bluuebunny/crossref_metadata_2025 huggingface dataset:
Basic Zinc Chlorides
Authors: Hoffman JW , Lauder I
Published: September 2010

Two basic zinc chlorides
identified by chemical and X-ray analysis as ZnOHCl and
ZnCl2,4Zn(OH)2,H2O
respectively were prepared. The thermal decomposition of these basic chlorides
at temperatures up to 250� may be represented by the equations :

2ZnOHCl + ZnCl2+ZnO +H2O (1)and

ZnCl2,4Zn(OH)2,H2O → ZnCl2
+4ZnO +5H2O (2)

Mass spectrometric
measurements show that, in proportion to the water, there is little hydrogen
chloride evolved on heating. The dissociation pressures
of the compounds are given by the equations:

ZnOHCl loglop log10P(atm) = -1.93 x 103/T + 4.22

ZnCl2,4Zn(OH)2,HzO log10P
(atm) = -1.95 x l03/T + 3.93

The value of ΔH0
for dissociation is approximately the same for the two compounds, namely, 9
kcal/mole. Pure zinc chloride can be
separated from zinc chloride contaminated with basic chloride by sublimation
along a tube which is being continuously evacuated.
Transformations of podocarpic acid
Authors: Davis BR , Watkins WB
Published: September 2010

Methyl 12-methoxypodocarpa-8,11,13-trien-16-oate (11) has been converted
by two routes into the C13 3'-carboxypropyl
derivative (VIII). Friedel-Crafts cyclization of the
corresponding acid chloride gave the D-homosteroid
(IV). Reformatsky reaction of the 13-succinyl compound gave the lactone (VI); model experiments
are also described. The rearrangement of the C12 O-allyl ether gave both the
normal C13 allyl phenol (XI) and the coumaran (XIII).
Peracid oxidation of (11) gave the expected quinone
(XIV) and hydroxy dienone (XV). Photolysis of the unsaturated ketone (XVII) in
methanol gave only the corresponding saturated ketone (XXI).
Raman spectra of mercury(I) and mercury(II) iodides in the solid state
Authors: Cooney RPJ , Hall JR , Hooper MA
Published: September 2010

The Raman spectrum of
yellow Hg2I2 contains features
at 110 and 192 cm-l assignable to Hg-Hg
stretching and Hg-1 stretching respectively. The spectrum of yellow HgI2 at c. 150� shows bands at 33 cm-1
(I-Hg-1 bending) and 133 cm-1 (Hg-I stretching). The Raman
shifts for red HgI2 are 24, 111, and 137 cm-l,
attributable to I-Hg-1 bending, symmetric and asymmetric Hg-1
stretching respectively. Assignments are made on the basis of factor group
analyses on the Bravais unit cells. Some force
constants are calculated.
Flavan derivatives. XXIII. Preparation and synthetic applications of Flav-3-enes
Authors: Clark-Lewis JW , Jemison RW
Published: September 2010

2'-Hydroxychalcones
and α-alkoxy-2'-hydroxychalcones are converted
by sodium borohydride in isopropanol into flav-3-enes and
3-alkoxyflav-3-enes in the convenient new synthesis
which makes these flavenes readily available. Catalytic reduction of the flavenes
gives the corresponding flavans or 3-alkoxyflavans in
high yield, and the latter are obtained mainly in the 2,s-cis-form. The flavenes immediately give flavs
lium cations in the cold when treated with acids in
air, and oxidation of 5,7,3',4'-tetramethoxyflav-3-ene with benzoquinone in an acidic
medium gave the flavylium salt, isolated as the ferrichloride. Reduction of 5,7,3',4'-tetramethoxy-flavylium
chloride with lithium aluminium hydride gave 5,7,3',4'-tetramethoxy-flav-2-ene
identical with the flavene obtained from (-)-epicatechin tetramethyl ether, and confirms an earlier
investigation by Gramshaw, Johnson, and King. In its
N.M.R. spectrum the heterocyclic-ring protons of this flav-2-ene
give an ABX multiplet which is easily distinguished
from the ABX multiplet at much lower field
characteristic of flav-3-enes.
Nuclear magnetic resonance of some fluoro-substituted phenyl and benzyl mercurials
Authors: Kitching W , Adcock W , Hegarty BF
Published: September 2010

l9F and lH nuclear
magnetic resonance data are reported for the para and meta fluoro-phenyl
and -benzyl mercurials of types R2Hg and RHgX where X is a halide. The 19F data for the fluorophenyl mercurials provide no evidence for direct
aryl-mercury conjugation, and mercuri substituents
exert very feeble electronic effects. The shielding for the fluorobenzyl
mercurials suggests a quite pronounced o-p electron donating effect for the metallomethyl group (NCH2-). Some 199Hg-lH spin coupling constants are
derived from the proton spectra of the benzyl mercurials.
Nitrones and oxazirans. I. Preparation of 1 -pyrroline 1-oxides and 1-pyrrolines by reductive cyclization of γ-nitro carbonyl compounds
Authors: Bapat JB , Black DS
Published: September 2010

A series of new pyrroline I-oxides and their related pyrrolines
is described. Preparation of these
compounds by reductive cyclization of y-nitro carbonyl compounds is discussed.
This method is critically dependent on the reducing agent in the preparation of
pyrroline 1-oxides and various procedures are
assessed. Zinc in aqueous ammonium
chloride is successful only in the formation of 2-aryl-5,5-dimethyl-substituted
pyrroline 1-oxides and reduced iron in a mildly
acidic medium is the method of choice for the corresponding 2-alkyl-substituted
compounds. Pyrrolines were prepared either by deoxygenation of pyrroline
1-oxides or reductive cyclization of suitable γ-nitro carbonyl
derivatives. Details of the N.M.R.
spectra of these compounds are discussed.
The p-methoxybenzyl ester group in peptide synthesis
Authors: Stewart FHC
Published: September 2010

p-Methoxybenzyl esters of
protected amino acids and peptides have been

prepared by imidazole-promoted condensation of the
corresponding p-nitrophenyl

esters with p-methoxybenzyl
alcohol. The products included several o-nitrophenylsulphenyl
dipeptide p-methoxybenzyl
esters, and the use of p-methoxybenzyl as a
carboxyl-protecting group was illustrated by the synthesis of a protected

pentapeptide fragment of a modified insulin A-chain sequence
involving selective

acidic cleavage of a-nitrophenylsulphenyl.
The determination of the stability constants of the fluoride complexes of tin(II) using the fluoride electrode
Authors: Hall FM , Slater SJ
Published: September 2010

The stability constants for
the fluoride complexes of tin(11) have been determined by e.m.f.
measurements, over a range of temperature, using both a tin amalgam electrode
and the recently available fluoride ion activity electrode. The significance of the values ΔG -11480
cal/mole, ΔH 10350 cal mole-l, and ΔS 73.2 cal deg-1
mole-1 for the SnF3-
complex is discussed and compared with those for the chloro and bromo complexes
of tin(11).
Sulphur-bridged complexes involving the ligand 2,2'-dimercaptodiethyl sulphide
Authors: Barclay GA , McPartlin EM , Stephenson NC
Published: September 2010

The ligand 2,2'-dimercaptodiethyl sulphide has been prepared and complexes formed
with divalent Ni, Pd, Pt, Pb, Hg, and Co. In each of
these compounds there is a 1 : 1 molar ratio of ligand to metal. Spectral, magnetic,
and conductivity measurements for the nickel(11) and palladium(11) compounds
are consistent with molecular configurations involving four-coordinate,
neutral, sulphur-bridged structures.
An ion-exchange process with thermal regeneration. VI. Factors influencing the titration curve shape of weak electrolyte resins
Authors: Bolto BA , McNeill R , MacPherson AS , Siudak R , Weiss DE , Willis D
Published: September 2010

An experimental study is
presented which establishes that if the titration curve of a weak electrolyte
resin is to exhibit a well-defined pH plateau, it must have a structure which
is homofunctional and which is not too polar. Homofunctional mono- and di-alkylamino
groups in a cross-linked hydrocarbon polymeric structure exhibit such a
plateau. Polymers with non-polar backbones and primary amino or carboxyl groups
possess sloping titration curves. The results can be accounted for by the
formation of ion pairs with monovalent counter ions in the less polar
structures, or with multivalent counter ions in more polar structures.
The thermal decomposition of t-butyl methyl ether
Authors: Daly NJ , Wentrup C
Published: September 2010

The rates of the thermal
decomposition of t-butyl methyl ether have been measured in the range 433-495�.
The reaction products are isobutene and methanol, and the kinetic form is first
order. The Arrhenius equation

K1 = 1014.38exp(-61535/RT)
sec-1

describes the variation of
rate with temperature. The reaction behaviour is consistent with a unimolecular mechanism. Comparison of the results with
those obtained for the production of isobutene from various t-butyl compounds
indicates that the reaction has some degree of heterolytic character.
Conformational analysis in carbohydrate chemistry. II. Equilibria between reducing sugars and their glycosidic anhydrides
Authors: Angyal SJ , Dawes K
Published: September 2010

The position of the equilibria between aldohexoses
and 3-deoxyaldohexoses and their 1,6-anhydrides, and
between heptuloses and their 2,7-anhydrides, has been
determined by gas chromatography. The results are in good agreement with data
calculated from conformational interaction energies. D-Talose
gives equal amounts of the 1,6-anhydropyranose and
the 1,6-anhydrofuranose. D-glycero-D-gulo-Heptose
gives 66% of the 1,7- and
only 9% of the 1,6-anhydride.
Activity coefficient assumptions in the determination of the association constant of thallium(I) chloride. IV. Spectrophotometric measurements on thallium(I) chloride solutions
Authors: Macaskill JB , Panckhurst MH
Published: September 2010

Precise measurements are
reported of the optical absorbance of aqueous solutions of thallium(I) chloride
in mixture with other electrolytes at 25�. Two types of activity coefficient
expressions are used to analyse the measurements in terms of association of
thallium(I) chloride. The method of analysis is similar to that used for solubility
measurements1-3 and the different types of measurements lead to
different values for the association constants.
Cyclitols. XXVIII. Methyl esters of inositol phosphates. The structure of phytic acid
Authors: Angyal SJ , Russell AF
Published: September 2010

Methylation of phytic acid
with diazomethane gives a crystalline dodecamethyl ester; a similar crystalline
ester was also obtained from scyllo-inositol
hexaphosphate. The methyl esters of many myo-inositol
polyphosphates can be separated from each other by thin-layer or column
chromatography. Phosphate migration occurs when the hydroxyl groups of
partially phosphorylated inositols are methylated.
Electron impact studies. XXXVII. Skeletal-rearrangement fragments in the mass spectra of alkyl and aryl isoxazoles
Authors: Bowie JH , Kallury RKMR , Cooks RG
Published: September 2010

The mass spectra of
substituted isoxazoles are reported and discussed. The spectra of isoxazoles
are strikingly different from those of oxazoles because the initial fragmentations
of isoxazoles involve N-O bond fission. Specific skeletal-rearrangement processes
are observed in many spectra, and it is proposed that they proceed through
azirine and oxazole intermediates. Certain fragmentations have been studied by
deuterium labelling. The hydrogens attached to an isoxazole ring do not
randomize with the hydrogens of the methyl and phenyl substituents.
Zwitterion ratios of aminobenzoic acids
Authors: Serjeant EP
Published: September 2010

Relations have been
established between the pKa values for the non- zwitterionic forms
of meta- and para-aminobenzoic acids, pKB,
and the pKa values of the corresponding methyl and ethyl esters, pKE. For methyl m-aminobenzoate, the expression
is pKB = pKE
+ 0.09, whilst for the ethyl ester it is pKB
= pKE + 0.03. The corresponding relations
for p- aminobenzoic acid derivatives are pKB
= pKE + 0.06 for the methyl ester, and pKB = pKE +
0.03 for the ethyl ester. The mioroscopic constants
pertaining to the zwitterionic equilibria are given, and are used to establish
the Hammett substituent constants, σm,
for the following meta substituent groups: NH2, 0.00; NH3+,
0.98; NHCH2COOEt, -0.10; COOH, 0.30; COOMe, 0.33; COOEt, 0.31; COO-,
0.01.
Tumour inhibitory plants. The alkaloids of Bruguiera sexangula and Bruguiera exaristata (Rhizophoraceae)
Authors: Loder JW , Russell GB
Published: September 2010

Tropine and tropine esters
of acetic, propionic (a new natural ester), n-butyric (a new natural ester),
isobutyric, α-methylbutyric or isovaleric, and benzoic acids have been
identified in crude alkaloid mixtures from the bark of B. sexangula and B.
exaristata. The major component of the mixtures from both species was a new
alkaloid, brugine, (+)-tropine 1,2-dithiolan-3-carboxylate.
Phosphonium salts. I. The alkaline hydrolysis of some bis-phosphonium salts
Authors: Brophy JJ , Gallagher MJ
Published: September 2010

Ethane- and
ethene-1,2-bisphosphonium salts are cleaved by alkali into a phosphine and a
phosphine oxide with loss of the two-carbon bridge. When the phosphorus atom
carries benzyl substituents, loss of the benzyl groups is competitive with loss
of the bridge. ��� Based on a kinetic study, a synchronous
mechanism, analogous to the alkaline hydrolysis of acyclic monophosphonium
salts, is proposed to account for the fragmentation. ��� With 6-membered 1,4-diphosphonio
heterocyclic salts the nature of the products is dependent on whether alkali or
phosphonium salt is present in excess. With an excess of alkali a synchronous
mechanism again appears to operate, while with an excess of salt the reaction
proceeds stepwise and without loss of the bridge. A partial explanation of
these facts is advanced in terms of non-bonded interactions in the intermediate
phosphoranes. ��� The synchronous reaction appears to be
favoured by coplanarity of the P-C-C-P system.
Molecular polarizability. The dipole moments, molar Kerr constants, and conformations of some chloroformic esters
Authors: Aroney MJ , Le FFvre RJW , Pierens RK , The HLK
Published: September 2010

Dipole moments and molar
Kerr constants are reported for methyl, ethyl, and phenyl chloroformates in
carbon tetrachloride and in benzene. The experimental data are analysed to
provide information on the conformational preferences of the solutes in the
?inert? CCl4 environment and on solute-solvent associations in
benzene.
Chemistry of the Podocarpaceae. XXI. Preparation of 3-oxo derivatives of 12-Methoxy-18,19-bisnorpodocarpa-4,8,11,13-tetraene and 18,19-Bisnorabieta-4,8,11,13-tetraene
Authors: Bennett CR , Cambie RC , Franich RA , Fullerton TJ
Published: September 2010

12-Methoxypodocarpa-8,11,13-trien-19-oic
acid (11) has been converted into the 3-oxo compound (XX) via the C 3
benzylidene derivative of 12- methoxy-18,19. bisnor-5β-podocarpa-8,11,13-trien-4-one
(VIII). The route follows a modification of a sequence used by Zeiss and Martin
to convert abieta-8,11,13-trien-18-oic acid (III) into a tricyclic steroid
analogue. The latter conversion has been reinvestigated and modified to give a
higher yield of 18,19-bisnorabieta-4,8,11,13-tetraen-3-one (XXI).
The biosynthesis of brefeldin A
Authors: Coombe RG , Foss PS , Jacobs JJ , Watson TR
Published: September 2010

[1-14C]-, [2-14C]-Malonate,
and [1-14C]acetate incorporation into brefeldin A confirms its
biosynthesis by the normal polyketide pathway.
Solution of complex equilibria using random numbers
Authors: Mackie JC
Published: September 2010

A random number technique
is developed to calculate equilibrium compositions in a complex set of
reactions. The technique requires minimal computer memory and is
straightforward to programme. In all cases studied convergence to equilibrium
is rapid and the equilibrium position is stable.
Studies of anhydrous metal nitrates. III. Vibrational spectra and the nature of nitrato coordination
Authors: James DW , Kimber GM
Published: September 2010

The infrared and Raman
spectra of ammonium hexanitratocerate(IV), anhydrous mercury(II) nitrate, and
anhydrous cobalt(II) nitrate are reported. The spectrum of (NH4)2[Ce(NO3)6]
is analysed on the basis of the recent detailed structural determination. A similar
analysis is then made for Co(NO3)2 and Hg(NO3)2
the structures of which are not known. The usefulness of vibrational spectra to
establish the coordination of the nitrato ligand is examined.
Isoflavonoids. II. Synthesis of pterofuran and its derivatives
Authors: Cooke RG , McQuilkin RM
Published: September 2010

The copper-catalysed
reactions of diazoacetophenone with resorcinol and its mono-ethers are
described. With suitably substituted reactants this process has been adapted to
the synthesis of pterofuran and its derivatives, thus confirming the previously
proposed structures.
Steroid hormones. XXII. Total syntheses of (±)-equilenin methyl ether and (±)-oestrone methyl ether
Authors: Birch AJ , Subba Rao GSR
Published: September 2010

Total syntheses of oestrone methyl ether and equilenin
methyl ether are described, based on the Robinson intermediate (1). The key
steps are a stereo-specific introduction of the 18-methyl group and the reduction of ring B
of the equilenane skeleton, rendered possible by the
presence of an 11-carbonyl.
The reaction between peroxomonosulphuric acid and cerium(IV) in dilute sulphuric acid solutions
Authors: Billing WHO , Bridgart GJ , Wilson IR
Published: September 2010

The reaction of cerium(1V)
with peroxomonosulphuric acid in aqueous sulphuric
acid has been shown to involve a short radical chain. Rates of reaction of cerium(1V)
have been measured in dilute sulphuric acid solutions. A substantial difference
was found between the apparent rate law in the early stages of reaction and
that observed later. This is not due to the presence of hydrogen peroxide in
the peroxomonosulphate solutions. A tentative
mechanism is proposed.
Thallium(I) Schiff base compounds
Authors: Cozens RJ , Murray KS , West BO
Published: September 2010

Complexes of thallium(1)
and N-substituted salicylaldimines have been prepared of general
formulae Tl(sal-NR), Tl2(salen), Tl2(salophen), and Tl2(sa1-N-(2-OC6H4)).
The infrared, ultraviolet, p.m.r., and mass spectra
of the complexes are discussed in the light of their probable structures. It is
shown that these thallium(1) complexes provide a facile and efficient route to
the preparation of other metal and organometallic Schiff base
chelates.
The thermal decomposition of RDX at temperatures below the melting point. II. Activation energy
Authors: Batten JJ , Murdie DC
Published: September 2010

The activation energy has
been determined in the temperature range 170-198�. If the sample was spread the
activation energy was independent of the definition of the kinetic parameter
substituted in the Arrhenius equation and was 63 kcal
mole-1. In the case of the unspread
samples the activation energies of the induction, acceleration, and maximum
rates were 49, 43, and 62 kcal mole-1 respectively. The effect that sample
geometry has on the activation energy is attributed to gaseous decomposition
products influencing the reaction.
Determination of activity coefficients of aqueous solutions of urea in the ultracentrifuge
Authors: Woods EF
Published: September 2010

Apparent molecular weights
of aqueous urea solutions have been determined by equilibrium sedimentation over
the concentration range 1-9M. At the speeds used in the ultracentrifuge (39460
to 67770 r.p.m.) there was evidence of the effect of
pressure on the sedimentation of urea. Apparent molecular weights of urea were
therefore calculated at the solution-air meniscus where the solution is at l atm. The derived activity coefficients
showed a similar type of oncentration dependence to
published data for urea but there were significant quantitative differences.
The significance of the results from the point of view of calculating
theoretical distributions in the ultracentrifuge is discussed.
The ternary system BaO-ZnO-SiO2
Authors: Segnit ER , Holland AE
Published: September 2010

The equilibrium
relationships in the greater part of the ternary system

BaO-ZnO-SiO2 have been determined. Fifteen ternary invariant
points have been located; six of these are eutectics, and the minimum melting
point in the system is 1100� at a composition of 41.7% BaO,
17.00/0 ZnO, 41.3% SiO2
by weight. Five ternary compounds with
molar ratios of BaO : ZnO :
SiO2 of 1 : 1 : 1, 1 : 1 : 3, 1 : 2 : 2, 2
: 1 : 2, and 2 : 3 : 3 are described.
Catalysis by hydrogen halides in the gas phase. XX. Propionic acid and hydrogen bromide
Authors: Kairaitis DA , Stimson VR
Published: September 2010

Hydrogen bromide catalyses
the decomposition of propionic acid at 405-468�. The
initial products are ethyl bromide, carbon monoxide, and water; however, ethyl
bromide decomposes into ethylene and hydrogen bromide at rates comparable with
those of the initial reaction. The kinetic form of an individual run is
therefore not simple, and initial pressure change has been used to measure the
rate. The reaction,is first order in each reactant,
and the variation of rate with temperature is given by

K2 = 1.36 x 1012exp(-30850/RT)
s-1 ml mol-1

Comparison with the
hydrogen bromide catalysed decarbonylations of other
acids and esters has been made. Isobutene added to the reaction affects the
kinetic form of individual runs slightly and mainly through its effect on the
decomposition of ethyl bromide.
Quantum theory of inner sphere electron transfer reactions
Authors: Schmidt PP
Published: September 2010

This paper reports a theory
of inner sphere electron transfer reactions for which, in addition to the
electron transfer, there is bond formation and/or destruction. We assume that
steps in the reaction sequence which involve bond synthesis take place in intermediate
activated complex states. The problem of inner sphere electron transfer is
large and complicated. The theory described applies to one aspect of the
problem, namely, the dynamics of simultaneous electron transfer and bond break
in the transition state complex. However, we assume the intermediate complex
exists in steady state equilibrium with the reactants. The theory developed in
this paper reveals features important in the unimolecular
decay of the transition state. In particular, the importance of the
Franck-Condon restrictions on bond forming and breaking steps is demonstrated.
The kinetics of decarboxylation of benzoylacetic acid and its p-methoxy and p-nitro derivatives in dioxan-water mixtures
Authors: Hay RW , Tate KR
Published: September 2010

The kinetics of the
decarboxylation of benzoylacetic, p-nitrobenzoylacetic, and p-methoxybenzoylacetic
acids and their anions, have been studied in 50/50 v/v dioxan-water
at I 0.20M over a range of
temperatures. Substituents in the aromatic ring have little or no effect on the
relative rates of decarboxylation of the free acids. Values of ΔH? and ΔS?
are the same within experimental error. Apparently polar effects are
"swamped" by the polarization effect of the proton either partly or
fully transferred to the carbonyl group. Polarization effects of this type do
not occur with the anions and the expected substituent effects are observed,
thus at 35.6� the relative rates are p-NO2
(16) > pH (1) > p-OMe (0.26).
Geminal interproton coupling constants in some methyl derivatives
Authors: Lacey MJ , Macdonald CG , Pross A , Shannon JS , Sternhell S
Published: September 2010

The geminal inter-proton
coupling constants J(H-C-H) were obtained from the N.M.R. spectra of
suitably deuterated compounds MenX where X = C, Ge, Sn, Pb, 0, S, I,
N, and Li. The relation between the magnitudes of J(H-C-H), J(13C-H),
and electronegativity of X in this series is explored and some correlations are
proposed. The data for methyllithium do not fit with the remainder of the
results. It is tentatively concluded
that in this series of compounds J(H-C-H) is a periodic property.
Aromatic amides. V. Intramolecular hydrogen bonding in ortho-substituted anilides
Authors: Appleton JM , Andrews BD , Rae ID , Reichert BE
Published: September 2010

The proton magnetic resonance spectra of deuterochloroform solutions of a
number of ortho-substituted anilines and their S-acyl derivatives have been measured.
Variations in the acylation shifts of the ring protons are explained in terms of
intramolecular hydrogen bonding between the amide proton and the ortho-substituent.
Calculations of the contribution made to the acylation shifts by the anisotropy of
the amide group were found to be too sensitive to the molecular geometry to be of
any real value. Acylation shifts for a series of 4'-substituted 2'-nitroacetanilides
correlate well with the σp values of the 4'-substituents.
The experimental electronic and vibrational spectra of fulvene
Authors: Brown RD , Domaille PJ , Kent JE
Published: September 2010

The infrared spectrum of fulvene has been observed from 250 to 4000 cm-1 in the gas phase, and as a
glass and a polycrystalline layer at liquid nitrogen temperature. On the basis
of gas-phase contours and P-R separations 14 of the 30 fundamental vibrations
have been assigned. The electronic absorption
spectrum of fulvene has been recorded from 400 to 167
nm in the gas phase and four electronic transitions have been identified. The
lowest-energy transition was found to be broad and structureless
while the three higher-energy transitions showed an extensive vibrational fine
structure. The electronic transitions have been tentatively assigned on the
basis of VESCF-MO calculations and a partial analysis of the vibronic structure has bees made.
The theory of titration of polybasic acids. II. Conditions for the existence of inflexions near equivalence points
Authors: Hamann SD
Published: September 2010

Calculations have been made
of the conditions that are necessary for the existence of vertical equivalence
point inflexions in the titration curves of dibasic, tribasic,
and polybasic acids. Account has been taken of the effects of finite acid
concentration, of finite concentration of the titrating base, of finite
strength of the titrating base, and of activity coefficients. As a rule, each
of these effects causes a flattening of the titration
curves and the ultimate disappearance of inflexions.
The effect of pressure on the conductance of some iodides in acetone and 2-Methylpropan-1-ol
Authors: Ewald AH , Scudder JA
Published: September 2010

The conductance of
4-methoxycarbonyl-N-methylpyridinium iodide was measured in acetone at 293.1,
303.1, and 313.1�K and in 2-methylpropan-1-ol (Bu1OH) at 303.1�K at pressures up to 3 kbar. Similar measurements were made on solutions of sodium
iodide in Bu1OH at 298.1 and 308.1�K.
Limiting conductances and ion pair association
constants are derived and show incomplete dissociation of the salts at all
concentrations.
Studies in the stereochemistry of zinc(II). VII. Zinc complexes with dialkyldithiophosphates
Authors: Dakternieks DR , Graddon DP
Published: September 2010

A series of bis(O,O-dialkyldithiophosphato)zinc(11) complexes, ZnL2 (LH = (R0)2PS2H;
R = Et, Pri, Bu, Bui, Bus, cyclohexyl),
has been isolated. Pyridine adducts ZnL2(py)2 (R = Et, Pr, Pri,
Bui) and ZnL2(py) (R = Pr, Pri,
Bui) have also been obtained. Basic complexes ZnO,3ZnL2
(R = Et, Pr) have been isolated. Molecular weight data show that ZnL2 associates in benzene. When R = Pri

2ZnL2 ↔ Zn2L4 ΔG0c
-6kJ mol-1

The adducts ZnL2(py) are stable. Adducts ZnL2(py)2
dissociate in benzene; when R = Pr

ZnL2(py) + PY + ZnL2(py)2 ΔG0c-7kJmol-1

(ΔG0
calculated from molal concentrations). Infrared data cannot
distinguish between chelate, bridging, and unidentate PS2 groups.
Co-crystallization of ZnL2(py)2
and XiL2(py)2 could not be
achieved, suggesting ZnL2(py)2
is cis-octahedral.
Pigments of marine animals. X. Substituted naphthopyrones from the crinoid Comantheria perplexa
Authors: Kent RA , Smith IR , Sutherland MD
Published: September 2010

Acetone extraction of the flesh of the comatulid crinoid Comantheria perplexa (H. L. Clark) yields a mixture of substances from which the sodium salt of the sulphuric ester (12) of 8-hydroxy-5,6-dimethoxy-2-methyl-4H-naphtho[2,3-b]pyran-4-one (8) has been isolated. Acid hydrolysis of (12) yields the phenol (8) which on methylation is converted into rubrofusarin dimethyl ether and on partial demethylation yields a product identical with a dehydration product (10) of fonsecin.
Hydrolysis of the crude extract from C. perplexa yields (8), (10), and 8-hydroxy-5,6-dimethoxy-2-n-propyl-4H-naphtho[2,3-b]pyran-4-one (13). The structures of the isolated substances suggest a polyketide-type synthetic activity by this species.
The stalked crinoids Endoxocrinus parrae (Gervais) and Neocrinus decorus (Wyville Thomson) yield negligible quantities of aromatic polyketides.
Observations on the texture of the products of the dehydration of calcium sulphate dihydrate
Authors: Molony B , Beretka J , Ridge MJ
Published: September 2010

Studies of the topography
of the surfaces of grains of hexagonal calcium sulphate and calcium sulphate
hemihydrate, and of the systems of pores they contain, have been made by
electron microscopy and the sorption of oxygen, nitrogen, and argon. As the hemihydrate
ages, the area of the apparent surface falls and geometric features develop.
Hysteresis loops for the sorption of oxygen contract, showing that the finer
pores tend to disappear. The topography and area of the surfaces of grains of
hemihydrate are not greatly affected by cycles of dehydration and rehydration,
showing that these processes are of the zeolitic type.
Organophosphorus compounds. IX. Vinylphosphonium salts as reagents for proteins
Authors: Swan JM , Wright SHB
Published: September 2010

Triarylvinylphosphonium salts are investigated as potential reagents for the
radioactive labelling of immunoglobulins and other proteins. A new synthetic
route to these vinylphosphonium salts via hydroxyethyl and chloroethyl
derivatives is reported. The addition reactions of the vinylphosphonium salts
with amines, thiols, and proteins are described and the effects of substituents
discussed. In these reactions the functional groups NH2 and SH are
replaced by NHCH2CH2-�PAr3
and SCH2CH2- +PAr3
respectively.
Some studies in inorganic complexes. XXVI. Complexes of 6-Methyl-2-thioamidopyridine
Authors: Sutton GJ
Published: September 2010

Several complexes of the
chelating ligand 6-methyl-2-thioamidopyridine have
been prepared end studied. Infrared spectra indicate that the sulphur atom of
the thioamido group is bonding in the complexes: [CoL2(H2O)2][ClO4]2, [NiL2Br2],
[CuL2]I, [Ru2L4Cl2O]Cl2, [OsL2Cl2],
[AuL][AuCl1],
and [HgLI2] whereas nitrogen bonding
occurs with [FeLCl3]2, [ZnL3][ClO4]2,
[SnLI4], and the deprotonated species [In(L-H)3].
Copper(II) was reduced to copper(I),
e.g. [CuL2][CuBr2].
Studies in the visible spectrum, magnetic measurements, and conductances in
both nitrobenzene and dimethylformamide were also made.
The exchange of acetonitrile on iron(II) in acetonitrile solvent. A nitrogen-14 nuclear magnetic resonance study
Authors: West RJ , Lincoln SF
Published: September 2010

A 14N n.m.r. study of the exchange reaction Fe(CH3CN)62+ ╲ CH3CN in
CH3CN solvent is reported. The value for k 1 (25°C) from the rate law
R = 6k1[Fe(CH3CN)62+] is (5.5 ± 0.8) × 105 s-1, ΔH‡ = 9.7 ± 0.7 kcal mol-1,
ΔS‡ = 0.3 ± 2.2 cal mol-1 K-1, and A/h = 5.0 × 106 Hz. These data are compared
with those of related systems.
Molecular susceptibility. Molar Cotton-Mouton constants of liquids
Authors: Le Fevre RJW , Murthy DSN , Ritchie GLD
Published: September 2010

Molar Cotton-Mouton
constants, mCliq, are reported for about 40 pure
aliphatic liquids. For some of these substances infinite dilution values,
∞(mC2), are also recorded. The relationship between
mClig and ∞(mC2) is
investigated for both aliphatic and aromatic liquids.
The acylated isoflavone glycosides from subterranean clover and red clover
Authors: Beck AB , Knox JR
Published: September 2010

Formononetin and biochanin
A 7-O-glucosides (1a and 2a) and their malonate hemi-ester derivatives (1b and
2b) have been isolated from red clover and from the Yarloop
strain of subterranean clover. Structure (2b) is a correction of an earlier
structural assignment to this compound. Small amounts of the derived methyl
esters (1c and 2c) are also present in both clovers. Similar derivatives of
genistein have been obtained from the Yarloop strain,
although only the 7-O-glucoside (3a) has been isolated in pure form. Studies on
red clover and on nine strains of subterranean clover have demonstrated in all
cases that the acidic malonate esters account for the predominant proportion of
the glycosides.
Halogenated terpenoids. V. Terpinolene tetrabromide
Authors: Carman RM , Venzke BN
Published: September 2010

The structures of two
terpinolene tetrabromides have been determined and their interrelationship
studied. A facile bromination of a cyclohexenyl system proceeding through an
unstable conformer has been discovered. The incorporation of radioactive
bromide into the intramolecular diaxial → diequatorial rearrangement of
vicinal dibromides has been studied. Some steroidal vicinal dibromides have
been reinvestigated.
The gas-phase decomposition of ethyl bromide
Authors: Kairaitis DA , Stimson VR
Published: September 2010

The gas-phase decomposition
of ethyl bromide at 423� in the presence of both ethylene and hydrogen bromide
has been investigated. These additives, which are also the products, each
influence the rate strongly but in opposite ways. The variation of initial rate
with reactant pressure is given by (P in cm)

������������� k1 (min-1)
= 15.2x10-3+19.5x10-3(PEtBrPHBr/PEne)1/2

This has been interpreted
in terms of a unimolecular decomposition together with a bromine atom carried
chain reaction with simple steps that involve the products. Some insight into
the unaccompanied decomposition has been gained. Some remarks about the role of
olefinic inhibitors in reactions producing hydrogen bromide have been made.
Donor-acceptor complexes formed by perfluoro-organo bromides and iodides with nitrogenous and other bases. II. Band shapes and widths in the absorption spectrum of gaseous CF3I-N(CH3)3
Authors: Mishra A , Pullin ADE
Published: September 2010

The absorption band centred
at c. 77 cm-1 in gaseous mixtures of CF3I and N(CH3)3
previously reported and attributed to the N-I stretching mode of the complex CF3I-N(CH3)3
has been carefully re-examined. This band is of interest as an example of a low
frequency ?dissociative type? vibrational mode of a weak molecular complex. The
band is asymmetric and apparently structureless with a half intensity width at
room temperature of 28-30 cm-1. The width of the band may be
accounted for as arising from transitions vi + vi+1 where
vi is the vibrational quantum number of the N-I stretching mode with
vi up to c. 10 making appreciable contribution to the intensity on
the low wave-number side. Centrifugal distortion in the complex is considered.
Centrifugal stretching and consequent weakening of the bond may shift the band
envelope 2-3 cm-1 to lower wave numbers. Assessment of these and
other factors affecting the band shape suggest that the fundamental frequency
is probably c. 90 cm-1. The band
shape of the vibrational mode of the complex at c. 272 cm-1 is briefly
discussed. Many of the considerations presented in this paper should apply to
vibration-rotation band shapes in other weak molecular complexes. Some general
consequences of anharmonicity for the interpretation of the spectra of weak
molecular complexes are discussed.
Spectroscopic studies of 2,6-dihydroxypyridine and some of its derivatives. Tautomerism in solution, and very strong hydrogen bonding in solid 2,6-dihydroxypyridine and its N-methylated derivative
Authors: Spinner E , Yeoh GB
Published: September 2010

Ultraviolet, infrared, and
proton magnetic resonance spectra were measured for 2,6-dihydroxypyridine,
6-hydroxy-1-methylpyrid-2-one, α,α,γ-trichloro- and α,α,γ-tribromo-glutaconimide,
with special reference to the hydroxypyridone-pyridinediol-glutaconimide
equilibrium. The ratio [pyridol]/[pyridone] is much smaller for 2,6- dihydroxy-than
for 6-methoxy-2-hydroxy-pyridine, especially in hydroxylic solvents. The
hydroxypyridone form is the main or predominant tautomer for
2,6-dihydroxypyridine in water, dimethyl sulphoxide, ethanol, and 5%
ethanol-95% cyclohexane, and for the 1- methylated derivative in ethanol. The
glutaconimide form is the main or predominant tautomer for 2,6-dihydroxy-pyridine
in dioxan, and for the 1-methylated derivative in water, dioxan, and chloroform.
In the solid state 2,6-dihydroxypyridine and the 1-methylated derivative show a
very broad intense infrared OH band with a plateau extending from c. 1300 cm-1
to, respectively, 800 and 450 cm-1, and with some transmission ?windows?;
there is very strong hydrogen bonding, various aspects of which will be
discussed. The solids probably consist of 6-hydroxypyrid- 2-one molecules
linked by very short unsymmetrical hydrogen bonds; though, for the unmethylated
compound, an alternative ?macromolecular? structure, consisting of units in
which the heavy-atom skeletons have C2v symmetry, and are linked
together by symmetrical hydrogen bonds, cannot be ruled out entirely on the
present evidence.
Relative basicities of substituted acetanilides in acetic acid and acetic anhydride. A potentiometric and spectrophotometric investigation
Authors: Johnson WD , Sherwood JE
Published: September 2010

The relative basic
strengths of a series of substituted acetanilides in acetic acid have been
determined both potentiometrically and spectrophotometrically. The relative potentials at half-neutralization
of the bases with perchloric acid, in both acetic acid
and acetic anhydride, have been determined. Ionization constants of the bases
with perchloric acid were obtained using N,N-diethyl-2,4-dinitroaniline as indicator base. The effect
of substitution on basic strength is discussed.
Mass spectrometric studies. X. Phenacylpyridinium enol-betaines
Authors: Calder IC , Porter QN , Richards CM
Published: September 2010

Phenylpyridinium enol-betaines have mass
spectra containing abundant molecular ions which
decompose by loss of a hydrogen atom to give intense M- 1 species. Both ions
eliminate CO and CHO units, and the courses of the various decompositions have
been established by making use of deuterium labelling. The ion at m/e 92 in the
spectrum of the parent compound is best described by an azatropylium
structure.
The volatile constituents of the scent gland reservoir of the fruit-spotting bug, Amblypelta nitida
Authors: Baker JT , Blake JD , Macleod JK , Ironside DA , Johnson IC
Published: September 2010

Using combined gas
chromatography and mass spectrometry, ten components of the scent-gland complex
of the coreoid Amblypelta nitida Stal
have been identified. Of specific interest is the presence in the gland
reservoir of 2-n-butyloct-2-enal, the aldol condensation-dehydration
product of hexanal.
Iron(III) complexes of DL-methionine
Authors: Halbert EJ , Rogerson MJ
Published: September 2010

Few iron(111) complexes of
amino acids have been isolated although attempts have been made to measure
their stabilities in solution. Iron(111) in the presence of various amino acids
showed no complex formation during pH titration in aqueous solution. Using
oxidation-reduction and spectrophotometric techniques Perrin measured the
stabilities of 1 : 1 complexes of iron(111) with different amino acids in
solutions of low pH. Rapid hydrolysis of iron(111) occurred when the pH was
increased even in the presence of a large excess of amino acids.

Bielig and Bayer reported the isolation of a bis-complex of
iron(111) and methionine prepared in aqueous
solution. McAuliffe, Quagliano, and Vallarinoe reported a tris-complex made in ethanol, though
their iron analysis was not consistent with the required structure. In both
cases magnetic and infrared studies were used to characterize the products. Our
attempts to repeat these preparations were unsuccessful. This paper describes the
preparation of two 1 : 1 complexes of methionine and
iron(111) and an investigation of their properties by analysis of infrared,
magnetic, and N.M.R. measurements.
1-Thioisoflavanones and related compounds
Authors: Katekar GF , Thomson RM
Published: September 2010

Several 1-thioisoflavanones
and 1-thioisoflavones have been synthesized. Addition of a thiophenol to atropic acid and
cyclization of the resultant thio acids is shown to
give rise to a 1-thioisoflavanone. Some reactions of these compounds are
described.
The 4A2g → 2Eg transitions in acid erythro, a binuclear chromium(III) complex
Authors: Dubicki L
Published: September 2010

The ground-level energies
H = -∑2Jab,bjsaiSbj

Spin-orbit coupling only
slightly perturbs the pair energies but exerts a marked influence on the pair
intensities.
The pyrolysis of pinanes. VII. The pyrolysis of some hydroxypinane derivatives
Authors: Coxon JM , Garland RP , Hartshorn MP
Published: September 2010

The gas-phase pyrolyses of nopinol (I), neoisoverbanol(4), and isopinooampheol
(5) are described.
Complexes of carbohydrates with metal cations. I. Determination of the extent of complexing by N.M.R. spectroscopy
Authors: Angyal SJ
Published: September 2010

The tautomeric equilibrium
of D-allose in aqueous solution is altered by the
presence of some cations which form complexes with the α-pyranose and the α-furanose
but not with the β-pyranose and the β-furanose forms. Determination of the proportions of the tautomeric
forms by N.M.R. allows a comparison of the complexing ability of cations.
Lanthanum, calcium, and strontium form the strongest complexes. The behaviour of D-lyxose, D-ribose, and D-glycero-D-gulo-heptose on
complexing is described.
Constituents of Dipterocarpaceae Resins. IV. Triterpenes of Shorea acuminata and S. resina-nigra
Authors: Cheung H , Yan T
Published: September 2010

Application of N.M.R.
methyl resonance data led to revision of the structures given to the two cis 2,3-diols resulting from osmium tetroxide oxidation of methyl oleana-2,12-dien-28-oate
(10). 2α,3α-Dihydroxyolean-l2-en-28-oic acid (6a), a new natural
product, occurs in Shorea acuminata
resin. Other constituents are 2α-hydroxy-ursolic acid (14a), mangiferonic acid (15b), and asiatic
acid (14c). S. resina-nigra
contains β-amyrin (16a), ursolaldehyde
(14f), and Ψ-taraxesterol(17a).
Indolizines. IV. Reductive cleavage of acyl groups from acetylindolizines. C-Protonation and fragmentation of Indolizine-3-carbinols
Authors: Dainis I
Published: September 2010

Sodium borohydride in
ethanol has effected cleavage of 3-acetylindolizines to indolizines
in those cases where the intermediate 3-carbinols are readily protonated at C3. Reduction of
3-acetyl-2-methylindolizine in EtOD has demonstrated
that fragmentation proceeds via
C-protonation, and has also provided a selective method for the 3-deuteration
of reactive indolizines. 1-Acetyl- and
1,3-diacetyl-indolizines gave unstable product mixtures on reduction excepting
the one case where the product carbinol was stabilized
by a resistant, electron-withdrawing 3-substituent. 3-Ethoxyoarbonyl groups
were not affected.
The pyrolysis of oxindoles at 850°C. II. Oxindoles methylated at N1 and at C3
Authors: Brown RFC , Butcher M
Published: September 2010

The products of pyrolysis
of 1-methyl-, 3-methyl-, 3,3-dimethyl-, and 1,3,3-trimethyl-oxindole at
850�/0.2-0.4 mm have been examined. 1- Methyloxindole
and 3-methyloxindole gave mainly complex mixtures of decarbonylated and
rearranged products, but 3,3-dimethyloxindole gave 2-quinolone (52%) and indole
(25%). Similarly, 1,3,3-trimethyloxindole gave 1-methyl-2-quinolone (30%).
Quantum effects in dipolar gases
Authors: Pompe A , Spurling TH
Published: September 2010

The second-order
translational and rotational quantum corrections to the second virial
coefficient for the Stockmayer potential have been
derived and numerical values computed with parameters appropriate for water
vapour. The second-order corrections amount to about 10% of the first-order
corrections at room temperature.
Thermodynamics of aqueous sodium and potassium dihydrogen orthophosphate solutions at 25°C
Authors: Childs CW , Downes CJ , Platford RF
Published: September 2010

The osmotic coefficients of
aqueous NaH2PO4 and aqueous KH2PO4
over the ranges 1.0-6.5 mol kg-1 for the sodium salt and 0.85-2.2
mol kg-1 for the potassium salt were determined at 25�C by the
isopiestic method. Our data were combined with the data of Scatchard and
Breckenridge for low concentrations in order to calculate smooth values of
osmotic and activity coefficients for concentrations down to 0.1 mol kg-1.
Haemodorin - A phenalenone pigment
Authors: Bick IRC , Blackman AJ
Published: September 2010

The isolation and
structural determination of haemodorin, a new phenalenone pigment obtained from
Haemodorum distichophyllum
(Hook.) (Haemodoraceae), is described.
Glass transition temperatures, density and conductivity data, and far-infrared spectra of fused zinc chloride + β-aminoethanol hydrochloride mixtures
Authors: Easteal AJ , Kelly CB
Published: September 2010

Densities and
conductivities of fused ZnCl2 + β-aminoethanol hydrochloride
mixtures containing up to c. 72 mole % ZnCl2 are reported for the
temperature range from 293 K (approximately) to 393 K. Molar volume isotherms
are almost linear throughout the composition range, while thermal expansivity
isotherms have minima in the vicinity of 8 mole % ZnCl2 and maxima
at about 25 mole % ZnCl2. ��� Mixtures are glass-forming from c. 11 mole
% ZnCl2 to at least 72.5 mole % ZnCl2. The glass
transition temperature is almost invariant from 11 to 25 mole % ZnCl2,
and increases linearly from 30 mole % ZnCl2. ��� Infrared spectra (500-200cm-1)
of liquid samples supercooled to room temperature, are reported for mixtures
containing 20,26, 33, 63, and 77 mole % ZnCl2.
The pyrolysis of cyclic sulphites from 2,3-endo- and 2,3-exo-Bornanediols
Authors: Cole RFJ , Coxon JM , Harshorn MP
Published: September 2010

The cyclic sulphites (6),
(7), and (8) from cis-endo-bornane-2,3-diol and cis-exo-bornane-2,3-diol have
been prepared and their pyrolysis products identified.
Reaction of 2-(m-Tolyl)-4-arylmethylene-2-oxarolin-5-ones with amines
Authors: Islam AM , Khalil AM , El-Houseni MS
Published: September 2010

A facile route for the
preparation of 1,2-diaryl-4-arylmethylene-2-imidazolin-5-ones was established
by the direct interaction of primary aromatic amines with 2-(m-tolyl)-4-arylmethylene-2-oxazolin-5-ones
in acetic acid containing catalytic amounts of sodium acetate. The same
imidazolones were also obtained by cyclization of the aryl- carboxamides of
α-arylcarboxamido-β-arylacrylic acids under the same reaction conditions.
A possible reaction mechanism was discussed.
On the stability of Benzonorbornadienone and Tricarbonyl(benzonorbornadienone) chromium
Authors: Wege D , Wilkinson SP
Published: September 2010

Benzonorbornadienone could
not be isolated at 0�, nor detected at -45� in the hydrolysis of
7,7-dimethoxybenzonorbornadiene (9,9-dimethoxy- 1,4-dihydro-1,4-methanonaphthalene)
(5). Reaction of (5) with chromium hexacarbonyl gave endo-tricarbonyl(7,7- dimethoxybenzonorbornadiene)chromium
(14) (1 %) and a new type of alkene-ether complex of composition (7,7-
dimethoxybenzonorbornadiene)-Cr(CO)4 (36%). Hydrolysis of (14)
gave-only tetracarbonyl(naphthal-ene)chromium (24), and naphthalene. Oxidation
of exo- and endo- tricarbonyl(anti-7-benzonorbornadienol)chromium with silver
carbonate on Celite at 40� gave mainly tricarbonyl(1-naphthaldehyde)chromium,
accompanied by a small amount of (24). It is concluded that benzonorbornadienone
and tricarbonyl(benzonorbornadienone)chromium are unstable at -45�, and 40�,
respectively. The factors contributing to the instability of these ketones are
briefly discussed.
The thermal degradation of μ-Diphenylacetylene-bis(tricarbonylcobalt)
Authors: Dickson RS , Michel LJ
Published: September 2010

The thermal decomposition
of Co2(CO)6(PhC2Ph) has been investigated in
detail. Differential scanning calorimetry was used to determine the most
suitable temperature range for the study. At 180�, Co2(CO)6(PhC2Ph)
decomposes to form cobalt, carbon monoxide, tetraphenylcyclopentadienone,
hexaphenylbenzene, and other organic compounds. Variation in the temperature,
the time, and the solvent used for the degradation reaction causes significant
changes in the yields of the organic products. An investigation of the effects
of adding stoichiometric amounts of free alkyne, tetra-phenylcyclopentadienone,
and hexaphenylbenzene has been initiated in an attempt to understand the
degradation mechanism.
Insect Moulting Hormones: Dacrysterone, a New Phytoecdysone From Dacrydium intermedium
Authors: Russell G , Fraser J
Published: September 2010

Dacrysterone, a new
phytoecdysone, has been isolated from the bark of Dacrydium intermedium and
shown to be 5β-hydroxymakisterone A (6). Makisterone A also occurs in this
plant.