1-alkenyl-9,10-anthraquinones

Abstract

Abstract THERE ARE DISCLOSED CERTAIN 1-ALKENYL-9, 10-ANTHRAQUINONES OF THE FORMULA 1-(CH2=C(-R4)-CH(-R3)-CH2-),2-R2,3-R1-ANTHRAQUINONE, OR 1-(CH3-C(-R4)=C(-R3)-CH2-),2-R2,3-R1-ANTHRAQUINONE WHEREIN EACH OF R1 AND R4 IS AN ALKYL GROUP, OR EITHER IS AN ALKYL GROUP AND THE OTHER IS HYDROGEN; AND EACH OF R2 AND R3 IS AN ALKYL GROUP OR HYDROGEN, PROVIDED THAT R2 IS ALWAYS HYDROGEN WHEN EACH FO R1 AND R3 IS HYDROGEN, WHICH ALKYL GROUP OR GROUPS ARE 1-8 CARBON STRAIGHT CHAIN HYDROCARBON ALKYL GROUPS. ALSO DISCLOSED IS A METHOD FOR PREPARING SUCH SUBSTITUTED ANTHRAQUINONES OF FORMULA IIIA WHICH INVOLVES EFFECTING A DIELS-ALDER CONDENSATION BETWEEN 1,4-NAPHTHOQUINONE AND AN ALKYL SUBSTITUTED 1,3,7OCTATRIENE OF THE FORMULA CH2=C(-R1)-C(-R2)=CH-CH2-CH(-R3)-C(-R4)=CH2 WHEREIN R1, R2, R3 AND R4 ARE AS DEFINED ABOVE; PARTIALLY OXIDIZING THE RESULTING ADDUCT WHICH IS A 1,4,4A,9A-TETRAHYDRO-1-ALKDENYLANTHRAQUINONE WITH EITHER CUPRIC ACETATE, OR WITH OXYGEN OR AIR INTHE PRESENCE OF A WEAK BASE TO OBTAIN A 1,4-DIHYDRO-1-ALKENYL-ANTHRAQUINONE; AND THEN FURTHER OXIDIZING THE LATTER WITH OXYGEN OR AIR IN THE PRESENCE OF A STRONG BASE SUCH AS POTASSIUM HYDROXIDE. ALTERNATIVELY, THE ADDUCT FROM THE DIELS-ALDER CONDENSATION CAN BE CONVERTED DIRECTLY TO THE ANTHRAQUINONE OF FORMULA IIIA BY OXIDATION WITH OXYGEN OR AIR IN THE PRESENCE OF A STRONG BASE SUCH AS POTASSIUM HYDROXIDE. HEATING THE COMPOUNS OF FORMULA IIIA IN THE PRESENCE OF A STRONG ACID SUCH AS P-TOLUENE SULFONIC ACID REARRANGES THEIR STRUCTURE TO THAT OF FORMULA IIIB. THE ABOVE 1-ALKENYL ANTHRAQUINONES CAN BE CONVERTED TO TETRAHYDRO-1-ALKYLANTHRAQUINONES THAT ARE OUTSTANDINGLY USEFUL AS WORKING INTERMEDIATED IN CYCLIC REDUCTION-OXIDATION METHODS FOR PRODUCING HYDROGEN PEROXIDE.

Inventors

• 👤 A Josey
• 👤 J Kirchner

Bibliographic Details