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United States Patent (19) 11 Patent Number: 4,746,461 Zielske (45) Date of Patent: May 24, 1988

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United States Patent (19) 11 Patent Number: 4,746,461 Zielske (45) Date of Patent: May 24, 1988 United States Patent (19) 11 Patent Number: 4,746,461 Zielske (45) Date of Patent: May 24, 1988 54 METHOD FOR PREPARING 4,041,051 8/1977 Yamado et al. ..................... 260/371 1,4-DIAMINOANTHRAQUINONES AND 4,661,293 4/1987 Zielske ................................ 260/377 INTERMEDIATES THEREOF FOREIGN PATENT DOCUMENTS 75 Inventor: Alfred G. Zielske, Pleasanton, Calif. 2014178 8/1979 United Kingdom................ 260/377 2019870 1 1/1979 United Kingdom ..... ... 260/377 73 Assignee: The Clorox Company, Oakland, Calif. 2100307A 5/1980 United Kingdom ................ 260/377 (21) Appl. No.: 945,906 OTHER PUBLICATIONS 22 Filed: Dec. 23, 1986 Morrison & Boyd, Organic Chemistry, 3rd ed., 1973, pp. 458, 456,527, 528. s Related U.S. Application Data Chemical Abstract, vol. 88, #10498g&h, Schultz et al., 60 Division of Ser. No. 868,884, May 23, 1986, Pat. No. 1978, "Synthesis of Meso-Substituted Hydroxyantha 4,661,293, which is a continuation of Ser. No. 556,835, rones with Laxative Activity Parts I & II' Arch. Dec. 1, 1983, abandoned. Pharm, vol. 310, No. 10, pp. 769-780, 1977. 51 Int. Cl." ...................... C11D 15/02; C11D 13/00 Primary Examiner-Glennon H. Hollrah 52 U.S. C. .................................... 260/370; 260/371; Assistant Examiner-Raymond Covington 260/374 Attorney, Agent, or Firm-Majestic, Gallagher, Parsons 58 Field of Search ............... 260/370, 371, 377, 378, & Siebert 260/374 (57) ABSTRACT (56) References Cited Aminoanthraquinones are generally useful as dyes and U.S. PATENT DOCUMENTS coloring agents. But known methods of synthesizing 2,174,751 10/1939 Koerberle ........................... 260/367 unsymmetrically substituted 1,4-diaminoanthraquinones 2,183,652 12/1939 Lord ............. ... 260/378 are tedious and complex. A simple and efficient method 2,185,709 1/1940 Ogilvie et al. ... ... 260/378 is provided for preparing 1,4-diaminoanthraquinones, 2,188,369 8/1940 McNally et al. ... 260/371 particularly unsymmetrically substituted 1,4- 2,191,030 7/1940 McNally et al........................... 8/40 2,211,943 8/1940 Wilder .......... ... 260/378 diaminoanthraquinones, by means of novel monoamino 2,727,025 12/1955 Weitkamp. ... 260/96.5 monotosyloxy-anthraquinones. 2,995,584 8/1961 Klingsberg ..., ... 260/370 3,486,837 12/1969 Neeffet al. ......................... 260/371 11 Claims, No Drawings 4,746,461 1. 2 1,4-diaminoanthraquinones, particularly unsymmetri METHOD FOR PREPARING cally substituted 1,4-diaminoanthraquinones. 1,4-DIAMINOANTHRAQUINONES AND It is another object of the present invention to pro INTERMEDIATES THEREOF vide novel monoamino-monotosyloxy-anthraquinones 5 which are useful as key intermediates in making 1,4- This is a division of application Ser. No. 868,884 filed diaminoanthraquinone dyes. May 23, 1986 now U.S. Pat. No. 4,661,293 which is a Additional objects, advantages, and novel features of continuation of application Ser. No. 556,835 filed Dec. the invention will be set forth in part in the description 1, 1983 now abandoned. which follows, and in part will become apparent to 10 those skilled in the art on examination. TECHNICAL FIELD In one aspect of the present invention, a 9,10 The present invention relates generally to a method anthraquinone is provided having a tesyloxy group and for preparing 9,10-anthraquinones substituted at the an amino group at the 1- and 4-positions thereof. Such 1,4-positions, and particularly to a method of preparing a 9,10-anthraquinone having a tosyloxy and an amino unsymmetrically substituted 1,4-diaminoanthraquinones 15 substituent may be readily prepared and isolated in high by means of intermediate monoaminomonotoasyloxy yield by reacting a 1,4-ditosyloxanthraquinone with an anthraquinones. excess of a primary or secondary, aliphatic amine at a mild temperature and in the presence of an organic BACKGROUND ART solvent or by reacting a 1,4-ditosyloxyanthraquinone Aminoanthraquinones are generally useful as dyes 20 with an excess of an aromatic amine at an elevated and coloring agents for the coloring of materials such as temperature in the presence of an organic solvent. cellulose derivatives and for coloring artificial composi In another aspect of the present invention, unsymmet tions such as oils, waxes, detergents, and granulated rically substituted 1,4-diaminoanthraquinones may be bleaches. For example, U.S. Pat. Nos. 2,050,704 (issued prepared via a monoamino-monotosyloxy-anthraqui Aug. 11, 1936), 2,121,928 (issued June 28, 1938), 25 none intermediate. 2,191,029 (issued Feb. 20, 1940), 2,191,030 (issued Feb. 20, 1940), and 2,188,369 (issued Jan. 30, 1940) all dis BEST MODE OF CARRYING OUT THE close substituted anthraquinone compounds and their INVENTION uses as dyes. More recently, U.K. patent application As is well known, the structure of 9,10-anthraquinone Nos. 2,014, 178 (published Aug. 22, 1979) and 2,019,870 30 (published Nov. 7, 1979) have disclosed a class of (hereinafter referred to as "anthraquinone") is as illus halogenoanthraquinones useful for dying and printing trated by FIG. 1 below. textile materials. U.S. Pat. No. 2,121,918, issued to Peter, discloses a O FIG. 1 method of synthesizing substituted aminoanthraquinone 35 8 compounds by condensing certain aromatic amines 7 2. with halogen, sulpho-, or alkyl-substituted anthraqui 6 3 none compounds at elevated temperatures in the pres 5 I 4 ence of a catalyst. O U.S. Pat. No. 2,183,652, issued to Lord, discloses a method of synthesizing substituted aminoanthraquinone Conventional numbering of the anthraquinone mole compounds by reacting quinizarin (1,4-dihydroxyan cule is also shown by FIG. 1. Since the 8,5positions are thraquinone), 1,4,5-trihydroxyanthraquinone or 1,4,5,8- equivalent to the 1,4 positions for the 9,10-anthraqui tetrahydroxyanthraquinone with an aliphatic amine none molecule, references hereinafter to the 1 and/or 4 compound in a dilute aqueous caustic alkali solution and 45 positions can alternatively be read to mean the 8 and/or in the presence of a metal catalyst. 5 positions. U.S. Pat. No. 2,188,369, issued to McNally, provides Among the many known anthraquinone derivatives is for syntheses of substituted 1,4-diaminoanthraquinones 1,4-dihydroxyanthraquinone, or quinizarin, which is wherein the 1-amino group is N-substituted with an commercially available. alkylene sulfonic acid group. 50 Quinizarin can be reacted with a suitable sulfonyl U.S. Pat. Nos. 2,050,704, 2,185,709, and 1,191,029, chloride, such as p-toluenesulfonate, to form a 1,4- issued to Koeberle, Ogilvie, and McNally, respectively, ditosyloxyanthraquinone. This aromatic tosylate is eas disclose methods of synthesizing N-substituted 1,4- ily prepared at room temperature or with refluxing (40 diaminoanthraquinones from leuco-1,4-diaminoan C.) methylene chloride and triethylamine as shown by thraquinone compounds as starting materials. 55 U.K. patent application Nos. 2,014, 178 and 2,019,870 the reaction scheme illustrated in Reaction I below. describe methods of preparing unsymmetrically substi tuted 1,4-diaminoanthraquinone compounds haloge Reaction I nated at either the 6- or 7-positions. Known methods of synthesizing unsymmetrical ami O OH noanthraquinones for the most part comprise multi-step, O lengthy reactions. Methods given in the literature for I synthesizing such compounds have been tedious and -- 2C, CH3 O complex. I 65 SUMMARY OF THE INVENTION O OH Accordingly, it is an object of the present invention to provide a simple and efficient method for preparing 4,746,461 3 4. -continued Reaction I 5 ---No.O CH3 For convenience, and unless otherwise specified, the abbreviation "Ts' shall include not only the p toluenesulfonyl moiety (i.e., tosyl, or 10 O O CH3 ---CH) but also ---Cl O O 15 The 1,4-ditosyloxyanthraquinone is stable, and may be stored at room temperature for long periods, with no -i--B, and ---No. apparent decomposition. O O Example I below illustrates preparation of 1,4- 20 ditosyloxyanthraquinone. Novel intermediates in accordance with the present EXAMPLE I invention are readily prepared from 1,4-ditosyloxyan thraquinone and its analogs by reaction with an excess For preparation of 1,4-ditosyloxyanthraquinone, to of a primary or secondary aliphatic amine or an aro quinizarin (100 g, 41.7 mmole, Aldrich Chem. Co.) 25 dissolved in methylene chloride (400 ml) was added matic amine. With the correct solvent and temperature, triethylamine (24 ml, 170 mmole) and p-toluenesulfonyl it is possible to stop the reaction at this intermediate chloride (16g, 84 mmole). The solution was stirred for stage and to isolate the novel intermediates. With alkyl 24 hours at room temperature, washed with water and amines, relatively low temperatures and a non-polar dried over anhydrous magnesium sulfate. The course of organic solvent having a dielectric constant of between the reaction could be followed by TLC (silica gel, about 2 to about 10 at about 20 C., such as methylene CH2Cl2). The methylene chloride was evaporated and chloride, carbon tetrachloride or chloroform, are ap the residue stirred with carbon tetrachloride (30 ml) at propriate reaction conditions, and will have a fairly room temperature for 3 hours. Filtration of the slurry high yield of the intermediate monoamino gave a bright yellew solid. The dried yellow solid (17.8 monotosyloxy-anthraquinone compound. With aro g) represented a yield of 78% and had m.p. 221-225 C. 35 matic amines, because of their poor nucleophilicity, it is (d). Material recrystallized from chloroform-petroleum preferred to use an organic solvent having a higher ether had m.p. 225-226 C. (d). Mass spectrum, m/e dielectric constant, such as DMSO or DMF as a sol 548 (M+), 394 (M-CHSO2+H), 239 (M- vent, and to use higher temperatures. 2C7H7SO2+H 155 (C7H7SO2), 91 (C7H7); 1H-NMR 4 The intermediates produced have an amino group (CD2Cl2)68.02-7.94 (m, 2H), 7.91-7.69 (m, 6H), 7.45 (s, and a tosyloxy group substituted on one of the anthra 2H), 7.33-7.24 (m, 4H), 2.35 (s, 6H); IR (Nujol) 1335 quinone aromatic rings in a "para' relationship, i.e., on cm- 1310 (asymmetric SO2 stretch), 1175 cm-1, 1190 the 1 and 4 ring positions, respectively.
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