bluuebunny/crossref_metadata_2025 huggingface dataset:
Effects of O3 and H2O oxidants on C and N-related impurities in atomic-layer-deposited La2O3 films observed by in situ x-ray photoelectron spectroscopy
Authors: Park Tae Joo , Sivasubramani Prasanna , Coss Brian E. , Kim Hyun-Chul , Lee Bongki , Wallace Robert M. , Kim Jiyoung , Rousseau Mike , Liu Xinye , Li Huazhi , Lehn Jean-Sebastien , Hong Daewon , Shenai Deo
Published: September 2010

The effect of H2O and O3 oxidants on the behavior of residual C and N-related impurities as well as Si out-diffusion and interfacial layer formation in atomic-layer-deposited La2O3 films grown at 250 °C were examined using in situ x-ray photoelectron spectroscopy. The silicate formation was suppressed in a La2O3 film grown using O3 compared to that deposited using H2O, but interfacial layer growth was enhanced. The accumulation of C and N-related residues with low binding energy, which originated from incomplete reactions, was suppressed in La2O3 films grown using O3. However, the use of O3 resulted in La-carbonate phase in film.
PO
2
dependant resistance switch effect in highly epitaxial (LaBa)Co2O5+δ thin films
Authors: Liu Jian , Collins Gregory , Liu Ming , Chen C. L. , Jiang Jiechao , Meletis Efsftathios I. , Zhang Qingyu , Dong Chuang
Published: September 2010

Giant resistance switching behavior in mixed conductive (LaBa)Co2O5+δ epitaxial thin film were discovered in high temperature and reducing environments during the reduction and reoxidation process. A reproducible resistance response of over 99% was achieved in the films during a change of 4% H2/96% N2 to oxygen at temperature range of 400–780 °C. The results indicate that at, low oxygen partial pressure, the extension of oxygen deficiency is an essential factor to the high temperature physical properties of (LaBa)Co2O5+δ and demonstrates its potential application as a chemical sensor device for reducing environments at high temperature.
China, others dig more and deeper underground labs
Authors: Feder Toni
Published: September 2010

From tiny to gargantuan, experiments are in the works to exploit the shielding from cosmic rays that being deep underground offers.
Alkaloids of the Australian Rutaceae: Acronychia baueri. III.The Structure of Acronycine
Authors: Drummond LJ , Lahey FN
Published: September 2010

Oxidative degradations of acronycine with
nitric acid and ozone have been studied. Hot concentrated nitric acid converts
noracronycine and nordihydroacronycine into l-methyl-4-quinolone-3-carboxylic
acid while nitric acid on acronycine under the same conditions yields first
trinitroacronycine and finally 6.nitro-l-methyl-4-quinolone- 3-carboxylic acid.
Ozonolysis of acronycine gives a phenolic aldehyde, C16H13O4N,
which has been deduced to be 1- or
3-formyl-2-hydroxy-4-methoxy-10-methylacridone (V or VII). These data together
with information supplied in Part II indicate acronycine to be either
4-methoxy-2',2',l0-trimethyl-α-pyrano-(5',6'-1,2)acrid-5-one (IV) or
4-methoxy-2',2',10-trimethyl-α-pyrano.(5',6'-3,2)acrid-5-one (VI).
On the Dynamics of the General Atmospheric Circulation
Authors: Priestley CHB
Published: September 2010

The annual flow of angular momentum across
latitudes 30-35� effected by north and south currents lying side by side
(cyclonic and anticyclonic " eddies ") appears insufficient to
balance the angular momentum generated at the surface in lower latitudes. The
discrepancy suggests that there must be also a mean poleward drift of air at
upper tropospheric and lower stratospheric levels across the latitudes of the
mean surface high pressure belt, with a counterdrift which occurs at least in
part in near-surface levels. A variety of auxiliary evidence supports the
existence of these flows, which are indicated as intermittent or fluctuating
components with mean speed over a long period of the order of a few miles per
hour and so, at upper levels, only on the margin of direct observation. The
origin of the poleward component is associated with the strong anticyclonic
shear to equatorward of the jet stream axis.

Since these drifts are found in latitudes
where the vertical wind shear is greatest, - they constitute an important
agency in the transport of angular momentum from its source region in the
tropics to the sink region of higher latitudes. This significant contribution
is masked in studies of interchange which invoke the assumption of geostrophic
wind.

The " index " representing the
total strength of the tropical easterly surface winds, which fluctuates
considerably, relates closely to the rate of generation of angular momentum in
the tropics. On the basis of the drifts referred to above, a descriptive theory
of the index cycle is developed, which links the fluctuations of index with the
fluctuations in strength and in latitude of the jet stream. Quantitative checks
are applied to this theory wherever possible and no discrepancy appears, while
the normal sequence of synoptic events agrees broadly with that ascribed to the
mutual interactions of surface wind strength, jet-stream, and drift.
Self-Diffusion in Polycrystalline Tin
Authors: Fensham PJ
Published: September 2010

The rate of volume diffusion in
polycrystals of tin, as indicated by the darkening of photographic films, is in
general agreement with the previous measurements of the rate of self-diffusion
in different crystallographic directions. The rate of diffusion along the grain
boundaries is generally considerably higher than that of volume diffusion
except when the boundary is that between twins or between crystals of similar
orientations. These observations are discussed in terms of recent theories of
the grain boundary and the vacancy mechanism of diffusion.
Polarography with Alternating Currents. I. Outline of Theory, Apparatus, and Technique
Authors: Breyer B , Gutman F , Hacobian S
Published: September 2010

A method of polarographic analysis
employing the superposition of a small sinusoidal alternating field of low
frequency upon the direct potential applied to the dropping mercury electrode
has been further developed. Equations are given for the calculation of the
ionic concentration from the alternating current (maximum differential current)
at the characteristic " summit potential " (analogous to E+ in
conventional polarography). This current is proportional to the concentration
of the ion species undergoing discharge. The advantages of the method over
conventional polarography can be summarized as follows :

(i) A.C.
polarography can be carried out in solutions containing dissolved oxygen, i.e.
in air.

(ii) Tedious curve plotting is substituted
by a single current reading at the summit potential which yields directly both
the half-wave potential and the concentration of the electro-reducible
substance. �� (iii) Small amounts of less noble ions can
be estimated even in the presence of a large excess of nobler ions.

(iv) Polarographic waves only 40 mV. apart
are clearly separable.

(v) An improved all round reproducibility
is obtained.

(vi) There is a simplified system of
recalibration in case of capillary replacement.

vii) The use of a delicate galvanometer is
eliminated.
The Growth of Cloud Drops by Condensation. I. General Characteristics
Authors: Squires P
Published: September 2010

Condensation in 'cloud is studied to
demonstrate certain general characteristics, without special assumptions about
the condensation nuclei or the vertical velocity. The equation of growth of a
droplet is constructed, taking account of ventilation due to its falling
velocity. Lifting is assumed to occur adiabatically. An approximate value is
found for the supersaturation of cloud air, which under certain conditions can
be computed from observable quantities-the cloud droplet spectrum and the
vertical velocity. Growth of drops at small sizes is very rapid : at constant
supersaturation, in a period of a few seconds, a drop in general either grows
beyond r= 1μ, or else comes so close to equilibrium at some smaller size
that growth practically ceases. When the supersaturation is moderate or large,
a threshold effect appears : the size of the condensation nucleus determines
whether or not the drop shall grow, but, if it does, has little influence on
its final size. The definition of the size of a small condensation nucleus is
reviewed and a more precise interpretation is suggested.
On the mechanism of the Polarographic reduction of Oxygen
Authors: Hacobian S
Published: September 2010

Investigations of the A.C. and D.C.
polarography of oxygen in neutral and alkaline media have shown that the
reduction process is univalent and reversible. It has also been shown
experimentally that hydrogen peroxide is reversibly oxidized to oxygen in the
presence of alkali. In order to explain the nature of the A.C. and D.C.
polarograms, thus obtained, a one electron reduction mechanism involving the
hydroxyl radical and either the oxygen atom or the oxygen molecule is
discussed.
The volume change on ionizatin of weak electrolytes
Authors: Hamann SD , Lim SC
Published: September 2010

The standard partial molar volumes of some
strong and weak electrolytes have been measured in water and three other
solvents. The results have been used to estimate the volume changes which
accompany the ionization of weak electrolytes. Solvent effects are discussed.
The partial degradation of ring A of lanostenol
Authors: Curtis RG , Schoenfeld R
Published: September 2010

Bromination of lanostenone (I) followed by
alkaline hydrolysis caused contraction of ring A to give an α-hydroxy acid
(IV). This compound was subjected to a sequence of reactions terminating in the
scission of the contracted ring A.
Water-soluble constituents of fruit. II. The separation of acids on anion-exchange resins: the isolation of l-auinic acid from Apricots
Authors: Anet EFLJ , Reynolds TM
Published: September 2010

Displacement chromatography on columns of
strongly basic anion-exchange resins has been used to separate, isolate, and
purify some water-soluble organic acids. The order of emergence of 27 acids
from these columns is recorded. Using this method pure l-quinic, succinic, L-malic, and citric acids were isolated from
the flesh of the apricot fruit. The method was also used for the purification
of hydroxy-acids. The detection of acids on paper chromatograms
with a silver nitrate reagent is described ; silver nitrate-sodium hydroxide
was used to detect acids having a vic.-glycol or α-keto group. The RF values
for 30 acids in two solvent systems are recorded.
Alternating current polarography of organic compounds. III. Chloranilic acid
Authors: Breyer B , Bauer HH
Published: September 2010

The behaviour of chloranilic acid at the
dropping mercury electrode has been techniques of ordinary and of alternating
current polarography. A new type of tensammetric wave has been encountered,
which is probably an outcome either of multilayer adsorption and/or of a change
in state of the adsorbed film. At the same time, a new tensammetric phenomenon,
the exchange of one species of surface-active molecules against another, has
been observed.

Alternating current polarography can be
used for estimating chloranilic acid at concentrations as low as 10-7M,
whereas conventional polarography does not permit analysis at concentrations
below 10-5M.
The influence of the supporting electrolyte on tensammetric waves
Authors: Breyer B , Haobian S
Published: September 2010

The influence of the supporting
electrolyte on the height and frequency dependence of tensammetric waves is
examined. Anions generally affect the positive tensammetric waves whereas
cations have little effect on either positive or negative waves. A tentative
explanation of the underlying phenomena is given and the possible mechanism
discussed.
The chemical constituents of Himantandra species. II. The isolation of the alkaloids of Himantandra baccata Bail. and H. belgraveana F.Muell
Authors: Brown FFC , Drummond R , Fogerty AC , Hughes GK , Pinhey JT , Ritchie E , Taylor WC
Published: September 2010

Ten new alkaloids have been isolated from
the barks of Himantandra baccata Bail. and H. belgraveana F. Muell.
Oxidation reactions in monolayers of long-chain unsaturated compounds
Authors: Gilby AR , Alexander AE
Published: September 2010

The kinetics of the oxidation of
long-chain unsaturated compounds when spread as monolayers on KMnO4 solutions has been determined from
measurements of the changes in area with time. The effects of number of double
bonds (unconjugated),of chain length, and of permanganate concentration were
studied, as well as the behaviour of the dihydroxy compounds believed to be the
first stage of the oxidation process.

The velocity constant
has been found to increase markedly for each additional double bond, and to be
independent of chain length, thus providing a quantitative measure of degree of unsaturation in
unconjugated long-chain compounds.

Mixed films of
unsaturated and dihydroxy acids have been studied and the results used to allow
for deviation from additivity of areas in the reacting systems. On this basis
the overall area-time curve, which goes through a maximum, has been
quantitatively accounted for.
Electrostatic, Polar, and steric factors in the Acid Hydrolysis of the Dipeptides
Authors: Martin RJL
Published: September 2010

Published kinetic data concerning the
rates of hydrolysis of dipeptides are discussed and interpreted in terms of the
expected electrostatic, polar, and steric influences of the constituent groups.
The evidence is consistent with a reaction mechanism in which a proton is first
added reversibly to the peptide nitrogen, and the amide cation so formed reacts
at the carbonyl carbon atom with a water molecule in a rate-controlling bi
molecular substitution.

Substitution at the glycyl carbon atom of
the parent substance glycylglycine will alter the steric hindrance to
substitution by the water molecule. On the other hand, the polar effect of
these substituents will be small and will have little influence on the rate of
reaction.

Substituents at the glycine carbon atom
introduce polar factors only with little evidence of steric effects. This
absence of a steric effect applies both to the formation of the amide cation
and to the substitution by the water. Electron repelling groups decrease the
rate of hydrolysis and must be considered to have a greater effect on
decreasing the electron accession to the peptide nitrogen necessary for the
rupture of the bend than on increasing the concentration of the amide cation.
Electron attracting substituents act in the reverse manner.

There is some evidence for a small amount
of steric compression between groups on either side of the peptide bond for the
bimolecular reaction with water.
Arylation of Aromatic Compounds. IV. Iodosobenzene dibenzoates with nitrobenzene and chlorobenzene
Authors: Lynch BM , Pausacker KH
Published: September 2010

When nitrobenzene reacts with
iodosobenzene dibenzoate both nitrodiphenyls and nitrophenyl benzoates are
formed. Isomer ratios are reported and discussed.

The reactions of iodosobenzene dibenzoate,
di-p-toluate and dianisate with chlorobenzene have been investigated. The
relative yields of the various products have been determined.
Heats and mixing. III. Acetone and Alcohol solutions
Authors: Brown I , Fock W
Published: September 2010

The heats of mixing at 45.00 �C have been
measured at intervals over the whole concentration range for the following
systems : acetone+benzene, acetone+carbon tetrachloride, aoetone+acetonitrile,
acetone+nitromethane, n-propanol+benzene, and n-butanol+benzene. The heats of
mixing are discussed in the light of the authors' earlier results for similar
systems.
The alkaloids of Crotalaria retusa L
Authors: Culvenor CCJ , Smith LW
Published: September 2010

In addition to monocrotaline, retronecine N-oxide and three new alkaloids, retusine,
retusamine, and an incompletely characterized base, m.p. 130-132°C, have been isolated
from Crotalaria retusa L. The proportion of alkaloid occurring as N-oxide varied
from 2 to 70 per cent. in different plant specimens. Hxdrolysis of retusine gives 2,3,4-
trimethyl-4-hydroxyglutaric acid 1,4-lactone (dihydroanhydromonocrotalic acid) and
an amino alcohol, C8H15O2N, probably hastanecine.
Kinetics of chemical reactions in Adiabatic systems
Authors: Parts AG
Published: September 2010

The kinetics of first- and second-order
reactions in adiabatic systems are discussed and a solution of the differential
equations is given.
The synthesis of the stereoisomeric hexadeca-2,4-dienoic acids and their isobutylamides
Authors: Wailes PC
Published: September 2010

The four stereoisomeric
hexadeca-2,4-dienoic acids have been synthesized together with their
isobutylamides and ethyl esters. The four acids, hexadeca-2,4-diynoic,
hexadeca-trans-2-en-4-ynoic, hexadeca-trans-4-en-2-ynoic, and
hexadeca-cis-4-en-2-ynoic acids were obtained as intermediates. The
insecticidal activities of the isobutylamides of these acids have been
determined.
Chemistry of Non-Enzymic Browning. VIII. The Hydrolytic reactions of Aldose Bisulphite addition compounds
Authors: Ingles DL
Published: September 2010

A study has been made of the hydrolytic
reactions of aldose bisulphite addition compounds (Ingles 1959a, 19596).
Addition compounds which had a hydroxyl group at C1 were stable in
10 per cent, acetic acid but decomposed in water and sodium hydroxide forming
the a-form of the parent D-aldose. Compounds in which the hydroxyl at C1
was replaced by an amine group were unstable in water, 10 per cent. acetic
acid, and sodium hydroxide. In the last solvent breakdown to the α-form of
the D-glycosylamine was observed.

Decomposition in sodium hydroxide appears
to occur with inversion of configuration at C1. The configurations
at C1 of the bisulphite addition compounds have been listed.
Observations on the systems Th-S, Th-Se and Th-Te
Authors: Graham J , McTaggart FK
Published: September 2010

A reinvestigation of these systems has
indicated the marked effect of the purity of materials on the phases formed.
New polychalcogenides have been found (ThS2.5, and ThSe2.5
having tetragonal symmetry, and ThTe3 monoclinic), as also has a
sesquitelluride (Th2Te3, with hexagonal symmetry) which
is probably non-stoichiometric. Discrepancies between the present results and
those of previous workers are discussed.
Some Studies in Inorganic Complexes. VI. Nickel(II) with 2-Picolylamine
Authors: Sutton GJ
Published: September 2010

Complexes of the type Nipic2X2,
Nipic3X2.nH2O, and Nipic3(ClO4)2.H2O
have been prepared and studied, where X is Cl, Br, or I and pic
is the chelating ligand 2-picolylamine. Conductance measurements in
nitrobenzene, nitromethane, methanol, and water show that the blue compounds Nipic2X2, whilst being hexacovalent
complexes in the solid state, are progressively ionized in the respective
solvents as halogen is replaced by solvent molecules. Conductance measurements
also verified a hexacovalent structure for the Ni pic32+
ion complex whose salts are bi-univalent electrolytes. Magnetic measurements
show that a11 the complexes are paramagnetic with a mean moment of 3.0 B.M.
Their absorption spectra in the near ultraviolet region are characteristic of
that of the ligand. A study in the visible spectrum was also made.
Intramolecular Hydrogen Bonding in Mononitronaphthylamines
Authors: Bryson A , Werner RL
Published: September 2010

The presence of intramolecular hydrogen
bonding in 2-nitro-1-naphthylamine,
1-nitro-2-naphthylamine, 3-nitro-2-naphthylamine, and 8-nitro-1-naphthylamine
is inferred from a study of the NH frequencies of the 14 isomeric
mononitronaphthylamines in the solvents carbon tetrachloride and pyridine.

The NH stretching frequencies are
decreased in pyridine as a result of hydrogen bonding between the amino group
and the solvent. The extent of this decrease is quite uniform for all
nitronaphthylamines except those in which the nitro and amino groups are
adjacent, and in these cases the decrease is about half that observed from the
remaining compounds. This is interpreted as indicating the presence of
intramolecular hydrogen bonding in the latter group, the extent of which
reduces the degree of solvent-solute interaction.
The Chemistry of Ants. IV. Terpenoid Constituents of Some Dolichoderus and Iridomyrmex Species
Authors: Cavill GWK , Hinterberger H
Published: September 2010

Terpenoid constituents have been isolated
from the following Dolichoderus and Iridomyrmex ants. Dolichodial, a novel
dicarbonyl compound (C10H14O2), has been
extracted from D, acanthoclinea clarki (Wheeler), and D. acanthoclinea dentata
(Forel). It has also been obtained from I. myrmecodiae (Emery). The known
compounds, methylheptenone and iridodial, have been isolated from I. nitidiceps
(Andre).

D. diceratoclinea scabridus (Roger) yields
(i) methylheptenone and iridodial, or (ii) isoiridomyrmecin, or (iii)
dolichodial, dependent on the ant colony. Such variations in the nature of the
chemical secretion of different colonies of ants, which are taxonomically
indistinguishable, have not previously been reported. Similarly, I. rufoniger
(Lowne) yields (i) methylheptenone and iridodial, or (ii) dolichodial.
A Stirred-Flow Reactor for Investigating the Kinetics of Gaseous Reactions: Application to the Decomposition of Di-t-butyl Peroxide
Authors: Mulcahy MFR , Williams DJ
Published: September 2010

The uncertainty regarding temperature and
flow conditions which attaches to the conventional flow method of determining
the rate of a gaseous reaction can be substantially reduced by using a
stirred-flow reactor. The reagents, products, and carrier-gas (if any) are
mixed sufficiently vigorously for the composition of the gas in the reactor to
be virtually uniform. A reactor designed to achieve the required degree of
mixing at pressures of about 1 cmHg and reaction times of the order of 1 sec to
1 min is described.

The rate constant of the decomposition of
di-t-butyl peroxide was determined over the temperature range 430-550 �K. The
values derived on the assumption of complete mixing in the reactor were
independent of the degree of conversion and in excellent agreement with those
obtained by previous authors using the static method.
A Study of the Thorpe-Ingold Effect: The Reaction of Potassium Hydroxide with a Lactone of Ethyl α-Bromo-α'-hydroxy-1,1-cyclohexane Diacetate
Authors: Larson HO , Sung GSK
Published: September 2010

Treatment of a lactone of ethyl α-bromo-α?-hydroxy-1,1-cyclohexane
diacetate with aqueous potassium hydroxide formed αα'-dihydroxyl-1,1-cyclohexanediacetic
acid. The cyclohexanespirocyclopropanol-2,3-dicarboxylic acid (I), an important
member of a series of compounds illustrating ring-chain tautomerism, was not
observed.
Charge-Transfer Complexes of Brominated Polycyclic Aromatic Hydrocarbons
Authors: Spotswood TM
Published: September 2010

Charge-transfer complex formation between
the donors 1-bromonaphthalene. 9-bromophenanthrene, 9-bromoanthracene,
3-bromopyrene, and 7-bromobenz[a]-anthracene and the acceptors iodine,
tetrachlorophthalic anhydride, 1,3,5-trinitrobenzene, and 2,4,7-trinitrofluorenone
has been investigated. The positions of the charge-transfer absorption maxima,
apparent molar extinction coefficients, and equilibrium constants have been
determined in carbon tetrachloride solution and the results compared with those
for the corresponding unsubstituted polycyclic aromatic hydrocarbons. The
positions of the absorption maxima of the charge-transfer bands of the
brominated hydrocarbons were anomalous but the apparent molar extinction
coefficients and equilibrium constants were similar to those obtained for the
parent hydrocarbons. The strength of charge-transfer bonding in molecular
complexes of brominated polycyclic aromatic hydrocarbons is shown to be of the
same order as that in molecular complexes of the unsubstituted hydrocarbons.
Flavan Derivatives. VII. The Stereochemical Course of the Synthesis of 2,3-cis-Flavan-3,4-trans-diol Diacetates, and the 2,4-cis-Stereochemistry of Flavan-4β-ols
Authors: Clark-Lewis JW , Spotswood TM , Williams LR
Published: September 2010

Lithium aluminium hydride reduces
2,3-trans-3-bromo-4'-methoxy-6-methyl-flavanone to 2,3-trans-3,4-trans-3-bromo-4'-methoxy-methylflvan-4-ol
which is converted by acetic anhydride-potassium acetate into
3,4-trans-diacetoxy-4'-methoxy-6-methyl-2,3-cis-flavan. Similar reactions with
the 3',4'-dimethoxy analogue give 3,4-trans-diacetoxy-3',4'-dimethoxy-6-methyl-2,3-cis-flavan.
The corresponding cis-bromoflavanones are reduced to
2,3-cis-3,4-cis-3-bromoflavan-4-ols.
Some Studies in Inorganic Complexes. XIV. Reactions of 2-Methyl-6-aminopyridine and 2-Thioamidopyridine with Some Transition Metal Ions
Authors: Sutton GJ
Published: September 2010

The following complexes of the chelating
ligands 2-methyl-6-aminomethylpyridine (6-methyl-2-picolylamine or mepic) and
2-thioamidopyridine (thiopic) have been prepared and studied: [Cu mepic2X]X, where X = Cl, Br, I, NO3,
ClO4, [Cu mepic2C2O4],
[Ni mepic3][ClO4]2,
[M(II) thiopic3][ClO4]2,
[M(III) thiopic3][ClO4]3,
(M(II) = Co, Ni; M(III) = CO, Fe), and [Co thiopic3]Cl2. Conductance measurements in ethanol,
nitromethane, and nitrobenzene indicate that the [Cu mepic2X]X
complexes are 5-covalent whilst the other complexes studied are 6-covalent. All
the complexes are "spin free" excepting those of Co(III). Absorption
spectra of the copper complexes in the near ultraviolet region were also made.
Van Der Waals Attraction between Colloidal Particles: The Retardation Correction for Flat Plates of Arbitrary Thickness
Authors: Hunter RJ
Published: September 2010

An analysis is given of the van der Waals
attraction between two flat plates of infinite extent but of finite thickness,
taking account of the retardation correction. Four cases are recognized and the
four distinct equations are shown to be mutually consistent. A table of
correction factors is given for various values of the particle thickness and
separation.
Addition of Propiolic Acid to Aryl-substituted Propiolic Acids
Authors: Campbell AD , Grimmett MR
Published: September 2010

Examples are given of the Diels-Alder type
addition of propiolic acid to aryl substituted propiolic acids. Using this
method aromatic systems have been extended by one ring. For example propiolic
acid with phenylpropiolic acid gives naphthalene-2,3-dicarboxylic anhydride.
The cardiac glycosides of Gomphocarpus fruticosus R.Br. III. Gomphoside
Authors: Coombe RG , Watson TR
Published: September 2010

The β-anhydroaglycone of gomphoside
has been shown to be 2α,3β-dihydroxy-5α-carda-14,20(22)-dienolide
and the structure of the glycoside is proposed as a derivative of a
4,6-dideoxyhexosone which has the normal glycosidic link (C1?) with
the 3β-hydroxyl group of the steroid and a hemiketal structure between the
carbonyl group (C2?) of the hexosone and the 2α-hydroxyl group
of the aglycone.
Alkaloids of the Australian Leguminosae. IV. Cinnamoylhistamine, the alkaloid of Acacia argentea and A. polystacha
Authors: Fitzgerald JS
Published: September 2010

The alkaloid present in Acacia argentea
and in A. polystacha is shown to be Nα-cinnamoylhistamine.
Activity coefficient assumptions in the determination of the association constant of thallous chloride
Authors: Macaskill JB , Panckhurst MH
Published: September 2010

The solubility of thallous chloride has
been measured in sodium chloride and sodium perchlorate solutions at an ionic
strength less than 0 1M. The association constant of thallous chloride has been
determined from these measurements using two different types of ionic activity
coefficient expression, one of them incorporating Br�nsted's principle of
specific interaction. The method for determining the association constant gives
all the parameters in the treatment but the two activity coefficient expressions
give different sets of parameters. These are discussed.
The oxidation of ammonium sulphate solutions by silver(II) oxide
Authors: Pickering WF
Published: September 2010

The oxidation by silver(II) oxide of
ammonium sulphate solutions varying in concentration from 0.1 to 1.0M has been
studied in the temperature range 40-60�. The products of the oxidation were
found to be nitrogen and nitrate ions in solutions of pH greater than 3, the
proportion of nitrogen formed increasing with pH. With solutions having a pH
less than 3, the products formed were oxygen and nitrate ions, the proportion
of nitrate decreasing rapidly with increasing acidity. The kinetics of the
reaction have been examined and a possible mechanism is discussed.
The chemistry of the nasutins
Authors: Moore BP
Published: September 2010

The termite metabolites nasutins A, B, and
C are shown to be related to ellagic acid. Nasutin A, which has been
synthesized, is the dilactone (I) of
2,2'-dicarboxy-4,6,4',6'-tetrahydroxydiphenyl and is thus identical with a
pigment isolated by Lederer from the castoreum of the Canadian beaver. Nasutins
B and C are identical with 3,4,3'-tri-O-methylellagic and 3,3'-di-O-methylellagic
acids, respectively.
Photochemical reactions of azo compounds. III. Photochemical cyclodehydrogenations of substituted azobenzenes
Authors: Badger GM , Drewer RJ , Lewis GE
Published: September 2010

2,4,6-Trimethylazobenzene has been shown
to undergo photochemical cyclodehydrogenation in sulphuric acid to give
2,4-dimethylbenzo[c]cinnoline and 1,2,4-trimethylbenzo[c]cinnoline. The
formation of the former involves cyclization with the loss of a methyl
substituent : the formation of the latter involves cyclization with the
migration of a methyl substituent. The reaction involves a photochemical
disproportionation: 4-(4-aminophenyl)-2,4,6-trimethylcyclohexa-2,5-dienone was
also isolated, having been formed by acid-catalysed rearrangement (and
hydrolysis) from 2,4,6-trimethylhydrazobenzene.

Substituted azobenzenes having a carboxy,
iodo, or chloro substituent in the 4-, 3-, or 2-position have also been
irradiated and the resulting benzo[c]cinnolines and benzidines isolated and
characterized. Irradiation of 2-substituted azobenzenes has been found to give
the parent benzo[c]cinnoline as well as the 4-substituted benzo[c]-cinnoline,
showing that carboxy-, iodo-, and chloro-substituents can be ejected as well as
methyl substituents. The irradiation of azobenzene-3-carboxylic acid has given
1-hydroxybenzo[c]cinnoline-10-carboxylic acid lactone in addition to
benzo[c]-cinnoline-3-carboxylic acid.
Heats of mixing. V. Systems of n-alcohols with n-hexane
Authors: Brown I , Fock W , Smith F
Published: September 2010

Heats of mixing have been measured at 25�,
35�, and 45� for mixtures of ethanol, propan-1-ol, butan-1-ol, hexan-1-ol, and
octan-1-ol with n-hexane and for methanol with n-hexane at 45�.

These heats of mixing were found to
increase with an increase in temperature and to decrease with an increase in
the size of the alcohol molecule. They showed anomalies for the systems
containing methanol and ethanol. An explanation of these anomalies has been
given.

The contribution of the hydroxyl groups to
the enthalpy of any mixture of a n-alcohol with a n-alkane is defined as the
enthalpy change on replacing the alcohol by its homomorphic alkane. The
experimental results given here are consistent with the postulate that the
contribution of the hydroxyl groups (per mole of alcohol) to the enthalpy
depends only on the ratio of the number of hydroxyl groups to that of
hydrocarbon units in the mixture. This postulate, if generally true, can be
used for the prediction of the heats of mixing of any n-alcohol with a n-alkane
and of the enthalpy difference between any n-alcohol and its liquid homomorphic
alkane.

Other data support the conclusion that the
postulate holds for all concentrations of alcohol, but show that the analogous
postulate applied to free energies holds only for infinitely dilute solutions
of alcohols. The interaction of the hydroxyl groups with the hydrocarbon units
contribute -7.8 and -4.5 kJ/mole of alcohol to the enthalpies and free energies
respectively of these infinitely dilute solutions.

The required values of the heats of mixing
of the lower alkanes with n-hexane were estimated from the enthalpies of the
alkanes using the principle of congruence; these were found to be appreciable
and negative. They are in sign agreement with values extrapolated, from
measured data at a higher temperature, using a principle of corresponding
states for chain molecules.
Synthetic studies in the 1,2-Dithiole series. II. Routes to 4-Methylamino-1,2-dithiole-3-thione
Authors: Brown RFC , Rae ID , Sternhell S
Published: September 2010

4-Amino-1,2-dithiol-3-one has been
converted via methylation of its N-tosyl derivative into the
4-methylamino-3-thione (Vb). Methylation of 4-benzamido-1,2- dithiole-3-thione
with methyl iodide and a strong base gives 4-bis(methylthio)-methylene-2-phenyl-2-oxazoline-5-thione
(VII). The N.M.R. and ultraviolet spectra of the
oxazoline thione (VII) and of the corresponding oxazolinone (VIII) and
thiazolinone (IX) are discussed in terms of their probable non-planarity. Some
examples of long-range spin-spin coupling between protons of non-equivalent
methyl groups in isopropylidene structures are reported.
Synthesis of [Carboxyl-14C]3,4-dehydro-DL-proline
Authors: Hudson CB , Robertson AV
Published: September 2010

[carboxyl-14C]3,4-Dehydro-DL-proline,
of value in biological studies, has been synthesized.
Wilzbach tritiation studies. II. stereospecificity in the tritiation of alcohols
Authors: Crawford BR , Garnett JL
Published: September 2010

The mechanism of tritium labelling by the
Wilzbach gas exposure method has been examined in terms of stereochemical
effects on solid and liquid alcohols. Predominant retention of configuration is
observed with (+)- and (-)-oct-2-yl hydrogen phthalate whilst octan-2-ol
racemizes to the extent of 80%. Theories have been developed to explain the
effect of phase on the extent of inversion and on the relatively fast rate of
tritiation of the hydrogen attached to the asymmetric carbon of octan-2-ol,
Aryl hydrogens of the esters tritiate ten times faster than alkyl hydrogens.
Coordination compounds of substituted 1,10-phenanthrolines and related dipyridyls. X. Complexes of iron, cobalt, and nickel, and 4,6,4',6'-Tetramethyl-2,2'-bipyridine
Authors: Hall JR , Litzow MR , Plowman RA
Published: September 2010

The following complexes of
4,6,4',6'-tetramethyl-2,2'-bipyridine (tmb) have been
prepared: MCl2 tmb,
where M = Fe, Co, and Ni; M(NO3)2 tmb,H2O,
where M = Fe and Co; [CoNO3 tmb2]ClO4;
and Ni tmb2 (NO3)2,H2O.
The structures of these compounds have been determined, as far as possible, by
means of magnetic susceptibility and conductivity measurements, and by studies
of their infrared and visible absorption spectra.
Substituent effects in naphthalene. III. Saponification of 6- and 7-substituted Methyl 2-naphthoates and application of the Hammett equation
Authors: Wells PR , Adcock W
Published: September 2010

The rates of alkaline hydrolysis in 70%
v/v aqueous dioxan at 25� have been determined for the 6-and 7-NO2,
6- and 7-CN, 6- and 7-F, 6- and 7-Cl, 6- and 7-NMe2,
6-Me and 6-OMe substituted methyl 2-naphthoates, methyl 2- naphthoate,
m-NO2, p-NO2, p-Me substituted methyl benzoates, and
methyl benzoate.

An examination of the application of the
Hammett equation reveals that this linear free energy relationship applies with
high precision but that it yields different p values for different substituent-reaction
centre dispositions. This may be a general feature for all aromatic systems
although in many cases the differences are not larger than the experimental
uncertainties.
An ion-exchange process with thermal regeneration. II. Properties of weakly basic resins
Authors: Weiss DE , Bolto BA , McNeill R , MacPherson AS , Siudak R , Swinton EA , Willis D
Published: September 2010

Weakly basic ion-exchange resins have been
synthesized by treating cross-linked chloromethylated
polystyrene beads with primary and secondary amines and with polyamines.
Titration curve data show that such resins may be either homo-functional and
possess flat titration curves, or heterofunctional
and possess sloping titration curves, depending on whether the basic sites
within the resin have the same or different basicities. A comparison of the
titration curves determined at c. 20� or 80� reveals that all amine resins
become weaker bases when heated, but the maximum effect is shown by the resins
with homo-functional structures; e.g. the plateau-shaped curves at c. 20� and
80� of a polyvinylbenzyldiethylamine resin differ by
about 1.2 of a pH unit at half neutralization. The effect is fully reversible.

The influence of amino group substituents,
cross-linking, salt concentration, sulphate ions, and temperature on the
titration curves of weakly basic amine resins has been studied. Titration
curves of a variety of commercial amine resins have been determined at c. 20�
and 80� and show that at least two resins with homo-functional structures are
commercially available.
Halides and oxide halides of molybdenum and tungsten. II. Magnetic evidence for trinuclear clusters in tungsten(V) halides
Authors: Colton R , Tomkins IB
Published: September 2010

The magnetic properties of tungsten
pentachloride, WCl5, and tungsten pentabromide, WBr5,
have been re-examined as a function of temperature. The anomalous magnetic
moment of each compound is rationalized on the basis of trinuclear clusters of
tungsten atoms in the compounds. Evidence is presented for the presence of one
ionic halide atom per molecular weight, the compounds thus being formulated as
[W3X12]3+X3-.
The ternary system Na2O-ZnO-SiO2
Authors: Holland AE , Segnit ER
Published: September 2010

The equilibrium relationships in a large
part of the system Na2O-ZnO-SiO2
have been determined. Of the eleven invariant points located, four are
eutectics, the minimum melting point in the system being 680� at a composition
of 21.5% Na2O, 12.0% ZnO,
66.5% SiO2 by weight. Four ternary
compounds with molar ratios of Na2O : ZnO : SiO2 of 1 : 1 : 1, 1 : 1 : 2, 1 : 2 : 2, 2
: 2 : 3, all with incongruent melting points, are described.
Some metabolites of Nectria radicicola Gerlach & Nilsson (syn. Cylindrocarpon radicicola Wr.): The structure of radicicol (monorden)
Authors: Mirrington RN , Ritchie E , Shoppee CW , Sternhell S , Taylor WC
Published: September 2010

Culture filtrates of Nectria radicicola Gerlach & Nilsson yielded
two products: a peptide fraction, "radicicolin",
and a phenolic substance, radicicol (monorden), C18H17ClO6.
Chemical and spectroscopic studies showed that radicicol
was a macrolide with structure (Ia).
Brefeldin A was isolated from filtrates of other
strains of the organism.
The synthesis of [18]Annulene 1,4:7,10-Dioxide-13,16-sulphide
Authors: Badger GM , Lewis GE , Singh UP
Published: September 2010

[18]Annulene 1,4:7,10-dioxide-13,16-sulphide
has been synthesized. The physical properties indicate that this compound is an
aromatic system in which there is significant delocalization of the peripheral
electrons. However, the compound undergoes addition rather than substitution
reactions and therefore exhibits only limited classical aromaticity.
The aquation of cis-Chlorodi(methyl sulphoxide)bisethylenediaminecobalt(III), cis-Chlorodimethylformamidebisethylenediaminecobalt(III), and cis-Chlorodimethylacetamidebisethylenediaminecobalt(III) ions
Authors: Lantzke IR , Watts DW
Published: September 2010

The aquation of each of
three octahedral chloro(solvent)bisethylene- diaminecobalt(III) ions, involving the solvent ligands
dimethyl sulphoxide (DMSO), dimethylformamide (DMF), and dimethylacetamide
(DMA), has been examined in solutions of different pH. In solutions of pH less
than 6, the predominant reaction is replacement of the solvent molecule by
water in an SN1 process, involving a trigonal bipyramidal transition
state and resulting in a mixture of the trans- and cis- chloroaquo complexes.
The slow loss of chloride ion is an accompanying side reaction. In solutions of
pH greater than 6 base hydrolysis becomes important, and in alkaline solutions
the rate of solvent loss is too fast to measure by conventional techniques. The
rate of liberation of chloride ion is also greatly increased with increasing
pH. Values of the activation energy, and entropy of activation, are reported
for the solvent replacement reaction at a pH of 1.90.
Pyrimidine reactions. XIV. The butylaminolysis of substituted methoxy-and methylthio-pyrimidines
Authors: Brown DJ , Forster RV
Published: September 2010

Aminolyses of 2- and
4-methoxy (or methylthio) pyrimidines bearing C- methyl, CC?-dimethyl, 5-bromo,
or 5-nitro substituents have proved of value, in the absence of added solvent,
for preparing the corresponding n- and t-butyl-aminopyrimidines.
When these displacements are followed spectrometrically,
the apparent first-order rate constants indicate mild deactivation by
additional methyl substituents, moderate activation by a bromo substituent, and
profound activation by a nitro substituent. Ionization constants and
ultraviolet spectra of relevant pyrimidines are recorded.
Bivalent nickel complexes of 2,4,6-Tri(2'-pyridyl)-1,3,5-triazine
Authors: Vagg RS , Warrener RN , Watton EC
Published: September 2010

The preparation of a series
of new coordination compounds of bivalent nickel with the terdentate ligand
2,4,8-tri(2?-pyridyl)-1,3,5-triazine and various anions (Cl-, Br-, I-, CNS-, or
ClO-4) is reported. Compounds
having metal-ligand ratios of 1 : 2, 1 : 1, and 2 : 1 were isolated, and in the
last case the possibility of simultaneous terdentate and bidentate behaviour is
discussed.

In all cases the compounds formed were
high-spin with magnetic moments ranging between 3.1 and 3.3 B.M. In general,
octahedral coordination is proposed for these compounds. The additional
possibility of five-coordination in the case of the 1 : 1 complexes is
discussed, but such coordination could not be confirmed by the investigations
employed. The isolation of a series of coordination
compounds containing a protonated form of the ligand is also reported.
The far infrared spectra of tetrahalogenozincate(II) complexes with mixed halide ligands
Authors: Deacon GB , Green JHS , Taylor FB
Published: September 2010

The far infrared spectra
(400-40 cm-1) of the complexes (MePh3As)2
ZnBrnCl4-n (n = 0, 1, 2, 3, or 4), (Et4N)2ZnBrnCl4-n
(n = 1, 2, or 3), (Me4N)2ZnBr2Cl2, (pyH)2ZnBr2Cl2,
(Et4N)2ZnBrnI4-n
(n = 0, 1, 2, 3, or 4), and (Et4N)2ZnClnI4-n (n =
1 or 2) have been recorded. Vibrational assignments have been made for the
zinc-halogen frequencies and the spectra are discussed in terms of known or
probable structures.
Synthesis of diacylmethanes by chemical reduction of enol betaines
Authors: Cornforth JW , Gigg R , Tute MS
Published: September 2010

Chemical reduction of
1-(diacylmethyl)pyridinium enol betaines (II) affords 1,3-diones (III) in good
yield.
Some simple theorems concerning crystal lattice sums of electric potential, electric field, and electric field gradient in crystals
Authors: Coogan CK
Published: September 2010

The conditions under which
direct lattice sums of electric potential, field, and field gradient converge
are discussed. The analogous conditions under which differences in these
lattice sums, for two points in the crystal, converge are also outlined. These
conditions are applied to direct lattice sum calculations in crystals in which
the ideal lattice is distorted close to a defect of some kind. The conver- gence conditions are then
applied to the case of determining the direct lattice sums in crystals in which
higher symmetry properties can be invoked, which leads to a knowledge by
inspection of the lattice sum at one point in the unit cell.
Reactions of lead tetraacetate. II. Formation of carbamic acid esters from primary carboxamides
Authors: Acott B , Beckwith ALJ , Hassanali A
Published: September 2010

Treatment of primary
carboxamides with lead tetraacetate in benzene-alcohol mixtures or neat alcohol
affords a convenient, flexible, and efficient method for the preparation of
N-substituted carbamic acid esters. The reaction is applicable to amides and alcohols
of a wide range of structural types including compounds containing oleflnic,
ester, aromatic, and other reactive functions. The reaction mechanism appears to involve
intermediate formation of isocyanates.
Molecular polarizability: Symmetrically substituted mesitylenes
Authors: Calderbank KE , Le Fevre RJW , Pierens RK , Radford DV
Published: September 2010

Molar Kerr constants ( x 10-12)
are reported for 2,4,6-trichloromesitylene, 2,4,6.tribromomesitylene, and 2,4,6-triiodomesitylene
as solutes in carbon tetrachloride and for 2,4,6-trinitromesitylene
as a solute in benzene. Microwave absorption measurements indicate the
non-polarity of all four solutes and the small apparent dipole moments observed
for some of these solutes can be ascribed to atomic polarization. The
substituents are not therefore staggered as has previously been suggested for
2,4,6-trinitromesitylene. Estimates of the
polarizability semi-axes for these molecules are given.
Infrared spectra of complexes of isoquinoline with cobalt(II), nickel(II), and zinc(II) sulphates
Authors: Ahuja IS
Published: September 2010

The complexes formed by isoquinoline with cobalt(11), nicke1(11),
and zinc(11) sulphates have been prepared. These complexes have been
examined spectroscopically in the solid state and the possible structures
discussed. It is suggested that these complexes are polymeric structures.
Allocations for the possible metal-oxygen modes have also been made.
Copper(II) complexes of o-hydroxyarylcarbonyl compounds
Authors: Graddon DP , Mockler GM
Published: September 2010

A series of copper(11)
complexes has been prepared of the type CuL2Bn,
where L is an
o-hydroxy-aryl-, or naphthyl-, aldehyde, ketone, or
ester, B is water or 4-methylpyridine, and n = 0, 1,
or 2. All these complexes have a strong infrared band in the region 1600-1660 cm-l,
showing that the oxygen atoms in the chelate ring are non-equivalent ; their
magnetic moments fall in the range usual for copper(11) compounds. Equilibrium constants
determined for the addition of one molecule of 4-methylpyridine
to the anhydrous compounds in chloroform solutions fall in the range 0.5 < k
< 40 and are comparable to the constant for the addition of 4-methylpyridine to bis(acetylacetonato)copper(11)
(b 2.7). Increased stability of the adducts can be associated with the inductive
effects of ligand substituents. Ligand field spectra in the
solid state and in solution closely resemble those of corresponding bis(acetylaoetonato)copper(11) complexes and provide evidence
for square-planar structures of the anhydrous complexes and square-pyramidal
structures of the 1 : 1 adducts with 4-methylpyridine
or water. No evidence is available for the structures of 1 : 2 adduots which may be formed in solutions in 4-methylpyridine; these solutions are unstable, but the
nature of the slow reactions which occur in these solutions is not known.
Catalytic deuterium exchange reactions with organics. XL. Pyridine, the quinolines, azines, and aniline on unsupported Group VIII transition metals
Authors: Calf GE , Garnett JL , Pickles VA
Published: September 2010

Pyridine, the quinolines,
pyridazine, pyrimidine, pyrazine, s-triazine, and
aniline have been exchanged with heavy water on the following Group VIII
transition metals: Fe, Co, Ni, 0s. Ru, Rh, Pd, Ir,
and Pt. Three types of catalyst activation have been used, including
self-activation, hydrogen and sodium borohydride reduction of the inorganlo salts. Platinum is the most useful catalyst for
general exchange whereas cobalt possesses valuable specificity for selective a
exchange in a large number of the heterocyclic compounds. A kinetic study of
the deuteration of pyridine on platinum has been
performed. The exchange results have been rationalized in terms of
charge-transfer adsorbed intermediates. E.s.r. has been used to support this
conclusion for the interaction between pyridine and potassium chloropalladite. π-Complex mechanisms have been
proposed to explain the observed deuteration
behaviour.
Studies using radioisotopes. I. The incorporation of anthranilic acid into acronidine
Authors: Prager RH , Skurray GR
Published: September 2010

Synthesis of [6-T]anthranilic acid and
[3,5-T]anthranilic acid are reported.

After administration to Acronychia
baueri only the second gives rise to radioactive acronidine, thereby conforming the structure previously
based on N.M.R. evidence.

The dimethylchromene ring probably
arises from mevalonic acid.