bluuebunny/crossref_metadata_2025 huggingface dataset:
The spectra and equilibria of nitrosonium ion, nitroacidium ion, and nitrous acid in solutions of sulphuric, hydrochloric, and phosporic acids
Authors: Bayliss NS , Watts DW
Published: September 2010

The ultraviolet spectrum of sodium nitrite
in aqueous sulphuric acid is essentially that of nitrous acid below 40 per
cent, acid, and that of nitrosonium ion above 70 per cant. acid. In the
intermediate range there is evidence that the nitroacidium ion (H2NO2+)
is an important constituent of the solution. Equilibria involving the three
species have been calculated using activity data for water and sulphuric acid.
Similar results are obtained in aqueous phosphoric acid as a solvent. In
hydrochloric acid of low water activity the high chloride activity causes what
appears to be almost total conversion to nitrosyl chloride.

The ultraviolet spectrum of the
nitrosonium ion is a structureless transition with εmax.=3850
at about 46 kK (2200 Ǻ). The nitroacidium ion does not absorb appreciably
within the accessible range.
The stretching frequency of the AZO-group
Authors: Le Fevre RJW , Werner RL
Published: September 2010

Infra-red absorptions now reported for 25
azoaryl derivatives bring the number of N=N- containing structures examined so
far up to 83. Indications previously recognized, that the azo-stretching
frequencies in azobenzenes lie between 1400 and 1450 cm-1, are
confirmed by the present measurements.
The Alkaloids of Lupinus varius L. II. Alkaloids of the Leaf
Authors: Crow WD , Michael M
Published: September 2010

The aerial parts of Lupinus varius L.
contain the alkaloids LV-I (0.10 per cent.) and (+)-epilupinine (0.50 per
cent.) previously reported in the seeds, together with (-)-sparteine (0.006 per
cent.) and small amounts of two mono-nitrogen bases LV-3 (C20H27O4N,
containing one methoxyl group) and LT7-4 (C17H23O5N).
The proportion of LV-1 present in the leaves is higher than that in the seeds,
while the amount of (+)-epilupinine-N-oxide is much lower.
The Kinetics of the Acid Hydrolysis of some Dipeptides in Acetic acid
Authors: Martin RJL
Published: September 2010

Glycylglycine and a number of its C-methyl
derivatives have been hydrolysed with excess perchloric acid in aqueous acetic
acid as solvent, and by varying the water content of the medium its effect on
the reaction rate has been determined. It has been found that small changes in
the water concentration cause reversals in the relative rate sequences in both
series of dipeptides studied.

In aqueous acetic acid containing more
than 2 per cent. water the relative rate sequence in the first series is glycylglycine
> alanylglycine > α-aminoisobutyrylglycine, but at water
concentrations less than 2per cent. α-aminoisobutyrylglycine reacts faster
than glycylglycine. It is concluded that increasing methylation has produced a
change in mechanism whereby α-aminoisobutyrylglycine reacts by a
unimolecular heterolysis rather than by the bimolecular mechanism given in the
previous paper (Martin 1957).

For the second series of dipeptides, the
relative rate sequence is glycylglycine > glycylalanine > glycyl-α-aminoisobutyric
acid for water concentrations greater than 2 per cent. At water concentrations
less than 2 per cent. the rate sequence is reversed, so that glycyl-α-aminoisobutyric
acid > glycylalanine > glycylglycine. This reversal is attributed to
changes in the polar effect of the terminal carboxyl group which is brought
about by increasing methylation.
Amino Acids and Peptides. IV. Intermediates for the synthesis of certain cystine-containing peptide sequences in insulin
Authors: Maclaren JA , Savige WE , Swan JM
Published: September 2010

The synthesis is described of various
derivatives of the peptides L-glutaminyl-S-benzyl-L-cysteine, L-glutaminyl-S-benzyl-L-cysteinyl-S-benzyl-L-cysteine,
S-benzyl- L-cysteinyl-S-benzyl-L-cysteine, S-benzyl-L-cysteinyl-L-alanine,
S-benzyl-L-cysteinyl-L-alanyl-L-serine, L-alanyl-L-serine,
L-valyl-S-benzyl-L-cysteine, L-alanyl-L-seryl-L-valyl-S-benzyl-L-cysteine,
S-benzyl-L-cysteinyl-L-alanyl-L-seryl-L-valyl-S-benzyl-L- cysteine,
S-benzyl-L-cysteinylglycine, and L-leucyl-S-benzyl-L-cysteinylglycine.
Alkaloids of the Australian Rutaceae: Lunasia quercifolia. I. 7-Methoxy-1-methyl-2-4-quinolone
Authors: Johnstone R , Price JR , Todd AR
Published: September 2010

Bark of Lunasia quercifolia contains c.
4-4.5 per cent. alkaloids consisting of c. 3-3.5 per cent. water-soluble bases
and c. 1 per cent. tertiary bases. Three component tertiary bases have been
isolated ; these are the previously described alkaloids lunacrine and lunine
and an undescribed base C17H15O2N. This new
base is shown by degradative processes and by synthesis to be 7-methoxy-1-methyl-2-phenyl-4-quinolone
(I). The products of the action of nitric acid on the alkaloid include mono-
and dinitro derivatives which undergo hydrolytic fission, giving rise to
2-methylamino-o-nitroacetophenones.
The reaction of Carbon with Hydrogen at High Pressure
Authors: Blackwood JD
Published: September 2010

A study has been made of the reactions of
a number of carbons with hydrogen at pressures up to 40 atm and in the
temperature range 650-870 �C. The effect of total pressure and hydrogen partial
pressure has been examined and the rate of methane formation for a given carbon
can be expressed as ��������������������� rate= kpH2. Values of log k when
plotted against 1/T give a straight line and the "apparent" energy of
activation is approximately 30 kcal mole-1.

The value of the constant k for a given
temperature of reaction is dependent on the oxygen content of the carbon which
is, in turn, dependent on the temperature of preparation of the carbon. For
carbons containing no oxygen the methane rate is zero, The oxygen appears to be
associated with at least two types of active centres. One type, considered to
have a lactone structure, is responsible for an initial rapid evolution of
methane and water and is destroyed during the first few minutes of
hydrogenation. The other centre, responsible for the slow steady evolution of
methane, appears to be associated with structures such as chromene or benzpyran
which activate certain sites on the carbon crystallite. Neither steam nor
carbon dioxide will activate the carbon for the formation of methane.
Theory and applicatin of the Gilfillan-Polanyi micropyknometer technique
Authors: Lauder I
Published: September 2010

An investigation of the theory and
application of the Gilfillan-Polanyi micropyknometer technique (Gilfillan and
Polanyi 1933), used for the estimation of the heavy forms of water, has been
carried out. An improved technique was developed and the accuracy of the
isotopic analysis of water by this method is now comparable with that obtained
by routine mass-spectrometric analysis. The time required for one measurement is
50-60 min. The pyknometers may be calibrated by using nitrogen to change the density
of the water in which the pyknometers float.
A Xanthene Polymer with Semiconducting Properties
Authors: McNeill R , Weiss DE
Published: September 2010

A series of xanthene polymers has been
prepared as the first stage of a study of the potentialities of organic
semiconductors for the synthesis of model enzymes, and for the development of
ion-exchange adsorbents capable of direct electrical regeneration. The polymer
is composed of condensed xanthene residues cross-linked with phenyl bridges.
The polymers are p-type semiconductors and the best has a specific resistance
of 7 x 103 Ω cm which is less than that of crystalline organic
semiconductors by a factor of at least 104. The conductivity is not
due to the diradicals of the quinonoid resonance form of quinolphthalein, but
is more probably due to a resonating carbonium cation arising from partial
ionization of the xanthylium-lactone bond. The effect of polymerization
conditions on the resistance of the polymer has been studied.
Compounds Derived from β-Substituted Glutaric Acids: Glutarimides, Glutaramic Acids, 1,5-Pentane Diols
Authors: Handley GJ , Nelson ER , Somers TC
Published: September 2010

A series of β-substituted
glutarimides have been prepared via the Guareschi synthesis of αα?-dicyano-ββ-dialkylglutarimides,
the scope of which is discussed.

Two related series, ββ-dialkylglutaramic
acids and 3,3-dialkylpentane diols, have been investigated. Representative αα'-dicarboxyamidoglutarimides
and 1,1,3,3-tetra-carboxylic acid propane di-hides, intermediates in the acid
hydrolysis of the αα'-dicyanoglutarimides to glutarimides have been
incidentally prepared.

Pharmacological findings for these series
are briefly reported.
Chemistry of Australian Lichens. II. A New Depsidone from Parmelia conspersa (Ehrh.) Ach
Authors: Gream GE , Riggs NV
Published: September 2010

A new compound, norlobaridone, from
Parmelia conspersa is shown to have structure Ia by conversion of its
monomethyl ether (lobaridone (Ib)) into lobariol (IIb). The depsidone ring is
readily cleaved by basic reagents to give products containing a new cyclic
system and including an isomeric γ-enol lactone (IIIa), norlobariol (IIa),
and the oxime anhydride (IVa) of the latter. Ultraviolet and infra-red spectra
support structural assignments. Norlobaridone (Ia) presents an exception to the
acetate theory of biogenesis in the position of its ketonic oxygen atom.
Amino acids and peptides. VI. Studies on cystine and αα'-dimethylcystine in relation to the alkaline degradation of protein disulphides
Authors: Stapleton IW , Swan JM
Published: September 2010

The synthesis and properties of α-methyl-DL-cysteine
and of racemic αα?-dimethyl-cystine and its dimethyl ester are
recorded. The new disulphide is very much more stable to aqueous alkali than is
cystine, its dimethyl ester is quite stable to methanolic triethylamine whereas
cystine dimethyl ester breaks down readily with liberation of sulphur. These
results support the β-elimination hypothesis for the alkaline degradation
of cystine and its derivatives, namely, that attack occurs at the amino acid α-carbon
atom, with synchronous displacement of a sulphenyl thiol anion, RSS-.
Simplified Analogues of Lysergic Acid. III. Hydroxy- and Carboxy-Substituted N-Alkyl Derivatives of 1,2,3,4-Tetrahydro-2-naphthylamine
Authors: Craig JC , Moore B , Temple DM
Published: September 2010

The preparation of some hydroxy- and
carboxy-substituted N-alkyl derivatives of 1,2,3,4-tetrahydro-2-naphthylamine
is described, and preliminary pharmacological tests reported.
The Triterpenoid Constituents of the Hong Kong Ericaceae
Authors: Arthur HR , Tam SW , Angsusingh V
Published: September 2010

α-Amyrin, lupeol, and a new
triterpene alcohol, simiarol, have been isolated from the leaves of
Rhododendron simiarum; α-amyrin, β-amyrin, and lupeol have been
isolated from the leaves of R. westlandii ; and epifriedelanol has been
isolated from the leaves of R. championae. This paper completes the chemical
survey for triterpenoid and flavonoid compounds of the endemic species of the
family Ericaceae of Hong Kong.
Molecular Vibrations in the Exciton Theory for Molecular Aggregates. I. General Theory
Authors: McRae EG
Published: September 2010

A molecular aggregate is defined as an
ordered array of identical molecules. This definition includes molecular
crystals, dimers, and certain polymeric aggregates of dye molecules.

The vibronic states of an electronically
excited molecular aggregate are studied theoretically. The aggregate is treated
as an array of non-rigid molecules in a rigid lattice. The simplest form of the
exciton theory is assumed to be correct except with regard to intramolecular
vibrations. The molecules in the aggregate are considered as harmonic
oscillators with one vibrational degree of freedom, whose individual wave
functions are Born-Oppenheimer separable. The molecules are assumed to interact
by a purely electronic mechanism.

Born-Oppenheimer separable wave functions
for the whole aggregate, here called E-V functions, are defined. It is shown
that the interaction integrals between E-V functions may be expressed in terms
of integrals which depend only on the properties of individual molecules.
Explicit expressions are given for the latter integrals.

The resonance interactions between E-V
functions are described. On this basis, the limiting conditions under which the
E-V functions steadily approach exact vibronic state functions of the aggregate
are specified.

The vibrational overlap integrals between
E-V and electronic ground-state wave functions are studied. These integrals may
be expressed as sums of products of vibrational overlap integrals for
individual molecules. Explicit expressions for the latter integrals are
obtained through an approximation to Hutchisson's theory.
Studies in Waxes. XX. The Quantitative Analysis of Hydrolysed Carnauba Wax by Gas Chromatography
Authors: Downing DT , Kranz ZH , Murray KE
Published: September 2010

The hydrolytic products of carnauba wax,
previously shown to consist mainly of straight-chain alcohols, α,ω-diols, alkanoic acids, and ω-hydroxyalkanoic
acids, have been reexamined by gas chromatographic methods to provide a
qualitative and quantitative knowledge of the components. These components,
shown to be almost entirely straight chain in character, are largely even
carbon numbered compounds, but odd chain-lengths are present. The hydrocarbons
are likewise of odd and even carbon number with the odd members (90%)
predominating.

An unidentified compound, possibly an
unsaturated steroid diol, has been isolated from the unsaponifiable fraction.
Direct Measurement of the Thermal Pressure Coefficient of Water
Authors: Malcolm GN , Ritchie GLD
Published: September 2010

A constant volume thermometer has been
used to measure the thermal pressure coefficient of water over a wide range of
temperature and pressure. The results show satisfactory agreement with values
calculated from the appropriate data for the coefficients of thermal expansion
and isothermal compressibility of water.
5-(10-Pentadecenyl)resorcinol from Grevillea pyramidalis
Authors: Occolowitz JL , Wright AS
Published: September 2010

The major constituent of the vesicant
exudate from the seed pods of Grevillea pyramidalis (family Proteaceae) has
been identified as 5-(10-pentadecenyl)resorcinol (I).
The Dipole Moment of Tri-isopropanolamine Borate in Benzene
Authors: Pugh JM , Stokes RH
Published: September 2010

Solutions of the cyclic boric acid ester,
tri-isopropanolamine borate, in benzene have been studied by dipole moment
measurements at 25 and 50�C. The molecule has a dipole moment of 6.69 D, and
the concentration dependence of the polarization indicates association of the
solute, with end-to-end association predominating.
The Infrared Spectra of Quaternary 'onium Cations of Group VB Elements. II. Vibrational Assignments for Some Tetraphenyl-, Triphenylmethyl-,Triphenylethyl-, Tetraethylphosphonium Salts
Authors: Deacon GB , Jones RA , Rogasch PE
Published: September 2010

The infrared spectra of five
tetraphenylphosphonium salts, seven triphenylmethylphosphonium salts, five
triphenylethylphosphonium salts, and three tetraethylphosphonium salts are
reported, and tentative vibrational assignments are given for the majority of
the observed bands.
The Formation of 3-Phenyl-2-thiohydantoins from Phenylthiocarbamyl Amino Acids
Authors: Ilse D , Edman P
Published: September 2010

In an attempt to extend the application of
the phenylisothiocyanate degradation of peptides it was found necessary to
study the kinetics of the conversion of phenylthiocarbamyl amino acids into
phenylthiohydantoins. The conversion was found to obey first-order kinetics and
to be catalyzed by hydrogen ions. A set of conditions with regard to time,
hydrogen ion concentration and temperature was found, which allowed the
quantitative or near quantitative conversion of all phenylthiocarbamyl amino
acids into phenylthiohydantoins with the only exception of the
phenylthiohydantoin of serine, which was returned in a yield of 20%.
Synthetical applications of activated metal catalysts. XX. The action of degassed Raney nickel on some N-Alkyl-o-alkylanilines
Authors: Jackson GDF , Sasse WHF
Published: September 2010

At temperatures not exceeding 230�
degassed Raney nickel caused stepwise dealkylation of the o-alkyl groups of
o-propylaniline, o-ethylaniline, N-methyl-o-ethylaniline, and
N-ethyl-o-toluidine. N-Alkyl groups were removed simultaneously. Indole was isolated
from o-propylaniline, o-ethylaniline, and N-methyl-o-ethylaniline.
2-Methylindole was obtained from o-propylaniline, and 3-methylindole was
isolated from N-methyl-o-ethylaniline. N-allylaniline and o-propylaniline
formed traces of 3-methylindole; N-ethyl-o-toluidine gave traces of indole and
2-methylindole. Indoline was mostly dehydrogenated but it also underwent
dealkylation. Small amounts of 2-alkylcyclohexanones were isolated from
o-propylaniline, o-ethylaniline, and N-methyl-o-ethylaniline. The last amine
also formed carbazole.
Synthetical applications of activated metal catalysts. XXIII. The desulphurization of thianthren
Authors: Badger GM , Cheuychit P , Sasse WHF
Published: September 2010

��� The desulphurization of thianthren with a
degassed (hydrogen-poor) Raney nickel has been shown to give benzene, biphenyl,
dibenzothiophen, and a little triphenylene. Chromatography on a column of Raney
cobalt has been used to separate a mixture of biphenyl and dibenzothiophen. The
results have been discussed with reference to two radical intermediates (III
and V, or VI).
The occurrence of 5-Hydroxy-7,4'-dimethoxy-6-methylflavone in Eucalyptus waxes
Authors: Lamberton JA
Published: September 2010

5-Hydroxy-7,4'-dimethoxy-6-methylflavone (II)
has been shown to occur with 5-hydroxy-7,4'-dimethoxy-6,8-dimethylflavone (I)
in the leaf waxes of Eucalyptus torelliana F. Muell. and E. urnigera Hook. The
nuclear magnetic resonance spectra of (II) and related compounds have been
measured, and it is shown that N.M.R. spectroscopy is useful in determining the
relative proportions of the two components at equilibrium in a Wessely-Moser
rearrangement. Leaf waxes from several Angophora species also contain compound
(I).
Porphyrins. IV. Further preliminary studies on the synthesis of porphyrin a
Authors: Badger GM , Harris RLN , Jones RA
Published: September 2010

A second unsuccessful attempt to prepare
the unsymmetrically substituted porphyrin (IV) is reported. The intermediate (II)
required for, the East Side was prepared and found to be extremely unstable.
The dipyrromethene (I) required for the West Side was prepared (as a
derivative) in such small yield that the projected synthesis (I → IV) was
abandoned.
Internal rotation in 1,2-dichloroethane
Authors: Le FFvre RJW , Orr BJ
Published: September 2010

The magnitudes of dipole moment and molar
Kerr constant of 1,2-dichloroethane as solute in carbon tetrachloride,
previously recorded by Aroney, Izsak, and Le F�vre, are discussed in relation
to internal rotation in the molecule. The results are found to be consistent
with a mixture consisting of 31.3% of gauche-isomer and 68.7 % of trans-isomer.
Estimation of the potential energy barriers restricting intramolecular rotation
is attempted and the results found to be satisfactory.
The pyrolysis of alkyl chlorides on the surface of Pyrex glass
Authors: Shapiro JS , Swinbourne ES , Young BC
Published: September 2010

A study has been made of the
surface-catalysed dehydrochlorination of a selection of gaseous chlorinated
hydrocarbons on Pyrex glass. For primary chlorides at 413� the rate sequence:
ethyl<n-propyl<isobutyl<neopentyl was observed for 200 mm initial pressure
of reagent. Ethyl chloride decomposes at 400-450� according to a first-order
law, and the overall Arrhenius activation energy for the heterogeneous reaction
is 24.1 kcal/mole; the rate is slightly depressed by the addition of propene
and slightly enhanced by hydrogen chloride. Catalysis by hydrogen chloride was
observed to be much more marked in the case of isopropyl chloride decomposition
at 190-250�, but reproducible behaviour for this reaction was not readily
attained.

The catalytic action of Pyrex glass is
accounted for by the polar surface assisting in the separation of charges
within the reacting molecule, emphasis being placed upon the polarization of
the carbon-chlorine bond as the important rate-determining factor.
The stereochemistry of tritium substitution by the Wilzbach method. II. The distribution of tritium
Authors: Angyal SJ , Fernandez CM , Garnett JL
Published: September 2010

When (-)-inositol is submitted to the
Wilzbach labelling procedure, tritium- labelled myoinositol is formed as a
by-product. It is shown by degradation that the (-)-inositol is labelled nearly
at random, whereas all the tritium in the myoinositol is attached to the carbon
atom on which the configurational inversion has occurred.
Festucine, an alkaloid from tall fescue (Festuca arundinacea Schreb.): Chemistry of the functional groups
Authors: Yates SG , Tookey HL
Published: September 2010

The most abundant alkaloid of tall fescue
hay, termed festucine by the authors, was isolated by preparative paper
chromatography. The empirical formula of the free base is C8H14N2O,
and the molecular weight is 154. One nitrogen of festucine is tertiary, the
other secondary. The alkaloid also contains a cyclic ether which can be cleaved
by treatment with hydrochloric acid at 160�. The chemical evidence for
festucine is consistent with its structural formulation as a positional isomer
of loline, a pyrrolizidine alkaloid from the seed of a related grass (Lolium
cuneatum Nevski).
Polarizability of non-bonding electron pairs
Authors: Aroney MJ , Le Fevre RJW , Saxby JD
Published: September 2010

A number of approximate procedures are
used to estimate, from molecular refractivity data, the refractions and mean
polarizabilities of electron pairs occupying non-bonding molecular orbitals.
Coordination compounds of substituted 1,10-Phenanthrolines and related dipyridyls. V. Complexes of cobalt and 2,9-Dimethyl-1,10-phenanthroline
Authors: Fox DB , Hall JR , Plowman RA
Published: September 2010

A series of complexes of cobalt(II) and
2,9-dimethyl-1,10-phenanthroline (dmp) has been prepared. Complexes of formula CoX2dmp (X = Cl, Br, I, KCS) are monomeric in
acetone and camphor and non-electrolytes in nitrobenzene and nitromethane. The
magnetic moments and visible absorption spectra favour the assignment of
tetrahedral stereochemistry about the Co atom. Complexes containing 2 moles dmp
per Co appear to have octahedral arrangements of ligands about the Co atom.
These are of the type [CoNO3(H2O)dmp2]X, (X = NO3, ClO4, BPh4) and Co(NCS)2dmp2.
The magnetic moments, visible and infrared spectra, and conductances in
nitrobenzene and nitromethane support this conclusion. With other mono-dmp
complexes (CoX2dmp, X = NO3, �SO4)
and bis-dmp complexes {CoXdmp,ClO4,H2O
(X = Cl, Br) ; Codmp2(ClO4)2},
stereochemical assignments could not be made.
A study of the interaction of copper(II). zinc(II), and cadmium(II) with transfusion gelatin
Authors: Malik WU , Muzaffaruddin M
Published: September 2010

The binding of copper, zinc, and cadmium
with transfusion gelatin has been measured indirectly by observing the
displacement of hydrogen ions from the acidic groups of transfusion gelatin. It
is seen that the binding data obtained from pH measurements agree well with
those obtained from equilibrium dialysis. Copper, zinc, and cadmium show the
characteristic binding with the carboxyl groups in the pH range 3-5.5 for which
the log K values are found to be 2.18, 1.87, and 1.96 respectively.
Potentiometric titration data also indicate that the interaction is a
competitive one, i.e. the metal ions compete with the hydrogen ions for common
sites. The extent of copper and zinc binding increases with increase in pH,
whereas cadmium binding remains unaffected. It is, therefore, concluded that
copper and zinc combine with the imidazole groups
also (log K values are 3.40 and 2.91 respectively), but cadmium fails to react
with the imidazole groups.
Alkaloids of the Australian Rutaceae: Halfordia scleroxyla. III. Mass spectrometry of halfordinol and related oxazoles
Authors: Crow WD , Hodgkin JH , Shannon JS
Published: September 2010

Comparative studies by mass spectrometry
of halfordinol [2-(3-pyridy1)-5-(4-hydroxyphenyl)oxazole] and other derivatives
of the new oxazole alkaloid N-methylhalfordinium chloride with model
aryloxazoles confirmed the structure of the alkaloid. One of the main features
of the decomposition of 2,5-diaryloxazole ions in the mass spectrometer
involved a novel concerted elimination of HCN and CO. A mechanism has been
proposed for this and other reactions of oxazole ions, including those of 4,5-
and 2,4-diphenyl derivatives.
Protodemercuration of organomercuric chlorides. II. Heterocyclic 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 2- and
3-furyl, 2-thienyl, and 2-selenophenylmercuric chlorides. The reactions of
these compounds with aqueous alcoholic hydrochloric acid were first order in
hydrogen ion, first order in RHgC1, and zero order in chloride ion, when the
latter was present at concentrations less than 0.1M. At 70�, the relative rates
were: 3-furyl, 1; 2-furyl, 27; 2-thienyl, 11; 2-seleno- phenyl, 25. At higher
chloride concentrations, the rate increases; this is discussed in terms of
formation of complex anions of the type RHgCl32- and in
terms of H+Cl- ion pair attack. The dominant influence of
entropy effects in the case of furan compounds emphasizes the danger of trying
to account for observed relative rates in terms of π-electron effects
alone.
The surface tension of liquid sodium and liquid potassium
Authors: Jordan DO , Lane JE
Published: September 2010

A vertical-plate balance has been used to
measure the surface tension and temperature coefficient of surface tension of
liquid sodium and potassium. A value of 200.2�0.6 dyn
cm-1 was obtained for the surface tension of liquid sodium at the
melting point (97.8�), with a temperature coefficient of -0.11 dyn cm-1
deg-1. For liquid potassium the surface tension was found to be
110.3�1.0 dyn cm-1 at the melting point
(64�), with a temperature coefficient of -0.06 dyn cm-1
deg-1. These results are compared with other published values of
these quantities. A discussion, based on the statistical mechanics of a
quasi-crystalline model of the liquid state, suggests that the chemical
impurities present in the liquid metals are unlikely to have significantly
increased the surface tension values above those of the pure metals.
The molar Kerr constants of certain aromatic azo derivatives
Authors: Armstrong RS , Le Fevre RJW
Published: September 2010

Molar Kerr constants at
infinite dilution in benzene at 25� are reported for eight compounds in which
azo or azoxy groups form part of a conjugated system.
Interpretation of the new data is attempted in terms of anisotropic bond
polarizabilities, molecular conformations, etc. Problems arising from the
colours and/or structures of these solutes are discussed.
Ion-molecule reactions in acetone-water mixtures
Authors: de Souza BC , Green JH
Published: September 2010

Mass-spectrometric studies of ion-molecule
reactions in acetone-water mixtures at 70 eV and 20 eV electron energies are
described. The results provide evidence in favour of the proton transfer
mechanism rather than for a hydrogen atom transfer process for the production
of M + 1 ions.
The formation of aromatic hydrocarbons at high temperatures. XXV. The pyrolysis of [3-14C]indene
Authors: Badger GM , Jolad SD , Spotswood TM
Published: September 2010

The pyrolysis of [3-14C]indene
at 700� has given a tar from which six compounds have been isolated in
sufficient quantity and purity for radiochemical analysis. All were found to
have activity corresponding approximately to two labelled atoms. It is concluded
that scission of the weakest carbon-carbon bonds in indene gives three
"primary" radicals which then undergo "dimerization" to
give the major products.
Hydrolysis of amides. II. Substituent effects in dilute acid and alkali
Authors: Bolton PD
Published: September 2010

Energies and entropies of activation for
the hydrolysis in dilute acid of six aliphatic amides are reported.

These results, in conjunction with those
of other workers, indicate the dilute acid hydrolysis of primary aliphatic
amides to be governed by a combination of steric and hyperconjugative
substituent effects and to be independent of polar effects. The reaction series
is well correlated by the Taft-type equation

�������������� logk = 0.858 EC/S-0.493(n-3)+logk0

in which EC/S denotes a pure
steric substituent parameter and n is the number of α-hydrogens in the
substituent.

The alkaline hydrolysis of a similar
series of amides is well correlated by the equation

������������ log k = 2.05�*+ 1.08 EC/S -O.743(n-3)+ log ko.
The reaction of Chloridobis(cyclopentadienyl)titanium(III) with disulphides
Authors: Coutts RSP , Surtees JR , Swan JM , Wailes PC
Published: September 2010

Chloridobis(cyclopentadienyl)titanium(111)
(cp2TiCl) cleaves dialkyl and diaryl disulphides to give monothio compounds, cp2Ti(Cl)SR,
together with varying amounts of cp2TiCl2
and cp2Ti(SR)2. The latter bisthio compounds were prepared independently by the
reaction of cp2TiCl2 with the
sodium salts of the corresponding thiols.
The chemistry of pyrrolic compounds. III. The free radical nature of the oxyporphyrins
Authors: Clezy PS , Looney FD , Nichol AW , Smythe GA
Published: September 2010

The preparation of
a-meso-oxy-1,2,3,4,5,8-hexamethyl-6,7-bis-(2?- ethoxycarbonylethyl)porphin
(Ib), a new member of the oxyporphyrin series, is
described. The structure of molecules of this type, which have now been shown
to exhibit radical character, is further discussed.
Multidentate chelating agents from Quinoline-8-aldehyde. I. Tridentate and quadridentate Schiff bases from primary diamines
Authors: Dekkers J , Goodwin HA
Published: September 2010

Complexes of 1,2-bis(8-quinolylmethyleneimino)ethane with cobalt(II), nickel(II),
and copper(II) are described. The copper complexes are five-covalent and, it is
suggested, trigonal bipyramidal. Reaction of the Schiff base with iron(II),
cobalt(III), and, under certain conditions, nickel(II) leads to its partial
hydrolysis, and complexes of the tridentate 1-amino-2-(8-quinolylmethyleneimino)ethane
are obtained. The hydrolysis of the Schiff base in the presence of metal ions
is discussed in terms of steric effects within the base and of the
stereochemical demands of the metal ions.

Complexes of 1,2-bis(8-quinolylmethyleneimino)benzene
and its hydrolysis derivative 1-amino-2-(8-quinolylmethyleneimino)ethane are
also described.
The preparation of sequential polypeptides containing glycyl and γ-Ethyl-L-glutamyl residues
Authors: Stewart FHC
Published: September 2010

Polypeptides with repeating
unit sequences, in which a glycyl residue is flanked progressively by from one
to five γ-ethyl-L-glutamyl residues, have been prepared by polymerization
of appropriate peptide p-nitrophenyl esters. Synthesis of the hexapeptide active
monomer involved the use of the new 2,4,6-trimethylbenzyl acid-sensitive
carboxyl-protecting group.
Flavan derivatives. XIX. Teracacidin and isoteracacidin from Acacia obtusifolia and Acacia maidenii heartwoods; Phenolic hydroxylation patterns of heartwood flavonoids characteristic of sections and subsections of the genus Acacia
Authors: Clark-Lewis JW , Dainis I
Published: September 2010

7,8,4?-Trihydroxyflavonol
and (-)-cis-cis-7,8,4?-trihydroxyflavan-3,4- diol
(teracacidin) have been isolated from the heartwoods of A. obtusifolia
and A. maidenii; a flavanone and a dihydroflavonol
(presumably 7,8,4?-trihydroxyflavonoids) were also
detected in the heartwood extracts. trans-4-Hydroxy-L-pipecolic acid was
isolated from A. maidenii heartwood. The
hydroxylation patterns of flavonoids in the heartwoods of Australian Acacia
species examined have been found to be characteristic of the sections and
subsections within the genus. The flavonols from the heartwoods of A. flavescens, A. havilandii, A. oswaldii, A.pendula, A. rhodoxylon, and A. shirleyi were
identified by paper chromatography.
The extraction of sulphuric acid with Di- and Tri-(3,5,5-trimethylhexyl)amines
Authors: Cattrall RW
Published: September 2010

Equilibrium constants have
been obtained for the distribution of sulphuric acid between aqueous solutions
and isoamyl alcohol solutions of di- and tri-(3,5,5-trimethylhexyl)amines
forming the normal amine sulphates and the amine bisulphates. The extraction
follows a simple equilibrium law using a solvent for the amines (isoamyl
alcohol) in which it has also been shown that no aggregation phenomenon of the
amine salts occurs.
Cryoscopy in molten pyridinium chloride
Authors: Bloom H , Reinsborough VC
Published: September 2010

The molal cryoscopic
constant in molten pyridinium chloride (m.p. 146.0�) has been found to be 17.4�
(subject to confirmation by calorimetry) and the cryoscopic heat of fusion,
2310�40 cal mole-1. In pyridinium chloride as a solvent, iodides
appear to dissociate completely while bromides do not yield the expected
depression possibly because of solid solution. Tetraalkylammonium and alkyl-pyridinium
halides of high molecular weight are ideally dissociated in extremely dilute
solution but with increasing concentration apparently form micelles.
Coordination complexes of amino acids:isomerism and dimorphism of the copper(II) complexes of phenylalanine and tyrosine
Authors: Laurie SH
Published: September 2010

(D-Phenylalaninato)(L-phenylalaninato)copper(II) has been obtained in two
isomeric forms which, from their diffuse reflectance spectra, are designated as
the cis and trans forms. The trans isomer is converted into the cis on
suspension in hot water. An unstable monohydrate was also isolated. Under
similar conditions only the trans form of bis(L- phenylalaninato)copper(II)
was obtained. The aqueous solution spectra in the visible region of all forms
were identical. Blue
trans-(D-tyrosinato)(L-tyrosinato)copper(II) is converted into a mauve coloured
form when suspended in hot water. The diffuse reflectance spectrum of this
latter form indicates that it is 4-coordinate and possibly cis in
configuration. A second, unstable, trans complex of different crystalline form
was also obtained. Two crystalline forms of bis(~-tyrosinato)copper(II) were
isolated. Spectral differences between the two can be attributed to a
difference in coordination number and their different crystalline forms. The
solution spectra in the visible region of all forms were identical.

No isomerism or dimorphism was found for
the complexes of DL- and L-tryptophan.
Ligand field stabilization energies and stereochemistry of early second and third row transition elements
Authors: Colton R , Canterford JH
Published: September 2010

The elements of the second
and third row transition series towards the left of the Periodic Table show
clearly defined trends in their observed stereochemistries.
These trends are summarized and an
explanation for the experimental facts is suggested.
Halides and oxide halides of molybdenum and tungsten. III. Oxo-bridged species of tungsten(IV) and molybdenum(V)
Authors: Colton R , Rose GG
Published: September 2010

The compound formulated in
the literature as K2W(OH)Cl5
has been shown to be the oxo-bridged dimer
K4[WT2Ocl10], and
the diamagnetic dimer formed by the partial hydrolysis of the MOOCl2- ion has been isolated for the
first time and shown to be the oxo-bridged [Mo2O3Cl8]4-
ion.
Aromatic nitrogen bridgehead compounds. II. The synthesis of 1-Acylmethyl-2-(2-pyridyl)pyridinium salts and their cyclization to 6-substituted Dipyrido[1,2-c:2',1'-e]imidazolium salts
Authors: Calder IC , Sasse WHF
Published: September 2010

The interaction of 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl,
5,5'-dimethyl- 2,2'-bipyridyl, or l,l0-phenanthroline
with aromatic or aliphatic α-haloketones, or
with ethyl bromoacetate, gives high yields of 1-acylmethyl-2-(pyridyl)pyridinium
salts. These salts can be converted in good yields into 6-substituted dipyrido-[1,2-c:2',1?-e]imidazolium
salts by treatment with either bromine and pyridine or p-toluenesulphonyl
chloride and pyridine. The mechanisms of these cyclizations
are considered.
Carbonyl halides of the Group VI transition metals. XI. Dithiocyanatocarbonyl derivatives of molybdenum and tungsten(II)
Authors: Colton R , Scollary GR
Published: September 2010

Reaction of ammonium
thiocyanate with dihalocarbonyls of molybdenum and

tungsten(11) leads to the
elimination of ammonium chloride and the formation of a dithiocyanatocarbonyl
complex of the transition metal. Although the thiocyanatocarbonyls
themselves have not been isolated in a pure state, a number of substituted
derivatives with phosphorus donor ligands have been prepared and characterized.
In general these complexes are less stable than the corresponding carbonyl
halide derivatives.
Absolute stereochemistry of calopiptin
Authors: Mc Alpine JB , Riggs NV , Gordon PG
Published: September 2010

The α,α?-diaryl-β,β-dimethyltetrahydrofurenoid
lignan, calopiptin, from

Piptocalyx moorei has been converted by demethylenation
and methylation into veraguensin, now also isolated
from Trimenia papuana (both
species, family Trimeniaceae). Ozonolysis yields
(-)-2,3-dimethylsuocinic acid which establishes the
absolute trans configuration of the
methyl groups. The benzylic proton giving a signal at low field from
the other in the p.m.r, spectrum is assigned as trans to the adjacent methyl group by
shielding and spin-decoupling arguments. The signal moves to even lower field
on nitration of one of the aryl groups, identified as 3,4-dimethoxyphenyl
by competitive nitration experiments and high-resolution mass spectrometry.

Calopiptin is 2R-(3,4-dimethoxyphenyl)-3S,4S-dimethyl-5S-(3,4-methylenedioxyphenyl)tetrahydrofuran.
The acylation of wool with active esters
Authors: Holt LA , Leach SJ , Milligan B
Published: September 2010

The reaction of wool with
radioactive acetylating agents, viz. p-nitrophenyl [1-14C]acetate, N-[l-14C]acetoxysuccinimide, p-nitrophenyl [l-14C]-n-decanoate, and di-p-nitrophenyl
[l,10-14C]sebacate, has been studied using
acetic acid, triethylamine, or (in some cases) imidazole as catalyst. An
indirect method of amino acid analysis, in which the acylated
wool is first treated with 1-fluoro-2,4-dinitrobenzene,
was used to estimate the sites
and extents of acylation. However, it was found that
the method was unsatisfactory for studying the acylation
of seryl, threonyl, and tyrosyl residues. In contrast to previous
workers, we found that the above active esters are not specific for the ?-amino
groups of lysyl residues but react also with the
hydroxyl groups of seryl, threonyl,
and tyrosyl residues, especially under vigorous
conditions. The O-acyl groups could be selectively removed by treating the acylated wool with hydroxylamine, although the conditions
required were more vigorous than those necessary for the removal of O-acyl
groups from soluble proteins. Using these conditions the
relative rates of N- and O-acylation of wool with a
variety of (radioactive) acylating agents were
measured.
Quench frequency effects on the nuclear quadrupole resonance of orthoiodophenol
Authors: Clarkson TS , Sullivan WPA
Published: September 2010

When the quench frequency
of a self-quenched spectrometer is varied, the plot of the 127I nuclear
quadrupole resonance signal against quench frequency in o-iodophenol,
at room temperature, exhibits a number of maxima. Hitherto, analogous plots
with chlorine compounds, using self-quenched spectrometers, gave only a
maximum; this is briefly discussed.
Rates of substitution of the hydrated beryllium cation by hydrogen fluoride and fluoride ion
Authors: Baldwin WG , Stranks DR
Published: September 2010

The rate of formation of
the monofluoroberyllium species Be(OH2)3F+
was measured by a conductimetric stopped-flow technique. At acid
concentrations exceeding 0.01M two parallel reaction paths were identified:

Be(OH2)42+ +F- ↔ Be(OH2)3F+ (k1,k-1)

Be(OH2)42+ +HF- ↔ Be(OH2)3F+H+(k2,k-2)

At 25� and an ionic
strength of O.2M, k1 = 724 � 95 l. mole-l sec-1
and k2 = 73 � 3 l. mole-1 sec-1. Both substitution paths
exhibit activation energies of 8.9 � 0.8 kcal/mole. The data are interpreted in
terms of an SN11P mechanism which is also proposed for the analogous
Be2+ + SO42-
reaction. Outer-sphere ion pairs of Be(OH2)42+
with respectively F-, HF, and SO42- undergo substitution
with the same activation energy. A linear free energy relation exists between
the rate of formation of the inner-sphere complexes from the outer-sphere ion
pairs and the accompanying free energy changes.
Preparation of some substituted fluoranthenes: A synthetic approach to the corannulene ring system
Authors: Craig JT , Robins MDW
Published: September 2010

A number of methods for the
preparation of 7,l0-disubstituted fluoranthenes have
been investigated and fluoranthene-7,l0-diacetic acid
has been synthesized. Attempts to cyclize this to a derivative of ibenzo[ghi,mno]fluoranthene were unsuccessful.
VESCF-MO studies of molecules containing atoms from the second row of the Periodic Table. II. Properties of the fluorides of silicon, phosphorus, sulphur, and chlorine for a minimal basis set excluding 3d-orbitals
Authors: Brown RD , Peel JB
Published: September 2010

A study has been made of
the electronic structures of the fluorides of silicon, phosphorus, sulphur, and chlorine by the VESCF molecular-orbital method
with a minimal basis set, not including 3d-orbitals
on the central atom. It proves possible to understand variations in bond
lengths and charges on fluorine ligands, dipole moments, force constants, and
some n.q.r. data. The calculations are found to be sensitive to assumptions
about scaling factors for monocentric coulomb
repulsion integrals and penetration integrals. We have not discovered any
justification for including 3d-orbitals in the
description of the electronic structure of these molecules.
Organomercury compounds. VIII. The preparation of pentafluorophenylmercury compounds by mercuration reactions
Authors: Deacon GB , Taylor FB
Published: September 2010

Pentafluorophenylmercuric carboxylates, C6F5HgOCOR
(R = CF3, CHF2, CH2F, or CH3),
have been prepared by reaction of pentafluorobenzene with the appropriate
mercuric carboxylate. The compounds are monomeric in toluene, and their
infrared spectra suggest the presence of unidentate carboxylate groups. Mercuration
of pentafluorobenzene with mercuric trifluoroacetate, followed by reaction of
the crude product with sodium iodide in aqueous ethanol, gives a good yield of bispentafluorophenylmercury.
A study of alkylthioantimonites Sb(SR)3
Authors: Mehrotra RC , Gupta V , Chatterjee S
Published: September 2010

Alkylthio derivatives of
antimony(111) Sb(SR)3 (R = Et, Pr, Pr1, Bu, Bu1,
Bus, But, and Pentt)
have been synthesized in high yields by reaction of SbCl3
with thiol in the presence of ammonia. An attempt has been made to throw some
light on the mode of their decomposition.
Raman spectra of rnercury(II) nitrate in aqueous solution and as the crystalline hydrate
Authors: Cooney RPJ , Hall JR
Published: September 2010

Raman spectra of mercury(II)
nitrate in concentrated aqueous solutions (0.7-7.0M) indicate that the nitrate
groups are present as associated ions or covalently bound groups. A gradual
alteration in the appearance of the nitrate spectrum with increasing concentration
is explained in terms of changes in the nature of mercury-nitrate interaction.
A Raman line assignable to the stretching of a mercury-nitrate covalent bond
has been observed at c. 270 cm-1. The spectrum of solid Hg(NO3)2,H2O
differs from spectra of the aqueous solutions, mainly in the region 1300-1450
cm-1. Additional features are attributed to the influence of
hydrogen bonding in the crystal lattice or to correlation field effects
(anion-anion coupling).
Some A-ring functionalized kaurenes
Authors: Ghisalberti EL , Jefferies PR , Middleton EJ
Published: September 2010

The preparation of some
(-)-kaur-16-enes carrying A-ring functionality analogous to some of the
gibberellins is described. Thus kaura-2,16- dienes, chosen as analogues of
gibberellin A5, have been derived from the succinate (VII) and the kaurenol
(VIII). The succinate has also provided a simple route to (-).kaur-16-ene-3β,19-diol.
Intramolecular opening of the 2β,3β-epoxy function by the 19-hydroxyl
group provides the oxetane (XXIV) from which (-)-kaur-16-ene-2α,19-diol
has been prepared.
Quantum theory of bridge group assisted charge transfer between ions in solution
Authors: Schmidt PP
Published: September 2010

By means of the
second-order time-dependent perturbation theory we present a synthesis of the
charge transfer theory of Levich and Dogonadze and the model of bridge assisted transfer
proposed by Halpern and Orgel.
Synthesis of Benz[b]indolizinies and related compounds
Authors: Dalton LK , Teitei T
Published: September 2010

Ethyl 2-pyridylacetate
reacted with p-benzoquinone and p-toluoquinone in acetic acid to give
3-hydroxy- and 1-methyl-3-hydroxy-10- ethoxycarbonylbenz[b]-indolizine
respectively, while 1,4-naphthoquinone yielded the known
12-ethoxy-carbonyl-6,11-dioxo-6,11-dihydronaphth[2,3- b]indolizine. Ethyl
2-pyridylacetate reacted with 2-chlorocyclohexanone and 2-bromocyclohexane-1,3-dione
to give small yields of 10- ethoxycarbonyl- and 10-ethoxycarbonyl-4-oxo-1,2,3,4-tetrahydrobenz-
[b]indolizine respectively.
Nuclear quadrupole resonance of charge-transfer complexes. II. The aminehalogen complexes
Authors: Bowmaker GA , Hacobian S
Published: September 2010

Nuclear quadrupole
resonance frequencies have been measured for some of the halogen nuclei in a
number of crystalline charge-transfer complexes of amines with bromide, iodine,
iodine monobromide, and iodine monochloride. From these measurements it has been
possible to calculate approximate charge distributions for the bromine, iodine
monobromide, and iodine monochloride complexes of 3,5-di-bromopyridine.
The results correlate well with a three-centre delocalized LCAO-MO bonding
theory. The correlation of this MO description with Mulliken's
charge-transfer bonding scheme for n-σ complexes is discussed. This
approach indicates the importance of considering an ?ionic? structure (which
does not involve transfer of charge from the donor to the acceptor) in the electronic
ground state of these complexes.
Alkaloids of Schelhammera pedunculata (Liliaceae). I. Isolation of the alkaloids and the structures of the homoerythrina alkaloids schelhammerine and schelhammeridine
Authors: Fitzgerald JS , Johns SR , Lamberton JA , Sioumis AA
Published: September 2010

The structures of schelhammerine (VIIIa) and schelhammeridine (IX), two major alkaloids from Schelhammera pedunculata F. Muell., have been established. They are the first described
homoerythrina alkaloids, and their relationship to other alkaloids of the family
Liliaceae is discussed. A detailed study has been
made of the 100-MHz N.M.R. and mass spectra of schelhammerine
and schelhammeridine, and the isolation of a number
of other alkaloids from S. pedunculata is described.
Metal complexes of tridentate hybrid ligands. I. Cobalt and nickel conlplexes of ligands containing the donor sequence As-N-O
Authors: Chiswell B , Lee KW
Published: September 2010

The interaction of the new
tridentate ?hybrid? ligand, N-o- dimethylarsino-phenylsalicylaldimine (As-N-O),
with cobalt(II) salts leads to the formation of cationic octahedral cobalt(III)
complexes of the type [Co(As-N-O)2]+. No cobalt(II)
complex entities containing the ligand could be isolated. With nickel(II) salts
three types of octahedral complexes were obtained: (a) [Ni(As-N-O)2],H2O,
(b) Ni(As-N- O)X,-xH2O (X = Cl, Br, or NCS), (c) [Ni2(As-N-O)3ClO4].
Electronic spectra, conductivity measurements, and magnetic data have been used
to determine the structure of the complexes isolated. The ?hybrid? ligand
appears to operate overall as a relatively weak field ligand.