bluuebunny/crossref_metadata_2025 huggingface dataset:
Preparation of bisulphite addition compounds of 5-Amino-5-deoxy-D-xylose
Authors: Ingles DL
Published: September 2010

Sulphurous acid alone and in admixture
with other stronger acids has been used to hydrolyse 5-amino,
5-N-cyclohexylamino, and 5-N-piperidino derivatives of 5-deoxy-l,2-O-isopropylidene-D-xylose.
The bisulphite addition compounds of the corresponding amino sugars were thus
isolated. Similarly, methyl 5-amino-5-deoxy- 2,3-O-isopropylidene-D-riboside
was hydrolysed to yield the bisulphite addition compound of
5-amino-5-deoxy-D-ribose.

Treatment of the bisulphite addition
compound of 5-amino-5-deoxy-D-xylose with barium hydroxide gave the free amino
sugar as a syrup in 96% yield. Removal of bisulphite from the addition compound
of 5-X-cyclohexylamino-5-deoxy-D-xylose gave the free sugar in 30% yield
together with an amino acid (XVI).
Octahedral cobalt(III) complexes in dipolar aprotic solvents. V. The substitution of chloride and thiocyanate into the cis-chlorodimethylformamidebisethylenediaminecobalt(III) ion in anhydrous NN-dimethylformamide
Authors: Lantzke IR , Watts DW
Published: September 2010

The kinetics and mechanism of the
substitution of chloride ion and thiocyanate ion into the cis-chlorodimethylformamidebisethylenediaminecobalt(111) ion, cis-[CoCl(DMF) en2]2+,
have been studied in ,NN-dimethylformamide (DMF).

The chloride entry shows mixed kinetics
which are accounted for by two paths, a slow ion pair dissociation, and a fast
bimolecular attack of chloride on an ion pair. The steric course of the
reaction, which is chloride dependent, shows that the ion pair dissociative
mechanism is more important at low chloride concentrations.

The thiocyanate entry shows similar
characteristics. Thiocyanate enters faster than chloride in the bimolecular
path, but in the ion pair dissociative path, which is significant at lower
anion concentration, both chloride and thiocyanate enter at the same rate.
Octahedral cobalt(III) complexes in dipolar aprotic solvents. VI. Spectrophotometric determination of ion association of halide ions with cis-chlorodimethylformamidebisethylenediaminecobalt(III) ion and cis-chlorobromobisethylenediaminecobalt(III)ion in anhydrous NN-dimethylformamide
Authors: Lantzke IR , Watts DW
Published: September 2010

Using a spectrophotometric technique the
ion association constants for three systems of octahedral cobalt complexes and
halide ions have been determined at three temperatures in NN-dimethylformamide.
The values of K, ΔH�, and ΔS� for each system have been calculated.
At 30� they are as follows:

cis-[CoCl(DMF) en2]2+ + Cl-
↔ ion pair

K=1.51�0.03 x 104 1.mole-1(ΔH0=
0.93 � 0.02 kcal mole-1,ΔS�= 22.l+0.4 e.u)

cis-[CoCl(DMF) en2]2++2Cl- ↔ ion triplet

K= 1.21�0.05 X 106
1.2 mole-2(ΔH�=-3.8�0.lkcal
mole-1, ΔS�=15.41� 0.5 e.u)

cis-[CoCl(DMF) en2]2++Br- ↔ ion pair

K= 9.20�0.18 X 103
1.1 mole-1(ΔH�=-7.2�0.lkcal
mole-1, ΔS�=42� 1.0 e.u)

cis-[CoBrCl en2]+
+ Br- ↔ ion pair

K = 690�l41. mole-1 (ΔH� = 1.27�0.03 kcal mole-1,
ΔS�= 8.8�0.2 e.u.)

The dependence of the measured K, the
association constant, on the wavelength of measurement, small amounts of water
in the solvent, and the anion of the complex salt, has also been investigated.
The use of 2,4,6-trimethylbenzyl esters in peptide synthesis
Authors: Stewart FHC
Published: September 2010

Model experiments with the
2,4,6-trimethylbenzyl esters of N-acylamino acids
have shown that this ester group is cleaved by hydrogen bromide in acetic acid
under reaction conditions which do not affect benzyl esters appreciably, but
which result in removal of benzyloxycarbonyl amino-protecting groups.
2,4,6-Trimethyl- benzyl esters, however, are unaffected by methanolic hydrogen
chloride under the conditions used to cleave o-nitrophenylsulphenyl and trityl protecting groups. These selective differences have
been utilized for the synthesis of various benzyloxycarbonyl peptide
2,4,6-trimethylbenzyl esters up to the hexapeptide
level. Some of these derivatives have been converted into the corresponding
free peptides by the action of hydrogen bromide in acetic acid.

The 2,4,6-trimethylbenzyl group is more
readily cleaved by hydrogen bromide than p-nitrobenzyloxycarbonyl
and the possible application of this situation to peptide synthesis is
considered.
Thermodynamics of binary liquid mixtures with hydrogen bond interaction
Authors: Naidu PR , Krishnan VR
Published: September 2010

Excess volumes and adiabatic excess
compressibilities of the systems dioxan- phenol, dioxan-o-chlorophenol, dioxan-guaiacol,
dioxan-o-cresol, dioxan-m-cresol,
and dioxan-p-cresol are presented at 35�.

These data have been used to postulate
hydrogen bonding between the components and the influence of the substituent on
the strength of the hydrogen bridge between dioxan and substituted phenols is
discussed.
Synthesis and stereochemistry of 1-Thiaflavan-4-ols
Authors: Katekar GF
Published: September 2010

Lithium aluminium hydride or sodium
borohydride reduced 1-thiaflavanone, 6-methyl-1-thiaflavanone,
and 4'-chloro-1-thiaflavanone to the corresponding
2,4-cis-1-thiaflavan-4-ols. Deamination of 2,4-cis-4-amino-1-thiaflavans with nitrous acid gave rise to the 2,4-trans-1-thiaflavan-4-ols. N.m.r.
measurements were used to determine the stereochemistry of these compounds.
Selective acid hydrolysis of 2,4,6-trimethylbenzyl esters and its application in peptide synthesis
Authors: Stewart FHC
Published: September 2010

Experiments with various
N-acylamino acid 2,4,6-trimethylbenzyl esters have shown that the ester group
is cleaved selectively by cold trifluoroacetic acid without affecting
benzyloxycarbonyl, formyl, or phthaloyl amino-protecting groups present. The
possible value of this selective behaviour in peptide syntheses where the use
of alkaline conditions would be detrimental is illustrated by the synthesis of
certain dipeptide derivatives.
Electron impact studies. II. Mass spectra of quercetagetin derivatives
Authors: Bowie JH , Cameron DW
Published: September 2010

The mass spectra of 11
quercetagetin derivatives are reported and discussed. The spectra are generally
simple and amenable to analysis. 4 number of fragmentation processes have been
substantiated by exact mass measurements, appropriate metastable ions, and
deuterium labelling.
The amine catalysed dealdolization of diacetone alcohol
Authors: Hay RW , Tate KR
Published: September 2010

The hydroxide ion catalysed
decomposition of diacetone alcohol (CH3)2- C(OH)CH2COCH3
→ 2CH3COCH3 has been investigated at 25� and I =
0.4M. The catalytic effect of ethylamine, diethylamine, benzylamine, and
isopropylamine on the reaction has been studied. A possible mechanism for the
amine catalysis involving a carbinolamine intermediate is considered.
Diffusion coefficients at 25° for the systems water-ε-caprolactam, water-glycine anhydride, and water-glycine anhydride-ε-caprolactam
Authors: Cussler Jr EL , Dunlop PJ
Published: September 2010

Diffusion coefficients,
refractive index increments, and solution densities at 25� are reported for the
binary systems H2O-glycine anhydride and H2O-ε-caprolactam,
and the ternary system H2O-glycine anhydride-ε-caprolactam. The
values of the ternary cross-term diffusion coefficients, (D12)V
and (D21)V, in Table 2 are not sufficiently large to
H O

| ||support the idea that hydrogen
bonding between the -N-C- groups of ε-caprolactam and glycine anhydride is
taking place to an appreciable extent.
Electrochemical studies of molten salts. II. Diffusion potentials for the binary systems PbBr2 + CsBr, PbBr2 + RbBr, and PbBr2 + KBr
Authors: Bloom H , Easteal AJ
Published: September 2010

Diffusion potentials have
been determined, as a function of temperature and composition, for liquid
junctions formed in the molten salt systems, PbBr2
+ CsBr, PbBr2 + RbBr, and PbBr2 + KBr. The results are interpreted to indicate the existence
of complex lead bromide species in these mixtures, particularly the ion PbBr-3.
The synthesis of 7,8-Dihydrobenzo[4,5]cyclohepta[1,2,3-de]naphthalene and a derivative of Cyclohepta[opqr]benzo[c]phenanthrene
Authors: Craig JT
Published: September 2010

7,8-Dihydrobenzo[4,5]cyclohepta[1,2,3-de]naphthalene
has been prepared, and attempts to dehydrogenate this are discussed. The
synthesis of a derivative of cyclohepta[opqr]benzo[c]phenanthrene
is also described.
The dipole moments and molar Kerr constants of beryllium complexes of certain Schiff bases
Authors: Green RW , Le FFvre RJW , Saxby JD
Published: September 2010

Five bis(N-alkylsalicylaldiminato)beryllium complexes have been
examined as solutes in benzene. When the alkyl groups are Me, Et, Prn, and Bun the moments and molar
Kerr constants are between 4.86 and 4.92 D and -1440x10-12 and
-1705x10-12 respectively. With the But derivative the
polarity is lower (4.20 D) and the mK less negative (-1260x10-12).

Such data are reconcilable with
tetrahedral coordination around the Be atom in the Me, Et, Prn,
and Bun cases, and with a slightly twisted configuration when the molecule
contains the more bulky Me3C groups.
Cassytha alkaloids. II. Alkaloids of Cassytha pubescens R. Br
Authors: Johns SR , Lamberton JA , Sioumis AA
Published: September 2010

Three aporphine alkaloids
isolated from Cassytha pubescens R.Br. have been
identified as nantenine, domesticine, and isoboldine, all of which were previously
known to occur in Nandina domestica,
and a fourth as laurelliptine, an alkaloid of Beilschmiedia
elliptica. One other aporphine alkaloid from C.
pubescens is new, namely (+)-1-hydroxy-2- methoxy-9,10-methylenedioxynoraporphine
(nor-domesticine).

A sixth and minor alkaloid from C.
pubescens, identified as sinoacutine, the (-)-enantiomer of salutaridine,
appears to be the first example of a morphine group alkaloid to be found in the
family Lauraceae.
Kinetics of the Decarboxylation of Acetoacetic acid
Authors: Hay RW , Bond MA
Published: September 2010

The decarboxylation of acetoacetic
acid CH3COCH2CO2H → CH3COCH3+CO2
and its anion have been studied in aqueous solution over a range of
temperature. Although the acid decomposes approximately 50 times faster than
the anion at 37�, the activation energy of the acid (23.7 kcal mole-1)
is comparable with that of the anion (22.9 kcal mole-1) and the
large difference in reactivity is due to an entropy effect. The significance of
these results is discussed and a comparison made with other β-keto acid
decarboxylations.
Geiparvarin: Proton magnetic resonance studies
Authors: Carman RM , Lahey FN , Macleod JK
Published: September 2010

Proton magnetic resonance
studies on geiparvarin herniarin (II), and the synthetic dihydrofuran (IV)
support the structure (I) for geiparvarin. The structure of the acid cleavage
product (III) of geiparvarin is confirmed by its p.m.r.
spectrum.
Comparative acidic cleavage experiments with methyl-substituted benzyl esters of amino acids
Authors: Stewart FHC
Published: September 2010

The action of
trifluoroacetic acid and hydrogen bromide in acetic acid, respectively, on the
benzyl, p-methylbenzyl, 2,4,6-trimethylbenzyl, and penta-methylbenzyl
esters of some amino acid derivatives has been investigated by thin-layer
chromatography. Methyl substitution greatly enhances the lability of the ester
groups. The possible bearing of the results on solid-phase peptide synthesis is
discussed.
A new monoterpenoid alkaloid (RW47) from Rauwolfia verticillata (Lour.) Bail. of Hong Kong
Authors: Arthur HR , Johns SR , Lamberton JA , Loo SN
Published: September 2010

A new monoterpenoid
alkaloid, isolated from Rauwolfia verticillata
(Lour.) Bail. of Hong Kong, has been shown to be related to the alkaloids of
the actinidine group and is considered to be (I).
Sequential polypeptides containing γ-Benzyl-L-glutamyl residues
Authors: Ledger R , Stewart FHC
Published: September 2010

Polypeptides with dipeptide
repeating units have been prepared from the corresponding dipeptide
p-nitrophenyl ester p-toluenesulphonates. Most of the
products contained γ-benzyl-L-glutamyl and related substituted benzyl
ester residues.
Activity coefficient assumptions in the determination of the association constant of thallium(I) chloride. III. Effects of other association reactions
Authors: Khoo KH , Panckhurst MH
Published: September 2010

Measurements are reported
of the solubility of thallium(I) chloride in aqueous solutions of sodium
acetate and thallium(I) perchlorate and in solutions of sodium chloride, barium
chloride, and sodium perchlorate in 16.7, 30, and 60 wt. % methanol-water mixtures.
The measurements in water are used to test the merits of two types of ionic
activity coefficient expression. It is shown that it is necessary to take
account of specific interactions between free ions and that this also allows
for small amounts of other association reactions in the same solution. The
possibility of allowing for subsidiary association without using specific
interaction coefficients is discussed, and it is concluded that this cannot be
done in a completely satisfactory way. Measurements in mixed solvents are used
to determine association parameters for the complex TlCl.
Polarographic and nuclear quadrupole resonance studies of some organic iodo compounds. I. Correlation of nuclear quadrupole resonance frequency and polarographic half-step potential
Authors: Cadwell RA , Hacobian S
Published: September 2010

Using the techniques of
d.c. polarography and nuclear quadrupole resonance spectroscopy the correlation
between the half-step reduction potential and the corresponding nuclear
quadrupole interaction frequency of a number of organic iodo
compounds is investigated. The expected trend of the half-step potentials of
the substituted iodobenzenes with the degree of interaction, by the substituent
groups, on the iodine atom is confirmed. The trend is such that positive or
negative deviations from the half-step potential of iodobenzene
are indicative of a corresponding decrease or increase in the electron density
on the iodine atom.
Complexes of cobalt(II) halides with 4-substituted pyridines
Authors: Graddon DP , Heng KB , Watton EC
Published: September 2010

Complexes have been
obtained from cobalt(11) chloride, bromide, iodide, and thiocyanate with eight
4-substituted pyridines, NC5H4R, where R = CH2C6H5,
p-CH2C,6H,4Cl, CH2OH,
Cl, Br, C02C4H9, COC6H5,
and CN, in order of decreasing basicity. Twenty-nine of the compounds prepared
are of the type CoX2B2,
thirteen of the type CoX2B4,
three CoX2B33 two CoX2B5, two CoX2B2(H2O)2,
and one CoX2B(CH3OH). The
stereochemistry of the cobalt atom has been assigned in each case on the basis
of magnetic properties and reflectance spectra. In all cases but one the cobalt
appears to exhibit octahedral or tetrahedral stereochemistry and to have the
high-spin configuration; diiodotris(p-chloropyridine)cobalt(11)
is probably an example of a low-spin
5-coordinate compound. The stereochemistry is largely determined by the
halogen, the preference for octahedral stereochemistry increasing in the order
I � Br < C1 � NCS. There is also a small effect due to the base, octahedral
stereochemistry being favoured by the weaker bases. The behaviour of the
compounds in nitrobenzene solution has also been studied.
The effect of doping on the non-stoicheiometry of zinc oxide
Authors: Norman VJ
Published: September 2010

Chemical methods previously
described have been applied, with minor modifications, to the analysis of the
non-stoicheiometry of polycrystalline zinc oxide
which had been doped with gallium or lithium by heating in air. It is shown
that, under these conditions, the methods provide a direct measure of electron
concentration, and of the concentration of the impurifying
element occupying substitutional positions in the
zinc oxide lattice. Under the specified conditions of doping, electron
concentrations ranged from 6.9 x 1018 electrons cm-3 for
samples doped with gallium to an electron deficiency of 2.6 x 1018
holes cm-3 for lithium-doped samples. The effect of doping on the
electrical conductivity is briefly shown. The methods provide a convenient and
accurate means of determining rates of substitutional
diffusion in zinc oxide. The diffusion coefficient of gallium at 950� was
calculated to be 4.7 x 10-15 cm2
sec-1.
Antimony 8-hydroxyquinolinates
Authors: Cardwell TJ , Nasouri FG , McConnell HH , Magee RJ
Published: September 2010

Precipitation from
homogeneous solution or by conventional means with 8-hydroxyquinoline in the
presence of tartaric acid has been successfully employed for the determination
of antimony. The complex produced corresponds to the formula SbOQ,2HQ. Antimony
cannot be determined in the absence of tartaric acid, as the resulting compound
SbQ3 is co-precipitated with antimony oxychloride. Thermo-gravimetric
and spectroscopic studies were also carried out on the precipitates obtained.
Structure of an isoindole pigment from the interaction of phenylmagnesium bromide and trans-o-Cyano-β-bromostyrene
Authors: Brown GM , Curtis RG , Davies W , Dopheide TAA , Hawthorne DG , Hlubucek JR , Holmes BM , Kefford JF , Osborne JL , Robertson AV , Slater EC
Published: September 2010

The action of heat on the
complex from phenylmagnesium bromide and

trans-o-cyano-β-bromostyrene gives some 1-phenylisoquinoline
and a crystalline, unstable, blue compound, in addition to much polymeric
material. Structure (IV), which bears a formal resemblance to half a phthalocyanine molecule, is proposed for the blue compound.
Oxide chlorides of osmium
Authors: Colton R , Farthing RH
Published: September 2010

The product obtained by the
reduction of osmium tetraoxide in hydrochloric acid
solution, followed by evaporation to dryness, has been shown to be p-oxo-hexachlorodiosmium(1V), Os2Ocl6.
Infrared, magnetic, and mass spectrometric evidence are presented to substantiate
this formulation. Salts of the p-oxo-decachloro-diosmate(1V)
ion are readily isolated from hydrochloric acid solutions of the oxide chloride.
Unsuccessful attempts were
made to repeat the preparation of the compound said to be p-oxo-octachlorodiosmium(v). Reduction of osmium tetraoxide
with thionyl chloride was shown to give osmium
tetrachloride.
Catalysis by hydrogen halides in the gas phase. XV. Trimethylacetic acid, isopropanol, and hydrogen bromide
Authors: Cross JTD , Stimson VR
Published: September 2010

Isopropanol decomposes to propene and
water in the presence of trimethyl-acetic acid and hydrogen bromide at 407� via
isopropyl trimethylacetate. This takes place by isopropanol reacting with an intermediate in the hydrogen
bromide catalysed decomposition of trimethylacetic
acid. The reaction is first order in each of the acids and first order in the
alcohol at low alcohol pressures and zero order at high pressures.
Substituent effects on the thermodynamic functions of ionization of metasubstituted anilinium ions
Authors: Bolton PD , Hall FM
Published: September 2010

Thermodynamic acidity
constants of the meta-methoxyanilinium, meta-

chloroanilinium, meta-bromoanilinium, and meta-iodoanilinium ions have been measured spectrophotometrically
over the temperature range 5-50� and those of the meta-nitroanilinium ion over the
temperature range 5-60�. The thermodynamic functions of ionization, ΔG25,
ΔH25, ΔS25, and ΔCp,25,
have also been calculated for each ion. For a series of seven meta-substituted anilinium
ions the acidity constants show close obedience to the Hammett equation over
the temperature range 10-50� with the reaction parameter p being a precise
linear function of 1/T. The same reaction series also shows a well-defined isoequilibrium relationship of negative slope.
Carbonyl halides of the Group VI transition metals. IX. Complexes with Bis(diphenylarsino)methane: Some further carbon monoxide carriers
Authors: Anker MW , Colton R , Tomkins IB
Published: September 2010

Complexes of the types MX2(CO)3(dam)2
and MX2(CO)2(dam)2 [M = Mo, W; X = Cl, Br; dam =
bis(diphenylarsino)methane] have been prepared and characterized. The compounds
are all non-electrolytes; in the tricarbonyls both of
the potentially bidentate arsenic ligands are in fact acting only as monodentates, but in the dicarbonyls
there is mixed coordination with one ligand monodentate and the other
bidentate. The dicarbonyl complexes
absorb carbon monoxide in solution at room temperature and pressure, a
metal-arsenic bond of the bidentate ligand is broken, and the corresponding
tricarbonyl compound is produced. The reaction is readily reversible; thus the
system is an example of a carbon monoxide carrier.
Polarographic and nuclear quadrupole resonance studies of some organic iodo compounds. II. The dependence of the half-step potential on the ionic character of the carbon-iodine bond
Authors: Caldwell RA , Hacobian S
Published: September 2010

Nuclear quadrupole coupling
constant data are utilized to determine the ionic character of the
carbon-iodine bond in a number of substituted iodobenzenes and related to the
half-step potential of the corresponding substituted iodobenzene.
A semi-empirical discussion
using the Kirkwood-Westheimer relation for the interaction
of poles in a continuous medium is given as the basis for such a relationship.
Surface tensions and densities of solutions of large organic ions in molten pyridinium chloride
Authors: Bloom.H . , Reinsborough VC
Published: September 2010

Surface tension and density
data obtained with cetyl and myristyl
cationic soaps dissolved in molten pyridinium chloride at 155� are interpreted
in terms of micelle formation. The critical micelle concentrations determined
by each method are in agreement at 0.060 molal for
the solute cetyldimethylbenzylammonium chloride.
Partial molar volumas for this same solute are
calculated and discussed in concepts similar to the
"hydrophobic hydration" theory of aqueous solutions.
Photochemical reactions of azo compounds. XVI. Reactions with acetyl chloride leading to Di-, Tri-, and Tetra-chloroazobenzenes
Authors: Lewis GE , Mayfield RJ
Published: September 2010

A previously reported
method for converting azobenzene into 4-chloroazobenzene (via N,N'-diacetyl-4-chlorohydrazobenzene)
has been extended to the preparation of di-, tri-, and tetra-chloroazobenzenes.
Electrode currents and concentrations for transfer by diffusion and chemical reaction
Authors: Johnson CHJ
Published: September 2010

In the present paper we
compute the time-dependent diffusion field around an electrode, which may be a
plane or a sphere of constant radius, for an electrochemical system in which a
single depolarizing species A through a rapid reversible electrode reaction
gives rise to a transitory species B which is converted into a stable species C
by a slow irreversible reaction solution. The mathematical solution method is such that by suitable
choice of variables it is possible to solve the plane and sphere problems in
one operation. The functions yielding concentrations and electrode currents are
obtained as definite integrals which are evaluated numerically. By appropriate choice of
weighting function the present results can be applied to the expanding sphere
problem (dropping mercury electrode). The results are consistent with the
spirit of the Ilkovic analysis. Numerical results for
planar and spherical electrodes are presented in graphical form.
Complexes of Bis(cyclopentadienyl)titanium(III) chloride with some bidentate ligands
Authors: Coutts RS , Wailes PC
Published: September 2010

Bis(cyclopentadienyl)titanium(111)
chloride (cp2TiCl) complexes with 1,l0-phenanthroline
(phen), 2,2?-dipyridyl (dipy),
o-phenylenediamine (phm),
and α-picolylamine (picam)
in anhydrous tetrahydrofuran to give cp2TiCl,1.5L
where L is the bidentate ligand. In air-free water all showed the conductivity
of 1 : 1 electrolytes, but were insoluble in the common organic solvents.
Ionization current measurements and the energy required to form an ion pair in γ-ray irradiated gases
Authors: Cooper R , Mooring R
Published: September 2010

Ionization current
measurements in cobalt-60 γ-ray irradiated gases have been used to
determine the average energy required to form an ion pair (W value) in a series of gases. Using well-established values of W
for six gases (H2, He, air, N2, Ar,
and C2H2), two methods of determining W from further
experimental data have been devised. Correlation of W with observed ionization
current data has been achieved using (a) a modified version of
the Bethe equation, and (b) available stopping
powers. W values for a number of
other gases have been determined by both treatments, and the results from each
method compared.
The absorption spectra of the anions of quinones and other acceptors in solution and as solids
Authors: Fulton A
Published: September 2010

The visible and
near-infrared spectra of the negative ion-radicals of electron acceptors were
studied. A linear relationship was found between the longest-wave-length π*π*
bands of the semi-p-benzoquinones and the electron affinities of these
molecules. The effect of the addition
of a single electron on the ππ* transitions
of p-fluoranil, p-bromanil,
and p-chloranil was also considered.
Electron capture by some molecules of biological significance and the determination of absolute electron affinities
Authors: Fulton A , Lyons LE , Morris GC
Published: September 2010

The electron capture method
was applied to protoporphyrin IX and meso- porphyrin
IX dimethyl esters, metal-free phthalocyanine,
chlorophyll, riboflavine, nicotinamide,
tetracene, and pentacene.
The energy quantities obtained correlated with calculated energies of the
lowest empty molecular orbitals of these molecules.
The influence of the solvent on the extraction of iron(III) from aqueous sulphate solutions by Di(3,5,5-trimethylhexyl)amine
Authors: Cattrall RW , West BO
Published: September 2010

The extraction of iron(111) from aqueous sulphate solutions by di(3,5,5-
trimethylhexy1)amrnonium sulphate has been examined using 14 solvents of differing
chemical types. The results are discussed in terms of the aggregation of the amine
sulphate in solution, the dielectric constant of the solvent, and interfacial tensions
between amine sulphate solutions in the solvents and water. An interfacial
mechanism for the extraction is proposed.
The hydrolysis of chloroform and carbon tetrachloride by anion-exchange resins
Authors: Ryan HF
Published: September 2010

Chloroform in acetone or
ethanol solvent was rapidly hydrolysed to carbon monoxide and formate by Amberlite XE-78 in the
OH-form. Hydroxyl sites on the resin were converted into chloride. The apparent
loss in capacity of the resin which occurs during the reaction cannot be wholly
accounted for by production of formate. The most
probable explanation for the phenomenon is the adsorption of carbon trichloride
anions at resin sites. Carbon tetrachloride in ketonic solvents also gave carbon monoxide and

formate in the presence of the OH-form of the resin, but in
alcohol or ether solvent carbon dioxide and phosgene were formed.
Molecular constants of Group V hydrides by Green's function analysis
Authors: Ramaswamy K , Swaminathan S
Published: September 2010

The evaluation of potential
energy constants, mean amplitudes of vibration, rotational distortion
constants, and Coriolis coupling constants for Group V hydrides was attempted
by the method of Green's function analysis. It is shown that these molecular constants
can be calculated without recourse to any specific force field. The values of
these molecular constants obtained by this method are, in general, in very good
agreement with those obtained by the usual normal coordinate analysis.
Studies of some octathiocyanate complexes of thorium(IV) and uranium(IV). I. Infrared spectra in the v(CN) region
Authors: Grey IE , Smith PW
Published: September 2010

Infrared spectra have been
recorded for compounds of formula A4IMIV(NCS)8,-
xH2O (M = Th, U; A = Cs, Rb, NH4) in the region 2200-265 cm-1. The band
splittings in the v(CN) region, both in solution and in the solid state, have
been examined in detail and compared with the number of active modes predicted
for eight-coordinate ions with D2d (dodecahedral), D4d (square-antiprism), and Oh
(cubic) symmetry. The results suggest that both the [Th(NCS)8]4-
and [U(NCS)8]4- complexes adopt the configuration of an
Archimedean antiprism in solution, but in the solid state the symmetry is
lowered to dodecahedral.
The alkaloids of Acronychia haplophylla
Authors: Lahey FN , McCamish M , McEwan T
Published: September 2010

Three alkaloids have been
extracted from the leaves of A. haplophylla. One is the known
4-hydroxy-2,3-dimethoxy-10-methylacridone. The other two are the new alkaloids
acrophylline, 9-(3-methylbut-2-enyl)-7- methoxyfuro[2,3b]quinol-4-one, and
acrophyllidine, 9-(3-hydroxy-3- methylbutyl)-7-methoxyfuro[2,3-b]quinol-4-one.
These structures have been determined and confirmed by synthesis of a reduction
product.
Transition metal complexes of substituted alkynes. IV. Some bridging alkynecobalt complexes
Authors: Dickson RS , Yawney DBW
Published: September 2010

Two new organocobalt
complexes, Co2(CO)4(CF3C2CF3)3
and Co2(CO)4(CF3C3H)2-
CF3C2CF3, have been isolated from the
appropriate reactions of hexafluorobut-2-yne with octacarbonyldicobalt and of 3,3,3- trifluoropropyne with
μ-hexafluorobut-2-yne-hexacarbonyldicobalt. The
probable structures of these compounds are discussed in light of their infrared
and nuclear magnetic resonance spectra. ��� The direct formation of complexes of the
type Co3(CO)9CCH2R
has been established in the reactions of several terminal alkynes, RC2H
(R = H, CF3, C6H5), with octacarbonyldicobalt.
The spectroscopic properties of the products so obtained are given.
Electrochemical studies of molten salts. IV. Electromotive forces of concentration cells with transference and diffusion potentials for PbCl2+KCl mixtures
Authors: Easteal AJ , Heron SJ
Published: September 2010

The e.m.f.'s
of concentration cells with transference containing PbCl2+KCl
molten mixtures have been measured as functions of temperature and electrolyte
composition, and compared with previously published data. Graphs of cell e.m.f.
against temperature are sets of intersecting straight lines, as are graphs of
cell e.m.f. against the negative logarithm of the mole fraction of PbCl2. ��� Diffusion potentials for junctions between
pure PbCl2 and PbCl2+KCl
mixtures have been evaluated, as functions of temperature and mixture
composition. ��� The interpretation of the results supports
the hypothesis of the existence of complex lead-chloro ionic species in the
electrolytes.
The system ABXYM in nuclear magnetic resonance spectroscopy. Analysis of 3,4-dehydroprolinamide spectra by ABXYM and ABCDE methods
Authors: Batterham TJ , Riggs NV , Robertson AV , Simpson WRJ
Published: September 2010

The wide range of deceptive
simplicities observed in spectra of 3,4- dehydro-prolinamide in different
solvents makes analysis extremely difficult. The power of an approach using
ABXYM tables combined with iterative computation is demonstrated to obtain accurate
parameters for spectra of saturated solutions in deutero-chloroform and
deuterium oxide. A detailed study of the effects of small changes in parameters
on the observed spectral patterns provides a satisfactory explanation for each
case of deceptive simplicity and, in particular, gives reasons for the added
simplicity of spectra measured at 100 Mc/s. A trans- homoallylic coupling
constant (J2,5) of 5.8 c/s was observed and a synergistic four-bond
coupling through the heteroatom is suggested to explain its magnitude. The
stereochemistry of pyrrolines and similar heterocycles is discussed in the
light of this large trans-coupling.
Elaeocarpus alkaloids. I. The structures of (±)-elaeocarpine, (±)-isoelaeocarpine, and (±)-isoelaeocarpicine, three new indolizidine alkaloids from Elaeocarpus polydactylus
Authors: Johns SR , Lamberton JA , Sioumis AA , Willing RI
Published: September 2010

Three new interrelated
alkaloids have been isolated from Elaeocarpus poly-dactylus Schltr. (family Elaeocarpaceae). Two of these alkaloids, (�)-elaeocarpine
(I) and (�)-isoelaeocarpine (II), are isomeric and the structure and complete
stereochemistry of (�)-elaeocarpine have been established from an X-ray crystal
structure analysis of (�)- elaeocarpine hydrobromide.1
From a detailed analysis of the spectroscopic properties of (�)-elaeocarpine
and (�)-isoelaeocarpine, and in particular of their 100-Mc/s n.m.r. spectra, it
has been shown that the alkaloids are epimeric at C7 and that (�)-isoelaeocarpine
has a cis ring junction at C7,C8, whereas (�)-elaeocarpine is known to have a
C7,C8 trans configuration. In methanolic sodium hydroxide solution
(�)-elaeocarpine and (�)-isoelaeocarpine are interconvertible.

(�)-Isoelaeocarpicine (VIa)
is closely related to (�)-elaeocarpine and (�)-iso-elaeocarpine,
and has been so named because the configuration at C7,C8 corresponds to that of
(�)-isoelaeocarpine. (+)- Isoelaeocarpicine is phenolic, differs from (�)-elaeocarpine
and (�)- isoelaeocarpine in molecular composition by the elements of water, and
is converted into a mixture of elaeocarpine and isoelaeocarpine by the action
of methanolic sodium hydroxide solution. Study of the 100-Mc/s n.m.r. spectrum
of (+)-isoelaeocarpicine has established the complete stereochemistry shown in
(VIa).
The structures indicated for the three
alkaloids (I), (II), and (VIa) depict relative
stereochemistry only and are not intended to imply a particular absolute
configuration.

Study of the reaction between (+)-isoelaeocarpicine
(VIa) and acetic anhydride shows that an O-acetyl
derivative (VIb) is formed rapidly, but that with
longer reaction periods the amide (VIIIa) is obtained.
The steric requirements of the borohydride reduction of (I) and (II) have been
studied, and it has been found that the n.m.r. spectra of solutions of the
alcohol (XIIa) in CD3CO2D or of
its hydro- chloride in CD3OD indicate an equilibrium between two deuteronated
forms of (XIIa), one of which is considered to have a
cis and the other a trans ring junction for the indolizidine ring.
A minor alkaloid, C17H21N3,
amounts to <1% of the total alkaloids, and a minor non-alkaloidal
constituent has been identified as 2- hydroxy-6-methylacetophenone.
4,5-Seco-4,6-cyclosteroids. IV. Physical properties and the conformation of ring A
Authors: Collins DJ , Hobbs JJ , Rawson RJ
Published: September 2010

Conformational analysis, together
with i.r., N.M.R., and o.r.d.
data, indicate preferred conformations of seven-membered ring A in a number of
4,5-seco-4,6-cyclosteroids.
A re-examination of gingerol, shogaol, and zingerone, the pungent principles of ginger (Zingiber officinale Roscoe)
Authors: Connell DW , Sutherland MD
Published: September 2010

The dried rhizomes of
ginger (Zingiber officinale Roscoe) yield, to acetone, a complex mixture of
substances including a series of S-(+)- gingerols (i.e. 1-(4?- hydroxy-3?-methoxyphenyl)-5-hydroxyalkan-3-ones)
with 10,12, and 14 carbon atom side-chains, essential oil, palmitic and other
fatty acids, and other unidentified substances. The substances, shogaol and
zingerone, described by Nomura as ginger constituents appear to be absent but
are formed by the action of alkalis or heat on gingerol or the oleoresin. The
gingerol with the 11-carbon side-chain, claimed by Lapworth, Pearson, and Royle
as the principal pungent substance in ginger, is also absent. Ginger oleoresin
may be qualitatively analysed by thin-layer chromatography on silica gel with
hexane-ether (1 : 1).
Normal coordinate analysis of diacetylene and dicyanoacetylene
Authors: Ramaswamy K , Spinivasan K
Published: September 2010

The potential energy
constants of diacetylene and dicyanoacetylene were obtained by the method of ?characteristic
set of valence coordinates? of Herranz and Castano. The values of the various
interaction force constants were determined without any assumptions regarding
force fields. The mean amplitudes of vibration for the various characteristic
bonds were calculated by Cyvin's method. It is shown that the conventional set
of symmetry coordinates, usually characterized by individual chromophores,
leads to abnormally large values for the force constants in the case of
dicyanoacetylene. Hence a different set of symmetry coordinates taking into
account the whole unit of CC bonds has to be chosen to get a reasonable set of
force constants.
Photochemistry of α-diketones. II. Some photo-oxidation reactions
Authors: Gream GE , Paice JC , Ramsay CCR
Published: September 2010

The photochemical behaviour
of 1,1,4,4-tetramethyl-2,3-dioxotetralin (I) in the presence of oxygen has been
thoroughly investigated in the solvents methanol and benzene. Products which
are formed as a result of the presence of oxygen include α,α?-o-phenylenediisobutyric
anhydride (II), α,α?-o-phenylenediisobutyric acid (III), the peroxy
acid lactone (XXI), the lactone (XXV), α-(o-isopropenyl)phenylisobutyric
acid (XXVII), and the half-ester methyl hydrogen α,α?-o- phenylenediisobutyrate
(XXVI). An attempt to prove that the reported preparation of the anhydride (II)
from (I) by the action of sodium ethoxide in ethanol-ether in the presence of
air was in fact a photochemical oxidation failed when it was found that no
anhydride could be isolated under the reported conditions. The major product
was 2-ethoxycarbonyl-2-hydroxy-1,1,3,3-tetramethylindane (XXXII, R = C2H5),
formed by a benzilic ester rearrangement. ��� A less thorough investigation of the
photo-oxidation of camphorquinone, benzil, 3,3,5,5-tetramethyl-1,2,dioxocyclopentane,
and phenanthrene-9,10-quinone is also reported. ��� A mechanism is suggested for the formation
of anhydrides by photo- oxidation of α-diketones. Studies with benzil and
dibenzoyl peroxide indicate that the intermediate formation of diacyl peroxides
cannot account for the production of acids (or diacids from cyclic α-
diketones) when α-diketones are photolytically oxidized.
The diterpenes of Dacrydium colensoi. VIII. Sandaracopimaradien-19-ol and 2α-Carboxycolensen-2β-ol
Authors: Grant PK , Huntrakul C , Robertson JM
Published: September 2010

The isolation and
characterization of two diterpenes from Dacrydium colensoi as
sandaracopimaradien-19-ol (I) and 2α-carboxycolensen-2β-ol (VI) is
reported. The structure of the acid has been confirmed by the synthesis of the
methyl ester from 2-oxomanoyl oxide. In addition, ferruginol and β-sitosterol
have been isolated from the extract.
Molecular susceptibility. The diamagnetic anisotropies of some polynuclear aromatic hydrocarbons
Authors: Le Fevre JW , Murthy DSN
Published: September 2010

Molar Cotton-Mouton
constants are reported for certain aromatic hydrocarbons as solutes at infinite
dilution in benzene or carbon tetrachloride. Relative anisotropies (i.e. the
ratio of the anisotropy in the diamagnetic susceptibility of the molecule concerned
to that of benzene) are calculated for these and other molecules for which data
have been recorded previously.1
Moulting hormones of insects and crustaceans: The synthesis of 22-deoxycrustecdysone
Authors: Galbraith MN , Horn DHS , Middleton EJ , Hackney RJ
Published: September 2010

A partial synthesis of the
title compound (III) has been accomplished from crustecdysone (I). Chromic acid
oxidation of crustecdysone afforded the ketone (VI) which was converted into
the corresponding acetonide silyl ether (IX). Alkylation of (IX) with the
Grignard reagent from (XI) and hydrolysis of the protecting groups afforded the
required compound (III). An alternative route which facilitates tritium
labelling afforded the same product. The biological activity and spectral
properties of the product are discussed.
Tumour inhibitory plants. Amides of Piper novae-hollandiae (Piperaceae)
Authors: Loder JW , Moorhouse A , Russell GB
Published: September 2010

A new amide, Δαβ-dihydropiperine
(I), has been isolated from the wood of Piper novae-hollandiae and synthesized.
Two amides, N-isobutyl-trans- 2,trans-4-octadienamide and
3,4-methylenedioxycinnamoylpiperidide, previously unreported from natural
sources but known from synthesis, were present as were five amides already
established as plant constituents, namely, N-isobutyl-trans-2,trans-4-decadienamide,
fagaramide, piperlonguminine, piperine, and an isomer of piperine, probably
chavicine, as well as the essential oil, dillapiole. Δαβ-and
Δβγ-Dihydro-piperlonguminine, (VIII) and (IX), and
Δβγ-dihydropiperine (III) were also synthesized.
Pyridopyridazines. II. Some reactions of Pyrido[2,3-d]- and Pyrido[3,4-d]-pyridazine
Authors: Paul DB , Rodda HJ
Published: September 2010

Pyridopyridazines have been oxidized under acid and alkaline
conditions and the sites of oxidation have been rationalized on the basis of
charge densities. Pyrido-[2,3-d]pyridazine has been brominated, aminated, and
made to react with hypo-chlorous acid and with
peracids. The positions of substitution and addition are discussed in relation
to calculated π-electron densities and bond lengths. Attention is drawn to
some unusual features of the N.M.R. spectra of 1,2-diazine N-oxides.
Pyridopyridazines. III. The synthesis and reactions of 5- and 8-Chloropyrido[2,3d]pyridazine
Authors: Paul DB , Rodda HJ
Published: September 2010

Pyrido[2,3-d]pyridazin-5-one
and -8-one have been synthesized by several methods and converted into 5- and
8-chloropyrido[2,3- d]pyridazine. These latter compounds were also prepared by
dehydrazination of the requisite chlorohydrazino- pyrido[2,3-d]pyridazines.
Some nucleophilic reactions of the chloropyrido[2,3-d]- pyridazines have been studied.
Cyclization of 5- and 8-hydrazino- and 5,8-dihydrazino-pyrido[2,3-d]pyridazine
with formic acid has led to the new heterocyclic compounds pyrido[2,3-d]- and
pyrido[3,2-d]-s- triazolo[4,3-d]pyridazine.
Some studies in inorganic complexes. XXV. Cobalt(II) and nickel(II) complexes of 2-Acetamidopyridine and 2-Aminomethyl-6-rnethylpyridine, and the cobalt(II) complex of 2-Methylpyridine-6-carboxylic acid
Authors: Shaw KH , Sutton GJ
Published: September 2010

Complexes of cobalt(II) and
nickel(II) with the ligands 2- acetamidopyridine (acpy) and
2-aminomethyl-6-methylpyridine (mepic) have been prepared and studied. They
included [Co(acpy)2X2], [Co(mepic)2X2],
[Ni(acpy)2X2], and [Ni-(mepic)2X2],
in which X is Cl, Br, I, or NCS; [Co(acpy)2(NO3)2],
[Co(mepic)2(NO3)2], [Ni(acpy)2(NO3)2],
[Ni(mepic)3NO3]NO3, [Co(acpy)3](ClO4)2,
[Co(mepic)3](ClO4)2, [Co(mepic)3](CoCl4),
[Ni(acpy)2(H2O)2](ClO4)2,
and [Ni(mepic)2(H2O)2](ClO4)2.
The inner complex of 2-methylpyridine-6- carboxylic acid [Co(mepiac)2,2H2O)]
was also isolated. In all cases, the magnetic properties, conductances,
reflectance spectra, absorption spectra, and infrared spectra are in agreement
with the concept that they are spin-free, six-coordinate octahedral complexes.
The substance [Ni(mepic)2NO3]NO3 contains both
bidentate and ionic nitrate.
E.S.R. of nitroxide radicals. II. Photosensitization of indoles, phenols, and thiols by a diphenylpyrazoline
Authors: Leaver IH , Ramsay GC
Published: September 2010

Indoles, phenols, and
thiols have been shown to undergo photosensitization by a diphenylpyrazoline in
non-polar solvents. The intermediate radicals produced have been trapped using
a nitrosoalkane scavenger, and the resulting nitroxide radicals examined in
situ by e.s.r. Fluorescence studies of these systems have shown that indoles
and phenols strongly quench the singlet excited state of the diphenyl-
pyrazoline, whereas thiols have no effect.
Synthesis of 6-Oxaellipticine, 5,11-Dimethylbenzofuro[2,3-g]isoquinoline, and related heterocycles
Authors: Elmes BC , Swan JM
Published: September 2010

6-Oxaellipticine, 5,11-dimethylbenzofuro[2,3-g]isoquinoline, has been synthesized
by a three-step procedure from 1,4-dimethyldibenzofuran utilizing a Pomeranz-Fritsch cyclization. The structures of the
intermediate 2-formyl-1,4-dimethyldibenzofuran and of 6-oxaellipticine were
confirmed by application of the nuclear Overhauser effect. The parent
heterocycle, benzofuro[2,3-g]isoquinoline, has been prepared similarly from
dibenzofuran, and this product converted successively into 2-methylbenzofuro[2,3-g]isoquinolinium iodide,
2-methyl-1,2,3,4- tetra-hydrobenzofuro[2,3-g]isoquinoline, and 2-methyl-1-oxo-1,2,3,4- tetrahydrobenzofuro-[2,3-g]isoquinoline.
��� Benzothieno[3,2-h]isoquinoline has been
prepared from 4- formyldibenzo-thiophen formed
together with the 2-formyl derivative by reaction of dibenzothiophen with
dichloromethyl methyl ether in the presence of stannic chloride.
The thermokinetics and integral thermal effects of the action of various liquids on some protein fibres
Authors: Balcerzyk E , Kozlowski W , Wlodarski G
Published: September 2010

The thermokinetics and
integral thermal effects of the action of methanol, ethanol, n-propanol,
n-butanol, and acetic acid on u~ool, silk, and casein fibre Wipolan have been
studied by a microcalorimetric method. ��� It has been found that the rate of penetration
depends first of all on the structure of accessible regions in protein fibres
and on the dimensions of the penetrant molecule and its ability to react with
functional groups of these fibres. By selecting a penetrant molecule of
suitable dimensions one may cause the penetration process to become a slow
phenomenon, being a characteristic for the structure of accessible regions in
the given fibre. Such penetrant liquids for protein fibres are ethanol and
acetic acid. �� It has been shown that the accessible phase
in protein fibres has a discontinuous structure within the spacing of
structural elements in the intermicrofibrillar and intermolecular regions.
The effect of thiourea and formaldehyde treatment on the chemical analyses of wool. I. Tryptophan, thiol, and disulphide analyses
Authors: Gruen LC , Nicholls PW
Published: September 2010

Conventional chemical
analyses for tryptophan, thiol, and disulphide give erroneous results when
applied to wool that has been treated with thiourea and form-aldehyde. This
work presents data on such analyses and discusses the origins of the interference.
Dihydroxyanthraquinone complexes of zirconium
Authors: Florence TM , Farrar YJ , Zittel HE
Published: September 2010

The nature of the zirconium
complexes of alizarin red S (1,2-dihydroxy- anthraquinone-3-sulphonate),
alizarin (1,2-dihydroxyanthraquinone), and hystazarin
(2,3-dihydroxyanthraquinone) were studied using
spectrophotometric, kinetic, and voltammetric techniques. In HClO4- NaClO4,
75% methanol media, these compounds form 1 : 1 complexes with zirconium. The
equilibrium constants, KC, for the reaction of zirconium with
alizarin red S, alizarin, and hystazarin were found to be 2.8 x 105,
3.0 x 103, and 6.9 x 102, respectively, at 25� and μ
= 1.0M. The concentration acid dissociation constants, pKca,
for the dihydroxyanthraquinones in 75% methanol were
determined as: alizarin red S 6.71 and 11.35; alizarin 7.31 and 11.84;
hystazarin 7.57 and 11.40; at 25� and μ 1.0M. Zirconium reacts slowly with
alizarin red S and alizarin, and mainly via the hydrolysed Zr(OH)22+
species, whereas the reaction with hystazarin is rapid. Rate constants were
determined for the first two reactions. The zirconium-alizarin red S complex includes
two coordinated hydroxyl groups, the alizarin complex one, and the hystazarin
complex contains none. It is suggested that these coordinated hydroxyl groups
hydrogen-bond to the sulphonate and/or quinone groups and enhance both the
stability and colour of the zirconium complexes.
Thermodynamics of chelation. II. Iron(II) and zinc(II) complexes of 6-Methylpyridine-2-aldehyde 2'-pyridylhydrazone
Authors: Green RW , Goodwin WG
Published: September 2010

6-Methylpyridine-2-aldehyde
2?-pyridylhydrazone is a stronger base but weaker ligand than its parent,
paphy. Equilibrium constants are reported for seven temperatures from 5� to 60�
and over a range of ionic strength. The properties of the ligand are discussed
in terms of the derived enthalpies and entropies of reaction.
Studies using radioisotopes. II. Hydroxylation-induced migration of tritium during the biosynthesis of furoquinoline alkaloids
Authors: Hall CR , Prager RH
Published: September 2010

[4-T]Anthranilic acid has
been synthesized and administered to Acronychia baueri. The furoquinoline alkaloids skimmianine (I) and
acronidine (II) have considerable residual radioactivity, but acronycidine (IV)
is only feebly radioactive. A partly specific ?N.I.H. shift? is postulated and
its implication to the order of introduction of hydroxyl groups in vivo is
discussed.