Ireland results

More recently, pharmaceutical medicine has been recognized and listed as a medical speciality in four countries, Switzerland, Mexico, United Kingdom and Ireland, resulting in accreditation of the physician specialists as the outcome of their training. 

In contrast to the acyclic aUyl silyl ketene acetals, cyclic substrates may preferentially rearrange through either the chair or boat transitions states. In 1981 Bartlett and Pizzo reported that treatment of cyclohexenyl propionates under either set of conditions reported by Ireland resulted in the formation of the same major isomer (Scheme 4.17) [20]. They concluded that the -silyl ketene acetal rearranged preferentially via a chair-hke transition state, while the Z-silyl ketene acetal rearranged via a boat-like transition state. These conclusions were recently supported computationally by Houk et al., who reported a 1.0 kcal/mol preference for the boat transition state for the Z-geometry in the analogous OMe ketene acetal and a 1.4 kcal/mol preference for the chair transition state for the -geometry in the OMe ketene acetal [18]. 

Schemes 28 and 29 illustrate Curran s synthesis of ( )-hirsutene [( )-1]. Luche reduction58 of 2-methylcyclopentenone (137), followed by acetylation of the resulting allylic alcohol, furnishes allylic acetate 138. Although only one allylic acetate stereoisomer is illustrated in Scheme 28, compound 138 is, of course, produced in racemic form. By way of the powerful Ireland ester enolate Clai-sen rearrangement,59 compound 138 can be transformed to y,S-unsaturated tm-butyldimethylsilyl ester 140 via the silyl ketene acetal intermediate 139. In 140, the silyl ester function and the methyl-substituted ring double bond occupy neighboring regions of space, a circumstance that favors a phenylselenolactonization reac-...

The synthesis in Scheme 13.44 is also based on a carbohydrate-derived starting material. It controlled the stereochemistry at C(2) by means of the stereoselectivity of the Ireland-Claisen rearrangement in Step A (see Section 6.4.2.3). The ester enolate was formed under conditions in which the T -enolate is expected to predominate. Heating the resulting silyl enol ether gave a 9 1 preference for the expected stereoisomer. The... 

In western and northwestern England, Ireland, Scotland, and Norway and in the Hebrides and Orkney Islands, peasants neglected their farms and herds three months of the year to cut seaweed and haul it ashore. Instead of using it to manure their fields or overwinter their cattle, they dried and burned the seaweed, boiled the ashes, evaporated the liquid, and earned pennies for their pains. The result, called kelp, was only 5 to 8 percent sodium and potassium carbonate. Kelp made big landowners wealthy, but it impoverished peasant farmers. 

The national indoor air radon survey commenced in the autumn of 1985. In this first phase of the work radon detectors were sent to 400 randomly selected households throughout Ireland, A further 400 households are scheduled to receive detectors by the end of April 1986. At the time of writing radon detectors from a total of 220 households have been recovered and processed. The principal results obtained are shown in Table II, together with the results of the earlier pilot survey and the cumulative results for both sets of data. 

Zinc normally aids wound healing in terrestrial invertebrates. Wounding of the optic tentacle, foot tissue, and partial shell removal in Helix aspersa, a terrestrial gastropod, resulted in deposition of zinc in the wound area after 2 to 5 days. Increased zinc in Helix wound areas may be necessary to promote protein synthesis, collagen formation, and mitotic cell division (Ireland 1986). 

M. D. Schmitz, S. A. Bowring, and T. R. Ireland. Evaluation of Duluth Complex Anorthositic Series (AS3) Zircon as a U-Pb Geochronological Standard New High-Precision Isotope Dilution Thermal Ionization Mass Spectrometry Results, Geochim. Cosmochim. Acta, 67(2003) 3665-3672. 

The double bond of butenolides reacts under Diels-Alder conditions and the resulting chiral bicycles have served as precursors of prostacycline analogs and chrysanthemic acids (250,251). The butenolide 248 was obtained by the procedure described by Ireland et al. (237). A bicyclo[4.3.0] ring system (254) was prepared by Diels-Alder reaction of 248 with butadiene in the presence of aluminum trichloride. Reduction of 254 (LiBH4) yielded the... 

Further variations of the Claisen rearrangement protocol were also utilized for the synthesis of allenic amino acid derivatives. Whereas the Ireland-Claisen rearrangement led to unsatisfactory results [133b], a number of variously substituted a-allenic a-amino acids were prepared by Kazmaier [135] by chelate-controlled Claisen rearrangement of ester enolates (Scheme 18.47). For example, deprotonation of the propargylic ester 147 with 2 equiv. of lithium diisopropylamide and transmetallation with zinc chloride furnished the chelate complex 148, which underwent a highly syn-stereoselective rearrangement to the amino acid derivative 149. 

Titanium-calcium. The first evidence for isotopic anomalies in the iron-group was found in Ti showing up to 10% excesses of Ti in hibonites from the Murray CM2 meteorite (Hutcheon et al. 1983 Fahey et al. 1985 Ireland et al. 1985 Hinton et al. 1987). Further studies in Murchison showed that Ti extended from -7% to +27% associated with Ca variation from -6% to +10% (Ireland 1988 Ireland 1990). Except for the magnitude of the variations, this is similar to the results from Allende inclusions. Only a few samples display mass-dependent fractionation for which it ranges up to 1.3 %/amu. In the majority of the samples, it is absent or very low (less than 1 %o/amu) for Ca-Ti. There is no correlation between the presence of linear fractionation and the magnitude of Ti effects. Ti variations are also present, but about an order of magnitude smaller than Ti. Variations affecting these two isotopes are related but not strictly correlated (Ireland 1988). 

As for Allende s inclusions, variable contributions of a component produced in neutron-rich nuclear statistical equilibrium best explains the Ti- Ca data. Some parts of the solar nebula were depleted in these isotopes as deficits are also seen. There are several possibilities for explaining the variations in Ti. 1) The neutron-rich component itself may be heterogeneous and incorporate locally less neutron-rich statistical equilibrium products (Hartmann et al. 1985). 2) Ti may result from another process like explosive Si or He burning (Clayton 1988). This component would be associated with the neutron-rich component but not completely homogenized. In all cases, carriers are solid grains which may have behaved differently than the gaseous nebula during the formation of the solar system. A minimum number of components may be calculated to account for the Ca and Ti isotopic data, which number up to 3 (Ireland 1990) but to be conservative at the 5ct level, clearly resolved effects are present only on 3 isotopes ( Ca, Ti, Ti). 

The kinetic enolization of esters with amide bases such as lithium diisopropylamide (LDA) and the resultant aldol condensations with representative aldehydes have been investigated by several groups (2,32,33). The enolate stereochemical assignments were determined by silylation in direct analogy to studies reported by Ireland (34). The preponderance of (E )-enolate observed with LDA (THF) in these... 

Only limited precedent exists for the stereoselective enolization and subsequent condensation of a-heteroatom-substituted esters 48a and 48b (eq. [29]). Ireland has examined the enolization process for a-amino ester derivatives where the Claisen rearrangement (chair-preferred transition states) was employed to ascertain enolate geometry (Scheme 10) (43). These results imply that 48a [X = N(CH2Ph)2 ] exhibits only modest selectivity for ( )-enoIate formation under the... 

Figure 7.2. (A) The greased-gap technique for recording depolarizations of the rat isolated vagus nerve. (B) The effect of ondansetron on depolarizations of the rat isolated vagus nerve induced by 5-HT. Symbols indicate controls (9) or in the presence of ondansetron at I x 10 M (O), 3 X 70" M (M), I X 10 M (O) or 3 x 10 M (A). Results are the mean + S.E.M. of at least four determinations. Experiments were performed as described by Ireland and Tyers [21J. (C) Data from the experiments illustrated in B plotted according to Arunlakshana and Schild [22]. Each point is the result from a separate tissue. The gradient of straight line (95 Vo confidence limits) was determined using linear regression analysis.

In Ireland, compliance with toxicity limits for selected industries is ascertained by annual or biannual test on representative samples of effluent. The test species most commonly used is the rainbow trout (Salmo gairdneri). Control authorities normally require results from 96-hour tests. The toxicity values are expressed as the minimum acceptable proportion of effluent (as a percentage) in a test resulting in 50% fish mortality after 96 hours of exposure. The toxic units (TU) are defined as the maximum number of times an effluent may be diluted to produce the test criteria (TU = 100/96-hour LC50, with LC50 expressed as the percentage of effluent in the test) (Fig. 5). 

Production processes used in the pharmaceutical/fine chemical, cosmetic, textile, rubber, and other industries result in wastewaters containing significant levels of aliphatic solvents. It has been reported that of the 1000 tons per year of EC-defined toxic wastes generated in Ireland, organic solvents contribute 66% of the waste [27]. A survey of the constituents of pharmaceutical wastewater in Ireland has reported that aliphatic solvents contribute a significant proportion of the BOD/COD content of pharmaceutical effluents. Organic solvents are flammable, malodorous, and potentially toxic to aquatic organisms and thus require complete elimination by wastewater treatment systems. 

Sigmatropic rearrangements proceed via closed transition states in the Claisen-Ireland variation a silyl-enol ester, 27 or 28, is used, which may be selectively generated in (Z) or (E) configuration12 (Section A. 1.6.3.1.). As shown in the transition states 32 and 29, this results in the formation of 30/31 and 33/34. 

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