1176
hydroxyarenes 21,23,25. In all cases were obtained Table (method C). A further way of isolation is to filter the
G. Ziegler and W. Kantlehner • Orthoamides, LVI
dried toluene solution over a short column (5 cm) filled
with basic alumina (Sigma-Aldrich Nr. 19.944-3). The
filtrate was evaporated und the residue dried (method D).
The reactions can be performed also on a smaller scale.
The following example is given as a typical procedure.
the corresponding formic acid esters (6,8,10,12,14,
16, 18, 20, 22, 24, 26). The results are summarized
in Table 2.
Obviously the method is also suitable for the S-
formylation of arenethiols since 1-thionaphthol (27)
is readily converted to 1-naphthyl thioformate (28),
by treatment with the amide 2.
1-Bromo-2-naphthylformate ( b)
8
l-Bromo-2-naphthol (3.35 g, 0.015 mol), N,N-
diformylacetamide (1) (2.07 g, 0.018 mol) and
praseodymium(III) trifluoromethansulfonate (4 mg) were
heated for 2 h at 90 °C. Toluene (20 ml) was then added,
followed by hexane (15 ml). After cooling the unreacted
naphthol was filtered off, the filtrate was carefully ex-
tracted with water (2 x 20 ml). The organic layer was
dried over sodium sulfate. The solvents were removed at
12 Torr. The residue was destilled in vacuo. Yield: 2.43 g
(65%); b. p. 123 °C/0.1 mmHg, m. p. 64 °C.
Experimental
Arylformates
General procedure
To a mixture of the appropriate phenol (0.200 mol)
and the formylating agent 1or 2, respectively, (
were added as catalyst 5 mg (5-10 mol) of sodium difor-
mamide. In some examples (see Tables 1 and 2) another
catalyst was used. The mixtures were heated for 2 h at
85 °C. In some cases the products could be isolated by di-
rect destination of the mixture (method A). In the second
workup procedure, toluene (50 ml) was added to the hot
0
. 2
0
0
mol)
“
5
Acknowledgements
The present work was supported by the BMBF
reaction mixture. On slow cooling of the mixture, difor- Bonn (FKZ 170330), the Ministerium für Wissenschaft,
mamide or N-acetylformamide, respectively, separated as Forschung und Kunst, Baden-Württemberg (Innovatives
a solid, which was filtered off with suction and washed Projekt: Katalytische, ressourcenschonende Synthese für
with toluene (2 x 50 ml). The organic layer was extracted aromatische Aldehyde).
with cold water (2 x 50 ml) and dried with sodium sul-
fate. After removal of the toluene at 12 Torr in vacuo,
We thank the Verband der Chemischen Industrie
(Fonds der Chemischen Industrie) for financial support.
the residue was distilled over a 20 cm Vigreux column We also thank the companies BASF AG, Ludwighafen
in vacuo (method B). In some cases the solid reaction and Bayer AG, Leverkusen for supporting our work by
products were recrystallized from the solvent given in the
gifts of chemicals.
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