bluuebunny/crossref_metadata_2025 huggingface dataset:
Micellar catalysis of organic reactions. VIII. Kinetic studies of the hydrolysis of 2-acetyloxybenzoic acid (aspirin) in the presence of micelles
Authors: Broxton TJ
Published: September 2010

The hydrolysis of
2-acetyloxybenzoic acid in the pH range 6-12 has been studied in the presence
of micelles of cetyltrimethylammonium bromide (ctab) and cetylpyridinium
chloride (cpc). In the plateau region (pH 6-8) the
hydrolysis is inhibited by the presence of micelles, while in the region where
the normal BAC2 hydrolysis (pH > 9) occurs the reaction is
catalysed by micelles of ctab and cpc. The mechanism of hydrolysis in the
plateau region is shown to involve general base catalysis by the adjacent
ionized carboxy group both in the presence and
absence of micelles. This reaction is inhibited in the presence of micelles
because the substrate molecules are solubilized into
the micelle and water is less available in this environment than in normal
aqueous solution.
Methyleneketenes and methylenecarbenes. XVII. Generation of methyleneketene intermediates by pyrolysis of N-alkenoylpyrazoles and synthesis of simple phenols
Authors: Besida J , Brown RFC , Colmanet S , Leach DN
Published: September 2010

Flash
vacuum pyrolysis of 1-acyl-3,5-dimethylpyrazoles
forms ketenes, but the conditions may lead to
decarbonylation of the ketene. The 1-cinnamoyl derivative (4) forms
phenylacetylene at 750°/0.02 mm, via benzylideneketene and benzylidenecarbene.
Simple phenols (2-naphthol, phenol, 4-methylphenol, 2,4-dimethylphenol, and
3,5-dimethylphenol) are obtained in high yield on pyrolysis of the appropriate
dienoylpyrazoles (10), (13), (16), (18) and (21); the reaction proceeds by way
of cyclization
of dienylketenes.
Nucleophilic alkenes. IX. Addition of 1,1-dimethoxyethene to azanaphthoquinones: synthesis of bostrycoidin and 8-O-methylbostrycoidin
Authors: Cameron DW , Deutscher KR , Feutrill GI
Published: September 2010

Reaction of
1,1-dimethoxyethene with azanaphthoquinones leads to
pairs of isomeric dimethoxy-azaanthraquinones by
means of 1:2-addition. A photochemical procedure has been developed for
substituting these dimethoxy products by a further methoxy, amino or a hydroxy group
peri to
carbonyl. In this way the antibiotic bostrycoidin (1)
and its 8-O-methyl derivative (2),
the only natural 2-azaanthraquinones, have been synthesized for the first time.
Pairwise intermolecular interaction energies between molecules of arbitrary symmetry: rotational averages in the weak interaction limit
Authors: Schipper PE
Published: September 2010

The fully expanded
expression for the Boltzmann-averaged pairwise intermolecular interaction energy of two molecules
B and C of arbitrary symmetry is determined in the weak interaction limit (<kT), including
all electrostatic, induction and dispersion interactions having an r-n
dependence (where r is the B-C separation) for which n < 11. The method exploits the 'point moment function' (PMF)
approach in which the Boltzmann-averaged energy is
shown to reduce to a sum of terms, each containing a product of a PMF on B, and
one on C. The point moment functions may be obtained in a general analytic form
by averaging an arbitrary multipolar product for the
isolated molecule. Two types of PMF (Δ, point chirality
function, and Λ, point achirality function) are
identified, leading to a natural division of contributions to the
intermolecular interaction energy into those that are insensitive (ΛΛ
contributions) and sensitive (ΔΔ contributions) to molecular chirality.
Ferromagnetic exchange coupling in sodium biscarbonatocuprate(II) trihydrate
Authors: Gregson AK , Moxon NT , Weller RR , Hatfield WE
Published: September 2010

The magnetic properties of
sodium biscarbonatocuprate(II) trihydrate,
Na2Cu(CO2)2,3H2O, have been
measured in the temperature range 1.8-42 K. Magnetic susceptibility and
magnetization measurements provide evidence for ferromagnetic interactions in
this linear-chain compound. The magnetic susceptibility data are compatible
with a Heisenberg linear chain; the best-fit parameters for the complete data
set are: J 1.22 �0.04cm-1, g
2.18 � 0.01, and zJ'-0.28 � 0.02cm-l. Data in the temperature range
7-42K yield the best-fit parameters J1.37
� 0.08 cm-1, g 2.12 �
0.01, and zJ'
0.0 cm-1. The g value from
this fit agrees with the g value of
2.10 obtained from a fit of the data in the temperature range 10-42 K to the
Curie-Weiss law.
A proton magnetic resonance study of ligand exchange on tetrakis(N,N-diethylacetamide)beryllium(II)
Authors: Tkaczuk MN , Lincoln SF
Published: September 2010

A lH
n.m.r. study shows that ligand exchange on tetrakis(N,N-diethylacetamide)beryllium(II)
in both CD3NO2 and CD3CN solution is
charaterized by the rate law:
Exchange rate = 4(k1 +
k2[OCMe(NEt2)]free)[Be{OCMe(NEt2)}42+]
In CD3NO2
solution k1
(340K) is 2.3 � 0.1 s-1, ΔH‡.76.4 � 2.2 kJ mol-1, ΔS‡
-14.6 � 6.4 JK-1 mol-1, k2 (340K) 19.9 � 0.3 dm3 mol-1s-1,
ΔH‡ 68.5 � 0.8kJ mol-1, ΔS‡ -19.6 � 2.4 JK-1
mol-1, and somewhat different magnitudes are observed in CD3CN
solution. The k1 term is assigned to a dissociative
(D) ligand exchange mechanism, and the k2
term is assigned to either an associative (A)
or an interchange (I) mechanism.
These data are discussed in conjunction with ligand exchange data for other
beryllium(II) systems.
The microwave spectrum of propynethial, HC≡C-CHS
Authors: Brown RD , Godfrey PD , Champion R , Woodruff M
Published: September 2010

We have demonstrated that
the flash pyrolysis of dipropargyl sulfide yields propynethial, HC≡CCHS,
among the products. The microwave spectrum of the major isotopic species of
propynethial and of HCCCH34S have been analysed. The derived
rotational constants for these species enable us to eliminate any alternative
structures for the pyrolysis product. The measured dipole moment components [μa
= 1.763(1) D; μb = 0.661(1); μtotal = 1.883(1)]
are discussed in terms of simple resonance structures.
Ion-ion-solvent interactions in solution. I. Solutions of LiClO4 in acetone
Authors: James DW , Mayes RE
Published: September 2010

Vibrational spectra and 7Li, 13C and 35Cl
n.m.r. spectra have been obtained for solutions of LiClO4 in acetone
for salt concentrations from 0.05 to 6 M. Infrared spectra give qualitative
indications of ion association. Analysis of the Raman band due to C-C
stretching in acetone yields solvation numbers for
the Li+ ion of the order of 3. Component band analysis of the ClO4-
symmetric stretching vibrational band and the various
n.m.r. spectra lead to the identification of solvent-separated ion pairs,
contact ion pairs and ion aggregates, in addition to free solvated ions. The
dependence on salt concentration of all four species has been determined. The
association quotient for the association equilibrium
(Li+)s(ClO4)- ↔
[Li+(acetone)ClO4-)s
was determined to be 1.4 � 0.3
dm3 mol-1.
Magnetic exchange in trans-Tetraamminedinitronickel(II)
Authors: Figgis BN , Kennedy BJ , Murray KS , Reynolds PA , Wright S
Published: September 2010

Measurements of the
magnetic anisotropy of single crystals, and the high-field magnetization of
powder specimens of trans-tetraamminedinitronickel(II), Ni(NH3)4(NO2)2,
have been determined. These, and previous susceptibility measurements, are
fitted by a one- or two-dimensional Heisenberg exchange model in which the
total exchange, ∑ijJij equals about -2 to -3 cm-1. The
absolute magnitudes of the single-ion anisotropy parameters, D and E, are required to be smaller than about 2 cm-1. The
previous explanation of the low-field magnetic susceptibility as arising from a
D value of 10.4 cm-1 is now an inadequate description of all the
magnetic data.
Cycloserine derivatives as ligands. The coordinating ability of 4,4'-[1,4-Phenylenebis(methylidynenitrilo)]bis(isoxazolidin-3-one) towards chromium(III), ruthenium(III) and rhodium(III) halides
Authors: Preti C , Tassi L , Tosi G , Zannini P , Zanoli AF
Published: September 2010

The complexes of the cycloserine derivative, 4,4'-[1,4-phenylenebis(methylidynenitrilo)]bis(isoxazolidin-3-one) or terizidone, with chromium(III), ruthenium(III) and
rhodium(III) have been synthetized; their structures
have been suggested on the basis of analytical, conductivity, spectral
(visible, infrared and far-infrared) and magnetic data, and the thermal
analyses have revealed the extent of coordinated water among the chromium and
ruthenium complexes. The various ligand field parameters have been evaluated;
the B' values suggest a strong covalency in the
metal-ligand σ bond and the Dq values show a
medium-strong ligand field. The position and multiplicity of the metal-halogen
stretching modes in the far-infrared region have been extensively investigated
and discussed; the results are particularly useful in distinguishing between
the mer-
and fac-isomers
in the octahedral compounds of the ML3X3 type. The ligand
is monodentate O-bonded
or N-bonded through the oxygen of the
keto group or through the nitrogen of the imino group of the isoxazole
ring. We have never observed a metal-induced cycloserine
ring opening under the present experimental conditions.
The synthesis, isomerization and stability of some enol-lactones
Authors: Doyle IR , Massy-Westropp RA
Published: September 2010

The
photoisomerization of enol-lactones
is described. Thermal decomposition of (E)
and (Z)
ethyl 3-oxo-1,3,3aβ,4α,7α,7aβ-hexahydro-4,7-methanoisobenzofran-1-yideneacetates provides
a good route to (E) and (Z) ethyl
5-oxo-2,5-dihydrofuran-2-ylideneacetates. Other
examples of this retro-Diels-Alder reaction are
reported. The relative stabilities of (E) and (Z) enol-lactones
from the Wittig reaction between substituted succinic
anhydrides and ethoxycarbonylmethylenetriphenylphosphorane
have
been determined. These Wittig reactions are under
kinetic control.
Crystal structure of 2-(2,6-Dichlorophenylcarbamoyl)benzoic acid
Authors: Kennard CHL , Smith G , Katekar GF
Published: September 2010

The crystal structure of
2-(2,6-dichlorophenylcarbamoyl)benzoic acid has been determined by direct
methods from three-dimensional X-ray diffraction data and refined to R 0.076
for 971 'observed' reflections. Crystals are monoclinic, space group P21/c
with Z4 in a cell of dimensions a
12.150(6), b l3.629(6), c 8.368(4) �, β lO3.75(4)�. The molecules form centrosymmetric
hydrogen-bonded cyclic dimers [O. . .O, 2.64(1) �] with the carboxylic acid
group lying in the approximate plane of the attached benzene ring (dihedral
angle 7.63�). This is in turn almost parallel to the 2,6-dichlorophenyl
substituent group on the acid amide (dihedral angle 4.14�). The amide group is
synclinally related to the ring systems in a similar way to that found in other
phthalamic acids.
The stereochemistry of organometallic compounds. XXII. The stereochemistry of metal-catalysed hydrogen cyanide addition to olefins
Authors: Jackson WR , Lovel CG
Published: September 2010

Reactions of
(E)-3,3-dimethyl(1,2-D2)but-1-ene with hydrogen cyanide and of
(E)-3,3-dimethyl-(1-D)but-1-ene with deuterium cyanide have been shown to
proceed in a completely stereospecific cis fashion when a catalyst system based
on Pd(diop)2 was used. Reaction between
4-t-butylcyclo-hexene and deuterium cyanide with the catalyst system gave only
the equatorial nitriles trans-
4-t-butylcyclohexane-1-carbonitrile and cis-3-t-butylcyclohexane-1-carbonitrile
with cis incorporation of deuterium.
Use of a catalyst system based on Ni[P(OPh)3]4
and zinc chloride led to significant amounts of isotopic exchange and
rearrangement. These results are compared with those from hydroformylation
of the olefins, and the mechanism of hydrocyanation
is discussed.
Crystal structure of 2-Methyl-2-(2,4,5-trichlorophenoxy)propionic acid
Authors: Kennard CHL , Smith G , Duax WL , Swenson DC
Published: September 2010

The crystal structure of
2-methyl-2-(2,4,5-trichlorophenoxy)propionic acid was
determined. C10H9Cl3O3, Mv 283.5, triclinic, P1, a 9.859(2), b 11.542(2), c 6.247(1) �, α(100.13(2), β
97.26(2), γ 114.68(2)�, pc 1.52 g cm-3, Z 2, F(000) 288, μ (CuKα)
66.1 cm-1. It was solved by direct methods and refined to a final R
of 0.051 for 1249 observed reflections. The molecules of the acid form the
usual hydrogen bonded cyclic dimers [O. . .O,2.638(5) �] and have the synplanar-synplanar
(carbonyl) side-chain conformation common to the phenoxyacetic
acids and 2-phenoxypropionic acids but different from previous determinations
of phenoxyisobutyric acid analogues.
The chemistry of aryllead(IV) tricarboxylates. Reaction with silyl enol ethers
Authors: Bell HC , Pinhey JT , Sternhell S
Published: September 2010

The
trimethylsilyl enol ether
of acetophenone (1) and p-methoxyphenyllead
triacetate (2) react to give (p-methoxyphenyl)phenacyllead(IV)
diacetate
(4) in high yield. This plumbation reaction has been
studied for a number of ketone trimethylsilyl enol ethers and aryllead
triacetates, and it would
appear
that it is probably limited to aryl ketone trimethylsilyl
enol ethers. The trifluoroacetic
acid catalysed break down of these α-plumbated ketones to substituted deoxybenzoins
has been examined in considerable detail. The thermal decomposition of one of
the lead compounds to a deoxybenzoin derivative has
also been examined.
Purine analogues as amplifiers of phleomycin. VII. Some 1H-imidazo-[4,5-b]pyrazines and related compounds
Authors: Barlin GB
Published: September 2010

Preparations of 2-hydroxy-
and 2-mercapto-1H-imidazo[4,5-blpyrazines from pyrazine-2,3-diamines are
described. Methylation of 1H-imidazo[4,5-b]pyrazine-2(3H)-thione with methyl iodide and
diazomethane gave some S, N1, N3 and N4 methyl derivatives; and 1H-imidazo[4,5-b]pyrazin-
2(3H)-one with diazomethane gave products which involved O, N1, N3 and N4 methylation. These products showed slight activity
as amplifiers of phleomycin but the benzothiazoles (10b) and (10c) (as
hydrobromides) showed three and four star activity respectively.
Metabolites from the lichen genus Psoroma
Authors: Elix JA , Lajide L , Galloway DJ
Published: September 2010

The
depsidones dechloropannarin
(I), isovicanicin (11) and allorhizin
(16) have been isolated from Psoroma lichens and the structures confirmed by
synthesis.
Photochemistry of 2,2'-dinitrodiphenylmethanes. II. Irradiation of 5,5'-dimethyl- 2,2'-dinitrodiphenylmethanes in neutral, acidic and alkaline media
Authors: Christudhas M , Joshua CP
Published: September 2010

Photolysis of 5,5'-dimethyl-2,2'-dinitrodiphenylmethanes(1)in
propan-2-ol yielded 2,9-dimethyl-11 H-dibenzo[c,f][1,2]diazepin-11-one 5-oxides(2) as the major product.
5-Methyl-3-(5'-methyl-2'- nitrophenyl)-2,1-benzisoxazoles
(3), 2,9-dimethyldibenzo[c,f][1,2]diazepin-11-ones (4),2,2'-dinitro-tenzophenones (5), acridinones (6), N-hydroxyacridinones
(7), dibenzo[c,f][1,2]diazepin-11-one
5,6-dioxide (8)and 2,2'-dinitrosobenzophenone(9)were also formed in varying amounts.
Irradiation of (1) in
acidic ethanol afforded benzisoxazoles (3) as the
major product. In benzene medium, the major photoproduct of (1) was
2,2'-dinitrobenzophenones (5). Irradiation of (1) in triethylamine afforded dibenzo[c,f][1,2]diazepines (12) also in
addition to the other products. A plausible mechanism to account for the
formation of various products in these photoreactions is discussed.
Structural studies of technetium complexes. III. The crystal structure of Tris[2-aminobenzenethiolato(2 - )-S, N]technetium(VI) : a trigonal-prismatictechnetium geometry
Authors: Baldas J , Boas J , Bonnyman J , Mackay MF , Williams GA
Published: September 2010

Tris[2-aminobenzenethiolato(2–)-S,N]technetium(VI), Tc(NHC6H4S)3,
has been prepared by the reaction of ammonium pertechnetate
with 2-aminobenzenethiol in 0.1 M hydrochloric acid solution at room
temperature. The crystal structure of Tc(NHC6H4S)3
has been determined by single-crystal X-ray diffraction methods at 17�C.
Crystals are orthorhombic, space group P212121,
with a 10.696(2), b 11.363(1), c l5.220(2) �, and Z 4. Automatic diffractometry
has provided significant Bragg intensities for 1413 independent reflections,
and the structure of the correct enantiomorph has
been refined by full-matrix least-squares methods to R 0.044. The compound,
which is isostructural with the molybdenum analogue,
consists of discrete molecules of Tc(NHC6H4S)3.
The environment about the technetium atom closely approximates a trigonal-prismatic geometry. This is the first example
where this geometry has been established with technetium. Differences in detail
between the structures of TC(NHC6H4S)3 and its
molybdenum analogue are discussed. In particular the S3N3
coordination polyhedron in TC(NHC6H4S)3is
contracted and the distortions from ideal trigonal-prismatic
geometry are less than in the molybdenum analogue.
A mechanism for methanol conversion over HZSM-5 catalyst
Authors: Sayed MB , Cooney RP
Published: September 2010

Mechanistic stages in the
conversion of methanol into hydrocarbons, over the zeolitic
catalyst HZSM-5, have been studied by means of infrared spectroscopy. Data are
reported for both internal surface and gas-phase species. Evidence is presented
on the following aspects: the involvement of Lewis sites in the initial
dehydration of methanol; the existence of carboxylate side reactions generating
CO and CO2; a role for intermediate isobutene; and the reformation
of methanol. The extent of the CO2 side reaction appears to
correlate with the extent of aromatic product formation. This is interpreted in
terms of the involvement of the co-product, hydrogen, in the disproportionation of aromatic products. These observations
are embodied in a mechanism invoking both organic species and surface sites for
the overall process.
The structures of paraensidimerin A and C, two bisquinolinone alkaloids from Euxylophora paraensis
Authors: Jurd L , Wong RY , Benson M
Published: September 2010

Single-crystal
X-ray diffraction studies and n.m.r. spectral measurements have now shown structure
of paraensidimerin A, a bisquinolinone
alkaloid from the heartwood of Euxylophora paraensis (Rutaceae),
to be (6aα,7β,15β,16aα)-(�-6,6,9,15,18-pentamethyl-6,6a,7,9,15,16,16a,18-octahydro-7,15-methano-8H,17H-quino[3',4'
:5',6'] pyrano[3',4':5,6] oxocino[3,2-c] quinoline-8,17-dione (8). Paraensidimerin C is a stereoisomer, (6aα,7β,15β,16aβ)-(�)-6,6,9,15,18-pentamethyl-9,15,16,16a,18-octahydro-7,15-methano-8H,17H-quino
[3',4':5',6'] pyrano
[3',4': 5,6] oxocino [3,2-quinoline-8,17-dione (9).
Possible biosynthetic routes to these and other dimeric quinolinone
alkaloids are suggested.
The reaction of N-dichloromethylene-N,N-diethylammonium chloride with some carbohydrate alcohols and diols
Authors: Copeland C , Stick RV
Published: September 2010

An
improved synthesis of N-dichloromethylene-N,N-diethylammonium
chloride is reported, and some reactions with various
carbohydrate alcohols and diols are compared with those employing the usual N-dichloromethylene-N,N-dimethylammonium chloride
(Viehe's salt). A decreased reactivity of the diethyl salt is noted, with some
interesting repercussions.
Intermediate-stage alkaline earth ion exchange in zeolites X and Y
Authors: Chatterjee M , Ganguli D
Published: September 2010

The saturation levels of
exchange of alkaline earth ions M2+ (Ba2+, Ca2+,
Mg2+) in zeolites NaX (SiO2/A12O3
2.75) and NaY(SiO2/Al2O3 4.33) at intermediate
stages before equilibrium were found to be dependent on a critical value of the
equivalent counterion supply in the solution, given by 2M2+/Na+.
The results suggested that the value of 2M2+/Na+ at
maximum exchange was more dependent on the zeolite structure (e.g. pore
geometry) than on its counterion content.
Nitrations of 3,5-Dichloro-2,4,6-trimethylphenol and 1,3,5-Trichloro-2,4,6-trimethyl-benzene; acyloin rearrangement studies of some 2,5-dinitrocyclohex-3-enones;X-ray crystal structure of 1-Acetyl-3,t-5-dichloro-c-2,4-dimethyl-2,5-dinitrocyclopent-3-en-r-1-ol
Authors: Clemens AH , Hartshorn MP , Richards KE , Robinson WT , Sutton KH , Vaughan J , Wright GJ
Published: September 2010

Nitration of dichloromesitol (11) or
1,3,5-trichloro-2,4,6-trimethylbenzene (1) gives the 6-hydroxy-
2,5-dinitrocyclohex-3-enones (12) and (13). Acyloin
rearrangements of these and related substituted
6-hydroxy-2,5-dinitrocyclohex-3-enones (9), (10), (14a) and (14b) are reported,
together with the X-ray crystal structure analysis of the trans-dinitro cyclopentenol
derivative (24). Some stereochemical features of these acyloin
rearrangements are discussed.
Stereospecific synthesis of tetrahydrobenzisoquinoline derivatives
Authors: Gellert E , Kumar N , Tober D
Published: September 2010

A new synthesis of
optically active tetrahydrobenzisoquinolines is
described. Cyclization of N-aryl- alkylalanines with retention of configuration was achieved
by mild intramolecular Friedel-Crafts acylation. The compounds synthesized this
way represent simple analogues of phenanthroindolizidine
alkaloids. Some features of the n.m.r. spectra of cyclized and open-chain
intermediates are discussed.
Structural studies in the ruthenium(II)/(±)-ortho-Phenylenebis{methyl(phenyl)-phosphine/arsine) system. II. Crystal structure of trans-Dichloro[(±)-ortho-phenylenebis{methyl(phenyl)-phosphine}][(±)-ortho-phenylenebis(methyl(pheny1)-phosphine) P-oxide]ruthenium(II)
Authors: Hall SR , Skelton BW , White AH
Published: September 2010

The crystal and molecular
structure of the title complex, trans-[RuCl2{(�)-o-C5H4(PMePh)2}{(�)- o-C5H4(PMePh)(P(O)MePh)}], has been established by a single-crystal X-ray
diffraction study at 295(1) K, being refined to a residual of 0.037 for 2669
independent 'observed' reflections. Crystals are orthorhombic, P212121,
a 16.655(5), b 15.805(4), c 14.823(8)
�, Z 4. The chlorine atoms lie trans
to each other in the coordination sphere of the six-coordinate ruthenium, with
the O-C6H4(PMePh)2
and o-C6H4(PMePh)(P(O)MePh) ligands being P,P? and O,P' bidentate respectively.
The ruthenium-chlorine distances are 2.434(2) and 2.425(2) �; the two mutually trans ruthenium- phosphine distances are
2.310(3) and 2.346(2) �, but that which is trans
to the oxygen is unusually short, being 2 219(2) �. The ruthenium-oxygen
distance is 2.166(5)�.
Structural studies in the ruthenium(II)/(±)-ortho-Phenylenebis{methyl(phenyl)-phosphine/arsine} system. III. Crystal structures of Dichlorocarbonyl(dimethyl sulfoxide)-[ortho-phenylenebis {methyl(phenyl)phosphine}]ruthenium(II) and of cis-dicarbonyldichloro[(±)-ortho-phenylenebis{methyl(phenyl)arsine}]ruthenium(II)
Authors: Hall SR , Skelton BW , White AH
Published: September 2010

The crystal and molecular
structure of the title complex, cis-[Ru(CO)Cl2(dmso)(opmpp)] (1) (dmso ≡ dimethyl
sulfoxide, Me2SO; opmpp ≡ (�)-ortho-phenylenebis
{methyl(phenyl)phosphine},[o-C6H4(PMePh)2]), has been determined by a
single-crystal X-ray diffraction study at 295(1) K, being refined to a residual
of 0.050 for 6115 independent 'observed' reflections. Crystals are monoclinic,
P21/c, a 11.180(7), b 12.957(6), c 17.567(9) �, β 90.88(5)�, Z 4. The ruthenium-chlorine
distances, trans to phosphine and
carbonyl ligands, respectively, are 2.469(2), 2.446(2) �; the
ruthenium-phosphine distances, trans
to the chloride and dimethyl sulfoxide ligands, respectively, are 2.292(1),
2.313(2) �. Ruthenium-sulfur (dmso) is 2.380(2) �,
while the ruthenium-carbon(CO) is c. 1.72 �. For cis-[Ru(CO)2Cl2(opmpa)] (2) (opmpa ≡ (�)-ortho-phenylenebis{methyl(phenyl)-
arsine}, [o-C6H4(AsMePh)2]), refinement led to a residual of
0.036 for 2423 independent 'observed' reflections. Crystals are monoclinic, P21/c,
a 10.497(3), b 11.586(7), c 20.341(9) �,
β 105.31(4)�, Z 4. Ruthenium-arsine distances, trans to carbonyl and chlorine ligands, respectively, are 2.404(1),
2.455(1) �. Ruthenium-chlorine distances,
trans to arsine and carbonyl ligands, respectively, are 2.443(3), 2.433(2) �,
while ruthenium-carbon(CO) distances, trans
to arsine and chlorine ligands, respectively, are 1 .920(8), 1 .872(8) �.
Explosive Meisenheimer complexes formed by addition of nucleophilic reagents to 4,6-dinitrobenzofurazan 1-oxide
Authors: Norris WP , Spear RJ , Read RW
Published: September 2010

The reaction between
4,6-dinitrobenzofurazan 1-oxide (1) and a number of nucleophilic oxygen and
nitrogen reagents has been studied. The exceptional electrophilic power of (1)
leads to formation of 1 : 1 Meisenheimer complexes as the general reaction observed.
Ammonia and hydrazine also form bis-adducts
in the presence of excess (1). All the adducts were isolated as stable, but
highly explosive, cystalline solids, and have been
characterized by micro-analysis and spectroscopy. The adducts from N3-
and I- have been observed spectroscopically
but not isolated. The monomethoxy adduct (8)
undergoes a novel internal oxidation-reduction to form a gem-dimethoxybenzofurazan complex(6).
The chemistry of aryllead tricarboxylates. Synthesis of some α-aryl α,β-unsaturated carbonyl compounds
Authors: Kopinski RP , Pinhey JT
Published: September 2010

The treatment of
4-benzoyltetrahydrofuran-2,3-dione (2a) with 2 equiv. of phenyllead
triacetate (3a) in chloroform gives 1,2-diphenylpropenone (4a) in excellent
yield. This reaction has been investigated with a number of similar derivatives
of tetrahydrofuran-2,3-dione and a number of aryllead triacetates. It has been
found to be very sensitive to the nature of the substituent at C4, and it would
appear to be limited to the synthesis of a-methylene carbonyl compounds since a
5-methyl substituent inhibits the reaction.
Diels-Alder dimerization of a hexenylidene-substituted Benzofuran-2(3H)-one
Authors: Becker H , Hall SR , Skelton BW , White AH
Published: September 2010

(Z)-7-t-Butyl-5
methoxy-3-[(Z)-2?-methoxy-5,5'-dimethyl-4'-oxohex-2'-enylidene]benzofuran-2(3H)-one
has been found to undergo Diels-Alder dimerization in which the exocyclic
double bond adds to the s-cis diene
moiety. The stereochemistry of the Diels-Alder dimer was established by a
single-crystal X-ray structure determination. Crystals of the dimer, C44H56O10,
are monoclinic, P21/n, a 12.23(1),
b 19.43(2), c 18.71(2) �, β 107.76(7)�, Z 4; a residual of 0.046 was
obtained for the 2519 'observed' reflections. In the dimer, two benzofuranone moieties are situated so as to be vicinal spiro substituents of the cyclohexene
formed in the Diels-Alder addition. The bond between the two benzofuranone units is unusually long [1.597(6)�]. The
shielding of one aromatic hydrogen in the n.m.r. spectrum of the dimer results
from the disposition of the two aromatic systems.
The structure and function of oestrogens. V. Synthesis of (9,12,12-2H3)- and (11ζ 12,12-2H3)-oestradiol
Authors: Collins DJ
Published: September 2010

17,17-Ethylenedioxy-3-methoxy(9,12,12-2H3)-9β-oestra-l,3,5(10)-trien-11-one (3) was reduced to
the mixture of 11-epimeric alcohols (4) which upon elimination of DHO gave the
(12,12-2H2)-9(11)- dehydrooestrone
derivative (5b). Treatment of (5b) with (2H6)diborane
followed by oxidation afforded the (9,12,12-2H3)alcohol (8a);
hydride reduction of the corresponding tosylate then
gave 17,17-ethylenedioxy-3-methoxy(9,12,12-2H3)oestra-l,3,5(l0)-triene (7). Acid hydrolysis of (7), followed by demethylation, and reduction with sodium borohydride yielded (9,12,12-2H3)oestradiol
(10). Sodium borohydride reduction of (11&12,12-2H3)oestrone
(6),prepared in several steps from the 9β,12,12-trideutero ketone (3),
gave (11 ξ,12,12-2H3)oestradiol (9). [The two trideuterated
oestradiols (9) and (10) were required for biological
studies.]
Synthesis and properties of N-Phenyl derivatives of 4,4'-Diaminobenzophenone
Authors: Evans NA
Published: September 2010

Variations in the reaction
conditions during the Ullmann condensation of
4,4'-diaminobenzophenone with iodobenzene and the
Goldberg diphenylamine synthesis with 4,4'-dibromobenzophenone and acetanilide
or 4,4'-bis(acetamido)benzophenone
and iodobenzene yielded the five possible partially and
completely N-phenylated 4,4'- diaminobenzophenones.
By choice of starting materials, 4,4'-bis(phenylamino)benzophenone could be obtained in satisfactory yield. The
infrared, ultraviolet, 1H and 13C nuclear magnetic resonance
and mass spectra of the benzophenones are reported.
Structure and stereochemistry in 'f-block' complexes of high coordination number. VII. The [M(unidentate X)2(unidentate Y)6] system: Crystal structure of hexaaquadichloroeuropium(III) chloride (a redetermination)
Authors: Kepert DL , Patrick JM , White AH
Published: September 2010

The crystal structure of
the title compound [EuCl2(OH2)2]Cl ('europium trichloride hexahydrate') has
been redetermined from single-crystal diffractometer
data at 295 K and refined to a residual of 0.040 for 1094 independent
'observed' reflections. Crystals are monoclinic, P2/n, a 9.659(3), b 6.529(2), c 7.936(4) �, β 93.67(4)�, Z 2. The europium atom lies on a
crystallographic twofold axis, which passes between the two planes of a square-antiprismatic coordination environment in which the two
chlorine atoms, on opposite faces, lie cis
to each other. Eu-O distances range from 2.401(6) to
2.431(5) �; Eu-Cl is 2.774(2) �.
Equilibrium hydrogen fluoride pressures over metal hydrofluorides, fluorophosphates and metal difluoride systems
Authors: Bottomley GA , Farrow JB , Lincoln FJ
Published: September 2010

The equilibrium pressures
of hydrogen fluoride gas over barium, sodium, potassium and caesium
monohydrofluorides have been measured in the general
pressure range from 0.01 Pa to 1000 Pa. Nitrogen gas is transported through the
powdered solid, then the acquired HF gas is absorbed on membrane filter papers
for subsequent analysis with a fluoride ion specific electrode. By similarly
using nitrogen with water vapour the equilibrium
hydrogen fluoride pressures generated by the hydrolysis of sodium, potassium,
barium and lead monofluorophosphates, and zinc, lead
and cobalt difluorides were studied. The results for
all systems are represented by linear logKp
against reciprocal temperature equations from which, where the corresponding
chemical reaction has been identified with considerable certainty, the reaction
enthalpy, entropy and other thermodynamic quantities have been deduced.
The chemistry of aryllead(IV) tricarboxylates. Reaction with α-hydroxymethylene ketones : a route to α-arylated ketones
Authors: Pinhey JT , Rowe BA
Published: September 2010

α-Hydroxymethylene ketones
have been shown to react with aryllead triacetates in tetrahydrofuran containing pyridine to give
α-aryl α-formyl ketones, unstable compounds, which were hydrolysed directly with alkali to
α-aryl ketones. The procedure has been used to produce in good yield 2-(p-methoxyphenyl)cyclohexanone,
2-(p-tolyl)cyclohexanone and the corresponding derivatives of4-t-butylcyclohexanone, and
2α-(p-methoxypheny1)-5α-cholestan-3-one and 3β-hydroxy-16α-(pmethoxypheny1)-5α-androstan-17-one.
Experiments directed towards the synthesis of anthracyclinones. VII. Model studies with allyl naphthalenyl ethers
Authors: Boddy IK , Cambie RC , Dixon G , Rutledge PS , Woodgate PD
Published: September 2010

The Claisen rearrangement
of some allyl naphthalen-1-yl ethers has been examined, together with methods for modification of
the resulting 2-ally1 side chain. Isomerization of the C-allyl substituent to a prop-1-enyl group
followed by ozonolysis gives a formyl derivative, while ozonolysis of a 2-(2-methylprop-2-enyl)
moiety or mercuriation of a 2-(2-chloroprop-2-enyl) substituent leads to an acetonyl derivative. Treatment of phenols with
iodine(I) acetate and an excess of silver(I) acetate gives 4-hydroxyaryl acetates, probably via
dienone intermediates.
The mechanism of extraction of iron(III) from 6 M hydrochloric acid by long chain amines in chloroform
Authors: Ilic MZ , Cattrall RW , Davey DE
Published: September 2010

The mechanism of transfer
of FellI between 6.0 M HCl and five amine
chlorides in chloroform has been studied by means of the single-drop technique.
It is suggested that the (1,1) complex forms at the interface by fast
ion-exchange and that the rate determining step involves the replacement of the
complex at the interface by one molecule of reagent monomer from the bulk
organic phase. Additional heterogeneous aggregates are formed in the bulk
organic phase by fast reactions with reagent monomer. Support for this
mechanism is obtained through the excellent agreement between the extraction
equilibrium constants calculated from the rate data for the (1,1) complexes and
the values obtained previously by two phase titration studies.
The crystal and molecular structure of dipyrrolidylthiuram disulfide
Authors: Williams GA , Statham JR , White AH
Published: September 2010

The crystal structure of dipyrrolidylthiuram disulfide has been determined by
single-crystal X-ray diffraction techniques at 295 K. Crystals are monoclinic,
space group C2/c, unit cell a 13.835(3), b 10.422(2), c 9.427(3) �,
β 97.08(2)� and Z 4. Automatic diffractometry has provided significant
Bragg intensities for 1402 independent reflections, and the structure has been
refined by least-squares methods to R 0.037. The structure consists of discrete
C4H8NC(S)S2C(S)NC4H8
molecules. Half of each molecule is crystallographically unique with distances
S-S 2.002(1), and C-S 1.804(2) and 1.645(2) �. The dihedral angle between
planar C2NC(S)S portions is 87.9�. The relevance of the derived
structural parameters to the question of why the tris(pyrrolidine-1-carbodithioato)iron(III)
complex is, uniquely, high spin is discussed.
Reactions of propargyl alcohols. VII. Lithium aluminium hydride reductions of 1-methoxy-2-phenylpent-3-yn-2-ol, 1-methoxy-3-phenylhex-4-yn-3-ol and 7-methoxy-4-phenylhept-2-yn-4-ol
Authors: Blunt JW , Hartshorn MP , Soong LT , Munro MHG , Vannoort RW , Vaughan J
Published: September 2010

Lithium aluminium hydride
reductions in ether solvents of 1-methoxy-2-phenylpent-3-yn-2-ol (7a), 1-methoxy-3-phenylhex-4-yn-3-ol
(7b) and 7-methoxy-4-phenylhept-2-yn-4-ol (7c) are reported. Evidence for
methoxy group participation in the reduction process for (7a) and (7b) is
presented. Reductions of alkynols (4b), (4c), (7a),
(7b) and (7c) with lithium aluminium hydride in benzene are described; alkynol (4a), lacking a methoxy function, failed to react
under these reaction conditions.
The synthesis and 13C N.M.R. spectral assignments of some 2,4,4-trimethylcyclopentan-1-ones
Authors: Eaton PJ , Jogia MK , O'Conner AW , Weavers RT
Published: September 2010

Some substituted
2,4,4-trimethylcyclopentan-1-ones were synthesized and carbon resonances
assigned. The geometry of several substituted methylene derivatives was
analysed by lH n.m.r. in a situation where 13C n.m.r.
provided little assistance.
Photochemistry of dimethyl quinoline-3,4-dicarboxylate N-oxides
Authors: Irvine RW , Summers JC , Taylor WC
Published: September 2010

The photochemical
rearrangement of 2-methyl and 2-aryl substituted dimethyl
quinoline-3,4-dicarboxylate N-oxides
has been studied. In methanol or methanol/chloroform solutions the major
product was the 1-methyl-or 1-aryl-quinolin-2(1H)-one in which the substituent
at C2 has migrated to nitrogen. The yield of these products was increased in a
dark reaction subsequent to the irradiation. In acetonitrile
solutions the inital major product was the
corresponding 3,1-benzoxazepine; subsequent reactions yielded inter alia indole derivatives.
A 'biogenetic like' synthesis of perloline, 6-(3,4-Dimethoxyphenyl)-5-hydroxy-5,6-dihydrobenzo[c][2,7]naphthyridin-4(3H)-one
Authors: Duong T , Prager RH , Were ST
Published: September 2010

9H-Indeno[2,1-c]pyridine-1(2H),9-dione,
prepared by a new efficient route, reacts with 3,4-dimethoxy- phenyllithium to form the keto alcohol (7), which
rearranges with hydrazoic acid to form 5-(3,4- dimethoxyphenyl)benz[c][2,7]naphthyridin-4(3H)-one. The N-oxide photolyses
smoothly to yield dehydroperloline as the sole
product.
A synthetic approach to peptides of o- and p-aminobenzoic acids
Authors: Stewart FHC
Published: September 2010

Active esters of o-and p-aminobenzoic acids served as coupling
components in peptide syntheses without concomitant protection of the
relatively inert aromatic amino group. The products were then treated directly
with benzyloxycarbonylamino acid symmetrical
anhydrides to form higher peptide derivatives. An analogue of leucine-enkephalin with the glycylglycyl
segment replaced by a p-aminobenzoyl residue has been synthesized by this route.
Further studies of the diazo coupling reactions of pyrimidines
Authors: Hurst DT
Published: September 2010

6-Arylazo derivatives of
the following pyrimidines have been obtained: 2-acetamido-4,5-dihydroxy-,
4-amino-2,5-dihydroxy-, 2,4-diamino-5-hydroxy- and 4-amino-5-hydroxy-2-methyl-pyrimidine.
However, some 5-substituted pyrimidines having other electron-releasing groups
failed to undergo diazo coupling.
2,4-Dihydroxypyrimidin-5-yl acetate and 2-acetamido-4-hydroxypyrimidin-5-yl
acetate lost the 5-acetyl group during the introduction of
the arylazo group into the 6-position. However, 2-hydroxy-4,6-dimethylpyrimidin-5-yl acetate
undergoes diazo coupling at the 4(6)-methyl
substituent without loss of the 5-acetyl group. The mechanisms for these diazo
couplings are discussed.
Eliminations promoted by weak bases. IX. Stereochemistry of olefin formation from trans-2-Phenylcyclopentyl p-bromobenzenesulfonate promoted by lithium chloride in acetone
Authors: McLennan DJ , Lim C
Published: September 2010

Parker, Winstein,
and their coworkers have previously established that in the E2C elimination of
trans-2-phenylcyclopentyl p-bromobenzenesulfonate induced by Bu4NCl in
acetone some 9% of the olefinic product is produced
by a syn-elimination.
In view of the current idea that syn-eliminations in solution are assisted by association of
the base with its counterion, the stereochemistry of
the reaction induced by lithium chloride in acetone has been studied. There is
no increase in the amount of syn-elimination, and kinetic analysis reveals that lithium
chloride ion pairs are completely unreactive.
1-Phenylcyclopentene is not produced by rate-limiting attack of chloride ion on
a preformed symmetrical phenonium ion pair. These
results do not serve to distinguish between two alternative models of the E2C transition state.
Concerning the problem of the isokinetic relationship. I. A statistical mechanical model
Authors: Linert W , Kudrjawtsev AB , Schmid R
Published: September 2010

The equation for the rate constant derived from the statistical theory of kinetics is compared
with the common Arrhenius equation. Thereby the pre-exponential factor and the activation energy
can be expressed by means of the theoretical quantities, frequency factor (Z0), oscillator number (s),
and potential barrier height (E). In these terms the isokinetic relationship can be represented by
the equation (c- c) = b(E-E) where c is s- 1 and the bars denote the means in the reaction series
under consideration. The empirical coefficient b, in connection with the numerical value of the
isokinetic temperature, is proposed to be used as a criterion for the classification of reaction series.
The model is exemplified by means of an organic SN2 reaction.
Catalysis by α-substituted pyridines in the hydrolysis of aryl acetates and acetic anhydride
Authors: Deady LW , Finlayson WL
Published: September 2010

Results for the hydrolysis of p-nitrophenyl acetate, 2,4-dinitrophenyl acetate and acetic anhydride,
catalysed by various substituted 2-amino- and 2-methyl-pyridines, are reported. The results seem
consistent with nucleophilic catalysis throughout, contrary to some literature reports.
The reactions of t-butoxyl with unsaturated hydrocarbons: Structure and reactivity of allylic radicals
Authors: Cuthbertson MJ , Rizzardo E , Solomon DH
Published: September 2010

A radical trapping technique employing 1,1,3,3-tetramethylisoindolin-2-yloxy(1) as scavenger has
been used to study the reactions of t-butoxy radicals with propene, 2-methylpropene, but-1-ene,
(E)- and (Z)-but-2-ene, 3-methylbut-1-ene, buta-1,3-diene and 2-methylbuta-1,3-diene. Relative
rates of double bond addition and of allylic hydrogen abstraction have been measured and are discussed,
as are the relative stabilities of the products formed. The allylic radicals generated in these
systems react with (1) mainly by coupling at the more substituted terminus of the radical π system.
Substituent effects on this regioselectivity may be explained in terms of the electrophilicity of (1).
The crystal structure of 5-O-Acetyl-1,2 : 3,4-di-O-isopropylidene-α-D-glucoseptanose, C14H22O7, by use of X-ray and neutrondiffraction data
Authors: Wood RA , James VJ , Rae AD , Stevens JD , Moore FH
Published: September 2010

The crystal structure of 5-O-acetyl-1,2:3,4-di-O-isopropylidene-α-D-glucoseptanose [P212121,
Z 8, a 14.329(5), b 22.075(5), c 10.012(5) �] has been determined by X-ray and neutron diffraction
analyses. For the neutron diffraction analysis, the acetate group and the
trans-O-isopropylidene group were
deuterated. Constrained refinement was used in the neutron diffraction analysis
to counter over parameterization in the block-diagonal least-squares
refinement. Final unweighted R-values were 0.038 [X-ray for 3070 reflections
with [Fo > 2.58σ (Fo)] and 0.061 [neutron for
1118 reflections with Fo > 4σ ([Fo)]The neutron
refinement revealed a disordering of the acetate methyl group in each of the
two independent molecules in the asymmetric unit. The septanose ring in each
molecule adopted the same twist-chair conformation but the dioxolan rings
assumed different twist and envelope conformations.
Structure of 3α,4α:5β,6β-Diepoxyandrostan-17-one
Authors: Kamenar B , Pauptit RA , Waters JM
Published: September 2010

The X-ray crystal structure
of 3α,4α:5β,6β-diepoxyandrostan-17-one has been determined.
Crystals of the title compound (C19H26O3)are
monoclinic, space group P21, with a 9.208(2), b 9.620(4), c 9.312(3) �, β 99.14(2)�, V 814.5
Ǻ3 and Z 2. The structure was solved by direct methods and refined
to R 0.039 for 887 observed reflexions. The 3α,4α:5β,6β
configuration of the epoxide rings confirms the assignment based on proton
n.m.r. studies.
Reactions of 2,6-Di-t-butyl-4-methylphenol with nitrogen dioxide; X-ray crystal structures of 2,6-Di-t-butyl-c-6-hydroxy-4-methyl-r-4,c-5-dinitrocyclohex-2-enone and 2,6-Di-t-butyl-4-methyl-r-4,c-5,c-6-trinitrocyclohex-2-enone
Authors: Hartshorn MP , Sutton KH , Vaughan J
Published: September 2010

Reaction of
2,6-di-t-butyl-4-methylphenol (6) with nitrogen dioxide in benzene gives the trinitro ketone (11), but in cyclohexane gives both trinitro ketone (11) and the hydroxy dinitro
ketone (12),in addition to the 4-nitro dienone (10). Some reactions and X-ray
crystal structures of compounds (11) and (12) are described.
Metal template reactions. XXI. Synthesis and coordination chemistry of diamino dialdehydes based on pyrimidines and related enaminones
Authors: Black DSC , Rothnie NE
Published: September 2010

4,6-Dichloropyrimidine-5-carbaldehyde
(1) has been converted into the diamino dialdehydes (2)-(5). The related
compound (6) could not be obtained but the pyrimido-diazepine (7) was formed
instead. Copper(II) and nickel(II) complexes (8) were formed from the compounds
(4) and (5). Forcing conditions were required for the formation of the
macrocyclic complexes (9)-(12) from the precursors (4) and (5). The
chloropyrimidines (2) and (3) underwent alkaline hydrolysis to give the
enaminones (16) and (17) respectively. These compounds in turn gave rise to the
complexes (21)-(23). Vigorous conditions were required for the formation of the
macrocyclic complex (23) and the complex (22) was obtained by an amine exchange
process.
The intramolecular cyclization of unsaturated benzo derivatives of Bicyclo[3.3.2]decane
Authors: Amini . , Bishop R
Published: September 2010

When treated with
electrophilic reagents the benzo derivatives of
bicyclo[3.3.2]decane, 7,11-dimethyl-ene-6,7,8,9-tetrahydro-5,9-propano-5H-benzocycloheptene and
11-methylene-5,6,8,9-tetrahydro-5,9- propano-7H-benzocyclohepten-7-one, both exclusively undergo intramolecular
cyclization to form derivatives of 6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene (benzohomo-adamantene)
in high yield. The latter reactant also cyclizes to
form derivatives of 5,6,7,8,9,10-hexa- hydro-5,8:7,10-dimethanobenzocyclooctene
(benzohomonoradamantene) when reduced with sodium in
moist ether or under Wolff-Kishner conditions.
Central nervous system active compounds. XIII. The use of aminomethylene phthalides in the synthesis of phthalideisoquinoline alkaloids
Authors: Clarke SI , Kasum B , Prager RH , Ward AD
Published: September 2010

Dimethylaminomethyleneisobenzofuranones react with alkoxyphenylethylamines
in aqueous acidic solution to give phthalide isoquinolines (tetrahydroisoquinolinylisobenzofuranones)
in moderate yields. N-Methylation
gives the naturally occurring phthalideisoquinoline
alkaloids. A number of examples of this reaction sequence are reported,
including the synthesis of (�)-cordrastine, (�)-corlumine and (�)-adlumine.
Triterpenes of Lantana tiliaefolia. 24-Hydroxy-3-oxours-12-en-28-oic acid, a new triterpene
Authors: Johns SR , Lamberton JA , Morton TC , Suares H , Willing RI
Published: September 2010

The known triterpenes ursonic acid, oleanonic acid, ursolic acid, oleanolic acid and 24-hydroxy-3-oxoolean-12-en-28-oic acid
occur in Lantana tiliaefolia
Cham., together with a new
triterpene,24-hydroxy-3-oxours-12-en-28-oic acid. A detailed 13C
n.m.r. study has been made of a number of olean-12-enes and urs-12-enes, and
the 1H n.m.r. signals from the secondary methyl groups in
urs-12-enes have been investigated. N.m.r. evidence shows significant
conformational differences in ring A between a number of 3-oxo derivatives that
differ in their ring A substituents. Methyl ursonate and
methyl oleanonate have been separated on columns of Spherosorb A5Y alumina.
A convenient preparation of vic-iodo-isocyanates
Authors: Cambie RC , Hume BA , Rutledge PS , Woodgate PD
Published: September 2010

vic-Iodo-isocyanates are conveniently prepared by treatment of alkenes
with iodine/thallium(1) cyanate or with iodine(I)
chloride/thallium(I) cyanate. Treatment of the phenylurea (5) with silver perchlorate
or m-chloroperbenzoic acid gives the oxazoline (29).
Generalized van der Waals theory. XII. Application to ionic solutions
Authors: Nordholm S
Published: September 2010

The recently developed
generalized van der Waals (GvdW) theory of fluids is applied to ionic solutions, and
shown to yield the Poisson-Boltzmann equation when
short-range effects are neglected, and the Debye-Huckel
theory when non-linear effects are also neglected. The linear GvdW theory, retaining excluded-volume and energetic
correlation effects, then yields a corrected Debye-Huckel
(CDH) theory. We consider electrolytes in the restricted primitive model and
find that the excluded-volume effects then vanish. Two different methods for
the evaluation of the energetic correlation effects are examined. In the first
method, these effects are treated in a simple local approximation which leads
to a DH theory with a decreased Debye length valid as
long as this length is much greater than the hard-sphere diameter of the ions.
In the second method, we assume a DH-type charge density, a constant number
density and determine the Debye length by minimizing
the linearized GvdW
free-energy functional. The results for the internal energy, osmotic
coefficient and mean ionic activity coefficient of 1-1 and 2-2 electrolytes in
the concentration range 0-2 M are obtained and compared with corresponding
simulation results. The agreement is good for 1-1 electrolytes, but significant
deviations are observed for 2-2 electrolytes.
Gas-gas immiscibility in hydrogen mixtures
Authors: Missen BN , Young CL
Published: September 2010

Measurements are reported
of the slope of the critical locus of binary mixtures of a series of
hydrocarbons, and two fluorocarbons, with hydrogen near the critical point of
the hydrocarbon (or fluorocarbon).These systems exhibit
gas-gas immiscibility of the first kind. The results are compared with predictions
from the one-fluid model together with 'a hard sphere + attractive term'
equation of state proposed by Guggenheim.
The results can be predicted from the theory provided the energy
interaction parameter, ξ, is allowed to be somewhat less than that
calculated from the Hudson and McCoubrey rule. This
is discussed in terms of values of ξ from other measurements, and possible
deficiencies in the theory.