bluuebunny/crossref_metadata_2025 huggingface dataset:
The influence of pressure on electrolytic conduction in alkali silicate glasses
Authors: Hamann SD
Published: September 2010

This paper reports measurements of the
electrical resistances of some lithium, sodium, and potassium silicate glasses
between 1 and 2000 atm and from 15 to 35�C. The resistances of all the glasses
increased with increasing pressure, and the change was greatest for the
potassium glass. The apparent volumes of activation for the conduction process
were found to be slightly greater than the volumes of the alkali metal ions
that carried the current.
The synthesis of [18]annulene trisulphide
Authors: Badger GM , Elix JA , Lewis GE
Published: September 2010

[18]Annulene 1,4:7,10:13,16-trisulphide
has been synthesized. It has been found to be a stable non-planar non-aromatic
system in which the three thiophen rings are linked by three essentially
olefinic vinylene groups.
Moretenol and other triterpenes from Ficus macrophylla Desf
Authors: Galbraith MN , Miller CJ , Rawson JWL , Ritchie E , Shannon JS , Taylor WC
Published: September 2010

From the exudate of the bark of Ficus
macrophylla Desf., cycloartenol, butyrospermol, and lupeol were isolated as
their acetates. The leaves contained nonacosane, triacontane, hentriacontane,
dotriacontane, tritriacontane, "ceryl alcohol", and a new triterpene,
moretenol. By degradative and mass spectrometric studies, the latter was shown
to b3 3β-hydroxy-2lαH-hop-28-ene.
Flavan derivatives. XIII. The formation of 1,3-Diarylpropan-2-ols and 2,3-Diarylpropan-1-ols from Flavan-3-ols
Authors: Clark-Lewis JW , Ramsay GC
Published: September 2010

No change in specific rotation of
(-)-1-(3,4-dimethoxyphenyl)-3-(2,4,6- trimethoxyphenyl)propan-2-ol was observed
during attempted resolution, so that the propanol is probably close to optical
purity in spite of its low specific rotation. (-)-Epigallocatechin pentamethyl
ether was reduced with sodium and liquid ammonia to an analogous
hexamethoxydiarylpropan-2-ol. Several conditions for reducing ( +)-catechin
tetramethyl ether with lithium aluminium hydride-aluminium chloride mixtures
were examined, and the reduction method was applied to (-)- epiafzelechin
trimethyl ether and to (-)-epigallocatechin pentamethyl ether. The mechanism of
formation of the (-)-2,3-diarylpropan-1-ol from (+)-catechin and
(-)-epicatechin tetramethyl ethers is discussed. The 5,7,4'-trimethyl ethers of
(-)-epiafzelechin and (�)-dihydrokaempferol were found to form a 1 : 1
molecular complex.
Thio derivatives of β-diketones and their metal chelates. I. Some Monothio-β-diketones and their nickel(II) chelates
Authors: Chaston SHH , Livingstone SE , Lockyer TN , Pickles VA , Shannon JS
Published: September 2010

Monothio-β-diketones of general
formula RC(SH)=CHCOR? (R = Me, R* = Me, Ph, OEt; R =
Ph, R' = Ph, OEt; R = α-thienyl, R' = CF3;
and 12 = R' = CMe,) have been prepared in order to
study their metal complexes. Five of these thio derivatives are new and were
prepared by treatment of a dilute solution of the corresponding β-diketone
in alcohol with hydrogen sulphide at low temperature. Mass spectrometric
examination has established the structures of MeC(SH)=CHCOPh and RC(SH)=CHCOCF, (R = α-thienyl).

The red compounds PhC(SH)=CHCOPh (VI) and MeC(SH)=CHCOPh (V) can be oxidized to yellow products. The
structure of the yellow compound (XV) obtained from (VI) was established by
mass and n.m.r. spectroscopy as the disulphide PhCOCH=C(Ph)SSC(Ph)=CHCOPh. The molecular ion of (XV) undergoes novel
rearrangement reactions involving, inter alia, elimination of H2S to
produce a thiophene ion.

The nickel chelates Ni(RCS=CHCOR')2
are brown, diamagnetic, and soluble in organic solvents. Unstable paramagnetic
bis-pyridine adducts, derived from two of the nickel chelates, were isolated.

The infrared spectra of the monothio-β-diketones
and their nickel chelates are reported. The spectra of the monothio-β-diketones
show no SH band at c. 2570 cm-1 ; this indicates strong chelation of
the thiol hydrogen between the sulphur and oxygen atoms. The monothio-β-diketones
display four characteristic bands which are assigned as follows : 1670-1590 cm-1,
v(C--O) ; 1638-1530 cm-1, v(C=C) ; 1267-1190 cm-1, v(C=S)
; 837-805 cm-1, provisionally assigned as v(C=S) + δ(C-H). The
nickel chelates exhibit five characteristic bands: 1590-1535 cm-1,
V(C=C); 1542-1477 cm-1, v(C-0); 1261-1220 cm-1, v(C--S);
817-800 cm-1, provisionally assigned to v(C-S)+ δ(C-H); 499-451
cm-1, v(Ni-O). No band corresponding to v(Ni-S) was detected above
250 cm-1. However, the metal-sulphur stretching frequency was
observed as a peak of medium intensity within the range 360-308 cm-1
in the spectra of bis(o-methylthiobenzenethiolo)-nickel(II) and the diethyl
dithiophosphate complexes of nicke1(II), palladium(II), chromium(III), and
cobalt(III).
Some reactions of acronycidine and related compounds
Authors: Batterham TJ , Lamberton JA
Published: September 2010

The conversion of 4-O-alkylfuroquinolines
into N-alkylfuroquinolones and other reactions of the furoquinoline alkaloids
are studied with the aid of N.M.R. spectra. The N.M.R. spectra of
isoacronycidine and several other N-alkylquinolones show a sharp peak in the
range δ 2.0-4.0, attributed to strongly retained water molecules.
Nickel-catalysed hydrogen exchange of alkylaromatic hydrocarbons and toluic acid derivatives with deuterium oxide
Authors: Macdonald CG , Shannon JS
Published: September 2010

The selective hydrogen exchange of alkyl
groups of some alkylaromatic hydrocarbons and toluic acid derivatives was
achieved by allowing these compounds to react with deuterium oxide over nickel
on kieselguhr at 99�. The observed deuterium distributions and the results of
catalyst poisoning experiments can be interpreted in terms of initial π-bonding
of the substrates to the catalyst followed by dissociative adsorption at a
benzylic carbon atom and transfer of adsorption through the alkyl group by an α-β
process. Some nitro- and halo-toluenes underwent little or no exchange.
Synthetic studies in the 1,2-dithiole series. III. Attempts to convert dithioles into pyrrolodithioles
Authors: Brown RFC , Rae ID
Published: September 2010

��� Some unsuccessful attempts to convert
4-acylamino-1,2-dithiole derivatives into pyrrolodithioles are described, and
the failure of the critical cyclization step is discussed. The reaction of
4-acetoacetamido-1,2-dithiol-3-one with sodium ethoxide has given
5-carbethoxy-2,3-dihydro-4H-1,4-thiazin-3-one
(XI).
Coordination compounds of substituted 1,10-Phenanthrolines and related dipyridyls. VI. Complexes of copper(II) and 4,6,4',6'-Tetramethyl-2,2'-bipyridine
Authors: Hall JR , Litzow MR , Plowman RA
Published: September 2010

The following complexes of copper(II) and
4,6,4',6'-tetramethyl-2,2'-bipyridine (tmb) have been
prepared: CuX2tmb, where X = NO3,Cl,Br, and �SO4; Cu(tmb)2X2, nH2O,
where X = NO3 (n = 1) and ClO4, (n = 0, 1, and 2); and
Cu(tmb)2X(ClO4), nH2O, where X = NO3 (lz = 1) and Cl (n = 0). The magnetic moments of the
compounds range from 1.89 to 2.05 B.M. The results of conductivity, molecular
weight, and spectral measurements suggest the occurrence of four-, five-, and
six-coordinate copper(II).
Nuclear magnetic resonance studies. V. The tautomerism of tasmanone and related β-triketones
Authors: Bick IRC , Horn DHS
Published: September 2010

From a nuclear magnetic resonance study of
the tautomerism of tasmanone and 1,1,3,3-tetramethylphloroglucinol (syncarpic
acid), it is deduced that tasmanone consists of a mixture of tautomers (I) and
(II) with the tautomer (I) present in the larger proportion. Similarly it is
deduced that the tautomers of agglomerone (XI; R = CHMe2), 3-acetyl-O-methylfilicinic
acid (XI R; = Me), ceroptene (XI; R = CH=CHPh), and usnic acid (XIII) with the
extended conjugation are the more stable and populated ones.
The preparation of substituted γ-Benzyl-L-glutamates and β-Benzyl-L-aspartates
Authors: Ledger R , Stewart FHC
Published: September 2010

Substituted γ-benzyl-L-glutamates and
β-benzyl-L-aspartates have been obtained from the alkali metal salts of
the corresponding amino acid copper complexes and substituted benzyl halides
under various experimental conditions. The use of a sequestering agent to
remove the copper from the intermediate ester complexes allows the introduction
of relatively sensitive ester groups. Several other types of ester were also
prepared in the same way.
Nuclear magnetic resonance spectra of pyrrolizidine alkaloids. I. The spectra of retronecine and heliotridine
Authors: Culvenor CCJ , Heffernen ML , Woods WG
Published: September 2010

The chemical shifts and coupling constants
of the protons in retronecine and heliotridine are derived by detailed analysis
of the nuclear magnetic resonance spectra of these compounds. The factors which
influence the appearance and ease of interpretation of spectra of pyrrolizidine
derivatives, principally the chemical shift difference of the H 6 protons and
conformational averaging, are discussed.

The conformations of retronecine and
heliotridine are discussed in relation to their coupling constants; the former
compound is exo-buckled whereas the latter is a mixture of rapidly
interconverting exo- and endo-buckled forms.
Chemistry of pyrrolic compounds. II. Some aspects of the chemistry of dipyrryl ketones
Authors: Clezy PS , Nichol AW
Published: September 2010

The synthesis of 3,5,4',5?-tetramethyl-2,2'-dipyrrylketone
is described and the tautomeric structure of the compound investigated. It is
concluded on spectroscopic grounds that this ketone and other members of the
class exist mainly as the keto tautomer. The synthesis of a new heterocyclic
system, the dipyrrolopyrimidones, is described.
Octahedral cobalt(III) complexes in dipolar aprotic solvents. III. A new spectrophotometric method for the determination of ion association constants
Authors: Millen WA , Watts DW
Published: September 2010

A spectrophotometric method for the
evaluation of ion association constants has been developed. This method
involves the preparation of solutions containing only the compound under
consideration. A function relating the association constants to the concentration
of compound and extinction coefficients has been derived.

The association constants are best
determined by an iterative method using a computer. The association constant
for the cis-diohlorobisethylenediaminecobalt(111)
cation, cis-[Co en2
Cl2]+, and chloride ion in NN-dimethylformamide
(DMF) at 30� has been calculated by this new method and is compared with that
of another established procedure. The association constant has also been
determined for the association of cis-[Co
en2 Cl2]+
and iodide in DMF at 30�.
The reaction of Bis(cyclopentadienyl)titanium(III) chloride with organic azides
Authors: Coutts RSP , Surtees JR
Published: September 2010

Bis(cyclopentadienyl)titanium(III)
chloride reacts with organic azides with the liberation of nitrogen and the
formation of nitrogen-bridged Ti1V
compounds of varying thermal stability. Whhen the
reaction is carried out in xylene, the initial products from phenyl and p-chlorophenyl azide can be isolated in an impure state,
although they disproportionate on attempted purification. In tetrahydrofuran
solution all the azides studied yield products which cannot be isolated, since
they are transformed rapidly into mixtures of bis(cyclopentadienyl)titanium
dichloride and other products.
The preparation of Thiazolidine-2-thiones from N-alkylglucosylamines
Authors: Dalton LK
Published: September 2010

N-Alkylglucosylamines
and carbon disulphide react to give 3-alkyl-5-hydroxy- 5-(D-arabino-tetrahydroxybutyl)thiazolidine-2-thiones (I), which dehydrate to the
corresponding Δ4-thiazolines,
isolated only as tetraacetates. A
thiazolidine-2-thione forms also from the action of carbon disulphide on 1-N-methylamino-1-deoxy-D-fructose.

l-Bromo-l-deoxy-2,3:4,5-di-O-isopropylidene-D-fructose
is obtained by the action of dibromotriphenoxyphosphorane
on 2,3:4,5-di-O-isopropylidene-D-fructose.
Some neutral constituents of Acronychia baueri
Authors: Prager RH , Thredgold HM
Published: September 2010

Five neutral compounds have been isolated
from the bark of Acronychia baueri
(Schott). One of these is bauerenol, and two others
are shown to be methyl p-geranyloxy-trans-oinnamate and methyl p-geranyloxyferulate.
The catalytic isomerization of allylbenzene in the presence of palladium(II) chloride
Authors: Cruikshank B , Davies NR
Published: September 2010

Allylbenzene has been shown to isomerize
rapidly in the presence of palladmm(11) chloride in acetic acid, mainly to trans-β-methylstyrene but to a
small extent to the cis isomer. The
reaction is not simple. The initial formation of an olefin complex is succeeded
by a further slow reaction involving the palladium complex before isomerization
takes place. The isomerization reaction itself is zero order with respect to
allylbenzene except nearing completion when it becomes first order in
allylbenzene concentration. The reaction is first order with respect to
catalyst. Rates have been measured by a technique involving N.M.R.
spectrometry. Substitution in allylbenzene inhibits isomerization in the case
of 2-bromoallylbenzene but not entirely in the case of the corresponding methyl
derivative. The mechanism is discussed in the light of an intermediate hydrido
complex.
The photoassociation of some substituted naphthalenes. I. Rate constants and thermodynamic data for excited dimer formation
Authors: Selinger BK
Published: September 2010

Rate constants and thermodynamic data for
the excited dimer formation of some naphthalene derivatives are presented. The
presence of excimers undetectable by fluorescence emission may be inferred from
such data.
Some reactions of 1,4-Bischlorocarbonylpiperazine
Authors: Rivett DE , Wilshire JFK
Published: September 2010

1,4-Bischlorocarbonylpiperazine reacts with
amines, amino acid esters, thiols, phenols, and imidazole to give crystalline
derivatives. Reaction with piperazine gives polyureas. The reagent appears to be too unstable to
aqueous solvents to act as a cross-linking agent for proteins.
Pyrrolizidine alkaloids from Planchonella species (family Sapotaceae). I. The alkaloids of Planchonella thyrsoidea C. T. White and P. anteridifera (White & Francis) H. J . Lam
Authors: Hart NK , Lamberton JA
Published: September 2010

Planchonelline, Cl2H1902NS, a, major
alkaloid of the leaves of Planchonella thyrsoidea C. T. White and P. anteridifera (White & Francis)
H. J. Lam., is the trans-β-methylthioacrylate ester of laburnine((+)-trachelanthamidine). In both species it occurs together
with the tiglate and benzoate of laburnine,
but only the tiglate and benzoate were isolated from
stored dried leaves of P. anteridifera.
Electrical conductivity of cation-exchange membranes in the hydrogen ion form
Authors: Arnold R , Koch DFA
Published: September 2010

Measurements are reported of the
conductivities of a number of different cation-exchange membranes in the
hydrogen-ion form. The membranes were equilibrated both with water and with
sulphuric acid solutions of concentrations up to 6N, and the amounts of water
and acid absorbed were also measured. Some of the membranes used were found to
undergo an irreversible expansion on heating.

When equilibrated with water, equivalent
conductivities of the homogeneous- type membranes could be fitted by the equation
Δ = A(1- Vp), where Vp
is the volume fraction of polymer and A is a constant whose value depends on
the concentration of ion-exchange groups but which is little affected by the
nature of the membrane.

In the presence of acid the conductivity changes
depend markedly on the presence of voids. This behaviour can be well described
in terms of the model of Sauer, Southwick, Spiegler,
and Wyllie, which treats the membrane as an assembly of solid resin and
continuous and discontinuous voids. Evaluation of these results in terms of
this model enables estimates to be made of the extent and nature of the voids.
On adding acid to a membrane there is at first a rapid rise in apparent
counter-ion mobility, followed by a fall at higher acid concentrations. The
initial rise in apparent mobility is attributed to the entry of acid into
discontinuous voids.
The mechanism of the oxidation of thiocyanate ion by peroxomonosulphate in aqueous solution. I. Stoicheiometry of the reaction
Authors: Smith RH , Wilson IR
Published: September 2010

The oxidation of thiocyanate ion by peroxomonosulphuric acid in aqueous solution results in the
formation of sulphate, cyanide, cyanate, and sulphur
dicyanide in proportions which depend upon the pH and the ratio of reactant
concentrations. Investigation of these dependences has given some information
about the manner in which reaction intermediates are involved.
Octahedral cobalt(III) complexes in dipolar aprotic solvents. VIII. The solvolysis of cis- and trans-[CoBr2 en2]+ ions in anhydrous dimethyl sulphoxideand mixtures of anhydrous dimethyl sulphoxide and NN-dimethylacetamide
Authors: Fitzgerald WR , Watts DW
Published: September 2010

The solvolysis reactions

(see diagram in article)

have been studied in
anhydrous dimethyl sulphoxide (DMSO) over a range of bromide concentrations and
at various mole fractions of DMSO in NN-dimethyl-acetamide (DMA). The
solvolysis of both isomers results in nearly complete removal of first bromide
in pure DMSO while in DMA almost insignificant solvolysis occurs. The influence
of ion association on the measured rates is discussed. Activation energies are
presented for all reactions.
Electrochemical studies of molten salt mixtures. I. The electromotive forces of concentration cells with transference containing the molten electrolytesystems PbBr2 + CsBr, PbBr2 + RbBr, and PbBr2 + KBr
Authors: Bloom H , Easteal AJ
Published: September 2010

The e.m.f.'s
of concentration cells with transference (i.e. with liquid junction),
containing the binary molten salt systems, PbBr2+CsBr,
PbBr2+RbBr, and PbBr2+KBr,
have been measured as functions of temperature and electrolyte composition. The
cell e.m.f.'s have been found to vary with
temperature and electrolyte composition in a discontinuous manner: graphs of
cell e.m.f. against temperature are in general a number of intersecting
straight lines, as are graphs of cell e.m.f. against the negative logarithm of
the mole fraction of one component.
The configuration of mercury(II) chloride in benzene
Authors: Le FFvre RJW , Radford DV , Ritchie GLD , Saxby JD
Published: September 2010

The configuration of mercury(II)
chloride as a solute in benzene has been investigated through measurements of
dielectric absorption, apparent molar weight (490�100), and specific Kerr
constant [(2.3�0.3) x 10-12]. Tentative values for the
polarizability semi-axes of the mercury-chlorine bond are deduced from the
infrared stretching frequency of mercury(II) chloride. The experimental results
are consistent with the presence of a non-polar dimeric solute species, or with
an equilibrium mixture involving several polymeric forms.
An unsaturated ketohexose and derived hexenetetrols
Authors: Anet EFLJ
Published: September 2010

The unsaturated ketose,
3,4-dideoxy-D-glycero-hex-trans-3-enulose, was prepared from 3-deoxy-2-O-methyl-β-D-erythro-hex-2-enofuranose by
reduction with sodium borohydride followed by an allylic rearrangement under
mild acid conditions. Further reduction of the ketose with sodium borohydride
yielded erythro- and D-threo-hex-trans-3-ene-1,2,5,6-
tetrols. The 1,2:5,6 di-O-isopropylidene derivatives
of the tetrols were also prepared. The main evidence for the trans
configuration of the double bonds of these five compounds is that they have a
large value for J3.4 (15.4-16.4 c/s).
Extractives of Australian timbers. VII. Bayin
Authors: Eade RA , Salasoo I , Simes JJH
Published: September 2010

Bayin, a phenolic compound
from the wood of Castanospermum australe Cunn. & Fras., has been shown to
be 8-C-β-D-glucopyranosyl-7,4?- dihydroxyflavone,
Homopolypeptides derived from substituted β-Benzyl-L-aspartates and γ-Benzyl-L-glutamates
Authors: Ledger R , Stewart FHC
Published: September 2010

Homopolypeptides have been
obtained by polymerization of the N-carboxy anhydrides of various substituted
β-benzyl-L-aspartates and γ-benzyl-L- glutamates. The substituted
benzyl groups concerned are o-, m-, and p- nitrobenzyl, 2,4,6-trimethylbenzyl,
p-iodobenzyl, and 1-naphthylmethyl.
The degradation of aromatic rings: the action of hypochlorite on phenols
Authors: Moye CJ , Sternhell S
Published: September 2010

The reaction of phenol with
hypochlorite in strongly alkaline solution gives variable yields of
3,5,5-trichloro-1,4-dihydroxycyclopent-2- enecarboxylic
acid, which on treatment with 36N sulphuric acid produces
3,5-dichloro-2-hydroxy-4-oxocyclopent-2-enecarboxylic
acid. Dry distillation of this product under reduced pressure gives the
mono-en01 of 2,4-dichlorocyclopentane-1,3-dione. The nature of these reactions
is discussed.
Some 3-arylacetylacetones: Their reactivity and their metal complexes
Authors: MacDermott TE
Published: September 2010

Variously substituted 3-arylacetylacetones are shown to form thermally robust non-ionic
complexes with copper(II), nickel(II), and cobalt(II). The possibility of
restricted rotation about the benzene-acetylacetone bond is postulated, and
failure to prepare analogues of bis(acetylacetone)ethylenediamine is discussed.
Infrared spectra of lignin model compounds and of lignins from Eucalyptus regnans
Authors: Michell AJ
Published: September 2010

Infrared spectra in the O-H
and C=O stretching regions of lignin model compounds and of lignins isolated in
various ways from Eucalyptus regnans F. Muell. have been obtained for samples
both in the solid state and in solution.

The effects of solvents on the stretching
vibrations of free and intramolecularly bonded hydroxyl groups have been
examined for a number of the model compounds, including some in which the
groups are subject to steric hindrance. The results have been used to interpret
the O-H stretching frequencies of the lignins in the same solvents. In the
lignin macromolecules all hydroxyl groups appear to be involved in hydrogen
bonds, and the phenolic groups are sterically hindered.��� Different solvent effects have also been
observed in model compounds between the C=O stretching frequencies of carboxyl
groups and those of aldehyde, ketone, and ester groups. The solvent dependence
of the 1665 cm-1 band in the lignin spectra supports its assignment
to a conjugated aldehyde or ketone group, but the dependence of the 1725 cm-1
band suggests that both carboxyl and carbony1 groups may contribute to the band
envelope.
Photochemical reactions of azo compounds. XII. Dark reaction of cis-azobenzene with acetyl chloride
Authors: Lewis GE , Mayfield RJ
Published: September 2010

cis-Azobenzene has been
shown to react with acetyl chloride in the absence of light to form N,N?-diacetyl-4-chlorohydrazobenzene and N?- acetyl-4-chloro-hydrazobenzene
as the principal products; 4- phenylaminoazobenzene and acetanilide are also
formed in small amounts. In the course of the reaction a metastable dark blue
product arises, and, although this could not be satisfactorily characterized,
it was found to yield 4-phenylaminoazobenzene on decomposition in methanolic
potassium hydroxide or in acetyl chloride.

The intense blue-purple coloration, which
occurs as soon as the reactants are mixed, enables cis-azobenzene to be readily
distinguished from its trans isomer.

The nature of the currently reported
reaction is discussed in relation to the previously reported photo-induced
reaction of trans- azobenzene with acetyl chloride, which yields N,N?-diacetyl-4-
chlorohydrazobenzene practically exclusively.
The coumarins of Geijera parviflora Lindl
Authors: Lahey FN , Macleod JK
Published: September 2010

Two new coumarins have been
isolated from the leaves of Geijera parviflora Lindl. One of these, dehydrogeijerin,
has been shown to be 6-(β,β-dimethylacrylyl)-7-methoxycoumarin (I) and the other, geiparvarin, to be
7-(4,7-epoxy-3,7-dimethyl-6-oxoocta-2,4- dienyloxy)coumarin (IX).
Residue rotations of L-leucine in the Di-,Tri-,Tetra-, and Penta-peptides of L-leucine and Glycine containing one L-leucyl residue
Authors: Beechham AF
Published: September 2010

The molecular rotations, in
aqueous solution, at 589 mμ, are tabulated for
two hexapeptides and all the di-, tri-, tetra-, and penta-peptides of L-leucine
and glycine containing one L-leucyl residue. The molecular rotations of the
corresponding N-benzyloxycarbonyl peptides are also listed. It is shown that
the ?residue rotation? of L-leucine varies widely, not only between those
compounds in which the site of the residue is N-terminal, C-terminal, or
internal, but also within these categories. Syntheses of certain of the
compounds are described.
The nuclear magnetic resonance spectra and stereochemistry of 4-Benzoyloxy-1-thiaflavans
Authors: Katekar GF , Moritz AG
Published: September 2010

The nuclear magnetic
resonance spectra of cis- and trans-4-benzoyloxy- 1-thiaflavan in
deuterochloroform have been investigated at 60 Mc/s. The spectral parameters
for the heterocyclic ring protons have been obtained by analysis of the
frequency-sweep double-resonance spectra and verified by an iterative technique
using a digital computer. Long- range coupling constants were observed between
the protons at C 4 and C 5 (J 0.8 c/s) and between the protons at C 2 and C 4
(J 0.2 c/s) for the cis isomer.
Magnetism, electronic spectra, and structure of transition metal alkoxides IV. cobalt(II) methoxy halides
Authors: Kakos GA , Winter G
Published: September 2010

The series Co(OMe)X where X = Cl, Br, and I have been prepared and their
magnetism and electronic spectra examined. The results clearly show the effect
of increasing ligand size on the stereochemistry of the alkoxide. Whereas Co(OMe)I appears to be octahedral and unable to solvate, Co(OMe)Br is tetrahedral but is capable of solvation by
methanol to form an octahedral species. Co(OMe)I is tetrahedral and apparently
incapable of solvation.
The alkaloids of Cynoglossum australe R.Br. and C. amabile Stapf & Drummond
Authors: Culvenor CCJ , Smith LW
Published: September 2010

Two new pyrrolizidine
alkaloids, cynaustraline and cynaustine, have been isolated from Cynoglossum australe R,.Br., and echinatine and a third new
alkaloid, amabiline, from C. amabile Stapf & Drummond. Cynaustraline, cynaustine, and
amabiline are, respectively, (+)- isoretronecanol,
(+)-supinidine, and (-)-supinidine esters of viridifloric acid. This is the
first isolation of an ester of a (+)- enantiomer of an allylic amino alcohol.
Catalytic deuterium exchange reactions with organics. XXXVI. The labelling of ( - )-inositol on self-activated platinum oxide with and without radiation
Authors: Angyal SJ , Fernandez CM , Garnett JL
Published: September 2010

Exchange of (-)-inositol
with curie levels of tritiated water on self- activated platinum oxide leads to
incorporation of tritium of which 92.5% is found at C l and C 6, 3.7% at C 2
and C 5, and 3.8% at C 3 and C 4. Isotope scavenging indicates that inversion
occurs only at C1 yielding labelled myoinositol. Exchange is accelerated in the
presence of u.v. light without extensive degradation. A comparison has been
made between the Wilzbach gas irradiation technique
and the catalytic method for labelling (-)-inositol. Possible mechanisms for
tritium incorporation in (-)-inositol are discussed for the various experimental
conditions used.
Thio derivatives of β-diketones and their metal chelates. VIII. Adducts of metal chelates of fluorinated monothio-β-diketones
Authors: Ho RKY , Livingstone SE , Lockyer TN
Published: September 2010

Complexes of l,l,l-trifluoro-4-mercapto-4-phenylbut-3-en-2-one, PhC(SH)= CHCOCF3, with cobalt(111), nicke1(11), palladium(11), platinum(11), copper(11), zinc(11),
cadmium(11), and mercury(11) have been prepared and characterized. Their infrared spectra and the spectra of
metal complexes of two other fluorinated monothio-β-diketones
are discussed. Adducts of nickel (11)
palladium(11), platinum(11), zinc(11), cadmium(11), mercury(11), and lead(11)
complexes of the fluorinated monothio-β-diketones,
RC(SH)=CHCOCF3 (R = Ph, α-thienyl, or
Me), with pyridine, α-picoline, γ-picoline, 2,2'-bipyridyl,
1,l0-phenanthroline, 2,9-dimethyl-1,l0-phenanthroline, 2,2',2"-terpyridyl, or triphenylphosphine are described. Molecular
weight and visible spectral measurements on PdL2(PPh3)2
(L = C4H3SC(SH)=CHCOCF3) show that in nitro- benzene and toluene
solution one phosphine moiety is lost. Similarly, ZnL2
pic2 (pic
= α- or γ-picoline) loses one molecule of picoline in nitrobenzene
solution. The infrared data indicate
that in the adducts nickel, zinc, and probably cadmium are six-coordinate and
palladium, platinum, mercury, and lead are four-coordinate, while zinc is five-coordinate
in the mono-adducts ZnL2 pic.
Organoaluminium compounds. XIII. Association through aryl and phenylethynyl bridges
Authors: Jeffery EA , Mole T , Saunders JK
Published: September 2010

Proton magnetic resonance
spectrometry has been used to show that

dimethylphenylaluminium and dimethyl-p-tolylaluminium
dimers are held together by aryl bridges. Phenylethynyl
groups serve as bridges in the dimer of dimethyl-(phenylethynyl)aluminium.
Mixed aryl-methyl, phenylethynyl-methyl, and phenyl-phenylethynyl bridges have also been shown to exist.
Charge-transfer complexes of purines and pyrimidines
Authors: Fulton A , Lyons LE
Published: September 2010

The spectra of 20 purines and pyrimidines with chloranil, bromanil,
and p-benzoquinone in dimethyl sulphoxide were studied. Most of the systems exhibited
absorption bands which were concluded to be charge transfer in nature. The ionization energies of
the molecules, derived from the positions of the bands, correlated well with
the highest occupied molecular orbital energies calculated using the simple H�ckel method and were also in good agreement with
ionization energy values calculated by a semi-empirical self-consistent field
method.
Catalysis by hydrogen halides in the gas phase. XIV. Methyl trimethylacetate and hydrogen bromide and the effects of added alcohols
Authors: Cross JTD , Stimson VR
Published: September 2010

Hydrogen bromide and
hydrogen chloride catalyse the decomposition of methyl trimethylacetate
into isobutene, carbon monoxide, and methanol at 370-442� and 450-48O�,
respectively. The kinetic form, which is basically 1 : 1, is severely modified
by the effect of methanol either produced in the reaction or added initially.
Water or alcohols react with an intermediate in the catalysed decomposition of trimethylacetic acid or its methyl ester in esterification-like reactions; some of the resultant esters
subsequently decompose to olefin and acid.
Substitution reactions of some bis(2,2'-bipyridine) and mixed 2,2'-bipyridine, 2,2',2'-terpyridine complexes of ruthenium(II). II. The kinetics of substitution of nitrite and other nucleophiles
Authors: Davies NR , Mullins TL
Published: September 2010

The rates of substitution
of the complex ions [Ru11(H2O)bipytrpy]2+ and [Ru11(H2O)2
bipy2]2+, where bipy = 2,2'-bipyridine and trpy = 2,2',2"-terpyridine,
by a number of nucleophilic reagents in aqueous solution, have been determined
as a function of temperature. The reactions were observed to be second order
and rates fall in the sequence Ni > NO2 > SCN-> pyridine.
The range of Arrhenius parameters is very large with
some unusually low frequency factors. The diaquo
complex appears to undergo substitution leading to disubstituted derivatives in
a single step. In the case of substitution by nitrite, there is evidence that
the final products are nitro complexes formed by rapid isomerization of
intermediate nitrito complexes.
Rates of hydrolysis of a monochlorotriazine dye in presence of non-ionic surfactant
Authors: Craven BR , Datyner A , Doyle TP
Published: September 2010

The presence of nonylphenol-poly(oxyethylene)
surfactant decreases the rate constant for the
hydrolysis of a monochlorotriazine dye, the effect
being enhanced by increasing the surfactant to dye ratio and diminishing by
increasing the temperature. At 80� and 100�, the longer the ethylene oxide
chain length of a surfactant the more effective it is in reducing the rate
constant. At 60�, however, all of the surfactants used appear to be equally
effective. At 80� and 100�, extrapolation of rate constants to zero surfactant
to dye ratio gives a value very close to the rate constant in the absence of
surfactant, but at 60� the rate constant for NPl0
extrapolated to zero surfactant to dye ratio is close to the value from the
surfactant-free run, but values obtained with the
other surfactants are much higher and similar to that obtained in presence of a
polyether glycol. It is suggested that this anomaly is due to the initial
aggregation of the dye at 60� so that the addition of small quantities of
surfactant other than NPl0 causes initial disaggregation and an increase in the rate of hydrolysis.
Further increases in the amount of surfactant cause dye-surfactant complex
formation which produces a decrease in the rate of hydrolysis.
Carbonyl halides of the Group VI transition metals. VII. Nitrosyl halide derivatives of molybdenum and tungsten(II)
Authors: Anker MW , Colton R , Tomkins IB
Published: September 2010

The previously reported dihalodinitrosylbis(triphenylphosphine)molybdenum and tungsten(11)
type complexes, M(NO)2L2X2 (M = Mo, W; L = PPh3, AsPh3,
SbPh3; X = Cl, Br), have been prepared by
a new method involving the action of nitric oxide on the corresponding
tricarbonyl derivatives. The new feature of this method is that, unlike the
previous methods, it is not stereospecific, and in some cases all three
possible cis isomers are formed. The identification of the various isomers has
given a natural explanation of the apparently anomalous order of π-bonding
effects in these complexes previously reported by Cotton and Johnson.
Meisenheimer salts. II. Stabilities and spectra of some metal methoxide adducts with anisoles
Authors: Dickeson JE , Dyall LK , Picles VA
Published: September 2010

N.m.r. spectral studies
demonstrated that Meisenheimer salts were formed by addition of alkali metal methoxides to 4-cyano-2,6-dinitroanisole,
4-methoxy-3,5-dinitropyridine, and 2,6-dinitroanisole, but not with 2-methoxypyrimidine.
Crystalline salts were isolated after
addition of methoxide to the cyanodinitroanisole and methoxydinitropyridine. The stabilities of the Meisenheimer
salts were found to be heavily dependent on the ability of ring substituents to
accept negative charge.
The control of phosphate contamination in an acid alumina process
Authors: Davey PT
Published: September 2010

In concentrated aluminium sulphate solutions, such as are used in an acid alumina
process, phosphate is very powerfully complexed and
no satisfactory methods for its removal from solution have been previously
described. The procedure herein uses zirconium sulphate
to precipitate phosphate from acid solutions containing up to 50 g/l. Al2O3. Faster precipitation is
achieved by prior heating of the aluminium solutions to 100� for a short period
and a residual liquor containing less than 50 p.p.m.
P2O5 is readily obtained. The procedure has been
successfully applied to the preparation of specification-grade alumina from an
Argentine laterite (0.1 % P2O5)
using the CSIRO acid alumina process.
Magnetism, electronic spectra, and structure of transition metal alkoxides. VI. Chromium(III) chloro alkoxides
Authors: Dubicki L , Kakos GA , Winter G
Published: September 2010

In the compound Cr(OMe)C12,2CH3OH
one molecule of methanol can be replaced by one molecule of acetone,
acetonitrile, or dioxan. The magnetism and spectra
are interpreted in terms of dimeric models. On heating the dimethanolate
one molecule of methanol is lost and for this compound a tetrameric
structure is proposed.
The digitanols of the root bark of Calotropis procera R.Br
Authors: Chandler RF , Coombe RG , Watson TR
Published: September 2010

Benzoyllineolone and benzoylisolineolone
were isolated from the root bark of C. procera R.Br. Saponification
gave lineolone and isolineolone.
Analysis of the mass spectra of the isomers was used to obtain the conformation
of the side-chain at C17.
Thio derivatives of β-diketones and their metal chelates. X. The anomalous paramagnetism of some iron(III) chelates of monothio-β-diketones
Authors: Ho RKY , Livingstone SE
Published: September 2010

The magnetic
susceptibilities of the iron(111) chelates Fe(R1CS=CHCOR2)3
(R1 = Ph, p-MeC6H4, p-MeOC6H4,
p-BrC6H4, 2-thienyl,
2-furyl, R2 = CF3; R1 = Ph, R2
= Ph, OEt) have been investigated over a temperature range. The iron(111)
complex of ethyl thiobenzoylacetate (R1 =
Ph, R2 = OEt) is of the high-spin type and obeys the Curie-Weiss law
with θ =-8�k. The moments of the other complexes vary between 2.31 and
6.61 B.M. at room temperature and are temperature-dependent, ranging from 1.86
to 4.07 B.M. at 80�k, depending on the nature of R1 and R2
This behaviour is postulated to be due to a thermal equilibrium between the
nearly equi-energetic spin-paired (t5/2g) and
spin-free (t3/2ge2/g) configurations of the iron
atom, resulting from the approximately equal magnitudes of the ligand field (Δ)
and the pairing energy (π) in these complexes. The ligand field and
consequently the magnetic behaviour are sensitive to the nature of R1
and R2: electron-withdrawing groups appear to be the most effective
in increasing the population of the spin-paired configuration.
Platinum complexes of some deprotonatable tridentate ligands
Authors: Chiswell B
Published: September 2010

Platinum(11) and
platinum(IV) complexes of 1,3-bis(2'-pyridyl)-1,2-diazaprop-2-ene and ligands of similar structure, but with
methyl "blocking groups" adjacent to the pyridine nitrogen atoms,
have been studied. In neutral solution these ligands lose a proton upon
interaction with either platinum(11) or platinum(1V) salts to yield highly
coloured complexes soluble in organic solvents. Protonated
compounds of both oxidation states can be obtained, but such compounds are
unstable in neutral solution and readily yield deprotonated complexes.
Urey-Bradley potential constants for second-row fluorides
Authors: Brown RD , Peel JB
Published: September 2010

To provide an internally
consistent set of force constants for the fluorides of second-row elements, a
normal coordinate analysis, based on the Urey-Bradley
potential function, has been performed for SiF2,
SiF4, PF3, PF5, SF4,
SF6 ClF, ClF3,
and ClF5. Some limitations of this
potential function, imposed by molecular symmetry, are indicated. aluminium
removal from the clay surface.
A re-evaluation of the proton magnetic resonance spectra of some olefinmercury(II) systems
Authors: Kitching W , Smith AJ , Wells PR
Published: September 2010

The 60-MHz and 100-MHz
proton spectra of some oxymercurials derived from
ethylene and propylene have been examined. Such spectra, contrary to other
reports, provide no evidence for the existence of the mercurinium
ion in detectable amounts. A more plausible
interpretation of the spectra is presented.
Molecular interactions and infrared dichroism of crystalline monosaccharides related to xylan
Authors: Michell AJ
Published: September 2010

The infrared spectra
(4000-670 cm-l) have been obtained of methyl β-D-

xyloside and methyl 1-thio-β-D-xyloside
in the form of single crystals and potassium chloride disks. Deuteration shifts in the disk spectra and polarization
measurements in the single crystal spectra were used to assign the various
bands to infrared-active fundamental modes. Molecular interactions in
the crystals have been studied by comparing the observed dichroism with that
predicted from a knowledge of the structures. Problems involved in elucidating
the structures of crystalline carbohydrates, e.g. higher oligomers
of xylan and cellulose, from studies of their
infrared dichroism are discussed.
Chemistry of the Podocarpaceae. XVII. Ring-A modifications of O-methylpodocarpic acid
Authors: Bennett CR , Cambie RC , Fullerton TJ
Published: September 2010

Methods for the conversion
of 0-methylpodocarpic acid (I) into 12-methoxy-16-norpodocarpa-8,11,13-trien-4-amine (11) have been examined,
a Curtius reaction on the acid chloride (IV) followed
by hydrolysis of the isocyanate (111) with 85% w/w
sulphuric acid affording the highest overall yield (44%). Some "simple deaminations" involving no change in oxidation state,
have been investigated as possible routes to alkenes suitable for further
modification of the A ring of podocarpio acid. These
include nitrous acid deamination, treatment of the
N-benzoate (VIII) with phosphorus pentabromide or pentachloride, and pyrolysis of the tertiary amine oxide
(VII) or quaternary methylammonium iodide.
Studies in chrome mordanting. II. The binding of chromium(III) cations to wool
Authors: Hartley FR
Published: September 2010

The reactions of a number
of chromium(111) salts with wool have been investigated. It was found that
chromium(111) was not displaced from wool by washing in water. Chromium(111)
was bound to wool by the carboxyl groups. Other groups such as sulphonate and thiol groups also bound chromium(111) when
these were present, but no evidence was found for binding by amino groups. A
mechanism is suggested for the reaction of chromium(111) with wool.
Octahedral chromium(III) complexes in dipolar aprotic solvents. II. The isomerization of cis- and trans-[CrCl2 en2]+ ions in anhydrous dimethyl sulphoxide
Authors: Palmer DA , Watts DW
Published: September 2010

The equilibria
represented by the following equations:

(See diagram in paper)

have been studied in
anhydrous dimethyl sulphoxide at various chloride ion
concentrations. The mechanisms of the reactions are interpreted as dissociative
and this assignment is consistent with the radiochloride
exchange data. The kinetic and equilibria results are
dependent on ion association which is separately treated by conductance
measurements in the case of cis-[CrCl2 en2]+Cl-.
Activation energies are recorded.
4,5-Seco-4,6-cyclosteroids. II. Synthesis of 4,5-Seco-4,6-cyclo-6β-cholestan-5α-ol
Authors: Collins DJ , Hobbs JJ , Rawson RJ
Published: September 2010

5-oxo-4,5-secocholestan-4-oic
acid methyl ester (XIIIb) was converted into the
corresponding cyclic ethylene acetal (XIVb) which,
upon successive reduction with lithium aluminium hydride and acid hydrolysis,
gave 4-hydroxy-4,5-secochol-estan-5-one (XVa), converted into the tosyl ester (XVb).
Base-catalysed intra-molecular alkylation of the latter gave mainly A-homo-4a-oxacholest-5-ene (XVII), together with 4,5-seco-4,6-cyclo-6β-cholestan-5-one (IIIc),
reduced with lithium aluminium hydride to 4,5-seco--1,6-cyclo-6β-cholestan-5α-ol (IIb). This
was identical with material previously prepared by transformation of 4,5-seco-4,6-cyclo-6β-cholestane-3β,5α-diol (IIa), obtained from reductive rearrangement of
6β-bromo-4β,5-epoxy-5,β-cholestan-3β-ol
(I). ��� Some other approaches to the synthesis of
4,5-seco-4,6-cyolo-6β- cholestane derivatives
are described.
The influence of vapour pressure on the formation of anhydrous zirconium sulphates
Authors: Bear IJ
Published: September 2010

The anhydrous products
resulting from the dehydration of Zr(SO4)2,4H2O
in external atmospheres of controlled H2SO4 and SO3
partial pressures consist of three polymorphs, two of which, γ- and
β-Zr(SO4)2, are metastable
and equilibrate to the stable phase, α-Zr(SO4)2.
��� The rates of decomposition of these anhydrous
sulphates to cubic ZrO2 have been measured
and activation energies for the processes calculated. From these data the
vapour pressure-temperature diagram for the anhydrous region of the ZrO2-SO3-H2O system has
been delineated. This shows the existence range of γ-Zr-(SO4)2
lies within that of β-Zr(SO4)2
while both lie within that of the stable α-phase. ��� The function of physical factors, such as
particle and sample size and heating technique, in controlling phase formation
during dehydration in air is interpreted in terms of the vapour pressure- temperature
diagram.
The SN mechanism in aromatic compounds. XXXVII. Reactivity of amines
Authors: Miller J
Published: September 2010

A semi-empirical
theoretical procedure utilizing bond-dissociation, solvation, and ionization
energies as the main terms is used to calculate reactivity of amines, which
constitute the main class of neutral nucleophiles, with some typical neutral
aromatic substrates in protic solvents; and their reverse, i.e. reactivity of
anionic nucleophiles with cationic (ammonio) substrates. The procedure has
previously been used successfully to calculate reactivity of anionic
nucleophiles with neutral substrates. In each class the calculations also lead
to estimates of other important parameters such as leaving group mobility. The
procedure is applicable in principle to reactions of nucleophiles with other
organic and with inorganic substrates and to reactions in aprotic solvents. ��� In this paper, the procedure is applied to
some representative reactions of amines with neutral aromatic substrates in
protic solvents and predicts, in accordance with experimental data where
available, (i) reactivity in the order: NH3 < MeNH2
< Me2NH > Me3N; PhNH2 > PhNHMe >
PhNMe2; MeNR2 > PhNR2 (R = H or Me); (ii)
leaving group mobility in the order: F > Cl (and other heavy halogens) in
the reactions of aliphatic amines and aniline; F > Cl in the reactions of
N-methylaniline; and F < Cl in the reactions of N,N-dimethylaniline; (iii)
small values of ΔE? ( ≈ ΔH? in solution reactions). Small
values of log B (very negative values of ΔS?) are predictable on general
theoretical grounds, and these are modified by steric factors. ��� Similar amine reactivity patterns are
common with non-aromatic substrates, and the explanations given by the
procedure are of general application, apart from differences in the steric
factors.
Chemical and spectroscopic studies in metal β-diketonates. VIII. Electronic spectral studies on some trivalent 3d metal diketonates and their γ-substituted derivatives
Authors: Singh PR , Sahai R
Published: September 2010

Electronic absorption spectra
of solutions of chromium(III), iron(III),
and cobalt(III) β-diketonates have been measured in the 200- 1200mμ region. Detailed interpretation of the spectral
data are provided in terms of the πg →
π4, the electron transfer (dε → π4),
and the ligand field (d → d*) transitions of the various components. The
effects of γ-substituents on the chelate rings upon the positions of
different transitions are discussed. Substitution of a halogen results in
bathochromic shift in π3 → π4, dε
→ π4, and d → d* transitions of each chelate,
presumably due to extension of conjugation, interaction among dε
and π3 orbitals (which raises dε orbitals to a
higher energy), and decrease in ligand field effect respectively. The
hypsochromic shifts observed in the cases of NO2, SCN, Ac, and CHO
γ-substituents are perhaps due to the steric inhibition of resonance with
the chelate ring.
The potential dependence and upper limit of electrochemical charge transfer rates
Authors: Matthews DB
Published: September 2010

A theory is developed to
predict the potential dependence at high rates, and the upper limit, of
electrochemical charge transfer reactions. The theory utilizes a constant
symmetry factor and shows how the properties of the overlapping electron
distribution functions produce a non-linear dependence of log(rate) on
electrode potential, and hence a dependence of the effective symmetry factor on
electrode potential.
The pyrolysis of polycarbonyl compounds. IV. Pyrolysis of 3,3-dimethylindane-1,2-dione and o-isopropenylbenzaldehyde at 600° and 800°
Authors: Brown RFC , Butcher M
Published: September 2010

Pyrolysis of
3,3-dimethylindane-1,2-dione (IV) at 600�/0.6 mm with short contact time gave
benzofulvene (V), o-isopropenylbenzaldehyde (VI), and
3-methyl-indan-1-one (VII). The aldehyde (VI) was shown by deuterium labelling
to undergo randomization of hydrogen atoms between the aldehyde and isopropenyl
groups at 600�. Pyrolysis of the dione (IV) at 800�/0.6 mm gave the hydrocarbons
phenyl-acetylene, styrene, α- methylstyrene, o-methylstyrene, indene,
benzofulvene, and naphthalene; the formation of these from the products (VI)
and (VII) is discussed.