bluuebunny/crossref_metadata_2025 huggingface dataset:
The role of t-butyl chloride as an intermediate in the hydrogen chloride catalysed decomposition of t-butyl isopropyl ether
Authors: Daly NJ , Steele LP , Stimson VR
Published: September 2010

The possible formation of t-butyl chloride as an intermediate in the hydrogen
chloride catalysed decomposition of t-butyl isopropyl ether according to the reactions
is examined. Rates for t-butyl chloride decomposition and for the overall catalysed
reaction are measured at 311�C and both a fourth-order Runge-Kutta method and
Hamming's modified predictor-corrector method of numerical integration are used in
computing the pressure-time curves due to the assumed reaction model using experi-
mental values for k , and various assumed values for k2. It is found that no values for
k2 can be found which generate the experimental curves and it is concluded that t-butyl
chloride is not an intermediate of the reaction. If the hydrogen chloride catalysed
decomposition of t-butyl isopropyl ether is typical of the family of catalysed decompo-
sitions then alkyl halides generally have no role as intermediates.
Dipole moments of some aromatic diketones
Authors: Cheng CL , Gore PH , Ritchie GLD
Published: September 2010

Experimental dipole moments
at 25�C are reported and discussed for the isomeric dibenzoylbenzenes and
dimesitoylbenzenes, dibenzoylmesitylene, and dibenzoyldurene as solutes in
carbon tetrachloride.
Reactions of Stenhouse salts. II. The reaction between Stenhouse salts and sodium sulphite
Authors: Lewis KG
Published: September 2010

The previously assigned
structure of the sodium salts formed by the treatment of the Stenhouse salts
derived from primary aromatic amines with sodium sulphite has been shown to be
incorrect on spectral evidence. On the basis of the spectral data a new structure
is proposed.
Experiments on the synthesis of some coumarin derivatives
Authors: Krajniak ER , Ritchie E , Taylor WC
Published: September 2010

Evidence has been obtained
that the reaction between a phenol and maleic or fumaric acid in the presence
of sulphuric acid to yield a coumarin derivative, the Ponndorf reaction, is a
variant of the Pechmann reaction. The scopes of the two reactions appear to be
similar. ��� Attempts to effect the oxidative
cyclization of hydroxyaryl cinnamates to 4-arylcoumarins, a key step in
Seshadri's scheme for the biogenesis of neoflavanoids, were unsuccessful.
4-Aryl-3,4- dihydrocoumarins, which are readily available, are smoothly
converted into 4-arylcoumarins by iodine and potassium acetate in acetic acid.
Cathodic action of lead malate complexes at the dropping mercury electrode
Authors: Khurana SC , Gupta CM
Published: September 2010

The electrode reduction
reaction of lead malate, involving deprotonated malate ion and a proton,
between pK1 and pK2 values of the acid has been
investigated. At pH < pK1 protonated ion participates and a
proton is involved. The effect of ligand concentration on the half-wave
potential of Pb2+ has been investigated and the stability constants
of species so formed computed.
Magnetic properties of some copper(II) complexes of benzimidazolylalkanols
Authors: Hamilton GJ , Kokot E
Published: September 2010

The magnetic susceptibility
in the temperature range 80-400 K is reported for copper(II) complexes of the
general formula CuLX, where L is benzimidazole substituted in the 2-position by
α- or β-hydroxyalkyl groups and in some cases also in the N-position
by a methyl group and X is Br-, Cl-, or acetate. The
magnetic behaviour of 1-(benzimidazol-2- yl)alkanolato complexes is interpreted
in terms of antiferro- magnetically exchange-coupled pairs of copper atoms. The
2- (benzimidazol-2-yl)-alkanolato complex is a linear antiferromagnet.
Annelated furans. XI. The reactions of 2-vinylfurans with acetylenic esters
Authors: Davidson WJ , Elix JA
Published: September 2010

In general dimethyl
acetylenedicarboxylate and methyl propiolate have been found to react with
2-vinylfurans to give the corresponding dimethyl benzofuran-4,5-di-carboxylates
and methyl benzofuran-4- carboxylates respectively. In several instances
dimethyl acetylenedicarboxylate did not react exclusively with the exocyclic
diene system of the 2-vinylfuran and here the corresponding dimethyl
3,6-epoxy-3-vinyl-3,6-dihydrophthalates were obtained by Diels-Alder addition
to the furanoid diene system. At 80� 2-vinylfuran and dimethyl
acetylenedicarboxylate formed the 1 : 2 adduct (11), the formation of which can
be interpreted as involving an ene addition of a second mole of the acetylenic
ester to the initially formed Diels-Alder adduct.
Annelated furans. XIV. Synthetic analogues of usnic acid
Authors: Elix JA , Tronson D
Published: September 2010

The cycloaddition of
dimethyl acetylenedicarboxylate and methyl propiolate to
2-isopropenyl-3-methylbenzofurans afforded a convenient and versatile route to
9b-methyl-3,9b-dihydrodibenzofurans and 9b- methyl-1,9b-dihydrodibenzofurans,
which are synthetic analogues of usnic acid. Selenium dioxide oxidation of
dimethyl 4,9b-dimethyl-3,9b- dihydrobenzofuran-1,2-dicarboxylate (5; R1
= R2 = H) has been shown to proceed by oxidative rearrangement and
demethylation to give a mixture of dimethyl 1-hydroxy-4,9b-dimethyl-1,9b-dihydrodibenzofuran-1,2-
dicarboxylate (9), dimethyl 4-methyldibenzofuran-1,2-dicarboxylate (10), and
dimethyl 6-(o-hydroxy-phenyl)-4,6-dimethyl-5-oxocyclohexa- 1,3-diene-1,2-dicarboxylate(8).
Evidence concerning the mechanism of this reaction is discussed. Autoxidation
of methyl 4,9b-dimethyl-3,9b- dihydrodibenzofuran-1-carboxylate (12) proceeded
smoothly to give methyl 4a-hydroperoxy-4,9b-dimethyl-4a,9b-dihydrodibenzofuran-1-
carboxylate (17) and methyl 4-methyldibenzofuran-1-carboxylate (16). Reduction
of the hydroperoxide (17) with triethyl phosphite gave methyl
6-(o-hydroxyphenyl)-4,6-dimethyl-5-oxocyclohexa-1,3-diene-1-carboxylate (19),
which could also be obtained by oxidation of the ester (12) with selenium
dioxide. Methyl 4,9b-dimethyl-3-oxo-3,9b-dihydrodibenzofuran- 1-carboxylate
(22) and the corresponding 4,4a-epoxide (23) were obtained together with the
dibenzofuran (16) and the phenol (19), by oxidation of (12) with chromium
trioxide.
Thermodynamic evidence for complex formation between carbon tetrachloride and triethylamine
Authors: Fenby DV
Published: September 2010

The molar excess enthalpy
of the system carbon tetrachloride+ triethylamine has been measured at 298.15
K. The results are consistent with complex formation between the unlike
molecules and provide further evidence for the electron acceptor ability of
carbon tetrachloride.
Adsorption at solid-liquid interfaces. II. Models of the electrical double layer at the oxide-solution interface
Authors: Wright HJL , Hunter RJ
Published: September 2010

An extension has been made
to Gouy-Stern-Grahame models of the double layer on mineral oxide surfaces.1
In this work and an earlier paper,2 the Stern isotherm is used for
adsorption of p.d. ions at the surface. This is essentially an inversion of the
modified Nernst equation given by Levine and Smith.3 The development
of the surface charge and potential is considered by two different but related
methods. Comprehensive calculations show that the zeta potential of oxide
systems may be reasonably simulated with such models but the calculated surface
charge is much less than that found experimentally. It is suggested that a
model in which this surface charge is incorporated into a gel layer may be more
appropriate.
Changes occurring at surfaces during reactions between powdered iron(III) oxide and some carbonates
Authors: Beretka J , Ridge MJ
Published: September 2010

The spikes, platelets, and
other features with extensive surfaces observed on the particles of the product
of the reaction of barium carbonate with iron(III) oxide or aluminium oxide
result from reaction with carbon dioxide in the atmosphere in the presence of
water vapour. They do not appear to be features of the solid state reaction as
was thought earlier.
The effect of irradiation on electrode processes. The hydrogen peroxide electrode
Authors: Airey PL
Published: September 2010

A study has been made of
the effect of 60Co γ and 1 MeV
electron beam irradiation on the hydrogen peroxide electrode in acid solutions.
The small positive potential shifts which are observed are due to the effect of
the irradiation on the electrode reactions defining the hydrogen peroxide mixed
potential. It is deduced from steady state polarization studies that the HO2
radical generated radiolytically in the bulk solution is not electrochemically
significant. On prolonged irradiation the electrode potential falls to a value
negative to E(H2O2) if the concentration of radiolytic H2
builds up sufficiently to establish the H2-H+ exchange as
an electrochemically significant process.
Copper(II)-promoted solvolyses of nickel(II) complexes. III. Tetradentate Schiff base ligands containing various diamine segments
Authors: Fee WW , Pulsford JD
Published: September 2010

The large variations in the
rates of the copper(II)-promoted solvolyses of various nickel(II) complexes,
containing Schiff base ligands with varying diamine substituents, is attributed
to steric effects. The important rate differences occur for reactants whose
stereochemistries and electronic properties appear little different. However,
the steric effects cannot be viewed definitely from either nickel-diamine
dissociation or copper-diamine formation. Nickel reactants which may be
distorted from planarity give trimeric products on reaction with copper in dmso
and dmf, if the reactions are carried out at high initial concentration ratios
of copper(II) to nickel complex. Ligand substitution studies indicate a
differing reactivity sequence for the diamine-substituted ligands in their
capacities as entering, compared to leaving, groups.
N.M.R. spectra of the carbolines. I. Spectral parameters
Authors: Balkau F , Heffernen ML
Published: September 2010

The N.M.R. spectra of
carbazole and the four isomeric azacarbazoles, α-, β-, γ-,
δ-carboline, have been studied in dimethyl sulphoxide and acetone and,
where possible, in tetrahydrofuran and chloroform. Spin decoupling and n.O.e. experiments have been used to aid in the assignment
of the spectra and to determine the relative signs of coupling constants. The
spectra have been fully analysed and the trends in the values of the spectral
parameters for this series of related molecules are discussed. In two of these
compounds small couplings across the tertiary nitrogen atoms, similar to that
observed in pyridine, were found.
Some reactions of O,O-diphenylphosphoryl azide
Authors: Cremlyn RJW
Published: September 2010

Diphenylphosphoryl azide,
in contrast to N,N?-disubstituted phosphorodiamidic azides, undergoes
nucleophilic displacement of the azido group by reaction with water, butanol,
ammonia, and amines. Possible mechanisms for the conversion of diphenyl-phosphoryl
azide into urethanes and amides are briefly discussed. Pyrolysis of N,N?-
dicyclohexylphosphorodiamidic azide gave the phosphenimidic amide dimer.
Cation effects in molten nitrates. Their influence on the solubility product of silver bromide
Authors: Temple RB , Thickett GW
Published: September 2010

This paper reports a study
of how a particular chemical equilibrium, namely the solution of silver bromide
in molten potassium nitrate, is affected by the replacement of alkali-metal
cations by alkaline-earth ones or by Li+. ��� Concentration cells with silver electrodes
were employed to measure ΔG�, ΔH�, and ΔS� for the solution
process and along with calculations made using Born-Haber
cycles and the Sackur-Tetrode equation have provided
values of ΔG�, ΔH�, and ΔS� for the solvation of AgBr in the various melts. AgBr is
found to become increasingly insoluble as the proportion of divalent ion is
increased. Some generalizations have been drawn from the tabulated results. ��� The solubility has also been studied in the
hydrate melts Mg(NO3)2,6H2O and Ca(NO3)2,4H2O
and the results compared to the anhydrous nitrate melts of the other cations of
Group IIA.
Chemistry of the Podocarpaceae. XLV. Heterocyclic derivatives of 12-Hydroxypodocarpa-8,11,13-trien-19-oic acid
Authors: Beresford GD , Cambie RC , Mathai KP
Published: September 2010

The preparation of chromone
(11), methylbenzoxazole (18), methylbenzisoxazole (17), flavonoid (12), and
benzofuran (19) derivatives from 12-hydroxypodocarpa-8,11,13-trien-19-oic acid
(1) is reported. Treatment of the chromone (11) with hydrazine hydrate affords
the 3?-phenylpyrazole (20) while treatment with hydroxylamine hydrochloride
affords the 3?-phenylisoxazole (21).
The reaction of cystine and Alanine-3-sulphinic acid with halogens
Authors: Gordon PG
Published: September 2010

Aqueous chlorine and
bromine react with cystine, cysteine, alanine-3- sulphinic acid, and cystine
S,S-dioxide to give cysteic acid (3) and cysteicylcysteic acid (2).' When the
reaction is performed in the presence of other amino acids it is possible to
obtain mixed peptides. The mechanism of formation of the peptide bond is
discussed and a sulphonic-carboxylic acid mixed anhydride is proposed as an
intermediate.
The transport numbers of hydrochloric acid in glycerol-water mixtures at 25°C
Authors: Khoo KH
Published: September 2010

Transport numbers of
hydrochloric acid have been determined in glycerol-water mixtures by means of a
simple e.m.f. method.
Circular dichroism spectra of N,N-Dimethyl-L-amino acids
Authors: Hawkins CL , Lawrance GA
Published: September 2010

The circular dichroism
spectra in the region 190-300 nm have been measured at pH 1 and pH 13 in
aqueous solution for a series of N,N-dimethyl-L-amino acids. A dominant
positive Cotton effect is generally observed between 205 and 225 nm as has been
found previously for the parent L-amino acids. These results are consistent
with the same conformer being dominant for both series of compounds.
Triterpenoids of Achras sapota (Sapotaceae)
Authors: Hart NK , Lamberton JA , Triffett ACK
Published: September 2010

Four free triterpene acids
from Achras sapota wood have been identified as hederagenin, bayogenin,
polygalacic acid, and protobassic acid, and hederagenin and bayogenin have been
obtained by hydrolysis of the saponins.
The bridgehead proton spin coupling in endo-cis-5,6-Dibromonorbornene
Authors: Browne K , Kagi RI
Published: September 2010

The signals due to the
vinyl and bromomethine protons in the 60-MHz p.m.r. spectrum of
endo-cis-5,6-dibromonorbornene have been analysed in detail by means of the
computer program LAOCN3. All non-zero coupling constants in the system are
obtained. The value for the bridgehead- bridgehead coupling constant J1.4 corrects
a reported value obtained by an incorrect analysis procedure.
4,4'-Bipyridine complexes with some uranyl salts
Authors: Ahuja IS , Singh R
Published: September 2010

The complexes formed by
4,4?-bipyridine with uranyl chloride, sulphate, and nitrate of the type UO2(4,4?-bipyridine)X2,
where X = Cl or 1/2SO4, and UO2(4,4?-bi-pyridine)1.5(NO3)2
have been prepared and their infrared spectra in the rock salt and low-frequency
region (down to 200 cm-1) studied in the solid state. I.r. spectra of these complexes show that 4,4?-bipyridine
acts as a bidentate ligand bridging between two metal atoms. It is suggested
that the sulphate and nitrate groups act as bidentate chelating ligands and the
complexes are polymeric structures.
Thermodynamics of metal-ligand bond formation. VI. Trimerization and base addition of nickel(II) β-diketonates
Authors: Ang LT , Graddon DP
Published: September 2010

Five nickel(II) complexes
of β-diketones (LH) have been studied by calorimetric titration with
pyridine in benzene solution. Trimerization of the complexes NiL2 is
endothermic and entropy-driven, probably as a result of desolvation of the
low-spin monomers. Reaction with pyridine occurs in two steps, forming
successively Ni2L4(py) and NiL2(py)2.
The enthalpy of formation of NiL2(py)2 from the
intermediate adduct is about -40 kJ mol-1 and shows no evidence for
bulkiness of the ligand leading to steric instability in Ni2L4(py).
Variations in the relative stabilities of the monomeric and trimeric forms of
NiL2 seem more likely to be due to electronic than steric effects.
The influence of cations on the formation of high oxidation state compounds of manganese in molten salts
Authors: Temple RB , Thickett GW
Published: September 2010

The reactions of various oxo compounds of manganese were examined in several melts
and peroxide- and/or superoxide-melt solutions. Whilst MnO43-
appears to be the most stable species in NaNO2 and Na2O2-NaNO2
solutions, the green MnO42- ion is favoured in KNO2
melts and also in nitrate melts in which K+ predominates over Na+.
Terpenoid chemistry. XXII. The trans,trans- and cis,cis-nepetalinic acids
Authors: Grant HG , Sutherland MD
Published: September 2010

A study of the trans, trans-nepetalinic
acids has resolved the numerous discrepancies in the literature concerning the
physical constants of these reference compounds and has correlated these
properties and the stereochemistry of the two epimers. Thus (2S,2?S,3?S)-2(2?-carboxy-3?-
methylcyclopentyl)propanoic acid shows m.p. 123.4-123.6�, [α]D
-39� (1%, CHCl3+1% EtOH) and the (2R,2?S,3?S) epimer, m.p.
121.5-122�, [α]D -52� (1%, CHCl3+1% EtOH), or m.p.
142-143� for the (�)-acid. ��� The cis,cis-nepetalinic acids have also
been prepared and their stereochemistry assigned as (2S,2?R,3?S), m.p. 157-158�,
[α]D +18.6� (1%, CHCl3+1% EtOH), and (2R,2?R,3?S),
m.p. 68�, [α]D -36� (1%, CHCl3+1% EtOH).
The identification of ( - )-γ-Amorphene with ( - )-γ-Muurolene
Authors: Briggs LH , White GW
Published: September 2010

Reconsideration of the
physical and chemical properties of (-)-γ- amorphene indicates that it is
identical with (-)-γ-muurolene.
Halogenated terpenoids. IX. Further terpinolene tetrahalide derivatives
Authors: Carman RM , Venzke BN
Published: September 2010

The syntheses of new
1,2,4,8-, 1,2,8,9-, and 1,4,7,8-tetrahalides of p- menthane are described in
both optically active and racemic series. Vicinal dihalo rearrangements in the
optically active terpinolene (1,2,4,8-) series provide proof of the involvement
of the C4, C8 bromines during the rearrangement of terpinolene tetrabromide.
Dialkylaminofluorophosphine complexes of rhodium(I)
Authors: Bennett MA , Turney TW
Published: September 2010

Diethylaminodifluorophosphine, PF2NEt2, forms dimeric, halogen-bridged
rhodium(1) complexes [RhX(PF2NEt2)2]2 (X = C1 or I) which react reversibly with
an excess of the ligand to give non-ionic, five-coordinate complexes RhX(PF2NEt2)4.
Dimethylaminodifluorophosphine, PF2NMe2, forms analogous complexes but, in
contrast with diethylaminodifluorophosphine, the complex RhC1(PF2NMe2), decom-
poses thermally to give initially an isolable tris complex RhC1(PF2NMe2),, which has
no known counterpart in CO or PF, chemistry. The tris-complex decomposes thermally
to give [RhC1(PF2NMe2),l2. Bis(dimethylamino)fluorophosphine, PF(NMe&, forms
a tris complex, RhCl{PF(NMe2)2)3, but a dimeric bis-ligand complex could not be
isolated. In contrast with tertiary phosphines and phosphites, the fluorophosphines do
not form ionic rhodium(1) species. Monomeric derivatives such as R ~ ( ~ C ~ C ) ( P F ~ N E ~ ~ ) ~ ,
Rh(C5H5)(PF2NEt2)2, RhC1(PF2NEt2)(PPh3), and RhC1(PPh3)(PF2NEt2)2 have been
prepared. The complexes [RhCl(CO)2]2 and [RhC1(PF2NEt2)2] undergo ligand
redistribution on mixing, the product consisting mainly of [RhC1(CO)(PF2NEt2)]2.
19F n.m.r, data are reported and used inter aha to show that R ~ ( ~ C ~ C ) ( P F ~ N E ~ ~ ) ~ , but
not Rh(C5H5)(PF2NEt2)2, exchanges rapidly with free PF2NEt2, and that, in RhC1-
(PPh3)(PF2NEt2)2, the fluorophosphine ligands are mutually cis. Bands in the infrared
arising from P-F vibrations are reported and discussed. The dialkylaminofluoro-
phosphines appear to be poorer n-acceptors and/or better o-donors than PI?, but are
better n-acceptors than phosphites.
Thermodynamics of metal-ligand bond formation. VII. Pyridine adducts of nickel(II) salicylideneiminato complexes
Authors: Dakternieks DR , Graddon DP
Published: September 2010

Thermodynamic data have
been obtained by calorimetric titration in benzene solution at 30�C for the
reaction: NiL2+2py = NiL2(py)2 for 16
different nickel(II) complexes of Schiff bases of salicylaldehyde, 5- chlorosalicylaldehyde,
and 5-chloro-2-hydroxybenzophenone. It has also been possible to obtain data
for the trimerization of bis(N-phenyl-5- chlorosalicylideneiminato)nickel(II),
and for two of the complexes estimates have been obtained for the addition of
base in two successive steps. ��� Pyridine adducts, NiL2(py)2,
of N-aryl complexes have enthalpies of formation about -40 kJ mol-1,
those of N-alkyl complexes about -60 kJ mol-1 and a small inductive
effect can be observed due to chloro substitution, but variations in
stabilities of the adducts arise mainly from entropy effects. In the two
systems studied most of the enthalpy of adduct formation is associated with
addition of the second molecule of base.
The polarography of some substituted azobenzenes in acetonitrile. IV. The effect of 'intermediate' strength proton donors
Authors: Boto KG , Thomas FG
Published: September 2010

The addition of proton
donors to azobenzene derivatives in the aprotic solvent acetonitrile gives rise
to polarographic waves at more positive potentials than the normal azo
reduction waves. These waves have been ascribed to the reduction of azonium
species formed by protonation of the azo compound. For the ?intermediate?
strength proton donors (e.g. acetic acid) the azonium wave exhibits definite
splitting which can be explained in terms of mixed general and specific
protonation steps prior to the reduction of the azonium species. Evidence to
support the mixed general and specific protonation effects is presented.
The kinetics of isomerization of allylbenzene homogeneously catalysed by palladium(II) in acetic acid
Authors: Cruikshank BI , Davies NR
Published: September 2010

The changes in the kinetics
observed during the isomerization of allylbenzene catalysed by palladium(II)
are interpreted in terms of the slow formation of a hydrido complex of
palladium(II) which subsequently attains a constant concentration in an
equilibrium system. The kinetics during these phases are shown to be consistent
with first-order dependence on the concentration of an active catalyst formed
in a bimolecular reaction from a mononuclear palladium(II) complex and with a
regenerative hydrido-π-alkene-σ-alkyl mechanism of isomerization. The
hypothesis that a further stage in the kinetics reflects a change in the rate
determining step to one involving alkene displacement from the catalyst is
supported by the experimental evidence. The concentration of active catalyst is
shown not to fall appreciably until all the allylbenzene has undergone
isomerization, but thereafter there is a slow reduction of catalytic activity
which is not completely restored by the addition of further allylbenzene. It is
suggested that the slow formation of a π-allylic complex is responsible.
The reduction of uranium hexafluoride by hydrogen at room temperature
Authors: Levy JH , Wilson PW
Published: September 2010

The reaction between
uranium hexafluoride and hydrogen is catalysed by hydrogen fluoride, especially
in the presence of platinum metal. The catalysed reaction has an observable
rate at room temperature. The reaction provides the basis for the preparation
of β-uranium pentafluoride on a laboratory scale.
4,5-Diazafluoren-9-one from the oxidation of 1,10-Phenanthroline by permanganate
Authors: Eckhard IF , Summers LA
Published: September 2010

4,5-Diazafluoren-9-one is a
co-product of the oxidation of 1,10- phenanthroline with alkaline potassium
permanganate along with 2,2?- bipyridyl-3,3?-dicarboxylic acid.
A nitrogen-14 magnetic resonance study of the exchange of acetonitrile on cobalt(II) complexes
Authors: Lincoln SF , West RJ
Published: September 2010

A 14N N.M.R.
study of the exchange of acetonitrile on high-spin Co(triol)(MeCN)32+ (kex = (23 � 2) x 104
s-1 at 298 K; ΔH? = 40 � 2 kJ mol-1; ΔS? = -9.6
� 6.2 J mol-1 K-1), high-spin Co(trenol)(MeCN)~2+ (kex ≥ 2-x 106
s-l at 223 K), and low-spin Co(cyclam)(MeCN)n2+ (where it is considered that
n = 1 or 2 and kex ≥ 8
x 106 s-1 at 266 K) is reported, as are the magnetic
moments and visible spectra of these complex ions.
The reaction of benzonorbornadiene and related compounds with iron carbonyls
Authors: Lombardo L , Wege D , Wilkinson SP
Published: September 2010

Reaction of benzonorbornadiene, 7-isopropylidenebenzonorbornadiene
(1,4-dihydro-9-isopropylidene-1,4-methanonaphthalene) and
1,4-dihydro-1,4-epoxynaphthalene (7-oxabenzonorbornadiene) with dicarbonyldinitrosyliron, Fe(CO)2(NO)2,
gave in good yields the corresponding dimers having the exo-trans-exo configuration. Treatment of a mixture of benzonorbornadiene and norbornadiene
with Fe(CO)2(NO)2 gave a 'crossed dimer', in addition to
the dimers derived from benzonorbornadiene and norbornadiene. The reaction of benzonorbornadiene
with pentacarbonyliron at 100� gave the exo-trans-exo dimer and a ketone derived
by dimerization and carbonyl insertion. This ketone, and the analogous ketone
obtained from 7-isopropylidenebenzonorbornadiene, have been assigned the exo-trans-exo configuration. Reaction of
1,4-dihydro-1,4-epoxynaphthalene with enneacarbonyldiiron,
Fe2(CO)9, at room temperature gave tetracarbonyl(l,4-dihydro-l,4-epoxynaphthalene)iron(0),
in which the olefinic ח-bond is bonded to the metal. In
solution at 63� this complex gave naphthalene.
Derivatives of cis-photodimers of 2-alkoxynaphthalenes
Authors: Collin PJ , Sugowdz G , Teitei T , Wells D , Sasse WHF
Published: September 2010

U.V. irradiation of
2-methoxynaphthalene gives besides the trans-dimer
(1) a ketone, for which the cis
structure (3) is proposed on spectral and chemical grounds. Ketone (4) is
similarly obtained from 2-ethoxynaphthalene.
The chemistry of pyrrolic compounds. XXV. The chemistry of acetal and thioacetal derivatives of pyrrolic systems
Authors: Clezy PS , Fookes CJR , Lau DYK , Nichol AW , Smythe GA
Published: September 2010

The synthesis of acetal and
thioacetal derivatives of simple pyrroles
is described. Methods are reported which allow the use of the thioacetal function as a means of protecting a formyl group in a pyrrolic molecule during the preparation
of a dipyrrylmethane. By this procedure certain α-formyldipyrrylmethanes, not accessible by other methods,
have been obtained.
The chemistry of pyrrolic compounds. XXVI. Porphyrins with negative groups in opposite pyrrolic ring systems
Authors: Clezy PS , Fookes CJR
Published: September 2010

The use of 4-acetyl(or ethoxycarbonyl)-5-formyl-2,2'-dipyrrylmethanes in the
synthesis of porphyrins substituted with negative
(electron-withdrawing) groups in opposite pyrrolic ring systems is discussed. A
range of such porphyrins has been prepared including
2-formyl-6-vinyldeuteroporphyrin 11 diethyl ester, the synthesis of which
duplicates the chromophoric system present in
porphyrin-a, the prosthetic group of cytochrome oxidase.
Halogenated terpenoids. X. Optically active terpinolene tetrabromides
Authors: Carman RM , Venzke BN
Published: September 2010

The syntheses of optically
active terpinolene tetrabromides
are discussed and the chirality of these products is
followed through various rearrangement reactions.
The anisotropy of the aliphatic C-C bond
Authors: Pierens RK
Published: September 2010

In the conformational
analysis of organic molecules by electric birefringence and Rayleigh
scattering techniques, the value assigned to the aliphatic C-C bond, γC-C, is of fundamental
importance. Thiscommunication discusses the
implications of recent changes in the experimental parameters used to derive γC-C.
Thermodynamics of metal-ligand bond formation. IX. Trimerization and base addition of Bis(2,6-dimethylheptane-3,5-dionato)nickel(II)
Authors: Graddon DP , Nyein TT
Published: September 2010

The equilibrium constant
for trimerization of bis(2,6-dimethylheptane-3,5-dionato)nicke1(11) in benzene
solution at 30�C has been determined spectrophotometrically, K = 2 x 103
I2 mol-1; the heat of trimerization has been determined
calorimetrically, ΔH = -7 kJ (g-atom Ni)1. Thermo- dynamic data
have also been obtained for the base addition reactions with pyridine leading
to first Ni2L4(py) then NiL2(py)2.
Results are compared with those previously obtained for other nickel(11) β-diketone
complexes.
75As nuclear quadrupole resonance in some arsenic ring compounds
Authors: Bastow TJ , Elmes PS
Published: September 2010

75As nuclear quadrupole resonance has been observed in
a number of cyclic and heterocyclic organoarsenic compounds.
In cases where the structure has been determined, the multiplicity of the
resonancesagrees with the number
demanded by the structure. Where the structure has not been determined the
results indicate the existence of certain molecular symmetry elements in the
solid state.
Some substituted ureidobenzenesulphonohydrazides
Authors: Cremlyn RJW , Martin RA
Published: September 2010

Chlorosulphonation of o-chlorophenyl
and o-tolylurea
afforded the corresponding 3-substituted 4-ureidobenzenesulphonyl chlorides
(2). With m- and p-tolylurea low yields of sulphonyl
chlorides were obtained. The m-isomer
gave 2-methyl-4-ureidobenzenesulphonyl chloride, but n.m.r, studies indicated
that the p-isomer afforded a mixture
of mainly 2-methyl-5-ureido- and some 5-methyl-2-ureido-benzenesulphonyl
chloride. The various sulphonyl chlorides have been converted intohydrazides, hydrazones and azides. 3-Methyl-4-ureidobenzenesulphonyl
azide (11) undergoes pseudohalogen replacement of the
azido group, on treatment with butylamine, to give the corresponding N-utylsulphonamide (12).
Attempts to obtain nitrene-insertion reactions
by heating the azide (11) with naphthalene andanisole were unsuccessful.
Halogenated terpenoids. XII. The identity of Wallach's tetrabromides C10H14Br4
Authors: Carman RM , Venzke BN
Published: September 2010

The identity of the two tetrabromides, products from the reaction of r-l,t-4,8-tribromo-p-menthane (1) with sodium ethoxide
followed by bromination, is determined.
Solvation of ions. XIX. Thermodynamic properties for transfer of single ions between protic and dipolar aprotic solvents
Authors: Cox BG , Hedwig GR , Parker AJ , Watts DW
Published: September 2010

Standard molar free
energies, enthalpies and entropies of transfer of some uni-univalent
electrolytes from water to methanol, N-methylformamide, formamide, dimethyl sulphoxide,
N,N-dimethyl- formamide, propylene
carbonate, sulpholane, N-methylpyrrolidone and acetonitrile are
presented. They have been divided into the corresponding thermodynamic
properties for single ions by means of extrathermodynamic
assumptions. Changes in the chemistry of anions on transfer from protic to
dipolar aprotic solvents are mainly a function of enthalpy changes. There is a
substantial loss of entropy on transferring both anions and cations from water
to non-aqueous solvents. Entropies of transfer can be interpreted in terms of
ordering and disordering solvent molecules and a uniquely extensive water
structure. Evidence for solvation of the first and second kind in water is
presented. Enthalpies of transfer from water are exothermic for cations but
endothermic for many anions.
The reaction of amines with conjugated dienes in the presence of alkali naphthalenide. A new synthesis of geranyl acetate
Authors: Fujita T , Suga K , Watanabe S
Published: September 2010

Reaction of a conjugated
diene with diethylamine using sodium naphthalenide in tetrahydrofuran gives a mixture of β,γ-unsaturated amines. From myrcene,
N,N-diethyl-2-ethylidene-6-methylhept-5-enylamine,
N,N-diethylnerylamine and N,N-diethylgeranylamine are obtained.
Reaction of β,γ-unsaturated amines with
acetic anhydride gives a mixture of β,γ-unsaturated
acetates. From N,N-diethylgeranylamine, a mixture of neryl
acetate and geranyl acetate is obtained.
Synthesis of exo- and endo-2,3,3-Trimethylnorbornane-2-carboxylic acid
Authors: Gream GE , Pincombe CF
Published: September 2010

Successful as well as
several unsuccessful routes for the synthesis of exo- and endo-2,3,3-trimethylnorbornane-2-carboxylic
acid are described.
The camphenehydro (methylcamphenilyl) and isobornyl (bornyl) cations. III. Oxidative decarboxylation of carboxylic acids with lead tetraacetate
Authors: Gream GE , Pincombe CF , Wege D
Published: September 2010

The oxidative decarboxylation of exo- and endo-bornane-2-carboxylic acid, exo- and endo-2,3,3-
trimethylnorbornane-2-carboxylic acid and a-campholenylcarboxylic acid [3-(2',2',3'-trimethyl-
cyclopent-3'-eny1)propanoic acid] with lead tetraacetate in benzene and dimethyl sulphoxide (each
containing pyridine) in the presence, and absence, of cupric acetate has been investigated. The mode
of formation of almost all the products can be satisfactorily rationalized in terms of the initial
generation of radicals. In the case of exo- and endo-bornane-2-carboxylic acid, the derived bornyl
radical forms organolead and organocopper derivatives that decompose in three ways: (1) by
heterolysis by the direct route to give the equilibrating isobornyl and camphenehydro cations,
(2) by a cyclic cis-elimination to give bornylene and (3) by an SNi process to give isobornyl and bornyl
acetates. exo- and endo-2,3,3-Trimethylnorbornane-2-carboxylic acid yield the 2,3,3-trimethyl-
norborn-2-yl radical which is converted into the equilibrating camphenehydro and isobornyl cations
either by one-electron oxidation by lead species or via organolead or organocopper derivatives
which undergo heterolysis. Processes involving cyclic cis-elimination and SNi substitution may also
operate in the organometallic derivatives derived from the tertiary radical.
a-Campholenylcarboxylic acid yields the a-campholenyl radical which, in the absence of cupric
acetate, undergoes in the main cyclization to give the 2,3,3-trimethylnorbornyl radical. The resulting
mixture of products is similar to that obtained from exo- and endo-2,3,3-trimethylnorbornane-2-
carboxylic acid. In the presence of cupric acetate, the a-campholenyl radical is trapped at least to
the extent of 50% in benzene and 80% in dimethyl sulphoxide to give the corresponding organo-
copper derivative which undergoes a cyclic elimination to give 2,3,3-trimethyl-4-vinylcyclopentene
and may undergo heterolysis by the x-route to give the camphenehydro and isobornyl cations.
A marked change in the composition of the products on changing the solvent from benzene to
dimethyl sulphoxide is observed only in the case of a-campholenylcarboxylic acid in the presence
of cupric acetate.
The structure of monoclinic Tris(1,3-diphenyltriazenato)cobalt(III)-toluene(1/1) : An octahedral complex containing three four-membered chelate rings
Authors: Corbett M , Hoskins BF
Published: September 2010

Crystals of the toluene
solvate of tris(l,3-diphenyltriazenato)cobalt(111) [abbreviated as Co(dpt)3], monoclinic with space group C2/c with a = 20.73(1), b =
16.30(3), c = 13.34(1) �, β =
120.4(1)� containing four molecules per unit cell, are composed of discrete
molecules of Co(dpt)3 and toluene, each
separated from its neighbours by normal van der Waals distances. The six
terminal nitrogen atoms of the three dpt groups bond
to the cobalt atom, forming the three four-membered chelate rings.
Dithiochelates of the Bis(η-cyclopentadienyl)vanadium(IV) moiety. II. N,N-Dialkyldithiocarbamate and O,O'-dialkyldithiophosphate complexes
Authors: Casey AT , Thackeray JR
Published: September 2010

Two series of complexes,
believed to be of the forms

(R1 = R2 = Me, Et, Pri, Bu
and R1 = H, R2 = Me)

and

(R = Me, Et, C2H4Cl,
Pr, Bu, n-C8H17) have been prepared. A large anion X was
used to precipitate the green compounds, which are monomeric and 1 : 1
electrolytes in solution. Infrared, electronic and e.s.r. spectra are reported
together with magnetic susceptibility measurements. The phosphorus hyperfine
coupling observed in the dithiophosphates is discussed in the light of current
models.
Formation of borate complexes of inosamines (aminodeoxyinositols) and their separation by paper electrophoresis
Authors: Frahn JL , Mills JA
Published: September 2010

The electrophoretic
mobility of an inosamine in borate buffer is very dependent on configuration,
and a set of 10 inosamines showed a wide range of mobilities. The order of
mobilities within the set changed as the pH of the buffer was changed in the
range 7.7-9.5. Paper electrophoresis in borate buffers can effectively separate
mixtures of inosamines. The probable site of reaction between an inosamine and
borate ions has been identified for some isomers. In aminodeoxy-scyllo-inositol and 3-amino-3-deoxy-epi-inositol the amino group is involved
in the formation of a tridentate borate complex of adamantane-type structure,
which is electrically neutral over the above range of pH values. Aminodeoxy-scyllo-inositol simultaneously combines
with a second molecule of borate, forming a bis-tridentate complex with one
anionic centre. There is evidence that in other isomers protonation of the
amino group and formation of anionic borate complexes at hydroxyl groups are
not independent reactions. Paper electrophoresis in non-complexing buffers
provides evidence for the relative basicities of inosamines.
DL-2-Amino-2-deoxy-epi-inositol,
which has an interaction between axial amino and hydroxyl group in the
preferred conformation, was the strongest base in the set, whereas the bases
with an axial amino group free of such an interaction were the weakest.
Inosamines form N-carboxyl
derivatives in the normal way on exposure to carbon dioxide in the presence of
strong alkali.
Unusual products from the cyanide displacement reaction of methyl 5-Chloromethylfuran-2-carboxylate
Authors: Cresp TM , Sargent MV
Published: September 2010

Treatment of the title
chloro compound (9) with sodium cyanide in N,N-dimethylformamide
or dimethyl sulphoxide yielded methyl 2-cyan;-2,5-dihydro-5-(5'-methoxycarbonylfurfurylmethylene)-furan-2-carboxylate
(12) and methyl 2-cyano-2,5-dihydro-5-[bis(5'-methoxycarbonylfurfuryl)methylenelfuran-2-carboxylate
(13) as well as methyl 5-cyanomethylfuran-2-carboxylate (8).
N.M.R. and absorption spectra of nitrotoluidines
Authors: Yokoyama T
Published: September 2010

N.m.r. chemical shifts of ring protons and absorption spectra of 4-substituted 2-nitroaniline deriva-
tives were investigated. It was ascertained that the rotations of dimethylamino and/or 2-nitro
groups are influenced by the resonance interaction of the dimethylamino group with 4-substituents
and the C1 → C2 absorption band is displaced bathochromically by resonance saturation with
4-substituents. The long-range coupling of NH with H5 in N-methyl-2-nitro-p-toluidine was found
to be absent and it is considered that the intramolecular hydrogen bonding of amino hydrogen with
the 2-nitro group is ruptured by ROH and polar solvents.
Non-empirical valence-electron molecular orbital calculations. The NEVE method for first-row diatomic molecules
Authors: Peel JB
Published: September 2010

A non-empirical
valence-electron method suitable for molecular orbital calculations on large
molecules containing heavy atoms is described. The method uses a minimum STO
basis for the valence orbitals and accounts for
core-valence interactions by means of a simple pseudopotential
which affords corrections to the diagonal F matrix elements. All integrals
involving one and two centres are included, and these are evaluated
theoretically. The method produces electronic energies and electron density
properties which are comparable with those of corresponding all-electron ab-initio
calculations. In this paper two versions of the method are described, the basic
non-parametric method and the parametric method which involves a simple
modification for the two-centre integrals involving atoms of different size or electronegativity. Results of calculations on first-row
diatomic molecules are described. It is hoped that the method will be suitable
for calculations on larger molecules and molecules containing heavier atoms.
Studies of organophosphorochloridates. Some derivatives of o-biphenylyl and p-cumenylphenyl phosphorodichloridates
Authors: Cremlyn RJW , David J , Kishore N
Published: September 2010

The preparation of o-biphenyl and p-cumenylphenyl phosphorodichloridates and the corresponding
dichloridophosphorothioates are discussed. The phosphorodichloridates have been
converted into some of the corresponding dialkyl phosphates, N,N'-disubstituted phosphorodiamidates,
and phosphorodihydrazides. The N-arylphosphoramidic
chloridates were converted into mixed phosphorodiamidates, hydrazides and
azides. The phosphorodichloridates were hydrolysed to the corresponding
dihydrogen phosphates, but the reaction failed with the dichloridophosphorothioates.
Attempts to obtain nitrene-insertion reactions, by heating the phosphoramidic
azides with diphenyl ether, were also unsuccessful; however, the azide did
undergo pseudohalogen replacement by treatment with ethylamine or morpholine.
The biological activity of some of these compounds is briefly discussed.
Studies on intramolecular alkylation. VII. The preparation of phenanthrene derived tetracyclic ketones : Intermediates for gibberellin synthesis
Authors: Klose TR , Mander LN
Published: September 2010

The 1,2,3,4,9,10-hexahydrophenanthrenecarboxylic
acids (9), (10) and (12) have been prepared and converted via their diazomethylcarbonyl derivatives to the
1,2,3,9,10,10a-hexahydro-2,l0a-ethano- phenanthren-12-one derivatives (2), (3)
and (4), respectively, by short and efficient routes.
Complexes of acetic anhydride and Lewis acids and bases
Authors: Malhotra KC , Katoch DS
Published: September 2010

Acetic anhydride forms
compounds of 1 : 1 composition with trihalides of
boron, aluminium, with antimony pentachloride, and
with the trioxides of sulphur and selenium, of 1 : 2
composition with tetrahalides of tin and titanium.
From molar conductance, molecular weight determinations and i.r.
spectral studies, these are found to be simple donor-acceptor complexes.
However, in the case of antimony pentachloride and
aluminium tribromide, the presence of acetylium ion is indicated.A number of bases also form
1 : 1 compounds with acetic anhydride. From molar conductance and i.r. spectral
studies, their structures have also been elucidated.
The stereochemistry of freelingyne and the synthesis of dihydrofreelingyne
Authors: Ingham CF , Massy-Westropp RA
Published: September 2010

An unambiguous synthesis of
the phenyl analogue of freelingyne from the Wittig
reaction of a C5 butenolide phosphorane
with (E)-2-methyl-5-phenylpent-2-en-4-yn-l-a1 has confirmed that freelingyne is
(2Z,4Z,6E)-9-(3'-furyl)-2,6-dimethylnona-2,4,6-trien-8-yn-4-olide (1). A
similar stereo-selective synthesis has shown that the naturally occurring dihydrofreelingyne is (2Z,4Z,6E,8E)- 9-(3'-furyl)-2,6-dimethylnona-2,4,6,8-tetraen-4-olide
(2).
Synthesis of 8-deoxygartanin. Trapezifolixanthone and related xanthones
Authors: Anand SM , Jain AC
Published: September 2010

Reaction of
1,3,5-trihydroxyxanthone (6) with 3-methylbut-2-enyl bromide in the presence of
methanolic sodium methoxide yields a mixture of
2,4-di(3-methylbut-2-enyl)-5-(3-methylbut-2-enyloxy) derivative (7), natural
8-deoxygartanin (3) and the 2-(3-methylbut-2-eny1)-5-(3-methylbut-2-enyloxy) derivative (8). Cyclodehydrogenation of (3) and (8) with DDQ affords
natural trapezifolixanthone (5) and
5-(3-methylbut-2-eny1oxy)-6-deoxyjacareubin (9) respectively.
Chronopotentiometric diffusion coefficients of silver(I) in molten KNO3-Ba(NO3)2 eutectic
Authors: Bansal NP
Published: September 2010

The application of chronopotentiometry as an electroanalytical
technique for the in situ
determination of silver(1) in molten KNO3-Ba(NO3)2
(87.6 : 12.4 mole%) eutectic has been described. Reduction of silver(1) on
platinum microelectrode is found to be a reversible, single-step one-electron
process. Diffusion coefficients, D (cm2 s-l), of
silver(1) in the melt have been determined and its temperature variation in the
range 578-697 K could be expressed by the relation (R = 8.314 J K-1
mol-1):

D = 0.913 x 10-3 exp(-19810/RT)

Effect of the presence of
the divalent Ba2+ cations in the fluid on the diffusion process has
been discussed.
The conformations as solutes of meso-2,2,2',2'-Tetrachlorobicyclopropyl, meso-2,2,2',2'-Tetrabromobicyclopropyl, meso-1,2:3,4-Diepoxybutane and 1,1-Dichloro-2-vinylcyclopropane
Authors: Aroney MJ , Calderbank KE , Stootman HJ
Published: September 2010

Electric dipole moments and
molar Kerr constants are reported for meso-2,2,2',2'-tetrachlorobicyclopropyl(0.78
D, -4.5 x 10-12), meso-2,2,2r,2'-tetrabromobicyclopropyl
(0.54 D, 12.3 x 10-12), meso-l,2:3,4-diepoxybutane
(2.83 D,-56.1 x 10-12) and 1,l-dichloro-2-vinylcyclopropane (1.96 D,
6.4 x 10-12)examined as solutes in cyclohexane. The experimental
data are analysed to deduce the preferred solution-state conformations.
A dimeric nickel(II) complex of 7-azaindole
Authors: Brookes RW , Martin RL
Published: September 2010

The synthesis and
properties of the red dimeric nickel(11) complex [Ni2(C7H,N2)4],
where C7H5N2-is the anion of
7-azaindole (1H-pyrrolo[2,3-b]pyridine), are reported. The diamagnetism and electronic
spectrum are consistent with a square-planar environment about each nickel
atom. Adimeric molecular structure
with four anionic 7-azaindole ligands bridging a pair of bonded nickel atoms is
proposed.
Reactions of thioureas and thioamides with aroylphenylacetylenes
Authors: Basyouni MN , Omar MT
Published: September 2010

p-Methoxybenzoyl-, p-chlorobenzoyl- and benzoyl-phenylacetylenes (1a-c) reacted with a
variety of thiocarbonyl compounds (2a-f) in methanol to give mixtures of
(Z,Z)-3,3'-thiodi(1-aryl-3-phenyl- prop-2-en-1-ones) (3) and their
(E,Z)-isomers (4). Configurational assignments of the products were based on
N.M.R. as well as i.r. and u.v. spectra. Conversion of (4) into the
corresponding (3) was also undertaken. Refluxing (3) and (4) with hydrazine or
phenylhydrazine gave the corresponding pyrazoles (5) or (6).
Spectroscopic studies on some sulphur-containing amino acid complexes of cobalt, nickel and copper
Authors: Magee RJ , Mazurek W , O'Conner MJ , Phillip AT
Published: September 2010

The synthesis of three
potentially sexadentate optically active sulphur-containing amino acids, 2,9-
diamino-4,7-dithiadecanedioic acid [(R,R)-ebc], 2,ll-diamino-5,8-dithiadodecanedioic
acid [(S,S)- ebhc] and 2,7-di(3'-thiabuty1)-3,6-diazaoctanedioic acid [(S,S)-ebm]
are described. Some metal complexes of the acids with cobalt, nickel and copper
are characterized by spectroscopic measurements. The complex�� (-)589[Co{(S,S)-ebm}] ClO4
is formed stereospecifically and an X-ray structural analysis shows it to have
the Δ-trans(O) configuration.
The c.d. spectrum shows the presence of three bands due to the splitting of the
T1g energy level by the effective C2 symmetry of the
ligand field. Some polymeric cobalt(11) and nickel(11) complexes are also
described. Spectral measurements indicate an octahedral coordination of the
ligands involved. Several copper(11) complexes are also described.
Aza analogues of pteridine. VIII. 3-Amino- from 3-Alkoxy-pyrimido[5,4-e]-as-triazin- 5-ones prepared by cyclization of 3-Ethoxy-1,2,4-triazines or other means
Authors: Brown DJ , Lynn RK
Published: September 2010

Syntheses of hitherto
unknown 3-aminopyrimido[5,4-e]-as-triazin-5-ones
are described. One route involves selective hydrolysis of 3,5-di- or
3,5,7-tri-alkoxypyrimidotriazines at the 5-position followed by aminolysis.
Another is exemplified thus: 3-ethoxy-5-methoxypyrimidotriazine (2a) is
converted by methanolic hydrochloric acid into methyl 6-amino-3-ethoxy-1,2,4-triazine-5-carboxylate
(3a) which then undergoes successive ammonolysis to the corresponding amide
(3b), cyclization by triethyl orthoformate-acetic anhydride to 3-ethoxypyrimidotriazin-5-one
(1d) and final ammonolysis to the corresponding amine (1a). The second route
may be modified to furnish 3-aminopyrimidotriazine- 5,7-dione (5c) and its
6-methyl derivative (5d). Dehydration of the above amide (3b) with phosphoryl
chloride gives both the corresponding nitrile (3h) and an unusual hydrolytic
product, 6-amino-3- ethoxytriazin-5-one (6). The ionization constants and the
u.v., N.M.R. and mass spectra are discussed.