes. The tarry material crystallized but did not all dissolve. After chilling in the refrigerator overnight the solid was collected on an 18-cm. Biichner funnel and most of the solvent was re moved. The solid was dissolved in 2500 cc. of boiling 95% alcohol, the solution was filtered and the filtrate chilled for 3 days at 0 although this time may be shortened.
The hard, granular red crystals were collected, washed with cc. of 95% alcohol and dried in the steam cabinet. The yield was 72 g. (76.2%), M. .P. 149--150 (softening at 147). The filtrate was diluted with 1500 cc. of water and chilled overnight giving 6.0 g. more, M. P. 146-149 which was satisfactory for use.
The total yield was 78 g. (82.5
Seventy-two grams (0.168 mole) of 6-(2,5-dichlorophenylazo) 1 ([3 methylsulfonamidoethyl) -1,2,3,4-tetrahydroquinoline, '100 cc. of absolute alcohol, a liberal amount of Raney nickel catalyst and 1.0 g. of sodium carbonate were placed in the small hydrogenation apparatus and reduction was eifected at 80 and 50 pounds per square inch pressure.
The reaction mixture-was filtered-and the'catalyst was washed with 25 cc. of absolute alcohol. The filtrate was concentrated on a steam bath under a vacuum using a 3-1. round-bottomed flask. The residual oil was heated at reflux with l -l. of benzene for 15 minutes and filtered from a little insoluble tar. The filtrate was cooled and the inside of the flask was scratched. After standing overnight, the tan crystals were collected on a Biichner funnel and dried in air. The yield was 32 g. '(71 M. P. -1'12.
6 -aminO-1 (,8-methylsulfonamidoethyl) 18.104.22.168-
tetrahydroquinoline hemisulfate S-amino-1a(/8-methylsulfonamidoethyl) -1,2,3,- 4-tetrahydroquinoline (26.9 g.; 0.1 mole) was dis- Solved in 400 cc. of hot 95% alcohol and asolunamidoethyl)1,2,3,4-tetrahydroquinoline tion of 2.8 cc. (0.05 mole) of concentrated sulfuric acid in cc. of water was added rapidly with mixing. The resulting solution deposited crystals in a few seconds while still hot. The mixture was chilled to 5 for A hour. The crystals were col lected on a Biichner funnel, washed with two 50- cc. portions of 95% alcohol and 100 cc. of ether.
After drying in a vacuum desiccator over sulfuric acid, the pinkish-white crystals weighed 29.0
g. (91.2%) and melted at 179-182.
4 tetrahydr0quin0line A mixture of 22.1 g. (0.15 mole) of 7-methy1-1,- 2,3,4-tetrahydroquinoline, 30.3 g. (0.15 mole) of fi-methylsulfonamidoethyl bromide, 13.9 g. (0.165 mole) of sodium bicarbonate, cc. of water and 70 cc. of 95% alcohol was treated at reflux in a 500-cc. flask for 2 hours.
The reactionmixture was concentrated under a vacuum on the steam bath until most of the water was removed. The residue was partitioned between 100 cc. of chloroform and 100 cc. of water. The aqueous layer was extracted with 50 cc. of chloroform and the combined extracts were dried over magnesium sulfate. Concentration gave 37 g. of an oil which was fractionally distilled. The main fraction, boiling at 210 -225/ 1.5 mm., nearly all at 223/1.5 mm., weighed 22.8 g. (57%).
6 (2,5 dichlorophenylazo) #7 methyl I-(pmethylsuljonamidoethyl) 1,2,3,4 tetmhydroquinoline H01 NH1+ NaNoz Qmoi i CH2 o1 0H7 NSOCOCH; N201 1 H N (humus 020B;
The diazonium solution was added slowly to 22.1 g. (0.0825 mole) of 7-methyl-1-(B-methylsulfoin 25 cc. of concentrated hydrochloric acid and 500 cc. of water at 05. When about half of the diazonium solution had been added the reaction mixture thickened. One hundred grams of sodium acetate 1 was added, followed by the rest of the diazonium solution and 100 g. more of sodium acetate.
After 2 hours at 0", the dye was collected and washed with three ZOO-cc. portions of cold water. After drying in the steam cabinet the dye weighed 30 g. but was somewhat tacky. The material was dissolved in 2-1. of hot alcohol and kept overnight at 0. The beautiful fine red crystals were collected and washed with 50 cc. of alcohol. The yield was 11.1 g. (30.5% M. P. 183-484".
6-amino-7-methyl 1 3 methylsulfonamidoethyl) 12,3,4-tetrahydroquinoline hemz'sulfate hydrate Two and two-tenths grams (0.005 mole) of 6- (2,5-dichlorophenylazo) -7-methyl-1 (pi-methylsulfonamidoethyl) -1,2,3,4-tetrahydroquinoline, 20 cc. of absolute ethanol, a liberal amount of Raney nickel catalyst and a little sodium carbonate were placed in a hydrogenation apparatus and redution was effected at 80 and 50 pounds per square inch pressure. 1 I
The reaction mixture was filtered and the apparatus washed with 5 cc. of absolute ethanol. A solution of 0.14 cc. (0.0025 mole) of concentrated sulfuric acid in 1 cc. of water was added- After cooling in an ice bath for one half hour the crystalline precipitate was collected and washed with two 5-cc. portions of cold alcohol. After drying in a vacuum desiccator over sulfuric acid the Pure white crystals weighed 1.25 g. (71.4%) and analysis identified the material as the hemisulfate hydrate.
1 (li-methylsuljonamidoethyl) -2,3-dihydroindole alcohol ZHlNESOiC A mixture of 4.8 g. (0.04 mole) of 2,3-dihydroindole, 8.1 g. (0.04 mole) of p-methylsulfonamidoethyl bromide,'3.7 g; (0.044 mole) of sodium bicarbonate, 7.5 cc. of water and 20 cc. of a1- cohol was heated at reflux on the steam bath for 1 hour.
The reaction mixture was concentrated under a vacuum on a steam bath to an oil. The oil was separated between 25 cc. of water and 25 cc. of ether. The aqueous layer was extracted with 25 cc. of ether and the combined extracts were dried over sodium sulfate, concentrated and distilled. The main fraction was 7.3 g. (76%) boiling at 216-219/1.5 mm. Hg.
5 (2,5 dichlorophenylazo) -1-(,6-methylsulfonamz'doethyl) -2,3-dihy droindole nor @NIEU NaNOr N201 01 01 C1 CH2 hH NHSOzCH3 a 01 CH2 The clear diazonium salt solution was added to a solution of 7.0 g. (0.029 mole) of l-(p-methylsulfonamidoethyl)-2,3-dihydroindo1e in 15 cc. of concentrated hydrochloric acid and 25 cc. of water at -'5 with shaking. In a few minutes crystals formed and solidified the reaction mixture. After chilling in an ice bath for one-half hour, the crystals were collected and drawn to a dense cake. The moist product was dissolved in 200 cc. of acetone and 50 cc. of water on a steam bath and the solution chilled.
The crystals were collected, washed with two 25-00. portions of acetone and dried in a steam cabinet. The yield was 8.1 g. (65.3%) of purple needles with a copper luster which melted at 145-147".
0112 Hz H2804 HzN CH2 Four and one-tenth grams (0.01 mole) of (2,5-dichlorophenylazo) -1- ([3 methylsulfonamidoethyl) -2,3-dihydroindole, 50 cc. of absolute alcohol and Raney nickel catalyst were placed in the hydrogenation apparatus and reduction was effected at 70, 40 pounds per square inch pressure in minutes.
The catalyst was removed by filtration and Washed with 5 cc. of 95% alcohol. A solution of 0.28 cc. (0.005 mole) of concentrated sulfuric acid in 5 cc. of 95% alcohol was added.
The slurry was chilled overnight and the solid was collected and washed with 10 cc. of 95% alcohol followed by 5 cc. of 95% alcohol, then two 5-cc. portions of acetone. After drying in the steam cabinet 1.9 g. (63%) of pure white product was obtained. Analysis indicated the compound to be 5 -amino-1-(fl rnethylsulfonamidoethyl)- 2,3-dihydroindole hemisulfate.
When used for the formation of colored photographic images, the developers of our invention may be used in conjunction with any well-known coupler compounds such as those described in Fischer U. S. Patent 1,102,028, granted June 30, 1914, Mannes and Godowsky U. S. Patent 8 2,108,602, granted February 15, 1938, or Mannes and Godowsky and Peterson U. S. Patent 2,115,394, granted April 26, 1938, and 2,126,337, granted August 9, 1938. I
The following example illustrates adevelopin solution which may be used according to our invention.
A. 6 Amino-1-(,8-methylsulfonamidoethyl)- 1,2,3,4-tetrahydroquinoline grams 2.5 Sodium sulfite (anhydrous) grams 2 Sodium carbonate grams 30 Potassium bromide grams 2 Water to 1 liter B. Coupler (o-phenyl phenol) grams 2 Sodium hydroxide (10% solution) cc. 20
For use, B is added to A.
The developing agents described in the present application may be used to form photographic images, the development of exposed silver halide contained in the usual gelatin carrier or in carriers such as collodion, water-permeable cellulose ester or water-permeable synthetic resins. Our developing agents may be used with photographic films containing the coupler in the emulsion layer as described in Mannes and Godowsky U. S. Patent 2,304,940, granted December 15, 1942, or Jelley and Vittum U. S. Patent 2,322,027, granted June 15. 1943. When used in thisway, the developing solution of Part A in the above example is suitable.
It will be understood that the examples included herein are illustrative only and that our invention is to be taken as limited only by the scope of the appended claims.
1. A photographic developing solution comprising as the silver halide developing agent a compound having the formula:.
r (S HQNH S 01011;
and a compound which couples with the oxidation product of the developing agent to form a colored image.
2. A photographic developing solution comprising as the silver halide developing'agent a compound having the formula:
zEhNH S 020133 and a compound which couples with the oxidation product of the developing agent to form a colored image.
3. A photographic developing solution comprising as the silver halide developing agent a compound having the formula:
I C H4NH S 0 013;
and a compound which couples with the oxidan product of the v l p agent to form pound which couples with the oxidation product colored image. of the developing agent to form a colored image.
4. A developing solution for producing a, colored photographic image comprising a silver JOHN R, TI-IIRTLE. halide developing agent having the formula: 5 ARNOLD WEISSBERGER.
x Hm REFERENCES CITED 7 2 H The following references are of record in the Y 0 file of this patent:
UNITED STATES PATENTS ENHSmR Number Name Date where X is selected from the group consisting of 2163320 Wflmanns June 27, 1939 -CH2- and a single chemical bond, Y iS selected 2 193 015 weissberger Mar. 12 1940 from the roup co i i of hydrogen and 15 2,196,739 Peterson Apr, 9, 194
methyl and R is a, lower alkyl group, and a com-