bluuebunny/crossref_metadata_2025 huggingface dataset:
Intramolecular hydrogen bonding in some ortho-nitrodiphenylamines and related compounds. A proton magnetic resonance study
Authors: Gale DJ , Wilshire JFK
Published: September 2010

.Proton magnetic resonance spectra of a wide variety of substituted 2-nitro-
and 2,4-dinitro-diphenylamines and related compounds reveal that long-range
coupling occurs between the NH proton and the 5-proton of the nitrophenyl ring in
non-polar or weakly polar solvents. However, in the case of the 2,4-dinitrodiphenyl-
amines, this coupling is absent in highly polar solvents, except when the non-nitrated
ring carries powerful electron-donating substituents, e.g. methoxyl or dimethylamino,
ortho or para (but not meta) to the NH group. An examination of these phenomena
leads to the conclusion that such long-range coupling provides evidence that
intramolecular hydrogen bonding occurs between the NH and the 2-nitro groups.
N-Benzyl-2,4-dinitroaniline also exhibited similar long-range coupling but, in
dimethyl sulphoxide solut'ion, this coupling was temperature-dependent. The
chemical shift data of the ortho-nitrodiphenylamines suggest that they adopt a
non-planar skew conformation in solution.
A six-bond H-F coupling was observed between the fluorine atom and the
6-proton of 2'-fluoro-2,4-dinitrodiphenylamine.
Colouring matters of the Aphididae. XXXIX. Deoxyprotoaphin
Authors: Banks HJ , Cameron DW
Published: September 2010

The distribution of protoaphins in aphid species is discussed. Species in some
genera, particularly Aphis and Dysaphis, contain
mixtures of -fb
and -sl
stereoisomers. A new component, deoxyprotoaphin, has
been obtained from Dactyfiotus species and detected
in several others. Rhododactynaphin glucosides have been obtained pure for the first time. The
absolute stereochemistry of rhodoaphin-be has been assigned.
The thermal decomposition of RDX at temperatures below the melting point. V. The evolution of occluded volatile matter prior to the decomposition, and the influence of past history of the sample on the rate of decomposition
Authors: Batten JJ
Published: September 2010

It is fist demonstrated
that the occluded solvents and gases which are often present in RDX are
expelled prior to zero reaction time of thermal decomposition. Thus they do not seriously interfere with the
use of pressure increase as a measure of the extent of thermal decomposition. The rate of thermal decomposition of sublimed
RDX at 195�C is then compared with the rate after the following treatments,

(i) preliminary grinding of
the crystals, (ii) preparation of the
crystals by different techniques, (iii) mixing RDX with
various solid additives, (iv) interruption of the
reaction by cooling, and (v) pre-irradiation with
ultraviolet light.

The results indicated that
treatments (i), (ii), and (iv) had little effect on the rate, whereas (iii) and
(v) could markedly influence the rate. Their effects are discussed in terms of
the mechanism of decomposition. The results also indicated that there was a
post-irradiation reaction of RDX at ambient temperature.
The reaction of crotonic acid with ketones using lithium naphthalenide
Authors: Suga K , Watanabe S , Fujita T
Published: September 2010

Lithium naphthalenide
reacts with crotonic acid in the presence of diethyl-amine to give the α-anion
of lithium crotonate. The reaction of this anion with
various ketones gives the corresponding hydroxy acids in good yield. For
example, from cyclohexanone and crotonic acid, ω-(1?-hydroxycyolohex-1'-yl)crotonic
acid was obtained.
Acid-catalysed, thermal, and photochemical reactions of N-Nitroso-5H-dibenz[b,f ]azepine
Authors: Bendall MR , Bremner JB , Fay JFW
Published: September 2010

The acid-catalysed,
thermal, and photochemical reactions of N-nitroso-6H-dibenz[b,f]azepine (2) have been studied and two general reaction
types delineated. The first involves
ring contraction to give acridine (3), acridine-9-carboxaldehyde (5), and 9-methylacridine
(4). The yields of these products are dependent on the reaction conditions,
particularly the presence or absence of oxygen and the nature of the solvent.
In the second type, the parent heterocyclic nucleus is retained, and 5H-dibenz[b,f]azepine
(1) and 2-nitro-5H-dibenz[b,f]azepine (6) are the main products. These results are
compared with those observed for (1), and some mechanistic details of the
transformations are discussed.
Dipole moment studies of some derivatives of 4-pyridone
Authors: Batts BD , Madeley AJ
Published: September 2010

The dipole moments of 13
derivatives of 4-pyridone were measured. Attempts to
obtain a value for 4-pyridone were unsuccessful but a
value of 6.O D is compatible with other evidence. Dipole moment and n.m.r, evidence
indicated that for N-phenyl-4-pyridone the phenyl
group is inductively electron-repelling (in contrast to that reported)1,2
for N-phenylpyrrole) and that the rings are probably
collinear.
Conformation of 1,3-dichloroacetone
Authors: Huang HH , Tan ELK
Published: September 2010

The molar Kerr constant (35
x 10-12) and dipole moment (2.29 D) of 1,3-dichloroacetone in
carbon tetrachloride are shown to be compatible with an equilibrium mixture of
planar cis/non-planar gauche (6) and
non-planar gauche/non-planar gauche (8) conformers with the latter
predominating.
Substituted carbonyl derivatives of the Group VI transition metals. III. Complexes with π-bonded bridging triarylphosphines
Authors: Bowden JA , Colton R
Published: September 2010

The reactions of chromium hexacarbonyl with triphenylphosphine, tri(m- tolyl)- phosphine (pmt), and tri(p-tolyl)phosphine
(ppt) at high temperature yield two series of
complexes Cr(CO)3L and [Cr(CO)2L]2, although
only the latter could be isolated in a pure state. These dimeric derivatives
were characterized by analysis, infrared, N.M.R., and mass spectral
measurements. All the data are consistent with a molecular arrangement
incorporating π-bonding between chromium and one of the arene rings of the
ligand which is also σ-bonded through phosphorus to the other metal atom,
thus forming a novel, highly unsymmetrical bridge system.
Fluorocarbon-aluminium compounds. IV. Reactions of some chloropolyfluorobenzenes with lithium tetrahydroaluminate
Authors: Dickson RS , Sutcliffe GD
Published: September 2010

The reaction of lithium
tetrahydroaluminate with chloropentafluorobenzene
yields mainly p-chlorotetrafluorobenzene. The nature
of the solvent influences the formation of other fluorocarbon compounds in the
reaction. p-Chlorotetrafluoro-benzene reacts further
with LiAlH4 in tetrahydrofuran, but not in diethyl ether, to give
predominantly 1-chloro-2,3,5-trifluorobenzene and 1-chloro-2,3,6- trifluorobenzene.
In turn, the trifluorobenzene compounds react with LiAlH4 in
tetrahydrofuran to give mainly 1-chloro-2,5-difluorobenzene. The major products
are formed by a combination of (i) direct nucleophilic
displacement of fluorine in the chloropolyfluorobenzene
compounds by hydride, and (ii) hydrolysis of the compounds LiAl(C6F4Cl)H2F,
LiAl(C6F3HCl)H2F,
and LiAl(C6F2H2Cl)H2F.
The fluorocarbon- aluminium compounds have not been isolated from solution but
they were characterized by quantitative determination of the products of
hydrolysis and by 1H and 19F N.M.R. spectroscopy.
Fluorocarbon-aluminium compounds. V. Reactions of some fluorotoluene compounds with lithium tetrahydroaluminate
Authors: Dickson RS , Sutcliffe GD
Published: September 2010

In tetrahydrofuran at -45�
and in diethyl ether at 20�, the reaction of α-bromo-
2,3,4,5,6-pentafluorotoluene with lithium tetrahydroaluminate yields
2,3,4,5,6-penta-fluorotoluene. In tetrahydrofuran at 20�, the same reaction
occurs initially but the pentafluorotoluene then reacts further with LiAlH4.
LiAlH4 attacks the para-fluorine atom of 2,3,4,5,6- pentafluorotoluene
to form 2,3,5,6-tetrafluorotoluene and the fluoro- carbon-alane complex LiAl(C6F4CH3)H2F.
The reaction between LiAlH4 and C6F5CH3
is complete after 0.5 hr at 65�. In turn, 2,3,5,6- tetrafluorotoluene reacts with
LiAlH4 in refluxing tetrahydrofuran to form the fluorocarbon-alane
complexes LiAl(C6F4CH3)nH4-n,
n = 1-3. ��� The fluorocarbon-aluminium compounds have
not been isolated from solution but were characterized by quantitative
determination of the products of hydrolysis and by 1H and 19F
N.M.R. spectroscopy.
Studies on the application of the quinhydrone electrode in formamide. I. The ionization constant of acetic acid from E.M.F. measurements at 25°
Authors: Nayak B , Dash UN
Published: September 2010

The quinhydrone electrode
in conjunction with the silver-silver chloride electrode has been used in the
cell

���������� Ag-AgCl | NaCl(m3), CH3CO2Na(m2),
CH3CO2H(m1), QH2-Q | Pt

to redetermine the
ionization constant of acetic acid in formamide. The ionization constant is
found to be 1.096 x 10-7 and is in good agreement with the value
1.230 x 10-7 obtained from the study of the cell

���������� Pt, H2|CH3CO2H(m1),
CH3CO2Na(m2), NaCl(m3)|AgCl-Ag

The results confirm the
reversibility and reproducibility of the quinhydrone electrode in formamide.
Studies on the application of the quinhydrone electrode in formamide. II. The ionization constants of phthalic acid from E.M.F. measurements at 25°
Authors: Nayak B , Dash UN
Published: September 2010

The first and the second
ionization constants of phthalic acid have been determined, in formamide, at
25� with the help of cells without liquid junction using quinhydrone and
silver-silver chloride electrodes. The values of pK1a and pK2a
were found to be 4.214�0.02 and 7.716�0.01, respectively, at this temperature.
Trifluorosilyl derivatives of some transition elements
Authors: Redwood ME , Reichert BE , Schrieke RR , West BO
Published: September 2010

The compounds F3SiMn(CO)5,
F3SiMn(CO)4PPh3, F3SiRe(CO)5,
F3SiFe- (π- C5H5)(CO)2, and F3SiMo(W)(π-C5H5)(CO)3
have been prepared by the reaction of SiF3H with appropriate
binuclear carbonyls. The infrared, mass, and 19F n.m.r, spectra for
the compounds are discussed, together with some chemical properties.
Mechanisms of aromatic nucleophilic substitution by the ambident thiocyanate ion
Authors: Giles DE , Parker AJ
Published: September 2010

Sulphur/nitrogen reactivity
ratios in a series of aromatic nucleophilic substitution reactions of ambident
thiocyanate ion have been determined. There are profound differences from the
pattern found in SN2 reactions at a saturated carbon atom. Abnormal
transition states, involving interactions between entering and leaving group,
are likely in the bond-breaking step of the intermediate complex in reactions
of thiocyanate ion with 1-fluoro-2,4-dinitrobenzene and with 2,4- dinitrophenyl
4-toluenesulphonate. The nitro-substituted aryl thiocyanates are shown to be
tri-functional electrophiles, with reactive centres at aromatic carbon, at
cyanide carbon, and at sulphur. Aryl 4-toluenesulphonates are bifunctional
electrophiles with reactive centres at aryl carbon and sulphonyl sulphur. The
site of attack by nucleophiles depends on the nature of the nucleophile. The
sulphur/nitrogen reactivity ratio of ambident SCN-, and the
electrophilic reactivity of tri- and bi-functional substrates, are in most
instances consistent with the Hard and Soft Acids and Bases principle.
Exceptions to the principle in some instances reveal differences between the SNAr
and SN2 mechanisms, and in others indicate abnormal transition
states.
The preparation of adducts of 2,5-Diphenyl- and 2,5-Di(2'-pyridyl)-3,4-diazabicyclo[4,2,0]octa-2,4,7-triene
Authors: Warrener RN , Elix JA , Wilson WS
Published: September 2010

The [π4s+π2s]
cycloaddition between cyclobutene derivatives and s- tetrazines formed unstable
adducts which readily lost nitrogen to yield the complex dihydro-pyridazines
(17). The structure of these products was assigned on the basis of spectral
data. In addition, the thermolysis of these compounds has been investigated as
a potential route to 1,2-diazocines (or valence isomers thereof). These results
have been discussed and compared with the related mass spectral fragmentations.
While the free 1,2-diazocines could not be isolated by this scheme it did afford
a versatile route to the [π4s + π2s]
cycloadducts of the valence isomeric 3,4-diazabicyclo[4,2,0]octa-2,4,7- triene
system. In particular 1,8-di(2?-pyridyl) and 1,8-diphenyl-13,14-
diazapentacyclo-[6,4,2,13,6,02,7,09,12]pentadeca-4,10,13-triene
(24a,b) were prepared, the exact stereochemistry being confirmed by studies of
the lanthanide-induced chemical shift. ��� The reaction of cis-3,4-dichlorocyclobutene
and 3,6-di(2?-pyridyl)- s-tetrazine formed an ionic compound,
8a-amnia-3,4-diazaphenanthrene chloride (13), which contains a new heterocyclic
ring system. This structure has been confirmed by a single-crystal X-ray
analysis.
Aromatic fluorocarbon mixtures. II. Carbon tetrachloride+hexafluorobenzene
Authors: Ruenkrairergsa S , Pasco NF , Fenby DV
Published: September 2010

The molar excess enthalpies
and molar excess volumes of carbon tetra- chloride + hexafluorobenzene have
been measured at 298.15 K and 308.15 K. The values for the equimolar mixture at
298 15 K are 490 J mol-1 and 0.875 cm3 mol-1
respectively. The results are compared with the values for other liquid
mixtures containing a fluorocarbon as one component, and discussed in terms of
solubility parameter theory.
Pyrimidine reactions. XXIV. The dehalogenation of 2-halogenopyrimidines by hydriodic acid
Authors: Brown DJ , Waring P
Published: September 2010

2-Halogenopyrimidines
underwent dehalogenation conveniently on treatment with hot hydriodic acid;
4,6-dimethyl-, 4,6-diphenyl-, 5- methyl-, 4-methyl-, and 4-amino-pyrimidine
were so prepared from their respective 2-chloro derivatives, of which the
second and third were made by improved methods; unsubstituted pyrimidine was
obtained similarly from its 2-chloro, 2-bromo, or 2-iodo derivative, of which
the last was made in a pure state for the first time. In contrast, 4-
chloro-2,6-dimethylpyrimidine underwent hydrolysis in hot hydriodic acid and transhalogenation to give its 4-iodo analogue at lower
temperatures; both 2-chloro-4-methoxy-pyrimidine and 5-chlorouracil gave uracil
with hot hydriodic acid; and 4-chloro- 2,6- dimethoxypyrimidine
gave 6-iodouracil under similar conditions.
The kinetically effective stoichiometry of reactions in the carbon-sulphur dioxide system
Authors: Easteal AJ , Khoo PH
Published: September 2010

Conductivities of fused
PbBr2+KBr mixtures, containing up to c. 90 mole % KBr, have been
determined as a function of temperature. The data are represented well by
quadratic functions of temperature, and the best- fit parameters of the
quadratic functions are reported for each mixture. ��� The conductivity data vary isothermally
with composition in a different manner than do the literature data for this
system. However, the isotherms are very similar to these obtained previously
for PbCl2 + KCl mixtures.

� Interpretations
of physicochemical properties of PbBr2+KBr mixtures are reviewed
briefly, and a close parallel between structural models applicable to PbBr2
+ KBr and PbCl2 + KCl melts containing up to 50 mole % KBr or KCl is
suggested.
Side chain nitration of polymethylbenzenes in nitric acid-acetic anhydride mixtures
Authors: Blackstock DJ , Fischer A , Richards KE , Wright GJ
Published: September 2010

Product distributions
resulting from nitration of polymethylbenzenes in nitric acid-acetic anhydride
mixtures have been determined by gas chromatography. Nitration of a methyl
group occurs in all the substrates studied; such nitration occurs only at a methyl
group para to the methyl most activated to ipso nitration. These results
support the view that side chain nitration occurs through the diene
intermediates which lead to ring acetoxylation.
Computing methods in mass spectrometry. Programming for aliphatic amines and alcohols
Authors: O'Brian JF , Morrison JD
Published: September 2010

A discussion is given of
the principles involved in developing computer programs for the interpretation
of the mass spectra of aliphatic alcohols and amines. In many cases a parent
ion is not observed, and the molecular weight has to be deduced by indirect
methods. Limitations on the present state of the programs are the fact that it
is assumed that the compound being studied is known to be a saturated acyclic
monoamine or alcohol and, for the most part, no attempt is made to distinguish
between isomeric alkyl substituents. The performance of the programs developed
is described.
Reaction of 2-Aryl-4-arylmethylene-2-oxazolin-5-ones with amines
Authors: Islam AM , Khalil AM , Abd El-Gawad II
Published: September 2010

1,2-Diaryl-4-arylmethylene-2-imidazolin-5-ones
were prepared by the interaction of primary aromatic amines with
2-aryl-4-arylmethylene-2- oxazolin-5-ones in the presence of acetic acid and
sodium acetate. The same imidazolones were also obtained by the cyclization of
the arylamides of α-arylamido-β-arylacrylic
acids under the same reaction conditions. A possible reaction mechanism was
postulated.
Atomic polarization in metal chelates. II. Dielectric loss measurements on some diketone chelates of tin(IV)
Authors: Hayes JW , Nelson WH , Radford DV
Published: September 2010

Dipole moments and
relaxation times determined by dielectric loss measurements at 3.109 and 9.400
GHz are reported for bis(pentane-2,4- dionato)dimethyltin(IV) and its dimethyl
and diphenyl analogues with tropolone. All of these compounds show true orientation
polarization in accord with the assignment of cis structures. High atomic
polarizations are observed in all cases and it is suggested that this may be a
characteristic of metal chelates in general.
Sulphur-nitrogen chelating agents. X. Metal complexes of the tridentate ligand 2,2'-Dithiodianiline and the quinquedentate a, α,α-[Dithiobis(o-phenylenenitrio)]di-2-picoline
Authors: Livingstone SE , Nolan JD
Published: September 2010

Metal complexes of the disulphides 2,2?-dithiodianiline (dta)
and α,α- [dithiobis-(o-phenylenenitrilo)]di-2-picoline (dtpp)
have been investigated. In the complexes Ni(dta)X2
(X = Cl, Br) the ligand is coordinated by one sulphur
and two nitrogen atoms. In the complexes [M(dtpp)X]X,
nH2O (M = Mn, Ni; X = Cl,
Br), [Ni(dtpp)Cl]-ClO4,
[Ni(dtpp)X] BF4 (X = Cl,
Br), and [Mn(dtpp)I] ClO4
the disulphide dtpp acts as a quinquedentate, being
bound by one sulphur and four nitrogen atoms. The compound [Ni(dtpp)Br] Br,H2O was obtained by reaction of Ni(dta)Br2 with pyridine-2-carbaldehyde. �� Under certain conditions dtpp
is reduced in the presence of nickel ions to give complexes of 2-(2?-pyridylmethylene)aminobenzenethiol (pabtH). Two
complexes of empirical formula Ni(pabt)Cl were isolated: the reddish-brown, diamagnetic square-planar
complex Ni(pabt)Cl and a
green paramagnetic complex Ni(pabt)2,NiCl2
which may have a thio-bridged structure.
Vanadium(III) chloro and bromo complexes with tetradentate Schiff base ligands
Authors: Murray KS , Simm GR , West BO
Published: September 2010

Vanadium(III) Schiff base
chelates of the types V(chel)Cl,py (chel = saen, saph) and V(saen)Cl,py2
have been synthesized by allowing VCl3 and the ligand to react in
pyridine solutions. The bromo derivatives V(saen)Br,py and V(saph)Br,py2
can be obtained by LiBr substitution. The magnetic and spectral properties of
the complexes are consistent with tetragonally distorted octahedral structures,
though the μeff value for V(saen)Cl,py is slightly lower than
expected and difficult to explain with certainty.
Mass spectra of nitrogen heterocycles. II. Pyridyl Schiff bases
Authors: Halbert EJ , Goldsack RJ , Wilson JG
Published: September 2010

A number of anils of
pyridine aldehydes and benzylideneaminopyridines were used to study positional
effects of aromatic substituents and heteroatom placement on electron impact
mass spectra. The simple fragmentation pattern of aromatic Schiff bases was obtained
with all 3- and 4-pyridyl compounds when the other aromatic ring was
unsubstituted phenyl, or in the case of anils, had a chloro or 3-methoxy
substituent. Marked changes were brought about by a pyridyl ring at either end
of the azomethine group when the heterocyclic nitrogen was adjacent to it.
Displacement and rearrangement reactions then became dominant. Methoxy
substitution para to the azomethine in all anils studied gave loss of methyl
radical as the major reaction.
Constituents of Eupomatia Species. 3. New Eupomatenoid Lignans From the Leaves and Wood of Eupomatia laurina
Authors: Picker K , Ritchie E , Taylor WC
Published: September 2010

The leaves of Eupomatia
laurina R.Br. gave seven substances previously isolated from the bark together
with a flavone identified as 3,7,3?- trimethylquercitin,
and the new lignans, eupomatenoid-9 and -10, which were shown to be
erythro-5-(1?,2?-dihydroxypropyl)-2-(4?-hydroxy-3?- methoxyphenyl)-3-methylbenzofuran
and 2-(4?-hydroxy-3?-methoxyphenyl)-3-methylbenzofuran-5-carbaldehyde,
respectively. ��� The wood yielded seven substances which
also occur in the bark, together with eupomatenoid-11 and -12, and eupodienone-2
and -3. Eupomatenoid-11 was found to be (R)-5-(2?-hydroxypropyl)-2-(3?,4?- methylenedioxyphenyl)-3-methylbenzofuran and
eupomatenoid-12 to be the methyl ether of eupomatenoid-7.
Meerwein arylations of 2-furoic acid and methyl 2-furoate
Authors: Khan MA , Polya JB
Published: September 2010

5-Aryl-2-furoic acids and
their methyl esters have been prepared by Meerwein arylation. Spectroscopic (i.r. and u.v.) characteristics of the products are
tabulated.
Adsorption at solid-liquid interfaces. I. Thermodynamics and the adsorption potential
Authors: Wright HJL , Hunter RJ
Published: September 2010

To facilitate model studies
of the double layer at charged surfaces, an analysis is made of the
thermodynamics of the dissociation phenomena which take place at mineral oxide
surfaces. Two alternative equations may be used to describe the dependence of the
surface potential and charge upon the concentration of potential determining
ions in the solution. The two different approaches are similar to those given
previously1,2 but analysis is made of the specific adsorption
potential which is expressed in a form which permits it to be theoretically
calculated. While specifically developed for insoluble oxides, the theory is
equally applicable to other systems.
Study of transition temperature through mixed crystal formation. III. Orthorhombic zinc sulphate and magnesium sulphate
Authors: Purkayastha BC , Das N
Published: September 2010

Distribution studies with
orthorhombic zinc sulphate and magnesium sulphate as hosts and 54Mn
as guest have been carried out in order to determine the transition
temperatures of different phases. The change in morphology of either the host
or the guest is always indicated by a prominent change in distribution values
at the point of transition. In the present study, with zinc sulphate as host
and 54Mn as guest, the transition temperatures of the two
components, orthorhombic MnSO4,7H2O and MnSO4,6H2O,
were found to be 10� and 42.5�C respectively. The host component ZnSO4,7H2O
transforms to its lower hydrate ZnSO4,6H2O at 38.95�C.
Distribution studies with MgSO4,7H2O as host and 54Mn
tracer as guest also confirm that MnSO4,6H2O undergoes
transition at 42.5�C. Isolation of MnSO4,6H2O in finite
concentration has been achieved by cocrystallizing with stable and well defined
ZnSO4,6H2O at 42�C.
P.M.R. study of intramolecular hydrogen bonding in ortho-amidoanilides and its relation to the spectra of α-acylamidocinnamamide
Authors: Prasad KK , Venkataratnam RV
Published: September 2010

Proton magnetic resonance spectra of some ortho-amido-benzanilides and
-acetanilides have been studied. While the secondary amido substituents in the
2-position have been found to form a strong hydrogen bond with the anilide proton, the
tertiary amide function is sterically prohibited from doing so with consequent shielding
of H 6 from its normal position in the 2-methoxycarbonyl substituted anilides. The
abnormal shielding of Hβ in α-acylamidocinnamamides observed earlier has been
discussed in relation to the present findings. A convenient method for the preparation
of ortho-amidoanilides has been described.
Mass spectrometric studies of some substituted Cyclohexane-1,2-diols
Authors: Cole RFJ , Coxon JM , Hartshorn MP , Little GR
Published: September 2010

The (M-H2O)+/M+
ratio in the mass spectra for the stereoisomeric 4-t- butyl-cyclohexane-1,2-diols
is markedly dependent on their stereochemistry. No such dependence is found for
the 1-methyl, 2- methyl, and 1,2-dimethyl derivatives.
The formation of nitriles by pyrolysis of N-substituted chloroacetamides
Authors: Brown RFC , Butcher M , Fergie RA
Published: September 2010

Pyrolysis of
chloroacetamides RNHCOCH2Cl at 780-850�C/0.1-0.4 mm with short
contact time gives nitriles RCN in 45-60% yield (R = phenyl, o- tolyl, p-tolyl, benzyl, or
cyclohexyl). A mechanism is proposed involving the formation of the iso-nitrile RNC, formaldehyde, and hydrogen chloride.
N-Chloroacetylbiphenyl-2-amine gives biphenyl-2- carbonitrile (45%) and
phenanthridine (15%).
Copper(II)-promoted solvolyses of nickel(II) complexes. II. Tridentate and tetradentate Schiff base ligands containing remote substituents
Authors: Fee WW , Pulsford JD , Vowles PD
Published: September 2010

The kinetics of copper(II)-promoted
solvolyses of two series of nickel(II) complexes containing polydentate Schiff
bases with various remote substituents, in dimethyl sulphoxide (dmso), are
discussed from the viewpoints of rate constants and of enthalpies and entropies
of activation. Appearance of an isokinetic relation for the tridentate (ONS
donors) reactants may indicate a common mechanism operative within this
reactant series. Rate constants appear related to σp values in
such a way that a dissociative mechanism appears important for the tridentate
reactants, while characterization in terms of associative behaviour is
indicated for the tetradentates.
The rate of reaction of nitrous acid and 4-aminobenzenesulphonamide in nitric acid
Authors: Bhattacharyya PK , Saini RD
Published: September 2010

On the basis of the
competitive reaction of nitrous acid with hydrogen peroxide in nitric acid
medium the rate constant of the reaction of 4- aminobenzenesulphonamide
with nitrous acid has been determined to be 6.4 l2 mol-2
s-1 at 22�C and has been found to be independent of nitric acid concentration
in the range 0.5-2M.
The polarography of some substituted azobenzenes in acetonitrile. III The effect of strong proton donors
Authors: Boto KG , Thomas FG
Published: September 2010

The d.c.
and a.c, polarographic
behaviour, observed on the addition of strong proton donors such as sulphuric
acid, hydrogen chloride, and hydrogen bromide to some 4-monosubstituted
azobenzenes in acetonitrile is discussed. Diffusion controlled waves are observed
at potentials up to 1.7 V more positive than the normal azobenzene reduction
waves observed in the absence of proton donors. It is proposed that the
reduction of azonium species, formed in labile equilibria by proton exchange
between the acid and the azo compound, give rise to these waves. A general
mechanism to account for the appearance of the prewaves is proposed. Unusual
and complicated adsorption behaviour was observed in the
4-methoxyazobenzene-sulphuric acid system.
The reaction of ortho-dinitrobenzenes with sodium borohydride
Authors: Bird KJ , Rae ID , White AM
Published: September 2010

The reaction of
o-dinitrobenzene with sodium borohydride in aqueous dimethyl sulphoxide at room
temperature gives nitrobenzene and benzofurazan in low yields. Deuterium is
incorporated specifically into the ortho position of nitrobenzene when the
reaction is performed with sodium borodeuteride. 2,3-Dinitrotoluene gives
mainly m-nitrotoluene, but 3,4-dinitrotoluene gives both m- and
p-nitrotoluenes.
Carbonyl halides of the Group VII transition metals. III. Carbonyl halide complexes of rhenium(I)
Authors: Colton R , Garrard JE
Published: September 2010

A new series of carbonyl
halide complexes of rhenium(I) has been prepared. The complexes, which have the
empirical formula Re(CO)3X (X = Cl, Br,
I), are prepared by thermal decomposition of the corresponding halide
complexes, Re(CO)5X.
Conformations of Di(4-pyridyl) disulphide and Di(2-pyridyl) disulphide
Authors: Cheng CL , Ritchie GLD
Published: September 2010

Experimental dipole moments
and molar Kerr constants at 25�C are reported for di(4-pyridyl) disulphide
(1.68 D, + 11 x 10-12 e.s.u. mol-1) and di(2-pyridyl)
disulphide (3.95 D, -240x10-12 e.s.u. mol-1) as solutes
in carbon tetrachloride. Analysis of results yields information concerning the
preferred conformations of these molecules.
Steroidal alkaloids of Marsdenia rostrata. II. The isolation and structure of a new alkaloid, rostratamine
Authors: Gellert E , Summons RE
Published: September 2010

A new alkaloid, rostratamine,
was isolated from Marsdenia rostrata (Asclepia-daceae). Its structure was elucidated as deacetylmetaplex-igenin 12-nicotinate.
Organomercury compounds. XVIII. Thermal decomposition reactions of mercuric arenesulphonate pyridinates
Authors: Cookson PG , Deacon GB
Published: September 2010

The mercuric arenesulphonate
pyridinates, Hg(O3SR)2,(py)2 (R = C6X5,
p- HC6X4, o-HC6X4, or m-HC6Cl4;
X = Cl or F) and Hg(O3S-m-HC6F4)2,(py)3,
have been prepared by treatment of the appropriate mercuric arenesulphonate
dihydrates with pyridine. Thermal decomposition of the compounds Hg(O3SR)2,(py)2
(R = C6X5, p-HC6X4, or m-HC6Cl4)
and Hg(O3S-m-HC6F4)2,(py)3
at c. 120-240� under vacuum gave the corresponding diarylmercurials (yields:
45-90%) and the complex (py),SO3 in all cases, together with (- m-HgC6F4SO3-)n,
and low yields of polyfluorobenzenes and/or polyfluorobenzenesulphonic acids.
Similar decomposition of the compounds Hg(O3S-o-HC6X4)2,(py)2
gave (-o-HgC6X4SO3-)n, (py),SO3,
o- HC6X4SO3H, and o-H2C6X4,
and there was some evidence for formation of a trace of o-(o-HC6Cl4-
SO3Hg)C6Cl4SO3HgO3S-o-HC6Cl4.
The derivatives (- HgC6X4SO3-)n,
were identified by established degradation procedures.
Preliminary classification of mass spectral patterns using a simplified learning machine
Authors: Mathews RJ
Published: September 2010

A simplified learning
machine technique is presented which is suitable for forming preliminary
classification of patterns. This technique allows preliminary compression of
data prior to the training process, and generates a reliable classifier even
when there are linearly inseparable data in the training set. This method has
been used to form an eight-feature pattern classifier which identifies,
directly from their mass spectra, compounds of the structure (RO)2P(=X)Y
where R is H, Me, or Et; X is O or S; and Y is any functional group.
Synthesis of 2,6,7-Trimethoxy-3,4-methylenedioxyphenanthene, a degradation product of ocoteine
Authors: Moltrasio GY , Giacopello D , Vernengo MJ
Published: September 2010

The synthesis of
2,6,7-trimethoxy-3,4-methylenedioxyphenanthrene (3) by the application of the
Pschorr reaction is reported. The product was identical with that obtained by
degradation of the aporphine alkaloid ocoteine (2).
The synthesis of agglomerone
Authors: Baigent DR , Bick IRC
Published: September 2010

The naturally occurring
β-triketone agglomerone has been synthesized by a method which confirms
the pair of structures previously proposed for it.
Nitrones and oxaziridines. VI. Deoxygenation of oxaziridines by sulphurcontaining nucleophiles
Authors: Black DSC , Watson KG
Published: September 2010

The treatment of simple and
fused oxaziridines with sulphur-containing nucleophiles such as thiourea,
potassium thiocyanate, potassium ethylxanthate, potassium selenocyanate, and
triphenylphosphine sulphide, results in the formation of the related imines. It
is suggested that the deoxygenation is effected by conversion of the
oxaziridines into thiaziridines, followed by rapid loss of sulphur.
Structure elucidation of some ent-clerodane diterpenes from Dodonaea boroniaefolia and Cyanostegia augustifolia
Authors: Jefferies PR , Knox JR , Scaf B
Published: September 2010

Two diterpene alcohols (1)
and (2) and a hydroxy acid isolated as the ester (7) have been obtained from D.
boroniaefolia. Their structures have been established
by correlation with the acid (10) by way of the cyclopropane intermediate (17)
and its product of ring opening (22). The diacid (24) from Cyanostegia
angustifolia has also been correlated with (22)
through the diol (29) and keto acid (31).
Oxidative addition reactions with Bis(dithioacetylacetonato)cobalt(II)
Authors: Ho RKY , Martin RL
Published: September 2010

The synthesis of cationic
cobalt(III) complexes of the [CoS4N2]+ type
can be readily effected by oxidative addition of Co(SacSac)2
with molecular oxygen in the presence of chelating nitrogenous ligands. The
N.M.R. spectra of the complexes are consistent with the molecular point
symmetry C2 for the cation.
An electron spin resonance study of the dimeric form of Bis(dimethylglyoximato) copper(II)
Authors: Toy AD , Smith TD , Pilbrow JR
Published: September 2010

The triplet state e.s.r.
spectra of bis(dimethylglyoximato)copper(II) in
ethanol solutions have been recorded and the results interpreted in terms of a
magnetic dipole-dipole interaction between pairs of copper(II) ions in a
dimeric complex. Consideration of a spin Hamiltonian which takes into account
the symmetry relationship of the transition metal ions in the dimeric complex
has provided a set of structural and magnetic parameters by computer lineshape
simulation procedures. The results indicate that the symmetry of the pair
system is similar to that observed for the dimeric units in the solid complex
but that the calculated distance between the metal ions is somewhat larger than
that determined by crystallographic methods for the solid complex.
Optical spectra of the tetrahedral tetrabromocobalt(II) complex ion in molten tetrabutylphosphonium bromide
Authors: Islam N
Published: September 2010

Optical spectra of CoBr42- in molten
tetrabutylphosphonium bromide are recorded and the bands interpreted as due to
charge-transfer and ligand-field transitions. The resolved spin-allowed bands
are similar to those reported earlier in organic solvents. Cobalt(II)-bromide-rich
mixtures with tetrabutylphosphonium bromide are found to supercool
to a glassy material. The effect of temperature on these bands has also been
studied.
The polarography of some substituted azobenzenes in acetonitrile. V. The effects of weak proton donors
Authors: Boto KG , Thomas FG
Published: September 2010

The polarographic behaviour
observed on addition of the weak proton donors, water and diethyl malonate, to
azobenzene derivatives in acetonitrile is reported. Polarographic and direct
spectroscopic kinetic studies were carried out in an attempt to establish the
mechanism of the reduction process giving rise to the observed enhancement of
the first reduction wave. A disproportionation- regeneration mechanism with the
rate-controlling step being the protonation of the monoanion is indicated by
the direct spectroscopic kinetic studies but the polarographic results do not
lead to an unambiguous mechanism for the electrode reactions.
Synthesis of heterocyclics via enamines. I. Formation of 1,4-Dihydropyrimidine-2-thiols and 2-Amino-1,3-thiazines in reactions of ethyl β-aminocrotonates with β-keto isothiocyanates: role of solvents
Authors: Singh H , Singh S
Published: September 2010

Ethyl β-aminocrotonate
(1) on condensation with the β-keto isothiocyanate (2; R = Me) in hexane,
benzene, or toluene formed the 1,4-dihydropyrimidine-2-thiol (3; R = Me) as the
major product and the 2-amino-1,3-thiazine (4; R = Me) as the minor component. The
use of ether, acetonitrile, butan-2-one, ethyl acetate, chloroform as solvents
reversed the product ratio. In the reaction with (2; R = Et), the yields of (3
and 4; R = Et) formed were similarly affected by change of solvent.
Metal ion and ligand dependency of the redox behaviour of some first row transition metal dithiocarbamates
Authors: Chant R , Hendrickson AR , Martin RL , Rohde NM
Published: September 2010

The one-electron oxidation
and reduction processes for some 80 dithiocarbamates of Cr, Mn, Fe, Co, Ni, and
Cu reveal a marked dependence of redox potential on the metal 3dn
electron configuration. For all the complexes examined, the relative ordering
of the redox potentials with the dithiocarbamate substituents is remarkably
consistent for both oxidation and reduction processes.
Search for surface structural effects in electrocatalysis. II. Platinized platinum electrodes
Authors: Biegler T
Published: September 2010

The adsorptive properties
of platinized electrodes, as indicated by cyclic voltammetry, depended on the
potential of platinum electrodeposition. Electrodes deposited above 0.05 V v.
reversible hydrogen electrode were similar to smooth platinum, while those
deposited at negative potentials showed anomalous behaviour, particularly with
regard to hydrogen sorption. Measurements with such electrodes over a range of
sweep rates showed slow sorption of about two hydrogen atoms in excess of the
usual fast adsorption of one hydrogen atom per surface platinum atom. Freshly
electrodeposited platinum had a specific activity for methanol oxidation of
one-quarter to one-half that of smooth platinum. The lower activity was
attributed to the effects of disordered surface structure and/or small particle
size. Anodic-cathodic cycling produced surface recrystallization and activities
close to that for smooth platinum.
Studies in the indazole series. Ring opening of some 1-Arylindazole-3-carboxylic acids during decarboxylation
Authors: Gale DJ , Wilshire JFK
Published: September 2010

Indazole reacted readily
with 4-fluoronitrobenzene and with 2-fluoro-5- nitro-benzonitrile to give the
corresponding isomeric 1- and 2-nitroarylindazoles. The isomeric 2-(N-indazolyl)-5-nitrobenzonitriles behaved differently towards
acid; the 1-derivative gave the corresponding 2-carboxylic acid whereas the
2-derivative gave a product which contains the hitherto unknown indolo[1,2-b]indazole
ring system. ��� The decarboxylation of several
1-arylindazole-3-carboxylic acids in boiling quinoline gives not only the
expected 1-arylindazole but also the product of heterocyclic ring fission,
namely the isomeric N- arylanthranilonitrile. The
proportion of this latter compound is particularly marked when the 1-aryl
substituent carries an electron- withdrawing (nitro or chloro) group. If the
1-aryl substituent carries a nitro group, ring fission also occurs when the
solid acid is heated above its melting point, but to a lesser extent than in
refluxing quinoline. ��� The preparation of several of the
1-arylindazole-3-carboxylic acids was achieved by a route which had as its
starting point the reaction of lead tetraacetate with an ethyl or methyl
α-(arylhydrazono)phenylacet-
ate to form the corresponding azoacetate. The failure of this reaction to occur
when the arylhydrazone possessed an ortho-nitro group is discussed.
An electron spin resonance study of metal ion separations in dimeric vanadyl (DL)- and (DD)-tartrates
Authors: Toy AD , Smith TD , Pilbrow JR
Published: September 2010

The e.s.r. spectra of
frozen aqueous solutions containing vanadyl (DL)- and
(DD)-tartrates are consistent with the formation of
dimeric species. Computer simulation of the spectra, assuming a monoclinic dimer
model, has enabled the determination of the magnetic parameters associated with
vanadyl ions, the internuclear
separations between the metal ions in the dimers and their relative
orientation. For vanadyl (DL)-tartrate
dimer, the excellent agreement between structural parameters for the solid and frozen
glass was taken to indicate that the same structure exists in both states. In
the case of vanadyl(DD)-tartrate,
however, although the overall symmetry is maintained, a slight reduction in the
vanadyl vanadyl separation
is believed to occur as a result of incorporation into an ethylene glycol-water
glass.
The partial rate factor for nitration ipso to a methyl group
Authors: Fisher A , Wright GJ
Published: September 2010

The partial rate factor for
nitration ipso to a methyl group is
c. three times that for substitution at the meta
position.
Chemical Studies of the Proteaceae. Vii. An Examination of the Woods of 17 Species for Resorcinol Derivatives
Authors: Cirigottis K , Cleaver LEA
Published: September 2010

No phenols could be
isolated from the woods of nine Proteaceae species,
but eight others yielded mixtures of 5-n-alk(en)ylresorcinols.
Two of these also contained substances of the striatol
type.

Cardwellia sublimis gave a high yield of (-)-bornesitol.Syntheses of
5-heptadecylresorcinol, bilobol and some degradation
products of 5-n-alkenylresorcinols are described.
Psychotridine, a C55H62N10 Alkaloid From Psychotria beccarioides (Rubiaceae)
Authors: Hart N , Johns S , Lamberton J , Summons R
Published: September 2010

Psychotridine, the major
alkaloid from Psychotria beccarioides
Wernh. has the molecular composition C55H62N10.
It has been shown to be related to hodgkinsine, and a structure (4) derived
from five Nb-methyltryptamine units is proposed. Mass spectral
evidence for the structure is supported by the conversion of psychotridine
through a pentamethiodide into a penta-indolenine base, analogous to the
tri-indolenine base derived from hodgkinsine Nb,Nb',Nb?-trimethiodide.
The structure is also supported by comparison of the 13C N.M.R.
spectra of hodgkinsine and psychotridine.
Crystal structure of collinsite
Authors: Brotherton PD , Maslen EN , Pryce MW , White AH
Published: September 2010

The crystal structure of a
substantially pure sample of collinsite, MgCa2(PO4)2,2H2O,
has been determined from diffractometer data (379 independent reflections) and
refined by full-matrix least squaresmethods to a residual of
0.033. Crystals are triclinic, PI, a
= 5.7344(8), b = 6.780(1),c = 5.4413(9) �, α = 97.29(1), β=
108.56(1), γ = 107.28(1)�, Z = 1.
Synthesis of some 9-(Indol-3'-yl)xanthene derivatives
Authors: Evans NA
Published: September 2010

9,9-Dichloroxanthene reacts
with 1-substituted, 2-substituted and 1,2-disubstituted indoles
to yield blue solids which are converted into 9-(indol-3'-y1)xanthenes by water
or by sodium ethoxide in ethanol. With a
3-substituted indole, reaction occurs at the 2-position.
Reactions of ethylene oxides. VI. The mechanism of formation of dioxolans from acetone and 6-t-Butyl-1-oxaspiro[2,5]octanes
Authors: Coxon JM , Hartshorn MP , Sutherland BLS
Published: September 2010

Reaction of cis- and trans-6-t-butyl-1-oxaspiro[2,5]octane with acetone in the presence
of BF3 gave, in each case, a mixture of the epimeric
8-t-butyl-l,3-dioxaspiro[4,5]decanes (5) and (6). The
mechanism of the reaction is discussed.
Aluminium chloride catalysed reactions of cinnamoyl chloride with naphthalene, phenanthrene, chrysene and pyrene
Authors: Williams HJ , Shotter RG
Published: September 2010

Homogeneous reactions of cinnamoyl chloride with naphthalene in chlorobenzene and in
nitrobenzene in the presence of 1 molar proportion of aluminium chloride give
mixtures of 1-naphthyl styryl ketone (1) and
2-naphthyl styryl ketone (2) as initial products. An
increase in the molar ratio of (2) to (1) with the time of the reaction at
higher temperatures was noted. This variation was shown to be due to subsequent
reactions of the cinnamoylnaphthalenes, with (1)
reacting more readily than (2), and not due to isomerization of (1) to (2).
Reaction of cinnamoyl chloride under similar
conditions with

phenanthrene, chrysene and pyrene has
been examined.
Some wave functions for the four-electron threecentre bonding of four- and eight-π-electron systems
Authors: Harcourt RD , Sillitoe JF
Published: September 2010

For symmetrical four-electron three-centre bonding units, the standard valence-bond (VB), delocalized
molecular orbital (MO), increased-valence (IV) and non-paired spatial orbital (NPSO) representations
of the electrons are

Diagram
O3, NO2- and CF2 with four π-electrons, and N3-, CO2 and NO2+ with eight π-electrons, have
respectively one and two four-electron three-centre bonding units for these n-electrons. By means
of Pople-Parr-Pariser type approximations, the MO, standard VB, IV and NPSO wave functions for
these systems are compared with complete VB (or best configuration interaction) wave functions
for the ground states. Similar studies are reported for the n-electrons of N2O. Further demonstration
is given for the important result obtained elsewhere that the IV formulae must always have
energies which are lower than those of the standard VB formulae, provided that the same technique
is used to construct electron-pair bond wave functions. The extra stability arises because IV formulae
summarize resonance between the standard VB formulae and long-bond formulae of the type
Diagram
As has been discussed elsewhere, the latter structure can make appreciable contributions to
the complete VB resonance when its atomic formal charges are either zero or small in magnitude.If two-centre bond orbitals are used to construct the wave functions for the one-electron bond(s)
and the two-electron bond(s) of IV formulae, then the IV and MO wave functions are almost identical
for the symmetrical systems. Further numerical evidence is provided for this near-equivalence.
Organophosphorus compounds. X. A new synthesis of 1,2,3,4-tetrahydrophosphinolines
Authors: Rowley LE , Swan JM
Published: September 2010

A new synthesis of the
1,2,3,4-tetrahydrophosphinoline ring is described. Reaction of 3-phenyl- propylphosphonous dichloride with zinc chloride at 170�
followed by hydrolysis with hot concentrated hydrochloric acid, then oxidation
with bromine, gave 91% of 1-hydroxy-1,2,3,4-tetrahydrophosphinoline 1-oxide
(20b). Under conditions where oxidation was incomplete,
1,2,3,4-tetrahydrophosphinoline 1-oxide was isolated. On a small scale the
reaction of 3-phenylpropylphosphonous dichloride with a catalytic amount of
aluminium chloride at 220� gave 60% of l-chloro-
1,2,3,4-tetrahydrophosphinoline (18). Treatment of (20b) with thionyl chloride gave
1-chloro-1,2,3,4-tetrahydrophosphinoline 1-oxide which, upon reaction with the
appropriate Grignard reagent, afforded 1-ethyl or
1-phenyl-1,2,3,4- tetrahydrophosphinoline 1-oxide.
1-Ethyl-1,2,3,4-tetrahydrophosphinoline 1-oxide was reduced with trichlorosilane to the phosphine, which upon reaction with sulphur yielded the corresponding phosphine sulphide. The methyl and ethyl esters of (20b) are
described.
Preparation and properties of some rare-earth phthalocyanines
Authors: MacKay AG , Boas JF , Troup GJ
Published: September 2010

The preparations and
magnetic and spectral properties of one ytterbium and two gadolinium phthalocyanines are described and comparisons made with
previous studies. The susceptibility of all three compounds followed a
Curie-Weiss law, with � small, and the magnetic moments were typical for
trivalent rare-earth compounds with little or no coupling between the metal
ions. The e.p.r. signals observed were due to the
metal ions. Structures proposed are Cl(pc)YbCl,2H2O
(where pc = C32H16N8) for ytterbium, and (pc)Gd(pc)H and an associated anionic form for gadolinium. Both
gadolinium materials are stable under certain solution conditions, although the
anionic material tends to decompose and is difficult to obtain from solution. A
polymeric form of phthalonitrile (m.p. 306�C) was
isolated during purification. A simple acid-base equilibrium is proposed for
the gadolinium compounds but it is complicated by the separation procedures and
by the nature and purity of the solvent.