bluuebunny/crossref_metadata_2025 huggingface dataset:
Polarography of some coordination compounds of Platinum. III. Ions of the tetrammineplatinum(II) type
Authors: Hall JR , Plowman RA
Published: September 2010

A number of tetrammine ions of divalent
platinum, in which the ligands were ammonia, methylamine, dimethylamine,
ethylenediamine, pyridine, aniline, and combinations of some of these, were
studied at the dropping mercury electrode. Some of the ions showed maxima in
their current-voltage curves (c-v curves). The formation of hydrogen interfered
with the c-v curves of other ions, so that limiting currents were not
obtainable. A method was devised for the measurement of a voltage by means of
which the ease of reduction of the ions could be compared. Using a supporting
electrolyte of 0.1M KCl and 0.01% gelatin, the order of increasing ease of
reduction was found to be [Pt{(CH3)2NH)4]2+
= [Pt(NH3)4]2+ = [Pt(NH3)3(C5H5N)]2+
= [Pt{C2H4(NH2)2}2]2+
< cis-[Pt(NH3)2(C5H5N)2]2+
< trans-[Pt(NH3)2C5H5N)2]2+
< [Pt(CH3NH2)4]2+ = [Pt(NH3)(C5H5N)3]2+
<[Pt(C6H5N)4]2+ < cis-[Pt(NH3)2(C6H5NH2)2]2+
< trans-[Pt(NH3)2(C6H5NH2)2]2+.
When the ammonia groups of
[Pt(NHS),l2+ were successively replaced by pyridine groups, the resulting e-v
curves shifted progressively to more positive voltages. It was also found that
cis- and trans-isomers of [PtA,B,I2+ reduced at different voltages. The
trans-isomer reduced more readily.
The alkaloids of Atherosperma moschatum Labill. I. Isolation of the alkaloids and structure of Berbamine
Authors: Bick IRC , Clezy PS , Crow ED
Published: September 2010

The bark of Atherosperma moschatum Labill.
of the family Monimiaceae contains the known bisbenzylisoquinoline alkaloids
berbamine (1.6 per cent.) and isotetrandrine (0.06 per cent.), together with
isocorydine (0.007 per cent.) and three new alkaloids atherosperminine, C20H23O2N
(0.005 per cent.), atherospermidine, C18Hl3O4N
(0 006 per cent.), and spermatheridine, C17H11O3N
(0.002 per cent.). The last two alkaloids are bright yellow and weakly basic.
In addition to the bases listed above the leaves contain a trace of another
alkaloid spermatherine. Both bark and leaves contain . phenolic alkaloids which
were not further investigated. The position of the hitherto unlocated hydroxyl
group in berbamine is unequivocally established by fission of O-ethylberbamine with sodium in liquid ammonia.
The reaction of Sodium Acetylide with Benzil and related compounds
Authors: Cymerman-Craig J , Moyle M , Rowe-Smith P , Wailes PC
Published: September 2010

Attempted condensation of benzil and
benzoin with sodium acetylide in liquid ammonia caused fission of the central
carbon-carbon bond of these substances, giving 3-phenylprop-1-yn-3-ol.

Condensation of α-bromodeoxyanisoin
with the same reagent gave several non-acetylenic products which have been
identified.
Studies in the chemistry of phenothiazine. II. Dichloro phenothiazines, and some observations on the Herz reaction and the smiles rearrangement
Authors: Farrington KJ , Warburton WK
Published: September 2010

The preparation of some
dichlorophenothiazines is described. Some limitations of the Herz reaction and
of the Smiles rearrangement are discussed. The orientation of some substitution
products is established.
Studies of the optically active compounds of Anacardiaceae Exudates. IV. The structures of the rearrangement products from the long chain alicyclic ketoalocohol of Tigaso oil in Alkali
Authors: Lamberton JA
Published: September 2010

The structure IIIa previously proposed for
the β-diketone with an unsaturated side chain, obtained by the action of
alkali on the optically active compound of Tigaso oil, is confirmed by the
formation of methyl stearyl ketone and resorcinol monomethyl ether in the
pyrolysis of the methyl ether (IV). An anomalous lithium aluminium hydride
reduction of the methyl ether (IV) and other reactions are discussed.
Unsuccessful attempts have been made to synthesize the tribasic acid resulting
from sodium hypobromite oxidation of the β-diketone (IIIb).
Chemistry of non-enzymic Browing. IV. Determination of Amino acids and amino acid-deoxyfructoses in Browned Freeze-dried Apricots
Authors: Ingles DL , Reynolds TM
Published: September 2010

1-(N-Amino acid)-1-deoxyfructoses have
been determined by elution chromatography on columns of a buffered cation
exchange resin following the method described by Moore and Stein (1954a) for
the determination of amino acids. This method has been used to determine the
free amino acids and ammonia in freeze-dried apricots before and after storage
for 12 months at 25 �C and 70 per cent. R.H., as well as to determine the
1-(N-amino acid)-1-deoxyfructoses and related compounds formed (Anet and
Reynolds 1957) during storage. The total free amino acid decreased by 61 per
cent. and the ammonia by 9 per cent., the changes in individual amino acids
ranging from 22 to 81 per cent. The amino acid-deoxyfructoses and related
compounds accounted for 90 per cent. of the free amino acid lost, the actual
discrepancy being 1.2 mM/100 g dry weight of fruit.
The preparation of compounds related to S-2-Aminoethyl-L-cysteine
Authors: Lindley H
Published: September 2010

The present paper describes the
preparation of benzyloxycarbonyl-2-bromoethylamine,
benzyloxycarbonyl-2-iodoethylamine, S-2-benzyloxycarbonylaminoethyl-L-cysteine,
S-2-aminoethyl-L-cysteine, and polymers of the last two compounds. The
preparation of carboxymethyl 2-aminoethyl sulphide is also described and it is
reported that the latter compound does not act as an inhibitor for the
hydrolysis of toluene-p-sulphonyl-L-arginine methyl ester by trypsin.
The reaction of thiol and disulphide groups with mercuric chloride and methylmercuric iodide. I. Simple thiols and soluble proteins
Authors: Leach SJ
Published: September 2010

The polarographic behaviour of MeHgCl,
MeHgI, HgCl2, neohydrin (3-chloromercuri-2-methoxypropylurea) and
its iodo-derivative are described. Their chemical reactivity and -SH
specificity have been investigated and MeHgI shown to have advantages as an -SH
reagent on account of its high reactivity, stability, and " ideal "
polarographic behaviour.

The reaction of protein -SS- groups with Na2SO3 proceeds slowly to completion
in the presence of HgCl2 or MeHgI and it is shown that with bovine
plasma albumin, ribonuclease, and insulin the polypeptide chains may be
separated for preparative or structural studies under milder conditions than
are customary.

In the presence of urea at pH 9 the
reaction is sufficiently rapid to form the basis of amperometric titration
procedures for determining -SS- groups in eight intact proteins. The methods
are especially valuable for proteins which have been previously converted to
their -SR, -SO3-, or -SSO3-;
derivatives since the destructive hydrolytic step may be avoided. The mechanism
and stoichiometry of the reactions are discussed.
Surface Properties of Liquid Metals: Bismuth, Lead-Bismuth, Tin
Authors: Bradhurst DH , Buchanan AS
Published: September 2010

Dissolved oxygen was shown to have
inappreciable surface activity in liquid bismuth up to 700 �C. Introduction of
lead as a third solute in the liquid bismuth however increased the surface
activity of oxygen. The solutes oxygen, sulphur, selenium, and tellurium showed
the same order of surface activity in liquid tin as in liquid lead.
Stereochemistry of Cyclohexane Derivatives. VII. The 4-Aminocyclohexanols
Authors: Della EW , Jefferies PR
Published: September 2010

The structures assigned to the 4-aminocyclohexanols
have been confirmed and some fundamental reactions studied. Solvolysis of
trans-4-benzamidocyclohexyl toluene-p-sulphonate has shown absence of
participation in the rate-determining step although product analysis indicates
that the reaction proceeds with retention of configuration. The bromination of
4-benzamidocyclohexene and solvolysis of the products have been studied.
The Chemistry of Eremophila Species. II. A Novel Unsaturated Fatty Acid from E. oppositifolia R.Br
Authors: Jefferies PR , Knox JR
Published: September 2010

From the leaves of Eremophila
oppositifolia R.Br., a fatty acid C17H26O4 has
been isolated. Its structure is shown to be 5-acetoxymethyltetradeca-trans-2,trans-4,trans-6-trienoic
acid.
The Kinetics of the Reduction of Lead Monoxide by Hydrogen
Authors: Culver RV , Matthew IG , Spooner ECR
Published: September 2010

The rate of reduction of fused lead
monoxide particles in a differential reactor with H2-N2
and H2-H2O mixtures has been measured by absorbing the H2O
of reaction or chemically analysing the product, Pb-PbO.
After falling from a high initial value, the reduction rate remains virtually
constant until 40-50% of the PbO has been reduced,
and then slowly declines. The rate of reduction is independent of the gas flow
rate from 5-151. S.T.P./min and not markedly influenced by variations in
particle size from -36+52 to -7+10 mesh B.S.S. With H2-N2
mixtures the rate of reduction of PbO at 575 and 675 �C
is proportional to pH2,
and with H2-H2O mixtures at 575 �C it is proportional to pH2/(1+0.5pH2O),
where pH2,
and pH2O
are the partial pressures of H2 and H2O, respectively.
The activation energy for reduction with H2-N2 and H2-H2O
mixtures over the temperature range 475-775 �C is 39 kcal/g-mole. Chemisorption
of H2 on the PbO appears the most likely
rate controlling step at the Pb-PbO interface. Rates
of reduction over the steady rate period, k0,
are correlated by the expression k0=f(R)[pH2/(1+0
5 pH2O)]
exp(-39 000/RT), where f(R) is a parameter
related to particle shape and size.
Degradation of carbohydrates: III. Unsaturated hexosones
Authors: Anet EFLJ
Published: September 2010

Two unsaturated osones have been isolated
as byproducts from the decomposition of 1,1'-(carboxymethylamino)bis-[1-deoxy-D-fructose].
They were shown to be the trans- and cis-forms of unsaturated
3,4-dideoxy-D-glucosone, D-glycero-1,1,5,6-tetrahydroxy- trans-hex-3-en-2-one,
and D-glycero-1,5-epoxy-lαβ,6-dihydroxy-cis-hex-3-en-2-one
respectively, by their chemical properties and by ultraviolet, infrared, and
proton magnetic resonance spectroscopy.
The Effects of Substituents on the pKα, Values of "meta"-Substituted 1- and 2-Naphthols
Authors: Bryson A , Matthews RW
Published: September 2010

pKa
values (H2O at 25�C) have been measured for 3-substituted
1-naphthols and 4-substituted 2-naphthols and the results show that the
behaviour of these compounds is similar to that of the equivalent
naphthylamines. ΔpKa
values satisfy equations of the type: ΔpKa = ρIσI + ρRσR,
where σI and σR are inductive and mesomeric
constants applying to meta-substituents. Reaction constants ρI
and ρM are interpreted in terms of the energy terms involved
and can be correlated with the a-electron distributions in the molecular
species concerned.
The reaction of methanol vapour with silver(I) oxide
Authors: Allen JA
Published: September 2010

The reaction of methanol with silver(I)
oxide has been studied in the temperature range 56.5-78.4�. For complete
reduction of the oxide at 78.4�, the available oxygen is fully accounted for by
the products, formaldehyde, formic acid, carbon monoxide, carbon dioxide, and
water. In the temperature range 56.5-70.2� the net measured rates of formation
of these products are expressed by equations of the form, ������������������ rate = Aexp(-E/RT), and the kinetic data are
interpreted as the consecutive formation of the products on the surface without
complete desorption to the gas phase between each step. For the dominant
product, carbon dioxide, at the mean temperature the values of A and E are 1028.5
μg oxygen per minute and 41.3 kcal mole-1 respectively. The
former is interpreted in terms of a simple collision model and the latter
compared with values obtained for the thermal decomposition of the oxide.
The zeta potential of synthetic sapphire
Authors: Street N
Published: September 2010

In contrast to powdered specimens, bulk
samples of synthetic sapphire do not exhibit an isoelectric point even at pH as
low as 1.65.
The mass spectra of some naturally occurring oxygen heterocycles and related compounds
Authors: Barnes CS , Occolowitz JL
Published: September 2010

The mass spectra of some naturally
occurring and synthetic α- and γ-pyrones, benzofurans, and
2,2-dimethylchromenes have been determined. Under electron impact compounds
derived from coumarin lose oxygen atoms as CO, usually forming a stable
benzofuran ion. 2,2-Dimethylchromenes lose a methyl radical to give a stable
benzopyrylium ion, while the most prominent fission of flavanoid compounds
occurs by breaking both bonds β to the A ring.
Colouring matters of Australian plants. XII. Quinones from Dianella revoluta and Stypandra grandis
Authors: Cooke RG , Sparrow LG
Published: September 2010

A new pigment, dianellinone, has been
isolated from the roots of Dianella revoluta and Stypandra grandis in yields of
0.09 % and 0 025 % respectively. S. grandis also contains a second pigment,
stypandrone, which has been identified as 6-acetyl-5-hydroxy-7-methyl-1,4-naphthoquinone.
Chemical and spectroscopic evidence indicates that dianellinone is the
corresponding 3,3'-dinaphthoquinone.
Three new staphylonuclear chloromolybdates : K6Mo3Cl12, (NH4)7Mo3Cl13,H2O, and Cs6Mo4Cl16
Authors: Anderson IR , Sheldon JC
Published: September 2010

The new compounds, K6Mo3IICl12;
(NH4)7Mo3IICl13.H2O;
and Cs6Mo4Cl16 (containing molybdenum in
oxidation state +2.5) have been precipitated by the appropriate cation from solutions
of molybdenum(II) acetate in 12M hydrochloric acid. The absorption spectra of
potassium and ammonium salts are similar in the solid state and solution. Since
the compounds are strong reducing agents and short-lived in solution, their
formulation as a staphylonuclear (i.e. metal-clustered) trimer or tetramer
rests on their diamagnetism, stoicheiometry, and spectral similarities.

It is proposed that the chloromolybdates
adopt entirely novel, compact polymers by stacking the chlorine atoms into
"close packed" layers. The Mo3Cl13 group
consists of two layers of chlorine atoms (seven and six) generating three
octahedral locations for the molybdenum atoms at the corners of a regular
triangle. The Mo3Cl12 group is similar but deficient in
one chlorine atom. The Mo4Cl16 group is related to Mo3Cl13
and consists of three layers of chlorine atoms (seven, six, and three)
providing four octahedral locations for the molybdenum atoms at the corners of
a tetrahedron.
Protodeboronation of thiophenboronic acids
Authors: Brown RD , Buchanan AS , Humffray AA
Published: September 2010

The relative rates of protodeboronation of
benzene-, thiophen-2-, and thiophen-3-boronic acids at 70� determined by an
extrapolation procedure, are 1 : 7.1 x 103 : 8.5 x 105.
The relative reactivity for 2-substitution thus exceeds that found for any other
electrophilic substitution of thiophen.
The nuclear magnetic resonance spectra of the codeine isomers and their derivatives
Authors: Batterham TJ , Bell KH , Weiss U
Published: September 2010

The nuclear magnetic resonance spectra of
codeine, isocodeine, pseudocodeine, allopseudocodeine, neopine, isoneopine, and
some of their derivatives have been studied and the patterns produced by the
protons on dl rings except the N-heterocyclic ring have been analysed by
first-order methods. Allylic, homoallylic, and other long-range couplings have
been observed. Differences in chemical shift between protons in different
isomers have been explained in terms of the anisotropy of the double bond or
the aromatic ring.
Molecular susceptibility. The diamagnetic anisotropies of sixteen aromatic molecules at infinite dilution in carbon tetrachloride
Authors: Le Fevre RJW , Murthy DSN
Published: September 2010

A photometric method for the determination
of Cotton-Mouton constants of liquids and solutions is introduced. It
advantageously replaces the visual technique used previously. Anisotropies of
diamagnetic susceptibility are recorded for 16 aromatic molecules, and
preliminary estimates drawn therefrom of the apparent longitudinal and
transverse susceptibilities of Car-X bonds, where X = halogen,
methyl, etc.
Poly-L-alanylglycyl-L-alanylglycyl-L-serylglycine: A synthetic model of Bombyx mori Silk Fibroin
Authors: Stewart FHC
Published: September 2010

The sequential polypeptide [Ala-Gly-Ala-Gly-Ser-Gly]n has been prepared by
polymerization of a hexapeptide p-nitrophenyl ester.
This polymer contains the repeating sequence of amino acid residues present in
the crystalline regions of Bombyx mori silk fibroin. The o-nitrophenylsulphenyl
amino-protecting group was used extensively in the synthesis of the hexapeptide active monomer from which the polypeptide was
obtained.
The synthesis of [18]annulene trioxide
Authors: Badger GM , Elix JA , Lewis GE
Published: September 2010

[18]Annulene 1,4:7,10:13,16-trioxide has
been synthesized. It is a deep red stable compound, and its spectral properties
indicate that it is an aromatic system in which there is significant
delocalization of the 18 peripheral π electrons.
Reactions of excited molecules. I. A thermal four-centre migration in phenylhydrazones
Authors: Crow WD , Solly RK
Published: September 2010

Phenylhydrazones of
carbonyl compounds C6H5-CO-R (R = H, Me, Et, Ph) have
been subjected to vapour-phase pyrolysis at temperatures ranging from 650 to
1100�K. Analysis of the products indicates that a four-centre reaction is
involved in which the group R migrates to the α- nitrogen of the
phenylhydrazone moiety, with a concomitant production of benzonitrile. The
mechanisms of this and competing reactions are discussed.
Phenanthroline and bipyridine chelates of molybdenum
Authors: Marzilli PA , Buckingham DA
Published: September 2010

The previously reported preparations of [Mo bipy3]Cl3 and [Mo phen3]Cl3 have been reinvestigated and found to result
in mixtures of (bipyH)[MoCl4
bipy], [Mo2O3Cl4
bipy2], NH4[MoCl4
bipy] and (phenH)[MoCl4 phen], [Mo2O4Cl2 phen2],H2O, K(phenH)2[MoCl6], respectively. All attempts to prepare
[Mo bipy3]Cl3
and [Mo phen3]Cl3
have been unsuccessful. [MoCl2 bipy2][MoCl4
bipy] has been prepared from the direct reaction of K3MoCl6 and bipyridine under vacuum. [MoCl3 py phen] and [MoCl3 py bipy] have been obtained from
[MoCl3 py3].
Infrared and visible spectra of the compounds are discussed along with the
e.s.r. spectrum of [MoOCl3 bipy].
The formation of 5-hydroxymethylfurfural from hexoses
Authors: Moye CJ
Published: September 2010

In the acid catalysed
conversion of hexoses to furans, the yield of 2- furyl hydroxymethyl ketone
(FHK) relative to that of 5- hydroxymethylfurfural
(HMF) is the same when either glucose or fructose is used as the starting
material. The significance of this result is discussed in relation to the
various reaction mechanisms proposed for the formation of these products.
Dodecahydrothianthrene, a product formed by pyrolysis of a polymer from the interaction of cyclohexene sulphide and mercaptoethanol
Authors: Culvenor CCJ , Davies W , Hawthorne DG , Macdonald PL , Robertson AV
Published: September 2010

Cyclohexene sulphide and
alkaline mercaptoethanol form 2-hydroxyethyl 2-mercaptocyclohexyl
sulphide and much polymer. Pyrolysis of the polymer gives an oil containing a
low yield of the trans-anti-trans isomer of dodecahydrothianthrene,
whose structure has been determined. Several attempts to synthesize this new
tricyclic series failed, although the bicyclic analogue,
hexahydrobenzo[b]-[1,4]-dithian, was readily accessible. Water, 1,4-thioxan, 1,4-dithian,
acetaldehyde, 2- methyl-1,3-oxathiolan, and 2-methyl-1,3-dithiolan have been
identified amongst the pyrolysis products of thiodiglycol.
Chloroaquo complexes of titanium(III). The 2T2g→2Eg absorption band
Authors: Gardner HJ
Published: September 2010

If the chloride ion content
of aqueous titanium(III) solutions is gradually increased there is a continuous
shifting of the 2T2g → 2Eg peak from c. 20100 cm-1
to c. 14500 cm-1. By applying the rule of average environment it is
possible to draw a ?formation curve? for the number of chloride ions complexed
to the central titanium(III) ion and hence to determine the equilibrium
constants of the successive chloroaquo complexes as chloride ion replaces water
in the octahedral environment. Of these, the first, K1 = {Ti(H2O)5Cl2+}aw/{Ti(H2O)3/6+}{Cl-}, was determined to be 0.07-0.2. The reflectance
spectra of purple titanium trichloride hexahydrate (TiCl3,6H2O)
and a 5% solution of a-titanium trichloride in KCl-LiCl
eutectic mixture at 25� are shown to give ligand field bands in agreement with
the above range of wave numbers.
N-Substituted salicylaldimine complexes of chromium(III)
Authors: O'Conner MJ , West BO
Published: September 2010

Tris(salicylaldehydato)chromium(111)
reacts readily with primary amines or ammonia to give complexes of the form Cr(sal-NR)3 where R = n-C3H9,
i-C4H9,
p-C6H4CH3, p-C6H4Br.
The complexes are monomeric in benzene, and have magnetic moments in the range
3.77-3.81 B.M. at room temperature. Crystal field splitting energies have been
obtained for the complexes from their spectra. Ethylenediamine
reacts with the salicylaldehyde complex to give a
cationic complex containing the tridentate ligand -0-C6H4-CH=NCH2CH2-NH2.
Coordination complexes of amino acids: Preparation and properties of some Amino-acidatobis(acetylacetonato)cobalt(III) and Bis(amino-acidato)(acetylacetonato)cobalt(III) complexes
Authors: Laurie SH
Published: September 2010

Complexes of the type [Co(acac)2(aa)] have been
synthesized, in which the amino acid is DL- and L-phenylalanine, L-valine, L-leucine, L-proline,
DL-, L-,and D-alanine, and glycine. The complexes
were characterized by means of analyses, molecular weights, and their infrared,
visible, and ultraviolet absorption spectra. During the syntheses several of the bis(amino-acidato) complexes, [Co(acac)(aa)2], were also formed; the
L-phenylalanine and glycine complexes were isolated and characterized. The complexes prepared from
the optically active amino acids exhibited Cotton effects in the
region of the visible absorption band (lA1g,
+ 1T1g). These effects have been attributed to induced
asymmetry rather than stereoselectivity. Amino acids of the same
configuration gave rise to Cotton effects of the same sign, ie.
(-)590-[Co(acac)2(L-aa)], (-)6590-[Co(acac)(L-aa)2], and (+)590-[Co(acac),(D-aa)].
Thermodynamics of chelation. I. Iron(II) and zinc(II) complexes of Pyridine-2-aldehyde-2'-pyridylhydrazone
Authors: Green RW , Godwin WG
Published: September 2010

In dilute solution,
pyridine-2-aldehyde-2'-pyridylhydrazone can behave as a diacid base or as a
tridentate chelating agent. Its cationic bis complexes further undergo two
stages of deprotonation. Equilibrium constants have
been measured at seven temperatures from 5� to 60� and over a range of ionic
strength. They have been used to derive values of enthalpies and entropies of
reaction with H+, Fe2+,
and Zn2+.
The chemistry of the Euphorbiaceae. XIX. Diterpene and flavonoid constituents of Beyeria latifolia
Authors: Jefferies PR , Retallack RW
Published: September 2010

Structures have been
established for three new diterpenes, 16,8-(-)-kaurane-3α,16,17,19-tetrol
(XVII), 16β-( -)-kaurane-3α,l6,19-trio1
(XXIII), and 16β-(-)-kaurane-3α,l6,17-trio1
(111), which have been obtained from B. latifolia, the latter pair as diacetates. Two known
flavones have also been isolated from the ether extract.
Additive substituent effects on the ionization of meta-substituted phenols
Authors: Bolton PD , Hall FM , Kudrynski J
Published: September 2010

Thermodynamic ionization
constants of 3-ethoxyphenol; 3,5-diethoxyphenol,
3,5-dichlorophenol, 3,5-dibromophenol,
3,5-diiodophenol, and 3,5-dinitrophenol
have been measured spectrophotometrically within the
temperature range 5-60�, and the thermodynamic functions
of ionization ΔG25, ΔH25, ΔS25,
and ΔCp.25 calculated. These results, in
conjunction with others measured previously, indicate that, for this reaction
series, substituent effects on the free energies of ionization are precisely
additive, and on the entropies of ionization closely additive. An assessment of
the results in terms of Hepler's internal/external
enthalpy theory is made.
A new synthesis of tetramisole hydrochloride, (°)-6-Phenyl-2,3,5,6-tetrahydroimidazo[2,1- b]thiazole hydrochloride
Authors: Baklien A , Leeding MVKJ
Published: September 2010

Tetramisole hydrochloride, a potent anthelmintic,
has now been synthesized by condensation of styrene oxide and ethylenimine. The product, 1-(P-hydroxy-phenethyl)aziridine, reacts with thiourea or thiocyanic
acid to yield 3-(P-hydroxy-phenethyl)-2-iminothiazolidine. Following chlorination with thionyl chloride, a base-catalysed cyclization gives tetramisole. The method provides a general route to 2,3,5,6-tetrahydroimidazo[2,l-b]thiazoles.
The binding of copper(II) to mohair keratin
Authors: Guthrie RE , Laurie SH
Published: September 2010

Measurements of the uptake
of copper(11) by the insoluble keratin, mohair, as a function of the copper(11)
concentration and of the pH, between 3 and 6, are given. From these and other
data on copper(11) uptake and its effects the conclusion is drawn that carboxyl
groups are the primary, but not the sole sites of copper(11) binding in mohair
keratin below pH 5.
The effect of temperature on the electronic spectra of octahedral iron(II) complexes
Authors: Winter G
Published: September 2010

Spectral changes in
iron(11) complexes caused by temperature changes have been examined. When the
iron(11) ion is surrounded by six equivalent ligands (FeC12,
FeBr2, FeI2,
FeSiF6,6H2O) the band
separation that arises from the splitting of the 5Eg
level decreases on cooling. The variation is proportional to the
magnitude of the band separation. In complexes with tetragonal distortion (FeCl2,2H20, FeCl2,-
2CH3OH,FeCl2,4pyridine, FeCl2,2pyridine, FeCl2,4isoquinoline,
FeBr2,4isoquinoline) the variation in band
separation with change in temperature is smaller and is inversely related to
the magnitude of the band separation.
The ligand field spectra of trinuclear chromium(III) and iron(III) basic acetates
Authors: Dubicki L , Martin RL
Published: September 2010

The visible spectra of
trinuclear chromium(III) acetates [Cr3O(CH3CO2)6R2]+
can be successfully analysed by means of the ligand field theory for tetragonal
fields. The ligands R (R = H2O, NH3, py, DMSO) are
relatively labile and may be replaced by several ligands of varying donor
strength. The spectra of trinuclear iron(III) acetates [Fe3O(CH3CO2)6R3]+
are poorly resolved but can be interpreted on the basis of a d5
configuration in octahedral fields.
The constituents of Eriostemon trachyphyllus. The structure of trachyphyllin, a new coumarin
Authors: Lassak EV , Pinhey JT
Published: September 2010

Traohyphyllin, a new coumarin occurring in Eriostemon trachyphyllus, has been shown to have structure (I) mainly
on spectroscopic evidence. Also present in the tree are α-pinene, ethyl
valerate, eugenol, methyleugenol, the coumarins bergapten and xanthoxyletin,
and the alkaloid edulinine. The nitration and bromination reactions of
xanthoxyletin are discussed.
Alkaloids of Schelhammera pedunculata (Liliaceae). III. The structures of schelhammericine and alkaloids A, B, E, G, H, J, and K
Authors: Johns SR , Lamberton JA , Sioumis AA
Published: September 2010

The structures of the new
homoerythrina alkaloids, schelhammericine (III), alkaloids A (IV), G (VII), E
(IX), B (X), H (XI), J (XII), and K (XIII), from Schelhammera pedunculata
(Liliaceae) have been established. The major alkaloid isolated from another Schelhammera
species, S. multiflora R.Br., has been shown to be alkaloid E (IX).
The electronic spectra of acid and basic rhodo salts of chromium(III)
Authors: Dubicki L , Martin RL
Published: September 2010

.The diffuse reflectance spectra of basic rhodo perchlorate, [(NH3)5OCr-
(NH3)5](ClO4)4, a t 300°K and 77°K show evidence for both allowed and forbidden
hot electronic bands. The near-ultraviolet region containing the well-established
four sharp bands in fact contains at least six bands, consisting of two sets of three.
The two sets have inverted intensities and originate from different electronic ground
states.
The spectrum of acid rhodo chloride, [(NH3)5Cr(OH)Cr(NH3)5]Cl5,H2O,
resembles that of a d3 configuration in a near-octahedral field.
Some experiments on the Smith reaction
Authors: Henrick CA , Ridley DD , Ritchie E , Taylor WC
Published: September 2010

Three possible mechanisms
for the Smith reaction, the base-catalysed condensation of acetophenone
and benzoin to desylacetophenone,
were considered but no evidence was obtained for two of them. The third
mechanism, involving an aldol condensation, dehydration,
enolate formation, and reprotonation
at a different site, accounted for the products formed in the reactions of two
unsymmetrical benzoins with acetophenones, provided
an equilibrium existed between the stable and labile forms of the benzoins under the reaction conditions.

Deoxybenzoins and 1,4-diketones required for product
identification were synthesized.
Steroid hormones. XXI. Some testosterone derivatives substituted at C19
Authors: Birch AJ , McKague B
Published: September 2010

Addition of but-1-en-3-one
to (1) produced the adducts (28) and (2b) which undergo ring fission with acid
to give (3). Methylmagnesium iodide on (2a) and (2b)
gives the alcohol mixture (4) which is converted by acid into (5). A similar
series of reactions with derivatives of l,2-dihydrooestrone
methyl ether gives the steroid (10) and the 17β-OH analogue, and (11)
containing an angular isoprene unit.
Structure of 1-Acyl-2-alkyl-2-thiopseudoureas
Authors: Brown BT , Phillips JN
Published: September 2010

Deprotonation of 1-acyl-2-alkyl-2-thiopseudouronium
salts has been shown to involve the loss of a proton from the 1 rather than the
3 position in those cases where both nitrogens carry at least one hydrogen
atom. This results in an acylated 2-thiopseudourea in which the C=N is conjugated to the
carbonyl group.
Ion-molecule reactions in Trihalo- and Tetrahalo-methanes
Authors: McAskill NA
Published: September 2010

The ion-molecule reactions
of eight highly halogenated derivatives of methane were studied in the
gas phase using a mass spectrometer operated at high pressures. The compounds
studied were CHCl3, CHCl2F,
CHClF2, CHF3, CCl4, CCl2F2,
CClF3, and CF4. These ionic
systems were found to be less reactive than those of methane or the methyl and
methylene halides. The main reactions observed were described as being halide
ion transfer processes. The energy dependence of the cross sections and the
rate coefficients of the reactant ions were determined.� Many rate coefficients for reactions
between ions and polar molecules were found to be independent of the ion
energy. Brief studies of the negative spectra at high pressures were also made.
Octahedral cobalt(III) complexes of the chloropentammine type. XXI. The preparation, properties, and reactions of some Chloro(amine)bis(ethylenediamine)cobalt(III) salts containing unidentate glycinenitrile and glycinamide as influencing ligands
Authors: Chan SC , Chan FK
Published: September 2010

Salts of one isomeric
series of chloro(amine)bis(ethylenediamine)cobalt(111)
type of cations have been prepared from trans-dichlorobis(ethy1enediamine)-cobalt(111)
chloride by replacing one of its chloro ligands with either glycinenitrile
or glycinamide.
These complexes have been assigned a cis-configuration
on the basis of spectral observations. For the glycinenitrile
system, the cis-chloro(cyano-methylamine)bis(ethylenediamine)cobalt(111) cation rearranges to the trans-chloro(aminoacetonitrile)
isomer in aqueous solution at rates very much higher than those for the aquation of both forms. This isomerization is retarded by
acid and accelerated by base. The kinetics of base hydrolysis are also
reported. On the other hand, for the glycinamide
system, the corresponding isomerization proceeds at rates comparable to those
of chloride release, the latter leading to the formation of the chelated N,O-glycinamidebis(ethylenediamine)cobalt(111) species. Consequently, it has not been possible to
isolate the other linkage isomer in the pure state. Furthermore, although the aquo(glycinamide)bis(ethylenediamine)cobalt(111) species is not formed in non-basic
spontaneous chloride release, its hydroxo counterpart
can be readily obtained by base hydrolysis. The mechanistic implications of
these observations are discussed.
Heterocyclic compounds from alloxan and amines. XII. Tetrahydroquinoxalinespirobarbituric acids and 5-(1-Benzimidazolio)-4-barbiturates from 2-Dialkylaminoanilines
Authors: Clark-Lewis JW , Moody K , Thompson MJ
Published: September 2010

The betaine formed from 2-dimethylaminoaniline and alloxan
is shown to be 5-(3-methyl-1-benzimidazolio)-4-barbiturate
by synthesis from 1-methylbenzimidazole; it's
N,S-dimethyl derivative (1,3-dimethylbarbiturate) was
also synthesized. A number of analogous betaines was
prepared from alloxan and 1-o-aminophenyl
derivatives of secondary amines, and it was shown by tracer studies that
enamines are not intermediates in
the reaction. A probable mechanism is discussed. 2-Amino-N-mesityl-N-methylaniline and the N-ethyl analogue gave tetrahydroquinoxaline-spirohexahydrotrioxopyrimidines with alloxan instead of betaines, and
alkaline hydrolysis led to the related 4-mesityltetrahydroquinoxalinohydantoins.
Some of the betaines, and one of the spirans, were also obtained by oxidation of uramils. Mass spectra of the betaines are discussed, and N.M.R. data are reported. Ring
expansion occurs during conversion of 5-(3-methyl-1-benzimidazolio)-4-barbiturate
into the related tetrahydroquinoxalinespirobarbituric
acid by reduction with sodium borohydride.
Infrared spectra of some Bis(8-amino-2-methylquinoline)metal complexes. Evidence for cis configurations
Authors: Litzow MRPLF , Tait AM
Published: September 2010

The infrared spectra of a
number of bis- and mono-complexes of 8-amino-2- methylquinoline
(maq) have been recorded and the possibility of a cis configuration of the two bidentate
ligands in the bis-chelated complexes
is discussed with respect to the complexity in the 850-700 cm-l
region.
Sulphur-nitrogen chelating agents. IX. Complexes of iron(II), cobalt(II), and nickel(II) with the NSSN quadridentate 1,6-Bis(2-pyridyl)-2,5-dithiahexane
Authors: Livingstone SE , Nolan JD
Published: September 2010

Mono-ligand complexes of
the quadridentate ligand 1,6-bis(2-pyridyl)-2,5-dithiahexane (NSSN) of the type MX2(NSSN) (M =
Fe, Co, Ni; X = Cl, Br, I. NCS) have been prepared. The complexes are only
sparingly soluble in polar organic solvents. They have appreciable
conductivities in nitromethane due to replacement of X by a molecule of
solvent, Magnetic and spectral data and stereochemical considerations indicate
that the complexes have a cis-octahedral
configuration.
Diterpenoids. XXV. Dundathic acid and polycommunic acid
Authors: Carman RM , Cowley DE , Marty RA
Published: September 2010

Dundathic acid is a polymer
consisting principally of units (4) derived from communic acid. Experiments
designed to show the major structural features are described.
Circular dichroism spectra of amino acid complexes. II. Chelated amino acid complexes with the CoN5O chromophore
Authors: Hawkins CJ , Lawson PJ
Published: September 2010

The circular dichroism
spectra of a series of optically active (α-aminocarboxylato)tetraamminecobalt(111) complexes have been measured in
aqueous solution, and in the presence of salts of polarizable
anions. The observed spectra in the visible region have been analysed to
determine the signs of the Cotton effects of the three components of the 1A1g ↔ 1T1g
cobalt(111) transition. For L-amino acids, the transition with A2g(D4h)
parentage is negative, and the two transitions with Eg(D4h) parentage have opposite
signs. Published circular dichroism spectra of complexes of the type [Co(en)2(L-am)]2+
were similarly interpreted in terms of a perturbed tetragonal chromophore, and
it was shown that the vicinal effect of the L-amino acids imposed the same
signs onto the component transitions as for the tetraammines
and for a similar series of pentaamminecobalt(111) complexes.
Pigments of marine animals. IX. A synthesis of 6-Acetyl-2,3,5,7-tetrahydroxy-1,4-naphthoquinone; Its status as an echinoid pigment
Authors: Gough JH , Sutherland MD
Published: September 2010

6-Acetyl-2,3,5,7-tetrahydroxy-1,4-naphthoquinone (1) is obtained from 1,2,3,4,5,7-hexaacetoxynaphthalene by Fries rearrangement, hydrolysis,
and oxidation, but differs in properties from the substance described in the
literature as a spine pigment of Echinothrix diadema Linn., E. calamaris Pallis,
and Echinometra
oblonga Blainville and claimed to be (1). The synthetic quinone (1)
is very probably identical with Lederer's spinochrome G from Paracentrotus lividus Lamarck. Paperchromatographic data for various echinoid pigments and
other naphthoquinones is presented.
Polyamine ligands. II. Nickel(II) complexes with the tridentate ligand 5-(2'-Pyridyl)-3-azapentan-1-amine
Authors: Casey AT , Peters W , Phillip AT
Published: September 2010

The tridentate amine 5-(2'-pyridyl)-3-azapentane-1-amine (pap) forms a series of stable nickel(II) complexes of the composition Ni(pap)X2 (X = Cl, Br, I, NO3, SCN, �SO4) and [Ni(pap)2]X2 (X = ClO4, I). Measurements of their electronic absorption spectra, infrared spectra, molar conductance, and magnetic susceptibility indicate that the complexes contain the amine coordinating as a tridentate ligand. In general, the Ni(pap)X2 compounds appear to possess a tetragonally distorted, octahedral structure with bridging anions in the solid state and a solvated complex structure in solution. The [Ni(pap)z]X2 compounds contain two tridentate ligands coordinated to one nickel ion, forming the octahedral NiN6 structure. Geometrical isomerism has been observed in the [Ni(pap)2]I2 compound which can be isolated as a yellow or a pink modification; this isomerism has been attributed to the alternative modes of coordination by the tridentate ligand. The isomerization of the unstable yellow form to the more stable pink form has been followed spectrophotometrically at 28� and appears to be first order in concentration.
Reactivity of transition metal fluorides. VIII. Reactions of rhenium heptafluoride and hexafluoride
Authors: Canterford JH , O'Donnell TA , Waugh AB
Published: September 2010

Oxidation-reduction and
halogen-exchange reactions of the higher fluorides of rhenium with a series of
selected reagents have been investigated. The results correlate with studies of
reactivities of higher fluorides of other transition metals previously reported.
The reactions reported provide markedly improved preparative routes to the
hexachloride, pentabromide, and pentafluoride of rhenium.
Diterpenoids. XXVI. A new diterpenoid acid from the oleoresin of Callitris columellaris
Authors: Carman RM , Deeth HC
Published: September 2010

A new diterpenoid acid,
labda-8(17),13(16),14-trien-19-oic acid, has been isolated from the oleoresin
of Callitris columellaris.
Diphenylpiperidines: Synthesis and properties of some methoxy-substituted 3,4-diphenylpiperidine derivatives
Authors: Gellert E , Rudzats R , Summons RE , Worth BR
Published: September 2010

The α- and β-racemates
of a series of methoxy-substituted N-ethyl-3,4- diphenylpiperidines
have been synthesized by reductive cyclization of the appropriately substituted
ethyl 3,4-diphenyl-4-cyanobutanoates prepared by Michael condensation of the
corresponding phenylacetonitriles with ethyl cinnamate derivatives. The
mechanism of the reduction, the stereochemistry, and the N.M.R. spectra of the
racemates are discussed.
New imidazole alkaloids from Cypholophus friesianus (Urticaceae). The structures and synthesis of cypholophine and O-acetylcypholophine
Authors: Hart NK , Johns SR , Lamberton JA , Loder JW , Nearn RH
Published: September 2010

Two new imidazole alkaloids
cypholophine (1a) and O-acetylcypholophine (1b), isolated from Cypholophus friesianus (family Urticaceae),
have been synthesized. A non-alkaloidal constituent of Cypholophus decipiens
has been identified as the previously known terpenoid lactone, loliolide (2).
Pigments of marine animals. XI. Angular naphthopyrones from the crinoid Comanthus parvicirrus timorensis
Authors: Smith IR , Sutherland MD
Published: September 2010

Green specimens of the
comatulid crinoid, Comanthus parvicirrus
timorensis J. Muller, yield to acetone three yellow
water-soluble colouring matters, comaparvin sulphate, 6-methoxycomaparvin
sulphate, and 6-methoxycomaparvin 5-methyl ether sulphate in approximately 0.1
%, 0.7 %, and 0.7 % yield respectively of the dry weight of the animal, Mild
acid hydrolysis yields the corresponding phenols, the structures of which have
been deduced largely by spectral studies as very probably 5,8-dihydroxy-10-methoxy-2-n-propyl-4H-naphtho[1,2-b]pyran-4-one
(1), the 6-methoxy derivative of (1), and the 6-methoxy methyl ether of (1) respectively.
A yellow colour variant of the same species yielded the same colouring matters
in slightly different proportions. The calcareous skeleton contains what are
probably polyhydroxynaphthoquinones in combined form.
The synthesis and rearrangement of methyl 2,2,4,4-Tetramethylbicyclo[1,1,0]-butane-1-carboxylate
Authors: Hamon DPG , Lill CF
Published: September 2010

The title compound (4) was
prepared by the intramolecular alkylation of methyl 3-tosyloxy-2,2,4,4-tetramethylcyclobutane-1-carboxylate
(3). Compound (3) was prepared by two different routes. ��� Heating compound (4) in the vapour phase at
c. 150� gave three products isomeric with (4). Two of these products, methyl trans-3-
isopropenyl-2,2-dimethyl-cyclopropane-1-carboxylate and methyl 2- isopropenyl-4-methylpent-3-enoate,
were shown to be products of an acid-catalysed rearrangement; the third
product, methyl 2- isopropylidene-4-methylpent-3-enoate, was shown to be the
true product of pyrolysis.
Chlorine nuclear quadrupole resonance in mercury chlorides and complex chlorides
Authors: Scaife DE
Published: September 2010

Chlorine nuclear quadrupole
resonance frequencies are reported for solid compounds of known structure containing
linear molecules HgCl2 and Hg2Cl2, approximately
trigonal HgCl3-, and a variety of distorted octahedral forms
including NH4HgCl3, CsHgCl3, and K2HgCl4,H2O.
Compounds of unknown structure of the type (cation+)HgCl3,
(cation+)2HgCl4, (cation+)Hg2Cl5,
(cation+)2Hg9Cl20, and (cation+)4HgCl6
have also been studied. There are clear correlations between observed n.q.r.
frequencies and Hg-Cl infrared stretching frequencies and bond distances. These
correlations show the dependence of the degree of covalent bonding in the Hg-Cl
bond with distance. The n.q.r. data confirm that many of the complex chlorides
of mercury are built up by the joining of octahedral HgCl6 units,
distorted in such a way as to preserve to varying extents the identity of the
HgCl2 molecule. ��� Predictions of the structures are made for
some complex chlorides of unknown structure, and the role of bridging in
building up the compounds is discussed in terms of observed n.q.r. data for
bridging chlorines.
Radiation dosimetry with acetylene
Authors: McLaren KG
Published: September 2010

The suitability of
acetylene as a gas-phase radiation dosimeter has been studied. Yields were
obtained on an absolute basis, using ionization current dosimetry. Radiolysis
of acetylene produces two products, benzene and polymer. The yield of benzene
is dependent on dose, dose rate, presence of hydrogen or free radical
scavengers, and temperature, and is of no value for estimating dose. ��� For 60Co
γ irradiation at a dose rate of 4.1 x 1013 eV
cm-3 mmHg-1 hr-1 and acetylene pressure 500
mmHg (6.6x104 N m-2) at 30�C, G(-C2H2)
= 82.1�0.5. ��� 1-MeV electron
irradiation at a dose rate of 3.9 x 1016 eV
cm-3 mmHg-1 hr-1 gave a much lower yield, G(-C2H2)
= 55.0�1.9, believed to be due to a dose rate effect. G(-C2H2)
increased by about 67% when the temperature was increased from 25�C to 125-250�C.
��� Comparison with ethylene indicates the
latter is the more useful dosimeter, as the yields do not vary significantly
over a wide range of dose rates and temperatures.
Polarography of coordinated oximes
Authors: Nambiar OGB , Subbaraman PR
Published: September 2010

The polarographic reduction
of dimethylglyoxime, cyclohexane-1,2-dione dioxime (nioxime), α-furil
dioxime, and salicylaldoxime chelated to cobalt(II) and iron(II) has been
investigated. Unlike the parent ligand, the reduction of the coordinated ligand
proceeds in two equal steps in acid solutions. The intermediate half-way stage
is suggested to be the hydroxylamine of the oxime. Results of the controlled
potential electrolysis of the cobalt(II)-dimethylglyoxime chelate also supports
this view. In alkaline solution reduction stops at the half- way stage since
the product of half-way reduction, presumably the corresponding hydroxylamine,
is not further reduced in the available potential range. The first step of
reduction occurs invariably at a potential less negative than that of the
parent ligand.
Free-radical acetoxy group migration: an E.P.R. spectral study
Authors: Beckwith ALJ , Tindal PK
Published: September 2010

E.p.r. spectra have been
recorded for a number of radicals generated in a flow cell from cyclic ethers,
1,3-dioxolans, 1,3-dioxans, and other cyclic and acyclic substrates. The cyclic
radicals do not undergo detectable fragmentation, but the rearrangement of the
radical (9) derived from t-butyl acetate has been observed. The mechanism of
acetoxy group migration in radicals is discussed in the light of these results.
��� The spectral data, including, in some
cases, values of 13C hyperfine splitting factors, indicate that
there is considerable deviation from planarity at the radical, centres of some
cyclic species, and this phenomenon is accompanied by a change in sign of
α-proton splitting factors. The reducing power of radicals derived from
cyclic ethers has been investigated.
Chemistry of the Podocarpaceae. XXXIV. Some oxidation products of (13R)-Labda-8(17),14-dien-13-ol (Manool)
Authors: Cambie RC , Joblin KN , Preston AF
Published: September 2010

Some products from the
oxidation of manool (3) are examined. Potassium permanganate gives, inter alia, the hitherto unreported compound (16) while sodium
dichromate gives the methyl ketone (5) and, as the major product, a mixture of (Z)-
and (E)-α,β-unsaturated aldehydes (21).
Hypoiodite oxidation of the methyl ketone (5) gives the α-hydroxy acid
(26) in addition to the expected acid (6). Products of nucleophilic
substitution have also been obtained from the hypoiodite oxidation of the
methyl ketones (9) and (37). Peracid oxidation of the methyl ketone (5) gives
the epoxy acetate (41) which, on reduction with lithium aluminium hydride,
affords the diol (7), from which the odoriferous oxide (30) can be prepared.
Oxidations leading to formation of the dione (10) are investigated.
Excess free energies of mixing at temperatures below 25°. Isopiestic measurements on the systems H2O-NaCl-Na2SO4 and H2O-NaCl-MgSO4
Authors: Childs CW , Platford RF
Published: September 2010

Isopiestic vapour pressure
measurements have been made on the systems H2O-NaCl-Na2SO4
and H2O-NaCl-MgSO4 at 15� and
0�. Excess free energies of mixing the aqueous salts hare been calculated for
various ionic strengths, and the results have been compared with those
previously obtained at 25�. ��� Within experimental uncertainty the excess
free energies of mixing of aqueous NaCl with aqueous Na2SO4 are the same at 0�, 15�, and
25�. However, the excess free energy of mixing aqueous NaCl
with aqueous MgSO4 shows differences which
may be just larger than experimental uncertainty over the same temperature
range.