US 4,661,293 AGranted

Method for preparing 1,4-diaminoanthraquinones and intermediates thereof

AssigneeThe Clorox Company

InventorAlfred G. Zielske

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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-monotosyl-anthraquinones.

Claims8

Dependent claims

A method of preparing an unsymmetrical 1,4-diaminoanthraquinone comprising:

providing a monoamino-monotosyl-anthraquinone having the structure ##STR18## wherein R.sub.1 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, and R.sub.2 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl haaving 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group,
reacting said monoamino-monotosyl-anthraquinone with an excess of a primary or secondary amine in the presence of an organic solvent at an elevated temperature to form an unsymmetrical 1,4-diaminoanthraquinone, said amine having the formula R.sub.3 R.sub.4 NH wherein R.sub.3 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, and R.sub.4 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, when R.sub.3 and R.sub.4 are hydrogen, alkyl or cycloalkyl the organic solvent being pyridine, and when at least one of R.sub.3 and R.sub.4 is aryl the organic solvent being dimethyl sulfoxide or dimethyl formamide.

A method for preparing an unsymmetrical 1,4-diaminoanthraquinone comprising:

providing a first compound having the structure ##STR20## reacting said first compound with an excess of a first primary or secondary amine to form an intermediate reaction product, said first amine having the formula R.sub.1 R.sub.2 NH wherein R.sub.1 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, and R.sub.2 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, the reacting being in the presence of a first organic solvent, when neither of R.sub.1 and R.sub.2 is aryl the first organic solvent being methylene chloride, carbon tetrachloride or chloroform and when at least one of R.sub.1 and R.sub.2 is aryl the first organic solvent being dimethyl sulfoxide or dimethyl formamide;
admixing said intermediate reaction product with a second primary or secondary amine in the presence of a second organic solvent, said second amine having the formula R.sub.3 R.sub.4 NH, wherein R.sub.3 is hydrogen, alkyl cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, R.sub.4 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, said second organic solvent being pyridine when R.sub.3 and R.sub.4 are hydrogen, alkyl or cycloalkyl and being dimethyl sulfoxide when either R.sub.3 or R.sub.4 is aryl, and wherein said first and said second amines are different;
and
heating the admixture to between about 60.degree. to about 100.degree. C. when said second organic solvent is pyridine and to between about 150.degree. C. to about 180.degree. C. when said second organic solvent is dimethyl sulfoxide to form a 1,4-diaminoanthraquinone reaction product having the structure ##STR21## where the --NR.sub.1 R.sub.2 moiety is different than the --NR.sub.3 R.sub.4 moiety.

1 more element

Dependencies are inferred from the claim text.

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Abstract

A method of preparing an unsymmetrical 1,4-diaminoanthraquinone comprising:

providing a monoamino-monotosyl-anthraquinone having the structure ##STR18## wherein R.sub.1 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, and R.sub.2 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl haaving 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group,
reacting said monoamino-monotosyl-anthraquinone with an excess of a primary or secondary amine in the presence of an organic solvent at an elevated temperature to form an unsymmetrical 1,4-diaminoanthraquinone, said amine having the formula R.sub.3 R.sub.4 NH wherein R.sub.3 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, and R.sub.4 is hydrogen, alkyl, cycloalkyl or aryl, the alkyl having 1 to about 4 carbons, the cycloalkyl having about 6 to about 9 carbons, the aryl being unsubstituted or substituted phenyl or benzyl, the substituent thereof being one or more of an alkyl group having 1 to about 4 carbons, an alkoxy group having 1 to about 3 carbons, a cyclohexyl group, a phenoxy group, or an acylamino group, when R.sub.3 and R.sub.4 are hydrogen, alkyl or cycloalkyl the organic solvent being pyridine, and when at least one of R.sub.3 and R.sub.4 is aryl the organic solvent being dimethyl sulfoxide or dimethyl formamide.