bluuebunny/crossref_metadata_2025 huggingface dataset:
Solvent Extraction of Mono(salicylato)beryllium, and the pH Titration of the System Beryllium-Salicylic Acid
Authors: de Bruin HJ , Kairaitis D , Szego L
Published: September 2010

It has been shown that a
salicylatoberyllium complex can be extracted from aqueous solutions by
aliphatic alcohols. The distribution ratio is a symmetrical function of the
logarithm of the free ligand concentration and passes through a maximum value ;
the stability constants of the mono- and bis(salicylato)beryllium complexes
have been determined from the data for points of equal extraction. The values
obtained in this way are β1 = 4.1 x 1012 and β2
= 4.3 x 1022, in an ionic strength of 0.15. They agree fairly well
with those obtained by pH-titration procedures, which are β1 = 6.1 x 1012
and β2 =7 x 1022.
Further Constituents of Alphitonia Species
Authors: Guise GB , Ritchie E , Taylor WC
Published: September 2010

In addition to alphitonin and ceanothic
acid, the wood of Alphitonia excelsa Reiss. also contains betulic acid. The
wood of A. petriei Braid & White yields in addition to these substances,
alphitolic acid and β-sitosterol, but the wood of A. whitei Braid is
rather different, containing maesopsin instead of alphitonin. There is also
present ceanothic acid, betulic acid, alphitolic acid, betulin, and β-sitosterol.

The structures of maesopsin and alphitolic
acid are deduced.
Infrared Spectra of 2,9-Dimethyl-1,10-phenanthroline, Its Hydrates and Acid Perchlorate
Authors: Grigg ECM , Hall JR , Plowman RA
Published: September 2010

Infrared absorption spectra of
2,9-dimethyl-1,10-phenanthroline (dmp), dmp 0.5H2O, dmp 2H2O,
and dmp HClO4 have been obtained over the range 4000-650 cm-1.
Bands between 1610 and 1545 cm-1 are attributed to stretching vibrations
within the phenanthroline ring system. The in-phase out-of-plane motion of the
ring hydrogen atoms is associated with intense absorption at 845 cm-1.
A strong band is observed at 728 cm-1 which cannot be accounted for
in terms of an out-of-plane CH deformation. The perchlorate is characterized by
shifts of the strongest absorption bands observed in the spectra of dmp and the
hydrates.
Semiconducting Polymers Containing Coordinated Metal Ions
Authors: Bolto BA , Weiss DE
Published: September 2010

Ligands of the bis-(8-hydroxyquinoline) type were selected for the preparation of
semiconducting coordination polymers. After some preliminary investigations in
solvents, melt techniques with reaction temperatures of at least 250°C were found to
be necessary for the formation of a conducting product from chloranil, o-phenylene-
diamine, and a metal salt, which is postulated to involve polycoordination of a quinoxalo-
phenazine derivative. Of 13 different metals studied, the FeCl2 polymer was found to
be the best conductor, having a resistivity of 38 kΩ cm with a preparation temperature
of 350°C, the resistivity remaining at this level for preparation temperatures up to
450°C.
Studies of the reactions of the FeCl2 and FeCl3 polymers suggest intermolecular
linking other than through the metal, a t least two types of organic cross-linking being
evident. The presence of phenazinium salt structures in both polymers is postulated
to account for the large amounts of chloride ion liberated by alkali.
The conducting properties are attributed to interaction between donor nitrogens
and acceptor groups such as the metal ion, quinones, and quaternary nitrogens linked
within a fully conjugated polycyclic system. The existence of the metal in more than
one oxidation state, which might occur with the FeCl2 polymer, may be of further benefit.
The Interaction of Azo-Dyes with Proteins. II. The Ultraviolet Spectral Changes Occurring on adding Protein to Aqueous Solutions of Methyl Orange
Authors: Forbes WF , Milligan B
Published: September 2010

An examination of the ultraviolet spectra
of methyl orange and related dyes in various solvents has indicated that the
spectral changes occurring on adding proteins to an aqueous solution of methyl
orange are not the result of strong electrostatic interactions (PNH3+
. . . -02SR) as suggested by earlier workers. It is
proposed that the interaction of methyl orange with protein generally produces
two types of spectral effect : (i) an absorptivity increase and bathochromic
shift resulting from electronic interaction of dimethylamino, azo, and/or
sulphonate groups in the dye with the protein, and (ii) an absorptivity
decrease and hypsochromic shift resulting from out-of-plane twisting of the
dye's conjugated system by the establishment of the above electronic
interactions. In most cases the second effect predominates, giving the
absorptivity decrease and hypsochromic shift usually observed.
The Synthesis of Some Peptides of L-Leucine and Glycine
Authors: Beecham AF
Published: September 2010

The synthesis is described of certain
peptides and derivatives including benzyloxycarbonyl-L-leucylglycylglycylglycyl-L-leucylglycylglycylglycyl-L-leucylglycylglycylglycine.
The work affords some comparison between two standard methods of peptide synthesis
applied in aqueous alkaline media.
The Adsorption of Hydrogen on Silver(I) Oxide
Authors: Allen JA
Published: September 2010

Hydrogen is physically adsorbed on silver(I)
oxide in the temperature range, 77-188�K, with an isosteric heat of 300 cal
mole-1. The adsorption and desorption isotherms are described by a
generalized equation of the Langmuir type with some departures at low values of
the coverage. The specific rate of desorption is accurately predicted by the
quantum mechanical treatment of physical adsorption.

In the temperature range, 250-288�K,
activated chemisorption described by the Elovich equation ensues with an
activation energy of 5000+3000θ
cal, where θ is the coverage.
The parameters of the Elovich equation are comparable with those obtained for
hydrogen on several other metal oxides.
Degradation of carbohydrates IV. Formation of cis-unsaturated hexosones
Authors: Anet EFLJ
Published: September 2010

Two stereospecific methods are described
for the formation of the cis-isomer of unsaturated D-hexosone, 1,5-epoxy-lαβ,6-dihydroxy-D-glycero-hex-cis-3-en-2-one
(X). One method is to heat 3-deoxy-D-erythro-hexosone with dilute acid, and the
other to treat 2,3-di-0-methyl-D-glucose first with calcium hydroxide then with
acid. The 6-methyl ether of (X) is formed from 2,3,6-tri-O-methyl-D-glucose and
from 2,3,4,6-tetra-O-methyl-D-glucose by the calcium hydroxide treatment
method. The unsaturated osones are probably formed from an intermediate, the
enolic form of a 3-deoxyosone, by an acid-catalysed oxotropic rearrangement.
Organo-Aluminium Compounds. II. Nucleophilic Displacement of Base from Triphenylaluminium Complexes
Authors: Mole T
Published: September 2010

Some complexes of triphenylaluminium with
ethers, amines, and benzonitrile are described. Proton magnetic resonance
spectrometry and ebulliometry have been used to study equilibria of the type:

Basex
? Ph3Al.Basey Ph3Al.Basex
+ Basey.

Such equilibria may be
attained at measurably slow rates, and catalysis by added ether has been
observed in the case, Basex = Basey = triethylamine. The favoured mechanism
for displacement is analogous to the SN2
reaction at a saturated carbon atom.
Molecular polarizability: the anisotropy of the -N=N- group
Authors: Armstrong RS , Le Fevre RJW
Published: September 2010

Consideration of molar Kerr constants,
dielectric polarizations, etc., now found for azoethane and azoisopropane as
solutes in benzene, leads to the conclusions that the polarizability ellipsoid
for the N=N group has semi-axes (in 10-23 C.O. units) as follow: bLN:N = 0.285, bTN:N = 0.100, and bVN:N = 0.079. No
photo-isomerism can be recognized with azoisopropane analogous to that which is
well known with azo-aryls.
Palladium-catalysed olefin isomerization
Authors: Davies NR
Published: September 2010

The mechanism whereby olefins undergo
isomerization in the presence of sodium chloropalladate(II) has been shown to
involve the stepwise movement of hydrogen atoms from the one carbon atom to its
nearest neighbour. Evidence leading to this conclusion is furnished by an
examination of the products of isomerization both by vapour phase
chromatography which gave the product distribution, and by N.M.R. which, in
conjunction with selective labelling of the olefin using deuterium, enable a
picture to be drawn of the pattern of hydrogen migration.
Alternating current polarography at large amplitudes of the alternating voltage
Authors: Bauer HH , Foo DCS
Published: September 2010

Experimental studies of the variation of
the faradaic admittance with amplitude of the
alternating voltage have shown that only one of three proposed theoretical
expressions can be valid; the results in fact substantiate this theory in
absolute terms. As a result, it is possible to measure the effective amplitude
of the alternating voltage more reliably than by measurement of the absolute
magnitude of the faradaic admittance, or by
correction for the voltage drop across the resistances in series with the
interface region. In some cases, useful information may also be obtained about
the number of electrons involved in the reversible electron-transfer step.
An examination of Quercus championi of Hong Kong
Authors: Arthur HR , Hui WH , Lam CN , Szeto SK
Published: September 2010

The leaves of Quercus championi yield hop-17(21)-en-3β-ol
(Ia), hop-17(21)- en-3β-yl acetate (Ib), β-amyrenyl acetate,
friedelin, and friedelan-3α-ol. Neither the hopenol nor its acetate have
been obtained from plants before; nor has this acetate ever been obtained in a
pure state before.
Flavan derivatives. XI. Teracacidin, melacacidin, and 7,8,4'-trihydroxyflavonol from Acacia sparsiflora, and extractives from Acacia orites
Authors: Clark-Lewis JW , Dainis I
Published: September 2010

(-)-Teracacidin
(7,8,4'-trihydroxy-2,3-cis-flavan-3,4-cis-diol) has been isolated from Acacia
sparsiflora, and obtained crystalline for the first time. The leucoanthocyanidin
was accompanied by melacacidin and 7,8,4'-trihydroxyflavonol.
Reactions of free radicals with aromatic compounds in the gaseous phase. I. Kinetics of the reaction of methyl radicals with toluene
Authors: Mulcahy MFR , Williams DJ , Wilmshurst JR
Published: September 2010

The kinetics of abstraction of hydrogen
atoms from the methyl group of the toluene molecule by methyl radicals at
430-540�K have been determined. The methyl radicals were produced by pyrolysis
of di-t-butyl peroxide in a stirred-flow system. The kinetics ,agree
substantially with those obtained by previous authors using photolytic methods
for generating the methyl radicals.

At toluene and methyl-radical
concentrations of about 5 x 10-7 and 10-11 mole cm-3
respectively the benzyl radicals resulting from the abstraction disappear
almost entirely by combination with methyl radicals at the methylenic position.
In this respect the benzyl radical behaves differently from the iso-electronic
phenoxy radical, which previous work has shown to combine with a methyl radical
mainly at ring positions.

The investigation illustrates the
application of stirred-flow technique to the study of the kinetics of
free-radical reactions.
Derivatives of orthoacids. II. The preparation of olefins from 1,2-diols
Authors: Crank G , Eastwood FW
Published: September 2010

Ethyl orthoformate reacted with pinacol to
form 2-ethoxy-4,4,5,5-tetramethyl-1,3-dioxolan (I) which decomposed on heating
to yield ethanol, carbon dioxide, and 2,3-dimethylbut-2-ene. When subjected to
the same reaction sequence diethyl- D-tartrate, diethyl-meso-tartrate,
meso-1,2-diphenylethane-1,2-diol, and cis-cyclo-hexane-1,2-dial underwent
specific cis-elimination to yield diethyl fumarate, diethyl maleate,
cis-stilbene, and cyclohexane respectively. Glycerol, butane-1,2,4-trial, and
pentane-1,2,5-triol formed polymers which decomposed to yield allyl alcohol,
but-1-en-4-ol, and pent-1-en-5-ol respectively.

Pyrolysis of the monoformyl esters of
cis-cyclohexane-1,2-diol, glycerol, butane-1,2,4-triol, and pentane-l,2,5-trio1
gave the respective products enumerated above whereas the monoformyl ester of
pinacol yielded pinacolone.

When compound (I) was heated in the
presence of p-toluenesulphonic acid it gave ethyl formate, pinacolone,
2,3-dimethylbutadiene, and water.
Azaindoles. I. Introduction
Authors: Badger GM , Rao RP
Published: September 2010

Unsuccessful attempts have been made to
extend the Reissert indole synthesis and the Harley-Mason synthesis to the
preparation of 5-azaindoles. Satisfactory methods for the preparation of
4-anilinonicotinic acid 1-oxide and 4-methylaminonicotinic acid 1-oxide have
been devised.
The structure and partial synthesis of canaric acid
Authors: Carman RM , Cowley D
Published: September 2010

Canaric acid, the triterpene acid present
in Canarium muelleri oleoresin, is shown by proton magnetic resonance studies,
and by synthesis from lupeol, to have the 3,4-seco structure (VI).
Amino acids and peptides. X. The reduction of cystine and related disulphides by cuprous copper in the presence of ascorbic acid
Authors: Swan JM
Published: September 2010

Cystine, and penicillamine disulphide, are
quantitatively reduced by cuprous copper in the presence of ascorbic acid to
give the cuprous mercaptide, according to the equation RSSR + 2Cu+ +2e (from ascorbate) + 2RSCu. In practice,
cupric copper can be used as titrant, the overall equation then being RSSR + 2Cu++ + 2C6H8O6
→ 2RSCu + 2C6H606
+4H+. The reactions can be followed polarographically and cystine
determined amperometrically by measuring the current due to Cu+,
which appears on further addition of Cu++ beyond the end-point.

Protein disulphides fail to react, but
thiols interfere according to RSH + Cu+ + RSCu
+ H+. Hence cysteine can also be determined amperometrically by
titration with Cu++ in the presence of ascorbic acid.
The direction of platinum-catalysed hydrogenation of an unsymmetrical anhydride in the norbornane series
Authors: Brown RFC , Sternhell S , Warrener RN
Published: September 2010

The products of hydrogenation of 2-exo-methylbicyclo[2,2,1]hept-5-ene-2,3-endo-dicarboxylic
anhydride (VI) have been shown to be the hemiacylal
(VII) and the lactone (IX), both formed by reduction of the less hindered
carbonyl group. These structures were assigned by consideration of the N.M.R.
spectra of the hemiacylal (VII) and of its
ring-opened anion (XI) formed with alkali in water or deuterium oxide. The
anion (XI) has been shown to undergo slow base-catalysed isomerization
(accompanied, in deuterium oxide, by deuteration at C 3) to give an equilibrium
mixture from which has been isolated the trans-isomer, 3-exo-formyl-2-exo-methylbicyclo-2,2,1,heptane-2-endo-carboxylic
acid (XIII).
The effect of pressure on excimer formation
Authors: Seidel H , Selinger BK
Published: September 2010

The formation of excited dimers by
aromatic hydrocarbons in solution was found to be influenced by hydrostatic
pressure. The increase in the viscosity of the solvent with pressure is the
dominant factor for the more stable excited dimers and this causes a decrease
in the amount of dimer with increasing pressure. Where there is a true
equilibrium between excited dimer and monomer an increase in pressure causes an
increase in dimer concentration. The change in molar volume for the formation
of an excited dimer of 1,6-dimethylnaphthalene from a ground state molecule and
one in the excited state was found to be -20 cm3
mole-1, representing a 10% reduction.
Nitration of the methoxynaphthalenes
Authors: Alcorn PGE , Wells PR
Published: September 2010

The isomer distributions and the rates
relative to naphthalene have been determined using gas chromatography for the
nitration of 1- and 2-methoxynaphthalenes. The derived partial rate factors are
discussed in terms of the methoxy-substituent effect and possible reagents
effective in nitration.
Disulphide monoxide groups in oxidized proteins
Authors: Maclaren JA , Savige WE , Sweetman BJ
Published: September 2010

Peracid oxidation of wool or bovine plasma
albumin greatly increases the apparent thiol contents of the proteins as
estimated by reaction with organomercuric halides. This apparent anomaly
results principally from reaction of the mercurials with disulphide monoxide
(thiolsulphinate) groups present (as S-monoxycystyl residues) in the protein.
SS-Dioxycystyl residues may also react under some conditions. The mercurial
reagents similarly combine with cystine (�)-S-monoxide.
Reactions of o-quinones with 1-vinylnaphthalene
Authors: Corbett TG , Davies W , Porter QN
Published: September 2010

1,2-Benzoquinone,
4-benzamido-l,2-benzoquinone, and l,2-benzoquinone
dibenzimide are shown to react exclusively as dienes with 1-vinylnaphthalene.
Molten salt mixtures. X. The thermochemistry of the binary molten salt systems CdCl2+PbCl2, CdCl2+NaCl, CdCl2+KCI, PbCl2+NaCl, PbCl2-KCl, and CdI2+KI
Authors: Bloom H , Tricklebank SB
Published: September 2010

The enthalpy change on cooling molten and
solid salts and their mixtures from temperatures as high as 850� down to 26.9�
has been measured by means of a Bunsen-type fusion calorimeter. The enthalpy of
formation of solid mixtures has also been measured using a water solution
calorimeter. From the combined results, heats of mixing have been determined
for the molten salt systems investigated. In each system, with the exception of
CdCl2 + PbCl2,
the process of mixing is exothermic and the relative magnitude of the results
can be explained by the formation of complex ions in the systems CdC12 +NaCl, CdCl2 +KCl, PbCl2
+KCl, and CdI2 +KI. Complex ions have not
been detected in the other systems.
Optical rotation and structure in the labdane series of diterpenoids
Authors: Carman RM
Published: September 2010

The correlation between optical rotation
and structure in the labdane series of bicyclic diterpenoids is discussed with reference to 143 compounds.
N.M.R. spectra of 'p-nitrosophenol' and its methyl derivatives
Authors: Norris RK , Sternhell S
Published: September 2010

On the basis of N.M.R. spectra, supported
by u.v. and i.r. data, it
can be concluded that "p-nitrosophenol" and
several of its methyl derivatives exist predominantly in the benzoquinone monoxime form in organic solvents and that in aqueous
solutions the corresponding potassium salts have the negative charge largely on
the oxime oxygen. The
protons on the α-carbon syn to
the quinone monoxime hydroxyl are deshielded
with respect to the anti protons but this relationship appears to be reversed
in the anions.

The N.M.R. spectra of some p-nitrosoanisoles and quinone monoxime
methyl ethers are given and syn-anti
equilibria and long-range spin-spin coupling are discussed.
Thio derivatives of β-Diketones and their metal chelates. III. Metal chelates of some fluorinated Monothio-β-diketones
Authors: Ho RKY , Livingstone SE , Lockyer TN
Published: September 2010

Metal chelates of
1,1,1-trifluoro-4-mercapto-4-(2-thienyl)but-3-en-2 one, C4H3SC(SH)=CHCOCF3
(TTMBH), and 1,1,1-trifluoro-4-mercaptopent-3-en-2-one, MeC(SH)=CHCOCF3
(TMPH) have been prepared. Inner complexes of both TTMBH and TMPH were obtained
with cobalt(III), nicke1(II), palladium(11), platinum(II), zinc(II), cadmium(11),
mercury(11), and lead(II); they are readily soluble in organic solvents. TTMBH
gives the spin-free complex Fe(TTMB)3, the copper(II) complex
Cu(TTMB)2, and the μ-dioxo-bridgedvanadium(1V)
compound V2O2(TTMB)4. Iron(III) and copper(II)
oxidize TMPH to the disulphide (TMP)2; however, a polymeric copper(I)
complex Cu(TMP) was isolated. The complexing ability of TMPH appears to be
weaker than that of TTNBH.
The stereochemistry of some α,β-Di-(2-thienyl)acrylonitriles and β,β'-Di-(2- thienyl)-α,α'-(2,5-thiophen)diacrylonitriles
Authors: Badger GM , Elix JA , Lewis GE
Published: September 2010

It has been shown that condensation of
thiophen-2-aldehyde with 2-thienyl- acetonitrile gives trans-α β-di-(2-thienyl)acrylonitrile; but
condensation of thiophen- 2-aldehyde with 2-thienylacetic acid yields cis-α,β-di-(2-thienyl)acrylic acid. Similarly, condensation of
thiophen-2-aldehydes with 2,5-biscyanomethylthiophen gave trans-trans-β,β'-di-(2-thienyl)-α,α'-(2,5-thiophen)diacrylonitriles; but condensation with
thiophen-2,5-diacetic acid gave cis-cis-β,β'-di-(2-thieny1)-α,α'-(2,5-thio-phen)diacrylic acids.
The dielectric polarizations of formic and other carboxylic acids in benzene
Authors: Le Fevre RJW , Pierens RK , Radford DV
Published: September 2010

Infrared absorptions of solutions of eight
acids in benzene have been examined over the 3500 cm-1 region.
Quantities Q, defined as (area under
a "free" O-H bond) + (weight fraction of solute present), can be
extrapolated to zero concentration, giving Q,
for each acid, much more certainly than can the dielectric polarizations
published for the same systems by Pohl et al.1-3
The quotients Q/Q0 appear
rectilinearly related to partial molar polarizations over major portions of the
entire concentration range; using this observation, new estimates are made of
polarizations and dipole moments for the acid monomers concerned.
Measurement of the temperature variation of virial coefficients. II. The second virial coefficients of benzene
Authors: Bottomley GA , Spurling TH
Published: September 2010

New measurements of the temperature
variation of the second virial coefficient of benzene from 35� to 184� are
reported, combined with selected direct measurements up to 33j0, and used to
evaluate the parameters for various intermolecular potential energy functions.
Vilsmeier-Haak formylation of 2,2'-bithenyl
Authors: Badger GM , Elix JA , Lewis GE
Published: September 2010

The Vilsmeier-Haak
formylation of 2,2?-bithenyl, using the complex prepared from phosphorus
oxychloride and dimethylformamide, has been shown to give 5,5?-diformyl-2,2?-bithenyl and 1-[5-(5-formyl-2- thenyl)methyl-2-thienyl]-2,3-di(5-formyl-2-thienyl)propene.
Two minor products, 5-formyl-2,2?-bithenyl and 1-(5-formyl-2-thienyl)-2-(2-
thienyl)ethylene were isolated as the corresponding 2,4- dinitrophenylhydrazones.
The structures of the formylation products were established by analysis, and by
infrared and ultraviolet spectroscopy.
Nuclear magnetic resonance spectra of α,β,β-trimethylstyrenes
Authors: Newsoroff GP , Sternhell S
Published: September 2010

N.m.r, data for 14 α,β,β-trimethylstyrenes are given. The
aromatic ring shields the β-methyl group cis to it relative to the β-methyl
group trans to it. The magnitude of this relative shielding is greatest with
ortho-substituted benzene rings. The cisoid homoallylic coupling constants in α,β,β-trimethylstyrenes (and indeed in all
examples available from the literature) are smaller than the transoid
homoallylic coupling constants.
Triterpenes of the friedelane series. VI. The structure of Friedelan-y-al
Authors: Courtney JL , Stern W
Published: September 2010

The preparation of a number
of compounds of the friedelane series having an oxygen function at C 24 is
described. Mass spectrometric considerations indicate that friedelan-y-al
is either friedelan-24-al or friedelan-25-al. A
comparison shows that the C 24 derivatives are not identical with the natural
products. The natural product must therefore have an oxygen function at C 25.
Positive chemical proof of this assignment has been obtained by conversion of
friedelane-3,x-dion- 25-oic
acid into 5β-hydroxyalnusane-3,x-dion-25-oic acid 5(25)-lactone.
Studies in the stereochemistry of zinc(II). IV. Complexes of zinc halides with heterocyclic bases
Authors: Graddon DP , Heng KB , Watton EC
Published: September 2010

Complexes of zinc halides
with heterocyclic bases of the types ZnX2B2, ZnX2B3,
and ZnX2B4 have been prepared, where X = Cl, Br, I, or NCS and B = pyridine, 4-methylpyridine, or
2-methylpyridine. Infrared spectra and isomorphous incorporation of cobalt(II) indicate
that in the solid state these compounds are tetrahedral, 5-coordinate, and octahedral
respectively. Molecular weights and conductivities in nitrobenzene solution
show that the compounds ZnX2B3 and ZnX2B4
dissociate in solution to ZnX2B4 and free base.
Sulphur-nitrogen chelating agents. II. Metal complexes of 2-(2-Methylthioethyl) pyridine
Authors: Chia PSK , Livingstone SE , Lockyer TN
Published: September 2010

2-(2-Methylthioethyl)pyridine
(N-SMe) has been prepared and its structure has been
confirmed by N.M.R. measurements. Complexes with palladium(II), platinum(II),
copper(II), copper(I), silver(I), and mercury(II) were obtained but
attempts to prepare complexes of cobalt(II) and nickel(II) were unsuccessful.
The mono-chelated complexes MX2(N-SMe) (M
= Pd, Pt; X = Cl, Br, I, SCN), CuX2(N-SMe) (X = Cl, Br), AgClO4(N-SMe), and HgCl2(N-SMe), and the
bis-chelated complexes [M(N-SMe)2](ClO4)2 (M = Pd, Pt, Cu, Hg) and
[Cu(N-SNe)2]ClO4
were characterized.

Conductimetric titrations of [Pd(N-SMe)2](ClO4)2
in nitrobenzene gave end-points after the addition of two equivalents of halide
ion due to the loss of one molecule of ligand to yield PdX2(N-SMe). The platinum complex [Pt(N-SMe)2](ClO4)2 gives two end-points, the
first corresponding to the formation of [Pt(N-SMe)2X]+
(X = Br, I).

The solid reflectance spectra of CuX2(N-SMe) differ
from the absorption spectra in nitromethane solution, indicating a polymeric
tetragonal structure in the solid state. The ligand molecules in [Cu(N- SMe)2](ClO4)2
are readily replaced by pyridine. This complex can be reduced to the copper(I)
complex [Cu(N-SNe)2]ClO4.
The infrared spectrum of AgClO4(N-SMe) seems to indicate that the perchlorato groups are
coordinated and the insolubility of the compound suggests a polymeric
structure. The mercury complexes apparently contain tetrahedral mercury(II).
Photochemical reactions of azo compounds. VIII. Photochemical rearrangement of 2,2'-dimethylazoxybenzene
Authors: Lewis GE , Reiss JA
Published: September 2010

It has been found that the
photochemical rearrangement of 2,2?- dimethyl-azoxybenzene to 2-hydroxy-6,2?-dimethylazobenzene
(major product) is accompanied by the formation of 4-hydroxy-2,2?- dimethylazobenzene
and 2-hydroxy-4,2?-dimethylazobenzene in small yields. α-2,4,6-Trimethylazoxybenzene
was shown not to isomerize when irradiated. It is concluded that the minor
photochemical products from 2,2?-dimethylazoxybenzene do not arise as a result
of migration of ring substituents. A reaction mechanism, which would account
for the minor products, is tentatively suggested.
Thio derivatives of β-diketones and their metal chelates. V. Acid dissociation constants of some Monothio-β-diektones and stability constants of anickel(II) and a copper(II) chelate
Authors: Chaston SHH , Livingstone SE
Published: September 2010

The acid dissociation
constants (PKD) of the monothio derivatives of acetyl-acetone,
dibenzoylmethane, and 3,3,3-trifluoro-1-(2- thenoyl)acetone,
viz. 4-mercap-topent-3-en-2-one (I), 3-mercapto-1,3-
diphenylprop-2-en-1-one (II), and 1,1,1-trifluoro-4-mercapto-4-(2- thienyl)but-3-en-2-one (III), were determined in dioxan/water
solutions with varying mole fraction (n2) of dioxan. Over a range of
n2 from 0.18 to 0.44 the values of pKD
were found to vary linearly with n2 as given by the equations: (I) pKD = 5.7+12.0n2; (II) pKD = 7.0+10.9n2; (III) pKD = 3.55 + 9.2n2. The thio derivatives (I), (II), and (III) have pKD values 2.0-2.7 log units lower than their
oxygen analogues.

The logarithm of the stability constants
(log β2) for the nickel(II) and copper(II) complexes of (II)
were found to be 21.7 and 22.2, respectively. For both complexes K2
> K1. Comparison with the stability constants of the
dibenzoylmethane complexes shows that for nickel(II) the complex of the
monothio-β-diketone is more stable than that of the β-diketone while
the converse is true for copper(II).
The infrared spectra of complexes of transition metal halides with substituted pyridines
Authors: Gill NS , Kingdon HJ
Published: September 2010

The infrared spectra, in
the region 1600-200 cm-1, of a series of complexes formed by
transition metal halides with substituted pyridines have been recorded. The
assignment of the vibrational bands of the ligands and their shifts in
frequency on coordination with a metal ion are discussed. A study of the
metal-nitrogen stretching frequencies of tetrahedral complexes of the type, MX2
L2, where the metal is cobalt or zinc, shows that no simple
relationship exists between the magnitude of these frequencies and the nature
of either the metal ion or the substituted pyridine ligand.
The reduction of wool keratin by tertiary phosphines
Authors: Sweetman BJ , Maclaren JA
Published: September 2010

Reduction of the disulphide
groups in wool keratin by various substituted phosphines has been studied.
Tri(hydroxymethyl)phosphine and tri(diethylaminomethyl)phosphine
effect considerable reduction but with these reagents side reactions also
occur, probably due to the formation of formaldehyde, as they hydrolyse in
aqueous solution.

With tri-n-butylphosphine the reduction is
apparently specific and nearly quantitative. Only a slight excess of this
reductant is required.
Measurement of the temperature variation of virial coefficients. III. The second virial coefficient of Carbon Disulphide, Methyl Chloride, Acetone, and Methanol, and certain of their binary mixtures
Authors: Bottomley GA , Spurling TH
Published: September 2010

Second virial coefficients
have been determined for carbon disulphide, methyl chloride, acetone, and
methanol over the temperature range of 50-150� with some additional results at
lower temperatures. Similar work has been conducted on the selected mixtures
methyl chloride-carbon disulphide, methyl chloride-acetone, acetone-carbon
disulphide, and methyl chloride-argon. Methanol, exceptionally, shows very
significant third virial contributions in the sub-atmospheric pressure range. A
comparison is made with recent models pertaining to molecular interactions
between unlike molecules possessing dipolar and quadrupolar contributions to
the intermolecular forces.
Metal complexes of hydrogenated Schiff bases
Authors: O'Conner MJ , West BO
Published: September 2010

N-Substituted
o-hydroxybenzylamines formed by the hydrogenation of the C=N bond in N-arylsalicylideneimines were prepared, and found to be
slightly stronger bases but much weaker acids than the corresponding Schiff
base.

They react with copper(II) acetate give
crystalline derivatives of empirical constitution (copper(II) : ligand :
acetate). Magnetic moments and infrared measurements indicate that the
complexes are associated in the solid state.

Reaction with copper(II) nitrate yields
complexes of two types dependent on the aryl substituent. The o-tolyl derivative contains a covalently bound nitrato group
while other derivatives have ionic nitrate groups.

The quadridentate ligand
N,N?-ethylenebis(o-hydroxybenzylamine) reacts readily
with copper(II), nickel(II), and zinc(II)
ions to give crystalline products which are probably associated in the solid
state.
Photochemical reactions of azo compounds. XIII. Photochemical reaction of 11H-Dibenzo[c,f]-[1,2]-diazepine under acidic conditions
Authors: Joshua CP , Lewis GE
Published: September 2010

11H-Dibenzo[c,f]-[1,2]-diazepine is converted into a mixture of
dibenzo[c,f]-[1,2]-diazepin-11-one, 2,2?-diaminobenzophenone, and 2,2?- diaminodiphenylmethane
when irradiated in weakly acidic ethanol. Irradiation of the same compound in
concentrated sulphuric acid appears to give only a sulphonic acid derivative of
diaminobenzophenone. No photochemical reaction occurs
in neutral ethanol or in benzene.
Activity coefficients in some alkaline earth metal perchlorate-hydrochloric acid mixtures at 25°
Authors: Weeks IA
Published: September 2010

Trace activity coefficients
have been determined of both electrolyte components in the aqueous systems Mg(ClO4)2-HCl,
Sr(ClO4)2-HCl, and Ba(ClO4)2-HCl at 25�. The systems are basically similar to the Ca(ClO4)2- HCl
system but the agreement with Guggenheim?s1
theory of mixtures improves with increasing molecular weight of the 2 : 1
electrolyte. Calculations based on the assumption that the linear form of Harned?s2 rule applies to both components are
particularly in error for the Mg(ClO4)2-HCl system.
Phosphato complexes of cobalt(III). II. Reversible chelation and ring-opening reactions
Authors: Lincoln SF , Stranks DR
Published: September 2010

The bidentate phosphato complex Co en2PO40;
has been shown to exist in rapid reversible equilibrium with the monodentate
complex Co en2OH.HPO40
A detailed kinetic analysis of the opposed ring-opening and ring-closing (or
chelation) reactions has evaluated rate constants for each of the protonated forms in acid and basic media. The ring-opening reaction
is subject to both acid and base catalysis. However, within the pH range 6-9,
the bidentate form containing a four-member phosphate ring is thermodynamically
more stable than the monodentate form. This is ascribed to a rapid chelation
reaction arising from a favourable cis hydrogen-bonded transition state.
The magnetic properties of the Tris(2-methyl-1,10-phenanthroline)iron(II) ion
Authors: Goodwin HA , Sylva RN
Published: September 2010

The magnetism of the salts
[Fe mephen3]X2 (X = I-, ClO4-, BF4-, PF6-; mephen = 2-methyl- 1,l0-phenanthroline) has been
investigated over the temperature range c. 100-300�K. The compounds exhibit
anomalous behaviour, and this has been qualitatively interpreted as being the
result of the presence of nearly equi-energetic
ground terms 1A1 and 5T2 of the complexed iron(11) ion, a thermal equilibrium between these
terms causing the magnetic moments to be markedly temperature dependent. This
behaviour is apparently the result of the sterie
hindrance to the coordination of an iron(11) ion induced by the presence of the
methyl group in the ligand and the consequent lowering of the effective
strength of the ligand field. The colour of the salts varies with temperature,
and this has been discussed in terms of π-bonding between the iron(11) ion
and the ligand.
Catalysis by aromatic aldehydes and carbon dioxide of the hydrolysis of the p-nitrophenyl esters of L-leucine, glycine, and L-β-phenylalanine
Authors: Hay RW , Main L
Published: September 2010

The aromatic aldehyde and
bicarbonate catalysed hydrolyses of the p-nitro-phenyl esters of L-leucine, glycine, and L-β-phenylalanine have been
studied over a range of pH. The pH-rate profile for bicarbonate catalysis
indicates that carbon dioxide is the active carbonate species, which presumably
reacts with the substrates to give the carbamic acid,
which hydrolyses by intramolecular nucleophilic participation by the
carboxylate group. In the case of the aldehyde
catalysis, aldehydes containing electron withdrawing groups in the aromatic
ring are more effective than those with electron donating groups. The pH-rate
profile for the catalysed reactions indicates attack by the free amino group of
the ester on the aldehyde. The active species in the reaction is probably a carbinolamine, with the ester group undergoing hydrolysis
with intramolecular nucleophilic participation by the hydroxyl group. The
kinetics are consistent with the view that decomposition of the carbinolamine intermediate is rate-determining.
Synthetical applications of activated metal catalysts. XXVI. The formation of biaryls from azahydrocarbons under the influence of rhodium-on-carbon
Authors: Carey JC , Sasse WHF
Published: September 2010

The action of degassed
rhodium-on-carbon on 14 azahydrocarbons has been examined. 2,2'-Biaryls are
formed in 15-50% yield from quinoline, 6-methyl-quinoline, 7-methylquinoline, 4-phenylpyridine, and 4-benzylpyridine
at their boiling points, and from benzo[f]quinoline
at 320-330�. By-products formed from quinoline
include 2,3'-biquinolyl, two triquinolyls,
and the products of hydrogenolysis previously obtained from experiments with quinoline and degassed Raney nickel. The methylquinolines
undergo demethylation; methylation occurs at the 2- and 4-positions in quinoline. 2-Methylquinoline
forms inter alia bis(2-quinolyl)methane, tris(2-quinolyl)methane, and 1,2-bis(2-quinolyl)ethane.
The results obtained with rhodium-on-carbon are compared with those obtained
with degassed Raney nickel.
Azepinones. IV. A synthetic route to some Dihydro- and Tetrahydro-1,3-diazepines
Authors: Desmarchelier JM , Evans NA , Evans RF , Johns RB
Published: September 2010

lH-4,5,6,7-Tetrahydro-2-methyl-1,3-diazepine (1), 4H-1,5-dihydro-3-methyl-
benzo[e]-[1,3]-diazepine (11), and 3H-4,5-dihydro-2-methylbenzo[d]-[1,3]-diazepine
(IV) have been synthesized in good yields by treating suitably substituted 1,4-
diaminobutanes with acetamidine
hydrochloride under mild experimental conditions. This synthetic method may
well be a general one for such compounds. When protonated,
the compounds exist as amidinium salts, and the free
bases (1) and (11) have basicities comparable to the 1,4,5,6,-tetrahydropyrimidines. I.r.,
N.M.R., and mass spectra data are reported for (1), (11), and (IV).
A vapour-pressure study of mixtures of bromine and chlorine
Authors: Chessman GH , Scott DL
Published: September 2010

Phase equilibria
in the system bromine-chlorine have been examined by vapour-pressure
measurements, with a primary view to obtaining information on the nature of the
solid mixtures. The work has led to some modification of the earlier phase
diagrams and to a general discussion on the thermodynamic properties of this
binary system in which compound formation is known to occur.
Electronic absorption spectra of KMnF3, RbMnF3, and MnF2
Authors: Ferguson J
Published: September 2010

The absorption spectra of KMnF3 and RbMnF3
in the region 17000-47000 cm-l are reported in detail for room
temperature and 20�K. Excellent
agreement between experiment and a ligand field calculation using the free atom
representation is obtained for the bands with energy less than 35000 cm-l.
The analysis of the bands with energy greater than this requires an explanation
involving the simultaneous excitation of pairs of manganese ions, and
consistent assignments of these bands for the spectra of KMnF3,
RbMnF3, and MnF2
are given. The relative order of the 4A1g
and 4Ega states is
established, and a theoretical argument to support this uses differences in
inter-electronic repulsion energies for the 4Ega;
and 4Egb states.
The theoretical line shapes for the magnon-exciton
bands of MnF2 at 25000 cm-1 are
compared with the observed shapes.
The isomerization of n-phenylbutenes catalysed by palladium complexes
Authors: Davies NR , DiMichiel AD , Pickles VA
Published: September 2010

4-Phenylbut-1-ene
isomerizes to a mixture of cis- and trans-1-phenylbut-2-ene
and trans-1-phenylbut-1-ene in the presence of bis(benzonitrile)dichloropalladium(11). The products are not formed entirely in
consecutive reactions but direct conversion of 4-phenylbut-1-ene
into trans-1-phenylbut-1-ene
occurs extensively. Similarities are observed in the
kinetics with those observed previously for allylbenzene.
The isomerization of 1-phenylbut-2-ene to 1-phenylbut-1-ene
is comparatively slow in spite of conjugation between the aromatic ring and the
double bond in the side-chain within the latter compound. The rate-controlling
step in the isomerization of 1-phenylbut-2-ene is
believed to be an olefin displacement reaction, but an induction period renders
the conclusions with regard to the kinetics of the initial isomerization of 4-phenylbut-1-ene less certain.
Magnetically anomalous thio complexes of iron(III) and nickel(II)
Authors: Ewald AH , Sinn E
Published: September 2010

Thioxanthate complexes closely resemble the xanthates and the dithiocarbamates. Like the corresponding xanthates and dithiocarbamates, thioxanthates
of iron(111), nickel(11), and copper(11) are black and those of cobalt(111) are
dark green. In sufficiently dilute
solutions, iron(111) and nickel(11) thioxanthates are
more red than xanthates and dithiocarbamates which
are brownish red. The pressure and temperature dependences of the magnetism
show that the ferric thioxanthates exhibit a
high-spin + low-spin electronic equilibrium, like the ferric dithiocarbamates and xanthates, though the low
spin form predominates for the xanthates and thioxanthates.
Pyridine forms green
paramagnetic adducts in the solid with the nickel(11) complexes which lose
pyridine if left in the open, while in solution a concentration dependent
equilibrium is set up between the planar thioxanthates
and its bis-pyridine adduct. In general the complexes
are rather unstable at room temperature, but some kept fairly well if stored
frozen in sealed tubes. The iron(111) thioxanthates
Fe(S2C-S-R)3 are at least as stable as the corresponding
xanthates. Analogously to the case of the xanthates, the stability of the thioxanthates decreases and the ability of the ligand to
reduce the central metal atom increases with increasing chain length when R is
an alkyl group. Some long-chain ligands are capable of reducing the central iron atom to form
an iron(11) complex. Complexes with branched alkyl chains are more stable than
the straight-chain analogues.
The uptake of aluminium by wool
Authors: Hartley FR
Published: September 2010

The uptake of aluminium by
scoured and chemically modified wool from aqueous solutions of
aluminium sulphate, chloride, and fluoride has been
investigated. The effects of temperature, length of treatment, pH,
concentration of aluminium salt, anion present, and the presence or absence of
swelling agents have been determined. For maximum aluminium uptake an aluminium
concentration of about 0.01M aluminium at pH 3.5-4 should be used. In general,
it was found that aluminium could be removed by washing sufficiently. It was
shown that the aluminium was bound ionically to
carboxylate or sulphonate groups present on the wool, as well as by Van der Waals forces to non-specific
sites on the wool.
Thio-chelates of germanium and tin
Authors: Sukhani D , Gupta VD , Mehrotra RC
Published: September 2010

Thio-chelate derivatives of
dibutylgermanium, dibutyltin, germanium(1V),

and tin(1V), have been prepared from the corresponding
alkoxides. Some mixed alkoxyl derivatives of germanium have also been isolated.
The influence of pH on the reaction between tartaric acid and metaperiodic acid
Authors: Verma PS , Grover KC
Published: September 2010

Tartaric acid in phosphate
buffer (pH 6.6) at 30� consumed 2,003 � 0.001 molar proportions of periodic
acid in 2.5 hr. The reaction has been shown to be of second order. It is
suggested that the oxidation proceeds through the disproportionation
of a coordination compound intermediate involving the bitartrate
and IO4 or H4IO4 ions, followed by the
subsequent slow oxidation of glyoxylic acid to give
formic acid.
The thermal decomposition of t-butyl ethyl ether
Authors: Daly NJ , Wentrup C
Published: September 2010

The rates of decomposition
of t-butyl ethyl ether have been measured in the range 433-484�. The
reaction products are ethanol and isobutene, and the kinetic form is first
order. The Arrhenius equation

k1 = 1017.18exp(-59740/RT)sec-1

is followed. The reaction
behaviour is consistent with a unimolecular mechanism
for the decomposition.
The pyrolysis of 6a,11b-Dihydro-7-thiabenzo[c]fluorene 7,7-dioxide and some of its derivatives
Authors: Davies W , Ennis BC , Porter QN
Published: September 2010

It is shown that heat in
the absence of a solvent converts the title compound into benzo[k,l]thioxanthen 7,7-dioxide, 7-thiabenzo[c]fluorene, and o-(1-naphthyl)-benzenesulphonic acid. From these results and a
consideration of the related pyrolyses of the 3,10-
and 1,8-dimethyl derivatives of the title compound, a free-radical
rearrangement mechanism is proposed to explain the observations.
Studies on the tannins of avaram (Cassia auriculata) bark
Authors: Theresa YM , Bhanu KU , Naudamma Y
Published: September 2010

The amorphous material
extracted by acetone from Cassia auriculata bark consists largely of (-)-auriculacacidin (5,2',4'-trihydroxyflavan-3,4-diol),
a compound of novel type characterized by crystalline derivatives. Its
constitution has been demonstrated by oxidation of the trimethyl ether with
potassium permanganate to 2,4-dimethoxybenzoic acid
and 2-hydroxy-6-methoxybenzoic acid and by periodic acid to 2-hydroxy-6-methoxybenzaldehyde.
Derivatives of orthoacids. IV. Acid-catalysed thermal eliminations and baseinduced eliminations of some 2-Ethoxy-1,3-dioxolans
Authors: Josan JS , Eastwood FW
Published: September 2010

A series of phenyl
substituted 2-ethoxy-1,3-dioxolans (orthoformates) has been prepared and their
stereochemistry assigned. When heated in the presence of a carboxylic acid they
underwent a stereospecific cis elimination
to form the corresponding olefins, carbon dioxide, and ethanol. Provided that
one 4 or 5 position in these dioxolans was unsubstituted, they reacted with
butyllithium through elimination of the elements of ethyl formate and the
formation of a carbonyl compound. The eliminated portion was always converted
by the butyllithium into nonan-5-ol. A simple preparative method for cis-stilbene is described.
The pyrolysis of polycarbonyl compounds. III. Pyrolysis and mass spectrometry of 1,1,4,4-Tetramethyltetralin-2,3-dione and related compounds
Authors: Brown RFC , Gream GE , Peters DE , Solly RK
Published: September 2010

The pyrolysis of 1,1,4,4-tetramethyltetralin-2,3-dione (I) or of 1,1,3,3-tetra-methylindan-2-one (11) at 800�/0.01-0.2 mm with short
contact time gave a hydrocarbon pyrolysate containing
naphthalene (c.60%), accompanied by smaller amounts of indene, 2- and 3-methylindenes, 1,2-dihydronaphthalene,
benzofulvene, 1- and 2-methylnaphthalenes, dimethylnaphthalenes, and several unidentified minor components. Pyrolysates of similar composition were obtained from o-isopropyl-a-methylstyrene (111), 1,1,3-trimethylindane
(IV), and 1,l-dimethyl-indene (V). Benzofulvene (VI)
was partly converted into naphthalene at 800�. The last four compounds are
suggested as possible intermediates in the conversion of (I) and (11) into
naphthalene. The pyrolytic
behaviour of these compounds correlates well with their 70-eV
mass spectra; this apparent correlation is a more complex case than has
previously been reported.
Terpenoid chemistry. XV. 1,5-Dimethylcyclodeca-1,5,7-triene, the precursor of geijerene in Geijera parviflora (Lindley)
Authors: Jones RVJ , Sutherland MD
Published: September 2010

Geijera parviflora leaves which yield geijerene
when worked up under the usual conditions of steam-distillation and fractional
distillation have been found to contain a new hydrocarbon, Cl2H18
(pregeijerene), and only a trace of geijerene. The structure of pregeijerene
has been shown by degradative and spectral
examination to be 1,5-dimethylcyclodeca-1,5,7-triene,
the disubstituted double bond having a cis
configuration. The hydrocarbon forms a crystalline adduct with silver nitrate
and rearranges thermally to
yield geijerene.
Schiff base equilibria. VI. n- and t-Butylimines of pyridine-2-aldehyde
Authors: Green RW , Rogerson MJ
Published: September 2010

Equilibrium constants at 25�
have been measured for the formation of Schiff bases of pyridine-2-aldehyde
with n-butylamine (1.45 x 108) and t-butylamine (93). The Schiff base of salicylaldehyde with t-butylamine has a formation constant
9.1 x 108 and pK 13.0.
Nitrones and oxazirans. II. Formation of 2,2'-bipyrrolidinyls by reductive dimerization processes
Authors: Bapat JB , Black DS
Published: September 2010

The reduction of some
y-nitro aryl ketones, 1-pyrroline 1-oxides, or 1-pyrrolines with zinc in
aqueous ammonium chloride at room temperature results in the formation of
2,2'-bipyrrolidinyl compounds. These can also be obtained by reductive
dimerization of 1-pyrrolines with aluminium amalgam in moist ether.
Nitrones and oxazirans. III. Photolysis of 1-pyrroline 1-oxides and their related oxazirans
Authors: Bapat JB , Black DS
Published: September 2010

Oxazirans have been prepared from a number of 1-pyrroline 1-oxides by

photoisomerization and from the related 1-pyrrolines
by oxidation with perbenzoic acid. This oxidation was
found to be highly stereoselective in reaction with unsymmetrical pyrrolines, and 3,5-cis-disubstituted
oxazirans were formed exclusively. A mixture of 3,5-cis- and trans-disubstituted oxazirans was formed
in the photolysis of unsymmetrical 2-methyl-substituted pyrroline
1-oxides but stereo-selectivity was observed in the photolysis of similar
2-aryl-substituted pyrroline 1-oxides, in which cases
only the trans-isomer was obtained.

Photoisomerization of cis-5-phenyl-substituted
oxazirans to their trans-isomers was also observed, while other oxazirans
were found to be photo-stable.