Stereochemical studies on protonated bridgehead amines. ^1H NMR determination of cis and trans B-C ring-fused structures for salts of hexahydropyrrolo [2,1-a] isoquinolines and related C ring homologs. Capture of unstable ring-fused structures in the solid state

Acid-addition salts of tricyclic isoquinolines 2a/b, 3a/b, 4a-4c, 5, 6a/b, 7, 8a/b, 9a/b, and 17a/b were studied by high-field ^1H NMR in CDCl_3 solution. Cis (e.g., 14 and 15 in Figure 1) and trans (e.g., 13)B-C ring-fused structures were identified by using the vicinal ^3J(CH-NH) coupling constants, which demonstrate a Karplus-like behavior. In some cases, we initially observed a trans form, which converted to a cis A form by N H proton exchange. For 4c.HBr, the exchange process was slowed by addition of trifluoroacetic acid. In many cases, cis A and cis B structures were preferred in solution. The pendant phenyl group exerted a strong influence on the preferred solution structure. Observation of the initial, unstable trans-fused structures was related to their capture in the solid state and release intact on dissolution. X-ray diffraction was performed on the HBr salts of 2a (B-C cis), 2b (B-C cis), and 4c (B-C trans). The result for 4c.HBr confirmed the connection between the initial trans form in solution and the solid state. For 17b.HCI two conformers, associated with hindered rotation about the bond connecting the 2,6-disubstituted phenyl group to the tricyclic array, were detected at ambient probe temperature; however, rotamers were not observed for either of the two forms (trans and cis A) of 17a.HBr. Two conformers were also found for 16b.HBr. Temperature-dependent behavior was recorded in the ^1H NMR spectra of 17b.HBr and 16b.HBr; the activation free energy for interconversion of conformers was estimated to be in the vicinity of 17 kcal/mol for the former and 14-15 kcal/mol for the latter. The ^1H NMR spectrum of butaclamol hydrochloride (20.HC1), a potent neuroleptic agent, in Me_2SO-d_6 revealed two species in a ratio of 81:19, which were assigned as trans and cis A forms, respectively. ^1H NMR data for various free bases are also presented and discussed. Empirical force field calculations on three model hydrocarbons are discussed from a perspective of finding an explanation for the configurational/conformational behavior of the bridgehead ammonium salts. Diverse literature examples of structures for protonated bridgehead amines are also discussed. A tentative rationale is suggested for the preference of cis A forms in some protonated tetrahydroisoquinoline derivatives

Microwave and Physical Electronics

Contains reports on six research projects.Office of Scientific Research and Development (OSRD) OEMsr-26

Physical Electronics

Contains reports on four research projects

Microwave and Physical Electronics

Contains reports on seven research projects

Microwave and Physical Electronics

Contains reports on seven research projects

Microwave and Physical Electronics

Contains reports on six research projects

Fast Photon Detection for Particle Identification with COMPASS RICH-1

Particle identification at high rates is an important challenge for many current and future high-energy physics experiments. The upgrade of the COMPASS RICH-1 detector requires a new technique for Cherenkov photon detection at count rates of several $10^6$ per channel in the central detector region, and a read-out system allowing for trigger rates of up to 100 kHz. To cope with these requirements, the photon detectors in the central region have been replaced with the detection system described in this paper. In the peripheral regions, the existing multi-wire proportional chambers with CsI photocathode are now read out via a new system employing APV pre-amplifiers and flash ADC chips. The new detection system consists of multi-anode photomultiplier tubes (MAPMT) and fast read-out electronics based on the MAD4 discriminator and the F1-TDC chip. The RICH-1 is in operation in its upgraded version for the 2006 CERN SPS run. We present the photon detection design, constructive aspects and the first Cherenkov light in the detector.Comment: Proceedings of the Imaging 2006 conference, Stockholm, Sweden, 27-30 June 2006, 5 pages, 6 figures, to appear in NIM A; corrected typo in caption of Fig.

Fast photon detection for the COMPASS RICH detector

The COMPASS experiment at the SPS accelerator at CERN uses a large scale Ring Imaging CHerenkov detector (RICH) to identify pions, kaons and protons in a wide momentum range. For the data taking in 2006, the COMPASS RICH has been upgraded in the central photon detection area (25% of the surface) with a new technology to detect Cherenkov photons at very high count rates of several 10^6 per second and channel and a new dead-time free read-out system, which allows trigger rates up to 100 kHz. The Cherenkov photons are detected by an array of 576 visible and ultra-violet sensitive multi-anode photomultipliers with 16 channels each. The upgraded detector showed an excellent performance during the 2006 data taking.Comment: Proceeding of the IPRD06 conference (Siena, Okt. 06

The Fast Read-out System for the MAPMTs of COMPASS RICH-1

A fast readout system for the upgrade of the COMPASS RICH detector has been developed and successfully used for data taking in 2006 and 2007. The new readout system for the multi-anode PMTs in the central part of the photon detector of the RICH is based on the high-sensitivity MAD4 preamplifier-discriminator and the dead-time free F1-TDC chip characterized by high-resolution. The readout electronics has been designed taking into account the high photon flux in the central part of the detector and the requirement to run at high trigger rates of up to 100 kHz with negligible dead-time. The system is designed as a very compact setup and is mounted directly behind the multi-anode photomultipliers. The data are digitized on the frontend boards and transferred via optical links to the readout system. The read-out electronics system is described in detail together with its measured performances.Comment: Proceeding of RICH2007 Conference, Trieste, Oct. 2007. v2: minor change

First Measurement of Chiral Dynamics in \pi^- \gamma -> \pi^- \pi^- \pi^+

The COMPASS collaboration at CERN has investigated the \pi^- \gamma -> \pi^- \pi^- \pi^+ reaction at center-of-momentum energy below five pion masses, sqrt(s) < 5 m(\pi), embedded in the Primakoff reaction of 190 GeV pions impinging on a lead target. Exchange of quasi-real photons is selected by isolating the sharp Coulomb peak observed at smallest momentum transfers, t' < 0.001 (GeV/c)^2. Using partial-wave analysis techniques, the scattering intensity of Coulomb production described in terms of chiral dynamics and its dependence on the 3\pi-invariant mass m(3\pi) = sqrt(s) were extracted. The absolute cross section was determined in seven bins of $\sqrt{s}$ with an overall precision of 20%. At leading order, the result is found to be in good agreement with the prediction of chiral perturbation theory over the whole energy range investigated.Comment: 10 pages, 5 figure