Alizarin from coal-tar anthracene: the madder dye repeated in the laboratory

1868-1869 Fire and matter method

An industrial synthesis of alizarin, the colouring principle of madder, from the anthracene of coal tar. For the first time not a 'similar' dye but the same natural dye itself, repeated from its analysed structure.

Alizarin had been used by dyehouses with mordants for thousands of years: red with alum, violet with iron. In 1868 the Germans Carl Graebe and Carl Liebermann showed that it is a derivative of anthracene, a hydrocarbon of coal tar, and sketched a route to its synthesis. In 1869 Heinrich Caro at BASF and William Perkin in England independently found commercial routes; a single day's difference in filing decided who would have the world outside Britain.

The cultivation of madder declined thereafter. Travis notes that historians usually pass alizarin by and linger on the mauve of 1856, although by 1874 the trade in artificial alizarin was already putting the whole aniline trade in the shade.

Why this date

Exact within two years. Graebe and Liebermann in Berlin found in 1868 that alizarin is an anthracene derivative, established its partial structure and sketched a route to its synthesis; commercial routes were found independently in 1869 by Caro at BASF and by Perkin in England, and manufacture began in 1869-70 (Travis 2008). Perkin filed his patent one day after the BASF group (Nagendrappa 2010). The axis value is 1869, the year of the commercially usable synthesis; the event is sometimes dated 1868, from the work on the structure.

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