bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthetical Applications of Activated Metal Catalysts. XVII. The Hydrogenolysis of Aromatic Ethers by Raney Nickel
Authors: Chandler GS , Sasse WHF
Published: September 2010

W7 Raney nickel reacts with diphenyl ether
at atmospheric pressure to give benzene and cyclohexanol. Traces of phenol are
also formed. Less cyclohexanol and more phenol are produced when this reaction
is carried out either at room temperature or with a degassed Raney nickel
catalyst. W7 Raney nickel has also been reacted with 4,4'-dimethyl diphenyl
ether (to give toluene and trans-4-methyl-cyclohexanol), with
4,4'-dicarboxydiphenyl ether (to give benzoic acid and p-hydroxy-benzoic acid),
with anisole (to give benzene and methanol), with dibenzofuran (to give
trans-2-phenylcyolohexanol), and with cyclohexyl phenyl ether (to give benzene
and cyclohexanol). Dicyclohexyl ether is not affected by W7 Raney nickel.

These results are discussed in terms of a
mechanism which involves the following steps (i) adsorption of the ether on the
catalyst via the oxygen atom; (ii) fission of one of the carbon-oxygen bonds to
give the more-stable hydrocarbon anion and phenol (or alcohol for an alkyl aryl
ether) ; and (iii) hydrogenation of the phenol to give a cyclohexanol. The
effect of variation of the structure of the ether on each of these steps is
discussed.

In agreement with this mechanism, an
excess of W7 Raney nickel reduces at atmospheric pressure phenol and p-cresol
(as the anions) to give cyclohexanol and trans-4-methylcyclohexanol
respectively, while p-hydroxybenzoic acid and benzoic acid are largely
recovered.

cis-4-Methylcyclohexanol is not epimerized by
W7 Raney nickel.
Alkaloids of Crotalaria trifoliastrum Willd. II. 1-Methoxymethyl- 12-epoxy-pyrrolizidine
Authors: Culvenor CCJ , Morrison JD , Nicholson AJC , Smith LW
Published: September 2010

An alkaloid, C9H15O2N,
previously isolated from Crotalaria trifoliastrum, is shown to be
1-methoxymethyl-1,2-epoxypyrrolizidine.
β-Bromopicrotoxinin
Authors: Carman RM
Published: September 2010

β-Bromopicrotoxinin is shown to have structure (III).
Molecular Vibrations in the Exciton Theory for Molecular Aggregates. IV. Excited States of Weakly-coupled Systems
Authors: McRae EG
Published: September 2010

The theory of the vibronic states of an
electronically excited molecular aggregate is developed for the case of weak
intermolecular interaction. The resulting description is complementary to that
derived for the case of strong intermolecular interaction in Parts I-III of
this series.1

The intermolecular interaction term in the
Hamiltonian is treated as a small perturbation. A particular set of
zeroth-order functions for the problem, here called m-m functions, is defined.
The interaction integrals between m-m functions are studied and certain of the
m-m functions are corrected to the first order of perturbation theory. A
criterion for the validity of the perturbation treatment is given.

The effect of molecular vibrations in
exciton theory is to inhibit intermolecular interaction. Expressions are
obtained for the vibrational inhibition factors, and their properties are
related to the molecular distortion in the vicinity of the electronically
excited molecule.

All theoretical results are discussed in
comparison with those of Parts I-III. The results of the two methods of
treatment are combined to give a general description of the excited states of
molecular aggregates. It is shown that an exciton together with the associated
molecular distortion in polymeric aggregates may be regarded as a quasiparticle
analogous to the polaron in a molecular crystal.
The Exchange of Metal Ions with Quadridentate Complexes. II. Copper Ions with Several Nickel Complexes
Authors: Fee WW , West BO
Published: September 2010

The rates of reaction of copper ions with
five quadridentate nickel complexes have been determined and the results
interpreted in terms of the effect of substituents on the ease of dissociation
of the ligand.
Conductances of electrolytes in solutions of the sucrose polymer Ficoll
Authors: Stokes RH , Weeks IA
Published: September 2010

The limiting equivalent conductances of
several electrolytes have been measured at 25� in aqueous solutions of the
synthetic sucrose polymer Ficoll. Though the viscosity of the solutions is
several times that of sucrose solutions of the same percentage by weight of
solute, the limiting conductances of small ions in them are little different
from those in sucrose solutions. It is concluded that the polymer molecules
form loose networks to a large extent permeable to small ions.
Mono- and Bis-(2,2'-bipyridine) and (1,10-phenanthroline) chelates of ruthenium and osmium. IV. Bis chelates of bivalent and tervalent osmium
Authors: Buckingham DA , Dwyer FP , Goodwin HA , Sargeson AM
Published: September 2010

Osmium complexes of the type [OsB2X2]n+ where B =
2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen),
X = Cl, Br, I, py, NH3; 2X = glycinato, acetylacetonato, ethylenediamine, oxalato, phen,
or bipy and = 0, 1, 2, 3 are described. [OsB2X2]0 has the cis
configuration. Usually compounds in both oxidation states (II) and (III) were
stable and could be isolated. The compounds did not disproportionate and the
unidentate ligands were replaced only with difficulty. The [Osbipy2phen]2+
and [Osbipyphen2]2+ ions were
resolved through their (+) antimonyl tartrate salts and were found to be
optically stable in both the Os(II) and Os(III) states.
Tributyltin isothiocyanate and isocyanide
Authors: Cummins RA , Dunn P
Published: September 2010

Infrared evidence has been used to demonstrate
that tributyltin isothiocyanate is formed when certain tributyltin compounds
are reacted with inorganic thiocyanates or thiourea. Molecular refraction data
supporting this contention are also reported.

�� The
preparation of tributyltin isothiocyanate by several different methods and of
tributyltin succinimide is described.
Nuclear magnetic resonance spectra of flavonoids
Authors: Batterham TJ , Highet RJ
Published: September 2010

The nuclear magnetic resonance spectra of
the aromatic, olefinic, and hydroxyl protons of 41 flavonoids have been
examined. It is found that these spectra reveal the pattern of oxygen
substitution on the aromatic rings, the nature of the heterocyclic ring, and,
often, the nature and arrangement of the oxygen-borne groups.
The cardiac glycosides of Gomphocarpus fruticosus (R.Br.). IV. The nuclear magnetic resonance spectrum of gomphoside
Authors: Carman RM , Coombe RG , Watson TR
Published: September 2010

Nuclear magnetic resonance spectroscopy
supports the proposed structure (I) for gomphoside.
Pyrrole studies. II. The structure of 2-pyrrolylmethyleneimines
Authors: Jones A
Published: September 2010

2-Pyrrolylmethyleneimines (III) are shown
to exist as such and not in the alternative tautomeric form (IV). The graph
obtained on plotting the long wave- length ultraviolet band of the aryl
compounds (III: R = aryl) against their Hammett σ value is non-linear.
This is explained in terms of the relative energies of the ground and excited
states of the compounds and is also due to the overall electron-donating effect
of the pyrrole ring.
The oxidation of aldehydes with bromine. II. Study of the general base catalysis
Authors: Cox BG , McTigue PT
Published: September 2010

It is shown that the oxidation with
bromine of four aliphatic aldehydes to the corresponding carboxylic acids
involves a rate-determining proton transfer. It is concluded that the aldehyde
hydrate is the reactive entity in these oxidations.
Some studies in inorganic complexes. XVII. 2-Thioamidopyridine complexes of copper(I) and copper(II)
Authors: Sutton GJ
Published: September 2010

The following copper complexes of the
chelating ligand 2-thioamidopyridine (thiopic) have been prepared and studied:
[Cuthiopic2][CuX2],
where X = Cl, Rr, I, and SCN (two isomers); [Cuthiopic2]I; [Cuthiopic2ClO4].ClO4.H2O; [Cuthiopic2OH]ClO4;
[Cuthiopic2NO3]NO3.H2O;
[Cuthiopic2NO3]PF6.H2O;
and [Cuthiopic2][PF6]2.
4H2O. Conductance measurements in nitrobenzene, nitromethane, and
ethanol; and absorption studies in the infrared, visible, and ultraviolet
regions of the spectrum were carried out and magnetic measurements were also
determined.
The reaction of DL-glyceraldehyde with ammonia
Authors: Grimmett MR , Richards EL
Published: September 2010

DL-Glyceraldehyde rapidly browns at 37� in
ammoniacal solution with the concurrent formation of a number of carbohydrates
and imidazolic compounds. Dihydroxyacetone, glucose, fructose, mannose,
aldopentoses, 4(5)-methylimidazole, 4(5)-hydroxymethylimidazole, 4(5)-(2-hydroxyethyl)imidazole
and 2-hydroxymethyl-4(5)-methylimidazole have been identified. The rates of
formation of the imidazoles have been studied.
The cardiac glycosides of Cerbera species. I. The isolation of cerbertin and cerbertatin
Authors: Cable J , Coombe RG , Watson TR
Published: September 2010

Two new cardiac glycosides, cerbertin C32H46O10
and cerbertatin C32H46O11, and the
corresponding deacetyl compounds have been isolated from Cerbera floribunda and
C. dilatata.
Flavan derivatives. XII. Conversion of Flavan-3,4-cis-diols into trans-Diacetates, and a new route to 3,4-trans-Diacetoxy-2,3-cis-flavans
Authors: Clark-Lewis JW , Williams LR
Published: September 2010

Reaction of trans-trans-3-bromoflavan-4-ols
with ethanolic potassium acetate is shown to lead to
2,3-cis-3,4-trans-4-ethoxy- and -4-acetoxy-flavan-3-ols, as well as to
2,3-cis-flavan-3,4-trans-diols. Flavan-3,4-cis-diols are converted into
3,4-trans-diacetates by acetylation with a mixture of acetic acid, acetic
anhydride, and potassium acetate. cis-cis-Flavan-3,4-diols are thus converted
into 3,4-trans-diacetoxy-2,3-cis-flavans, and 2,3-trans-flavan-3,4-cis-diols
give trans-trans-diacetates. Epimerization of cis-cis-glycols to
cis-trans-diacetates provides the most convenient route to
3,4-trans-3',4'-dimethoxy-6-methyl-2,3-cis-flavan, and to the corresponding
4'-methoxy analogue, and reduction with lithium aluminium hydride then gives
the 2,3-cis-flavan-3,4-trans-diols.
3',4'-Dimethoxy-6-methyl-2,3-cis-flavan-3,4-trans-diol prepared in this way was
converted into the corresponding carbonate, which is the first example of a
2,3-cis-3,4-trans-carbonate and completes the set of the four possible
racemates in this series. The bromine atom is unreactive in
cis-cis-3-bromo-3',4'- dimethoxy-6-methylflavan, but reductive dehalogenation
with lithium aluminium hydride gave the ,β-flavan-4-ol (2,4-cis).
Some studies in inorganic complexes. XVIII. 2-Thioamidopyridine and N-methyl-2-aminomethylpyridine complexes of palladium(II) and platinum(II)
Authors: Sutton GJ
Published: September 2010

The following palladium and platinum
complexes of the chelating ligands 2-thioamidopyridine (thiopic) and
N-methyl-2-aminomethylpyridine (picmene) have been
prepared and studied: [PdthiopicX2], [PdpicmeneX2], [Pdpicmene2]I2,
[PtthiopicX2], [Ptthiopic(NO2)2],
[Ptthiopic2](ClO4)2,
and [PtpicmeneX2], where X = Cl, Br, I,
SCN.
Some studies of Nb6Cl14,7H2O and analogous compounds
Authors: Allen RJ , Sheldon JC
Published: September 2010

The previously known staphylonuclear
halides, Nb6Cl14,7H2O;
Nb6Brl4,7H2O (in
trifling yield) ; Ta6Cl14,7H2O
; and Ta6Br14,7H2O
have been prepared, but intended studies of these have been frustrated by their
instability and insolubility. It has been possible, however, to obtain
approximate molar conductivities in water and ethanol which support the
formulation of (Nb6Cl12)Cl2,7H2O as a 2 : 1 electrolyte, and
evidence by pH titration of the existence of the complex ion [(Nb6Cl12)(OH)4- (H2O)p]2-
in alkaline solution.

The absorption spectra of the four halides
have been obtained over the range 8-50 kK in neutral
and alkaline aqueous solution and in the solid state. It is proposed that the
very strong bands in the visible and infrared region result from transitions
from metal-to-metal bonding to metal-to-metal anti-bonding levels. Excellent
agreement can be obtained between the experimental frequencies of the (Nb6Cl12) group and those predicted
from the molecular orbital energy diagram of Cotton and Haas.

It is proposed that Harned's
brown chloride is a similar material to the green Nb6Cl14,7H2O
but additionally contains μ-hydroxo derivatives of the type [Nb6Cl(12-n)(OH)n]Cl2, resulting from the mode of preparation of
the material.
Wilzbach tritiation studies. I. Isotope distribution in tritium-labelled anthranilic acid, isopropanol and phenyl allyl ether
Authors: Garnett JL , Law SW , Till AR
Published: September 2010

Isotope distribution studies with
anthranilic acid labelled by the Wilzbach method indicate that positions 3 and
5 have respectively 49.8% and 27.4% of the total activity, tritium
incorporation thus tending to be highest at the most electronegative positions.
In isopropanol the hydroxyl group contains approximately three times as much
isotope as at any other hydrogen position, while tritiation of the secondary C-H
is slightly more efficient than the primary C-H. In the tritiation of phenyl
ally1 ether, the predominant process is polymerization after reasonable
exposure time, little radiation-induced Claisen rearrangement or saturation of
the double bond being observed. A free radical mechanism has been proposed to
account for the above distributions which have also been compared with results
obtained by catalytic exchange. From these model compounds the relative
preparative applicability of the Wilzbach and catalytic techniques has been
discussed.
Long-range spin-spin coupling in avenaciolide and related compounds
Authors: Brookes D , Sternhell S , Tidd BK , Turner WB
Published: September 2010

The allylic system in avenaciolide (I)
offers an example of exceptionally large allylic coupling constants with a
reversed order of relative magnitude (Jcisoid 2.17 c/s; Jtransoid
2.56 c/s). Allylic coupling in related cyclic systems is discussed.
Hydrolysis of amides. I. The hydrolysis of acetamide and chloroacetamide in dilute acid
Authors: Bolton PD , Wilson IR
Published: September 2010

Kinetic studies of the hydrolysis of
acetamide in dilute acidic solution are reported. These reveal the presence of
systematic errors in some previous work on this compound. A consistent
treatment is given, leading to values of the energy and entropy of activation
(at 75�) of 19.8 kcal and -17.8 e.u. and satisfactory correlation of most
previous results.

Similar defects are present in recent work
on chloroacetamide hydrolysis and the same approach is used in a
reinterpretation.
Acid hydrolysis of acetamide in aqueous acetic acid
Authors: Martin RJL
Published: September 2010

The hydrolysis of acetamide
in acetic acid has been studied over a wide range of reactant and salt
concentrations. The various acid-base and ionic association equilibria must be
considered in the interpretation of the data. It is shown that the mechanism is
a bimolecular reaction between water and the acetamidium
ion and that the acetamidium ion pairs and triple
ions have no reactivity. Polar substances such as water and acetamide,
apart from undergoing reaction, also increase the reaction rate by favouring
the dissociation of the ion pairs. Salts exhibit strong ionic strength and
ion-pair effects.
Cerium Tetrafluoride. I. Preparation and reactions
Authors: Asker WJ , Wylie AW
Published: September 2010

Pure anhydrous cerium tetrafluoride is
best prepared by fluorinating cerium dioxide at 350-500�. A monohydrate can be
obtained from aqueous solution in a variety of ways, but it cannot be
dehydrated without decomposition. It loses water "zeolitically" in
vacuum, showing relatively small changes in lattice parameters for loss of 70%
of its water content. Thereafter the lattice collapses, forming
well-crystallized cerium trifluoride and poorly crystallized
"anhydrous" cerium tetrafluoride.

The refractive indices of anhydrous
monoclinic cerium tetrafluoride have been measured and its fluorine
dissociation pressure at 500� shown to be less than 0.5 mm. At higher
temperatures the tetrafluoride sublimes incongruently, and at 835-841� it melts
with extensive decomposition into a fluorine-poor liquid and a fluorine-rich
vapour.

Cerium tetrafluoride is easily reduced to
the trifluoride by ammonia and by water vapour at low temperatures. At higher
temperatures it is quantitatively converted by water vapour to cerium dioxide
and hydrogen fluoride. When heated with cerium dioxide it is reduced to the
trifluoride with liberation of oxygen.
The chemistry of the Euphorbiaceae. XII. Compounds derived from a new Beyeria species
Authors: Jefferies PR , Payne TG
Published: September 2010

Four new and six known diterpenes, and a
new flavone (XXI), have been obtained from a new Beyeria species. Evidence is
presented which defines the structure of the new diterpenoids as (I), (IV),
(VIII), and (IX).
The degradation of lactose by interaction with casein
Authors: Richards EL
Published: September 2010

Lactose and casein react to give a complex
mixture of sugars and acids from which lactulose, D-galactose, D-tagatose,
5-hydroxymethylfurfural, lactic acid, glycollic acid, phosphoric acid, and the
lactones of 2-deoxy-D-glycero-tetronic and 3-deoxy-D-erythro-pentonic acids
have been isolated and identified.
Nuclear magnetic resonance spectra of pyrrolizidine alkaloids. II. The pyrrolizidine nucleus in ester and non-ester alkaloids and their derivatives
Authors: Culvenor CCJ , Woods WG
Published: September 2010

Chemical shifts and coupling constants are
tabulated for the protons of the pyrrolizidine nucleus in 40 pyrrolizidine
alkaloids and derivatives. The effect of acylation of hydroxyl substituents on
C7 and C9 and the very large difference in chemical shift of the H9 protons in
the macrocyclic diester alkaloids is discussed. The direction of buckling of
the saturated ring can be ascertained from the H5,H6 vicinal coupling constants
or from the width of the H7 multiplet if H7 bears an oxygen substituent. In
general, retronecine derivatives are exo-buckled whereas heliotridine
derivatives consist of interconverting exo- and endo-buckled forms.
Chemistry of pyrrolic compounds. I. Synthesis of oxyporphyrins
Authors: Clezy PS , Nichol AW
Published: September 2010

The condensation of
5,5'-diformyl-3,4,3',4'-tetramethyl-2,2'-dipyrrylketone (XIb) with
3,4,3',4'-tetramethyl-2,2'-dipyrrylmethae (XIVb) has
produced meso-oxy-l,2,3,4,5,6,7,8-octamethylporphin in 63% yield. The
tautomeric structure of this compound is discussed and its spectroscopic
properties compared with an early intermediate in the oxidative breakdown of
haemoglobin to give bile pigment.
Derivatives of orthoacids. III. Sulphonamide derivatives
Authors: Crank G , Eastwood FW
Published: September 2010

Ethyl orthoformate reacts with
N-(2-hydroxyethy1)toluene-p-sulphonamide, and NN'-di(toluene-p-sulphonyl)ethylenediamine
to form 2-ethoxy-N-(toluene-p-sulphonyl)oxazolidine, and 2-ethoxy-NN'-di(toluene-p-sulphonyl)imidazolidine
respectively. Analogous products are formed from the corresponding
methane-sulphonyl compounds. Triisobutyl orthoformate reacts with N,N?,N"-tri(toluene-p-sulphonyl)-2-aminomethyl-2-methylpropane-1,3-diamine
to form 4-methyl-N,N?,N"-tri(toluene-p-sulphonyl)-2,6,7-triazabicyclo[2,2,2]octane
(X).
The thermal decomposition of diisopropyl ether
Authors: Daly NJ , Stimson VR
Published: September 2010

The rates of decomposition of diisopropyl
ether at 423-487� have been measured. Propene and isopropanol (70-90%) and
propane and acetone (10-30%) are the major products, and the production of the
latter pair is significantly inhibited by isobutene. An interpretation in terms
of a molecular reaction producing the first pair and a radical chain reaction
producing all four is put forward.
Terpenoid chemistry. XI. ( - )-β-Sesquiphellandrene
Authors: Connell DW , Sutherland MD
Published: September 2010

A new natural sesquiterpene, (-)-β-sesquiphellandrene, has been isolated from oil of ginger by
distillation and chromatography on silver-nitrate-treated alumina. The
structure deduced from spectral data has been confirmed by isomerization to zingiberene. (-)-β-Sesquiphellandrene
is (l'R,6S)-2-methy1-6-(4'-methylene-
cyclohex-2'-enyl)hept-2-ene.
Pyrrole studies. IX. The infrared spectra of 1-substituted pyrroles
Authors: Jones RA
Published: September 2010

The positions and intensities of the
characteristic infrared absorption bands of the pyrrole nucleus in the region
2000-600 cm-1 of 45 1-substituted pyrroles, 2,5-dimethylpyrroles,
and 3,4-dimethylpyrroles are recorded and discussed.
Coordination compounds of Group IB metals. I. Triethylphosphine complexes of gold(I) mercaptides
Authors: Coates GE , Kowala C , Swan JM
Published: September 2010

Various triethylphosphine
coordinated gold(1) mercaptides of formula Et3PAuSR (R = Me, Et, Pr, Bu, Bu1, Ph, CH2Ph,
β-C10H7, and CH2CH(NH2)C02H),
and related sulphur derivatives of formula Et3PAuY
(Y = SCN, SC(S)Net2, SC(S)OEt, and SC(NH2)NH2+Br-)
have been prepared. Under appropriate conditions, displacement of the sulphur
group from the gold atom is observed, either by another sulphur nucleophile,
e.g. Et3PAuSR + Et2NCSS- → Et3PAuSC(S)Net2 + RS-, or by a. nucleophile such
as Cl-, Br-, I-, NO3-, or CN-.
Coordination compounds of Group IB metals. III. Triethyl- and triphenylphosphine complexes of cuprous, argentous, and aurous NN-dialkyldithiocarbamates
Authors: Kowala C , Swan JM
Published: September 2010

Triethylphosphine
and triphenylphosphine complexes of various NN- dialkyldithiocarbamates of
gold(1), silver(1), and copper(1) are
described, of formulae (I; R = Et; R' = Pr); (111; M = Ag, Cu; R' = Me, Et, Pr,
Bu); and (IV; M = Ag, Cu; R' = Me, Et, Pr, Bu). Certain complexes of formula (1)
are unstable, and lose the phosphine moiety during attempted preparation.
Complexes (111) and (IV) are prepared by reaction of the appropriate metal
dithiocarbamate with triethyl- or triphenyl-phosphine
respectively. Complexes (111; M = Ag, Cu; R' = Et) gave monomeric molecular
weights in chloroform solution, but the apparent molecular weights of complexes
(IV; M = Ag, Cu; R' = Et) indicated extensive dissociation in both chloroform
and benzene. The present evidence suggests an ionic dissociation in the sense
(Ph3P)2M+ R2NCSS-.

An improved preparation of cuprous
NN-dialkyldithiocarbamates is given.
Infrared spectra in the Ag2O-CO2-Ag2CO3 system
Authors: Allen JA , Scaife PH
Published: September 2010

The infrared spectrum of
silver oxide, Ag2O, has been clarified by
comparison with that of silver carbonate. In the region 4000-400 cm-l
the spectrum consists of one broad band centred around 530 cm-l,
other bands being accounted for in terms of normal, basic, and complex
carbonates and surface hydroxyl groups, which are frequently present as
contaminants. Conditions for the preparation, storage, and purification of
silver oxide to minimize carbonate contamination are defined.
An ion-exchange process with thermal regeneration. IV. Equilibria in a mixed bed of weak-electrolyte resins
Authors: Weiss DE , Bolto BA , McNeill R , MacPherson AS , Siudak R , Swinton EA , Willis D
Published: September 2010

The titration curve data at c. 20� and 80�
for weakly basic amine and carboxylic acid resins suggest that if a mixed bed
of such resins is in equilibrium with a salt solution, then when the
temperature of the system is raised, protons will be transferred from the base
to the acid resin to an extent determined by the overlap of the titration
curves of the resins. Maximum overlap would occur with two resins of
appropriate acid and basic strength and which possess plateau-type titration
curves, but such acid resins are not available. The theory has been confirmed
by experiment.

The change in salt adsorption on heating
(effective capacity) depends critically on pH and may be enhanced for amine
resins of homo-functional structure by increasing the ratio of acid to base
resin. It is shown that to achieve the maximum effective capacity for each
resin combination there is an optimum pH value and resin ratio. A screening
procedure, which uses titration curve data at c. 20� and 80� and allows for the
effect of pH and resin ratio, has been devised for selecting resin
combinations.

In a 0.030M salt solution the effective
capacity of the commercial resins studied is greatest, for a
poly(vinylbenzyldiethy1amine) resin in combination with a poly(acry1ic acid)
resin. A-rigorous procedure has been devised for obtaining equilibrium data,
which are presented for this resin combination at c. 20� and 80� in sodium
chloride solutions with concentrations ranging from 0.0017 to 0.13M.
The mechanism of hydrogenation of coal to methane
Authors: Blackwood JD , McCarthy DJ
Published: September 2010

It has been shown that the overall
kinetics of hydrogenation of coal can be explained on the basis of a two-stage
reaction mechanism. The first stage involves the very rapid reaction of
hydrogen with groupings in the coal which are associated with oxygen, and can
be considered to be instantaneous in practical systems. At temperatures in
excess of 700� the yield of hydrocarbons from the groups in coal which contain
oxygen is a function of the hydrogen partial pressure, which in turn is limited
by equilibrium of the water gas shift reaction.��� Hydrogenation of the volatile matter results
in the formation of a less readily hydrogenated structure which is
predominantly carbon. The rate of hydrogenation of the residual carbon can be
expressed in the form which was proposed for the system carbon-hydrogen-methane
:

(see formula in article)

where kl,
k2, k3, and k4 are constants, and pl,
p2 are the partial pressures of hydrogen and methane respectively.
It has been shown that the β-graphite equilibrium applies to the system
char-hydrogen-methane and is independent of the reactivity of the char. This
fact can be used to simplify the rate expression and write the constants in
terms of ratios of quantities which can be readily measured.

The initial high reactivity noted by the
authors and other workers can be produced repeatedly by adsorbing hydrogen on
the surface of the char at low temperature and desorbing this hydrogen as
methane at high temperature. This behaviour was predicted from the proposed
kinetic scheme.
The infrared spectrum of 32SO2, 34SO2, and 35SO2
Authors: Grigg ECM , Johnston GR
Published: September 2010

The potential constants of the SO2
molecule are determined from the fundamental frequencies of the 32SO2
and 34SO2 isotopic species, and the rotational constants
for both 32SO2 and 34SO2 calculated
from their rotational-vibrational bands. The fundamental frequencies for 35SO2
have been obtained from its infrared spectrum.
D.C. and sine-wave polarographic studies of the nitrophenols. II. Mechanism of inhibited reduction with special reference to m-nitrophenol
Authors: Cheah EPT , Hacobian S , Harle AJ
Published: September 2010

The modes of the free and
inhibited reduction of the nitrophenols, and in particular m-nitrophenol, in
basic media are discussed using sine- wave and conventional d.c.
polarography. The mechanism of the initial single-electron transfer step of
m-nitrophenol in the presence of inhibitor is attributed to the stabilization
of the m-nitrophenol radical ion.
1,2.3,4,6,7-Hexahydro-12H-indolo[2,3-a]quinolizine, an alkaloid from Dracontomelum mangiferum Bl. (family Anacardiaceae)
Authors: Johns SR , Lamberton JA , Occolowitz JL
Published: September 2010

The major alkaloid of Dracontomelum mangiferum Bl. (family Anacardiaceae) has
been identified as (-)-1,2,3,4,6,7-hexahydro-12H- indolo[2,3-a]quinolizine, which has not been found previously in nature
although the (�) form has been synthesized.
Covalent bond refractions and the Periodic Table. II. Bonds to aliphatic carbon
Authors: Christopher PM
Published: September 2010

On the assumption that the
parachor, P, and the Lorentz-Lorenz refraction, R, are empirically related by
the equation, P = aRn+b, where a, b, and n
are constants, corresponding values of P and R for covalent bonds between the
elements of Groups IVB-VIIB and aliphatic carbon were introduced, and the
constants evaluated by means of a least-squares calculation on the I.B.M. 1620
computer. In the present instance, the resulting equations confirm many of the
reported experimental refractions, and they have also been employed for the
calculation of R for several bonds hitherto unreported.
The rates of solvent aquation of a series of halogeno-cobalt(III) complexes
Authors: Bosnich B , Dwyer FP
Published: September 2010

The rates of aquation and
temperature coefficients of a series of homoisomeric cations ω-[CoX en
dien]2+ (X = Cl, Br, I) together with those of the isomer
ε-[CoCl en dien]2+ and the analogous cation [CoCl ibn cytam]2+
are recorded. A consideration of the factors determining the rates of these
reactions leads to the conclusion that there is an element of bond making in
the transition state.
Note on the wave functions used for point-ion-lattice calculations of F-centres
Authors: Coogan CK , Hecht HG
Published: September 2010

Slater type ns wave
functions, differing from the spherically symmetrical wave functions used by Gourary and Adrian, have been tried as a basis set for
calculating wave functions of electrons in F-centres in alkali halides.
Combinations of 1s, 2s, and 3s Slater functions still yielded ground state
energies slightly higher than that calculated by Gourary
and Adrian. It is concluded both that the GA wave functions were very well
chosen and that more significant changes, particularly in the calculated
hyperfine coupling, would come from adding terms of higher-order harmonics,
compatible with the crystal symmetry, to the spherical wave functions.
The rate of exchange of propylenediaminetetraacetic acid with its cadmium complex
Authors: Bosnich B , Dwyer FP , Sargeson AM
Published: September 2010

The polarimetric rates of
exchange between optically active propylene- diaminetetraacetic
acid (PDTA) and its cadmium complex, and that between
ethylenediaminetetraacetic acid (EDTA) and the cadmium propylenediaminetetraacetato
complex, have been measured in the pH range 4.75-7.00. An analysis of the
reaction kinetics indicates that the exchange, in either case, occurs
simultaneously by a first-order and second-order process, and it is concluded
that both bimolecular and unimolecular pathways are operative in the exchange
process.
The release of halide ions from some primary haloalkylamines
Authors: Chan SC , Leh F
Published: September 2010

The kinetics for the
release of halide ions from some haloalkylamines and
the corresponding haloalkylammonium ions have been
investigated in aqueous solutions under different conditions. In basic
solutions, the free amines react according to a two-term rate law

����������������������� kobs = k1+k2[OH-]

and their reactivities are
in the order: 2-chloroethylamine ≈ 2-chloro- n-propylamine �
3-chloro-n-propylamine. The products formed are the corresponding iminoalkanes
and the possible mechanisms are briefly discussed. In neutral solutions, the haloalkylammonium ions release halide ions by a
considerably slower first-order reaction, which is retarded by acid. Since here
there is not much difference in reactivity between 2-chloro-n-propylamine and
3-chloro-n-propylamine, the reaction probably involves a single-stage
bimolecular attack by the solvent, leading to the formation of aminoalkanols.
In both cases, the reactivities of 2-bromoethylamine me greater than those of
the corresponding chloro compound.
Thermochemistry of biscyclopentadienyl metal compounds
Authors: Turnbull AG
Published: September 2010

Standard free energies of
formation for the temperature range 298- 1000�K are calculated for C5H5,
C5H6, and the biscyclopentadienyl compounds of iron,
ruthenium, nickel, and magnesium by combining reported heats of formation at
298�K with calculated ideal-gas thermodynamic properties. The results are used
to predict the thermodynamic feasibility of three types of reactions-the
formation of biscyclopentadienyl metal compounds, their thermal decomposition,
and their reduction with hydrogen. It is shown that the predictions are in
agreement with qualitative chemical observations.
Flavan derivatives. XVII. Epimerization of the benzylic 4-hydroxyl group in flavan-3,4-diols and the formation of 4-alkyl ethers by solvolysis
Authors: Clark-Lewis JW , Williams LR
Published: September 2010

Epimerization and
solvolysis of the benzylic 4-hydroxyl group is shown to be a general property
of flavan-3,4-diols, and the diols give 4- ethoxyflavan-3-ols
with ethanolic hydrochloric acid (1%). The diols are first converted into
epimeric mixtures of 3,4-cis- and 3,4-trans-diols and in aqueous media
cis-cis-flavan-3,4-diols yield mainly 2,3-cis-3,4- trans-diols. These
2,3-cis-3,4-diols undergo solvolysis to yield 2,3- cis-3,4-trans-4-ethoxyflavan-3-ols in which the 3,4-trans- stereochemistry is controlled
by participation of the neighbouring 3ax- hydroxyl
group. 2,3-trans-Flavan-3,4-diols give mixtures of trans- trans-diols and
2,3-trans-3,4-cis-diols and solvolysis first yields
2.3-trans-3,4-cis-4-ethoxyflavan-3-ols and then
mixtures of the 3,4- cis- and 3,4-trans-ethers; the final proportion of these
two ethers is controlled by thermodynamic factors. Solvolysis under mild
conditions gives minor products considered to be 3-oxoflavans (or their enols)
because of their immediate conversion into antho-cyanidins
by cold acids in the presence of air, and from the formation of an enol-ether
on prolonged solvolysis under more vigorous conditions. The relevance of these
observations to the mechanism of formation of anthocyanidins from
flavan-3,4-diols is discussed. Other by-products of solvolysis reactions
include a dimeric cyclic ether (dioxan derivative) of 2,3- trans-3,4-cis-7,8,4?-trimethoxyflavan-3,4-diol.
The structure and stereochemistry of solvolysis products were established by
N.M.R. data; the 4-ethoxyl group in the ethers generally gave rise to an ABX3
multiplet.
Shock-initiated exothermic reactions. III. The oxidation of hydrogen
Authors: Drummond LJ
Published: September 2010

Reactions were initiated
with reflected shocks in mixtures of hydrogen with oxygen or nitrous oxide or
nitric oxide which were diluted with argon. Comparison of measured and computed
reflected shock speeds indicates that the H2-O2 system
does not convert to equilibrium products immediately behind the shock. The
intermediate stage of reactivity is not the partial equilibrium state as
defined by Schott. Absorption spectroscopy at 3070 Ǻ gave the induction
periods (T) for OH formation. The activation energy of the
rate-determining reaction for OH formation is available from plots of log(T[O2])
against inverse temperature for oxygen-rich and stoicheiometric mixtures.
However, log(T[O2]1/2[H2]1/2)
should be used for fuel-rich mixtures. ��� Activation energies determined, for the H2-N2O
and H2-NO reactions suggest that rate-controlling mechanisms are not
simple. The former reaction leads to equilibrium products immediately behind
the shock but, at temperatures below 3000�K, the latter reaction is incomplete
due to regeneration of nitric oxide in the reaction OH + HNO → H2O
+ NO.
Electro-osmosis and hydrogen-ion transport in cation-exchange membranes
Authors: Arnold R , Swift DA
Published: September 2010

Hydrogen-ion transport
numbers, water transference numbers, and acid absorption are reported for some
cation-exchange membranes in presence of 0.1N, 1.0N, and 5.0N sulphuric acid.
The transport numbers of hydrogen ion remain fairly close to unity even at the
highest acid concentration; this is largely due to the retardation of the
anions by the electro-osmotic water flux. With increasing acid concentration
the water transference number falls to a lower limit of 1.0 mole per faraday;
with the driest membrane used this value is obtained at all acid concentrations
used. This behaviour suggests that when there are less than about 11 moles of
water available per hydrogen ion in the membrane, association occurs between
sulphonate groups and hydrogen ions, with consequent immobilization of the
latter.
The infrared spectra of alkali metal amide salts
Authors: Crispin PD , Werner RL
Published: September 2010

The infrared spectra of
sodium acetamide and lithium, sodium, and potassium propionamide have been
obtained over the range 4000-400 cm-1. A satisfactory assignment of
fundamentals has been made which shows a close correspondence to that of
acetate and propionate salts.
Isothiazole chemistry. IV. Cyanide cleavage of the S-N bond in 3-hydroxyisothiazole
Authors: Crow WD , Gosney I
Published: September 2010

Nucleophilic attack on 3-hydroxyisothiazole by cyanide ion, yielding cis-3-thiocyanoacrylamide, has been investigated over the pH
range 0.00-5.50. Rate constants have been measured both for direct attack by
cyanide ion and from the effect of cyanide ion in retarding the cyclization of
the thiocyanoacrylamide; in both cases the derived
rate constants agree. The pH-rate profile of the reaction reveals the existence
of two kinetically discrete mechanisms. Within the range 5.50-4.00 the
dominating mechanism is one involving a slow direct attack on 3-hydroxyisothiazole itself, while at pH less than 3.50 the
conjugate acid of this molecule is subjected to a much faster attack.
Equilibrium studies have been made for the system, and the effect of
temperature on the equilibrium constant has been used to derive thermodynamic
parameters.
Carbonyl halides of the Group VI transition metals. V. Carbon monoxide carriers and some sulphur and nitrogen derivatives of molybdenum halocarbonyls
Authors: Colton R , Scollary GR , Tomkins IB
Published: September 2010

The blue compounds MX2(CO)2(Ph3P)2 (M = Mo and W, X = Cl and Br) have been shown to absorb
carbon monoxide very readily indeed to form the corresponding tricarbonyls, and as reported earlier, the tricarbonyls may be easily converted into the dicarbonyls. The dicarbonyl is therefore a carbon monoxide
carrier. The compounds Mo(CO)3 dtc2 and Mo(CO)2 dtc2
(dtc = diethyldithiocarbamate) also represent a carbon monoxide carrying
system, but in this case both compounds are rather unstable. The compounds MoX2(CO)2 btp2
(btp = N-n-butylthiopicolinamide;
X = Cl, Br) have been prepared by
direct interaction of the ligand and the appropriate halocarbonyl. Although
these compounds are believed to be monomeric they do not absorb carbon
monoxide.
Electrometric investigations of an acid-thiomolybdate system and the formation of polyanions
Authors: Saxena RS , Jain MC , Mittal ML
Published: September 2010

The acidification of sodium
thiomolybdate with progressive addition of HCl has been studied by pH
and conductometric measurements, which have revealed the formation of
three different polymerized species, viz. (MO4S15)6-,
(MO2S7)2-, and (Mo4S13)2-
at pH ranges 7.5-8.5, 4.2-5.3, and 2.8-3.3 respectively. It was observed that at higher hydrogen ion
concentration (pH < 2.5), thiomolybdate decomposes into hydrated molybdenum
trisulphide, MoS3,H2O.
Molecular polarizability. The dipole moments, molar Kerr constants, and conformations of some dialkyl and diaryl disulphides
Authors: Aroney MJ , Le Fevre RJW , Pierens.R.K . , The HLK
Published: September 2010

Dipole moments and molar
Kerr constants are reported for five organic

disulphides R2S2 (where R is methyl,
t-butyl, phenyl, p-chlorophenyl, and β-naphthyl)in carbon tetrachloride solution. The experimental
data are analysed to show (a) that each molecule has
a skew structure with dihedral angles in the range 88-85� between the planes C?-S-S
and S-S-C"; (b) that the anisotropic
electron polarizabilities of the S-S group in
dimethyl disulphide are bL = 4.66 �3,
bT = bv
= 2.25 �3; and (c) that in the aromatic disulphides the aryl group planes are nearly coplanar with
their respective Car-S-S groups.
Electronic absorption spectrum of nickel(II) in cubic perovskite fluorides. III. The ultraviolet spectrum
Authors: Ferguson J
Published: September 2010

The ultraviolet absorption
spectrum of divalent nickel is shown to be dependent on concentration for
crystals of composition KMgxNil-xF3
with 0 < x < 1. The eight
ultraviolet absorption bands have intensities which are directly related to the
number of nearest neighbour nickel ions per nickel ion. Three of the bands can
be assigned to states of the 1G and 1S terms while the
remaining five have energies which can be equated to combinations of the
energies of the excited singlet states lEga
ITa2g and 1Aag
and are simultaneous electronic excitations.
Copper(II) complexes of the bidentate chelate di(2-pyridyl) sulphide
Authors: Driver R , Walker WR
Published: September 2010

Copper(11) complexes
containing the chelate di(2-pyridyl)
sulphide (dps) are described for the first time. They
include (i) mono complexes of the
type Cu dpsX2 (X = Cl, Br, NO2,
and 2X = SO4); (ii) five-coordinate bis
complexes of the type [CuX dps2]ClO4 (X = Cl, ���Br, SCS, and NO,); and (iii) the bis complex
Cu dps,-(ClO4)2,H2O.
Attempts to prepare the
compound with X = I yielded the yellow copper(1) complex Cu dpsI.
These compounds have been investigated by physicochemical methods and are
discussed in the light of known copper(11) complexes containing nitrogen
chelates.
Oxidative cyclizations. II. Kinetic studies of the reaction of 2-nitroaniline with phenyliodoso acetate in toluene solution
Authors: Dyall LK , Evans JOM , Kemp JE
Published: September 2010

A kinetic study of the
oxidation of 2-nitroaniline by phenyliodoso
acetate in toluene solution reveals that the reaction is first order in both
amine and oxidant. The mass action effects of products on oxidation rate
demonstrate that at least two stages are involved in the reaction, and that the
mass action effect of acetic acid is exerted only by its monomer. Evidence is
obtained for the formation of an intermediate containing trivalent iodine. All
these facts are consistent with the mechanism previously proposed by us for
this reaction.
Vapour phase composition and activities for the molten PbBr2+KBr system
Authors: Bloom H , Hastie JW
Published: September 2010

Vapour pressures above
molten PbBr2+KBr mixtures have been
measured over a range of
temperatures by a transpiration method. The vapours
have been investigated also by mass spectrometry and the presence of the
complex KPbBr3 has been
established. The enthalpy and entropy of formation of this compound from PbBr2(g) and KBr(g)
are similar to values obtained for the analogous chloride species. By combining
the results of both methods, the true activities of lead bromide in the melt
have been calculated as a function of composition, and the results have been
interpreted to show that PbBr3 is the
major complex ion present in the molten mixtures.
Beryllium-chrome-azurol-S complexes
Authors: Baldwin WG , Stranks DR
Published: September 2010

Complex formation between
the aquated beryllium cation and the tetrabasic dyestuff chrome-azurol-S
(H4CAS) has been studied by spectrophotometric, potentiometric,
electrophoretic, and ion-exchange techniques. At least two complexes are shown
to exist within the pH range 3-6. The major species is the anionic complex BeHCAS- for which log β11, = 4.66 � 0.08 at
25� and at ionic strength 0.lM (NaClO4)
Coordination of beryllium is considered to occur at the quinonoid-,).

carboxylato site in the HCAS8- ligand. The stability constant
for the dinuclear species Be2CASO
is shown to be log β21 = 15.8 � 0.1 under the same medium
conditions. The dinuclear complex interferes with
spectrophotometric measurements at beryllium concentrations exceeding 2.5 x 10-4.
The acidity constants of H4CAS were determined at 25� and at an
ionic strength 0.IM (NaClO,) as pK2a
= 2.25 � 0.10,pK3a, = 4.88 � 0.05, pK4, = 11.75 � 0.05, whilst pK1a
= -1.2 � 0.4.
Nitrogenous chelate complexes of transition metals. V. Binuclear hydroxybridged copper(II) complexes of 1,10-phenanthroline and 2,2'-bipyridyl
Authors: Harris CM , Sinn E , Walker WR , Woolliams PR
Published: September 2010

A series of compounds of the type
OH
[chelate Cu ' \Cu chelate]X,,nH20
\OH/
[where chelate = 1,lO-phenanthroline; X = 01 (n = 3), Br (n = 4), I (n = 2),
NCS (n = 2), C10, (n = 1); 2X = SO, (n = 5), PtCl, (n = 4), and where chelate =
22'-bipyridyl; X = C1 (n = 3), Br (n = 4), I (n = 3), NCS (n = l), PF6 (n = 2),
C10, (n = 1); 2X = SO4 (n = 5) and PtC1, (n = 3)] have been prepared and their
properties investigated.
In dilute aqueous solution the compounds are ionized forming the solvated
[chelate Cu(OH,)Cu chelateI2+ species which exhibit similar visible absorption
spectra (where chelate = p,h, ,eAn, = 630 mp and 6 = 97, and where chelate =
b ,i,p,Ay, = 620 mp and E = 105).
In nitrobenzene solution some of these compounds have been shown from
electrical conductivity and spectrophotometric measurements to involve coordination
of the anion to the copper(11) atoms. This effect has also been verified in the
solid state by the measurement of diffuse reflectance spectra.
The compounds all exhibit room temperature magnetic moments of the
order of 2.0 B.&I. per copper atom. A study of the magnetic susceptibility of the
sulphate [bipy Cu(OH),Cu bipy]S04,5H,0 over the temperature range 83-293'~
showed no antiferromagnetic interaction between pairs of hydroxy-bridged copper
atoms, and the results obey a Curie-Weiss law (8 -13'~). The average value of
the corrected moment is 1.91 B.M. per copper atom. A value for g of 2.20 was estimated
from these data, and is in agreement with the average g value of 2.19
obtained from an e.s.r. measurement.
Catalysis by hydrogen halides in the gas phase. XVI. Methyl trimethylacetate, isopropanol, and hydrogen bromide
Authors: Cross JTD , Stimson VR
Published: September 2010

In the presence of hydrogen
bromide at 407�, methyl trimethylacetate decomposes to isobutene,
carbon monoxide, and methanol. Isopropanol reacts
with an intermediate to form isopropyl trimethylacetate,
which decomposes quickly to propene. Methanol
competes effectively with isopropanol. Some ratios of
individual rate constants are obtained from the rate reductions in the
competition reactions.
The measurement of electron affinities by the gaseous electron capture technique
Authors: Lyons LE , Morris GC , Warren LJ
Published: September 2010

Improvements of the gaseous
electron capture technique for the measurement of absolute electron affinities
of organic molecules are described. The dependence of the electron concentration
on each of the parameters, pulse amplitude, pulse width, pulse interval, flow
rate, and temperature is determined experimentally. Theoretical explanations
for each of these dependences, except temperature, are given. The experimental results also lead to values of
the drift velocity of electrons. Probable reaction schemes with and without an
electron acceptor present are considered. Steady state concentrations
of electrons are calculated in each case. The effect of the above parameters on
the decrease in electron concentration in the presence of an electron acceptor
is determined. Under these standardized conditions, the decrease in electron
concentration is measured as a function of temperature. This measurement leads to a
value of 0.57 � 0.01 eV for the electron affinity of anthracene. Under
our experimental conditions, the method does not yield electron affinity values
for 9,10-anthraquinone or nitrobenzene.
The ionization energies of some phenothiazine tranquillizers and molecules of similar structure
Authors: Fulton A , Lyons LE
Published: September 2010

Charge-transfer
spectroscopy was used to determine the ionization energies of ten phenothiazine
tranquillizers and similar molecules which are stimulants, in order to throw
light on the proposed relation between physiological action and
electron-donating power, and to compare the ionization energies of the phenothiazines
with molecular orbital calculations. All the ionization energies
obtained lie in the range 7.0-8.4 eV. The phenothiazines are thus
strong electron donors, in agreement with calculations. There is little difference in ionization
energies and equilibrium constants of complex formation between tranquillizers
and either non-tranquillizers or stimulants. The difference in physiological action of the
drugs therefore cannot be dependent on electron-donating power
alone.