bluuebunny/crossref_metadata_2025 huggingface dataset:
Experimental Designs Balanced for the Estimation of Residual Effects of Treatments
Authors: Williams EJ
Published: September 2010

Where an experiment can be carried out by
applying different treatments in succession to the same unit of experimental
material, accurate comparisons can be made between the effects of different
treatments. To allow for the residual effect of previous treatments on the
result obtained for any given treatment, it is desirable to adjust the results
for such effects. Methods of constructing balanced designs for the estimation of
these residual effects are described in this paper, and are summarized as follows.
Designs balanced for effect of single
preceding treatment: When n, the number of treatments, is even, a
balanced design is possible with n replications ; when n is odd, 2n
replications are required.Designs balanced for the effects of any
number of preceding treatments, ignoring the interaction of residual effects:
When n is a prime or a power of a prime, a balanced design is possible
in n(n-1) replications, which may be set out as a set of n-1 mutually
orthogonal Latin squares, with the same first columns. Designs which are not
expressible as mutually orthogonal Latin squares are also possible. Designs balanced for the effect of the
two preceding treatments and their interactions : A design can be developed from a set of n-l mutually
orthogonal Latin squares obeying certain restrictions.

The method of analysis of designs of this
type is set out in detail, together with a numerical example. Direct effects of
treatments are shown to be only slightly confounded, the maximum confounding
being 4 per cent., when there are three treatments.

These designs have wide applicability
wherever successive treatments can be applied to the same unit of experimental
material.
Estimation of the Error at a Point on a Least-Squares Curve
Authors: Guest PG
Published: September 2010

The estimation of the errors in the values
obtained by fitting a least-squares polynomial to a number of equally-spaced
observations of a variable quantity is discussed. Curves and tables of the
weight function are obtained.
Observations of the Spectrum of High-Intensity Solar Radiation at Metre Wavelengths. III. Isolated Bursts
Authors: Wild JP
Published: September 2010

Observations are described of the spectrum
of " isolated bursts" of solar radio-frequency radiation in the
frequency range 70-130 Mc/s. These bursts last for a few seconds and have a
bandwidth of the order of tens of megacycles per second. Prior observations
indicate that they are not circularly polarized. They occur sporadically, often
in small groups ; many hours sometimes elapse between successive bursts or
groups. Although, in general, their spectra show diverse features, some of them
(referred to as " type III " bursts) are of a distinct type
characterized by a rapid drift, with time, of the frequency of maximum
intensity towards the lower frequencies, at a rate of the order of 20 Mc/s. per
second. Characteristics of the spectra of type III bursts are described in
detail.

The results are discussed and hypotheses
of origin examined. It is shown in particular that the frequency drift of type
III bursts cannot be attributed to the selective group retardation of waves in
the solar atmosphere emanating from a fixed source. The frequency drift may,
however, be associated with the rapid motion of a source travelling outwards
through the solar atmosphere.
Alkaloids of the Australian Eutaceae: Evodia xanthoxyloides F. Muell. II. Isolation of the Alkaloids from the Leaves
Authors: Hughes GK , Neill KG , Ritchie E
Published: September 2010

From the leaves of Evodia xanthoxyloides
nine alkaloids, evoxanthine, melicopidine, evoxine, xanthevodine, xanthoxoline,
evoxanthidine, evodine, evolidine, and evoxoidine were isolated. There was also
obtained a tenth nitrogenous substance (X) which was shown to be
4-hydroxy-2,3-dimethoxy-10-methylacridone. This is not claimed to be an
alkaloid as it may have been formed by demethylation during the isolation.
A Preliminary Survey of 1420 Mc/s. Line Emission from Galactic Hydrogen
Authors: Christiansen WN , Hindman JV
Published: September 2010

A preliminary survey of 1420 Mc/s. hydrogen-line emission has been
made over 270� of galactic longitude extending through the galactic centre, and
anticentre. The radiation source is in the form of a band of varying intensity
along the galactic equator. The maximum brightness temperature is about 100 �K,
in the direction of the galactic anticentre.

Measurements of
line-profile show considerable variation, with a minimum width of 0.12 Mc/s.
Double lines are evident between galactic longitudes 170 and 240� and it is
suggested that these may originate in major structural features of the Galaxy.

The change in the peak
brightness of the line along the galactic equator may result from line
broadening due to galactic rotation. On the other hand it may reveal the existence
of highly emitting regions. The latter interpretation is supported by the
agreement in position of the bright areas for both the line emission and the
continuous spectrum galactic emission.
The dielectric constant of a liquid
Authors: Buckingham AD
Published: September 2010

Some earlier theories in which attempts
have been made to allow for the influence of molecular shape on the static
dielectric constant of a liquid are shown to be inaccurate. A general equation
is derived for the dielectric constant of a liquid, and this is then applied to
a molecular model consisting, in the first instance, of an ellipsoid uniformly
polarized in a principal direction, and secondly, to an optically anisotropic
ellipsoid ; in both cases the surroundings are assumed to form a continuum. The
results of this more general approach applied to several substances are more
satisfactory than those obtained by the original Onsager theory. The theory is
also applied to mixtures, and in the special case of a dilute solution in a
non-polar solvent, the equation of Ross and Sack is obtained when the ellipsoid
is isotropic. A correlation has been noted in the discrepancies found when the
dipole moment of a substance is calculated by means of observations on the pure
liquid and on dilute solutions in a non-polar solvent, using the equations
derived in the present paper.
The alkaloids of Gyrocarpus americanus Jacq
Authors: McKenzie AW , Price JR
Published: September 2010

The bark of Gyrocarpus americanus Jacq.
contains 0.4-0.6 per cent. phaeanthine and 0.6-0.7 per cent. of the quaternary
base d-magnocurarine. The leaves
contain 0.03 per cent. phaeanthine only.
The sesquiterpene alcohol of Myoporum crassifolium Forst
Authors: O'Brien KG , Penfold AR , Sutherland MD , Werner RL
Published: September 2010

The principal sesquiterpene alcohol
(anymol) of the wood oil of Myoporum crassifolium Forst. is a stereoisomer of
bisabolol. A convenient method of detecting methyl groups attached to the
hydroxyl-bearing carbon of tertiary alcohols involves the infra-red examination
of the pyrolysate of the phenylazophenylurethane for bands due to =CH2.
Polarography of some coordination compounds of platinum. I. Hexammineplatinum (IV) and Tris(ethylenediamine)platinum(IV) ions
Authors: Hall JR , Plowman RA
Published: September 2010

The polarographic reduction of
tris(ethylenediamine)platinum(IV) and the hexammineplatinum(IV) ions has been
studied in potassium chloride, potassium nitrate, and potassium nitrate plus
ammonia solutions. Both ions were reduced irreversibly producing similarly
shaped waves, showing well-defined diffusion current regions corresponding to
two-electron reductions of the complexes. A linear relationship existed between
diffusion current and concentration within the range examined. In aqueous
potassium chloride and potassium nitrate media, the waves contained slight
inflexions at positions corresponding to one-electron additions. The phenomenon
suggested the transient presence of platinum(III) ions, and indicated that the
half-wave potential of the reduction of the complexes to the trivalent state
was very close to the half-wave potential of the reduction from platinum(IV) to
platinum(II). The values were so close together as to indicate the
improbability of isolating the trivalent complexes. Gelatin enhanced the
inflexion in the wave but shifted the wave in a more negative direction. An
increased concentration of supporting electrolyte also shifted the wave to a
more negative position. In all cases a continuous discharge began at about -1.3
V (v. S.C.E.). This discharge was so far removed from that of the potassium
ions of the supporting electrolyte that it was attributed to the discharge of
hydrogen. Since the initial reduction of the platinum complexes corresponded to
a two-electron change, it can be represented by reduction to a tetrammine ion.
It is postulated that at higher applied potentials (namely, -1.3 V v. S.C.E.)
the reduction proceeded further, producing platinum metal. This platinum metal
would be in an active state, insoluble in mercury, and being on the surface,
would lower the overvoltage of hydrogen leading to its discharge at a more
positive potential than on a pure mercury surface. This view was supported by
the fact that gas bubbles were observed at the dropping electrode when a
voltage greater than -1.3 V was applied to the electrode for some time. When
ammonia was added to the supporting electrolyte, a wave, without an inflexion,
and corresponding to an irreversible two-electron reduction, was obtained at
more negative potentials. The bivalent tetrammineplatinum(II) and bis(ethylenediamine)platinum(II)
ions also gave polarograms showing the continuous discharge of hydrogen.
New molecular compounds of the layer lattice type. IV. New molecular compounds of boron nitride
Authors: Croft RC
Published: September 2010

Conclusions, arising from theoretical
treatment of data obtained for graphite, indicated that the formation of
intercalation compounds should also be possible with other crystalline
materials possessing accessible intracrystalline space and the capacity for
electronic interaction with intercalated substances.

Crystalline boron nitride, which is
notable as a structural analogue of graphite, was selected as one of the
materials with which to test this hypothesis.

Electronic interaction between boron
nitride and intercalated substances appeared possible by means of either (i)
electron transfer involving normally latent fourth sp3 boron bonds, or (ii)
coordination of intercalated cations by unshared pairs of nitrogen valence
electrons.

The experimental results confirmed these
conclusions.

Failure to intercalate boron trifluoride
and boron trichloride in boron nitride suggests that the unshared pairs of
nitrogen valence electrons are partially conjugated in the boron nitride
planes.

�� Results
of this investigation strongly favour the view that molecular intercalation
shown by graphite is a general phenomenon, likely to occur with any other
crystalline substance which satisfies the two necessary conditions noted
earlier.
Methylsteroids. 2. 3β Hydroxy-4,4,14-Trimethylallopregnan-20-one, a progresterone analogue
Authors: Barnes CS
Published: September 2010

The title compound has been prepared from
lanosterol and may have progestational activity.
The surface conductance of kaolinite
Authors: Street N
Published: September 2010

The surface conductance of kaolinite
particles has been determined and compared with values calculated from measured
ζ-potentials. A reasonable measure of agreement between these values
suggests that the theory is adequate, and indicates that further information
about the behaviour of kaolinite suspensions might be gained from careful
measurements of this phenomenon. The information can also be used to determine
the axial ratios of clay particles.
The separation of sugars on Carbon Columns by Gradient Elution
Authors: Jermyn MA
Published: September 2010

The influence of various factors on the elution of sugars from charcoal columns
by concentration gradients of organic substances dissolved in water can be readily
explained, to the first approximation at least, by considering the sugar and the desorbing
agent as competitors for the same active surface. It is possible to predict the behaviour
of various systems on this hypothesis and to show how various types of separation
can best be achieved. It is possible to separate the series of cello-oligoglucosides from
acid-hydrolysed cellulose with the minimum of manipulation by using suitable conditions
suggested by this study.
Spectra of sulphonyl derivatives. IV. Sulphonic esters
Authors: Freeman DE , Hamble AN
Published: September 2010

The symmetric and asymmetric SO2
stretching frequencies (1190, 1365 cm-1) and the SO2
deformation frequency (565 cm-1) in esters of arylsulphonic acids
are similar to those for sulphonyl chlorides. A frequency of about 800 cm-1
can be correlated with the presence of the SO2.OR group and is
probably the S-OR bond stretching vibration. The corresponding frequencies in
methyl methane sulphonate are slightly lower. A doubling of some frequencies is
attributed to the occurrence of rotational isomerism in the sulphonic ester
group.

The frequency noted by Ham and Hambly
(1953b) and suggested as characteristic of aromatic sulphonyl derivatives
corresponds to a very constant vibration 1098-1099 cm-1 in the
aromatic esters studied.
The sulphides, Selenides, and Tellurides of Titanium, Zirconium, Hafnium, and Thorium. I. Preparation and characterization
Authors: McTaggart FK , Wadsley AD
Published: September 2010

The nine systems Ti-S, Ti-Se, Ti-Te, Zr-S,
Zr-Se, Zr-Te, Hf-S, Hf-Se, and Hf-Te have been investigated by X-ray techniques
for the occurrence of phases between the compositions AXmax.
and AX. Compounds were prepared from materials of high purity by direct
synthesis from the elements, or by degradation of a higher to a lower phase.
All manipulation was done in dry argon. Several new compounds are reported,
some major differences in the type of phase formed by zirconium and hafnium are
noted, and a different interpretation of the X-ray data for the AX3
compounds is discussed.
The Second Virial Coefficients of Some Cyclic Hydrocarbons
Authors: David HG , Hamann SD , Thomas RB
Published: September 2010

This paper reports some measurements of the second virial coefficient B of cyclopropane in the temperature range 300 to 400°K . It also gives some values of B for
cyclohexane and benzene, derived from critical analyses of the published vapour densities
and P-V-T properties of these gases between 300 and 650°K . In each case the results
have been fitted to the relation
B = α + β/T + γ/T2 + δ/T3
The following conclusions can be drawn :
(i) The values of B for benzene and cyclohexane are consistent with the effects of
pressure on the enthalpies and heat capacities of the gases.
(ii) cycloHexane and benzene show large and almost equal deviations from the
law of corresponding states for monatomic gases, but cyclopropane shows a much smaller
deviation.
(iii) It is impossible to fit the second virial coefficients of benzene and cyclohexane
to the theoretical curve for a Lennard-Jones (12,6) gas. But they can be fitted to the
curve for a (28,7) gas, and the associated force constants are physically reasonable.
It appears that the interaction potential for cyclopropane molecules is intermediate
between the (12,6) and (28,7) potentials.
Reactions of carbon with atomic gases
Authors: Blackwood JD , McTaggart FK
Published: September 2010

Wood chars were reacted at atmospheric
temperature with hydrogen atoms, oxygen atoms and carbon monoxide, hydrogen
atoms and hydroxyl radicals, produced by the action of a radio frequency field
on hydrogen, carbon dioxide, and water vapour respectively. The chars were
prepared at different temperatures and contained different amounts of oxygen.
The experimental results showed that the gases must be present in the atomic
form before reaction with the carbon can take place and that such species react
on the carbon-surface independently of active sites.

In normal gasification processes the
atomic species appear to be produced at active centres, which for the chars
used could be correlated with specific oxygen groups remaining in the carbon.
It is suggested that these groupings may have a pyran structure. An explanation
has been put forward for the retardation of the carbon-water vapour reaction by
hydrogen, and of the carbon-carbon dioxide reaction by carbon monoxide. These
are considered as due to reverse mechanisms which decrease the concentration of
the atomic species and not to the blocking of active sites by adsorption of the
retardant.
The Variable Electronegativity Method. IV. Glyoxaline, Its Cation and Anion
Authors: Brown RD , Heffernan ML
Published: September 2010

Results of VESCF calculations of the π-electron
distribution and ionization potentials in glyoxaline and its cation and anion
are reported. The electron distributions in these systems are in accordance
with the electrophilic substitution reactions observed for glyoxaline and bear
out the concept of electronegativity reversal in the anion previously suggested
to account for chemical properties of glyoxaline.

The dipole moment of glyoxaline, evaluated
from the calculated π-electron distribution, agrees with the observed
moment, providing further vindication for the VESCF method and support for the
suggestion that σ-bond polarizations in heterocycles are slight.

Values of the Huckel coulomb and resonance
parameters required to make the H�ckel method reproduce the VESCF results for
these heterocycles are considered in some detail and it seems feasible to set
up empirical rules for selecting appropriate values for the coulomb parameters.
Intramolecular van der Waals-London Cohesions and Chemical Reactivity: The Transition State in the Bimolecular Nucleophilic Displacement Reaction of Halide Ion with Alkyl Halide
Authors: Spinner E
Published: September 2010

The intramolecular London-van der Waals
cohesions in the transition states Hal�-.
. . CH3 . . . Hal�-
in which both halogen atoms are identical should be greater than the following
: Hal=F, 0.09 ; Hal=Cl, 0.64 ; Hal=Br, 0.94 ; Hal=I, 1.15
kcal/mole. It is concluded that these cohesions make a significant contribution
to the observed increase in the velocity of the above displacement reaction as
the polarizability of either entering or leaving halogen atom increases.
The Chemistry of Sugar-Cane Wax. I. The Nature of Sugar-Cane Wax
Authors: Lamberton JA , Redcliffe AH
Published: September 2010

Distillation of sugar-cane cuticle wax
under reduced pressure gives a high yield of long-chain aldehydes, which are
considered to occur in the wax in polymeric form. The products obtained from
the wax under normal saponification conditions are apparently produced from the
aldehydes by a Cannizzaro reaction, and by aldol condensation with subsequent
dehydration. The cuticle wax also contains hydrocarbons and free alcohols and
acids, but there is no conclusive evidence for the presence of esters.
A Corresponding States Treatment of the Speed of Sound in Simple Liquids
Authors: Hamann SD
Published: September 2010

It is shown that the speed of sound in the
simple liquids A, N2, O2, CH4 conforms to the
principle of corresponding states as formulated by de Boer in molecular units.
The lighter liquids H2 and He show negative deviations which are
proportional to their quanta1 parameters Λ*. CCl4
shows a positive deviation which is most likely due to a difference in the form
of its intermolecular potential from that of the other liquids.

A simple theory is presented for the speed
of sound in a hypothetical liquid at absolute zero. The calculated value is
consistent with the experimental data at finite temperatures.
The Reaction of Thiol and Disulphide Groups with Mercuric Chloride and Methylmercuric Iodide. II. Fibrous Keratins
Authors: Leach SJ
Published: September 2010

The reaction of HgCl2 with wool
has been studied polarographically over the pH range 1 to 9 under various
conditions. At pH 1 to 6 the salt appears to be bound in the un-ionized form
probably at amide and peptide group sites. The binding is greatly suppressed in
the presence of complexing anions such as Cl- and S2O3=.
SO3= also has this complexing effect but in addition
produces new -SH binding sites by reversibly splitting -SS- bonds. This
splitting proceeds to completion at pH 7 to 10 in the presence of an excess of
mercurial, HgCl2 requiring several days and MeHgI several hours. The
reaction of keratins with SO3= and mercurials may be
followed polarographically and has provided a convenient method of preparing
keratins with zero or decreased -SS- bond contents.

The reaction rate increases in the
presence of 8~ urea and then forms the basis for new analytical methods of
measuring the -8s- content of intact keratins. The keratin (7.5 mg or more) is
reacted with Na2SO3 in 8M urea
(5 ml) for at least 24 hr (with excess HgCl2) or 2 hr (with excess
MeHgI) at 20 �C. Single current readings at -1 0 and -0.8 V (v. S.C.E.)
respectively at the dropping mercury electrode indicate the residual mercurial
and hence by difference the (-SS- plus -SH) content. The -SH content of intact
keratins is estimated by reacting say 25 mg with excess MeHgI at pH 7 for at
least 4 hr at 20 �C in the absence of SO3=. This
mercurial reacts much more rapidly with the -SH sites in keratin than do other
mercurials.
Terpenoid Chemistry. V. Preparation of Pure Humulene
Authors: Hildebrand RP , Sutherland MD
Published: September 2010

Humulene may be purified by
recrystallization of the silver nitrate adduct, C15H24.2AgN03,
followed by regeneration of the hydrocarbon by either steam distillation or
treatment with aqueous ammonia solution. The pure hydrocarbon, isolated as 25
above from the essential oil of Agonis abnormis, has b.p. 123 �C/10 mm, [α]D25
� 0.0�, nD25 1.5015, and d425
0.8865.
The Formation of 4-Pyridine Methanol from Isonicotinic Acid Hydrazide (Isoniazid) by Mycobacteria
Authors: Youatt J
Published: September 2010

4-Pyridine methanol has been isolated and
identified as a breakdown product of isonicotinic acid hydrazide (isoniazid) by
Mycobacterium tuberculosis B.C.G. The methiodide and hydrochloride mere
prepared and analysed and mixed melting points were determined with synthetic
4-pyridine methanol derivatives. Ultraviolet and infrared spectra are shown.
Deuterium Exchange Reactions with Substituted Aromatics. II. The Monohalogenated Benzenes and Naphthalenes
Authors: Garnett JL , Sollich WA
Published: September 2010

The platinum-catalysed exchange between
heavy water and the monohalogenated benzenes and naphthalenes has been studied
at 130-180 �C. Rate of exchange is found to decrease with increasing size of
halogen substituent. Naphthalene derivatives exchange more slowly than the
corresponding members of the benzene series. Rate of exchange increases with
increasing ionization potential. From this correlation it is postulated that
chemisorption of aromatic molecules on active platinum occurs through π-complex
formation. In the benzene series, exchange in the ortho-position is slower than
in the meta- or para-positions which react at approximately the same speed.
ortho-Exchange increases with increasing size of halogen substituent. This
deuteration technique is applicable to tritium labelling especially for
aromatics since radiochemical by-product formation is minimized.
The Synthesis of Ethyl β-(4-Cyano-5-benzyloxy-3-indole)propionate
Authors: Robinson P , Slaytor M
Published: September 2010

The synthesis of ethyl β-(4-cyano-5-benzyloxy-3-indo1e)propionate in 10 steps from 3-cresol is
described.
Alkaloids of the Australian Apocynaceae: Kopsia longiflora Merr. III. Preliminary Degradation of the Alkaloids
Authors: Crow WD , Michael M
Published: September 2010

Graded alkaline hydrolysis of the monoacid
tertiary bases kopsiflorine (C23H28O5N2),
kopsilongine (C24H30O6N2), and
kopsamine (C24H28O7N2) shows that
they contain two methoxycarbonyl groups. All but one of the residual oxygen
atoms are accounted for as aromatic ether linkages. One of the methoxycarbonyl
groups is responsible for the deactivation of the other nitrogen atom (N(a))
present, since anew basic centre is generated by partial hydrolysis and
subsequent decarboxylation of the acid produced. The alkaloids are tentatively
formulated as blocked indoline bases containing a urethane grouping at N(a).
The fourth alkaloid, kopsinine (C21H26O2N2)
is similarly formulated, but in this case N(a) is weakly basic, the urethane
methoxycarbonyl group and the additional oxygen atom being absent.
The Interaction of Various Ligands with Halogen-Bridged Anionic Complexes of Bivalent Platinum and Palladium
Authors: Livingstone SE , Whitley A
Published: September 2010

The interaction of various unidentate
ligands (L) with the halogen-bridged anionic complexes [NEt4]2[M2X6]
(M=Pt,Pd; X=Br, I) has been investigated in acetone
solution. Compounds of the type [NEt4][MLX3]
were isolated in a number of instances when M=Pt, but in only one instance when
M=Pd.
The Preparation and Resolution of the Bis(oxalato)-2,2'-bipyridinechromate(III) and Bis(oxalato)-1,10-phenanthrolinechromate(III) Ions
Authors: Broomhead JA
Published: September 2010

The new mixed complexes, potassium
bis(oxa1ato)-2,2?-bipyridinechromate(II) and potassium bis(oxalato)-1,10-phenanthrolinechromate(III)
have been prepared by the reaction of the monobipyridine or phenanthroline
chromium(III) complex with potassium oxalate in aqueous formamide solution.
Both complexes have been resolved using optically active
oxalatobis(ethylenediamine)cobalt(III) chloride. The optical forms were
observed to racemize in solution.
Electrochemical Studies on Eriochrome Violet B and Its Lanthanide Complexes. II. Controlled-potential Coulometric Studies
Authors: Florence TM , Aylward GH
Published: September 2010

Controlled-potential coulometric studies
of Eriochrome Violet B (5-sulpho-2-hydroxy-benzeneazo-2-naphthol) using a
stirred mercury pool cathode have shown that four electrons per molecule of dye
are required for the reduction and that the amines are the final reduction
products both in acidic and basic media. The lanthanide-dye complexes are
reduced in a similar manner to the free dye.

The reduction of Eriochrome Violet B does
not obey first-order kinetics, and the observed reaction rate may be related
qualitatively to a disproportionation mechanism involving an unstable hydrazo
compound. The coulometric and polarographic behaviour of Eriochrome Violet B
has been compared with that of the uranium system, which is well known to
involve a disproportionation step.
Kinetics of Alkyl-oxygen Fission in Ester Hydrolysis: Tertiary Amyl and α-Methylallyl Esters
Authors: Harvey GJ , Stimson VR
Published: September 2010

The rates and Arrhenius parameters for the
acid-catalysed hydrolyses of tertiary amyl 2,4,6-trimethylbenzoate and benzoate
and α-methylallyl 2,4,6-trimethylbenzoate,
benzoate, and acetate in aqueous acetone imply that reaction occurs by
mechanism AALl
for the former group and that a transition from mechanism AALl to AAC2 occurs between the
benzoate and acetate in the latter series.
Coordination Compounds of Substituted 1,lO-Phenanthrolines and Related Dipyridyls. IV. Physicochemical Study of Complexes of Copper and 2,9-Dimethyl-1,10-phenanthroline
Authors: Hall JR , Marchant NK , Plowman RA
Published: September 2010

The magnetic susceptibilities,
conductivities, and infrared spectra of some complexes of copper and
2,9-dimethyl-1,10-phenanthroline (dmp) have been obtained. The magnetic moments
of the copper(II) compounds lie in the range 1.9 to 2.0 B.M. Complexes of
formula CudmpX2, where X = NO3,
Cl, and Br, are nonelectrolytes in nitrobenzene. The substances Cu(dmp)2X2H2O
and hydrated forms of the compounds Cu(dmp)2XClO4,
where X = NO3, Cl, and Br behave as 1 : 1 electrolytes. The copper(II)
ion in the bis complexes is at least five-coordinate and it is proposed that
the donor nitrogen atoms take up a flattened tetrahedral arrangement. The
complexes of formula Cu(dmp)2X, where X = NO3, ClO4,
Cl, Br. I, and I3 are diamagnetic solids, 1 : 1 electrolytes in
nitrobenzene, and are expected to have a tetrahedral arrangement of the four
donor nitrogen atoms about the copper atom. The mono complexes CudmpX, where X = Cl, Br, and I are diamagnetic,
practically insoluble in organic solvents, and probably dimeric with a tetrahedral
arrangement of the ligand donor atoms.
Copper(II) Complexes of 2-Pyridinaldoxime
Authors: Green RW , Svasti MCK
Published: September 2010

2-Pyridinaldoxime (HL) forms complexes
with copper(II) from which the oxime proton may or may not be lost. In addition
to the species Cu(HL)22+ and CuHL2+,
already known, this paper describes the uncharged complexes CuHLCl2,
CuL(OH).H2O, and CuL2.�H2O,
together with salts of the polynuclear cation, Cu3L3OH2+.
The Formation of Aromatic Hydrocarbons at High Temperatures. XVII. The Pyrolysis of a Petrol
Authors: Badger GM , Donnelly JK , Spotswood TM
Published: September 2010

The pyrolysis of a premium grade petrol at
700�C has given a tar in which 46 different aromatic compounds have been
identified. The relative concentrations of some of the polynuclear hydrocarbons
present have been compared with those obtained from the analysis of vehicular
exhaust tars.
Flavan Derivatives. VIII. The Configurations of Some Flavan-3,4-diols Determined by Oxidation with Lead Tetra-acetate
Authors: Clark-Lewis JW , Williams LR
Published: September 2010

Rates of oxidation with lead tetra-acetate
have been used to establish the geometrical configurations of some
flavan-3,4-diols. Mollisacacidin trimethyl ether is thereby shown to be a
trans-glycol, and it is confirmed that (-)-teracacidin trimethyl ether and
(-)-melacacidin tetramethyl ether are cis-glycols.
Tosyl-a-amino Acids. III. The Acid-catalysed Degradation of Tosyl-α-amino Acids and Derivatives
Authors: Beecham AF
Published: September 2010

Tosyl-α-amino acids, their chlorides
and esters, evolve carbon monoxide when dissolved in concentrated sulphuric
acid. Toluene-p-sulphonamide and a carbonyl compound are produced when water is
added to the resulting solutions. The ease of degradation depends upon the
nature of the substituents at the α-carbon atom. The relationship of these
to similar degradations of substituted α-amino acids is discussed.
Synthetical applications of activated metal catalysts. XXI. The formation of carbazole from aniline and related compounds in the presence of degassed Raney nickel
Authors: Jackson GDF , Sasse WHF
Published: September 2010

Trace amounts of carbazole are formed by
the action of W-7J Raney nickel on aniline, diphenylamine,
2,2'-diaminobiphenyl, and 2-aminobiphenyl. Aniline yields also
N-cyclohexylaniline, diphenylamine, 2,2'-diaminobiphenyl, and 2-aminobiphenyl;
2,2'-diaminobiphenyl gave 2-aminobiphenyl also. Carbazole was not detectably
affected by the catalyst. These results suggest that aniline is slowly
converted to carbazole (a) by way of diphenylamine; (b) by way of 2,2'-diamino-
biphenyl and 2-aminobiphenyl; and (c) by way of 2,2'-diaminobiphenyl. The last
route appears to be the most efficient one.
Correlation of N.M.R. chemical shifts of amino protons of anilines with Hammett substituent constants
Authors: Dyall LK
Published: September 2010

The chemical shift of the amino protons in
20 anilines in acetonitrile solution has been correlated with the Hammett
constant of the meta or para substituent. The excellent linear correlation for
18 of these anilines has been used to determine the σ- value
for the benzoyl substituent. A less precise linear correlation was observed for
the 13 anilines soluble enough to study in carbon tetrachloride solution. A
similar relationship can be obtained from deuterochloroform solution spectra.
Theory of Faradaic distortion: Equation for the second-harmonic current
Authors: Bauer HH
Published: September 2010

An equation is derived for the magnitude
of the second-harmonic current under ax. polarographic conditions. It is shown
that the concentration changes of the depolarizer at the electrode surface do
not contain second-harmonic components.

The theory permits determination of the
rate constant and transfer coefficient, for processes of greater speed than are
amenable to elucidation by faradaic-impedance measurements. Furthermore, the
major experimental difficulties in faradaic-impedance studies (base current,
voltage drop in the series resistances) are virtually absent in second-harmonic
work.

Second-harmonic studies also promise to be
advantageous in the elucidation of adsorption effects in electrochemical
reactions.
Rate expressions for chain reactions catalysed by molecules of type HX
Authors: Failes RL , Stimson VR
Published: September 2010

Rate expressions for some chain reactions
with catalysed chains or catalysed initiation, or both, are listed.
Heats of formation of zirconium hydrides
Authors: Turnbull AG
Published: September 2010

Heats of solution in 3.83N HF have been
measured for zirconium metal and for five zirconium hydrides to evaluate the
following heats of formation AHf0298:
ZrH2 -39.7, ZrH1.85 -38.2, ZrH1.70. -34.7, ZrH1.43 -30.05, ZrH1.23 -25.3 kcal/mole hydride. A
review of heat capacity and entropy data for zirconium hydrides has enabled a
good correlation to be made between calorimetric and dissociation pressure
studies, so that the effect of composition on all thermodynamic properties is
established.
Reactions of alkoxy radicals. IV. Intramolecular hydrogen-atom transfer in the presence of cupric ion: A novel directive effect
Authors: Acott B , Beckwith ALJ
Published: September 2010

2-Methyl-2-hexyloxy radical (V), generated
by ferrous-ion reduction of 2-methyl-2-hexyl hydroperoxide, undergoes
intramolecular hydrogen-atom transfer to the extent of 44%, yielding
2-hydroxy-2-methyl-5-hexyl radical (XIII). Oxidation of the latter with cupric
ion in acetic acid affords a mixture of 2-methyl-4-hexen-2-ol (XXI) and
2-methyl-5-hexen-2-ol (XX). Similar results were obtained using radicals
derived from 2,5-dimethyl-2-hexyl hydroperoxide and 2-methyl-2-heptyl
hydroperoxide. In each case the preponderant formation of the unsaturated
alcohol having an olefinic link in the δ-position with respect to the
hydroxy group demonstrates the operation of a novel directive effect, for which
a possible mechanism is discussed. Some other examples of metal-ion oxidation
of alkyl radicals are described. No product arising from intramolecular
hydrogen-atom transfer was isolated from ferrous-ion reduction of
2,4,4-trimethyl-2-pentyl hydroperoxide.
Infrared spectrum, potential constants, and structure of thio-thionyl fluoride
Authors: Brown RD , Pez GP , O'Dwyer MF
Published: September 2010

An investigation of the infrared spectrum
of gaseous thio-thionyl fluoride (SSF2) results in the following
assignment of fundamentals: A': v1 760.5�0.2cm-1, v2
718.5�0.2 cm-1, v3 411.2�0.4cm-1, v4
364.1�0.3 cm-1. A": v5 692.3�0.8cm-1,
v6 337.6�0.4 cm-1. A normal coordinate
vibrational analysis has been performed and a set of ten force constants
evaluated. Some conclusions are given regarding the electronic structure of SSF2.
Thermodynamic functions based on the usual assumptions have been calculated for
SSF2. A set of potential constants has been evaluated for disulphur monoxide, SSO, using the available infrared data.
An analysis of the band envelopes of the trans and gauche tin-carbon stretching frequencies
Authors: Cummins RA
Published: September 2010

An attempt has been made to explain the
apparent absence of symmetric and asymmetric components in the absorption bands
of the tin-carbon stretching frequencies of certain alkyltin compounds.
Although the number of possible conformations increases with degree of alkyl
substitution on the tin atom, results indicate that certain conformations are
preferred. Although in the crystalline state the stable conformation is trans,
it is shown that on successive replacement of alkyl groups by chlorine atoms it
is the gauche form that is preferred, although never exclusively.
Glycolamide esters of N-acylamino acids and peptides
Authors: Stewart FHC
Published: September 2010

The glycolamide esters, RNHCHR'CO2CH2CONH2,
of several N-acylamino acids have been prepared. Model experiments indicate
that the glycolamide group possesses weak acylating ability in simple peptide
coupling reactions, but that it can be dehydrated under mild conditions with
formation of cyanomethyl esters, which are known to be active acylating agents.
The possible application of the glycolamide derivatives in peptide synthesis is
considered. A number of protected dipeptide glycolamide esters were also
synthesized.
Substituent effects in naphthalene. I. The syntheses of 4,5,6,7, and 8-substituted 2-naphthoic acids
Authors: Adcock W , Wells PR
Published: September 2010

The syntheses of 44 2-naphthoic acids
substituted in the unhindered 4, 5, 6, 7, and 8-positions are described. The
substituents are the nitro, cyano, fluoro, chloro, bromo, iodo, methyl,
hydroxy, methoxy, amino, and dimethylamino groups.
Photochemical reactions of azo compounds. V. Photochemical cyclodehydrogenations of Amino-, Acetyl-, and Nitro-azobenzenes
Authors: Badger GM , Joshua CP , Lewis GE
Published: September 2010

4-Benzdaminoazobenzene and
4,4'-bisbenzalaminoazobenzene have been shown to undergo photochemical
cyclodehydrogenation in concentrated (98%) sulphuric acid to give
2-aminobenzo[c]cinnoline and 2,9-diaminobenzo[c]cinnoline respectively in
excellent yields; but 4-aminoazobenzene and 4,4'-diaminoazobenzene were not
cyclized. 3-Arninoazobenzene and 3-benzalaminoazobenzene both gave
3-aminobenzo[c]cinnoline. 3-Nitro- and 3-acetyl-azobenzenes gave 3-nitro- and
3-acetyl-benzo[c]cinnolines; and 4-nitro- and 4-acetyl-azobenzenes gave
2-nitro- and 2-acetyl-benzo[c]cinnolines.
Proton magnetic resonance spectra of some β-methylstyrenes, β,β-dimethylstyrenes, and α-methylstilbenes; and a discussion of long-range shieldingand coupling effects in these and related systems
Authors: Rottendorf H , Sternhell S , Wilmshurst JR
Published: September 2010

The preparation of some new β,β-dimethylstyrenes
and α-methylstilbenes is described and their p.m.r. spectra are reported.
The long-range shielding effects in β,β-dimethylstyrenes and other
styrene derivatives are discussed. The differences between the cisoid and
transoid allylic coupling constants in β,β-dimethylstyrenes are much
smaller than the corresponding differences in simple propenes. No appreciable
(J ≥ 0.3 c/s) coupling between the non-equivalent methyl protons in β,β-dimethylstyrenes
has been observed. Long-range coupling in the compounds investigated appears to
be independent of ring substitution. Some general features of allylic coupling
are discussed.
Thio derivatives of β-diketones and their metal chelates. II. α-Substituted Monothio-β-diketones as ligands
Authors: Ho RKY , Livingstone SE , Lockyer TN
Published: September 2010

The α-methyl substituted monothio-β-diketones,
4-mercapto-3-methylpent-3-en-2-one, MeC(SH)=C(Me)COMe, and
3-mercapto-2-methyl-1,3-diphenylprop-2-en-1-one,
PhC(SH)=C(;Me)COPh, were prepared; the former was not
obtained pure. The complexing ability of these ligands appears to be weaker
than that of other monothio-β-diketones; this can be partly explained on
the basis of steric hindrance caused by the methyl group attached to the
central carbon atom. The diamagnetic complexes, Ni(MeCS=CMeCOMe)2, Co(MeCS=CMeCOMe)3, and Ni(PhCS=CMeCOPh)2 were obtained but attempts to prepare
other metal complexes of these ligands were unsuccessful. The infrared spectra
of the three metal chelates display four characteristic bands for which
assignments are given: 1570-1540 cm-1, v(C--C); 1525-1500 cm-1, v(C-0); 1230-1223 cm-1, v(C--8); 497-458 cm-1, v(M-0).
Octahedral cobalt(III) complexes in dipolar aprotic solvents. II. Association between cis- and trans-dichlorobisethylenediamine cobalt(III) cations,[Co en2 Cl2]+, and chloride and bromide ions in the solvents NN-dimethylformamide, dimethyl sulphoxide, and LVN-dimethylacetamide
Authors: Millen WA , Watts DW
Published: September 2010

Ion association constants
at 30� have been determined for the cis-[Co en, Cl2]+Cl-
ion pair in NN-dimethylformamide (DMF), NN-dimethylacetamide
(DMA), and at 20.0�, 25.0�, and 30.0� in dimethyl sulphoxide
(DMSO), by a spectrophotometric method. Association constants for the cis-[Co en2
Cl2]+Br- and the trans- [Co en2
Cl2]+Cl- ion pairs
have also been determined in DMF at 30�.
Catalysis by hydrogen halides in the gas phase. IX. Tertiary butyl ether and hydrogen bromide
Authors: Stimson VR , Watson EJ
Published: September 2010

The hydrogen bromide catalysed
decomposition of t-butyl ethyl ether takes place at 263-337�. Two major
reactions occur, one producing isobutene by kinetics first order in each
reactant, and the other isobutane by kinetics first order in the ether and zero
order in hydrogen bromide. The latter is extensively inhibited by cyclohexene
and is a radical chain reaction; the former is not inhibited and is presumably
molecular, and on this basis its properties form a smooth sequence with those
of other similar hydrogen halide catalysed decompositions.
Pyrrole studies. VIII. The NH stretching frequencies of substituted pyrroles Acetyl and benzoyl substituents
Authors: Guy RW , Jones RA
Published: September 2010

The infrared spectra of a number of acylpyrroles have been examined in the NH and CO stretching
region under high resolution in carbon tetrachloride. Analysis of the data
show-s that the effect of each group on the NH stretching frequency is
independent of other substituents and additive. Pyrroles having the acyl
substituent in the β-position show two concentration-independent bands.
The lower frequency band arises from interaction with the out-of-plane
deformation of the NH group, producing a hot band.
Magnetism, electronic spectra, and structure of transition metal alkoxides. I. methoxides and ethoxides of chromium(II), manganese(II), Iron(II), cobalt(II), nickel(II), copper(II), titanium(III), chromium(III), and iron(III)
Authors: Adams RW , Bishop E , Martin RL , Winter G
Published: September 2010

The magnetic moments and electronic
spectra are reported for the following divalent transition metal methoxides: Cr(OCH3)2, Mn(OCH3)2,
Fe(OCH3)2, Co(OCH3)2, Ni(OCH3)2,
and Cu(OCH3)2. These measurements when coupled with the involatility and insolubility of the compounds favour
structures based on infinite lattices composed either of regular (Mn, Fe, Co,
and Ni) or distorted (Cr and Cu) MO6 octahedra.
The spectral data place the ligand field parameter, Δ, for the methoxide
group very close to that of water.
The mass spectra of Schiff bases. I. Simple fissions and rearrangements
Authors: Elias DJ , Gillis RG
Published: September 2010

Under electron impact, Schiff bases give a
stable molecular ion which undergoes simple fission at the ring-nitrogen and
ring-carbon bonds. Ortho substitution
leads to ions derived from five-membered heterocycles. Derivatives of o-methoxy-benzaldehyde exhibit a
two-hydrogen transfer with fission of the azomethine
double bond to give the amine radical-ion.
D.C. and sine-wave polarographic studies of the nitrophenols. I. General properties
Authors: Cheah EPT , Hacobian S , Harle AJ
Published: September 2010

The mode of reduction of o-, m-, and p-nitrophenols in the presence and absence of inhibitors
using the combined techniques of d.c, and sine-wave
polarography is discussed. The nitrophenol molecule
is reduced in the adsorbed state at the mercury surface in a stepwise process.
The transfer of the first electron is shown to be reversible and the mechanism
of the initial electrochemical reaction is discussed.
The effect of ionic lattices on the electronic structures of polyatomic ions. I. The triiodide ion
Authors: Brown RD , Nunn EK
Published: September 2010

A VESCF molecular-orbital
study of the electronic structure of the triiodide anion in its crystalline
environment in caesium triiodide and in tetraphenylarsonium
triiodide reveals the effect of the lattices upon the electronic structures.
The calculated total valence-electron energy as a function of the position of
the central iodine nucleus provides an understanding of the observed geometries
of the anion in the two crystals. The energy plot also implies that the
asymmetric stretch of the triiodide is strongly anharmonic in the crystal.

A satisfactory correlation exists between
observed iodine : iodine bond lengths and computed bond orders.
Mixed bidentate and tridentate complexes of cobalt
Authors: Bosnich B , Dwyer FP
Published: September 2010

Two of the three possible
geometric isomers of the ion
chloroethylenediamine-(diethylenetriamine)cobalt(III) ([CoCl en dien]2+)
have been isolated and characterized. A series of complexes of the formula [CoX
en dien]2+ (where X = Cl, Br, I, NCS, and NO3), having
the same isomeric configuration, have been prepared. The preparation of the
complex ion, chloroisobutylenediamine(1ax,3ax,5ax-tri-
aminocyclohexane)cobalt(III) ([CoCl ibn cytam]2+), and of the ligand
isobutylene-diamine is described.
The cyanato and thiocyanato derivatives of Bis(cyclopentadienyl)titanium(IV) and Bis(cyclopentadienyl)zirconium(IV)
Authors: Coutts RSP , Wailes PC
Published: September 2010

The cyclopentadienyl metal
compounds, cp2Ti(NCO)2, cp2Ti(NCS)2, cp2Zr-
(NCO)2, and cp2Zr(NCS)2,
have been prepared and the modes of attachment of the cyanato and thiocyanato
ligands determined by infrared spectroscopy. All are bonded to the metals
through nitrogen and are therefore isocyanato and isothiocyanato derivatives. Cp2Zr(NCO)2 is sensitive to moisture
which converts it into the bridged oxide cp2Zr(NCO)-O-Zr(NCO)cp2. This
reaction can be reversed with anhydrous cyanic acid.
Vibration-spectral studies of compounds formed by the combination of methylformamide and dimethylformamide with some strong acids
Authors: Spinner E
Published: September 2010

A determination of the
infrared spectra of the solid hydrochlorides of methylformamide and
dimethylformamide and of the Raman spectra of their aqueous solutions showed
that certain spectral features change with the medium used. The infrared
spectra of the two amides in concentrated and in aqueous sulphuric acid, and in
concentrated hydrochloric acid (HCl and DCl), are
consistent with the existence of two amide/acid reaction products for each
amide: one (certainly ionic) form predominates in sulphuric acid solutions; a
second form, of unknown structure, is present in the solid hydrochlorides, and
in hydrochloric acid the two forms coexist in equilibrium.
Interaction of acids with halogenated aromatic compounds. I. Infrared spectrum of hydrogen chloride in fluorobenzene and related solvents
Authors: Henry MP , Hambly AN
Published: September 2010

The complex infrared
absorption band of HCl in fluorobenzene at c. 2800 cm-1 is due to
the presence of three solute species; free molecules in cavities, which produce
rotational side bands, molecules hydrogen- bonded to fluorine which give a
sharp absorption band, and molecules bonded to the aromatic π-electron
system which contribute a broader, overlapping band at lower frequency. Similar
multiple absorptions are found for solutions of HCl and DCl
in other fluorinated aromatics, and the asymmetry of the central absorptions
for these solutes in chloro-, bromo-, and iodo-benzenes is attributed to an
unresolved overlap of absorption bands due to halogen-bonded and T-bonded
solute. The specific solvent-solute interaction theory of Bellamy for the
infrared spectra of solutes in mixed solvents is thus extended to single
solvents containing structures which give slightly different interaction
energies with the solute.