bluuebunny/crossref_metadata_2025 huggingface dataset:
An α-diketone from the condensation product of glucose and ethyl acetoacetate
Authors: Dalton LK
Published: September 2010

When the product from the condensation of
glucose and ethyl acetoacetate, ethyl 2-D-arabino-tetrahydroxybutyl-5-methyl-4-furoate
(Ia), is heated in ethanolic hydrogen chloride, an a-diketone (IVa) is
produced. It exists as a mono-enol in solution and in the solid state. Although
this diketone is formed with an aliphatic side chain, there is at first a
predominant, but reversible, cyclization to the "difuran" (II). With
hydrogen peroxide the diketone yields 2-carboxymethy1-5- methyl-4-furoic acid
(VII), and with alkali it undergoes a benzilic acid rearrangement.
Terpenoid chemistry. VIII. The structure of δ-elemene
Authors: Gough JH , Sutherland MD
Published: September 2010

The sesquiterpene δ-elemene, isolated
from Dysoxylon frazeranum wood oil and from a gurjun balsam from Chittagong,
Pakistan, is shown by spectral and degradative studies to be (�)-3-isopropenyl-1-isopropyl-4-methyl-4-vinylcyclohexene
and to share with the closely related terpenoid geijerene the peculiarity of
complete optical inactivity despite the presence of two asymmetric centres.
Organophosphorus compounds. VI. The 'abnormal' Michaelis-Becker reaction. Diethyl 1-phenylepoxyethylphosphonate and diethyl 1-phenylvinylphosphate from diethyl phosphonate and phenacyl chloride
Authors: Meisters A , Swan JM
Published: September 2010

Phenacyl chloride reacts with sodium
diethyl phosphonate in liquid ammonia solution to yield a 7 : 3 mixture of
diethyl 1-phenylepoxyethylphosphonate (Ia) and the isomeric diethyl
1-phenylvinyl phosphate (IIa). Reaction of phenacyl chloride with diethyl
phosphonate and triethylamine in benzene gives only diethyl 1-phenylvinyl
phosphate.

The action of hydrogen chloride on the
epoxide (Ia) gives diethyl 2-chloro-1-hydroxy-1-phenylethylphosphonate (IV).
This chlorohydrin reacts with sodium amide in liquid ammonia or with sodium
hydroxide in ethanol to again yield a mixture of (Ia) end (IIa); with
triethylamine in benzene, the product is mainly the vinyl phosphate (IIa).
The aniline catalysed decarboxylation of oxaloacetic acid
Authors: Hay RW
Published: September 2010

Aniline catalysis of the decarboxylation
of oxaloacetic acid, HO2CCOCH2CO2H + CH3COCO2H
+ CO2, has been studied in water and ethanol as solvent at 25�. In
aqueous solution a maximum occurs in the pH-rate profile at pH 3.9, indicating
the participation of a single proton in the transition state. Experiments with
the half ester HO2CCOCH2CO2Et, which does not
decarboxylate in the presence of amines, suggest that in aqueous solution the
intermediate in the reaction is a carbinolamine formed between the amine and
the keto group of the acid, and not a Schiff's base as has been previously
suggested. In ethanol solution the intermediate is a Schiff's base, and
formation of the Schiff's base is the rate-determining step, the actual
decarboxylation being a fast process.
Azaindoles. II. The synthesis of Pyrazolo[4,3-c]pyridines
Authors: Badger GM , Rao RP
Published: September 2010

3-Hydroxy-1H-pyrazolo[4,3-c]pyridine, 3-hydroxy-1-phenyl-1H-pyrazolo-[4,3-c]pyridine, 3-hydroxy-1-methyl-1H-pyrazolo[4,3-c]pyridine, and their
5-oxides have been prepared for testing as tumour inhibitors. Lactam-lactim
tautomerism in these compounds is discussed.
Metal complexes of Schiff bases derived from Thiophen-2-aldehyde
Authors: Ho RKY , Livingstone SE
Published: September 2010

A number of metal chelates of NN'-ethylenebis(2-thenylideneimine)
(S-N-N-S) are described. The compounds [Cu(S-N-N-S)2][CuX2]
(X = Cl, Br, I), Pd(S-N-N-S)X2, (X = Cl, Br, NO2) and the
low-spin complex [Ni(S-N-N-S)2]- (ClO4)2,2H2O
are unaffected by boiling water. On the other hand, the compounds M(S-N-N-S)X2
(M = Co, Cu, Zn, Cd; X = Cl, Br, I, or NCS), which were prepared from alcoholic
solution, are converted slowly in cold and rapidly in hot water into the
corresponding metal bisethylenediamine complexes owing to hydrolysis of the
coordinated Schiff base. Paramagnetic complexes Ni(S-N-N)2X2
(X = Br, I) containing the partially hydrolysed Schiff base
N-2-aminoethyl-2'-thenylideneimine (S-N-N) were obtained when solutions of the
nickel halides were treated with NN'-ethylenebis(2-thenylideneimine). Evidence
is produced to show that in these metal complexes the ligand is coordinated
through both nitrogen atoms and that the sulphur atom in the thiophene ring is
not coordinated. except possibly in the polymeric palladium complexes. Some
metal chelates of NN'-trimethylenebis(2-thenylideneimine) were also isolated.

Complexes of palladium(II) and cobalt(11)
with NN'-1,2-phenylenebis(2-thenylideneimine) were prepared; in these complexes
the Schiff base acts as a unidentate ligand since coordination through both
nitrogen atoms would require a gross deformation of the bond angles.

Palladium(II) complexes of
N-n-propyl-2-pyridylmethyleneimine and NS'-tri-methylenebis(2-thenylideneimine)
were also characterized. However, attempts to isolate metal chelates of
NN'-ethylenebis(2-pyrrolylmethyleneimine) were unsuccessful.
Nuclear magnetic resonance studies. IV. The analysis of the spectra of two thiophene derivatives
Authors: Coogan CK , Horn DHS , Lamberton JA
Published: September 2010

Complete analyses of the nuclear magnetic
resonance spectra of 5-(but-3-en-1-yny1)-2,2'-bithienyl (I) and α-terthienyl
(II) were carried out. The chemical shifts and coupling constants obtained for
the ABC systems present are compared with those determined by the approximation
method of Hoffman and Gronowitz. This method affords remarkably good chemical
shift values for even very strongly coupled systems.
Pyrimidine reactions. IX. The amination of chloropyrimidines with branched alkylamines and Di-n-alkylamines
Authors: Brown DJ , Lyall JM
Published: September 2010

The reactions of
2-chloro-4,6-dimethylpyrimidine and 4-chloro-2,6-dimethylpyrimidine with some
branched-alkyl- and dialkyl-amines have been followed from 30� to 70� in the
absence of solvent. At comparable temperatures, alkylamines with β- or γ-branching
approximated in reactivity to n-alkylamines, whereas those with α-branching
and the di-n-alkylamines had only about 5% of the above reactivity;
t-butylamine with two a-branches had but 0.1% of the reactivity of
n-butylamine. Optimum conditions of time and temperature, calculated from these
measurements, have been used to prepare 16 new alkylaminopyrimidines in good
yield.
An investigation of the nickel gluconate system
Authors: Joyce LG , Pickering WF
Published: September 2010

Spectrophotometric, polarographic,
conductometric, and potentiometric techniques were used to examine the nickel
gluconate system. Three complex species were identified: a cationic species,
NiG+, in solutions of pH < 7; an anionic complex, Ni2(OH)4G-,
in solutions of pH > 9; and an insoluble product, Ni2(0H)3G,
in solutions of pH 7-9; the symbol G represents the gluconate ion CH20H(CHOH)COO-.
Values have been calculated for the dissociation constants of these three
species at 25�.
Cell model for quantum fluids. III. Compressional waves in liquid hydrogen
Authors: Chen R , Henderson D , Reed RD
Published: September 2010

The velocity of sound is calculated for
each of the isotopic forms of liquid hydrogen using the quantum cell model. The
velocity of sound increases as the pressure increases and decreases as the
temperature increases. Also the reduced velocity of sound decreases as the
value of the quantum parameter, Λ*, increases. In addition, the
thermodynamic properties of liquid hydrogen compressed by a shock wave are
calculated.
The infrared spectra of the solid phases in the system BeO-H2O
Authors: Bear IJ , Lukaszewski GM , Turnbull AG
Published: September 2010

Chemical and structural information
relating to the BeO-H2O system is
discussed and correlated. The infrared spectra of α, β, and amorphous
Be(OH)2 have been studied in the range 650 to 10,000 cm-1.
These show that the constitution of the three hydroxides is similar. The
spectra are interpreted to arise from the coupled vibrations of Be(OH)4
structural groups and from hydroxyl interactions. The hydroxyl vibrations are
identified by spectroscopic shifts observed on partial deuteration and by means
of spectroscopic-structural relations. Tentative assignments are made by
comparing the spectra from BeO, Be(OH)2,
and other systems containing similar structural groups. The complex nature of
the spectra is discussed.
Internal conversion in aromatic and N-heteroaromatic molecules
Authors: Byrne JP , McCoy EF , Ross IG
Published: September 2010

A previous semi-empirical approach to the
calculation of the rate of internal conversion, regarded as a tunnelling
process, is reformulated on a sounder theoretical basis. Following Robinson and
Frosch, tunnelling rates are correlated with Franck-Condon factors for the
associated transition. The total Franck-Condon factor, S2max,
is a product of three terms, associated respectively with skeletal stretching,
CH stretching, and skeletal angle bending vibrations. The value of S2max
may be controlled by one term only of the product, or by two or more (mixed
tunnelling). Tunnelling rates should be slowed down by deuteration only when CH
vibrations participate significantly; specific predictions are made here.
Skeletal-angle bending vibrations are of negligible importance in internal
conversion in aromatic molecules, but they are very significant in transitions
between states of π,π* and n,π* type in heteroaromatics. Correlation between S2max
and estimated tunnelling rates is encouraging for four aromatic molecules and
certain monocyclic azines; but the failure of pyridine and pyridazine to show
luminescence is still unexplained. The case of pyrazine is discussed in detail.
The absolute configuration of ( - )-angolensin
Authors: Ollis WD , Ramsay MVJ , Sutherland IO
Published: September 2010

Oxidation of (-)-angolensin isolated from
the heartwood of Pterocarpus angolensis has yielded (-)-2-(4-methoxyphenyl)propionic
acid (Ia). This establishes that the isoflavonoid, (-)-angolensin, has the
R-configuration (II) and the relation between this absolute stereochemistry and
that of other isoflavonoids is discussed.
Pyrimidine reactions. XI. Amination rates for two chlorodimethylprimidines without solvent
Authors: Brown DJ , Lyall JM
Published: September 2010

Second-order rate constants, Arrhenius
parameters, and isokinetic temperatures are presented for the reactions of
2-chloro-4,6-dimethylpyrimidine and 4-chloro-2,6-dimethylpyrimidine with some
n-alkyl-, branched alkyl-, and dialkylamines in the absence of a solvent. The
differences between these values and those available for the same reactions in
a solvent are briefly discussed. An equation is derived for satisfactorily
converting the apparent first-order rate constants previously reported by us
into second-order rate constants.
A model describing the variation in free energy in compound and single phase regions in binary systems containing miscibility gaps
Authors: Esdaile JD
Published: September 2010

A model is derived to represent the
variation of free energy of combination of one gram-atom of two components,
represented by A and B, in intermediate single, or compound, phases in a binary
system as a function of composition at constant temperature, and with a minimum
of experimental data. The derivation of the model involves the, assumption that
the straight lines representing the free energy of the two phase fields
adjacent to a compound phase, on an isothermal integral free energy against
atomic fraction diagram, intersect at the mid-point of the compound phase. A
relation between logaA, logaB, and the atomic fraction NB is
developed so as to conform with the preceding requirement and yield an almost
horizontal tangent to the curve representing the compound phase at NB
= � for a hypothetical symmetrical isothermal diagram. The equations developed
on these bases are extended to non-symmetrical systems. These are shown to be
successful in predicting the variation in free energy of compound phases, as a
function of composition, in binary systems for which experimental data are
available.
Kinetic medium effects. II. Hydrolysis of esters in electrolyte solutions
Authors: McTigue PT , Watkins AR
Published: September 2010

Rate constants have been measured for the
acid-catalysed hydrolyses of t-butyl acetate and methyl chloroacetate in
various aqueous electrolyte solutions; the activity coefficients of the esters
in these electrolyte solutions have also been measured. The results are used to
test a recently proposed method of determining transition state hydration
numbers for reactions in aqueous media.
Tlie alkaloids of Atherosperma moschatum Labill. II. Non-phenolic alkaloids
Authors: Bick IRC , Douglas GK
Published: September 2010

Of the new non-phenolic alkaloids
previously reported in the bark of Atherosperma moschatum Labill.,
atherospermidine has been shown to have the methoxylspermatheridine structure (II),
while atherosperminine (VIII) and a further new base, methoxyatherosperminine
(IX), have proved to be members of the small group of phenanthrene alkaloids.
A device for enhancing the sensitivity of N.M.R. spectrometers
Authors: Dehlsen DC , Robertson AV
Published: September 2010

A simple, inexpensive
device for increasing the sensitivity of the Varian Associates A60 n.m.r, spectrometer is described.
Cassytha alkaloids. I. New aporphine alkaloids from Cassytha filiformis L
Authors: Jones SR , Lamberton JA
Published: September 2010

Cassythine, C19H19N05,
the major phenolic alkaloid of Cassytha filiformis L., is a new aporphine.
Its NO-dimethyl derivative has been identified as the known alkaloid (+)-ocoteine (11), and from spectroscopic data cassythine is considered to be (Ia).
A new non-phenolic base, cassythidine, C19H17NO5,
is considered to be(IV).
Molecular polarizability: The molar Kerr constants of diazoaminobenzene and four of its derivatives.
Authors: Armstrong RS , Le Fevre RJW , Singh AN
Published: September 2010

The molar Kerr constants of
diazoaminobenzene and its 4,4'-dimethyl, 4,4'-clichloro, 4,4'-dibromo, and
4-nitro derivatives at infinite dilution in benzene at 25� are recorded. No
abnormalities in the molar Kerr constant-concentration curves due to dimeric
association can be found with any of the above solutes.
Some studies in inorganic complexes. XIX. 2-Mercaptomethylpyridine, 2-thioamidopyridine, and 2-aminomethylpyridine reactions
Authors: Sutton GJ
Published: September 2010

The following compounds have been prepared
and studied: the inner complexes [M picmer2],
[M2Cl2 picmer2],
and [Sn2I6 picmer2]
where H-picmer is 2-mercaptomethylpyridine
and M is divalent nickel, palladium, and platinum. The 2-thioemidopyridine(thiopic) complexes [Bi thiopic3][ClO4]3 and [Sn2I6
picmer2] and the salts [thiopic-H]2[BiX5],[thiopic-H][SbX4], and
[thiopic-H][AsX4]
(X = Cl, Br, I) as well as the 2-aminomethylpyridine (pic)
complexes [Os pic3][ClO4]3,
[Os pic2 pic-H]-
[ClO4]3, [Os pic (pic-H)2]Br2, and [SnI4
pic] are also described.
Activity coefficient assumptions m the determination of the association constant of thallons chloride. II. Effect of interactions between freeions
Authors: Macaskill JB , Panckhurst MH
Published: September 2010

The solubility of thallous
chloride has been measured in solutions of hydrochloric acid, caesium chloride,
caesium perchlorate, barium chloride, and in various mixtures of sodium
chloride and sodium perchlorate. These measurements are analysed to give the association
constant for thallous chloride, paying particular attention to ionic activity
coefficient formulae. It is shown that an activity coefficient expression which
assumes no specific interactions between free ions is unsatisfactory in
contrast to an expression which assumes such interactions. The consequences of
this are discussed.
The formation of aromatic hydrocarbons at high temperatures. XXVII. The pyrolysis of isoprene
Authors: Badger GM , Donnelly JK , Spotswood TM
Published: September 2010

As a further contribution to the study of
the mode of formation of polycyclic aromatic compounds in cigarette tar, the
pyrolysis of isoprene at 700� has been investigated. A complex tar containing
many aromatic hydrocarbons was obtained and mechanisms for the formation of
these compounds are discussed. Isoprene may be an important precursor of
polynuclear hydrocarbons in cigarette tar.
Chemical studies of amphibole asbestos. I. Structural changes of heat-treated crocidolite, amosite, and tremolite from infrared absorption studies
Authors: Patterson JH , O'Connor DJ
Published: September 2010

The thermal dehydroxylation,
oxidation, and decomposition of the amphiboles: crocidolite, amosite, and
tremolite have been investigated with infrared spectroscopy. Changes in the
spectra with temperature have been related to these processes.

The dehydroxylation
of crocidolite and amosite
in air causes only small structural rearrangements but dehydration of tremolite occurs at higher temperatures during
decomposition of the amphibole structure. For both crocidolite
and amosite the temperature of dehydroxylation
is higher and the decomposition temperature lower in vacuum than in air. These
differences are discussed in terms of variation in chemical composition and
changes in the mechanism of dehydroxylation. For crocidolite it is suggested that certain hydroxyl groups
are removed preferentially.��� Small structural rearrangements associated
with oxidation and dehydroxylation cause a broadening
and shifting of the main absorption bands but decomposition of the structure
produces marked changes in the spectra.
Metal complexes of a sexadentate ligand: The occurrence of some solvent clathrates
Authors: Lindoy LF , Livingstone SE , Lockyer TN , Stephenson NC
Published: September 2010

Complexes of iron(II), cobalt(11), nicke1(II),
and copper(II) with the sexadentate ligand
1,5-bis-[2-(2-pyridylmethyleneimino)-phenyl]-l,5-dithiapentane (sexa) have been prepared. The iron(II) and cobalt(11)
compounds are low-spin while the nickel(II) compounds are high-spin. Evidence
is produced to support the contention that the metal atoms are six-coordinate.

Many of the complexes were obtained as clathrates containing one or more molecules of water,
alcohol, dimethylformamide, or acetone. The infrared spectra indicate that
these solvent molecules, which are not readily lost, are not coordinated to the
metal ion. A thermogravimetric study of [Fe sexa][FeCl4]2,(CH3)2CO
showed that one molecule of acetone is lost at 260� whereupon the complex begins
to decompose. X-ray diffraction data show that this compound has a host
framework of four molecules per unit cell; the structure contains cavities into
which the acetone molecules fit. These guest molecules determine the type of
structure adopted by the clathrate compound.
The basic hydrolysis of amino acid esters
Authors: Hay RW , Porter LJ , Morris PJ
Published: September 2010

The kinetics of alkaline hydrolyses of
nine amino acid esters by the process H,2NCHRCO2R'+OH-
+ H2NCHRCO2-+R'OH have been studied at 25� and
an ionic strength of 0.1M in water over a range of pH. The acid ionization
constants of the various amino acid esters have been determined, and these are
roughly 2 pK units lower than those of the corresponding amino acids. The
kinetic measurements are interpretable on the basis of electrostatic and steric
effects.
Synthesis of four geometrical isomers of Hexadeca-2,6.8,12-tetraenoic acid. The insecticidal properties of their isobutylamides
Authors: Meisters A , Wailes PC
Published: September 2010

��� The four stereoisomers of hexadecs-2,cis-6,cis-8,12-tetraenoic acid have been synthesized. The insecticidal
activities of their isobutylamides towards the housefly, Musca domestica, have been examined.
The isobutylamides of 7-Phenylhepta-2,4-dienoic acid, 7-Phenylhepta-2,4,6-trienoic acid, and p-(2-Phenylethyl)benzoic acid
Authors: Meisters A , Wailes PC
Published: September 2010

7-Phenylhepta-2,4-dienoic acid and
7-phenylhepta-2,4,6-trienoic acid have been synthesized as their all-trans isomers. In addition
p-(2-phenylethyl)benzoic acid has been prepared and the insecticidal activities
of the isobutylamides of these three acids towards the housefly, Musca domestics, have been examined.
Some volatile constituents of terrestrial slaters
Authors: Cavill GWK , Clark DV , Hinterberger H
Published: September 2010

The common terrestrial
dater, Porcellio scaber, yields a volatile extractive, slaterol, which comprises
cis- and trans-dec-3-en-1-ol (80%), together with cis- and trans-non-3-en-1-ol
and nonan-1-ol (5%). The remaining and unsaturated component of slaterol (A,
15%), which gives decan-1-ol on reduction, has yet to be characterized. An
undescribed Armadillidium sp. yields a single constituent, octan-1-ol.
Cyclitols. XXV. Benzyl ethers of ( - )-inositol. Lack of selectivity in O-substitution
Authors: Angyal SJ , Stewart TS
Published: September 2010

Several partially
benzylated derivatives of (-)-inositol have been synthesized. None of the
reactions tried showed marked preference towards equatorial hydroxyl groups but
in one instance-benzylation in benzyl chloride as solvent-an axial hydroxyl
group reacted preferentially.
Chemical constituents of Eriococcus confusus Maskell. I. The quinonoid pigments
Authors: Chan AWK , Crow WD
Published: September 2010

Eriococcus confusus Maskell., growing
on both Eucalyptus caesia and maculosa, contains a
number of anthraquinone pigments. Emodin has been identified as one of the
major components, and the other is tentatively assigned the structure
1,2,3,8-tetrahydroxy-6-methylanthrquinone.
Chromatographic and p.m.r, data are presented for a
number of anthraquinones, including the new compounds 1,3,5-trihydroxy-6- methylanthraquinone and
1,3,5-trihydroxy-7-methylanthraquinone.

In addition to the pigments, the insects
are covered with a waxy secretion, which probably consists of a mixture of
long-chain, saturated ketones in the C20-C24 range.
Characterization of solid inorganic and coordination compounds by their near infrared reflection spectra
Authors: Reid AF
Published: September 2010

The near infrared
combination spectra of a number of classes of solid inorganic and coordination
compounds have been recorded and assigned. The spectra are shown to be typical
of particular ligands regardless of the compounds in which they are contained,
and to serve as an experimentally convenient means of characterization of solid
coordination or organometallic compounds.
The reaction of ferricinium ion with phenylazotriphenylmethane
Authors: Beckwith ALJ , Leydon RJ
Published: September 2010

Ferricinium tetrafluoroborate, when treated with phenylazotriphenylmethane
in acetic acid, affords inter alia phenylferrocene and a trace of 1,1?-diphenylferrocene
both of which products probably arise by attack of free phenyl radicals on
ferricinium ion. Produced in the same reaction are triphenylmethylferrocene
and 1,1?-di-(triphenylmethyl)ferrocene, and these
compounds are also formed by treatment of ferrocene with triphenylcarbinol. The
relevance of these results to the mechanism of the arylation of ferrocene with
diazonium salts is discussed.
Naphtho[1,8-bc]thiophens. I. Synthesis
Authors: Hawthorne DG , Porter QN
Published: September 2010

Syntheses of some
derivatives of the as yet unknown heterocycle naphtho-[1,8-bc]thiophen
are described, and it is shown that this potentially tautomeric ring system
preferentially exists in the naphthalenoid form.
Fluorocarbon-aluminium compounds. I. Reactions of some fiuorocarbon halides with lithium tetrahydroaluminate
Authors: Dickson RS , West BO
Published: September 2010

Treatment of solutions of
lithium tetrahydroaluminate with bromopenta- fluorobenzene, C6F5Br,
or iodopentafluorobenzene, C6F5I, yields perfluorophenyl-aluminium
compounds. The thermally stable complex lithium tris(pentafluorophenyl)bromoaluminate,
LiAl(C6F5)3Br,
has been isolated. Similar reactions between lithium tetrahydroaluminate and
perfluoroalkyl iodides are discussed. These reactions are known to yield
thermally unstable perfluoroalkyl-aluminium compounds, and the present paper
reports an investigation of the possible use of solutions of these compounds as
perfluoroalkylating reagents. Although perfluoro- alkyl groups can be
transferred from aluminium to tin and lead, the reactions are complicated and
cannot be considered as useful synthetic pathways to perfluoroalkyl-tin or
-lead compounds.
Transmission line equivalents for the electrode impedance of associated homogeneous reactions
Authors: Elliott D , Buchanan GS
Published: September 2010

A method is described for
deducing the exact transmission line equivalents for associated homogeneous
reactions in a.c. electrolysis. The equivalents are
standard forms, the characteristics of which are available under many input
conditions. ��� The method is extended to consider the
equivalent circuit for partly covered electrode surfaces.
The vibrational spectrum of the N-methylpentadeuteropyridinium ion
Authors: Spinner E
Published: September 2010

A comparison of the
vibrational spectra of the N-methylpyridinium and N-methylpentadeuteropyridinium
ions has shown that ring deuteration modifies the pattern of the
?substituent-sensitive? bands in the Raman spectrum considerably. This is
expected if N-CMe stretching mixes largely
with an aromatic CH in-plane bending rather than with purely skeletal
vibrations. The effective symmetry of the ion is lower than C2v.
A Reaction between Mandelonitrile and Benzaldehyde
Authors: Davies W , Ternai B
Published: September 2010

The reaction of
cyanohydrins with aldehydes under the influence of bases or HCl
is described. It is shown that cyanohydrins give substituted oxazoles on
standing or in the presence of a base. A mechanism is proposed for the
formation of imidazoles in the presence of hydrogen chloride.
Notes on the classical derivation of the nuclear quadrupole energy levels for half-integral spin systems
Authors: Britz S , Hacobian S
Published: September 2010

The derivation of the
energy levels for nuclear quadrupole (n.q.r.) spectra
is critically examined. The interpretation of the experimental results in terms
of parameters which characterize the two interacting systems, the nuclear
charge and the electronic charges, is discussed, and found to be inaccurate. An
accurate quadrupole moment which corresponds to that measured in other fields
of research is larger than the one defined in n.q.r,
and related to it by a function of spin I. This relationship is found using the
transformation properties of the nuclear quadrupole tensor and referring it to
the coordinate system of its own principal axis. The importance of this
relationship in evaluating the properties of both the nucleus itself and the
electron bonding in the molecule, described by the field gradient and its
asymmetry, is discussed.
Thermodynamics of aqueous urea solutions
Authors: Stokes RH
Published: September 2010

A compilation of heat
capacity, heat of dilution, and activity data for aqueous urea solutions is
made from published sources. The existing apparent volume data are supplemented
by new measurements at 0�, 40�, and 50�.

The thermodynamic data are interpreted in
terms of association models, and it is found that the use of Flory-Huggins statistics for the entropy of mixing of the
various associated species and the solvent gives a much better description than
mole-fraction statistics. Heats of association and equilibrium constants are
evaluated.
Cyclitols. XXVII. The reaction of tosylinositols with sodium benzoate in dimethylformamide. Anomalous opening of epoxides
Authors: Angyal SJ , Stewart TS
Published: September 2010

The reactions of several
tosyl derivatives of (+)- and (-)-inositol in boiling dimethylformamide with
and without sodium benzoate have been studied. A tosyloxy group with a trans
acetoxy neighbour is displaced with inversion. A tosyloxy group with a trans neighbouring
hydroxyl group forms an epoxide which is subsequently cleaved with the
production of two compounds in proportions contrary to the rule of ?diaxial?
opening. An explanation is suggested for this anomaly. In the absence of trans
acyloxy or hydroxy neighbours direct displacement of tosyloxy groups occurs in
most oases, though it may be prevented by adjacent bulky groups. Compounds with
two cis vicinal tosyloxy groups tend to undergo an elimination reaction with
the formation of enol tosylates.
Benzo[c]cinnoline derivatives. I. Preparation and spectral characterization of N,N-dialkylaminobenzo[c]cinnolines
Authors: Lewis GE , Reiss JA
Published: September 2010

Reactions of 1-, 2-, 3-,
and-4-chlorobenzo[c]cinnoline with dialkylamines have yielded the four
corresponding dimethylaminobenzo[c]cinnolines and 2-diethyl-aminobenzo[c]cinnoline.
A compound formerly described in the literature as 2- diethylaminobenzo[c]cinnoline
is clearly not the same compound as that now reported. The N.M.R. and
ultraviolet-visible spectral characteristics of the new compounds provide ample
confirmation of the respective molecular structures. A discussion of the
possible structures of the first conjugate acids is presented, following
comparisons of the ultraviolet-visible spectra of amino- and dialkylamino-benzo[c]cinnolines
in dilute acid.
Covalent bond refractions and the periodic table. III. Homopolar bonds
Authors: Christopher PM
Published: September 2010

The empirical equation, P =
aRn+b, where P is the parachor,
R the Lorentz-Lorenz refraction, and a, b, and n are constants, has been
applied in the present instance to the calculation of R for bonds involving the
elements of Groups IVB-VIIB when linked to themselves.
Catalytic deuterium exchange reactions with organics. XXXI. Accelerative effects of ionizing radiation and ultraviolet light on self-activated platinum oxide
Authors: Garnett JL , Rains A , Wong PK
Published: September 2010

The effect of
preirradiation with γ-rays from cobalt-60 and ultraviolet light from a
low-pressure source on the exchange between benzene and heavy water in the
presence of self-activated platinum oxide has been studied. Both rates of
multiple and stepwise exchange processes are accelerated under these
conditions. Of 14 oxides examined, including the Group VIII transition metals,
platinum is the only one to catalyse exchange up to 130�. Preliminary
experiments indicate that radiation-induced oxygen desorption from the surface
of the oxide is responsible for the accelerative effect. Internal radiation
sources such as tritium oxide also increase initial exchange rates.
Cholesterol, naphthalene, dibenzyl, diphenyl, benzoic acid, and diphenyl ether
have been studied with tritium oxide. The results can be rationalized in terms
of π- complex mechanisms for exchange. A catalytic model for the mechanism
of the radiation-induced effect is proposed.
The chemical constituents of Australian Zanthoxylum species. IV. Two new coumarins from Z. suberosum C. T. White (syn. Z. dominianum Merr. & Perry; Z. ovalifolium Wight)
Authors: Guise GB , Ritchie E , Senior RG , Taylor WC
Published: September 2010

The bark of Zanthoxylum dominianum Merr.
& Perry gave suberosin and canthin-6-one in about the same high yields that
were previously reported from Z. suberosum C. T.
White. The result confirms the previous work and supports the recently
expressed view that the names are synonymous.

Minor constituents isolated were palmitic
acid, ?sitosterol?, β- amyrin, isopimpinellin, 7-methoxycoumarin-6-aldehyde,
and two new coumarins, ?suberenol? and ?cyclobisuberodiene?.
The structure of suberenol has been established as (X), and evidence in favour
of (XXI) as the structure of cyclobisuberodiene
obtained.
Structural changes of flavylium salts. III. Polarographic and spectrometric examination of 3,7,4'-trihydroxyflavylium perchlorate
Authors: Harper KA
Published: September 2010

The molecular changes
undergone by 3,7,4?-trihydroxyflavylium perchlorate
in aqueous methanolic solutions with increasing pH were followed by
polarography and spectrometry, and the effect of the hydroxyl at C3 observed by
comparison with the behaviour of 7,4?- dihydroxyflavylium
perchlorate. The trihydroxyflavylium ion is less
stable above pH 2 than the dihydroxy compound and forms the open-chain α-diketone,
probably via the 3-keto pseudobase. The stability of the enolic form of the
pseudobase increases at higher pH and is favoured from pH 5 to pH 9. At pH 6.5
the anhydrobase appears in the equilibrium mixture and at pH 9 becomes stabilized
by ionization. Although the α- hydroxychalcone was not detectable at lower
pH, at pH 10 ring opening gives the ionized a-hydroxychalcone, rather than the
ionized diketone, and equilibrium shifts in this direction as the pH is raised
further.
Transition metal complexes of substituted alkynes. II. Pentafluorophenylacetylene complexes of iron and cobalt
Authors: Dickson RS , Yawney DBW
Published: September 2010

Treatment of pentacarbonyliron with pentafluorophenylacetylene
has given the stable complex tricarbonyl-2,5-bis(pentafluorophenyl)cyclopentadienoneiron. There is no evidence of the
formation of other structural isomers. The complex is also formed from pentafluorophenylaoetylene and nonacarbonyldiiron
or dodecacarbonyltriiron. Two alkyne-cobalt complexes
have been isolated from the interaction of

octacarbonyldicobalt and pentafluorophenylacetylene.
One of these is a bridging alkyne complex of molecular stoicheiometry
Co2(CO)6(C6F6CCH);
the second is a complex of formula Co3(CO)9(CCH2C6F5).
The infrared and nuclear
magnetic resonance spectra of the complexes are given, and the probable
structures of the compounds are deduced from these spectroscopic properties.
Flavan derivatives. XX. A new glycoside and other extractives from Acacia ixiophylla: Rhamnitrin (rhamnetin 3α-L-rhamnoside)
Authors: Clark-Lewis JW , Dainis I
Published: September 2010

Rhamnitrin, a new glycoside from the shrub Acacia ixiophylla, is shown to be quercetin
7-methyl ether 3α-L-rhamnoside. A quercetin diglucoside (considered
to be the 3,3'-diglucoside), quercitrin,
queroetin, rhamnetin, apigenin, apigenin 7,4'-dimethyl
ether, and (-)-epicatechin were also isolated. The
extractive consisted mainly of mixtures of condensed tannins derived from
5,7,3',4'-tetrahydroxy-flavan-3-o1 and -3,4-diol
monomers, and the lower polymers appear to be responsible for the antitumour activity of the extractive.
Correlation of diterpenes of the ( - )-kaurane series and atractyligenin
Authors: Ghisalberti EL , Jefferies PR , Passannanti S , Piozzi F
Published: September 2010

19-Nor-16α- and
19-nor-16β-(-)-kaurane (11) and (111) have been
prepared by unambiguous methods from 16α-( -)-kaurane-3α,l7,19-triol
(IV) and (-)-kaur-16-ene-3α,l9-diol (V) and have
been identified with samples derived from atractyligenin,
thus providing conclusive proof for the skeleton of the latter.
Catalysis by hydrogen halides in the gas phase. XVII. Isobutyric acid and hydrogen bromide
Authors: Cross JTD , Stimson VR
Published: September 2010

Hydrogen bromide catalyses
the decomposition of isobutyric acid into

propene, carbon monoxide, and water at 369-454�. Hydrogen
bromide is not lost. Individual runs follow the first-order rate law, and the
rate constants are proportional to the hydrogen bromide pressure. The Arrhenius parameters are: E = 33.17 kcal mole-1 and
A = 1012.87 sec-1 ml mole-1, and the reaction
is homogeneous and molecular. Added water or methanol retards the reaction.
The photoassociation of some substituted naphthalenes. II. The photodimers of naphthol ethers
Authors: Wilairat P , Selinger B
Published: September 2010

β-Methoxynaphthalene
in solution shows excimer fluorescence and also forms a stable dimeric
photoproduct on prolonged irradiation. Both these processes were examined in
detail for a set of related compounds and the nature of the photoproducts was
investigated.
Carbonyl halides of the Group VIII transition metals. II. Aquo adducts of Halobis(triphenylphosphine)dicarbonyls of cobalt(I)
Authors: Bowden JA , Colton R
Published: September 2010

Aquo adducts of halobis(triphenylphosphine)dicarbonylcobalt(1), Co(CO)2- (PPh3)2(H2O)X
(X = Cl, Br, I), have been prepared by direct halogenation
of the cation CO(CO)3(PPh3)2+,
followed by addition of water. All of the compounds are stable in the solid state
but they appear to undergo exchange reactions in solution.
Molecular orbital calculations for sulphur-nitrogen heterocycles. I. The 3-hydroxyisothiazole system
Authors: Christie JR , Selinger B
Published: September 2010

LCAO-SCF calculations of
various types have been performed for 3-hydroxy-isothiazole
and related species. A perturbation analysis has shown that the values assigned
to some of the semi-empirical parameters affect the results to a greater extent
than has been supposed. Some of the chemical properties can be rationalized on
the basis of these calculations.
A study of solid nickel gluconates
Authors: Melson GA , Pickering WF
Published: September 2010

Structures are proposed for
nickel gluconate Ni(C6H11O7)2,2H2O
and nickel

hydroxygluconate Ni2(OH)2(C6H10O7)22H2O
on the basis of infrared spectra, visible reflectance
spectra, magnetic properties, and thermal decomposition behaviour. The
nickel(11) ion is present; in both cases in the high spin state and a distorted
octahedral environment. The hydroxy compound is considered to be a polymer
containing hydroxy and aquo bridges.
Pentamethylbenzyl esters of α-hydroxy acids and their use in depsipeptide synthesis
Authors: Stewart FHC
Published: September 2010

Pentamethylbenzyl esters of several a-hydroxy acids have been prepared
as possible intermediates in depsipeptide synthesis.
Potentially useful features of pentamethylbenzyl as a
carboxyl-protecting group are the crystalline nature of the esters, and the rapid
cleavage of the group under mild acidic conditions. The glycollate,
lactate, and mandelate were coupled with various
protected amino acids to form crystalline aminoacyl
hydroxy acid derivatives. Selective cleavage of the ester group in these
compounds was readily effected with cold trifluoroacetic acid, and the products were
used in the synthesis of some representative protected depsipeptides.
The equilibrium constant of the reaction Cr2O72- + H2O ↔ 2HCrO,4- at 15° to 45°
Authors: Linge HG , Jones AL
Published: September 2010

The equilibrium Cr2O2-7,+H2O
+ 2HcrO4 has been studied in acid solution

spectrophotometrically. Values have been obtained for the thermodynamic equilibrium constant at
15°, 25°, 35°, and 45°.
Binuclear complexes of copper(II) and zinc(II) halides with bidentate and quadridentate Schiff base complexes
Authors: Batley GE , Graddon DP
Published: September 2010

Binuclear complexes of the
types CuB,CuCl2, CuB,ZnCl2,
ZnB,ZnCl2, and

CuL2,CuCl2 have been obtained where BH2 is a
quadridentate Schiff base derived from salicylaldehyde
and a polyrnethylenediamine and LH is an N-alkylsalicylaldimine. The stereochemistry of the copper atoms in the
binuclear complexes is inferred from comparisons of their reflectance spectra
with the spectra of the simple copper complexes CuB
and CuL2. The structures of the zinc
complexes are discussed by reference to near ultraviolet spectra of the ligands
and infrared spectra in the 1500-1560 cm-1 region. The evidence suggests that
in the complexes of the type MB,M'Cl2
either but not both metal atoms may approach a tetrahedral environment. The
chemistry of the complexes ZnB,ZnCl2 is
complicated by the possibility of either or both zinc atoms becoming 5 coordinate
by addition of solvent molecules; in some of these complexes the zinc chloride
appears to be attached to a solvent molecule in a 5-coordinate Schiff base
unit, rather than by bridging through phenolic oxygen atoms. The oomplexes
CuL2,CuCl2 apparently have a
symmetrical binuclear structure based on a trans arrangement of the Schiff base
units rather than an unsymmetrical structure resembling that of the complexes CuB,CuCl2. Complexes of the types CuL2,ZnCl2 and ZnL2,ZnCl2
could not be obtained.
Organoaluminium compounds. XVI. The mechanism of exchange between trimethylaluminium and triphenylaluminium in the presence of pyridine
Authors: Jeffery EA , Mole T
Published: September 2010

The kinetics of exchange of
a methyl group of trimethylaluminiunl for a phenyl
group of triphenylaluminium have been studied by the
use of proton magnetic resonance (p.m.r.)
spectroscopy. An excess of pyridine was always present. Results obtained using
a large excess support a bimolecular mechanism without loss of pyridine from
the organoaluminium complexes prior to exchange. When
the excess of pyridine is small, the rate of exchange depends on the
concentration of excess pyridine. Here reaction may proceed by a mechanism in
which loss of pyridine from one of the organoaluminium
complexes occurs prior to exchange.
Halides and oxide halides of molybdenum and tungsten. IV. Preparation of tungsten(VI) oxide bromides and the magnetic properties of molybdenum(V) oxide halides
Authors: Colton R , Tomkins IB
Published: September 2010

A simple method for the
preparation of tungsten(V1) oxide bromides is described. The magnetic
properties of molybdenum oxide triohloride,
molybdenum oxide tribromide, and molybdenum dioxide
chloride over a wide temperature range are reported, together with infrared
data.
Halides and oxide halides of technetium. I. Technetium(V) oxide halides and the reaction of thionyl chloride with ammonium pertechnetate
Authors: Colton R , Tomkins IB
Published: September 2010

Chlorination of technetium
dioxide has been shown to give technetium oxide trichloride as the major
product. The presence of an unstable second product, thought to be the oxide
tetrachloride, was confirmed. Bromination of technetium dioxide gives only technetium
oxide tribromide.

Thionyl chloride reacts with ammonium pertechnetate
to give ammonium

dioxotetrachlorotechnetate(V1), which was isolated as its sulphuryl
chloride adduct, (NH4),[TcO2Cl4],SO2Cl2.
Studies related to naturally occurring acetylene compounds. XXXIV. Some Australian members of the genus Cotula L
Authors: Sorensen JS , Ve B , Anthonsen T , Sorensen NA
Published: September 2010

Seven Australian species of
the genus Cotula
L. have been investigated with particular regard to their content of acetylenic compounds. Six contained acetylenic
compounds. There was no perceivable simple relationship between the acetylenic compounds isolated, over the whole of that
portion of the genus so far examined, or within the subgenera. Two of the acetylenic compounds are new. C. bipinnata Thunb.
contained the hydrocarbon pentadeca-2,8,10,14-tetraene-4,6-diyne
(XX), and C. plumosa
(Hook. f.) Hook. f., the alcohol 2-cis-heptadeca-2,8 10-triene-4,6-diyn-1-ol
(XV), the cis isomer of oenanthetol. Acetylenes were not found in C. australis (Sieb. ex Spreng.) Hook. f., but
methyl 4-isopantenoxycinnamate (XXII) was isolated
from it in fair yield, and the new ester, 3,5-dimethoxy-l-α-propenylphenyl
4-isovalerate (XIX) was isolated from C. filicula
(Hook. f.) Benth.
Spectrophotometric studies of chelate formation of lanthanum and thorium with picramine azo dyes
Authors: Goyal SS , Tandon JP
Published: September 2010

0,O'-Dihydroxypicramine
azo dyes form water-soluble yellowish pink complexes with thorium and lanthanum
in the pH ranges 1.5-4 and 6-9 respectively. The compositions of the complexes
determined by continuous variations and molar ratio methods were found to be 1
: 2 in thorium-Picramine CA and 1 : 1 in lanthanum-Picramine R systems. The order of the formation constant of
thorium-Picramine CA complex is 1011 and
that of lanthanum-Picramine R is 105. The
free energy changes of formation are also
calculated.
Electrochemical studies of molten salts. III. E.M.F.'s of concentration cells with transference and diffusion potentials for PbCl2+CsCl mixtures
Authors: Bloom H , Easteal AJ
Published: September 2010

The e.m.f.'s
of concentration cells with transference containing PbC12
+ CsCl molten mixtures have been
measured as functions of temperature and electrolyte composition. Graphs of
cell e.m.f. against temperature are sets of
intersecting straight lines, as are graphs of cell e.m.f.
against the negative logarithm of the mole fraction of PbCl2.
Diffusion potentials for
junctions between pure molten PbCl2 and
molten

PbCl2 + CsCl mixtures have been determined, as functions of
temperature and mixture composition. The results are interpreted to indicate
the existence of complex lead-chloride ionic species in the mixtures.
Conformational analysis in carbohydrate chemistry. I. Conformational free energies. The conformations and α : β ratios of aldopyranoses in aqueous solution
Authors: Angyal SJ
Published: September 2010

The relative free energies
of the aldopyranoses in aqueous solution have been
calculated, taking non-bonded interaction energies and the anomeric effect into
account. It is shown that the calculated free-energy values correctly predict
the predominant conformation of the α- and β-pyranose
forms of each aldose. The α- to β-pyranose ratios of the aldoses in
aqueous solution, calculated from these values, are in reasonable agreement
with those determined experimentally.
Kinetics and mechanism of the osmium-tetroxide-catalysed oxidation of mandelate ion by hexacyanoferrate(III) ion
Authors: Singh NP , Singh VN , Singh MP
Published: September 2010

The osmium-tetroxide-catalysed oxidation of mandelate
ion by hexacyanoferrate(111) ion has been studied
kinetically. The reaction rate has been found to be independent of hexacyanoferrate(111) ion while the order with respect to
both osmium tetroxide and mandelate
ion comes out to be unity. The reaction rate follows first-order kinetics at
low hydroxyl ion concentration and becomes zero order at higher concentrations. The course
of the reaction has been considered to proceed through the formation of an activated
mandelate-OsO4, complex which decomposes
in alkaline medium giving reduced osmium(V1) followed by a fast oxidation by hexacyanoferrate(111) ion. The probable course of the
reactions is also described with the help of its oxidation product, benzoic acid.
Rearrangement of cross-conjugated methylenecyclohexadienes
Authors: Baker KM , Bell KH , Davis BR
Published: September 2010

Acid-catalysed
rearrangement of a number of polycyclic cross-conjugated

methylenecyclohexadienes possessing an angular methyl group (for example (I))
has led to the corresponding substituted 1,4-dimethylbenzenes.
The reaction parallels the dienone-phenol rearrangement, but, unlike the
latter, the course of the rearrangement is not sensitive to the reaction
conditions.
Isolation of 2,4,5-trimethoxyallylbenzene from Caesulia axillaries oil
Authors: Devgan ON , Bokadia MM
Published: September 2010

The phenolic ether obtained
from the essential oil of Caesulia axillaries has
been shown to be 2,4,5-trimethoxyallylbenzene (I), on
the basis of chemical and spectroscopic evidence. It has tentatively been named
as γ-asarone.
Flavan derivatives. XXV. Mass spectra of 3-hydroxyflavanones, flavan-3-ols, and flavan-3,4-diols
Authors: Clark-Lewis JW
Published: September 2010

Mass spectral data are
reported for eight 3-hydroxyflavanones, ten flavan-3-ols, and twelve flavan-3,4-diol derivatives. The principal
fragmentation of each of these three classes of compound yields ions derived by
retro Diels-Alder fission of the heterocyclic
nucleus, accompanied in the case of 3-hydroxyflavanones
and flavan-3-ols by hydrogen transfer from the
3-hydroxyl group to the A ring fragment. Deuteration
experiments with flavan-3-ols confirmed the origin of
the hydrogen atom transferred. Flavan-3,4-diols show two
characteristic fragmentation patterns depending on the insertion technique.
Mass spectra obtained by indirect insertion of flavan-3,4-diols showed a very
marked enhancement of the intensities of the M-18 and M-18-28 peaks, and of
their fragmentation ions, compared with spectra obtained by direct insertion.
The occurrence of triterpenoid, phenolic, and other compounds in the leaves of six endemic Castanopsis species of Hong Kong
Authors: Arthur HR , Ko PDS
Published: September 2010

From the leaves of six
Castanopsis species of Hong Kong 35 isolations of compounds have been made.
These include 12 different triterpenoid compounds (five related to friedelane including
the recently isolated canophyllol, two to hopane, glutinol, lupeol, and
taraxasterol), ellagic acid, digallic acid, and β-sitosterol.