bluuebunny/crossref_metadata_2025 huggingface dataset:
The formation and molecular structure of the Di-μ-oxo-di[di(benzenethiolato)-oxomolybdate(v)] dianion
Authors: Dance IG , Wedd AG , Boyd IW
Published: September 2010

The orange-red complexes (R4N)2
[Mo2O4(SPh)4] (R =
Me, Et), (Et4N)2 [Mo2O4(SCH2CH2-
CH2S)2] and (Et4N)2 [Mo2O4{SCH2(CHOH)2CH2S}2]
have been synthesized. Crystalline (Me4N)2 [Mo2O4(SPh)4], space group P1, contains two [(μ-O)2(OMo(SPh)2)2]2-
complexes in each of which two approximately square-pyramidal (Ob)2Mo(Ot)(SPh)2 coordination spheres (b, bridging; t,
terminal) share an Ob--Ob edge with cis-bent
stereochemistry. Important average dimensions are Mo-Mo 2.61, Mo-S 2.45, Mo-Ot
1.68, Mo-Ob 1.94 Ǻ, Mo 0.71 Ǻ above the (Ob)2S2
basal plane. There occur two different orientations of S-C vectors, relative to
the Mo-Mo vector, associated with two clearly distinct classes of S-Mo-S
angles, 81.9�0.5 and 73.8�0.4°. The latter abnormally small angle, concomitant
with an interligand S--S distance of 2.94 Ǻ, occurs only in the
conformation where S--S σ-orbital overlap is possible, and suggests the
existence of some interligand bonding. Crystal data: a 12.376, b 14.513, c
11.307 Ǻ, α 104.00, β 99.55, γ 71.32°, cell contents 2xMo2S4O4N2C32H44,
3207 reflections, R 0.033.
Electron impact studies. CXXI. Release of kinetic energy during negative-ion fragmentations. The loss of NO+ from substituted nitrobenzene molecular anions
Authors: Bowie JH , Blumenthal T , White PY
Published: September 2010

Kinetic energy release
values [T(50%) values] between 0.05 and 0.8 eV have
been noted for the unimolecular decomposition M- → (M-NO.)-
of the molecular anions of variously substituted nitrobenzenes. Large T values
are observed when the substituent is strongly electron-withdrawing. Composite
peaks are obtained for m-nitrobenzoic acid and m-nitroacetophenone, showing
the occurrence of two distinct processes in these cases.
Acetylenic acids. III. The synthesis of pyridylpropiolic acids and esters and their reaction with thionyl chloride
Authors: Lok WN , Ward AD
Published: September 2010

A variety of synthetic
routes to pyridinylpropiolic acids and esters have been investigated. The most
convenient route to the esters involves the formation of the corresponding
ethyl 3-oxo-3-pyridinyl-2-triphenylphosphoranediylpropanoates
and their subsequent pyrolysis. The acids can be obtained by careful hydrolysis
of the esters. The reaction of thionyl chloride with these compounds has been
examined; in one case a low yield of a thieno[2,3-b]pyridine was obtained.
Synthesis and spectroscopic studies of RSHgII complexes, including complexes of ButSHgX (X = Cl, Br) and RSHgO2CMe (R = Me, Et) with pyridine
Authors: Canty AJ , Kishimoto R , Tyson RK
Published: September 2010

The complexes RSHgX (R = Et, But; X = Cl,
Br) may be prepared by reaction of the alkanethiol with HgX2 in
ethanol, and the 2- methylpropane-2-thiolates crystallize from pyridine as (ButSHgCl)2-C5H5N
and ButSHgBr,C5H5N. The complexes RSHgO2CMe
(R = Me, Et) may be prepared by reaction of mercuric acetate with Hg(SR)2
in water, and form crystalline RSHgO2CMe,C5H5N
when dissolved in pyridine. Infrared and Raman spectra indicate coordination of
pyridine in the pyridinates. Mercury-sulfur stretching vibrations of RSHgO2CMe
(R = Me, Et, Pr, Bu) are discussed.
The electric-field dependence of intrinsic photoconduction in anthracene for 104 < E < 105 V m-1
Authors: Milne KA , Lyons LE
Published: September 2010

The steady-state
electric-field dependence of the intrinsic photoconduction yield in anthracene
has been measured for 104 < E < 105 V m-1,
the region where yields are reduced compared to those predicted by the Onsager
geminate recombination theory. A theory is proposed to explain the experimental
yield-field relationship. It assumes bulk recombination between free and
trapped carriers and adequately explains the experimental results. These
steady-state results are in agreement with the pulsed measurements of Chance
and Braun (1973).
Oxidation of alkoxyphenols. XXII. Some cross-coupled trimeric spiro acetals
Authors: Hewgill FR , Howie GB
Published: September 2010

Oxidation of several binary
mixtures of phenols to trimeric spiro acetals shows that both C-O and C-C
cross-coupling is possible.
The Structure and Synthesis of Cytokinin Metabolites. 1. The 7- and 9-β-D-Glucofuranosides and Pyranosides of Zeatin and 6-Benzylaminopurine
Authors: Cowley DE , Duke CC , Liepa AJ , Macleod JK , Letham DS
Published: September 2010

The structures of the major
stable plant metabolites of the cytokinins zeatin and 6-benzylaminopurine have
been confirmed by synthesis to be 7- and 9-β-D-glucopyranosides. The small
quantities of metabolites initially isolated (< 100 μg)
precluded assignment of the glucose ring size or configuration of the anomeric
linkage so that synthesis of both the furanose and pyranose forms of
7-β-D- and 9-β-D-glucosylzeatin and 6-benzylaminopurine was
undertaken which allowed direct u.v., m.s. and t.l.c. comparison with the metabolites. Numerous synthetic
routes to the unusual 7-glucosides of the two cytokinins were explored, the
most successful utilizing a one-pot pyrimidine ring closure of an imidazole
derivative to afford directly in high yield the required 7-glucosides of zeatin
and 6-benzylaminopurine.
The preparation and acid-catalysed rearrangement of a spiro epoxy alcohol in the benzo-fused norbornene series
Authors: Lee TS , Russell RA , Warrener RN
Published: September 2010

Epoxidation of 3-(1?-methylethylidene)-1,2,3,4-tetrahydro-1,4-
methanonaphthalen-exo-2-ol (1) with meta-chloroperbenzoic acid formed
exclusively the exo-epoxide (2). Acid-catalysed rearrangement of this spiro
epoxy alcohol yielded two ring-expanded keto alcohols, exo-8-
hydroxy-6,6-dimethyl-6,7,8,9-tetrahydro-5,9-methano-5H- benzocyclohepten-7-one
(24) and exo-8-hydroxy-7,7-dimethyl-6,7,8,9- tetrahydro-5,9-methano-5H-benzocyclohepten-6-one
(21), with the former predominating. Chemical and spectroscopic (including l.i.s.)
methods were used to determine the structure of (21) and (24).
The synthesis of 1,6-anhydrohexofuranoses
Authors: Angyal SJ , Beveridge RJ
Published: September 2010

On heating aldohexoses in
dimethylformamide solution with toluene-p- sulfonic acid, and removing the
water formed azeotropically, the 1,6- anhydrofuranoses are formed as main
products, rather than the more stable 1,6-anhydropyranoses.
A Phytochemical Investigation of Erythroxylon australe F. Muell
Authors: Griffin WJ
Published: September 2010

(�)-6β,7β-Dihydroxytropan-3α-yl
benzoate was isolated in low yield (0.001%) from the roots of Erythroxylon
australe. The aerial parts were found to contain meteloidine
(0.014%), (�)-6β-hydroxytropan-3α-yl tiglate (0.001%),
(+)-3α-hydroxynortropan-6β-yl tiglate (0.002%) and an unknown base
(0.003%) which was tentatively identified as (+)-7- hydroxy-6-tigloyloxynortropan-3-yl
2-hydroxy-3-phenylpropionate. The configuration of the unknown base was not
determined. Structures were indicated by N.M.R. and mass spectral analysis and
the phenyl propionic acid moiety identified by gas chromatography.
Chemical Modification of Triterpenes From Lantana camara. 22β-Ester Analogues of Lantadene A
Authors: Beeby P
Published: September 2010

The partial syntheses of
the hepatotoxic triterpenes lantadene A (1) and lantadene B (2) are described.
A number of new C22 ester analogues of lantadene A were also synthesized. The
preferred route to these esters involved esterification of diphenylmethyl 22β-hydroxyoleanonate
(8) and selective cleavage of the diphenylmethyl ester function. In some cases,
the hydroxy acid (3) was esterified directly. In the
N.M.R. spectra of the diphenylmethyl esters, some signals appeared at unusually
high field due to anisotropic shielding.
The reaction of isopropenyl methyl ether with aldohexoses and their derivatives
Authors: Copeland C , Stick RV
Published: September 2010

Methyl α-D-mannopyranoside,
D-mannose, D-gulose and D-galactose have been converted into their 4,6-O-isopropylidene
derivatives by use of isopropenyl methyl ether. The same reagent converts D-gulono-
and D- galactono-1,4-lactones into their 5,6-O-isopropylidene derivatives.
Thermodynamics of bromoform + methanol mixtures
Authors: Singh PP , Sharma BR , Sidhu KS
Published: September 2010

Vapour pressures and heats
of mixing of bromoform+methanol as a function of
concentration have been determined at 303.15 K. The results have been analysed
in terms of Barker's theory. Interaction energies have been determined and used
to discuss the nature of interactions between the components.
The crystal structures of potassium Tris(oxalato)-chromate(III) and -aluminate(III) trihydrate: A reinvestigation
Authors: Taylor D
Published: September 2010

The crystal structures of
the isomorphous complexes K3 [M(oxalate)3],3H2O,
M = CrIII and AlIII,
have been determined from three- dimensional diffractometer intensity data by
conventional Patterson and difference Fourier techniques. The crystals are
monoclinic; M = Cr, a 7.714(1), b 19.687(4), c 10.361(2) Ǻ, β
108.06(3)�; M = Al, a 7.712(1), b 19.518(3), c 10.286(2) Ǻ, β
108.21(3)�; space group P21/c with Z = 4. Block-diagonal
least-squares refinement of all non-hydrogen atoms con- verged at R 0.040, Rw
0.051 (M = Cr); R 0.048, Rw 0.056 (M = Al). The structures are
comprised of discrete M(ox)33- anions, K+ cations and
water molecules. One potassium ion and one water molecule appear to be
cooperatively disordered over two possible pair sites (α, β) with
occupancy ratios α/Ǻ c. 3 : 1. The geometries within the M(ox)33-
anions are as expected with  1.969(13),  1.896(15)
Ǻ. The oxalate ligands are non-planar with  1.284(6),
1.279(12);  1.223(5), 1.223(10) and  1.538(16),
1.534(21) Ǻ for the two structures.
Reactions of tin(II) and tin(IV) xanthates: crystal structure of Tetrakis(O-ethylxanthato)tin(IV)
Authors: Raston CL , Tennant PR , White AH , Winter G
Published: September 2010

Tin(II) xanthates form
adducts with donor molecules and react with excess xanthate to form the
tris-xanthato ion, Sn(EtOCS2)3-.
No such reactions are observed with tin(IV) xanthates. Reaction of quinolin-8- ol with tin(IV) ethylxanthate results in the replacement of
two xanthate moieties by two oxinato ions. ��� The crystal structure of [Sn(EtOCS2)4] has been determined by
single-crystal X-ray diffraction at 295 K and refined by least squares to a
residual of 0.038 for 2378 'observed' reflections. The tin(IV) coordination
environment resembles that observed in the N,N- diethyldithiocarbamate
analogue, two of the xanthate ligands being monodentate and coordinating cis [Sn-S, 2.488(2), 2.499(2) Ǻ] in the six-coordinate
coordination sphere while the other two ligands are bidentate, the Sn-S distances trans to the monodentate ligands being slightly
longer [2.617(2), 2.627(2)Ǻ] than the other two [2.562(2),
2.539(2)Ǻ]. Crystals are monoclinic, P21/c, a 10.341(5), b
10.465(4), c 21.88(1) Ǻ, β 98.36(4)°, Z 4.
Synthesis of benzofuranoid systems. VI. The total synthesis of (±)-scabequinone
Authors: Macleod JK , Worth BR , Wells RJ
Published: September 2010

The total synthesis of (�)-scabequinone,
an unusual 6,7-dihydro-5H-furo[3,2-g][1]benzopyran-4,9-quinone
from Cyperus scaber, is
reported.
Reactions directed towards the synthesis of 5-(β-hydroxyethyl)-2-isopropylcyclohexanone
Authors: Murphy R , Prager R
Published: September 2010

Reduction of perillaldehyde
by lithium in ammonia gives products the structures of which depend on reaction
conditions. Shisool (p-menth-8- en-7-ol) undergoes double-bond migration in the
presence of acids. The corresponding aldehyde, with dimethylsulfonium
methylide, forms an oxiran which is comparatively unreactive, double-bond
rearrangement or reduction accompanying the opening of the oxiran. The
conversion of shisool into 5-(β-hydroxyethyl)-2-isopropylcyclohexanone
was frustrated by only partial migration of the double bond.
Three-electron bonds and a valence-bond study of the rotation barrier for N2O4
Authors: Harcourt RD
Published: September 2010

From molecular orbital studies, a number of previous workers have concluded that a most significant
contribution to the barrier to rotation around the NN bond of N2O4 arises from the overlap of pairs
of atomic orbitals located on the cis oxygen atoms of the planar conformation. A valence-bond
study of this overlap contribution is reported. It is calculated that the 'long OO bond' formed by
overlap of singly occupied 2pπ-orbitals in the valence-bond structure (3) for the planar conformation
has negligible strength, and that insufficient stabilization is obtained when this structure participates
in resonance with ionic structures of the type (5a).
Diagram
The primary overlap stabilization for the planar conformation is calculated to arise from resonance
between structures of the types (2a) and (7). The O. :O ↔ 0: .O resonance that pertains here is
equivalent to the formation of a Pauling 'three-electron bond' O...O between the two atoms.
Therefore, the development of this type of bond in the planar conformation can be associated with
the cis OO overlap contribution to the barrier to rotation around the NN bond. Another type of
Pauling three-electron bond resonance, namely (4) ↔ (6), is calculated to produce a smaller but not
insignificant stabilization of the planar conformation.
Stereoselective and regioselective condensation reactions of coordinated aminoacetone
Authors: Gainsford AR , Sargeson AM
Published: September 2010

Treatment of cis-[Co(en)2(NH2CH2R)(NH2CH2COCH3)]3+
ions (R = H, Me, CH2Br, Ph, p-C6H4Cl) with
base leads to imine complexes where the coordinated aminoacetone has reacted
with a bound monoamine RNH2 or an ethylenediamine moiety. The
product distribution appears to be determined by the relative acidity of the
monoamine and the ethylenediamine amine centres; condensation is preferred at
the most acidic site. Reduction of the imine group in these complexes with BH4-
ion leads to new complexes of the type [Co(en)2(NH2CH2CH(Me)NHCH2R)]3+
and [Co(en)(NH2CH2CH2NHCH(Me)CH2NH2)(NH2CH2R)]3+
in which the reduced ligand is synthesized stereospecifically.
A study of the reactions of 2-Aryl-3,3-dimethylbicyclo[2,2,1]heptan-2-ols with acid
Authors: Coxon JM , Projer PM , Steel PJ , Rae ID , Jones AJ
Published: September 2010

The 13C and 1H
N.M.R. spectra of a series of 2-aryl-3,3- dimethylbicyclo[2,2,1]hept-2-yl
cations generated in strong acid at low temperatures are reported. The chemical
shifts of carbons proximate to the cation centres are discussed with reference
to related cations. At higher temperatures, 2-aryl-3,3-dimethylbicyclo[2,2,1]hept-2-yl
cations in fluorosulfonic acid give substituted 7,8-dimethyltetracyclo-
[7,4,0,02,7,04,8]trideca-1(9),10,12-trienesulfonyl fluorides.
Substituted 7,8-dimethyltetracyclo[7,4,0,-02,7,04,8]trideca-1(9),10,12-trienes
and 7,8-dimethyltetracyclo[7,4,0,02,7,04,8]trideca-1(9),10,12-triene
were prepared from 2-aryl-3,3-dimethylbicyclo[2,2,1]heptan-2-ols by reaction
with perchloric acid under carefully controlled conditions.
Some amino acid esters - An improved preparative method
Authors: Maclaren JA
Published: September 2010

This paper describes an
improvement to an earlier method for preparing some esters of amino acids.
Amino acids react with ethyl acetoacetate and the strong base N,N,N',N'-tetramethylguanidine
in dimethylformamide to form the salt of the corresponding enamine. Addition of
a substituted benzyl or picolyl halide to this solution results in rapid
esterification. The amino-protection can then be removed by cold methanolic
hydrogen chloride to give the amino acid ester hydrochloride. For asparagine,
protection of the amide group is also necessary. With tryptophan, ethyl
acetoacetate cannot be used but can be replaced by acetylacetone. No
racemization has been detected.
The crystal structure of [MeHg(py)]+ [NO3]-, a complex with linear geometry for methylmercury(II)
Authors: Brownlee RTC , Canty AJ , Mackay MF
Published: September 2010

Crystals of
methyl(pyridine)mercury(II) nitrate are orthorhombic and belong to the space
group P nma, with a 13.230(3), b 6.538(1), c 9.808(5)
Ǻ and Z 4. The diffractometer data, measured with Mo Kα
radiation, have been refined to an R index of 0.062 for the 857 observed terms.
The crystals are composed of [MeHg(py)]+ cations and uncoordinated nitrate anions.
The C-Hg-N moiety is linear, 179.7(6)°, and the N-Hg and C-Hg bonds have lengths
of 2.12(2) and 2.04(3) Ǻ respectively.
The absolute configuration of actinioerythrin
Authors: Foss PS , Green PJ , Rickards RW
Published: September 2010

Actinioerythrin (1),
3,3'-diacyloxy-2,2'-dinor-β,β-carotene-4,4'-dione, constitutes the
major pigment of the sea anemone Actinia tenebrosa. The fatty acids involved in
esterification differ from those reported for actinioerythrin from A. equina.
Chemical and chiroptical studies establish the absolute configuration of
actinioerythrin as 3S,3'S.
Relative migratory aptitudes in the Schmidt reaction of arylpropanones and 2-arylcyclohexanones
Authors: Prager RH , Tippett JM , Ward AD
Published: September 2010

The relative migratory
aptitude of benzyl and alkyl groups in the reaction of arylpropanones and
2-arylcyclohexanones with hydrazoic acid depends on the solvent, temperature
and nature of the substituents in the aryl ring. It is suggested that at low
temperatures electron- donating groups in the aromatic ring favour a
charge-transfer interaction which affects the relative migratory aptitudes.
The hydrazinolysis of heterocyclic compounds. V. Reactions of 1-Amino-4,6-dimethylpyrimidin-2(1H)-one hydrazone in water
Authors: Dickinson RG , Jacobsen NW , Pitman IH
Published: September 2010

The cation of
1-amino-4,6-dimethylpyrimidin-2(1H)-one hydrazone (1) is stable in aqueous
solutions. By contrast the neutral molecule species decomposes to yield
3,5-dimethylpyrazole (3) and 1-amino-4,6- dimethylpyrimidin-2(1H)-one (6) as
major products, and 1,2,4-triazole-3,4,5-triamine (7) and other unidentified
compounds as minor products. Covalent hydration and substituent effects in the
cation species of (1) are discussed in seeking an explanation for anomalous
ultraviolet spectra. Hydrogen deuterium exchange in methyl substituents is
reported.
Reaction of molybdenum pentoxide/pyridine/hexamethylphosphoramide with Grignard reagents. Conversion of organic bromides into hydroxy derivatives
Authors: Lewis NJ , Gabhe SY
Published: September 2010

The reaction of molybdenum
pentoxide/pyridine/hexamethylphosphoramide for selective conversion of organic
bromides into alcohols and phenols was evaluated from the corresponding Grignard intermediates. The transition-metal complex
readily reacted with primary, secondary, and tertiary alkylmagnesium bromides.
The conversion of bornyl and norbornyl Grignard
reagents into the hydroxy derivatives proceeded with retention of configuration
which suggests the utility of this complex for stereoselective syntheses.
The absolute configuration of cryptopleurine and tylocrebrine
Authors: Gellert E , Rudzats R , Craig JC , Roy SK , Woodard RW
Published: September 2010

The absolute configurations
of cryptopleurine and (-)-tylocrebrine have been established as R and S respectively
by comparison of their optical rotatory dispersion and circular dichroism
spectra with those of tylophorine.
An infrared and Raman spectroscopic study of some Group 1B halide complexes containing an M4X4 core
Authors: Bowmaker GA , Knappstein RJ , Tham SF
Published: September 2010

The infrared and Raman
spectra of [Et3PcuI]4 and [Et3AsCuI]4
have been measured, and bands have been assigned to vibrations of the ligand
and of the Td Cu4I4 core. The far-infrared
spectra show two strong T2 v(CuI) bands at
about 90 and 140 cm-1, the higher frequency member of which has a
Raman counterpart which shows possible longitudinal-transverse splitting. The
Raman spectra also show an intense band at about 50 cm-1. Similar
features have been observed in the low-frequency vibrational spectra of [Et2S]3
[CuI]4, [C5H5NcuI]4,
[C5H11NAgI]4, [Et3PAgBr]4
and [Et3PagCl]4, although the last two compounds gave
only a single broad band in the v(MX) region.
Ion-molecule reactions of formic acid. I. Proton-transfer reactions
Authors: Freeman CG , Harland PW , McEwan MJ
Published: September 2010

Rate coefficients are
reported for a number of proton-transfer reactions with formic acid. These
reactions can be represented by the general equation
�������������������������� XH++HCOOH
→ (HCOOH)H+ +X :
(X = CH4, H2O,
N2, CO, HCN, HCHO, CH3OH and H2S). Reasonable
agreement was obtained between our observed results and predictions based on
the average-dipole-orientation (ADO) model except that ADO theory may slightly
underestimate the collision rate.
19F nuclear magnetic resonance studies of the interaction of inhibitors with chymotrypsin. N-Acetyl derivatives of fluorophenylalanines
Authors: Knight HJ , Williams EH , Spotswood TM
Published: September 2010

Binding parameters, ΔB
and KI, for the three competitive inhibitors N-
acetyl-o-fluoro-D-phenyl-alanine, N-acetyl-m-fluoro-D-phenylalanine and
N-acetyl-p-fluoro-D-phenylalanine have been determined by Fourier- transform 19F
n.m.r, techniques. Association between the enzyme aromatic binding site and the
three inhibitors appears to result in greater immobilization of the aromatic
rings than is the case for the analogous N-trifluoroacetyl compounds. A balance
between the enzyme-inhibitor interactions at the aromatic and amido binding
sites is believed to be responsible for the observed effects. The relationship
between KI and KS values of inhibitors obtained from
kinetic data and KI values obtained by N.M.R. methods is discussed.
The limited scope of azabicyclohexane synthesis from δ,ε-unsaturated amines
Authors: Black DSC , Doyle JE
Published: September 2010

The reported synthesis of
1-azabicyclo[3,1,0]hexanes from β,β-diphenyl
δ,ε-unsaturated alkylamines has been
verified and extended. However, similar treatment of alkyl-substituted δ,ε-unsaturated alkylamines with bromine and
sodium hydride fails to afford azabicyclohexanes and unsaturated acyclic
products are formed. It is concluded that satisfactory synthesis of
azabicyclohexanes from δ,ε-unsaturated amines is contingent on the
presence of suitable bulky substituents.
Synthesis of some substituted 4-Aminobut-2-enoic acids as analogues of the neurotransmitter GABA
Authors: Allan RD , Twitchin B
Published: September 2010

Allylic bromination of a
series of α,β-unsaturated acids with N- bromosuccinimide
gave crude products which could be aminated conveniently in liquid ammonia to
prepare the substituted 4-aminobut-2- enoic acid (4-aminocrotonic acid)
derivatives (4a-f) in low to moderate yields. The assignment of the trans
configuration of the carboxyl and aminomethyl groups about the double bond of
the amino acid products is supported by chemical studies and proton magnetic resonance
spectral data. The procedure worked conveniently with methylamine to give the
unsaturated secondary amino acids (8a,b). Methylamine was also shown to remove
a phthalimido protecting group cleanly in the presence of an α,β-unsaturated acid functionality.
Synthesis of heterocyclics via enamines. VI. Acid-catalysed transformation of 4,6,6-Trimethyl-3,6-dihydropyrimidine-2-thiols. Functionalized cyclic enamines
Authors: Singh H , Singh P , Mehta RK
Published: September 2010

On heating with HCl or H2SO4,
4,6,6-trimethyl-3-phenyl-3,6- dihydropyrimidine-2-thiol (1; R = Ph) formed
phenylthiourea and 4,6,6- trimethyl-2-phenylamino-6H-1,3-thiazine (3; R = Ph)
and not 4,4,6- trimethyl-2-phenylamino-4H-1,3-thiazine (2; R = Ph) as reported
by Ignatova. In a similar reaction,
4,6,6-trimethyl-3,6-dihydropyrimidine- 2-thiol gave thiourea,
2-amino-4,6,6-trimethyl-6H- 1,3-thiazine (3; R = H) and
4,6,6-trimethyl-4-(4',4',6'-trimethyl-1',4'-dihydropyrimidin-2'-ylthio)-tetrahydropyrimidine-2(1H)-thione (9).
Intramolecular reorientation, an electron spin relaxation process in solutions of discrete paramagnetic transition-metal complexes
Authors: Doddrell DM , Pegg DT , Bendall MR , Gregson AK
Published: September 2010

Time modulation of the
g-tensor by intramolecular reorientation between structurally equivalent
molecular arrangements is postulated to dominate electron spin relaxation in
solutions of some paramagnetic transition-metal complexes. The process is
treated theoretically and it is shown that the resulting electron spin
relaxation time depends on the correlation time for intramolecular
reorientation. The temperature dependence of the nuclear T1 thus
yields information concerning the potential energy profile for intramolecular
reorientation. Experimental results on the field dependence of the temperature
dependence of T1 of the methyl proton in Ru(acac)3 are in accord with the theory.
Crystal structure of ab-Bis(3-methylpyridine)-dc,fe-bis(pentane-2,3,4-trione 3-oximato)iron(II)
Authors: Figgis BN , Raston CL , Sharma RP , White AH
Published: September 2010

The crystal structure of
the title compound has been determined at 295 K by single-crystal X-ray
diffraction and refined by least squares to a residual of 0.062. Crystals are
monoclinic, P2/c, a 19.102(8), b 8.117(4), c 16.610(8) Ǻ, β
111.90(3)°, Z. Unlike the tris(α-oxyimino ketonato)iron(II) complexes
which are fac, the present derivative is based upon substitution of the two
picoline moieties into a mer derivative, trans to the
nitrogen atoms of the chelate ligands.  is 2.020;
 1.880, 1.952 Ǻ.
The kinetics and mechanism of the reaction between nickel(II) and dithiocarbamate ions in dimethyl sulfoxide. Evidence for the ID mechanism for a bidentate uninegative ligand
Authors: Nichols PJ , Grant MW
Published: September 2010

13C Fourier-transform N.M.R. has been used to measure
the rate of exchange of dimethyl sulfoxide with hexakis(dimethyl
sulfoxide)nickel(II) cation. The parameters obtained, kex(25°C)(9.8�4.6)
× 103 s-1, ΔH‡ 50�2 kJ mol-1
and ΔS‡ 0�4 J K-1 mol-1, are in excellent agreement
with those of the most recent 1H N.M.R. study. The reaction between
Ni(Me2SO)62+ and diethyldithiocarbamate (dtc-)
gives only Ni(dtc)2. When dtc- is in excess, the rate of formation
of Ni(dtc)2 is first order in Ni2+ and dtc-.
The ionic-strength and temperature dependences of the second-order rate
constants are consistent with the rate-determining formation of an unstable
Ni(dtc)+ complex by an ID mechanism.
Carbon-13 N.M.R. studies of some β-adrenergic agents
Authors: Pasaribu SJ , Brophy GC
Published: September 2010

Carbon-13 chemical shifts
of some beta-adrenergic agents of disubstituted phenylaminoethanol derivatives
have been measured. It was observed that the ortho-substituent to the alcohol
side chain exerted an upfield shift on the methine carbon of the aminoethanol
group, whereas the methyl carbons of isopropylamine were found to be
magnetically non-equivalent. It was also found that the methylene and methine
carbons of the alcohol side chain of 1-isopropylamino-3-
naphthyloxy-propan-2-ol (propranolol) were shielded at
a similar magnitude as the 2,5-disubstituted phenyl-aminoethanol derivatives.
Crystal structure of Bis(tri-2-pyridylamine)cobalt(II) diperchlorate
Authors: Kucharski ES , McWhinnie WR , White AH
Published: September 2010

The crystal structure of
the title compound, [Co((C5H4N)3N)2]
(ClO4)2, has been determined by single-crystal X-ray
diffraction at 295(1) K, i.e. in its pseudo-'high-spin' form, and refined by
least squares to a residual of 0.061 for 4639 'observed' reflections. Crystals
are monoclinic, P21/a, a 12.811(7), b 17.644(7), c 8.375(4) Ǻ,
β 120.15(3)°, Z 2. Whereas in the iron(II) ('low-spin') analogue, the
metal atom coordination geometry deviates only trivially from octahedral
( 1.982 Ǻ,  within the one ligand
88.1°), in the present compound Co-N ranges from 2.100(2) to 2.152(2) Ǻ
and the intraligand N-Co-N angles range from 84.86(7) to 86.09(8)°.
Chemistry of the Coccoidea. VI. Pigments of the lac insect Austrotachardia acaciae (Hemiptera): Chemistry and crystal structure
Authors: Cameron DW , Feutrill GI , Patti AF , Raston CL , Raverty WD , White AH
Published: September 2010

Pigments of the Australian
lacciferid, Austrotachardia acaciae Maskell, differ
from those of Indian lac insects in that the major
constituent is xantholaccaic acid B (9) rather than a
mixture of laccaic acids. Its structure has been determined by single-crystal
X-ray diffraction of a new hexamethyl derivative. Xantholaccaic acids have not
previously been found in nature.
New quinones from a dictyoceratid sponge
Authors: Kazlauskas R , Murphy PT , Warren RG , Wells RJ , Blount JF
Published: September 2010

Five new quinones have been
isolated from a sponge tentatively classified as Stelospongia conulata.
Isospongiaquinone (7) has a rearranged drimane skeleton whereas spongiaquinone
(19), cyclo- spongiaquinone-1 (20), cyclospongiaquinone-2 (21) and dehydrocyclospongiaquinone-1
(22) have a normal drimane skeleton. The structures of these were derived from
chemical and spectral evidence.
Crystal structure of 2,4-Di-t-butyl-6-(3,5-di-t-butyl-2-hydroxyphenyl)-6-morpholinocyclohexa-2,4-dienone
Authors: Hall SR , Hewitt DG , Raston CL , White AH
Published: September 2010

The crystal structure of
the title compound, C32H49NO3, has been
determined by single-crystal X-ray diffraction at 295(1) K and refined by least
squares to a residual of 0.061 for 1721 'observed' reflections. Crystals are
orthorhombic, Pcab, a 18.63(2), b 18.58(2), c
18.19(2) Ǻ, Z 8. The structure determination confirms that proposed on
chemical grounds and shows an unusual t-butyl N.M.R. chemical shift to be a
consequence of an unusual orientation.
Nitration of phenanthrene in acetic anhydride
Authors: Lane DMD , Richards KE , Wright GJ , Fischer A
Published: September 2010

Nitration of phenanthrene
in acetic anhydride gives 10-acetoxy-10'-nitro-9,9',10,10'-tetrahydro-9,9'-biphenanthryl
as major product.
Field-Dependence of Chemical Shifts in Colbalt(III) N.M.R. Spectroscopy. Theoretical Predictions
Authors: Doddrell DM , Pegg DT , Bendell MR
Published: September 2010

Ramsey's suggestion of
fourth-order perturbation theory contribution to a field-dependent chemical
shielding arising from paramagnetic currents is more closely examined. The
effect is shown to be opposite in sign to the field-invariant chemical
shielding tensor and, for cobalt(111) chemical shifts, only becomes important
for some complexes for field strengths in excess of 20T.
Chemistry and Crystal Structures of Some Constituents of Zingiber cassumunar
Authors: Amatayakul T , Cannon J , Dampawan P , Dechatiwongse T , Giles RF , Huntrakul C , Kusamran K , Mokkhasamit M , Raston C , Reutrakul V , White A
Published: September 2010

The novel aromatic
compounds cis-3-(2',4',5'-trimethoxyphenyl)-4-[(E)-2''',4''',5'''-trimethoxy-styryl]cyclohex-1-ene(1),
cis-3-(3',4'-dimethoxyphenyl)-4-[(E)-3''',4'''-dimethoxystyryl]cyclohex-1-ene (2), a substance assigned the tentative
structure cis-3-(3',4'-dimethoxyphenyl)-4-[(E)-2''',4''',5'''-
trimethoxystyryl]cyclohex-1-ene (3),(E)-4-(3',4'-dimethoxypheny1)but-3-en-1-ol
(5), (E)-4-(3',4'-dimethoxypheny1)but-3-en-1-yl acetate (6), and
8-(3',4'-dimethoxyphenyl)-2-methoxynaphtho-1,4- quinone (7) have been isolated
from the rhizomes of Zingiber cassurnunav Roxb. (Zingiberaceae). The
crystal structures of the cyclohexene derivative (1)
and the quinone (7) have been determined from X-ray diffractometer data at 295
K and refined by block diagonal least squares to residuals of 0.046 (2099
'observed' reflections) and 0.093 (1246), respectively. Crystals of compound
(1) are triclinic, P1, a 18.027(12), b 10.037(9), c 6.530(5) α, 84.22 (7), β 81.87 (6), γ 85.72 (6)�,
Z 2. Crystals of the quinone (7) are monoclinic, P21/a, a 22.89 (1), b 8.022 (5), c 8.458 (5) �,
β 91.98 (5)�, Z 4. Although the latter crystal structure determination is
imprecise, due largely to the very small size of the crystal available, the
solution is unambiguous. A simple two-step synthesis of the quinone (7) has
been achieved.
Hydrogen Isotope Exchange in Aromatic Compounds in the Presence of Raney Nickel Alloy
Authors: Finlayson AC , Kallury RKMR , Prager RH
Published: September 2010

Aromatics undergo rapid
proton-deuterium or -tritium exchange in aqueous solutions containing Raney
nickel alloy. The specificity of exchange in benzoic acid, anthranilic acid,
pyridine and aniline is investigated by degradation and mass and N.M.R. spectrometry.
Positions meta and para to carboxylate are most readily
exchanged.
A New Way of Forming Lignin-Carbohydrate Bonds. Etherification of Model Benzyl Alcohols in Alcohol/ Water Mixtures
Authors: Hemmingson JA
Published: September 2010

The etherification
reactions of vanillyl alcohol and veratryl
alcohol in alcohol/water mixtures have been studied. It is concluded that
lignin-carbohydrate bonds could be formed subsequent to lignification
of the plant cell wall, through etherification of the p-hydroxybenzyl alcohol structures in the
lignin polymer.
Structural Studies of RSHgII Complexes Containing (-Hg-SR-)n Rings and Chains
Authors: Canty AJ , Raston CL , White AH
Published: September 2010

Crystals of
acetato(methanethiolato)-γ-picolinemercury(11), MeSHgO2CMe,C6H7N
(I), are monoclinic, P21/a, a
16.617(9), b 7.271(3), c 20.476(2) � β 113.31(5)�, Z 8.
The structure resembles that of its pyridine analogue, being based on a
polymeric (-Hg-SMe-)n
chain with acetate and picoline groups coordinated at each mercury; a similar
structure is found for EtSHgO2CMe,C5H5N (2),
monoclinic, P21/c, a
9.344(2), b 17.917(9), c 7.179(2) �,β 106.24(3)�, Z 4.
The structure of tetrachlorotetra(2-methylpropane-2-thiolato)di(γ-picoline)
tetramercury(11), (BUtS)4Cl4Hg4(C6H7N)2
(3), also resembles that of its pyridine analogue being based on an unusual
tetranuclear grouping of mercury atoms linked by chloride and thiolate bridges.
Crystals of (3) are monoclinic, P21/c a 12.334(7), b 17.468(9),
c 9.999(5) �, β 91.18(4)�, Z 2.
Crystals of MeSHgBr (4) are monoclinic, P21/c, a 7.770(9), b 7.500(5), c 7.945(10) �, β 91.71(3)�, Z 4,
and contain parallel chains (-Hg-SMe-)n
with neighbouring chains linked by bridging bromine atoms into parallel sheets.
Each bromine is triply bridging, being coordinated to two mercury atoms in one
chain, and one mercury atom in an adjacent chain. The structure of MeSHgCl
appears to be isomorphous.
Properties and Structures of the Five-Coordinated Copper(II) and High-Spin Nickel(II) Complexes of 3,3'-Dichloro-2,2'-(1,12-diphenyl-2,6,11-triazadodeca-1,11-diene-1,12-diyl)bisphenol
Authors: Freyberg DP , Mockler GM , Sinn E
Published: September 2010

The copper(II) and
nickel(II) complexes of the potentially pentadentate ligand (acpn) derived from
the Schiff base condensation of 4-azaoctane-1,8-diamine and
5-chloro-2-hydroxybenzophenone have been synthesized and their crystal
structures and magnetic and spectral properties determined. The ligands act as
pentadentates, in contrast with the coordination reported for some analogous
Schiff base ligands. The metal environments are intermediate between square
pyramidal and trigonal bipyramidal, with that of [Cu(acpn)] being closer to
square pyramidal. The apical bond in the square-pyramidal representation of
[Cu(acpn)] is elongated (2.291 �), though to a markedly smaller degree than in
the related complex [Cu(smpn)] (2.374 �) and the thioether analogue [Cu(scps)]
(2.686�). The crystal structures were determined from full-matrix least-squares
refinement of counter data: [Cu(acpn)], space group C2/c,Z 4, a 11.065(4), b 18.481(6), c 14.019(3) �,
β 93.53(3)�, R 3.4% for 2198 reflections; [Ni(acpn)], space group C2/c, Z
4, a 11.084(2), b 18.224(6), c 14.197(6) �,
β 92.57 (3)�, R 3.0% for 1820 reflections.
The Relative Reactivities of the Seven Nuclear Positions of Isoquinoline to Free-Radical Phenylation
Authors: Dyall LK , Pullin CJ
Published: September 2010

Free-radical phenylation of
isoquinoline has been effected both by photolysis of phenylthallium(III)
di(trifluoroacetate) and by the action of pentyl nitrite on aniline. Analysis
of the isomeric phenyl isoquinoline mixture by g.l.c. and h.p.l.c. established
the reactivity order in the isoquinoline nucleus to be 1 > 5 > 8 > 4
> 3,6,7. This experimental order is compared with the eight published
theoretical predictions, none of which is correct.
Amine Reactions with Bis(thioamides)
Authors: Ewin G , Hill JO
Published: September 2010

The reaction between N,N'-ethylenebis(thiobenzamide) and ethylenediamine
in the presence of mercuric oxide yielding 2-phenyl-2-imidazoline is shown to
proceed in two steps since the intermediate, 2-phenyl-1-thiobenzoyl-2-imidazoline,
has been isolated and characterized. An amine exchange reaction involving a
bis(thioamide) is reported which is a new variation of the Wallach reaction.
Isentropic Compressibilities of Butylamine+n-Alkane at 303.15 and 313.15 K
Authors: Sreenivasulu M , Naidu PR
Published: September 2010

Isentropic
compressibilities of binary mixtures of butylamine + hexane, butylamine + heptane,
and butylamine + octane were determined at 303.15 and 313.15 K. The three
mixtures exhibit positive deviations in compressibility. This is ascribed to a
structure-breaking effect of n-alkanes. The deviation becomes more positive
with increase in chain length of n-alkanes and with increase in temperature.
Oxidative Cyclizations. V. The Oxidation of ortho-Substituted Benzenamines with Lead(IV) Tetraacetate
Authors: Dyall LK
Published: September 2010

Lead(IV) tetraacetate has
been used to oxidize 1-aminoanthraquinone, 1-arylazonaphthalen-2-amines and
benzenamines whose ortho-substitutents
were arylazo, nitro, or benzopl. Only the amines with ortho-arylazo substituents underwent oxidative cyclization, to
yield triazoles; the others yielded azo compounds and polymers. Experimental
evidence shows that neither nitrenes nor arenamino ('anilenium') cations can be
the reactive intermediates in some of these reactions. All the results can be
rationalized in terms of the conjugate acid-base pair of intermediates,
arenamine cation ArNH2+' and arenamino ArNH.
Studies of Australian Soft Corals. XI. Two New Cembranoid Diterpenes from a Sarcophyton Species
Authors: Bowden BF , Coll JC , Mitchell SJ , Stokie GJ
Published: September 2010

The structure of two
cembranoid diterpenes is deduced by chemical and spectroscopic means. The first,
C20H30O2, isosarcophytoxide
(2) is a monoepoxy dihydrofuran-containing
cembrane, isomeric with the previously reported sarcophytoxide (1), while the second compound is the
related bisepoxide (3). Chemical correlations of the
compounds (1), (2) and (3) are reported.
The Photoelectron Spectra of the N-Chloro and N-Bromo Derivatives of Dimethylamine
Authors: Carnovale F , Gan T , Peel JB
Published: September 2010

The He I and He II spectra
obtained for chlorodimethylamine (CH3)2NCl,
and bromodimethylamine (CH3)2NBr,
complete the study of the N-chloro
and N-bromo derivatives of the small
amines. The valence photoelectron spectra are interpreted with the aid of SPINDO
molecular orbital calculations. Trends in the observed ionization energies for
both series of small halo amines are described in terms of variations in
inductive and resonance effects, the latter particularly concerning the nN/nx lone-pair interactions observed
in the low ionization energy range.
Organothallium Compounds. XV. Thallation of Polyfluoroaromatic Compounds
Authors: Deacon GB , Tunaley D
Published: September 2010

Thallic trifluoromethanesulfonate has been prepared by reaction of trifluoromethanesulfonic acid
with either thallic oxide or solutions of thallic trifluoroacetate in trifluoroacetic acid, and has been
isolated as the trihydrate on crystallization fromnitromethane. The polyfluoroarenes,p-CH3OC6F4H,
p-CH3C6F4H, m-H2C6F4, o-H2C6F4, p-H2C6F4, C6F5H, 1,3,5-F3C6H3 or 1,2,4-F3C6H3, have been
thallated by thallic trifluoromethanesulfonate in trifluoroacetic acid, giving the corresponding poly-
fluorophenylthallium(III) bis(trifluoromethanesulfonates), which have been characterized spectroscopically and by conversion into the corresponding (polyfluoro)iodobenzenes on treatment with sodium
iodide. Only slight thallation of m-BrC6F4H and m-O2NC6F4H was observed. By contrast with
thallic trifluoromethanesulfonate, thallic trifluoroacetate in trifluoroacetic acid induced little thallation
of the most reactive polyfluorobenzene, p-CH3OC6F4H. Thallic trifluoromethanesulfonate also
thallated p-CH3OC6F4H in nitromethane, sulfolane, and with the substrate as solvent, but
p-CH3C6F4H failed to react. Treatment of the polyfluorophenylthallium(III) bis(trifluoromethane-
sulfonates) with boiling aqueous sodium acetate caused symmetrization into the corresponding
acetatobis(polyfluorophenyl)thallium(III) compounds. A similar reaction between 2,4,6-trifluoro-
phenylthallium(III) bis(trifluoromethanesulfonate) and sodium acetate at room temperature yielded
2,4,6-trifluorophenylthallium(III) diacetate. 2,3,4,6-Tetrafluorophenylthallium(III) bis(trifluor0-
methanesulfonate) was converted by boiling water into bis(2,3,4,6-tetrafluorophenyl)thallium(III)
trifluoromethanesulfonate.
Methylation of Purin-8-ones
Authors: Bergmann F , Brown DJ
Published: September 2010

In general, electrophilic
alkylation of purin-8-ones takes place at the same sites as protonation.
Exceptions are observed only for 3-methyl derivatives, in which cation
formation involves N9, whereas methylation proceeds both at position 1 and 9.
This dichotomy of alkylation is ascribed to steric interference between 3- and
9-methyl substituents.
The 6-(but-2'-enylidene)-1,5,5-trimethylcyclohex-1-enes: Important volatile constituents of the juice of the purple passionfruit Passiflora edulis
Authors: Whitfield FB , Sugowdz G
Published: September 2010

Two important flavour components of the juice of the purple passionfruit Passflora edulis (Sims) have been shown by g.l.c.,
mirco-reaction g.l.c., u.v., i.r., N.M.R., mass
spectrometry, and by synthesis to be (6E,2'E)- and
(6Z,2'E)-6-(but-2'-enylidene)-1,5,5-trimethylcyclohex-1-ene (2a) and (2b).
Evidence is also reported for the presence in this juice of trace amounts of
the stereoisomers (2c,d). The
6-(but-2'-enylidene)-1,5,5-trimethylcyclohex-1-enes are very susceptible to
oxidation and, in dilute acetic acid solution, are rapidly converted into 'ionene', 1,1,6-trimethyl-1,2,3,4-tetrahydro- naphthalene
(10). The significance of this reaction in the loss of flavour
during pasteurization of passionfruit juice is
discussed.
Crystal Structure of N-Acetylkynurenine
Authors: Kennard CHL , Matsuura Y , Tanaka N , Kakudo M
Published: September 2010

The crystal structure of N-acetylkynurenine
[o-NH2C6H4COCH2CH(COOH)NHCOCH3]
was determined by direct methods. The crystals are monoclinic, a 11.200(2), b 9.708(1), c 11.451(1) �,β 90.16(2)�, space group P21, with Z 4.
The structure was refined by least squares to R 0.033 with 1909 unique
reflections, collected on an automated four-circle diffractometer. The
structure is similar to the related L-trytophan
hydrochloride. The two molecules in the asymmetric unit (A,B) are generally
similar structurally but differ slightly in the conformation of the N-acetyl chain which has dihedral angles
with the plane of the benzene ring of 78.0� (A) and 81.5� (B). Torsion angles
about the C(α)-C(β) bond between C(γ) and both the carboxyl and
the amino groups make them mutually gauche.
There is an extensive hydrogen-bonding system between the two distinct
molecules and between similar molecules either to form a dimer or a linear
polymer.
Products of 1,8-Cineole Oxidation by a Pseudomonad
Authors: Macrae IC , Alberts V , Carman RM , Shaw IM
Published: September 2010

A bacterium having close
affinity with Pseudomonas flava was isolated from eucalypt leaves for its ability
to utilize 1,8-cineole (1) as a carbon source. The bacterium is also capable of
utilizing α-terpineol, camphor, isoborneol and geraniol but
failed to grow on borneol, limonene and piperitone. Growth of the organism in mineral salts medium
containing 1,8-cineole resulted in the formation of four oxidation products. Keto lactone (2), alcohols (3)
and (4) and ketone (5) arereported as natural
products arising from the oxidation of 1,8-cineole by the bacterium.
A CNDO/2 Molecular Orbital Study of Shared Tetrahedral Edge Conformations in Olivine-Type Compounds
Authors: McLarnan TJ , Hill RJ , Gibbs GV
Published: September 2010

Semi-empirical molecular
orbital calculations have been used to study the shortening of tetrahedral
shared edges in olivine-type compounds. The shared edge conformation in forsterite was modelled by a
cluster of SiO3(OH)Mg3(OH)107-
composition, consisting of a silicate tetrahedron sharing edges with three
magnesium-containing octahedra. Predicted tetrahedron
edge lengths agree well with observed values. Calculations on similar clusters
representing shared edge conformations in sinhalite, chrysoberyl, and γ-Na2BeF4 also
predict shortening of shared edges with d(X2-X3) < d(X3-X3), (X = O,F), as
observed. Calculations on Mg2SiS4 fail to predict
shortened shared edges. Detailed analysis of the individual molecular orbital
energy terms indicates that the minimum energy configuration is determined by a
complex sum of one- and two-centre energies. Distortions due to dimensional
misfit of polyhedra in olivine structure space group P bnm appear to have relatively
little importance in shortening the shared edges of the tetrahedron.
Reactions of Aryl Diazonium Salts and Arylazo Alkyl Ethers. IV. Substituent Effects on the Rates of Some Reactions of syn-Arylazo Ethyl Ethers in Ethanol
Authors: Broxton TJ
Published: September 2010

Substituent effects on the
rates of ionization (kIS), decomposition (kD) and syn-anti interconversion (kp)
for a number of syn-arylazo
ethyl ethers have been measured. The rates of ionization and syn-anti interconversion correlate well with sigma while the rates
of decomposition correlate with σ+. Substituent effects on the
ionization of the syn-ethers
are compared to those for ionization of the anti-ethers.
Substituent effects on the rate of syn-anti interconversion support the proposed ionization-recombination
mechanism.
Initiation and Termination Group Identification in Polymers by 13C N.M.R. Spectroscopy
Authors: Hawthorne DG , Johns SR , Solomon DH , Willing RI
Published: September 2010

A 13C N.M.R.
inversion/recovery method is described for the identification of initiation and
termination groups in low molecular weight polymers.
On the Thermal Reversibility of the Photochemical Di-π-methane Rearrangement of Bicyclo[2,2,2]octadienones. Confirmation of Regiospecificity and Stereochemistry by X-Ray Structure Analyses
Authors: Becker H , Ruge B , Skelton BW , White AH
Published: September 2010

Thermolysis of the tricyclic
photo-isomer obtained by di-
π-methane rearrangement of a
t-butyl-substituted bicyclo[2,2,2]octadienone
regenerates a new bicyclo[2,2,2]octadienone in which
the oxo- substituted C2-bridge has undergone a 1,3-migration. The
structures of the three isomers involved were established by X-ray analyses.
The Reaction of Epoxy Benzocycloalkenes with Diborane
Authors: Marshall PA , Prager RH
Published: September 2010

The epoxides
formed from the following olefins have been treated with diborane and the
products characterized: 1H-indene,
1,2-dihydronaphthalene, 6,7-dihydro-5H-benzocycloheptene,
5,6,7,8-tetra- hydrobenzocyclooctene,
6,7,8,9-tetrahydro-5H-benzocyclononene, 1- and 2-methyl-1H-indene, and 4-and 3-methyl-1,2-dihydronaphthalene. The major
product from the unsubstituted epoxides
is the β-hydroxy compound, but the proportion of the cehydroxy compound
increases with increasing ring size. The methyl-substituted oxirans generally
evolve hydrogen on treatment with diborane, and oxidation leads to diol
products.
Studies of Australian Soft Corals. XII. Further Cembranolide Diterpenes from Lobophytum crassospiculatum and a Correction of a Previous Stereochemical Assignment
Authors: Ahond A , Bowden BF , Coll JC , Fourneron J , Mitchell SJ
Published: September 2010

Three new cembranolide diterpenes from Lobophytum crassospiculatum are reported. The
structure of one of these was deduced from spectroscopic data and chemical
degradation, then confirmed as (E,E,E)-6,10,14-trimethyl-3-methylene-trans-3a,4,7,8,11,12,15,15a- octahydrocyclotetradeca[b]furan-2(3H)-one (3), by synthesis from the
previously reported (2). The other two diterpenes,(4) and (5), are shown to be
the epimeric 15-acetoxyl derivatives of (2).