3
BENŒNOIDS
A. Simple Benzene Derivatives
1. PHENOLS AND DERIVATIVES
The observation that the red alga Polysiphonia fastigiata (syn. P. lanosa)
contains a phenolic substance was perhaps first recorded by Colin and Augier
(1939). In a follow-up study Leman (1944) isolated the substance as an
off-white crystalline powder and confirmed its phenolic character. Results of
elemental analyses further seemed to point toward the presence of two potassium sulfonate groups and one chlorine atom. Five years later, Mastagli and
Augier (1949) reisolated this phenol from the same red alga and characterized
it as a dibromo-dipotassium sulfonate-hydroxybenzoic acid, which by brief
treatment with 5% hydrochloric acid on a steam bath was converted to a
crystalline dibromohydroxybenzoic acid. These conditions would seem rather
mild and without precedent for desulfonation of a benzenesulfonic acid.
Mastagli and Augier (1949) incidentally made no reference to Leman's
(1944) chlorine analysis. It may be surprising, but it is a fact, that through 1970
no organic chlorine compound had been unequivocally identified from a
marine organism. Bromine, on the other hand, had long been recognized as
an algal constituent, although valence state and bonding of the bromine
were subjects of controversy. Augier and Henry (1950) compared the bromophenol of Mastagli and Augier (1949) with a phenolic substance that Lamure
(1944) had isolated from the red algae Vidalia volubilis and Halophytis
88
BENŒNOIDS
A. Simple Benzene Derivatives
1. PHENOLS AND DERIVATIVES
The observation that the red alga Polysiphonia fastigiata (syn. P. lanosa)
contains a phenolic substance was perhaps first recorded by Colin and Augier
(1939). In a follow-up study Leman (1944) isolated the substance as an
off-white crystalline powder and confirmed its phenolic character. Results of
elemental analyses further seemed to point toward the presence of two potassium sulfonate groups and one chlorine atom. Five years later, Mastagli and
Augier (1949) reisolated this phenol from the same red alga and characterized
it as a dibromo-dipotassium sulfonate-hydroxybenzoic acid, which by brief
treatment with 5% hydrochloric acid on a steam bath was converted to a
crystalline dibromohydroxybenzoic acid. These conditions would seem rather
mild and without precedent for desulfonation of a benzenesulfonic acid.
Mastagli and Augier (1949) incidentally made no reference to Leman's
(1944) chlorine analysis. It may be surprising, but it is a fact, that through 1970
no organic chlorine compound had been unequivocally identified from a
marine organism. Bromine, on the other hand, had long been recognized as
an algal constituent, although valence state and bonding of the bromine
were subjects of controversy. Augier and Henry (1950) compared the bromophenol of Mastagli and Augier (1949) with a phenolic substance that Lamure
(1944) had isolated from the red algae Vidalia volubilis and Halophytis
88