Short total syntheses of both the putative and actual structures of the clerodane diterpenoid (+/-)-sacacarin by double annulation.
[reaction: see text] The putative structure of the naturally occurring clerodane diterpenoid (+/-)-sacacarin has been prepared in only 10 steps, six of which are C-C bond-forming steps, in a chemo-, regio-, and diastereoselective manner. The key part of the synthesis is the double annulation (double Michael, Pinner, and Dieckmann reaction) of a tethered carbon diacid and 3-butyn-2-one. A corrected structure for sacacarin is proposed, and the structure is proven by synthesis.
Terpenoids from Croton cajucara
The bark of Croton cajucara afforded two novel clerodane-type furano-diterpenes, t-cajucarin B and sacacarin, in addition to the previously isolated nor-clerodane diterpenes t-crotonin, t-dehydrocrotonin, cajucarin B and cajucarinolide. The triterpene acetyl aleuritolic acid, was also obtained. Structure elucidation was achieved by spectroscopic measurements including 2D-NMR experiments.
Influence of filler addition, storage medium and evaluation time on biaxial flexure strength and modulus of adhesive systems
Abstract Objective. This study evaluated the effects of filler addition, storage medium and time on biaxial flexural strength and flexural modulus of six adhesive systems. Materials and methods. The adhesives were either unfilled resins: Single Bond, Prime&Bond 2.1 and One-Step; or filled resins: Single Bond Plus, Prime&Bond NT and One-Step Plus. Resin discs of each product (0.5 mm thick × 6.0 mm diameter) were prepared using silicon molds (n = 10). The discs were stored dry, in water, mineral oil or ethanol for 1 week or 3 months before biaxial flexural testing. Data were statistically analyzed by 3-way ANOVA and Tukey's post-hoc test (α = 0.05). The specimens were tested in a universal testing machine at 1.27 mm/min until failure occurred. Results. In general, the storage in ethanol led to significantly lower flexural strength and flexural modulus values than the other storage conditions for all adhesives in both storage periods. Filler addition increased flexural strength and flexural modulus for Prime&Bond NT, when it was stored dry or in water for 1 week. For Single Bond Plus, the filler addition resulted in higher flexural modulus, when it was stored for 1 week in oil and in ethanol. No significant differences in flexural modulus were observed between One-Step and One-Step Plus in any storage medium. Conclusions. Results suggested that filler addition does not necessarily have to increase the flexural strength and flexural modulus. Ethanol and oil storages tended to yield opposite effects.