bluuebunny/crossref_metadata_2025 huggingface dataset:
Some reactions of 1,l-diphenylethylene
Authors: Millar IT , Richards KE
Published: September 2010

1,l-Diphenylethylene
gives with p-benzoquinone a 2 : 1 adduct whose structure has been established
as 5,12-diphenyl-7,14-dibenz[a,h]
anthraquinone whereas with dimethyl acetylenedicarboxylate a 1 : 2 adduct is
formed by an initial Diels-Alder addition followed by
an indirect substitutive addition.
Ultraviolet spectra of non-alternant hydrocarbons: The significance of non-neighbour resonance integrals and of configuration-interaction
Authors: Brown RD , Burden FR , Williams GR
Published: September 2010

A study has been made of
the way in which the calculated positions of excited states of non-alternant
hydrocarbons are affected by (a) including all resonance integrals rather than
just those for nearest neighbours (b) including configuration-interaction. The VESCF
molecular-orbital technique, with two
alternative methods for deriving basic integrals, was employed. Predicted positions of
excited states are found to be sometimes appreciably altered when all resonance
integrals are included, and are somewhat dependent upon the method of
evaluation of basic integrals. We conclude that one should be cautious in
interpreting U.V. spectra from an isolated molecular-orbital calculation on a
non-alternant hydrocarbon. The study of the effect of
configuration-interaction for the excited states of fulvene
and dimethylenecyclobutene yields results analogous
to those found by Koutecky and co-workers for
benzene. The predicted relative positions of some excited states are altered
when doubly excited configurations are included, but the general level of
energies predicted for lower excited states when only singly excited
configurations are used is probably close to the result that would be found
when up to triply excited configurations are included.
Electron impact studies. XXXII. Negative-ion mass spectra of aromatic compounds containing the =N-O- substituent
Authors: Bowie JH , Lawesson SO , Larse BS , Lewis GE , Schroll G
Published: September 2010

The negative-ion mass
spectra of aromatic azoxy compounds, nitrones, and
N-oxides exhibit pronounced molecular ions and simple fragmentation processes. No skeletal-rearrangement fragments are
produced upon electron impact, in marked contrast to those exhibited in the
positive-ion spectra of these compounds.
Studies in chrome mordanting. I. The binding of chromium(VI) anions to wool
Authors: Hartley FR
Published: September 2010

When wool is immersed at
room temperature in solutions containing chromium(V1) anions, these
anions are absorbed and are bound to the positively charged amino groups in the
wool. The anions can be washed out by rinsing the wool in solutions of high pH.
The nature of the chromium(V1) species absorbed by wool depends on the pH of
the treatment; at low pH, dichromate ions were found on wool, whereas at high
pH chromate ions were found.
Vibrational spectra of arsenic triiodide
Authors: Hooper MA , James DW
Published: September 2010

The Raman spectrum of AsI3 has been determined in solution in CS2
and in the solid state. For the
solution the assignment of Stammreich, Forneris, and Tavares has been confirmed by polarization
studies. In the solid state it is shown that assignment of the spectrum is only
possible on the basis of space group symmetry and an earlier assignment based
on point group C3v is in error. The solid
state frequencies (R3 symmetry) are v1(Ag) 185 cm-l,
v2(Ag) 75 cm-l, v3(Au)
201 cm-l, v4(Au) 102 cm-1, v5(Eg) 205 cm-1, v6(Eg) 50 cm-l, v7(Eg) 216 cm-1, v8(Eg) 74 cm-1.
Long-range coupling in substituted coumarins
Authors: Jarvis MW , Moritz AG
Published: September 2010

The proton magnetic
resonance spectra of some substituted coumarins and

furanocoumarins have been examined under very high resolution (0.1
Hz). Trans-annular long-range spin-spin couplings across four, five, six, and
seven bonds are reported.
Carbonyl halides of the Group VI transition metals. XII. Isolation of halocarbonyls and halocarbonyl anions of molybdenum and tungsten
Authors: Bowden JA , Colton R
Published: September 2010

Dibromotetracarbonylmolybdenum, Mo(CO)4Br2,
and the dihalotetracarbonyltungsten compounds, W(CO)4X2
(where X = Cl, Br), have been isolated and characterized. These highly reactive
compounds are all diamagnetic. The trihalotetracarbonyl
anions [M(CO)4X3]- (M = Mo, W) have been isolated as
their tetraethylammonium salts from the parent halocarbonyls.
These yellow diamagnetic compounds are the first tetracarbonyl
derivatives to be prepared from the parent halocarbonyls.
Metabolites of Aspergillus indicus: The structure and some aspects of the biosynthesis of dihydrocanadensolide
Authors: Birch AJ , Qureshi AA , Rickards RW
Published: September 2010

Aspergillus indicus grown on a semi-synthetic medium produces a number of metabolites including kojic acid, succinic acid, fumaric acid, β-nitropropionic
acid, indazonic acids, fumaryl-~danine,
and dihydrocanadensolide. The last compound is shown
to have the formula (I) and is biosynthesized in part from "acetate"
units; the rest of the molecule may come from pyruvic
acid.
The effect of various solutes on the fluorescence of tyrosyl and tryptophyl residues
Authors: Bhatnagar GM , Gruen LC , Maclaren JA
Published: September 2010

The quenching of the
fluorescence of tryptophan, tyrosine, and model compounds containing these
residues has been investigated over a range of conditions with phosphate and
Tris buffers in aqueous solution. Various thiols and their corresponding
disulphides have been studied as quenchers of fluorescence emitted by the model
chromophores. All the sulphur compounds quenched the emission but it was not
possible to separate the contributions due to "true" quenching and to
competing absorption of the excitation radiation by these compounds
("pseudo" quenching). A method is described for evaluating the
relative quenching power of different substances on the emission from model
tryptophan and tyrosine derivatives.
Molecular orbital, increased valence, valence bond and non-pairing spatial orbital formulae for three-centre bonding
Authors: Harcourt RD
Published: September 2010

The simple valence-bond and molecular orbital formulae for three-centre
bonding involving four electrons and three atoms Y, A, and B are
Y 4-B - Y-A 'P, and Y---A---B
Increased-valence formulae that have been developed recently are
Y-A . B and Y . A-B
If Y and B are the same type of atom, and bond-orbitals are used as wave functions for
Y-A and A-B bonds, then the near-equivalence of the molecular orbital and
increased-valence wave functions is demonstrated.
Bond-orders (or numbers) for these and Linnett's5s6 non-pairing spatial orbital
formula
Y . A . B
are calculated.
A new variation of the Pschorr synthesis
Authors: Chauncy B , Gellert E
Published: September 2010

A new variation of the
Pschorr phenanthrene synthesis giving improved yields is described. In
addition, the ester of the newly prepared by-product of this reaction,
2-iodo-4,5-dimethoxy-α-phenylcinnamic acid, cyclizes to the corresponding
phenanthrene-9-carboxylic acid derivative on irradiation with ultraviolet
light.
Reactions of some conjugated diynes with cobalt carbonyl compounds
Authors: Dickson RS , Tailby GR
Published: September 2010

Treatment of dodecacarbonyltetracobalt with the conjugated diynes RC≡CC≡CR
(R = CH3, C6H5) yields complexes of
stoicheiometry [Co2(CO)6]2-
(RC2C2R). The same complexes are obtained from octacarbonyldicobalt and the appropriate diyne. ��� A similar type of complex was obtained from
para-(C6H5C2)2C6H4
and Co4(CO)12. Surprisingly,
this complex was not isolated on reaction of the diyne with Co2(CO)8.
��� The infrared, nuclear magnetic resonance,
and mass spectra of the complexes are given, and the probable structures of the
compounds are deduced from these spectroscopic properties.
The configurations and P.M.R. spectra of iodo lactones and oxymercurials derived from some 5-Norbornene-2-endo-carboxylic acids
Authors: Ford DN , Kitching W , Wells PR
Published: September 2010

Iodo lactones and chloromercuri lactones derived from a number of 2- and
3-methyl-5-norbornene-2-endo-carboxylic acids have been prepared and characterized.
Analyses of 60-MHz and 100-MHz proton magnetic resonance spectra have estab-
lished their configurations, which conform to a general pattern of trans-addition.
Criteria for stereochemical assignments in this system can be based upon identifiable
vicinal, geminal, and some long-range 1H-1H and 1H-199Hg coupling constants.
These criteria are used to establish that 5-norbornene-2-endo,3-endo-dicarboxylic
acid and its derivatives do not follow the cis-oxymercuration route previously
suggested.
The nuclear magnetic resonance spectra of pyrrole and [N-D]pyrrole
Authors: Katekar GF , Moritz AG
Published: September 2010

The proton magnetic
resonance spectrum at 60 MHz of pyrrole, spin- decoupled from 14N,
has been studied under high resolution. Similar studies have been made on [N-D]pyrrole
in which the proton spectrum was obtained simultaneously spin-decoupled from
both the 14K and 2H nuclei. Analysis of the 13C-H
spectra of pyrrole and [N-D]pyrrole, observed in natural abundance, gave values
for all six proton-proton spin-spin couplings. Values for some of the couplings
have been obtained directly and unambiguously from the spectra of samples of
[S-H]pyrrole and [N- D]pyrrole in which the C-H protons have been predominantly
exchanged for deuterium. The values for the couplings derived are J1,2
2.60, J1,3 2.45, J2,3 2.69, J2,4 1.44, J2,5
1.87, and J3,4 3.34 Hz.
Electron impact studies. XLVIII. Specific hydrogen-rearrangements in the mass spectra of ortho-alkoxyanils
Authors: Bowie JH , Hoffmann PJ
Published: September 2010

The mass spectra of anils
with ortho-alkoxyl substituents in the aromatic ring derived from the aldehyde
contain pronounced peaks prod- uced by C=N bond cleavage accompanied by one
and/or two hydrogen transfers to the nitrogen-containing fragment. Deuterium-labelling
studies show that the hydrogen atoms involved are those attached to the
α-carbon (α to oxygen) of the alkoxyl group. The extent of the
hydrogen rearrangements may be altered by the addition of further substituents
to the aromatic rings.
Shock-initiated exothermic reactions. VI. The oxidation of ethylene oxide and cyclopropane
Authors: Drummond LJ , Kikkert J
Published: September 2010

Mixtures of ethylene oxide
or cyclopropane with oxygen and argon were ignited with reflected shock waves
In a shock tube. The temperature dependences of the ignition delay and the
growth of light emitted during the induction period to explosion of C2H4O-O2
mixtures indicate that the rate-controlling reaction is that of formaldehyde
oxidation. The temperature dependence of induction periods for C3H6-O2
mixtures suggests that a complicated but undetermined mechanism controls the
delay to ignition.
Phosphonium salts. III. The action of cyanide ion and other nucleophiles on some bis-phosphonium salts
Authors: Brophy JJ , Gallagher MJ
Published: September 2010

Cyclic and acyclic
bis-phosphonium salts with a two-carbon bridge are smoothly cleaved to
phosphines in high yield by potassium cyanide in dimethyl sulphoxide. Evidence
is presented that the reaction proceeds by an elimination-addition sequence. An
elimination reaction also occurs when sodium methoxide, sodium azide, sodium
acetate, and triethylamine react with ethane-1,2-bis(tri-phenylphosphonium)
dibromide. ��� In a novel reaction, triphenylphosphine is
converted into its oxide by a mixture of sodium azide and dimethyl sulphoxide.
Interactions in block copolymers in solution: The effect of hetero-contacts on the segmental interactions in block copolymers of poly(isoprene : styrene) in solution
Authors: Urwin JR
Published: September 2010

Binary cluster integrals or
excluded volumes for chemically different segment pairs in block copolymers of
poly(isoprene : styrene) have been calculated from the equation derived by
Froelich and Benoit for a two- sequence block copolymer. Expansion factors have
been recalculated assuming a linear relation for [η]θ with
respect to composition employing published values for polystyrene and
polyisoprene. The results are discussed in relation to possible conformations
of block copolymers.
Chemistry of the Podocarpaceae. XX. Epoxides of ring-A-unsaturated 12-Methoxypodocarpa-8,11,13-trienes
Authors: Canbie RC , Denny WA
Published: September 2010

Selective epoxidation of
the methoxy alkene mixture (IX) from oxidative decarboxylation of
12-methoxypodocarpa-8,11,13-trien-19-oic acid (I)
provides a method of obtaining a high yield of the exocyclic alkene (VII) from
the mixture. Isolation of the 3α,4α-epoxide
(X) during the epoxidation allows the formation of C 3 oxygenated derivatives
of 12- methoxypodocarpa-8,11,13-trien-19-oic acid. ��� Methods for opening the epoxide ring of (X)
and of the 4α,5α- and 4α,19-epoxides,
(XI) and (XII), have been examined, and the structures of the products from
rearrangement of each epoxide with boron trifluoride have been assigned.
Some simple cyanoformaldehyde phenylhydrazones
Authors: Brecknell DJ , Carman RM , Deeth HC , Kibby JJ
Published: September 2010

The triazole ring of
2-phenyl-1,2,3-triazole-4-carboxylic acid is cleaved by alkaline treatment. The
synthesis and stereochemistry of some simple cyano-formaldehyde
phenylhydrazones is discussed.
The convergence of perturbation expansions in classical statistical mechanics
Authors: Henderson D , Barker JA
Published: September 2010

The most successful theory
of liquids is perturbation theory in which the attractive energy is treated as
a perturbation on the hard-sphere potential and the canonical partition
function expanded in powers of the perturbations. The convergence of perturbation
theory in the constant pressure, canonical, and grand canonical ensembles is
investigated for a one-dimensional square-well fluid, where the calculations
are not too lengthy and where a comparison with exact results can be made. At
high temperatures, the convergence is excellent in all three ensembles but, at
lower temperatures, the convergence is excellent in the canonical ensemble but
only fair in the constant pressure and grand canonical ensembles.
Helix to coil transition in Poly-L-amino acids. III. Kinetic scheme for Poly-γ-benzyl-L-glutamate
Authors: Bradbury JH , Fenn MD , Moritz AG
Published: September 2010

Double resonance
experiments show that the α-CH proton magnetic resonance in poly-γ-benzyl-L-glutamate
(PBLG) is not coupled to the 14N nucleus but is coupled to the NH
and β-CH2 protons. The breadth of the resonance in the random
coil form of the polypeptide is due to this coupling and is independent of
degree of polymerization. ��� The coupling of NH and α-CH protons
and the occurrence of NH proton resonances are indicative of slow exchange of
NH protons with solvent. In addition, the occurrence of two α-CH
resonances indicates slow exchange between the two-proton magnetic states.
However, the rate of the helix to coil transition in PBLG obtained by other
workers is about 104 times as fast as these exchange processes. ��� The experimental data are rationalized by a
kinetic scheme which envisages a rapid equilibrium between helical and coil
residues, and a slow equilibrium involving protonation of the peptide groups by
the strong organic acid. The upfield α-CH resonance is attributed to the
uncharged helical and coil residues and the downfield resonance to the charged
helical (if present) and charged coil residues.
Carbonyl halides of the Group VI transition metals. XVI. Reactions of Bis(diphenylphosphino)methane with Diiodotetracarbonyltungsten(II)
Authors: Colton R , Rix CJ
Published: September 2010

Compounds of the general
formulae W(CO)3dpmI2 and W(CO)2(dpm)2I2
[dpm = bis(diphenylphosphino)methane] have been prepared by direct interaction
of the ligand with diiodotetracarbonyltungsten(II). However, this apparently
simple system is complicated by the existence of two isomers of the tricarbonyl
complex and three isomeric forms of the dicarbonyl. The various isomers have
been separated and characterized individually and the interconversions between
all the complexes have been investigated. The overall reaction scheme contains
a partial carbon monoxide carrying system and an example of an unusual type of
isomerism:

�������������������� W(CO)2(dpm)2I2
→ [W(CO)2(dpm)2I]I

that is, isomerism of a
molecular species to an ionic species.
Comparison of ring bending strain with infrared bending vibrations
Authors: Miller IJ
Published: September 2010

An empirical formula which
has been shown to give good values for ring bending strain in small rings has
been applied to infrared bending vibrations. The derived dynamics are of a
?pendulum? character, and reasonable agreement is obtained in calculating the
C-C-C bending force constant from the empirical formula constant. Resultant
anharmonicities are calculated from the ?pendulum? dynamics, and good agreement
is obtained with experimentally determined levels up to the 060 level of CO2
and 040 for HCN.
A total synthesis of mycophenolic acid
Authors: Birch AJ , Wright JJ
Published: September 2010

Mycophenolic acid (I) has
been synthesized by a method adaptable to the synthesis of analogues and of
possible biogenetic intermediates. The aromatic nucleus was elaborated by a
novel application of the Alder- Rickert dime
synthesis.
The synthesis of peptide derivatives related to evolidin
Authors: Stewart FHC
Published: September 2010

Protected peptides with
amino acid sequences present in the cyclic phytopeptide evolidin have been
prepared. The synthetic work involved application of the 2,4,6-trimethylbenzyl
carboxyl-protecting group. Acetyl was used to mask serine side-chain hydroxyl,
and high-dilution cyclization of one of the products, an O-acetyl heptapeptide
p- nitrophenyl ester, gave a low yield of O-acetylevolidin,
which was converted into evolidin by hydrazinolysis.
The adsorption of methyl red at the dropping mercury electrode
Authors: Boto KG , Thomas FG
Published: September 2010

Surface excess
concentrations of methyl red at the mercury-solution interface have been
determined at pH 7.00, 9.80, and 12.30 from electrocapillary
measurements using 0.lM sodium nitrate as supporting
electrolyte. The results are interpreted in terms of a reorientation of the
methyl red anion between -0.4 V and -0.6 V (v.
S.C.E.)
General methods of synthesis of indole alkaloids. VIII. An attempted approach to the Iboga-Voacanga series
Authors: Wenkert E , Dave KG , Dainis I , Reynolds GD
Published: September 2010

Methyl 5-formylnicotinate (5) has been synthesized and condensed
with a-cyanomethyltryptophol and with acetone. The
products were converted into 3-methoxycarbonyl-2-piperideines
and their acid-catalysed transformation into isoquinuclidines
attempted.
Studies in chrome mordanting. V. Kinetics and mechanism of the interaction of chromium (III) salts with wool
Authors: Hartley FR
Published: September 2010

The rate of uptake of
chromium(111) by wool depends on the nature of the chromium(111) salt used and
decreases in the order: chromium(111) fluoride > chromium(111) formate chromium(111) sulphate ≈
chromium(111) chloride. This order arises from a combination of differences in
the rates of diffusion of chromium(111) salts into the fibre
and differences in the rates of reaction of the chromium(111) species present
with the carboxyl groups in wool. It is shown that the different rates of
reaction of chromium(111) species with the carboxyl groups in wool are
consistent with the slow step of this reaction involving the loss of a water
ligand from the inner coordination sphere of the chromium(111) species. This
slow step is preceded by a rapid equilibrium involving the formation of ionized
carboxylate groups in wool. Comparisons of the chromium contents of the wool
samples with the decrease in the number
of carboxyl groups capable of being protonated in
acid solution indicate that of the salts examined only ohromium(111)
chloride definitely introduces cross-links between carboxyl groups in wool.
Studies in chrome mordanting. VII.The nature of the chromium-dye complex formed during the chrome mordant dyeing of wool
Authors: Hartley FR
Published: September 2010

When pre-chromed wool is
immersed in a boiling solution of a mordant dye, the dye is rapidly absorbed by
the wool. This is followed by a slower reaction in which the dye reacts with
the chromium(111) in the wool to form either a 1 : 1 or a 1 : 2 chromium(111)-dye complex.
With solo-chrome violet RS only a 1 : 2 complex could be detected in agreement
with the results of earlier workers, but with solo-chromate fast red both 1 : 1
and 1 : 2 complexes were detected in the wool. The equilibrium

[Cr(dye)L(H2O)2] + dye ←→ [Cr(dye)2]
+ L + 2H2O

lies further to the right
when L is a negatively charged ligand such as SO42- or F-
than when L is a neutral ligand such as H2O. This accounts for the
preferential formation of 1 : 2 complexes in wool, where L is a carboxylate
ion. It is shown that on average 1 : 1 chromium(111)-dye complexes are bound to
slightly more than one carboxyl group. An explanation is advanced for the
higher wash-fastness of the 1 : 1 and 1 : 2 chromium(111)-dye complexes
relative to the corresponding free dyes.
Some skeletal-rearrangement processes of phosphoranes upon electron impact
Authors: Gara AP , Massy-Westropp RA , Bowie JH
Published: September 2010

The mass spectra of acyl phosphoranes exhibit peaks which arise by P-O bond
formation. The problem of thermal against electron impact rearrangement is considered
and the rearrangements have been studied by deuterium labelling. The formation
of the fluorenyl cation (m/e 165) has also been
investigated.
New alkaloids from Cryptocarya pleurosperma (Lauraceae): The structures of cryptopleuridine and cryptopleurospermine
Authors: Johns SR , Lamberton JA , Sioumis AA , Willing RI
Published: September 2010

Two new alkaloids,
cryptopleuridine and cryptopleurospermine, have been isolated from the bark of Cryptocarya pleurosperma
White & Francis. From analysis of the 100-MHz n.m.r, spectra of
cryptopleuridine and O-acetylcryptopleuridine, and
the relationship of cryptopleuridine to cryptopleurine
established from other spectroscopic data, cryptopleuridine is considered to be
(5a). Spectroscopic and

degradative evidence has shown that cryptopleurospermine
is 2-dimethylaminoethyl-3'-hydroxy-4'-methoxy-4,5-methylenedioxybenzil (8).
The thermal decomposition of t-butyl isopropyl ether
Authors: Daly NJ , Ziolkowski FJ
Published: September 2010

t-Butyl isopropyl ether
decomposes in the range 409-475� by two reactions, one giving isobutene and isopropanol, the other giving propene
and t-butanol. The rate constants are described by the equations

kl(isobutene) = 1013.37 exp(-55530 � 450/RT) sec-1

kl(propene) = 1012.96exp(--56480
� 950/RT) sec-1

Both reactions appear unimoleoular.
Solvent effects on the infrared spectra of anilines. VII. 2-Substituted 4-nitroanilines
Authors: Dyall LK
Published: September 2010

Measurements of N-H
stretching frequencies of 4-nitroanilines in the
presence of hydrogen bond acceptors show that the ease of forming a second
intermolecular hydrogen bond in the presence of an ortho substituent decreases in the order hydrogen > methyl > bromo,
methoxyl > nitro. This order demonstrates the importance of repulsions
between lone pair orbitals on the ortho substituent and the acceptor
molecule. Weak intramolecular hydrogen bonds are detected in 2-iodo- and 2-bromo-aniline, and such bonds can be
strengthened by introduction of a 4-nitro substituent.
Synthesis and infrared spectra of some dithiocacodylate complexes
Authors: Casey AT , Ham NS , Mackey DJ , Martin RL
Published: September 2010

The synthesis of dithiocacodylate complexes of the metals chromium(111),
indium(111), manganese(11), cobalt(11), nicke1(11),� zinc(11), and copper(1) is described. The compounds can be
prepared either from sodium dithiocacodylate Na[S2As(CH3)2] or by passing
hydrogen sulphide through a methanolic solution of the metal cacodylate in the presence of hydrogen chloride. The
infrared spectra in the region 4000-40 cm-1 of the new compounds
have been recorded and assigned by a comparison with the spectra of several
compounds which are closely related. The arsenic-sulphur
and metal-sulphur
stretching frequencies occur in the region of 450 cm-1 and 260-340
cm-1, respectively.
Conformations of acyclic sugar derivatives. Acetylated methyl 5-hexulosonates and keto-hexuloses
Authors: Angyal SJ , James K
Published: September 2010

The conformations of the
methyl 2,3,4,6-tetra-O-acetyl-5-hexulosonates have been determined by analysis of their
N.M.R. spectra. The arabino
and lyxo
isomers are preponderantly in the planar zig-zag form,
whereas in the xylo and ribo isomers rotation around the
C2-C3 or C3-C4 bond had occurred to a gauche
arrangement in order to relieve the steric interaction (in the zig-zag form) between the acetoxy groups on C2 and C4. The
location of the gauche arrangement
depends on the size of the groups attached to C2 and C4. Acylated
derivatives of keto-D-fructose,

keto-L-sorbose,
and keto-D-psicose
have similar conformations.
Alkaloids of Alchornea javanensis (Euphorbiaceae): The isolation of Hexahydroimidazo[1,2-a]pyrimidines and guanidines
Authors: Hart NK , Johns SR , Lamberton JA , Willing RI
Published: September 2010

Alchornea jawanensis (Bl.) Muel1.-Arg.
(family Euphorbiaceae) has been found to contain both hexahydroimidazo[l,2-a]pyrimidine and guanidine alkaloids.

Alchornine has been shown to be (1), and alchornidine
is either (6) or (7). Hydrolysis of alchornidine with
ethanolic potassium hydroxide affords 2,2-dimethylacrylic
acid and alchornine, but hydrolysis of alchornidine with dilute acetic acid gives isoalchornine (8), which can be converted into alchornine in high yield by reaction with alkali. One guanidine alkaloid, now
shown to be N1,Nl-diisopentenylguanidine
(14), was incorrectly formulated as N1,N2-diisopentenylguanidine
in a preliminary communication. Another guanidine has been shown to be Nl,N2,N3-triisopentenylguanidine by synthesis of its
hexahydro derivative, Nl,X 2,N 3-triisopentylguanidine.
2,2-Dimathylacrylamide has also been isolated from
extracts of A. javanensis.
The specific refractive index increments of polyisoprenes in various solvents
Authors: Reed PJ , Urwin JR
Published: September 2010

Specific refractive index
increments of polyisoprenes with high cis-1,4 content have been determined in
six solvents at 20� and λ 546 nm. A linear relationship was found between
the refractive index increment dn/dc = n and the
refractive index of the solvent nl :

N45620 = 1.687 - 1.105n1
The results are compared
with the best values reported for natural rubber which are usually employed for
polyisoprene in light scattering measurements.
Dihydropyrrolizines. III. Preparation and reactions of derivatives related to pyrrolizidine alkaloids
Authors: Culvenor CCJ , Edgar JA , Smith LW , Tweeddale HJ
Published: September 2010

1,2-Dehydropyrrolizidine
derivatives, mainly the hepatotoxic alkaloids and
their amino alcohols, are converted into 6,7-dihydro-5H-pyrrolizine
derivatives. The dehydro derivatives of the amino alcohols are prepared with
chloranil. Oxidation by manganese dioxide or potassium permanganate, or
catalytic dehydrogenation, also leads to the desired dihydropyrrolizines
together with products at a higher oxidation level such as 7-oxo and 1-formyl derivatives. The dehydro derivatives of the ester
alkaloids are best prepared by the action of acetic anhydride on the N-oxides. The
reactions of the dihydropyrrolizines with alcohols
and amines, and their N.M.R. spectra, are discussed.
Metal template reactions. III. Synthesis of macrocyclic quadridentate nickel(II) complexes from a suitable diamino dialdehyde
Authors: Black DSC , Lane MJ
Published: September 2010

N,N-Bis(2-formyl-4-nitrophenyl)ethyleneiamine
has been synthesized by a sequence of reactions
involving the alkylation of ethylenediamine with the
ethylene-dioxy derivative of 6-chloro-3-nitrobenzaldehyde and hydrolysis of the resulting product.
Neutral macrocyclic nickel(11) complexes have been prepared by the reaction of
this diaminodialdehyde with ethylenediamine,
o-phenylenediamine, and 1,8-diaminonaphthalene
respectively, in the presence of nickel(11) acetate tetrahydrate.
Macrocyclic complexes could
not be obtained by the reaction of the neutral nickel(11) complex of N,N'-bis(2-formyl-4-nitrophenyl)ethylenediamine
with ethylene-diamine. Other experiments towards
the synthesis of a diamino dialdehyde
suitable for metal template reactions are described.
Metal template reactions. V. Reactions of 2,2'-pyridil and related compounds promoted by copper(II) ions
Authors: Black DSC , Srivastava RC
Published: September 2010

The reaction of hydrated
copper(11) acetate with 2,2'-pyridil in the presence
of air results in the formation of bis(2-picolinato)copper(11).
Similar behaviour occurs in the case of 2,2'-quinaldil
but oxidation is not observed with l-phenyl-2-(2'-pyridyl)ethane-l,2-dione,
which undergoes methanol addition. Reaction of 2,2'-pyridil
with hydrated copper(11) chloride or perchlorate gives rise to the formation of
carboxylic esters (by alcohol addition and oxidative cleavage): complexes of
these esters and also mixed ester-acid complexes are formed under slightly
different conditions. No benzilic acid rearrangement
occurs.
Annelated furans. IV. Diels-Alder synthesis of dibenzofurans
Authors: Davidson WJ , Elix JA
Published: September 2010

The Diels-Alder
reaction of 2-vinylbenzofurans with acetylenic dienophiles has been shown to provide a valuable
synthetic route to polyfunctional dibenzofurans.

Ethylenic dienophiles also react readily with 2-vinylbenzofurans and provide access to 1,2,3,11-tetrahydrodibenzofurans. The structure of the euparin-maleic anhydride adduct has been established.
Complexes of binucleating ligands. II. Geometrical models for potential nitrogen fixing systems
Authors: Robson R
Published: September 2010

The synthesis and some properties of a series of complexes, LCu2(X), are discussed where L is the binucleating trianion derived from d-methylisophthal-aldehyde di-2'-hydroxyanil [2-hydroxy-5-methyl-1,3-xylene-�,�'-diylidenebis(2-hydroxyphenylamine)] and X- is OH-, OR- ; pyrazolate anion; binuclear structures are assigned to these compounds on the basis of spectral and magnetic evidence. In the compound formulated as (L,H2O)Cu2(OCH3) it is suggested that the water molecule is added across one Schiff base link in L. The possible relevance of the results to a long-term project concerned with the synthesis of potential nitrogen-fixing systems is briefly discussed.
Electron spin resonance study of the copper(II) chelates of certain thio ligands
Authors: Pilbrow JR , Smith TD , Toy AD
Published: September 2010

Electron spin resonance measurements have been made on the copper(II) chelates of o-methylmercaptobenzoic acid, S-carboxydiethyldithiocarbamic acid, thiazolidine-4-carboxylic acid, 5-hydroxy-1,3-benzoxathiol-2-one and diacetyl bisthiosemicarbazone. The e.s.r. spectra of dimethylformamide solutions of the chelates have been interpreted in terms of dimeric species which are believed to exist at room temperature, as well as in frozen solutions in the case of o-methyl-mercaptobenzoic acid, S-carboxydiethyldithiocarbamic acid, and 5-hydroxy-1,3-benzoxathiol-2-one, whereas the dimeric forms of the remaining chelates are formed solely in frozen solution. The results have been interpreted as arising from dipole-dipole coupling between the copper(II) ions in their dimeric forms, and a line simulation procedure employed to extract the distance between the copper(II) dipoles. This information has been used to suggest the possible structures of the dimeric species. The effect of the introduction of zinc(II) ions during the formation of the copper(II) chelates has been assessed in each case.
Transition metal complexes of substituted alkynes. VIII. Complexes of cobalt derived from 1,1,1-Trifluorobut-2-yne
Authors: Dickson RS , Fraser PJ
Published: September 2010

The complex Co4(CO)10(CF3C2CH3)
is formed at room temperature from dodecacarbonyltetracobalt and 1,1,1-trifluorobut-2-yne.
Another monoalkyne complex Co2(CO)6(CF3C2CH3)
has been prepared from octacarbonyldicobalt and 1,1,1-trifluorobut-2-yne at
room temperature. Treatment with triphenylphosphine converts the complex into
Co2(CO)4[P(C6H5)3]2(CF3C2CH3).

At 150�, reaction of Co2(CO)6(CF3C2CH3)
and 1,1,1-trifluorobut-2-yne gives a small amount of a purple complex which is
believed to be Co2(CO)4(CF3C2CH3)3.
Similar reactions involving Co2(CO)4(CF3C2CH3)
and the alkynes hexafluorobut-2-yne and 3,3,3-trifluoropropyne give the
complexes Co2(CO)4(CF3C2CH3)(CF3C2CF3)2
and Co2(CO)4(CF3C2CH3)(CF3C2H)2.
Spectroscopic studies have led to an assignment of the substitution pattern in
these latter complexes. Tris-alkyne complexes were not isolated from similar
reactions between 1,1,1-trifluorobut-2-yne and the complexes Co2(CO)6(CF3C2CF3)
and Co2(CO)6(CF3C2H).

Three isomers of the π-cyclopentadienone-π-cyclopentadienylcobalt
complex, [(CF3C2CH3)2CO]Co(π-C5H5),
were obtained from (π-C6H6)Co(CO)2 and
1,1,1-trifluorobut-2-yne after U.V. irradiation for several days. The isomers
vary in the arrangement of the substituents attached to the cyclopentadienone
ring.

All reactions involving
1,1,1-trifluorobut-2-yne have been compared with similar reactions involving
the related alkynes hexafluorobut-2-yne and but-2-yne.
The chemistry of pyrrolic compounds. XIV. meso-Hydroxyprotoporphyrin IX and its derivatives
Authors: Clezy PS , Liepa AJ
Published: September 2010

The preparation of the acetate and benzoate derivatives of �-hydroxy-protoporphyrin IX is described and the hydrolysis of these enolic esters examined. The general properties of these porphyrins are discussed together with the oxidation of this system to a bile pigment identical with biliverdin IX�: with regard to spectroscopic and chromatographic characteristics.
Complex formation equilibria between copper(II) and Pyridine-2-carbaldehyde
Authors: Green RW , Rogerson MJ
Published: September 2010

Copper(II) complexes of
pyridine-2-carbaldehyde can be derived either from the neutral molecule (A) or
from the anionic form (AOH-) of the hydrate, so that there are two sets of
complexes, CuAn2+ and Cu(AOH)n2-n
(n = 1, 2), related to each other as acid to conjugate base. There is also a
mixed complex, CuA(AOH)+. In solution,
several species are always present together in equilibrium, with the de-
protonated species beginning to predominate above pH 5. The complete system of
equilibria at 25� has been worked out and the constants have been evaluated by
a combination of spectrophotometry and pH titrations.
Annelated furans. V. Selective Wittig synthesis of euparin and dehydrotremetone
Authors: Elix JA
Published: September 2010

Three-step syntheses of
euparin (5-acetyl-6-hydroxy-2- isopropenylbenzofuran) and dehydrotremetone
(5-acetyl-2- isopropenylbenzofuran) are described. The key step involves the
selective attack of methylenetriphenylphosphorane on the appropriate 2,5-diacetylbenzofurans.
Ring strain and the negative pole. IV. Relationships dependent on localized electric field
Authors: Miller IJ
Published: September 2010

The acidity, infrared
stretching frequency, and bond length of a substituent atom on a strained ring
is linearly dependent on the contribution of the ring atom to the negative pole
as previously defined. Bond strengths are similarly, but non-linearly, proportional.
A qualitative explanation for the stability of the molecules of the Group V
elements is offered. An explanation for the Schmidt rule is also offered, and
it is deduced that this rule should be applicable to any bond α,β to a strained alicyclic small ring.
Organomercury compounds. XI. Some coordination derivatives of bispentafluorophenylmercury
Authors: Canty AJ , Deacon GB
Published: September 2010

The complexes (C6F5)2HgL (L = 4,4?-dimethyl-2,2?-bipyridyl, 2,2?- biquinolyl,
2,2?:6?,2?-terpyridyl, 2,4,7,9,-tetramethyl-1,10- phenanthroline,
ethylenediamine, o-phenylenediamine, diphenylamine, pyridine, 4-cyanopyridine,
triphenylphosphine, triphenylphosphine oxide, or 1,2-bisdiphenylarsinoethane),
(C6F5)2HgL2
(L = di-2- pyridylamine), and [(C6F5)2Hg]2L (L = bisdiphenylphosphinomethane
or bisdiphenyl-arsinomethane) have been prepared, and their constitution,
solution stabilities, and structures studied, together with those of the known
complexes (C6F5)2HgL
(L = 2,2?- bipyridyl, 1,10-phenanthroline, or 1,2-bisdiphenylphosphinoethane).
Coordination of triphenylarsine oxide to bispentafluorophenylmercury
in solution has also been detected, but the complex could not be isolated.
Organometallic complexes in synthesis. II. Further applications of tristriphenylphosphinechlororhodium
Authors: Birch AJ , Walker KAM
Published: September 2010

Tris(triphenylphosphine)chlororhodium
is shown to possess some important advantages over heterogeneous catalysts in
cases where it is applicable. Some uses are discussed in the synthesis of new
types of compound, or in improvements of synthetic routes. The hydrogenation of
butadiene rubbers is reported.
Extractives of Australian timbers. XI. The stereochemistry of ceanothic acid
Authors: Eade RA , Grant PK , McGrath MJA , Simes JJH , Wootton M
Published: September 2010

An examination of the
N.M.R. spectra of ceanothic acid and derivatives has led to its formulation as
2α-carboxy-3β-hydroxy-A(1)-norlup-20(29)- en-28-oic
acids (1; R = H) in which the carboxy and hydroxy groups attached to ring A
have the inverse of the trans configuration originally assigned to them by de
Mayo and Starratt.1
The isolation of a combined zirconium-chromium(III) basic sulphate complex
Authors: Montgomery KC , Scroggie JG
Published: September 2010

The isolation and
characterization of a relatively stable, highly basic zirconium-chromium(III)
sulphate complex is described. This compound has an empirical formula
corresponding to Na2O,3ZrO2,Cr2O3,4SO3,12H2O
and appears to exist as the disodium salt of a complex anion Na2[Zr3Cr2(SO4)4(OH)12,6H2O].
Its properties indicate useful applications not only as a model compound to
study the binding of transition metal complexes to proteins and peptides but
also as a potential tanning agent for use in the leather industry.
Solvolysis of sulphonyl halides. VIII. Reaction of methane and ethane sulphony1 chlorides with methanol, ethanol, and mixed solvent systems
Authors: Foon R , Hambly AN
Published: September 2010

At room temperature
methanesulphonyl chloride reacts more rapidly than ethanesulphonyl chloride in
solvolysis by ethanol. Their rates of reaction with methanol are approximately
equal while ethanesulphonyl chloride is the more reactive in hydrolysis. The enthalpies
and entropies of activation have been determined for the solvolysis of
ethanesulphonyl chloride in mixtures of ethanol with benzene, carbon
tetrachloride, or 2,2,4-trimethylpentane. A comparison of the excess enthalpies
and entropies of mixing in the formation of these solvents with the
corresponding parameters for reaction shows that the effects on reaction rate
are not due merely to the modification of the initial state of the system. The
effect of the polar aprotic solvent nitrobenzene on the rate of reaction with
methanol is attributed to an increase in the nucleophilic tendency of the
methanol rather than to solvation of the reactive centre in the transition
state.
Polysaccharides of tropical pasture herbage. III. The distribution of the major polysaccharide components of Townsville lucerne (Stylosanthes humilis) during growth
Authors: Way CP , Richards GN
Published: September 2010

Stylosanthes humilis, the
predominant pasture legume in North Queensland, has been collected at three
different stages of growth, viz. flowering, seeded, and senescence. The plants
have been divided into stem, leaf, root, seed, and pod and each fraction has
been analysed for the following types of polysaccharide components: water- solubles,
pectic substances, hemicelluloses, and cellulose. The absolute monosaccharide
composition of each of these fractions has been determined by hydrolysis and
gas chromatography. Most of the polysaccharide components are similar in nature
to those previously found in temperate pasture legumes (e.g. Medicago sativa),
but the seeds are unusual among legumes in containing no galactomannan and
there is evidence of the presence of a glucomannan in all parts of the plant.
The oxidation of thiols in the presence of pyrroles
Authors: Beveridge S , Harris RLN
Published: September 2010

The oxidation of aliphatic,
aromatic, and heterocyclic thiols in the presence of pyrroles with
iodine-potassium iodide gives pyrrolyl alkyl, aryl, or heteroaryl sulphides in
addition to the expected disulphides. A mechanism is proposed which involves
the initial reaction of iodine and the thiol to give a sulphenyl iodide
species, followed by electrophilic attack of this species on the pyrrole
nucleus. Several of the sulphides were oxidized by hydrogen peroxide in acetic
acid to the corresponding sulphones. Suitably substituted pyrrolyl aryl
sulphides were cyclized to several new fused heterocyclic ring systems.
Studies with Bicyclo[2,2,2]octenes. III. Adducts of 2,3-dihydrobenzyl alcohol and its acetate with ethyl acrylate
Authors: Botica I , Mirrington RN
Published: September 2010

The structures and
stereochemistry of the Diels-Alder adducts of 2,3- dihydro-benzyl alcohol (1a)
and its acetate (1b) with ethyl acrylate have been established. ��� The directing effect of the hydroxymethyl
group in (1a) was such that 82% ?ortho? and 18% ?meta? adducts were obtained.
The reaction of ethyl acrylate with 2,3-dihydrobenzyl acetate (1b) was slower
than with (1a) but gave a similar proportion of meta adduct (21%). ��� Numerous attempts to prepare lactone (9) by
an intramolecular Diels-Alder reaction with 2,3-dihydrobenzyl acrylate (1c)
were unsuccessful.
Reaction of 2-(4'-Thiazolyl)benzimidazole (thiabendazole) with alkyl halides
Authors: Maynard JA , Rae ID , Rash D , Swan JM
Published: September 2010

2-(4?-Thiazolyl)benzimidazole
(thiabendazole) is alkylated at a benzimidazole nitrogen by reaction with
sodium hydride and an alkyl halide. With 1,3-dibromo-propane and
1,2-dibromoethane, the thiazole nitrogen is also alkylated to give quaternary
salts containing the 6,7- dihydro-5H-thiazolo[3?,4?:1.2][1,4]diazepino-[8,9-a]benzimidazole
and 5,6-dihydrothiazolo[3?,4?:1,2]pyrazino[7,8-a]benzimidazole ring systems
respectively. The structures proposed for these tetracyclic products are
supported by spectroscopic examination of the products formed by alkali fission
of their thiazole rings.
Phenolic constituents of Persoonia elliptica (Proteaceae)
Authors: Cannon JR , Metcalf BW
Published: September 2010

5-n-Undecylresorcinol (1)
and persoonol, which has been shown to be (2)-5-undec-3-enylresorcinol (3),
have been isolated from a vesicant extracted from the wood of Persoonia
elliptica R. Br. ��� The structure of persoonol (3) has been
confirmed by synthesis of its dimethyl ether (4).
The chemistry of pyrrolic compounds. XVI. β-Electronegatively substituted dipyrrylmethines
Authors: Clezy PS , Liepa AJ
Published: September 2010

The chemistry of dipyrrylmethines bearing β-electronegative
substituents is reported. The presence of these electrophilic groups makes the
preparation of α-bromomethyl derivatives difficult and this imposes
certain limitations on the type of porphyrin which can be prepared by way of
these intermediates. Acetyl groups located in the 3- position readily cyclize
with one of the pyrrolic nitrogen atoms to give the tricyclic pyrroloindolizine system.
Deceptive simplicity in ABMX N.M.R. spectra. I. Dibenzothiophen and 9,9'-dicarbazyl
Authors: Balkau F , Fuller MW , Heffernan ML
Published: September 2010

Analyses of the spectra of
dibenzothiophen and 9,9?-dicarbazyl in several solvents are reported. It is
found that most of these spectra are partly or wholly deceptively simple. The
criteria for deceptive simplicity in ABMX spectra are discussed in some detail
and it is shown that the parameters given by a LAOCN3 analysis have a much
larger uncertainty for these spectra than the probable errors suggested by the
program. As in the case for deceptively simple three-spin spectra, an accurate
analysis is not possible because the results depend on the methods used to
estimate the positions of weak and overlapping lines. By using solvent shifts
to break the deceptive simplicity, accurate analysis became possible, and the
results were confirmed by examination of 13C-H satellite spectra.
The relative signs of the coupling constants of dibenzothiophen were determined
by tickling experiments.
Synthesis of 2,2-dimethylchromens
Authors: Hlubucek J , Ritchie E , Taylor WC
Published: September 2010

α,α-Dimethylpropargyl
ethers of simple phenols are readily prepared in high yields. Thermal
rearrangement of them affords 2,2- dimethylchromens, also in high yields. These
reactions are used to prepare the natural products, ageratochromen, evodionol
methyl ether, lapachenole, seselin, luvangetin, and braylin. ��� A base-catalysed Wessely-Moser
rearrangement is reported.
Monocyclopentadienyltitanium(III) compounds. I. Halides and their tetrahydrofuran complexes
Authors: Coutts RSP , Martin RL , Wailes PC
Published: September 2010

The halides of rnonocyclopentadienyItitanium(~~~) with the general formula
cpTiXz (where X = C1, Br, and I ; and cp = T-cyclopentadienyl) have been prepared
by pyrolysis from their tetrahydrofuran complexes (cpTiXz,THF). The THF com-
plexes were prepared from the appropriate cyclopentadienyltitanium(~v) trihalide by
reduction in THF. They are believed to be monomers of the form shown below,
involving a pseudo-tetrahedral stereochemistry about the central titanium atom:
The chemistry of pyrrolic compounds. XVII. Furan and thiophen analogues of oxyporphyrins
Authors: Clezy PS , Diakiw V
Published: September 2010

The preparation of a
thiophen and a furan analogue of the oxyporphyrins is described. The properties
of these compounds and their derivatives are discussed and the general
chemistry of these macrocycles compared with the tetrapyrrolic oxyporphyrins.
The reduction of zinc(II) in concentrated lithium halide solutions
Authors: Aylward GH , Buchanan GS , Lee RW , Watton EC
Published: September 2010

The reduction of zinc(11)
in lithium halide solutions has been studied using a.c.
and d.c. polarography over an electrolyte concentration range of 1-20m for
lithium chloride and lithium bromide solutions, and 1-12m for lithium iodide
solutions. The degree of reversibility for the reduction increased with
increase in electrolyte concentration in the order LiI
> LiBr > LiCl. Faradaic impedance techniques were utilized to evaluate the
rates of the electron-transfer processes.
Thermodynamic functions of ionization of t-butyl-substituted and methoxysubstituted phenols
Authors: Bolton PD , Hall FM , Kudrynski J
Published: September 2010

Thermodynamic ionization
constants of 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol,
3,5-di-t-butylphenol, and 3,5-dimethoxyphenol have been measured in aqueous
solution by an e.m.f./spectrophotometric method
within the temperature range 5-60�C and the thermodynamic functions of
ionization ΔG25, ΔH25, ΔS25, and ΔCp25
calculated. These results confirm the
additivity of substituent effects noted previously for the ionization of 3,5-disubstituted
phenols and indicate that this ionization process is relatively insensitive to
steric effects.
Deceptive simplicity in ABMX N.M.R. spectra. III. The spectrum of benzothiophen
Authors: Balkau F , Heffernan ML
Published: September 2010

The analysis of the high
resolution spectrum of benzothiophen in several
solvents is reported. It is noted that the conditions are close to those
leading to deceptively simple spectra, but under very high resolution
sufficient lines could be resolved to give an unambiguous analysis. The
inter-ring, long-range coupling constants, as well as their relative signs,
could be determined from these spectra as a

result of the strong coupling between protons.