bluuebunny/crossref_metadata_2025 huggingface dataset:
Diels-Alder additions of hexachlorocyclopentadiene to some 7-substituted norbornadienes
Authors: Byrne LT , Rye AR , Wege D
Published: September 2010

In contrast to the normal
addition mode of hexachlorocyclopentadiene (3) to norbornadiene, which yields mainly (but not exclusively) aldrin having the endo-exo-1,4:5,8-dimethanonaphthalene
skeleton, the reaction of (3) with norbornadien-7-yl acetate gives three
adducts: 1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-endo-endo-1,4:5,8-dimethanonaphthalen-syn-9-yl and -anti-9-yl
acetates [(7) and (9)] and the 'normal'
1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-endo-exo-1,4:5,8-dimethanonaphthalen-syn-9-yl acetate (11). The addition of
(3) to 7-t-butoxynorbornadiene yields mainly the anti-9-t-butoxy-endo-endo
adduct, analogous to (9), while the addition of (3) to 7-methylnorbornadiene
gives mainly syn-9-methyl-endo-exo-adduct,analogous to (11). The
structure of these adducts has been determined by spectroscopic (N.M.R. and
infrared) and chemical (photochemicalcyclization of the endo-endo systems) means.
Studies in the synthesis of furocoumarins. XXIII. Synthesis of substituted psoralenes from 2-bromoresorcinol
Authors: Shah KR , Trivedi KN
Published: September 2010

The synthesis of four
different substituted psoralenes from 2-bromoresorcinol is described.
Metal complexes of 1,10-Phenanthroline derivatives. VIII. Complexs of 1,10-Phenanthroline-2-carbaldehyde imines
Authors: Goodwin HA , Mather DW
Published: September 2010

Iron(11), cobalt(11) and
nickel(11) complexes [ML2] [BF4]2 of a series
of related tridentate imine derivatives of 1,l0-phenanthroline-2-carbaldehyde [N-(l,l0-phenanthrolin-2-ylmethylene)alkyl-(or
aryl)amines in which the alkyl or aryl group is methyl, ethyl, propyl,
isopropyl, butyl, s-butyl, t-butyl, phenyl or benzyl] are described. From the
electronic spectra of the nickel complexes an order of field strengths is
established which correlates reasonably well with the bulkiness of the imine
moiety. All the ligands except that where R = But effect
spin-pairing in iron(11) at room temperature. When R = But the
iron(11) complex is essentially high-spin at room temperature but is
predominantly low-spin at 83 K. The magnetism of this substance is typical for
that of iron(11) systems in which a gradual spin transition, 5T2
←→ lAl occurs. In
the complexes where R = Bu Bu8, Ph, a significant rise in the
magnetic moment above room temperature is observed, indicating the presence of
some metal atoms in the 5T2 state. Certain of the ligands
of high field strength (R = Me, Et, Pr, Pr1) yield cobalt(11)
complexes whose magnetism is indicative of a gradual quartet-doublet
transition. The remaining cobalt(11) complexes are high spin.
Cyclometallation reactions. IX. 2-(Phenylazo)phenyl complexes of iridium(III)
Authors: Bruce MI , Goodall BL , Stone FGA , Thomson BJ
Published: September 2010

Iridiurn(111) complexes containing chelating
2-(pheny1azo)phenyl ligands have been obtained by oxidative addition of
azobenzene or 2-bromoazobenzene to IrCl(CO)(PPh3)2;
some reactions of these derivatives are also described.
The reaction of carboxylic acids with epoxides using lithium naphthalenide
Authors: Fujita T , Watanabe S , Suga K
Published: September 2010

Lithium naphthalenide
reacts with carboxylic acids in the presence of diethylamine to give the α-anions
of lithium carboxylates. Reaction of these anions with various epoxides gives
the corresponding y-hydroxy acids in good yield. The γ-hydroxy acids easily
cyclize to give γ-butyrolactones.
Bromo Analogues of the Systemic Fungicides Triforine and N-(2,2,2-Trichloro-1-methoxyethyl) Formamide
Authors: Carter G , Chamberlain K , Summers L , Wain R
Published: September 2010

N,N-[Piperazine-l,4-diylbis(2,2,2-tribromoethylidene)]bisformamide,
N-(2,2,2-tribromo-1-methoxyethyl) formamide
and related arylaminoethyl- and aryloxyethyl-formamides have been prepared and examined
as fungicides against a number of plant pathogens. The most interesting
compounds are N-(2,2,2-tribromo-1-methoxyethyl)formamide
and N-(2,2,2-tribromo-1-s-butyloxyethy1)formamide
which show considerable systemic fungicidal activity against wheat mildew,
Erysiphe graminis, when applied to plant
roots.
Colouring matters of Australian plants. XVII. Synthesis of lomandrone
Authors: Cooke RG , Rainbow IJ
Published: September 2010

The structure of lomandrone, one of the principal pigments of Lomandra hastilis, is confirmed
as 3-ethyl-5-hydroxy-2,6,7-trimethoxy-l,4-naphthoquinone by a synthesis
starting from gallic acid.
The structure of alectoronic acid and related lichen metabolites
Authors: Elix JA , Ferguson BA , Sargent MV
Published: September 2010

Spectroscopic evidence is
presented to show that the lichen depsidone alectoronic acid is a tautomeric
compound which exists predominantly in a novel, six-membered, pseudo-acid
(hydroxy lactone) form. The existence of this pseudo-acid tautomer was confirmed
chemically by esterification with acidic methanol, whereupon the corresponding
pseudo-ester was produced. P.m.r. spectroscopy
indicated that the related depsidone, α-collatolic acid, and the lichen
depside, microphyllinic acid, exhibit analogous ring-chain tautomerism.
Routes to 18-nor and 19-nor steroids
Authors: Chapman JC , Pinhey JT
Published: September 2010

17-Oxo-18-nor-5α,13β-androstan-3β-yl
acetate (6) and the 13α-epimer (7) have been synthesized by two routes,
both of which involve initially an ?abnormal? Beckmann rearrangement of the
oxime of 17-oxo-5α-androstan- 3β-yl acetate to the 13,17-seco nitrile
(4). In the shorter but lower- yielding sequence, the mixture of epimeric
epoxides obtained from (4) was converted into a mixture of (6) and (7) in 25%
yield with boron trifluoride in refluxing toluene. A higher yield was achieved
by a Dieckmann condensation of the nitrile esters (9)
and (10), readily prepared from the above epoxides via the aldehydes. ��� The latter method was also found to be
useful for the synthesis of 1-oxo-19-nor-5α,10β-androstan-17β-yl
acetate (22) from 1-oxo-5α- androstan-17β-yl acetate.
Competitive Michael and carbonyl addition of hydrazines to 4-Benzylidene-2-phenyloxazol-5(4H)-one: Synthesis of some new Pyrazolidin-3-ones
Authors: Iyengar DS , Prasad KK , Venkataratnam RV
Published: September 2010

2-Aryl- and
-heteroaryl-4-benzamido-5-phenylpyrazolidin-3-ones (8), (10), (12a), (12b),
(14a) and (14b) were prepared by the action of the respective hydrazines on
4-benzylidene-2-phenyloxazol-5(4H)-one (1) in refluxing ethanol. The coproducts
formed in lower yields were the isomeric cyclic products (9), (11) and (13),
tentatively formulated as 1-substituted pyrazolidin-3-ones and the corresponding
hydrazides (3)- (6) of α-benzamidocinnamic acid.
However, phenylhydrazine produced more of the hydrazide than of the
4-benzamido-2,5-diphenylpyrazolidin-3-one (3). When the reaction was carried
out in refluxing benzene, the major product was the hydrazide irrespective of the
hydrazine used. It is concluded that pyrazolidin-3-ones were formed by an
initial Michael addition of hydrazine to the benzylidene carbon of the
azlactone (1) followed by a cyclization which involves an opening of the
azlactone ring.
Reactions of substituted hydroxybenzofurans. III. Acylation of 5- and 6-Methoxy-2,3-diphenylbenzofurans
Authors: Hishmat OH , Abd el Rahman AH
Published: September 2010

Vilsmeier-Haack formylation of 5-methoxy-2,3-diphenylbenzofuran (1a)
and 6-methoxy-2,3-diphenylbenzofuran(2a) gave the corresponding 6- formyl
derivative (1b) and 5-formyl derivative (2b) respectively. Friedel-Crafts
acetylation of (1a) and (2a) gave products of the same orientation. The
aldehydes (1b), (2b) were converted by standard methods into the corresponding
methyl ketones and substituted 2,3- diphenyl-6H-furo[2,3-g][1]benzopyran-6-ones
and 2,3-diphenyl-7H- furo[3,2-g][1]-benzopyran-7-ones respectively.
2,2'-Vinylidenedipyridine and its diquaternary salts
Authors: Eckhard IF , Summers LA
Published: September 2010

2,2?Vinylidenedipyridine,
the first example of a vinylidenedipyridine, has been
prepared from di-2-pyridyl ketone by way of a Wittig reaction. It forms
diquaternary salts with dimethyl sulphate and ethylene dibromide.
The Stern-Geary and related methods for determining corrosion rates
Authors: Matthews DB
Published: September 2010

Calculation of the current-potential relations for corroding electrodes as a function of the cathodic
and anodic transfer coefficients and as a function of the difference between the corrosion and reversible
potentials demonstrates the deficiencies of the Stern-Geary equation for determining corrosion rates.
The calculations also demonstrate that a linear current-potential relation is not predicted except
over very small ranges of potential, e.g. 2 mV. As a consequence, it is essential in using the Stern-
Geary and related methods to determine the slope dE/di at the corrosion potential.
The Stern-Geary method is not applicable for systems where the corrosion potential is close to
the reversible potential for either of the participating reactions and fortuitous linearity of currentvoltage
plots may be erroneously interpreted as indicating that the Stern-Geary method is applicable.
Methods of determining the corrosion rate which depend upon measuring the difference ΔE in
corrosion and reversible potentials are not likely to be successful because of their sensitivity to the
value of ΔE. A new derivation of the slope dE/di at the corrosion potential is presented and it is shown that
the Stern-Geary and Mansfeld-Oldham equations may be derived as special cases. This new derivation
is not immediately useful for determining the corrosion rate but it is shown that by measuring
the dependence of the corrosion potential on concentration of cathodic reactant then the new
derivation can be useful for rapid and accurate corrosion rate measurements even for small values
of ΔE.
Physico-chemical studies in non-aqueous solvents. X. Conductance and solvation studies of 1 : 1 electrolytes in N,N-dimethylacetamide
Authors: Paul RC , Banait JS , Narula SP
Published: September 2010

Conductances of some 1 : 1
electrolytes have been measured in the concentration range 1-120 x 10-4
mol l-1 in N,N-dimethylacetamide at 25�. The conductance data have
been analysed by Fuoss-Onsager-Skinner equations for dissociated and associated
electrolytes, and limiting equivalent conductances, ion-size parameter and
association constants (where appropriate) for various electrolytes have been
obtained. The ion-size parameter (3.7 � 0.3Ǻ) has been found to be about
the same for all the electrolytes. Alkali metal salts are fully dissociated
while the substituted ammonium salts are slightly associated in this solvent.
The ionic association increases with increase in the size of cations. Transference
numbers of lithium chloride, potassium thiocyanate and silver perchlorate have
also been measured in the concentration range 1.1-18.4 x 10-2mol l-1
in this solvent. Limiting cation transference numbers are determined from the
linear plots of cation transference numbers against square root of
concentration. Ionic mobilities, effective ionic radii and solvation numbers of
various ions in solution have been calculated. Higher solvation numbers of
cations than those of anions of comparable sizes are consistent with the
aprotic nature of the solvent.
Infrared spectra and hydrogen bonding in some methyl α-glycopyranosides
Authors: Michell AJ
Published: September 2010

Spectra in the OH
stretching and out-of-plane bending regions of four methyl α-glycopyranosides
of known crystal structure have been obtained at ambient and sub-ambient
temperatures. Partial deuteration has been used to uncouple the stretching
vibrations and assist in assignments of the out-of-plane bending vibrations.
Use of a paramagnetic broadening agent to assign the 13C N.M.R. spectra of some aliphatic amines. Substituent effects of the amino group
Authors: Doddrell D , Burfitt I , Riggs NV
Published: September 2010

Copper acetylacetonate
produces differential line broadening in the 13C N.M.R. spectra of
some simple aliphatic amines. The effect operates through electron-nuclear
hyperfine coupling and exhibits a strong dependency on the relative geometrical
arrangement of the interacting centres. The effect is useful in assigning the 13C
N.M.R. spectra of some isomeric methylcyclohexylamines.
Substituent effects of the amino group are discussed.
Synthesis of meta-Divarinol and Olivetol depsides
Authors: Elix JA , Norfolk S
Published: September 2010

Unambiguous syntheses of
the lichen depsides scrobiculin, sekikaic acid, homosekikaic acid, boninic
acid, ramalinolic acid, paludosic acid, merochlorophaeic acid,
cryptochlorophaeic acid and 4-O- methylcryptochlorophaeic acid are reported.
Dye-sensitized photooxidation of some substituted 1,3-Diphenyl-2-pyrazolines
Authors: Evans NA
Published: September 2010

1,3-Diphenyl-2-pyrazolines substituted in the 4- and
5-positions with phenyl groups undergo dye-sensitized photooxidation at widely
different rates depending on the substitution pattern. Depending on both the
solvent and the substitution pattern, two types of reaction are usually
observed: (a) dehydrogenation to the corresponding pyrazole and (b)
incorporation of oxygen with ring opening to yield carbonyl compounds.
Infrared, N.M.R. and mass spectral studies on 3-Amino-4-aryl-5-aryl(or alkyl)imino-4,5-dihydro-1,2,4-thiadiazoles
Authors: Joshua CP , Rajasekharan KN
Published: September 2010

Some
3-amino-4-aryl-5-aryl(or alkyl)imino-4,5-dihydro-1,2,4-thiadiazol, previously
prepared and assigned structures on chemical evidence, are now confirmed in
structure by a detailed study of their spectra. While i.r, and n.m.r, spectral
data confirm the nature of the ring present in these compounds, mass spectra
confirm the assignment of substituents on the ring. Mass spectra of these
compounds exhibit specific fragmentation patterns and consequently are useful
in structure elucidation of substituted 4,5-dihydro-1,2,4-thiadiazoles.
Chemistry of the Podocarpaceae. LII. Demethylation involving partial inversion of cofiguration at two remote centres
Authors: Cambie RC , Davis BR , Hayward RC , Woodgate PD
Published: September 2010

Treatment of optically pure
(+)-12-methoxypodocarpa-8,11,13-triene (2) with HI/HBr/HOAc and a trace of H3PO2
gives, as the major product, a non-racemic mixture of (+)-podocarpa-8,11,13-trien-12-ol
(3) and its enantiomer (14).
Substituent effects on the stability and reactivity of norbornenyl and nortricyclyl radicals
Authors: Burrows TG , Jackson WR
Published: September 2010

The products of addition of
thioacetic acid to norbornadiene, and of tributyltin hydride and triphenyltin hydride
reduction of exo-2-bromo- anti-7-thioacetoxynorborn-5-ene (7), and
trans-5-bromo-3- thioacetoxynortricyclene (8), have
been examined. In contrast to results obtained with the corresponding acetoxy
compounds, the product ratios vary with the reducing reagent and the starting
material and the ratio of (rate of rearrangement)/(rate of hydrogen atom
abstraction) is significantly less for the thioacetoxy
substituted radicals.
Iminocyclopropa[l]phenanthrenes by the condensation of diarylaminoguanidines with 9,10-phenanthraquinone - a reinvestigation
Authors: Halton B , Harrison SAR , Spangler CW
Published: September 2010

Heating of the
phenanthraquinone 4-aryl-3-(arylimino)semicarbazones (3a) and (3b) led to the phenanthraquinone
4-arylsemicarbazones (6a) and (6b). A statement in the literature that this reaction
gives rise to 1-arylimino-1H-cyclopropa[l]phenanthrenes could not be confirmed.
The constitution of (6a) was confirmed by independent synthesis from 4- phenylsemicarbazide
and phenanthraquinone.
Molecular asymmetry in sugar derivatives
Authors: Gall RE , Tarasoff L
Published: September 2010

The N.M.R. spectra of a
series of derivatives of the four trihydroxyglutaric acids (1)-(4) have shown non-equivalence
of the hydrogen atoms attached to C 2 and C 4 in the D- and L-arabino series (3) and(4) which is not observed in the
derivatives of symmetrical D- ribo and D-xylo acids (1) and (2). Vicinal coupling constants have led
to predictions regarding the major conformations.
Interactions of 7-diethylamino-4-methylcoumarin with wool and indole
Authors: Zdysiewicz JR
Published: September 2010

At relatively low
concentrations, the fluorescence emission and excitation spectra of
7-diethylamino-4-methylcoumarin (dmc) on wool are structureless and shifted to longer wavelengths compared
with the spectra of dmc on polyethylene. With certain
reservations, these effects are interpreted to signify an interaction between dmc and wool. The interactions between dmc
and indole were investigated in paraffin in an effort to understand the nature
of the interactions between dmc and wool. From
ultraviolet and infrared spectroscopy and from thermodynamic data, it is
proposed that dmc and indole form a hydrogen- bonded
complex involving the carbonyl group of dmc and the
NH group of indole. There are indications of a further interaction between the
two molecules.
Redox reactions in acetic anhydride
Authors: Malhotra KC , Katoch DS
Published: September 2010

Redox reactions in acetic
anhydride have been followed both conductometrically and visually. Chlorine,
bromine, iodine, iodine monochloride and nitrosyl chloride have been used as
oxidizing agents and phosphorus(III), arsenic(III) and antimony(III) compounds
as reducing agents. Some new compounds have been isolated and characterized.
Synthesis of phenethanolamine derivatives with potential β-adrenergic antagonistic activity
Authors: Pasaribu SJ , Williams LR
Published: September 2010

The mass spectra of
bromonitroacetophenones, intermediates in the synthesis of phenethanolamine
derivatives containing a nitro and bromo group in the aryl ring, have been
studied. The acetophenones were converted into the corresponding α,β-epoxystyrenes, which were then treated with
various amines, and proton magnetic resonance and mass spectral studies were
used to confirm the direction of ring opening and purity of the products.
Heterocyclic ambident nucleophiles: The alkylation of sodium N6-acyladenides
Authors: Rasmussen M , Chan JHS
Published: September 2010

In the alkylation of N6-acyladenines
in dimethylformamide, changes in the site of alkylation caused by variations in
the alkylating agent and the acyl group were investigated. Almost exclusive
alkylation at the imidazole ring nitrogens, N7 and N9, was observed in all
cases. The alkylation pattern, expressed as the N7 : N9 ratio was, however,
found to vary widely, from 40 : 1 to 1 : 13, with changes in the alkylating
agent. These divergent alkylating patterns are rationalized by considering the
looseness or tightness of the SN2 transition states involved for a
particular alkylating agent; these considerations then allow the relative
importance of the thermodynamic, charge density and, particularly, steric factors
to be assessed. Cases of ?abnormally? high preference for alkylation at the
hindered N7 position are explained in terms of a special hydrogen bonding
association between the N6-acylamino NH group of the substrate and
an acceptor group in the alkylating agent.
Colouring Matters of Australian Plants. XVIII. Constituents of Anigozanthos rufus
Authors: Cooke R , Thomas R
Published: September 2010

Four new phenylphenalenone
pigments have been isolated from Anigozanthos rufus Labill. and their structures
have been determined. The known compound 2-phenylnaphthalic anhydride was also isolated
from the plant. The synthesis of one of the new pigments, and of some related
compounds, is described.
Annelated furans. XV. The autoxidation of tetrahydrodibenzofurans
Authors: Brewer JD , Elix JA
Published: September 2010

The autoxidation of N-phenyl-1,2,3,9b-tetrahydrodibenzofuran-1,2-dicarboximide and the corresponding
4-methyl and 4-phenyl derivatives, in benzene solution, produced a mixture of the
respective stereoisomeric 4-hydroperoxy-1,2,3,4-tetrahydrodibenzofuranisn each case. This reaction
was shown to be a ground state process and resulted in the rearrangement of the 1,2,3,9b-tetrahydrodibenzofuran
system to the thermodynamically more stable 1,2,3,4-tetrahydrodibenzofuran moiety.
The introduction of a 4-acetoxy or 3-methoxycarbonyl substituent into the 1,2,3,Yb-tetrahydrodibenzofuran
system appeared to facilitate the autoxidation process, and the initial N-phenyl-1,2,3,9b-tetrahydrodibenzofuran-
1,2-dicarboximides could not be isolated in these instances.
Some reactions of c-4- and t-4-hydroperoxy-4-methyl-N-phenyl-1,2,3,4-tetrahydrodibenzofuran-r-1,c-2-dicarboximide have been investigated. These hydroperoxides decomposed on warming in
chloroform solution to produce 4-methyl-N-phenyl-1,2-dihydrodibenzofuran-1,2-dicarboximide and
4-methyl-N-phenyldibenzofuran-1,2-dicarboximide In addition to the latter product, treatment of
the mixture of hydroperoxides with p-toluenesulphonic acid in chloroform solution resulted in
cleavage of the heterocyclic ring to give 5-ethoxy-3-(2'-hydroxyphenyl)-5-methyl-4-oxo-N-phenylcyclohex-
2-ene-1,2-dicarboximide (44).
The autoxidation of 4-methyl-1,2,3,9b-tetrahydrodibenzofuran-1,2-dicarboxylic acid anhydride
(48) proceeded by an alternative route and gave a novel peroxylactone, 6-methyl-3-oxo-3,3a,4,5-
tetrahydrobenzofuro[2,3-h]-1,2-benzodioxoe-4-carboxylic acid (50), in addition to the fully aromatic
species, 4-methyldibenzofuran-1,2-dicarboxylic acid anhydride (59) The synthesis and autoxidation
of 1-acetyl-4-methyl-1,2,3,9b-tetrahydrodibenzofurawn as also studied.
Finally the reaction of N-phenylmaleimide with 2-(3'-benzofuranyl)but-1-ene (72) was shown to
give 1-ethyl-N-phenyl-2,3,4,4a-tetrahydrodibenzofuran-3,4-dicarboximide (73 ). Autoxidation of the
latter compound proceeded with rearrangement to give r-1-ethyl-1-hydroperoxy-N-phenyl-1,2,3,4-
tetrahydrodibenzofuran-t-3,t-4-dicarboximide (74).
Annelated furans. XVII. The Wittig reaction of benzofuranones
Authors: Chan JHT , Elix JA , Ferguson BA
Published: September 2010

Benzofuran-3(2H)-ones have
been shown to undergo efficient Wittig reactions with resonance-stabilized
phosphoranes at elevated temperatures, thus providing a convenient synthesis of
benzo-furans functionally substituted at the 3-position. The initial reaction
products, the 3-methylene-2,3-dihydrobenzofurans, were found to undergo facile
thermal, acid- or base-catalysed rearrangement to the corresponding
benzofurans. The reaction of benzofuran-3(2H)-ones with acetylmethylene-triphenylphosphorane
were complicated by competing aldol condensations in
which 2-isopropylidene-benzofuran-3(2H)-ones were formed. ��� Benzofuran-2(3H)-one displayed parallel
reactivity with these phosphoranes and afforded the corresponding 2-substituted
benzofurans. In these cases rearrangement of the initial Wittig products to the
corresponding benzofurans was more facile and even when lower temperatures and
shorter reaction times were employed only the rearranged products were
observed. �� The 3?-benzofurylacetonitriles, formed by the
reaction of benzofuran-3(2H)-ones with cyano-methylenetriphenylphosphorane,
were reduced by lithium aluminium hydride to give the physiologically active
2-(3?-benzofuryl)ethylamines. The formylation of methyl 6?-methoxy-3?- benzofurylacetate
was also studied.
An aldol condensation induced by a transition metal complex
Authors: Bennett RL , Bruce MI
Published: September 2010

The reaction between benzyl methyl ketone and MnMe(CO)5 affords
Mn(CO)3[η5-CHPhCMeCHC(CH2Ph)O]
in which the unsaturated ligand, formed by condensation between two molecules of the ketone, acts
as an acyclic heteroatom five-electron donor.
3-Hemiacetals of 3,4-Dihydrospiro[2H-1-benzopyran-2,1'(3'H)-isobenzofuran]-3,4-dione
Authors: Clark-Lewis JW , McGarry EJ
Published: September 2010

Oxidation of 2?-hydroxymethylfiavonol
with periodic acid in methanol gives 3,4-dihydro-3-hydroxy-3-methoxyspiro[2H-1-benzopyran-2,1'(3'H)-
isobenzofuran]-4-one.
Hydrogenation of 1,10-phenanthroline
Authors: Eckhard IF , Fielden R , Summers LA
Published: September 2010

Hydrogenation of 1,10-phenanthroline
with Raney nickel catalyst affords 1,2,3,4-tetrahydro-l,10-phenanthroline and
1,2,3,4,7,8,9,10-octahydro- 1,10-phenanthroline.
Thermal decomposition in the solid state
Authors: Ng W
Published: September 2010

The foundation of solid
state decomposition kinetics is based on the well known theory of nucleation
and nucleus growth put forward by Jacobs and Tompkins. It has now been shown
that all the kinetic equations thus derived can be represented by a general differential
form:

������������������������� dα/dt
= kα1-p(1-α)1-q

in which α, t and k
are respectively the fractional decomposition, time and rate constant; while p
and q are parameters lying between zero and unity inclusively. A method has
been suggested to find p and q experimentally, thereby enabling one to find the
appropriate kinetic form for the chemical decomposition. The conventional
method involves the testing of various existing equations to the decomposition
data. Different equations are found to fit over different ranges of the decomposition
curve so that it is difficult to decide which is the correct kinetic equation
for a particular reaction. The present approach however eliminates this
complication.
Complexes of carbohydrates with metal cations. IV. Cyclitols
Authors: Angyal SJ , Hickman RJ
Published: September 2010

Cyclitols which contain an
axial-equatorial-axial sequence of three hydroxyl groups form complexes with
cations. Complex formation can be detected by the downfield shifts of the
signals in their p.m.r. spectra; the signal of the
hydrogen atom attached to the central carbon atom of the ax-eq-ax
sequence shifts to the greatest extent. Equilibrium constants of complex
formation have been determined by measuring the calcium ion concentration with
an ion-selective electrode. cis-Inositol appears to
form some 2 : 1 complex in addition to the prevalent 1 : 1 complex. Complexes
of epi-inositol with calcium and strontium chloride
have been isolated.
Observations of transient intermediates during flash photolysis of 1,3-diphenyl-2-pyrazoline and its sulphonated derivative in solution
Authors: Langley KF
Published: September 2010

At least two transient
species have been observed during flash photolysis of a sulphonated derivative
of 1,3-diphenyl-2-pyrazoline in aqueous solution. One of these, with absorption
bands at 455 and 625 nm, has also been generated by sensitization with methylene
blue and eosin Y, and appears to be a semi-oxidized species.
The constituents of Phebalium nudum. III. The structures of phebalin and phebalarin
Authors: Brown KL , Burfitt AIR , Cambie RC , Hall D , Mathai KP
Published: September 2010

Structures for phebalin (1)
and phebalarin (5), two constituents of the bark of the New Zealand shrub Phebalium nudum Hook., are
established. A synthesis of the (Z,Z)-isomer (7) of phebalarin is described.
The chemical constituents of Australian Flindersia species. XX. An examination of F. pimenteliana
Authors: Bowden BF , Cleaver L , Ndalut PK , Ritchie E , Taylor WC
Published: September 2010

The bark of F. pimenteliana F. Muell. yielded
seselin, xanthyletin, betulin, sitosterol and traces of dictamnine and
skimmianine. The leaves gave rutin, skimmianine,
betulin and sitosterol. From the wood only sitosterol could be isolated and a
trace of alkaloid detected.
1H N.M.R. and infrared spectra of trimethylplatinum(IV) Schiff base complexes
Authors: Hall JR , Swile GA
Published: September 2010

A range of trimethylplatinum(IV) complexes of the types [PtMe3(salnr)]2 and [PtMe3(salnr)X] where salnr is an
N-substituted salicylaldiminate anion and X =
3,5-lutidine or triphenylphosphine have been prepared from the reaction between
[PtMe3]2SO4,4H2O and Ni(salnr)2. A detailed study of the 1H
N.M.R. spectra of these compounds is reported, and some features of the
infrared spectra are discussed.
The mass spectra of the Schiff base derived from ethylenediamine and trifluoroacetylacetone and its metal complexes
Authors: Livingstone SE , Mayfield JH
Published: September 2010

The mass spectrum of the
Schiff base formed by the condensation of ethylenediamine and trifluoro-acetylacetone shows that the compound is
N,N-ethylenebis(1,1,1-trifluoro-4-iminopentan-2-one). The mass spectra of the
nickel(II), palladium(II) and copper(II) chelates of the Schiff base confirm
this structure for the ligand. Mechanisms are proposed for some of the
fragmentation reactions which occur in the mass spectrometer.
Complexes of 2-Mercaptopyrimidin-4-ol(2-thiouracil) with RhIII, PdII, PdIV, PtII and PtIV
Authors: Khullar IP , Agarwala U
Published: September 2010

Complexes of
2-mercaptopyrimidin-4-ol with RhIII, PdII, PdIV,
PtII and PtIV
have been prepared. Their tentative structures have been assigned on the basis
of infrared and electronic spectra and magnetic and analytical data. The ligand
behaves as a bidentate bridging ligand towards metal ions except for PtII. Crystal field parameters have also been
calculated.
Annelated furans. XVIII. The photocyclization of 2-methoxyphenyl phenyl ethers
Authors: Elix JA , Murphy DP
Published: September 2010

Irradiation of the
polyfunctional 2-methoxyphenyl phenyl ethers obtained by degradation of lichen
depsidones results in the formation of dibenzofurans by ring closure involving
elimination of the elements of methanol. In contrast, simply substituted methoxyphenyl
phenyl ethers underwent rearrangement on irradiation and produced
hydroxybiphenyls. A mechanistic rationalization of these results has been
proposed which invokes the initial formation of a diradical species upon
irradiation. The formation of a stable product from this diradical intermediate
can then be achieved by a variety of reaction pathways.
Pyrazolidine-3,5-diones with heterocyclic substituents. IV. Ionization constants
Authors: Woodruff M , Polya JB
Published: September 2010

Spectrophotometric pKa
determinations are reported for N1-3-phenyl-1 H- 1,2,4-triazol-5-ylpyrazol-idine-3,5-diones
and N-phenyl analogues; 4- monoalkyl derivatives are too unstable for this
purpose unless both nitrogen centres of the pyrazolidinedione are substituted.
Substitution of the pyrazolidinedione by triazolyl instead of phenyl increases
the acidity by 0.54-1.74 pK units; a comparable strengthening of the acidity of
the triazole moiety by the pyrazolidinedione is observed. The nature of alkyl
substituents has little effect on the value (+0.10 to +0.15) of the Hammett
σm calculated for anions of the investigated
pyrazolidinediones. Keto and en01 tautomers of 4-benzyl-1-phenyl-2-(3- phenyl-1H-1,2,4-triazol-5-yl)pyrazolidine-3,5-dione
have been isolated.
Action of Grignard reagents on N-Alkylidene- and N-Arylmethylene-aminophthalimides
Authors: Awad WI , Ismail MF , Kandile NG
Published: September 2010

N-Alkylidene- and
N-arylmethylene-aminophthalimides react with organomagnesium halides to give different
products depending upon the nature of the Grignard reagent. Thus the reaction
may proceed by addition of two moles of the reagent to give (2) or (3) or it
may proceed through addition and cleavage of the molecule to give phthalazin-1-ones
(5). These phthalazin-1-ones can also be obtained in much better yields by the
action of Grignard reagents on N- aminophthalimide. Structures are based on
infrared and ultraviolet spectra and the synthesis of authentic samples in some
cases.
A comparison of homogeneous and heterogeneous platinum as catalysts for the deuteration of polyphenyl aromatic hydrocarbons
Authors: Davis KP , Garnett JL
Published: September 2010

Polyphenyl aromatic
compounds exchange with heavy water in the presence of both homogeneous and
heterogeneous platinum with high M values. Diphenyl, m- and p-terphenyls
exhibit similar isotope orientations during initial rates in both catalytic
systems whereas o-terphenyl does not. The first three compounds show ortho
steric effects and appear to exchange by n-dissociative processes. In m- and
p-terphenyls, the deactivated ortho protons exchange heterogeneously at rates
which may be directly related to their degrees of steric hindrance. With o- terphenyl,
all ortho hydrogens are deactivated in homogeneous exchange whereas
heterogeneously, all centre ring ortho hydrogens exchange readily. A novel
catalytic intermediate has been proposed to explain this orientation. These
results show that o-terphenyl is a unique compound for differentiating between
homogeneous and heterogeneous metal catalysed exchange processes. The data from
the polyphenyls and the condensed polycyclics support the π-complex theory
of catalysis.
The C6H5N energy surface. IV. Isotopic labelling studies in phenylnitrene isomerizations
Authors: Crow WD , Paddon-Row MN
Published: September 2010

Gas phase pyrolysis of
phenyl azide gives rise to aniline, cyclopentadienecarbonitrile
and pyridine as isomerization products from phenylnitrene. Isotopic labelling
studies (14C, 13C) are used to examine the isomerization
processes which occur in phenylnitrene prior to product formation. ��� At the lowest energy level of the
intermediate little or no label randomization occurs and aniline evidently
arises from hydrogen capture at this stage. Higher levels of the intermediate
involve a cycloperambulatory motion of the nitrene nitrogen atom, followed by
ring contraction to cyclo- pentadiene-1-carbonitrile. The pyridine formed
possibly arises from a ring-expanded intermediate, which may not have undergone
the cycloperambulation of the nitrene nitrogen atom.

� The
aniline and cyanocyclopentadiene derived from 5- pyridyltetrazole pyrolysis
appear to exhibit very similar behaviour to those from phenyl azide as far as
isotopic migration is concerned.
On the alkylation of α-bromo ketones by trialkylboranes
Authors: Prager RH , Reece PA
Published: September 2010

The reaction of
2-halocycloalkanones with organoboranes in the presence of base has been
studied. The transfer of an alkyl group from boron to carbon is the
rate-limiting step, and the nature of the intermediate is discussed.
2-Bromocyclopentanones react faster than 2- bromocyclohexanones
than 2-bromocycloheptanones, but α-chloro- and α- iodo-cyclohexanones do not undergo alkylation. The
stereochemistry of reagent and product is discussed and an efficient one-pot
alkylation of cycloalkanones is described.
Rearrangement during attempted allylation of 2α-Bromo-5α-cholestan-3-one
Authors: Woodgate PD , Davis BR , Lee MH
Published: September 2010

Treatment of
2α-bromo-5α-cholestan-3-one with zinc and allyl bromide in
benzene-dimethyl sulphoxide yields, amongst other products, the ring-A
contracted compounds 2α-(but-3?-en-1?-oyl)-A-nor-5α-cholestane (3)
and 2α-[4?-(4?-hydroxyhepta-1?,6?-dienyl)]-A-nor-5α-cholestane (5).*
The structure of galbinic acid. A depsidone from the lichen Usnea undulata
Authors: Elix JA , Engkaninan U
Published: September 2010

The depsidone, galbinic
acid (α-acetylsalazinic acid) (4), has been
isolated from the lichen Usnea undulata
together with usnic, norstictic and salazinic acids. The structure of the
compound (4) followed from a combination of spectroscopic and chemical data and
was confirmed by comparison with a synthetic sample. The acetylation of
salazinic acid was further investigated.
[1,4]Benzodioxino[2,3-g]isoquinolines and [1,4]Dioxinodiisoquinolines
Authors: Browne EJ
Published: September 2010

Examples of the new ring systems
[1,4]benzodioxino[2,3-g]isoquinoline,
[1,4]dioxino[2,3-g:5,6-g?]di-isoquinoline and
[1,4]dioxino[2,3-g:6,5- g?]diisoquinoline have been prepared. A route starting
with chloromethylation of dibenzo[b,e][1,4]dioxin (1a)
yielded a reduced tetracyclic derivative (2b) and mixed isomeric reduced
pentacyclic derivatives (3b) and (4b). The latter differed in the p.m.r. resonances arising from the protons in positions 5,
7, 12 and 14. Initial di- chloromethylation of (1a)
had thus occurred in both the 2,7- and 2,8- positions, whereas acylation
normally gives only 2,7-disubstitution. The pentacyclic compound (3b) was
prepared unambiguously from 2,7- dimethyl-dibenzo[b,e][1,4]dioxin.
A low yield of the fully aromatized tetracyclic compound (2) was obtained by Pictet-Gams cyclization of N- {2-(dibenzo[b,e][1,4]dioxin-2-yl)-2-hydroxyethyl}benzamide.
The flash photolysis of ethenetetracarbonitrile
Authors: Carson D , Cook CL , Kilpin D , Napier IM
Published: September 2010

The flash photolysis of
ethenetetracarbonitrile gives rise to two short-lived diffuse absorption bands
at 299.0 and 321.2 nm which are tentatively attributed to the dicyanocarbene
radical. Flash photolysis of ethenetetracarbonitrile which has been photolysed
or heated for a prolonged period yields a similar pair of bands with a lifetime
of many minutes. The identity of the carrier of these bands is not known, but
some possibilities are discussed.
The photolysis of aqueous nitrate solutions
Authors: Bayliss NS , Bucat RB
Published: September 2010

Data have been obtained
relevant to the mechanism of formation of nitrite, oxygen and peroxynitrite by
the photolysis of aqueous sodium nitrate solutions. In alkaline solutions, the
origin of O2 as determined by the use of 18O-enriched
water, and the lowering of nitrite yields by various solutes, are consistent
with the dissociative process �������������� ����������������������������� (NO3-)*→
NO2-+Orather than with ����������������������������� (NO3-)*→
NO2+O-

The effect of these solutes
is attributed to reduction of (NO3-)*. It is proposed
that peroxynitrite (OONO-) is formed by intramolecular rearrangement
of the pyramidal (NO3-)* in the 3ππ
state. Peroxynitrite is not a precursor to NO2-. The
quantum yield depends on both wavelength and temperature, and the apparent
energy of activation decreases with decreasing wavelength. These results are
interpreted in terms of the different reactivities of (NO3-)*
produced in the nπ* and the ππ*
absorption bands. ��� Low initial yields at low pH can be
explained by protonation of (NO3-)* followed by

���������������������������������
(HOONO)*→ OH+NO2and ���������������������������������� OH+NO2→
H++NO3

The self-inhibition process
evident in acidic conditions is consistent with the formation of NO3
(from NO2 and O) which re-oxidizes NO2-. Sharp yield
increases on the addition of some reagents are due to scavenging of the OH
intermediate in the (HOONO)* → NO3- reversion.
Constituents of Bosistoa euodiformis (Rutaceae). Structure and synthesis of bosistoin, a triterpene with a C33 skeleton
Authors: Croft JA , Ritchie E , Taylor WC
Published: September 2010

From the wood of Bosistoa euodiformis F. Muell. only 8-sitosterol could be isolated. The bark yielded
the same substance together with limonin and a small amount of skimmianine. The
leaves gave substances: limonin, friedelin, epifriedelanol,
franklinone, two new related substances,(S)- franklinol and franklinene, and also the new triterpene
bosistoin, C34H58O. By degradation and synthesis from
lanosterol, bosistoin was shown to be 25-ethyl-24-methylenelanost-9(11)-en-3β-yl
methyl ether.
Photochemical studies of a sulphonated derivative of 1,3-Diphenyl-2-pyrazoline
Authors: Leaver IH , Ramsay GC , Stephens LJ
Published: September 2010

The photochemistry of the
sulphonated pyrazoline fluorescent whitening agent sodium 4-(3?-phenyl-2?-pyrazolin-1?-yl)benzenesulphonate
has been examined in aqueous solution, in films of poly(vinyl alcohol) and in
the wool fibre. Photooxidation to give the pyrazole occurs almost
quantitatively in solution, but accounts for only half of the photoproducts
formed in the polymer. In the wool fibre, pyrazole formation accounts for more
than half of the pyrazoline whitener destroyed during exposure to simulated sunlight.
The spectrum of the intermolecular vibration of water
Authors: Vetrov AA , Kondratov OI , Yuhnevich GV
Published: September 2010

This analysis has been made
with the purpose of evaluating the influence on the intermolecular vibration
spectrum of the size and structure of water molecular associations and the
angle of turn of a molecule in relation to the H-bonds. Force constants for ice
and for a number of molecular associations(mostly stable by quantum-mechanical
calculations) have been determined. For the associations concerned,
intermolecular vibration spectra have been calculated after taking into account
some spectral effects of hydrogen bonds. It has been shown that the two
observed libration bands of liquid water resulted from two modes of vibration
of bonded water molecules, not from two kinds of molecules in the liquid phase.
The synthesis of volatile barbituric acid derivatives
Authors: Dilli S , Pillai DN
Published: September 2010

The synthesis of several
new N,N?-dialkyl barbituric acids is reported. The compounds are the diethyl derivatives
of pentobarbital and amobarbital, and the bis(chloroethyl) derivatives of
pentobarbital, amobarbital and phenobarbital. Separation and isolation of mono-
and di-methyl, mono- and diethyl derivatives of the
three barbituric acids are also described. Infrared, mass and N.M.R. spectral data
are given.��� Of the derivatives, only the methylated
compounds are significantly more volatile than the parent acids.
Preparation of 2,2,7-Trimethyloct-6-en-3-one from cineole
Authors: Kachel CD , Rae ID , Redwood AM
Published: September 2010

2,2,7-Trimethyloct-6-en-3-one
is formed by decomposition of two tetrahydropyran derivatives derived from
cineole. A rational synthesis of this ketone from 3,3-dimethylbutan-2-one and 1-bromo-3-methylbut-2-
ene is also reported.
The crystal structures of two isomers of a macrocyclic binuclear compound each containing both divalent and trivalent cobalt
Authors: Hoskins BF , Williams GA
Published: September 2010

The compound Lco2Br3,2H2O (where L is a binucleating ligand derived from the macrocycle
LH2 formed by condensation of two molecules each of propane-1,3-diamine and 2-hydroxy-5-
methylisophthalaldehyde) was found to occur in two crystalline forms. The structures of both have
been determined by single-crystal X-ray diffraction techniques, revealing that each corresponds to a
different geometrical isomer of composition Lco2Br3,2H2O. Each structure was determined by the
conventional Patterson-Fourier method and refined by a least-squares procedure, with only the
Co, Br, N and O atoms being refined anisotropically. The first form, designated the A-isomer,
crystallizes in the orthorhombic space group Pn21a with four formula units in a cell of dimensions
a 15.173(1), b 17.370(2) and c 10.493(1) Ǻ. The structure refined to a conventional R-factor of
0.074 by means of 1883 unique reflections collected by counter methods. The second form, or
B-isomer, crystallizes in the monoclinic space group P21 with two formula units in a cell of dimen-
sions a 10.676(1), b 15.235(2), c 9.304(1) Ǻ and β 111.83(2)°. The structure refined to a conventional
R-factor of 0.101 by means of 2006 independent reflections collected by counter methods. Both
isomers are composed of discrete bromide anions together with discrete binuclear cations of com-
position [Lco2Br2,2H2O]+, each containing one cobalt(II) and one cobalt(III) atom with a Co...Co
distance of 3.13 Ǻ. In both isomers the cobalt atoms are in octahedral environments. In the
A-isomer two bromine atoms are bonded to the cobalt(III) atom in positions perpendicular to the
ligand N2O2 donor plane, with the two water molecules occupying similar positions about the
cobalt((II). But in the B-isomer, one water molecule and one bromine atom are bonded to each of
the cobalt(III) and the cobalt((II) atoms in the comparable positions. In both structures the ionic
bromide is involved in a hydrogen-bonding scheme with the coordinated water molecules.
Constituents of Eupomatia species. IV. Structure and synthesis of eupolauridine (EL base-1) and some observations on the structures of eupolauramine (EL base-2) and hydroxyeupolauramine (EL base-3)
Authors: Bowden BF , Picker K , Ritchie E , Taylor WC
Published: September 2010

On the assumption that
eupolauridine (EL base-1), eupolauramine (EL base-2) and hydroxyeupolaur-amine
(EL base-3) were structurally related, a consideration of the spectral
properties of the alkaloids suggested that eupolauridine was
3,4-diazafluoranthene. This base was synthesized but found to be different from
eupolauridine. However, 1,6- diazafluoranthene, which
was also synthesized, was identical with eupolauridine. With the two synthetic
bases available in quantity it was possible to show that eupolauramine and
hydroxyeupolauramine were not related to either of them.
Chemistry of pyrrolic compounds. XXX. An approach to the synthesis of porphyrin a
Authors: Clezy PS , Diakiw V
Published: September 2010

Synthesis of the porphyrin
(1e) has been achieved by the oxidative cyclization of an appropriately
substituted 1,19-dideoxy-1,19- dimethylbilene-b. It is hoped to use this
tetrapyrrole to complete the synthesis of porphyrin a, the prosthetic group of
cytochrome oxidase. New syntheses of Spirographis porphyrin and its isomer are
reported. 2,4-Diacetyl- and 4-acetyl-2-methoxycarbonyl-deutero-porphyrin IX
dimethyl ester have been prepared through bilene-b intermediates constructed in
the ?east-west? rather than the ?north-south? mode.
General equations for the reaction kinetics of solids
Authors: Taplin JH
Published: September 2010

The index-of-reaction
equation (i.r.e.):

dF/dtZ = kZ(l - βF)m
is compared with a
generalized Prout-Tompkins equation (g.P.T.e.):

dF/dt = kn(l - βF)y

With the boundary condition
F = 0, t = 0 the equations are equivalent for z = 2 or m = 0 or β ≤
1 and the i.r.e, is closely approximated by the g.P.T.e. for other values of the parameters by use of the
following approximation

∫(1- F)-m dF ≈ AF(1-BF)5 The parameter s is a function of m. Both A and B are close to unity for 1/3 < m < 3. The i.r.e. is recommended as being more useful than the g.P.T.e. because the i.r.e. has a
better theoretical basis and because it is more readily integrated and fitted
to experimental data.
The analytical approach to synthesis : Twistane
Authors: Hamon DPG , Young RN
Published: September 2010

A detailed analysis, for
synthetic purposes, of the structure of twistane is
given. It is hoped that this will serve, for teaching purposes, to illustrate
the concept of the analytical approach to synthesis. A description of the
synthesis of 3-oxobicyclo[3,3,l]nonan-6-ylmethyl methanesulphonate
and its cyclization to twistan-4-one and an isomer, tricyclo[3,3,1,14,6]decan-3-one,
is given. This synthesis illustrates the remaining single-bond process for
constructing the twistane skeleton.
Cyclophanes. V. Biphenylnaphthalenophanes and the synthesis of Hexa[7]circulene
Authors: Jessup PJ , Reiss JA
Published: September 2010

2,13-Dithia[3,3](3,3')biphenyl(2,7)naphthalenophane (5) was prepared from 3,3'-bis(bromomethyl)- biphenyl and 2,7-bis(mercaptomethyl)naphthalene. Ring
contraction of (5) followed by elimination of the sulphur
function gave [2,2](3,3')biphenyl(2,7) naphthalenophane-l,ll-diene
(11) which on photochemical oxidative ring closure yielded hexa[7]circulene (3) a non-alternant hydrocarbon. The thermal
elimination of methylsulphenic acid under vacuum is
shown to be an efficient method for the
Oxygen equilibration in the mass spectra of 2-benzoylbenzoic acid
Authors: Lacey MJ , Shannon JS
Published: September 2010

Positional integrity of the
label is maintained in the molecular ions of 2-ben~oyl[18O]benzoic acid prior to a number of
primary fragmentation modes. Positional integrity is also evident for some
source and metastable reactions of the protonated
molecular ions formed in its chemical ionization (H2) mass spectrum.
The (M-Ph)+ ions formed in the electron impact mass spectrum,
however, fragment further after complete equilibration of their oxygen atoms.
13C N.M.R. spectra of pyrrolidines and piperidines. Structure of the Perhydroisoindol-5-ones and 3-Azabicyclo[3,3,1]nonan-6-imines formed by the cyanoisopropyl radical induced cyclization of N-Methyl-N,N-bis(2-alkylallyl)amines
Authors: Hawthorne DG , Johns SR , Willing RI
Published: September 2010

The 13C N.M.R.
chemical shifts of a series of substituted pyrrolidines and piperidines are
documented and substituent parameters determined. These data have been used to
assign structures to the polymers and bicyclic products formed in the
cyanoisopropyl radical induced cyclizations of a series of N-methyl-N,N-bis(2-a1kylallyl)amines.
The formation of perhydroisoindol-5-one and/or 3-azabi-
cyclo[3,3,1]nonan-6-imine depends upon the bulk of the 2-alkyl substituent and
correlates with the presence of pyrrolidine and/or piperidine units in the
polymer structure.