bluuebunny/crossref_metadata_2025 huggingface dataset:
Acridone studies. VII. Mechanistic implications of bromination studies
Authors: Prager RH , Thredgold HM
Published: September 2010

The function of alcohols in
the addition of bromine to highly oxygenated acridones is discussed, and
pathways proposed to explain the structure of the products. The most important
factors appear to be the relief of ring strain by addition across a double bond
substituted by a methylenedioxy group, and the intermediacy of bromonium ions.
Chemistry of the Podocarpaceae. XXII. Aspects of the chemistry of Totara-8,11,13-trien-13-ol
Authors: Cambie RC , Crump DR , Duve RN
Published: September 2010

Attempts have been made to
effect fragmentation reactions with bromo- tetralone
systems related to 6α-bromo-13-hydroxytotara-8,11,13-trien-7- one (VII), a
compound which affords a secoditerpenoid (IX) when treated with DMSO-NaHCO3. On treatment with sulphuric acid in
acetone, the mono- epoxide derivative (XXVIII) of the methyl ether of the
secoditerpenoid undergoes a novel aromatization to a naphthalenic aldehyde (XXXI)
by successive transannular cyclization and fragmentation reactions. ��� A 7β-hydroxy configuration has been
confirmed for the major product from reduction of
13-acetoxytotara-8,11,13-trien-7-one (VIII) with lithium aluminium hydride. 13-Methoxytotara-8,11,13-triene
(II) has been deisopropylated and then subjected to Birch reduction in an attempt
to effect a high yield conversion into (+)-podocarp-8(14)-en- 13-one (XXXVII),
a potentially useful intermediate for synthesis.
Alkaloids of Zanthoxylum conspersipunctatum (Rutaceae): The structure of a new alkaloid isomeric with protopine
Authors: Johns SR , Lamberton JA , Tweeddale HJ , Willing RI
Published: September 2010

Extraction of the bark of Zanthoxylum conspersipunctatum Merr. & Perry (Rutaceae) has given the known alkaloid
α-allocryptopine (β- homochelidonine), the amide (�)-N-benzoyl-2-hydroxy-2-
(4?methoxyphenyl)ethylamine (I), and hesperidin. A
new alkaloid isomeric with protopine has been shown to be (II).
Energy dependence of ion-molecule reactions. I. Methane
Authors: McAskill NA
Published: September 2010

The ion-molecule reactions
of gaseous methane were studied at source pressures of up to 70 μ using a
mass spectrometer operated without the usual source magnets. The range of ion
exit energies used (0.2-1.8 eV) was obtained by using different ion path lengths
as well as different field strengths. The operation of the mass spectrometer
was checked by measuring the rate for the proton transfer reaction of CH4+.
The energy dependence and the rate of the reactions inside the ion chamber of
all the primary ions in CH4 were determined by plotting the cross
section against the term, (ion exit energy)-1/2.
Derivatives of transition metal carbonyls. I. Complexes of chelating nitrogen ligands with molybdenum hexacarbonyl
Authors: Casey AT , Horsley RA
Published: September 2010

Compounds of the type Mo(CO)4(ligand)
have been prepared for pyridine-2- aldehyde 2?-pyridylhydrazone
and three homologues. It appears that the ligands are bidentate in these
compounds.
Silver-induced coupling of methyl 4-Bromobut-2-enoate
Authors: Della EW , Kendall M
Published: September 2010

The reaction of methyl
4-bromobut-2-enoate and silver has been reinvestigated and the coupled product
shown to consist of dimethyl octa-trans-2,trans-6-dienedioate
(45%), dimethyl 5-vinylhex-trans-2- enedioate (53%), and dimethyl 2,3-dimethylsuccinate
(2%). The second constituent is found to undergo isomerization during
hydrolysis. None of the isomeric cis-dienes were detected in the coupled
product. Coupling does not appear to proceed via free radicals.
Cycloneolitsin, a cyclopropanoid triterpene ether with a novel side-chain
Authors: Ritchie E , Senior RG , Taylor WC
Published: September 2010

From the leaves of Neolitsea dealbata R.Br. Merr. were isolated taraxerol and sitosterol together with
a new triterpene, ?cycloneolitsin?, C33H56O.
By converting both it and cycloartenol into a common derivative, the structure
was established as 3β-methoxy-24,24- dimethyl-9,19-cyclolanost-25-ene
(Ib).
Carbonyl halides of the Group VI transition metals. XVII. Reactions of Bis(diphenylphosphino)methane with Trihalotetracarbonylmolybdate(II) anions
Authors: Colton R , Howard JJ
Published: September 2010

Compounds of the general
formulae [Mo(CO)2(dpm)2X]X (X =
Cl, Br, I; dpm =
bis(diphenylphosphino)methane) and [Mo(CO)2(dpm)1.5X2]2
(X = Cl, Br) have been prepared and characterized.
There are significant variations in the properties of these compounds as the
halogen is varied, and there are also significant differences between these
complexes and the previously reported dpe
derivatives.
The Sn mechanism in aromatic compounds. XXXVIII. Comparative reactivity of 1-Halogeno-2,6-dinitrobenzenes and some other halogenonitrobenzenes
Authors: Biffin MEC , Miller J , Roper R
Published: September 2010

The reactivity of
1-halogeno-2,6-dinitrobenzenes with methanolic methoxide has been studied
quantitatively and compared with the results of similar studies of o- and p-halogenonitrobenzenes and 1-halogeno- 2,4-dinitrobenzenes.
Adverse steric interactions of the ortho-nitro group are very small in the
o-halogenonitro- and 1-halogeno-2,4- dinitrobenzenes. The interactions are
substantially larger in the reactions of 1-halogeno-2,6-dinitrobenzenes in
displacement of Cl, Br, and I, but not of F, but they
are small compared to steric interactions found in many other classes of
reactions. ��� Steric effects are observed as a reduction
in rates affecting values of the Substituent Rate Factors of the o-nitro group,
and affecting also the mobility as a leaving group of Cl,
Br, and I, but not of F. However, since Cl is the
usual reference standard for leaving group mobility, that of F appears as
having an unusually high value. Nevertheless a depression of the mobility of
iodine from its typical range is also evident.
Interaction of heterocycles and nucleophiles: Sigma complexes formed from methoxide ion and some 5-nitropyrimidines and comparison with those from 2,4,6-trinitroanisole
Authors: Biffin MEC , Miller J , Moritz AG , Paul DB
Published: September 2010

The sigma complexes formed
from the reaction of methoxide ion with 6- nitro-pyrimidine and its monomethoxy
derivatives have been examined spectroscopically. Structural ambiguities
resulting from the lower symmetry of the nitropyrimidines compared with the trinitrobenzenes
have been resolved by selective deuteration. Comparison is made with sigma
complex formation from 2,4,6-trinitroanisole and the question of kinetic
against thermodynamic control is considered with reference to theoretically
derived P.E.-reaction coordinate profiles for protic solvents. The calculations
are extended qualitatively to consider reactions in an aprotic solvent.
The saturated pyrrolizidine diols. III. A partial synthesis of turneforcidine
Authors: Aasen AJ , Culvenor CCJ
Published: September 2010

Turneforcidine has been
prepared by the oxidation of methyl 7α-hydroxy- 8α-pyrrolizidine-1α-carboxylate
to the 7-keto compound and stepwise reduction with hydrogen/platinum and
lithium aluminium hydride. 7β- Hydroxy-8α-pyrrolizidine-1β-carboxylic
acid is not epimerized by alkali but converted into the stable γ-lactone
(VI).
Metal complexes as ligands. IX. Crystalline binuclear complexes containing two molecules of chloroform per complex molecule, and their unsolvated analogues
Authors: Coles RB , Harris CM , Sinn E
Published: September 2010

Some new binuclear
antiferromagnetic complexes of copper(11) derived from bidentate salicylaldimine ligands have been isolated with two
molecules of chloroform per complex molecule. The chloroform could be driven
off by heating. The chloroform-solvated complexes form as large crystals, while
the unsolvated complexes are amorphous. A comparative
study of the solvated and unsolvated complexes was
carried out to determine the effect of the chloroform on the properties of the
binuclear complex. It appears that for most properties not related to the
crystal habit, the presence of the chloroform may be ignored. Thus, strong
coordination of chloroform to copper atoms can be ruled out and though very
weak coordination remains a possibility, it does not seem probable. The
chloroform molecules may be held to the phenyl rings of the salicylaldimines
by the same (weak) interaction that is known in mixtures of chloroform and
benzene. The most probable mechanism of
the interaction of the chloroform molecules with the complex is by weak
hydrogen bonding with the two bridging salicylaldimine
oxygens of the complex.
The effect of thiourea and formaldehyde treatment on the chemical analysis of wool. II. Amino acid analyses
Authors: Nicholls PW , Gruen LC
Published: September 2010

The anomalous amino acid
analyses obtained for some amino acids, from the hydrolysates
of thiourea-formaldehyde and formaldehyde-treated wool samples, are due largely
to reactions with formaldehyde during acid hydrolysis. A new technique has been
developed, involving hydrolysis in refluxing hydrochlorio
acid in an atmosphere of nitrogen. This method improves the recovery of amino
acids and has also been of assistance in explaining the abnormal analyses
observed for oystine, tyrosine, lysine, and threonine in the presence of formaldehyde.
Magnetic behaviour of bivalent copper complexes of some tridentate Schiff bases
Authors: Ison K , Kokot E
Published: September 2010

The magnetic
susceptibilities in the temperature range 90-400�K are reported for� copper(11) complexes of the general formula CuL, where L is a tridentate Schiff base. The magnetic
behaviour of some of the complexes is interpreted in terms of pairwise antiferromagnetic interaction and of others in
terms of linear antiferromagnetism involving infinite
chains of copper atoms.
Syntheses in the cyclohexanone series. II. The syntheses of 4-Ethylcyclohex-2- enone, 4-Ethylcyclohex-3-enone, and 4-Ethylidenecyclohexanone
Authors: Lewis KG , Williams GJ
Published: September 2010

An attempt to synthesize 4-ethylcyclohex-2-enone by a Robinson-type ring closure gave
a mixture of conjugated and non-conjugated ketones from which the conjugated
isomer was isolated. 4-Ethylcyclohex-3-enone on
treatment with acid yielded the same mixture of ketones. Pyrolysis of 4-carboxy-4-vinylheptanedioic acid with barium carbonate
formed 4-ethylidenecyclohexanone.
Vibrational spectra of alkali chlorates and nitrites in crystalline and molten states
Authors: James DW , Leong WH
Published: September 2010

The infrared and Raman
spectra of NaClO3 and NaNO2
are reported in crystalline and molten
states. The Raman spectra of melts of LiClO3,
KClO3, AgClO3,
and KKO2 are also reported. The melts all show well-developed
lattice-like vibrations which are quite distinct from the crystalline
vibrations both in energy and intensity. The spectra are interpreted
on the basis of a lattice-like structure in the melt.
Radiation-induced reactions with cellulose. VII. Effect of temperature and substituted styrenes in the copolymerization process
Authors: Dilli S , Garnett JL
Published: September 2010

The temperature dependence of the radiation-induced grafting of styrene
to cellulose has been studied. The system cellulose-styrene-methanol was examined
in the temperature range from 40° to -196° in order to observe possible ionic
contributions to the reaction mechanism. This effect was further investigated using a
series of substituted styrenes containing both electron-donating and electron-
withdrawing substituents. The 17 monomers used included o-, m-, and p-mono-
halogenated styrenes, a number of alkylstyrenes and the p-methoxy derivative.
An attempt has been made to correlate the grafting results with the Hammett
constants for the substituent. The consumption of monomer during grafting of
styrene to cellulose has also been investigated.
INDO calculations of spin density
Authors: Scarlett MJ , Casey AT , Craig RA
Published: September 2010

Calculations of spin
density on the ligand have been made by the "intermediate neglect of
differential overlap" method for nickel complexes. The ligands studied are
substituted pyridines and pyridine N-oxides and also benzonitrile. The agreement between theory
and N.M.R. and e.s.r. measurements is superior to previous calculations. The
calculations show that in all ligands except benzonitrile the direction of spin
transfer is from ligand to metal.
Reaction of oximes and α-hydroxyimino ketones with aqueous alkaline sodium borohydride
Authors: Bell KH
Published: September 2010

Reaction of saturated oximes with aqueous alkaline sodium borohydride at
reflux gives the corresponding alcohols in good yields whereas oximes of conjugated
carbonyl compounds do not react. α-Hydroxyimino ketones (1) yield 1,2-diols in
good yields under the above conditions.
The synthetic applications and a possible mechanism of these reductions
are discussed.
The decomposition of Bicyclo[3,3,1]nonan-9-ylidene
Authors: Allan RD , Wells RJ
Published: September 2010

The intramolecular
decomposition products of bicyclo[3,3,1]nonan-9-ylidene,
generated by thermal decomposition of the sodium salt of bicyclo[3,3,1]nonan-9-one-tosylhydrazone, have been investigated in
protic and aprotic solvents and also without solvent. When bicyclo[3,3,1]nonan-9-ylidene is generated in the presence of excess base
in aprotic solvents product analysis indicates that 1,3 insertion is
predominant with some carbene rearrangement. When a protic solvent is used the
product composition indicates a predominantly cationic intermediate. Decomposition
of the carbene in the presence of a limited amount of base, even under aprotic conditions,
gives rise to products resulting from both cationic and carbenoid
intermediates.
Radiation-induced reactions with cellulose. VIII. Effect of additives on copolymerization with styrene using the simultaneous technique
Authors: Dilli S , Garnett JL
Published: September 2010

The effect of additives
upon the grafting of styrene to cellulose has been studied for the system
cellulose-styrene-methanol irradiated in air at dose-rates ranging from
0.045-0.77 Mrad/hr in a cobalt-60 facility. The
additives included glycol, acetic acid, ethyl acetate, chloroform, acetone,
aniline, benzaldehyde, hydroquinone, thiourea, thiophen, pyridine, benzene,
naphthalene, pyrene, phenanthrene,
durene, hexamethylbenzene, stilbene,
acridine, and fluoro-,
chloro-and bromo-benzene. At a low concentration (10-2M) of the
non-aromatic additives, a reduction in grafting
yields is observed whereas at a higher concentration (10-1M) of the
same additives sensitization is common. Radical scavengers such as hydroquinone
and thiourea suppress grafting provided their concentration in the grafting
solution is sufficiently high. With the aromatic additives, little change in
grafting yields is observed except for anthracene and
acridine. Possible reaction mechanisms are discussed.
Preliminary studies are also reported for the effect on grafting of chemically
bound lignin and non-cellulosic material present in
the trunk polymer.
Isomeric oximes from 4,4,9,9-Tetramethyl-5,8-diazadodecane-2,11-dione
Authors: Fraser JW , Hedwig GR , Morgan MM , Powell HKJ
Published: September 2010

The preparation is reported
of the ,&amino ketoxime 4,4,9,9-tetramethyl-5,8-diazadodecane-2,ll-dione dioxime. The
synthesis yields a mixture of the syn
(methyl) and anti isomers. The isomers are readily interconverted
in solution in the presence of metal salts, acids, or alkali. Isomerically pure samples were isolated as di- and tetra-hydrochloride salts (syn isomer) and a dihydroperchlorate salt
(anti isomer). The isomers have
been characterized by the use of N.M.R. and infrared spectroscopy.
Dihydropyrrolizines. IV. Manganese dioxide oxidation of 1,2-dehydropyrrolizidines
Authors: Culvenor CCJ , Edgar JA , Smith LW , Tweeddale HJ
Published: September 2010

1,2-Dehydropyrrolizidine
derivatives with 7-OH or 1-CH2OH substituents are readily oxidized
by manganese dioxide. The principal products are dihydropyrrolizine
derivatives with the hydroxyls still present or changed to carbonyl, or N-(2'-formylethyl)pyrroles resulting
from fission of the C7-C8 bond of the pyrrolizidine
ring. The several reaction pathways are defined and interpreted on the basis of
mechanisms involving formation and fission of manganate
esters.
The effects of γ radiation on the gas yields and crystallinity of polytetrafluoroethylene
Authors: Pinkerton DM , Sach BT
Published: September 2010

Polytetrafluoroethylene (PTFE) has been γ-irradiated in the presence of
gaseous radical scavengers. Irradiations in a vacuum resulted in small yields
of low-molecular-weight fluorocarbons. The presence of methane during
irradiation led to G(CH3F) = 0.06. Although hydrogen is a major
product from the radiolysis of ethylene, none could be detected when
PTFE-ethylene mixtures were irradiated. G(H2) from PTFE-methanethiol was significantly reduced from that expected
from methanethiol alone. Both ethylene and methanethiol scavenged PTFE radicals and it is suggested
that hydrogen atoms react rapidly with the polymer radicals. Oxygen caused a
marked increase in G(gaseous products), the additional gas being due almost
entirely to the formation of carbonyl fluoride. The crystallinity
of PTFE is shown to increase with radiation dose in the order oxygen >
vacuum > methanethiol > ethylene. Initiation of
a polymerization reaction of ethylene by PTFE radicals is considered to explain
the low rate of crystallinity increase observed in
ethylene. The results are shown to be consistent with the view that permanent
scission is a predominant reaction in irradiated PTFE. However, the extent of
the degradation appears to depend on recombination of fragments resulting from
chain scission. Oxygen and methanethiol, by
interfering with the recombination processes, accelerate the rate of
degradation in relation to PTFE irradiated in vacuum.
Reactions of ethyl azidoformate with aromatic compounds. I. Naphthalene, 2,3- Dimethoxynaphthalene, Veratrole, and N-Methylquinol-4-one
Authors: Chauhan MS , Cooke RG
Published: September 2010

A study has been made of
the photochemical and thermal reactions of ethyl azidoformate
with four aromatic compounds selected to provide a ride range of electron
distribution and reactivity. Examples of substitution, addition, and insertion
reactions have been observed and the nature and yields of products under
different conditions are discussed in relation to the mechanisms proposed for
these reactions.
Rearrangements in the furan series. I. The reaction between furfuraldehyde and aniline
Authors: Lewis KG , Mulquiney CE
Published: September 2010

Treatment of furfuraldehyde with 2 mol of aniline yields a colourless product which, from its spectral properties and those of its products of hydrogenation, has been shown to possess the structure 2,4-dianilinocyclopent-2-enone. A number of other simple aromatic amines have been shown to form products of similar structure.
INDO calculations of spin densities. II. Further calculations on nickel(II) complexes and on a variety of acetylacetone complexes
Authors: Scarlett MJ , Casey AT , Craig RA
Published: September 2010

Calculations of spin
density on the ligand have been made by the INDO method on nickel(II) complexes
of quinoline N-oxides, water, ammonia, aliphatic amines, aromatic nitriles, and
isonitriles as well as on the acetylacetonates of a variety of metals. Three
cases are distinguished: (1) the ligand could be considered purely as a cation
or anion; (2) the ligand could be considered as a hybrid of cation and anion;
(3) neither of these approaches is satisfactory, indicating that neglect of
metal orbitals causes serious errors.
C-O, C-S, and M-S vibration frequencies of metal xanthates
Authors: Hunt MR , Kruger AG , Smith L , Winter G
Published: September 2010

Changes of coordination
from four to five or six in the xanthates of nickel, lead, zinc, and cadmium
result in a shift towards lower energy of the M-S vibration, a small shift to
higher energy of the C-S vibration, and an unexpected large shift to lower frequency
of the C-O vibration.
Mechanisms for magnetic exchange in some binuclear halide complexes of chromium(III) and molybdenum(III)
Authors: Grey IE , Smith PW
Published: September 2010

Magnetic exchange has been
studied in a series of compounds of formula AI3MIII2X9
(A = univalent cation, M = Cr or Mo, X = Cl or Br) over the range 90-450�K. By
correlating the variations observed with X-ray data on bond angles and
metal-metal distances in the M2X93- binuclear
entity, information on the relative contributions of the different mechanisms
for spin-coupling has been obtained. ��� In the case of the molybdenum compounds
direct exchange predominates. Superexchange through the bridging halogens constitutes
a minor proportion of the total exchange but the relative contributions of the
ferromagnetic and antiferromagnetic superexchange are affected by structural
variations. ��� For the corresponding chromium compounds,
in which the total exchange is smaller by a factor of 50 or more, superexchange
is comparable in magnitude with direct exchange.
Chemistry of the Podocarpaceae. XXVII. Ring-c modifications of methyl abieta-8,11,13-trien-18-oate
Authors: Cambie RC , Franich RA
Published: September 2010

Functionalization of the
isopropyl group of methyl abieta-8,11,13- trien-18-oate (8) has been achieved by intramolecular
cyclizations of the 12-carboxy derivative (10) with lead tetraacetate and by
thermolysis of the diazomethyl ketone (11). ��� Nitration of methyl 12-acetylabieta-8,11,13-trien-18-oate
(9) has given the products (21) and (30), arising from nitrodeacylation and
nitrodealkylation reactions, respectively. The nitro ketone (30) has been
converted into methyl 13-hydroxypodocarpa-8,11,13-trien-18-oate
(38) in 26% overall yield from the ester (8). Birch reduction of the methyl
ether of the phenol (38) afforded the enone (50), a potentially useful
intermediate for synthesis.
Photosensitized oxygenation of α-farnesene
Authors: Cavill GWK , Coggiola IM
Published: September 2010

The photosensitized
oxygenation of α-farnesene gave a series of hydroperoxides. After
reduction, the following sesquiterpenoid alcohols were isolated and spectroscopically
characterized: 2,6,10- trimethyldodeca-3,6,9,11-tetraen-2-ol
(2), 6,10-dimethyl-2- methylenedodeca-6,9,11-trien-3-ol
(3), 3,11-dimethyl-7-methylenedodeca- 1,3,10-trien-6-ol
(5), and 7,11-dimethyl-3-methylenedodeca-1,6,10- trien-4-ol
(7). 3,7,11-Trimethyldodecan-4-ol, -5-ol, and -6-ol were synthesized as
reference compounds.
Studies on the reaction between strontium carbonate and iron(III) oxide
Authors: Beretka J , Brown T
Published: September 2010

The reaction between strontium
carbonate and iron(III) oxide has been studied in a system open to the
atmosphere and in a vacuum. The extent of reaction was calculated from the
analysis of the solid products by X-ray diffraction and, in the case of the experiments
in vacuum, from the amount of carbon dioxide evolved from the system also. ��� In vacuum, the monoferrite SrFe2O4
results from the direct reaction of strontium carbonate and iron(III) oxide at
comparatively low temperatures, while the hexaferrite SrFe12O19
is formed by the reaction of Sr2Fe2O4 with
iron(III) oxide at higher temperatures. The formation of the ferrite Sr2Fe2O5
depends upon the prevailing atmosphere, since this compound was present only as
an intermediate phase when the experiments were carried out in air and not in
vacuum. Only three compounds of strontium, iron, and oxygen were found, namely
the ferrites SrFe2O4, Sr2Fe2O5,
and SrFe12O19. ��� The observataions appear to be explicable
in terms of Tammann temperatures.
Palladium(II) and platinum(II) complexes of 2,9-Dimethyl-1,10-phenanthroline. I. Halide compounds
Authors: Plowman RA , Power LF
Published: September 2010

Complexes of
2,9-dimethyl-1,10-phenanthroline with palladium(II) and platinum(II) halides
are described. The methyl groups of the ligand introduce strong steric
hindrance in some of the normal geometries of these transition-metal complexes,
and evidence is presented for five- coordination in the bis(dmp) compounds of
these two metals.
The N.M.R. spectra of some tricyclic heterocycles related to phenothiazine
Authors: Calder IC , Johns RB , Desmarchelier JM
Published: September 2010

The high-resolution N.M.R.
spectra of ten tricyclic heterocycles related to phenothiazine in which the heteroatoms
are combinations of O, N, S, Se, Te, and As are reported. The coupling
constants are discussed in terms of substituent effects for the heteroatoms.
Long- range coupling of the NH and solvent effects are used to make assignments
of the protons.
New heterocycles derived from 2-aminothiophenol
Authors: Huppatz JL , Moore RMJ
Published: September 2010

2-Aminothiophenol reacted
with β-propiolactone in ethanol to give β-[o- (β-carboxyethylamino)phenylthio]propionic
acid (1) which underwent cyclodehydration in polyphosphoric acid to give
derivatives of two new heterocyclic ring systems, viz., 1,8-dioxo-1,2,3,4,5,6,7,8-octahydro-4-
thia-5-azaphenanthrene (2) and 4,8-dioxo-3,4,7,8-tetrahydro-2H,6H- [1,4]thiazepino[2,3,4-ij]quinoline
(3). Analytical and spectral data are presented which support the structures
proposed for these compounds. ��� Alternative synthesis of each heterocycle
was achieved by using media other than polyphosphoric acid to cyclize the
dicarboxylic acid (1). Phosphoryl chloride gave β-(4-oxo-2,3,4,5-tetrahydro-1,5-
benzothiazepin-5-yl)propionic acid (4), which was cylodehydrated smoothly to the
thiazepine (3). Concentrated sulphuric acid afforded β- (4-oxo-1,2,3,4-tetrahydroquinol-8-ylthio)propionic
acid (6) which was converted into the thiazaphenanthrene (2) by polyphosphoric
acid. ��� Bromination reactions and reduction with
sodium borohydride of the thiazepine (3) are also described.
Hydrolysis of amides. IV. Dilute acid hydrolysis of amides of the type R2CH-CONH2 and R3C-CONH2
Authors: Bolton PD , Jackson GL
Published: September 2010

Enthalpies and entropies of
activation have been derived from rate constants measured over a range of
temperature for the dilute acid hydrolysis of isobutyramide, diethylacetamide,
α-methylbutyramide, cyclohexaneoarboxamide, cyclopentane-carboxamide, and
trimethylacetamide. ��� These data, in combination with data for
other amides produced earlier, show the hydrolysis rate constants to be
dominated by steric influences but with a perturbing effect which is
proportional to the number of α-hydrogens present in the substituent. The
"α-hydrogen bonding" concept of hyperconjugation appears to
offer a reasonable explanation of these perturbations. ��� Controlled steric changes are shown to be
non-additive for this reaction and to exert their influence primarily through
the enthalpy component of the observed free energy changes.
The physical properties of anomalous water
Authors: Mansfield WW
Published: September 2010

The properties of anomalous
aqueous condensates, prepared in the manner described by Deryagin,1
vary with aqueous vapour pressure. The changes of column length and of melting
point are similar to those of ordinary aqueous solutions. There is no sound
evidence that the condensate exhibits abnormal viscosity, density, electrical
conductivity, or surface tension.
Solvolysis of sulphonyl halides. VII. Hydrolysis of some aromatic sulphonyl chlorides in aqueous dioxan
Authors: Tonnet ML , Hambly AN
Published: September 2010

The rates of reaction and
the parameters of activation have been determined for the hydrolysis of
4-nitro-, 3-nitro-, 4-bromo-, 4- methoxy-, 4-methyl- and unsubstituted
benzenesulphonyl chlorides m aqueous dioxan containing mole fractions of water
between 0.9 and 1.00. Further evidence is also found for Vizgert's
hypothesis that 2,4,6- trimethylbenzenesulphonyl
chloride hydrolyses by the SN1 mechanism. In all other cases the
inversion of the effects of substituents which occurs as the water content of
the solvent is decreased, the passage of the rate through a maximum in certain cases,
and the failure of the Hammett free energy correlation can be accounted for in
terms of 8,2 type mechanisms for hydrolysis in which both bond-making and
bond-breaking processes are of importance but are differently biased by the
various substituents.
Variation in the Raman spectrum of thallium(I) nitrate with phase change: the anisotropic wing in solid and liquid phases
Authors: James DW , Devlin JP
Published: September 2010

The Raman spectra are
reported for the three solid phases and the melt of thallium(I) nitrate.
Partial infrared spectra of the melt are also included. The internal
frequencies are discussed in terms of known crystalline space groups and
compared with spectra of isostructural salts. The changes in the external
frequencies with change of crystal structure are also described and discussed.
It is shown that a remarkable similarity exists in the low frequency spectrum
of the disordered solid phase I and the melt. This similarity extends to both
the anisotropic wing centred on the exciting frequency and the external lattice
modes. The origin of the low frequency spectrum is discussed in terms of
two-phonon scattering processes.
Nickel peroxide as a selective oxidant in the pyrimidine series. The synthesis of N1-substituted orotic and 2-thioorotic acids
Authors: Warrener RN , Cain EN
Published: September 2010

A versatile route to the synthesis of iV1-substituted orotic or 2-thioorotic
acids is described. The method involves three st>eps: (i) Preparation of 6-hydroxy-
methyl-2-thio-1,3-thiazine (24); (ii) conversion of the 1,3-thiazine into the 1-
substituted 2-thiouracil by reaction with a primary amine (see Scheme 8); (iii)
oxidation of the 6-hydroxymethyl group to a carboxyl group.
3,4-Dihydro-6-hydroxymethyl-4-oxo-2-thio-2H-1,3-thiazine was prepared
directly from the reaction of dithiocarbamio acid with ethyl γ-hydroxytetrolate (an
improved synthesis of this ester is described). Reaction of the thiazine with primary
Bmines was straightforward and produced the related 6-hydroxymethyl-2-thio-
uracils in high yield (see Table 2). Similar reactions with O-benzylhydroxylamine
formed the 0-benzyl derivative of the Nl-hydroxy-2-thiopyrimidine (40).
Nickel peroxide has served as a very selective oxidant in the pyrimidine
series. Smoot'h oxidation of the hydroxymethyl group to carboxyl is demonstrated
by the conversion of the 6-hyclroxymethyluracils into the corresponding orotic acids.
The same products result from the 2-thiouracils on treatment with excess reagent
because additional oxidative desulphurization of the 2-thione group occurs. More
interestingly, seleotive oxidation of the 6-hydroxymethyl group can be achieved
in the presence of the 2-thione group using two equivalents of nickel peroxide, to
form a 1-substituted 2-thioorotic acid (Scheme 9).
Application of this method to the preparation of I-hydroxyorotic acid mas
successful, but only in the presence of excess nickel peroxide reagent. Under other
conditions rapid decarboxylation occurred to form either 1-benzyloxyuracil or
1-benzyloxy-2-thiouracil and this has been developed into a useful synthetic route
to these products. The role of nickel complexes in this deoarboxylation is discussed
in terms of the hard/soft, acid/base theory.
P.m.r. data on all compounds are reported.
Mass spectrometric studies. IX. Benzylidenemalonic esters and related compounds
Authors: Porter QN , Ramsay CR
Published: September 2010

Skeletal rearrangements
resulting from alkoxy-group migrations are prominent in the mass spectra of
some benzylidenemalonic esters, and involve elimination of C3O2
as a neutral fragment. Similar rearrangements of a chloride atom dominate the
mass spectra of benzylidenemalonyl chloride, but migrations of alkyl and aryl
groups are unimportant in the mass spectra of structurally related benzylidene β-diketones.
The rearrangements observed have been rationalized as the result of a
four-centre migration to a carbonium ion centre.
Vibrational spectrum and molecular structure of methyl pyruvate
Authors: Wilmshurst JK , Horwood JF
Published: September 2010

The infrared spectrum of
methyl pyruvate in the liquid phase in the vapour phase, in solution, and as a
glassy and crystalline solid has been obtained from 4000 to 200 cm-1,
together with the Raman spectrum of the liquid. The data are consistent with
the assumption of a planar pseudo-trans isomer in the crystalline state, and a
mixture of this isomer with a less stable planar pseudo-cis isomer in the other
phases investigated. The energy difference between the two isomers in the
liquid state was found to be c. 650 cal mol-1. A complete
assignment, with the exception of the torsional modes, has been made for both
rotational isomers.
Isolation and identification of some photo-oxidation products of tryptophan
Authors: Savige WE
Published: September 2010

When an aerated aqueous
solution of tryptophan at pH 6-9 is irradiated by visible light in the presence
of a photosensitizing dye, N?- formylkynurenine is usually a major product. However,
a similar irradiation in dilute ammonia at pH 8-9 gives mainly 4-(2-amino-2- carboxyethyl)quinazoline,
a new amino acid; formyl-kynurenine 1s shown not to be an intermediate in the
photoreaction. Tryptophan methyl ester and 2-methyltryptophan give
photoproducts analogous to those of tryptophan. On the other hand, N-acetyltryptophan
and indole-3- propionic acid give the formylkynurenine analogue either in the
absence or presence of ammonia, no quinazoline being detected.
The pyrolysis of some derivatives of β-pinene
Authors: Coxon JM , Garland RP , Hartshorn MP
Published: September 2010

The gas-phase pyrolyses of
cis-pinocarveol (6), trans-pinocarveol (11a), and trans-pinocarvyl acetate (11b)
are described. The mode of formation of aldehyde (10) from cis- and
trans-pinocarveol was determined by deuterium labelling experiments. Photolysis
of verbenene (22) gives the triene (17).
The interaction between a series of acid azo dyestuffs and nonionic surfactants in aqueous solution
Authors: Datyner A , Delaney MJ , Holliger H
Published: September 2010

The diffusion of a series
of seven acid dyes in aqueous solutions in the absence and presence of nonionic
surfactants has been investigated. Some indications have been obtained
regarding the mechanism of interaction between the two species in solution.
Preparation, properties, and structure of some organotin acrylates
Authors: Cummins RA , Dunn P , Oldfield D
Published: September 2010

A series of organotin
esters of 2-cyano-3,3-diphenylacrylic acid has been prepared. The esters
decarboxylated on heating to give the corresponding organotin olefins. The
thermal stability, fungicidal activity, and structure of these esters have been
investigated.
New tropane alkaloids, (+)-(3R,6R)-3α-Acetoxy-6β-hydroxytropane and (+)-2α-Benzoyloxy-3β-hydroxynortropane, from Peripentadenia mearsii (Euphorbiaceae)
Authors: Johns SR , Lamberton JA , Sioumis AA
Published: September 2010

Two new alkaloids,
(+)-(3R,6R)-3α-acetoxy-6β-hydroxytropane (2) and (+)-2α-benzoyloxy-3β-hydroxynortropane
(6), together with the known tropacocaine (3β-benzoyloxytropane), have been isolated from leaves of the
Queensland species Peripentadenia mearsii (family Euphorbiaceae).
A model for the thermal regeneration of ion-exchange resins, Part II
Authors: Hamann SD
Published: September 2010

The model described in Part
I1 has been extended to allow for two factors which may explain the
abnormally flat titration curves of some amine ion-exchange resins. They are
(a) the possible formation of ion pairs within a resin and (b) a possible
increase in the ionization constant of the functional groups in a resin as its
degree of ionization increases. It is suggested that the change (b) may occur
if the di- electric constant of a resin is increased
sufficiently by the absorption of ions and water as titration proceeds. ��� Calculations have been made of the
influence of both effects on thermal regeneration equilibria.
The thermal decompositions of carbamates. I. Ethyl N-Methyl-N-phenylcarbamate
Authors: Daly NJ , Ziolkowski F
Published: September 2010

Ethyl N-methyl-N-phenylcarbamate
decomposes in the gas phase over the range 329-380� to give N-methylaniline,
carbon dioxide, and ethylene. The reaction is quantitative, and is first order
in the carbamate. First-order rate constants are described by the equation

������������������� k1 = 1012.44
exp(-45,380/RT) (s-1)

and are unaffected by the
addition of cyclohexene or by increase in the surface to volume ratio of the
reaction vessel. The reaction is considered to be unimolecular and likely to
proceed by means of a mechanism of the type represented by the pyrolyses of
acetates, xanthates, and carbonates.
Nuclear magnetic resonance spectra of Di-t-butylaryl carbinols
Authors: Gall RE , Landman D , Newsoroff GP , Sternhell S
Published: September 2010

The preparation and N.M.R.
spectra of five title compounds, none of which were substituted at the aryl 2
or 6 positions, is described. Appreciable (ΔG* c � 1 kcal/mol) barriers to
rotation about the sp2-sp3 carbon-carbon bonds exist in
this series and the hydroxyl oxygen atom is in the plane of the aryl ring in
the energetically favoured conformers. Two unequally populated low
energy conformers were identified in the title compounds carrying different
substituents at the 3 and 5 positions of the phenyl ring. Some general aspects
of the determination of activation parameters from variable-temperature N.M.R.
spectra are discussed.
2-Methylenebutyrolactones. I. Monoaryl derivatives
Authors: Dalton LK , Elmes BC
Published: September 2010

The Mannich
reaction of a dialkylamine and formaldehyde with 2-carboxy-

butyrolactones leads directly to isolable
2-methylenebutyrolactones. It is suggested that this happens through a
concerted decarboxylation-elimination mechanism. 2-Methylene-3- and -4-phenylbutyrolactones
and their cysteine addition products, and
3-methylene-2-oxo-cis-2,3,3a,4,5,9b-hexhydronaphtho[1,2-b]furan
and its di-methylamine addition product have been
prepared. 3-Oxo-2,3,4,4a,6,6-hexahydro-naphtho[l,2-c]pyridazine has also been
synthesized.
Molybdenum(Iv) halide complexes with the chelating ligands Schiff bases, acetylacetoae, and 8-hydroxyquinoline
Authors: van den Bergen A , Murray KS , West BO
Published: September 2010

A range of molybdenum(1V)
complexes of the type Mo(che1ate)2X2 have been prepared where (chelate) =
N-substituted salicylaldimine, acetylacetone, and
8-hydroxyquinoline; X = halogen. They can be prepared by direct substitution of
chlorine from MoCl4(MeCN)2 by a
chelating group or by oxidative substitution of MoX3py3.
The magnetic and spectroscopic properties of these six-coordinate d2 complexes
are discussed.
Kinetic medium effects. IV. Transition state activity coefficients in mixed solvents
Authors: McTigue PT , Watkins AR
Published: September 2010

The kinetics of acid hydrolysis
of a number of aliphatic acetals have been studied in
dimethyl sulphoxide-water and dioxan-water
mixtures. Where possible, experimentally measured medium activity coefficients
for the acetals in the solvent systems have been used
in order to calculate the transition state activity coefficients as a function
of solvent composition. These activity coefficients are compared with those
calculated for the transition states of other hydrolytic reactions, and with
the known activity coefficients of some stable ions. The results show no
features inconsistent with the assumptions of transition state theory.
Flavan derivatives. XXXIII. 2-Methoxyflavan-3,4-dione and 2-Methoxyflavan-3,4-diol derivatives
Authors: Clark-Lewis JW , Dainis I , McGarry EJ , Baig MI
Published: September 2010

Sodium borohydride
reduction of 3-hydroxy-7-benzyloxy-2,3,4'-trimethoxy-flavanone and of
3-hydroxy-2,3,7,4'-tetramethoxyflavanone is shown to yield mainly trans-trans-2-methoxyflavan-3,4-dials, a
novel class of flavan derivatives. The 7-benzyloxy hemiacetal also gave a minor quantity of the cis-cis-2-methoxyflavan-3,4-dial and
less of the corresponding 2,3-cis-flavan-3,4-trans-dial. Catalytic hydrogenation over
palladium, or reduction with complex metal hydrides at room temperature or above,
converted the hemiacetals into the flavonols from which they were originally prepared by
oxidation with periodic acid in methanol.
A new synthesis of azocines
Authors: Elix JA , Wilson WS , Warrener RN , Calder IC
Published: September 2010

Methyl and ethyl
7,8-diphenylazocine-2-carboxylate have been prepared by the reaction of
dimethyl tricyclo[4,2,2,02,5]deca-3,7,9-triene-7,8-dicarboxylate
with methyl or ethyl 5,6-diphenyl-1,2,4-triazine-3-carboxylate. The flexibility
of this azocine ring system has been studied by p.m.r. spectroscopy and it was found that a higher
temperature was required to effect rapid ring inversion in this case, in
comparison with the related cyclooctatetraenes. A
related bridged dihydroazocine (8) has been
synthesized by the [π2s + π4s] cycloaddition of dimethyl tricyclo-[4,2,2,02,5]deca-3,9-diene-7,8-dicarboxylate
to ethyl 5,6-diphenyl-1,2,4-triazine-3-car-boxylate. In contrast to previously
described dihydroazocines, this compound exists
entirely in the monocyclic form. Other [π2s + π4s] cycloadditions have also been described in which the π4s
component was part of a triazine or a 3-azabicyclo-[4,2,0]octa-2,4-diene
ring system.
The electronic spectrum of binuclear copper acetate monohydrate
Authors: Dubicki L
Published: September 2010

The near-ultraviolet
spectrum of copper(11) acetate monohydrate consists of at least two bands
centred at 360 and 325 nm, and polarized parallel and perpendicular to the
copper-copper axis, respectively. From the temperature dependence of intensity
the two bands are identified as singlet-singlet transitions. Their
polarizations and intensities are consistent with the charge transfer
assignments,

lAlg → lA2u [b2u(py)
→ bIg(x2-y2)]
and lAlg → lEu [eg(px) → bu2(x2-y2)],
where b2u(py) and eg(px) are nonbonding ligand
molecular orbitals composed of out-of-plane and
in-plane oxygen 2p-orbitals, respectively.
The effect of illumination on the adsorption of dyes on zinc oxide
Authors: Norman VJ
Published: September 2010

The adsorption of uranine and rhodamine B, from ethanolic solution, onto
high-purity polycrystalline zinc oxide has been determined in the dark, in
natural room-light, and under ultraviolet irradiation. It is shown that the amount
of uranine chemisorbed in room-light is approximately
60% greater than that chemisorbed in the dark. Ultraviolet irradiation effected
a threefold increase in the amount of uranine
chemisorbed, with a corresponding decrease in physisorption
and total adsorption. The adsorption of rhodamine
B, which is exclusively chemisorption, is significantly increased in
room-light, and is approximately doubled by ultraviolet irradiation.
[1,4]Thiazino[2,3,4-ij]quinoline derivatives and related heterocycles
Authors: Katekar GF
Published: September 2010

Reaction of
2H-1,4-benzothiazin-3(4H)-one, 2H-1,4-benzoxazin-3(4H)-one, 2,3-dihydro-1,5-benzothiazepin-4(6H)-one,
and 2,3-dihydro-1,6-benzoxazepin-4(5H)-one with propiolactone
gave rise to the corresponding 3-propionic acids (1) and (4) in good yields. Cyclization
of 3-(3-0~0-3,4-dihydr0-2H-1,4-benzothiazin-4-yl)-propionic
acid with polyphosphoric acid gave 3,7-dioxo-2,3,6,7-tetrahydro-5H [1,4]thiazino[2,3,4-ij]quinoline (2a).
The 1,4-oxazino analogue (2b) (oxajulolidine) and
3,8-dioxo-2,3,7,8-tetrahydro-4H,6H-[1,5]oxazepino[2,3,4-.ij]quinoline (5b; R = H) were prepared by a similar route.
Some reactions of these compounds are described.
Mean amplitudes of vibration for some pyramidal axial XY3ZUV type molecules
Authors: Devarajan V , Cyvin SJ
Published: September 2010

Mean amplitudes of
vibration for 12 XY3ZUV type molecules (methyl-, silyl-,and
germyl-acetylenes, methylhaloacetylenes)
have been determined. Bastiansen-Morino linear
shrinkages for the chain XZUV have also been evaluated. The results were found
to differ significantly from the results of previous workers.
The Mills-Nixon effect. III. Detritiation of veratrol, 1,3-benzodioxole, and 1,4-benzodioxan
Authors: Czernohorsky JH , Richards KE , Wright GJ
Published: September 2010

The rates of detritiation of [3-T]- and [4-T]-veratrol,
[4-T]- and [5-T]-1,3-benzodioxole, and [5-T]- and [6-T]-1,4-benzodioxan have
been measured at 30� in anhydrous trifluoroacetic acid. The observed order of reactivities can be explained in terms of a balance of
strain and hybridization effects imposed by the fused ether rings, and
differences in the extent of Ar-O delocalization among the three substrates.
Fluorine magnetic resonance studies. I. para-Substituted β,β-difluorostyrenes
Authors: Rae ID , Smith LK
Published: September 2010

A series of seven para-substituted β,β-difluorostyrenes
has been prepared and their proton and fluorine magnetic resonance spectra
recorded. The fluorine spectra show interesting correlations with the σ-
values for the para substituents, the
fluorine resonances moving to lower field and the geminal fluorine-fluorine
coupling constant decreasing as σ- increases. These trends parallel those
observed in the analogous styrenes but rather more
precise relationships have been established for the fluorine compounds. Long
range fluorine-fluorine spin-spin coupling over six and seven bonds,
respectively, has been observed in the β,β,β,3- and β,β,4-trifluoro-styrenes.
The surface chemistry of kaolinite. II. Catalysis of n-butane decomposition
Authors: Buchanan AS , Oppenheim RC
Published: September 2010

The catalytic activity of kaolinite before and after acid leaching for the
decomposition of n-butane between 669 and 727 K has been compared with that of
alumina natural and precipitated, and silica. The catalysis of hydrocarbon
reactions on oxide surfaces appears to involve oxygen atoms which may be
attached to the solid surface either physically adsorbed as the gas, as part of
the lattice, or possibly as attached hydroxyl
groups. Dehydrogenation of the
hydrocarbon appears to be the first important step, suggesting that adsorption
of the reactant involves interaction of the hydrogen atoms with lone pair
electrons of surface oxygen atoms.
γ-Radiolysis of some 1,4-quinones in benzene
Authors: Wilson JG , Sweeting JW
Published: September 2010

The γ-radiolysis of
several 1,4-quinones in benzene solution has been studied.� 1,4-Benzoquinone, 1,4-naphthoquinone, and
2-phenylnaphthoquinone undergo nuclear phenylation in deaerated solution. In
aerated solution 1,4-benzoquinone is exceptional in being converted into
4-hydroxydiphenyl ether (13). Possible mechanisms for the formation of the
radiolysis products are discussed.
Insect Moulting Hormones: The Phytoecdysones of Dacrydium Intermedium
Authors: Russell G , Fenemore P , Horn DS , Middleton EJ
Published: September 2010

The 2-cinnamate esters of β-ecdysone,
polypodine B, and ponasterone C and the
3-p-oournarate ester of β-ecdysone have been isolated from the bark of Dacrydium intermedium
as new natural ecdysone esters. β-Ecdysone, polypodine
B, ponasterone C, and pterosterone also occur in this plant.
A charge transfer theory of the photoelectrochemical effect
Authors: Matthews DB
Published: September 2010

A model based on the Gurney
theory of charge transfer is used to obtain a theory of the photo-electrochemical
effect at the metal electrode-electrolyte interface. The theory leads to a
means of measuring the effective electronic work function at the metal-solution
interface and to a means of testing the proposed model.