bluuebunny/crossref_metadata_2025 huggingface dataset:
Isothiazole chemistry. VI. Reactions of carbanions with N-Ethyl-3-isothiazolone
Authors: Crow WD , Gosney I
Published: September 2010

N-Ethyl-3-isothiazolone
undergoes cleavage of the S-N bond when subjected to nucleophilic attack by
carbanions, yielding a series of cis-3-alkylmercapto-acrylamides. Under basic
conditions the reaction is shown to be reversible, the stability of the product
being apparently dependent upon the degree of substitution at the carbanion
site. Resonance-stabilized carbanions derived from primary carbon acids E-CH3
(E = electrophile) react with two moles of the isothiazolone to give E-
CH(S-CH=CH-CONHEt)2 as well as E-CH2-S-CH=CH-CONHEt,
whereas those derived from secondary carbon acids (E-CH2R) give only
the product E- CHR-S-CH=CH=CONHEt. When carbanions from tertiary carbon acids
E-CHR2 are employed, no stable product incorporating the carbon acid
is obtained; a competing side reaction of the base on N-ethyl-3-isothiazolone
itself results in the formation of a dimer (C5H7ONS)2.
��� It is proposed that the formation and
subsequent stability of the products of carbanion attack depend upon their
ability to form a carbanion adjacent to the sulphur atom, and that, in the
absence of such a carbanion site, reversion to starting materials will be
brought about by bases. Factors relevant to this are discussed.
Chemistry of the Podocarpaceae. XXIII. Preparation and reactions of some lactone derivatives of 12-Methoxypodocarpa-8,11,13-trien-19-oic acid
Authors: Cambie RC , Denny WA
Published: September 2010

The parent lactone (V) of a
series of 12-methoxypodocarpa-8,11,13- trien-19-oic acid derivatives has been
prepared by successive dehydration and hydrogenation of the 7α- and
7β-hydroxy lactones (VII) and (VIII), and also by reduction of the 7-keto
lactone (IV) with diborane. Attack by nucleophiles on the 7β-hydroxy
lactone (VIII) is a convenient method for the preparation of less readily
available 7α- substituted lactones. Treatment of the 7-keto lactone (IV)
with sodium hydroxide in methanol effects a fragmentation reaction to give the
diosphenol (XXIV), providing a potential method for the formation of hitherto
inaccessible 6,7-diketones with a trans-fused A/B ring junction. Treatment of
the diosphenol (XXV) with potassium hydroxide affords the cis-fused A/B ring
junction diketo acid (XXXI) rather than the product of an expected benzilic
acid rearrangement.
Sulphur-selenium compounds
Authors: Ailwood CR , Fielding PE
Published: September 2010

The characterization of
various mixtures obtained by fractional recrystallization of sulphur-selenium
melts is described. Optical absorption spectra of thin films, mass spectra, and
X-ray diffraction data reveal two distinct ranges of homogeneity, the break
occurring at 14 at. % Se. The optical absorption edge of crystals containing
less than 14 at. % Se varies linearly with composition. A direct optical
transition to the conduction band of S8 and a transition due to
trapped excitons are thought to contribute to the excessive width of this
absorption edge.
Flavan derivatives. XXVIII. Stereochemistry of products synthesized from flav-3-enes and flavanones
Authors: Clark-Lewis JW , Jemison RW
Published: September 2010

Further applications of flav-3-enes for synthesis of flavan
derivatives are reported, with discussion of stereochemical aspects.
Hydrogenation of three 3-sub-stituted flav-3-enes gave the corresponding 2,3-cis-flavans, viz. (�)-epiafzelechin
tetramethyl ether, and (�)-epicatechin
pentamethyl ether and pentaacetate.
Hydroxylation of 5,7,3',4'-tetramethoxyflav-3-ene with osmium tetroxide
gave 5,7,3',4'-tetramethoxy-2,3-trans-flavan-3,4-cis-diol.
The trans-trans isomer of this diol
proved configurationally unstable towards hot acetic anhydride and sodium
acetate, and gave the 2,3-trans-3,4-cis diacetate in addition to the normal trans-trans diacetate. Two 2,4-cis-flavan-4-01s
were found to give 2,4-trans-4-ethoxyflavans, and thus resembled flavan-3,4-diols in their solvolytic
reaction with ethanol.

Meerwein-Ponndorf reduction of flavanone
gave 2,4-cis-flavan-4-ol
(i.e. the quasi-equatorial alcohol).
Coordination compounds of substituted 1,10-phenanthrolines and related bipyridyls. XII. Complexes of copper(I), silver(I), and nickel(II) with 2-Methyl-1,10-phenanthroline
Authors: Ainscough EW , Plowman RA
Published: September 2010

Copper(1) salts of the type
Cu(mep)2X (X = NO3, ClO4) (mep = 2-methyl-
1,l0-phenanthroline)
were obtained by boiling the appropriate bis copper(11) complex in water or by
reduction with hypophosphorous acid. They are
expected to have a tetrahedral arrangement of donor nitrogen atoms about the
copper(1) ion. Complexes Cu(mep)X (X = Br,I) were obtained by reduction of the appropriate
copper(11) salt in hot water with hypophosphorous
acid. These may be dimeric in the solid state with a tetrahedral arrangement
of the ligand donor atoms. Complexes of the type Ag(mep)2X
(X = NO3,ClO4) were prepared
and are believed to be tetrahedrally coordinated. Ag(mep)Br
was also prepared and in the solid state may be a dimeric structure involving
the bromo ligand as the bridging unit. Nickel complexes of the type Ni(mep)X2 (X = Cl, NO3) and Ni(mep)2X2,yH2O (X = Cl, y = 4; X
= NO3, y = �) were prepared and structures determined as far as
possible by means of magnetic susceptibility and conductivity measurements, and
by infrared and reflectance measurements.
The oxidations of DL-atrolactic and 2-hydroxyisobutyric acids by cerium(IV) in sulphuric acid solutions
Authors: Grover VK , Gupta YK
Published: September 2010

Oxidations of DL-atrolactic and 2-hydroxyisobutyric
acids by cerium(IV) in sulphuric acid solution occur in accordance with the
empirical rate law:

(see equation in article)

where k1 is a
complex rate constant and A is an unspecified constant. Spectrophotometric
results suggest complex formation between cerium(1v) and the organic acid, but
no kinetic evidence was obtained. Manganese(11) catalyses the reactions. DL-Atrolactic acid is more reactive than 2-hydroxyisobutyric
acid. The products of oxidations were acetophenone
and acetone respectively.
Heterocyclic compounds from alloxan and amines. XI. Uramils, dialuric acids, and related compounds
Authors: Clark-Lewis JW , Moody K
Published: September 2010

Preparation of a number of uramils and 5-aryldialuric acids
from

o-substituted anilines is described.
Methylation of the uramils gave dimethoxy-N-monomethyl
pyrimidine derivatives accompanied by minor amounts of trimethoxy-pyrimidines,
and the dialuric acids gave 1,3-dimethylpyrimidines
or 5-methoxy-1,3-dimethylbarbituric acids (with an
excess of diazomethane). Ring contraction of the 1,3-dimethyldialuric
acids gave the isomeric 5-N-methylcarbamoyloxazolidine-2,4-diones. The dialuric acid from dimedone gave
a trimethyl derivative (a methoxycyclohexenyl-1,3-dimethyldialuric
acid). Anthranilic acid and alloxan
in acetic acid gave a benzoxazonespirobarbituric
acid, but in aqueous ethanol yielded a dialuric acid
which was characterized by conversion into several derivatives. Infrared and N.M.R. data
are recorded for the uramils, dialuric
acids, and their derivatives.
Light scattering and viscosity study of Poly-L-methionine
Authors: Bradbury JH , Chapman BE
Published: September 2010

Poly-L-methionine
samples have been produced by polymerization of L-

methionine-N-carboxyanhydride and their properties studied by light scattering and
viscometry in organic solvents. In trifluoroacetic
acid viscosity studies reveal a polyelectrolyte effect, hence the poly-L-methionine is charged. Furthermore, it is a random coil and
fits the same Mark-Houwink equation as does
poly-γ-benzyl-L-glutamate in dichloroacetic
acid. Poly-L-methionine is a helical rod in ethylene
dichloride + 2% dichloroacetic acid and shows the
same viscometric behaviour as poly-y-benzyl-L-glutamate
in dimethylformamide. Comparison of five different organic soluble polypeptides
shows that there is an approximate correlation between the rigidity of the
helix and its stability.
Cyclitols. XXXI. Synthesis of Amino- and Nitro-cyclopentanetetrols
Authors: Ahluwalia R , Angyal SJ , Luttrell BM
Published: September 2010

Condensation of 2,3-O-cyclohexylidene-erythro-tetrodialdose
with nitromethane gave a mixture of diastereomers of
2,3-O-cyclohexylidene-5-nitro-1,2,3,4-cyclo-pentanetetrol,
one of which was isolated. After hydrogenation of the mixture, (1,4,5/2,3)- and
(1,4/2,3,5)-5-amino-2,3-O-oyclohexylidene-l,2,3,4-cyclopentanetetrol
were isolated, the latter conveniently as its condensation product with
acetone.

Deamination of the 1,4/2,3,5 compound gave an epoxide (8).
Heating the nitro compounds with sodium hydrogen carbonate in methanol caused
methylation of the two hydroxyl groups.
Alkaloids of the genus Cinnamomum. II. The alkaloids of the bark of Cinnamomum sp. T.G.H. 13077
Authors: Gellert E , Summons RE
Published: September 2010

The major alkaloids of the
bark of Cinnamomum sp. T.G.H. 13077 have been
identified as the benzylisoquinolinea (+)-1-(4'-hydroxybenzyl)-6,7-methylenedioxy-1,2,3,4-tetrahydroisoquinoline
(norcinnamolaurine) (l), (-)-cinnamolaurine (2), (+)-reticuline
(3), and the aporphine (+)-corydine
(4). The structure of norcinnamolaurine, a new alkaloid, was elucidated by
N.M.R. and mass spectroscopy and was confirmed by conversion into
cinnamolaurine and by synthesis of its racemate.

0.r.d. spectra indicate that both (-)-cinnamolaurine and
(+)-norcinnamolaurine belong to the D-series of benzylisoquinoline
alkaloids.
Complexes of binucleating ligands. III. Novel complexes of a macrocyclic binucleating ligand
Authors: Pilkington NH , Robson R
Published: September 2010

By reaction of 5-methylisophthalaldehyde with 1,3-diaminopropane in the presence of various metal salts the following complexes have been isolated: MCu2Cl2,6H2O, MCu2(ClO4)2,2H2O, MCu2(HSO4)2,H2O, MNi2Cl2,2H2O, MCo2Cl2,2CH3OH, MFezCl2,2CH3OH, MMn2Cl2,2H2O, MZn2Cl2,2H2O, (MH2)Ni(ClO4)2,2H2O where MH2 represents the macrocyclic tetrakis-Schiff base obtained by condensation of two molecules each of the diamine and dialdehyde components and M represents the derived dianion which behaves as a novel macrocyclic binucleating ligand. On the basis of magnetic and spectral evidence the complexes are assigned binuclear structures in which the cations are in an approximately square-pyramidal environment. These structural features have been confirmed in the case of MCu2Cl2,6H2O by an independently conducted X-ray crystallographic analysis. It is suggested that (MH2)Ni(ClO4)2,H2O is closely related to the others in that the nickel environment is square-pyramidal and that essentially the same organic ligand framework is present, with two protons rather than a metal ion occupying the second cavity of M.
Lithium aluminium hydride-aluminium chloride reduction of steroidal cyclic acetals
Authors: Ahmad MS , Logani SC
Published: September 2010

Lithium aluminium hydride-aluminium
chloride (1 : 1, AlH2Cl) reduction of 3,3-ethylenedioxycholest-5-ene
(5), 3,3-ethylenedioxy-5α-oholestane (7),
6,6-ethyl-enedioxy-5α-cholestane (7), and 3,3-(1?- methylethylenedioxy)cholest-5-en
(8a), gave the glycol ethers (9), (17), (21a), and (24), respectively. The
structures of the ethers (9), (17), (21a), and (24) have been established by
their spectral properties and chemical transformations. A mechanism of the
hydrogenolysis is presented.
Chemistry of the Podocarpaceae. XXX. Conversion of 8α,13-Epoxylabd-14-ene into a compound with an ambergris-type odour
Authors: Cambie RC , Joblin KN , Preston AF
Published: September 2010

Manoyl oxide (1) has been
converted into the five-membered oxide (7), a compound with an ambergris-type
odour which has been previously prepared from sclareol (13). The route involves
the intermediates (14), (15), (17), (10), and (32), and gives an overall yield
of 17% from manoyl oxide. The oxide (7) has also been prepared from manoyl
oxide in two steps by oxidation with chromium trioxide followed by reduction of
the lactone (10) with diborane.
Preparations, infrared spectra, and structures of some zinc and cadmium arenesulphinates
Authors: Cookson PG , Deacon GB
Published: September 2010

The complexes, M(O2SR)2,2H2O
(M = Zn or Cd; R = Ph or p-MeC6H4), have been prepared by
metathesis reactions from the corresponding sodium arenesulphinates or
arenesulphinic acids. Zinc benzenesulphinate has also been obtained from the
reaction of diphenylzinc with sulphur dioxide and from the reduction of
mercuric benzenesulphinate with zinc dust. Anhydrous zinc and cadmium
arenesulphinates, M(O2SR)2, have been prepared by heating
the dihydrates, and each cadmium complex has been obtained in two crystalline
forms. From their isomorphism with the corresponding cobalt complexes, the zinc
and cadmium arenesulphinate dihydrates have been shown to have octahedral
stereochemistry. Both the hydrated and the anhydrous arenesulphinato complexes
have sulphur- oxygen stretching frequencies indicative of O-sulphinate
coordination, and polymeric structures based on bridging bidentate O-sulphinate
groups are likely for all the complexes.
Catalysis by hydrogen halides in the gas phase. XXIII. 1,1-Dimethoxyethane and hydrogen bromide
Authors: Stimson VR
Published: September 2010

Hydrogen bromide catalyses
the gas-phase decomposition of 1,1- dimethoxy-ethane at 233-322� into methyl
vinyl ether and methanol. The reaction, first-order in each reactant, is
believed to be homogeneous and molecular. ��� The Arrhenius equation

������ �����������k2 = 1.3x1013exp(-22160/RT)
s-1 cm3 mol-1

is followed. This
decomposition is much faster than the analogous reactions of alcohols and
ethers. The catalyst is effective when present in only 1% proportion.
Hydrolysis of amides. V. Alkaline hydrolysis of alkyl-substituted amides
Authors: Bolton PD , Jackson GI
Published: September 2010

Enthalpies and entropies of
activation have been derived from rate constants measured over a range of
temperature for the alkaline hydrolysis of acetamide, propionamide,
n-butyramide, n-valeramide, isovaleramide, phenylacetamide,
cyclohexylacetamide, methoxyacetamide, cyclohexanecarboxamide, cyclopentane carboxamide,
α-methylbutyramide, isobutyramide, and trimethylacetamide. ��� These results are discussed in terms of
their correlation by Taft- type equations which have been extended to incorporate
a factor based upon the ?α-hydrogen bond? concept of hyperconjugative
stabilization. The rate constants of these 13 amides under these conditions
appear to be governed by a combination of polar, steric, and hyperconjugative
factors.
Kinetics, stoicheiometry, and mechanism in the bromination of aromatic heterocycles. I. Aqueous bromination of pyrazole, 1-methylpyrazole, and 3,5-dimethylpyrazole
Authors: Boulton BE , Coller BAW
Published: September 2010

A procedure is described
for monitoring the reactivity of a substrate towards bromine in aqueous bromide
solutions, as a function of extent of reaction, by following the changes of
electrode potential with time in the intervals between successive periods of
electrolysis. ��� The title compounds show 1 : 1
stoicheiometry with substitution in the 4-position. The observed rate behaviour
may be understood in terms of direct attack by molecular bromine on the neutral
substrate molecules, rate coefficients for dilute aqueous solution at 25�C
being:

����� k20(Br2+pyrazole) = 3.8x105 dm3 mol-1 s-1, kH/kD
= 1.39;����� k20(Br2+1.methylpyrazole) = 8.0x105 dm3 mol-1 s-1;����� k20(Br2+3,5-dimethylpyrazole) = 1.4x109 dm3 mol-1 s-1, kH/kD
= 1.08

Values of pKa(pyrazole-H+)
= 2.58 and pKa(3,5-dimethylpyrazole-H+) = 4.11 were
determined by potentiometric titration methods.
Studies with Bicyclo[2,2.2]octenes. IV. Acid-catalysed fragmentation of Bicyclo[2,2,2]octenyl dialkyl carbinols to aromatic compounds
Authors: Gregson RP , Mirrington RN , Schmalzl KJ
Published: September 2010

Attempts to prepare the
conjugated ester (1) by dehydration of the hydroxy ester (2) failed with a
variety of acidic reagents, and the major product in each case was the aromatic
ester (3). Similarly, the carbinols
(13) and (14) rearranged to (15) under acidic conditions. In particular, the
use of acidified methanol produced a variety of intermediates, eight of which
were isolated by preparative gas chromatography. The mechanism of the
rearrangement is discussed.
2-Methylenebutyrolactones. II. Fluorene and diaryl derivatives
Authors: Dalton LK , Elmes BC , Kolczynski BV
Published: September 2010

Ethyl sodiomalonate
with fluorene-9-spiro-2'-oxiran gave two carboxybutyro-lactones,
(2a) and (3a). Fluorene-9-spiro-4'-(2'-methylenebutyrolactone) (3c) and
2-methylene-4,4-diphenylbutyrolactone (6c) have been prepared by the action of diethylamine and formaldehyde on their respective
2-oarboxybutyrolaotones. The reaction of trimethylsulphonium
iodide with 4,4'-diethoxybenzophenone gave 2,2-bis(4'-ethoxypheny1)vinyl
alcohol (6a) and not the oxiran.
Elaeocarpus Alkaloids. V. The Alkaloids of Elaeocarpus kaniensis
Authors: Hart N , Johns S , Lamberton J
Published: September 2010

The leaf alkaloids of Elaeocarpus kalziensis Schltr. are a
complex mixture, from which eight new alkaloids have been separated.
Spectroscopic evidence has shown that these alkaloids are a closely
interrelated group of indolizidines and structures have been assigned to
elaeokanine A (1), elaeokanine B (8), elaeokanine C (10), elaeokanine D (12),
elaeokanine E (17), and elaeokanidine A (18), Elaeokanidine B and elaeokanidine
C are stereoisomers of elaeokanidine A, but the spectroscopic evidence is
insufficient for the structures of these alkaloids to be assigned unequivocally.
The assigned structures in all cases indicate relative and not absolute stereochemistry.
The structures established
for elaeokanine A, elaeokanine B, and elaeokanine C by spectroscopic methods
have been confirmed by synthesis. Catalytic hydrogenation of synthetic
8-n-butyryl-7-oxoindolizidine (22) over platinum oxide in ethanol afforded (�)elaeokanine
C in 30% yield. Under these hydrogenation conditions a major product was
8-n-butyryl-7-oxo-8,9-dehydroindolizidine (23) formed by loss of hydrogen from (22).
Indolizines. I. A direct synthesis of acylindolizines from substituted pyridinium salts
Authors: Dainis I
Published: September 2010

Several routes to
1-formylmethyl-2-methylpyridinium bromide have been investigated. Chichibabin cyclization of this salt to indolizine
fails because the reaction system favours an
intermolecular aldol condensation. A general one-step
synthesis of acyl-and diacyl-indolizines from 1-(β-oxo)-alkyl-2-alkyl-
and 1-(β-oxo)alkyl-2-benzyl-pyridinium salts is described. This synthesis,
as effected by the anhydride of a weak aliphatic acid and its sodium salt, also
gives isomeric products and these have provided a mechanistic reaction scheme of
three competing pathways. 1-Acyl-2,3-disubstituted
and 3-acyl-1,2-disubstituted indolizines are formed
from the relevant salts by Chichibabin cyclization
and subsequent in situ acylation. 1-Acetonyl-2-methylpyridinium
bromide gives useful yields of 3-acyl-and 1,3-di-acyl-indolizines by this
pathway and also via 1-acetonyl-2-acetylmethylene-l,2-dihydropyridine. The
reaction of the corresponding 1-phenacyl salt involves acylated
intermediates of type (14)
and (15), and has provided evidence for the rearrangement of the diacylmethylides (15) to acylmethines
(14). A facile thermal
cyclization of 2-phenylpyridinium diphenacylmethylide
to 3-benzoyl-1,2-diphenylindolizine is reported.
Anthracene fluorescence at low temperatures. I. Purified single crystals
Authors: Lyons LE , Warren LJ
Published: September 2010

The low-temperature
fluorescence spectrum of purified vapour-grown

anthracene single crystals is presented and the free-exciton emission distinguished from a number of defect or
impurity bands present even in the purest crystals. In assigning the observed
bands the symmetry of the active vibrations and the origin of background
fluorescence and deformation bands are discussed. The phonon structure in the
region of the fluorescence origin was found to be almost completely b-polarized.
Emission of electronic origin (25103 cm-1) was too weak to be
observed. Polarization ratios of the
principal vibronio bands at 5.6 K are given.
Indolizines. III. Studies on the acylative cyclization of stabilized Methylene-1,2-dihydropyridines. A novel synthesis of 3-phenyl-1,2-phthaloylindolizines
Authors: Dainis I
Published: September 2010

Cyclization of
l-benzyl-2-ethoxycarbonylmethylene-1,2-dihydropyridine in acetic anhydride is
shown to depend on the basicity of the reaction medium. The reaction between
activated 2-methylpyridinium salts and ethyl chloroformate in aqueous base has
provided a novel synthesis of 2-ethoxycarbonyl-methylene-l,2-dihydropyridines.
Nass spectra of four 2-methylene-l,2-dihydropyridines are presented together
with N.M.R. evidence for their 2-E configuration. Pyrophthalone (15) reacted
with benzyl chloride in boiling nitrobenzene to give 2-benzylpyrophthalone.
With phenacyl bromide, pyrophthalone gave 3-phenyl-1,2-phthaloylindolizine
(6-phenylbenzo[f]pyrido[1,2-a]isoindole-7,12-dione) rather than the
3-benzoylindolizine (18). Quinophthalone reacted similarly, and the formation
of both phthaloylindolizines has been attributed to a novel rearrangement of the
2-phenacylindan-l,3-dione system in the intermediate, alkylated products. Mass spectra of both
phthalones and three phthaloylindolizines are presented.
The chemistry of food flavour. I. Volatile constituents of passionfruit, Passiflora edulis
Authors: Murray KE , Shipton J , Whitfield FB
Published: September 2010

The volatile constituents
of the purple-skinned passionfruit (Passifora edulis Sims)
have been investigated. The volatiles were concentrated, fractionated by gas
chromatography and chromatography on silica gel, and the resulting fractions
examined by combined gas chromatography-mass spectrometry. The majority of the
components identified are esters derived largely from combinations of the
alkan-1-ols (C1,2,4,6,8) the alkan-2-ols (C5,7),(Z)-and
(E)-hex-3-en-1-ol,(2)-hex-4-en-1-ol,and benzyl alcohol, with acids of even carbon
number (acetic, butanoic, hexanoic, octanoic, hex-3-enoic, oct-3-enoic, and 3-hydroxyhexanoic).
The non-ester constituents include many of the above free alcohols,
acetaldehyde, alkan-2-ones (C3,5,7,9,11), monoterpenes
((E)-β-ocimene, 1,8-cineole, linalool, α-terpineol, citronellol, geraniol, citronellyl acetate,
(Z) and(E) five-membered ring linalool oxides), and 1,1,6-trimethyl-
l,2-dihydronaphthalene, β-ionone, γ-hexanolac-tone,
γ-octanolactone, and the lactone of
2-hydroxy-2,6,6-trimethylcyclohexylidene- acetic acid. Preliminary odour
assessment of the constituents has indicated that volatile passionfruit flavour
is complex. Many components, especially certain esters, are clearly important
and one component, not yet completely characterized, may have particular
significance.
A kinetic study of the acid autoxidation of tryptophan
Authors: Stewart M , Nicholls CH
Published: September 2010

The decomposition of tryptophan in aqueous HC1 at 100�C has been shown to proceed by a
free-radical autoxidation mechanism. The acid
functions by protonating the amino acid at either the
1- or 3-positions prior to autoxidation and so
1-methyltryptophan is also decomposed under these conditions. Impurities
present in the soda glass containers used are shown to be responsible for the
initiation of the reaction. The decomposition of tryptophan
during the acid hydrolysis of proteins is considered in the light of these
results.
Tumour Inhibitory Plants. Two New Bisbenzylisoquinoline Alkaloids From Pycnarrhena ozantha (Menispermaceae)
Authors: Loder J , Nearn R
Published: September 2010

Two new phenolic alkaloids
from Pycnarrhena ozantha have
been identified as N,N-bisnoraromoline (1) and 2-N-norobamegine (2) on spectroscopic evidence and by conversion into
known compounds.
An arsenic-75 nuclear quadrupole resonance study of α and β As4S3
Authors: Bastow TJ , Campbell ID , Whitfield HJ
Published: September 2010

The nuclear quadrupole
resonance frequencies of 75As in the α and β forms of As4S3
have been measured at 77, 195, and 293 K. The frequencies at 77 K were:

α phase 64.87 65.94 79.56 MHz

β phase 65.42 67.16 79.65 MHz

An analysis is presented in
terms of Townes-Dailey theory and of the temperature
dependence in terms of Bayer-Brown theory. The differences in frequencies of
the α and β forms were attributed to the effect of electrostatic
field gradients, estimated by lattice sums. Allowance must be made for the
thermal expansion of the lattice to obtain a consistent interpretation.
A magnetic study of a series of dihydroxy-bridged copper compounds of 2,2'-bipyridyl and 1,10-phenanthroline
Authors: Casey AT
Published: September 2010

The magnetic susceptibility
of the compounds [(amine)Cu(OH)]2X2,nH2O, where amine =
2,2'-bipyridyl or 1,l0-phenanthroline; X = Cl, I, NCS, NCSe,
or �SO4; and n varies from 5 to 1 depending on the complex, has been
measured in the liquid nitrogen temperature range. The magnetic data are
consistent with a triplet ground state for the sulphate
and iodide salts.
Studies of vanadium(III) aqua chloro complexes and some related compounds
Authors: Podmore LPSPW
Published: September 2010

Preparative and structural
studies on several series of vanadium(111) aqua chloro complexes and related
compounds are reported. Results indicate that all compounds contain
vanadium(111) in pseudo-octahedral coordination. Evidence is presented from
electronic, infrared, and nuclear quadrupole resonance spectra, X-ray powder
diffraction, and magnetic data. The compounds of empirical
formulae VX3,6H2O (X = Cl, Br), RbVCl4,6H2O,
and Cs2VX5,nH2O
(X = Cl, n = 4; X = Br,n = 5) are all shown to
contain the green trans-[V(OH2)4X2]+
ion. For compounds of formula AI2VCl5,H2O (A
= Cs, Rb, K, NH4) prior methods of preparation are
reexamined and a new method of preparation is given. Physical studies confirm
that these compounds contain the red complex ion [V(OH2)Cl5I2-. The salts comprise
structures of two types, one for A = Cs, the other for A = K, NH4, Rb; the latter salts are isostructural
with K2FeCl5,H2O. The anhydrous compounds A12VCl5 (A = Cs, Rb) are also examined and the preparation of the rubidium
salt is reported for the first time. For these compounds the magnetic results
are interpreted in terms of a weak antiferromagnetic interaction in a proposed
polymeric structure and this is supported by other evidence. Some data are reported for VBr3 and VI3.
The preparation and reactivity of some potassium Purine-, Quinazoline-, and Tetrahydroquinazoline-sulphonates
Authors: Brown DJ , Hoskins JA
Published: September 2010

The potassium salts of
purine-6(and 8)-, 9-methylpurine-6-, quinazoline-2(and 4)-, 5,6,7,8-tetrahydroquinazoline-4-, and 5,6,7,8-
tetrahydro-2-methylquinazoline-4-sulphonic acid are prepared by treatment of
the corresponding thiones with aqueous potassium permanganate. All the
suphonates undergo ready hydrolysis to the corresponding oxo
derivatives in acid and also in alkali (except for the first two purines which
are stabilized as dianions therein) ; t1/2 values at H0 -
1 (25�) are all less than 8 min; at pH 14 (40�) they vary from 2 to 190 min.
Potassium quinazoline-4-sulphonate undergoes hydrazinolysis to 4-hydrazinoquinazoline;
quinazoline-2-sulphonyl fluoride (prepared by chlorine oxidation of
quinazoline-2-thione in the presence of potassium hydrogen difluoride) reacts
with appropriate amines to give 2-diethylamino-, 2-dipropylamino-, and 2-amino-
quinazoline; and purine-6-sulphonyl fluoride with hydrazine gives
purine-6-sulphonohydrazide or 6-hydrazinopurine, according to conditions.
Nuclear magnetic resonance studies of the interaction of inhibitors with chymotrypsin. N-Trifluoroacetyl derivatives of phenylalanine
Authors: Nicholson BC , Spotswood TM
Published: September 2010

The binding of
N-trifluoroacetyl derivatives of phenylalanine to the enzyme chymotrypsin has
been studied by 19F nuclear magnetic resonance spectroscopy.
Separate resonances are observed for the D- and L- enantiomers in the presence
of chymotrypsin and their difference in chemical shift is dependent on the
molar ratio of inhibitor to enzyme. The results are interpreted in terms of the
known structure of the active site and possible modes of reorientation of the
aromatic ring in its binding site. Approximate and accurate methods of
quantifying the data are discussed and values for the dissociation constant (KI)
of the EI complex, and the change in chemical shift on binding, are reported
for the D-isomers.
Isopimara-9(11), 15-Diene-3β, 19-diol from Newcastlia viscida (Verbenaceae)
Authors: Jefferies PR , Ratajczak T
Published: September 2010

The title diterpenoid has
been separated after base treatment of acidic and neutral extracts. Its
structure is assigned by conversion into isopimara-8,15-diene and by
spectroscopic data. The stereochemistry follows from chemical and spectroscopic
examination of the 11α,16-diol formed by hydroboration of the ethylidene
derivative.
The total synthesis of (±)-laurinterol and related compounds
Authors: Feutrill GI , Mirrington RN , Nichols RJ
Published: September 2010

(�)-Debromolaurinterol
acetate (21c) has been synthesized from 2,4- dibromo-5-methoxytoluene by an
eight-step sequence which constitutes a formal total synthesis of each of the
racemates of laurinterol (1), debromolaurinterol(2), aplysin (3), and debromo-aplysin (4), because of previous interconversions
of these sesquiterpenes.
The constituents of Phebalium dentatum. The structure of a new flavone
Authors: Pinhey JT , Southwell IA
Published: September 2010

Chemical investigation of
the leaf of Phebalium dentatum Smith (Rutaceae) yielded the coumarin phebalosin (2) and a new
prenylated flavone for which we propose the structure (3).
Perimidine-2-carbaldehyde
Authors: Browne EJ
Published: September 2010

Perimidine-2-carbaldehyde
has been prepared and found to consist of a mixture of the free aldehyde (1a)
and the dimeric cyclic hemiaminal (2) in the solid state. This dimerization is
analogous to that observed in many N-unsubstituted azole aldehydes. The aldehyde
(1a) initially forms as the hydrate (1c) on hydrolysis of its diethyl acetal. ��� The condensation of imidates or imidate
salts with 1,8- diaminonaphthalene is a useful route
to 2-substituted perimidines or their salts.
Thermodynamic properties of alcohol+alkane mixtures. II. Contributions to the excess energies other than those due to hydrogen bonding.
Authors: Smith F , Brown I
Published: September 2010

Measured N.M.R. chemical
shifts of the OH proton are reported for a number of n-alcohol + n-alkane
systems at 30�C. When plotted as a function of OH group concentration these
data show a remarkable similarity to the results obtained for the enthalpy of
mixing (HM) per mole of alcohol. For these systems, excluding the
lower alcohols, the available i.r., HM, and N.M.R. data correlate
separately and each type of data is used to deduce the fraction of free OH as a
function of concentration. The three deduced results are contradictory and it
is postulated that the results from i.r. are correct whereas those from the HM
and also those from the N.M.R. data are invalid at high alcohol concentrations
due respectively to a dipole-dipole enthalpy contribution and a related
reaction field chemical shift. This also explains the similarity found between
the two sets of data. At higher dilutions the results from i.r. and from HM
data are in very good agreement on the assumption of an effective hydrogen bond
enthalpy of 25 kJ/mol while the infinite dilution results require a decreased
value for lower multimers which is in accord with other evidence. The deduced
dipole-dipole contribution to the enthalpy appears reasonable from other
estimates and makes a large contribution to the enthalpies of mixing. A brief
note on alcohol + alcohol systems is included.
Extractives of Australian Timbers. XIII. Jingullic Acid, a Triterpene of the Lupane Series Containing a C28 → 29 Lactone Group
Authors: Eade RA , Ellis J , Harper P , Simes JJH
Published: September 2010

Jingullic acid, a nor-triterpene isolated from Emmenospermum alphitonioides F.Muell., has been
shown to possess structure (5), 19β-
hydroxy-A(1)-norlupa-2,20(29)-diene-27,28-dioic acid 28,19β-lactone, by
chemical and spectroscopic investigation and by convergent synthesis from
ceanothenic acid.
Extractives of fungi. V. Microbial transformation products of piperitone
Authors: Lassak EV , Pinhey JT , Ralph BJ , Sheldon T , Simes JJH
Published: September 2010

The products obtained from
the transformation of (�)-piperitone (1) by Pro-actinomyces roseus, a species
of Fusarium, and Aspergillus niger have been examined. Major transformation
products include (�)-trans-6- hydroxy-p-menth-1-en-3-one (2) and (�)-7-hydroxy-p-menth-1-en-3-one
(3); a minor transformation product has been tentatively identified as (�)-8-hydroxy-p-menth-1-en-3-one
(4).
Substituted phenanthrolines and their metal chelates
Authors: Halbert EJ , Harris CM , Sinn E , Sutton GJ
Published: September 2010

Substituents at and adjacent
to the nitrogen atoms in 2,2?-bipyridyl and 1,10-phenanthroline are most likely
to cause drastic changes in the magnetic properties of complexes with these
ligands. Complexes of the N-oxides (2,2?-bipyridine 1,1?-dioxide, and 1,10-phenanthroline
1- oxide) with copper, and of 2-substituted phen
(substituent = Cl, CONH2) with iron(II)
are investigated, and a new one-step reaction to convert phno
into cphn is reported. The copper complex Cu(bpyo)Br2 shows antiferromagnetic interactions,
but other complexes Cu(bpyo)X2 (X = Cl, NO3) with this ligand are magnetically
normal, as are Cu(phno)Cl2 and Cu(phno)Br2. The complex [Fe(cphn)3]
(ClO4)2 lies near the high spin-low spin crossover for
iron(II), and its magnetic moment is normal at room temperature but falls with
decreasing temperature. The dioxide of phen appears
not to be formed by the literature method and no successful synthesis can be
reported here.
Thermodynamics of metal-ligand bond formation. V. Adducts of mercury(II) halides with Lewis bases
Authors: Farhangi Y , Graddon DP
Published: September 2010

Thermodynamic data have
been obtained for the reactions of mercury(II) halides with Lewis bases in
benzene solution at 30�C. With tributyl- and triphenyl-phosphines 1 : 1 and 2 :
1 adducts were observed in solution, the 1 : 1 adduct with tributylphosphine being
associated. With tetrahydrofuran, tributylamine, pyridine, 2-methylpyridine, 4-
methylpyridine, tetrahydrothiophen, and triphenylarsine only 1 : 1 adducts were
observed in solution, monomeric and three-coordinate, except for HgI2AsPh3,
which probably associates to some extent. In most cases the enthalpies of
formation of 1 : 1 adducts in solution are about -70 kJ mol-1; lower
enthalpies of formation of the tributylamine adducts, about -40 kJ mol-1,
are attributed to the absence of π-bonding and much lower enthalpies of
formation of tetrahydrofuran adducts to the ?B character? of mercury. Wide
variations in the stabilities of the adducts are mainly due to entropy effects,
probably arising from differences in the solvation of the adducts.
Protonation of azobenzene derivatives. I. Methyl orange and ortho-methyl orange
Authors: Bolton PD , Ellis J , Fleming KA , Lantzke IR
Published: September 2010

Thermodynamic acidity
constants have been measured over the temperature range 5-50� for aqueous
solutions of sodium 4?-dimethylaminoazobenzene- 4-sulphonate (methyl orange)
and sodium 4?-dimethylaminoazobenzene-2- sulphonate (ortho-methyl orange). From
these data values of the standard enthalpy, entropy, and heat capacity changes
have been calculated for these compounds. These results are discussed in
conjunction with previous spectrophotometric and other data with reference to
the nature of the equilibrium systems involved in these protonation reactions.
It is concluded that existing evidence does not allow an unequivocal assignment
of the sites of protonation of these and related molecules.
Spectrophotometric studies of the metavanadate system. I. Solution equilibria
Authors: Rieger PH
Published: September 2010

Spectrophotometric
absorbance measurements on sodium metavanadate solutions in the region 240-300
nm were made at 10�, 25�, and 40�C on: (1) a series of solutions 2.46 x 10-5M
in vanadium and covering the pH range 7-9; and (2) a series of solutions at
constant pH and covering the concentration range from 4x10-5 to
1.2x10-2M. All solutions contained 3.0M NaClO4 and 0.10M
Tris buffer. From these data were computed the extinction coefficients of HVO42-,
H2VO4-, and (VO3-), as
well as the pKa of H2VO4- (7.62�0.07).
Metavanadate is probably a mixture of V3O93-
and V4O124- under the conditions of the
experiment. Upper limits on the formation constants at 25� are K3 =
10.8�0.5x106 12 mol-2 and K4 = 73�7x
10913 mol-3. The temperature dependence of the
data gives for the enthalpy of polymerization, ΔH� = -21�2 kJ mol-1
H2VO4-.
Reduction by dissolving metals. XIX. A synthesis of 4-Isopropylcyclohexa-1,4-dienecarbaldehyde
Authors: Birch AJ , Dastur KP
Published: September 2010

A method of protecting
benzaldehyde carbonyl groups during metal- ammonia reductions by intermediate
conversion into the N,N?- dimethylimidazolidine by
reaction with N,N?-dimethylethylenediamine, has been
exemplified by conversion of 4-isopropyl-benzaldehyde into its 2,5-dihydro
derivative. This is a principal flavouring matter of cumin seeds.
Comparison of acidity function and linear free energy basicity constants of amides, phenylureas, and nitroanilines
Authors: Barnett JW , O'Conner CJ
Published: September 2010

The Bunnett-Olsen linear
free relationship1 has been used to determine the thermodynamic
basicity constants, KBH+, of 22 amides, 8 phenylureas, and 9 nitroanilines.
These values have been compared with the basicity constant determined by
plotting log I against the appropriate acidity function. For amides and
phenylureas the two values of pKBH+ differ by <0.3 logarithm
units, whereas for nitroanilines the difference increases with decreasing
basicity and may be as large as 2.1 logarithm units.
Synthesis of evodionol and alloevodionol
Authors: Lahey FN , Stick RV
Published: September 2010

The Hoesch reaction with
acetonitrile and 7-benzyloxy-5-methoxy-2,2- dimethyl-chroman (7) yields mainly
8-acetyl-7-benzyloxy-5-methoxy-2,2- dimethylchroman (9); subsequent
debenzylation and dehydrogenation forms alloevodionol (2). Both the Hoesch
reaction with acetonitrile on 5- methoxy-2,2-dimethylchroman-7-ol (12) and the
methylation of 8-acetyl- 2,2-dimethylchroman-5,7-diol (15) yield
dihydroalloevodionol (11), convertible into alloevodionol (2) by
dehydrogenation. 6-Acetyl-2,2- dimethylchroman-5,7-diol (14) is benzylated at
the C7 hydroxyl and methylation, debenzylation, and dehydrogenation lead to
evodionol (1).
Synthesis of some derivatives of Benz[a]acridine and Benz[c]acridine
Authors: Mock J , Ritchie E , Taylor WC
Published: September 2010

The base-catalysed reaction
between o-aminobenzaldehyde and naphthalene-1,3-diol gave benz[a]acridin-5-ol
which was converted into 5-methoxy-7-methylbenz[a]-acridone. The structure of
the latter was established by N.M.R. spectroscopy. ��� Some previous reports on the synthesis of
benz[a]acridine and benz[a]acridin-5-ol from o-nitrobenzyl chloride and of
benz[c]acridone by the Tanasescu reaction have been confirmed.
Nitrones and oxaziridines. IX. Cycloaddition reactions of nitrones with thioketones and the thermal and photochemical properties of some resulting 1,4,2-oxathiazolidines
Authors: Black SC , Watson KG
Published: September 2010

A series of stable
1,4,2-oxathiazolidines (11)-(22) have been prepared by the cycloaddition of the
aliphatic thioketones (4)-(6) to the aldonitrones (1), (7)-(10). Thermolysis of
the adducts led to their dissociation but the mode of photochemical decomposition
of some of these adducts was found to be consistent with the possible formation
of intermediate thiaziridines.
Studies of the intermediate phases in the reaction between barium carbonate and aluminium oxide
Authors: Beretka J , Brown T
Published: September 2010

A study was made of the
reaction of barium carbonate with aluminium oxide both in a vacuum and in
systems open to the atmosphere. Only three compounds of barium, aluminium and
oxygen were found, namely BaAl2O4,
BaAl12O19, and Ba3Al2O6. With the
reactants in the molecular ratio 1 : 1 the only solid product was BaAl2O4. With the ratios of 1 : 6 and
3 : 1 the barium carbonate reacts first with the aluminium oxide to give the
intermediate compound BaAl2O4,
which then reacts with the excess reactants to give BaAl12O19,
or Ba3Al2O6,
respectively. The reactions appear to take place as a direct interaction of the
carbonate with aluminium oxide since no barium oxide was detectable at any
stage. The results are discussed in terms of Tammann
temperatures.
Bonding in d10 transition metal complexes. II. Infrared, Raman, and N.Q.R. studies of some iodocuprate(I) complexes
Authors: Bowmaker GA , Brockliss LD , Earp CD , Whiting R
Published: September 2010

The infrared and Raman spectra
of a number of iodocuprate(I) complexes have been studied. None of the solid
complexes studied appears to contain the discrete diiodocuprate(I), CuI2-,
or triiododicuprate(I), Cu2I3-, ions which
have previously been reported in solution studies, but bright yellow compounds
which may contain the hexaiodotetracuprate(I) ion, Cu4I62-,
have been prepared with methyltriphenylphosphonium and methyltriphenylarsonium
cations. A structure based on a tetrahedron is proposed for the Cu4I62-
ion, the copper atoms lying at the corners, and the iodine atoms bridging the
copper atoms and lying along the edges of the tetrahedron. The evidence for
this structure, and the information concerning the bonding in the ion
obtainable from the vibrational and n.q.r. (63Cu, 65Cu, 127I)
spectra are discussed.
Ab initio molecular orbital calculations on acetyl cations. Relative hyperconjugative abilities of C-X bonds
Authors: Radom L
Published: September 2010

Ab initio molecular orbital calculations have been carried out for the
substituted acetyl cations RCO+ (R = CH3, CH3CH2,
(CH3)2CH, (CH3)3C) and XCH2CO+
(X = CH3CH2, CH2=CH,CH=C, C=N, OH, F). The
stabilities of the ions RCO+ are found to follow the normal inductive
order of the substituents R. The calculations suggest that C-C hyper-conjugation
is more effective than C-H hyper-conjugation.
Non-additivity of intermolecular forces: effects on the fourth virial coefficient
Authors: Johnson CHJ , Spurling TH
Published: September 2010

In this paper we give the
results of computing the effect of non-additivity of long range forces on the
fourth virial coefficient of a Lennard-Jones 12-6 gas. We have considered only
dipolar effects but have included all terms up to the fourth order of perturbation
theory. We have also calculated the effect of the fourth-order triple-dipole
term on the third virial coefficient. For the fourth virial coefficient we find
that the dispersion non-additivity, while being positive at low reduced
temperatures, goes through a negative minimum at a reduced temperature of about
1.25 before becoming small and positive at high temperatures. This is in
contradistinction to the behaviour of the third virial co-efficient where the
dispersion non-additivity is always positive.
Kinetics of acid-catalysed hydrolysis of the α and β Carbonato(4,7-dimethyltriethylenetetramine) cobalt(III) ions
Authors: Francis DJ , Searle GH
Published: September 2010

The synthesis and
separation of the complexes α-[Co(dmtr)CO3]
ClO4 and β-[Co(dmtr)CO3]
C1O4,H2O (dmtr =
4,7-dimethyltriethylenetetramine or N,N'-bis(2-aminoethyl)-N,N'-dimethylethane-1,2-diamine) are
described. The kinetics of the acid hydrolysis of both complexes, studied in perchloric acid at 25�C and μ = 1.0M (LiC1O4),
follow rate laws of form

-d[complex]dt=(k0
+ k1[H+I)[complex]

The values of ko and k1 for the K-complex are 1.0 x
10-3 s-1 and 1.8 x 10-2 1. mol-1 s-1
respectively, while for the β-complex the corresponding values are 3.6 x
10-5 s-1 and 5.6 x 10-4 1. mol-1 s-1.
Comparisons of these rate constants with the values for similar carbonato(tetramine)cobalt(111)
complexes previously studied suggest that the ko
path could involve O-C bond cleavage in the present dmtr
complexes. The values of the acid dissociation constants of dmtr,4HCl,
determined by potentiometric titration, are 1.61,
5.86, 8.18 and 9.95.
Desulphurization of thioesters
Authors: Ellis J , Schibeci RA
Published: September 2010

Desulphurization of thiophenylacetates with deactivated Raney nickel gives β-phenylethenyl ethers.
The N.M.R. spectra of some homologous thioesters,
esters and ethers are compared.
Halogenated terpenoids. XI. β-Phellandrene tetrabromide
Authors: Carman RM , Venzke BN
Published: September 2010

Structures are deduced for
crystalline β-phellandrene tetrabromide
and for a tribromide obtained from both α-and β-phellandrene.
α-Terpinene nitrosite
Authors: Carman RM , Singaram B , Vergheses J
Published: September 2010

α-Terpinene nitrosite
is shown to have the nitro oxime structure (14).
Rates of N-methylation of N-methylpyrazole, isothiazole and isoxazole and their 2,1- and 1,2-benzologues
Authors: Davis M , Deady LW , Homfeld E
Published: September 2010

The rates of quaternization of N-methylpyrazole, isothiazole and isoxazole and of their 2,l- and 1,2-benzologues with methyl
iodide in dimethyl sulphoxide and with dimethyl sulphate are reported. All compounds quaternized
at 33� and a number of new compounds were isolated. The order of reactivity in
each series is NMe > S > O. Benzofusion
was shown to be rate-diminishing with one exception. 2,l-Benzisoxazole reacted
faster than did isoxazole and the reason for this
behaviour is discussed.
Bromine nuclear quadrupole resonance in zinc bromide and in lead bromide
Authors: Bastow TJ , Whitfield HJ
Published: September 2010

Nuclear quadrupole
resonances of 79Br and 81Br have been observed in both
ZnBr2 and PbBr2 at 77, 195 and 298 K. For ZnBr2
three closely spaced lines at 81.425, 83.100 and 84.137 MHz (81Br,
77 K) of relative intensities 1 : 2 : 1 are in accord with three non-equivalent
lattice sites of space group I41/acd.
For PbBr2 two lines observed at 20.669 and 27.824 MHz (81Br,
77 K), consistent with space group P bnm, have been assigned to their respective lattice
sites on the basis of point-charge model calculations.
Molecular interactions in the spectra of diaza-aromatics
Authors: Honner JR , Nott PR , Selinger BK
Published: September 2010

A reported variation of the
electronic absorption spectra of diaza-aromatics in
non-polar solvents with temperature appears to be explicable in terms of three
effects. Hydrogen bonding interactions occur in all but exhaustively dried
non-polar solvents. Microcrystals form readily at low
temperatures at even quite low concentrations (c. 10-5M). The
solutions are sensitive to exposure to light. The diaza-aromatics
undergo photochemical change forming, in some cases, photoadducts
with the solvent.
Synthetic plant growth regulators. I. The synthesis of (±)-14-Norhelminthosporic acid and related compounds
Authors: Mander LN , Turner JV , Coombe BG
Published: September 2010

Cuminic acid (9) was converted by reductive methylation into
1,2,3,6-tetrahydro-4-isopropyl-1- methylbenzoic acid
(12). Acid-catalysed cyclization of the diazomethyl ketone (8) derived from
(12), followed by hydrogenation, gave the bicyclo[3,2,l]octanone
derivative (7), which was then converted through the allylic
bromide mixture of (18) and (19) into the p-toluenesulphonyldithiocarbazone (21) and the allylic ammonium bromide (25). The [2,3]-sigmatropic rearrangement of the dithio-
carbene derived from (21) and the ylid derived from
(25) afforded the dithioester (22) and pyrrolidine (26), respectively, from which the alcohol
(24), aldehydes (27) and (28), and acids (5) and (6) were prepared. Bioassay of
(5), (6), (27) and (28) indicated gibberellin-like
properties for all these compounds with potency comparable with that of helminthosporic acid (2).