A method for preparing a diaryl-p-phenylenediamine compound of Formula I comprises the steps of reacting a compound of Formula II and a compound of Formula III in a condensation dehydrogenation reaction in the presence of a solvent, a hydrogen acceptor, a water-carrying agent, and a catalyst; wherein R.sub.1, R.sub.2 and R.sub.3 are independently selected and each is H, a C1-C8 alkyl, a C3-C8 cycloalkyl, a C1-C8 alkoxy, a C3-C8 cycloalkoxy, or phenyl; a and c are independently selected and each is an integer of 0 to 5, and b is an integer of 0 to 4:

##STR00001##

A method for preparing a diaryl-p-phenylenediamine compound of Formula I comprises the steps of reacting a compound of Formula II and a compound of Formula III in a condensation dehydrogenation reaction in the presence of a solvent, a hydrogen acceptor, a water-carrying agent, and a catalyst; wherein R.sub.1, R.sub.2 and R.sub.3 are independently selected and each is H, a C1-C8 alkyl, a C3-C8 cycloalkyl, a C1-C8 alkoxy, a C3-C8 cycloalkoxy, or phenyl; a and c are independently selected and each is an integer of 0 to 5, and b is an integer of 0 to 4:

##STR00001##

In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.

In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.

A compound represented by the formula: ##STR00001## wherein R is selected from the group consisting of (i) substituted or unsubstituted alkyl with C=0 to 12 inclusive; (ii) substituted or unsubstituted aryl; and (iii) substituted and unsubstituted alkylaryl; wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are each selected from the group consisting of alkyl, aryl, alkylaryl groups and hydrogen; wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each selected from the group consisting of alkyl, aryl, alkylaryl groups and hydrogen and R.sup.2 and R.sup.3 may optionally be bridged by a polymethylene group; wherein when C=0 in R, the combined group R.sup.1 R.sup.2 is the same as the combined group R.sup.3 R.sup.4; and wherein when C=1 in R, each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are hydrogen.

A compound represented by the formula: ##STR00001## wherein R is selected from the group consisting of (i) substituted or unsubstituted alkyl with C=0 to 12 inclusive; (ii) substituted or unsubstituted aryl; and (iii) substituted and unsubstituted alkylaryl; wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are each selected from the group consisting of alkyl, aryl, alkylaryl groups and hydrogen; wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each selected from the group consisting of alkyl, aryl, alkylaryl groups and hydrogen and R.sup.2 and R.sup.3 may optionally be bridged by a polymethylene group; wherein when C=0 in R, the combined group R.sup.1 R.sup.2 is the same as the combined group R.sup.3 R.sup.4; and wherein when C=1 in R, each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are hydrogen.

A method for preparing 3,3-diaminobenzidine, the method comprising the following steps: subjecting 4,4-biphenol and N,N-dimethylsulfamoyl chloride to an esterification reaction in a specified solvent at 40-70? C. to obtain 4,4-biphenyl bis(N,N-dimethylaminosulfonate) as a first intermediate; subjecting the 4,4-biphenyl bis(N,N-dimethylaminosulfonate) to a chlorination reaction with a chlorinating reagent under acidic conditions to obtain 3,3-dichloro-4,4-biphenyl bis(N,N-dimethylaminosulfonate) as a second intermediate; subjecting the second intermediate 3,3-dichloro-4,4-biphenyl bis(N,N-dimethylaminosulfonate) to an ammonolysis reaction with anammoniation reagent in the presence of a combined catalyst to obtain a crude product of 3,3,4,4-tetraaminobiphenyl, wherein the combined catalyst is a mixture of proline, a cuprous salt and a phase transfer catalyst; and subjecting the crude product of 3,3,4,4-tetraaminobiphenyl to a post-treatment to obtain a purified 3,3,4,4-tetraaminobiphenyl product. In the present invention, 4,4-biphenol is used as a raw material, a brand-new synthesis route is used, the product purity is high, and pollution of three kinds of waste is reduced.

A method for preparing 3,3-diaminobenzidine, the method comprising the following steps: subjecting 4,4-biphenol and N,N-dimethylsulfamoyl chloride to an esterification reaction in a specified solvent at 40-70? C. to obtain 4,4-biphenyl bis(N,N-dimethylaminosulfonate) as a first intermediate; subjecting the 4,4-biphenyl bis(N,N-dimethylaminosulfonate) to a chlorination reaction with a chlorinating reagent under acidic conditions to obtain 3,3-dichloro-4,4-biphenyl bis(N,N-dimethylaminosulfonate) as a second intermediate; subjecting the second intermediate 3,3-dichloro-4,4-biphenyl bis(N,N-dimethylaminosulfonate) to an ammonolysis reaction with anammoniation reagent in the presence of a combined catalyst to obtain a crude product of 3,3,4,4-tetraaminobiphenyl, wherein the combined catalyst is a mixture of proline, a cuprous salt and a phase transfer catalyst; and subjecting the crude product of 3,3,4,4-tetraaminobiphenyl to a post-treatment to obtain a purified 3,3,4,4-tetraaminobiphenyl product. In the present invention, 4,4-biphenol is used as a raw material, a brand-new synthesis route is used, the product purity is high, and pollution of three kinds of waste is reduced.

Provided herein are (phenylene)dialkanamines, and methods of producing such (phenylene)dialkanamines from various furanyl and benzyl compounds. Such furanyl compounds may include, for example, bis(nitroalkyl)furans, bis(aminoalkyl)furans, and nitroalkyl(furan)acetonitriles. Such compounds may include, for example, bis(nitroalkyl)benzenes. Provided herein are also alkyldiamines, and methods for producing such alkyldiamines from furanyl compounds.

Provided herein are (phenylene)dialkanamines, and methods of producing such (phenylene)dialkanamines from various furanyl and benzyl compounds. Such furanyl compounds may include, for example, bis(nitroalkyl)furans, bis(aminoalkyl)furans, and nitroalkyl(furan)acetonitriles. Such compounds may include, for example, bis(nitroalkyl)benzenes. Provided herein are also alkyldiamines, and methods for producing such alkyldiamines from furanyl compounds.