2-Thiabicyclo[3.2.0]hepta-3,6-Dienes. 1. Aluminum Chloride Catalyzed Thermal [2 + 2] Cycloaddition of 2-Butynedinitrile with Alkyl-Substituted Thiophenes

Tetra- and Trialkylthiophenes 4–6 React with 2-Butynedinitrile in the Presence of 1 Equiv of Aluminum Chloride in Dichloromethane at 0 °C Via [2 + 2] Cycloaddition to 2-3.2.0] hepta-3,6-Diene-6,7-Dicarbonitriles 7–10 as the Major Products. Reaction of 4 and 5 Also Gave Small Amounts (4% and 6%) of 1,2-Benzenedicarbonitriles 11 and 12 Which Result from [4 + 2] Cycloaddition and Subsequent Extrusion of Sulfur. 4,5,6,7-Tetrahydro-1,3-Dimethylbenzo[C]thiophene (6) Reacts with 2-Butynedinitrile under the Same Conditions to Give an Ene Adduct (13) in Addition to the [2 + 2] Cycloadduct 10. 2,5-Dimethylthiophene (3) Gave a 2:1 Reaction Product 14, the Formation of Which Can Be Explained Via Friedel-Crafts Alkylation of 3 by the Initially Formed [2 + 2] Cycloadduct. the 2-3.2.0] hepta-3,6-Dienes 7–10 and the Ene Adduct 13 Show Intramolecular Charge-Transfer Absorptions in the UV Spectra. © 1982, American Chemical Society. All Rights Reserved

2-Thiabicyclo[3.2.0]-hepta-3,6-dienes. 2. Thermal and photochemical isomerization of 2-thiabicyclo[3.2.0]hepta-3,6-dienes. An example of the antarafacial-antarafacial Cope rearrangement

Thermal Rearrangement of 2-3.2.0] hepta-3,6-Diene-6,7-Dicarbonitrile8 1–3 to their 4,5-Dicarbonitrile Isomers 4–6 Takes Place at 110–140 °C in Yields of 82–84%. the Reactions Are First Order with Rates Almost Independent of the Polarity of the Solvent. Activation Parameters (ΔH‡ = 120–140 KJ Mol−1 and ΔS‡ ≈ 0 J K−1 Mol−1) Are in Agreement with a Concerted Symmetry-Allowed Antarafacial-Antarafacial Cope Rearrangement. Compounds 1–3 Rearrange Photochemically Via Cleavage of the C-1-S Bond to the 1,7-Dicarbonitrile Isomers 7–9. Isomer 9 Rearranges Further on Prolonged Irradiation to Give 10. a Tentative Mechanism for This Rearrangement is Given. © 1982, American Chemical Society. All Rights Reserved

Inotropic effects of propofol, thiopental, midazolam, etomidate, and ketamine on isolated human atrial muscle

Background: Cardiovascular instability after intravenous induction of anesthesia may be explained partly by direct negative inotropic effects. The direct inotropic influence of etomidate, ketamine, midazolam, propofol, and thiopental on the contractility of isolated human atrial tissue was determined. Effective concentrations were compared with those reported clinically. Methods: Atrial tissue was obtained from 16 patients undergoing coronary bypass surgery. Each fragment was divided into three strips, and one anesthetic was tested per strip in increasing concentrations (10 -6 to 10 - 2 M). Strips were stimulated at 0.5 Hz, and maximum isometric force was measured. Induction agents were studied in two groups, group 1 (n = 7) containing thiopental, midazolam, and propofol, and group 2 (n = 9) consisting of etomidate, ketamine, and propofol. Results: The tested anesthetics caused a concentration-dependent depression of contractility resulting in complete cessation of contractions at the highest concentrations. The IC 50s (mean ± SEM; μM) for inhibition of the contractility were: thiopental 43 ± 7.6, propofol 235 ± 48 (group 1), and 246 ± 42 (group 2), midazolam 145 ± 54, etomidate 133 ± 13, and ketamine 303 ± 54. Conclusions: This is the first study demonstrating a concentration-dependent negative inotropic effect of intravenous anesthetics in isolated human atrial muscle. NO inhibition of myocardial contractility was found in the clinical concentration ranges of propofol, midazolam, and etomidate. In contrast, thiopental showed strong and ketamine showed slight negative inotropic properties. Thus, negative inotropic effects may explain in part the cardiovascular depression on induction of anesthesia with thiopental but not with propofol, midazolam, and etomidate. Improvement of hemodynamics after induction of anesthesia with ketamine cannot be explained by intrinsic cardiac stimulation

Long Range Order at Low Temperature in Dipolar Spin Ice

Recently it has been suggested that long range magnetic dipolar interactions are responsible for spin ice behavior in the Ising pyrochlore magnets ${\rm Dy_{2}Ti_{2}O_{7}}$ and ${\rm Ho_{2}Ti_{2}O_{7}}$. We report here numerical results on the low temperature properties of the dipolar spin ice model, obtained via a new loop algorithm which greatly improves the dynamics at low temperature. We recover the previously reported missing entropy in this model, and find a first order transition to a long range ordered phase with zero total magnetization at very low temperature. We discuss the relevance of these results to ${\rm Dy_{2}Ti_{2}O_{7}}$ and ${\rm Ho_{2}Ti_{2}O_{7}}$.Comment: New version of the manuscript. Now contains 3 POSTSCRIPT figures as opposed to 2 figures. Manuscript contains a more detailed discussion of the (i) nature of long-range ordered ground state, (ii) finite-size scaling results of the 1st order transition into the ground state. Order of authors has been changed. Resubmitted to Physical Review Letters Contact: [email protected]