bluuebunny/crossref_metadata_2025 huggingface dataset:
The Reaction of Carbon with Carbon Dioxide at High Pressure
Authors: Blackwood JD , Ingeme AJ
Published: September 2010

A study has been made of the reactions of
purified carbon with carbon dioxide at pressures up to 40 atm and in the
temperature range 790-870 �C. The effect of carbon monoxide has been examined
by adding varying proportions of this gas to the carbon dioxide supplied to the
reactor bed.

At high carbon dioxide and carbon monoxide
partial pressures, the rate of formation of carbon monoxide is greater than
would be expected from the mechanism proposed by Gadsby et al. (1948). A
mechanism has been proposed whereby the increased rate may be explained by
additional steps involving the interaction of a carbon dioxide molecule with an
adsorbed carbon monoxide to produce adsorbed oxygen, thus :

������������������ CO2 + (CO)
→ 2CO +(O)

A general rate equation has been derived
which includes this step and satisfies the experimental results. The reverse
mechanism by which carbon monoxide can disappear is not the simple reverse of
the forward process and at high pressures equilibrium cannot be expressed by
the usual expression derived for the simple single-stage reversible process.

The possible nature of active sites has
been examined by studying the reactivity of a series of chars prepared at
different temperatures. The reactivity appears to be related to the oxygen
content of the chars and the type of active centres involved may be different
from those which control the carbon-steam mechanism.
Terpenoid Chemistry. III. The Essential Oils of Eucalyptus deglupta Blume and E. torelliana F. Muell
Authors: Sutherland MD , Webb LJ , Wells JW
Published: September 2010

The essential oils of two eucalypts, which
are exceptional in that they normally grow within the margin of tropical
rain-forest, have been examined. The oil from Eucalyptus deglupta Blume was
found to contain isovaleraldehyde, (�)-α-pinene, (-)-α-phellandrene,
p-cymene, ocimene, (-)-carvotanacetone, and (+)-nerolidol. The oil from E.
torelliana F. Muell. contained benzaldehyde, (�)- and (+)-α-pinene, (-)-β-
pinene, ocimene, (+)-aromadendrene, and sesquiterpene alcohols. Of these
constituents, ocimene, carvotanacetone, and nerolidol have not previously been
identified in eucalyptus oils.

The conclusion is reached nevertheless,
that because of the inadequacy of the published data on eucalyptus oil
compositions, no significance can be attached as yet to the presence of these
unusual constituents.
An Examination of the Rutaceae of Hong Kong. VI. Graveoline, A New Alkaloid from Ruta graveolens
Authors: Arthur HR , Cheung HT
Published: September 2010

A new alkaloid, graveoline, C17H13O3N,
has been isolated in 0.002 per cent yield with kokusaginine and skimmianine
from Ruta graveolens. Evidence is cited which suggests that graveoline is a
1-methyl-methylenedioxyphenyl-4-quinolone (see note added in proof).
Heats of Mixing. IV. Systems of n-Alcohols with Benzene at 25, 35, and 45°C
Authors: Brown I , Fock W
Published: September 2010

A new apparatus has been made for the
precise measurement of heats of mixing of liquids. With this apparatus
measurements can be made in the absence of air, vapour, or mercury for systems
which have volume changes on mixing of up to 1 ml per mol of mixture.

The apparatus has been used to measure the
heats of mixing of ethanol, 1-propanol, and 1-butanol with benzene at 45 �C for
comparison with previous measurements. New measurements have also been made
over the concentration range for heats of mixing of ethanol, 1-propanol, and
1-butanol with benzene at 25 and 35 �C and for methanol, 1-hexanol, and
1-octanol with benzene and ethanol with toluene at 35 �C.

For these systems the heat of mixing per
mol of mixture has a maximum at a mole fraction of alcohol from 0.30 to 0.35.
The results show that the heats of mixing at a mole fraction of alcohol of 0.30
increase linearly with increase in temperature and at a given temperature they
increase with the molecular weight of the alcohol but at a lower rate for the
higher alcohols.
The Cardiac Glycosides Present in Mistletoes Growing on Nerium oleander
Authors: Boonsong C , Wright SE
Published: September 2010

Three species of mistletoe growing on
Nerium oleander have been shown to extract selectively cardiac glycosides from
the host plant. The substances selected were the three most polar glycosides
present in the leaves of N. oleander and have been identified as strospeside,
neritaloside, and odoroside H. These glycosides had been previously isolated
from the seeds of N. oleander.
Alkaloids of Crotalaria trifoliastrum Willd. and C. aridicola Domin. I. Methyl Ethers of Supinidine and Retronecine
Authors: Culvenor CCJ , Smith LW
Published: September 2010

In some samples of Crotalaria
trifoliastrum Willd., the major alkaloids are 1-methoxymethyl-1,2-dehydro-8α-pyrrolizidine
and 7β-hydroxy-1-methoxymethyl-1,2-dehydro-8α-pyrrolizidine, the
methyl ethers of supinidine and retronecine respectively ; in other samples,
the former alkaloid is largely replaced by a third non-ester alkaloid, C9H15O2N.
The first two are the major alkaloids also of C. aridicola Domin.
Virial Coefficients of Three Organic Sulphides
Authors: Bottomley GA , Coopes IH
Published: September 2010

The second virial coefficients at two
temperatures somewhat above room temperature have been determined for the three
substances dimethyl sulphide, diethyl sulphide, and methyl ethyl sulphide by e
precision differential compressibility method, and the numerical values
compared with determinations by the indirect thermodynamic method using vapour
specific heats and latent heats of evaporation.
Some Studies in Inorganic Complexes. XIII. Chromium(III) and Molybdenum(III) with 2-Aminomethylpyridine (2-Picolylamine)
Authors: Sutton GJ
Published: September 2010

A study has been made of complexes of
chromium(III) and molybdenum(III) with the chelating ligand
2-aminomethylpyridine (2-picolylamine). They are of the type Crpic33+, Crpic2(H2O)23+,
and Mopic33+, in
which pic is the ligand 2-picolylamine. Conductance measurements in methanol
and nitromethane are in agreement with their structures as six-coordinate
complexes. The magnetic moments were found to be in the vicinity of 3.7 B.M. in
all oases, showing that the chromium(III) and manganese(III) atoms are spin-free.
The following salts were prepared and studied : [Crpic3]2[SO4]3.3H2O,
[Crpic3]Cl3.3H2O,
[Crpic2(H2O)2]Br3, [Crpic2(H2O)2][ClO4]3,
and [Mopic3][ClO4]3.3H2O.
The Structure of the Nitrocamphor Anhydrides
Authors: Larson HO , Levand O , Barnes L , Shoolery JN
Published: September 2010

Three isomeric nitrocamphor anhydrides
have been isolated. The structure assigned to the anhydrides without indication
of the stereochemistry is that shown in (II).
The Thermal Decomposition of Tertiary Butyl Chloride in the Presence of Sulphur Hexafluoride
Authors: Failes RL , Stimson VR
Published: September 2010

No acceleration of the gas-phase
decomposition of tertiary butyl chloride at 284-309 �C occurs in the presence
of sulphur hexafluoride. This behaviour contrasts with that of a variety of
unimolecular decompositions probably occurring via triplet states where an
extension of the simple theory of activation has been found necessary.
The Extraction of Anionic Beryllium Complexes by Tri-iso-octylamine
Authors: de Bruin HJ , Kairaitis D , Temple RB
Published: September 2010

The extraction of beryllium from aqueous
solution by long-chain tertiary amines has been observed in the presence of
ligands giving rise to anionic complexes. The nature of the oxalate complex
extracted by solutions of tri-iso-octylamine in chloroform has been studied in
detail and the species formed in the organic phase were shown to have the
composition Be(C2O4)2.{NH(i-C8H15)3}2.

The complexes formed in aqueous solution
between beryllium and several anionic complexing agents have been examined by
the method of pH-titration. Conditional stability constants have been obtained
for the complexes formed with oxalic, malonic, maleic, succinic, phthalic, and
salicylic acids. Differences in their extractabilities can be explained
semiquantitatively with the help of the stability constants and the acid
association constants of the complexing agents.
The Conformations as Solutes of Diethyl Maleate, Fumarate, and Azodiformate
Authors: Armstrong RS , Aroney MJ , Le Fevre RJW
Published: September 2010

Dipole moments and molar Kerr constants,
previously recorded by Le F�vre, Le F�vre, and Oh (1957) with only a
qualitative discussion pending availability of information on the anisotropic
polarizabilities of the C=C and N=N bonds, are here used to indicate the
apparent conformations of diethyl maleate, diethyl fumarate, and diethyl
azodiformate as solutes in carbon tetrachloride.
Investigations of Suint. I. The Composition of the Organic Acids from Fleeces of Different Origin
Authors: Kowala C , Kranz ZH , Murray KE
Published: September 2010

A major part of the organic acids of the
suint from each of seven samples of wool fleece of different origin has been
examined by gas chromatography of the methyl esters. Twenty-three acids have
been identified in one or more of the samples by the retention times of the
esters. The composition of all samples was complex and differed considerably
both quantitatively and qualitatively.
Spreading from Solid Hexadecanol
Authors: Mansfield WW
Published: September 2010

Within experimental error, the coefficient defining the rate of spreading from
the edge of a crystal of hexadecanol into a water surface is constant up to the
equilibrium spreading pressure. The corresponding coefficient for powdered hexade-
can01 also remains constant.
The equilibrium spreading pressure of the crystal edge is significantly less
than that of powdered hexadecanol.
Synthesis of Some Linear Benzochromanones
Authors: Bell KH , Duewell H
Published: September 2010

A series of 8-substituted
6,7-benzochromanones has been prepared by cyclization of the corresponding
3-(1-X-2-naphthy1oxy)propionic acids (X = CH3, 0CH3, Br,
NO2) with polyphosphoric acid. Direct cyclization of the related
3-(1-X-2-naphthyloxy)propionitriles
(X = CH3, OCH3, Br, NO2) with sulphuric acid
was successful only with X = Br, NO2. An improved synthesis of
1-methoxy-2-naphthol is reported.
The Mass Spectra of Phenyl Methyl Ethers
Authors: Barnes CS , Occolowitz JL
Published: September 2010

Fragmentation of a phenyl methyl ether
under electron impact normally occurs by fission of either C-O bond to give
ions due to loss from the parent of a methyl radical or, with rearrangement of
one hydrogen, a formaldehyde molecule. In the latter case a hydrogen atom may
be subsequently lost if a stable tropylium ion may thereby result. If there are
present ortho- or para-substituents which are capable of forming a quinonoid
structure involving the ether oxygen after removal of a methyl radical, then loss
of formaldehyde does not occur.
The Formation of 5-Hydroxymethylfurfural from Hexoses
Authors: Moye CJ , Krzeminski ZS
Published: September 2010

Gas chromatography has been used to
demonstrate the existence of the equilibrium; fructose, during the conversion of fructose, free
from glucose, into 5-hydroxymethylfurfural under conditions of acid catalysis.
The relationship of this equilibrium to subsequent stages in the conversion is
discussed.

The conversion of fructose into
5-hydroxymethylfurfural under conditions described by Bourne, in the presence
of iodine, has been shown to be due to acid catalysis.
Reaction of Naphthyl Radicals with Naphthalene
Authors: Badger GM , Whittle CP
Published: September 2010

Reaction of 1-naphthyl radicals with
naphthalene has given 1,1'-binaphthyl, 1,2'-binaphthyl, and several related
condensed hydrocarbons. Reaction of 2-naphthyl radicals with naphthalene gave
1,2'-binaphthyl and 2,2'-binaphthyl.
Hydrogen Bonding in Organic Compounds. VIII. Aromatic Primary Amines with ortho-Carbonyl Groups
Authors: Hambly AN , O'Grady BV
Published: September 2010

The NH stretching frequencies of the amine
group in a number of aromatic primary amines with o-carbonyl groups have been
studied as the fundamental and first overtone absorption bands, both before and
after deuteration. Several correlations are established between functions of
the vibration frequencies which seem to be related to the strengths of the
hydrogen bonds that have been formed. These correlations, established for
carbonyl as the acceptor, extend to some other classes of hydrogen bond acceptor.
When bilateral hydrogen bonds are formed to two o-carbonyl groups the NH2
stretching frequencies do not conform to the equation of Bellamy and Williams.
Further evidence in favour of the interpretation of the spectrum of
1-aminoanthraquinone given by Hambly and Bonnyman is offered. The preparation
of 5-chloro-2-t-butylaniline is described and some further details of the
spectra of anilines with tertiary butyl substituents are given.
Extractives of Australian Timbers. IV. Castanogenin (Medicagenic Acid) and Bayogenin, C30H48O5, from Castanospermum australe Cunn. et Fras
Authors: Eade RA , Simes JJH , Stevenson B
Published: September 2010

Castanogenin, the major genin produced on
hydrolysis of the saponin of Castanospermum australe Cunn, et Fras. is shown to
be identical with medicagenic acid (2β,3β-dihydroxyolean-12-en-23,28-dioic
acid). Further proof of several of the structural features of medicagenic acid
is given. The minor sapogenin, bayogenin, C30H48O5,
is shown to be 2β,3β,23-trihydroxyolean-12-en-28-oic acid by
conversion into the same tetrol as is formed from medicagenic acid and by the
formation of a γ-lactone by interaction of the carboxyl function and the
12,13-double bond.
Terpenoid chemistry. VII. The structure of geijerene
Authors: Sutherland MD
Published: September 2010

Degradative and other evidence is
presented to show that the natural hydrocarbon geijerene, C12H18,
from Geijera parviflora leaves is precisely racemic 3-isopropenyl-4-methyl-4-vinylcyclohexene
(I).
Volatile flavouring constituents of the pineapple. I. Some esters, alcohols, and carbonyl compounds
Authors: Connell DW
Published: September 2010

Investigation of the volatile constituents
of pineapples received at a Brisbane cannery in the summer of 1961-62 has
resulted in the identification of methanol, ethanol, n-propanol, isobutanol,
n-pentanol, ethyl acetate, ethyl n-butyrate, methyl isovalerate, methyl
n-caproate, ethyl n-caproate, methyl n-caprylate, n-amyl n-caproate, ethyl
lactate, methyl β-methylthiolpropionate, ethyl β-methylthiol-
propionate, and diacetyl. The presence of at least 12 other constituents was
indicated by gas chromatography.
Organo-aluminium compounds. IV. Exchange reactions between trialkylaluminiums and triphenylaluminium
Authors: Mole T , Surtees JR
Published: September 2010

Dimethylphenylaluminium,
diethylphenylaluminium, di-isobutylphenylaluminium, and
isobutyldiphenylaluminium have been prepared as solids by reaction of
triphenylalurninium with the appropriate amount of trialkylaluminium.
Dimethylphenylaluminium is more conveniently prepared from triphenylaluminium
etherate and excess trimethylaluminium. All four compounds undergo thermal
disproportionation, that of the isobutyldiphenylaluminium occurring in
cyclohexane at 40�.

Disproportionation of dimethylphenylaluminium
occurs in benzene with a half-time of less than 10-1 sec even in the
presence of more than one equivalent of ether or tetrahydrofuran. In the
presence of more than two equivalents of ether or tetrahydrofuran, or in either
of these two solvents alone, disproportionation is slower; the half-life is
then in the range 10-1-102 sec. It is concluded that
exchange of methyl for phenyl groups can occur when at least one of the two
participating aluminium atoms is bound to an ether or tetrahydrofuran molecule.
The occurrence of 11,12-dehydroursolic lactone acetate in Eucalyptus waxes
Authors: Horn DHS , Lamberton JA
Published: September 2010

��� 11,12-Dehydroursolic lactone acetate,
previously reported as a reduction product of 11-ketoursolic acid, has been
isolated from several Eucalyptus waxes. The waxes from Acacia iteaphylla F.
Muell. and Acacia suaveolens Willd. contain lupeyl acetate, and wax from
Echeveria secunda Booth ex Lindl. contains β-amyrenyl acetate.
Quench frequency effects on the nuclear quadrupole resonance of some halogen compounds
Authors: Bogaard MJ , Hacobian S , Hay W , Sullivan EPA
Published: September 2010

The effect of quench frequency on 35Cl
and 127I nuclear quadrupole resonances of some halogen compounds has
been investigated at various temperatures using pulsed type oscillators. The
observed signal-to-noise ratio of the nuclear signal versus quench frequency
curve for each compound studied shows a number of maxima which can be explained
in terms of nuclear induction phenomena.
The formation of aromatic hydrocarbons at high temperatures. XX. The pyrolysis of [1-14C]naphthalene
Authors: Badger GM , Jolad SD , Spotswood TM
Published: September 2010

The pyrolysis of [1-14C]naphthalene
at 700� has given a tar from which 1,1'-, 1,2'-, 2,2'-binaphthyls, and 10,11-,
11,12-benzofluoranthenes were isolated in sufficient quantity and purity for
radiochemical analysis. All were found to have activity corresponding, within
experimental error, to two labelled carbon atoms. It is concluded that
carbon-hydrogen fission gives naphthyl radicals, which react with naphthalene
to yield binaphthyls, and that cyclodehydrogenation of the binaphthyls leads to
the benzofluoranthenes. A small amount of perylene was also identified; this
was probably formed in the same way. Some 3,4-benzopyrene was detected; it is
suggested that some hydrogenation of the naphthalene occurs, and that the
3,4-benzopyrene is formed following cleavage of a saturated carbon-carbon bond
in this hydrocarbon.
Hydrogen bonding in organic compounds. IX. Intramolecular actions between the primary amine group and amino, nitro, sulphide, and sulphone groups in aromatic compounds
Authors: Hambly AN , O'Grady BV
Published: September 2010

Spectroscopic evidence for the existence
of intermolecular hydrogen bonds between aniline molecules has been obtained.
Examples show the existence of intramolecular hydrogen bonds in orthodiamines,
some amino-derivatives of heterocycles, 2-nitro-amines, 2-amino-sulphones, and
2-amino-sulphides.

Some new observations, which do not agree
with Krueger's interpretation of the profile of the overtone bands due to NH2
stretching vibrations, are recorded.
Porphyrins. III. Preliminary studies on the synthesis of porphyrin a
Authors: Badger GM , Harris RLN , Jones RA
Published: September 2010

An unsuccessful attempt to prepare the
porphyrin (VII) is reported. The proposed synthesis (III → VII) was
frustrated by the fact that neither of the intermediate dipyrromethanes (III
and IV) could be prepared.
The formation of aromatic hydrocarbons at high temperatures. XXIII. The pyrolysis of anthracene
Authors: Badger GM , Donnelly JK , Spotswood TM
Published: September 2010

The pyrolysis of anthracene at 700� has
given a tar containing ten polycyclic hydrocarbons all of which are probably
formed by the scission of carbon-hydrogen bonds to give anthryl radicals
followed by further reaction with anthracene. The pyrolysis of anthracene at
950� gave a much more complex tar in which 25 aromatic hydrocarbons have been
identified. The major constituent was found to be phenanthrene. It is suggested
that this is formed via tetrahydroanthracene and tetrahydrophenanthrene. It is
also suggested that the complexity of the tar is due to the scission of the
saturated carbon-carbon bonds in tetrahydroanthracene and
tetrahydrophenanthrene, followed by further reaction of the fragments.
Porphyrins. VIII. A stepwise synthesis of porphyrins
Authors: Badger GM , Jones RA , Laslett RL
Published: September 2010

1,2,3,4,5,6,7,8-Octanlethylporphin and α,γ,1,2,3,4,5,6,7,8-decamethylporphin have been
prepared by the acid-catalysed condensation of 5,5'-diformyl-3,4,3',4'-tetramethylmethanes
(VI; R = H or CH3) with the corresponding dicarboxylic acid
derivatives (VII), followed by oxidation. For the preparation of
meso-substituted porphyrins the method seems to be more satisfactory than those
already in the literature, and can be developed further.
Some properties of artificial orthorhombic anhydrite
Authors: Ridge MJ , Surkevicius H , Goto M
Published: September 2010

The properties were examined of a number
of samples of soluble anhydrite and calcium sulphate hemihydrate in which
substantial conversion to orthorhombic anhydrite had taken place. Large
deviations from the properties of the mineral were found in the density and
reactivity of orthorhombic anhydrite formed at low temperatures.

The experimental results are discussed in
relation to the nature, formation, and determination of orthorhombic anhydrite
present in preparations of calcium sulphate hemihydrate and soluble anhydrite.
Conclusions drawn from previous work on the reactivity of calcium sulphate
hemihydrate are evaluated in the light of the present findings.
Organophosphorus compounds. IV. The reaction of Alk-1-ynes with phosphorus pentachloride, and a new route to Alka-1,2-dienes
Authors: Meisters A , Swan JM
Published: September 2010

The addition of phosphorus pentachloride
to four representative linear alk-1-ynes is accompanied by an allylic shift of
a hydrogen atom. Hydrolysis of the resulting complexes yields
2-chloroalk-2-enylphosphonic acids rather than 2-chloroalk-1-enylphosphonic
acids as reported in the literature. The 2-chloroalk-2-enylphosphonic acids
undergo fragmentation in hot alkali yielding 1,2-alkadienes, chloride, and
phosphate ions. The sequence alk-1-yne → 2-chloroalk-2-enylphosphonic
acid → l,2-alkadiene constitutes a new and mild method for effecting this
isomerization.
Characterization of Bis[chloridodi(cyclopentadienyl)zirconium] oxide, a compound containing the Zr-O-Zr linkage
Authors: Reid AF , Shannon JS , Swan JM , Wailes PC
Published: September 2010

The previously reported reaction of
dichloridodi(cyclopentadienyl)zirconium [(C5H5)2ZrCl2]
with aniline or other bases has been shown to involve water as a reactant, with
formation of the oxygen-bridged bis[chloridodi(cyclopentadienyl)- zirconium]
oxide, [(C5H5),ZrCl]2O, containing the linkage
Zr-0-Zr. The compound is diamagnetic, stable to air and water, and can be
sublimed in a vacuum at 200-220�. The crystals are monoclinic, with four
molecules per unit cell. The structure was established by mass, infrared, near
infrared, and proton magnetic resonance spectral examination, and by reaction
of the compound with deuterium-labelled and tritium-labelled hydrogen chloride
to regenerate unlabelled dichloridodi(cyclopentadienyl)-zirconium.
Photochemical reactions of azo compounds. IV. Further photochemical cyclodehydrogenations
Authors: Badger GM , Jamieson NC , Lewis GE
Published: September 2010

1,1'-, 1,2'-, 2,2'-Azonaphthalenes, and
2-phenylazonaphthalene are not cyclized photochemically under conditions in
which azobenzene is converted into benzo[c]cinnoline and benzidine; but
1-phenylazonaphthalene has been shown to give naphtho[1,2-c]cinnoline, and
4-phenylazobenzene gave 2-phenylbenzo[c]cinnoline. Although 4-styrylazobenzene
showed some evidence of cyclization, the reaction was extremely slow and was
accompanied by considerable decomposition. 4-Phenylezoazobenzene was cleaved by
sulphuric acid, and no cyclized product was obtained. Irradiation of
4,4'-bis(phenylazo)biphenyl gave two cleavage products, and two
benzo[c]cinnoline derivatives. Simultaneous reduction and oxidation apparently
occurred within the same molecule.
Kinetics and mechanisms of mercuration of aliphatic carboxylic acids
Authors: Kitching W , Wells PR
Published: September 2010

The kinetics of the mercuration of acetic
acid by mercuric acetate under anhydrous and aqueous conditions have been
studied. The reaction is first order in mercuric acetate and possibly first
order in acetic acid. Radicals are not involved. The reaction is insensitive to
added salts and is not catalysed by acetate. Enol or carbanion intermediates
are excluded by the absence of H-D exchange. A four-centre (SF2) mechanism is suggested.
The reaction is accelerated by perchloric acid and this is attributed to
mercuration by acetoxymercuric perchlorate probably in the form of an ion pair.
Mercuric perchlorate and mercuric nitrate are more effective mercurating agents
than mercuric acetate. Although the perchloric acid catalysed reaction may
follow the SE2 mechanism
an SF2 pathway is
preferred.

Propionic acid is mercurated exclusively
at the α-carbon atom and trimethylacetic acid is unreactive. Acetic acid
is 2.7 times as reactive as propionic acid. Optically active methylethylacetic
acid appears to be mercurated stereospecifically.
By-products in the reaction of 2-picoline N-oxide with acetic anhydride
Authors: Ford PW , Swan JM
Published: September 2010

In support of earlier work by Okuda, the
apparently homogeneous product from reaction of 2-picoline N-oxide with acetic
anhydride, described in the literature as 2-acetoxymethylpyridine, is shown to
consist of about 66% of this substance, together with approximately equal
amounts of 3-acetoxy-2-picoline and 5-acetoxy-2-picoline. The N.M.R. and mass
spectra of these isomeric acetoxy compounds are discussed.
Nitration of the methylnaphthalenes
Authors: Alcorn PGE , Wells PR
Published: September 2010

The nitration of naphthalene,
1-methylnaphthalene, and 2-methylnaphthalene has been studied under a variety
of conditions. Relative rates by competition and isomer distributions have been
determined using gas chromatographic analyses. The derived partial rate factors
are discussed in terms of various nitration mechanisms and the effect of the
methyl group on reactivity in the naphthalene system.

A simple route to
1-methyl-8-nitronaphthalene is described.
Carnaubadiol, a triterpene from carnauba wax
Authors: Barnes CS , Galbraith MN , Ritchie E , Taylor WC
Published: September 2010

By chemical and spectroscopic methods,
carnaubadiol, C31H54O2, a constituent of
carnauba wax, was shown to contain one secondary and one tertiary hydroxyl
group, and one isopropenyl group. A series of degradative reactions yielded a
heptanorketone, identical with the known 3β-acetoxyhexanordammaran-20-one,
previously obtained from dammarenediol. The structure and configuration of the
side-chain were established by oxidation of dihydrocarnaubadiol to the known
(-)-(S)-5,6-dimethylheptan-2-one. Carnaubadiol was thus shown to be 24β-methyl-
dammar-25-ene-3β,20ξ-diol.
Determination by mass spectrometry of the structure of bisbenzoylacetoneethylenediimine and its metal chelates
Authors: Chaston SHH , Livingstone SE , Lockyer TN , Shannon JS
Published: September 2010

The mass spectra of
bisbenzoylacetoneethylenediimine (B) and its cobalt(II), nickel(II), and copper(II)
complexes have been rationalized in terms of form (II) for B in which the imino
nitrogens are attached to the same carbon atoms as the methyl groups and not to
the same carbon atoms as the phenyl groups, as previously proposed in the
literature. Compound B is thus NN'-ethylenebis(benzoylisopropylideneimine).
Novel ion-rearrangement reactions and examples of changes in metal valency in
the mass spectrometer are described.
Adducts of copper(II) b-diketone chelates with heterocyclic bases. II. Chelates with 3-alkylacetylacetones
Authors: Graddon DP , Schulz RA
Published: September 2010

Copper(II) chelates have been prepared
from a series of 3-alkylacetylacetones, R(acac) (R =
CH3, C2H5, n-C4H9, n-C7H15,
n-C16H33, and CH2C6H5).
Their absorption spectra have been examined in the solid state and in solution
in benzene and heterocyclic bases. Formation constants for 1 : 1 adducts with
pyridine, 2-methyl-pyridine, and 4-methylpyridine are smaller than those for
Cu(acac)2 and not affected by variation of
R. Analysis of the absorption spectra throws further light on the assignment of
absorption bands in the ligand field region. Instability of solutions of the
chelates in heterocyclic bases is due to cleavage of the β-diketones with
the formation of acetate, followed by further decomposition of unknown nature.
The absolute configurations of ( - )-angolensin and some related 1,2-diarylpropanes
Authors: Clark-Lewis JW , Jemison RW
Published: September 2010

(-)-Angolensin has been converted into
(+)-(2S)-1-(2,4-dimethoxyphenyl)-2-(4-methoxyphenyl)propane, an analogue of
(+)-(2S)-1-(2,4,6-trimethoxyphenyl)-2-(3,4-dimethoxyphenyl)propane. The stereochemistry
of angolensin is thereby correlated with that of catechin and epicatechin.
Oxidation of (+)-(2S)-1-(2-hydroxy-4-methoxyphenyl)-2-(4-methoxyphenyl)propane
gave (+)-3-(4-methoxyphenyl)- butyric acid, in agreement with the established
absolute configuration of (-)-angolensin. The (+)-butyric acid was also prepared
by resolution of the synthetic racemate with quinine, and by homologation of
(-)-2-(4-methoxyphenyl)propionic acid.
The electronic structure of N2O4. II. The 'π-only' structure
Authors: Brown RD , Harcourt RD
Published: September 2010

Molecular orbital studies for the "π-only"
electronic structure for N2O4 are presented. They
indicate that such a structure is unsatisfactory because it (i) implies a
paramagnetic ground state for the molecule, (ii) predicts incorrect trends in
NO bond lengths, strengths, and ONO angles, and (iii) is of considerably higher
energy than an alternative structure previously described. It also would seem
to imply a non-planar conformation for the molecule.
The circular dichroism and rotatory dispersion of cobalt(III) oxalatoacetylacetonato and oxalato-glycinato complexes
Authors: Dwyer FP , Reid IK , Sargeson AM
Published: September 2010

The preparation, resolution, circular
dichroism, and spectra of the complexes, sodium
bis(oxalato)acetylacetonatocobaltate(III), sodium oxalatobis(acetylacetonato)cobaltate(III),
and sodium bis(oxalato)glycinatocobaltate(III) are described. The configurations
of the ions are discussed relative to the tris(oxalato)- and tris(ethylenediamine)-cobalt(III)
ions of known configurations.
The constituents of Melicope broadbentiana F. M. Bail. The structures of melibentin. melicopol, and methylmelicopol
Authors: Ritchie E , Taylor WC , Vautin TK
Published: September 2010

From both the wood and the bark of
Melicope broadbentiana F. M. Bail. the known flavones, meliternatin and
melisimplexin, were isolated together with a new flavone, melibentin. The
latter was shown to be 3,5,6,7,8-pentamethoxy-3',4'-methylenedioxyflavone.

The leaves contained the known flavones,
melisimplin and meliternatin, triacontanol, and two new related phenols,
melicopol and methylmelicopol. On the basis of chemical degradation and
spectral properties, the structure of melicopol was established as methyl
2-geranyloxy-4,6-dihydroxy-3-hydroxymethylbenzoate and that of methylmelicopol
as its 4-methyl ether.
The synthesis of [18]annulene 1,4-Oxide-7,10:13,16-disulphide
Authors: Badger GM , Lewis GE , Singh UP
Published: September 2010

[18]Annulene
1,4-oxide-7,10:13,16-disulphide has been synthesized. It has been found to be a
stable system; but its spectral characteristics indicate that it is
non-aromatic and that the three heterocyclic rings are linked by three
essentially olefinic vinylene groups.
Correlation of N.M.R. chemical shifts of N-methyl protons of substituted dimethylanilines with Hammett substituent constants
Authors: Rae ID , Dyall LK
Published: September 2010

The proton magnetic resonance chemical
shifts of N-methyl protons in para-substituted
NN-dimethylanilines have been correlated with the
Hammett �- value of the para
substituent. The correlation yields �- values of 1.57 � 0.09 and 0.85 � 0.09
for the para nitroso and para 4'-dimethylaminobenzoyl
substituents, respectively. The solvent shift of the N-methyl protons between
chloroform and benzene solutions also fits a linear correlation with Hammett �-,
and yields �- = 1.52 � 0.11 for the para-nitroso
substituent.
Molecular susceptibility. The relative ring currents in pyridine, thiophen, furan, and pyrrole
Authors: Le Fevre RJW , Murthy DSN
Published: September 2010

Molar Cotton-Mouton constants at infinite
dilution in carbon tetrachloride are reported; from these, in conjunction with
available polarizability and susceptibility data, the diamagnetic anisotropies
of the solutes are evaluated. Using known molecular dimensions the π
electron ring currents appear, relatively to benzene as 1, to be 1.06 : 0 .19 :
0.57 : 0.37 respectively for the four heterocycles in the title.
Determination of the aqueous solubility of fatty acids and alcohols
Authors: Robb ID
Published: September 2010

The solubility of fatty acids
and alcohols in water at 25� has been measured by a new technique involving a film
balance. For both, the logarithm of the solubility varies linearly with chain
length, and the deviation from this for fatty acids as found by earlier workers
is shown to be due to ionization of the acids in water. The ionization constant
of tetradecanoic acid in water at 25� was estimated to be 1.26 x 10-5.
Catalytic deuterium exchange reactions with organics. XXVII. The alkylbenzenes on self-activated Group VIII transition metals
Authors: Fisher BD , Garnett JL
Published: September 2010

Exchange reactions between
heavy water and the alkylbenzenes have been investigated on the following
self-activated Group VIII transition metal oxides: PtO2,2H2O;
PdO; Rh2O3;
IrO2,2H2O; RuO2,H2O;
ReO2; and Ni2O3.
All oxides except Ni2O3 are
self-activated by benzene up to 180�. Order of ease of self-activation is Pt
> Pd > Rh, Ru, Ir > Re > Ni. Trends in deuteration rates of the
alkylbenzenes on self-activated platinum oxide are generally similar to those
obtained on hydrogen prereduced platinum. At 130�, some differences in
reactivity are observed and these are attributed to reagent displacement
effects from the presence of small percentages of dimer (1%) associated with
the self-activation process. Compared with hydrogen prereduced catalysts,
significant differences in isotope orientation are observed with certain
alkylbenzenes on self-activated catalysts. Multiple deuteration effects which
are accentuated on self-activated catalysts have been used to confirm isotope
orientation and also the participation of a π-complex mechanism for the
exchange process. Isomerization and exchange in cis- and trans-stilbenes on
self-activated platinum have also been interpreted by the dissociative
n-complex substitution mechanism. The advantages of self-activated catalysts in
general deuterium and tritium labelling work have been evaluated. Possible
correlations between exchange results and electron spin resonance data for
charge-transfer adsorption on the above oxides are discussed. Preliminary
kinetic studies with self-activation are also reported.
Thermodynamic functions of ionization of the Anilinum and Toluidinium Ions
Authors: Bolton PD , Hall FM
Published: September 2010

The application of the
spectrophotometric method to the measurement, over a range of temperature, of
the thermodynamic acidity constants of ions of the anilinium type is described.

The thermodynamic functions of ionization ΔG25,
ΔH25, ΔS25, and ΔCp,25
of the anilinium ion and the three toluidinium ions are given and compared with
those of previous determinations.
Carboxylic Esters as Ligands. II. Transition metal complexes of Diethyl Acetonedicarboxylate, Ethyl Acetoacetate, and Diethyl oxaloacetate
Authors: Hay RW , Caughley BP
Published: September 2010

The preparation, infrared
spectra, magnetic data, and reactions of a variety of transition metal
complexes of diethyl acetonedicarboxylate are described. The infrared spectra
indicate chelate ring formation with a metal-oxygen bond with the carbonyl group
of the ester. Transesterification reactions with alcohols occur much less
readily with these complexes than with the corresponding metal oxaloacetates.

Bis(ethyl acetoacetato)copper(II) undergoes methanolysis
rather than trans-esterification on refluxing with methanol to give a bright
blue methoxy-bridged polymer with an abnormally low magnetic moment (μeff
1.14 B.M. at 17�), presumably indicating metal-metal interaction. The magnetic
moments of various transition metal complexes of ethyl acetoacetate and diethyl
oxaloacetate have also been determined.

The β-keto esters have been condensed
with 1,2-diaminoethane to give N,N?-bis Schiff bases which exist predominantly
as the enamine tautomer in the solid state and in solution. Attempts to prepare
copper(II) complexes of these Schiff bases in aqueous ethanol have been
unsuccessful as the ligands rapidly hydrolyse in the presence of copper(II)
ions.
Spectroscopic, crystal, and halogen-exchange studies of halogenotrimolybdates(II)
Authors: van Bronswyk W , Sheldon JC
Published: September 2010

Quantitative solid
(potassium halide disk) and hydrochloric acid solution adsorption spectra of
halogenotrimolybdates(II) indicate that the compounds are of a common
structural type, both in solid and solution, but that at least two kinds of
chloro- or bromo-molybdate(II) are present. Variation of absorption intensities
with hydrochloric acid molarity suggests the equilibrium (Mo3Cl12)6-+Cl-
↔ (Mo3Cl13)7-, and moreover similar
intensity changes occur when K6Mo3Cl12 is in
KCl.

X-ray diffraction powder photographs of K6Mo3Cl12
and AI7Mo3Cl13,H2O (AI
= NH4 or Rb) have been indexed on a pseudo-tetragonal unit cell and
indicate 15 and 18 molybdenum atoms per unit oell respectively. The values are
decisive for trimers (Mo3) if it is assumed that all the compounds
have similar structures.

Halogen-exchange studies support the (Mo3X13)7-
parental structure, having four bridging, and nine terminal and labile,
halogeno groups, since (NH4)7Mo3Cl13,H2O
rapidly exchanges only nine chlorine atoms in 1M hydrochloric acid.
Organoaluminium compounds. XII. A kinetic study of alkyl group exchange between trimethylaluminium and dimethylethylaluminium etherates
Authors: Ham NS , Jeffery EA , Mole T , Saunders JK
Published: September 2010

Proton magnetic resonance
spectrometry has been used to investigate the exchange of alkyl groups between
trimethylaluminium etherate and dimethylethyl-aluminium etherate in toluene in
the presence of ether. The dependence of rate upon concentration of ether,
total aluminium concentration, and temperature leads to the conclusion that the
organoaluminium compounds undergo exchange while
still complexed with ether.
Pyrimidine reactions. XVI. Thermal rearrangement of substituted 2- and 4-alkoxypyrimidines
Authors: Brown DJ , Lee T
Published: September 2010

Thermal rearrangement of
methyl, bromo, and nitro derivatives of 2- and 4-alkoxy-pyrimidines produced
their N-alkyl isomers. These were identified by p.m.r.
spectral comparison with synthetic specimens of unambiguous or proven
structure. The rates for such isomerizations were
measured conveniently by changes in ultraviolet spectra. The C-methyl
derivatives rearranged more slowly than the parent alkoxypyrimidines,
but the bromo, and especially the nitro, derivatives did so much more quickly.
Among the derivatives of each methoxy-pyrimidine, the rate of rearrangement
increased as the basic pKa value fell and as the methoxyl protons
moved downfield, thus affording a qualitative correlation with properties
reflecting the electronic effect of each substituent.
Radiation-induced reactions with cellulose. V. Mechanism studies of copolymerization with styrene in non-wetting solvents
Authors: Dilli S , Garnett JL
Published: September 2010

A study is reported of the radiation-induced grafting of the
monomers

styrene, methyl methacrylate, vinyl
acetate, 2- and 4-vinylpyridine to cellulose in solvents
of the cellulose non-wetting type. Generally, poor grafting yields were achieved
irrespective of the variables such as dose rate, total dose, and monomer concentration.
Under certain conditions, an oxygen effect on the grafting reactions was
observed. The results have been interpreted in terms of possible radical scavenging
reactions, in particular, a charge-transfer theory, and the limited access of
the monomer in these solvents to the active sites within the trunk polymer.

The inclusion of small amounts of methanol in the solvent is shown
to enhance the grafting yields.
Nuclear quadrupole resonance of charge transfer complexes. I. The trihalide ions
Authors: Bowmaker GA , Hacobian S
Published: September 2010

The nuclear quadrupole
resonance frequencies of the halogen atoms in the trihalide
ions 13 and Ibr2 in some of
their crystalline salts have been measured. The results have been correlated with a simple
LOAD-MO bonding description and the charge distributions in the ions have been
calculated. These ions can be regarded as charge-transfer complexes as
described by Mulliken. The effect of the crystal
field on the charge distribution in the I3 ion has been
investigated.
Reactions of excited molecules. II. Reactions of phenylhydrazones on electron impact
Authors: Crow WD , Occolowitz JL , Solly RK
Published: September 2010

Electron impact data are
presented for the phenylhydrazones of a series of
aromatic ketones C6H5-CO-R (R = H, CH3, CD3,
C2H5, C6H6), and are discussed in
comparison with the results of thermal excitation. Whereas pyrolysis resulted
in extensive four-centre migration of R to nitrogen, followed by (or
synchronous with) cleavage of the N-X bond, the electron-impact breakdown is
largely dominated by N-N bond cleavage. A semi-quantitative assessment is made
of the rearrangements which do occur, and the stereochemistry of these and
related reactions is discussed.
Peroxychromium compounds
Authors: Armstrong R , Gibson NA
Published: September 2010

The formulae and properties
of certain blue and violet peroxyohromium compounds have been
investigated, and structures suggested. The blue adducts can be represented as
organic base, Cr(O2)2O, blue anions as Cr(O2)2OX-
where X is Cl or Br, and the violet anions as Cr(O2)2O2H-,
where His thought to be hydrogen-bonded between two oxygen atoms. A
relationship between these different forms is suggested. The various properties
investigated for the peroxychromium compounds include magnetic
susceptibilities, number of peroxy groups, conductivities, molecular weight
measurements, and visible, infrared, and N.M.R. spectra.
Gas chromatography of polar solutes in electron acceptor stationary phases
Authors: Brown I , Chapman IL , Nicholson GJ
Published: September 2010

Two useful electron
acceptor stationary phases have been developed which give a different pattern
of solute retention behaviour from that found in electron donor type phases.
These are the di-wH-octafluoropentyl ester of tetranitrodiphenic acid and tetrameric
bis(l,l,9-trihydrohexadecafluorononyl) phosphonitrilate. They were chosen as a result of a
study of the retention behaviour of solutes of various types in a number of new
stationary phases. The initial specific
retention volumes and Kovats indices of a number of
solutes from ten homologous series were determined at 100� and 150� in these
acceptor phases, in the non-polar phase Apiezon L and
in the electron donor poly(ethyleneglycol succinate) for comparison. The two acceptor phases
studied show large differences in solute retention behaviour from the non-polar
and from the donor-type polar phase. The former have been shown to be suitable
for solute identification, the analysis of perfluoro
compounds, and useful in the study of electron donor-acceptor interactions by
gas chromatography. From the specific retention
volumes of these solutes the contributions to the changes in free energy, heat,
and entropy, due to various functional groups, were determined for the process
of transfer of the solutes from dilute vapour to solution in the liquid
solvent. It was found that the
retention of polar solutes in the polar solvents was dependent on both dipole
interaction and specific donor-acceptor interaction between solute and solvent.
The retention behaviour of two
homologous series of perfluoro alcohols in poly(ethyleneglycol succinate) was
found to be anomalous; the higher members of the series had lower retention
volumes than the lower members. This was shown to be due to the combination
of very weak interactions of the lyophobic perfluoroalkyl groups with the solvent molecules and the
relatively strong interactions between the solvent molecules themselves.
Reactivity of transition metal fluorides. Vi. Halogen-exchange reactions of vanadium pentafluoride
Authors: Canterford JH , O'Donnell TA
Published: September 2010

In an earlier paper in this
series, it was indicated that halogen-exchange reactions between vanadium
pentafluoride and covalent chlorides are very complex. The present work shows that the results may be
rationalized on the basis of an initial halogen-exchange reaction, producing
vanadium tetrachloride, chlorine, and the appropriate fluoride. As soon as some
vanadium tetrachloride is formed, competitive reactions commence, thus making
the exact elucidation of the reaction schemes very difficult. In order to
clarify the situation, some reactions of vanadium tetrachloride itself were
studied.
The acidity constant of the hydrogen chromate ion in the range 5-60° in water
Authors: Linge HG , Jones AL
Published: September 2010

The equilibrium HCrO4-;
↔ CrO42-+H+ in water has been studied by
potentiometric and
independent spectrophotometric methods between 5� and 60�. The thermodynamic
quantities ΔS0, ΔH0, and ΔCp
have been evaluated.
The surface chemistry of kaolinite. I. Surface leaching
Authors: Buchanan AS , Oppenheim RC
Published: September 2010

Aqueous suspensions of
kaolinite from Mt. Egerton, Victoria, have been
leached at pH 2.25 and 6.0. More ions, in particular aluminium, than predicted
from the published cation-exchange capacity have been detected in the leachate. An activation energy of 5 kcal/mole has been
calculated for this process of surface leaching. Using a supporting electrolyte
of, for example, 10-4M KCl, the electrophoretic mobility of leached
and raw clay has been examined as a function of pH, and differences in mobility
have been correlated with aluminium removal from the clay surface.
Shock-initiated exothermic reactions. IV. The oxidation of carbon monoxide
Authors: Drummond LJ
Published: September 2010

Reflected shocks have been
used to process mixtures of CO with O2 or N2O or NO in the presence of
argon. Results for CO-O2 mixtures led to the value of 19.4 kcal/mole
for the activation energy of the rate controlling reaction during the induction
period to explosion. The presence of a small amount of hydrogen caused a marked
decrease in the ignition delay and it is estimated that about 600 p.p.m. were sufficient for this effect to be significant.
The ignition period to explosion of CO-N2O mixtures appeared to be
governed by the rate of N2O decomposition. ��The measured value of the activation energy
indicates that energy transfer from CO to NzO
molecules has occurred. The influence of H2 on this system is
reported also. No reaction was induced in CO-KO-Ar mixtures.
Organoaluminium compounds. XVIII. Mechanism of methyl group exchange between trimethylaluminium and dimethyl(phenylethynyl)aluminium
Authors: Ham NS , Jeffery EA , Mole T
Published: September 2010

The exchange of methyl
groups between trimethylaluminium and dimethyl- (phenylethyny1)aluminium has
been studied by proton magnetic resonance spectro- scopy. The kinetics indicate
that a monomer of trimethylaluminium attacks a dimer of dimethyl(phenylethynyl)aluminium
in the rate-determining step.
Chemical studies of the Proteaceae. III. The structure determination and synthesis of striatol, a novel phenol from Grevillea striata R. Br
Authors: Rasmussen M , Ridley DD , Ritchie E , Taylor WC
Published: September 2010

From the wood of Gevillea striata R.
Br., a phenol, striatol, C28H42O4,
was isolated. Chemical and spectroscopic evidence indicated its structure to be
1,14-bis(3,5-dihydroxy-4-methylphenyl)tetradecane. The structure was confirmed by synthesis.
An analysis of the vibrational spectra of orthorhombic mercury(II) oxide and hexagonal mercury(II) sulphide
Authors: Cooney RPJ , Hall JR
Published: September 2010

Ramen spectra of
orthorhombic mercury(II) oxide and hexagonal mercury(II) sulphide are reported
here. The former contains lines at 331 and 550 cm-1, and the latter
at 250, 284, and 343 cm-1. These spectra, together with previously
reported infrared spectra, have been interpreted in terms of factor group
analyses of repeat units of the chain polymers.