US2552240A - N-beta-methylsulfonamidoethyl-p-phenylenediamines - Google Patents

Description

Patented May 8, 1951 N -fl-1\IETHYLSULFONAMIDOETHYL-p- PHEN YI-IENEDIAMINES Arnold Weissberger, Dudley B. Glass, and Paul W. Vittum, Rochester; N. Y., assignors to Eastman Kodak Company; Rochester, N. Y., a corporation of :Newflersey No Drawing. Application March 18, 1949, Serial No. 82,281

7 Claims. (01. 260-556) This invention relates to photographic devel-. opers and more particularly to photographic developers of the substituted p-phenylenediamine type.

This application is a continuation-in-part of: our application Serial No. 731,420, filed February 27, 1947, now U. S. Patent 2,548,574, which is a continuation-in-part of application Serial No. 654,528, filed March 14, 1946, now abandoned.

consisting of alkoxy groups and;substitutedalkoxW -roups; R1 represents a member selected% from the group consisting of hydrogen, alkyl groups, andwsubstituted alkyl groups; Rz represents an alkylene radical selected from the group consisting of ethylene and propylene; andlita represents a member selected from the group consisting of alkyl groups and hydrogen.

Specific compounds which we contemplateus- It is known that p-phenylenediamine photos 10 m include; graphic developers are valuable compounds for 1 02m producing fine grain black-and-white photographic images, and also, that these compounds, especially when they contain alkyl substituents, (OHl),NHs02oH,- are useful as developers in processes for produc- 002E m colored photographic images. The Phen- -1-amin0 3-ethoxy-N-ethyl N (18methylsulfonamideethyl). ylenediamine developers, however, have several amlme defects. A common difliculty encountered when 2 using these developers is their low activity and H2N N the low contrast and emulsion speed obtained 20 I \(CH)2NHSO CH3 with them. Other disadvantages are their low 00H. solubility in developing solutions and their aller- 4 in N meth 1 N (B methylsu1f namidoethy1).m genie character, that is, their poisonousness to anisidine the humanskin. I heselatter defects have. been 3, GZHE, solved,.. according. to v Weissberger U. S1 Patentl Y J 2,193,015, by adding. a. sulfonamidegroup. to one -Q of the nitrogen atoms. of p-phenylenediamine. CHmNHSO'flHg Developers of this, type, however, exhibit low d velo i g activity. 4-'amino'-'N-ethy1 N (B methylsulfonamidoethyl) -m- A principalob'ject. of. the. present invention amsldme istherefbre, to. provide new developing agents 4 O3H7 of the. substituted p-phenylenediamine type. hav- HQN ing high developing activity and which are capable of giving high-contrastand emulsion speed. o0 H1 (OHMNHS 02cm We have discovered that thev rate of develop- 4, 1N th 1 H ment with. sulfonamide substituted p-phenyleneammo' {Jmpoxy g fi gy h fff l y Onaml diaminesis remarkably increasedby substituting, an alk'oxy group in. the, benzene ring, in ortho 5? 02B: positionwith respect to the. primary amino group. These. novel compounds have the followinggen- 40 N: eral. formula: worn) zNHS'O 5011 X R, 4-'amino=3-metl1oxy-5 methyl-N-ethyl N (B methylsulfon amidoethylyanilin'e- H21: N- 7 RiNH'SmRp 6 1411.

wherein X represents a member selected from the group consistingttof hydrogen, alkylgroups; (OHZMNHSONHB alkoxy groups, and substituted alkoxy groups; Yrepresents a member selected from the group The preparation of these compounds is illuswas evaporated. The residue was distilled under t a by the p p o of 4-amino-3-eth0xyreduced pressure collecting the portion that N ethyl-N-(p-methylsulfonamidoethyl) -aniline, boiled at 105-110/1 mm. as the desired product. which may be synthesized by the following The yield was 80 per cent. methods: 5 N -ethyl-m-phenetidine.0ne mole of N-ethyl- NO: NH:

2 51 r on 00,115 catalyst 00,11,

NHCzHs or alternately: (b) C O CH; VBIKCHI) :NHzJIB 1 N flL N 2 I sM M 011.com l OH I OH hydrolyze CH CHgNHSOgCH; CH2CHINHSO2CH3 CHQOHZNH:

NCgH; NCzHs NCgH;

HONO CHaSO1C1 4- ocm, 00,115 7 00 B,

H: catalyst CHQGHNHSOQGH;

NCzH

The preparation of 4 amino N ethyl N- m-acetophenetide was boiled with 150 ml. of

(6 methylsulfonamidoethyl) m phenetidine water and 150 ml. of concentrated hydrochlorid (Compound 1) may be illustrated by the followacid for six hours. The reaction mixture was ing procedure: cooled, made alkaline with 200 m1. of 40% N-ethyZ-m-acet0phenetide.-A mixture of one caustic solution and the amine was extracted mole of m-phenetidine and one mole of ethyl with ether. The etheral solution was dried over iodide was warmed in a waterbath to 40 at solid sodium hydroxide and the ether was which temperature an exothermic reaction evaporated. The residue was distilled under rebegan. The temperature was allowed to rise duced pressure collecting the portion that boiled to and then was maintained at this temperaat, l48-150/l7 mm. as the desired product. The ture for one hour first by coolin and as the yield amounted to per cent. exothermic reaction subsided by warming. After N (5 mm'noethyl) N ethyl m phenotstanding overnight, the reaction mixture was 60 idine.--A mixture of 1 mole of N-ethyl-mstirred with 200 ml. of water and ml. of 40% phenetidine and 0.5 mole of fl-bromoethylamine caustic until all of the solid had gone into soluhydrobromide was stirred and heated at tion. The amines were extracted with ether, for two and one-half hours. At the end the etheral solution was dried over solid sodium of this time the reaction mixture was cooled hydroxide and the ether was evaporated. The 65 and 225 ml. of Water and 75 m1. of 40% caustic residue was added to 100 g. of-acetic anhydride solution were added. After all of the organic with stirring and cooling so that the temperasalts had dissolved, the product was extracted ture did not rise above 50. This mixture was with ether. The etheral solution was dried over heated on the steam bath for thirty minutes, solid sodium hydroxide and the ether was evapocooled and then stirred with 150 ml. of water 70 rated. The residue was distilled under reduced until all of the excess anhydride had decompressure collecting the portion that boiled at posed. The mixture was made alkaline with at 148-150/l7 mm. as the desired product. The 40% caustic solution and the product was exyield was 80 per cent.

tracted with ether. The etheral solution was N (5 aminoethyl) N ethyl m phenotdried over solid sodium sulfate and the ether m-phenetidine.---A mixture of 0.625 mole of N (,6 aminoethyl) N ethyl m phenetidine and 250 ml. of water was stirred vigorously, and 80 g. (0.7 mole) of methanesulfonyl chloride was added during a period of .30 minutes, the temperature of the reaction mixture being kept at l5i5 during the addition of the chloride. After each quarter of the acid chloride had been admitted, one-fourth of a solution of 28 g. (0.7 mole) of sodium hydroxide in 75 ml. of water was introduced. Ihe mixture was then stirred for two hours at -25 and made alkaline with ammonium hydroxide. The amide was extracted with chloroform, the chloroform solution was washed with water and dried over sodium sulfate. The chloroform was evaporated under reduced pressure. The residue of crude amide amounted to 90 per cen N ethyl N ([3 methylsuljonamidoethyU- 4 nitroso m phenetidinQ.-.+One half mole of N g ethyl N (5 methylsulfonamidoethyD- m-phenetidine was dissolved in a mixture of 140 ml. of concentrated hydrochloric acid and 500 ml. of hot water. This solution was cooled quickly to 5 and maintained at this tempera? ture while a solution of 39 g. (0.56 mole) of sodium nitrite in 50 ml. of water was added, with stirring, during a period of 20 minutes.

After standing at 5 for one hour, the reaction mixture was made alkaline with ammonium hydroxide. The precipitate was filtered with suction and washed with water. The moist product was recrystallized twice from 500 m1. portions of 3-A alcohol and dried in air. The yield was 85 per cent.

4 amino N ethyl N (5 methylsulfonamidoethyl) m phenetidine oxalate-Onehalf mole of N ethyl N (B methylsulfonamidoethyl) 4 nitroso m phenetidine was dissolved in 500 ml. of absolute alcohol and reduced in the presence of Raney Nickel at a a? hydrogen pressure of 45 lbs./in. and a temperature of 60. After the reduction was complete, the catalyst was filtered off and 0.5 mole of powdered, anhydrous oxalic acid was added. The mixture was warmed until all of the oxalic acid had dissolved and then was cooled to 0 and allowed to stand until crystallization was complete. The crystals were filtered off, washed with absolute alcohol and dried in a vacuum desiccator over sulfuric acid. The yield was 80 per cent.

4 amino N ethyl N ([3 methylsulfonamidoethyl) m anisidine (Compound 3), 4 amino 3,5 diethoxy N ethyl N ({3- methylsulfonamidoethyl) aniline (Compound 6) and 4 amino 3 methoxy 5 methyl- N ethyl N (B methylsulfonamidoethyl)- aniline, 3,5 diethoxyaniline and 3 methoxy- 5-methylaniline respectively.

4-amino -N-methyl-N (.B methylsulfonamidoethyl) -manisidine (Compound 2) can be prepared from m-anisidine and 4-amino-3-propoxy- N-propyl N (fi methylsulfonamidoethyl) -aniline (Compound 4) from 3-propoxyaniline by this procedure if instead of using ethyl iodide in the first step of the syntheses, methyl iodide is used for the first compound and propyl iodide is used for the second.

The introduction of more than one ethoxy group in the ortho positions with respect to the primary amino group as well as the introduction of an alkyl group in one ortho position and an alkoxy group in the other must be considered part of the present invention. Instead of ethoxy groups, other alkoxy groups may be used, in-

eluding alkoxy groups with additional substitucuts in the aliphatic radical, such as OI-I, C1, OR, etc.

Where we refer to lower alky we mean a methyl, ethyl or propyl group, and where we refer to lower alkoxy we mean a methoxy, ethoxy or propoxy group.

When used for the formation of colored photo,- graphic 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, June 30, 1914; Mannes and Godowsky U. S. Patent 2,108,602, February 15,1938;Mannes, Godowsky and Peterson U. S. Patent 2,115,934, April 26, 1938; and Marines, Godowsky and Peterson U. S. Patent 2,126,337, August 9, 1938.

The following example, which are illustrative only, indicate developing solutions which may be used according to our invention.

Example 1 4-amino-3-ethoxy-N-ethyl-Ne (pmethylsulfonamidoethyl) -aniline grams 1 Sodium sulfite do, 0.5

Sodium carbonate do 20 Water to cc 1000 Coupler gram 1 Acetone cc 50 AddBtoA EzrampleZ For the formation of a fine grain black-andwhite image, the following developing solution may be used:

4 amino N ethyl N (p methylsulfonamidoethyD-m-anisidine grams 5 Sodium sulfite do 30 Sodium carbonate do 30 Water to cc 1000 eral formula:

wherein R. and R represent lower alkyl groups, and X is selected from the class consisting of hydrogen, lower alkyl, and lower alkoxy groups.

2. An amino compound of the following general formula:

CH hNHSOzCH;

wherein R and R represent lower alkyl groups.

3. An amino compound of the following general formula:

R! HgN N\ R (CHzhNHSO GH,

wherein R and R represent lower alkyl groups. 4. An amino compound of the following formula 5. An amino compound of the following formula:

CH2) ZNHSO CH,

a m nm N lofiomfisoqom 0H,

6. An amino compound of the following general formula:

OCzHu RI 11,: N

R (CHflgNHSOgCHz wherein R and R represent lower alkyl groups.

'7. An amino compound of the following formula:

Claims (1)

1. AN AMINO COMPOUND OF THE FOLLOWING GENERAL FORMULA: