bluuebunny/crossref_metadata_2025 huggingface dataset:
Soluble wool Proteins. II. Light scattering and viscosity in formic acid and dichloroacetic acid solutions
Authors: Harrap BS , Woods EF
Published: September 2010

The light scattering and viscosity
behaviour of S-carboxymethylkerateine 2 (SCMK2) and α-keratose have been
investigated in formic and dichloroacetic acids. The viscosity at 25 �C of
formic acid solutions of SCMK2 and α-keratose showed a large decrease with
time over a period of 4 weeks. On the other hand, no parallel changes in light
scattering were observed and no conclusive evidence for peptide bond hydrolysis
could be found. Time effects in dichloroacetic acid were negligible. SCMK2, but
not α-keratose, behaved as a polyelectrolyte in formic acid, the reduced
viscosity increasing at low concentrations an effect which was eliminated by
the addition of salt. The effects of salt concentration on the plots of K90c/R90 against c for solutions of
SCMK2 in formic acid were typical of those for highly charged proteins in
aqueous solution. Solutions of α-keratose in formic acid and of both
proteins in dichloroacetic acid did not show these effects at low ionic
strengths.

The solvents employed did not disaggregate
the wool proteins to the same extent as 8M urea, 10M acetic acid, or sodium
dodecyl sulphate. Variability of the physical properties of different
preparations in the two non-aqueous acids is attributed to varying degrees of
aggregation.
Acetylenic acids from fats of Santalaceae and Olacaceae: Seed and root oils of Exocarpus cupressiformis Labill
Authors: Hatt HH , Triffett ACK , Wailes PC
Published: September 2010

Octadec-trans-11-en-9-ynoic acid
(ximenynic acid) forms over 60 per cent, of the acids present as glycerides in
the seed fat of Exocarpus cupressiformis Labill. The roots of this tree contain
an oil which is mainly a fat with octadec-trans-13-en-9,11-diynoic acid forming
89 per cent. of the fatty acids. These two acids are also major components
respectively of the seed and root fats of the related species E. stricta R.Br.
The root fat of Ximenia americana Linn. is rich in acetylenic acids.
1-Methylenepyrrolizidine, the major, alkaloid of Crotalaria anagyroides H.B.K.
Authors: Culvenor CCJ , Smith LW
Published: September 2010

The principal alkaloid of Crotalaria anagyroides H.B. & K. has been identified as
1-methylenepyrrolizidine.
The 'Variable Electronegativity ' Method. II. Pyrrole
Authors: Brown RD , Heffernan ML
Published: September 2010

The properties of the π-electron
system in pyrrole have been studied by a " variable electronegativity
" self-consistent field molecular-orbital method and the results compared
with those obtained by the conventional SCF procedure. The π-electron distribution
calculated by the conventional SCF procedure cannot be satisfactorily
reconciled with the observed dipole moment, but the distribution calculated by
the VESCF method leads to a predicted dipole moment in good agreement with
observation. Polarization of σ-bonds makes a negligible contribution to
the dipole moment.Derivation
of the coulomb parameters for the simple H�ckel molecular-orbital method from
the VESCF results is considered and the factors responsible for auxiliary
inductive effects are discussed. The π-electron ionization potential and
the positions of the lowest excited states of pyrrole have been calculated by
the VE method.
Peroxides in Carbon Black
Authors: Garten VA , Eppinger K
Published: September 2010

The varying ability of carbons to oxidize FeII, to produce H2O2 when
exposed to air in an acid medium, and to form a latent photographic image, has
been studied on a graded set of carbon blacks. Mechanisms are discussed for
these three types of activity and it is shown how they agree with the
phenol-lactone-chromene concept of carbon black chemistry.
The Vibrational Spectrum of Methyl isothiocyanate
Authors: Costoulas AJ , Werner RL
Published: September 2010

Methyl isothiocyanate has been studied in
the infra-red region from 10,000 to 250 cm-1 as vapour, solid, and
melt, while the Raman spectrum has been recorded in the molten condition. The
molecule is close to a symmetric top and the bands of the vapour exhibit
contours generally similar to that type of molecule.

A satisfactory assignment of all
fundamentals has been made. Of interest is the pseudo-symmetric NCS stretching
mode which has been assigned to the parallel band at 676 cm-1 in the
vapour. In the Raman spectrum, the corresponding mode is observed as a strong
polarized line at 656 cm-1.
Studies of Casein. I. Some Observations on the Heterogeneity of Casein Fractions
Authors: McKenzie HA , Wake RG
Published: September 2010

The heterogeneity of casein is discussed
in the light of methods currently used for the fractionation of casein. In
particular, the possible heterogeneity of certain preparations of α-casein
is considered. This is important because it has been generally considered that α-casein
is the protective colloid which is altered when the enzyme, rennin, acts on
casein micelles. Recently, Waugh and von Hippel (1956) have suggested that
their new component x-casein, and not α-casein, is the protective colloid.
These two viewpoints could be reconciled if α-casein samples previously
examined contained x-casein as well. In the present work, a study is made of
filter paper electrophoresis, micelle-forming properties, and sedimentation of
casein fractions. It is shown that x-casein is concentrated with α-casein
in fraction A during the alcohol fractionation method of Hipp et al. (1952). On
the other hand fraction B contains α-casein essentially free of x-casein.
The a-casein obtained in the urea fractionation method of Hipp et al. also
contains x-casein. Thus only alcohol fraction B is a suitable source of pure α-casein.

During the paper electrophoretic
examination of casein fractions a number of minor protein components are
observed. A component moving more slowly than γ-casein is present in acid
casein, second-cycle casein-fraction P, and an alcohol fraction. This component
was first observed in the latter fraction by Hipp et al. (1952) when preparing γ-casein.
Electropherograms of second-cycle casein-fraction S indicate the presence of
x-, β-, and γ-casein, and two minor components moving between x- and β The way in which these components arise is briefly
discussed.
Studies of Casein. II. Moving Boundary Electrophoresis of Casein Fractions with Particular Reference to α-Casein
Authors: McKenzie HA , Wake RG
Published: September 2010

A moving boundary electrophoretic study is
made of acid casein, total milk protein, first-cycle casein, second-cycle
casein-fractions P and S, α-casein (free of x-casein), and β-casein.

Two acid-casein preparations are examined
over the pH range 6.3 to 8.8 (I 0.02
and 0.1). The two preparations behave slightly differently from each other, but
both show differences from that examined by Warner (1944). In veronal buffer,
pH 8, the splitting of the " α peak " is observed only after
prolonged electrophoresis. However, it occurs even at l per cent. concentration
and in phosphate buffer of pH 6 to 7. An abnormal distribution of areas,
similar to that attributed by Krecji, Jennings, and Smith (1941, 1942) and
Warner (1944) to α-β interaction, is observed.

The patterns of α-casein (free of
x-casein) over the pH range 3-8 show no marked splitting. Preparations of
previous workers showing this heterogeneity probably contain x-casein. The
splitting of the a peak in acid casein is due, at least in part, to the α-
and x-components and their state of aggregation. The patterns of the other
fractions examined do not provide further unequivocal evidence of this. The
detection of true heterogeneity is further complicated by other interaction
effects.

The composition of second-cycle
casein-fraction S is also discussed.
The Variable Electronegativity Method. VI. Azulene
Authors: Brown RD , Heffernan ML
Published: September 2010

Results of a variable-electronegativity
SCF treatment of azulene, using the method used in previous VESCF studies, are
reported. A slightly more elaborate method in which non-neighbour core
resonance integrals are included has also been used. The π-electron
distributions obtained by these methods correspond to dipole moments of 1.85
and 1.33 D respectively, the experimental value being about 1 D.

The calculated bond orders accord with the
rather incomplete experimental data on bond lengths. The π-electron
densities account for the relative chemical reactivities of the azulene
positions. The ionization potentials and proton magnetic resonance spectrum of
azulene are also briefly considered.

The concept of electronegativities of
conjugated atoms in non-alternant systems is discussed in some detail on the
basis of the VESCF results. It is shown that the assumption that the
electronegativity of a carbon atom depends only on its π-electron density
is an oversimplification for non-alternant systems.
The Synthesis of 5,7-Dichlorocoumaran-3-one and Related Problems
Authors: Armarego WLF
Published: September 2010

5,7-Dichlorocoumaran-3-one has been
prepared from methyl 2-hydroxy-3,5-dichlorobenzoate by a three stage synthesis.

It could not be prepared by (i)
intramolecular cyclization of 2,4-dichlorophenoxy- acetic acid or
2,4-dichlorophenoxyacetyl chloride or (ii) by the reaction of ω-bromo-2-hydroxy-3,5-dichloroacetophenone
with bases.

The reaction of 2,4-dichlorophenoxyacetic
acid with phosphorus pentoxide in benzene gave 2,4-dichlorophenol,
2',4'-dichlorophenyl 2,4-dichlorophenoxyacetate, and diphenylmethane. By the
use of 14C-labelled acids the methylene carbon atom of the
diphenylmethane was shown to be derived from the methylene carbon atom of
2,4-dichlorophenoxyacetic acid. A possible mechanism is proposed for this
reaction.
The Thermodynamic Properties of the Lower Chlorides of Titanium
Authors: Head RB
Published: September 2010

The free-energy values for titanium
trichloride were determined to within 0.5 kcal per mole, using a " null
" method with mercury and silver as reductants. Attempts to obtain
free-energy values by means of the hydrogen reduction of titanium tetrachloride
vapour failed to give reliable results owing to reactions between the
trichloride and the glass ampoule. Thermodynamic data for titanium dichloride
were obtained by vacuum disproportionation of the trichloride.
Chemical Studies of the Myrtaceae. II. The Constituents of Syncarpia laurifolia Tenn
Authors: Hodgson D , Ritchie E , Taylor WC
Published: September 2010

The bark of Syncarpia laurifolia Tenn.
yields p-sitosterol, betulinic acid, ursolic acid, and " syncarpic acid
" which is identified as 1,1,5,5-tetramethylcyclohexan-2,4,6-trione (I).
Some reactions of this substance are described.
A procedure for the absolute identification of anthocyanins: the pigments of blackcurrant fruit
Authors: Chandler BV , Harper KA
Published: September 2010

A procedure is outlined for the isolation
of pure anthocyanins and their identification without recourse to comparison
with reference glycosides. The isolation involves cellulose and polyamide
column chromatography and the identification depends on simple but selective
oxidative and hydrolytic reactions, adapted to a microscale using paper
chromatography.

By this method the anthocyanin pigments
present in extracts of black currant fruit have been unequivocally identified
as cyanidin and delphinidin, their 3-glucosides and 3-rutinosides.
Studies on Sulphamic Acid and Related Compounds. I. Kinetics and Mechanism of Hydrolysis of Sulphamic Acid
Authors: Fleischfresser BE , Lauder I
Published: September 2010

The kinetics of hydrolysis of sulphamic
acid, NH2SO2OH + H2O → NH4HSO4,
have been studied in water, in aqueous perchloric acid solution, and in
acetone-water mixtures. The rate data obtained in water did not give good
first-order plots - a fact attributed to a variation in the degree of
dissociation of sulphamic acid with concentration, and to the production of
hydrogen ions by dissociation of bisulphate ions formed in the reaction - but
in the presence of perchloric acid good first-order plots were obtained. The
rate data for hydrolysis in aqueous acetone (in the absence of HClO4) gave good first-order plots. For
[water]<l mole l-1 the rate constant at 35 �C is independent of
the water concentration and is about 1000 times that in water at the same
temperature. It seems probable that the rate controlling step in aqueous
acetone and also in water involves a unimolecular decomposition of the
zwitterion form of sulphamic acid, namely +NH3 SO3-.
Studies on Sulphamic Acid and Related Compounds. II. Kinetics and Mechanism of Hydrolysis of Trimethylamine- and of Triethylamine Sulphur Trioxide Addition Compounds
Authors: Fleischfresser BE , Lauder I
Published: September 2010

The kinetics of hydrolysis of trimethylamine- and of triethylaminesulphur
trioxide addition compounds have been studied in water and in aqueous acetone.
Reaction occurs according to the equation,������������� f - + R,N.SO,+H,O-tR,XH+HSO~.The solvolysis reactions
are first-order and are not catalyzed by acids. The halide ions, Cl', Br', and 1', show only a normal salt effect on the
rate of hydrolysis of + - (CH,),N.SO, but in the presence of fluoride ions, the
rate constant for the production + - of acid from (C,H,),N.SO, in water at 95
OC is about one-seventh of that in the absence of fluoride under the same
conditions. It is suggested that the fluorosulphonate
ion is formed rapidly, and that this ion then undergoes slow hydrolysis :�In
the presence of alkali, using water as the solvent, second-order kinetics are
observed, the equation for the reaction being,�������������� + - R,N.SO,+~OH-+R,X+SO~= +H,O. Assuming the reaction with
water is bimolecular, the ratio of the (bimolecular) rate constants at 35 OC, ko~-/k~,o is approximately lo8 for each complex. In aqueous
acetone, at low water concentrations, the hydrolysis reactions of the trialkylaminesulphur trioxide complexes show second-order
kinetics. At 35 OC for the hydrolysis of + - (CH,),N.SO, the ratio of the
second-order rate constant in aqueous acetone to the + - (calculated)
second-order rate constant in water is approximately 550 ; for (C,H,),N.SO, the
same ratio is 6900.

It is considered that hydrolysis occurs in
water and in aqueous acetone via a bi- molecular attack at sulphur.
Alkaloids of Ochrosia poweri Bailey. I. The Leaf-bases
Authors: Doy FA , Moore BP
Published: September 2010

Leaves of Ochrosia poweri Bail. furnished
reserpine, isoreserpiline, and four new indole alkaloids, elliptamine (C24H30O5N2),
powerine (C21H26O4N2), poweridine
(C24H30O5N2), and poweramine (C23H30O4N2),
together with traces of others as yet uncharacterized. Powerine is an
alkali-labile alkaloid which appears to be a derivative of 5-methoxyindole.
Poweridine is probably a methoxy-O-acetylyohimbine.
A Force Field for Formaldehyde
Authors: Freeman DE , Hunt GR
Published: September 2010

A seven parameter valence force is used to
account for the 15 planar frequencies of H2CO, HDCO, D2CO
with an average deviation of less than 0.8%. Bond moments and dipole
derivatives have been recalculated.
Transformation Products of Some 2,6-Diacetoxycyclohexanones
Authors: Cavill GWK , Solomon DH
Published: September 2010

The specific transformation of a
2,6-diacetoxycyclohexanone into a cyclohexane-1,2-dione in the presence of acid
or base, is described. Reduction of the 2,6-diacetoxy-ketone with sodium in
butanol gives a 1,2-diol whose structure corresponds to that of the l,2-dione.
The diols are useful intermediates in the synthesis of
alkylhexane-1,6-dialdehydes.
The Chemical Constituents of Australian Flindersia Species. XVI. The Constituents of the Wood of Flindersia laevicarpa C. T. White & Francis
Authors: Breen GJW , Ritchie E , Taylor WC
Published: September 2010

From the wood of Flindersia laevicarpa C.T. White & Francis, there has been isolated skimmianine, hesperidin, β-sitosterol, and two alcohols. One of these was identified as 1,5-diphenylpentan-3-ol, and the other was shown by degradation and synthesis to be (-)-erythro-1,5-diphenylpentan-1,3-diol.
The Chemistry of Eucalypt Kinos. IV. Eucalyptus hemiphloia Kino
Authors: Hillis WE , Carle A
Published: September 2010

The kino exuded by Eucalyptus hemiphloia
contains (+)-hemiphloin, isohemiphloin, (-)-eudesmin, aromadendrin, kaempferol,
engelitin, ellagic acid, and small amounts of gallic acid. Hemiphloin and
isohemiphloin appear to be 8-hexahydroxyhexyl derivatives of naringenin.
Association in Solutions of Tri-isopropanolamine Borate in Benzene
Authors: Pugh JM , Stokes RH
Published: September 2010

Boiling point elevation and freezing point
depression measurements are used to study the association resulting from dipole
interactions between molecules of tri-isopropanolamine borate in benzene.
The Major Alkaloid of Pultenaea altissima F. Muell. ex Benth., N(b)N(b)-Dimethyl-L-tryptophan Methyl Ester
Authors: Fitzgerald JS
Published: September 2010

The major alkaloid of Pultenaea altissima
F. Muell. ex Benth. has been identified as the methyl ester of N(b)N(b)-dimethyl-L-tryptophan.
Molecular Vibrations in the Exciton Theory for Molecular Aggregates. V. Electronic Spectra of Weakly-coupled Systems
Authors: McRae EG
Published: September 2010

The theory of the gross vibrational
structure in the electronic spectra of molecular aggregates is developed for
the case of weak intermolecular interaction. The electronically excited states
are represented by a set of m-m functions corrected to first order as described
in Part IV of this series.

An explicit treatment is given for
aggregates with two molecules per unit cell. Formulae are obtained for the
relative vibronic intensities, splittings, and polarization ratios in
absorption spectra, and for relative quantum yields and polarization ratios in
fluorescence spectra.

The theoretical results are compared with
those of the E-V coupling theory developed in Parts II and III. On the basis of
this comparison, a general equation is put forward to relate the theoretical
crystal splitting (i.e. the splitting for a rigid model) to observed
polarization ratios in spectra.

The theoretical results are compared with
the observed vibrational structure in the 3800 Ǻ band system of anthracene
crystal. The crystal splitting calculated from the observed polarization ratios
is 380 cm-1. The theory accounts, within the rather large
experimental error, for the observed variations of polarization ratio in both
the absorption and the fluorescence spectra of anthracene crystal.
The Chemical Constituents of Australian Flindersia Species. XVIII. The Structure of Ifflaionic Acid
Authors: Bosson JA , Galbraith MN , Ritchie E , Taylor WC
Published: September 2010

The structure of ifflaionic acid has been
shown to be 3-oxours-12-en-30-oic acid by degradation and by conversion to
derivatives of a-amyrin.

The acid has been isolated also from the
bark and the leaves of Flindersia ifflaiana F. Muell.; in addition, seselin and
sitosterol were obtained from the bark.
Equivalence Points and Inflexion Points in Acid-Base Titration Curves
Authors: Stokes RH
Published: September 2010

General equations are derived for the
relation between pH and stoichiometric degree of neutralization in the
titration of monoprotic and diprotic weak acids (or bases) with strong acid or
strong base. From these equations the number and position of inflexion points
in the curves is derived, and their relation to the equivalence points is
shown. Methods for determining ionization constants from inflexion points are
discussed.
The Chemical Constituents of the Leaves of Digitalis lanata
Authors: Lack R , Newman BC , Shoppee CW
Published: September 2010

From the cumulated first chromatographic
fractions of the methylene dichloride extract of the leaves of Digitalis
lanata, there has been isolated tigogenin, digitoxigenin, 3-epidigitoxigenin,
and digifolein.
A thermodynamic discussion of the use of a vertical-plate balance for the measurement of surface tension
Authors: Jordan DO , Lane JE
Published: September 2010

A rigorous thermodynamic method is used to
derive the equation for calculating the surface tension from the data obtained
with a vertical-plate balance using a smooth, rigid plate. The effect of
tilting the plate is discussed and equations are derived for plates with
regular vertical and horizontal grooves. The validity of measurements made with
a roughened plate is also discussed.
Mixed alkyl-perfluoroalkyl derivatives of Group VB elements
Authors: Pullman BJ , West BO
Published: September 2010

Trifluoroiodomethane reacts with
triethyl-phosphine, -arsine, and -stibine forming derivatives of the type (C2H5)2MCF3
together with (C2H5)4MI, while
pentafluoroiodoethane reacts with trimethyl-phosphine, -arsine, and -stibine
giving derivatives of the form (CH3)2MC2F5
together with (CH3)4MI. The infrared spectra of the
compounds are presented and the mechanism of the reaction discussed.
Reduction of aromatic hydrocarbons by lithium in ethylenediamine
Authors: Brooks JD , Durie RA , Silberman H
Published: September 2010

Various aromatic hydrocarbons, which can
be assumed to represent some of the aromatic structures present in coals and
chars, have been reduced under forcing conditions using lithium in
ethylenediamine.

It was found that:

(i) Aromatic hydrocarbons highly
substituted by alkyl or alicyclic groups are resistant to reduction.

(ii) The less substituted benzene
hydrocarbons and diphenyl-type structures yield, in addition to a proportion of
fully reduced material, compounds containing a single olefinic bond which tends
to resist further reduction. ��� (iii) Highly condensed hydrocarbons (such
as pyrene or coronene) yield some perhydro derivatives, but a part of the
product consists of less completely reduced compounds with aromatic and olefinic
features; these compounds are more resistant to further reduction than the
parent hydrocarbons. ��� (iv) Condensed polynuclear hydrocarbons
yield also some products containing hydroxyl (phenolic) and carbonyl groups.
Investigations of suint. II. The positive identification of some constituent organic acids
Authors: Kowala C , Kranz ZH , Murray KE , Nicholson AJC
Published: September 2010

Chiefly by the use of gas chromatography
and mass spectrometry the following acids have been positively identified as
constituents of the suint from a crossbred Merino fleece: Acetic, propionic,
butyric, valeric, hexanoic, isobutyric, 2-methylbutyric, 3-methylbutyric,
2-methylvaleric, succinic, glutaric, α-hydroxyglutaric, α-ketoglutaric,
benzoic, and phenylacetic.
Complexes of 2,2'-bipyridyl and 1,10-phenanthroline with bivalent palladium and platinum having covalencies greater than four
Authors: Livingstone SE , Wheelahan B
Published: September 2010

Conductimetric titrations of the
perchlorates [Pd(chel)2](ClO4)2 (chel =
2,2'-bipyridyl or 1,10-phenanthroline) with X- ions (X = Cl, Br, I)
in the solvents nitrobenzene and nitromethane give an end-point after the
addition of one equivalent of halide ion, owing to the formation of the ions
[Pd(chel)2X]+. Another endpoint is obtained after the
addition of a second equivalent of halide ion. Spectral evidence suggests that
in nitrobenzene the compound [Pd(bipy)2I2]
(bipy = 2,2'- bipyridyl) is formed. In nitromethane
the second end-point is regarded as due to the reaction [Pd(chel)2X]+
+ X- → [Pd(chel)X2]+ chel. The
compound [Pt(bipy)2](ClO4)2
was prepared and titrated conductimetrically with halide ions in nitrobenzene
and nitromethane. Only one end-point was obtained, indicating that the ions
[Pt(bipy)2X]+, unlike the
corresponding palladium complexes, are stable in the presence of excess halide
ion. It is assumed that in all these monohalogeno-complex ions the metal atom
is sexicovalent, due to the coordination of one molecule of solvent. Evidence
is presented for the occurrence of six-coordinated platinum(II) in the
compounds [Pt(bipy)2I(H2O)]I.H2O,
[Pt(bipy)zI(H2O)](ClO4)2.H2O,
and [Pt(bipy)2I2].
Isoflavonoids. I. Some new constituents of Pterocarpus indicus heartwood
Authors: Cooke RG , Rae ID
Published: September 2010

A new examination of the heartwood of
Pterocarpus indicus has revealed the presence of formononetin,
isoliquiritigenin, (-)-p-hydroxyhydratropic acid, and a new 2-arylbenzofuran.
The previously reported angolensin and pterocarpin were also isolated but no
homopterocarpin was detected.
The lability of 6-Bromo-Δ4-3-oxosteroids: Observations on the conversion of 6α- and 6β-Bromocholest-4-en-3-one to 5α-Cholestane-3,6-dione
Authors: Collins DJ , Hobbs JJ
Published: September 2010

Cholesta-4,6-dien-3-one,
cholest-4-ene-3,6-dione, 5α-cholestane-3,6-dione, cholest-4-en-6β-ol-3-one,
cholest-4-en-2α-ol-3-one, cholest-4-en-4-ol-3-one, and
cholesta-2,5-dien-3-ol-4-one, are formed in greater or lesser amounts during
chromatography of 6α- and 6β-bromocholest-4-en-3-one over neutral or
alkaline alumina.

The conversion of 6α- and 6β-bromocholest-4-en-3-one
to 5α-cholestane-3,6-dione by the action of methanolic hydrochloric acid
has been examined. The use of concentrated hydrochloric acid in this reaction
afforded 3,3-dimethoxy-5α-cholestan-6-one in good yield. Under similar
conditions, the same ketal was also obtainable from 6β-methoxycholest-4-en-3-one,
cholest-4-en-6β-ol-3-one, and 5α-cholestane-3,6-dione.

The course of the reactions of the
epimeric 6-bromocholest-4-en-3-ones with acidic ethanol, isopropanol, and
t-butanol is discussed.
Carboxylic esters as ligands. I. Metal chelates of diethyl oxaloacetate
Authors: Hay RW
Published: September 2010

The β-keto-ester diethyl oxaloacetate
forms stable non-ionic chelates with transition metal ions. The preparation of
the diethyl oxaloacetates of a number of bivalent metals is described (M = Cu,
Ni, Cu, Zn, Mn, Mg).

Infrared measurements show that the ligand
is bidentate in these chelates. The ethoxycarbonyl absorption is considerably
lowered, which indicates a direct interaction between the ethoxycarbonyl group
and the metal ion and this absorption follows the generally accepted stability
order.

Hydrolytic and ester exchange reactions
undergone by the copper(II) chelate suggest that coordination occurs via the α-ethoxycarbonyl
rather than the β-ethoxycarbonyl group of the ligand.
The formation of aromatic hydrocarbons at high temperatures. XXI. The pyrolysis of n-butylbenzene over a range of temperatures from 300° to 900° at 50° intervals
Authors: Badger GM , Kimber RWL , Novotny J
Published: September 2010

n-Butylbenzene has been pyrolysed over a
range of temperatures from 300� to 900�, at 50� intervals, and the resulting
tars analysed. The optimum temperatures for the formation of 15 polycyclic
aromatic hydrocarbons have been determined; these range from 660� to 740�.
Studies on the tannins of babul, Acacia arabica, bark
Authors: Bhanu KU , Rajadurai S , Nayudamma Y
Published: September 2010

The isolation and characterization of quercetin,
gallic acid, (+)-catechin, (-)-epicatechin, (-)-dicatechin, and (+)-leucocyanidin
gallate from the acetone extract of babul, Acacia Arabica, is reported. The
presence of (+)-dicatechin and (+)-leucocyanidin gallate was noted for the
first time in nature. Their structure was established on the basis of a number
of oxidative and degradative experiments.
Kinetics of the base-catalysed aldol condensation of acetaldehyde
Authors: Gruen LC , McTigue PT
Published: September 2010

Previously unreported complications have
been observed in the base-catalysed condensation of acetaldehyde in water. New
experimental data are presented which firmly establish a reaction mechanism.
Polarography of azobenzene and its p-sulphonic acids
Authors: Florence TM , Farrar YJ
Published: September 2010

The behaviour at the dropping mercury
electrode of trans-azobenzene and its p-sulphonic acids has been studied by
several techniques including d.c., a.c., single sweep, and Kalousek
polarography. Current-potential curves recorded at the streaming mercury
electrode provided information on the reversibility of the electrode processes,
while current-time and electrocapillary curves aided in elucidating the effects
of adsorption.

The results show that the rate of the
electrode reaction of the azo-hydrazo couple is dependent on pH, the minimum
rate occurring near pH 9 for azobenzene-4-sulphonic acid in aqueous media. At
very low and high pH values, the couple approaches full reversibility at the
dropping mercury electrode. This pH effect is apparently due to strong
adsorption of both the azo and hydrazo derivatives near the potential of the
electrocapillary maximum. Ammonium ions associate with azobenzene-4-sulphonate,
and improve the reversibility in intermediate pH regions.
The formation of aromatic hydrocarbons at high temperatures. XXII. The pyrolysis of phenanthrene
Authors: Badger GM , Donnelly JK , Spotswood TM
Published: September 2010

The pyrolysis of phenanthrene at 700� and
at 850� has given tars in which 7 and 13 aromatic compounds have been
identified respectively. Mechanisms for the formation of these compounds are
discussed, with special reference to the formation of anthracene by
rearrangement of the intermediate tetrahydrophenanthrene.
Organoaluminium compounds. VIII. The reactions of organoaluminium hydrides with phenylacetylene
Authors: Surtees JR
Published: September 2010

Organoaluminium hydrides react with
phenylacetylene under mild conditions to give various products resulting either
from substitution (metallation) of the acetylenic hydrogen or mono-addition or
di-addition across the triple bond. The alkyl groups of dimethyl- and
diethylaluminium hydrides take little or no part in the reaction, but in the
case of diphenylaluminium hydride reaction of both hydride and phenyl groups
can occur.

In the presence of triethylamine the
addition reaction between diphenylaluminium hydride and phenylacetylene is
completely suppressed, and a mixture of the two possible substitution products
is obtained.
Reactions of free radicals with aromatic compounds in the gaseous phase. II. Kinetics of the reaction of methyl radicals with phenol
Authors: Mulcahy MFR , Williams DJ
Published: September 2010

Knowledge of the reactivity of phenols towards simple free radicals is needed
to throw light on the behaviour of the phenolic substances involved in the pyrolysis
of coal and other organic materials. In the present investigation the reaction between
methyl radicals and phenol vapour has been studied a t total pressures from 0.5 to
3 cmHg and temperatures from 445 to 547°K, the concentrations of methyl radicals
and phenol being varied from 2 × 10-12 to 4 × 10-11 and 1 × 10-8 to 8 × 10-7 mole cm-3
respectively. The main products identified by gas chromatography were methane
and o- and p-cresol, together with a little anisole and 2,4- and 2,6-dimethylphenol.
The cresols are produced via hydrogen abstraction
Diagram
followed by combination of a methyl radical at a ring position of the phenoxy
radical either ortho or para to the oxygen atom, e.g. in the case of the para position:
Diagram
The kinetics can be explained by postulating (a) that the keto forms of the cresols
(methylcyclohexadienones) formed initially by reaction (6) have a finite lifetime in
the gaseous phase and (b) that these molecules, which contain a tertiary hydrogen
atom α to a system of a carbonyl bond and two carbon-carbon double bonds, partly
undergo hydrogen abstraction by methyl radicals before they are able to enolize:
CH3· + (HCH3 = C6H4 = O → CH4 + CH3C6H4O·
The mechanism is consistent with the kinetics of formation of methane, the distribu-
tion of the free electron in the phenoxy radical, the formation of o- and p-cresols as
major products, the kinetics of formation of the cresols, and the high reactivity of
the intermediate product towards methyl radicals.
Studies in aerial oxidation: Salts of methylbenzoic acids
Authors: Milne JW , Shannon JS , Sternhell S
Published: September 2010

In the course of an investigation designed
to provide a solid-state system for the study of aerial oxidation of coals it
was shown that the main products (conversions of approximately 60%) of
oxidation of solid salts of methylbenzoic acids with air between 240� and 300�
are the corresponding benzenedicarboxylic acids. The corresponding aldehydes
are probably intermediates which give rise to benzoic acid as a product of a
competitive reaction. Ion-transfer reactions between solids take place under
the conditions of the experiments.
Schiff base equilibria. I. Formation and distribution of N-n-butylsalicylideneimine
Authors: Green RW , Alexander PW
Published: September 2010

The equilibrium constant governing the
formation of a Schiff base from salicylaldehyde and n-butylamine in aqueous
solution has been evaluated by spectrophotometry as 5.62 x 104. The
pK of the phenolic group of the Schiff base is 12.0. These constants have been
used to account for the distribution of salicylaldehyde between water and
toluene in the presence of butylamine. The neutral form of the Schiff base has
a distribution coefficient of 1.9 x 103.
Antisymmetric features of atomic charge density: Their significance in studies of electron redistribution accompanying bonding, and their relevance to thegeneral problem of structure and properties of molecules
Authors: Dawson B
Published: September 2010

A discussion is given of aspects of atomic
charge density which possess the property of antisymmetry about the reference
nuclear centre. It is shown that components of electronic charge density
displaying this property must be an integral part of all bonded atoms
possessing non-centric environments. The significance of such components for
detailed X-ray diffraction studies of the electron redistribution which
characterizes covalent bond formation is demonstrated for the case of carbon in
diamond, and it is shown that the so-called "forbidden" 222 reflexion
there is a natural consequence of antisymmetric features required by the
non-centric (tetrahedral) disposition of bonded atoms in this lattice. Detailed
X-ray studies of anthracene, salicylic acid, and cyanuric acid are cited to
illustrate the importance and generality of antisymmetry concepts in accurate
examinations of molecular systems; their significance in explaining
long-standing discrepancies in the location of hydrogen atoms by X-ray and neutron
diffraction methods is also noted. The discussion also demonstrates the
relevance of antisymmetry to recent important neutron diffraction studies of
fluorite structures at different elevated temperatures. Here, the accessible
aspects of atomic charge density are those of nuclear charge density, i.e.
nuclear vibrational behaviour, and it is shown that the presence of significant
anharmonicity in the anionic vibrational pattern is responsible for the unusual
diffraction effects observed. This anharmonicity has the same antisymmetry
characteristics as those responsible for the 222 reflexion observed in X-ray
studies of diamond. It is predicted that .future neutron studies of diamond
structures (C, Si, Ge) at elevated temperatures should reveal a range of "forbidden"
reflexions produced by antisymmetric components in the nuclear motions about
their equilibrium positions.

The discussion concludes with brief
comments on the multipolar nature of bonded atoms arising from antisymmetric
components in their electronic charge densities. Preliminary remarks are made
on the relevance of the multipole concept to general problems of structure and
properties of molecular systems.
Polarography of aromatic azo compounds. II. Kinetic study of the disproportionation of 4-Aminohydrazobenzene-4'-sulphonic acid
Authors: Florence TM
Published: September 2010

Solutions of
4-aminoazobenzene-4'-sulphonic acid were reduced by controlled potential
electrolysis at a mercury cathode, and the disproportionation rate of the
hydrazo derivative determined by spectrophotometry and polarography. The
kinetics of the reaction were found to be first-order with respect to both
hydrazo and hydrogen ion concentrations, although the overall reaction involved
two molecules of the hydrazo compound. In the rate law, -d[hydrazo]/dt =
k[H+][hydrazo], k was calculated to be (5.0�0.3) x 106 l. mole-1
sec-1 from spectrophotometric measurements, and (4.5�0.5) x 106
l. mole-1 sec-1 by polarography (25�). A reaction
mechanism based on a rate determining step involving a quinonediimine
intermediate has been proposed.

Another value of the disproportionation
rate constant was obtained from the effect of drop time on the limiting
currents of 4-aminoazobenzene-4'-sulphonic acid at the dropping mercury
electrode. A value of k of (22�5) x
106 l. mole-1 sec-1 was determined by this
method. Reasons for the discrepancy between this result, and those found by
direct measurement, are discussed.
The analysis of the proton magnetic resonance spectra of heteroaromatic systems. V. Diazanaphthalenes
Authors: Black PJ , Heffernan ML
Published: September 2010

The proton magnetic resonance spectra of
the four isomeric diazanaphthalenes, quinoxaline, phthalazine, quinazoline, and
cinnoline, all as dilute solutions in carbon tetrachloride and acetone, have
been investigated at 100 Mc/s. The chemical shifts and coupling constants have
been obtained by direct calculation or, where appropriate, by an iterative
procedure. Long-range coupling constants between protons separated by five and
six bonds have been observed.
Observations on the reaction calcium sulphate hemihydrate + water ↔ gypsum
Authors: Goto M , Ridge MJ
Published: September 2010

A study by microscopy was made of the
dehydration and rehydration of grains and single crystals of gypsum. The
results confirm the view that, although dehydration of gypsum may be topotactic,
hydration of calcium sulphate hemihydrate is merely a matter of dissolution of
calcium sulphate hemihydrate, diffusion, nucleation (heterogeneous), and growth
of crystals of gypsum.��� Processes occurring during the dehydration of
gypsum are discussed, as are also theories for the hydration of calcium
sulphate hemihydrate. An equation accounting for the rate for the entire course
of hydration of calcium sulphate hemihydrate is discussed.
Equilibria in acetic acid: Ionic association constant of acetamidium perchlorate and acid-base equilibrium constant of acetamidium acetate at 105.7°
Authors: Martin RJL
Published: September 2010

In acetic acid at 105.7� acetamidium
perchlorate has an ionic association constant KA = 0.0491 x 106 l.
mole-1, a limiting equivalent conductivity A, = 79.4 cm2 Ω-1
equiv.-1, and a centre-to-centre distance between the ions � = 4.67 Ǻ.
The
acid-base equilibrium constant for acetamidium acetate KB = [ΣNH3Ac+
OAc-]/ [NH2Ac] increases slightly with increasing
dielectric constant.
Reactions of aroyl peroxides. VI. Reactions of mixed peroxides with benzene and nitrobenzene
Authors: Mingin M , Pausacker KH
Published: September 2010

Reactions of a number of mixed peroxides
and mixtures of peroxides, with benzene and with nitrobenzene, have been
studied. The complex nature of the reactions prevents quantitative comparison
of radicals, but some general features are discussed, particularly the relative
simplicity of the products obtained from p-nitro-substituted peroxides and/or
nitrobenzene.
The synthesis and polymerization of peptide p-nitrophenyl esters
Authors: Stewart FHC
Published: September 2010

Benzyloxycarbonyl peptide p-nitrophenyl
esters have been prepared by the mixed carbonic anhydride method using amino
acid or peptide p-nitrophenyl esters as amino components. Removal of the
N-protecting group produces higher peptide active esters, which can then be
used either in a further peptide coupling reaction with a benzyloxycarbonyl
amino acid, or polymerized to form sequential polypeptides. The advantages and
limitations of the procedure are discussed.
The cardiac glycosides of Cerbera species. II. The structure of cerbertin and deacetylcerbertin
Authors: Cable J , Coombe RG , Watson TR
Published: September 2010

Cerbertin has been shown to be the
monoacetyl-L-thevetoside of llβ,12β-epoxydigitoxigenin.
Protodemercuration of organomercuric chlorides. I. Aromatic mercuric chlorides
Authors: Brown RD , Buchanan AS , Humffray AA
Published: September 2010

The kinetics of protodemercuration, or
displacement of the HgCl group by hydrogen, have been measured for
phenylmercuric chloride, and also for its meta and para methyl-, chloro-, and
methoxy-substituted derivatives. The reactions of the compounds with aqueous alcoholic
hydrochloric acid were first order in RHgC1, first order in hydrogen ion, and
zero order in chloride ion. At 70" the relative rates, which were largely
determined by entropy factors, were: phenyl, 1; p-tolyl, 7; m-tolyl, 2.4;
p-chlorophenyl, 0.67; m-chlorophenyl, 0.26; p-methoxy, 150; m-methoxy, 0.71. A
plot of log k against σ+ gives a ρ value of -2.44, and
correlation coefficient of 0.986.
Chelate complexes of molybdenum. I. Thiolo-bridged molybdenum(III) complexes with low magnetic moments
Authors: Lindoy LF , Livingstone SE , Lockyer TN
Published: September 2010

Thiolo-bridged complexes of molybdenum(III)
have been obtained from the reaction in alcohol of lithium hexachloromolybdate(III)
enneahydrate with a number of chelating ligands containing a thiol group. These
multinuclear complexes have three bridging groups--either three thiolo-bridges
or two thiolo-bridges and one chloro-bridge-linking the molybdenum atoms which,
except in one complex, are probably eight-coordinate, Only two complexes were
obtained from the reaction of the ligands with potassium hexabromomolybdate(III)
in alcohol. The bromo-derivatives were similar to but less stable than their
chloro-analogues. All the complexes have anomalously low magnetic moments
ranging from 0.3 to 1.56 BAT. per molybdenum atom, owing to metal-metal
interaction either directly or via the bridging atoms.

A monomeric five-coordinate molybdenum(1v)
complex MoO[(PriO)2PS2]2
with a low magnetic moment (μ 0.9 B.M.) is also described.
The dissolution of beryllia in molten alkali metal hydroxides
Authors: Shying ME , Temple RB
Published: September 2010

Beryllium oxide shows a limited reversible
solubility in molten alkali-metal hydroxides only when dissolved water vapour
is present. The
reaction taking place has been studied in detail. The results obtained are
consistent with the reversible formation of the beryllate ion [Be(OH)4]2-
as the major product, according to the overall equation

BeO(solid) + H2O(dissolved)
+ 2OH- ↔ [Be(OH)4]2-(dissolved)

The
enthalpy of the reaction has been calculated to be 4.8 kcal/mole over the
temperature range 240-510�.
Aromatic nitrogen bridgehead compounds. I. The dipyrido[1,2-c:2',1'-e]-imidazolium and related cations
Authors: Calder IC , Sasse WHF
Published: September 2010

The preparation of the dipyrido[l,2-c:2?,1?-e]imidazolium cation (I) and some substituted cations from
2,2'-bipyridyls and gem-dihalides is described. As expected, (I) exhibits
reactions typical for both a-electron excessive and n-electron deficient aromatic
ring systems. Thus, (I) may be brominated, methylated, benzoylated, and
acetylated at the 6-position; the cation (I) also adds to methyl vinyl ketone.
The action of hydroxyl ions in the presence of air produces the corresponding
2,2'-bipyridyls, as does the action of light and air. The rate of bromination
of the 6-phenyl derivative (XII) to give the 2,10-dibromo cation (XVI) is
comparable to that of naphthalene. The 6-acyl derivatives (XIX) are converted
to the parent cation (I) by the action of either acid or base.
The chemistry of the Euphorbiaceae. XV. Further diterpenes from Ricinocarpus stylosus: 1a, 19-diliydroxy-16a-( - )-kauran-17-oic acid
Authors: Henrick CA , Jefferies PR
Published: September 2010

Another two diterpenes based on the
(-)-kaurane skeleton have been isolated from Ricinocarpus stylosus. One is the
known 16,17-dihydroxy-16β-(-)-kauran-19-oic acid
(IIb) and the other has been shown to be lα,l9-dihydroxy-16α-(-)-kauran-17-oic
acid (IVa). The N.M.R. spectra of various kaurane derivatives in chloroform and
benzene solutions are compared.
Proton magnetic resonance spectra of 3,4-dehydroproline derivatives
Authors: Johnson LF , Robertson AV , Simpson WRJ , Witkop B
Published: September 2010

Slight changes in the chemical shifts of
protons in 3,4-dehydroproline derivatives cause the appearance of their proton
magnetic resonance spectra to change markedly, and this can be effected by
taking one compound in two different solvents or by observing closely related
derivatives in the same solvent. The explanation involves a previously
undescribed type of deceptively simple coupling and the necessary conditions
are discussed. A first-order analysis of the ABMXX' pattern for
3,4-dehydroprolinamide in deuterium oxide is given. A full analysis is made of
the ABXX' and ABXY patterns for this amide in deuterium oxide and deuterochloroform
respectively after deuterium exchange of the labile H2; a very large homoallylic coupling is required. Two conformations exist
at 40� in solution for all N-benzyloxycarbonyl methyl esters of proline and its
derivatives due to restricted rotation about the amide bond. Free rotation of
the amide bond of corresponding N-acetyl and AT-benzoyl derivatives still
occurs at -50�. The deceptively simple spectrum of N-benzyloxycarbonyl-2,5-dihydroxy-Δ3-pyrolne
is discussed and that of its diacetate is analysed as an A2X2
system; a very small homoallylic coupling is
required.
The formation and isolation of a zirconium sulphate pentahydrate
Authors: Bear IJ
Published: September 2010

The hydration products of
crystalline zirconium sulphate, Zr(SO4)2,
at ambient temperatures have been studied, and a new well-defined, relatively
stable phase in which the zirconium sulphate is associated with 5 moles of
water has been isolated. This phase has also been prepared from supersaturated
solutions of zirconium sulphate tetrahydrate.
Catalysis by hydrogen halides in the gas phase. X. Tertiary butyl methyl ether and hydrogen chloride
Authors: Stimson VR , Watson EJ
Published: September 2010

The decomposition of t-butyl methyl ether
catalysed by hydrogen chloride takes place at 337-428�. It is first order in
each reactant and the rate is not affected by increase in surface area or
inhibitor. The rate equation is:

K2 = 1012.46exp(-32100/RT)
(sec-l ml mole-l)

The reaction is believed to
be molecular and its properties are in accord with those of other such
catalysed decompositions.
Spin-spin coupling in the system H-C-N-H. I. Weakly basic secondary amines
Authors: Rae ID
Published: September 2010

Proton-proton spin-spin coupling in the
system H-C-N-H has been observed in a series of N-methylanilines. At 25� in
deuterochloroform those bases with pKa >3.5 show no coupling
owing to the rapidity of proton exchange in solution. In pyridine, however,
this upper pKa limit is raised to 4.6. The temperature-dependence of
the coupling behaviour, and hence the proton exchange rates, have been
qualitatively explored.
Some copper(II) and nickel(II) amine-cyanide derivatives. II. Some crystalline derivatives
Authors: Curtis YM , Curtis NF
Published: September 2010

The preparations and properties of the
compounds Cu(A)]2CN(ClO4)3, M(tet α)CNClO4, and
Ni(tet α)(CN)2 are described, where
[Cu(A)]2+ is a cyclic tetradentate Schiff
base-amine complex (hexamethyltetraazacyclotetradeoadiene-
copper(11) formed by condensation of bisethylenediaminecopper(11)
with acetone), and where [M(tet α)]2+
is the copper(11) or nicke1(11) complex of the cyclic tetramine
(hexamethyltetraazaoyclotetradecane) formed by
reduction of the [M(A)]2+ complex. From consideration of the infrared
and metal ion spectra, it is concluded that the [Cu(A)]2+ compound
has a dimeric structure with bridging cyanide ions and five-coordinate
copper(11) ions, that the two monocyanide adducts
have six-coordinate polymeric structures with bridging cyanide ions, and that
Ni(tet α)(CN)2 has a six-coordinate
structure with terminal cyanide ions. The copper compounds are the first
reported stable, crystalline compounds with cyanide coordinated to copper(11).