bluuebunny/crossref_metadata_2025 huggingface dataset:
The reaction of 1-Fluoro-2,4-dinitrobenzene with some NH-Heterocyclic compounds
Authors: Wilshire JFK
Published: September 2010

I-Fluoro-2,4-dinitrobenzene
reacts with a wide variety of NH- heteroaromatic compounds to give N-2,4-dinitrophenyl
derivatives. The proton magnetic resonance spectra of these derivatives are
discussed. With some indoles (and pyrene), 1-fluoro-2,4-dinitrobenzene forms
stable charge-transfer complexes.
Usaramine, a new pyrrolizidine alkaloid from Crotalaria usaarmoensis E. G. Baker
Authors: Culvenor CCJ , Smith LW
Published: September 2010

The major alkaloid,
usaramine, of the seed of C. usaramoensis E. G.
Baker, is shown to be the geometric isomer of retrorsine; i.e. an ester of
retronecine with retronecic acid. Other alkaloids in the seed are integerrimine,
traces of senecionine and retrorsine, and two unidentified non-ester bases. The
previously reported usaramoensine1 was not
detected and is considered to be a mixture.
Kinetic medium effects. III. Solvent effects on A1 and A2 Hydrolyses in water-dimethyl sulphoxide mixtures
Authors: Cox BG , McTigue PT
Published: September 2010

The relative rates of the
concurrent A1 and A2 hydrolyses of t-butyl acetate have been measured as a
function of solvent composition in water-dimethyl sulphoxide (DMSO) mixtures. A
large difference in solvent effect is observed, which correlates well with observed
solvent effects on ethyl acetate (A2) and acetal (Al) hydrolyses in the same
solvent system. Activity coefficients have been measured for t-butyl acetate,
ethyl acetate, and acetal in various water-DMSO mixtures.
Some studies in inorganic complexes. XXI. Indium(III) nitrogen chelates
Authors: Sutton GJ
Published: September 2010

The following complexes
have been described for the first time:����������� [InX2
dimphen2]X, [InX2
amq2]X, and [InX2
mamq2]X;

where dimphen is
2,9-dimethyl-1,10-phenanthroline, amq is 8- aminoquinoline,
mamq is 2-methyl-8-aminoquinoline, and X is Cl, Br, I. The complexes behaved as uni-univalent
electrolytes in N,N?- dimethylformamide. Conductances were measured of
complexes of 2- acetamidopyridine (prepared for the first time),
1,10-phenanthroline, 2,2?-bipyridyl, 5-nitro-1,10-phenanthroline, and 2,2?,2?-terpyridyl;
i.e. [In acpy3]X3, [In phen3]X3, [In bipy3]X3,
[In nitphen3]X3, and [In terpy2]X3 respectively. The results
of these measurements were much less than the expected values and some degree
of halide bonding is indicated, particularly in the case of the iodide
complexes.
Formation of bidentate metal chelates from some related pyridine compounds
Authors: Black DSC
Published: September 2010

2,2?-Dipyridylamine (dpa), 2-pyridyl-2-thiazolylamine (pta),
2,2?- dipyridyl sulphide (dps), 2,2?-dipyridyl
sulphone (dpso), and 2,2?- dipyridylmethane (dpm) have been shown to function as bidentate chelating
agents with various metal ions. A qualitative consideration of their metal
complexes establishes the following stability sequence: dpa
≈ pta > dps > dpm > dpso.
Charge localization and the electron-impact fragmentation of carbonyl compounds
Authors: Occolowitz JL
Published: September 2010

Ionization and appearance
potential measurements on aliphatic and ω- phenyl carbonyl compounds show
that electron-impact fragmentation of these compounds α and β to the
carbonyl group resulting in charge retention on the hydrocarbon fragment can
occur without ionization of the carbonyl group.

Structures are assigned to ionic and
neutral fragments on the basis of their enthalpies, and evidence is presented
favouring the elimination of the neutral enol forms of acetone and acetaldehyde
in the hydrogen-rearranged β fission of ketones and aldehydes.
Magnetic properties and structure of some copper(II) complexes of pyridine and quinoline N-oxides
Authors: Gruber SJ , Harris CM , Kokot E , Lenzer SL , Lockyer TN , Sinn E
Published: September 2010

The magnetism of
various copper(II) complexes of pyridine
and quinoline N-oxides1 has been further investigated.
The compounds Cu(C5H5NO)nX2
(where n = 4 or 6, X = ClO4; n = 2, X =
Cl, Br, NCS; n = 1, X = Cl, Br, CH3COO)
and Cu(C9H7NO)nX2
where n = 4, X = ClO4; n = 2, X = Cl, Br, NO3; n = 1, X = Cl,
Br, CH3COO) have been studied. The variation of the magnetic
susceptibilities of most of these compounds is reported over a temperature
range.

The variation of the magnetic
susceptibility with temperature for the weakly paramagnetic complex Cu(C5H5NO)Cl2 is discussed in terms of the binuclear
oxygen-bridged structure previously postulated.1
The compound exhibits anti-ferromagnetic interaction between pairs of copper(II)
atoms with a singlet-triplet separation of 2.1 kcal/mole. The compounds Cu(C5H5NO)2Cl2, Cu(C5H5NO)Br2, and Cu(C9H7NO)X2
(X = Cl, Br) are more weakly paramagnetic due to a
larger singlet-triplet separation. The compound Cu(C5H5NO)2Br2 possesses a higher paramagnetic
susceptibility than those of the previous compounds, and its magnetic
properties are consistent with a dimeric structure involving a singlet- triplet
separation of 0.7 kcal/mole. The copper(II) acetate adducts, Cu(CH3COO)2,L
(L = C5H5NO or C9H7NO), possess
very similar magnetic properties to binuclear copper(II) acetate monohydrate
and presumably possess a similar structure, with the N-oxides replacing the
water molecules. These compounds exhibit singlet-triplet energies of c. 1
kcal/mole similar to values reported for a large number of copper(II)
alkanoates.

The compounds Cu(C5H5NO)2(NCS)2,
Cu(C5H5NO)4(ClO4)2,
Cu(C5H5NO)6- (ClO4)2,
Cu(C9H7NO)2X2 (X = Cl, Br, NO3), all obey the Curie-Weiss law and
possess mean magnetic moments of 1.89, 1.80, 1.93, 1.88, 1.96, and 1.88 B.M.
(corrected for θ values of -12, -7, -8, + -4, and -16�) respectively.
Octahedral cobalt(III) complexes in dipolar aprotic solvents. XI. Anation of cis-chlorodimethylformamidebisethylenediaminecobalt(III) by bromide ion, and solvolysis and isomerization of cis-and trans-bromochlorobisethylenediaminecobalt(III) ions in anhydrous N,N-dimethylformamide
Authors: Lantzke IR , Watts DW
Published: September 2010

The anation of the
cis-chlorodimethylformamidebisethylenediaminecobalt(III) ion (cis- [CoCl(DMF)
en2]2+) by bromide ion in N,N-dimethylformamide (DMF) has
been studied. The reaction has an SNIIP1 mechanism, and
when due allowance is made for ion association its activation parameters
closely parallel those of other SNIIP anation reactions in DMF.

The solvolysis and isomerization of the
dichlorobisethylenediaminecobalt(III) ions (cis- and trans-[CoCl2 en2]+)
and the bromochlorobisethylenediaminecobalt(III) ions (cis- and trans- CoBrCl
en2]+) in DMF have been examined over a range of anion
concentration. In all cases solvolysis reactions are important, although direct
isomerization appears to become an important path for the reaction of the trans
complexes at high anion concentrations. Solvolysis of the cis-[CoCl2
en2]+ ion involves an SN2 mechanism.1 The
cis-[CoBrClen2]+, trans-[CoCl2 en2]+,
and trans-[CoBrCl en2]+ ions all react by an SN1
mechanism.
Naphtho[1,8-bc]thiophens. II. Mass spectrometry
Authors: Hawthone DG , Porter QN
Published: September 2010

II.* MASS SPECTROMETRY By D. G. HAWTHORN,E~$ and
Q. N. PORTER^ [Manzlscript received March
6, 19671 The high-resolution mass
spectra of some derivatives of naphtho[l,S-be]- thiophen have been
analysed. The base peak in the spectra is usually the naphtho- [1,8-bclthienylium cation
(mle 171) or one of its substitution products; this emphasizes the stability of
this species. Structures are suggested for most of the other ions observed in the
spectra. INTRODUUTION In Part I, which dealt with
the synthesis of naphtho[l,8-bclthiophen derivatives, the mass spectra of the
2-methyl-2H- (I; R = CH,) and 2-phenyl-2H- (I; R = Ph) compounds were briefly
described. It was suggested that in each case the cleavage shown gave the ion of mle
171, for which the naphthothienylium cation structure ac was proposed. (1) ac; m/e 171 In this paper we present a
complete analysis of the spectra of these compounds, and of some related
naphtho[l,8-bclthiophen derivatives. For reasons outlined in
Part I of this series, it is not possible to write structures for fragment ions from
aromatic and heteroaromatic molecules with the confidence with which this can be done
for many less-aromatic systems. In writing ionic structures to formalize the
observed spectra, the following principles have been used: (i) Where the formation of
an odd-electron system is involved, the ion is, if possible, written as a
radical cation derivable from an aromatic system. There is * Part I, Aust. J. Chem.,
1966, 19, 1909. t Department of Organic
Chemistry, University of Melbourne, Vic. 3052. $ Present Address: Division
of Applied Mineralogy, CSIRO Chemical Research Labora- tories, Melbourne, Vic.
3001. Aust. J. Chem., 1968, 21,
171-83
Third virial coefficients of mixtures of gases
Authors: McHenry JT
Published: September 2010

For gases whose molecules
are not greatly different in size and have spherical or almost spherical fields
of force and whose third virial coefficients are describable by the principle
of corresponding states, it is shown that, with the help of this principle and
within the present rather large limits of experimental error, the following
combining rules :

(see article for formula)'
Spin-spin coupling between protons bonded to sp2 and sp3 hybridized benzylic carbon atoms and ring protons
Authors: Newsoroff GP , Sternhell S
Published: September 2010

Deviations from symmetry in
inherently symmetrical N.M.R. spectra were used to study long-range spin-spin
coupling between benzylic protons and ring protons. With both sp2 and sp3
hybridized benzylic carbon atoms, maximum coupling to the ortho ring protons
appears to be associated with out-of-plane conformations of the benzylic proton
and that to the meta ring protons
with in-plane conformations.
Benzo[c]cinnoline derivatives. II. Reactions of Benzo[c]cinnolines with lithium dialkylaniides
Authors: Lewis GE , Reiss JA
Published: September 2010

2-Chlorobenzo[c]cinnoline
has been found to yield 4-dimethylaminobenzo[c]-cinnoline
and 2,4,7-tris(dimethylamino)benzo[c]cinnoline on
reaction with lithium

dimethylamide. The same products are formed (although in a
different ratio) from benzo[c]cinnoline and lithium dimethylamide.
4-Dimethylaminobenzo[c]cinnoline gives the
2,4,7-tris(dimethylamino) compound in low yield with
lithium dimethyl-amide; but 2-dimethylaminobenzo [c]cinnoline
appears to be completely unreactive. 4-Diethylaminobenzo[c]cinnoline
is formed in the interaction of benzo[c]cinnoline and lithium diethylamide.
Cobalt(II) complexes of o-hydroxyaryl aldehydes and ketones
Authors: Graddon DP , Mockler GM
Published: September 2010

Cobalt(11) complexes of the
types CoL2, CoL2B2 have been prepared, where LH is an o-hydroxyaryl
aldehyde or ketone and B = water or 4-methylpyridine. The compounds CoL2B2
have magnetic and spectroscopic properties typical of octahedral cobalt(11)
complexes. The solid complexes CoL2 have μeff
4.7-5.0 and spectra typical of octahedral cobalt(11). They are soluble and
monomeric in toluene, and these solutions also have spectra typical of
octahedral cobalt(11) and quite distinct from those of
tetrahedral cobalt(11) complexes. It is concluded that these monomeric,
4-coordinate species are probably examples of high-spin square-planar
cobalt(11) complexes, the planar structure being stabilized by dπ� → pπ back-coordination
from the metal atom to the anti-bonding orbitals of a localized C=O double
bond.
Aluminium chloride catalysed reaction of phosphorus(III) halides and carbonyl compounds. II. Scope of the reaction
Authors: Freeman KL , Gallagher MJ
Published: September 2010

No abstract available.
Covalent bond refractions and the Periodic Table. IV. Bonds to oxygen
Authors: Christopher PM , Patterson TL
Published: September 2010

The empirical equation, P =
aRn+b, where P is the parachor,
R the

Lorentz-Lorenz refraction, and a, b, and n are constants,
has been applied in the present instance to the calculation of R for single
covalent bonds between the elements of Groups IVB-VIIB and oxygen.
Catalysis by hydrogen halides in the gas phase. XIX. 2,3-Dimethylbutan-2-ol and hydrogen bromide
Authors: Johnson RL , Stimson VR
Published: September 2010

The gas-phase decomposition
of 2,3-dimethylbutan-2-ol into 2,3-dimethylbut-1-ene, 2,3-dimethylbut-2-ene,
and water, catalysed by hydrogen bromide at 303-400�, is described. The rate is
first-order in each reactant and the Arrhenius
equation

k2 = 1011.88 exp(-26490/RT) sec-l ml
mole-1

is followed. The olefins
appear to be in their equilibrium proportions. The effects of substitutions in
the alcohol at Cα and Cβ on the rate are discussed.
The chemistry of the Euphorbiaceae. XXI. Compounds from Beyeria brevifolia: (15S)-15,16-Dihydroxy-3,4-seco-enantio-pimara-4(18),7-dien-3-oic acid
Authors: Chow PW , Jefferies PR
Published: September 2010

.The isolation of the title acid (I) together with a new flavone and known
diterpenes of the beyerane and kaurane series is described. The structure (I) assigned
to the new acid rests mainly on its conversion into 3,4-secobeyerane, which was
partly synthesized. The configuration of C 15 was assigned on the basis of a method
due to Horeau.
The structure (XXX) of the new flavone was determined by degradation of
the triethyl ether.
Hydroxamic acids. I. The oxidation of hydroxamic acids and their O-alkyl derivatives
Authors: Rowe JE , Ward AD
Published: September 2010

The generality of the
formation of an N,O-diacylhydroxylamine from the oxidation of hydroxamic acids in an inert solvent is confirmed for an
extended range of oxidizing agents. Oxidation of o-alkylhydroxamic
acids with a variety of oxidizing agents yields an ester and small amounts of
the corresponding carboxylic acid. No evidence was obtained for an oxidative
intramolecular cyclization of an O-alkyl-hydroxamic
acid, in cases where this was possible, either in the presence or absence of
ultraviolet irradiation.
Complexes of Di-2-pyridyl ketone. I. Complexes of first-row transition elements in normal oxidation states
Authors: Feller MC , Robson R
Published: September 2010

All the complexes of di-2-pyridyl ketone (DPK) described appear to involve
N,N-chelation of the ligand. In CU(DPK)2SO4,2H2O
the water molecules are added across the ketone groups yielding gem-dihydroxy functions. Several previously reported solvated
DPK-cupric complexes which were assigned N,O-chelated structures probably have
analogous N,N-chelated structures with solvent molecules (H2O or
alcohols) added across the ketone group. The compounds M(DPK)2Cl2 (M = MnII,
FeII, CoII,
NiII) are tentatively assigned cis-octahedral structures, and a number
of mono- and bis-DPK-cupric complexes appear to have the common tetragonal or
square-planar geometries. The compounds of stoicheiometry
Co(DPK)2(OH)2Cl,�H2O and
CO(DPK)2(OH)2NO3, prepared from the corresponding
cobalt(11) salts, are cobalt(111) derivatives in which one or both of the DPK
units is reduced and probably acts as a tridentate ligand.
Transition metal complexes of diethyl Cyclopentanone-2,5-diglyoxylate
Authors: Graddon DP , Townsend IT
Published: September 2010

Diethyl cyclopentanone-2,5-diglyoxylate
(ecgH2; IV) forms complexes of the type M(ecg)Bn with divalent transition metals, where M
= Mn, Fe, Co, Ni, Cu, Zn; B = H2O or a
heterocyclic base, and n = 1 (when M = Cu) or n = 2 (M = others). All complexes
have the high-spin configuration. Infrared spectra show the presence of chelate
β-diketone rings and free carbonyl groups. Visible and near-infrared
spectra support octahedral stereochemistry for the nickel(II) and cobalt(II)
complexes. Molecular weights show the complexes to be dimeric. These results
are consistent with an oxygen-bridged structure, M2L2B2n,
in which base molecules are added above and below a planar M2L2
unit (VI).
The infrared and Raman spectra of phenyl acetate, phenyl-d5 acetate, and phenyl acetate-d3
Authors: Lee H , Wilmshurst JK
Published: September 2010

The infrared spectra of
phenyl acetate, phenyl-d5 acetate, and phenyl acetate-d3
as solutions in carbon tetrachloride or carbon disulphide have been recorded in
the 4000-100 cm-1 region together with the Raman spectra of the pure
liquids. The data are consistent with the assumption of a single rotational
isomer and support the previous1
interpretation of the complex carbonyl region observed in the phenolic acetates
as arising from a single fundamental in Fermi resonance with one or more combination
tones.
Photochemical rearrangement of aromatic ethers
Authors: Kelly DP , Pinhey JT , Rigby RDG
Published: September 2010

The irradiation of various
types of aromatic ethers with ultraviolet light has been shown to yield o- and
p-substituted phenols, resulting from C-O bond fission followed by
recombination of the two fragments. Also formed in these photolyses was the
parent phenol, produced presumably by abstraction of hydrogen from the solvent
by the aryloxy fragment. The ethers investigated were aryloxyacetic acids,1 allyl aryl ethers,2
benzyl phenyl ether, and diphenyl ether. ��� Mixture experiments have shown that for both
the aryloxyacetic acids and allyl aryl ethers the rearrangement is
intramolecular and most probably proceeds by formation of a radical-pair
enclosed in a solvent cage.
Insect moulting hormones: Crustecdysone (20-hydroxyecdysone) from Podocarpus elatus
Authors: Galbraith MN , Horn DHS
Published: September 2010

The insect moulting hormone
crustecdysone has been isolated from the Australian brown pine, Podocarpus elatus R.Br., and detected in a number of other Podocarpus
species from various parts of the world. A series of acetates and acetonides of
crustecdysone has been prepared, and the mass and nuclear magnetic resonance
spectra of these compounds analysed. A simple micro method of measuring the
rate of acetylation of hydroxy groups in steroids has been developed to
determine the steric environment of these groups.
Chemistry of the Podocarpaceae. XIX. Oxidation of some Podocarpa-8,11,13-trien-19-oic acid derivatives with lead tetraacetate
Authors: Bennett CR , Cambie RC , Denny WA
Published: September 2010

A pathway involving the γ,δ-unsaturated acid (XIV) is suggested for the
formation of lactones (IX) and (XII) from the oxidation of 12-
methoxypodocarpa-8,11,13-trien-19-oic acid (I) with
lead tetraacetate. Support for this suggestion has been obtained from an
examination of the products from lead tetraacetate oxidations of
12-methoxypodocarpa- 6,8,11,13-tetraen-19-oic acid
(XIV), methyl 12-methoxy-podocarpa- 8,11,13-trien-19-oate (II), methyl
12-methoxypodocarpa-6,8,11,13- tetraen-19-oate (XV),
12-methoxypodocarpa-8,11,13-trien-19-oic acid
(XVIII), methyl 12-hydroxypodocarpa-8,11,13-trien-19-oate (III), methyl
12-acetoxypodocarpa-8,11,13-trien-19-oate (IV), 7-acetoxy-12- methoxypodocarpa-6,8,11,13-tetraen-19-oic acid (XVI), and methyl 7- acetoxy-12-methoxypodocarpa-6,8,11,13-tetraen-19-oate (XVII). ��� Evidence is presented confirming the
assignment of a 7α- configuration for the acetoxy group of the acetoxy
lactone (IX), and the preparation of some bromo 7-oxo-
and 6,7,19-hydroxy derivatives of 12-methoxypodocarpa-8,11,13-trien-19-oic acid (I) is described.
Structure of donor-acceptor complexes. X. Complexes of cyanoacetamide with Lewis acids
Authors: Paul RC , Chadha SL
Published: September 2010

Complexes of cyanoacetamide
with aluminium chloride and bromide, anti- mony(V)
chloride, boron(III) bromide, tin(IV) chloride and bromide, titanium(IV) chloride
and bromide, and zirconium(IV) chloride have been prepared. The molar
conductances of the complexes in nitrobenzene indicate their non-ionic nature.
The infrared spectra indicate bonding of the metal halides to the carbonyl
oxygen atom of the ligand. Metal- to-oxygen bonding also gets support from the
far-infrared spectral data.
Electrodeposition of zirconium diboride from oxides dissolved in fused salts
Authors: Anthony KE , Welch BJ
Published: September 2010

Zirconium diboride has been
cathodically electrodeposited from ZrO2
and B2O3 dissolved in an equimolar mixture of K2ZrF6+KBF4 at 600�. The
deposition process is controlled by the concentration of B2O3
in the molten salt solution, and at higher current densities zirconium is co- deposited.
Carbon dioxide is evolved simultaneously from a graphite anode.
Studies of metal halides. III. Far-infrared spectra of chromium(III) and molybdenum(III) complex halides of formula A3M2X9 and A3MX6
Authors: Grey IE , Smith PW
Published: September 2010

Far-infrared spectra are
reported for compounds of formula A3M2X9, with
M = Cr, Mo; X = Cl, Br; A = univalent cations, for
the region 400-200 cm

-1. Assignments for metal-terminal halogen and
metal-bridging halogen stretching vibrations in the binuclear anion are
proposed. Data on several related mono-nuclear hexahalo complexes are included
for comparison. An explanation is offered for differences in the spectral
features of the series of compounds in terms of distortions of the binuclear
anion which arise from cation-anion interaction in the crystal lattice.
Reactivity of transition metal fluorides. VII. Reactions of the tetrafluoride, pentafluoride, and intermediate fluorides of uranium
Authors: O'Donnell TA , Wilson PW
Published: September 2010

Following similar,
previously reported studies of reactions of uranium hexafluoride, selected
oxidation-reduction and halogen-exchange reactions of the tetra- fluoride,
pentafluoride, and intermediate fluorides of uranium have been investigated.
Studies in relation to biosynthesis. XL. Some aspects of the chemistry of o-isopentenylphenols and related compouncls
Authors: Birch AJ , Maung M , Pelter A
Published: September 2010

Several
2,2-dimethylchromene derivatives, including the natural flavonoids scandenin
and lonchocarpic acid, have been reduced by lithium in ammonia to
o-isopentenylphenols. Several hydroxyisopropyldihydrobenzofurans
can similarly be reduced, and one was converted by reaction with
N-bromosuccinimide into a benzofuran derivative lacking the isopropyl group.
Alkylations of catechol and aesculetin with isoprene dibromide were examined,
and in the latter case resulted in what is probably (�)-obliquin.
The structures of canescin-A and -B
Authors: Birch AJ , Birkinshaw JH , Chaplen P , Mo L , Manchanda AH , Pelter A , Riano-Martin M
Published: September 2010

Canescin from Aspergillus malignus has the
gross structure (VIII). It consists in fact of a mixture of the stereoisomers
(XI) (canescin-A) and (X) (canescin-B). The structure is established by
reactions and by spectra.
The synthesis and properties of annulene polyoxides
Authors: Elix JA
Published: September 2010

A convenient synthesis of
the higher annulene polyoxides is described. Sucrose was converted into
5-chloromethylfurfural which on reaction with triphenylphosphine gave the
corresponding phosphonium salt. Treatment of this salt with lithium ethoxide
accomplished a self-Wittig condensation and cyclic products isolated included
[18]annulene trioxide, two isomers of [24]annulene tetroxide, two isomers of
[30]annulene pentoxide, and an isomer of [36]annulene hexoxide. The properties
of these compounds are discussed in relation to their aromaticity.
Alkaloids of Schelhammera pedunculata (Liliaceae). II. Reactions of schelhammeridine
Authors: Johns SR , Lamberton JA , Sioumis AA , Suares H
Published: September 2010

Catalytic hydrogenation of
schelhammeridine (I) in acetic acid solution gives demethoxydihydroschelhammeridine
(II), 1,2,6α,7- tetrahydroschelhammeridine (III), dihydroschelhammeridine
(IV), and a tetrahydro derivative (V), the formation of which involves cleavage
of the C5-N9 bond. The major product from heating schelhammeridine with 10%
aqueous hydrochloric acid is the alcohol (VIIa) with the configuration at C 3
opposite to that in schelhammeridine. Other products are the alcohol (IX) and
two amino alcohols (Xa) and (XIIa) which have a diphenyl ring system formed by
the aromatization of ring A. The compounds (Xa) and (XIIa) have been shown to
be diastereoisomers with the same absolute configuration for the dissymmetric
diphenyl system, but the opposite configuration at C 7, and they have been
characterized as N-acetyl derivatives (Xb) and (XIIb) which have been assigned
the respective configurations shown in (XX) and (XVIII). On heating with acetic
anhydride, schelhammeridine is converted into the N,O-diacetyl compound (XVa)
which on hydrolysis affords (XVb), the optical antipode of (Xb). All three
stereo-isomeric N-acetylamides (Xb), (XIIb), and (XVb), are oxidized to the
same optically inactive ketone (XI). A mechanism for the acetic anhydride
reaction that explains the formation of only a single isomer is discussed, and
it has been shown that the formation of (XVa), enantiomeric with (Xc), in this
reaction necessarily involves inversion of the configuration of the diphenyl
system in the first-formed product, which must be the O-acetyl derivative of
(XVIII). It is concluded that amide alcohols (XVIII) and (XX) retain the
configuration for the diphenyl system that would be predicted from the known
absolute configuration of schelhammeridine, but that the initially formed O-acetyl
derivative of (XVIII) obtained in the reaction with acetic anhydride is
converted quantitatively at the temperature of the reaction mixture into the O-acetyl
derivative of (XXI) by inversion of the diphenyl configuration.
Organophosphorus compounds. VIII. Diphenylphosphinothioic acid derivatives as reagents for proteins
Authors: Spence RA , Swan JM , Wright SHB
Published: September 2010

Esters and other
derivatives of diphenylphosphinothioic acids are examined as potential agents
for the radioactive labelling of immunoglobulins and other proteins. Syntheses,
model reactions with amines, and mass spectra of the organo-phosphorus
compounds are discussed. The labelling of immunoglobulins by reaction with [32P]diphenylphosphinothioic
chloride, with [32P]diphenylphosphinothioic isothiocyanate, and with
[32P]diphenylphosphinodithioic acid in the presence of condensing
agents such as dimethylcyanamide and carbodiimides is reported.
Vibration-spectral and structural comparison of the 4-aminopyridine cation with the 4-hydroxypyridinium ion and 4-pyridone. The protio parent ions, N- and C-deuterated, and N-methylated ions. Relevant N.M.R. spectral studies
Authors: Batts BD , Spinner E
Published: September 2010

Infrared and Raman spectra
have been obtained for the 4-aminopyridine cation and its N?,N?,N?-D3,
2,3,5,6-D4, D7, and 1-Me derivatives, and for the 4-hydroxypyridinium cation and its N,O-D2,
2,3,5,6-D4, D6, and 1-Me derivatives. Throughout, the
vibrational spectrum of the 4- aminopyridine cations shows prominent features
that differ from those found for the corresponding 4-hydroxy-pyridinium ion,
but there is a strong resemblance to the spectrum of the corresponding
4-pyridone. These results are consistent with a structure of the
4-aminopyridine cation represented essentially by the iminium form (II), and
inconsistent with one to which the aminopyridinium
form (I) makes a large contribution. ��� The downfield shift of the CH proton
magnetic resonances on proton addition is much smaller for 4-aminopyridine than
for ordinary pyridines, indicating a loss of aromaticity in the cation of the
former. The average downfield shift on protonation of 1,4- dihydro-4-imino-1-methylpyridine
(V; NNe in place of NH, R = H), too, is somewhat
smaller than that found for pyridines, i.e. there is no sign of a gain in
aromaticity when the imine (V) forms a cation. All this fully supports the
above conclusion.
Chemical and spectroscopic studies in metal β-diketonates. IX. A novel intermolecular charge-transfer system involving metal acetylacetonate (donor) and iodine (acceptor)
Authors: Singh PR , Sahai R
Published: September 2010

A spectrophotometric study
of 1 : 1 charge-transfer complexes derived from five metal acetylacetonates
(donor) and iodine (acceptor) has been carried out.

Iomzation potential of each metal acetylacetonate
and the equilibrium constants for the formation of the chelate-iodine complex
have been evaluated. The plot of ionization potential of donors against hvCt values gave a straight line.
Solid-phase polymerizations at high pressures
Authors: Bradbury MG , Hamann SD , Linton M
Published: September 2010

The following compounds
have been found to polymerize spontaneously in the solid state at
pressures in the range 10-50 kbar, at temperatures
between 20 and 200�C: acrylamide, p-phenylstyrene, potassium p-styrenesulphonate,
itaconic anhydride, maleic
anhydride, maleimide, 1,2,3,6-tetrahydrophthalic
acid, 1,2,3,6-tetrahydrophthalic anhydride, acenaphthylene, p-benzoquinone, N,N'-p-phenylene-dimaleimide, sulpholene, diphenylacetylene, 8-trioxan. The pressure-temperature
requirements for polymerization have been determined in a
high-pressure "squeezer" apparatus and in a diamond optical cell
which permits infrared spectral analysis of a specimen while it is under
compression. Apart from diphenylacetylene and trioxan, the compounds that polymerized were either
monosubstituted ethylenes or cyclic 1,2-disubstituted
ethylenes. Non-cyclic 1,2-disubstituted ethylenes and tri-substituted and tetra-substituted ethylenes failed to polymerize. There is evidence that
shearing stresses played a part in some of the reactions. 1-Allyl-2-thiourea
did not polymerize, but transformed from its stable crystal form I to the
unstable modification 11.
An empirical force field for ethylenes
Authors: Ramaswamy K , Devarajan V
Published: September 2010

A new type of force field
on the lines of the hybrid bond force field has been suggested, and it has been
successfully applied to the case of the ethylene molecule. The value (∂r/∂λ)CH
and (∂R/∂X)cc (variation of bond length with respect to variation
in hybridization) has been found to be approximately equal to + 0.ll �.
Kinematical evaluation of force constants: application to trihalides of phosphorus and arsenic
Authors: Rai SN , Thakur SN
Published: September 2010

The F-matrix elements for
the two-dimensional symmetry species are dependent on one arbitrary
parameter in addition to the vibrational frequencies. This parameter has been
chosen as an angle � (0 ≤ � ≤ 2π) and the F-matrix elements
for the A1- and the E-species of trihalides
of phosphorus and arsenic have been studied as functions of �. It is found that
the best values of the force constants obtained from Coriolis
1; constants can be correlated with those values of the angle ξ for which
the bending force constant exhibits a minimum.
Adsorption of nitrogen on nickel-alumina
Authors: Narayanan S , Yeddanapalli LM
Published: September 2010

The nature of nitrogen chemisorption on nickel is still an interesting problem. The present investigation
shows that there is no strong adsorption of nitrogen that could not be
evacuated at -76� and also indicates the possibility of the dependence of nitrogen
adsorption on the nature of the adsorbent and on the support material used in
the preparation of the catalysts. The effect of pre-adsorbed gases on the
isotherms is also indicated.
Oxidation of carbohydrates with chromium trioxide in acetic acid. I. Glycosides
Authors: Angyal SJ , James K
Published: September 2010

Fully acetylated methyl β-D-hexopyranosides are oxidized by chromium trioxide in acetic acid to
acetylated methyl 5-hexulosonates. Catalytic
hydrogenation of these keto esters leads into the L-series. The corresponding
a-D-glycosides are not oxidized in the same way, with the exception of methyl
tetra-O-acetyl-α-D-idopyranoside. Both α-
and β-anomers of the acetylated fnranosides are oxidized to

aoetylated methyl 4-hexulosonates.
The octaacetates of α- and β-lactose are
similarly oxidized, the ring of the galactose moiety being opened. The methyl pyranoside of a branched-chain sugar, with no hydrogen atom
on C5, is oxidized to a 4-keto ester, acetyl migration occurring from O4 to O5.
The synthesis and properties of tris(dithioacetylacetonato) complexes of iron(III), ruthenium(III), and osmium(III)
Authors: Heath GA , Martin RL
Published: September 2010

The syntheses of the
iron(111), ruthenium(111), and osmium(111) complexes of dithioacetylacetone
are described. The tris chelates are neutral low-spin (S = 1/2)monomers.
Polarography in acetone reveals a ready one-electron reduction for each
complex. Infrared and e.s.r. spectra are reported. The magnetic
susceptibilities have been measured as a function of temperature. The
electronic absorption spectra are compared with those of the related cobalt(111)
group complexes, and some tentative assignments of charge transfer bands are
provided.
Cyclitols. XXXII. Cyclopentanepentols
Authors: Angyal SJ , Luttrell BM
Published: September 2010

Three cyclopentanepentols
have been synthesized: the 1,2,4/3,5-isomer by acid hydrolysis of an anhydro-cyclopentanepentol, DL-1,2-anhydro-4,5-O-cyclohexylidene-1,2,3/4,5-cyclopentanepentol;
the 1,2,3/4,5-isomer by deamination of
(1,4/2,3,5)-5-amino-1,3-di-O-acetyl-2,3-O-cyclohexylidene-l,2,3,4-cycopentanetetrol;
and the 1,2,3,4/5-isomer by solvolysis of two tetra-O-acetyl-O-tosylcyclopentanepentols. An equilibrium mixture of
the three cyclopentanepentols was obtained by heating
one of them with 95% acetic acid in the presence of a strong acid. The relative
stabilities of the three isomers are in the order 1,2,4/3,5 > 1,2,3/4,5 >
1,2,3,4/5.
The spectral properties of 8-Amino-2-methylquinoline and its metal complexes
Authors: Litzow MR , Power LF , Tait AM
Published: September 2010

The bidentate ligand
8-amino-2-methylquinoline (1) has been prepared and
characterized by ultraviolet, infrared, nuclear magnetic resonance, and mass
spectroscopy. The changes which occur in the ultraviolet and infrared regions
on complex formation are also discussed.
Photovoltages in tetracene films
Authors: Lyons LE , Newman OMG
Published: September 2010

Photovoltaic measurements
were made on vacuum-evaporated tetracene films sandwiched between an aluminium
and a gold electrode. For polychromatic illumination in air open-circuit
voltages of up to 1.2 V were observed with the gold electrode positive. The best
power conversion efficiency was better than 10-4%. Two modes of carrier
production were distinguished, the first resulting from photon absorption in
the first tetracene singlet-singlet electronic transition, and the second
associated with lower energy red light photons. ��� Persistent voltages were also found to be
generated in the dark, the magnitudes of both these and the photovoltages being
reversibly increased by the presence of air.
A study of the Szilard-Chalmers reaction of ethyl iodide at low thermal neutron fluxes
Authors: Brown BJ , Carswell DJ
Published: September 2010

Results reported in this
paper show that the simple interpretation of the Szilard-Chalmers
reaction in ethyl iodide, viz. bond rupture of the radiohalide and absence of
subsequent chemical exchange, is not entirely valid. The results also verify
and explain the apparently anomalous radiohalide yield of zero for neutron
irradiation of pure ethyl iodide in the absence of a γ flux. ��� At low neutron fluxes free radiohalide
yields in the liquid phase have been shown to be a function of irradiation and
post-irradiation time, γ pre-irradiation dose, and fast/thermal neutron
ratio. These results are consistent with the hypothesis that exchange occurs at
a rate which decreases as the free iodine concentration increases. ��� Neutron irradiation of ethyl iodide at 77�K
produces radioactive iodine in a metastable free state which does not undergo
recombination in the frozen solid phase. The rate of post-irradiation
recombination between free iodine-128 and the thawed liquid organic phase is
independent of irradiation time and was found to be significantly faster than
the rate corresponding to neutron irradiation at room temperature.
Nuclear magnetic resonance spectra of some aryl derivatives of mercury
Authors: Banney PJ , Wells PR
Published: September 2010

The proton magnetic
resonance spectra of a series of arylmercury chlorides containing methyl groups
or a single polar substituent have been determined paying particular attention
to mercury-proton spin-spin coupling. This is readily observed for protons or
methyl groups ortho or meta to mercury but rarely for the para derivatives. The
ortho coupling is relatively insensitive to structure whereas the meta coupling
shows considerable variations that appear to be associated with conformational
effects.
Thermal reactions of mesityl oxide
Authors: Daly NJ , Gilligan MF
Published: September 2010

Mesityl oxide
(4-methylpent-3-en-2-one) thermally decomposes in the range 412-490� give
methylbutenes, carbon monoxide, isobutene, and methane as major products. The
initial 20% of reaction follows first- order kinetics and is described by the
equation k1 = 1014.22exp(-63240/RT)
s-1. A Rice-Herzfeld chain is proposed. Addition of hydrogen bromide
leads to two reactions, one producing isobutene, carbon monoxide, and methyl
bromide, and the other leading to polymerization. Likely steps in the
polymerization are proposed.
Chemistry of the Podocarpaceae. XXXIII. The structure of pododacric acid
Authors: Cambie RC , Mathai KP
Published: September 2010

Pododacric acid, a
trihydroxy diterpenoid acid obtained from New Zealand Podocarpus species, has
been formulated as 12,16,17- trihydroxyabieta-8,11,13-trien-19-oic acid (2) and
its structure confirmed by partial synthesis from 12-hydroxypodocarpa-8,11,13-trien-
19-oic acid (1; podocarpic acid).
Halogan nuclear quadrupole resonance in tetrahedral halo complexes of zinc
Authors: Scaife DE
Published: September 2010

Halogen nuclear quadrupole
resonance data are presented for a number of compounds containing tetrahedral ZnX42- ions, where X = Cl, Br, and I. Characteristic mean frequencies are: for 35Cl in ZnCl42-
8.9 MHz ; for 81Br in ZnBr42-
60 MHz; and for 127I in ZnI42-
75 and 150 MHz. The number and relative intensities of the resonances for any
compound is found to be a useful indication of the site symmetry of the ZnX42- ion, and compounds
of unknown structure are examined in this light. 35Cl
data are also presented for Cs2CuCl4,
which has a mean frequency of 10.6 MHz at 298�K.
Pairwise additive third virial coefficients for multipolar molecules : Application to water vapour
Authors: Johnson CHJ , Spurling TH
Published: September 2010

Pairwise additive third
virial coefficients for axially symmetric multipolar molecules have been
calculated using a non-product multidimensional integration formula. Results
for the Stockmayer potential agree with the corrected
results of Rowlinson. It is found that the inclusion
of the dipole-quadrupole and quadrupole-quadrupole terms in the potential
function has a marked qualitative effect on the shape of the C-T curve. Values
of the third virial coefficient for water vapour calculated using a potential function
derived from gaseous viscosity and second virial coefficient data are in good
agreement with the experimental values.
The electrical conductance and transport parameters of pure fused lead + bromide
Authors: Easteal AJ , Khoo PH
Published: September 2010

The specific conductance of
pure fused lead bromide has been measured in the temperature range 373-810�.
The conductance is expressed by (a) a quadratic function of temperature, and
(b) a modified Arrhenius function. ��� Interionic friction coefficients have been
evaluated and the applicability of the Nernst-Einstein
equation examined. ��� The variation with temperature of the
friction coefficients and of departures from the Nernst-Einstein
equation are examined in the light of possible structural models for the fused
salt.
Ion-molecule reactions in methylene fluoride
Authors: Harrison AG , McAskill NA
Published: September 2010

The ion-molecule reactions
of CH2F2 in the gas phase were studied using two mass
spectrometers, one fitted with a medium-pressure ion source and the other with
an ion-trap source. The main reaction was the formation of CH2F+
from CHF2+. The molecular ion and its proton transfer
reaction forming CH3F2+ were of lesser
importance. The only condensation ion formed was C2H4F3+.
Reaction cross sections and rate coefficients for a number of ions at exit
energies of 0.2-3.3 eV were measured.
Elaeocarpus alkaloids. IV. The alkaloids of Elaeocarpus sphaericus
Authors: Johns SR , Lamberton JA , Sioumis AA , Suares H , Willing RI
Published: September 2010

From the leaves of Elaeocarpus sphaericus (Gaertn.) K. Schum., seven
isomeric alkaloids of molecular formula, C16H21NO2,
have been isolated. Two of the alkaloids are identical with (-)-isoelaeocarpiline and (+)- elaeocarpiline previously
isolated from E. dolichostylis. Complete structures
and absolute configurations have now been determined for the two previously
known alkaloids (1) and (6), and for the five new- alkaloids (4), (8), (10),
(11), and (12), and a study has been made of the products obtained by sodium
borohydride reduction of some of the isomeric alkaloids. The previously known Elaeocarpus alkaloids, elaeocarpidine, (�)-elaeo-carpine, and (�)-isoelaeocarpine have also been
isolated from E. sphaericus.
Chlorine nuclear quadrupole resonance in some chloro complexes of divalent copper
Authors: Scaife DE
Published: September 2010

Nuclear quadrupole
resonance for the 35Cl nucleus has been
observed in some chloro complexes of divalent copper. Square-planar complexes
each show two resonance lines, with the following frequencies (at 77�K): (CH3NH3)2CuCl4, 10.780, 12.157 MHz; (C2H5NH3)2CuCl4, 10.817, 12.074 MHz; (enH2)CuCl4, 10.271, 11.901 MHz; and (C3H7NH3)2CuCl4 at 223�K, 11.290 and 11.781
MHz. NH4CuCl3, containing
dimeric Cu2Cl62-
units, has resonances, at 77�K, at 11.907, 11.993, and 12.448 MHz. The trigonal
pyramidal anion in Co(NH3)6CuCl5
has two resonances at 9.642 and 10.352 MHz at 77�K. ��� These results are compared with previous
results for copper chloro complexes, and the implications of covalent bonding
are discussed. In particular, it is suggested that the long-bond interaction
between units in square-planar complexes amounts to 7-16% of the bonding
interaction within the units.
The solubility of silver chromate in water
Authors: Jones AL , Linge HG , Wilson IR
Published: September 2010

The solubility of silver
chromate in water has been studied between 5 and 80�C. Conductometric,
spectrophotometric, tracer, and pH measurements were used to evaluate and
confirm the solubility product as 2.76x10-12�3% at 298 K and

���������������������� ��ΔH0 = 93700-0.393T2
J (mol Ag2CrO4)-1

������������������������ ΔS0 =
210-0.79T J K-1 (mol Ag2CrO4)-1

In contrast to some
previous work, particles having approximate dimensions of 0.5 μm were found to have the same solubility as larger
crystals. Tracer-level labelling (specific activity 1 and 2mCi
(gAg2CrO4)-1 of 110mAg) with self irradiation for times as long
as six months did not change the solubility. The measurements were dependent on
the level of illumination.
Photochemical syntheses. IV.The formation of 1-Alkoxynaphthalene-diphenylacetylene photo-adducts and their acid-catalysed hydrolysis. A new route to 2a, 8b-Dihydrocyclobuta[α]naphthalenes
Authors: Sasse WHF , Collin PJ , Roberts DB , Sugowdz G
Published: September 2010

1-Methoxy-, 1-ethoxy-, and
1-isopropoxy-naphthalene react with diphenyl- acetylene (dpa) to give the
photo-adducts (2), (3), and (4) in 90-95% yield. The adducts (5), (6), and (7)
each account for less than 1%. Each 1-alkoxynaphthalene gives also less than 5%
of ketone (10) which is formed also by hydrolysis of two 4-alkoxy-1,2-diphenyl-
2a,8b-dihydrocyclobuta[a]naphthalenes. Several 2-substituted naphthalene-dpa
photo-adducts rearrange in the presence of acid quantitatively into
4-substituted 1,2-diphenyl-2a,8b-dihydrocyclobuta[a]naphthalenes Likely intermediates
in these rearrangements are discussed. 2-Methoxy-, 2-ethoxy-, and 2-isopropoxy-
naphthalene do not add dpa. The first two compounds form photodimers but
2-isopropoxynaphthalene does not do so, and photo-dimerization is not the cause
of the failure of 2-alkoxynaphthalenes to add dpa.
Metal complexes of 1,10-Phenanthroline derivatives. IV. Complexes of 1,10-Phenanthroline-2-carboxamide
Authors: Goodwin HA , Smith FE
Published: September 2010

Complexes of the tridentate
chelating agent 1,l0-phenanthroline-2- carboxamide,
with bivalent iron, cobalt, nickel, and copper are described. Bis-ligand,
six-coordinate complexes were obtained with all metals. A series of mono-ligand
complexes, which are also believed to be six-coordinate, was also obtained.
Infrared evidence indicates that the amide group is bound through the oxygen
atom. Electronic spectral and magnetic data indicate that the ligand produces a
relatively weak field and the iron complexes are high-spin. The tris-ligand
iron(11) complex of pyridine-2-carboxamide is also described. This too is
high-spin, although the bidentate amide apparently produces a slightly stronger
field than the tridentate.
Studies of oxidation by fenton's reagent using redox titration. I. Oxidation of some organic compounds
Authors: Ingles DL
Published: September 2010

Oxidations using Fenton's
reagent have not been followed previously by redox titration. This
procedure assists in defining the overall reaction and allows both an estimate
of relative rates of oxidation and a measure of the consumption of peroxide by
the organic substrate. The peroxide consumed in
the complete oxidation of substrate to inactive compounds has been measured by
titration at constant oxidation potential. Such measurements reflect the
peroxide consumed by the substrate and its consecutive oxidation products and
may therefore be used to assess the significance of oxidation pathways.
The pyrolysis of oxindoles at 850°C
Authors: Brown RFC , Butcher M
Published: September 2010

Pyrolysis of oxindole at 850�C/0.7 mm with short contact time gives a
complex mixture of products including benzene, benzonitrile,
2-vinylpyridine, o-toluidine, aniline, and o-aminostyrene. The pyrolysis has been investigated by using
1% and 13C labelling and by studying the effects of methyl and
phenyl substituents. The nitrile carbon of benzonitrile
thus formed is derived from C7a of oxindole, and not
from C3. Pyrolysis of 7-phenyloxindole forms 1-methylcarbazole, and 4-phenyl-oxindole
forms 1-aminofluorene. These results are
interpreted in terms of the formation and subsequent rearrangement of arylnitrenes and arylcarbenes. The
pyrolysis of oxindole is compared with pyrolyses of o-tolyl
azide and tropyl azide. The mass spectrum of oxindole is reinterpreted in the light of the pyrolytic results; the spectrum of [3-13Cloxindole
shows that loss of H13CN is a minor process (25-30%).
An electrostatic view of the bonding in aromatic and delocalized structures
Authors: Miller IJ
Published: September 2010

A method is outlined for
calculating the energy and some physical properties of molecules that have
delocalized bonds in fair agreement with experimental values. It is suggested
that some commonly used concepts, such as the "back-donation of a electrons",
may be overused.
Magnetic behaviour and structure of polymeric oxovanadium carboxylates
Authors: Casey AT , Morris BSSE , Thackeray JR
Published: September 2010

The synthesis and
properties of a series of oxovanadium(1V)
carboxylates (i.e. salts of organic acids) are described. The complexes closely
resemble each other in magnetic properties, the observed paramagnetism
being abnormally low for oxo-vanadium(1V) in the temperature range 90-350 K,
with a broad maximum around 200-250 K. After testing of all reasonable models,
the magnetic properties are interpreted in terms of
anisotropic (Ising) antiferromagnetic exchange along
infinite linear chains of interacting spins. On the basis of this model and
with the aid of infrared, e.s.r., and electronic spectra, the most probable
molecular structure for the series of complexes can be given. In our
interpretation of the evidence, the interactions are of the super-exchange
type.