bluuebunny/crossref_metadata_2025 huggingface dataset:
The 9-decalyl and related cations. III. Generation of the 8-hydrindyl cation by solvolysis
Authors: Gream GE , Serelis AK , Stoneman TI
Published: September 2010

Acetolysis of
4-(cyclopent-1'-enyl)butyl and 3-(2'-methylenecyclopentyl)propyl derivatives,
but not 3-(cyclohex-1'-enyl)propyl and 2-(2'-methylenecyclohexyl)ethyl
derivatives, occurs with π-bond participation (95 and 92%, respectively)
to give similar, including maybe identical, cationic species involving the
8-hydrindyl cation. On the basis of product composition, the 8-hydrindyl
cations when generated from spiro[4,4]non-1-yl (σ-route) and cis- and trans-8-hydrindyl derivatives (direct route) are each different and
are in turn different to those generated by the above π-routes. Reasons
for the differences are discussed and the possible role of the counter-ion in
ion-pairs is examined.
Preparation and thermal decarbonylation of some sterically compressed 5,6-endo-Disubstituted Norborn-2-en-7-ones
Authors: McCulloch RK , Rye AR , Wege D
Published: September 2010

Reaction of
1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene with norbornadiene
and benzo-norbornadiene gave adducts having the endo-exo-1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethano-naphthalene
and endo-exo-1,4,4a,9,9a,l0-hexahydro-1,4:9,l0-dimethanoanthracene
skeletons, respectively. These adducts were dechlorinated to give acetals, which were hydrolysed to give the corresponding
ketones. The initial adducts, and the derived acetals
and ketones, are all sterically compressed as a result of crowding of the C2-C3
etheno bridge against a methano
hydrogen atom syn to that bridge.
This steric compression manifests itself in a marked deshielding of the
relevant methano proton in the N.M.R. spectra of
these compounds, and in an increased rate of thermal decarbonylation
of the ketones. The location of the deuterium atom in benzonorbornadiene[7-anti-D]
(12) has been established chemically by observing an intramolecular deuterium
transfer during photochemical half-cage formation from the adduct of (12) and
1,2,3,4-tetrachloro-5,5- dimethoxycyclopentadiene.
Studies on intramolecular alkylation. VIII. The preparation of fluorene-derived tetracyclic ketones : Intermediates for gibberellin synthesis
Authors: Beames DJ , Mander LN , Turner JV
Published: September 2010

The
1,2,3,4-tetrahydrofluorene-2-carboxylic acids (7) and (13) were prepared and
converted via their diazomethylcarbonyl derivatives
(5) and (6) to give 1,2,3,9a-tetrahydro-7-methoxy-2,9a-ethano-fluoren-11-one (3)
and its 2-hydroxy derivative(4), respectively.
The alkaloids of Poranthera corymbosa (Euphorbiaceae)
Authors: Johns SR , Lamberton JA , Sioumis AA , Suares H
Published: September 2010

The alkaloids porantherine (1), porantheridine
(2), poranthericine (3), O-acetylporanthericine (4),and porantherilidine (9), the structures of which are known
from X-ray structure studies, are discussed.Another alkaloid, porantheriline (8), isomeric with O-acetylporanthericine, gives on
hydrolysis the alcohol (7). Poranthericine (3) and
alcohol (7) are considered to be epimeric at C1, and to have a Clβ-axial and a Clα-equatorial
ethyl substituent respectively. Oxidation of poranthericine
(3) and alcohol (7) gives the same ketone (6), which is considered to be formed
from poranthericine (3) by epimerization of the
initial oxidation product (5). Reduction of the ketone (6) affords alcohol (7)
as the sole product.
The action of arylamines on some substituted 2-Thiazolin-5-ones
Authors: Khalil AM , Abd El-Gawad II , Hammouda M
Published: September 2010

The heterocyclic ring in
2-aryl-4-arylmethylene- and 4-arylmethylene-2-benzylthio-2-thiazolin-5-ones is
readily opened by the action of primary aromatic amines in acetic acid
containing a catalyticamount of sodium acetate
with the formation of 1,2-diaryl-4-arylmethylene-2-imidazolin-5-ones and of
3-aryl-5-arylmethylene-2-thiohydantoins respectively. 4-Benzylidene-1-(p-chloropheny1)-2-phenyl-2-imidazolin-5-one
was also obtained by the cyclization of the anilide of α-(p-chlorothiobenzamido)-β-phenylacrylic
acid under the same reaction conditions. A possible reaction mechanism is postulated.
The anomalous reaction of 2-phenylacrylophenone with some arylhydrazines
Authors: Wilshire JFK
Published: September 2010

The reaction of
2-phenylacrylophenone with some arylhydrazines gives
a mixture of the corresponding 1-aryl-3,4-diphenyl-2-pyrazoline and
1-aryl-4,5-diphenylpyrazole. A mechanism is advanced for the formation of the
latter product. The 2-pyrazoline derivatives were dehydrogenated to the parent 1-aryl-3,4-diphenylpyrazoles,
the ultraviolet and proton magnetic resonance spectra of which are compared
with those of the corresponding 1-aryl-4,5-diphenylpyrazoles.
Preparation of ketimine derivatives of amino acids for peptide synthesis
Authors: Halpern B , Hope AP
Published: September 2010

Condensates of some
2-hydroxyaryl ketones with protein amino acids have been prepared. The reaction
has been shown to proceed without racemization and the derivatives have been
isolated as free acids. Their unusual stability is ascribed to the presence of a
strong intramolecular hydrogen bond. The N-arylmethylene function is cleaved under mild conditions of
acid hydrolysis. Ketimines derived from D-phenylglycine decarboxylate at
room temperature.
Kinetics of the reaction of the hydrophobic ester 4-nitrophenyl decanoate with long-chain N-alkylimidazoles above and below their critical micelle concentration
Authors: Oakenfull DG , Fenwick DE
Published: September 2010

The kinetics of the
reaction of 4-nitrophenyl decanoate with a series of
straight-chain N-alkylimidazoles
have been studied at 25� in water and aqueous ethanol. In water, below the
critical micelle concentration of the N-alkylimidazole, hydrophobic interaction between the
hydrocarbon chains of the reactants caused substantial increases in the
reaction rate (up to about 200-fold) compared with the rate of reaction of
4-nitrophenyl acetate with N-methylimidazole. The rate constants, though, differed from
those previously reported which were measured with a higher initial
concentration of ester. No increase in rate with increasing hydrocarbon chain
length could be detected in the presence of a large concentration of ethanol
(mole fraction of 0.31) but a rate increase did occur in the presence of a more
moderate concentration of ethanol (mole fraction of 0.10), confirming that
hydrophobic interactions persist in this mixed solvent. The long-chain ester
reacts rapidly with N-alkylimidazole micelles. Association constants (K) for
binding the ester to the micelles and rate constants for the reaction of the
bound ester (km) were estimated by following the conventional
treatment of the kinetics of micelle-catalysed reactions. The value of K was
found to increase sharply with increasing hydrocarbon chain length of the
micelle but km showed the opposite trend.
Chemistry of the Podocarpaceae. L. Conversion of 12-Hydroxypodocarpa-8,11,13-trien-19-oic acid (podocarpic acid) into 19-Hydroxypodocarp-8(14)-en-13-one
Authors: Cambie RC , Hayward RC , Missen AW
Published: September 2010

Detosylations of
derivatives of methyl 12-toluene-p- sulphonyloxypodocarpa-8,11,13-trien-19-oate
have been investigated using a modified W-7 Raney nickel catalyst. The final
steps in a conversion of podocarpic acid (1) into (+)-19-hydroxypodocarp-8(14)-en-
13-one (21), a useful intermediate for synthesis, have been effected.
Vibrational spectra of fulvene
Authors: Domaille PJ , Kent JE , O'Dwyer MF
Published: September 2010

A plausible assignment of
nearly all the thirty fundamental vibrations of the fulvene molecule has been
made.
Reaction of 2-Aryl-4-arylazo-2-oxazolin-5-ones with amines
Authors: Khalil AM , Abd El-Gawad II , Hassan HM
Published: September 2010

1,5,Nα-Triaryl-1,2,4-triazole-3-carboxamides
have been prepared by the interaction of primary aromatic amines with
4-arylazo-2-p-chlorophenyl- 2-oxazolin-5-ones.
Alkaloids of Anthocercis tasmanica (Solanaceae)
Authors: Bick IRC , Bremner JB , Gillard JW , Winzenberg KN
Published: September 2010

The major alkaloids of Anthocercis tasmanica are shown
to be hyoscine and nicotine.
Novel condensation products of 3-Hydroxy-2,2-dimethylpropionaldehyde with malonic acid
Authors: Johnson RN , Riggs NV
Published: September 2010

Reaction of
3-hydroxy-2,2-dimethylpropionaldehyde and malonic acid in acetic
anhydride-acetic acid yields 4,4-dimethylpent-2-en-5-olide, corresponding to
the normal product of condensation of one molecule of aldehyde and one molecule
of malonic acid, along with two novel related δ-lactones derived from two
molecules of aldehyde and one molecule of malonic acid: one is a saturated
lactone having a hydroxy-gem- dimethyltetrahydropyran
ring fused across the 2,3-bond of the above normal product, and the other is
the corresponding unsaturated fused dihydropyranolactone.
Synthesis of hindered diketones and keto esters
Authors: Ford PW
Published: September 2010

Bis(acyl halides) and haloformyl esters react with t-alkyl Grignard reagents in
the presence of cuprous salts yielding diketones and keto esters.
The dependence of the photocurrent at the metal-electrolyte interface on electrode potential
Authors: Matthews DB , Khan SUM
Published: September 2010

The Gurney theory of charge
transfer at the metal-electrolyte interface is extended to the case of
photoemission. It is found that the simple Gurney model is not sufficient to explain
the results observed by a number of independent workers. In order to explain
the observed linear dependence of the 0.4 power of the photocurrent on
electrode potential it is found necessary to allow explicitly for the existence
of a layer of solvent molecules at the metal surface. This layer of molecules
con- stitutes a potential energy barrier to electron
transfer with a width of about 0.28 nm and a height (with respect to the Fermi
level of the metal) of about 560 kJ mol-1 for water. The model is
geometrically quite similar to that used in the very successful Brodsky model
but differs in physical interpretation of the surface potential energy barrier.
The magnetic behaviour of some polynuclear methoxide complexes of iron(III) with aromatic acids
Authors: Kokot E , Mockler GM , Sefton GL
Published: September 2010

The magnetic susceptibility
between 80 and 350 K is reported for FeL(OMe)2 type complexes of iron(III) where L is
aromatic acid. The antiferromagnetism and the single C-O methoxide band at
1038-1052 cm-1 are interpreted in terms of a planar cluster of four
trigonal prismatic iron atoms sharing parallel edges and equivalent, bridging
methoxo groups.
The influence of pressure on the electronic absorption spectra of some aromatic molecules and ions
Authors: Hamann SD , Linton M
Published: September 2010

Measurements have been made
of the effects of raising the pressure from 1 bar to 2000 bar on the
frequencies and intensities of the low frequency electronic absorption bands of
57 aromatic molecules and ions in aqueous solution at 25�C. For comparison, measurements
have also been made of frequency shifts produced by changing the solvent from
water to ethanol at atmospheric pressure. ��� A remarkable feature of the results is that
although compression raises the dielectric constant and refractive index of water,
it produces red frequency shifts (shifts to lower frequencies) in the n →
π* bands of molecules. These bands are well known to undergo blue shifts
when one solvent is changed to another of higher polarity at atmospheric
pressure. The apparent anomaly can be explained in terms of McRae's theory of
frequency shifts, as arising from a decrease, with increasing pressure, of the
energy of interaction between permanent dipoles of the solvent and of the
absorbing molecules. The π → π* absorption bands of molecules
generally show red shifts with both increasing pressure and increasing solvent
polarity: this result is also consistent with McRae's theory. The absorption
bands of most of the ions show blue shifts which can be explained by charge
delocalization in the excited states. The intensity changes are in general
agreement with the predictions of current theories of oscillator strengths in
solution. �� The results provide indirect evidence of the
influence of pressure on the ionization constants of excited states of phenols.
The crystal and molecular structure of the bisnorditerpenoid, inumakilactone
Authors: Godfrey JE , Waters JM
Published: September 2010

Inumakilactone, (C18H20O8),
crystallizes in space group P212121 with a =
8.15(2), b = 11.15(1), c = 17.88(2) Ǻ, Z = 4. The structure was solved by
direct methods from visually estimated film data and refined to an R of 0.091
for 1338 independent reflections. The structure of the bisnorditerpenoid
molecule differs from that previously proposed in respect of the orientation of
the epoxy group on ring B.
Amino acid complexes of iron. I. Iron(II) complexes of thioglycollic acid, L-cysteine and related ligands
Authors: Murray KS , Newman PJ
Published: September 2010

A number of solid
complexes, most of which are extremely unstable in air, have been isolated from
reactions between aqueous iron(II) and the sulphur-containing ligands
thioglycollic acid, L-cysteine, L-cysteine methyl ester and DL-methionine. The
1 : 1 and 1 : 2 iron-ligand stoichiometries were obtained. Spectroscopic and
magnetic measurements have been used to deduce possible structures and in most
cases polymeric structures are indicated.
The photochemical formation of a quinone rnethide from coniferyl alcohol
Authors: Miller IJ , Smith GJ
Published: September 2010

It is proposed from flash
photolysis experiments that, on photolysis, coniferyl alcohol gives a free
radical by a monophotonic process and this radical either couples or undergoes
an acid-catalysed water elimination to yield a quinone methide. The possible
significance of this in terms of lignification is discussed.
Solvation of ions. XXV. Partial molal volumes of single ions in protic and dipolar aprotic solvents
Authors: Dack MRJ , Bird KJ , Parker AJ
Published: September 2010

Partial molal volumes at
25� are reported for some 1 : 1 electrolytes, and for triphenylmethane, in
dimethyl sulphoxide, N,N- dimethylformamide, acetonitrile, propylene carbonate,
formamide and hexamethylphosphoramide. The assumption that ΔV�tr(Ph4As+)
= ΔV�tr(BPh4-) was used to obtain ionic
partial molal volumes of transfer from water to the non-aqueous solvents.
Solvent compressibility appears to determine the partial molal volumes of non-electrolytes
and large hydrophobic ions in solution. Values of ΔV�tr for
cations and anions are discussed in terms of ion-solvent interactions,
solvent-solvent interactions and steric crowding of large solvent molecules
around the ions.
Mixed cations of sulphur in disulphuric acid
Authors: Bali A , Malhotra KC
Published: September 2010

Sulphur monochloride and
dichloride form S82+ and SCl3+ ions
when dissolved in disulphuric acid. In the presence of halogens, sulphur
dichloride forms SX3+ ions while sulphur monochloride
forms S2Cl3+ and S2Br3+
which disproportionate to form SX3+ and sulphur. SX3+
ions are formed when sulphur is dissolved in disulphuric acid containing
chlorine or bromine or when halogens are added to the colourless solution of S42+
ions in disulphuric acid.
Electron impact studies. XCVI. Negative ion mass spectra of naturally occurring compounds. Nitrophenyl esters derived from long-chain acids andalcohols
Authors: Bowie JH , Stapleton BJ
Published: September 2010

The positive ion mass
spectra of long-chain alcohols and acids are either devoid of molecular ions or
contain such species in low abundance. The negative ion spectra of
p-nitrophenyl esters of these compounds exhibit pronounced molecular anions,
showing the technique to be a useful analytical method for these classes of
compounds.
Annelated furans. XVI. The stereochemistry of tetrahydrodibenzofurans
Authors: Brewer JD , Elix JA
Published: September 2010

P.m.r, spectroscopy has been used to determine the
relative stereochemistry of a number of 1,2,3,9b-tetrahydrodibenzofurans and
1,2,3,4-tetrahydrodibenzofurans. As the alicyclic component of the
1,2,3,9b-tetrahydrodibenzofuran ring system was inflexible due to the
incorporation of a double bond and fused rings, these molecules were
conformationally ?frozen?. In contrast the alicyclic component of the
1,2,3,4-tetrahydrodibenzofuran ring system was quite mobile and here the conformational
preferences have had to be considered in the allocation of configuration.
Dielectric loss measurements for Bis(pentane-2,4-dionato)oxovanadium(IV) in benzene and dioxan
Authors: Aroney MJ , Angel RL
Published: September 2010

Dipole moments and
dielectric relaxation times determined by dielectric loss measurements are
reported for bis(pentane-2,4- dionato)oxovanadium(IV)
as a solute in benzene and in dioxan. Evidence is presented for VO(acac)2,dioxan complex formation.
Crenulatin, a formyl coumarin from Hesperathusa crenulata (Rutaceae)
Authors: Basa SC
Published: September 2010

A new coumarin, crenulatin
(1), was obtained from the roots of Hesperathusa crenulata. By means of spectroscopic data and chemical
degradation the compound was identified as 6-formyl-7-methoxycoumarin.
Cyclometallation reactions. XIII. Reactions of phenyl-substituted heterocyclic nitrogen-donor ligands
Authors: Bruce MI , Goodall BL , Matsuda I
Published: September 2010

The preparation of some
metallated complexes of manganese or rhenium derived from
2-phenylpyridine,1,4-diphenylquinoxaline, 1- phenylpyrazole,
4-phenylpyrimidine, 1,4-diphenylphthalazineand 2,5- diphenyloxazole
is described.
Di-π-methane photoisomerization of Dimethyl 9-Hydroxy- and 9-Acetoxy-9,10- dihydro-9,10-ethenoanthracene- 11,12-dicarboxylate
Authors: Richards KE , Tillman RW , Wright GJ
Published: September 2010

The di-π-methane
photoisomerization of dimethyl 9-acetoxy- and 9- hydroxy-9,10-dihydro-9,10-ethenoanthracene-11,12-dicarboxylate
has been investigated. The 9-acetoxy compound (28) rearranges regiospecifically
to give dimethyl 4b-acetoxy-4b,8b,8c,8d- tetrahydrodibenzo[a,f]cyclopropa[cd]pentalene-8b,8d-dicarhoxylate
(29), i.e. a dibenzosemibullvalene. Rearrangement of
the 9-hydroxy compound (16) gives one of two keto diesters (17) and (18)
depending on the solvent used. The keto diesters have been shown to be indeno[1,2-
alinden-9-ones epimeric at C 10 and are probably formed by further
rearrangement of one of the expected hydroxydibenzosemibullvalenes
(31). The regiospecific rearrangement of the
9-acetoxy and 9-hydroxy compounds (28) and (16) by alternative pathways is
explained in terms of the effect of hydrogen bonding and the electronegativity of the 9- substituents upon the reaction
profile.
Complexes of carbohydrates with metal cations. V. Syntheses of methyl glycosides in the presence of metal ions
Authors: Angyal SJ , Bodkin CLPFW
Published: September 2010

By the use of complexing
with calcium or strontium ions to alter the anomeric equilibria, the following
methyl glycosides have been synthesized in good yield: methyl
α-D-ribofuranoside, β-D-lyxo- furanoside
and -pyranoside, α- and β-D-mannofuranoside,
α-D- talopyranoside, α- and β-D-talo-furanoside, α-L-gulo-furanoside
and- pyranoside, and all the four methyl glycosides of D-glycero-D-gulo-
heptose.
Disappearing peaks in the nuclear magnetic resonance spectra of flavin coenzymes
Authors: Andrews PR , Fenn MD
Published: September 2010

In alkaline deuterium oxide
solution the N.M.R. spectra of flavin coenzymes exhibit selective broadening
and eventual disappearance of the signals assigned to the flavin ring protons.
The effect follows an induction period during which dissolved oxygen is gradually
depleted. Disappearance of the peaks reflects a reduction in relaxation times,
for which several alternative mechanisms are discussed.
Stability constants of the binuclear species of iron(III) with pentaammine-(substituted salicylato)cobalt(III) complexes
Authors: Dash AC , Nanda RK , Patnaik HK
Published: September 2010

The stability constants of
the binuclear species of iron(III) with some pentaammine(substituted
salicylato)cobalt(III) complexes have been measured spectrophotometrically. At
28�C and μ = 0.6M the values of the stability constants of the species (NH3)5Co{CO2C6H3(X)O)Fe4+
are found to be 4.22(�0.38)x1010 l. mol-1 (X = 5-SO3-),
5.29(�0.79)x1010 l. mol-1 (X = 5-Br) and 4.39 (�0.54)x109
l. mol-1 (X = 5-NO2). Both pKOH of the
cobalt(III) substrates and the stability constants of the binuclear species are
found to decrease in the order 5-Br > 5-SO3- > 5-NO2.
Alkaloids of Ochrosia poweri bail. The stereochemistry of poweridine and the identity of elliptamine and reserpiline
Authors: Johns SR , Lamberton JA , Moore BP , Sioumis AA
Published: September 2010

The alkaloid poweridine from Ochrosia poweri Bail. has been shown to have the same relative
configuration as yohimbine. Elliptamine, previously
obtained from O. poweri, has been identified as reserpiline.
Studies on the application of the quinhydrone electrode in formamide. V. The ionization constants of chloro- and phenyl-substituted acetic acids from E.M.F. measurements at different temperatures and the effect of substituents on the strength of acetic acid in formamide
Authors: Dash UN , Nayak B
Published: September 2010

From the study of the cell

������������������ Ag-AgCl|KCl(m3),
KA(m2), HA(m1), QH2-Q|Pt

(where HA stands for acid)
the ionization constants of chloroacetic acid in formamide have been determined
at 25, 30 and 35�, and those of phenylacetic acid at
nine different temperatures in the range 5-45�. The cell

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

has also been used to
redetermine the ionization constants of chloroacetic acid in formamide in the
range 5-45�; the ionization constants of chloroacetic are in good agreement
with those of an independent study. The effect of substituents on the strength
of acetic acid has been examined in formamide.
Thermal decomposition of alcohols. II. 2-Methylpropan-2-ol
Authors: Johnson WD
Published: September 2010

The thermal decomposition
of 2-methylpropan-2-ol has been investigated from 503 to 612�C, over initial
pressures ranging from 40 to 275 mm and in the presence of toluene from 520 to
602�C. The decomposition is homogeneous and first order with respect to the
initial concentrations of alcohol giving the Arrhenius equation (R = 8.31 J mol-1
K-1)

�������������������������� K=1012.7exp(-249,800/RT)
s-1

for the initial rate. The
decomposition of this alcohol is inhibited by the reaction products, mainly
2-methylpropene, and by the addition of toluene. There are contributions from
the unimolecular elimination of water (k = 1013.6exp(-268,000/RT)s-1)
and from a flee radical process (k = 1011.0 x exp(-227,000/RT) s-1).
A free radical mechanism, which explains the minor products of the reaction and
the varying results of other workers, is proposed.
Extractives of Australian timbers. XV. The synthesis of 7,4'-Di-O-methylbayin
Authors: Eade RA , Mcdonald FJ , Simes JJH
Published: September 2010

The reaction between 2,6-dimethoxyphenylmagnesium bromide
and tetraacetyl-α-D- glucosyl chloride gave mainly α-D-glucopyranosyl-2,6-dimethoxybenzene
(8) and the β-isomer (9). The a-isomer (8) was readily converted by acids
into the /?-isomer (9), whose structure was confirmed by comparison with
authentic material prepared by the degradation of 7,4?-di-O-methylbayin. The
reaction of the tetraacetate of (9) with acetyl chloride in the presence of
anhydrous aluminium chloride gave 3-β-D-glucopyranosyl-2-hydroxy-4-methoxyacetophenone
(11). Condensation of (11) with p-methoxybenzaldehyde
gave the chalcone (15) which, on reaction with selenium dioxide, formed
7,4?-di-O-methylbayin (8-C-β-D- glucopyranosyl-7,4?-dimethoxyflavone) (5).
The reactions of metal sulphides with molten potassium nitrate
Authors: Meehan BJ , Tariq SA
Published: September 2010

The reactions of TiS2,
VS, Cr2S3, MnS, FeS, CoS, NiS,
CuS and ZnS with molten
potassium nitrate were studied. In the melt, Ti, Ni, Cu and Zn metal cations
exhibited acid-base reactions and were precipitated as metal oxides whereas V,
Cr, Mn, Fe and Co metal cations showed
oxidation-reduction as well as acid-base reactions and were converted into VO3-,
CrO42-, MnO2, Fe2O3 and
Co3O4 respectively. The sulphide sulphur in all cases was
oxidized to sulphate and the nitrate melt was reduced to nitrite and oxides of
nitrogen. The stoichiometries of these reactions have been established.
Substituted endo-Tricyclo[3,2,1,02,4]oct-6-enes. II. Selective reductive dechlorination, hydrolysis and other reactions
Authors: Kagi RI , Johnson BL
Published: September 2010

Several reactions of some
chloro-, chloromethoxy- and methoxy- substituted endo-tricyclo[3,2,1,02,4]-oct-6-enes
and endo- tricyclo[3,2,1,02,4]octanes have been investigated. These
reactions include selective reductive dehalogenation and acetal as well as enol-
ether hydrolyses, which, together with other reactions, have furnished some
tricyclo[3,2,1,02,4]octyl derivatives suitable for magnetic
resonance studies.
The effect of solvent on the barrier to internal rotation in p-substituted nitrosoanilines
Authors: Furness AR , Buckley PD , Jolley KW
Published: September 2010

The solvent dependence of
the barrier to internal rotation about the Ar-NO bond
in N,N-dimethyl-p-nitrosoaniline and N,N-diethyl-p- nitrosoaniline has been
investigated by a complete N.M.R. line-shape method. Activation parameters are
reported for the nitrosoanilines in solution in acetone[D6],
chloroform[D], and toluene[D8]. The effect of solvent has been found
to be small.
Cyclometallation reactions. XV. ortho-Metallation of a sulphur-donor ligand
Authors: Bennett RL , Bruce MI , Matsuda I
Published: September 2010

The reaction between benzyl
methyl sulphide and Mn(CH2Ph)(CO)5
affords the ortho-metallated-complex Mn(C6H4CH2SMe)(CO)4.
Some other, non- metallated complexes of the sulphur-donor ligand with
ruthenium and palladium are described; with rhenium, a complex disproportionation
reaction occurs, apparently giving mixed [Re(CO)3(SR)]4
(R = Me, Ph or CH2Ph) complexes.
The influence of pressure on the infrared spectra of hydrogen-bonded solids. I. Compounds with O-H - - - O bonds
Authors: Hamann SD , Linton M
Published: September 2010

Measurements have been made
of the influence of pressures up to 40 kbar on the
hydrogen-bonded OH stretching and bending frequencies of a series of solids
whose hydrogen bonds cover the full range of strengths from very weak to very
strong. The bending frequencies all increase with increasing pressure, and the
stretching frequencies nearly all decrease. The exceptions to this general
pattern are shown by compounds with strong, symmetrical, hydrogen bonds, whose
stretching frequencies increase with increasing pressure. This reversal of
behaviour is consistent with the predictions of a simple model based on Lippincott and Schroeder's empirical potential energy
function for hydrogen bonds.
The crystal structure of a binuclear cobalt(II) complex of a macrocyclic ligand
Authors: Hoskins BF , Williams GA
Published: September 2010

The crystal and molecular
structure of LCo2Br2,CH3OH (where LH2
represents the macrocycle obtained by condensation of two molecules each of
propane-1,3-diamine and 2-hydroxy-5-methyl-isophthalaldehyde) has been
determined by single-crystal X-ray diffraction techniques. The compound
crystallizes in the monoclinic space group P21/c with two molecules
in a cell of dimensions a 9.8723(5), b 16.891(1), c 8.0745(5)Ǻ and
102.06(1)�. Counter methods were used to collect the 2004 independent
reflections above background and the structure was refined by least-squares
methods to a conventional R-factor of 0.049. The structure is molecular, consisting
of discrete binuclear units LCo2Br2,CH3OH,
containing two cobalt(II) atoms separated by 3.158(2) Ǻ. Each cobalt atom
is in an identical pseudo-square-pyramidal environment, in agreement with the
conclusion drawn from the electronic spectrum of the complex, with an N2O2
basal plane and a bromine atom coordinated at the apex. The methanol molecule
is disordered and partially occupies the sixth coordination site of each cobalt,
with a long bond of 2.503(9) Ǻ between the cobalt and the methanol oxygen
atom. The central carbon atom of the propane-1,3-diamine residue is also
disordered, occupying partially each of two positions.
Carbon-13 chemical shifts in some substituted furans and thiophens
Authors: Hearn MTW
Published: September 2010

The 13C N.M.R.
spectra of a number of substituted furans and thiophens have been determined
and individual resonances assigned. The substituent effects which are
comparable to those for substitutedbenzene or pyrrole derivatives are discussed. In 2,5-disubstituted
compounds, some correlation of the observed resonances and values calculated
from the additivity parameters is evident.
Flavonoid intermediates for the synthesis of mopanol trimethyl ether[trans-trans-7,7',8'-Trimethoxyisochromano(4',3':2,3)chroman-4-ol]
Authors: Clark-Lewis JW , Cox DP
Published: September 2010

Preparation of a number of
intermediates for the synthesis of (�)-mopanol
trimethyl ether is described, together with exploratory reactions with model
compounds, and especially with 7-methoxyflavanone-2'-carboxylic acid.
7-Methoxyflavan-4-ol, the initial product from reduction of
7-methoxyflavanone-2'-carboxylic acid with complex metal hydrides, was found to
undergo facile dehydration to a novel intramolecular dibenzyl ether [the cyclic
ether (19)*]. It was noted that the methoxymethyl
group, which may be used as a protecting group for phenols, did not survive the
conditions of methylation with dimethyl sulphate and
potassium carbonate in acetone.
The structure of lividic acid. A depsidone from the lichen Parmelia formosana
Authors: Elix JA , Engkaninan U
Published: September 2010

The depsidone, lividic acid
[1'-carboxy-2',3-dihydroxy-4.methoxy-6-(2"-oxoheptyl)-6-pentyldepsidone](1)
has been isolated from the lichen Parmelia formosana Zahlbr. The
structure of this compound followed from a combination of spectroscopic
properties and chemical interconversions. The overall
substitution pattern of this depsidone was confirmed by methylation with excess
diazomethane, whereupon methyl 3-methoxy-2',4,4'-tri-O-methylisophysodate was obtained. Further, lividic
acid was synthesized from 3-hydroxyphysodic acid by methylation of the
corresponding benzyl ester and subsequent hydrogenolysis.
The synthesis and characterization of azido and cyanato dithiocarbamato nitrosyl complexes of molybdenum : Reduction of coordinated azide in Azidobis(N,N-diethyldithiocarbamato)(dimethyl sulphoxide)nitrosylmolybdenum
Authors: Broomhead JA , Budge JR , Grumley WD , Norman TR , Sterns M
Published: September 2010

The new complexes [MoL(S2CNR2)2(Me2SO)NO]
(R = Et, L = NCO- or N3-; R = Me, L = NCO-)
and (R'4N) [MO(NCO)2(S2CNR2)2NO]
(R = R' = Et; R = Me, R' = Me or Et) have been isolated following the reactions
of cis MO(S2CNR~)2(NO)2]
with sodium azide and potassium cyanate. Use of 15N-labelled
azide has confirmed that molybdenum bonded to a single nitrogen atom must be
involved in the reduction of this ligand to ammonia and dinitrogen in strong
acid.
An ionic chain mechanism for the substitution of an acetate group by the 2-Nitropropan-2-ide ion in benzylidene diacetates
Authors: Freeman DJ , Newcombe PJ , Norris RK
Published: September 2010

The reaction of 16
arylmethylene diacetates [benzylidene diacetates; ArCH(OAc)2] with
lithium 2-nitropropan-2-ide in dimethyl sulphoxide has been studied. With the
exception of aryl rings bearing strongly electron-donating substituents a ready
reaction takes place giving l-aryl-2-methyl-2-nitropropyl acetates in good
yield. The mechanism of this reaction, in which an acetate group is formally
substituted by a (CH3)2C(N02) group, has been
shown to be an ionic chain mechanisminvolving nucleophilic
cleavage of the diacetate to catalytic quantities of the corresponding arene carbaldehyde
(ArCHO) which subsequently undergoes a Henry condensation followed by a
transacetylation reaction. In some cases (nitro heteroaromatic derivatives) a
subsequent elimination reaction gives enol-acetates [ArC(OAc)=C(CH3)2].
Complexes of niobium, tantalum and tungsten pentahalides with fluorinated ditertiary arsines
Authors: Kepert DL , Trigwell KR
Published: September 2010

The fluorinated ditertiary arsines 1,2-bis(dimethylarsino)-3,3,4,4-tetrafluorocyclobutene,
1,2-bis(di- methylarsino)-3,3,4,4,5,5-hexafluorocyclopentene,
and 1,2-bis(dimethy1arsino)-4-fluorobenzene react with niobium and tantalum pentachlorides and pentabromides,
and with tungsten hexachloride, to form MX5(diarsine). These are the first metal complexes containing fluoro ligands coordinated to metal atoms in such high
oxidation states.
Thermal decomposition of alcohols. III. 1-Methylcyclohexanol
Authors: Garnett JL , Johnson WD , Sherwood JE
Published: September 2010

The thermal decomposition
of 1-methylcyclohexanol has been studied over the temperature range 448-506�C.
Decomposition is homogeneous and involves two competing first-order reactions,
dehydration and ketone (propanone and butanone)
formation. Errors are quoted as 90% confidence limits, and R = 8.31 J mol-1
K-1. Dehydration is a concerted, unimolecular
elimination; calculations suggest that the four-centre transition state is
'tight'. Ketone formation involves several free-radical reactions initiated by
either carbon-carbon bond fission at the tertiary carbon or hydrogen atom
abstraction from the alcohol.
Pyrolysis of 1-methylcyclohexene and methylenecyclohexane
Authors: Garnett JL , Johnson WD , Sherwood JE
Published: September 2010

At 495� the decomposition
of both 1-methylcyclohexene and methylenecyclohexane
is homogeneous and first order overall, the rate constants (with 90% confidence
limits) being (6.01 � 0.40) x 10-4 and (6.53 � 0.23) x 10-4
s-1 respectively. Pressure is not a good measure of the rate of
decomposition of either isomer. Toluene inhibits the decomposition of both
olefins, although the effect is more marked for the exo-isomer. The two main
reaction pathways for 1-methylcyclohexene are a reverse Diels-Alder
reaction, giving 2-methylbuta-1,3-diene and ethene,
and a radical chain dehydrogenation to give toluene and benzene. Methylenecyclohexane cannot react through a reverse Diels-Alder reaction and ring fission gives a mixture of C3
and lower hydrocarbons. Dehydrogenation to give benzene and toluene is also
important. Isomerization is a much more favoured pathway for methylenecyclohexane as expected from the relative
thermodynamic stabilities of the isomers.
Synthesis and bromodemercuration of some permercurated arenes
Authors: Deacon GB , Farquharson GJ
Published: September 2010

Pentabromonitrobenzene,
pentabromobenzoic acid, pentabromobenzamide, pentabromoacetanilide, barium
pentabromobenzenesulphonate, 1,2,4,5 - tetrabromo -3-chloro-6-(trifluoromethyl)benzene,
2,3,5,6-tetrabromo-4-methoxytoluene 2,3,5,6-tetrabromo-4-methoxybenzamide,
methyl 2,3,5,6-tetra- bromo-4-methoxybenzoate, and
1,2,5-tribromo-3,4-dichloro-6-fluorobenzene have been synthesized in good yield
by bromodemercuration of the corresponding fully mercurated (permercurated)
arenes, e.g. C6(HgO2CCF3)5NO2,
which were prepared by reaction of an excess of molten mercuric tri-
fluoroacetate with suitable arenes at c. 180-245�. Permercuration of
p-methoxybenzoic acid was accompanied by complete decarboxylation giving, after
bromodemercuration, pentabromo(methoxy)- benzene, which was also obtained in
low yield from preparations of methyl 2,3,5,6-tetrabromo-4- methoxybenzoate and
2,3,5,6-tetrabromo-4-methoxybenzamide. Conditions have been devised for
conversion of phenylmercuric chloride into either a pentamercurated or a hexamercurated
benzene derivative, and hence into pentabromo-or hexabromobenzene. The results
establish permercuration/bromodemercuration as a simple and versatile route to
polybromobenzene.
Transannular methanol adducts of a photo-dimer from methyl 2-Methoxy-1-naphthoate
Authors: Teitei T , Wells D
Published: September 2010

U.v. irradiation of methyl
2-methoxy-1-naphthoate in methanol yielded two kinds of methanol adducts (3)
and (4), along with the cage-compound (2c). These methanol adducts, except
(4c), were easily hydrolysed by acid to ketones (5b), (6a) and (6b), respectively.
In the presence of methyl-1-methoxy-2-naphthoate the yield of the methanol
adducts increased at the expense of the cage-compound.
The kinetic theory of hot reactions. Reactions of ions and excited species
Authors: Cattell FCR
Published: September 2010

Removal of a product in a
manner which conforms to the Estrup-Wolfgang kinetic
theory is not sufficient proof that kinetic excitation alone is involved. There
may therefore be a need to reappraise some high-energy reactions of heavy
halogen atoms where reactions of charged and excited atoms are likely to
interfere.
Catalysed gas phase decompositions. XXIX. 2,2-Dimethoxypropane and trifluoroacetic acid
Authors: Stimson VR , Taylor ECTJW
Published: September 2010

Trifluoroacetic acid
catalyses the decomposition of 2,2-dimethoxypropane into methyl isopropenyl ether and methanol at 224-291� with rate:

k2 = 1014,30 exp(-94980/8.314T) s-l ml
mol-l

The products recombine on
being condensed together. The order of catalytic effectiveness is:

HBr > CF3COOH
> HC1 � CH3COOH
Crystal structure of Bis(O-ethylxanthato)-1,10-phenanthrolinecadmium(II)
Authors: Raston CL , White AH
Published: September 2010

The crystal structure of
the title compound, [Cd(C12H8N2)(CS2OEt)2],
has been determined by X-ray crystallography using diffractometer data at 295 K
and refined by full matrix least squares to a residual of 0.06 for 1350
'observed' reflections. Crystals are orthorhombic, P bcn, a = 14.870(4), b =
14.549(8), c = 10.249(1) �, Z = 4.
The molecule lies on a twofold crystallographic axis; the phenanthroline
ligand is symmetrically bidentate [Cd-N, 2.386(8) �], while the ethylxanthateligand is somewhat
asymmetric [Cd-S, 2.647(3), 2.727(3)4 with a correspondingly asymmetric C-S
geometry [C-S, 1.72(1), 1.66(1) �].
Reaction of diarylcarbinols and diarylolefins with thionyl chloride: A synthesis of 3-arylbenzothiophens
Authors: Blatt H , Brophy JJ , Colman LJ , Tairych WJ
Published: September 2010

Treatment of
1,l-diphenylalkan-1-ols and 1,l-diphenylalk-l-enes with thionyl
chloride gives 3-phenyl-benzo[b]thiophens in approximately 50% yields. Also
formed in these reactions are 2-chloro-1,l- diphenylalk-l-enes
and 1,2-dichloro-1,l-diphenylalkanes. 5,6-Dihydrobenzo[b]naphtho[l,2-dlthiophen
was formed from l-phenyl-3,4-dihydronaphthalene under these conditions.
General acid and general base catalysed hydrolysis of 4-Methyl- and 4-Nitro-phenylurea
Authors: Mollett KJ , O'Conner CJ
Published: September 2010

The hydrolysis of 4-methyl-and
4-nitro-phenylureas has been studied in buffer solutions at 101.0�C from pH 0
to 14, and parameters for general acid and general base catalyses have been
calculated.
Acid-catalysed reactions of the 7,8-Epoxyisopimar-15-enes
Authors: Blunt JW , Boyd GS , Hartshorn MP , Munro MHG
Published: September 2010

The acid-catalysed
reactions of 7α,8α-epoxyisopimar-15-ene (9) and 7β,8β-epoxyisopimar-15-ene(10)
are described. No tetracyclic products were identified among the products from
these reactions, and the requirements for such cyclization reactions are discussed.
Some piperidinomethyl quinols and quinones
Authors: Cameron DW , Cracknell RH
Published: September 2010

Tris- and tetrakis-piperidinomethylquinols have been synthesized by the Mannich procedure. The corresponding quinones, along with
those of related compounds, have been obtained as nitrate salts by oxidation
with oxides of nitrogen.
Investigation of ring and nitrogen inversion in N-Methyl-1,2,3,4-tetrahydroisoquinoline by dynamic N.M.R. methods
Authors: Davis M , Hugel HM , Lakhan R , Ternai B
Published: September 2010

ΔG? for the overall
ring and nitrogen inversion barriers in N-methyl-1,2,3,4-tetrahydroisoquinoline
has been found to be 35.2 kJ/mol in vinyl chloride, and 50.2 kJ/mol in aqueous
solution. Both measurements are believed to reflect the height of the nitrogen
inversion barrier. The difference is attributed to hydrogen bonding in the
aqueous solution. At low pH anomalous inversion rates were obtained.
The reaction of formaldehyde with mixtures of arylhydrazines and amines
Authors: Lamberton JA , Nelson ER
Published: September 2010

Phenylhydrazine, aniline and formaldehyde react under appropriate
conditions to give a high yield of phenyl(phenylazoethyl)amine
(1). Under analogous conditions N-methyl-N-phenylhydrazine,
N-methylaniline and formaldehyde give
2-(N-methy1anilino)acetaldehyde methylphenylhydrazone
(2). With morpholine and phenylhydrazine
formaldehyde gives a product C24H34N6O2
considered from spectroscopic evidence to be 2,5-di(morpholinomethyl)-1,4-diphenylhexahydro-s-tetrazine
(4) derived from an N-Mannich reaction between morpholine and 1,4-diphenylhexahydro-s-tetrazine.A change in the relative
proportions of phenylhydrazine, aniline and
formaldehyde results in the formation of a further compound C44H46N10
considered from spectroscopic data to be 2,5-di[Nphenyl-N-(phenylazoethyl)aminomethyl]-l,4-diphenylhexahyo-s-tetrazine
(7) derived from an N-Mannich reaction between
phenyl(phenylazoethyl)amine (1) and 1,4-diphenylhexahydro-stetrazine.
Tri-O-benzylidene-D-glucitol
Authors: Brecknell DJ , Carman RM , Kibby JJ , Nicholas LT
Published: September 2010

The known tri-O-benzylidene
derivative of D-glucitol has structure (la) while a
new diastereomer has structure (lb).
Theory of spin relaxation in the limit of slow motion. Nuclear and electron spin relaxation in paramagnetic transition-metal complexes
Authors: Pegg DT , Doddrell DM
Published: September 2010

A theory of spin relaxation
is developed which can be applied to cases where the Redfield limit (T2
� tt) does not hold. A simplification over the conventional approach
is achieved by working entirely in a reference frame in which the initial
density matrix is diagonal. This allows the general relaxation equations to be
written in a simple analytic form without the need for perturbation theory. In
the short correlation time limit this general form reduces to the usual
Redfield equations for the relaxation times. In the long correlation time limit
a corresponding result can be obtained, but is dependent on the assumed
ensemble distribution. Electron spin relaxation by
modulation of the quadratic zero-field splitting for S = 3/2 is treated
explicitly. The theory is used to analyse proton spin relaxation in some
halogenobis(N,N-diethyl-dithiocarbamato)iron(111) complexes.
The structure of the lichen depsidone hydroxyphysodic acid. A carbon-13 magnetic resonance study
Authors: Jones AJ , Elix JA , Engkaninan U
Published: September 2010

Unequivocal evidence for
the structure of the lichen depsidone 3-hydroxyphysodic acid has been provided
by analysis of long-range carbon-13-hydrogen coupling interactions and
carbon-13 chemical shifts. This approach was also used to establish the isocoumarin structure (16) for that of the key decarboxycyclodehydration product obtained by degradation
of 3-hydroxyphysodic acid. The breakdown of some carbon-13 additivity
effects in the sterically congested ring is discussed. A possible mechanism for
the formation of the isocoumarin (16) is outlined.
Steric effects in cyclization reactions
Authors: Hamann SD , Pompe A , Solomon DH , Spurling TH
Published: September 2010

Calculations of geometric
probability factors indicate that steric effects are important in determining whether
the cyclization of β-substituted diallylmethylammonium ions results in
five- or six-memberedrings. Evidence is obtained
of the direction of intramolecular attack.
Chemical studies of the Proteaceae. VIII. The conversion of grevillol into rapanone and experiments on the synthesis of ardisiaquinone A
Authors: Croft JA , Ritchie E , Taylor WC
Published: September 2010

Oxidation of grevillol dimethyl ether gave
2-methoxy-6-tridecyl-1,4-benzoquinone which on Thiele-Winter acetoxylation afforded the triacetate of
5-methoxy-3-tridecylbenzene-1,2,4-triol. Hydrolysisfollowed by oxidation and
demethylation then yielded rapanone.By the application of a
known reaction sequence involving the Stevens rearrangement, dodec-6-ynedioic
acid was converted into 5,5'-(hexadec-8-yne-1,16-diyl)diresorcinol
tetramethyl ether which was similarly oxidized to the
related diquinone. This substance could not be
converted into ardisiaquinone A because Thiele-Winter
acetoxylation was accompanied by attack on the triple
bond.However,
5,5'-(hexadecane-l,l6-diyl)diresorcinol dimethyl
ether by successive oxidation, acetoxylation, hydrolysis
and oxidation gave dihydroardisiaquinone A.
Diterpenoids. XXXIV. The C13 configuration of tetrahydroabienol
Authors: Carman RM , Zerner GW
Published: September 2010

Tetrahydroabienol is a quasiracemic compound
formed from C13 epimers.
Theory of injection photovoltages in organic insulators
Authors: Bonham JS
Published: September 2010

Development of an
open-circuit photovoltage, U, in an organic insulator by photoinjection of
charge carriers from the electrodes is treated theoretically. In the
single-carrier case (both electrodes injecting the same carrier) it is shown
that, in the absence of surface traps, U increases at a rate of 60 mV per
decade of light intensity, II, above a threshold value of II. Photoinjection
from the back (unilluminated) electrode by incompletely absorbed light causes U
to become independent of ll at high light intensity. The same process may also
cause U to change sign as the wavelength approaches an absorption minimum of
the organic. Traps in the bulk of the insulator do not affect the
single-carrier photovoltage, but traps at the surface may complicate the intensity
dependence of U if they are involved in the injection mechanism. They may for
example cause U to decrease and change sign at high n. Only shallow surface
traps are considered. Possible effects of surface states are discussed briefly.
The major assumption of this paper--neglect of all but injected charge
carriers-breaks down in principle in the two-carrier case. However, if there
are no sources of photovaltage in the bulk of the insulator the two-carrier
case gives a stronger dependence of U on II, and no saturation or possibility
of change of sign with wavelength variation. Predictions of the model are shown
to agree with the results for a number of systems reported in the literature.
Depsidone synthesis. VII. Vicanicin and norvicanicin
Authors: Sargent MV , Vogel P , Elix JA , Ferguson BA
Published: September 2010

The lichen Psoroma sphinctrinurn (Mont.) Nyl.
occurs in two or more chemical strains. 2,7-Dichloro- 3 - hydroxy -8-methoxy-
1,4,6,9 - tetramethyl - 11H- dibenzo[b,e][l,4]dioxepin- 11-one (vicanicin) (2),
a known depsidone, is a metabolite of one strain, and 2,7-dichloro-3,8-dihydroxy-1,4,6,9-tetramethyl-1lH-dibenzo[b,e][1,4]dioxepin-11-one
(norvicanicin) (3) is shown to be a metabolite of another. By oxidative
coupling of an appropriate benzophenone (7) and subsequent steps both of these
metabolites were synthesized.
Metal template reactions. IX. Syntheses of 'dibenzocorromin' and related complexes from 2,2'-(Iminoprop-2-enylideneimino)dibenzaldehyde
Authors: Black DSC , Hartshorn AJ
Published: September 2010

Macrocyclic metal complexes
containing ligand chromophores similar to that of corrin have been synthesized by metal template reactions of
2,2'-(iminoprop-2-enylideneimino)dibenzadehyde (5)
with nicke1(11), copper(11) or cobalt(11) acetates and diamines.
The dialdehyde (5) was prepared by condensation of o-aminobenzaldehyde
with malondialdehyde.
Iminyl radicals in gas-phase synthesis. II. Formation of a-branched nitriles from cycloalkanone azines
Authors: Crow WD , Khan AN
Published: September 2010

Gas-phase pyrolysis of cyclopentanone and cyclohexanone azines
results in the formation of iminyl radicals. These
undergo ring cleavage to the ω-cyanoalkyl
radicals, which stabilize, by internal hydrogen-atom transfer, to the
corresponding α-cyanoalkyl radicals.
Fragmentation of the latter yields acrylonitrile and
alkyl radicals, which can recombine with the α-cyanoalkyl
radicals to form α-alkylated nitriles. The mechanisms involved are
discussed with reference to isotopic labellingstudies.