bluuebunny/crossref_metadata_2025 huggingface dataset:
Psychosocial Assessment Following Self-Harm
Authors: Russell Gregor , Owens David
Published: August 2010

Background: Patients admitted to hospital because of self-harm should receive psychosocial assessment before discharge. In practice many of these assessments in the United Kingdom and elsewhere are undertaken by trainee rather than specialist psychiatrists. Aims: To compare psychosocial assessments, aftercare, and the pattern of non-fatal repetition for patients admitted to general hospital after self-harm: comparing assessments carried out by trainee psychiatrists, allocated to the task alongside other duties on a roster, or by mental health nurses with a designated role in self-harm services. Methods: Arrangements for aftercare and rates of non-fatal repetition of self-harm in 787 consecutive psychosocial assessments in a large UK city were compared, according to whether the assessments were carried out by trainee psychiatrists or mental health nurses. Results: Compared with nurses, psychiatrists were much more likely to arrange psychiatric admission or outpatient follow-up. Nurses more often pointed people towards voluntary sector help – such as drug, alcohol or relationship counselling. Repetition of self-harm was equally common among those assessed by nurses or psychiatrists (33%; hazard ratio 0.93, 95% confidence interval 0.71 to 1.2). Conclusions: Despite making fewer aftercare arrangements that involved statutory mental health care services, psychosocial assessment by mental health nurses showed no sign of detrimental effects on repetition of self-harm.
The Acceptability of Suicide Among Rural Residents, Urban Residents, and College Students from Three Locations in China
Authors: Li Xianyun , Phillips Michael R.
Published: August 2010

Background: Community attitudes about suicide and their relationship to suicidal behavior have not been adequately investigated in low- and middle-income countries. Aims: To compare the acceptability of suicide in different population cohorts in China, identify factors that affect the degree of acceptability, and assess the relationship of cohort-specific acceptability of suicide and suicide rates. Methods: A multistage stratified random sample of 608 rural residents, 582 urban residents, and 629 college students were administered a 25-item scale studying the likelihood they would consider suicide (on a 5-point Likert scale) if they experienced a variety of stressors ranging from “being disciplined at work” to “developing a chronic mental illness.” The internal consistency and test-retest reliability for the scale are excellent (Cronbach’s α = 0.92, ICC = 0.75). Results: College students had the most permissive attitudes about suicide, and urban residents were significantly more accepting of suicide as a response to serious life stressors than were rural residents. Multivariate analysis found that the overall acceptability score was higher in women, decreased with age, and increased with years of education. Conclusions: There was no clear relationship between cohort-specific acceptance of suicide and reported rates of suicide, highlighting the complexity of the relationship between attitudes about suicide (of which acceptability is only one component) and suicidal behavior.
A Study of the Irish System of Recording Suicide Deaths
Authors: Corcoran Paul , Arensman Ella
Published: August 2010

Background: Many studies have examined the reliability of national suicide statistics. Aims: To examine the Irish system of certifying suicide deaths and data collected by it. Methods: Data were recorded from a police form (Form 104) completed and sent to the Irish Central Statistics Office (CSO) after all inquested deaths that occurred in Ireland in 2002. Results: Of the approximately 1,800 inquested deaths, 6% (and 4% of suicides) were not included in routine mortality statistics because of late registration. Of the 495 deaths thought by the police to be suicide, 485 (98%) were so recorded by the CSO. Information relating to medical history and contributory factors was provided in just 54% and 34% of suicides, respectively. Suicide deaths showed significant variation by weekday (excess on Mondays) and calendar month (summer peak). The peak suicide rate (35 per 100,000) was among men aged 25–34 years. Persons separated, living alone, and unemployed had significantly elevated suicide rates. Conclusions: There is a need for a better understanding of national suicide recording systems, as this study has provided for Ireland. Such systems may routinely provide data relating to sociodemographic factors but not relating to medical and psychosocial factors.
Magnetotelluric pulses generated by volcanic lightning at Sakurajima volcano, Japan
Authors: Aizawa Koki , Yokoo Akihiko , Kanda Wataru , Ogawa Yasuo , Iguchi Masato
Published: September 2010

Continuous magnetotelluric (MT) measurements were conducted at Sakurajima volcano, Japan, revealing syn‐eruption electric pulses (and sometimes accompanying geomagnetic pulses). Movies of the eruptions, recorded with timing provided by a GPS clock, show a large number of volcanic lightning flashes. Some MT pulses occurred simultaneously with lightning flashes. Pulses were observed more than 10 seconds after the onset of the eruption, and tend to occur during eruptions that emit volcanic ash to high altitudes. Pulses were more common during mild eruptions rather than during Vulcanian eruptions. The observations suggest that the dominant mechanism of volcanic lighting is similar to that of lightning in thunderstorms, in that it requires the collision of particles and subsequent separation of positive and negative charge.
Plasma irregularities adjacent to auroral patches in the postmidnight sector
Authors: Hosokawa K. , Motoba T. , Yukimatu A. S. , Milan S. E. , Lester M. , Kadokura A. , Sato N. , Bjornsson G.
Published: September 2010

We demonstrate a close association between decameter‐scale plasma irregularities in the E region ionosphere and auroral patches in the postmidnight sector. In September 2009, campaign‐based measurements of the aurora were conducted in Iceland with a white light all‐sky camera (ASC) at Tjörnes (66.20°N, 17.12°W) and the SuperDARN radar at þykkvibaer (63.77°N, 20.54°W). On one night during the campaign period, the ASC observed the successive passage of auroral patches in the postmidnight sector after a small substorm‐like activity. The patches were drifting predominantly eastward across the field‐of‐view of the ASC with a speed of approximately 360–450 m s−1, which is consistent with the sunward convection in the postmidnight westward electrojet. The simultaneous radar measurements recorded strong radar backscatter echoes (>15 dB) within the gaps between adjacent auroral patches, while such echoes were not observed or were very weak in the region of the aurora. The Doppler velocity estimation showed that the electric field was clearly reduced within the patches, which was probably the result of the enhanced conductance associated with auroral precipitation. Thus, this reduction in the electric field suppressed the generation of irregularities (i.e., radar echoes) in the regions of auroral patches. This suggests that the conductance enhancement associated with precipitating electrons not only modified the electric field within the aurora but also affected the generation of small‐scale plasma structures in the vicinity of the patch‐type optical auroral forms.
Data‐derived spatiotemporal resolution constraints for global auroral imagers
Authors: Uritsky Vadim M. , Donovan Eric , Trondsen Trond , Pineau Deanna , Kozelov Boris V.
Published: September 2010

We present new data‐derived constraints on spatiotemporal resolution of global auroral imagers. The reported results are based on an extensive set of images from two previously flown instruments, POLAR UVI and IMAGE WIC, processed using the event detection methodology developed by Uritsky et al. (2002, 2003, 2006). We use the cross‐scale analysis of ground‐based and spacecraft observations of auroral emission regions by Kozelov et al. (2004) to derive the power law exponent relating spatial and temporal scales of auroral precipitation events, and estimate the normalization factor entering this relation using the satellite data. Our results show the existence of a nontrivial scaling relation between the relaxation time and the spatial dimension of auroral emission events. We use this relation as a proxi to the resolution scaling function providing non‐redundant combinations of spatial and temporal resolution of an optimized auroral imager consistent with the dynamics of multiscale auroral precipitation.
The Timing of Remediation and Compensation Rehabilitation Programs for Individuals With Acquired Brain Injuries: Opening the Conversation
Authors: Weissling Kristy , Prentice Carrie
Published: September 2010

This article describes the timing of AAC in the rehabilitation of individuals with acquired cognitive-linguistic deficits. Core concepts surrounding the timing of remediation and compensatory rehabilitation programs are explored including mutual exclusion, the perception of “giving up,” acceptance, fear of permanency, and the definition of compensation. A hybrid approach to rehabilitation, which encompasses both remediation and compensation, is proposed.
Turbulent oscillating channel flow subjected to a free-surface stress
Authors: Kramer W. , Clercx H. J. H. , Armenio V.
Published: September 2010

The channel flow subjected to a wind stress at the free surface and an oscillating pressure gradient is investigated using large-eddy simulations. The orientation of the surface stress is parallel with the oscillating pressure gradient and a purely pulsating mean flow develops. The Reynolds number is typically Reω=106 and the Keulegan–Carpenter number—the ratio between the oscillation period and advection time scale—is KC=80. Results compare favorably to the data from direct numerical simulations obtained over a single period. A slowly pulsating mean flow occurs with the turbulent flow essentially being statistically steady. Logarithmic boundary layers are present at both the bottom wall and the free surface. Turbulent streaks are observed in the bottom and free-surface layer. The viscous sublayer below the free surface is, however, much thinner. This observation is verified by simulations we performed for a purely wind-driven channel flow. For the oscillating flow, additional low-speed splats (localized regions of upwelling) occur at the free surface when the mean velocity and stress are in the same direction.
Shape of the Q band in the absorption spectra of porphyrin nanotubes: Vibronic coupling or exciton effects?
Authors: Stradomska Anna , Knoester Jasper
Published: September 2010

Absorption and linear dichroism spectra of self-assembled tubular aggregates of TPPS4 porphyrin are studied theoretically with special emphasis on the low energy part of the spectra (the Q band region) where the coupling with intramolecular vibrations is pronounced. The model Hamiltonian includes both the excitonic coupling between four molecular electronic excited states contributing to the porphyrin Q and B bands as well as the intermediate-strength linear exciton-phonon coupling to one effective high-frequency molecular vibrational mode. Good agreement between the calculated and experimental spectra is obtained. The results allow us to identify the nature of the peaks observed in the Q band region of the aggregate’s absorption spectrum; we show that the two most prominent peaks within the Q band originate from two different excitonic subbands. It is shown that the coupling between the Q and B bands plays an important role and the vibronic coupling affects the details of the absorption lineshape.
Space charge limited conduction with exponential trap distribution in reduced graphene oxide sheets
Authors: Joung Daeha , Chunder A. , Zhai Lei , Khondaker Saiful I.
Published: September 2010

We elucidate on the low mobility and charge traps of the chemically reduced graphene oxide (RGO) sheets by measuring and analyzing temperature dependent current-voltage characteristics. The RGO sheets were assembled between source and drain electrodes via dielectrophoresis. At low bias voltage the conduction is Ohmic while at high bias voltage and low temperatures the conduction becomes space charge limited with an exponential distribution of traps. We estimate an average trap density of 1.75×1016 cm−3. Quantitative information about charge traps will help develop optimization strategies of passivating defects in order to fabricate high quality solution processed graphene devices.
The Relative Stability of Internal Metal Complexes. I. Complexes of 8-Hydroxyquinoline, Salicylaldehyde, and Acetylacetone
Authors: Maley LE , Mellor DP
Published: September 2010

The stability constants of a series of
internal metal complexes derived from 8-hydroxyquinoline, salicylaldehyde, and
acetylacetone have been determined by means of an electrometric method.

A quantitative treatment of the chelation
of 8-hydroxyquinoline, based on the theory of step equilibria, is given and the
modifications required for dealing with the other substances investigated are
indicated.

Two important facts emerge from this
survey :

(1) The order of the metals (as regards stability
of their complexes) is substantially the same for each of the three chelating
substances studied.

(2) The order of the stability of the
complexes derived from the three chelating substances is independent of the
nature of the coordinating metal, the 8-hydroxyquinoline complex of a metal
being more stable than its acetylacetone complex which in turn is more stable
than its salicylaldehyde complex.

Measurements were made of the stability
constants in water-dioxan mixtures and the effect of changing the proportions
of the two components in the solvent mixture was studied in several instances.
The values of stability constants of internal metal complexes in water-dioxan
mixtures are greater than those in water. It is shown that insolubility of
internal metal complexes is not, in general, a criterion of their relative
stability. The possible significance of stability-constants in chemotherapy,
biochemistry, and analytical chemistry is briefly discussed.
The Catalytic Dehydration of 2,3-Butanediol to Butadiene. II. Adsorption Equilibria
Authors: Winfield ME
Published: September 2010

Further understanding of the reaction in
which 2,3-butanediol is dehydrated over thorium oxide to methyl vinyl carbinol
and butadiene has been gained by measuring the adsorption on thoria of water,
methyl ethyl ketone and the above-mentioned diol, carbinol, and diene, at
temperatures up to 200 �C. In some instances satisfactory isotherms could not
be obtained because sufficient chemisorption occurred, followed by
polymerization or dehydration reactions, to reduce seriously the area of thoria
surface available for adsorption. There was evidence to suggest that water,
alone of the vapours concerned, was taken up in greater amount than could be
accounted for by adsorption. The bearing of this on the dehydration and its
relation to the structure of the catalyst is briefly discussed. A suggestion in
a previous paper(1) that water is the product which retards the catalytic
dehydration is confirmed.

At temperatures little above 50 �C, methyl
vinyl carbinol is dehydrated by thoria to butadiene, while methyl ethyl ketone
at room temperature undergoes self-condensation on thoria to yield a methyl
heptenone. Also at quite low temperatures dimerization of butadiene brings
about appreciable reduction of available surface. Some loss of activity on this
account must therefore be expected when thoria is used to dehydrate
2,3-butanediol, even though butadiene is adsorbed only weakly.
Observations of the Spectrum of High-Intensity Solar Radiation at Metre Wavelength. II. Outbursts
Authors: Wild JP
Published: September 2010

Observations are described of the spectrum
of outbursts of solar radio-frequency radiation in the frequency range 70-130
Mc/s. In accordance with Part I of this series, an " outburst " is
defined as a burst having a particular type of " dynamic " spectrum,
characterized by a drift of spectral features, with time, towards the lower
frequencies at a rate of the order of � Mc/s. per second. The observed
outbursts are shown to have a close connexion with solar flares and their
geophysical accompaniments.

�� The
spectra are tentatively interpreted in terms of the motion of a physical agency
in the solar atmosphere. The possible identification of the agency with "
surge " prominences and the corpuscular streams that cause a type of
terrestrial magnetic storm is discussed. It is shown that the evidence is quite
consistent with the hypothesis that the agency corresponds to the magnetic
storm particles.
Studies on the Lignin of Eucalyptus regnans F Muell. X. The Ethanolysis of an Isolated Alkali Lignin
Authors: Merewether JWT
Published: September 2010

Alkali lignin of Eucalyptus regnans F.
Muell. has been treated with ethanol in the presence of hydrogen chloride to
yield ethanol alkali lignin. The reaction has been found to involve ethylation
of an acidic hydroxyl group, not acetalization of a carbonyl group.

From the analysis of derivatives of
ethanol alkali lignin, ethanol lignin, and alkali lignin, some inferences have
been drawn regarding the structure of protolignin.
Enthalpies and Entropies of Ion-Exchange Reactions
Authors: Duncan JF
Published: September 2010

By use of exchange isotherms determined at
different temperatures, the chemical potentials and partial molar heats and
entropies of the sodium-hydrogen ion-exchange reaction on a sulphonated
polystyrene exchanger are evaluated. These show that both species are almost
completely ionized in the exchanger, and very similar to their states in
aqueous solution. In the high concentrations obtainable in the exchanger,
however, there is some cation-cation interaction, which is practically linear
with composition. A similar treatment of the barium-hydrogen system indicates
that there is some interaction between the barium ion and the resinate
structure.
The Quinone-Hydroquinone character of activated carbon and carbon black
Authors: Garten VA , Weiss DE
Published: September 2010

There are two extreme types of activated
carbon and carbon black although structures intermediate between these two
extremes are more usual. This work has established that in one extreme, the
oxidized form (" H " carbon), the carbon has a pronounced quinonoid
structure which creates a number of fixed olefinic bonds. In the other, the
reduced form (" L " carbon), the structure is more aromatic and has the
characteristics of a hydroquinone. Carbons having properties intermediate
between those of a pure " H " or " L " carbon acquire some
semiquinone characteristics and become less diamagnetic. It is experimentally
shown that the chemical behaviour of these carbons parallels in many ways that
of simple quinone-hydroquinone compounds. The quinonoid structure of an "
H " carbon accounts for the formation of peroxygen complexes, its ability
to catalyse the ionization of oxygen in the presence of an electron donor, its
oxidizing properties, and its reactivity with rubber. The hydroquinone character
of an " L " carbon is responsible for its ability to adsorb alkali,
its reducing properties, and its ability to fog a photographic plate ("
Russell effect "). The change in properties which occurs in chars
carbonized above 650" C is due to the transition from an " L " to
an " H " carbon.
The structure of cryptopleurine and Hofmann degradation of some quinolixidine alkaloids
Authors: Gellert E
Published: September 2010

With the help of (-)-cryptopleurine-(14C)-methiodide
it has been shown that during attempted Hofmann degradation no structural
change takes place. Therefore, the structure of the alkaloid cryptopleurine is
I. The formation of racemic quaternary methiodides under conditions which
usually effect Hofmann degradation is discussed.
The catalytic Hydrogenation of Benzene and toluene over evaporated films of Nickel and Tungsten
Authors: Anderson JR
Published: September 2010

In the vapour-phase hydrogenation of
benzene and toluene over evaporated films of nickel and tungsten there is some
poisoning of the catalyst surface by adsorbed hydrocarbon residues, resulting
in falling rates of hydrogenation. Activation energies and frequency factors
are obtained from initial rates. On poisoned nickel, rates pass through a
maximum at about 90 �C. The rate and extent of poisoning increase with
temperature. Some cyclohexene is sometimes formed during the hydrogenation of
benzene over nickel. The hydrogenation of cyclohexene over nickel is extremely
rapid but strongly inhibited by benzene. On a benzene poisoned nickel surface
cyclohexene disproportionates to benzene and cyclohexane, and this reaction
also occurs to a small extent during hydrogenation of cyclohexene.
Chemistry of polynuclear compounds. III. The structures and absorption spectra of 1,1'-Dianthrimide and indanthrone
Authors: Durie RA , Shannon JS
Published: September 2010

In an investigation into the coking
mechanism of coal, polynuclear quinones have been adopted as models. The
vibrational and electronic absorption spectra of indanthrone (I), 1,1?-dianthrimide (II), and 1,2,2',1'-anthraquinoneazine (III)
are presented and discussed. The absorption spectra of I and II, together with
other available evidence, favour the tetraketo form rather than the enol form
as recently proposed by Wyman (1956) for structure I.
Synthesis of Heliotramide
Authors: Adams R , Culvenor CCJ , Robinson CN , Stingl HA
Published: September 2010

Both racemates of
4-methoxy-3-hydroxy-2-methylpentane-3-carboxamide are synthesized by reacting
isopropylmagnesium chloride with 2-methoxypropionitrile, converting the
resulting ketone into the cyanohydrin and hydrolysing to the amide. Comparison
with heliotramide shows that the lower melting racemate, m.p. 81-82 �C, is (�)-heliotramide
and thus of threo-configuration. The higher melting racemate, m.p. 145-146 �C,
is the erythro-amide. Attempts to hydrolyse the amides to the carboxylic acids
were unsuccessful.

Heliotramide is prepared by heating
heliotric acid with urea or by the usual acid chloride-ammonia procedure
following protection of the hydroxyl group.
The Movement of Molecules in Non-Uniform Electric Fields
Authors: Swinkels DAJ , Sullivan EPA
Published: September 2010

The motion of polar molecules as solute in
a non-polar solvent, under the action of a non-uniform electric field, has
received little attention.

The theory of such motion has been
developed and an experimental concentration separation of 25% achieved between
p-nitroaniline and carbon tetrachloride from solution.
Tritium-hydrogen exchange in studies of protein structure
Authors: Leach SJ , Springell PH
Published: September 2010

Tritiated water (THO) has been used in the
study of exchangeable H atoms in proteins to provide information on molecular
structure. On account of the high sensitivity of detection methods for tritium,
it need be used only in tracer amounts and this leads to several advantages
over deuterium : (i) there is less risk of conformational changes occurring in
the labelled protein, (ii) lower protein concentrations may be used (0.2 to
2.0%), and (iii) rates of exchange are slower.

The method has been used to study the T-H
exchange of ribonuclease dissolved in THO and the H-T exchange of the
N,O-tritiated protein dissolved in H2O between 0 and 70 �C. The
extent of exchange was measured in the former case by T-assay on aliquots of
dried protein and in the latter case by T-assay on water samples collected by
sublimation. Optimal conditions for sampling, drying, and T-assay are described
under which further exchange was minimized. In particular, it was found
unnecessary to dry at temperatures above 40 �C. The
number of exchangeable H atoms in the ribonuclease molecule was determined as a
function of temperature. As reported by Schildkraut and Scheraga (1960) there
appears to be a critical temperature below which certain H atoms will not
exchange within 24 hr. However, the number of such atoms (50-60) is greater,
and the critical temperature (42 �C) lower than previously reported. This
discrepancy is discussed as well as the significance of slow and rapid H
exchange in relation to protein conformation.
Solvolysis of Sulphonyl Halides. IV. The Hydrolysis of Some Substituted Aliphatic Sulphonyl Chlorides and of Ethanesulphonyl Bromide in Aqueous Dioxan
Authors: Foon R , Hambly AN
Published: September 2010

The effects of substitution in the alkyl
group of an alkanesulphonyl chloride, on the rate of hydrolysis, vary with the
solvent composition. The relative rates can be explained in terms of the theory
of Grunwald and Winstein that there is a continuous range of transition
complexes, with " bond making " between the water molecule and the
sulphur atom controlling the rate in the less aqueous media, while the
stretching and charging of the sulphur to chlorine bond controls the rate in
solvents of higher water content. The inhibition of the simple SN2 reaction, which gives
rise to a maximum rate constant as the composition of the solvent approaches
pure water, resembles that noted with methane- and ethanesulphonyl chlorides.�The
hydrolysis of ethanesulphonyl bromide, at 25 �C, proceeds at three to eight
times the rate for the corresponding sulphonyl chloride in solvents varying in
composition from 0.99 to 0.2 mole fraction of water with dioxan. Over most of
the solvent range both the entropy and enthalpy of activation are favourable to
a higher rate of solvolysis for the sulphonyl bromide.
Studies in Mass Spectrometry. II. Random Hydrogen Rearrangement in Aromatic Molecular Ions
Authors: Macdonald CG , Shannon JS
Published: September 2010

To provide data for investigations by, inter alia, mass-spectrometric methods
into the deuterium exchange of the aromatic hydrogen of some coal fractions, a
study was made which confirmed the occurrence of completely random hydrogen
rearrangement prior to or during the elimination of C2H2
in the molecular ions of benzene-1,2,3-d3, benzene-l,3,5-d3,
naphthalene-1,2,3,4-d4, naphthalene-1,4,5,8-d4, and
phenanthrene-9,10-d2, and in the phenyl ions derived from
o-bromobenzene-d, m-bromobenzene-d, and p-chlorobenzene-d, Similar but
incomplete hydrogen rearrangement was found to occur in the molecular ion of
carbazole-N-d prior to or during elimination of HCN. Such rearrangements, for
which mechanistic considerations are presented, must be taken into account when
the mass spectra of deuterium-substituted aromatic compounds are being
interpreted.
Rotatory Dispersion and Configuration of Cobalt(III) Complexes
Authors: MacDermott TE , Sargeson AM
Published: September 2010

The rotatory dispersion curves of 30
cobalt(III) complexes have been described and the absolute configurations of
some of the complexes have been assessed by relating their rotatory dispersion
curves to that of the D(+)-[Coen3]3+
ion. The assessment is supported by recent kinetic and stereochemical results.
The use of rotatory dispersion to detect stereochemical change is discussed.
Kinetics of the gas-phase oxidation of methanol catalysed by hydrogen bromide
Authors: Batten JJ
Published: September 2010

The homogeneous, gas-phase oxidation of
methanol, catalysed by small amounts of hydrogen bromide, has been studied in a
boric acid coated vessel at 310�. Under these conditions no reaction takes
place in the absence of hydrogen bromide. The kinetics of the reaction and the
rate of accumulation of formaldehyde in the products are compared with
previously published data on the nitric oxide catalysed reaction at 310� and
the uncatalysed reaction at 390�, i.e. at comparable rates of oxidation.

The kinetics of the reaction were studied
by means of pressure-time curves, and these were found to be of a similar shape
to those of the uncatalysed reaction at 390�, and the nitric oxide catalysed
reaction at 310�. The maximum rate was increased by the addition of
"inert" gas. This rate varied as the methanol and hydrogen bromide
pressures raised to the powers 0.7 and 1.3 respectively. On the other hand,
increase in the oxygen pressure inhibited the maximum rate. The overall
activation energy was 27 kcal mole-1. These kinetic data are similar
to those of the nitric oxide catalysed reaction but differ markedly from those
of the uncatalysed process at 390�. Under similar conditions, 15 mmHg hydrogen
bromide were required to give a rate approximately equal to that obtained when
using 2 mmHg nitric oxide. The
maximum pressure of formaldehyde in the products was only about one-tenth of
that obtained under similar conditions in the other two oxidations.
Quinoxaline derivatives. VIII. Betaine structures of dihydroquinoxalinium and benzimidazolium barbiturates formed from o-dialkylaminoanilines and alloxan
Authors: Clark-Lewis JW , Edgar JA , Shannon JS , Thompson MJ
Published: September 2010

Condensation of alloxan and
o-dimethylaminoaniline gives
1,2,3,4.tetrahydro-4-methylquinoxaline-2-spiro-5-(hexahydro-2,4,6-trioxopyrimidine)
(I) formed as a result of a unique ring-closure involving a methyl group of the
o-dimethylamino substituent. The structure of the closely related compound
previously formulated as its 3-hydroxy derivative (a carbinolamine) (II) is now
revised to the corresponding betaine, a dihydroquinoxalinium barbiturate (III;
R = H). The 6-methyl, 7-methyl, and 6,7-dimethyl analogues of the spiran (I),
like the parent compound, were regarded as anils by Rudy and Cramer. Betaine
structures (cf. III) may be assigned to the 6,7-dimethyl and 6,7-dichloro
analogue of the barbiturate (III; R = H). o-Diethylaminoaniline reacts differently
from o-dimethylaminoaniline with alloxan in giving a benzimidazolium
barbiturate (VIII; R = H). We propose a similar benzimidazolium barbiturate
structure for the analogous product from 4,5-dimethyl-2-dipropylaminoaniline.
Mass spectra of the lowly volatile betaines and some of their deuterated
derivatives were obtained and rationalized in terms of the assigned structures.
Several dihydrobenzimidazoles have been prepared, and their N.M.R. and light
absorption spectra recorded.
Organoaluminium compounds. VII. The reactions of organoaluminium compounds with phenylacetylene
Authors: Mole T , Surtees JR
Published: September 2010

The reactions of trimethyl-, triethyl-,
tripropyl-, tri-isobutyl-, and triphenylaluminium with phenylacetylene in the
presence and absence of benzene or toluene have been studied. In every case
phenylethynylaluminium compounds are formed. Dimethyl(phenylethynyl)aluminium
and diphenyl(phenylethynyl)aluminium are crystalline solids. The former
compound disproportionates partially in ethereal solution.

Side reactions competing with the
formation of phenylethynylaluminium compounds are also observed.
Triethylaluminium and tripropylaluminium add to phenylacetylene to give PhC(AlR2)=CHR
(R = Et, Pr), but these alkenylaluminium compounds metallate further
phenylacetylene and are so transformed to alkenes. A similar process occurs in
the reaction with triphenylaluminium, but in this case both possible products
of cis addition are observed. Tri-isobutylaluminium yields phenylethenyl
compounds by reduction of the triple bond in the principal side reaction.
Metal chelates derived from 2,4-Bis-(2-pyridyl)thiazole and 2-(2-pyridylamino)-4-(2-pyridyl)thiazole
Authors: Goodwin HA
Published: September 2010

The bases 2,4-bis-(2-pyridyl)thiazole and
2-(2-pyridylamino)-4-(2-pyridyl)thiazole have been prepared by an adaptation of
the Hantzsch thiazole synthesis. Each of these bases is capable of functioning
as a tridentate chelating agent and yields well-defined chelates with iron(II),
coba1t(II), nickel(II), and copper(II) salts. Complexes of the former base are
the less stable and this has been ascribed to greater distortion of its bond
angles induced on coordination. Neither base yields complexes of comparable
stability to corresponding complexes of terpyridine. The complexes of Fe(II), Co(II),
and Ni(II) isolated are spin-free.
Solvent effects on the infrared spectra of methanol, t-butanol, and phenol in the region 1350-900 cm-1
Authors: Cole ARH , Michell AJ
Published: September 2010

The effects of solvents on the absorption
bands of methanol, t-butanol, and phenol in the region 1350-900 cm-1
have been studied. The results support recent assignments of the O-H
deformation and C-O stretching modes in these compounds.
Organophosphorus compounds. V. Dialkyl alkylphosphonates from alkyl halides and sodium dialkyl phosphonates in liquid ammonia
Authors: Meisters A , Swan JM
Published: September 2010

Liquid ammonia is a useful solvent for the
reaction of various alkyl halides with sodium dialkyl phosphonates. In this
medium ethyl bromide, amyl bromide, octyl bromide, ally1 chloride, and benzyl
chloride give the corresponding dialkyl alkylphosphonates in good yield.

In other cases, alternative products are
formed. Thus sodium diethyl phosphonate reacts with carbon tetrachloride or
chloroform in liquid ammonia to give diethyl phosphoramidate; dibromomethane
gives diethyl methylphosphonate and an equivalent quantity of diethyl
phosphoramidate. p-Nitrobenzyl bromide gives mainly
1,2-di(p-nitrophenyl)ethane, 1-bromooct-1-yne is reduced to oct-1-yne, and
3-bromoprop-1-yne gives mainly propyne together with some diethyl prop-l-
ynylphosphonate.
Further experiments with the methylquinolizidines and their methiodides
Authors: Schofield K , Wells RJ
Published: September 2010

The synthesis of 4-methylquinolizidine has
been re-examined, and the purity of methylquinolizidines used in earlier work
established by gas chromatography.

A new synthesis of the cis-fused
methiodide of quinolizidine has been devised, and the course of the Hofmann
degradation of it and its stereoisomer examined.

The stereochemical course previously
deduced for the quaternization of the 1-methylquinolizidines has been confirmed
by experiments with optically active specimens of these compounds.
Convenient preparation of a crystalline derivative of meso-tartraldehyde
Authors: Angyal SJ , Gero SD
Published: September 2010

Periodate oxidation of 1,2-O-cyclohexylidenemyoinositol
gives cis-3,4-cyclohexylidenedioxy-2,5-dihydroxytetrahydrofuran (III), a
compound which liberates meso-tartraldehyde on mild acid hydrolysis.
Condensation with nitromethane provides a synthesis of 5-nitrocyclopentane-1,2,3,4-tetraols.
The synthesis of (±)-10-Hydroxy-1,2,9-trimethoxyaporphine
Authors: Clezy PS , Lau DYK
Published: September 2010

Following standard methods
of aporphine alkaloid synthesis, the racemic base,
10-hydroxy-1,2,9-trimethoxyaporphine (Ic) has been prepared.
The preparation of some sequential polypeptides by the p-Nitrophenyl ester method
Authors: Stewart FHC
Published: September 2010

A number of sequential
polypeptides have been obtained by polymerization of peptide p-nitrophenyl
esters. The majority of the products contained γ-ethyl-L-glutamyl and
S-benzyl-L-cysteinyl residues in various proportions. The active ester monomers
were synthesized by the mixed carbonic anhydride procedure using p-nitrophenyl
as a carboxyl-protecting group. Some of the limitations of this approach are
discussed.
Schiff base equilibria. V. Beryllium complexes of N-ethylsalicylideneimine
Authors: Green RW , Sleet RJ
Published: September 2010

The formation constant and
pK at 25� of the Schiff base N- ethylsalicylideneimine
(HL) have been found by spectrophotometry to be 2.75x104 and 11.8
respectively. The distribution coefficient of the base from water into toluene
is 160. The stability constants of the beryllium complexes determined by
solvent distribution are logβ1 10.4
and log β2 18.3, and the distribution coefficient of BeL2 is 260. At high pH the equilibria are complicated
by hydrolysis of the Be2+ ion
and by formation of the mixed complex, BeL(OH)-2.
The latter is formed according to the reaction BeL(H2O)+2
↔ BeL(OH)-2+2H+
with logKm2 -18.4.
Preparation of some Polyaryl-benzenes and -napthalenes
Authors: Craig JT , McNatty KP
Published: September 2010

Attempts have been made to
condense several aromatic α-diketones with diethyl ketone and dibenzyl
ketone.

1,1?-Binaphthoyl gave only di-1-naphthylglycolic acid, but 1- naphthyl phenyl diketone
gave mixtures of the products of condensation and benzilic acid rearrangement
reactions. The condensation product with dibenzyl ketone reacted normally in
Diels-Alder reactions with maleic anhydride, benzyne, and bicycloheptadiene. 2-Methylbenzil condensed readily with dibenzyl and diethyl
ketones, and the substituted cyclopentadienone resulting from condensation with
dibenzyl ketone underwent a Diels-Alder reaction with bicycloheptadiene.
A solvent effect on the conformation of aromatic nitro groups
Authors: Rae ID
Published: September 2010

The differences between
proton mangetic resonance spectra of aromatic nitro compounds in
deuterochloroform and dimethyl sulphoxide solutions are interpreted in terms of
increased steric requirements of the nitro group in the latter solvent. In
suitably ortho-substituted aromatic nitro compounds this leads to twisting of
the nitro group about the Ar- N bond.
Mass spectrometric studies. II. β-Phenylglycidic esters and amides
Authors: Baldas J , Porter QN
Published: September 2010

The mass spectra of some
β-phenylglycidic esters and amides have been analysed, and the spectra
have been rationalized on the basis of a number of impact-induced
rearrangements, including a novel one involving the migration of an alkoxy or
amino group. The N.M.R. spectra of the compounds are tabulated, and are used to
determine their stereochemistry.
Synthesis of the tumour-inhibitory alkaloids, ellipticine, 9-methoxyellipticine, and related pyrido[4,3-b]carbazoles
Authors: Dalton LK , Demerac S , Elmes BC , Loder JW , Swan JM , Teitei T
Published: September 2010

Orthophosphoric acid has
been found to accomplish the previously unsuccessful cyclization of azomethines
of 3-formylcarbazoles and aminoacetal to substituted pyrido[4,3-b]carbazoles
according to a scheme proposed by Cranwell and
Sexton. By this method, there have been prepared 6,11-dimethyl-(ellipticine),
5,6,11-trimethyl-, 5,9,11- trimethyl-, 9-methoxy-5,11-dimethyl- (9-methoxyellipticine), 9-methoxy- 5,6,11-trimethyl-,
9-bromo-6,11-dimethyl-, and 9-nitro-5,11-dimethyl- 6H-pyrido[4,3-b]carbazole.
Phosphato complexes of cobalt(III). III. Hydrolysis reactions in perchloric acid media
Authors: Lincoln SF , Stranks DR
Published: September 2010

Rates of hydrolysis of phosphato complexes of oobalt(111)
in perchloric acid media ranging from 10-3
to 11.4M have been measured by the rates of release of phosphate from 32P-labelled
phosphato complexes. First-order rate behaviour is
exhibited under all conditions and half-times range from hours to minutes
within the range 45-70�. Bidentate phosphato
complexes exhibit the same rates of hydrolysis as the corresponding monodentate
complexes due to a rapid conversion of the bidentate into the monodentate form.
Rate constants have been
measured for three distinct protonated complexes (PI,
P2, P3). At 60� these rate constants, expressed in the order of aquo-tetraammine, -penhammine,
and ?bisethylenediamine complexes, are

PI: 74.0, 1.20, 5.5 X 10-3
min-1; P2: 2.5, 1.20, 0.40 x 10-3
min-1; P3: 20.0, 9.0, 5.5 x 10-3
min-1.

A tetraprotonated
complex (P4) is incompletely generated even in 11.4M HClO4
where observed rate constants at 60� are 8.2, 3.4, 7.0 x 10-2 min-1
respectively. Intramolecular hydrogen
bonding is considered important in the P1 and P2 species, especially in the cis-aquophosphato
complexes. The rate of hydrolysis of P3 complexes is linearly dependent on the
activity of the water solvent consistent with a mechanism involving SN2
attack of water at a cobalt(111) centre. The P4 complex is
considered to hydrolyse via an SNICA
mechanism.
Sulphur-nitrogen chelating agents. V. Complexes of 2-Methyl-8-methylthioquinoline with some transition metals: The occurrence of tetrahedral complexes of cobalt(II), nickel(II), and copper(II)
Authors: Chia PSK , Livingstone SE
Published: September 2010

Complexes of 2-methyl-8-methylthioquinoline (mmtq) have
been obtained with cobalt(11), nicke1(11), palladium(11), platinum(11), copper(1), copper(11), silver(1), and gold(111). The 2-methyl group
of mmtq causes severe steric hindrance to other
ligands in a square plane. The complex AuCl3
mmtq contains five-coordinate gold(111).

Only one bis-chelated
complex, Pd mrntq2(ClO4)2,H2O,
was isolated and it is possible that the metal atom in this complex is
five-coordinate also. The solid reflectance
spectra of the compounds MX2 mmtq (M = Co,
Ni, Cu; X = Cl, Br) and CoI2 mmtq indicate a
pseudo-tetrahedral configuration about the metal atom in these complexes.
Flavan derivatives. XXII. 2'-Substituted flavanones and flavones; aroyl bromides by bromination of aromatic aldehydes
Authors: Clark-Lewis JW , Skingle DC
Published: September 2010

Flavanone-2'-carboxylic acid, its methyl ester, and 2'-hydroxymethyl-

flavanone were obtained from 3-o-hydroxyphenaoylphthalide.
Bromination of the flavanones gave the corresponding cis-3-bromoflavanones
which easily underwent base-catalysed dehydrobromination, and flavone-2'-carboxylic acid and its methyl ester were
prepared in this way. Bromination of o-tolualdehyde gave o-toluoyl
bromide in a known but hitherto neglected reaction which appears to offer a
useful route to aroyl bromides.
Excess volumes and viscosities of binary liquid mixtures
Authors: Raman GK , Naidu PR , Krishnan VR
Published: September 2010

Excess volumes of binary
mixtures of cyclohexane with phenol, o-ohlorophenol,
p-chlorophenol, o-cresol, m-cresol, and p-oresol have
been measured. The results have been used as an indication of relative
strengths of intermolecular hydrogen bonds in phenol and substituted phenols.
Viscosities of phenol, o-cresol, and o-chlorophenol in admixtures with
cyclohexane have also been measured and the results of viscosity data were
examined in the light of the relations developed for binary mixtures.
Aromatic nitrogen bridgehead compounds. III. The synthesis of 8a,10a-diazoniaphenanthrene and related cations
Authors: Calder IC , Sasse WHF
Published: September 2010

The acid-induced cyclization
of 1-acylmethyl-2-(2-pyridyl)pyridinium
salts to 9,10-dihydro-9-hydroxy-8a, l0a-diazoniaphenanthrene salts, and the reversal of this
reaction are described. These salts can be dehydrated to give 8a,l0a-diazoniaphenanthrene salts. 3a,8a-Diazoniapyrene
salts can be made similarly.
Cyclitols. XXIX. Polyphosphorylation of polyols. The synthesis of myo-inositol pentaphosphates
Authors: Angyal SJ , Russell AF
Published: September 2010

Heating myo-inositol
with an excess of the triethylammonium salt of N- benzoylphosphoramidic
acid in N,N-dimethylformamide results in phosphorylation of every hydroxyl
group. The method appears to be general for the complete phosphorylation of
unsubstituted or partially substituted inositols. Starting with 1-O-benzyl- and
4-O-benzyl-myo- inositol, phosphorylation and
subsequent hydrogenolysis gave DL-myo- inositol
1,2,4,5,6- and 1,2,3,4,5-pentaphosphate, respectively. Other methods of phosphorylation
were found unsuitable.
Synthetic evidence for the structure of xanthorrhone
Authors: Birch AJ , Dahl CJ , Pelter A
Published: September 2010

Reaction of
5,7-dimethoxyflavanone with sodium borohydride gives the flavanol, which
condenses in the presence of acid with phloroglucinol to give (III), and with
(-)-pinocembrin to give a small yield of a substance indistinguishable in its
mass spectrum from xanthorrhone (I).
The mass spectra of the furoquinol-4-one alkaloid acrophylline and quinol-2-ones related to hexahydroacrophylline
Authors: Lahey FN , Lauder I , McCamish M
Published: September 2010

The mass spectra of several
isofuroquinoline alkaloids (N- methylfuroquinol-4-ones)
including the new N-prenylfuroquinol-4-one, acrophylline, have been recorded.
The fragmentation of hexahydroacrophylline and related 3-ethyl-4-hydroxyquinol-2-ones
have also been determined by deuterium and oxygen-18 labelling and high
resolution measurements.
Carbonyl halides of the Group VI transition metals. XIV. Substitution derivatives of the trihalotetracarbonylmolybdenum(II) anions
Authors: Bowden JA , Colton R
Published: September 2010

The complete series of
substituted halocarbonyl anions [Mo(CO)3RPh3X3]-
(where R is P, Sb, As; X is Cl, Br) have been characterized as their
tetraethyl-ammonium salts. Each substituted anion has been prepared by two
distinct methods and all of the compounds can exist as two isomers. Except for
the α-isomer of [Mo(CO)3PPh3Br3]-
these complexes are reported for the first time.
Addition compounds of aldehydes
Authors: Cox BG , McTigue PT
Published: September 2010

Equilibrium constants at
298�K have been measured spectrophotometrically for the following reactions in
water:������� (i) Hydrogen-bonded addition of the
aldehyde hydrates ethane, propane-, and butane-1,1-diols to the anions
chloride, acetate, hydrogen carbonate, hydrogen phosphate, and dihydrogen
phosphate. ������ (ii) Nucleophilic addition of imidazole
to the aldehydes ethanal, propanal, and butanal. ������ (iii) Hydration (to 1,1-diols) of
ethanal, propanal, 2- methylpropanal, and butanal. ��� P.m.r. and kinetic evidence is presented to
support the assumed nature of the equilibria discussed.
The chemistry of aliphatic unconjugated nitramines. II. Intramolecular properties and crystal packing
Authors: Stals J
Published: September 2010

The VESCF(BJ)-MO electric
dipole moments, molecular ionization potentials, electronic bond energies,
charge distributions, and bond orders for nitramide, N-methylnitramine, and s-
and as-N,N- dimethylnitramines are reported. The
packing of nitramide, RDX, and HNX in their molecular crystals is rationalized
in terms of electrostatic and hydrogen-bonding interactions. Simple VB
structures do not readily predict their calculated MO charge distributions and
bond orders.
Terpenoid chemistry. XVII. ( - )-Ngaoine, a toxic constituent of Myoporum deserti. The absolute configuration of ( - )-Ngaione
Authors: Hegarty BF , Kelly JR , Park RJ , Sutherland MD
Published: September 2010

Varieties of the shrub Myoporum deserti A. Cunn. (Ellangowan poison bush),
which causes heavy losses of stock in inland Australia, yield at least nine
different essential oils, most of which are toxic. One oil from plant material
of the Longreach chemical race from Blackall, Clermont, Hannaford, Longreach,
Meandarra, Moree, and Roma
contains the toxic furanoid sesquiterpene ketone,
(-)-ngaione, as the principal constituent while two others (the Mitchell and
the Blackall races) contain lesser proportions of ngaione.
(-)-Ngaione comprises over half of the essential oil of a "greenish
leaf" variety of Eremophila latrobei F. Nuell. and a low
proportion of the oil of a "silver leaf" variety of the same species.
The trans isomer of ngaione
[(-)-epingaione], present in low concentration in
some of these essential oils, is formed from ( -)-ngaione during fractional
distillation or more rapidly by base-catalysed epimerization. "Isongaione
acetate" prepared from (-)-ngaione by treatment with acetic anhydride-sodium acetate is
shown to be a mixture of a, β- and β, γ-unsaturated ketones and
obtainable in optically active form contrary to literature statements. Oxidation of the optically
active β,γ-unsaturated ketone yields (-) acetylmalic acid from which it follows that (-)-ngaione is
l(S),4(R)-β-(4,8-dimethyl-6-oxo-1,4-epoxynonyl)furan,
ipomeamarone is the 1(R),4(S) enantiomer, and (-)-epingaione
is the 1(S),4(S) isomer.