bluuebunny/crossref_metadata_2025 huggingface dataset:
Some further observations on the Lewis-acid-catalysed oxygenation of ergosteryl acetate
Authors: Haynes RK
Published: September 2010

Some qualitative
observations on the catalytic activity of Lewis acids in converting ergosteryl
acetate into its 5α,8α peroxide are presented. The peroxide has an
inhibiting effect on the reaction, which is ascribed to complex formation
between it and the Lewis acid catalyst. This complex formation is used to
explain the dual thermal and photochemical activity displayed by FeCl3
and MoCl5. A mixed oxygenation experiment with ergosteryl and
lumisteryl acetates indicates that singlet oxygen is not an intermediate in
this reaction. ��� A model for the reaction, involving
formation of a diene cation radical within a charge-transfer complex, is
advanced.
Huckel theory with overlap for the three-electron bond
Authors: Harcourt RD
Published: September 2010

For a three-electron bond between
two equivalent atoms, Huckel molecular orbital theory
with overlap generates a resonance stabilization energy which is formally
identical to that obtained from molecular orbital theory when electronic
repulsions are included and the Mulliken approximation
(ab ≈ ½S(aa+bb))
is invoked. The latter energy is the constructive interference energy.
Ruthenium complexes with a tetradentate salicylaldimine Schiff base
Authors: Murray KS , Van den Bergen AM , West BO
Published: September 2010

New salicylaldimine
chelates of divalent and trivalent ruthenium have been synthesized from RuCl2(PPh3)3.
The RuII complex trans- Ru(salen)(PPh3)2
is stable in the solid but very unstable to oxidation in solution. The RuIII derivative, Ru(salen)Cl(PPh3), displays
magnetic and e.s.r. properties consistent with a low-spin d5 system
under a ligand-field of rhombic symmetry.
Methyleneketenes and methylenecarbenes. X. Precursors for the generation of methyleneketene and deuterated methyleneketenes for microwave spectroscopy
Authors: Blackman GL , Brown RD , Brown RFC , Eastwood FW , McMullen GL , Robertson ML
Published: September 2010

The synthesis of a mixture
of deuterated cyclopentadiene adducts (3) required for the pyrolytic
generation of CHD=C=C=O and CD2=C=C=O is described. Methyleneketene
is conveniently generated for microwave spectroscopy by flash vacuum pyrolysis
of acrylic anhydride at 510- 560°. Pyrolysis of diphenylmethyl
propiolate gives benzophenone and methyleneketene (or its decomposition
products)as the major process, but minor processes leading to diphenylmethane,
fluorene and 3-phenylphthalide also occur.
The structure of amphistictinic acid, a triterpenoid constituent of the lichen Pseudocyphellaria amphisticta
Authors: Ronaldson KJ , Wilkins AL
Published: September 2010

From the extractives of the
lichen Pseudocyphellaria amphisticta, a new triterpenoid acid designated
amphistictinic acid was isolated, the structure of which was shown to be
15α-acetoxy-22-hydroxy-hopan-24-oic acid.
1,2-Photoaromatization: entry into the Tetracyclo[4,2,0,02,4,03,5]oct-7-ene system
Authors: Warrener RN , Nunn EE
Published: September 2010

The synthesis of
1,2,3,4,5,6- hexakis(trifluoromethyl)tetracyclo[4,2,0,02,4,03,5]oct-7-ene
is describedby a three-step sequence
involving the application of a photofragmentation reaction in the final step.
Chemistry and crystal structures of 1,3-Bis(4'-bromophenyl)propane- 1,2,3-trione, 3,5-Diphenyl- 1,2-dithiolylium-4-olate and 4-Hydroxy-3,5-diphenyl-1,2-dithiolium perchlorate
Authors: Cannon JR , Potts KT , Raston CL , Sierakowski AF , White AH
Published: September 2010

In connection with studies
on possible mesoionic systems, syntheses of
1,3-bis(4'-bromophenyl)-propane-1,2,3-trione (5), 3,5-diphenyl-1,2-dithiolylium-4-olate
(9) and 4-hydroxy-3,5-diphenyl-1,2-dithiolium perchlorate (10) have been
reexamined. ��� The crystal structures of (5), (9) and (10)
have been determined by X-ray diffraction from diffractometer data at 295 K and
were refined by full-matrix least squares to residuals of 0.050 (1118
'observed' reflections), 0.072 (2388) and 0.087 (2000), respectively. Crystals
of (5) are monoclinic, C2/c, a 18.535(4), b 7.734(2), c 12.184(3) Ǻ,
β 126.60(3)°, Z 4. Crystals of (9) are orthorhombic, Pmcn,
a 26.047(6), b 7.170(2), c 6.431(2) Ǻ, Z 4. Crystals of (10) are
monoclinic, P21/a, a 18.601(7), b 10.636(4), c 8.152(2) Ǻ,
β 102.60(3)°, Z 4. ��� In (5) π-character is localized in the
phenyl rings and carbonyl groups [ 1.22(1) Ǻ] and the substance
is best represented as a normal vicinal triketone. In (9) and (10) S-S bonds
are present and (9) is correctly regarded as a heterocyclic system. The
geometry of the heterocyclic ring in (10) agrees well with that previously
found for the 1,2-dithiolium cation;  is 1.35(1) Ǻ. In (9) the
heterocyclic C-C distances [1.442(2)Ǻ] are longer than in (10); this
indicates diminished aromaticity on deprotonation. The C-C-C angle [111.2(2)°]
in (9) is also smaller than that [118.3(8)°] in (10) and  in (9) is
1.250(3) Ǻ. ��� The behaviour of
1,3-diphenylpropane-1,2,3-trione (4) and (9) with acetylenic dipolarophiles has
been studied but no evidence has been obtained that either substance undergoes
a 1,3-dipolar cycloaddition reaction.
Krypton adsorbed on the graphite basal plane
Authors: Spurling TH , Lane JE
Published: September 2010

A grand canonical Monte
Carlo simulation of the submonolayer adsorption of krypton onto the basal plane
of graphite has been executed. An adsorbed layer in registry with the substrate
could not be maintained during any simulation run but some correlation between
the adsorbate and adsorbent structure was observed.
Crystal structure of 2,3-Dichloro-5,8-dihydroxynaphtho-1,4-quinone
Authors: Feutrill GI , Raston CL , White AH
Published: September 2010

The crystal structure of
the title compound has been determined at 295 K by single-crystal X-ray
diffraction methods and refined by least- squares techniques to a residual of
0.049 for 1046 'observed' reflections. Crystals are monoclinic, P21/c,
a 11.584(6), b 5.449(7), c 15.273(8) Ǻ, β 92.44(4)°, Z4. The pair of
quinol hydrogen atoms are both located on the one benzene ring as the title
indicates.
The trans effect in cobalt(III) complexes. Kinetics and mechanism of substitution of cobalt(III) sulphito complexes
Authors: Yandell JK , Tomlins LA
Published: September 2010

Equilibrium constants K and
rate constants kf have been measured, at 25°C and ionic strength of
1.0, for the substitution of the labile water molecule in trans-[aquabis(ethylenediamine)sulphito-cobalt(III)]
ion by thiosulphate ion (K = 1.8×102 mol-1 1., kf
= 1.27×103 mol-1 1. s-1), thiocyanate ion (2.5×103,
2.75×102), nitrite ion (1.0×103, 2.06×102),
azide ion (2.9×102, 2.4×102) ferricyanide ion (-, 1.72×103),
hydrogen azide (< 1.2,1.4×10), ammonia (3.0, 6.7) and imidazole (2.6×102,
5.2). ��� The correlation of these rate constants
with charge on the incoming ligand, as well as a decrease in the apparent
second-order rate constants observed at high concentrations of the anionic
ligands, requires a rapid outer-sphere pre-equilibrium step followed by a rate-
determining dissociative interchange of the incoming ligand with the bound
water molecule. The activation energy of the thiocyanate substitution was found
to be 48 kJ mol-1. Aquation of cis-
[azidobis(ethylenediamine)-sulphitocobalt(III)] ion, in the range of hydrogen
ion concentration between 10-2 and 0.2 M, was found to give the
trans-aquasulphito complex with a first-order rate constant consistent with the
equation
��������������������������� k = 4.9×10-4[H+]+1.0×10-5
s-1
at 25°C and ionic strength
1.0.
The reaction of [Rh(CO)2Cl]2 with hexafluorobut-2-yne
Authors: Dickson RS , Johnson SH
Published: September 2010

The
reaction of [Rh(CO)2Cl]2 with
CF3C≡CCF3 gives a fluorocarbon-rhodium complex of
approximate formula [RhCl(CO)2 or 3(C4F6)]n,xH2O,yC6H6.
The complex is an intermediate in the formation of tetrakis(trifluoromethyl)cyclopentadienone from CF3C≡CCF3
and CO in the presence of[Rh(CO)2Cl]2.
The molecular structure of the complex remains obscure despite extensive study
of its spectroscopic and chemical properties. The major products formed in the
reactions of the complex with σ-cyclopentadienylthallium and with
triphenylphosphine are (η- C5H5)2Rh2(CO)2(CF3C2CF3)and
Rh(CO)Cl(PPh3)2
respectively.
On the kinetics of consecutive, bimolecular reactions
Authors: Darvey IG , Klotz AH , Ritter M
Published: September 2010

It is shown that the
differential equations governing the kinetics of consecutive, bimolecular reactions
can be reduced to an Abel equation.
Some ion-molecule reactions of hydrogen cyanide
Authors: Freeman CG , Harland PW , Liddy JP , McEwan MJ
Published: September 2010

Rate coefficients for the
reactions of several positive ions with HCN in the gas phase have been measured
by the flowing afterglow technique. The reactions are all of the form
������������������������ X++HCN
→ products .
where X+ and the
corresponding rate coefficient, in units of cm3 molecule-1
s-1, are: X+ = HCN+ (k 9.8×10-10);
C2N+ (k 3.1×10-10); CN+ (k 2.8×10-9
CH+ (k 3.2×10-9); H3O+ (k 4.5×10-9
and HCO+ (k 3.9×10-9).
Conformational analysis of coordination compounds. VII. Barrier to inversion of five-membered diamine chelate rings by N.M.R
Authors: Hawkins CJ , Peachey RM , Szoredi CL
Published: September 2010

The barriers to δ
↔ λ interconversion for the five-membered diamine chelate rings in
[M(CO)4(tmen)], where M is chromium(0),
molybdenum(0), or tungsten(0) and tmen is
N,N,N',N'-tetramethylethane-1,2-diamine, have been determined to be of the
order of 39 kJ mol-1 from a band-shape analysis of 13C
N.M.R. spectra of the compounds at low temperature. The results have been
rationalized in terms of the effects of M-N bond lengths on ring strain
energies and have been compared with the barriers determined previously for
analogous complexes with coordination numbers of four (tetrahedral) and eight.
The equivalent six-membered diamine chelate ring in [Mo(CO)4(tmtn)] was found to have a relatively low barrier to
chair-to-chair interconversion with an upper limit of 34 kJ mol-1.
Solvation of ions. XXVI. Free energies of transfer of ions to multi-site solvents and solvent mixtures
Authors: Parker AJ , Waghorne WE
Published: September 2010

The free energies of
solvent transfer of Ag+, K+, Cl-,
Br-, I- and ClO4- from acetonitrile
to glycolonitrile, 3-hydroxypropionitrile and mixtures of
2,2,2-trifluoroethanol or water with acetonitrile are reported. ��� The anion-solvating properties of a series
of hydroxylic solvents decrease by 24 kJ mol-1 in the order CF3CH2OH
> CNCH2OH > CNCH2CH2OH > CH3OH
> CH3CH2OH; Ag+-solvating properties
decrease by 70 kJ mol-1 in the order CH3CN > HOCH2CH2CN
> HOCH2CN > CH3CH2OH > CF3CH2OH;
and the K+- solvating properties decrease by 27 kJ mol-1
in the order CH3CN > HOCH2CH2CN ≈ CH3OH
≈ HOCH2CN ≈ CH3CH2OH > CF3CH2OH.
It is not possible to make more than qualitative generalizations as to the
ion-solvating properties of solvent mixtures if only the solvating properties
of the pure components are known. Multi-site solvents like CNCH2OH
are compared with related equimolar mixtures, like CH3CN/HOH, in
their ability to solvate ions.
Ipso nitration. XIX. Formation of cyclohexadiene adducts from nitration of 4-ethyltoluene and 1,4-diethylbenzene in nitric acid and acetic anhydride
Authors: Fischer A , Henderson GN , Thompson RJ
Published: September 2010

Nitration of 4-ethyltoluene
in acetic anhydride at -20° gives the diastereoisomers of 1-ethyl-4-methyl-4-nitrocyclohexa-2,5-dienyl
acetate and of 4-ethyl-1-methyl-4-nitrocyclohexa-2,5-dienyl acetate. Similar
nitration of 1,4-diethylbenzene gives the diastereoisomers of
1,4-diethyl-4-nitro-cyclohexa-2,5-dienyl acetate. Rearomatization of the
adducts of p-ethyltoluene in trifluoroacetic acid-trifluoroacetic anhydride
gives 4-ethyl-2-nitrotoluene from the 1-ethyl-4-methyl-4- nitro isomers and
4-ethyl-3-nitrotoluene from the 4-ethyl-1-methyl-4-nitro isomers. In aqueous
methanol 2-ethyl- 5-methylphenyl acetate is obtained from the
1-ethyl-4-methyl-4-nitro isomers and 5-ethyl-2- methyl-phenyl acetate from the
4-ethyl-1-methyl-4-nitro isomers.
Carbon-13 chemical shifts of some pyridines, 2,2'-bipyridyls and 1,10-phenanthrolines
Authors: Marker A , Canty AJ , Brownlee RTC
Published: September 2010

13C chemical shifts of pyridine, 2,2'-bipyridyl and
1,10-phenanthroline, and some of their methyl derivatives have been determined.
All measurements were made on 0.25 M solutions in CDCl3, thus
enabling comparisons of chemical shifts and substituent effects to be made
without complications from solvent effects. For the three classes of compounds,
common correlations exist between 13C chemical shifts and both
CNDO/2 and INDO calculated carbon total electron densities, with the results
suggesting that CNDO/2 calculations provide more suitable data for empirical
correlations with 13C chemical shifts.
Chemistry and crystal structures of tetrabenzoylethylene, its photolysis product and tetraacetylethylene
Authors: Cannon JR , Patrick VA , Raston CL , White AH
Published: September 2010

X-ray crystallographic
analysis has revealed that the light-sensitive form (A) and the light-stable
form (A') of tetrabenzoylethylene are not valence tautomers but are two
crystalline modifications of the same substance. The difference in the
stability of these forms to light appears to be a consequence of their
different molecular conformations and packing in the solid state. The molecular
conformation of the A form is represented by (8) and that of the A' form by
(9). The related tetraacetylethylene has the
conformation (10) in the solid state. X-ray crystallographic analysis has also
revealed that the photolysis product (B) of tetrabenzoylethylene is
4-phenoxy-3,4,6-triphenyl-1H,4H-furo[3,4-c]-furan-1-one
(11). ��� The crystal structures of (8), (9), (10)
and (11) were determined by X-ray diffraction: diffractometer data at 295 K
were refined by least-squares techniques to residuals of 0.064 (2161 'observed'
reflections) for (8), 0.057 (1310) for (9), 0.049 (1295) for (10) and 0.061
(1639) for (11). Crystals of (8) are monoclinic, P21/n, a 8.775(5),
b 17.352(9), c 30.985(8)Ǻ, β 93.01(3)°, Z 8. Crystals of (9) which
contain carbon disulfide are monoclinic, A2/a, a 21.21(2), b 6.181(4), c
20.35(2) Ǻ, β 102.77(7)°, Z 4. Crystals of (10) are monoclinic, P21/n,
a 7.540(2), b 4.392(2), c 14.770(4) Ǻ, β 96.29(2)°, Z 2. Crystals of
(11) are monoclinic, P1/n, a 14.820(4), b 15.000(3), c
10.819(4)Ǻ, β 106.02(2)°, Z 4.
6,6'-Di-O-t-butyldimethylsilylsucrose: Studies on the rearrangements accompanying deblocking of such silyl ethers
Authors: Franke F , Guthrie RD
Published: September 2010

Use of limited amounts of
t-butyldimethylsilyl chloride with sucrose in
pyridide have led to the 6,6'-disilyl ether isolable in 36% yield without
chromatography. ��� Removal of the silyl
ether groups from 2,3,4,1',3',4'-hexa-O-acyl- 6,6'-di-O-t-butyldimethylsilyl-sucroses
has been studied with dilute acid and with tetrabutylammonium fluoride. The
former reagent gave the expected hexa-O-acylsucroses,
whereas the latter method yielded 2,3,6,1',3',4'-hexa-O-acylsucroses formed by
a 4 → 6 acyl migration in the D-glucose moiety.
Studies of Australian soft corals. VII. Two new diterpenes from an unknown species of soft coral (genus Lobophytum)
Authors: Bowden BF , Coll JC , Mitchell SJ , Stokie GJ
Published: September 2010

Two new diterpenes have
been isolated from a soft coral of the genus Lobophytum. One is shown to be a
cembranolide diterpene (1) containing a novel a-keto epoxide grouping while the
second compound (2) is unique in the soft coral literature in that it possesses
a 13-membered carbocyclic ring. This was presumably derived from rearrangement
of (1) within the coral. The structure assignments rely heavily on
spectroscopy, but are consistent with chemical transformations.
Chemical constituents of Tapeinosperma pseudojambosa
Authors: Baigent DR , Lewis KG
Published: September 2010

Examination of the leaves
and bark of Tapeinosperma pseudojambosa has shown that, as in other
Myrsinaceae, a 'quinone' fraction is obtained in quantity. From the various
extracts of the leaves and bark there were obtained the known α- and
β-amyrin, bauerenol, quercetrin, primulagenin A and echinocystic acid.
Specific ionic interactions and solubility activity product of caesium perrhenate at 298.10 K
Authors: Chan C , Khoo KH , Panckhurst MH
Published: September 2010

The solubilities of caesium
perrhenate in aqueous CsCl, NaCl,
KCl and KReO4 solutions at 298.10 K are
reported. The solubility activity product for CsReO4 was determined
by using extrapolation functions involving two different mean ionic activity
coefficient expressions and the results were compared; the total ionic
strengths of all the saturated perrhenate solutions were less than 0.1 mol dm-3.
One of these expressions used is that proposed recently by Panckhurst and
Macaskill1,2 which is an extension of Guggenheim's approach,3,4
specific ionic interactions in aqueous solutions being explicitly taken into
account. Its use led to more consistent values for the solubility activity
product for CsReO4 than those obtained with the other expression
which does not incorporate specific interaction parameters. Values of specific
ionic interaction parameters for caesium, potassium and sodium perrhenates in dilute
aqueous mixtures with CsCl, KCl,
KReO4, KI or NaCl are also reported.
The effect of pH and ligands on the sorption of heavy metal ions by cellulose
Authors: Farrah H , Pickering WF
Published: September 2010

The adsorption of copper,
lead, cadmium and zinc ions by cellulose suspensions has been examined at pH
values ranging from 3.5 to 11. The chemical form of the metal ions has been
changed by adding ligands such as oxalic acid, citric acid, tartaric acid, ethylenediaminetetraacetic
acid, ethylene- diamine, glycine, cysteine and α,α'-bipyridyl.
Stable anionic complexes were not sorbed by the cellulose, and at a given pH
cationic complexes were sorbed less than hydrated ions. The presence of excess
ligand generally served to mask the precipitation of the metal- hydroxy species
which can occur in the pH 6-7 region. ��� The amount of metal cation sorbed increased
with pH. This has been attributed to increased ionization of acid functional
groups having a pKa value of around 4.4. ��� The implication of the results, in respect
to aqueous metal ion levels in natural systems, has been considered.
Micellar catalysis of anilide hydrolysis
Authors: Broxton TJ , Deady LW , Duddy NW
Published: September 2010

The rate of hydrolysis of
several anilides is catalysed by cationic micelles (cetyltrimethylammonium
bromide), and inhibited by anionic micelles (sodium lauryl sulfate). The
magnitude of catalysis is greatest for those anilides which contain the most
hydrophobic R groups (R = C7H15 and Ph) and is less for
those containing less hydrophobic R groups (R = Me). The magnitude of catalysis
is greater for compounds activated by nitro groups than for those activated by
a ring nitrogen atom. The catalysis is inhibited by added sodium bromide. There
is no evidence that anilide hydrolysis in a micellar environment involves
dianionic intermediates. Micellar catalysis of anilide hydrolysis is much
greater than for ester hydrolysis.
Studies on intramolecular alkylation. X. The acid-catalysed reactions of 5,8-Dialkoxy-1,2,3,4-tetrahydronaphthyl diazomethyl ketones
Authors: Johnson DW , Mander LN
Published: September 2010

5,8-Dimethoxy-3,4-dihydronaphthalen-1(2H)-one
was converted into diazomethyl 5,8-dimethoxy-1,2,3,4-tetrahydro-2-naphthyl
ketone (10) which, when treated with trifluoroacetic acid at 0°, gave 5,8- dimethoxy-4,4a-dihydro-3,4a-ethanonaphthalen-2(3H)-one
(13), but at -15° gave 8-methoxy-1,2,3,4-tetrahydro-3,4a-ethanonaphthalene-
5(4aH),10-dione (14). 6-Methoxy-3,4-dihydronaphtha-len-1(2H)-one reacted with
m-chloroperoxybenzoic acid to give 4,5-dihydro-1-benzoxepin-2(3H)-one (15)
which after hydrolysis, ethylation and polyphosphoric acid treatment gave
5-ethoxy-8-methoxy-3,4-dihydronaphthalen-1(2H)-one (17). This compound was
transformed into 5-ethoxy-8-hydroxy-1,2,3,4-tetrahydro-2-naphthoic acid (19)
and thence to the ethoxy analogue of (14).
The Benzo[3,4]cyclobuta[1,2]cycloheptenyl cation. A cycloheptatrienyl (tropylium) ion analogue of biphenylene
Authors: Lombardo L , Wege D
Published: September 2010

The title cation (5), which
is an analogue of biphenylene in which one of the benzenoid rings has been
replaced by a cycloheptatrienyl ion (tropylium) ring, has been prepared by
hydride ion abstraction from 6H- benzo[3,4]cyclobuta[1,2]cycloheptene (19) ('homobiphenylene'). The compound (19) was obtained by a
sequence of brominations and dehydrobrominations from 5,6,7,8,9,9a-hexahydro-4bH-
benzo[3,4]cyclobuta[1,2]cycloheptene (13). N.m.r. spectroscopy indicates that
the cation (5) is best considered as possessing two essentially independent
6π electron systems. Nucleophilic capture of cation (5) by methoxide ion
yields 9-methoxyfluorene, instead of the predicted product,
4b-methoxy-4bH-benzo[3,4]cyclobuta[1,2]cycloheptene. This rearrangement of
derivatives of 4bH- benzo[3,4]cyclobuta[1,2]cycloheptene to derivatives of
fluorene appears to be a general reaction, and mechanistic aspects of this
interesting transformation are discussed.
Crystal structure of (1,7,8,9-η-Bicyclo[5,2,0]nona-1(7),2,5,8-tetraen-4-one)tricarbonyliron(0)
Authors: Hall SR , Skelton BW , White AH
Published: September 2010

The crystal structure of
the title compound, [Fe(CO)3(C9H6O)], has been
determined from single-crystal X-ray diffraction data at 295 K and refined by
full-matrix least squares to a residual of 0.039 (2160 'observed' reflections).
Crystals are monoclinic, P21/c, a 9.326(5), b 12.293(5), c 10.342(4)
Ǻ, β 115.77(3)°, Z 4. The iron atom is symmetrically bound to the
four atoms of the cyclobutadiene ring ( 2.055 Ǻ).
An ab initio approach to creating a simple stable enol
Authors: Bouma WJ , Radom L
Published: September 2010

Ab initio molecular orbital
theory is used to examine the effect of four substituents (CN, NO2,
NO and CHO) which are π-electron acceptors and σ-electron acceptors
on the keto-enol equilibrium in the
acetaldehyde/vinyl alcohol system. Each substituent destabilizes the keto
isomer and stabilizes the enol isomer as desired and
hence decreases the enol-keto energy difference. For
the NO and CHO substituents, the effect is sufficiently large that the enol isomer is predicted to be slightly lower in energy
than the keto form. The conformational preferences of the keto isomers are
discussed in detail and a conformational potential energy map is presented for
malondialdehyde.
Organothallium compounds. XIV. Thermal decomposition of some Polyfluorobenzoatobis(polyfluorophenyl)thallium(III) compounds
Authors: Deacon GB , Phillips RJ
Published: September 2010

The organothallium carboxylates, R2TIO2CR (R = C6F5, p-MeOC6F4, p-HC6F4, m-HC6F4 or
o-HC6F4), prepared by reactions of appropriate halogenobis(polyfluorophenyl)thallium(III) compounds and sodium carboxylates, are considered to have associated structures with bridging carboxylate groups. Thermal decomposition of R2TlO2CR (R = C6F5, p-MeOC6F4 or p-HC6F4 or m-HC6F4)
in boiling pyridine resulted in decarboxylation and formation of the corresponding tris(polyfluorophenyl)thallium compounds, which were isolated in analytically pure form as the complexes R3Tl(diox)
(R = C6F5, p-HC6F4 or m-HC6F4; diox = 1,4-dioxan) and R3Tl(bpy) (R = C6F5 or p-MeOC6F4;
bpy = 4,4'-bipyridyl). However, no decomposition was observed when R = o-HC6F4. The ease
of decarboxylation decreased in the sequence R = C6F5 > p-MeOC6F5 ≥ p-HC6F4 ≈ m-HC6F4 S
o-HC6F4, and a possible mechanism is discussed. Pyrolysis of R2TIO2CR (R = C6F5, p-MeOC6F4,
p-HC6F4, m-HC6F4 or o-HC6F4) at 310° under nitrogen in the absence of a solvent gave tris(polyfluorophenyl)thallium compounds (R = C6F5, p-MeOC6F4, p-HC6F4 or m-HC6F4), isolated as the
dioxan complexes, thallous fluoride and polyfluorobiphenyls and polyfluoropolyphenyls. In addition,
decafluorobenzophenone was obtained when R = C6F5, methyl fluoride when R = p-MeOC6F4
and the corresponding tetrafluorobenzene C6H2F4 when R = p-HC6F4, m-HC6F4 or o-HC6F4.
Chlorobis(2,3,5,6-tetrafluoro-4-methoxyphenyl)thallium(III) was prepared by reaction of thallic
chloride with 2,3,5,6-tetrafluoro-4-methoxyphenyllithium, which was obtained from 2,3,5,6-tetra-
fluoroanisole and butyllithium.
Mechanisms for the acetylation of aminopyridines
Authors: Deady LW , Stillman DC
Published: September 2010

Rates of acetylation of
aminopyridines and some ring methyl-substituted derivatives, with acetic
anhydride in acetone at 36°, are reported. The results indicate that
rate-determining acetylation is directly at the amino nitrogen for all 2- and
3-aminopyridines studied. Reaction through a ring N-acetyl intermediate occurs
for 4-aminopyridine but the presence of a 2-methyl substituent blocks this
pathway.
Basic methanolysis of N-Aryl-N-methylthiobenzamides
Authors: Broxton TJ , Deady LW , Rowe JE
Published: September 2010

Rate data for reactions of
XC6H4CSNMeC6H4Y in methanol at 373
K are presented. The thioamides are less reactive than their oxygen analogues.
Linear Hammett plots were obtained for both series (series A: X = variable, Y =
4?-NO2; series B: X = 4-NO2, Y = variable), with p values
similar to those obtained for related oxyamides. There is a general trend to
higher activation energies but more favourable entropies in the thioamides. The
results are interpreted in terms of rate-determining breakdown of a tetrahedral
intermediate, irrespective of the nature of X and Y.
Microbial transformation of cannabinoids. I. Metabolism of ( - )-Δ9-6a,10a-trans-Tetrahydrocannabinol by Chaetomium globosum
Authors: Christie RM , Rickards RW , Watson WP
Published: September 2010

Chaetomium globosum isolated from
Cannabis sativa plant material converts (-)-Δ9-6a,10a-frans-tetrahydrocannabinol
(Δ9-THC) (1a) into a number of metabolic products, which
include the 3'-hydroxy, 11-hydroxy and 3',11-dihydroxy derivatives (1c), (1b)
and (1d) respectively. The structure of the 3'-hydroxy-Δ9-THC
(1c) has been confirmed by synthesis, whilst the structure of the
3',11-dihydroxy-Δ9-THC (1d) follows from mass spectroscopic
comparison with the 3'-hydroxy and 11-hydroxy derivatives.
Fluorescence decay of aromatic vapours. III. Single vibronic lifetimes and collision cross-sections for pyrimidine
Authors: Nott PR , Selinger BK
Published: September 2010

In this paper the results
of a lifetime study of the 1B1 state of pyrimidine vapour
in the pressure range 1.2-60 Pa are presented. These lifetimes show an
extraordinary pressure dependence, with collision cross-sections of 30-40 times
hard sphere. It is shown that pyrimidine behaves as a small molecule. The
collision-induced decay process is intersystem crossing and it is the most
effective collision-induced process yet reported for the small-molecule limit.
A comment on the structure of xenon hexafluoride
Authors: Kepert DL
Published: September 2010

Calculations based on the
minimization of the repulsion energy between electron pairs show that the
structure of xenon hexafluoride is predicted if the non-bonding electron pair
is situated close to the xenon atom. If a value of n = 6 is assumed in the repulsion
law, the distance between the xenon atom and the effective centre of repulsion
of the lone pair is approximately 10% of the distance between the xenon atom
and the effective centres of repulsion of the bonding pairs.
Reactions of But-2-yne and Hexafluorobut-2-yne with Dicarbonyl(η-pentamethylcyclopentadienyl)-cobalt, -rhodium and -iridium. Structure of the iridium complex (η-C5Me5)Ir2(CO)2(CF3C2CF3)3H
Authors: Corrigan PA , Dickson RS , Fallon GD , Michel LJ , Mok C
Published: September 2010

The reactions of but-2-yne and hexafluorobut-2-yne with the complexes (η-C5Me5)M(CO)2, M = CO,
Rh, or Ir, have been compared. A cyclopentadienone complex, (η-C5Me5)M[C4Me4CO]2 is the
major product formed in the reaction of but-2-yne with (η-C5Me5)M(CO)2, M = Co or Rh. The
cobalt system also gives some hexamethylbenzene whereas the rhodium system yields the pentadienone-dirhodium complex (q-C5Me5)2Rh2(MeC2Me)2CO. The cyclopentadienone complexes
(η-C5Me5)M[C4(CF3)4CO], M = CO and Rh, were major products from the reactions of hexa-
fluorobut-2-yne with (η-C5Me5)M(CO)2. Hexakis(trifluoromethyl)benzene and the tetrahapto-
benzene complexes (η-C5Me5)M[η4-C6(CF3)6], M = Co or Rh, were minor products from these
reactions. Small amounts of the dirhodium complexes (η-C5Me5)2Rh2(CF3C2CF3)2(CO)n, n = 1
or 2, were also isolated from the rhodium system under some reaction conditions.
No products could be isolated from the reaction between (η-C5Me5)Ir(CO)2 and but-2-yne, but
the reaction with hexafluorobut-2-yne gives two organoiridium complexes. One complex,
(η-C5Me5)Ir(CO)2(CF3C2CF3), incorporates an iridiocyclobutenone ring and one terminal carbonyl.
The second, (η-Ir5Me5)Ir2(CO)2(CF3C2CF3)3H, has been characterized crystallographically. The
compound crystallizes with four molecules in the orthorhombic space group Pnma in a cell of di-
mensions a 14.262(5), b 13.293(5), c 15.027(5) Ǻ. The structure has been refined by standard
methods to a conventional R factor of 0.072, based on 2061 reflections above background. The
environments of the two iridium atoms are markedly different. One forms part of a metallopentadiene
ring, and it is also attached to two terminal carbonyls, a σ-bonded C(CF3)=C(CF3)H group, and the
other iridium atom [Ir-Ir distance 2.737(1) Ǻ]. Overall, this iridium has a distorted octahedral
geometry. The second iridium is n-bonded in a conventional sandwich manner to the C5Me5 and
iridiocycle rings; these two rings have a staggered conformation and are close to parallel.
Preparation of some substituted Bicyclo[4,2,0]octa-1,3,5-trienes (benzocyclobutenes)
Authors: O'Leary MA , Stringer MB , Wege D
Published: September 2010

The reaction of benzyne
(generated by the thermolysis of o- diazoniobenzoate) with the following
alkenes has been examined: 1,1-dichloroethene (5)
(vinylidene chloride), 1,1-dichloro-propene (7), 1,1-dichloro-2-methylpropene
(17), 2-methylprop-1-en-1-yl acetate (18) and 2-chloro-prop-2-enenitrile
(α-chloroacrylonitrile) (22). Substituted bicyclo[4,2,0]octa-1,3,5-trienes
resulting from 2+2 cycloaddition were obtained from (5), (7), and (22), while
the reaction involving the en01 acetate (18) gave only 'ene'
product, and that involving (17) gave an intractable mixture. (Z)- and
(E)-1-Chloro-2-(o-chlorophenyl)propene were obtained
as minor products in the reaction of benzyne with (7): these products result
from a chlorine atom transfer to the aromatic ring, and a novel mechanism
involving a diradical → carbene rearrangement is postulated.
1H-1-Benzazepines. The reactions of laevulinic acid and β-benzoylpropionic acid with aniline and methoxyanilines
Authors: Candeloro V , Bowie JH
Published: September 2010

Treatment of laevulinic
acid with aniline yields 5-methyl-2,3-dihydro- 1H-1-benzazepin-2-one and
5-(2-methyl-5-oxo-1-phenylpyrrolidin-2-yl)-4- oxo-N-phenylpentanamide
In contrast, the reaction between β- benzoylpropionic acid and aniline
yields 4-(2-oxo-1,5-diphenyl-2,3- dihydropyrrol-3-ylidene)-N,4-diphenylbutanamide,
whose structure is confirmed by an independent synthesis. The yield of the
latter type of reaction is enhanced if p-methoxyaniline is used, whereas the
desired benzazepine is obtained if m-methoxyaniline is utilized. For example,
the reaction between β-benzoyl-propionic acid and m-methoxyaniline yields 8-methoxy-5-phenyl-2,3-dihydro-1H-1-benzazepine-2-one
as the major cyclized product.
Chemistry and crystal structure of leprolomin, a novel diphenyl ether from the lichen Psoroma leprolomum
Authors: Elix JA , Engkaninan U , Jones AJ , Raston CL , Sargent MV , White AH
Published: September 2010

The isolation and
structural elucidation of 3'-(2''-acetyl-3''-hydroxy- 5''-methoxy-4''-methylphenoxy)-2',4'-dihydroxy-6'-methoxy-5'-
methylacetophenone (leprolomin) (12), an unusual lichen metabolite probably
derived biogenetically by C-O phenolic coupling of two units of C-methylphloroacetophenone, is reported. Spectroscopic data
on leprolomin and its derivatives allowed the structure to be limited to six
possibilities; hence the crystal structure of leprolomin triacetate (15) was
determined by X-ray diffraction.
Space-charge-limited current theory for a spatially non-uniform trap distribution
Authors: Bonham JS
Published: September 2010

The theory of
space-charge-limited current, including diffusion, is discussed for an
insulator containing a shallow or exponential distribution of traps whose
concentration varies with position, being higher near the insulator surface
than in the bulk. Two simple step- function spatial distributions are
considered-one symmetric and one asymmetric. Analytic treatments are given for
the open-circuit situation in both cases. For the symmetric case simple
formulae are derived for the current-voltage relation. The current may be bulk-
or surface-limited or there may be a transition from the former to the latter
as the voltage is raised, giving rise to considerable structure in the
current-voltage curves not predicted by theory which neglects diffusion. An
asymmetric distribution may give rise to rectification at low voltages. This
can be treated by considering the region of high trap density near one
electrode to make an effectively blocking contact to the bulk of the insulator.
Comparison of open-circuit potential profiles for the step-function and
exponential spatial trap distributions suggests that the system is insensitive
at low voltage to the nature of the spatial distribution; only the trap density
in the vicinity of the surfaces is important.
Flory theory and excess thermodynamic properties of liquid mixtures containing one polar component
Authors: Reddy KS , Naidu PR
Published: September 2010

Excess volumes of the
binary mixtures, benzene + benzonitrile, benzene+ diethyl ketone and toluene+diethyl ketone, were determined at 303.15 K. The VE
data and HE data of the mixtures reported in the literature were
analysed in the light of both the original and modified forms of the Flory theory. The analysis showed that the modified Flory theory correctly predicts the sign of the excess
functions over the whole range of composition when the single interaction
parameter of the theory is treated as an energy parameter.
19F nuclear magnetic resonance studies of the interaction of inhibitors with chymotrypsin. Derivatives of tryptophan and phenylalanine
Authors: Nicholson BC , Spotswood TM
Published: September 2010

The binding of the
inhibitors N-trifluoroacetyltryptophan, N- trifluoroacetylphenylalanine, N-acetyl-tryptophan and N- acetylphenylalanine to chymotrypsin has been studied by 19F
N.M.R. spectroscopy at several pH values. Methods for determining the binding
parameters, KI and ΔB, including a model for enzyme
oligomerization and competitive inhibition from a second inhibitor, are
discussed and a general non-linear least-squares method is presented. Values of
KI and ΔB are recorded for D and L enantiomers of
tryptophan derivatives and for D-phenylalanine derivatives. The results are
discussed in terms of a model for the aromatic binding site of chymotrypsin.
Nitrones and oxaziridines. XXI. Electronic substituent effects in nitrone cycloadditions to highly polarized alkenes
Authors: Black DSC , Crozier RF , Rae ID
Published: September 2010

1,3-Dipolar cycloaddition
reactions of nitrones-particularly N-(2'- pyridylmethylene)aniline
N-oxide-with arylmethylene cyanoacetates exclusively yield 4,4-disubstituted isoxazolidines,
identifiable by 1H n.m.r, spectroscopy and isolable in some cases.
Comparative kinetic experiments provide evidence for at least non-synchronous
addition via a dipolar intermediate or possibly even two-step addition via a
discrete zwitterionic intermediate.
Hydroxylation of anthraquinones in oleum and in sulfuric acid
Authors: Banks HJ , Cameron DW , Raverty WD
Published: September 2010

The anthraquinone emodin
(9) was rapidly and efficiently converted into catenarin (13) by treatment with
a mixture of oleum and boric acid at room temperature. Chrysophanol (15)
similarly gave islandicin (16), while related anthraquinones were hydroxylated
in essentially the same way, though none as rapidly as emodin. The specificity
of such processes is synthetically useful in generally involving substitution
of the less highly hydroxylated ring. This is in contrast to hydroxylation with
persulfate in sulfuric acid which, for emodin, occurred chiefly in the more
highly hydroxylated ring, as did sulfonation.
The coordination of β-amino ketoximes with divalent iron, cobalt, nickel and zinc
Authors: Powell HKJ , Russell JM
Published: September 2010

The iron(II), nickel(II)
and zinc(II) complexes of the diamine dioxime ligand
4,4,9,9-tetramethyl-5,8-diazadodecane-2,11-dione dioxime (H2dddo)
and the cobalt(II), nickel(II) and zinc(II) complexes of its O-methyl ether (Hddmo) have been studied potentiometrically at 25°C, I
0.10M NaCl. Stability constant data are compared with
those obtained for the copper(II) and cobalt(II) complexes of H2dddo
and the copper(II) complexes of Hddmo. H2dddo
coordinates in the oxime-oximato form [M(Hdddo)]+
with iron(II), cobalt(II), nickel(II) and zinc(II) Hddmo forms complexes with the
ligand coordinated in the oxime form [M(Hddmo)]2+
and the oximato form [M(ddmo)]+. The
complexes [Zn(Hddmo)2]2+, [Zn(Hddmo)(ddmo)]+ and
[Co(ddmo)(OH)] were also characterized in aqueous solution.
The stability order FeII < CoII < NiII
< CuII > ZnII
was observed for the formation of 1 : 1 complexes with the ligands Hdddo- (log K = 8.8, 11.7, 15.2, 23.3, 12.0 for Fe to Zn
respectively) and Hddmo (5.7, 6.6, 12.1, 5.3 for Co
to Zn). The infrared spectra of the complexes [Ni(Hdddo)]
ClO4,H2O and [Zn(Hdddo)] ClO4
are discussed in terms of oxime-oximato hydrogen bonding.
Substitution reactions of nitrothiophens with the 2-Nitropropan-2-ide ion
Authors: Newcombe PJ , Norris RK
Published: September 2010

The reactions of the
lithium and tetraalkylammonium salts of 2- nitropropane with 2-nitrothiophen (3), 2,5-dinitrothiophen
(8), 2-iodo-5-nitrothiophen (7), 2,4-dinitrothiophen (16) and 2-(1-methyl-1-nitroethyl)-5-nitrothiophen (2) have been studied. The compounds
(3) and (16) give observable Meisenheimer adducts (11) and (17) respectively
whose N.M.R. data are discussed. Decomposition of adduct (11) gives, depending
on reaction conditions, 2-isopropyl-5- nitrothiophen
(5), 2,2-bis(5-nitro-2-thienyl)propane (6) and 2-(5-
nitro-2-thienyl)propan-2-ol (4). Possible mechanisms for these trans-
formations are proposed. Reaction of the nitro compounds (7) and (8) gives
initially the compound (2) by an SNAr
process. The SRN1 reactions of (2) with the above salts of
2-nitropropane, the sodium salt of diethyl 2-methylmalonate, and sodium
benzenethiolate are presented. The last-named reaction in the presence of
benzenethiol proceeds anomalously to give the reduced product (5) as well as
the normal SRN1 product 1-methyl-1-(5-nitro-2-thienyl)ethyl phenyl
sulfide (21).
Use of active polyester intermediates in the preparation of acid-labile benzyl esters of some phenolic carboxylic acids
Authors: Stewart FHC
Published: September 2010

2,4,6-Trimethylbenzyl and
other acid-labile esters of various nitro- and chloro-substituted phenolic
carboxylic acids have been prepared by imidazole-assisted alcoholysis of
stable, insoluble 'active polyester' intermediates obtained by the action of
N,N'-dicyclohexylcarbodiimide on the parent acids.
The anodic aromatization of 2,5-dihydroanisole derivatives
Authors: Birch AJ , Slobbe J
Published: September 2010

Electrolytic oxidation of
2,5-dihydroanisoles in an undivided cell leads initially to the corresponding
aromatic compounds, which in some cases undergo further oxidation. Half-wave
potentials have been measured for the dihydroaromatic and the aromatic derivatives,
and a reaction mechanism based on these data is proposed.
Vibrational spectra of mercury(I) nitrate in aqueous solution and of the crystalline hydrolysis products
Authors: Tan K , Taylor MJ
Published: September 2010

Aqueous solutions of
'mercurous nitrate' are shown by Raman spectra to contain the complexes [Hg2(OH2)NO3]+
and [Hg2(OH2)2]2+. Crystalline
dimercury(I) nitrate, Hg2(NO3)2,2H2O,
and its solid hydrolysis products Hg2(OH)2,3Hg2(NO3)2,
2Hg2(OH)2,3Hg2(NO3)2,H2O
and Hg2(OH)2,- Hg2(NO3)2
have been obtained: the vibrational spectra are reported and interpreted in
terms of possible structures. Modes v(Hg-Hg) appear in the range 170- 200 cm-1
and are sensitive to the particular combination of the ligands OH, ONO2,
and H2O attached to the dimercury(I) ion.
Crystal structure of diammonium aquapentachloroferrate(III)
Authors: Figgis BN , Raston CL , Sharma RP , White AH
Published: September 2010

The crystal structure of
the title compound, (NH4)2 [FeCl5(H2O)],
has been redetermined by single-crystal X-ray diffraction at 295 K and refined
by full matrix least squares to a residual of 0.054 for 1662 'observed'
reflections. Crystals are orthorhombic, Pnma, a 13.706(2), b 9.924(1), c
7.024(1)Ǻ Z 4. Fe-O is 2.110(4)Ǻ; Fe-Cl range between 2.323(1)Ǻ
(trans to OH2) and 2.350(1)-2.390(1) Ǻ (cis), the latter
distances being very dependent upon hydrogen-bonded interactions with nearby
species.
The identification of four new meta-depsides in the lichen Ramalina asahinae
Authors: Chester DO , Elix JA
Published: September 2010

The four new depsides,
2-O-methylsekikaic acid, 2,4'-di-O-methylnorsekikaic
acid, 4'-O-methyl-paludosic acid and 4,4'-di-O- methylcryptochlorophaeic
acid, have been prepared by unambiguous syntheses and shown to co-occur with
usnic acid and boninic acid in several Ramalina species.
Biosynthetic studies on alkaloids in Lunasia amara
Authors: Finlayson AC , Prager RH
Published: September 2010

Benzoic acid[14CO2H]
and sodium acetate[2-14C] are incorporated into 4- methoxy-2-phenylquinoline,the
major alkaloid in the leaves of L. amara. No radioactivity is found in the
quinoline when sodium acetate[1-14C] or phenylalanine[3-14C]
are administered; this suggests the alkaloid is derived from anthranilic acid
by the pathway suggested by Leete.1 Mevalonic acid[2-14C]
is incorporated into the furanoquinoline alkaloid lunacrine.
Thermodynamic Studies on Melting Some α- and β-Derivatives of Naphthalene
Authors: Khetarpal SC , Lal K , Bhatnagar HL
Published: September 2010

Methods for determining
volume changes on melting have been briefly reviewed. A new apparatus has been
described which is simple in operation, accurate in measurements and is free
from some of the major limitations of the apparatuses used earlier. It has been
used to determine volume changes on melting of α- and β-derivatives
of naphthalene (C10H7X; X = NH2, OH, COOH), as
well as coefficients of cubical expansion of the solid compounds (α) and
their melts (α'). The application of the apparatus has been extended to
determine the densities of the compounds at any temperature both when entrapped
air is present (d) and when it is completely absent (d'). An electrical method
using a modified glass calorimeter has been employed for the measurement of
latent heats of fusion, ΔHf. From the
experimentally determined values of ΔVf/Vs,d',
α and ΔHf, the molar volume of
the solid compound at the melting point (V8), that of the melt at
the melting point (V1), the entropy of fusion (ΔSf),
the variation of the melting temperature with pressure [(∂T/∂P)v]
and the compressibility coefficient of the solid compounds (β) have been
calculated and the results discussed.
Ion-Cyclotron Resonance Studies of Alkylsilyl Ions. I. The Reactions Between Alcohols and the Trimethylsilyl Cation
Authors: Blair IA , Phillipou G , Bowie JH
Published: September 2010

Nucleophilic attack of an
alcohol (ROH) at the electrophilic silicon centre of the trimethylsilyl cation
(Me3Si+) produces the 1 : 1 adduct Me3-O+(H)R(1).
The adduct may fragment by loss of methane to yield Me2Si+-O-R;
and this elimination is most pronounced when R = Me. When R ≥ C2H5,
the major decomposition pathway of (1) involves elimination of the alkene [R-H]
to produce Me3Si-O+H2, which may undergo
further reaction with the neutral alcohol to reform (1). The proton transfer
which accompanies the elimination of [R- H] from (1) originates predominantly
from C2 of the alcohol; this suggests the intermediacy of a four-membered
transition state in this reaction.
Crystal Structure of [N,N-Bis(2-aminoethyl)-ethane-1,2-diamine-N,N',N',N'](ethane-1,2-diamine)cobalt(III) Trichloride Dihydrate
Authors: Bottomley GA , Glossop LG , Skelton BW , White AH
Published: September 2010

The preparation of the
title complex, [Co(tren)(en)] Cl3,2H2O,
is reported together with the determination of its crystal structure at 295(1)
K. Crystals are monoclinic, P21/n, a 7.860(3), b 17.665(8),
c 12.020(4) �, β 91.17(3)�, Z 4.
Substituent Effects on the 1H N.M.R. Spectra of Substituted Benzamides and N-Alkylbenzamides
Authors: Calvert DJ , O'Conner CJ
Published: September 2010

The proton chemical shifts
(δNH and δCH) of 60 substituted benzamides and N-alkylbenzamides
and δCH of seven
substituted N,N-dialkylbenzamides
have been reported and compared with sub- stituent
effects. The chemical shifts (δNH and
δCH of H3,5) of N-alkylbenzamides correlate well with
Hammett σ values. The chemical shift δNH
also correlates well with the Taft substituent constant Es. All
other chemical shifts are independent of substituent effects.
Crystal Structure of Hexaamminecobalt(III) Chloride Chromate Trihydrate
Authors: Figgis BN , Skelton BW , White AH
Published: September 2010

The preparation of the
title compound [Co(NH3)6] (CrO4)Cl,3H2O
is reported together with the determination of its crystal structure at 295(1)
K. Crystals are orthorhombic, Pcmn, a 8.594(5),b 8.598(5), c 18.126(9) �, Z 4.
Statistical Mechanics of Deuterium Exchange Reactions: Recalculation of Thermodynamic Properties of Water-Methanol Reactions
Authors: Khurma JR , Fenby DV
Published: September 2010

Thermodynamic properties of
the reactions
CH3OH+HDO → CH3D+H2O
CH3OH+D2O → CH3OD+HDO
in the gas phase are
calculated from statistical mechanical equations. Two sets of calculated
harmonic frequencies are used: one obtained from an experimental force field
and the other from an ab initio force field. Thermodynamic properties of the
corresponding liquid-phase reactions are obtained by combining the gas-phase
values with vapour-pressure isotope effect results. The calculated properties
are compared with published experimental values.
Structures of the Steroidal Alkaloids 25-Isosolafloridine and Solacallinidine Isolated From Solanum callium
Authors: Bird GJ , Collins DJ , Eastwood FW , Swan JM
Published: September 2010

The two major alkaloids
isolated from Solanum callium are
25-isosolafloridine and solacallinidine, which have
the structures (25S)-22,26-epimino-5α-cholest-22(N)-ene-3β,16α
-diol (la) and (25s)- 3~-amino-22,26-epimino-5α -cholest-22(N)-en-l6α
-o1 (lla), respectively. The somewhat different
properties reported by previous workers for a synthetic compound described as
25-isosolafloridine indicate that it was probably not stereoisomerically
pure.
Soladunalinidine, a New Dibasic Analogue of Tomatidine Extracted From Solanum dunalianum
Authors: Bird GJ , Collins DJ , Eastwood FW , Swan JM
Published: September 2010

Tomatidine and a new alkaloid, soladunalinidine,
which has the structure (25S)-5α,22
βN-spirosolan- 3β-amine (1a), were
isolated from S. dunalianum.
The Reaction of N-Dichloromethylene-N,N-Dimethylammonium Chloride (Viehe's Salt) with Hydroxy Compounds: A Synthesis of Carbonates and Thiocarbonates
Authors: Copeland C , Stick RV
Published: September 2010

The reaction of Viehe's
salt (Me2Nt=CCl2 CI-) with benzene-1,2-diol,
phenol, 2,3-dimethylbutane-2,3-diol and trans-cyclohexane-1,2-diol gives stable
salts which may be readily converted into thecorresponding carbonates
and thiocarbonates. Both cis- and trans-cyclohexane-1,2-diol
give salts which rearrange, albeit at different rates, to the same trans chloro carbamate.