bluuebunny/crossref_metadata_2025 huggingface dataset:
Reductive removal by sodium borohydride of side-chain oxygen from phenolic ketones
Authors: Bell KH
Published: September 2010

The reduction of a variety
of phenolic carbonyl compounds with boiling aqueous alkaline sodium borohydride
has been studied. When the carbonyl group is ortho or para to a phenolic
hydroxyl, reduction proceeds to the methylene derivative, but stops at the carbinol
stage when the phenolic hydroxyl and carbonyl group are meta oriented. ��� The simplicity and selectivity of the
reaction makes it of synthetic value.
The gas-phase reaction of acetic acid with hydrogen bromide
Authors: Daly NJ , Gilligan MF
Published: September 2010

In the gas phase, acetic
acid reacts with hydrogen bromide in the temperature range 412-492� to give
methyl bromide, carbon monoxide, and water. The reaction is first order in each
reagent, and the variation of rate constant with temperature is described by
the equation �� ����������������� k2 = 1011.67exp(-30400/RT) ml mole-1 sec-1

Possible transition states
for the reaction are examined. A mechanism involving an intermediate of the
type CH3CO+Br- is
possible if the reaction is of the family represented by the hydrogen bromide
catalysed decompositions of trimethylacetic, isobutyric, and propionic acids.
Metal-ammonia reduction of some acyl phenols
Authors: Birch AJ , Subba Rao GSR
Published: September 2010

2- and
4-Hydroxyacetophenone on reduction with metal-ammonia solutions give mainly
pinacols with some of the alcohol; 3-hydroxyacetophenone gives no pinacol. In
no case is hydrogenolysis of the side-chain oxygen observed. 4-Hydroxy-propiophenone
gives a good yield of a mixture of stereoisomeric pinacols related to
hexoestrol.
Elaeocarpus alkaloids. II. (+)-Elaeocarpiline and ( - )-isoelaeocarpiline, new indolizidine alkaloids from Elaeocarpus dolichostylis
Authors: Johns SR , Lamberton JA , Sioumis AA
Published: September 2010

(+)-Elaeocarpiline and
(-)-isoelaeocarpiline, two new alkaloids isolated from the leaves of Elaeocarpus
dolichostylis Schltr., have been shown to be respectively (+)-15,16-dihydroelaeocarpine
(III) and (-)-15,16-dihydroisoelaeocarpine (IV). The relative configuration has
been assigned for all centres in (-)-isoelaeocarpiline, but the relative
configuration at C 16 in (+)-elaeocarpiline remains uncertain.
The preparation and some reactions of the irontricarbonyl complex of thebaine
Authors: Birch AJ , Fitton H
Published: September 2010

The methoxycyclohexadiene
ring of thebaine readily complexes with Fe(CO)3 to give (I; R = Me).
This group alters the reactivity of the thebaine molecule in a number of ways,
protecting the diene system and permitting ready fission of the cyclic ether to
give either reduced compounds, or carbonium salts such as (X), which undergo a
novel rearrangement.
Moulting hormones of insects and crustaceans: The synthesis of 2-Deoxy-3-epicrustecdysone
Authors: Galbraith MN , Horn DHS , Middleton EJ , Hackney RJ
Published: September 2010

The title compound has been
synthesized from crustecdysone. The biological activity and spectral properties
of the product are discussed and compared with those of related compounds.
Organotin complexes with ethyl and benzyl sulphoxides
Authors: Kitching W , Moore CJ , Doddrell D
Published: September 2010

A series of complexes of
methyltin halides with dibenzyl, diethyl, and methyl benzyl sulphoxides has
been prepared and characterized. Vibrational and proton magnetic resonance
spectra have been employed to allow suggestions as to the structures of the
complexes. The change from dimethyl sulphoxide to sulphoxides with larger
steric requirements and presumably dissimilar basicities is sufficient to allow
the isolation of complexes of different stoicheiometries and structures. The
magnetic inequivalence of the methylene groups Banking sulphur is influenced seriously
by oxygen coordination to tin.
New aporphine alkaloids from Beilschmiedia podagrica
Authors: Johns SR , Lamberton JA , Sioumis AA , Tweeddale HJ
Published: September 2010

Two new alkaloids from the
leaves of Beilschmiedia podagrica
Kostermans (family Lauraceae)
have been identified as (+)-2-hydroxy-1,9,10- trimethoxy-aporphine (Va), which has previously been prepared by O- methylation
of the alkaloid boldine, and (+)-2-hydroxy-1,9,10- trimethoxynoraporphine.
The leaves also contain three known aporphine alkaloids, glaucine, isocorydine,
and (+)-2,11-dihydroxy-1,10- dimethoxyaporphine, and
the bark contains the known alkaloid laurelliptine and probably also
isoboldine.
Acridone studies. IV. The bromination of melicopicine, melicopidine, and their nor-derivatives in methanol
Authors: Prager RH , Thredgold HM
Published: September 2010

Melicopicine
(1,2,3,4-tetramethoxy-10-methylacridone) and melicopidine (1,4-dimethoxy-10-methyl-2,3-methylenedioxyacridone)
react with bromine in methanol to yield compounds which have been formed by
addition of two methoxyl groups to the substituted aromatic ring, and are
isolated as salts of arylhypobromites. Normelicopicine and normelicopidine
undergo similar reactions, but unlike melicopine and normelicopine which give
the same product,1 the products are different from those obtained
from the methylated compounds. Some reactions of these compounds are described.
Potential dependence of methanol electrosorption on platinum
Authors: Biegler T
Published: September 2010

Adsorption of methanol from
acid solution onto a smooth platinum electrode is studied using fast anodic
potential sweeps to determine coverages. Between 0.15 and 0.6 V (against
reversible hydrogen electrode) the coverage is found to be almost independent of
potential. Below 0.15 V coverage measurements are unreliable because of the
very slow approach to the steady state and competition for the surface by trace
impurities. The results are consistent with the hypothesis that chemisorbed
methanol is a stable intermediate in a sequence of irreversible oxidation
stages and that the steady-stage coverage cannot be considered as a true
adsorption equilibrium.
Some studies in inorganic complexes. XXIV. Copper(II) complexes of 2-acetamidopyridine and 2-methylpyridine-6-carboxylic acid
Authors: Shaw KH , Sutton GJ
Published: September 2010

Complexes of copper(II)
with 2-acetamidopyridine (acpy) and with 2- methyl-pyridine-6-carboxylic acid
(mepiac-H) have been prepared. The compounds studied included [Cu(acpy)2Cl2],
[Cu(acpy)2Br2], [Cu(acpy)2(NCS)2],
[Cu(acpy)2(NO3)2], [Cu(acpy)2(H2O)ClO4]ClO4,H2O,
[Cu(mepiac)(mepiac-H)Cl], [Cu(mepiac)(mepiac-H)-Br], [Cu(mepiac)(mepiac-H)BrH2O],
and [Cu(mepiac)2H2O]. The magnetic properties,
conductances, reflectance and solution spectra, as well as infrared spectra,
are in agreement with the copper(II)
complexes of acpy being six-coordinate and those of mepiac-H having a five- coordinate
structure.
Energy dependence of ion-molecule reactions. II. Methyl chloride
Authors: McAskill NA
Published: September 2010

The ion-molecule reactions
of ions in methyl chloride were studied in the gas phase at source pressures of
up to 120 μ in a mass spectrometer using ions having exit energies which
ranged from 0.2 to 2.0 eV. The ions produced by secondary processes included CH4Cl+,
CH2Cl+, and C2H6Cl+. The
rate constant for the reaction of CH3Cl+ was found to be
independent of the ion energy in the energy range studied. A theoretical rate
constant which is independent of the ion energy was also derived for reactions
between ions and polar molecules. Negative ion spectra were briefly examined.
Flavan derivatives. XXVI. 3(3')-Hydroxyisochromano(4',3':2,3)chromans. Mechanism of formation of these hemiketals from 1'-Oxo-isochromono-(4',3':2,3)chromones
Authors: Clark-Lewis JW , Della EW , Mahandru MM
Published: September 2010

Reduction of the lactones
of flavonol-2?-carboxylic acids [1?- oxoisochromono-(4?,3?:2,3)chromones] to
hemiacetals by lithium aluminium hydride is shown to proceed by fission of the
lactone ring accompanied by direct reduction of the chromone carbonyl group
without fission of the chromone ring. The intermediate chrom-2-en-4-ols undergo
nucleophilic displacement of the allylic (and benzylic) hydroxyl group by
hydride ion attack at the 2- and 4-positions. Reduction of 7- methoxyisochromeno(4?,3?:2,3)chromone
with lithium aluminium deuteride led to 7-methoxyisochromeno(4?,3?:2,3)chromen
with 95% incorporation of two deuterium atoms.
Studies in relation to biosynthesis. XLI. Canescin
Authors: Birch AJ , Gager F , Mo L , Pelter A , Wright JJ
Published: September 2010

The biosynthesis of
canescin (I) has been investigated. The isocoumarin portion is derived from a
polyketide chain. One carbon atom of the γ- lactone ring and the carbon
atom of the methoxyl group originate from methionine whilst the other three carbon
atoms of the γ-lactone have a symmetrical C4-acid of the citric
acid cycle as their precursor. This metabolite is most unusual in that an
oxygenated methionine-derived carbon atom provides the growing point of a new carbon
chain. A possible mechanism for the attachment of the lactone is suggested.
The radiolysis of gaseous trifluoromethyl iodide
Authors: Shah PG , Stranks DR , Cooper R
Published: September 2010

γ-Radiolysis of
gaseous CF3I produces CF4 (G = 0.77), C2F6
(G = 3.0), C2F4
(G = O.89), and 12 (G = 4.08). In the presence of nitric oxide or bromine, the
fluorocarbon products are removed and high yields of scavenged products are
obtained. In the presence of NO, G(I2)
is 11.6; in the presence of Br2, G(CF3Br) is 20.1. Competition experiments using Br2 and Cl2
indicate that thermal free radicals are responsible for a major part of the
decomposition mechanism. The high radical yields may be due to short chain
reactions involving excited iodine atoms or recombination of ion
clusters.
Heterocyclic compounds from alloxan and amines. X. Amine purpurates
Authors: Clark-Lewis JW , Moody K
Published: September 2010

Secondary and tertiary alicyclic amines (piperidine,
morpholine, N-ethyl-piperidine, and N-methylmorpholine), and aromatic nitrogen heterocycles (benzimidazole, 2-methyl- and
2-t-butyl-benzimidazole, and pyridine), are shown to yield the heterocyclic
amine purpurates (murexide
analogues) by reaction with anhydrous alloxan in dry
acetic acid. The central nitrogen atom of the purpurate
anion, normally derived from ammonia, is considered to arise from degradation
of some of the alloxan, and is accompanied by liberation
of carbon dioxide. Pyrrolidine did not yield a purpurate (or carbon dioxide) under the reaction
conditions.
S-Sulphinates of cobalt(III) planar chelates and sulphur dioxide insertion into a cobalt(III)-carbon bond
Authors: Cozens RJ , Deacon GB , Felder PW , Murray KS , West BO
Published: September 2010

The reactivity of the
cobalt-carbon bond towards sulphur dioxide has been
investigated in the compounds Rco111(L)B
where L = N,N'-ethylenebis(salicyl-aldiminato), N,N'-phenylenebis(salicylaldiminato),
or bis(dimethylg1yoximato);B = water or pyridine. In
the Schiff base complexes, for R = alkyl, insertion into the cobalt-carbon bond
proceeds smoothly to give the corresponding sulphinato
derivatives. Reaction also occurs with methylcobaloxime
and a pentafluorobenzene- cobalt-Schiff base
compound, but the products are not so well defined. There is no reaction with
cobalt-aryl bonds for any of the chelates. The alkane-
and arene- sulphinato
complexes can be synthesized by an alternative oxidative-addition reaction NaCOL+RSO2Cl or a replacement reaction XCoL+AgSO2R or NaSO2R
(X = Cl,I). The infrared spectra of the complexes
show that the sulphinato group is bonded in the
manner shown:

(See diagram in article)

The p.m.r.
spectra of the complexes are discussed in some detail. Reactions of the sulphinato derivatives with donor molecules and the
halogens are briefly described.
Polyamine ligands. I. The stereochemistry of transition metal complexes with the ligand 1,8-Bis(2'-pyridyl)-3,6-diazaoctane
Authors: Phillip AT , Casey AT , Thompson CR
Published: September 2010

The new polyamine ligand
1,8-bis(2'-pyridyl)-3,6-diazaoctane
has been synthesized for the first
time by the reaction between 2-vinylpyridine and
ethyl-enediamine. The ligand could not be distilled
without decomposition and hence it was purified by converting it into the
crystalline copper(11) perchlorate complex, from which the ligand was liberated
by the reaction with sodium sulphide solution. The pure ligand was obtained in
an overall yield of 28%, based on starting materials. The complexes formed by the
ligand with the metal ions copper(11), nicke1(11),
palladium(11), zinc(11), and cobalt(111) were isolated and characterized by
physical measurements of their conductance in solution, magnetic moments,
infrared and electronic absorption spectra. The ligand adopts the planar-N4
configuration around the metal ion in the complexes with copper(11), nicke1(11), and palladiurn(11),
whereas it probably adopt's a tetrahedral-N4 configuration around
the zinc(11) complex ion. The nickel(11) perchlorate
complex is diamagnetic in the solid state and it most likely contains the metal
ion in square-planar cordination. When dissolved in
coordinating solvents, this complex undergoes a reversible,
temperature-dependent equilibrium between diamagnetic and solvated, paramagnetic
forms.
The condensations of urea with acetone, mesityl oxide, and phorone
Authors: Hatt HH , Lichtenwalter GD , Riesser GH
Published: September 2010

The principal products
formed in the condensations of urea with acetone, mesityl
oxide, and phorone have been shown to possess the
structures (4), (6), (7), and (11). The condensation of urea with mesityl oxide, which had previously been performed so as to
give mainly (7), has been modified so as to give (4) readily and in good yield.
Evidence is presented which makes knowledge of the course of these condensations
more precise. A triuret derivative (14) of triacetonamine has been prepared, as well as products (5)
and (12) from the hydrogenation of (4) and (6).
Some aryl substituted spiro-bishexahydropyrimidones
Authors: Hatt HH
Published: September 2010

The methylphenylhexadienone
(5), like phorone, condenses with urea to form a spiran. According to its structure (1) this spiran should exist in two stereoisomeric
forms, and these have been isolated. The same two stereoisomers have been
obtained from the condensation of the dimethyloxostyryltetrahydropyrimidine
(2b) with urea. Compound (2b) and related
compounds of its kind are readily formed by the thermal condensation of the trimethyloxotetrahydropyrimidine (3) with an aromatic
aldehyde and so provide a general synthetic route to spirans
(1). Compounds of type (2) dimerize in ethanolic
hydrochloric acid by a Diels-Alder condensation. Four
isomeric dimers of (2b) are described.
The thermal decomposition of RDX at temperatures below the melting point. I. Comments on the mechanism
Authors: Batten JJ , Murdie DC
Published: September 2010

Two mechanisms have
recently been proposed to explain the behaviour of the initial rate of
decomposition of RDX, with change in sample geometry. These are

(i)that the
decomposition proceeds by concurrent gas and liquid phase reactions, and

(ii) that gaseous
decomposition products influence the rate of decomposition of undecomposed RDX in the condensed phase. In this paper it is
concluded that mechanism (ii) is the more probable when the reaction is carried
out in the presence of nitrogen.
2 -Methoxy-5-(1,2,3,4 -tetrahydro-7-hydroxy-6-methoxy-2-methylisoquinol- 1-ylmethyl)phenyl 4-(1,2,3,4-Tetrahydro-6-hydroxy-7-methoxy-2-methylisoquind-1-ylmethyl)phenyl ether
Authors: Coutts IGC , Durbin AK , Schofield K
Published: September 2010

The synthesis of the
compound (3a), named in the title, which according to biogenetic theory could
furnish thalmine and 0-methylthalicberine
when oxidized, has been effected by two routes.
Kinetics and mechanism of the osmium tetroxide catalysed oxidation of tartrate and malate ions with alkaline ferricyanide
Authors: Singh NP , Singh VN , Singh HS , Singh MP
Published: September 2010

The alkaline ferricyanide
oxidations of tartrate and malate
ions have been studied in the presence of osmium tetroxide
used as catalyst. The rates are consistent with a mechanism involving as the
first step the formation of a 1 : 1 complex of osmium(v111) and the anion of
the organic acid followed by decomposition to intermediate products and the
osmium(v1) species with hydroxide ion. The osmium(V1) thus produced is rapidly
oxidized to osmium(V111) with ferricyanide. The kinetic data obtained
at higher tartrate concentrations indicate the
formation of an osmium(v111)-(tartrate)2
complex that is resistant to decomposition. The possibility of the formation of
osmium(V1)-organic anion complexes, causing a retarding effect on the reaction
velocity during a kinetic run, is also discussed. The oxidation products are
determined and a possible set of reactions for their formation is set out.
Ring strain and the negative pole. III. Strained rings as auxochromes
Authors: Miller IJ
Published: September 2010

From theory developed in
Part 2 it is shown that saturated strained rings should have marked effects on
electronic spectral transitions, generally producing bathochromic shifts,
unless the transition involves migration of electric charge towards the ring, in
which case a hypsochromic shift is produced. Experimental observations are in
good qualitative agreement with this theory, and when simple calculations are
possible, in reasonable quantitative agreement.
Imidazoles from the reaction of periodate-oxidized polysaccharides with ammonia
Authors: Richards EL
Published: September 2010

Periodate-oxidized amylose reacts with aqueous ammonia to give imidazole and
4(5)-(2-hydroxyethyl)imidazole while periodate-oxidized
dextran gives imidazole and 4(5)-methylimidazole.
Laminarin after periodate oxidation gives only traces
of imidazoles with ammonia. A mechanism is proposed
for the formation of these imidazoles from
periodate-oxidized polysaccharides. The nature of the imidazoles
formed is specific to the linkage in the parent polysaccharide and hence provides a basis for a
micro method for linkage analysis.
Diterpenoids. XXIV. A survey of the Agathis species of North Queensland. Two new resin acids
Authors: Carman RM , Marty RA
Published: September 2010

A phytochemical
survey of the diterpenoid resin acids of the North Queensland species of Agathis is presented. The methyl esters [(9)
and (14)] of two new resin acids are described.
Reactions of 1-Fluoro-2,4-dinitrobenzene with ambident thiocyanate ion
Authors: Giles DE , Parker AJ
Published: September 2010

The reactions of potassium
thiocyanate with 1-fluoro-2,4-dinitrobenzene are not
catalysed by thorium nitrate and give no more than 1% 2,4-dinitrothiocyanatobenzene
in methanol, and no more than 0.1% in dimethylformamide. The major product is
2,4,2',4'-tetranitrodiphenyl sulphide. The SNAr
intermediate complex is shown to decompose in an abnormal way and evidence for
its existence is presented. The ambident thiocyanate
ion attacks 1-fluoro-2,4-dinitrobenzene 67% through sulphur and 33% through nitrogen in both methanol and
dimethylformamide and in the presence and absence of thorium nitrate.
Complexes of Di-2-pyridyl ketone. II. Some chelated nickel(II) products of metal-promoted reactions at the ketones
Authors: Feller MC , Robson R
Published: September 2010

From reactions in aqueous solution between nickel(11) nitrate, di-2-pyridyl
ketone (DPK), and the reagents MeNH2, NH3, pyrazole ( C3H4N2) , HS03-,PhNHNH2,
and 82-, solid complexes with the following stoicheiometries were isolated:
Ni(DPK)z(MeNH2)2(N03)z(H2O)x (x: = 1, 0), Ni(DPK)z(NH~)(H2O)(NO3)3,
K~(DPK)z(C3H4NZ)2(NO3)Z(H2O)y(y = 3, O), Ni(DPK)Z(HSO4)Z(HZO), Ni(DPK)2-
(PhNHNH2)2(N03)2, and Ni(DPK)2(H2O)2S. Magnetic and spectral data indicate
pseudo-octahedral ligand fields in all cases. Except in the cases Ni(DPK)2(H20)2S
and Ni(DPK)2(PhNHNH2)2(NO3)2, for which the evidence is ambiguous, elementary
compositions and i.r. spectra indicate that the added nucleophile, HX, has condensed
with at least one of the two DPK units per nickel ion, yielding tridentate products,
(C5H4N)2(OH)X. I n the complexes of stoicheiometry Ni(DPK)2(C3H4N2)2(N03)2
and N~(DPK)z(M~NH~)z(NO~)Z both DPK units per nickel ion have condensed with
the nucleophile yielding products bound to the cation as tridentate N3 ligands. U.V.
spectral observations in aqueous solution indicate that with the reagents MeNH2,
NH3, C ~ H ~ N Z , and HS03- attack upon DPK occurs slowly, if a t all, in the absence of
nickel(11) a t room temperature, but in the presence of nickel(11) much more rapid
condensation occurs. These reactions constitute new types of metal-ion promoted
condensation. With cyanide ion as the nucleophile, attack occurs not a t the ketone
but a t nickel yielding [Si(DPK)2]2+[Ni(CN)4]z- in w-hich the cation is octahedral, the
anion square-planar, and some cyanide units are bridging.
Synthesis of (E,Z)-α-,(Z,Z)-α-, and (Z)-β-farnesene
Authors: Anet EFLJ
Published: September 2010

The three farnesenes
(E,Z)-or-, (Z,Z)-or-, and (2)-P- were synthesized from (cis) (2)-nerolidol by dehydration with
phosphoryl chloride in pyridine. The i.r., u.v., N.M.R., and mass spectra of the six possible α-
and β-farnesenes are compared as well as their behaviour on g.1.c. on several liquid phases. The α-farnesene which
predominates in apples was confirmed as being (E,E)-α-farnesene and the
minor isomer, previously thought to be (E,Z)-α-farnesene, was shown to be
(Z,E)-α- farnesene.
The measurement of surface tension by means of a vertical-plate balance
Authors: Lane JE , Jordan DO
Published: September 2010

A thermodynamic analysis of the measurement of surface tension using plates with either horizontal or vertical grooves of arbitrary cross section is presented. An exact description of the behaviour of horizontal grooves in a plate of infinite width and of vertical grooves in a plate of infinite height is given. The behaviour of a plate of finite height with vertical grooves can be the same as for an infinite plate, but in most instances this is not true. An approximate analysis of a finite plate with vertical grooves is developed and the errors in the curvatures of the resulting liquid-fluid surface are evaluated.
In general, it is found that a grooved plate partly immersed in liquid requires a greater force to balance it than a smooth plate of the same overall dimensions and mass and with zero contact angle against the liquid and fluid phases. The additional force required to balance the grooved plate is approximately independent of the groove orientation but increases with width (pitch) of the groove. It is shown that if the measurements are made with the bottom of the plate at the level of the liquid-fluid surface at an infinite distance from the plate, the additional force almost equals the gravitational force on the mass of liquid adhering to the plate after complete immersion and withdrawal from the liquid, the agreement improving as the groove pitch is decreased. This conclusion helps explain the good results obtained for surface tension measurements using roughened plates with scratched surfaces.
The important results are checked experimentally and in most cases the agreement is within the experimental error. The only exceptions to this are the results for finite plates with vertical grooves but even then the agreement is nearly quantitative.
Structures and bonding in some chloro complexes of trivalent metals
Authors: Scaife DE
Published: September 2010

Compounds of the type (cation+)MCl4- form isomorphous series when (cation+) = Ph4P+ and Ph4As+, and M = Al, Ga, In, Tl, V, and Fe in their trivalent states.
X-ray data, infrared data, and for the vanadium compounds, magnetic and electronic spectral data, also suggest that the series is isomorphous, with the MCl4- ion having a slightly distorted tetrahedral symmetry. 35Cl nuclear quadrupole resonance results for the Al and Tl compounds indicate a site symmetry of S4 for the MCl4- ion.
Magnetic data for the vanadium compounds, and also for (Bun)4NVCl4, show some antiferromagnetic interaction of the VCl4- ions in these lattices.
Infrared data are also presented for (Ph4As)2InCl5, Ph4PSbCl4, Ph4AsSbCl4, Ph4PBiCl4, and PhdAsTiCl4, none of which appears to contain tetrahedral MCl4- ions.
Circular dichroism spectra of amino acid complexes. III. Copper(II) compounds
Authors: Hawkins CJ , Wong CL
Published: September 2010

The solution circular dichroism spectra of the 1 : 1 and 1 : 2 copper(II) complexes of a series of �-amino acids are reported for the region 12500-25000 cm-1. These spectra and spectra of the isolated 1 : 2 complexes dispersed in KBr disks have been interpreted as arising from three Cotton effects with a -,+,- sign pattern for the L configuration, except for the L-proline spectra, which were analysed in terms of a +,-,+ pattern. A tentative assignment is made for these Cotton effects, and the relative contributions of vicinal and conformational effects to the rotational strength are discussed.
Metabolites of some Alternaria species. The structures of altenusin and dehydroaltenusin
Authors: Coombe RG , Jacobs JJ , Watson TR
Published: September 2010

Fungal metabolites from some Alternaria spp. are described. Structures for altenusin and dehydroaltenusin are proposed.
Solvolysis of sulphonyl halides. VI. Hydrolysis and deuterolysis of methanesulphonyl chloride at pressures to 2000 ATM
Authors: Tonnet ML , Hambly AN
Published: September 2010

The solvent isotope effect for the solvolysis of methanesulphonyl chloride in H2O and D2O is not changed significantly when the pressure is raised from 1 to 2000 atm though the rates of solvolysis at 25�C increase by a factor of c. 2.3. This indicates that the isotope effect is not due mainly to the differences in the initial hydrogen- bonded structures of the two solvents, as suggested by Robertson, since much of this structure is lost at 2000 atm.
The maximum in the rate of solvolysis produced by the addition of small amounts of dioxan at 1 atm disappears at higher pressures.
A total synthesis of indospicine, 6-Amidino-2-aminohexanoic acid
Authors: Culvenor CCJ , Foster MC , Hegarty MPW
Published: September 2010

Indospicine (1), the
hepatotoxic amino acid from Indigofera spicata Forsk. is synthesized from
2-amino-6-hydroxyhexanoic acid (6- hydroxynorleucine) by stepwise replacement
of hydroxyl by tosyloxy, cyano, imidoester, and amidine groupings.
Flavan derivatives. XXXI. Reduction products from Isochromeno(4',3':2,3)-chromones
Authors: Clark-Lewis JW , Mahandru MM
Published: September 2010

Some reduction products
(chromens, chroman-4-ols, and flavonols) obtained from isochromeno(4?,3?:2,3)chromone
and its 7-methoxy derivative with lithium aluminium hydride, sodium di(2- methoxyethoxy)aluminium
hydride, and catalytic hydrogenation are described. Allylic coupling is evident
in isochromano(4?,3?:2,3)- chrom-3-ens, and the absence of allylic coupling in
3-alkoxyflav-3-enes is therefore attributed to the latter occurring in the
conformation with the 2-aryl group axial (cf.1).
Extractives of fungi. II. The constituents of Trametes feei. 6α-Hydroxypolyporenic acid C
Authors: Pinhey JT , Ralph BJ , Simes JJH , Wootton M
Published: September 2010

Extraction of the mycelium
of the basidiomycete fungus Trametes feei grown on a synthetic medium has
yielded ergosterol and a mixture of tetracyclic triterpenoid acids (26% of
mycelial dry weight) which have been separated as their methyl esters. The major
components have been shown to be polyporenic acid C (5a), 3-O-acetyltumulosic
acid (6b), and a 1 : 1 mixture of tumulosic acid (6a) and dehydrotumulosic acid
(5e): a minor constituent has been shown to be the new tetracyclic triterpene
6α-hydroxypolyporenic acid C (7d) by spectroscopic means and by conversion
into derivatives of tumulosic acid.
The preparation and rearrangement of some 2,3-oxygenated 2-phenylbornanes
Authors: Coxon JM , Hartshorn MP , Lewis AJ
Published: September 2010

Reaction of the
r-2-hydroxy-2-phenyl-c-3-p-tolylsulphonyloxybornanes
(4b) and (10b) with base gave the epimeric 2,3-epoxy-2-phenylbornanes (1) and
(2). Acid-catalysed rearrangement of the endo-epoxide (2) gave 2-endo-phenylbornan-3-one
(8); similar reaction of the exo-epoxide (1) afforded the unsaturated aldehyde
(6) as the major product. Pyrolysis of the cyclic sulphites (16) and (17),
prepared from the 2,3-exo-diol (4a) by reaction with thionyl chloride, gave
mixtures of 2-endo- phenylbornan-3-one (8) and the aldehyde (5).
Some reactions of 2-phenylbornane derivatives
Authors: Coxon JM , Hartshorn MP , Lewis AJ
Published: September 2010

The reactions of 2-phenylborn-2-ene (1) with m-chloroperbenzoic acid,
diborane, hypobromous acid, and alkaline potassium permanganate are described.
Colouring matters of Australian plants. XVI. Minor constituents of Dianella revoluta and Stypandra grandis
Authors: Cooke RG , Down JG
Published: September 2010

Further examination of root
extracts of Dianella revoluta revealed the presence of methyl 2,4-dihydroxy-3,6-dimethylbenzoate,
(-)-4?-hydroxy- 7-methoxy-8-methylflavan,
5,7-dihydroxy-6-methyl-2-nonacosylchromone (with homologues), and a triquinone,
trianellinone. The root extracts of Stypandra grandis yielded (-)-4?-hydroxy-7-methoxyflavan
and the same mixture of chromones. The synthesis of some model chromones is
described.
Use of N-2-cyanoethylglycine derivatives in the synthesis of peptides of N-2-carboxamidoethylglycine, an isomer of glutamine
Authors: Stewart FHC
Published: September 2010

Derivatives of
N-2-cyanoethylglycine have been employed as coupling components in the
synthesis of protected peptides. The nitrile group in N-2-cyano-ethylglycine is
readily hydrated by hydrogen bromide treatment with formation of
N-2-carboxamidoethylglycine, which is an isomer of glutamine. This reaction,
conducted on cyanoethyl intermediates with simultaneous cleavage of appropriate
acid-labile protecting groups, was utilized to prepare several free peptides
containing N-2-carboxamidoethylglycine residues.
The diffusion coefficients of cadmium chloride and cadmium perchlorate in water at 25°
Authors: Reilly SRH
Published: September 2010

The diffusion coefficients
of cadmium chloride and cadmium perchlorate in water have been measured. The
cadmium chloride data have been interpreted by considering the species in the
solution and the mobilities of these species.
Preparation and chemistry of some 1-Iodo-1-phenylpropenes
Authors: Campbell JR , Pross A , Sternhell S
Published: September 2010

The oxidation of eight aryl
alkyl hydrazones with iodine in the presence of triethylamine gave mixtures of
1-iodo-1-arylpropenes and ketones in yields of 36-73% and 19-43% respectively.
Further evidence is presented in favour of an iodocarbonium ion intermediate
for this reaction. Aspects of the photochemistry of 1-iodo-1-arylpropenes and
their reaction with naphthylsodium are reported. The product distribution of
the naphthylsodium reactions is consistent with an intermediate sp2-hybridized
(?bent?) 1-arylpropenyl radical.
Synthesis and characterization of the twelve isomeric gem-dimethylphenylvalerolactones and some related compounds
Authors: Johnson RN , Riggs NV
Published: September 2010

The twelve isomeric gem-dimethylphenylvalerolactones may each in principle be
obtained by one of the general methods : (i) selective
reduction of the corresponding trisubstituted glutaric anhydride, (ii)
selective reduction of a gem-dimethyl-5-oxo-5-phenylvaleric acid, or (iii)
selective reaction of 2- or 3-phenylglutaric anhydride with 2 moles of
methylmagnesium iodide. ��� Substituted glutaric anhydrides for method
(i) were obtained by Michael addition of an
appropriate saturated ester to an appropriate α,β-unsaturated
ester, and reduced to the corresponding pairs of lactones. Two of the
intermediates for method (ii) may be obtained by Friedel-Crafts reaction of
2,2- or 3,3-dimethyl-glutaric anhydrides with benzene, but 4,4-dimethyl-5-oxo-5-phenylvaleric
acid is not produced in this way, and was obtained by an alternative method in
the literature. ��� Some of the required lactones were obtained
by variants of the general methods, and 5-t-butyl-3,3-dimethylvalerolactone
was prepared for comparison by reaction of 3,3-dimethylglutaric anhydride with
t- butylmagnesium chloride. The product lactones were structurally identified
from chemical shifts and the general nature of coupling patterns in their p.m.r. spectra, reinforced by values of geminal coupling
constants where available, and, in the case of 4,4-dimethyl-3- phenyl-valerolactone,
by results of nitration. Coupling constants obtained by iterative analyses of p.m.r. spectra for all but two of the lactones are
tabulated. Carbonyl-stretching frequencies for the solid state (or liquid
films) and for carbon tetrachloride solutions were also measured, and are
discussed.
Proton magnetic resonance spectra and conformation of mevalonolactone and 3,3-dimethylvalerolactone
Authors: Johnson RN , Riggs NV
Published: September 2010

The ring-proton spectrum at 60 MHz of mevalonolactone (3-hydroxy-3-
methylvalerolactone) has been examined in a range of solvents and that of 3,3-
dimethylvalerolactone in deuterochloroform a t 30°. All the spectra are complicated
by long-range coupling between the 2- and 4-methylene protons, but a complete set
of magnetic parameters, for the MM'XX' spectrum of the 4- and 5-methylene groups
of 3,3-dimethylvalerolactone may be extracted from the spectrum of the 5-methylene
(XX') protons alone. Such parameters as can be extracted for mevalonolactone
suggest there is little dependence of conformation on solvent. At 100 MHz in hexa-
deuteroacetone alone, or in mixtures with benzene, the 2-methylene protons show
only a small internal chemical shift and are readily completely decoupled; the
residual 4,5-methylene-proton four-spin spectrum gave a set of parameters used as
the starting point for iterative analysis of the complete six-spin ring-proton spectrum.
I t is proposed that mevalonolactone in solution is a rapidly inverting equilibrium
mixture of half-chair conformers in which the conformer having the hydroxyl group
axial is favoured c. 4.5 : 1 at 30°. The corresponding free-energy difference (c. 750
cal mol-1) is close to the difference of conformational free-energies of methyl and
hydroxyl groups in cyclohexane systems, which suggests that no special polar
factor is operating in the mevalonolactone equilibrium.
Heat capacities at constant volume, free volumes, and rotational freedom in some liquids
Authors: Deshpande DD , Bhatgadde LG
Published: September 2010

This paper presents the
experimental results on the velocity of sound, densities, and heat capacities
of eight organic liquids at 25�, 35�, and 45�C. Using Eyring's equation, the
free volumes have been calculated from the sound velocity data. For pure liquids,
a quantity Cv* = (Cv)L- (Cv)g-
Cstr called the residual heat capacity is found to be linearly
dependent on free volume. Analysis of the data for 34 liquids shows that a plot
of residual heat capacity against the free volume gives a series of straight lines
differing in slopes for different groups of liquids such as hydrocarbons,
halogen-substituted hydrocarbons, alcohols, etc. This behaviour is ascribed as
being due to different degrees of rotational freedom of molecules in these liquids.
Solvent extraction of salicylates. IV. Solvent extraction of iron(III) by substituted salicylic acids
Authors: Aggett J , Ow ES
Published: September 2010

The solvent extraction of
iron(III) into tributyl phosphate by a number of substituted salicylic acids
has been examined. It has been concluded that there is no difference in the
mode of extraction by the different acids, in each case the ex-tracted species
having the formula Fe(R- Sal)(R-HSal), and that the observed differences in
extraction behaviour are most probably associated with the strengths of
extracting acids.
The thermal decomposition of RDX at temperatures below the melting point. IV. Catalysis of the decomposition by formaldehyde
Authors: Batten JJ
Published: September 2010

The kinetics of the
decomposition of RDX have been investigated in the presence of formaldehyde over
the temperature range 170-197� with the RDX sample spread. This indicated a
marked increase in the positive- catalytic effect of the formaldehyde with decreasing
reaction temperature; however, the kinetics were not altered by the added
formaldehyde. ��� The activation energy was about 44 kcal mol-1.
It is suggested that the previously obtained activation energy of about this
figure, for the decomposition of heaped samples of RDX in the absence of added
formaldehyde, was due to catalysis of the reaction by the decomposition product
formaldehyde.
Mixture virial coefficients for the Hamann-Lambert model for globular molecules
Authors: Johnson CHJ , Spurling TH
Published: September 2010

The Hamann-Lambert
model for globular molecules using Lennard-Jones 12- 6
potential functions for the atomic interactions has been used to obtain second
virial coefficients for CH4, CF4, SF6, SiF4, CMe4,
SiMe4, and the mixtures CH4-CF4,
CH4-SF6, CH4-CMe4,
CH4-SiMe4, and CF4-SF6.
Additive third virial coefficients have been computed where experimental data
are available. Of the 18 parameter sets needed for the 12-6 interactions in the
above molecules and their combinations ten were obtained by a least-squares
fitting process using experimental values of second virial coefficients, five
were obtained from combining rules, and the remaining three from sources
independent of virial coefficient data. The computed values of the virial coefficients
agree well with the experimental data although in the case of the third virial
coefficients improved agreement would be obtained if some form of
non-additivity could be allowed for.
Flavan derivatives. XXXII. Structures and N.M.R. spectra of Flav-2-enes and Flav-3-enes; Hydroboration and hydroxylation of Flav-3-enes
Authors: Clark-Lewis JW , Baig MI
Published: September 2010

Reduction of 3-alkoxyflavylium salts with complex metal hydrides is shown
to yield 3-alkoxyflav-3-enes directly without the intermediate formation of
3-alkoxyflav-2-enes which has been demonstrated in the similar reduction of
3-alkoxyflavones. Reduction with complex metal hydrides of simple flavylium salts
lacking a 3-alkoxyl group gives flav-2-enes and is a convenient route to flav-2-enes.
Flavylium salts lacking a 3-alkoxyl group undergo nucleophilic attack by hydride
reagents at the 4-position (to yield flav-2-enes) but 3-alkoxyflavylium salts undergo
nucleophilic attack at the 2-position to yield flav-3-enes (with hydrides) or
2-alkoxyflav-3-enes (with alcohols).
Hydroboration of 4'-methoxyflav-3-ene gives no detectable flavan-3-01 (i.e.
homobenzyl alcohol) and yields mainly 2,4-trans-4'-methoxyAavan-4-01 in a useful
addition to synthetic routes to CL-flavan-4-01s (2,4-trans isomers).
Hydroxylation of flav-3-enes with peracetic acid leads mainly to 2,3-trans-
flavan-3,4-cis-diol derivatives accompanied by minor quantities of 2,3-cis-3,4-trans
derivatives which are easily removed by recrystallization.
N.m.r. data are presented on all the compounds examined.
Chemistry of the Podocarpaceae. XXXVI. Ring-B conformation of some ring-C aromatic diterpenoids
Authors: Cambie RC , Denny WA , Lloyd JA
Published: September 2010

The ring-B conformations of
some 6,7-diacetoxy, 7-acetoxy-6-hydroxy, 6-dehydro, and 7-oxo derivatives
of ring-c aromatic diterpenoids have been examined
from a study of their n.m.r, spectra.
The cobalt(II)-triethylenetetramine system in acetonitrile solution. A nitrogen-14 magnetic resonance and spectrophotometric study
Authors: Lincoln SF , West RJ
Published: September 2010

A nitrogen-14 magnetic
resonance and spectrophotometric study of the cobalt(11)-triethylenetetramine
(trien) system in acetonitrile solvent indicates the
presence of the predominant species Co(CH3CN)62+
Co(trien)(CH3CN)n2+
where n = 1 or 2, Co2(trien)34+,
and Co(trien)22+ in solution.
The lability of CH3CN in the first coordination sphere is shown to
be > 103 times that of CH3CN in the first coordination
sphere of CO(CH3CX)62+ at 258 K.
Quantum yields of the primary photoaquation reactions of octacyanomolybdic-(IV) acid and octacyanotungstic(IV) acid
Authors: Mitra RP , Sharma BK , Mohan H
Published: September 2010

The quantum yield of the
primary photoaquation reaction of octacyano-

molybdio(1V) acid and octacyanotungstic(IV)
acid has been determined by direct estimation of the two products of the
reaction, viz., a CN- ion and a red heptacyano-aquo
complex. The CN- ion was estimated polarographically,
the red photoproduct spectrophotometrically. Both the
methods gave the same value of the quantum yield, which was about 0.88 for the
molybdenum and 0.78 for the tungsten system. Photolysis was done at O�C.
This and the fact that acidic conditions were maintained during the photolysis
sufficiently stabilized the red species to reveal, if the time of irradiation
was not too long, an isosbestic point where only two
species, the red complex and the M(CN)84- ion, were in equilibrium.
The quantum yield was determined subject to the condition that the absorbance
curve of the photolysed solution passed through the isosbestic point and secondary reactions had not yet set
in.
Meniscus shapes and capillarity effects in wide tubes
Authors: Bottomley GA
Published: September 2010

Blaisdell's tables for the meniscus shape are extended to wider
circular tubes and summarized in forms convenient for precision manometry.
Chemistry of the Podocarpaceae. XXXVIII. Reduced ring-c transformations of 12-Methoxypodocarpa-8,11,13-trien- 19-ol
Authors: Cambie RC , Missen AW
Published: September 2010

Birch-type reductions of
12-methoxypodocarpa-8,11,13-trien-19-01 (2) have been investigated and the
products have been converted into the 13-oxo derivatives (7) and (30) which
have potential use as chiral intermediates for
synthesis. The C14 ketone (9) which is also of potential value, has been
prepared from the reduced derivative, methyl 12-oxopodocarp-13-en-19-oate (21).
The oxidation of N-(2-Pyridyl)thioureas. The synthesis of [1,2,4]Thiadiazolo-[2,3-a]pyridinium salts
Authors: Harris RLN
Published: September 2010

The oxidation of N-(2-pyridyl)thioureas with bromine or
sulphuryl chloride in inert solvents gives [1,2,4]thiadiazolo[2,3-alpyridinium
salts (5). Similar products are obtained by the oxidation of N-(2-pyridyl)thioamides and N-(2-pyridyl)dithio-carbamates. The
structure of this new ring system has been established by reduction to the
parent thiourea or thioamide by hydrazine, by hydrolytic degradation, and by
analytical and molecular weight evidence. 2-Phenylamino-substituted [1,2,4]-
thiazolo[2,3-alpyridinium salts undergo a rapid rearrangement on basification
or in one instance on being heated to give the isomeric
2-(2'-pyridylamino)benzothiazoles.
Chemistry of the Podocarpaceae. XLI. The decarbonylation of 12-Methoxypodocarpa-8,11,13-trien-19-oic acid and Abieta-8,11,13-trien-18-oic acid
Authors: Baguley BC , Cambie RC , Dive WR , Seelye RN
Published: September 2010

12-Methoxypodocarpa-8,11,13-trien-19-oic
acid (1), its acid chloride (3), and its methyl ester (4) undergo a
decarbonylation reaction on treatment with phosphoryl chloride. The products
have been identified as the octahydrophenanthrene (14), the tetrahydrophenanthrenes
(11) and (12), and the phenanthrene (9). A minor product has been tentatively
identified as the dimer (16). Decarbonylation of abieta-8,11,13- trien-18-oic
acid (28) gives similar products. A pathway leading to the above products is
discussed.
The origins of the colours of natural yellow, blue, and green sapphires
Authors: Ferguson J , Fielding PE
Published: September 2010

An analysis of the
absorption spectra of natural yellow sapphires shows that the absorption is due
to single Fe3+ ions and pairs of ions Fe3+-O2--Fe3+.
Assignments of all levels from the 4G, 4P, and 4D have been made as well as
four simultaneous electronic excitations of a pair of ions. The temperature
dependence of the intensity of the pair absorption shows that one pair is
mainly involved, probably the fourth- nearest neighbour pair. The value of the
Heisenberg exchange parameter (J Sa. Sb) lies in the range
30-40 K. Estimates of this parameter for various excited states have been made.
Synthetic yellow sapphires have spectra which duplicate the natural specimens.
Blue and green natural sapphires have, in addition to the bands present in the
spectra of yellow sapphires, spectra with bands at 17800 (┴C), 14200 (//c),
11500 (┴C), and 10000 om-1 (//c). The first two can be linked
to Fe,Ti pairs and the evidence favours the nearest neighbour pair Ti4+-O2?Fe2+
for the 17800 cm-1 band and possibly the first neighbour pair for
the 14200 cm-1 band. The second two can be produced in synthetic
crystals by growth from fluoride-containing flux and the evidence supports an
explanation involving second-nearest neighbour pairs Fe2+- O2--Fe3+
for the 11500 cm-1 absorption and first neighbours for the 10000 om-1
absorption.
2-Substituted and 2,6-disubstituted 1,4-benzoquinone 4-oxime methyl ethers
Authors: Norris RK , Sternhell S
Published: September 2010

The preparation and
physical properties of seven compounds in the title series are described. The
formation of glyoxal bis(aryl)nitrone derivatives as
by-products of methylation of some 1,4-benzoquinone 4-oximes is rationalized.
The syn and anti isomers of the title compounds can be equilibrated either
thermally or under conditions of acid catalysis. The effects of substituents at
C2 on the position of the syn-anti
equilibrium are very similar to their effect in other derivatives of the
corresponding 1,4-benzoquinone 4-oximes. N.m.r, parameters and other spectroscopic
data are listed and discussed.
New synthesis of 1-deoxyhexuloses
Authors: James K , Angyal SJ
Published: September 2010

By displacement of a
nitrobenzene-p-sulphonyloxy group by iodide ion from position
1 of 2,3:4,6-di-O-isopropylidene-α-L-sorbofuranose
and 2,3:4,5-di-O-iso-propylidene-β-D-fructopyranose, and subsequent
hydrogenolysis, 1-deoxy-L-sorbose and 1-deoxy-D-fructose, respectively, have
been synthesized. Inversion by oxidation with ruthenium tetroxide,
and subsequent reduction, provided new syntheses of D-tagatose
and 1-deoxy-L-psicose. The N.M.R. spectrum shows that the aqueous solution of
1-deoxy-D-fructose contains a considerable proportion of the keto form; this
proportion increases with increasing temperature.
Oxidation-induced electromigration failure of thin films of aluminium
Authors: Lyons LE , Riemer W
Published: September 2010

The failure mechanism of
very thin films (<10 nm) of aluminium exposed to oxygen at atmospheric
pressure was investigated. At an apparent current density of 100 A cm-2
two distinct types of film resistance increase on oxidation were observed. During the initial
increase, describable by the direct logarithmic law, the oxide thickness could
be expressed in terms of the film resistance. The second resistance increase,
leading to film failure, was consistent with electromigration
induced by the thinning by oxidation of the cathode contact film junction.
The structure of two new depsidones from the lichen Parmelia notata
Authors: Cresp TM , Elix JA , Kurokawa S , Sargent MV
Published: September 2010

Two new depsidones, 4-O-methylhypoprotocetraric acid
[l'-carboxy-2'-

hydroxy-4-methoxy-3,3',6,6'-tetramethyldepsidone,
(1)] and notatio acid [1'-

carboxy-2'-hydroxy-4-methoxy-3,6,6'-trimethyldepsidone,
(2)], have been isolated

from the Australian lichen Parmelia
notata Kurok and characterized.
Constituents of Alphitonia Species. III. Alphitexolide, a New Triterpene, and Other Extractives
Authors: Branch G , Burgess D , Dunstan P , Foo L , Green G , Mack JG , Ritchie E , Taylor W
Published: September 2010

The extractives of the
barks and leaves of Alphitonia excelsa, A. petriei,
and A. whitei,
and of the wood, bark, and leaves of A. macrocarpa have been examined. Ceanothic,
betulinic, and alphitolic
acids were isolated from all species, but A. macrocarpa was exceptional in
that its wood contained no benzylhydroxycoumarone
derivative, characteristic of the other species, and its leaves gave a small
yield of the alkaloid, adouetine X. From the bark of A. excelsa a new
triterpene, alphitexolide, was isolated in very small
amount. By spectroscopic methods and a partial synthesis its structure was
established as(1).