bluuebunny/crossref_metadata_2025 huggingface dataset:
A Survey of the Stress between the Ocean and Atmosphere
Authors: Priestley CHB
Published: September 2010

A survey is made of the mean east-west
component of stress between the ocean and atmosphere for each season and each
ocean, and for the mean of all oceans. The averaging is carried out for each
5" latitude zone from 55 �N. to 55 �S.

The results provide a first approximation
to the total torque about the Earth's axis, on the atmosphere as a whole, in
the various latitude belts. From them is derived a table showing the
distribution of total northward flux of atmospheric angular momentum for the annual
mean and the four seasons individually, allowing for the changes occurring
during spring and autumn.

A brief comparative discussion of both the
stress and flux results is given.
Alkaloids of the Australian Rutaceae: Pentaceras australis Hook. F. I. Isolation of the Alkaloids and Identification of Canthin-6-one
Authors: Haynes HF , Nelson ER , Price JR
Published: September 2010

Three alkaloids, with molecular formulae C14H8ON2,
C15H10O2N2, and C15H10OSN2,,
have been isolated from the ram-forest tree Pentaceras australis Hook. f. All
three are present in the bark of mature trees, the total yield of alkaloids
varying from c. 0.2 per cent. (branch bark) to c. 1 per cent. (root bark). The
wood contains 0.2 per cent. of a mixture of two of the alkaloids, C14H8ON2
and C15H10OSN2, while the leaves contain less
than 0.01 per cent. of a mixture in which the alkaloids C14H8ON2
and C15H10O2N2 are present.The
alkaloid C14H8ON2 is shown to be
representative of a ring system not previously found In the plant kingdom. It is
canthm-6-one (II). The principal reactions on which this structure is based are
(a) oxidation of the alkaloid to β-carboline-1-carboxylic acid and (b) the
reversible opening of a lactam ring with alkali to give cis-2-(1'-β-carbolyl)
acrylic acid (III) which may be transformed to the trans-isomer from which the
alkaloid is not regenerated. Other reactions of the alkaloid support the canthinone
structure. Among the compounds described is a dihydro-derivative (XI) of the
parent base canthine
Studies of aggregation in soap solutions containing salt and simple organic molecules
Authors: Stainsby G , Alexander AE
Published: September 2010

Using the synthetic soap cetyl pyridinium
chloride the effects of added chlorobenzene and sodium chloride upon various
physical properties, such as saturation solubilities, viscosity, osmotic
pressure, sedimentation velocity, and interfacial tension, have been
quantitatively measured. The results suggest that the soap micelle has a very
labile structure, the approximately spherical aggregates present in pure soap
solutions changing to more asymmetric shapes in the presence of suitable
concentrations of sodium chloride and chlorobenzene.
The reaction between acetone and ammonia. III. Reduced pyridine, deriviaties
Authors: Hancox NC
Published: September 2010

The preparation of
2,2,4,6-tetramethyldihydropyridine by the reaction of acetone and ammonia at
temperatures of 100-180 �C. has been studied; using an alkaline catalyst at 120
�C. for 3 hr, a yield of over 60 per cent. can be obtained. This dihydro-pyridine
is identical with the product obtained by Matter (1948) in the pyrolysis of
2,2,4,4,6-pentamethyltetrahydropyrimidine Possible mechanisms for its formation
are discussed. Catalytic hydrogenation over Raney nickel leads to
tetramethyl-piperidine, while with palladium a partial reduction product,
formulated as 2,2,4,6-tetramethyl-2,3,4,5-tetrahydropyridine is obtained ; the
chemistry of these reduction products has been examined.
Solvent effects in the spectra of Benzene, Toluene, and Chlorobenzene at 2600 and 2000 Ǻ
Authors: Bayliss NS , Hulme L
Published: September 2010

The ultraviolet spectra of benzene,
toluene, and chlorobenzene at 2600 and 2000 Ǻ have been measured in carbon
tetrachloride, chloroform, cyclohexane, 1%-hexane, ethanol, and water. Compared
with the gases the solution spectra are all displaced to the red by amounts
that agree qualitatively with the predicted effect of the solvent refractive
index and the transition intensity according to the theory of Bayliss (1950).
Quantitative agreement with this theory can be obtained only by assuming the
effective cavity occupied by the solute molecule to be considerably smaller
than the actual molecular size. The significance of this effect is discussed.
The intensities of the solution spectra vary with the solvent refractive index,
but in a way that is incompatible with the classical theory of Chako (1934). A
marked increase in the intensity (particularly in toluene) is found where the
solute absorption is close to an absorption band of the solvent, that is, for
the 2600 Ǻ transitions in carbon tetrachloride and to a less extent in
chloroform. In the 2600 Ǻ transition of benzene, a band appears in water,
chloroform, and carbon tetrachloride that is very close to the position of the
(0,0) band that is forbidden in the gas spectrum. The nature of this band is
discussed.
Natural derivatives of furan. I. Ngaione
Authors: Birch AJ , Massy-Westropp R , Wright SE
Published: September 2010

Ngaione has been isolated from the
volatile oil of Myoporum acuminatum R.Br. and assigned the formula II.
Different specimens of the oil contained other ketones.
The sesquiterpene Alcohols of Eucarya spicata Sprague & Summ
Authors: Birch AJ , Mostyn KMC , Penfold AR
Published: September 2010

The anomalous properties of the santalol
fraction of West Australian sandalwood oil have been explained by the detection
of a considerable proportion of farnesol, which can be reduced by sodium and
alcohol in liquid ammonia to dihydrofarnesene (I), and oxidized by manganese
dioxide to farnesal.
The Alkaloids of Heliotropium europaeum L.. I. Heliotrine and Lasiocarpine
Authors: Culvenor CCJ , Drummond LJ , Price JR
Published: September 2010

The chief crystalline bases of Heliotropium
europaeum L. are heliotrine and lasiocarpine. Three other bases are present,
one in major amount, as also are the N-oxides of all five alkaloids. A method
of assay has been developed, based on partition chromatography, which permits
the estimation of each of the 10 constituents in plant material.
Alkaloids of Evodia alata F. Muell
Authors: Gell RJ , Hughes GK , Ritchie E
Published: September 2010

From the bark of Evodia alata F. Muell.
the known alkaloids, evoxanthine, melicopidine, and kokusaginine have been
isolated.

The leaves contain evoxanthine and two new
alkaloids. These are 2,3,4-trimethoxy-10-methylacridone (I, R=CH3)
and a furoquinoline a kaloid, evolatine. Evolatine is shown by degradation to
be 7-(2',3'-dihydroxy-3'-methylbutoxy)-6-methoxydictamnine (V).
Theory of alternating current polarography. II. Significance of the Heyrovsky-Ilkovic equation and its relation to the production of A.C.Polarogrphic waves
Authors: Breyer B , Bauer HH , Hacobian S
Published: September 2010

The significance of the Heyrovsky-Ilkovic
equation is discussed and the relationship between reversibility of the
electrochemical reaction and polarographic reversibility critically examined.
It is shown that even reversible electrochemical processes might yield D.C.
polarograms of the irreversible type. The relationship between different types
of electrode reactions and the production of A.C. polarographic waves is
elucidated.
The Alkaloids of Erectites quadridentata D.C.
Authors: Culvenor CCJ , Smith DC
Published: September 2010

Senecionine, seneciphylline, and
retrorsine have been isolated from Erectites quadridentata D.C. where they
occur mainly in the form of their N-oxides. The alkaloids, hieracifoline and
pterophine, are shown to be mixtures of senecionine and seneciphylline.
The photolysis of gaseous aldehydes. IV. Mixtures of acetaldehyde with formaldehyde and acetone, and the photolysis of glyoxal
Authors: Dorman FH , Buchanan AS
Published: September 2010

The rate of acetaldehyde photolysis in
presence of acetone showed an increase due to chain initiation by methyl
radicals from the photo-decomposition of the acetone. In the presence of
formaldehyde the acetaldehyde rate decreased, implying that the decomposition
of formyl radicals was slower than that of acetyl. Glyoxal photolysis at long
wavelengths confirmed previously found low ratios of H2 to CO. Added
acetaldehyde and formaldehyde decreased the rate of the photolysis possibly
owing to collisional deactivation of excited glyoxal molecules.
The stretching frequency of the Azo-group in Formazans
Authors: Le Fevre RJW , Sousa JB , Werner RL
Published: September 2010

Infra-red spectra between 680 and 1600 cm-1
are recorded for 10 formazans and five copper complexes derived therefrom. A
common feature at c. 1450 cm-1 in the formazans is removed by
chelation ; it is therefore suggested that 1450 cm-l is the stretching
frequency of -N:N- as modified by conjugation and hydrogen-bonding in a system Ar.N:N.CAr:N-. Analogies with keto-enol systems indicate
that azo- groups in simpler environments would absorb a" higher
frequencies, so that of the two alternatives left open by Le F�vre, O'Dwyer,
and Werner (1953), namely, 1579 or 1406 cm-1, the larger is to be
preferred.
New molecular compounds of the layer lattice type. III. The intercalation of metal sulphides and oxides in graphite
Authors: Croft RC
Published: September 2010

It has been shown that a number of
sulphides and oxides of multivalent metals can be intercalated in graphite. The
results of this investigation support the conclusion, reached in Part II of
this series (Croft 1956a), that the electronic configuration of the cation of a
compound determines the possibility of its intercalation, and that the nature
of the anion has little significance. As in the case of chlorides reported in
Part I of this series (Croft 1956b), the cations of intercalated sulphides and
oxides are in higher valence states.
Thermodynamic properties of alcohol solutions. II. Ethanol and isopropanol systems
Authors: Brown I , Fock W , Smith F
Published: September 2010

New experimental data are given for the
heats of mixing of the systems ethanol+toluene at 35 �C,
ethanol+methylcyclohexane at 35 �C, and iso-propanol+benzene at 45 �C and for
the liquid-vapour equilibrium data for the latter system at 45 �C.

These data have been used together with
previously published data to calculate the excess free energy, heat and excess
entropy of mixing at even mole fractions for the above systems. These functions
have also been calculated from published data for the systems ethanol+benzene
at 45 �C and ethanol+2,2,4-trimethylpentane at 25 �C.
The alkaloids of Echium plantagineum L
Authors: Culvenor CCJ
Published: September 2010

Two new alkaloids, echiumine, C20H31O6N,
and echimidine, C20H31O7N, have been isolated
from Echium plantagineum L. Both have a retronecine nucleus esterified on the
7-hydroxyl group with angelic acid. The main esterifying acid of echiumine is
trachelanthic acid and of echimidine is 2-methyl-2,3,4-trihydroxypentane-3-carboxylic
acid, identical with the esterifying acid of heliosupine. The structure of
heliosupine, a diastereoisomer of echimidine, has been confirmed.
Kinetics of the reaction between Manganese Dioxide and Ferrous Ion
Authors: Koch DFA
Published: September 2010

The kinetics of the reaction between
manganese dioxide and ferrous ion in acid solution have been investigated by
using the potential of the ferrous-ferric couple as a measure of the extent of
reaction. The experimental conditions were such that the reaction rate was
independent of ferrous, ferric, manganous ions, and acid concentrations and the
agitation was sufficient to prevent bulk diffusion in the solution from being a
rate-determining factor.

The reaction rate of sized samples of
pyrolusite and γ-MnO2 in ferrous
sulphate solution was proportional to the surface area of the solid and was
constant (i.e. " zero-order ") until 50 per cent. of the solid was
consumed. γ-MnO2 reacted about twice
as rapidly as the pyrolusite. The reaction occurred most readily at certain
active sites on the particles and appeared to proceed along crystal boundaries
in such a manner that the active surface area was not significantly changed
during the first half of the reaction. In ferrous perchlorate the reaction rate
of 10 μ diameter pyrolusite was about one-hundredth of that in sulphate
and the reaction appeared to occur at a more even rate over the whole surface
of the particle so that the zero-order law was no longer obeyed. Activation
energies of 7.4 and 5 kcal in sulphate and perchlorate respectively, for the
temperature range 18 to 40 �C, suggest that the difference in rate is a result
of a change in the entropy factor of the Arrhenius equation. It is suggested
that this difference in rate may result from the activation, by sulphate ions,
of a less reactive lower oxide of manganese which is formed on the surface.
The kinetics of the pyrolysis of Cyclohexyl chloride.
Authors: Swinbourne ES
Published: September 2010

cycloHexy1 chloride has been shown to
decompose in the gas phase at 318-385 �C almost exclusively to cyclohexene and
hydrogen chloride. With clean glass-walled reactors the reaction was largely
heterogeneous, but after the walls were coated with a carbonaceous film a
homogeneous first-order reaction was found to predominate. For initial
pressures within the range 4-40 cm mercury the rate coefficients for the
homogeneous reaction were expressible as������� k = 5.88 x 1013exp(-50,000 cal/RT)
sec-1. There was some evidence for
the rate coefficient becoming pressure-dependent below 5-10 mm initial pressure
of reactant.

The reaction exhibited no induction
periods and the velocity was virtually unaffected by the addition of large
amounts of propene or cyclohexene and traces of chlorine or bromine. The
results were consistent with a unimolecular elimination of hydrogen chloride.
Magnetic moments of copper(II) complexes
Authors: Ito K , Ito T
Published: September 2010

Magnetic moments of octahedral,
tetrahedral, square planar, trigonal planar, and trigonal pyramidal Cu(II)
complexes have been discussed theoretically including the orbital contribution
on the basis of the molecular orbital theory. It has been shown that the
orbital contribution of electrons to the magnetic moment is expected only in
tetrahedral, trigonal planar, and trigonal pyramidal complexes. The effective
magnetic moment of tetrahedral Cu(II) complexes has been estimated to be about
2.2 at room temperature and that of tri-coordinated Cu(II) complexes to be
higher than the spin-only value. The hypothesis of electron promotion to a 4p
level in Cu(II) complexes has been criticized.
Pyrolytic carbon films from Ethyl Chloride
Authors: Knispel CC , Swinbourne ES
Published: September 2010

The formation of pyrolytic carbon films
during the gas phase decomposition of ethyl chloride at 450 �C has been
followed by measurement of the electrical conductance. On fresh glass surfaces
there was observed an initial induction period of approximately 30 min after
which the conductance rose steadily, the rate of change decreasing as ethylene
accumulated in the system. The time of induction varied with surface treatment
and has been attributed largely to the removal of some substance (e.g. water or
oxygen) from the glass surface. Pressure measurements indicated no appreciable
induction effect for the simultaneous decomposition of the ethyl chloride to
ethylene and hydrogen chloride.

The films of carbonized material were
semiconductive and their electrical resistance was estimated to be very much
greater than that of graphite. (One film had an estimated specific resistance
of 12Ω cm at room temperature.) The electrical properties of the films
were found to vary greatly with changes in the film thickness, the temperature,
the applied voltage, and the pressure of the gases in contact with them. For
these reasons the conductance measurements did not provide an accurate estimate
of the amount of carbon deposited although they did provide information
concerning the physical and chemical nature of the deposit. The behaviour of
the films was consistent with the presence of a high concentration of "
foreign " atoms, groups, and/or molecules at the intercrystal boundaries,
as suggested by other workers.�The
efficiency of these Elms in suppressing heterogeneous reactions is discussed in
terms of the formation of a continuous non-polar coating on the surface of the
glass.
A Method for the Determination of the Structure of Saturated Branched-Chain Fatty Acids
Authors: Murray KE
Published: September 2010

A method is described for the
determination of the structure of branched-chain fatty acids. It is found that
the carbon chain of methyl-branched acids can be readily degraded by potassium
permanganate in acetone, to give a series of acids of decreasing carbon number.
Where a branch occurs the acid series is interrupted and a methyl ketone, of
the same carbon number as a missing acid, is produced. Gas chromatographic
examination of the ketone(s) and esterified acids gives clear evidence for the
location of the branch(es).

The method is illustrated by application
to tuberculostearic acid (10-methyl-octadecanoic acid) and C27-phthianoic
acid (2,4,6-trimethyltetracosanoic acid). It appears also able to decide the
location of the ring in cyclopropane fatty acids.
Surface Properties of Liquid Sodium and Sodium-Potassium Alloys in Contact with Metal Oxide Surfaces
Authors: Bradhurst DH , Buchanan AS
Published: September 2010

Dissolved oxygen was shown to be surface
active in liquid sodium from measurements of surface tension and of contact
angle of the liquid on various oxide surfaces. When sufficient oxygen was
present wetting of UO2 by liquid sodium could be brought about at
temperatures above approximately 300 �C. Observations on the wetting of several
solid oxides by sodium gave some support to the hypothesis that wetting was
more effective on those oxides with larger cations. Sodium-potassium alloys
showed non-wetting contact angles when relatively free of oxygen but wetting
occurred when the oxygen content of the liquid was increased.
The Infrared Spectra of Picryl Compounds
Authors: Dyall LK
Published: September 2010

The infrared spectra of 17 picryl
compounds have been studied in the range 4000-670 cm-1, and
tentative assignments of the observed frequencies have been made.
Colouring Matters of Australian Plants. VIII. Naphthalene Derivatives from Dianella Species
Authors: Batterham T , Cooke RG , Duewell H , Sparrow LG
Published: September 2010

The roots of Dianella laevis contain a
crystalline glycoside, dianellin, and the corresponding aglycone, dianellidin.
Only dianellin has been isolated from D. caerulea. Dianellidin is identified as
1,8-dihydroxy-3-methyl-2-acetonaphthone and the glycoside has the sugars,
glucose and rhamnose, attached at the 8-position. Dianellin is readily
converted into plumbagin and is a possible natural precursor of this and other
naphthoquinones found in plants. There is some evidence for the occurrence of
traces of this type of compound in Dianella roots.
Stereochemistry of Cyclohexane Derivatives. VIII. Structures of Some p-Menth-1-ene-3,6-diols
Authors: Blumann A , Della EW , Henrick CA , Hodgkin J , Jefferies PR
Published: September 2010

A new p-menth-1-ene-3,6-diol, m.p. 112 �C,
has been obtained from Eucalyptus dives residues and by oxidation of (-)-α-phellandrene
with peracetic acid. The structures of the isomers, m.p. 165 and 54 �C, have
been established.
The kinetics of the system carbon-hydrogen-methane
Authors: Blackwood JD
Published: September 2010

In a study of the kinetics of the system carbon-hydrogen-methane, the methane
formation rate was determined at pressures up to 40 atm and in the temperature range
650 to 870°C, and the methane decomposition rate a t pressures up to 20 atm and in
the temperature range 850 to 725°C. The rate of methane formation, expressed as
gram moles per minute per gram of carbon originally in the bed, can be expressed by
the equation
Formula
where k1, k2, k3, k4, and k5 are constants and pH2 and PCh4 are the partial pressures, in
atmospheres, of the hydrogen and methane respectively. A mechanism has been
suggested which involves the formation of >CH2 groups on the carbon surface.
The Pyrolysis of 2-Phenylethylpyridine
Authors: Sweeting JW , Wilshire JFK
Published: September 2010

The pyrolysis of 2-phenylethylpyridine at
700 �C has been investigated and mechanisms are advanced for the formation of
the compounds found in the pyrolysate.
The Kolbe Electrolysis in Acetonitrile as Solvent
Authors: Wilshire JFK
Published: September 2010

The Kolbe electrolysis of benzoic acid in
presence of naphthalene in the aprotic solvent acetonitrile has been studied.
The formation of the benzoates of 1-naphthol and 4-hydroxy-1,1'-dinaphthyl is
ascribed to the intermediacy of benzoyloxy radicals and therefore supports the
currently accepted radical mechanism of the Kolbe electrolysis. The
electrolysis of phenylacetic acid in acetonitrile with triethylamine as
supporting electrolyte was also briefly examined.
The Electronic Structures of A2Y4 Molecules
Authors: Brown RD , Harcourt RD
Published: September 2010

A study of the electronic structures of A2Y4
molecules containing 34, 36, and 38 valence electrons has been made. An
approximate VESCF, molecular- orbital method was used, attention being
concentrated mainly on the delocalization of σ-electrons which are
classically regarded as lone-pairs on the Y atoms. The results provide
explanations of the main features of many of the observed AA- and AY-bond
lengths and YAY-bond angles of N2O4, C2O42-,
B2F4, B2Cl4,
C2F4, C2Cl4,
S2O42-, and N2F4. Other
A2Y4 systems which have either not been fully
characterized or not yet reported are also considered.

The extent of lone-pair delocalization is
shown to be governed by a parameter aσ,
related to the coulomb and resonance parameters of H�ckel molecular-orbital
theory. General trends in the value of aσ
can be predicted from values of the core charges of A and Y towards the
o-electrons concerned. A more detailed "adjacent charge" rule emerges.
It differs from the classical rule in that for A2Y4
systems, adjacent negative formal charges on the A atoms should not very
greatly affect the AA-bond properties.

Difficulties were encountered in
consistently interpreting the properties of some A2F4 and
A2Cl4 compounds. These deserve
further attention.
Studies on the Doebner-Miller, Skraup, and Related Reactions. II. Preparation and Cyclization of 4-(2'-Nitroanilino)-3-methylbutan-2-one
Authors: Badger GM , Ennis BC , Matthews WE
Published: September 2010

The intermediate adduct (e.g. III) formed
in Skraup and Doebner-Miller reactions has the nature of a Mannich base. It has
now been prepared from o-nitroaniline, formaldehyde, and methyl ethyl ketone by
the Mannich reaction. It has been cyclized to 3,4-dimethyl-8-nitroquinoline
under acidic oxidizing conditions; but it is not cyclized by neutral oxidants,
nor by non-oxidizing acids or Lewis acids.
The photochemistry of cis- and trans-1,1-Dimethyldecalin-10-carbonyl azides
Authors: Brown RFC
Published: September 2010

cis- and trans-1,1-Dimethyldecalin-10-carboxylic
acids have been synthesized from 10-ethoxyca~rbonyl-A1~g-octal-2-one by methylation
with methyl iodide and potassium t-butoxide, followed by hydrogenation and
Wolff-Kishner reduction. Photolysis of their acyl azides in cyclohexane gives
the corresponding isocyanates, the tricyclic δ-lactams (XI) (cis) and
(VIII) (trans), and other products.
Organotin carboxylates
Authors: Cummins RA , Dunn P
Published: September 2010

The homologous series of tributyltin
carboxylates ranging from the formate to the stearate and three substituted
tributyltin acetates have been prepared. Examination of the infrared spectra of
the compounds supports the recent view that organotin esters are covalent and
chelated in character rather than ionic compounds.
The chemistry of the Euphorbiaceae. V. The diterpenes from a Beyeria sp
Authors: Baddeley GV , Jarvis MW , Jefferies PR , Rosich RS
Published: September 2010

The isolation of three new diterpenes from
Beyeria brevifolia is described. Evidence is presented which places these in
the 16α-(-)-kaurane [(-)-β-dihydrokaurene] class of tetracyclic
diterpenes and defines the stereochemistry at the additional asymmetric
centres.
The preferred valence states of transition metals
Authors: Sheldon JC
Published: September 2010

It is proposed that the valence number, n,
for bonding in the elemental state may be estimated by n = rΔHf�/C,
where r is half the interatomic distance, -ΔHf� is the heat of formation of the elemental state,
and C is a constant and approximately 28 and 40 Ǻ kcal g-atom-1
for non-metals and metals respectively.

It is shown that the valence states of the
elementary transition metals, as given by n, correspond closely to the most
stable oxidation states (MSOS) displayed in binary transition metal fluorides,
chlorides, and related compounds.

It is concluded that the trend of the MSOS
of transition metal binary compounds results mainly from each metal possessing
a preferred valence state, which is strongly determined by the availability of
the (n-l)d orbitals for bonding as judged by their size relative to that of the
ns and p orbitals.
Spin-spin coupling between side-chain and ring protons and the effect of electron delocalization on allylic coupling
Authors: Rottendorf H , Sternhell S
Published: September 2010

The side-chain-ring coupling constants3 in
the three isomeric tetrachlorotoluenes are Jortho
0.63�0.02 c/s, Jmeta 0.36�0.02 c/s, and Jpara 0.63�0.01 c/s. The magnitudes of
side-chain coupling constants in benzene derivatives are discussed. In symmetrical
six-membered aromatic and heterocyclic compounds the magnitude of the ortho
side-chain coupling constants is approximately 0.6 c/s but varies from less
than 0.3 cis to 1.1 c/s in molecules where some bond localization occurs. Ortho
side-chain coupling constants in five-membered heterocyclic compounds also
appear to be affected by electron localization. It is therefore likely that the
magnitude of the ortho side-chain coupling constants may be a direct measure of
bond order. Long-range coupling data on indole derivatives are reported. In two
β,β-dimethylstyrenes the stronger side-chain to ring coupling is to
the ortho position. The relation between allylic coupling and electron
delocalization is explored and a new criterion for electron delocalization
proposed.
Pyrimidine reactions. VIII. Methiodides formed from some dimethylaminopyrimidines
Authors: Brown DJ , Teitei T
Published: September 2010

4.Dimethylaminopyrimidine and its
2-chloro-, 2-dimethylamino-, 6-chloro-, 6-methylthio-, and
6-dimethylamino-derivatives are quaternized by methyl iodide at N 1. The
structures of the resulting methiodides are proven by alkaline degradation to
known oxopyrimidines. 4-Dimethylamino-2-(and 6-)methoxypyrimidine and
2-dimethylamino-4-methoxypyrimidine all undergo quaternization on a nuclear
nitrogen atom followed by spontaneous loss of methyl iodide to yield
oxopyrimidines (cf. the so-called Johnson and Hilbert nucleoside synthesis).
The unique lability of the dimethylamino group in these quaternary compounds is
exemplified in the con- version of
2-dimethylamino-1,6-dihydro-1,3-dimethyl-6-oxopyrimidinium iodide into
1,3-dimethyluracil by mere dissolution in water or aqueous ethanol, and by the
reaction of 2,4-bisdimethylamino-I-methylpyrimidinium iodide with ethanolic
sodium hydrogen sulphide to give 4-dimethylamino-1,2-dihydro-1-methyl-2-thio-
pyrimidine.
The preparation of dimedone derivatives of amino acids and their use in peptide synthesis
Authors: Halpern B
Published: September 2010

The preparation of dimedone derivatives of
amino acids has been effected by saponification of the corresponding alkyl
esters, and also by catalytic hydrogenation of the respective benzyl esters.
The amino acid derivatives have been used to synthesize peptides in excellent
yields, employing dicyclohexyl carbodiimide as the condensing agent.
Structural investigations of the araban from guava, Psidium guajava L
Authors: Sengupta UK , Mukherjee AK , Rao CVN
Published: September 2010

The pulp of guava, Psidium guajava L.,
contains an araban which can be enriched by extraction with 70% ethanol.
Hydrolysis of the fully methylated pure araban, obtained during fractionation
of the methylated polysaccharide, yielded 2,3,5-tri-, 2,3-di-, and 2-O-methyl-L-arabinofuranose
in the molar ratio of 1 : 1.04 : 0.93, together with a small amount of
arabinose. A structure has been suggested from these results which was
corroborated by results from periodate oxidation studies. Sequence of branching
has been confirmed from Barry degradation studies. Information about molecular
size has been obtained from light scattering measurements.
The preparation of some benzyloxycarbonyl peptide p-nitrobenzyl esters derived from valine and glutamic acid
Authors: Stewart FHC
Published: September 2010

The preparation of three series of
benzyloxycarbonyl peptide p-nitrobenzyl esters is described. In these
derivatives a single L-valyl residue occupies different positions in a chain of
γ-alkyl-L-glutamyl residues. The relative merits of various synthetic
approaches to the compounds are also discussed.
Coordination compounds of substituted 1,10-Phenanthrolines and related dipyridyls. VIII. Complexes of silver and 2,9-Dimethyl-1,10-phenanthroline
Authors: Hall JR , Plowman RA , Preston HS
Published: September 2010

Addition of 2,9-dimethyl-1,10-phenanthroline
(dmp) in organic solvents to aqueous solutions of silver(1) salts yielded mono
complexes represented by AgXdmp, where X = NO3, Cl, Br, I; 2X = SO4,
and bis complexes Ag(dmp),Y, where Y = NO3, Cl04.
Water of crystallization was present only in the sulphate. The mono complexes
were empirically three-coordinate. Low solubility prevented the determination
of molecular weights. Infrared spectra indicated that the polyatomic anions
were covalently bound. The 1 : 1 electrolyte [Ag(dmp)(py)]ClO4
subsequently prepared seemed to be an example of three-coordination. The bis
complexes were 1 : 1 electrolytes in nitrobenzene and were most likely
tetrahedral.
The kinetics of the thermal decomposition of trifluoroacetaldehyde
Authors: Arthur NL , Bell TN
Published: September 2010

The thermal decomposition of
trifluoroacetaldehyde has been studied at temperatures between 471� and 519�,
and at pressures up to 180 mm. The main products of reaction are
trifluoromethane and carbon monoxide in equal amounts; small amounts of hexafluoroethane
and hydrogen are also formed. The experimental rate equation governing the
observed kinetics is of the form Rate = k?[CF3CHO]3/2,
where

k?
= 1012.2exp(-49000/RT) l.� mole-1 sec-1

A small surface effect is
apparent, an increase in surface area causing an increase in rate.

Inert gases, namely carbon monoxide and
dioxide, increase the rate of decomposition, the experimental rate equation
assuming the form

Rate = (k'[CF3CHO]3 + k"[CF3CHO]2.2[M])�

A mechanism is proposed which predict,^ the experimental form of the rate
equation and involves initiation through a second-order energy transfer process
followed by a radical chain mechanism, the length of which is 1200 with P(CF3CHO) = 200 mm.
Termination is considered to be through the third-order recombination of
trifluoromethyl radicals.
Some copper(II) and nickel(II) amine-cyanide derivatives. I. Solution equilibria
Authors: Curtis YM , Curtis NF
Published: September 2010

Addition of cyanide to aqueous solutions
of some copper(II) and nickel(II) tetramine complexes causes an immediate
colour change, from mauve to blue for the copper compounds and orange to pink
for the nickel compounds, these colours then slowly fading to colourless
[Cu(CN)4]3- and pale yellow [Ni(CN)4]2-
respectively as the amine complexes decompose. Spectrophotometric studies on
the solutions indicate that the immediate colour change is caused by the
formation of a monocyanide adduct, the formation constant being of the order of
102 for the copper(II) compounds and 10 for the nickel(II) compound
studied. Measurements of the absorption spectrum and magnetic susceptibility
show that the nickel(II) cyanide adduct has a triplet ground state.
Magnetism, electronic spectra, and structure of transition metal alkoxides. II. The preparation and magnetism of iron(III) alkoxides
Authors: Adams RW , Martin RL , Winter G
Published: September 2010

The iron(III) alkoxides,
Fe(OMe)3, Fe(OEt)3, and Fe(Obun)a
have been prepared by a procedure alternative to those previously described in the
literature. The trimeric nature of the three
compounds in benzene is confirmed by cryoscopy, and preliminary X-ray single
crystal data for the ethoxide are consistent with trimeric
entities in the solid. The
temperature variation of the magnetic susceptibilities for the three compounds
follows the Curie-Weiss law between 90 and 300�K but with large values of θ=-
200�K. The unusually low magnetic moments vary markedly with temperature, and
at room temperature remain depressed in benzene solution at peer μeff 4.4 B.M. This anomalous behaviour is
ascribed to the presence of weak antiferromagnetic exchange interactions within
the cluster of iron atoms which forms the core of the trimeric
species Fe3(0R)9.

The compounds are sensitive both to
hydrolysis and to heating. Hydrolysis decreases and pyrolysis increases the
magnetic susceptibility. This provides a convenient method for following the
progress of both types of reaction.
Organoaluminium compounds. X. Formation of dimethylaluminium alkoxides and phenoxides
Authors: Mole T
Published: September 2010

Dimethylaluminium methoxide, isopropoxide,
t-butoxide, and phenoxide have been prepared and were found to be stable with
respect to disproportionation in benzene and in ether, and upon distillation,
although dimethylaluminium methoxide disproportionated in tetrahydrofuran and
pyridine. Only one of the methyl groups of trimethylaluminium could be
exchanged for an isopropoxyl group of aluminium isopropoxide or methylaluminium
diisopropoxide in non-polar solvent at moderate temperature; no exchange occurred
in ether.
Structure of molten nitrates. I. Estimation of effective interionic distances
Authors: James DW
Published: September 2010

In the theoretical calculations of
physical properties of molten salts, the distance of closest approach of the
ions, rcj,
is a parameter of fundamental importance. For melts where all ions show
spherical symmetry rij
is a simple parameter. This situation can be assumed for molten nitrates in two
cases; either when the nitrate ion is rotating with a period of rotation
shorter than the period of oscillation of surrounding cations or when all anion
cation orientations are statistically averaged to give an effective spherical rij. Both the
assumption of free rotation of the nitrate ion and problems associated with
statistical averaging of anion-cation orientations are discussed on the basis
of available data.
Far infrared and Raman spectra of some crystalline halomercurate(II) complexes
Authors: Deacon GB , Green JHS , Kynaston W
Published: September 2010

The infrared spectra
(500-40 cm-1) of crystalline (Me4N)2HgCl4, Me4NHgCl3,
and (Et4As)2HgI4,
and the Raman spectra of the first two compounds, have been recorded.
Assignments of the vibrational frequencies are made and discussed in relation
to the structure of the anions.
Electron impact studies. I. High resolution mass spectra of some unsaturated cyclic ketones
Authors: Bowie JH
Published: September 2010

The mass spectra of some
2-cyclohexen-1-ones, tetralones, and indanones have been investigated. The
characteristic fragmentation processes, substantiated by appropriate metastable
peaks, exact mass measurements, and in some cases by deuterium labelling studies,
greatly facilitate the determination of both the type of system and the
position of substituents on that system.
The Elovich equation and chemisorption kinetics
Authors: Allen JA , Scaife PH
Published: September 2010

A generalized Elovich equation which takes account of features of chemi-
sorption not previously included is presented and discussed. A systematic procedure
for determining the parameters, the initial rates, and the corresponding apparent
activation energy is described.
A method based on a linear regression analysis which is capable of evaluating
the parameters more satisfactorily than graphical and numerical methods is
proposed and applied to a range of existing experimental data.
Some studies in inorganic complexes. XX. Further reactions of 2-thioaminopyridine
Authors: Sutton GJ
Published: September 2010

The following complexes of
2-thioamidopyridine (thiopic) were prepared and studied : [RhCl2
thiopic2]Cl,2H2O;
[RhCl2 thiopic2][RhCl4 thiopic]; [RhCl,
thiopic2]ClO4;
[RhBr2 thiopic2]ClO4; [RhI2
thiopic2]ClO4,H2O;
[Rh thiopic3][ClO4]3; [Ag thiopic]ClO4; [AuCl2
thiopic][AuCl4]; [Au thiopic2][AuI2]; [RuCl2
thiopic2], C2H5OH;
[Os thiopic3]Br3;
[Cr thiopic3]Br3;
[MnI3 thiopic2];
[In thiopic3]Cl3,H2O.
The following substances were also prepared and studied: [RhI2
pic2]I2,H2O; [RhCl, en,]Cl,H2O; [Rh phenan3]Br3 (where pic is
2-aminomethylpyridine, en is ethylenediamine, and phenan is 1,10-phenanthroline).
The conductances of all of the aforementioned substances in NN?-dimethylformamide
agreed with their structures as metal chelates as indicated. Studies of
absorption spectra in the visible region were also made, and infrared spectra
showed that bonding had occurred through the sulphur atom of the -C(=S)NH, group
in the case of rhodium(III), gold(I),
gold(III), ruthenium(II), osmium(III), and silver(I) complexes, whereas with
chromium(III), manganese(II), and indium(III) coordination was by the nitrogen
atom. Measurements of magnetic susceptibility showed that the
rhodium(III), gold(I), gold(III),
ruthenium(II), and osmium(III) complexes were spin-paired, whereas those of
chromium(III) and manganese(II) were spin free.
The mechanisms and steric course of substitution at a divalent ruthenium centre
Authors: Bosnich B , Dwyer FP
Published: September 2010

The thermal rates of
substitution of one pyridine group coordinated to the optically active complex
cation cis-[Ru phen2
py2]2+ (phen
= o- phenanthroline, py = pyridine) dissolved in dry
acetone have been measured using the anions Cl-, Br-,
I-, NCS-, N-3, and NO-2. It was
found that for all anions monosubstitution proceeded with complete retention of
absolute configuration.

The anions Cl-,
Br-, I-, and NCS- substituted at a rate which was independent of their nature
and concentration. The kinetics of substitution of the anions N-3
and NO-2 have not been fully resolved, but the rates of
reaction of these two anions appear to be faster than the other four.
Insulin peptides. I. Some protected peptides with sequences derived from the A-chain of ovine insulin
Authors: Stewart FHC
Published: September 2010

Syntheses are described of
two pentapeptide derivatives with the A5-9 and A17-21
sequences, respectively, of ovine insulin, and of a protected tetrapeptide with
a modified A1-4 sequence. Preparation of the three compounds
involved the use of the 2,4,6-trimethylbenzyl carboxyl-protecting group in
conjunction with the o-nitrophenylsulphenyl and benzyloxycarbonyl
amino-protecting groups.
Structural changes of flavylium salts. IV. Polarographic and spectrometric examination of pelargonidin chloride
Authors: Harper KA
Published: September 2010

Pelargonidin chloride has been examined polarographically
and spectrometrically in aqueous methanol over a wide
pH range and the molecular changes determined. In strongly acid solutions the flavylium ion is stable, but between pH3
and pH8 ring opening to the α-diketone occurs,
the process involving the pseudo-base and its 3-keto tautomer. The pseudo-base
is present in the equilibrium mixture from pH3 to pH12 in amount varying with the pH. The anhydrobase,
detected in the equilibrium mixture at pH6, is stable
above pH7, becoming ionized as the pH is raised. Unlike
the anhydrobase of the simpler flavylium
salts, the anhydrobase of pelargonidin
chloride does not undergo ring cleavage in strong alkali under the conditions
of these experiments. Ionization of the phenolic
group at C5 was indicated by a, small anodic wave in the polarograms above pH9.5, due to mercuration at C6. A similar reaction,
analogous to the known catalytic mercuration of ketones, was observed for
phloroglucinol and resorcinol in alkaline solutions.
Normal coordinate analysis of cyanoacetylene
Authors: Ramaswamy K , Srinivasan K
Published: September 2010

The potential energy
constants of cyanoacetylene were obtained by the method of characteristic
set. The values of the various bond pair-bond pair interactions were determined
without any assumptions regarding force fields. The mean amplitudes of
vibration for the various characteristic bonds were calculated by Cyvin's method. The results are explained on the basis of
the presence of conjugated structures for cyanocetylene.
Organoaluminium compounds. XV. The mechanism of the exchange reaction between Lewis-base complexed (CH3)2AlX and (CH3)2AlY
Authors: Ham NS , Jeffery EA , Mole T , Saunders JK
Published: September 2010

Kinetic studies have been
made by proton magnetic resonance spectroscopy of exchange reactions between

trimethylaluminium
and dimethylaluminium bromide,

trimethylaluminium
and dimethylaluminium chloride,

trimethyl-aluminium and dimethylphenylaluminium,
and

(iv)dimethylaluminium
chloride and dimethylaluminium bromide.

An excess of anisole was
present in all four cases. In reactions (i), (ii), and (iii) the exchange rates
were strongly dependent upon

excess anisole, but that of
(iv) was only slightly dependent. The exchange between dimethylaluminium
chloride and dimethylaluminium bromide was also studied using an excess of
ether and no dependence of rate upon excess ether was found.

It is proposed that: (a)
for (i), (ii), and (iii) removal of base from one of the organoaluminium
compounds occurs prior to exchange; (b) exchange between dimethylaluminium
chloride and dimethylaluminium bromide in the presence of ether proceeds
without loss of base from either organoaluminium
complex ; (c) for reaction (iv) exchange occurs partly with and partly without
prior loss of base.
The thermal decomposition of n-propyl bromide
Authors: Cross JTD , Stimson VR
Published: September 2010

Mechanisms already proposed
or formally possible for the decomposition of n-propyl bromide as a
312-order reaction are shown to be unsatisfactory, and the reaction has been
reinvestigated. Two reactions occur simultaneously: (a) a first-order reaction
identifiable with the maximally inhibited reaction and presumably molecular; (b) a reaction second order
in the initial concentration and somewhat autocatalysed as the
reaction proceeds. The rate constant is given by

k2 == 1018.1exp(-49300/RT)sec-1ml mole-1

Reaction (b) is catalysed
by hydrogen bromide and inhibited by propene, and a bromine atom chain
mechanism with hydrogen bromide catalysed initiation is proposed.
Bromine-catalysed decomposition has also been studied. The mechanism of the
inhibition is discussed.
Effect of pressure on the density of dioxan and dioxan-water mixtures at 25°
Authors: Pearce PJ , Strauss W
Published: September 2010

The compressions at 25� of dioxan-water mixtures containing 0, 25, 50, 70, 80, and 100
wt.% dioxan have been determined at pressures up to
1500 bars. The mixtures show a minimum compression at a composition between 25
and 50 wt.% dioxan. The freezing pressure of dioxan at 25� is estimated to be 625 bars but measurements
have been made on the metastable liquid at pressures up to 960 bars.
N-Substituted salicylaldimine complexes of iron(III). I. Synthesis, infrared and mass spectra
Authors: van den Bergen A , Murray KS , O'Connor MJ , Rehak N , West BO
Published: September 2010

Complexes of iron(111) and
N-substituted salicylaldimines have been prepared of
general formulae Fe(sal-NR)3,? Fe(sal-NR)2 sal, FeCl3(salH-NR)2,
Fe(sal-NR)2X (X = Cl, Br), and [Fe(sal-NR)2]2O. The complexes all show
spin-free magnetic behaviour with moments at room temperature of the order of
5.9 B.M. except for the oxygen-bridged complexes which have low moments (c.2
B.M.) believed due to a spin-exchange process. The infrared spectra and mass
spectra of the complexes are discussed.
Galactomannan from the seed of Lotus pedunculatus
Authors: Richards EL , Beveridge RJ , Grimmett MR
Published: September 2010

A galactomannan
composed of D-galactose (49%) and D-mannose (51%) was isolated in 2.2 % yield
from the seeds of Lotus pedunculatus by water extraction. On periodate oxidation it consumed 1.5 moles
of oxidant per hexose unit, releasing 0.53 mole of
formic acid. Hydrolysis of the methylated polysaccharide gave, as the major
products, 2,3,4,6-tetra-O-methyl-D-galactose (6 parts), 2,3-di-O-methyl-D-mannose
(6.25 parts), and 2,3,6-tri-O-methyl-D-mannose (1 part). It is concluded that the polysaccharide
contains essentially linear chains of l → 4-linked P-D-mannopyranose units with side-chains of a-D-galactopyranose units attached to C6 of approximately six
out of every seven D-mannopyranose units. The galactomannan is more highly branched than similar galactomannans
isolated from the seeds of other legumes.
Photochemical rearrangement of benzylenol ethers
Authors: Pinhey JT , Schaffner K
Published: September 2010

Evidence is presented for
the structures of the products isolated from the light-induced rearrangement of
benzylenol ethers of Δ4-3-oxo-steroids.
The products obtained on irradiation of benzyl vinyl ether indicate that the
rearrangement proceeds by homolysis of the
benzyl-oxygen bond. Nuclear magnetic
resonance evidence is presented for the existence of an internal phenyl-ketone
interaction in compound (X).
Complexes of methyl-tin and -lead halides with substituted pyridine N-oxides
Authors: Kitching W , Kumar Das VG
Published: September 2010

Complexes of some
methyl-tin and -lead halides with a range of 4-substituted pyridine N-oxides
have been prepared and characterized. The fluctuations in v(N-O) and in J(CH3-M)
have been examined as a function of substituent, and the resonance positions of
ring protons in the proton spectra are discussed.
Vibrational spectra of anhydrous lithium perchlorate in crystalline and molten states
Authors: Leong WH , James DW
Published: September 2010

Anhydrous lithium
perchlorate has been examined in the crystalline and molten state by infrared
and Raman spectroscopy. In the crystalline phase all degenerate modes are split
but the Raman and infrared spectra are essentially identical in the internal frequency
region. In the molten state the spectra are more simple but no coincidences
exist between infrared and Raman spectra. The spectra are interpreted in terms
of a crystalline symmetry perturbation for both the solid and molten salts. The
symmetry of the perturbing field is shown to change in going from the solid to
the melt. An explanation of the melt spectra in terms of contact ion pairs is
considered and dismissed. Observed vibrational frequencies and assignments are
given.
Thermodynamics of the dissociation of the pyridinium ion
Authors: Green RW
Published: September 2010

The pK of the pyridinium
ion at ionic strength 10-4 has been measured spectrophotometrically
at ten temperatures in the range 5-50�. At 25� the enthalpy of dissociation,
ΔH0, is 4.28�0.04 kcal mole-1; and the entropy of
dissociation, ΔS0, is -9.6�0.13 cal deg-1 mole-1.