Medicinal Chemistry, 2007, 3, 433-438 433
1573-4064/07 $50.00+.00 © 2007 Bentham Science Publishers Ltd.
6-Aryl-4-Oxohexanoic Acids: Synthesis, Effects on Eicosanoid Biosynthesis,
and Anti-Inflammatory In Vivo-Activities
Khaled Abouzid
1,2,*
, Petra Frohberg
3
, Jochen Lehmann
2
and Michael Decker
2,*
1
Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Ain Shams University, Cairo, Egypt;
2
Lehrstuhl für
Pharmazeutische/Medizinische Chemie, Institut für Pharmazie, Friedrich-Schiller-Universität Jena, Jena, Germany;
3
Institut für Pharmazie, Pharmazeutische Chemie, Martin-Luther Universität Halle-Wittenberg, Halle, Germany
Abstract: The synthesis of a series of 6-aryl-4-oxohexanoic acids is described: This involves condensation of an appro-
priate aldehyde (Ia-f) and levulenic acid using catalytic amounts of piperidine and acetic acid in toluene to afford the 6-
aryl-4-oxohex-5-enoic acids (IIa-f).The arylidene derivatives (IIa-d) were reduced by hydrogen at room temperature us-
ing palladium (10 %/carbon) as catalyst to produce 6-aryl-4-oxohexanoic acids (IIIa-d) as target compounds. In certain
instances, the lactone derivative (IVd) was obtained as a low-melting by-product. These compounds were tested in two
models used for evaluating the activity of non-steroidal anti-inflammatory drugs (NSAIDs). The first test is the effect of
the synthesized compounds on arachidonic acid metabolism in vitro using human whole blood assay. The second is the in
vivo carrageenan induced rat paw edema test. Compound IIe showed higher in vivo-activity compared to fenbufen at the
same dose level (50mg/kg).
Key Words: 6-Aryl-4-oxohexanoic acids, Inflammation, NSAIDs, rat paw edema test, 5-lipoxgenase, arachidonic acid metabo-
lism.
INTRODUCTION
Non-steroidal anti-inflammatory drugs (NSAIDs) are a
widely prescribed and applied class of medications with es-
tablished anti-inflammatory, analgesic, and antipyretic prop-
erties [1,2]. Despite these benefits, traditional NSAIDs such
as (2-acetyloxy)benzoic acid, propionic or acetic acid deriva-
tives have significant gastrointestinal (GI) toxicity as they
inhibit both COX-1 and COX-2 isoforms and frequently
cause gastrointestinal irritations or excessive bleeding [3-5].
These negative side effects prompted the development of
selective COX-2 inhibitors as promising gastroprotective
agents [6,7]. Many of these agents have been developed and
marketed such as celecoxib and refecoxib, which have been
extensively studied and showed exceptional anti-inflamma-
tory properties with reduced GI toxicity. Later on, some po-
tential limitations of long term certain COX-2 inhibitor ther-
apy were described including ulcer exacerbation in high-risk
patients, delayed gastroduodenal ulcer healing, thrombosis
due to prostacyclin deficiency and kidney toxicity. Thus
COX-2 inhibitors have not eliminated the need for improved
drugs in the NSAID area [8-11].
In an important report [12], the effect of some selective
COX-2 inhibitors and some dual (COX-1 and COX-2)
inhibitors on carrageenan pleurisy in the rat over a time
period ranging from 0 to 48 h after injection of the irritant
was studied. The result of this study showed that the COX-2
inhibitors confered anti-inflammatory activity early in the
inflammatory response, coincident with the expression of
COX-2 protein as did the older dual inhibitors such as
indomethacin. However, by 6 h the COX-2 inhibitors were
*Address correspondence to these authors at the Lehrstuhl für Pharmazeuti-
sche/Medizinische Chemie, Institut für Pharmazie, Friedrich-Schiller-
Universität Jena, Jena, Germany; E-mail: m.decker@uni-jena.de;
abouzid@yahoo.com
without effect although the dual inhibitors still showed
efficacy. At this point the COX-2 protein as shown by
Western blotting was no longer present. This study showed
the supremacy of conventional NSAIDs over the COX-2
inhibitors for chronic use. Moreover, withdrawal of rofecoxib
from market recently by its originators due to adverse
cardiovascular effects puts a question mark on the safety
profile of other COXIBs in the long-term therapy.
Attempts to develop alternative COX-2 inhibitors by
slight modification of the classical NSAIDs, resulted in dis-
covery of lumiracoxib [13], a close structural analog to the
well-known NSAID, diclofenac. Recently, a new approach
of anti-inflammatory therapy constitutes the use of inhibitors
of COX-1/2 and LOX pathways as an attempt to develop
new active leads which may provide novel NSAIDs [14-17].
RATIONAL AND DESIGN
In the present work, and in continuing efforts to find dis-
tinctive structural template to NSAIDs with a wider safety
margin, we reinvestigated many of the traditional carboxylic
acid NSAIDs in order to design modified new leads en-
dowed with possible potent and dual COX-1/2 and LOX
inhibitory activity. We utilized the -oxobutanoic acid struc-
tural moiety with suitable substitution at the phenyl ring as
structural template to the leads, since it was reported earlier,
that arylhexenoic acids possess only weak anti-inflammatory
activity in paw oedema test. Therefore, we became interested
in synthesizing modified congeners in attempts to improve
their activity [18]. To accomplish this goal, we designed a
novel series of compounds with aliphatic carboxylic acid
side chain in which 2 carbon spacer linker was used as a
connection unit between the ketonic group of oxobutanoic
acid and the aryl group mimicking certain NSAIDs such as
fenbufen [19], bucloxic acid [20], and trepibutone [21], re-
spectively. This linker could be an ethylene as in case or