bluuebunny/crossref_metadata_2025 huggingface dataset:
Kerr constant-dispersion measurements on cyclohexane
Authors: Le FFvre RJW , Pierens RK
Published: September 2010

Le Fbre
and Solomons recorded the Kerr constants Bγ of carbon tetrachloride and benzene over
the wavelength range 375-625 nm to make possible the use of these solvents in
examining the anisotropic polarizabilities of coloured solutes. Since, however, unsuspected hydrogen bondings may occur between π-electrons of benzene and
protons from a dissolved molecule, and/or because of the various risks of chemical changes when basic
substances are studied in carbon tetrachloride, an additional and more inert
medium became desirable. Cyclohexane seemed to be the least reactive of the
liquids which are available in quantity and easily purified, but no information
on the variation of its B constant with wavelength was in the literature; the
present measurements were therefore made to fill this gap.
Bridgehead 1J(13C-H) values in 1,8-disubstituted 1a,2,7,7a- Tetrahydro-1,2,7-metheno-1H-cyclopropa[b]naphthalene compounds
Authors: Collin PJ
Published: September 2010

The value of the bridgehead
13C-H coupling constant tends to increase as the degree of
"strain" increases in cyclic hydrocarbons. Thus, in the highly
"strained" 1,3-dimethyltricyclo[1,1,1,04,5]pentane, the
bridgehead J(13C-H) value is 212 Hz1 and in the slightly less
"strained" bicyclo[l,l,0]butane, the bridgehead 13C-H
coupling is c. 200 Hz.2 In both of these compounds the bridgehead
proton is attached to two three-membered rings. When the bridgehead proton is
common to two four-membered rings, such as in cubane
and bicyclo[l,l,l]pentane,2 the coupling constant is c.160 Hz. In
"unstrained" systems such as methane and cyclohexane the value is
c.125 Hz.
Mass spectrometric studies. XI. Skeletal rearrangements in acylhydrazines
Authors: Porter QN , Seif AE
Published: September 2010

The mass spectra of mono-
and di-alkyl-N,N'-dibenzoylhydrazines
contain rearrangement ions arising from initial migration of a benzoyl or alkyl group from one nitrogen atom to the other.
The spectra also contain ions resulting from N-N fissions accompanied by transfer of one or two hydrogen atoms.
The spectra of the mono- and di-phenyl compounds are
simpler, but that of the monophenyl compound contains
an ion in the formation of which two hydrogen atoms have been transferred to
the neutral product from a phenyl ring.
The theory of the nuclear quadrupole interaction in terms of irreducible tensors
Authors: Hollingworth RW , Hacobian S
Published: September 2010

Using irreducible tensors
throughout, the theory of the interaction of a quadrupolar
nucleus surrounded by electrons is presented. The theory is applied both to
pure and Zeeman n.q.r.
spectra. The relation between the spectrosoopic and
intrinsic quadrupole moments is derived.
Hindering of diffusion by pores
Authors: Conlon T , Craven B
Published: September 2010

Attempts were made to
measure the hindering of ionic and molecular diffusion in the pores of membrane
filters, but it was found that available membranes are not suitable for this
purpose. Polystyrene spheres in aqueous suspension were diffused through a thin
membrane with right cylindrical pores, and hindering was found to take place in
a way which does not agree with previous theory. A new theory is proposed, based on absolute
reaction rates.
Ionization constants of benzoic and mononitrobenzoic acids in formamide
Authors: Dash UN , Nayak B
Published: September 2010

The ionization constants of
benzoic acid and of three mononitrobenzoic acids, at
25� in formamide, have been determined from the measurements of the electro-motive
forces of the cells

Pt,H2/HA(m1),KA(m2)KCl(m3)AgCl-Ag

The values of the
ionization constants for benzoic acid, o-nitrobenzoic
acid, m-nitro-benzoio
acid, and p-nitrobenzoic acid thus
calculated from e.m.f. data are 4.37 x 10-7,
3.89 x 10-5, 3.98 x 10-6 and 1.32 x 10-6,
respectively. These values are smaller than those in water, and are in agreement
with a general behaviour exhibited by weak acids in solvents of this class.
Tetronic acid derivatives: Synthesis of an indolone-spiro-hydroxytetronimide
Authors: Amiet RG , Eastwood FW , Rae ID
Published: September 2010

The synthesis of
l-methylindol-2(3H)-one-3-spiro-2'-3',4'-dihydroxy5'-imino-2',5'-dihydrofuran
(4; R1 = R2 H) is described. The compound is readily
oxidized to yield 1-methylindole-2,3-dione and 2-oxomalonamic acid, which was
isolated as the phenylhydrazone, and on acetylation it forms a mono- or di-acetate.
It reacts with phenylhydrazine with opening of the tetronimide
ring to form
3-(2',3'-dihydro-l'-methyl-2'-oxoindo1-3'-yl)-3-oxo-2-phenylhydrazonopropanamide
(5). The latter compound can be cyclized to
yield a new pyranoindole (6).
Preparations, sulphinate coordination, and thermal decomposition of some bismuth triarenesulphinates
Authors: Deacon GB , Fallon GD
Published: September 2010

Bismuth triarenesulphinates,
Bi(02SR)3 [R = Ph, p-MeC6H4,
p-ClC6H4, 2,4,6-(Me2CH)3C6H2,
and p-MeCONHC6H4],
have been prepared by reaction of bismuth triacetate with the
appropriate arenesulphinio acids in glacial acetic
acid, and the first two compounds have also been obtained by reaction of triphenyl-bismuth with the appropriate mercuric arenesulphinates. The sulphur-oxygen
stretching frequencies of the bismuth sulphinates are
indicative of O-sulphinate
coordination, and the compounds are considered to be polymeric with bridging O-sulphinate
groups and six-coordinate bismuth. Thermal decomposition of
Bi(O2SR)3 (R = Ph, p-MeC6H4,
or p-CIC6H4) under vacuum gave the corresponding triarylbismuth compounds and sulphur
dioxide, the preparation of tri-p-chlorophenylbismuth being accompanied by formation of di-p-chlorophenyl
sulphone and S-p-chlorophenyl p-chlorobenzenethiosulphonate. Pyrolysis of the other triarenesulphinates did not yield organobismuth
compounds.
Electron transfer mechanism of aromatic 'nucleophilic' substitution
Authors: Singh PR , Kumar R
Published: September 2010

Mechanistic implications of
the ready formation of aryl iodides from aryldiazonium
salt solutions and the iodide ion (in contrast with the general need for
cuprous or other catalysts with other halides) have been studied. The reaction
between benzenediazonium fluoroborate
and potassium iodide in methanol at 0�C has been investigated. A new mechanism
involving initial one-electron transfer from the iodide anion to the benzenediazonium cation, resulting in the formation of
radical intermediates by heterolytic cleavage of a bond, has been proposed in order
to account for the products, viz. iodobenzene,
benzene, biphenyl, iodine, anisole, and formaldehyde, and the effect of
photochemical catalysis.
Synthetic studies related to mycobactins. II. Formation of mycobactin hydroxamic acid units by malonic ester synthesis
Authors: Black DSC , Brown RFC , Wade AM
Published: September 2010

6-(N-Hydroxy)lysine dihydrochloride and some related compounds have
been synthesized by a reaction sequence involving the alkylation of sodium
diethyl-phthalimidomalonate by 1,4-dibromobutane to
form diethyl 5-bromo-1-phthalimido-pentane-1,l-dicarboxylate. During the
transformation of this bromo compound to the corresponding nitro compound,
cyclization to diethyl l-(2'-carboxybenzoyl)piperidine-2,2-dicarboxylate
occurred.
The anodic oxidation of ethylxanthate on metal and galena electrodes
Authors: Woods R
Published: September 2010

The products of the
electrochemical oxidation of potassium ethylxanthate have been identified by
infrared analysis and microanalysis for the constituent elements. The current
efficiency for the formation of diethyl dixanthogen depends on the nature of the
electrode, and at 0.5 V was found to be 100, 98, 90, c. 50, and 0% for platinum, gold,
copper, galena, and lead respectively. The remainder of the current passed at
this potential resulted in the formation of the metal xanthate.� Dixanthogen is formed on lead electrodes only
at potentials of > 1.0 V, where lead xanthate is unstable with respect to
oxides of the metal. The lead xanthate produced
on a galena electrode at pH 9.1 involves the release of thiosulphate ions. The formation of lead xanthate by this
reaction, followed by its reduction to lead, is shown to change the surface
characteristics of a galena electrode to those of lead. However, the formation
and reduction of the initial layers which takes place on cycling the electrode
potential does not change a galena surface and cannot involve
loss of sulphur from the surface to the solution.
This supports the conclusion that the chemisorbed xanthate monolayer is first
covered by dixanthogen and that lead xanthate forms only when bulk layers are
produced.
E.P.R. studies of the anions of some peri-alkylnaphthalenes
Authors: Claridge RFC , Peake BM
Published: September 2010

The hyperfine coupling
constants for the radical anions of 2,3-dihydro-

phenalene (perinaphthane)
and 7,8,9,l0-tetrahydrocyclohepta[de]naphthalene have been determined from
analysis of the electron spin resonance spectra in solution. The results are
compared with data from other mono- and di-peri-
substituted naphthalenes. A simple H�ckel molecular orbital treatment is used
to describe the inductive effect of the aliphatic substituent.
Solvent dependence of pyridine aza sigma values determined from alkaline ester hydrolysis
Authors: Deady LW , Shanks RA
Published: September 2010

The alkaline hydrolysis of
a series of substituted alkyl benzoates and pyridine-carboxylates in aqueous
methanol, dioxan, acetone, and DMSO solvents has been
studied. Hammett correlations in all solvents are excellent and sigma values
for the 2-, 3-, and 4-aza groups have been derived.
These are effectively solvent independent except for a significant decrease in
the σ2N value in DMSO-containing
solvents.
ω-Hydroxyisodillapiole, a new cinnamyl alcohol from Piper novae-hollandiae
Authors: Falkiner M , Loder JW , Russell GB , Shelton M
Published: September 2010

A minor constituent of the
wood of Piper novae-hollandiae
is shown by synthesis from dillapiole to be the previously unknown ω-hydroxyisodillapiole (2)((E)-2,3-dimethoxy-4,5-methylenedioxyoinnamyl
alcohol).
The alkaloids of Schefferomitra subaequalis (Anonaceae)
Authors: Gellert E , Rudzats R
Published: September 2010

Eight alkaloids were
isolated from the bark of Scheferomitra subaequalis (Scheff.) Diels. In addition to the previously reported anonaine and liriodenine, three
known alkaloids, asimilobine, isoboldine,
and anolobine, and three new ones, aequaline, schefferine, and
alkaloid Y were isolated from the bark. The leaves yielded the six colourless alkaloids present in the bark, while the two
yellow ones,

liriodenine and alkaloid Y, were absent. The structure and
absolute configuration of aequaline was elucidated as
(S)-3,9-dihydroxy-2,l0-dimethoxytetrahydoproto-berberine
and that of schefferine as (8)-9-hydroxy-2,3,10-trimethoxytetrahydro-protoberberine.
The Coumarins From the Resin of Euodia vitiflora
Authors: Lassak E , Southwell I
Published: September 2010

Three coumarins isolated from the resin of Euodia vitiflora
have been shown by spectroscopic as well as chemical evidence to be 7-(3',3'-dimethylallyloxy)-coumarin (1),7-(3'-carboxybutoxy)coumarin (2), and
7-(3'-carboxybut-2'-enoxy)coumarin
(4).
The formation of organorhodium complexes from the reaction of hexafluorobut- 2-yne and (π-C5H5)Rh(CO)2
Authors: Dickson RS , Kirsch HP
Published: September 2010

The thermally initiated
reaction of hexafluorobut-2-yne with (π-C5H5)Rh(CO)2 has been studied in detail, and it is
found that the nature and yields of the products are sensitive to the reaction
conditions. The known complexes (π-C5H5)Rh-[(C4F6)2CO] and (π-C5H5)Rh(C4F6)3 and the new organorhodium complexes (π-C5H5)2Rh2(CO)2(C4F6),
(.π-C5Hs)3Rh3(C4F6)2,
(π-C5H5)2Rh2(CO)(C4F6)2,
and (π-C5H5)3Rh3(CO)(C4F6)
have been isolated from the reaction system. Each organorhodium
complex has been characterized by elementary and mass spectral analysis, and reasonable
structures for all complexes have been predicted from the appropriate i.r. and N.M.R. data. The monoalkyne
complex (π-C5H5)2Rh2(CO)2(C4F6)
is an intermediate in the formation of the other organorhodium
complexes.
3-Substituted 1,4-Benzoquinone 4-oximes
Authors: Norris RK , Sternhell S
Published: September 2010

The preparation and
physical properties of seven compounds in the title series are described. When
the 3-substituent is F, Cl, Br, I, Me, or OMe the compounds exist predominantly
(>95%) in the oxime form. The 3-methoxy-carbonyl derivative is estimated to exist
in the nitroso form to the extent of 23%.
The chemistry of pyrrolic compounds. XXIII. β-Aminoporphyrins and their derivatives
Authors: Clezy PS , Liepa AJ , Webb NW
Published: September 2010

Some aspects of the
chemistry of β-aminopyrroles are described including reactions which lead
to derivatives of β-aminoporphyrins. This type of tetrapyrrole has also
been obtained from oxime derivatives of β-acetylporphyrins by way of a
Beckmann rearrangement. Hydrolysis of the P-acetylaminoporphyrins gives the
corresponding aminoporphyrins which are stable enough to be examined spectroscopically.
Diterpenoids. XXXII. Labda-8,14-dien-13β-ol
Authors: Carman RM , Craig WJ , Shaw IM
Published: September 2010

The 13S compound 13-epiisomanool
(labda-8,14-dien-13β-ol) has been synthesized and its optical rotation
compared with that of the 13R isomer (isomanool) in
order to correct errors in the literature.
The determination of the cation distribution in olivine from single crystal Mössbauer studies
Authors: Duncan JF , Johnston JH
Published: September 2010

Mossbauer absorption
spectra of different orientations of single crystals of olivine (MgFe)2SiO4
have been determined. The variation of the ratio of peak areas of the
quadrupole split lines has allowed the M(1) and M(2) site positions of the Fe2+
ions to be identified, and has shown that the Fe2+ ions are evenly
distributed between these sites.
Chelate linkage isomers of (3-Hydroxyimino-4,9-dimethyl-5, 8-diazadodeca-4,9-diene-2,11-dionato) nickel(II)
Authors: Lacey M.J. , Macdonald CG , Shannon JS
Published: September 2010

Isomers of the named
compound and their 15N- and 18O-labelled analogues were
analysed by p.m.r., infrared, and mass spectrometry.
Evidence indicates that the isomers differ only in the mode of attachment of
the oxime group of the ligand to the nickel atom in each molecule. Significant
differences in carbonyl frequencies have been noted for the uncoordinated
acetyl groups attached to the five- and six-membered chelate rings.
Alkaloids of Nemuaron vieillardii (Monimiaceae)
Authors: Bick IRC , Leow HM , Preston NW , Wright JJ
Published: September 2010

Bark of the New Caledonian
monimiaceous plant Nemuaron vieillardii
contains the alkaloids laurotetanine, N-methyllaurotetanine, norisocorydine,
atheroline, O-methylflavinantine, and a new
bisbenzylisoquinoline alkaloid nemuarine, which is the major alkaloid of the
leaves. Nemuarine is shown to have a novel structure with a 5-6? ether link
between the isoquinoline residues.
The kinetically effective stoichiometry of reactions in the carbon-sulphur dioxide system
Authors: Blackwood JD , McCarthy DJ
Published: September 2010

The kinetically effective stoichiometry of reactions resulting from contacting
carbon and sulphur dioxide at elevated temperatures involves the five overall reactions:
2C + 2SO2 → 2CO2 + S2
C+ S2 + CO2 → 2COS
C+ 2COS → CS2 + 2CO
C+ COz -, 2C0
C+S, -+ CS,
The rates of the two reactions forming carbon disulphide are shown to have
similar temperature dependence in the range 800-950�C, while the carbon-carbon
dioxide reaction is shown to be more temperature sensitive than the carbon-carbonyl
sulphide reaction in the same temperature range.
The existence of parallel routes for carbon disulphide formation was detected
by using a mechanistic argument to remove the redundancy in the system where carbon
disulphide was concerned.
Syntheses of 5-n-Alkylresorcinol dimethyl ethers and 1,14-Bis(3,5-dimethoxyphenyl) tetradecane via β-keto sulphone intermediates
Authors: Cannon JR , Cheong PK , Fallick CJ , Hamilton BH , McDonald IA , Vinciguerra G
Published: September 2010

Alkylation of
3,5-dimethoxy-α-(methylsulphonyl)acetophenone followed by reduction of the
resulting monoalkylated products with zinc and acetic acid afforded the
corresponding 5-n-acylresorcinol dimethyl ethers. Hydrogenolysis of
5-n-undecoylresorcinol dimethyl ether, prepared in this way, yielded
5-n-undecylresorcinol dimethyl ether. ��� Alkylation of 1-(methylsulphonyl)alkan-3-ones
with 3,5- dimethoxybenzyl bromide gave a mixture of mono- and di-substituted products. Clemmensen reduction of the
monosubstituted products afforded 5-n-alkylresorcinol dimethyl ethers directly.
��� These reactions have been adapted to
provide two syntheses of 1,14- bis(3,5-dimethoxyphenyl)tetradecane.
The stereochemistry of Wallach's dicarvelones
Authors: Carman RM , Saraswathi GN , Verghese J
Published: September 2010

The structures of α-,
β-, and γ-dicarvelone are determined.
Structure of 4-Arylaminomethylene-3-methylisoxazol-5-ones
Authors: Summers LA
Published: September 2010

Study of the i.r., u.v.,
and N.M.R. spectra of 4-arylaminomethylene-3- methyl-isoxazol-5-ones indicates
that they exist in the tautomeric form (2). Four new halo derivatives of
4-anilinomethylene-3-methylisoxazol- 5-one have been prepared.
para-Substituted benzohydroxamic acids: Thermodynamic ionization constants and applicability of Hammett equation
Authors: Agrawal YK , Shukla JP
Published: September 2010

Thermodynamic ionization
constants were determined in aqueous media at 25�. An attempt was made to
correlate these constants with Hammett's equation.
The simplified ab initio method calculation of linear polarizability
Authors: Brown RD , Williams GR
Published: September 2010

The simplified ab-initio molecular-orbital method described previously is
particularly suited to the calculation of polarizabilities by the
non-perturbative coupled Hartree-Fock technique.
Trial calculations on CO and HF, for which comparison with corresponding ab-initio calculations is possible, show that the method
gives an adequate numerical performance. Minimal basis set calculations in
general tend to give values that are considerably too low because of inadequate
flexibility of the basis and this is the origin of the large discrepancy
between theory and experiment, especially for small molecules. ��� Results are also reported for N2O
and O3. For these larger systems the SAI results with minimal basis
sets are noticeably nearer experimental values. The polarizability anisotropy
for N2O is particularly well reproduced by the SAI method. �
The two C 8 epimers of 3β-Acetoxylanost-9(11)-en-7-one
Authors: Lassak EV , Pinhey JT , Simes JJH
Published: September 2010

Chromium trioxide-acetic
acid oxidation of 3β-acetoxylanost-8-ene (1) at approximately 50� yields
3β-acetoxylanosta-7,9(11)-diene (2), 3β-
acetoxylanost-8-ene-7,11-dione (3), 3β-acetoxylanost-8-en-7-one (4), and
3β-acetoxy-8β-lanost-9(11)-en-7-one (5). The α,β-unsaturated
ketone (4) is not an intermediate in the formation of (3), the oxidation
sequence being (1) → (2) → (5) → (3). ��� Mild 30% hydrogen peroxide-acetic acid
oxidation of (1) at 20� affords (2) in almost quantitative yield while further
reaction under the same conditions gives 3β-acetoxy-8α-lanost-9(11)-en-7-one
(6).
The Pschorr cyclization. III. The synthesis of Dibenz[c,e]azepines
Authors: Huppatz JL
Published: September 2010

The copper-catalysed
decomposition of diazonium salts derived from N- mesyl-dibenzylamines has been
examined. 2-Amino-N-mesyldibenzylamine (8a) gave 6-mesyl-6,7-dihydro-5H-dibenz[c,e]azepine
(9a) as the major product, together with benzaldehyde and N-benzylmethanesulphonamide
(6a). Derivatives of the amine (8a) bearing 4?-methyl (8b), 4?-chloro (8c),
2?-chloro (8d), and 4?-methoxy (8e) substituents were cyclized to the
appropriately substituted dibenz[c,e]azepines (9b-e). The corresponding aldehydes
(10b-e) and N-benzylmethanesulphonamide (6a) were also isolated from these
reactions. In addition, the compounds (8b), (8c), and (8d) gave
2-(N-mesylaminomethyl)-4?-methylbiphenyl (11b) and the 4?-chloro (11c) and
2?-chloro (11d) derivatives, respectively, as minor products. Possible
mechanisms for the formation of the byproducts of the cyclization reactions are
discussed. The
isomeric amines, o-amino-N-benzenesulphonyl-N-methylbenzylamine (12) and
N-(o-aminobenzenesulphonyl)-N-methylbenzylamine (13), were cyclized by copper-catalysed
decomposition of their respective diazonium salts to give
6-methyl-5H-dibenzo[d,f]thiazepine 7,7-dioxide (14) as the major product of the
reactions.
Mechanism and structure in chemical ionization mass spectrometry: tricyclic flavanoid compounds
Authors: Clark-Lewis JW , Harwood CN , Lacey MJ , Shannon JS
Published: September 2010

The chemical ionization mass spectra of a series of tricyclic flavanoid compounds
have been examined using isobutane and hydrogen as reagent gases and the fragmen-
tation modes have been correlated systematically in terms of structure. The technique
produces simple fragmentation patterns and abundant metastable ions. The use of
deuterium as reagent gas reveals the influence of extraneous water on the spectra and
facilitates the interpretation of the fragmentation pathways. The fragment ions appear
to arise from isomeric progenitors protonated at different sites in the molecules.
Isobenzofulvenes. I. The in situ preparation of 8,8-Dimethyl- and 8,8-Diphenylbenzo[b]fulveues and their pericyclic reactions with 2π-Cycloaddends
Authors: Watson PL , Warrener RN
Published: September 2010

A new route to the
generation of the previously undescribed 8,8- dimethyl- and 8,8-diphenyl-benzo[b]fulvene
(isobenzofulvenes)? is reported. This method involved the mild thermal
fragmentation of 3,6- di(2?-pyridyl)-15-(α,α-disubstituted methylene)-4,5-
diazatetracyclo[6,6,1,02,7,09,14]pentadeca-3,5,9,11,13-pentaene
(39), which was prepared from the benzyne adduct of the 7-(α,α-disubstituted
methylene)bicyclo[2,2,1]-hepta-2,5-diene (36) and 3,6-di(2?-pyridyl)-s- tetrazine
(37). This retroversion reaction is one of order [8π+6π] and, based
on the limited evidence available, appears to be a non-concerted process. The
isobenzofulvenes were readily isolated, in quantitative yield, as [8π+2π]
cycloadducts with a variety of electron deficient olefins (tetraenophiles).
Mixtures of exo- and endo-adducts were often obtained and their ratios
explained in terms of a combination of dipole-dipole, steric, and orbital
interactions operative in the respective transition states. Ozonolysis of these
adducts yielded products formally derived from cycloadditions to isoindenone,
and this represents an excellent route to these compounds. No spectral evidence
for the existence of the monomeric isobenzofulvenes could be obtained, although
acid-catalysed decomposition of the dimethyl precursor yielded significant
proportions of 2-isopropenylindene, which is logically derived from
8,8-dimethylbenzo[b]fulvene. P.m.r. and mass spectral data are reported for all
new compounds and briefly discussed where relevant.
Chemistry of the Podocarpaceae. XLVI. An unusual diterpenoid acetal
Authors: Cambie RC , Preston AF , Woodgate PD
Published: September 2010

The structure (9) has been
assigned to an acetal formed during attempts to prepare the 1,4-dioxan (1).
Effect of different gases on the intensity of the air after-glow
Authors: Williams DJ
Published: September 2010

The dependence of the
intensity of the air after-glow on the nature of the bulk gas (for fixed O and
NO concentrations) has been evaluated for H2, He, N2, O2,
Ar, CH4, CO2, N2O, SF6. The results
are interpreted in terms of the combined effects of the collision partner on
vibrational stabilization and electronic quenching of the emitting molecule.
Complex nickel nitrites. II. Linkage isomerism in complexes of ethylenediamine and N,N'-diethylethylenediamine
Authors: Green RW
Published: September 2010

Two pairs of linkage
isomers, NiL2X2, have been prepared. When L = N,N?-
diethylethylenediamine, the blue dinitrito form (X = ONO) is stable at room temperature,
but the metastable dinitro form (X = NO2) can be prepared and stored
for several days as red octahedral crystals. At -60� the dinitro complex is
the stable form. ��� When L = ethylenediamine there is a
transition temperature at 74�2�. The known stable red dinitro complex is
converted into a blue dinitrito isomer by heating. The blue form is metastable
at room temperature but again can be stored for several days. In each case the
isomerization reaction of the metastable to the stable isomer can be followed
by infrared spectrometry.
Electron impact studies. LXXIX. Negative-ion mass spectrometry of functional groups, 2-Aryl-1,3-oxathians and 1,3-Dioxans
Authors: Bowie JH , Ho AC
Published: September 2010

A general summary of the
formation of negative ions is given. The negative-ion mass spectra of
2-aryl-1,3-oxathians contain pronounced molecular anions together with fragment
ions produced by both simple and complex cleavage processes. Evidence is presented
which suggests that the decomposing molecular anions have low internal
energies. The spectra of nitroaryloxathians contain further examples of
specific hydrogen scrambling in negative ions, and that of the o-nitro
derivative exhibits a characteristic proximity effect. In contrast, the
isomeric nitrophenyl-1,3-dioxans give similar spectra and show neither hydrogen
scrambling nor proximity effects.
13C coupling in the E.S.R. spectrum of the pyrene anion in tetrahydrofuran
Authors: Claridge RFC , Kirk CM , Peake BM
Published: September 2010

Examination of the e.s.r,
spectrum of pyrene anion in tetrahydrofuran under conditions of high resolution
has yielded the 13C hyperfine coupling parameters for five of the
six carbon positions. The parameters agree well with those calculated by molecular
orbital methods. No evidence of ion pair formation was found under the
conditions used in these experiments.
Thermodynamic excess functions of regular and related solutions according to some equations of state based on the perturbed hard sphere model
Authors: Astin DK , Watson ID
Published: September 2010

The excess thermodynamic
functions of 12 mixtures, each representative of a certain type of system, have
been calculated by means of the van der Waals, Frisch,1 and Carnahan and Starling2
equation of state, in conjunction with one-fluid and two-fluid models of
conformal mixtures. In addition, the equation of state of hard sphere mixtures
of Mansoori et al.3 has been used. Though
none of the approaches give quantitative agreement for any of the systems
considered, they all give a qualitative account which broadly reflect the
trends in behaviour. In the cases where it is appropriate to comment on the
qualitative accuracy the two-fluid model, used with either the Frisch or
Carnahan and Starling equation of state, shows a slight superiority to the
others.
The synthesis of specifically deuterated analogues of Bicyclo[3,3,1]nonan-3-one
Authors: Cable J , Macleod JK
Published: September 2010

endo-Bicyclo[3,3,1]nonan-3-ol
(1), bicyclo[3,3,1]nonan-3-one (2), and a number of specifically deuterated
analogues of these compounds have been synthesized from bicyclo[3,3,1]nonane-3,7-dione
(3) by the following procedure. ��� Reduction of (3) with sodium borohydride
gave 1-hydroxy-2- oxaadamantane (4) which was
converted into 7-bromobicyclo[3,3,1]nonan- 3-one (6)
on treatment with hydrobromic acid. Triphenyltin hydride was used to achieve
replacement of the bromine atom by a hydrogen atom to give bicyclo[3,3,1]nonan-3-one
(2). ��� Substitution of sodium borohydride by sodium
borodeuteride gave endo-7-deuterobicyclo[3,3,1]nonan-3-one (2b) whereas the use
of triphenyltin deuteride in place of triphenyltin hydride led to exo-7- deuterobicyclo[3,3,1]nonan-3-one (2a). The scheme also
provided access to the [7-D2], [6,8-D4], and [6,7,8-D6]
bicyclo[3,3,1]nonan-3-ones.
Preparation of 2,4-trans-Flavan-4-ols by oxymercuration-demercuration of Flav-3-enes
Authors: Clark-Lewis JW , McGarry EJ
Published: September 2010

Oxymercuration-demercuration
of flav-3-enes has been found to give 2,4- trans-flavan-4-ols as the major products together with traces of
the 2,3-trans-3,4-cis-flavan-3,4-diols. Flav-3-enes having electron-releasing substituents in
conjugated positions on the A-ring react less readily than those lacking these
substituents. N.m.r. data are presented on the compounds obtained.
Kinetics of Schiff base ligand transfer and rate enhancement by metal ions
Authors: Fee WW , Gaetano A
Published: September 2010

The kinetics of the
transfer of Schiff base ligands between their nickel(II) and zinc(II) complexes
have been examined in dmso. Reactions completed in
the presence of added nickel(II) and zinc(II) ions indicate the occurrence of a
coordination chain reaction with rate acceleration prompted by one chain
initiating and one chain propa- gating step.
The reaction between 2,3-Diphenyl-2H-azirine and Phenyldiazomethane
Authors: Bowie JH , Nussey B , Ward AD
Published: September 2010

The reaction between
2,3-diphenyl-2H-azirine and phenyldiazomethane
produces the stable 1-azido-1,2,3-triphenylprop-1-ene
in good yield. The structure is confirmed by an alternative synthesis which
indicates that the double bond has the E-configuration.
Metal complexes of 1,10-phenanthroline derivatives. VI. Complexes of iron, cobalt, nickel, and copper with 1,10-Phenanthroline-2-carbothioamide or N Phenyl-1,10-phenanthroline-2-carbothioamide
Authors: Goodwin HA , Mather DW , Smith FE
Published: September 2010

Mono- and bis-ligand
complexes of iron, cobalt, nickel and mono-ligand complexes of copper with the tridentate
chelating agents 1,10- phenanthroline-2-carbo-thioamide
and N-phenyl-1,10-phenanthroline-2- carbothioamide
are described. Both ligands produce a strong field with iron(II) and the bis-ligand
complexes of cobalt(II) and the former display a temperature-induced spin
transition resulting in an anomalous temperature-dependence of their magnetism.
In all the mono-ligand complexes the metal atom is believed to be
six-coordinate. Both ligands may be deprotonated in their complexes and
deprotonation of the N- phenyl derivative occurs spontaneously when it
interacts with cobalt(II) or copper(II), the reaction with cobalt being accompanied
by oxidation of the metal. Both ligands coordinate through the sulphur atoms of
the thioamide group.
Conductometric study of hydrophobic interactions in aqueous solutions of double long-chain electrolytes
Authors: Oakenfull DG , Fenwick DE
Published: September 2010

We report measurements of
the equivalent conductance (Λ) of aqueous solutions of a series of decyl-
and hexadecyl-trimethylammonium carboxylates (acetate to undecanoate). In the
decyl series, measurements were made on both sides of the critical micelle concentration
(CMC). The CMC decreased when the hydrocarbon chain length of the carboxylate
ion increased. In the hexadecyl series, measurements were confined to micellar
solutions. ��� The results obtained below the CMC suggest
that hydrophobic interaction between the hydrocarbon chains of
decyltrimethylammonium undecanoate, decanoate, and nonanoate leads to the
formation of ion- pairs. There was no evidence, however, for formation of
ion-pairs by the shorter carboxylates. ��� By assuming that micellar ions obey the
Onsager equation, we have derived a theoretical relationship between Λ and
concentration above the CMC. An excellent fit of theoretical curve to
experimental points can be obtained by adjusting the value of a single parameter.
This parameter is {(m+1)/n}Kmic (where Kmic is the
association constant for binding the carboxylate ion to the micelle and m/n is
the ratio of tetra-alkylammonium ions to carboxylate ions in the micelle). ��� Plots of -RT ln[{(m+1)/n}Kmic]
against the number of methylene groups on the carboxylate ion are linear for
both series, which suggests that m/n is independent of the chain length of the
carboxylate ion. Both lines have a slope equal to N�methy and Scheraga's
estimate of the free energy of hydrophobic interaction between two methylene
groups (-1.40 kJ/mol).
Chemistry of 3-oxoflavans: Oxidation of (+)-catechin 5,7,3',4'-Tetramethyl ether to (+)-5,7,3',4'-Tetramethoxy-3-oxoflavan
Authors: Clark-Lewis JW , Ilsley AH , McGarry EJ
Published: September 2010

Crystalline (+)-5,7,3?,4?-tetramethoxy-3-oxoflavan has been prepared by oxidation of
(+)-catechin 5,7,3?,4?-tetramethyl ether, and characterized by ketonic
derivatives. The formation of acetals and of 3-alkoxyflav-3-enes
by interaction of the 3-oxoflavan with acidified alcohols has been
investigated, and the N.M.R. spectra of the products recorded. The
2R-configuration of the (+)-3-oxoflavan was confirmed by reducing it to a
mixture of (+)-catechin and (-)-epicatechin tetramethyl ethers. The 3-oxoflavan
readily gives the tetramethoxyflavylium cation when
heated with acids in air.
The chemistry of pyrrolic compounds. XXIV. The synthesis of an isomer of coproporphyrin and related compounds
Authors: Clezy PS , Diakiw V
Published: September 2010

Using a bilene-b intermediate
the acetylporphyrin (1e) has been prepared. This porphyrin has been converted
into the corresponding β- free (1i), hydroxyethyl (1f), vinyl (1h), and
ethyl (1g) derivatives. The latter porphyrin (1g) is an isomer of coproporphyrin.
Porphyrins (1g) and (1f) have been compared with the series of compounds
isolated from patients suffering from symptomatic cutaneous
hepatic porphyria. The synthetic porphyrins were not identical with material
isolated from porphyric patients.
Electron impact studies. LXXXIII. Negative-ion mass spectrometry of functional groups
Authors: Bowie JH
Published: September 2010

Fragmentations of the amide
group are not generally observed from molecular anions produced by the capture
of slow electrons. Enhancement of the internal energy of the molecular anions
by collision excitation allows the detection of the fragmentations of the
substituent in the field-free regions of the mass spectrometer. Fragmentation
of the amide group occurs α to either the carbonyl or amino functions.
Diterpene Constituents of Pinus contorta Bark
Authors: Manning TR
Published: September 2010

In addition to the
diterpenes previously isolated from the bark of P. contorta, the new diterpenes
(13S)-labda-8(17),14-diene-13β,18-diol(3) and
18-norlabda-8(17),13-diene-4α,15-diol (6), and the known diterpenes
pimaral [8(14), 15-pimaradien-18-al] (10), isopimaral (7,15- isopimaradien-18-al)
(8), pimarol [8(14),15-pimaradien-18-ol] (11), and isopimarol
(7,15-isopimaradien-18-ol) (9) have been identified.
Thermal stability and radiation damage in the phthalocyanines
Authors: Boas JF , Fielding PE , MacKay AG
Published: September 2010

The phthalocyanine
(pc) complexes of a number of metals have been prepared. The e.p.r. spectra of the paramagnetic pc complexes (VO2+,
Cr2+, Mn2+, Co2+, Cu2+, Mo2+)
show metal ion resonances, while those of the diamagnetic pc complexes (H22+,
Na22+, Mg2+, Ni2+, Zn2+,
Pd2+, Cd2+, Sn2+, Pt2+ and Pb2+)
generally give free spin resonances with g ≈ 2.003 and line widths less
than 1 mT. The preparative conditions have been shown
to affect the free spin concentration in H2(pc). Irradiation also
affects the e.p.r. signal intensity in H2(pc),
Zn(pc) and Ni(pc), and there are also changes in the near-infrared spectra of
most pc complexes. The results are due to the presence of two types of defect,
the first arising from decomposition during crystal growth and the second
arising from a possible local disorder in the crystals which is produced by γ-irradiation.
The latter may be due to a cross-linking of adjacent pc molecules. Oxygen
absorption does not seem to be the major factor in the origin of the free spin
resonances.
Thio derivatives of b-diketones and their metal chelates. XIII. Mass spectra of zinc and nickel chelates of some fluorinated monothio-b-diketones
Authors: Das M , Livingstone SE
Published: September 2010

The mass spectra of the
zinc(11) and nickel(11) chelates of four fluorinated monothio-β-diketones,
RC(SH)=CHCOCF3 (R = Ph, p-MeC6H4,
2-thienyl, Me), have been obtained. The mass spectra of the nickel chelates
have considerably more peaks due to metal-containing species than the spectra
of the zinc chelates, while the reverse is true for the metal-free fragments.
All the zinc chelates give peaks for M (molecular ion), M ? CF3, M -
L (LH = monothio-β-diketone), M - L ? CF2,
LH, L, L - F, RCSCH and RCS. All the nickel chelates give peaks for M, M - F, M
? CF3, M - COCF3, M - L, M- 2L and L. In addition, some of the
metal chelates give other peaks. Mechanisms are proposed for the reactions
giving rise to some of these species. All the zinc and nickel chelates give a
strong peak due to L+ arising from a valence change of the metal ion
from the bivalent to the univalent state as follows: [Me11L2]+
→ L+ + Me1L (Me = Zn, Ni). It is suggested that the
ion L+ has a resonance-stabilized cyclic structure.
Concerning periselectivity. A method for predicting the major route in thermal intermolecular two component cycloaddition reactions having manysymmetry-favoured pathways
Authors: Paddon-Row MN
Published: September 2010

The application of the
Woodward-Hoffmann rules to thermal, intermolecular two-component cycloaddition
reactions generates a set of 'symmetry favoured' pericyclic reactions. The
problem of choosing, within this set, the most favoured reaction (i.e. periselectivity)
is discussed. It has been found that a second order perturbational molecular
orbital (PMO) treatment, employing Huckel eigenvectors and eigenvalues, and
which is restricted to include only those terms containing highest occupied
(HOMO) and lowest unoccupied (LUMO) molecular orbitals, gives results which are
in satisfactory agreement with the available experimental data. The treatment
has been extended to cover the effect of substituents on the preferred mode of
cycloaddition.
Carbon magnetic resonance studies of some phenyl, furyl and thienyl organometallics. Some comments on carbon-metal scalar coupling
Authors: Doddrell D , Lewis KG , Mulquiney CE , Adcock W , Kitching W , Bullpitt M
Published: September 2010

13C chemical shift variations within a series of
phenyl, furyl and thienyl
Group IVB organometallics appear to be best
understood in terms of the usual alkyl and aryl substituent effects on 13C
chemical shifts and not variations in dπ ?pπ
metal-aryl
interactions. Large changes in 13C-metal scalar coupling constants
have been observed suggesting that other factors besides the s-character of the
carbon-metal bond is responsible in determining the coupling constant.
The photolysis of rhodamine B in solution
Authors: Langley KF
Published: September 2010

In the flash photolysis of
aqueous alcoholic solutions of rhodamine B, the semiquinone
radical of the dye is formed by absorption of light at wavelengths shorter than
300 nm. It is proposed that impurities in the alcohol sensitize the radical
formation.
Studies on diterpenes from genus Sideritis. XIII. Two new stachene derivatives from Sideritis angustifolia (Labiatae)
Authors: von Carstenn-Lichterfelde C , Valverde S , Rodriguez B
Published: September 2010

Two new stach-15-ene
(beyer-15-ene) derivatives have been isolated from Sideritis angustifolia Lag. (Labiatae).
Chemical and spectroscopic data, as well as the correlation with previously
described products (stachene and stachen-17-ol),
establish their structures. They are stach-15-ene-lα,l2β,17-trio1 (1)
(jativatriol) and stach-15-ene-7β,12β,17-triol
(30) (conchitriol).
Synthesis of an arylhydroxytetronimide and of 3-Hydroxy-4(1H)-quinolone derivatives
Authors: Evans DJ , Eastwood FW
Published: September 2010

o-(N-Methy1formamido)benzaldehyde
reacted with glyoxal bisulphite
and sodium cyanide in alkaline solution to yield 2-imino-5-[T-(N-methylformamido)phenyl]-2,5-dihydrofuran-3,4-diol.
Under the same reaction conditions o-amino-
and o-N-methylamino-benzaldehyde yielded
3-hydroxy-4(1H)- quinolone
(quinoline-3,4-diol) and 3-hydroxy-1-methyl-4(1H)-quinolone respectively.
Epoxidation and hydroxylation of Flav-3-enes, and synthesis of 2,3-trans-Flavan-3-ols
Authors: Clark-Lewis JW , McGarry EJ , Ilsley AH
Published: September 2010

Flav-3-ene epoxides cannot
be prepared by the reaction of peracetic acid with a flavene, which leads mainly to the 2,3-trans-3,4-cis-4-acetoxyflavan-3-ols.
The epoxides of flav-3-enes lacking electron releasing substituents in ring A
may be prepared under weakly basic conditions, and on reduction give 2,3-trans-flavan-3-ols. Flavenes
with electron-releasing substituents in conjugated positions in the A ring do
not give epoxides under acidic or basic conditions, but the 2,3-trans-flavan-3-ols can be prepared by
hydrogenolysis of the products obtained by interaction with peracetic
acid. Mechanisms are proposed to account for the products obtained in the peroxidation reactions, and N.M.R. was used to establish
the configurations of all the products. Migration of the acetyl group from the
4- to the 3-oxygen atom was observed in two cases, and the resultant 2,3-trans-3,4-cis-3-acetoxyflavan-4-ols showed virtual coupling of the 2- and
4-protons because of the accidental coincidence in chemical shift of the 2- and
3-protons. 2,3-cis-3,4-trans-3-Bromo-4,4'-dimethoxyflavan
showed similar virtual coupling owing to near equivalence in the chemical shift
of the 3- and the 4-protons.
Steroidal alkaloids of Marsdenia rostrata. III. Rostratine and dihydrorostratine
Authors: Gellert E , Summons RE
Published: September 2010

The ester alkaloids
rostratine and dihydrorostratine were isolated and characterized. On the basis
of the mass spectral fragmentation pattern their acetate ester groups were
assigned to the C12 and thenicotinate ester groups to
the C20 hydroxyl groups of the steroid skeleton.
Donor-acceptor complexes formed by perfluoro-organo bromides and iodides with nitrogenous and other bases. IV. Analysis of the infrared spectra of CF3I.N(CH3)3 and CF3Br.N(CH3)3 and related complexes
Authors: Cheetham NF , McNaught IJ , Pullin ADE
Published: September 2010

The infrared spectra of complexes of CF3I and CF3Br with trimethylamine, reported in Part III,
are considered in detail. The spectra are compared with those of related complexes. Considerable
regularities are found. It is suggested that published assignments to δa1(Nme3) and δE(Nme3)
in certain trimethylamine complexes should be reversed. The intensity of δA1(Nme3) is considerably
greater in its complexes with CF3I and CF3Br than in the free base: an explanation in terms of
variation of the extent of electron transfer with vibrational coordinate is suggested. Force constants
of the complex are calculated for several simplified models of the complex and possible errors are
considered in some detail. The N-I bond stretching force constant in the complex CF3I.N(CH3)3
for the room temperature gaseous, solution in carbon tetrachloride, and liquid phases and 80 K
solid phase are respectively 0.19 ± 0.05, 0.29 ± 0.03, 0.31 ± 0.03 and 0.53 ± 0.09 mdyn/Ǻ. Corresponding values for the C-I stretching force constant in the complex and (in parenthesis) values
for free CF3I are: 2.14 ± 0.04(2.44 ± 0.02); 2.02 ± 0.03(2.42 ± 0.02); 2.00 ± 0.03 (2.42 assumed);
1.85 ± 0.04 (2.32 ± 0.02). For CF3Br.N(CH3), (solid) N-Br and C-Br force constants are
0.29 ± 0.05, 2.59 ± 0.05 (3.15 ± 0.02). Less definite information was obtained about the other
force constants of the complex. The trimethylamine C-N stretching force constant decreases on
formation of the complex; the decrease is greatest for solid CF3I.N(CH,3),. Potential energy dis-
tributions are calculated. Possible causes of the changes of the A1 and E CF3 stretching frequencies
on formation of the complexes are considered; several factors appear to be involved.
The chemistry of Dodonaea spp. VII. ent-Labdanes from D. microzyga (Sapindaceae)
Authors: Jefferies PR , Knox JR , Scaf B
Published: September 2010

The structures (1) and (2)
are assigned to two new acids from the title plant. Interrelation was obtained
by borohydride reduction of the mesylation product of
the ester (3) which gave (4). Correlation with material of established
constitution was obtained by Huang-Minlon reduction
of the 2-ketone (8) leading to (10) which was prepared from the reference
compound (11).
Dammaradienyl acetate and taraxasterol from Eupatorium cannabinum: Mass spectrometric study of dammaradienyl acetate and its derivatives
Authors: Talapatra SK , Bhar DS , Talapatra B
Published: September 2010

Dammaradienyl acetate (1)
(0.01%), taraxasterol (6) (0.0008%) and stigmasterol (c. 0.005%) have been
isolated from the whole plant of Eupatorium cannabinum (Compositae). A mass
spectrometric study of dammaradienyl acetate (1) and its derivatives has been reported.
Strongly hydrogen-bonded molecular solids with 'highly anomalous' infrared OH absorption
Authors: Spinner E
Published: September 2010

The infrared spectra of
solid isonicotinic acid (1), 6-hydroxy-2-pyridone (2) and
6-hydroxy-l-methyl-2-pyridone (3) have very intense, broad, plateau-like, OH
absorption bands, centred near 1000 cm-1, with prominent
transmission windows. After O-deuteration
these bands remain very broad but become much less intense, and the centre of
gravity is shifted to higher frequencies, by c. 100-250 cm-1; most of the transmission windows become
much shallower, or disappear, or are replaced by ordinary bands pointing upwards.
Full explanations of the deuteration effects on the transmission windows cannot
be given, but it is clear that the amplitude of hydroxyl stretching must be
much greater for OH than for OD. This vibration must be very highly anharmonic,
and it is shown that any physically reasonable potential energy curve for it
must be highly unsymmetrical. For solids (2) and (3) the potential energy
hypersurface, for all stretching vibrations, may be symmetrical, with a double
minimum, but no such symmetry can be present in solid isonicotinic acid.
Nickel(II) and copper(II) complexes of some pyridinecarboxylic acids
Authors: Ellis VM , Vagg RS , Watton EC
Published: September 2010

Complexes of nickel(11) and
copper(11) with the ligands 6-methylpyridine-2-carboxylic, pyridine-2-
carboxylic and pyridine-3-carboxylic acids have been prepared from non-aqueous
media. In all cases, the magnetic properties and reflectance spectra indicate an
octahedral configuration for the nickel(11) complexes. Six-coordination is also
possible for the copper(11) complexes, although five-coordinate structures
cannot be discounted.
Kinetics and mechanism of oxidation of allyl alchohol by chloramine-T in hydrochloric acid medium
Authors: Mahadevappa DS , Naidu HMK
Published: September 2010

The kinetics of oxidation
of allyl alcohol by chloramine-T in presence of hydrochloric acid (0.04-0.13M )
has been studied at O�C. The reaction shows first-order dependence on
chloramine-T and hydrogen ion concentration and is independent of the
concentration of alcohol. The energy and entropy of activation of the reaction
have been found to be 12.3 kcal mol-1 and -33.2 e.u.
respectively.Ionic strength has very
little influence on the rate of reaction. A mechanism in terms of a fast interaction
between allyl alcohol and hypochlorous acid formed by
the hydrolysis of N-chloro-p-toluenesulphonamide in a
slow step is proposed.
The polarography of some substituted azobenzenes in acetonitrile. VI. Proton-donating substituents in the 4-position
Authors: Boto KG , Thomas FG
Published: September 2010

The polarographic
behaviour of azobenzene-4-sulphonic acid and of 4-hydroxyazobenzene in acetonitrile
is reported. Four reduction waves were observed in the polarograms
of azobenzene-4-sulphonic acid. The first two waves are attributed to the
reduction of half of the compound to hydrazobenzene-4-sulphonate ion via azonium species. The third and fourth waves arise from the
reduction of the remaining half, present as the azobenzene-4-sulphonate ion, in
two one-electron steps. The polarograms of
4-hydroxyazobenzene also exhibit four waves, the first three being poorly defined.
Tentative proposals are presented to account for these four waves.