bluuebunny/crossref_metadata_2025 huggingface dataset:
Association of alklurea molecules in solution
Authors: Werner RL , Duckworth VF , Schnitzerling HJ
Published: September 2010

The association of n-propyl and
n-butylurea in chloroform has been studied together with NN-dimethylurea, NN-di-n-butylurea,
and acetamide. The infrared spectra indicate that association occurs
preferentially between the carbonyl and primary amide NH2 groups and
that cyclic dimers are formed in the first instance.
Reactions of benzyne and 1,2-naphthyne with some dienes
Authors: Corbett TG , Porter QN
Published: September 2010

Benzyne reacts as a dienophil with
1-vinylnaphthalene and 3-vinylbenzo[b]-thiophen, and similarly 1,2-naphthyne
reacts with 1-vinylnaphthalene and 1,1'-bicyclohexenyl, to give otherwise
inaccessible polynuclear aromatic molecules.
The influence of pressure on the kinetics and orientation of Friedel-Crafts benzoylations
Authors: Coillet DW , Hamann SD , McCoy EF
Published: September 2010

It has been found that the second-order
rate constant for the benzoylation of benzene, catalysed by aluminium chloride
in benzoyl chloride solution at 29.6�, is doubled when the pressure is raised
from 1 atm to 1500 atm.

The same change of pressure has no
measurable effect on the orientation of benzoyl substitution in toluene.
Nuclear magnetic resonance spectra of polycyclic aromatic compounds. II. Substituted benz[a]anthracenes
Authors: Batterham TJ , Tsai L , Ziffer H
Published: September 2010

The nuclear magnetic resonance spectra of
benz[a]anthracene and a number of its derivatives have been analysed and
approximate solutions are given. Comparisons have been made between spectra run
at 60 Mc/s and 100 Mc/s.
6,7,8,9-Tetrahydropyridoquinazolines, a new class of alkaloids from Mackinlaya species (Araliaceae)
Authors: Fitzgerald JS , Johns SR , Lamberton JA , Redcliffe AH
Published: September 2010

Leaves and stems of Mackinlaya subulata Philipson and M. macrosciadia (F. Muell.) F. Muell.
(fam. Araliaceae) contain
two new alkaloids, 6,7,8,9-tetra-hydropyrido[2,1-b]quinazolin-11-one (I), and
6,7,8,9-tetrahydro-llH-pyrido[2,1-b]- quinazoline (11), and the known alkaloid anabasine. The new Mackinlaya
alkaloids had previously been prepared by synthesis1-3.
Coordination compounds of substituted 1,10-Phenanthrolines and related dipyridyls. IX. Complexes of silver and 4,6,4',6'-Tetramethyl-2,2'-bipyridine
Authors: Hall JR , Litzow MR , Plowman RA
Published: September 2010

The white complexes of silver(1), AgX tmb, where X is Cl, Br, and
I, and Ag tmb2 X, where X is NO3
and ClO4, have been obtained but
characterization of them was limited by their low solubility. Oxidation to the
silver(11) state was carried out with ozone, but such complexes were unstable
and could not be isolated from solution.
Schiff base equilibria. IV. N-Methylimines of m- and p-hydroxybenzaldehydes
Authors: Green RW , Sleet RJ
Published: September 2010

The formation of Schiff bases between
methylamine and m- and p-hydroxybenzaldehydes has
been studied by spectrophotometry. Because of
overlapping equilibria and ionic strength effects, the formation constants, KF,
of the neutral Schiff bases are determined with less precision than for the
ortho compound. In dilute solution they are estimated by extrapolation to be
1.0 x 103 and 1.0 x 104, respectively. The formation
constants, KA, of the anionic forms of the Schiff bases have been
more precisely measured as 1.45 x 102 and 5.52, respectively. The
equilibria are compared with those for salicylaldehyde.
The structure of acronycine
Authors: Macdonald PL , Robertson AV
Published: September 2010

1,3-Dimethoxy-2-methoxycarbonyl-l0-methylacridone,
obtained by total synthesis, is not identical with the product from ozonolysis,
methylation, oxidation, and esterification of acronycine. The degradation product is therefore
1,3-dimethoxy- 4-methoxycarbonyl-10-methylacridone, and acronycine
has structure (1), not (11).
The SN mechanism in aromatic compounds. XXXII. Reactivity of some perhalogenobenzenes
Authors: Ho KC , Miller J
Published: September 2010

Substituent effects in a series of pentafluorophenyl compounds (C6F5X)
ranging from powerful activating to powerful deactivating substituents are
considered, both as regards orientation and rates, and shown to be simply and
reliably predicted by considering the change as made up of two components, viz.
from C6F6 to C6F5H and from C6F5H
to C6F5X. The same principle applies generally to C6Hal5X compounds, and the necessary
orientation and rate data are obtainable from the existing large body of
substituent effects in aromatic SN reactions. Comparisons are thus
also easily possible with substituent effects in aromatic SE
reactions, and more generally. The reasons for predominant para direction for
almost all groups, except the more powerful deactivating substituents which are
meta directing, and the expectation of a few borderline cases, emerge clearly
from discussion.

While orientation is largely known
already, there have been very few precise rate determinations apart from the
present work.

Some brief consideration of the admixture
of dioxan with protic solvent is given.

The reactivities of hexafluorobenzene
and hexachlorobenzene are compared. The substantially greater reactivity
reported with the former is regarded as due solely to the greater mobility of
fluorine than chlorine, with first row nucleophdes in
protic solvents; whereas in contrast it is predicted that the C6Cl5 group is slightly more
activating for aromatic S, reactions than the C,F, group. The
relative reactivities of C6F6 and C6H5F,
and C6Cl6 and C6H5Cl are also compared. Rate ratios
are c.108; ΔΔE? c.15 kcal mole-1; and Δlog10B c.+1.
The chemistry of the Western Australian Rutaceae. V. The isolation of some coumarins and the structure of phebalosin
Authors: Chow PW , Duffield AM , Jefferies PR
Published: September 2010

The structure (II) has been
assigned to the coumarin phebalosin, obtained from Phebalium tuberculosum and
P. drummondii.
Catalytic deuterium exchange reactions with organics. XXIV. Electron spin resonance studies of adsorption on platinum oxide
Authors: Ernst IT , Garnett JL , Sollich-Baumgartner WA
Published: September 2010

The formation of paramagnetic species on
catalyst surfaces at room temperature through the interaction of polynuclear
aromatics in solid, liquid, or solute form with hydrated platinum oxide (PtO2,2H2O) is reported. The results
are attributed to the formation of charge-transfer complexes, where the
transferred electrons couple weakly, forming essentially a "diradicaloid" complex with a low-lying, thermally
populated, triplet state. The effect of solvent, particle size, oxygen, water
of crystallization, and temperature on the generation and stability of these
e.s.r. active species has been investigated. The possible importance of these
paramagnetic species in catalytic self-activation and hydrogen exchange
reactions has been discussed. The following Group VIII transition metal oxides
gave no e.s.r. spectra under relatively severe reaction conditions such as 1 hr
at 120�: PdO; Ru02,2H20;
RuO2; Rh2O3;
IrO2,2H2O; ReO2;
and NiO.
Long-range spin-spin coupling in 1,4-benzoquinones and some related compounds
Authors: Norris RK , Sternhell S
Published: September 2010

N.m.r, data for fifteen 1,4-benzoquinones,
four 1,4-naphthoquinones, and six cyclohex-2-ene-1,4-diones are tabulated. From
these, and previously available data, it is possible to obtain characteristic
ranges for methyl-allylic coupling constants (c 1.3 c/s) and methyl-methyl
homoallylic coupling constants (c. 1.3 c/s) for this for this series of
compounds as well as values for other long-range and vicinal interactions,
including a negative coupling across five bonds. On
the basis of both chemical shifts and coupling constants it was concluded that
1,4-benzoquinones have little aromaticity from the N.M.R. point of view.

The halogen atoms in
5,6-dihalogenocyclohex-2-ene-1,4-diones appear to be tram diaxial.
Reaction of amines with the bisulphite addition compound of 5-Amino-5-deoxy-D-xylose: Conversion to piperidine derivatives
Authors: Ingles DL
Published: September 2010

The bisulphite addition compound (1) of
5-amino-5-deoxy-D-xylose reacted with cyclohexylamine to form the acyclic derivative (11). With
ammonia, benzylamine, morpholine, and piperidine,
corresponding salts (IV) of the piperidine derivative D-ido(gluco)-3,4,5-trihydroxy-2-sulphopiperidine
(VIII), were isolated. Removal of the amine yielded the crystalline bisulphite
addition compound (VIII). Acetylation in the presence of pyridine of the
different amine salts (11, IV) and of (VIII) gave an identical acetate (VII),
l-acetyl-D-ido(gluco)-3,4,5-triacetoxy-2-sulphopiperidine,
isolated as the pyridine salt. Deacetylation of (VII)
with barium methoxide gave the barium salt (IX). Oxidation of (IX) with sodium
periodate liberated one mole of formic acid, confirming the presence of a
six-membered ring containing nitrogen.

The significance of these results in the
inhibition of non-enzymic browning by sulphur dioxide is discussed.
Piptoside, a novel alkali-labile glucoside from Piptocalyx moorei Oliv.
Authors: Riggs NV , Stevens JD
Published: September 2010

The β-D-glucopyranoside,
piptoside, is cleaved by hot dilute acid to glucose
and aglucone, the latter being partly converted with
loss of carbon dioxide into a furan keto acid. Glucose is also liberated by the
action of bases. With sodium methoxide, the aglucone
residue rearranges to a pair of isomeric dilactone
esters, whereas, with aqueous sodium hydroxide, fission of the carbon chain to
(-)-2,3-dimethylsuccinic acid occurs; with alkaline hydrogen peroxide,
oxidative chain fission yields a buty- rolactone-4,4-dicarboxylic
acid. The structure and partial stereochemistry of each of the products follows
from chemical and spectroscopic information. These results, as also those of
periodate oxidation, are accounted for by formulation of the aglucone as a system of two spiro-joined γ-lactone
rings, one of which is fused to a ketofuranose ring.
The reaction products are analogous to well-known products from simple sugars.
The hemiacetal hydroxyl group of the ketofuranose remains free in the glucoside and is unusally acidic towards diazomethane, the methyl
derivatives not being alkalilabile.��� Biogenesis of the aglucone
may follow Michael-type addition of a 3-dehydrohexonic acid (of unknown
stereochemistry) to angelic acid, or some variant.
Spectral and structural studies of some Group VIA dioxydihalides
Authors: Barraclough CG , Stals J
Published: September 2010

The infrared and mass spectra of MoO2Cl2,
MoO2Br2, WO2Cl2, and WO2Br2
in the gas phase have been studied. The vapours contain mostly monomeric
molecules but there is also a small amount of relatively unstable dimeric
species present in each case. In inert solvents MoO2Cl2
and MoO2Br2 are dimeric and the infrared spectra are
reported. In the solid state all four compounds are polymeric and the absence
of the characteristic M = O infrared frequency suggests that only bridging
oxygen atoms can be present. X-ray powder diffraction data suggest that the
four compounds are isomorphous.
Equilibrium phases in the BeSO4-H2O system
Authors: Bear IJ , Turnbull AG
Published: September 2010

The equilibrium phases of the BeSO4-H2O system were studied by
vapour hydration of BeSO4 and equilibration of thermally produced
mixtures. Tetra-, di-, and mono-hydrate are the stable hydrates with no solid
solution regions between them. X-ray and infrared spectra are presented for
these hydrates and a provisional phase diagram drawn.��� Reversible transitions of BeS04
were found at 588° and 639°, the latter showing a hysteresis splitting of 4° on
cooling. Transition heats of 1.2 ± 0.1 and 0.5 ± 0.1 kcal/mole respectively
were found by differential thermal analysis.
The calculation of positive ancl negative spin densities in aromatic free radicals
Authors: Adam FC , Laidlaw WG
Published: September 2010

A simple method of calculating the
unpaired π electron spin density is proposed which equates the unpaired
spin density to the difference between a density of n-1 electrons of a spin and
a density of n electrons of β spin. The α spin density is found from
an SCF-Pariser-Parr type calculation for 2(n+l) electrons in n + 1 closed shells and the β spin
density from a calculation on 2n electrons in n, closed shells. Positive and
negative spin densities are found which are in excellent agreement with experiment.
These results are compared to spin densities calculated by other methods, and
an improvement is noted in the representative cases considered.
Surface concentrations for a mixed transfer process at an expanding spherical electrode
Authors: Gorden CM , Matlak RF
Published: September 2010

An expression has been derived for the concentration
of oxidant and reductant at the surface of an
expanding spherical electrode as a function of time and the polarizing
potential in the case where a slow irreversible chemical reaction follows a
reversible electron transfer reaction under the conditions of a somewhat
idealized polarographic system.
The infrared spectra of gaseous and liquid sulphur trioxide
Authors: Grigg ECM , Johnston GR
Published: September 2010

The infrared spectra of both gaseous and
liquid sulphur trioxide have been investigated between 4000 and 650 cm-1.
A gas cell for use with very reactive compounds has been described.
Octahedral cobalt(III) complexes in dipolar aprotic solvents. IV. Solvolysis and isomerization of dibromobisethylenediaminecobalt(III) ions inanhydrous NN-dimethylformamide and NN-dimethylacetamide
Authors: Fitzgerald WR , Watts DW
Published: September 2010

The equilibrium system

(SOL)+Br-+cis-[CoBr2
em]+ =
cis-[CoBr(SOL) en2]2++2Br-

 

=trans[CoBr2en2]2++Br-+SOL

where SOL represents either
of the solvents NN-dimethylformamide (DMF) or NN-dimethylacetamide
(DMA), has been studied. The compounds cis-
[CoBr(DMF) en2](ClO4)2,
and cis-[CoBr(DMA) en2]XO3,ClO4,
have been isolated and thus it has been possible to study these equilibria
using as starting materials both the cis-
and trans-dibromo complexes (cis- and trans-[CoBr2 en2]+) and the solvento
complexes (cis-[CoBr(DXA) en2]2+ and cis-[CoBr(DMF) en2]2+).
The mechanism of the bromide entry reactions

cis-[CoBr(SOL) en2]2+
+Br- = cis- and trans-[CoBr2
en2]++SOL

is bimolecular in DMA while
in DMF the reaction is dissociative: the rate showing bromide concentration
dependence only in the concentration range where ion association is not
complete. In both systems the isomerization proceeds mainly through the solvento complex;
in dimethylacetamide there is evidence for a
seven-coordinated intermediate. The isomerization equilibria
are found to be bromide concentration dependent, cis-[CoBr2 en2]+
being favoured by high bromide concentrations. This is consistent with the
lower stability of the trans-[CoBr2 en2]-
ion pair with bromide ion.
The oxidation of hydrazine by silver(I) oxide
Authors: Hodges RJ , Pickering WF
Published: September 2010

At room temperatures, the oxidation of
hydrazine solutions by silver(1) oxide proceeds primarily in the solution
phase, the rate of reaction being directly related to the concentration of free
hydrazine and silver ions present. The reduction of the silver ions is
catalysed by a conducting surface, such as a silver film, and it is suggested
that the liberation of nitrogen involves the successive formation of several
short-lived hydro-nitrogen species. The rate of reaction is influenced also by
factors such as pH, particle size, and composition of the solution phase, since
these alter either the solubility of the solid or the activity of the silver
ions.
The pyrolysis of polycarbonyl compounds. I. Mass spectral and pyrolytic fragmentation of indanetrione
Authors: Brown RFC , Solly RK
Published: September 2010

Pyrolysis of indanetrione
at 500-800� produces benzyne, which was detected by its reaction with benzene
and with chlorobenzene and, in pyrolyses in vacuo, by
the formation of biphenylene and triphenylene. The isolation of the carbonyl compounds
benzocyclobutenedione, fluorenone, anthraquinone, and
phenanthrene-quinone from some pyrolyses suggests
that loss of carbon monoxide occurs in successive steps which parallel those in
the mass spectral fragmentation of the indanetrione
molecular ion. A species having the composition of benzocyclopropenone
(X) may be involved in the formation of fluorenone, anthraquinone, and phenanthrenequinone.
Second-harmonic alternating current polarography
Authors: Bauer HH , Foo DCS
Published: September 2010

The technique of second-harmonic a.c. polarography is discussed from the viewpoints of
theoretical basis, experimental requirements, and scope of application.

The theoretical relation is given for the
second-harmonic current-component of a straightforward electrochemical reaction
under conditions of a.c, polarography. It is shown how this relation can be
used to determine the kinetic parameters (rate constant and transfer
coefficient) of the electron-transfer step. Results obtained with the zinc(n)/zinc
(mercury) system are in good agreement with those reported in other
investigations by other methods.

The experimental aspects of
second-harmonic studies are examined, and the dependence of the accuracy and
reliability of results on various features of the instrumental arrangement is
brought out.��� Potential applications, particularly in
tensammetric studies and in analytical work, are indicated.
Oxygen chemisorbed on zinc oxide: The determination of reactive oxygen
Authors: Norman VJ
Published: September 2010

The changes in excess zinc content which
occur on heating zinc oxide in air are discussed, and are suggested as a means
of estimating oxygen chemisorbed on zinc oxide.

The published evidence for the existence
of at least two varieties of chemisorbed oxygen is confirmed, and it is
established that only one of these varieties is reactive chemically. The
results deduced from the heating experiments are confirmed directly by a rapid
photometric method which is described for the determination of reactive oxygen
chemisorbed on zinc oxide.

Oxygen is desorbed from the surface of the
zinc oxide by etching with ammonium chloride solution in the presence of
potassium iodide. By complexing the iodine liberated by reactive oxygen with
starch prior to dissolution of the sample in acid, reduction of iodine by
excess of zinc in the sample is avoided. Atmospheric oxidation of potassium
iodide is overcome by close control of acid concentration (pH 5.2) throughout
the determination. A reference solution is employed in which iodide is added
only after dissolution of the sample in acid has been completed. The necessary
compensation for oxidizable matter present in the
zinc oxide and reagents is achieved by the addition of standardized hydrogen
peroxide to both sample and reference solutions.��� Reactive chemisorbed oxygen on a number of
samples of zinc oxide ranged from 0 to 1.5 p.p.m. by
weight. The method gives good reproducibility, and is sensitive to 0.03 p.p.m. of oxygen by weight.
Organophosphorus compounds. VII. Electron-impact fragmentations of esters of phosphonic acids
Authors: Occolowitz JL , Swan JM
Published: September 2010

The mass spectra of some dialkyl and
diaryl esters of a variety of alkyl-, alkenyl-, alkynyl-, and aryl-phosphonic
acids are discussed. The spectra are in many cases similar to those observed
for simple dialkyl alkylphosphonates, but with some important differences
depending on the nature of the hydrocarbon group attached directly to the
phosphorus atom.

Some unusual rearrangements are observed, involving
migration of a hydro-carbon fragment from the ester group to the hydrocarbon
moiety attached to phosphorus, with simultaneous expulsion of a phosphinyl
radical. Thus diethyl vinylphosphonate gives an ion [C4H7]+;
diethyl 2-phenylvinylphosphonate gives a base peak at m/e 131 due to PhCH=CHCHCH3;
diphenyl 2-phenylvinylphosphonate gives an ion [C14H12O]+',
and from this, an ion [C14H10]+ which can be
formulated as the molecular ion of phenanthrene.
Polarography of nickel in concentrated chloride media
Authors: Florence TM
Published: September 2010

In concentrated chloride media, nickel is
reduced at far more positive potentials than in dilute solutions. The positive
shift in half-wave potential increases as the ionic strength is raised, and is
also greater when the cation of the supporting electrolyte has a high hydration
number. Evidence is presented to show that the reduction in overpotential
is due to the formation of a nickel chloride complex, [Ni(H2O)5Cl]+, which has a stoicheiometric stability constant of 0.094 � 0.009 at an
ionic strength of 10.0. Spectrophotometric results show that this nickel
species is not formed in low ionic strength solutions. In anhydrous methanol
saturated with lithium chloride, nickel is present as the tetrachloro
complex, [NiCl,]2-, which has
similar polarographic behaviour to the monochloro
complex.

Current-potential curves recorded at a
rotated pyrolytic graphite electrode enabled the
behaviour of nickel to be studied in the absence of specific adsorption of the
chloride ion. Nickel is reduced at more positive potentials at a dropping
mercury electrode than at the pyrolytic graphite electrode, and the results
indicate that this difference is due to specific adsorption of chloride on the
mercury electrode.
Sulphur-nitrogen chelating agents. I. Metal complexes of 8-methylthioquinoline
Authors: Lindoy LF , Livingstone SE , Lockyer TN
Published: September 2010

8-Methylthioquinoline (N-SMe) has been prepared
and complexes with nickel(II), palladium(11), platinum(11),� copper(11), copper(1),� silver(1), and mercury(II) have been
obtained. The complexes NiX2(N-SMe)2
(X = Cl, Br, I, NCS) are high-spin and presumably octahedral. The mono-chelated
complexes MX2(X-SMe) (M = Pd, Pt, Cu; X = Cl, Br) were isolated; the
sulphato-complex CuSO,(X-SMe),
2H,O is probably dimerio with bridging sulphato groups. The bis-chelated copper(II) complex
[Cu(X-SMe)2](ClO4)2
was obtained but attempts to isolate analogous complexes of nicke1(II),
palladium(11), and platinum(II) were unsuccessful. The complexes CuI(R'-SMe), [Ag(X-SMe)2]ClO4.
and HgCl2(X-SMe) were also characterized. �����

The paramagnetic red nickel(II) complex
Ni(N-S)2 (N-SH = 8-mercapto-quinoline) was
reinvestigated: a temperature-dependent magnetic study shows that the moment
does not vary with temperature. It is suggested that this compound is polymeric
and tetragonal.

Attempts to prepare a gold(III) complex of
8-methylthioquinoline led to demethylation of the ligand and the isolation of AuCl2(N-S).
The structures and vibrational spectra of methyl chloroformate and dimethyl carbonate
Authors: Collingwood B , Lee H , Wilmshurst JK
Published: September 2010

The infrared spectra of
methyl chloroformate and dimethyl carbonate in the vapour phase and as
solutions in carbon disulphide and carbon tetrachloride have been obtained from
4000 to 400 cm-1 together with the Raman spectra of the liquids. The
infrared band contours for both molecules are consistent with a cis
configuration of the carboxylate group and the spectra may be interpreted
satisfactorily on this basis.
The alkaloids of Amsinckia species: A. intermedia Fisch. & Mey., A. hispida (Ruiz. & Pav.) Johnst. and A. lycopsoides Lehm
Authors: Culvenor CCJ , Smith LW
Published: September 2010

Hepatotoxic pyrrolizidine
alkaloids have been isolated from Amsinckia species
occurring in Victoria and in California. A. intermedia Fisch.
& Mey. contains echumine and four new alkaloids,
intermedine, lycopsamine, sincamidine, and an incompletely characterized
alkaloid. The newly named alkaloids are retronecine esters of (+)-trachelanthic
acid, (-)-viridifloric acid, and an isomer of heliotric acid, respectively. A. hispida (Ruiz. & Pav.) Johnst. and A. lycopsoides Lehm. contain intermedine, lycopsamine, and a minor amount
of echiumine. N.m.r. data on intermedine, lycopsamine, and related alkaloids
are included.

Intermedine and lycopsamine have been
prepared from the component amino alcohol and esterifying acids. These
preparations constitute the first formal syntheses of hepatotoxic pyrrolizidine
alkaloids.
Organic compounds of niobium and tantalum. Reactions of niobium and tantalum pentaethoxides with ethyl benzoylacetate
Authors: Mehrotra RC , Kapoor RN , Prakash S , Kapoor PN
Published: September 2010

The following two types of
new compounds have been isolated: M(OEt)4- (etbzac) and M(OEt)3(etbzac)2 (where M is niobium or tantalum) by the
reactions of niobium and tantalum pentaethoxides with ethyl benzoylacetate.
Further replacement of the ethoxide group by the ligand is very slow. These
derivatives interchange their ethoxide groups with tertiary butanol, yielding
the corresponding tertiary butoxide derivatives. All these derivatives can be
purified by distillation under reduced pressure. Molecular weight
determinations show them to be monomeric in boiling benzene.
Acidic constituents of Dodonaea lobulata
Authors: Dawson RM , Jarvis MW , Jefferies PR , Payne TG , Rosich RS
Published: September 2010

The isolation of three new
diterpenes and of a new flavone from Dodonaea lobulata
is described. The diterpenes have been shown to be 8β-hydroxy-enantio-labdan-15-oic acid (Ia), 6β,8β-dihydroxy-enantio- labdan-15-oic
acid (Ib), and 7α,8β-dihydroxy-enantio-labdan-15-oic
acid (Ic). The new flavone is formulated as
5-hydroxy-3,6,7,4?- tetramethoxyflavone (XIa).
Bis-1,10-phenanthroline complexes of divalent ruthenium
Authors: Bosnich B , Dwyer FP
Published: September 2010

A series of divalent
ruthenium complexes of the type cis-[RuX phen2 py]2+
(phen = 1,10-phenanthroline, py
= pyridine, X = py, Cl, Br,
I, N3, NCS, NO2, CN, NH3, CH3CN),
have been isolated and characterized. The cation cis-[Ru
phen2 py2]2+
has been resolved into its optical isomers from which the optically active monosubstituted
complexes have been prepared.
Cassytha alkaloids. III. Aporphine alkaloids from Cassytha melantha R. Br
Authors: Johns SR , Lamberton JA , Sioumis AA
Published: September 2010

The major alkaloid of Cassytha melantha R.Br, and Cassytha glabella R.Br. is
(+)-9-hydroxy-10-methoxy-1,2-methylenedioxyaporphine
(cassythicine), which has not been previously found to occur naturally,
although the (�)-form has been synthesized by Tomita and Kikkawa. A minor
alkaloid from C. melantha, isolated only in the form
of an NO- diacetyl derivative, appears to be the noraporphine corresponding to
cassythicine and it is presumably identical with the known alkaloid
actinodaphnine.

A study has been made of the N.M.R.
spectra of a number of N- acetyl-N-methylaminoethylphenanthrenes,
obtained from aporphines by heating with acetic anhydride. These show not only
the expected splitting of the N-methyl and N-acetyl signals due to cis-trans
isomerism of the amide group, but also a long-range splitting of the signals
from certain aryl protons.
The preparation of reduced and S-alkykated wool keratins using Tri-n-butylphosphine
Authors: Maclaren JA , Sweetman BJ
Published: September 2010

When tri-n-butylphosphine
is used to reduce the disulphide groups in wool keratin, several different
methods can be used for the subsequent alkylation of the thiol groups formed. A
novel feature is that in some oases reduction and alkylation can be effected
using tri-n- butylphosphine and the alkylating agent acting simultaneously.

S-Alkyl kerateines have been prepared
using 11 alkylating agents of various chemical types. By means of such a
technique a quantitative and apparently specific conversion of cystinyl
residues in wool keratin to S.(2-aminoethyl)cysteinyl residues has been
achieved.
A synthesis of two-protected nonpeptide amides with the amino acid sequence of oxytocin
Authors: Stewart FHC
Published: September 2010

Two protected nonapeptide
amides with the amino acid sequence of oxytocin have been synthesized by a
route involving the use of benzyloxycarbonyl peptide p-nitrophenyl esters as
coupling components. One of the products is a compound which has been described
previously, and converted into oxytocin, by various authors. The present
approach is discussed in relation to the earlier syntheses.
The Phytosterols from Acacia species: α-Spinasterol and Stigmast-7-enol
Authors: Clark-Lewis JW , Dainis I
Published: September 2010

The heartwoods of eight
Acacia species have been shown to contain stigmast-7-enol
and α-spinasterol, which thus appear to be characteristic constituents of
the genus. Several species also contained 5α-stigmastanol, β-sitosterol,
and stigmasterol, and these were removed by preliminary fractional
crystallizations of the acetates.
Alkaloids of Choisya ternata H.B. & K. (family Rutaceae). The structure of choisyine
Authors: Johns SR , Lamberton JA , Sioumis AA
Published: September 2010

Choisyine, an alkaloid of Choisya ternata H.B. & K.,
has been shown to be (V). The dehydration product, anhydrochoisyine, which was
regarded as identical with the alkaloid acronidine by Frolova
and Kuzovkov, has been shown to be (VII).
Synthesis, chemical properties, and U.V. spectra of thio-thionyl fluoride and difluorodisulphane
Authors: Brown RD , Pez GP
Published: September 2010

The preparation of
difluorodisulphane, FSSF, by the silver fluoride/sulphur reaction is described.
Difluorodisulphane is unstable at room temperature and rearranges spontaneously
into thio-thionyl fluoride, SSF2. The largest observed first-order
half-life time of FSSP gas was 4.7 hr at 21.8 � 0.3�. The decomposition of FSSF
is catalysed by hydrogen fluoride and boron trifluoride. Chemical reactions of
the isomers with AgF2, Cl2,
BCl3, S2Cl2,
acetone, benzoic acid, Pyrex, and quartz were studied.

The absorption spectra of gaseous FSSF and
SSF2 were recorded in the range of 10000 to 53000 cm-1.
Medium to high intensity continua were noted with maxima for FSSF at 50200�250
and 41400�250 cm-1 and for SSF2 at 53000�500, 41400�250,
and 33800�400 cm-1.
The electronic spectra of osmium and ruthenium tetroxides
Authors: Wells EJ , Jordan AD , Alderdice DS , Ross IG
Published: September 2010

The spectrum of OsO4 has been measured in the vapour and in
solution. Detailed structure reported in the main absorption bands by Langseth and Qviller was not
reproduced. The irregularity of the main intervals between peaks, and their
sensitivity to temperature, bespeak a perturbed spectrum which is too diffuse
to analyse convincingly. Three fragmentary systems of quite different
appearance were observed in all samples and could well be weak forbidden
transitions. The spectrum of RuO, vapour is no better
resolved. Reproducible features of both spectra are tabulated.
Cyclic nitrones. II. Reactions of a cyclic α-keto nitrone with acetic anhydride, acetone, and methyl acetoacetate
Authors: Brown RFC , Crow WD , Subrahmanyan L , Barnes CS
Published: September 2010

The cyclic α-keto
nitrone 3,4,5,6-tetrahydro-5,5-dimethyl-3-oxopyridine 1-oxide (III) when
treated with acetic anhydride and sulphuric acid gave in low yield a compound
(XI) having both enol lactone and vinylogous amide functional groups.

Hydrolysis and decarboxylation of compound
(XI) with aqueous potassium hydroxide gave a vinylogous amide (V), also
obtained by acid- or base-catalysed condensation of compound (III) with
isopropenyl acetate or acetone. Base-catalysed condensation of (III) with
methyl acetoacetate gave an ester (XVII) closely related to compound (V).
The mass spectra of [18]annulene derivatives. Skeletal rearrangement upon electron impact
Authors: Badger GM , Bowie JH , Elix JA , Lewis GE , Singh UP
Published: September 2010

The mass spectra of a
series of [18]annulene derivatives are reported and discussed. The majority of
fragmentation modes exhibited in these spectra are produced by well-defined
skeletal reorganization. In the case of one compound, all the observed fragmentations
occur as the result of skeletal rearrangement processes. This appears to be the
first reported example of such a phenomenon.
Proton magnetic resonance spectra, configuration, and conformation of 4-substituted prolines
Authors: Andreatta RH , Nair V , Robertson AV
Published: September 2010

The proton magnetic
resonance spectra of a series of 4-oxoprolines, and cis- and
trans-4-substituted prolines, have been analysed. Correlations permitting
assignment of configuration from the spectra are presented. The difficulty of
deducing precise conformations from the spectral parameters is emphasized.
Phosphato complexes of cobalt(III). I. General structural and hydrolytic properties
Authors: Lincoln SF , Stranks DR
Published: September 2010

Phosphorus-32 tracer
experiments have demonstrated that the phosphato
ligand in [Co en2PO4]0
[Co(NH3)4PO4]O, [CO(NH3)4OH2HPO4]+,
and [Co en2OH2.HPO4]+
undergoes slow substitution in acid and alkaline media at 40-60� and that a
reversible hydrolysis equilibrium is established from pH 3 to 11. Outside this
pH range, acid and base hydrolysis of all these phosphato
complexes to diaquo or dihydroxo
complexes is complete. The infrared spectra of [Co en2PO4]0
and [Co(NH3)4PO4]0 are consistent
with a bidentate phosphato structure and with a
monodentate phosphato ligand in CO(NH3)5PO4
and probably [Co(NH3)4OH2HPO4]+I-.
The bidentate and monodentate complexes may be rapidly and reversibly interconverted but significant concentrations of the
bidentate complexes only persist in the range pH 5.5-7.5.

P.m.r, studies have established the predominantly cis configuration of the aquophosphato complexes. These complexes exhibit four
acidity constants, one due to the aquo ligand, and
three due to the monodentate phosphato ligand. The
bidentate [Co en2PO4]0 exhibits a single
acidity constant above pH 2. The aquophosphato
complexes undergo both acid and base hydrolysis entirely by Co-O bond rupture.
Acid hydrolysis of [Co en2PO4]0
also proceeds entirely by Co-O bond rupture but at pH 6.8 and in 0.25M NaOH hydrolysis proceeds by 60-65% Co-O bond rupture and by
30-35% P-O bond rupture.
Thiocarboxylato derivatives of Bis(cyclopentadienyl)titanium(III)
Authors: Coutts RSP , Wailes PC
Published: September 2010

Thioformato, thioacetato, thiopropionato, thiostearato, and
thiobenzoato derivatives of bis(cyclopentadienyl)titanium(111)
have been prepared by precipitation from air-free aqueous solutions of cp2TiCl (cp =π-C5H5).
The compounds are deep green in colour, readily oxidized by air, and are
paramagnetic monomers having one unpaired electron per titanium atom. Infrared and visible
spectral data are reported, together with conductivities in methanol, magnetic
properties, and molecular weight values.
Heats of mixing of carbon tetrachloride with diethyl ether, dimethyl sulphide, and pyridine
Authors: Gray DF , Watson ID , Williamson AG
Published: September 2010

The heats of mixing of
carbon tetrachloride with diethyl ether, dimethyl sulphide, and pyridine have
been measured at 25�. The negative values of HE are interpreted as
an indication of strong specific interactions between the donor atoms O, S, N,
and the CCl4.
Benzyloxycarbonylamino acid 2,6-Dichloro-4-nitrophenyl esters and the reaction of 2,6-Dichloro-4-nitrophenol with N,N'-Dicyclohexylcarbodiimide
Authors: Stewart FHC
Published: September 2010

2,6-Dichloro-4-nitrophenyl
esters of several benzyloxycarbonylarnino acids have
been prepared from 2,6-dichloro-4-nitrophenol by the
N,N'-dicyclohexyl-carbodiimide method. The course of
this reaction differed from the analogous preparation of related active esters
in that the phenol and the carbodiimide react to form
a 1 : 1 molecular complex of the phenol and N,N'-dicyclohexyl-0-2,6-dichloro-4-nitrophenylisourea.
This complex is readily isolated, and behaves as an active esterifying
agent.
Approaches to the preparation of 3'-deoxynucleosides
Authors: Johnston GAR
Published: September 2010

The stability of 3'-O-sulphonyl
derivatives of uridine towards nucleophilic displacement indicates that sulphonate replacement is unlikely to offer a general route
to 3'-deoxynucleosides. The preparation of 3'-deoxyuridine by direct iodination of 2',5'-di-O-trityluridine with triphenylphosphite
methiodide followed by catalytic hydrogenolysis is
discussed as such a general route dependent on the availability of suitably
protected nucleoside starting materials. Acyl migration takes place under the
conditions of the iodination reaction, limiting the choice of protecting
groups.
Physicochemical investigation on thiomalate complexes of nickel
Authors: Saxena RS , Gupta KC , Mittal ML
Published: September 2010

Potentiometric and conductometric studies
of the nickel-thiomalic acid system, in aqueous
medium of 0. lM KNO3, reveal the formation
of two complexes; one light violet 1 : 1 predominating at pH 6.5-7.5 and
another deep violet 1 : 2 in the pH range 8.5-10.0. The stability constants of
the complexes formed have been determined by applying Calvin and Melchior's extension of Bjerrum's
method at three different temperatures and were further refined by using
alternative methods. The logK values (final) for 1 :
1 and 1 : 2 complexes at 20, 25, and 30� have been found to be 7.86, 7.87,
7.96, and 6.24, 6.31, 6.39 respectively. The values of the overall changes in ΔG,
ΔH, and ΔS accompanying the reaction have also been evaluated at 25�
and found to be -19.31 kcal/mole, -8.77 kcal/mole, and +35.36 cal/deg
respectively.
On the synthesis of 3,4-dihydroxyprolines. I. cis-Glycolation of 3,4-dehydroproline derivatives
Authors: Hudson CB , Robertson AV , Simpson WRJ
Published: September 2010

The interaction of OsO4 and protected derivatives of
3,4-dehydro-DL-proline gives high yields of 2,3-trans-3,4-cis-3,4-dihydroxy-DL-proline derivatives, with only traces of the
2,3-cis-3,4-cis diastereoisomers. Corresponding α-glycolation with KMnO4
gives mixtures of the 2,3-trans-3,4-cis and 2,3-cis-3,4-cis isomers in the ratio 1 : 1. Separation of the components of
such mixtures is extremely difficult. The free amino acids in
these two families of the 3,4-dihydroxy-DL-prolines
have been characterized. Epimerization at C2 of 2,3-cis derivatives occurs readily. O-Tosylation
of the 2,3-cis series occurs more
readily than for other hydroxyprolines. Esters of N,O,O-tritosyl-2,3-trans-3,4-cis-3,4-dihydroxyproline are converted very rapidly by mild
alkali into the equivalent esters of X-tosylpyrrole-2-carboxylic
acid. For the corresponding N,O,O-tritosyl carboxylic
acid, decarboxylation also takes place during aromatization, to yield N-tosylpyrrole.
A multilayer model of a solid-regular solution interface
Authors: Lane JE
Published: September 2010

A multilayer model of the
interface between a solid and a regular solution
has been developed by
treating the solution phase in the grand canonical ensemble.

The partition functions
necessary for the evaluation of the grand partition function

are obtained using either
the quasi-chemical or Bragg-Williams approximations.

The equilibrium
concentration profile normal to the interface is then found from the

maximum term in the
multiple sum for the grand partition function. The adsorption,

surface tension, and heat
of wetting for the multilayer model are derived, and

methods of obtaining the
model parameters from experimental data are suggested.

A comparison has been made
between the quasi-chemical and Bragg-TVilliams
approximations for the multilayer
model. The monolayer model is also discussed, and

compared with the
multilayer for both the solid-regular solution and the low-density
vapour-regular solution
interfaces. It is shown that the monolayer model can often be

fitted to the multilayer model
by a suitable choice of parameters. It is concluded

that in the absence of
absolute methods of obtaining the area of the solid-solution
interface, the experimental
data may not provide outright support for the multi-

layer model, but internal
inconsistencies discourage the use of the monolayer model.
There is an increasing
interest in the properties of the interface between a solid

and a non-electrolyte
solution.1 The majority of experimental studies of this type

of interface have been
restricted to the measurement of adsorption, but in some

instances the heat of
wetting as a function of bulk phase composition has also been
determined. In most cases,
the complexity of the liquid phase and the surface region

has allowed only a
qualitative interpretation of the experimental results. Neverthe-

less, there have been a few
investigations in which solutions of comparatively simple
molecules have been used
and the experimental results have been treated in a

quantitative manner.2-5
Some simple monolayer models of the solid-solution inter-
face have been proposed for
which the structure of the solid phase has been ignored,

Division of Applied
Chemistry, CSIRO Chemical Research Laboratories, Melbourne,
Vic. 3001.

Kipling, J. J.,
"Adsorption from Solutions of Non-Electrolytes." (Academic Press:

London 1965.)

Billet, D. F., Everett, D.
H., and Wright, E. H. &I., Proc. chem. Soc. 1964, 216.

3 Blackburn, A., and
Kipling, J. J., J. chem. Soc., 1954, 3819.

4 Blackburn, A., Kipling,
J. J., and Tester, D. A., J. chem. Soc. 1957, 2373.

5 Wright, E. H. &I.,
Trans. Paraday Soc., 1966, 62, 1275.
Aust. J. Chem., 1968, 21,
827-51
Nickel(II) complexes of some o-hydroxyarylcarbonyl compounds. II. Some 5-substituted 2-hydroxyaryl ketones
Authors: Graddon DP , Mockler GM
Published: September 2010

Nickel(11) complexes of the
type NiL2Bn have been prepared
where L = 2-hydroxy-5-methylacetophenone, 2-hydroxy-5-methylbenzophenone,
or 5-chloro-2-hydroxybenzophenone; B = H2O
or 4-methylpyridine; n = 2 or 0. The properties of
these compounds closely resemble those of the unsubstituted
compounds described in Part I. Molecular weights of the anhydrous compounds NiL, indicate a monomer-polymer equilibrium in non-donor
solvents, the solute being almost wholly monomeric at concentrations below 10-2M.
Equilibrium studies in 2.5M 10-8M solution show that NiL2 reacts with 4-methylpyridine
in two stages with a five-coordinate
intermediate NiL2B, analogous to
corresponding copper(11) complexes. The properties of the monomeric form of NiL, are consistent with a high-spin square-planar
structure.
Exchange in alkylzinc alkoxides and alkylcadmium alkoxides
Authors: Jeffery EA , Mole T
Published: September 2010

Coupling of lllCd and ll3Cd
to both the methyl and alkoxyl protons has been observed in the proton
magnetic resonance spectra of methylcadmium

alkoxides. P.m.r. spectrometry has
also been used to investigate the exchange reactions of methylcadmium
and alkylzinc alkoxides. In
particular exchanges between Me2Cd and MeCdOR (R = Me, Et, Pr, and Ph), between R2Zn and RznOR? (R =
Me, Et; R' = Me, Et, Pr, and But), and between Me3Al
and MeZnOR' (R' = Et, Pr, and But), have
been examined.
Catalytic deuterium exchange reactions with organics. XLII. The picolines, lutidines, thiophen, and furan on unsupported Group VIII transition metals
Authors: Calf GE , Garnett JL
Published: September 2010

The picolines
(methylpyridines), lutidines
(dimethylpyridines), thiophen, and furan have been
exchanged with heavy water on a variety of Group VIII transition metals.
Platinum is the most reactive general labelling catalyst for the picolines and lutidines, whereas
cobalt catalyses exchange exclusively in the positions α to the nitrogen
atom. The labelling pattern in the picolines and lutidines is similar to that of the alkylbenzenes
in that

(i)positions ortho to a methyl group are severely deactivated and

(ii)positions
flanked by two methyl groups are completely

deactivated. Compensation
effects are observed involving steric hindrance to adsorption from the alkyl
groups and enhanced strength of adsorption from the nitrogen lone pair. The
compensation effect in this charge-transfer adsorption slightly favours the
nitrogen lone pair.
Thiophen and furan
generally do not exchange appreciably with pre-reduced Group VIII transition
metal catalysts. Thiophen exchanges rapidly on self-activated platinum oxide
whereas self-activated iridium oxide is the most useful for furan.

With nickel chloride, furan
exchanges exclusively in the or positions. A theory is proposed to account for
the novel exchange in both thiophen and furan.
Benzo[c]cinnoline derivatives. IV. Substituent effects in the mass spectra of substituted Benzo[c]cinnolines
Authors: Bowie JH , Lewis GE , Reiss JA
Published: September 2010

The mass spectra of a
series of benzo[c]cinnoline derivatives are reported and discussed. The spectra
are useful for analytical purposes, as all compounds give pronounced molecular
ions, and the fragmentation processes generally occur without skeletal-rearrangement.
Many benzo[c]cinnolines which are substituted in the
4-position may be differentiated from other isomers by the presence of
"proximity- effects" in their mass
spectra.
Mass spectra of α-diketones. I. Non-enolized α-diketones
Authors: Bowie JH , Cooks RG , Gream GE , Laffer MH
Published: September 2010

The mass spectra of a
series of a-diketones are reported and discussed. Fragmentation patterns have
been substantiated by exact mass measurements, metastable ions, and in two
cases, by deuterium labelling studies. The McLafferty
rearrangement is not observed in the spectra of aliphatic α-diketones;
fragmentation proceeds by α-cleavage. The fragmentation modes of those
cyclic α-diketones studied depend largely on the ring size. Molecular ions
are observed in all spectra.
Azepinones. V. The mechanisms of ring contractions of some 5-substituted 6H-4,5-Dihydro-3,7-diphenyl-1,2-diazepines
Authors: Amiet RG , Johns RB
Published: September 2010

The mechanism of the
rearrangement to 4-substituted-3,6-diphenylpyridazines
of 6H-4,5-dihydro-3,7-diphenyl-1,2-diazepine (I; R =
H) and its 5-methyl and -phenyl (I; R = CH3; C6H5)
derivatives when treated with N-chlorosuccinimide has been investigated by a
combination of u.v., N.M.R., and mass spectrometric
methods. The reaction involves a stereospecific 1,3-dehydrohalogenation
to form a diazanorcaradiene (111) intermediate. In
the presence of excess N-chlorosuccinimide, ring opening of the three-membered
ring occurs by radical attack on the protonated
intermediate. In the absence of N-chlorosuccinimide, ring opening proceeds by
protonation of the cyclopropane ring of the diazanorcaradiene to yield an appropriately 4-substituted
3,6-diphenylpyridazine. The data exclude the
participation of any 5H-1,2-diazepines, the valence tautomers of the norcaradiene
intermediates.
Pyridopyridazines. I. The synthesis and physical properties of Pyrido[2,3-d] pyridazine and Pyrido[3,4d] pyridazine
Authors: Paul DB , Rodda HJ
Published: September 2010

Pyrido[2,3-d]- and
pyrido[3,4-d]-pyridazine have been synthesized by removal of hydrazino, chloro, and mercapto groups from the substituted
derivatives and by preparation of pyridine-2,3- and -3,4-dialdehydes
from the corresponding lutidines followed by condensation
with hydrazine. In the latter reaction sequence the side-chain bromination of a
3-alkylpyridine has been achieved. The reaction of
hydrazine with aryl o-dinitriles and the oxidation of
arylhydrazines have been investigated. The pKa
values, ultraviolet spectra, and infrared spectra of the pyridopyridazines
are discussed. No covalent hydration could be detected in either the neutral pyridopyridazines or in their cations.
A new monoterpenoid alkaloid from Jasminum species and from Ligustrum novoguineense (family Oleaceae)
Authors: Hart NK , Johns SR , Lamberton JA
Published: September 2010

Jasminine, C11H12N2O3,
a new monoterpenoid alkaloid isolated from several Jasminum species and from Ligustrum novoguineense Lingelsheim,
has been shown to be (11), with the preferred conformation indicated in (IIa).
N-Substituted salicylaldimine complexes of iron(III). II. Magnetic properties
Authors: van den Bergen A , Murray KS , West BO
Published: September 2010

The magnetic
susceptibilities of iron(111) N-substituted salicylaldimine complexes of types
Fe(sal-XR)3, Fe(sal-NR)2X, [Fe(salH-KR)2X]X,
(X = Cl, Br), and [Fe(sal-NR)2]2O have been measured over
the temperature range 90-300�K.? The mononuclear complexes exhibit
normal high-spin (S = 5/2), Curie-Weiss behaviour. The binuclear oxygen-bridged
complexes show antiferromagnetic behaviour and the results have been analysed
using the spin-spin coupling mechanism. The
exchange interaction is found to be independent of the nature of the
N-substituent on the Schiff base. It appears that bulk susceptibility
measurements alone cannot unambiguously specify the formal spin state of the
ferric ion in these binuclear complexes.