Method for preparing 1,4-diaminoanthraquinones and intermediates thereof

Abstract

Aminoanthraquinones are generally useful as dyes and coloring agents. But known methods of synthesizing unsymmetrically substituted 1,4-diaminoanthraquinones are tedious and complex. A simple and efficient method is provided for preparing 1,4-diaminoanthraquinones, particularly unsymmetrically substituted 1,4-diaminoanthraquinones, by means of novel monoamino-monotosyloxy-anthraquinones.

Description

TECHNICAL FIELD

The present invention relates generally to a method for preparing 9,10-anthraquinones substituted at the 1,4-positions, and particularly to a method of preparing unsymmetrically substituted 1,4-diaminoanthraquinones by means of intermediate monoaminomonotoasyloxy-anthraquinones.

BACKGROUND ART

Aminoanthraquinones are generally useful as dyes and coloring agents for the coloring of materials such as cellulose derivatives and for coloring artificial compositions such as oils, waxes, detergents, and granulated bleaches. For example, U.S. Pat. Nos. 2,050,704 (issued Aug. 11, 1936), 2,121,928 (issued June 28, 1938), 2,191,029 (issued Feb. 20, 1940), 2,191,030 (issued Feb. 20, 1940), and 2,188,369 (issued Jan. 30, 1940) all disclose substituted anthraquinone compounds and their uses as dyes. More recently, U.K. patent application Nos. 2,014,178 (published Aug. 22, 1979) and 2,019,870 (published Nov. 7, 1979) have disclosed a class of halogenoanthraquinones useful for dying and printing textile materials.

U.S. Pat. No. 2,121,918, issued to Peter, discloses a method of synthesizing substituted aminoanthraquinone compounds by condensing certain aromatic amines with halogen, sulpho-, or alkyl-substituted anthraquinone compounds at elevated temperatures in the presence of a catalyst.

U.S. Pat. No. 2,183,652, issued to Lord, discloses a method of synthesizing substituted aminoanthraquinone compounds by reacting quinizarin (1,4-dihydroxyanthraquinone), 1,4,5-trihydroxyanthraquinone or 1,4,5,8-tetrahydroxyanthraquinone with an aliphatic amine compound in a dilute aqueous caustic alkali solution and in the presence of a metal catalyst.

U.S. Pat. No. 2,188,369, issued to McNally, provides for syntheses of substituted 1,4-diaminoanthraquinones wherein the 1-amino group is N-substituted with an alkylene sulfonic acid group.

U.S. Pat. Nos. 2,050,704, 2,185,709, and 1,191,029, issued to Koeberle, Ogilvie, and McNally, respectively, disclose methods of synthesizing N-substituted 1,4-diaminoanthraquinones from leuco-1,4-diaminoanthraquinone compounds as starting materials.

U.K. patent application Nos. 2,014,178 and 2,019,870 describe methods of preparing unsymmetrically substituted 1,4-diaminoanthraquinone compounds halogenated at either the 6- or 7-positions.

Known methods of synthesizing unsymmetrical aminoanthraquinones for the most part comprise multi-step, lengthy reactions. Methods given in the literature for synthesizing such compounds have been tedious and complex.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide a simple and efficient method for preparing 1,4-diaminoanthraquinones, particularly unsymmetrically substituted 1,4-diaminoanthraquinones.

It is another object of the present invention to provide novel monoamino-monotosyloxy-anthraquinones which are useful as key intermediates in making 1,4-diaminoanthraquinone dyes.

Additional objects, advantages, and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art on examination.

In one aspect of the present invention, a 9,10-anthraquinone is provided having a tesyloxy group and an amino group at the 1- and 4- positions thereof. Such a 9,10-anthraquinone having a tosyloxy and an amino substituent may be readily prepared and isolated in high yield by reacting a 1,4-ditosyloxanthraquinone with an excess of a primary or secondary, aliphatic amine at a mild temperature and in the presence of an organic solvent or by reacting a 1,4-ditosyloxyanthraquinone with an excess of an aromatic amine at an elevated temperature in the presence of an organic solvent.

In another aspect of the present invention, unsymmetrically substituted 1,4-diaminoanthraquinones may be prepared via a monoamino-monotosyloxy-anthraquinone intermediate.

BEST MODE OF CARRYING OUT THE INVENTION

As is well known, the structure of 9,10-anthraquinone (hereinafter referred to as "anthraquinone") is as illustrated by FIG. 1 below. ##STR1##

Conventional numbering of the anthraquinone molecule is also shown by FIG. 1. Since the 8,5 positions are equivalent to the 1,4 positions for the 9,10-anthraquinone molecule, references hereinafter to the 1 and/or 4 positions can alternatively be read to mean the 8 and/or 5 positions.

Among the many known anthraquinone derivatives is 1,4-dihydroxyanthraquinone, or quinizarin, which is commercially available.

Quinizarin can be reacted with a suitable sulfonyl chloride, such as p-toluenesulfonate, to form a 1,4-ditosyloxyanthraquinone. This aromatic tosylate is easily prepared at room temperature or with refluxing (40.degree. C.) methylene chloride and triethylamine as shown by the reaction scheme illustrated in Reaction I below. ##STR2##

The 1,4-ditosyloxyanthraquinone is stable, and may be stored at room temperature for long periods, with no apparent decomposition.

Example I below illustrates preparation of 1,4-ditosyloxyanthraquinone.

EXAMPLE I

For preparation of 1,4-ditosyloxyanthraquinone, to quinizarin (10.0 g, 41.7 mmole, Aldrich Chem. Co.) dissolved in methylene chloride (400 ml) was added triethylamine (24 ml, 170 mmole) and p-toluenesulfonyl chloride (16 g, 84 mmole). The solution was stirred for 24 hours at room temperature, washed with water and dried over anhydrous magnesium sulfate. The course of the reaction could be followed by TLC (silica gel, CH.sub.2 Cl.sub.2). The methylene chloride was evaporated and the residue stirred with carbon tetrachloride (30 ml) at room temperature for 3 hours. Filtration of the slurry gave a bright yellow solid. The dried yellow solid (17.8 g) represented a yield of 78% and had m.p. 221.degree.-225.degree. C. (d). Material recrystallized from chloroform-petroleum ether had m.p. 225.degree.-226.degree. C. (d). Mass spectrum, m/e 548 (M.sup.+), 394 (M-C.sub.7 H.sub.7 SO.sub.2 +H), 239 (M-2C.sub.7 H.sub.7 SO.sub.2 +H 155 (C.sub. 7 H.sub.7 SO.sub.2), 91 (C.sub.7 H.sub.7); .sup.1 H-NMR (CD.sub.2 Cl.sub.2).delta.8.02-7.94 (m, 2H), 7.91-7.69 (m, 6H), 7.45 (s, 2H), 7.33-7.24 (m, 4H), 2.35 (s, 6H); IR (Nujol) 1335 cm.sup.-1 1310 (asymmetric SO.sub.2 stretch), 1175 cm.sup.-1, 1190 (symmetric SO.sub.2 stretch), 290 cm.sup.-1, 895, 860, 810, 795, 780, 745, (SO--O--C stretch); UV/VIS max (CH.sub.2 Cl.sub.2) 331 nm (.epsilon.4820).

Anal. Calcd. for C.sub.28 H.sub.20 S.sub.2 O.sub.8 : C, 61.31; H, 3.65; S, 11.68. Found: C, 61.10; H, 3.81; S, 11.54.

As further described hereinafter, 1,4-ditosyloxyanthraquinone is useful as a precursor, or starting material, in practicing the present invention, as are certain analogs thereof. For example, each of the ##STR3## moieties of 1,4-ditosyloxyanthraquinone may have a halo rather than the methyl substituent, such as ##STR4## or may have a nitro rather than the methyl substituent, such a ##STR5## For convenience, and unless otherwise specified, the abbreviation "Ts" shall include not only the p-toluenesulfonyl moiety (i.e., tosyl, or ##STR6##

Novel intermediates in accordance with the present invention are readily prepared from 1,4-ditosyloxyanthraquinone and its analogs by reaction with an excess of a primary or secondary aliphatic amine or an aromatic amine. With the correct solvent and temperature, it is possible to stop the reaction at this intermediate stage and to isolate the novel intermediates. With alkyl amines, relatively low temperatures and a non-polar organic solvent having a dielectric constant of between about 2 to about 10 at about 20.degree. C., such as methylene chloride, carbon tetrachloride or chloroform, are appropriate reaction conditions, and will have a fairly high yield of the intermediate monoamino-monotosyloxy-anthraquinone compound. With aromatic amines, because of their poor nucleophilicity, it is preferred to use an organic solvent having a higher dielectric constant, such as DMSO or DMF as a solvent, and to use higher temperatures.

The intermediates produced have an amino group and a tosyloxy group substituted on one of the anthraquinone aromatic rings in a "para" relationship, i.e., on the 1 and 4 ring positions, respectively. The amino substituent of such an anthraquinone may be a primary, secondary or tertiary amino group. Novel anthraquinone intermediates (sometimes herein referred to as a monoamino-monotosyloxy-anthraquinones) have the structure shown by FIG. II below. ##STR7## R.sub.1 derives from a branched or unbranched acyclic hydrocarbon which may be either saturated or unsaturated (with one or more double bonds), or from a cycloalkyl or aryl group, with or without side chain substituents. R.sub.2 moieties may be as described for R.sub.1. Preferably, R.sub.1 and R.sub.2 are selected from hydrogen, alkyl, cycloalkyl or aryl, and particularly preferred moieties for R.sub.1 and R.sub.2 are --H, --CH(CH.sub.3).sub.2, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --(CH.sub.2).sub.3 CH.sub.3, phenyl and 3,5-dimethylphenyl. The R.sub.1 and R.sub.2 moieties may be the same or different.

R.sub.1 and/or R.sub.2 may be, for example, methyl, ethyl, isopropyl, n-, sec- or tert-butyl, cyclohexyl, and trimethylcyclohexylamino. Further, where at least one of R.sub.1 and R.sub.2 is a phenyl substituent, the phenyl ring can be further mono- or poly-substituted with substituents such a acylamino, one or more alkyl groups generally having 1 to 4 carbons, alkoxy groups such as methoxy, ethoxy, and propoxy.

Suitable amines for introducing the R.sub.1 and R.sub.2 groups are for example: methylamine, ethylamine, isopropylamine and butylamine; phenylamine, 2-methylphenylamine, 4-methylphenylamine, 4-isopropylphenylamine, 2,4-dimethylphenylamine, 3,4-dimethylphenylamine, 2,5-dimethylphenylamine, 2-methyl-5-methoxy-phenylamine, 2,3-dimethylphenylamine, 2,6-dimethylphenylamine, 2,4,6-trimethylphenylamine, 4-ethylphenylamine, 2-ethylphenylamine, 4-tert-butylphenylamine, 2-methoxyphenylamine, 2-ethoxyphenylamine, 4-methoxyphenylamine, 2,5-dimethoxyphenylamine, 4-butoxyphenylamine, 4-acetylaminophenylamine, 4-phenoxyphenylamine, 4-(4'-methyl)-phenoxyphenylamine, benzylamine and phenylisobutylamine; phenylcyclohexylamine; cyclohexylamine and 3,5,5-trimethylcyclohexylamine, as well as 4-cyclohexylphenylamine.

Where neither of the R.sub.1 and R.sub.2 moieties is aryl, the organic solvent in which the reaction is conducted is preferably methylene chloride, carbon tetrachloride, or chloroform, most preferably methylene chloride, and the mild or relatively low reaction temperature is preferably maintained at not greater than abot 50.degree. C.

Example II, below, illustrates the general method for preparing the novel monoamino-monotosyloxyanthraquinones where neither of the R.sub.1 and R.sub.2 moieties is aryl. Examples III, IV and V give the yield, melting point and spectral data for particular compounds prepared in accordance with the general method illustrated by Example II.

EXAMPLE II

The 1,4-ditosyloxyanthraquinone is dissolved in methylene chloride, the suitable primary or secondary alkyl amine added in excess and the solution refluxed from about 5 to 24 hours. The reaction can be followed by thin layer chromatography ("TLC") (such as silica gel, with hexane/ethyl acetate, 70:30). The starting material gives R.sub.f in the 0.40 region (dark spot under UV light), whereas the monoamino-monotosyloxy-anthraquinone is typically bright red, with R.sub.f usually in the 0.65 region, and there is sometimes a faint blue spot present at R.sub.f about 0.80 (a 1,4-bis-aminoanthraquinone). When reaction is complete, as judged by TLC, the liquids may be removed by evaporation, carbon tetrachloride added to the residue, and the slurry filtered. The red filtrate may be placed on a column of silica gel, the column eluted with hexane/ethyl acetate (70:30) and the red band collected. Further purification can be achieved, especially if any phenolic material (violet) is present, by chromatography through a short alumina column or by preparative TLC.

EXAMPLE III

1-(isopropylamino)-4-tosyloxyanthraquinone was prepared by reaction of 1,4-ditosyloxyanthraquinone with isopropyl amine. The isolated and purified reaction product has the structure illustrated below (where "Ts" is ##STR8## The yield was 76% and the m.p. 164.degree.-165.degree. C.; mass spec m/e/ 435 (M.sup.+), 420 (M-CH.sub.3), 280 (M-C.sub.7 H.sub.7 SO.sub.2), 238 (280-CH.sub.3 H.sub.7 +H), 210 (238-CO), 182 (210-CO), 155 (C.sub.7 H.sub.7 SO.sub.2), 91 (C.sub.7 H.sub.7); .sup.1 H-NMR (CD.sub.2 Cl.sub.2).delta.9.97 (br s, 1H), 8.19-8.10 (m, 2H), 7.85-7.67 (m, 4H), 7.27-6.97 (m, 4H), 4.02-3.68 (m, 1H), 2.30 (s, 3H), 1.38, 1.31 (d, 6H); IR (Nujol) 1180 cm.sup.-1 (symmetrical SO.sub.2 stretch), 890 cm.sup.-1, 860, 820, 780 (S--O--C stretch); UV/VIS max (Xylenes(500 nm (.epsilon.6660).

Anal. Calcd. for C.sub.24 H.sub.21 NSO.sub.5 : C, 66.21; H, 4.83; N 3.22; S, 7.36. Found: C, 66.35; H, 4.75; N, 3.25; S, 7.38.

EXAMPLE IV

1-(n-propylamino)-4-tosyloxyanthraquinone was prepared by reaction of 1,4-ditosyloxyanthraquinone with n-propyl amine. The isolated and purified reaction product has the structure illustrated below (where "Ts" is ##STR9## The yield was 73% and the m.p. 163.degree.-164.degree. C. Mass spec m/e 435 (M.sup.+), 406 (M-C.sub.2 H.sub.5), 280 (M-C.sub.7 H.sub.7 SO.sub.2), 252 (280-CO), 155 (C.sub.7 H.sub.7 SO.sub.2), 91 (C.sub.7 H.sub.7); .sup.1 H-NMR (CD.sub.2 Cl.sub.2).delta.10.01 (br s, 1H), 8.21-7.87 (m, 2H), 7.81-7.65 (m, 4H), 7.35-6.96 (m, 4H), 3.41-3.20 (m, 2H), 2.31 (s, 3H), 1.91-1.67 (m, 2H), 1.16-1.00 (t, 3H); IR (Nujol) 1368 cm.sup.-1 (asymmetrical stretch), 1170 cm.sup.-1 (symmetric stretch), 932, 898, 865, 830, 785 cm.sup.-1 (S--O--C stretch); UV/VIS max (Xylenes) 501 nm (.epsilon.6380).

Anal. Calcd. for C.sub.24 H.sub.21 NSO.sub.5 : C, 66.21; H, 4.83; H, 3.22; S, 7.36. found: C, 66.03; H, 4.83; N, 3.20; S, 7.51.

EXAMPLE V

1-(diethylamino)-4-tosyloxyanthraquinone) was prepared by reaction of 1,4-ditosyloxyanthraquinone with diethyl amine. The isolated and purified reaction product has the structure illustrated below (where "Ts" is ##STR10## The yield was 91% and the m.p. 140.degree.-141.degree. C. Mass spec m/e 449 (M+), 434 (M-CH.sub.3), 420 (M-C.sub.2 H.sub.5), 294 (M-C.sub.7 H.sub.7 SO.sub.2), 266 (294-CO), 155 (C.sub.7 H.sub.7 SO.sub.2), 91 (C.sub.7 H.sub.7): H-NMR (CD.sub.2 Cl.sub.2).delta.8.19-8.13 (m, 2H), 7.97-7.68 m, 4H), 7.30-7.15 (m, 4H), 3.48-3.24 (q, 4H), 2.26 (s, 3H), 1.22-1.06 (t, 6H); IR (Nujol) 1172 cm.sup.-1 (symmetrical SO.sub.2 stretch), 945 cm.sup.-1, 872, 830, 820, 800, 785, 765 (S--O--C stretch); UV/VIS max (Xylenes) 506 nm (.epsilon.3650).

Anal. Calcd. for C.sub.25 H.sub.23 NSO.sub.5 : C, 66.82; H, 5.12; N, 3.12; S, 7.13. Found: C, 66.86 H, 5.08; N, 3.04; S, 7.00.

Example VI, below, illustrates the general method for preparing the novel monoamino-monotosyloxyanthraquinones where one or both of the R.sub.1 and R.sub.2 moieties is aryl. Example VII gives the yield, melting point and spectral data for a particular compound prepared in accordance with the general method illustrated by Example VI.

EXAMPLE VI

Where at least one of R.sub.1 and R.sub.2 is aryl, then the organic solvent is preferably dimethylsulfoxide (DMSO) or dimethylformamide (DMF), and the reaction mixture is heated, most preferably to a temperature of not greater than about 150.degree. C. The reaction, as already described, may be followed by TLC. When complete the solution may be cooled, pured into 10% aqueous HCl, extracted with methylene chloride, and the methylene chloride layer washed with water and dried over anhydrous magnesium sulfate. After filtration, the sovlent may be evaporated and the residue dissolved in carbon tetrachloride. Further purification may be as already described in Example II above.

EXAMPLE VII

1-(anilino)-4-tosyloxyanthraquinone was prepared by reaction of 1,4-ditosyloxyanthraquinone with aniline. The isolated and purified creaction product has the structure illustrated below (where "Ts" is ##STR11## The yield was 79% and the m.p. 185.degree.-186.degree. C. Mass spec m/e 469 (M.sup.+), 314 (M-C.sub.7 H.sub.7 SO.sub.2), 155 (C.sub.7 H.sub.7 SO.sub.2), 91 (C.sub.7 H.sub.7); .sup.1 H-NMR (CD.sub.2 Cl.sub.2).delta.11.50 (br s, 1H), 8.26-8.12 (m, 2H), 8.02-7.84 (m, 2H), 7.79-7.62 (m, 4H), 7.54-7.13 (m, 7H), 2.31 (s, 3H); IR (Nujol) 1355 cm.sup.-1 (asymmetric SO.sub.2 stretch), 1184 cm.sup.-1 (symmetrical SO.sub.2 stretch), 945 cm.sup.-1, 872, 840, 822, 810, 800, 788, 755 (S--O--C stretch); UV/VIS max (Xylenes) 500 nm (.epsilon.7000).

Anal. Calcd. for C.sub.27 H.sub.19 NSO.sub.5 : C, 69.08; H, 4.05; N, 2.98; S, 6.82. Found: C, 68.82; H, 4.11; N, 2.85; S, 7.04.

The monoamino-monotosyloxy-anthraquinone intermediates in accordance with the present invention may be used in a novel process to synthesize either symmetrical or unsymmetrical 1,4-diaminoanthraquinones. Broadly, the particular monoamino-monotosyloxy-anthraquinone intermediate which is chosen is reacted with either an alkyl or an aromatic amine, preferably in an organic solvent with a higher dielectric constant than 10 for an alkyl amine, such as pyridine at approximately 100.degree. C., and preferably in DMSO at about 180.degree. C. for an aromatic amine, as is illustrated in Reaction II below. ##STR12##

More particularly, the monoamino-monotosyloxy-anthraquinone compound chosen is dissolved in the appropriate solvent, an excess of the suitable primary or secondary alkyl amine is added, and the solution is heated from about 3 to 24 hours. The reaction may be followed by TLC (silica gel, hexanes/ethyl acetate, 90:10). The final 1,4-diaminoanthraquinone compound gives a bright blue spot with a relatively high R.sub.f, in the 0.65 region.

Where neither the R.sub.3 nor the R.sub.4 substituents is aryl, the solvent used is pyridine or methylene chloride, preferably pyridine, and the reaction mixture is heated at a temperature preferably of about 100.degree. C. When the reaction is complete, the solution may be cooled, poured into 10% aqueous HCl, and extracted with methylene chloride. The methylene chloride layer is washed with water and dried over anhydrous magnesium sulfate. Further purification may again be achieved by silica gel chromatography followed by final purification through a short alumina column or by preparative TLC. The diaminoanthraquinone products may be recrystallized by dissolving in ethanol, adding a small amount of water to the hot solution, and then cooling.

Where at least one of R.sub.3 and R.sub.4 is aryl, the preferably solvent is DMSO. The procedure followed is substantially the same as that for alkyl N-substituents, except that a higher temperature is required, preferably a temperature of from about 150.degree. C. to about 180.degree. C.

Suitable amines for introducing the R.sub.3 and R.sub.4 groups are as previously given for the R.sub.1 and R.sub.2 groups.

Example VIII, below, illustrates the general method for preparing symmetrical or unsymmetrical 1,4-diaminoanthraquinones from monoamino-monotosyloxy-anthraquinone intermediates, where neither the R.sub.3 nor the R.sub.4 substituents is to be aryl, and Examples IX and X give the yield, melting point and spectral data for particular compounds prepared in accordance with the general method illustrated by Example VIII.

EXAMPLE VIII

The selected 1-(amino)-4-tosyloxyanthraquinone is dissolved in pyridine, the appropriate amine (about 800 molar excess) added, and the solution heated between 60.degree.-100.degree. C. for 3-24 hours. The reaction is conveniently followed by TLC (silica gel, hexanes/ethyl acetate, 90:10). The starting material gives a red spot (R.sub.f about 0.20) and the product gives a blue spot (R.sub.f about 0.65). When reaction is complete as judged by TLC, liquids are removed by evaporation, carbon tetrachloride added to the residue and the slurry filtered. The blue filtrate is placed on a column of silica gel, the column eluted with hexanes/ethyl acetate (90:10) and the blue band collected. Further purification can be achieved, especially if any phenolic material (violet) is present, by chromatography through a short alumina column or by preparative TLC. The compounds can be recrystallized by dissolving in ethanol, adding a small amount of water to the hot solution, and then cooling.

EXAMPLE IX

1-(isopropylamino)-4-(n-propylamino)anthraquinone was prepared by reaction of 1-(isopropylamino)-4-tosyloxyanthraquinone with n-propyl amine. The isolated and purified reaction product has the structure illustrated below. ##STR13## The yield was 67% and the m.p. 120.degree.-121.degree. C. Mass spec m/e 322 (M.sup.+), 307 (M-CH.sub.3), 293 (M-C.sub.2 H.sub.5), 279 (307-CO), 251 (M-2CO); .sup.1 H-NMR (CD.sub.2 Cl.sub.2).epsilon.10.99 br s, 1H), 10.88 (br s, 1H), 8.39-8.22 (m, 2H); 7.77-7.59 (m, 2H), 7.27 (s, 2H), 3.90 (m, 1H), 3.46-3.28 (m, 2H), 1.81-1.58 (m, 2H), 1.39, 1.32 (d, 6H), 1.26-1.07 (t, 3H); VIS max (Xylenes) 598 nm (.epsilon.14 100), 646 (16 200).

Anal. Calcd. for C.sub.20 H.sub.22 N.sub.2 O.sub.2 : C, 74.53; H, 6.83; N, 8.70. Found: C, 74.55; H, 6.92; N, 8.80.

EXAMPLE X

1-(anilino)-4-(n-butylamino)-anthraquinone was prepared by reaction of 1-(anilino)-4-tosyloxyanthraquinone with n-butylamine. The isolated and purified reaction product has the structure illustrated below. ##STR14## The yield was 90% and m.p. 118.degree.-120.degree. C. Mass spectrum, m/e 370 (M.sup.+), 327 (M-C.sub.3 H.sub.7), 299 (327-CO); .sup.1 H-NMR (CD.sub.2 Cl.sub.2).delta.12.17 (br s, 1H), 10.78 (br s, 1H), 8.37-8.27 (m, 2H), 7.76-7.39 (m, 4H), 7.33-7.10 (m, 5H), 3.65-3.05 (m, 2H), 1.72-1.38 (m, 4H), 1.07-0.92 (t, 3H): UV/VIS max (Xylenes) 388 nm (.epsilon.4000), 598 (14 200), 642 (15 600).

Anal. Calcd. for C.sub.24 H.sub.22 N.sub.2 O.sub.2 : C, 77.84; H, 5.98; N. 7.57 Found: C, 77.68; H, 5.94, N, 7.41.

Example XI, below, illustrates the general method for preparing symmetrical or unsymmetrical 1,4-diaminoanthraquinones where one (or both) of the R.sub.3 and R.sub.4 substituents is aryl, and Example XII gives the yield, melting point and spectral data for a particular compound so prepared.

EXAMPLE XI

The 1-(arylamino)-4-tosyloxyanthraquinone is dissolved in DMSO, the appropriate aromatic amine added (about 2000 molar excess), and the solution heated at 180.degree. C. for 3 hours. The reaction is followed by TLC as described by Example VIII. When reaction is complete, the solution is cooled, poured into 10% aqueous HCl, extracted with methylene chloride, the methylene chloride layer washed with water, and dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated and the residue dissolved in carbon tetrachloride. Purification proceeds as described by Example VIII above.

EXAMPLE XII

1-anilino-4-(3,5-dimethylanilino)anthraquinone was prepared by reaction of 3,5-dimethylaniline with 1-(anilino)-4-tosyloxyanthraquinone. The isolated and purified reaction product has the structure illustrated below. ##STR15## The yield was 56% and m.p. 219.5.degree.-220.5.degree. C. Mass spectrum, m/e 418 (M.sup.+); .sup.1 H-NMR (CD.sub.2 Cl.sub.2).delta.12.20 (br s, 2H), 8.41-8.30 (m, 2H) 7.80-7.69 (m, 2H), 7.52-7.34 (m, 7H), 6.90 (br s, 3H), 2.32 (s, 6H); UV/VIS max (Xylenes) 404 nm (.epsilon.6 600), 600 (13 400), 641 (14 400).

Anal. Calcd. for C.sub.28 H.sub.22 N.sub.2 O.sub.2 : C, 80.38; H, 5.26; N, 6.70. Found: C, 80.11; H, 5.14; N, 6.54.

Where one wishes to prepare a symmetrical 1,4-diamonoanthraquinone, it is typically simpler to proceed from the 1,4-ditosyloxyanthraquinone to the particular 1,4-diaminoanthraquinone desired without isolating any monoamino-monotosyloxy-anthraquinone intermediate. Example XIII, below, illustrates the preparation of 1,4-bis-(n-butylamino)-anthraquinone.

EXAMPLE XIII

1,4-bis-(n-butylamino)-anthraquinone having the structure illustrated below was prepared by reaction of 1,4-ditosyloxyanthraquinone with n-butyl amine in pyridine at 100.degree. C. ##STR16## The yield was 68% and m.p. 120.degree.-121.degree. C. Mass spectrum m/e 350 (M.sup.+), 307 (M-C.sub.3 H.sub.7); .sup.1 H-NMR (CD.sub.2 Cl.sub.2).delta.10.76 (br s, 2H), 8.34-8.19 (m, 2H), 7.74-7.57 (m, 2H), 7.20 (s. 2H), 3.48-3.27 (m, 4H), 1.88-1.30 (m, 8H), 1.06-0.91 (t, 6H); VIS max (Xylenes) 600 nm (.epsilon.15 000, 648 (17 300).

Anal. Calcd. for C.sub.22 H.sub.26 N.sub.2 O.sub.2 : C, 75.43; H, 7.43; N, 8.00. found: C, 75.50; H, 7.42; N, 7.84.

The foregoing examples illustrate certain embodiments of the present invention, and are not intended to limit the scope of the invention which is defined in the appended claims.

Claims

1. A 9,10-anthraquinone having a tosyloxy group and an amino group substituted on one ring thereof, said amino group and said tosyloxy group being in a para relationship on said one ring.

2. The anthraquinone as in claim 1 wherein said amino group is a primary, secondary or tertiary amino.

3. A compound having the structure ##STR17## wherein R.sub.1 is hydrogen, alkyl, cycloalkyl or aryl, R.sub.2 is hydrogen, alkyl, cycloalkyl or aryl, and X is methyl, chloro, bromo or nitro.

4. The compound as in claim 3 wherein R.sub.1 and R.sub.2 are selected from the group consisting of --H, --CH(CH.sub.3).sub.2, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --(CH.sub.2).sub.3 CH.sub.3, phenyl, and 3,5-dimethylphenyl.

5. A method of preparing the compound of claim 3 comprising:

providing a first compound having the structure ##STR18## where X is methyl, chloro, bromo or nitro; and reacting, in the presence of an organic solvent, said first compound with an excess of a primary or secondary amine having the formula R.sub.1 R.sub.2 NH wherein R.sub.1 is hydrogen, alkyl, cycloalkyl or aryl, and R.sub.2 is hydrogen, alkyl, cycloalkyl, or aryl.

6. The method as in claim 5 wherein said organic solvent is selected from the group consisting of methylene chloride, carbon tetrachloride, and chloroform when R.sub.1 and R.sub.2 are hydrogen, alkyl, or cycloalkyl and is dimethyl sulfoxide or dimethyl formamide when at least one of R.sub.1 or R.sub.2 is aryl.

7. The method as in claim 5 wherein said organic solvent is methylene chloride when R.sub.1 and R.sub.2 are hydrogen, alkyl or cycloalkyl and is dimethyl sulfoxide when at least one of R.sub.1 and R.sub.2 is aryl.

8. A method of preparing a monoamino-monotosyloxy-anthraquinone comprising:

providing a first compound having the structure ##STR19## admixing said first compound with an excess of a primary or secondary amine to form a reaction mixture, said amine having the formula R.sub.1 R.sub.2 NH wherein R.sub.1 is hydrogen, alkyl, cycloalkyl or aryl, and R.sub.2 is hydrogen, alkyl, cycloalkyl, or aryl, the reaction mixture including an organic solvent, when R.sub.1 and R.sub.2 are hydrogen, alkyl or cycloalkyl the organic solvent being methylene chloride, and when at least one of R.sub.1 and R.sub.2 is aryl the organic solvent being dimethyl sulfoxide;

maintaining a reaction temperature of the reaction mixture at not greater than about 50.degree. C. when R.sub.1 and R.sub.2 are hydrogen, alkyl or cycloalkyl and at not greater than about 150.degree. C. when at least one of R.sub.1 and R.sub.2 are aryl; and

isolating a reaction product from the reaction mixture having structure ##STR20##

9. The method as in claim 8 wherein the isolating includes separation of said reaction product from said reaction mixture by column chromatography.

10. A 9, 10-anthraquinone having two tosyloxy groups substituted on one ring thereof, said groups being in para relationship on one ring.

11. A method of preparing the compound of claim 10 comprising:

providing a first compound having the structure: ##STR21## reacting said first compound, in the presence of a nonnucleophilic organic solvent and a base, with a second compound having the structure ##STR22## the second compound being in a molar excess with respect to said first compound, wherein X is selected from methyl, bromo, chloro and nitro.