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  • Organic Chemistry  (5,568)
  • Aircraft Propulsion and Power
  • Industrial Chemistry
  • 1985-1989  (3,673)
  • 1950-1954  (3,418)
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  • 1
    Publication Date: 2019-06-28
    Description: A comparison of the operating characteristics of 75-millimeter-bore (size 215) cylindrical-roller one-piece inner-race-riding cage-type bearings was made using a laboratory test rig and a turbojet engine. Cooling correlation parameters were determined by means of dimensional analysis, and the generalized results for both the inner- and outer-race bearing operating temperatures are compared for the laboratory test rig and the turbojet engine. Inner- and outer-race cooling-correlation curves were obtained for the turbojet-engine turbine-roller bearing with the same inner- and outer-race correlation parameters and exponents as those determined for the laboratory test-rig bearing. The inner- and outer-race turbine roller-bearing temperatures may be predicted from a single curve, regardless of variations in speed, load, oil flow, oil inlet temperature, oil inlet viscosity, oil-jet diameter or any combination of these parameters. The turbojet-engine turbine-roller-bearing inner-race temperatures were 30 to 60 F greater than the outer-race-maximum temperatures, the exact values depending on the operating condition and oil viscosity; these results are in contrast to the laboratory test-rig results where the inner-race temperatures were less than the outer-race-maximum temperatures. The turbojet-engine turbine-roller bearing, maximum outer-race circumferential temperature variation was approximately 30 F for each of the oils used. The effect of oil viscosity on inner- and outer-race turbojet-engine turbine-roller-bearing temperatures was found to be significant. With the lower viscosity oil (6x10(exp -7) reyns (4.9 centistokes) at 100 F; viscosity index, 83), the inner-race temperature was approximately 30 to 35 F less than with the higher viscosity oil (53x10(exp -7) reyns (42.8 centistokes) at 100 F; viscosity index, 150); whereas the outer-race-maximum temperatures were 12 to 28 F lower with the lower viscosity oil over the DN range investigated.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E51I05
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  • 2
    Publication Date: 2019-06-28
    Description: A literature survey was conducted to determine the relation between aircraft ignition sources and inflammables. Available literature applicable to the problem of aircraft fire hazards is analyzed and, discussed herein. Data pertaining to the effect of many variables on ignition temperatures, minimum ignition pressures, and minimum spark-ignition energies of inflammables, quenching distances of electrode configurations, and size of openings incapable of flame propagation are presented and discussed. The ignition temperatures and the limits of inflammability of gasoline in air in different test environments, and the minimum ignition pressure and the minimum size of openings for flame propagation of gasoline - air mixtures are included. Inerting of gasoline - air mixtures is discussed.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-TN-2227
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  • 3
    Publication Date: 2019-06-28
    Description: Tests of two propellers having two blades and differing only in the inboard pitch distribution were made in the Langley 8-foot highspeed tunnel to determine the effect of inboard pitch distribution on propeller performance. propeller was designed for operation in the reduced velocity region ahead of an NACA cowling; the inboard pitch distribution of the modified propeller was increased for operation at or near free-stream velocities, such as would be obtained in a pusher installation. conditions covering climb, cruise, and high-speed operation. Wake surveys were taken behind the propellers in order to determine the distribution of thrust along the blades and to aid in the analysis of the results. Test results showed that the modified propeller was about 2.5 percent less efficient for a typical climb condition at all altitudes, 2 percent more efficient for one cruise condition, and 5 percent more efficient for high-speed operation. speed condition, the modified propeller showed a 6-percent loss in efficiency due to compressibility; whereas the original propeller showed an 11-percent efficiency loss due to compressiblity. The lower compressibility loss for the modified propeller resulted from the fact that the inboard sections of this propeller could operate at increased thrust loading after compressibility losses had occurred at the outboard sections.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-TN-2268
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  • 4
    Publication Date: 2019-06-28
    Description: As part of a general investigation of propellers at high forward speeds, tests of two 2-blade propellers having the NACA 4-(3)(8)-03 and NACA 4-(3)(8)-45 blade designs have been made in the Langley 8-foot high-speed tunnel through a range of blade angle from 20 degrees to 60 degrees for forward Mach numbers from 0.165 to 0.725 to establish in detail the changes in propeller characteristics due to compressibility effects. These propellers differed primarily only in blade solidity, one propeller having 50 percent and more solidity than the other. Serious losses in propeller efficiency were found as the propeller tip Mach number exceeded 0.91, irrespective of forward speed or blade angle. The magnitude of the efficiency losses varied from 9 percent to 22 percent per 0.1 increase in tip Mach number above the critical value. The range of advance ratio for peak efficiency decreased markedly with increase of forward speed. The general form of the changes in thrust and power coefficients was found to be similar to the changes in airfoil lift coefficient with changes in Mach number. Efficiency losses due to compressibility effects decreased with increase of blade width. The results indicated that the high level of propeller efficiency obtained at low speeds could be maintained to forward sea-level speeds exceeding 500 miles per hour.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-TR-999
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  • 5
    facet.materialart.
    Unknown
    In:  CASI
    Publication Date: 2019-06-28
    Description: An investigation has been made to explore the possibilities of axial-flow compressors operating with supersonic velocities into the blade rows. Preliminary calculations showed that very high pressure ratios across a stage, together with somewhat increased mass flows, were apparently possible with compressors which decelerated air through the speed of sound in their blading. The first phase of the investigation was the development of efficient supersonic diffusers to decelerate air through the speed of sound. The present report is largely a general discussion of some of the essential aerodynamics of single-stage supersonic axial-flow compressors. As an approach to the study of supersonic compressors, three possible velocity diagrams are discussed briefly. Because of the encouraging results of this study, an experimental single-stage supersonic compressor has been constructed and tested in Freon-12. In this compressor, air decelerates through the speed of sound in the rotor blading and enters the stators at subsonic speeds. A pressure ratio of about 1.8 at an efficiency of about 80 percent has been obtained.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-TR-974 , NACA-ACR-L6D02 , NACA-AR-36
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  • 6
    Publication Date: 2019-06-27
    Description: Sound pressure levels, frequency spectrum, and jet velocity profiles are presented for an engine-afterburner combination at various values of afterburner fuel - air ratio. At the high fuel-air ratios, severe low-frequency resonance was encountered which represented more than half the total energy in the sound spectrum. At similar thrust conditions, lower sound pressure levels were obtained from a current fighter air craft with a different afterburner configuration. The lower sound pressure levels are attributed to resonance-free afterburner operation and thereby indicate the importance of acoustic considerations in afterburner design.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E54G07
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  • 7
    Publication Date: 2019-06-27
    Description: An experimental investigation was conducted to determine the cooling effectiveness of a wide variety of air-cooled turbine-blade configurations. The blades, which were tested in the turbine of a - commercial turbojet engine that was modified for this investigation by replacing two of the original blades with air-cooled blades located diametrically opposite each other, are untwisted, have no aerodynamic taper, and have essentially the same external profile. The cooling-passage configuration is different for each blade, however. The fabrication procedures were varied and often unique. The blades were fabricated using methods most suitable for obtaining a small number of blades for use in the cooling investigations and therefore not all the fabrication procedures would be directly applicable to production processes, although some of the ideas and steps might be useful. Blade shells were obtained by both casting and forming. The cast shells were either welded to the blade base or cast integrally with the base. The formed shells were attached to the base by a brazing and two welding methods. Additional surface area was supplied in the coolant passages by the addition of fins or tubes that were S-brazed. to the shell. A number of blades with special leading- and trailing-edge designs that provided added cooling to these areas were fabricated. The cooling effectiveness and purposes of the various blade configurations are discussed briefly.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E51E23 , REPT-2203
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  • 8
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    In:  CASI
    Publication Date: 2019-08-16
    Description: An integrated control system for coaxial counterrotating aircraft propulsors driven by a common gas turbine engine. The system establishes an engine pressure ratio by control of fuel flow and uses the established pressure ratio to set propulsor speed. Propulsor speed is set by adjustment of blade pitch.
    Keywords: Aircraft Propulsion and Power
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  • 9
    Publication Date: 2019-08-16
    Description: Contents: Preliminary notes on the efficiency of propulsion systems; Part I: Propulsion systems with direct axial reaction rockets and rockets with thrust augmentation; Part II: Helicoidal reaction propulsion systems; Appendix I: Steady flow of viscous gases; Appendix II: On the theory of viscous fluids in nozzles; and Appendix III: On the thrusts augmenters, and particularly of gas augmenters
    Keywords: Aircraft Propulsion and Power
    Type: NACA-TM-1259
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  • 10
    Publication Date: 2019-07-11
    Description: Strain-gages were used to measure blade vibrations causing failures in the third stage of a production 11-stage axial-flow compressor. After the serious third-stage vibration was detected, a series of investigations were conducted with second-stage vane assemblies of varying angles of incidence. Curves presented herein show the effect of varying the angle of incidence of second-stage vane assembly on third-stage rotor-blade vibration amplitude and engine performance. A minimum vibration amplitude was obtained without greatly affecting the engine performance with a second-stage vane assembly of 9deg. greater angle of incidence than the assembly normally furnished with the engine.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE51F08
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  • 11
    Publication Date: 2019-07-11
    Description: An investigation was conducted to determine the effects of water injection on the over-all performance of a modified J33-A-27 turbojet-engine compressor at the design equivalent speed of 11,800 rpm. The water-air ratio by weight was 0.05. With water injection the peak pressure ratio increased 9.0 per- cent, the maximum efficiency decreased 15 percent (actual numerical difference 0.12), and. the maximum total weight flow increased 9.3 percent.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE50F14
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  • 12
    Publication Date: 2019-07-11
    Description: An investigation of the altitude performance characteristics of an Allison J35-A-17 turbojet engines have been conducted in an altitude chamber at the NACA Lewis laboratory. Engine performance was obtained over a range of altitudes from 20,000 to 60,000 feet at a flight Mach number of 0.62 and a range of flight Mach numbers from 0.42 to 1.22 at an altitude of 30,000 feet. The performance of the engine over the range investigated could be generalized up to an altitude of 30,000 feet. Performance of the engine at any flight Mach number in the range investigated can be predicted for those operating condition a t which critical flow exits in the exhaust nozzle with the exception of the variables corrected net thrust, and net-thrust specific fuel consumption.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E50I15
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  • 13
    Publication Date: 2019-07-11
    Description: The compressor from the XT-46 turbine-propeller engine was revised by removing the last two rows of stator blades and by eliminating the interstage leakage paths described in a previous report. With the revised compressor, the flow choking point shifted upstream into the last rotor-blade row but the maximum weight flow was not increased over that of the original compressor. The flow range of the revised compressor was reduced to about two-thirds that obtained with the original compressor. The later stages of the compressor did not produce the design static-pressure increase probably because of excessive boundary-layer build-up in this region. Measurements obtained in the ninth-stage stator showed that the performance up to this station was promising but that the last three stages of the compressor were limiting the useful operating range of the preceding stages. Some modifications in flow-passage geometry and blade settings are believed to be necessary, however, before any major improvements in over-all compressor performance can be obtained.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE50J10
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  • 14
    Publication Date: 2019-07-11
    Description: The power plant from a Mark 25 aerial torpedo was investigated both as a two-stage turbine and as a single-stage modified turbine to determine the effect on overall performance of nozzle size and shape, first-stage rotor-blade configuration, and axial nozzle-rotor running clearance. Performance was evaluated in terms of brake, rotor, and blade efficiencies. All the performance data were obtained for inlet total to outlet static pressure ratios of 8, 15 (design), and 20 with inlet conditions maintained constant at 95 pounds per square inch gage and 1000 F for rotor speeds from approximately 6000 to 18,000 rpm.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE50D12
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  • 15
    Publication Date: 2019-07-11
    Description: An investigation of a decoupler and a controlled-feathering device incorporated with the YT-56A turboprop engine has been made to determine the effectiveness of these devices in reducing the high negative thrust (drag) which accompanies power failure of this type of engine. Power failures were simulated by fuel cut-off, both without either device free to operate, and with each device free to operate singly. The investigation was made through an airspeed range from 50 to 230 mph. It was found that with neither device free to operate, the drag levels realized after power failures at airspeeds above 170 mph would impose vertical tail loads higher than those allowable for the YC-130, the airplane for which the test power package was designed. These levels were reached in approximately one second. The maximum drag realized after power failure was not appreciably altered by the use of the decoupler although the decoupler did put a limit on the duration of the peak drag. The controlled-feathering device maintained a level of essentially zero drag after power failure. The use of the decoupler in the YT-56A engine complicates windmilling air-starting procedures and makes it necessary to place operating restrictions on the engine to assure safe flight at low-power conditions,
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SA54I09
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  • 16
    Publication Date: 2019-07-12
    Description: The operational characteristics of a J57-P1 turbojet engine have been investigated at altitudes between 15,000 and 66,000 feet in the Lewis altitude wind tunnel. Included in this study is a discussion of fuel nozzle coking, the altitude operating limits with and without the standard engine control, the compressor surge characteristics, and the engine starting and windmilling characteristics. Severe circumferential turbine outlet temperature gradients which occurred at high altitude as a result of fuel nozzle coking were alleviated by the manufacturer's change in the fuel flow divider schedule and in a nozzle gasket material. Compressor air bleed is required to prevent surge of the outboard compressor in the low engine speed region. The maximum altitude at which the engine was operated without the control was about 66,000 feet at 0.8 flight Mach number and at a reduced engine speed to avoid compressor surge; with the engine control in operation, the altitude operating limit is reduced to approximately 59,000 feet. The maximum altitude at which the engine was started was about 40,000 feet.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE54C31
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  • 17
    Publication Date: 2019-07-12
    Description: An investigation to increase the compressor surge-limit pressure ratio of the XJ40-WE-6 turbojet engine at high equivalent speeds was conducted at the NACA Lewis altitude wind tunnel. This report evaluates the compressor modifications which were restricted to (1) twisting rotor blades (in place) to change blade section angles and (2) inserting new stator diaphragms with different blade angles. Such configuration changes could be incorporated quickly and easily in existing engines at overhaul depots. It was found that slight improvements in the compressor surge limit were possible by compressor blade adjustment. However, some of the modifications also reduced the engine air flow and hence penalized the thrust. The use of a mixer assembly at the compressor outlet improved the surge limit with no appreciable thrust penalty.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE52G03
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  • 18
    Publication Date: 2019-08-17
    Description: A propulsor blade for an aircraft engine includes an airfoil section formed in the shape of a scimitar. A metallic blade spar is interposed between opposed surfaces of the blade and is bonded to the surfaces to establish structural integrity of the blade. The metallic blade spar includes a root end allowing attachment of the blade to the engine.
    Keywords: Aircraft Propulsion and Power
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  • 19
    Publication Date: 2019-08-17
    Description: An integrated control system for coaxial counterrotating aircraft propulsors driven by a common gas turbine engine. The system establishes an engine pressure ratio by control of fuel flow and uses the established pressure ratio to set propulsor speed. Propulsor speed is set by adjustment of blade pitch.
    Keywords: Aircraft Propulsion and Power
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  • 20
    facet.materialart.
    Unknown
    In:  CASI
    Publication Date: 2019-08-13
    Description: The performance of a jet power plant consisting of a compressor and a turbine is determined by the characteristic curves of these component parts and is controllable by the characteristics of the compressor and the turbine i n relation t o each other. The normal. output, overload, and throttled load of the Jet power plant are obtained on the basis of assumed straight-line characteristics.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-TM-1258
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  • 21
    Publication Date: 2019-07-11
    Description: An investigation was conducted at simulated high-altitude flight conditions to evaluate the use of compressor evaporative cooling as a means of turbojet-engine thrust augmentation. Comparison of the performance of the engine with water-alcohol injection at the compressor inlet, at the sixth stage of the compressor, and at the sixth and ninth stages was made. From consideration of the thrust increases achieved, the interstage injection of the coolant was considered more desirable preferred over the combined sixth- and ninth-stage injection because of its relative simplicity. A maximum augmented net-thrust ratio of 1.106 and a maximum augmented jet-thrust ratio of 1.062 were obtained at an augmented liquid ratio of 2.98 and an engine-inlet temperature of 80 F. At lower inlet temperatures (-40 to 40 F), the maximum augmented net-thrust ratios ranged from 1.040 to 1.076 and the maximum augmented jet-thrust ratios ranged from 1.027 to 1.048, depending upon the inlet temperature. The relatively small increase in performance at the lower inlet-air temperatures can be partially attributed to the inadequate evaporation of the water-alcohol mixture, but the more significant limitation was believed to be caused by the negative influence of the liquid coolant on engine- component performance. In general, it is concluded that the effectiveness of the injection of a coolant into the compressor as a means of thrust augmentation is considerably influenced by the design characteristics of the components of the engine being used.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E52F20
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  • 22
    Publication Date: 2019-07-11
    Description: This report presents a compilation of static sea-level data on existing or designed American and British axial-flow turbojet engines in terms of basic engine parameters such as thrust and air flow. In the data presented, changes in the over-U engine performance with time sre examined as well as the relation of the various engine parameters to each other.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-51K29
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  • 23
    Publication Date: 2019-07-10
    Description: An investigation was made of the performance of nine conical cooling-air ejectors at primary jet pressure ratios from 1 to 10, secondary pressure ratios to 4.0, and a temperature ratio of unity. This phase of the investigation was limited to conical ejectors having shroud exit to primary nozzle exit diameter ratios of 1.06 and 1.40, with several spacing ratios for each. The experimental results indicated that the pumping range and amount of cooling-air flow obtained with a 1.06 diameter ratio ejector were relatively small for cooling purposes but that the maximum possible thrust loss, which occurred with no secondary flow, was only 7 percent of convergent nozzle thrust. The 1.40 diameter ratio ejector produced a large cooling air flow and showed a possible thrust loss of 29.5 percent with no cooling air flow. Thrust gains were attained with ejectors of both diameter ratios at secondary pressure ratios greater than 1.0. The limiting primary pressure ratio below which an ejector can operate at a specific secondary pressure ratio (cut-off point) may be estimated for various flight conditions from data contained herein.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E52F26
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  • 24
    Publication Date: 2019-09-20
    Description: The performance of a two-stage turbine with variable-area first-stage turbine nozzles was determined in the NACA Lewis altitude wind tunnel over a range of simulated altitudes from 15,000 to 44,000 feet and engine speeds from 50 to 100 percent of rated speed. The variable-area turbine nozzles used in this investigation were primarily a test device for compressor research purposes and were not necessarily of optimum aerodynamic design. The results of this investigation are indicative of effects of turbine-nozzle-area variation on turbine performance within the operating range allowed by the engine. The variable-area turbine nozzles were found to be mechanically reliable and to have negligible leakage losses. Increasing the turbine-nozzle-throat area from 1.15 to 1.67 square feet increased the corrected turbine gas flow or effective turbine nozzle area about 10 percent. At a given corrected turbine speed and turbine pressure ratio, changing the turbine nozzle area from 1.30 to 1. 67 square feet lowered the turbine efficiency 3 or 4 percent. The effect of increasing the turbine nozzle area from 1.15 to 1.67 square feet (decreasing the turning angle about 7 1/2 degrees) would be to lower the turbine efficiency about 5 or 6 percent.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E52J20
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  • 25
    Publication Date: 2019-07-13
    Description: This document compiles a comprehensive list of publications supported by, or related to, National Aeronautics and Space Administration Grant NSG-3048, entitled "Alternatives for Jet Engine Control". Dr. Kurt Seldner was the original Technical Officer for the grant, at Lewis Research Center. Dr. Bruce Lehtinen was the final Technical Officer. At the University of Notre Dame, Drs. Michael K. Sain and R. Jeffrey Leake were the original Project Directors, with Dr. Sain becoming the final Project Director. Publications cover work over a ten-year period. The Final Report is divided into two parts. Volume i, "Modelling and Control Design with Jet Engine Data", follows in this report. Volume 2, "Modelling and Control Design with Tensors", has been bound separately.
    Keywords: Aircraft Propulsion and Power
    Type: NASA-CR-175895 , NAS 1.26:175895
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  • 26
    Publication Date: 2019-07-11
    Description: Performance data obtained with recording oscillographs are presented to show the transient response of the General Electric Integrated Electronic Control operating on the J47 RXl-3 turbo-Jet engine over a range of altitudes from 10,000 to 45,000 feet and at ram pressure ratios of 1.03 and 1.4. These data represent the performance of the final control configuration developed after an investigation of the engine transient behavior in the NACA altitude wind tunnel. Oscillograph traces of controlled accelerations (throttle bursts),oontrolled decelerations (throttle chops), and controlled altitude starts are presented.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE50G12
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  • 27
    Publication Date: 2019-07-11
    Description: A method has been developed for modifying a rocket motor so that its exhaust characteristics simulate those of a turbojet engine. The analysis necessary to the design is presented along with tests from which the designs are evaluated. Simulation was found to be best if the exhaust characteristics to be duplicated were those of a turbojet engine at high altitudes and with the afterburner operative.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-L54I15
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  • 28
    Publication Date: 2019-07-11
    Description: A modified J33-A-27 compressor was operated over a range of equivalent impeller speeds from 6100 to 13,250 rpm in order to obtain the over-all compressor performance. At the equivalent design speed of 11,800 rpm, the maximum efficiency of 0.764 and peak pressure ratio of 4.56 occurred at an equivalent weight flow of 104.07 pounds per second. At the highest equivalent speed (13,250 rpm) a maximum efficiency of 0.711, a maximum equivalent weight flow of 123.00 pounds per second, and a peak pressure ratio of 5.76 were obtained.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE50D25
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  • 29
    Publication Date: 2019-07-12
    Description: Component data on the J35-A-23 compressor and two-stage turbine were used to determine the problems in matching the two units for operatio n in a turbojet engine. Possible operating regions were determined an d an equilibrium operating line was also determined for the assumed c onditions of zero flight speed and a jet nozzle area approximately 5. 5 percent greater than the wide-open nozzle area.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E51H15
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  • 30
    Publication Date: 2019-07-12
    Description: The stator-blade angles in the twelfth to fifteenth stages of a 16-stage high-pressure-ratio axial-flow compressor were decreased 3 deg The over-all performance of this compressor is compared with the performance of the same compressor with standard blade angles. The matching characteristics of the modified compressor and a two-stage turbine were also obtained and compared with those of the compressor with the original blade angles and the same turbine.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E51L03
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  • 31
    Publication Date: 2019-07-12
    Description: The performance of a 13-stage development comressor for the J40-WE-24 engine has been determined at equivalent speeds from 30 to 112 percent of design. The design total-pressure ratio of 6.0 and the design weight flow of 164 pounds per second were not attained, An analysis was conducted to determine the reasons for the poor performance at the design and over-design speed. The analysis indicated that most of the difficulty could be attributed to the fact that the first stage was overcompromised to favor part-speed performance,
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE53D17
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  • 32
    Publication Date: 2019-07-12
    Description: A .General Electric fuel and torque regulator was tested in conjunction with a T31-3 turbine-propeller engine in the sea-level static test stand at the NACA Lewis laboratory. The engine and control were operated over the entire speed range: 11,000 rpm, nominal flight idle, to 13,000 rpm, full power. Steady-state and transient data were recorded and are presented with a description of the four control loops being used in the system. Results of this investigation indicated that single-lever control operation was satisfactory under conditions of test. Transient data presented showed that turbine-outlet temperature did overshoot maximum operating value on acceleration but that the time duration of overshoot did not exceed approximately 1 second. This temperature limiting resulted from a control on fuel flow as a function of engine speed. Speed and torque first reached their desired values 0.4 second from the time of change in power-setting lever position. Maximum speed overshoot was 3 percent.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE1H20
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  • 33
    Publication Date: 2019-07-12
    Description: Altitude performance of a YJ71-A-7 turbojet engine, with afterburner inoperative, was determined in the NACA Lewis altitude wind tunnel over a wide range of flight conditions. Engine speed and exhaust-nozzle area were controlled independently during this investigation. The variation of corrected values of air flow, net thrust, and fuel flow with corrected engine speed was not defined by a single curve with changes in altitude at given flight Mach number. Changes in altitude had very little effect on minimum specific fuel consumption at altitudes up to 45,000 feet. There is one exhaust-nozzle schedule that is nearly optimum for all flight conditions. Performance calculated from pumping characteristics agreed with experimental values and can therefore be used to extend engine performance data.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E53E13
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  • 34
    Publication Date: 2019-07-12
    Description: At the request of the Bureau of Aeronautics, Department of the Navy, an investigation of the Westinghouse XJ34-WE-32 turbojet engine is being conducted in the NACA Lewis altitude wind tunnel to determine the steady-state and transient operating characteristics of the controlled and uncontrolled engine at various altitudes and ram pressure ratios. As part of this program, transient performance data that illustrate the operation of the engine is obtained in the form of oscillographic traces. Similar data for engine operation i n the afterburning range, covering a range of throttle settings from the minimum value giving rated speed (throttle position, 72 degrees) to full afterburning (throttle position, ll0 degrees), is presented herein. These data thus serve to indicate the transient characteristics of the engine when the throttle is advance into, withdrawn from, and moved within the afterburning range in a stepwise manner, as well as the steady-state stability of the engine during afterburning .
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE50L29
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  • 35
    Publication Date: 2019-07-12
    Description: A theoretical method for evaluating the stability characteristics and the amplitude and the frequency of pulsation of ram-jet engines without heat addition is presented herein. Experimental verification of the theoretical results are included where data were available. Theory and experiment show that the pulsation amplitude of a high mass-flow-ratio diffuser having no cone surface flow separation increases with decreasing mass flow. The theoretical trends for changes in amplitude, frequency, and mean-pressure recovery with changes in plenum-chamber volume were experimentally confirmed. For perforated convergent-divergent-type diffusers, a stability hysteresis loop was predicted on the pressure-recovery mass-flow-ratio curve. At a given mean mass-flow ratio, the higher.value of mean pressure recovery corresponded to oscillatory flow in the diffuser while the lower branch was stable. This hysteresis has been observed experimentally. The theory indicates that for a ram-jet engine of given diameter, the amplitude of pulsation of a supersonic diffuser is increased by decreasing the relative size of the plenum chamber with respect to the diffuser volume down to a critical value at which oscillations cease. In the region of these critical values, the stable mass-flow range of the diffuser may be increased either by decreasing the combustion chamber volume or by increasing the length of the diffuser.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E52I24
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  • 36
    Publication Date: 2019-07-12
    Description: A program was undertaken to determine the J73 turbojet engine compressor stall and surge characteristics and combustor blow-out limits encountered during transient engine operation. Data were obtained in the form of oscillograph traces showing the time history of several engine performance parameters with changes in engine fuel flow. The data presented in this report are for step changes in fuel flow at an altitude of 35,000 feet, at flight Mach numbers of 0.3, 0.8, and 1.2, and at several engine-inlet temperatures,
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE53F29
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  • 37
    Publication Date: 2019-07-12
    Description: This report summarizes the effects of fuel volatility and engine design variables on the problem of starting gas-turbine engines at sea-level and altitude conditions. The starting operation for engines with tubular combustors is considered as three steps; namely, (1) ignition of a fuel-air mixture in the combustor, (2) propagation of flame through cross-fire tubes to all combustors, and (3) acceleration of the engine from windmilling or starting speed to the operating speed range. Pertinent data from laboratory researches, single-combustor studies, and full-scale engine investigations are presented on each phase of the starting problem.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE51B02
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  • 38
    Publication Date: 2019-07-12
    Description: Method for controlling the clearance between rotating and stationary components of a gas turbine engine are disclosed. Techniques for achieving close correspondence between the radial position of rotor blade tips and the circumscribing outer air seals are disclosed. In one embodiment turbine case temperature modifying air is provided in flow rate, pressure and temperature varied as a function of engine operating condition. The modifying air is scheduled from a modulating and mixing valve supplied with dual source compressor air. One source supplies relatively low pressure, low temperature air and the other source supplies relatively high pressure, high temperature air. After the air has been used for the active clearance control (cooling the high pressure turbine case) it is then used for cooling the structure that supports the outer air seal and other high pressure turbine component parts.
    Keywords: Aircraft Propulsion and Power
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  • 39
    Publication Date: 2019-07-12
    Description: A rotary engine has a substantially trochoidal-shaped housing cavity in which a rotor planetates. A cooling system for the engine directs coolant along a single series path consisting of series connected groups of passages. Coolant enters near the intake port, passes downwardly and axially through the cooler regions of the engine, then passes upwardly and axially through the hotter regions. By first flowing through the coolest regions, coolant pressure is reduced, thus reducing the saturation temperature of the coolant and thereby enhancing the nucleate boiling heat transfer mechanism which predominates in the high heat flux region of the engine during high power level operation.
    Keywords: Aircraft Propulsion and Power
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  • 40
    Publication Date: 2019-07-12
    Description: A variable geometry device is provided for use with the compressor outlet of a turbine engine. The turbine engine includes a support housing, a compressor contained within the support housing and having a compressed air outlet and in which a pair of spaced walls define an annular and radially extending diffuser passageway. The inner end of the diffuser passageway is open to the compressed outlet while the outer end of the diffuser passageway is open to the combustion chamber for the turbine engine. A plurality of circumferentially spaced diffuser vanes are mounted to one of the diffuser walls and protrude across the diffuser passageway. An annular recessed channel is formed around the opposite diffuser wall and an annular ring is mounted within the channel. A motor is operatively connected to this ring and, upon actuation, displaces the ring transversely across the diffuser passageway to variably restrict the diffuser passageway. In addition, the ring includes a plurality of slots which register with the diffuser vanes so that the vane geometry remains the same despite axial displacement of the ring.
    Keywords: Aircraft Propulsion and Power
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  • 41
    Publication Date: 2019-07-12
    Description: A variable geometry device for use with the turbine nozzle of a turbine engine of the type having a support housing and a combustion chamber contained within the support housing. A pair of spaced walls in the support housing define an annular and radially extending nozzle passageway. The outer end of the nozzle passageway is open to the combustion chamber while the inner end of the nozzle passageway is open to one or more turbine stages. A plurality of circumferentially spaced nozzle vanes are mounted to one of the spaced walls and protrude across the nozzle passageway. An annular opening is formed around the opposite spaced wall and an annular ring is axially slidably mounted within the opening. A motor is operatively connected to this ring and, upon actuation, axially displaces the ring within the nozzle passageway. In addition, the ring includes a plurality of circumferentially spaced slots which register with the nozzle vanes so that the vane geometry remains the same despite axial displacement of the ring.
    Keywords: Aircraft Propulsion and Power
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  • 42
    Publication Date: 2019-07-12
    Description: Blade collective pitch control is provided for a rotor system by rotary actuators located between adjacent blades. Each actuator is connected to the leading edge of one adjacent blade and the trailing edge of the other adjacent blade.
    Keywords: Aircraft Propulsion and Power
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  • 43
    Publication Date: 2019-07-12
    Description: A program was undertaken to determine the J73 turbojet engine compressor stall and surge characteristics and combustor blow-out limits enc ountered during transient engine operation. Data were obtained in the form of oscillograph traces showing the time history of several engi ne parameters with changes in engine fuel flow. The data presented in this report are for step and ramp changes in fuel flow at an altitude of 45,000 feet and flight Mach numbers of 0 and 0.8.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE53F30
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  • 44
    Publication Date: 2019-07-12
    Description: A turbine blade with a porous stainless-steel shell sintered to a supporting steel strut has been fabricated for tests at the NACA by Federal-Mogul Corporation under contract from the Bureau of Aeronautics, Department of the Navy. The apparent permeability of this blade, on the average, more nearly approaches the values specified by the NAGA than did two strut-supported bronze blades in a previous investigation. Random variations of permeability in the present blade are substantialy greater than those of the bronze blades, but projected improvements in certain phases of the fabrication process are expected to reduce these variations.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE54D29
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  • 45
    Publication Date: 2019-07-12
    Description: An investigation is being conducted to determine the performance of the 12-stage axial-flow compressor of the XT-46 turbine-propeller engine. This compressor was designed to produce a pressure ratio of 9 at an adiabatic efficiency of 0.86. The design pressure ratios per stage were considerably greater than any employed in current aircraft gas-turbine engines using this type of compressor. The compressor performance was evaluated at two stations. The station near the entrance section of the combustors indicated a peak pressure ratio of 6.3 at an adiabatic efficiency of 0.63 for a corrected weight flow of 23.1 pounds per second. The other, located one blade-chord downstream of the last stator row, indicated a peak pressure ratio of 6.97 at an adiabatic efficiency of 0.81 for a corrected weight flow of 30.4 pounds per second. The difference in performance obtained at the two stations is attributed to shock waves in the vicinity of the last stator row. These shock waves and the accompanying flow choking, together with interstage circulatory flows, shift the compressor operating curves into the region where surge would normally occur. The inability of the compressor to meet design pressure ratio is probably due to boundary-layer buildup in the last stages, which cause axial velocities greater than design values that, in turn, adversely affect the angles of attack and turning angles in these blade rows.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE50E22
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  • 46
    Publication Date: 2019-07-12
    Description: An investigation of the effect of inlet pressure, corrected engine speed, and turbine temperature level on turbine-inlet gas temperature distributions was conducted on a J40-WE-6, interim J40-WE-6, and prototype J40-WE-8 turbojet engine in the altitude wind tunnel at the NAC.4 Lewis laboratory. The engines were investigated over a range of simulated pressure altitudes from 15,000 to 55,000 feet, flight Mach numbers from 0.12 to 0.64, and corrected engine speeds from 7198 to 8026 rpm, The gas temperature distribution at the turbine of the three engines over the range of operating conditions investigated was considered satisfactory from the standpoint of desired temperature distribution with one exception - the distribution for the J40-WE-6 engine indicated a trend with decreasing engine-inlet pressure for the temperature to exceed the desired in the region of the blade hub. Installation of a compressor-outlet mixer vane assembly remedied this undesirable temperature distribution, The experimental data have shown that turbine-inlet temperature distributions are influenced in the expected manner by changes in compressor-outlet pressure or mass-flow distribution and by changes in combustor hole-area distribution. The similarity between turbine-inlet and turbine-outlet temperature distribution indicated only a small shift in temperature distribution imposed by the turbine rotors. The attainable jet thrusts of the three engines were influenced in different degrees and directions by changes in temperature distributions with change in engine-inlet pressure. Inability to match the desired temperature distribution resulted, for the J40-WE-6 engine, in an 11-percent thrust loss based on an average turbine-inlet temperature of 1500 F at an engine-inlet pressure of 500 pounds per square foot absolute. Departure from the desired temperature distribution in the Slade tip region results, for the prototype J40-WE-8 engine, in an attainable thrust increase of 3 to 4 percent as compared with that obtained if tip-region temperature limitations were observed.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-E52H06
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  • 47
    Publication Date: 2019-07-12
    Description: An investigation was conducted at the NACA Lewis laboratory to determine whether simulated porous gas-turbine blades fabricated by the Eaton Manufacturing Company of Cleveland, Ohio would be satisfactory with respect to coolant flow for application in gas-turbine engines. These blades simulated porous turbine blades by forcing the cooling air onto the blade surface through a large number of chordwise openings or slits between laminations of sheet metal or wire. This type of surface has a finite number of openings, whereas a porous surface has an almost infinite number of smaller openings for the coolant flow. The investigation showed that a blade made of sheet-metal laminations stacked on a support member that passed up through the coolant passage was completely unsatisfactory because of extremely poor coolant flow distribution over the blade surface. The flow distribution for two wire-wound blades was more uniform, but the pressure drop between the coolant supply pressure and the local pressure on the outside of the blades was too low by a factor ranging from 3 to 3.5 for the required coolant flow rates. The pressure drop could be increased by forcing the wires closer together during blade fabrication.
    Keywords: Aircraft Propulsion and Power
    Type: NACA-RM-SE51C13
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  • 48
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 68 (1985) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 49
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The σ-orbital manifold of cubane 1, as suggested by its PE spectrum, is divided into two sets separated by a 3 eV gap extending from ∼ -10.5 eV to ∼ -13.5 eV. Halogen substituents with np AO basis energies falling into this gap (e.g. Cl or Br) will, therefore, hyperconjugate appreciably with both sets. Interaction with the lower-lying set will lead to the usual destabilization (‘normal’ hyperconjugation), whereas interaction with the set above will necessarily lead to a ‘stabilization’ (‘inverted’ hyperconjugation). As a result the lone-pair ionization energies of Cl or Br substituted cubanes (derived from PE spectra) are much larger than naively expected for an alkyl halide containing as much as 8 C-atoms. In particular no significant shift of the eg-1 lone-pair bands in the PE spectra of 1,4-dichloro- and 1,4-dibromocubane can be detected with respect to the first ionization energies of the free atoms Cl and Br, or of HCl and HBr.
    Additional Material: 7 Ill.
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  • 50
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title sponge is shown to contain eight new sesquiterpenoids for which a common, unusual biogenetic origin is postulated. The compounds are shown to be: (-)-(1R*,4R*)-3-(3′-furyl)methyl-2-p-menthen-7-yl acetate ((-)-8b); two diols separated as the monoacetates (-)-(1S*,4R*)-3-(3′-furyl)methyl-l-hydroxy-2-p-menthen-7-yl acetate ((-)-13a) and the (-)-(1R*,4R*)-epimer (-)-13b, the two C(4)-epimeric 4-ethoxy-3-(1′(7′),2′-p-menthadien-3′-yl)methyl-2-buten-4-olides ((+)-14a and (-)-14b), (-)-3-(3′-furyl)methyl-7-nor-2-p-menthen-l-one ((-)-11), (-)-(3Z)-1-(3′-furyl)-4,8-dimethylnona-3, 7-dien-2-yl acetate ((-)-17), and (+)-3-(5′,7′-seco-2′(10′)-pinen-7′-yl)methylfuran ((+)-15).
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  • 51
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemical synthesis and biological activities of a new α-melanotropin derivative are described. Nα-(5-Bromovaleryl)-Nα-deacetyl-α-melanotropin contains the 5-bromopentanoyl group as a chemical ‘handle’ in place of the acetyl group of the natural hormone. The synthesis involved a new protected intermediate which allowed the selective deprotection of either the Nα or Nα amino group. The title compound reacted with sodium thiosulfate to give Nα-deacetyl-Nα-(5-(sulfothio)valeryl)-α-melanotropin, a key intermediate for the preparation of tobaccomosaic virus/α-melanotropin disulfide conjugates. As a basis for the study of the conjugates, biological activities of the title compound on Cloudman S-91 mouse melanoma cell cultures (tyrosinase stimulation, binding, and cyclic AMP accumulation) were determined. They proved to be quite similar to the corresponding α-melanotropin activities. Differences in bindings may be explained by stronger hydrophobic interaction of the new derivative with the lipid phase of the target cell membranes.
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  • 52
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 68 (1985), S. 76-82 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The carbonyl group in lactones and, to a lesser extent, in lactams tends to show a C—C=O angle that is larger than the O—C=O or N—C=O angle, the difference increasing in magnitude as the ring size decreases. The observed trend provides information on ratios of force constants characterising the flexibility of the s-cis-ester group and may be interpreted in terms of incipient chemical reaction to -O—(CH2)n—C≡O+. Molecular orbital calculations (MINDO/3, MNDO, EH) for model compounds provide an electronic interpretation of this angle difference in terms of an anomeric interaction between the p-type lone pair on the carbonyl O-atom and the antibonding C-O or C-N orbital.
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  • 53
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 68 (1985), S. 110-118 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclic octa- and decapeptides have been prepared, and their ion selectivity in solvent polymeric membranes was studied. Cyclo(-LPro-DLeu-)5 behaves as an ionophore which selects Mg2+ over Ca2+ by a factor of 100. Cyclo(LPro-LLeu)5 induces selectivity in membranes for Mg2+ over Li+, Na+ and K+ by a factor of 400, 200 and 10, respectively, while selectivity of Mg2+ over Ca2+ is poor. Some evidence is presented which indicates that certain ionophores exhibit high selectivity for monovalent magnesium complexes.
    Additional Material: 6 Ill.
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  • 54
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Friedel-Crafts monoacylation of trans-η-[(1RS,2RS,4SR,5SR,6RS,7SR,8SR)-C,5,6,C-η:C,7,8,C-η-(5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octyl acetate)]-bis(tricarbonyliron) ((±)-5) is highly stereoselective and yields trans-η-[(1RS,2RS,4RS,5SR,6RS,7RS,8SR)-C,6-η,oxo-σ:C,7,8,C-η-(6,7,8-trimethylidene-5-((Z)-2-oxopropylidene)-2-bicyclo[2.2.2]octyl acetate)]-bis(tricarbonyliron) ((±)-8) which equilibrates with the trans-η-[(1RS,2RS,4RS,5SR,6RS,7RS,8SR)-C,5,6,C-η:C,7,8,C-η-(6,7,8-trimethylidene-5-((Z)-2-oxopropylidene)-2-bicyclo[2.2.2]octyl acetate)]-bis(tricarbonyliron) ((±)-9) on heating. Optically pure (-)-9 has been prepared from the corresponding optically pure alcohol (+)-4. The structure and absolute configuration of (-)-9 was established by single-crystal X-ray diffraction.
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  • 55
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 68 (1985), S. 155-161 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkylation in the 2-Position of (2S, 4R)-4-Hydroxyproline with Retention of ConfigurationO-Acetyl-4-hydroxyproline (1b) is condensed with pivalaldehyde to give a single stereoisomer of the 2-(tert-butyl)-4-oxo-3-oxa-1-azabicyclo[3.3.0]oct-7-yl acetate (3). This is converted to the enolates 4 or 5, reactions of which with alkyl halides, aldehydes, and acetone (→6,9,10,11) are diastereoselective (lk-1,3-induction). Cleavage of the corresponding products furnishes the enantiomerically pure 2-deuterio-, 2-methyl-, 2-allyl-, and 2-benzyl-substituted 4-hydroxyprolines 2a-2d.
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  • 56
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Steric Course of the Reaction of Enamines Derived from Open-Chain Aldehydes and Ketones with Nitro-olefins Yielding 2,3-Disubstituted 4-NitroketonesThe relative configuration of the nitro-ketone 12 obtained by the title reaction has been proved by a Baeyer-Villiger degradation and subsequent reduction to the amino-alcohol (±)-(u)-20, the relative configuration of which is identical with a sample prepared from 2-methyl-3-hydroxybutyrate of known configuration (Scheme 1). The stereochemical course of the title reaction is thus as predicted by our topological rule. It is assumed that the other nitro-ketones 13-18 described here are also formed by (lk)-combination of the trigonal centers of the educts (diastereoselectivity 〉 90%, see Formulae and Fig. 1). It is not possible to reverse this relative topicity by employing (Z)- instead of (E)-components of the starting materials, due to the reversibility of the primary step of these Michael additions (Schemes 2 and 3, and Fig. 2).
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  • 57
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 68 (1985), S. 207-211 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On singlet excitation (λ = 254 nm), the epoxydiene (E)-3 underwent (E)/(Z)-isomerization, electrocyclic ring closure of the diene side chain leading to the cyclobutenes 4A + B, and rearrangement to the cyclohexanones 5A + B. Compounds 5A + B were presumably formed in a series of processes including a 1,3-acyl shift of the homoconjugated ketone 8, arising from (Z)-3 by a 1,5-H-shift accompanied by cleavage of the C,O-bond of the oxirane.
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  • 58
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using readily accessible 10-sulfonamido-isoborneols as regenerable, chiral auxiliaries, highly face-selective C-C-bond formations at Cα and Cβ of carboxylates could be conveniently achieved. Thus, conjugated additions of RCu to enoates (1→2) furnished, after saponification, β-substituted carboxylic acids 3 in 94-98% e.e. Similarly, propionates 12 yielded after deprotonation, enolate alkylation, and reductive ester cleavage the (R)-alcohols 15 in 78-98% e.e. The acid (+)-3e was converted to the pheromone (-)-11.
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  • 59
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of the pentadentate ligand 2,6-bis(3-carboxy-1,2-dimethyl-2-azapropyl)pyridine yields a mixture of the racemic and meso-isomers which it was difficult to separate by column chromatography. When the cationic Co(III)-complex of this ligand was crystallized with hexafluorophosphate as anion, two distinct crystalline forms were produced. The complex of the racemic ligand, 1, has C2 symmetry and is a dihydrate; a = 8.999(8), b = 12.047(6), c = 20.65(1) Å, orthorhombic, space group Peen,Z = 4, R = 0.074 for 1439 observed reflections. The complex of the meso-ligand, 2, shows two independent molecules (2A and 2B) per asymmetric unit, both monohydrates with a resolved disordered H2O molecule in 2A; a = 10.109(4), b = 12.835(2), c = 16.651(3) Å, α = 89.5(1)°, β = 84.7(3)°, γ = 88.6(3)°, triclinic, space group P1, Z = 4, Rs = 0.054 for 4198 observed reflections. The coordination around the Co-atom is distorted octahedral in both complexes, with the coordinated H2O molecule trans to the pyridine N-atom. In the racemic form of the complex, 1, the pyridine ring is twisted about the Co-N(1) bond with respect to the plane defined by atoms Co, N(1), O(W1), N(2) and N(2P) by 17.2(2)°. In the meso-form of the complex, 2, the CH3 substituent C(8P) on atom C(4P), is now axial with respect to the 5-membered chelate ring. As a result of steric hinderance between atom O(1) and CH3(8P), the pyridine ring has been displaced from the best mean-plane formed by atoms Co, O(W1), N(2) and N(2P). The principal axis of the pyridine ring C(3)…N(1), makes an angle of 14.1(1)° (mean) with this plane. At the same time the pyridine ring is twisted about axis C(3)…N(1) with respect to this plane by 19.7(1)° (mean).
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  • 60
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Halochromic Molecules. Spectrophotometric Investigation of the Acidobasic Behaviour of Substituted 6,6-Diphenyl-6H-chromeno[4, 3-b]indolizines and their Aza-analoguesSubstituted 6,6-diphenyl-6H-chromeno[4,3-b]indolizines form ring-opened, intensely coloured (diphenyl)-indolizinylcarbenium salts with acid. UV/VIS spectra of the coloured salts are discussed on the basis of VEPPPCI calculations. The ∊pH* curves in buffered MeOH/H2O solutions and the pK* values are determined. The title compounds undergo very complex protonation equilibria.
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  • 61
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 68 (1985), S. 72-75 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Displacements of 1H-NMR chemical shifs for caffeine in D2O solution as a function of concentration conform to the behaviour expected for pure dimer formation according to the equilibrium 2(caffeine)⇄(caffeine)2 with a statistical probability of at least 95%. Confidence limits reported earlier for the dimerisation constant of caffeine represent the real statistical dispersion in the experimental data and do not reflect a systematic error such as tetramer formation.
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  • 62
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 68 (1985), S. 104-109 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the AlBr3-catalyzed adamantane rearrangement in CS2 of 1,2-exo-trimethylenenorbornane (1) to 2-endo,6-endo-trimethylenenorbornane (3), hydride-ion abstraction occurs at C(6) from the exo-side. The kH/kD value for competition between 1 and 5 (Dexo-C(6)) was 1.58 ± 0.05, whereas no kinetic isotope effect was operative for competition between unlabeled 1 and 4 (Dendo-C(5)) and between 1 and 6 (Dendo-C(6)).
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  • 63
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    Helvetica Chimica Acta 68 (1985), S. 95-103 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Racemic diaminosugars were easily obtained by a regio- and stereoselective three-step synthetis. In the first step, regiospecific hetero-Diels-Alder cycloadditions between 1,2-dihydropyridines 1a and 10 and nitrosobenzene led to the bicyclic compounds 2a and 11, respectively, cis-Glycol formation starting from these latter adducts, followed by hydrogenolysis of the N—O bond and by exhaustive acetylation of the OH-groups, led to the diaminolyxose 5, the diaminomannose 14 and the diaminoallose 15. When starting from benzyl 1,2-dihydropyridine-1-carboxylate (1b) and using the same reaction sequence, the racemic piperidine derivative 8 was obtained.
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  • 64
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isolation of Bafilomycin-A1-21-O-(α-L-rhamnopyranoside). Structural Determination by Chemical Correlation with Bafilomycin A1 and LeucanicidinFrom cultures of an actinomycete strain, the known antifungal and insecticidal antibiotic leucanicidin (1) and a hitherto unknown antifungal antibiotic, bafilomycin-A1-21-O-(α-L-rhamnopyranoside) (2), were isolated. The latter is spectroscopically closely related to 1 and bafilomycin A1 (3) and gave degradation products identical with compounds obtained by analogous degradation of 1 and 3.
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  • 65
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    Helvetica Chimica Acta 68 (1985), S. 119-125 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An empirical force-field for carbenium ions has been incorporated in Allinger's MM2 programme. Structural parameters of secondary carbenium ions calculated by this method are compared with those obtained with Schleyer's BIGSTRN calculations. The strain changes occurring upon solvolysis of secondary p-toluenesulfonates are evaluated by means of this force-field and correlated with the rate constants for solvolysis. The equation for correlation of acetolysis, relative to cyclohexyl p-toluenesulfonate, of 28 kc substrates is ΔGrel+ = 0.67 ΔEst - 0.20 (r = 0.958).
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  • 66
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparation of the Enantiomerically Pure cis- and trans-Configurated 2-(tert-Butyl)-3-methylimidazolidin-4-ones from the Amino Acids (S)-Alanine, (S)-Phenylalanine, (R)-Phenylglycine, (S)-Methionine, and (S)-ValineIn contrast to α-hydroxy and α-mercapto carboxylic acids, simple α-amino acids do not form acetal-type derivatives (2, X = NH) with pivalaldehyde. For the generation of amino-acid-derived chiral, nonracemic enolates (cf. 3), and hence, for the α-alkylation of amino acids without racemization and without an external chiral auxiliary, the imidazolidinones 12-14 were prepared diastereoselectively. To this end, the methyl or ethyl esters of amino-acid hydrochlorides were first converted to N-methylamides of amino acids which in turn were condensed with pivalaldehyde to give (neopentylidenamino)amides (11). These Schiff bases could be cyclized either to trans-or to cis-imidazolidinones (12, 14 and 13, respectively), which were obtained in enantiomerically pure form after recrystallization. The enantiomeric purities were confirmed by HPLC with chiral stationary phases or by 1H-NMR spectroscopy in the presence of chiral shift reagents. The configurations (cis, trans) were assigned by NOE measurements on 300- or 360-MHz 1H-NMR spectrometers.
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  • 67
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    Helvetica Chimica Acta 68 (1985), S. 144-154 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiomerically pure cis- and trans-5-alkyl-1-benzoyl-2-(tert-butyl)-3-methylimidazolidin-4-ones (1, 2, 11, 15, 16) and trans-2-(tert-butyl)-3-methyl-5-phenylimidazolidin-4-one (20), readily available from (S)-alanine, (S)-valine, (S)-methionine, and (R)-phenylglycine are deprotonated to chiral enolates (cf. 3, 4, 12, 21). Diastereoselective alkylation of these enolates to 5,5-dialkyl- or 5-alkyl-5-arylimidazolidinones (5, 6, 9, 10, 13a-d, 17, 18, 22) and hydrolysis give α-alkyl-α-amino acids such as (R)- and (S)-α-methyldopa (7 and 8a, resp.), (S)-α-methylvaline (14), and (R)-α-methyl-methionine (19). The configuration of the products is proved by chemical correlation and by NOE 1H-NMR measurements (see 23, 24). In the overall process, a simple, enantiomerically pure α-amino acid can be α-alkylated with retention or with inversion of configuration through pivaladehyde acetal derivatives. Since no chiral auxiliary is required, the process is coined ‘self-reproduction of a center of chirality’. The method is compared with other α-alkylations of amino acids occurring without racemization. The importance of enantiomerically pure, α-branched α-amino acids as synthetic intermediates and for the preparation of biologically active compounds is discussed.
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  • 68
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: tert-Butyl α,β-dioxobutyrate (hydrate; 1d) undergoes, at medium or high pH, the benzilic-acid rearrangement with exclusive 1,2-shift of the COO(t-Bu) group; the same is true for the corresponding isopropyl ester 1c and ethyl ester 1b at high pH, whereas at lower pH, the overall picture of these reactions is complicated by concurrent hydrolysis of the ester, followed by a 1,2-shift of the COO- group. Consequently, the shift of these electron-attracting groups cannot be considered to be systematically disfavoured (compared, e.g., with alkyl-group shifts). Kinetic measurements of the rearrangement show for both esters (as well as for the analogous ethyl ester 1b, and also for ethyl 3-cyclopropyl-α,β-dioxopropionate (4)) a characteristic rate profile: at relatively low pH, k is proportional to [HO-], approaching saturation with increasing [HO-] (interpreted as complete transformation of the substrate into the hydrate monoanion), which is followed at higher pH by another rate increase with k proportional to [HO-] (probably due to the reaction of the hydrate dianion). The similarity of k values for 1b-d shows that in the shift of COOR steric hindrance caused by R is negligible.
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  • 69
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On n,π*- as well as on π,π*-excitation, the 4,5-epoxy-α-ionones (E)-1, (E)-2, and (E)-3 undergo (E)/(Z)-isomerization and subsequent γ-H-abstraction leading to the corresponding 4-hydroxy-β-ionones (E/Z)-9, (E/Z)-13, and (E/Z)-17 as primary photoproducts. On photolysis of (E)-3, as an additional primary photoproduct, the β,γ-unsaturated σ,∊-epoxy ketone 18 was obtained. The other isolated compounds, namely the 2H-pyrans 10A + B and 14A + B as well as the retro γ-ionones 11 and 15A + B, represent known types of products, which are derived from the 4-hydroxy-β-ionones (E/Z)-9 and (E/Z)-13, respectively.
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  • 70
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    Helvetica Chimica Acta 68 (1985), S. 391-402 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolability of the antitumor antibiotic hedamycin (1) was investigated by irradiation in different solvents in the presence or in the absence of oxygen. The products formed were separated chromatographically and their structures determined by NMR spectroscopy. Photolysis of 1 in the presence of oxygen gave only one isolable product, photohedamycin A (3), where ring E of hedamycin had been transformed into an enol ether. The reaction in the absence of oxygen yielded the photohedamycins B, C, and D (5, 6, and 7, respectively). In these compounds, one of the epoxides of hedamycin had been opened reductively, and in photohedamycin D (7) the substituent at C(8) - originally ring E of hedamycin - was now acyclic. In addition to these compounds, the photolyses yielded a large number of unstable minor products, which could not be isolated.
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  • 71
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New procedures are described for the synthesis of α,β-ethylenic and acetylenic aldehydes from 2-butene- and 2-butyne-1,4-diol, respectively (see Scheme 1). These are applied to the preparation of a particular δ-acetylamino-α,β-ethylenic aldehyde ((E)-5) as well as of its acetylenic analogue 15. On heating in the presence of a silyl enol ether, the former undergoes a complete dehydrative cyclization affording the N-acetyl-1,2-dihydropyridine 19. The addition of HCl to aldehyde (E)-5 results in the production of the 4-chloro-1,2,3,4-tetrahydropyridine 22 which is hydrolyzed to the corresponding alcohol 23 on silica gel. Similarly, the addition of HCl or HBr to the δ-acetyl-amino-α,β-acetylenic aldehyde 15 leads to the previously unknown 4-halo-1,2-dihydropyridines 26; these are easily hydrolyzed to the 2,3-dihydro-4(1H)-pyridinone 27. The ring-forming process involves a N-acyl N,O-hemiacetal as intermediate which is eventually dehydrated.
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  • 72
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    Helvetica Chimica Acta 68 (1985), S. 450-455 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polar effects of substituents on reactivity in oxidation of 2-substituted anthracenes with tert-butyl hydroperoxide (TBHP)/Rh(PPh3)3Cl have been investigated and compared with those obtained with TBHP/VO(acac)2 and chromic acid. The anthracene reactivities obtained from competition experiments are correlated with Hammett's σp-constants. The P-values are -2.60 for chromic acid and 0.72 for TBHP/VO(acac)2. A poor correlation with p = -0.17 (r = 0.756) was obtained for TBHP/Rh (PPh3)3Cl. It is concluded that the Rh-catalyzed reaction does not consist in electrophilic oxygen transfer to the anthracene.
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  • 73
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    Helvetica Chimica Acta 68 (1985), S. 465-474 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of 3,3-Dimethylperhydro-1,4-diazepin-2,5,7-triones from 3-Dimethylamino-2,2-dimethyl-2H-azirine and Malonic Acid MonoamidesReaction of the aminoazirine 1 and malonic acid monoamides 5 in CH3CN yielded triamides of type 6 (Scheme 2), which were transformed to the corresponding phenylthioates 9 by treatment of a solution of 6 and thiophenol in CH3CN with HCl (Scheme 4). Cyclization of 9 to give the 1,4-diazepin-2,5,7-trione of type 10 was achieved with NaH in toluene at about 90°. It has been shown that 2-oxazolin-5-ones are intermediates in the selective cleavage of the therminal amide function of 6 (Scheme 3).
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  • 74
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nature and Stability of Some Metallic Complexes of Dinucleating Cryptands in Solution. I. A Polyazapolyoxa Cylindrical Macrotricycle and its Monocyclic SubunitpH-metry and UV spectrophotometry were used to study the complexing properties of the cylindrical macrotricycle, 1,7,13,19-tetraaza-4,16-dioxa-10,22,27,32-tetraoxatricyclo[17.5.5.5]tetratriacontane (1) and of its constitutive monocyclic subunit, 1,7-diaza-4,10-dioxacyclododecane (2) with some transition and heavy metal cations (Cu2+, Co2+, Ni2+, Zn2+, Cd2+, Pb2+, Ag+), in aqueous medium 0.1M Et4NClO4, at 25°. The protonation constants of the ligands as well as the nature and the stabilities of the complexes formed in the pH-regions studied were determined. The tricycle 1 only formed dinuclear M2L complexes with Cu2+, Zn2+, and Ag+, accompanied in the latter case by a protonated mononuclear MLH species, and with Cu2+ and Zn2+ at high pH-values by dinuclear hydroxo complexes. Only mononuclear complexes were evidenced with the other cations, ML being accompanied either by protonated or hydroxy mononuclear species. The mononuclear complexes of 1, when they existed, were more stable than the corresponding complexes of 2, except for cobalt which formed complexes of comparable stability with both ligands. In the other cases (Cd2+, Pb2+, Ag+), the stability differences between the complexes of 1 and 2 increased with the size of the cation.
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  • 75
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Planarisation of Tetracoordinate Carbon Atom, Synthesis of the Brigded all-cis-[5.5.5.5]Fenestrane 13-Oxapentacyclo[5.5.2.11,7.04,15.010,15]pentadecan-14-oneThe synthesis of the ketolactone 23 from (Z,Z)-1,5-cyclooctadiene is reported. Transannular carben insertion, achieved via photolysis of the deprotonated (2,4,6-trisisopropylphenylsulfonyl)hydrazone of 23 gives the bridged all-cis-[5.5.5.5]fenestrane 3.
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  • 76
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water exchange on hexaaquavanadium (III) has been studied as a function of temperature (255 to 413 K) and pressure (up to 250 MPa, at several temperatures) by 17O-NMR spectroscopy at 8.13 and 27.11 MHz. The samples contained V3+ (0.30-1.53 m), H+ (0.19-2.25 m) and 17O-enriched (10-20%) H2O. The trifluoromethanesulfonate was used as counter-ion, and, contrary to the previously used chloride or bromide, CF3SO3- is shown to be non-coordinating. The following exchange parameters were obtained: kex298 = (5.0 ± 0.3) · 102 s-1, ΔH* = (49.4 ± 0.8) kJ mol-1, ΔS* = -(28 ± 2) JK-1 mol-1, ΔV* = -(8.9 ± 0.4) cm3 mol-1 and Δβ* = -(1.1 ± 0.3) · 10-2 cm3 mol-1 MPa-1. They are in accord with an associative interchange mechanism, Ia. These results for H2O exchange are discussed together with the available data for complex formation reactions on hexaaquavanadium(III). A semi-quantitative analysis of the bound H2O linewidth led to an estimation of the proportions of the different contributions to the relaxation mechanism in the coordinated site: the dipole-dipole interaction hardly contributes to the relaxation (less than 7%); the quadrupolar relaxation, and the scalar coupling mechanism are nearly equally efficient at low temperature (∼ 273 K), but the latter becomes more important at higher temperature (75-85% contribution at 360 K).
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  • 77
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    Helvetica Chimica Acta 68 (1985), S. 534-544 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spontaneous Opening of the Pyrimidine Ring of Pyrrolo[2,3-d]pyrimidines after Intramolecular AcylationPhase-transfer alkylation of 4-methoxy-2-methylthio-7H-pyrrolo[2,3-d]pyrimidine (2) with ethyl 3-bromopropionate leads regioselectively to the ester 3a. After displacement of its methylthio group and saponification of the ester function, the acid 3e is obtained which can be transferred to the functionalized deazahypoxanthine 3f by either treatment with dry HBr/glacial AcOH or by nucleophilic displacement of the 4-methoxide. Reaction of 3f with a H2O-soluble carbodiimide results in an intramolecular acylation at N(1) by the activated ester; the intermediate 4 undergoes spontaneous hydroxylation and subsequent opening of the pyrimidine ring under formation of the pyrrolo[1,2-a]pyrimidine derivative 6. Its structure was proved by X-ray analysis. Subsequent deformylation of 6 in alkaline medium leads to the compound 7 in almost quantitative yield.
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  • 78
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new saponins, β-D-glucopyranosyl 3-O[O-βD-xylopyranosyl-(1→3)-O-(β-D-glucopyranosyluronic acid)]oleanolate (1) and 3-O-[O-β-D-xylopyranosyl-(1→3)-O-(β-D-glucopyranosyluronic acid)]oleanolic acid (2), have been isolated from the tubers of Talinum tenuissimum. The structures have been established mainly by 13C-NMR and FAB-MS. The monodesmosidic saponin 2 exhibits very strong molluscicidal activity against the schistosomiasis-transmitting snail Biomphalaria glabrata.
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  • 79
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transverse relaxation rate of H2O in Al(H2O)63+ has been measured as a function of temperature (255 to 417 K) and pressure (up to 220 MPa) using the 17O-NMR line-broadening technique, in the presence of Mn(II) as a relaxation agent. At high temperatures the relaxation rate is governed by chemical exchange with bulk H2O, whereas at low temperatures quadrupolar relaxation is prevailing. Low-temperature fast-injection 17O-NMR was used to extend the accessible kinetic domain. The samples studied contained Al3+ (0.5 m), Mn2+ (0.2-0.5 m), H+ (0.2-3.1 m) and 17O-enriched (20-40%) H2O. Non-coordinating perchlorate was used as counter ion. The following H2O exchange parameters were obtained: kex298 = (1.29 ± 0.04) s-1, ΔH* = (84.7 ± 0.3) kJ mol-1, ΔS* = +(41.6 ± 0.9) J K-1 mol-1, and ΔVex* = +(5.7 ± 0.2) cm3 mol-1, indicating a dissociative interchange, Id, mechanism. These results of H2O exchange on Al(H2O)63+ are discussed together with the available complex-formation rate data and permit also the assignment of Id mechanisms to these latter reactions.
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  • 80
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    Helvetica Chimica Acta 68 (1985), S. 571-580 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-O-Acetyl-1-O-demethylcolchicine, and acylated 1-O,2-O-didemethylthiocolchicines, in contrast to 2-O-acetyl-, 2-O,3-O-diacetyl- and 3-O-acetyl analogs, showed after standing in CHCl3 solution significant changes in optical rotation, a duplication of 1H-NMR signals, and the formation of new isomers on TLC. Solid-state X-ray diffraction of O-acetylated colchinoids and thio analogs, showed out of planar arrangements of the aromatic substituents, but the analysis could not help to explain the structures of the newly formed isomers in CHCl3 solution.
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  • 81
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    Helvetica Chimica Acta 68 (1985), S. 563-570 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phase-transfer glycosylation of 4-methoxy-1H-pyrazolo[3,4-d]pyrimidine with the 2-deoxyribofuranosyl chloride 9 formed the N(1)-β-nucleoside 10a as main product (39%). As by-products the α-D-anomer 11a (7%) and the N(2)-isomer 12a (18%) were isolated. Assignment of these isomers was made on the basis of their 1H- and 13C-NMR spectra. Removal of the sugar-protecting groups yielded the 4-methoxy-nucleosides 10b, 11b, and 12b, respectively. Nucleophilic displacement of the 4-MeO-group gave the 2-deoxyribofuranosides 1-4 of allopurinol and 4-amino-1H-pyrazolo[3,4-d]pyrimidine.
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  • 82
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    Helvetica Chimica Acta 68 (1985), S. 606-609 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Liquid crystals with negative Δ∊ can be obtained by incorporating a cyano group in the terminal alkyl substituent or in an ethylene bridge between the cyclic units of the rigid core. The clearing points of such compounds are higher than those of the corresponding derivatives where the cyano group is laterally attached to a phenyl moiety. In compounds where both cyclic units of the rigid core are cyclohexyl, this type of substitution leads to an optimal contribution to ∊⊥ in contrast to the cyanophenyl derivatives.
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  • 83
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    Helvetica Chimica Acta 68 (1985), S. 610-613 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3,7,10-Tribenzyl-3,7,10-triaza[3.3.3]propellane (4a), 3,7-dibenzyl-10-phenyl-3,7,10-triaza[3.3.3]propellane (4c), 3,7-dibenzyl-10-(p-tolyl)-3,7,10-triaza[3.3.3]propellane (4b), and 3-oxa-7,10-diaza[3.3.3]propellane (6) have been prepared.
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  • 84
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    Helvetica Chimica Acta 68 (1985), S. 618-622 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The glycopentapeptide H-(GlcNAcβ1-)Asn-Glu-Thr-Ile-Val-OH (10) representing the partial sequence A80-A84 of human fibroblast interferon was synthesized using the newly developed allyl-ester protection of carboxy functions. The allyl esters, which are stable to acids and to bases, can be cleaved under very mild, neutral conditions using tris(triphenylphosphine)rhodium(I) chloride or tetrakis(triphenylphosphine)palladium(0) as a catalyst. This synthetic method opens up a preparative route to glycopeptide model structures of glycoproteins of high biological interest.
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  • 85
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    Helvetica Chimica Acta 68 (1985), S. 651-660 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants (log k) for the solvolysis of 4e-substituted 2e- and 2a-adamantyl p-nitrobenzenesulfonates 14 and 15, respectively, in 80% EtOH correlate linearly with the respective inductive substituent constants σIq. Therefore, relative rates are controlled by the I effect of the substituents at C(4). The derived reaction constants, or inductivities, ρI of -0.80 and -0.64 for the series 14 and 15, respectively, are far smaller than those previously determined for 6-substituted 2-norbornyl and 2-bicyclo[2.2.2]octyl sulfonates, in which the partial structure containing the substituent and the leaving group is the same. The ratio of the retained and inverted adamantanols obtained upon hydrolysis of the series 14 falls from 2.85 for R = CH3 to ca. 1 for R = CN, i.e. as the substituent at C(4) becomes more electron-attracting. In the 2a-series 15 this ratio is uniformly higher. These findings confirm that the 2-adamantyl cation is weakly bridged and that through-space induction in carbocations involves graded bridging of the cationic center by neighboring C-atoms.
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  • 86
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The all-light-atom X-ray crystal-structure analysis of cyclosporin A (1), a cyclic undecapeptide containing seven N-methylated amino acids, reveals a conformation very similar to that of the previously analysed iodo derivative which is characterised by a twisted β-pleated sheet involving the residues Me-Val-11, MeBmt-1, Abu-2, Sar-3, MeLeu-4, Val-5, MeLeu-6, and Ala-7. The β-bend at Sar-MeLeu-4 is of type II′, and the loop of the residual amino acids involves a cis-peptide bond between MeLeu-9 and MeLeu-10. The NH proton of D-Ala-8 closes a yi-bend with a H-bond to the MeLeu-6 CO group. The crystal was grown from acetone. A closely similar backbone conformation in apolar solvents such as CDCl3 or C6D6 has been derived from the interpretation of the NMR spectral parameters (homo- and heteronuclear NOE effects, coupling constants, chemical-shift values of the C-, H-, and N-atoms). A minor variation in the backbone conformation between crystal and solution is observed in the region of D-Ala-8, where in solution a 3-center H-bond is established between the NH of D-Ala-8 und the carbonyl O-atoms of both MeLeu-6 (yi-turn) and D-Ala-8 (C5-bend). A recently proposed technique to identify intramolecular H-bond via heteronuclear NOE from NH proton to carbonyl C-atoms is critically analysed. The main difference between crystal and solution conformations lies in the orientation of the side chains of the unusual amino acid MeBmt (χ1 = +60° in solution, -168° in the crystal) and of MeLeu-10 (X1 = -60° in solution, +60° in the crystal). The differences in crystal and solution are caused by the break of the intermolecular H-bond of the OH group of MeBmt on dissolution of the crystal. The bifurcated H-bond of D-Ala-8 twists the backbone in this region. Molecular modeling demonstrates that this is the origin of the change in the side chain conformation of MeLeu-10. The intramolecular flexibility in the crystal indicated by the thermal parameters obtained from the X-ray refinement, and in solution by an analysis of spin-lattice relaxation times in the NMR experiments, indicate a fairly rigid backbone and fixed conformations for all the side chains except for that of Abu-2 and the distal atoms of MeBmt.
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  • 87
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    Helvetica Chimica Acta 68 (1985), S. 581-583 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of the title compound obtained from 2(1H)-quinoxalinone oxime by the template effect of Co(II) and Ni(II) ion has been determined by three dimensional X-ray analysis.
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  • 88
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    Helvetica Chimica Acta 68 (1985), S. 584-591 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochemical Syntheses of 3-Oxazolines which Possibly Exhibit Hypoglycemic ActivityReactions of photochemically generated benzonitrile methylides 2 with carbonyl compounds 3 yielded 3-oxazolines of the types 5 and 6 (Scheme 1). Photooxidation of 5-[p-(dimethylamino)phenyl]-2,2-dimethyl-4-phenyl-3-oxazoline (5a) gave 4′-(2,2-dimethyl-4-phenyl-3-oxazolin-5-yl)-N-methylformanilide (6r) which could be transformed to 2,2-dimethyl-5-[p-(methylamino)phenyl]-4-phenyl-3-oxazoline (6s) by photodecarbonylation. Thirty 3-oxazolines of types 5 and 6 have been synthesized and tested by oral and/or intraperitoneal administration to starved rats and obese-hyperglycemic mice.
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  • 89
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    Helvetica Chimica Acta 68 (1985), S. 600-605 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochemical and Chemical Syntheses of Biologically Active 3-OxazolinesUsing the photoreaction of 2H-azirines with carbonyl compounds, the 2,2-dimethyl-3-oxazolines 5a, 5b, and 6a have been obtained which bear a mono- or dichlorophenyl substituent at C(4) of the five-membered heterocycle and pyridyl at C(5). These compounds exhibit interesting activities against phytopathogenic fungi. Because 6a had been selected for field testing, its photochemical preparation was supplemented by a chemical synthesis. However, the overall performance of 6a in the field was inferior to some of the recently introduced agricultural fungicides of the ergosterol biosynthesis inhibitor type. Although 16 additional 3-oxazolines with varied substituents have been prepared, the fungicidal activity found with 6a could not be improved.
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  • 90
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    Helvetica Chimica Acta 68 (1985), S. 592-599 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Reactions of 5-[p-(Dimethylamino)phenyl]-2,2-dimethyl-4-phenyl-3-oxazolineThe title compound 8 has been synthesized in a one-pot reaction of 4′-(dimethylamino)benzoin (4) with 2-propanone and NH3. The preparation of the intermediate 4 from 3 is the first example of an acid-catalyzed transformation of the stable benzoin 3 into the corresponding less stable benzoin 4. Structures and yields of various by-products occurring under different reaction conditions during the synthesis of 8 from 4 are given. The O-atom of the 3-oxazoline ring in 8 could be replaced by S from P2S5 yielding the 3-thiazoline 14. Separation of the enantiomers of the racemate 8 could only be performed by transforming them into the trimethylanilinium salts 8b and 8c of (-)- and (+)-10-camphorsulfonic acid, respectively. Solid NaOAc in boiling toluene caused the precipitation of the 10-camphorsulfonic acids from the quaternary ammonium salts as sodium salts and the removing of the third methyl group from the quaternary ammonium salts as AcOMe to give the enantiomers (-)-(5S)-8 and (+)-(5R)-8. Their absolute configurations are deduced from an X-ray analysis of 8b.
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  • 91
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of the title compound with m-chloroperbenzoic acid affords a keto-lactone, two bis-lactones and a bis-spirolactone, in varying amounts depending upon the reaction conditions. The structures were established by means of X-ray diffraction, 1H- and 13C-NMR spectroscopy.
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  • 92
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    Helvetica Chimica Acta 68 (1985), S. 623-634 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Substituted CyclononatetraenesIn the course of an exploration of possible synthetic pathways to nonafulvenes, a series of 1-substituted cyclononatetraenes (CNT) 4b-1 have been prepared in yields of about 60%. Their structures follow from spectroscopic data as well as from the quantitative valence isomerisation to 1-endo-substituted cis-3a, 7a-dihydroindenes 8. Both all-cis-CNT- 1 and cis,cis,cis,trans-CNT- 2 have been used as nucleophiles. Whereas 2 is normally more nucleophilic than 1, the yield of cyclononatetraenes 4 prepared with 2 may be reduced due to by-products such as 9 and 10.
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  • 93
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1H-, 13C-, and 15N-NMR spectra of the immunosuppressive cyclic undecapeptide cyclosporin A (1) have been analyzed at 300 MHz in CDCl3, C6D6, and mixtures of these solvents. A combination of different homo- and heteronuclear two-dimensional NMR techniques enable complete assignment of all H-, C- and 4 N-signals. Recognition of the proton spin systems has been achieved via 1H,1H-COSY and double-quantum-1H-NMR spectroscopy. NOESY spectra yield some sequence assignments, but two techniques using coupling across amide bonds have been applied to get independent assignments of all amino acids in the sequence: (i) An 1H,1H-COSY spectrum optimized for small coupling constants enables the detection of long-range couplings from N-methyl groups to both α-protons attached to that amide bond. (ii) An 1H, 13C-COSY spectrum optimized for C,H-long-range couplings (J = 5 to 10 Hz) to the eleven CO groups again yields coupling to both α-protons attached to that amide bond. Additionally these two experiments yield the assignment of N-methyl protons and carbonyl C-atoms. Normal and relayed 1H,13C-COSY in both solvents have been applied to assign all C-atoms via their directly attached and remote protons. An 1H,13C-COLOC spectrum at 500 MHz in CDCl3, which uses H,C-long-range couplings confirms the assignment of all proton spin systems as well as the C-signals of each individual amino acid. Ambiguities in the assignment of the C(δ)'s of MeLeu have thus been removed. An 1H,15N-COSY spectrum enables the assignment of the 4 NH N-atoms.
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  • 94
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and photolyses of the epoxydiene (E)-5 are described. On triplet excitation (λ 〉 280 nm, acetone), (E)-5 undergoes initial cleavage of the C(5)—O bond leading to the intermediate c. Presumably an H-shift (c → e) followed by the fragmentation of the 1,4-diradical e leads (via the enol 37) to the diketones (E)-6 and (Z)-12. Alternatively cleavage of the C(6)—C(7) bond of c furnishes the diradical intermediate d which reacts by recombination leading to (E)-13A + B, 16, and 17A + B, or by an H-shift to the enol intermediate 38. The latter undergoes an aldol-type reaction to (E/Z)-14A + B and (E/Z)-15A + B, as well as a photochemical [2 + 2]-cycloaddition to 18. On singlet excitation (λ = 254 nm, MeCN), (E)-5 undergoes photocleavage to the carbene intermediates f and g. The vinyl carbene f reacts with the adjacent double bond furnishing the cyclopropene 22 as the main product. From the carbene intermediate g, compounds 23, 24, and 25 arise by carbene insertion into the neighboring C—C or C—H bond. Furthermore, the diastereomer of the starting material, the epoxydiene (E)-20, is formed via the ylide intermediate h.
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  • 95
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    Helvetica Chimica Acta 68 (1985), S. 724-733 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular structure of pyroergotamine has been determined by single-crystal X-ray diffraction analysis to be the pyruvoyldiketopiperazine 1. The diketopiperazine ring exists in a folded or boat conformation, with a dihedral angle of 40° between the two almost planar peptide units. The R-group of the phenylalanine residue occupies a quasi-axial position of the diketopiperazine ring, while that of the proline residue is in a quasi-equatorial position. Puzzling spectroscopic and chemical properties of the compound can be rationalised in terms of crowding within the molecule.
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  • 96
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    Helvetica Chimica Acta 68 (1985), S. 715-723 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electronic properties of dopamine were studied by the ab initio STO-3G MO method. The molecular electrostatic potential (MEP) around the aromatic ring and the catechol group remains practically the same in 3,4-dihydroxytoluene (a model compound) and in neutral dopamine examined in its two extended conformations, namely that found in the crystal (side-chain and aromatic ring almost perpendicular) and the one corresponding to 2-amino-6,7-dihydroxytetralin (6,7-ADTN) (side-chain and aromatic ring almost coplanar). In protonated dopamine and in dopamine hydrochloride, the electrostatic potential of the catechol moiety is overshadowed by the positive charge, but the main features remain discernible. The catechol moiety was examined in its two coplanar conformations containing a ‘flip-flop H-bond’. The electrostatic potential around the catechol moiety is quite complex, with alternating positive and negative maxima. At increasing distances above and away from the catechol moiety, only two peripheral maxima, one negative and one positive, remain perceptible. The ‘flip-flop’ mechanism results in an approximate interchange of these two potential maxima, a fact which tends to level out the structural differences between the α- and β-rotamer of dopamine. Based on these results and on the structure of rigid agonists, some pharmacophoric features of dopamine agonists are proposed.
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  • 97
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    Helvetica Chimica Acta 68 (1985), S. 760-769 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Hydrolysis of 4-Substituted 2-Adamantyl p-NitrobenzenesulfonatesSeveral 4e -substituted 2e- and 2a-adamantyl p-nitrobenzensulfonates have been prepared by new routes. Their hydrolysis products are described.
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  • 98
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In presence of a strong base, the 13-membered cyclic compound 3 yielded, by loss of acetonitrile or its equivalent, the bicyclic product 5 instead of the 17-membered compound 4 as expected (Scheme 2). Investigation of model compounds (Scheme 4) and of model reactions (Schemes 5 and 6) led to the conclusion that the reaction proceeds via an intermediate formaldehyde imine; a Schiff base, e.g. 3b (Scheme 5), which reacts intra- and intermolecularly with a nucleophile to form a Mannich-type product. It seems to be a general principle that N-substituted 3-aminopropanenitrile and 2-aminoacetonitrile derivatives behave in the presence of a strong base as Schiff -base equivalents (Schemes 5 and 6).
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  • 99
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    Helvetica Chimica Acta 68 (1985), S. 777-788 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The biradical 2,2-dimethyl-1,3-perinaphthadiyl (a) was generated from two different precursors, the naphthocyclopropane 1 and the azo compound 2, and from each by three different pathways (pyrolysis, direct photolysis, and triplet sensitization, Scheme 1). The combined evidence from flash photolysis, low-temperature spectroscopy, and product analyses provides a detailed mechanistic picture of the formation and decay of this reactive intermediate which is persistent at 77 K in the triplet ground state (3a) and rather long-lived (400 μs) at room temperature. When formed in its lowest singlet state (1a), the biradical is too short-lived to undergo intersystem crossing to 3a or bimolecular reactions. Thus, 3a is formed exclusively from the excited triplet state of the precursor compounds, 31* or 33*. The monomolecular decay of 3a is retarded by the spin barrier; 3a initiates the polymerization of acrylonitrile and is trapped by 3O2.
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  • 100
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    Helvetica Chimica Acta 68 (1985), S. 818-818 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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