bluuebunny/crossref_metadata_2025 huggingface dataset:
The Interaction between Copper and Sodium Dodecyl Sulphate Solutions in the Presence of Air
Authors: Cuming BD , Schulman JH
Published: September 2010

The interaction of oxide-covered copper
powder with solutions of sodium dodecyl sulphate has been studied as a function
of pH. In acid solutions copper ions dissolve from the oxide layer, the pH
rises, and dodecyl sulphate is precipitated, probably as the basic cupric salt.
If the final pH is greater than about 4, adsorption of dodecyl sulphate also
occurs. There is a range of pH (6-8.5 under the conditions used) where
precipitation is negligible or does not occur, but where adsorption is strong.
Above this range, adsorption becomes weaker, and at high pH there is little or
no reaction. The pH limits for these phenomena will vary with the dodecyl
sulphate concentrations and with other conditions. The results are analysed in
terms of the interfacial and solution equilibria in the system.
Reactions of Alkoxy Radicals. I. The Reactions of Di-tert.-butyl Peroxide with n-Butyric Acid and Ethyl n-Butyrate
Authors: Beckwith ALJ
Published: September 2010

The relative yields of meso- and
racernic-2,3-diethylsucoinic and 2-ethyl-3-methyl-glutaric acids from the
reaction of di-tert.-butyl peroxide with n-butyric acid indicate that
abstraction of hydrogen atoms from the acid by tert.-butoxy radicals occurs
preferentially at the α-position. A similar directive effect has been
noted in the reaction of ethyl n-butyrate with di-tert.-butyl peroxide. These
results suggest that the tert.-butoxy radical has negligible electron-acceptor
properties and that polar effects do not influence the course of its reactions.
Catalytic amounts of cupric chloride profoundly modify the reaction of
di-tert.-butyl peroxide with n-butyric acid.

New analytical methods for the separation
and determination of hydroxy- and dicarboxylic acids are described.
Bromination of 2,7-Dihydroxynaphthalene
Authors: Cooke RG , Johnson BL , Owen WR
Published: September 2010

Bromination of 2,7-dihydroxynaphthalene
gives a mixture of two dibromo derivatives which are now identified as the 1,6-
and 1,3-isomers. Reduction of these compounds gives the new
3-bromo-2,7-dihydroxpphthalene. Similar reduction of 1,3,6-tribromo-2,7-dihydroxynaphthalene
gives the previously unknown 3,6-dibromo-2,7-dihydroxynaphthalene. After
methylation this is readily converted into 2,7-dimethoxynaphthalene-3,6-dicarboxylic
acid by carbonation of the lithium derivative. It has not been possible to substantiate
claims that 2,7-dihydroxynaphthalene and its dimethyl ether give 1,3,6,8-tetrabromo
derivatives.
Terpenoid Chemistry. IV. The Turpentine of Araucaria cunninghamii Ait
Authors: Gallagher MJ , Sutherland MD
Published: September 2010

Contrary to Baker and Smith?s (1910)
statement, the turpentine from Araucaria cunninghamii Ait. does not contain
methanes or menthenes. Identified constituent* include n-nonane, n-undecane.
(-)- and (�)-α-pinene, (-)-β-pinene, myrcene,
(�)-limonene, terpinolene, caryophyllene, and humulene.
The Stereochemistry of Aromadendrene, Globulol, and Ledol
Authors: Graham BA , Jefferies PR , Melrose GJH , Thieberg KJL , White DE
Published: September 2010

The conversion of aromadendrene, obtained
from a variety of essential oils or by dehydration of globulol, to
apoaromadendrone has been studied, together with the further degradation of
apoaromadendrone. The reaction of apoaromadendrone with methyl magnesium iodide
has afforded globulol and epiglobulol. From the reactions of these compounds, structures
are proposed for aromadendrene (I), apoaromadendrone (II), globulol (III),
epiglobulol (IV), and ledol (V).
Chemistry of Non-Enzymic Browning. XI. The Reactions of Bisulphite with Reducing Sugars
Authors: Ingles DL
Published: September 2010

The reactions of reducing sugars with
bisulphite have been studied at 100 �C and lower temperatures. Reducing sugars
promoted the autoxidation of bisulphite to sulphur and sulphate, the ketoses
being more effective than the aldoses. During the autoxidation the aldoses were
oxidized, in part, to the corresponding aldonic acids. The ketose sugars
reacted more rapidly and extensively than the aldoses, only 32 per cent. of
unchanged fructose being recovered after 8 hr at 100 �C. Oxidation of the
ketoses probably occurred via the osone and gave a complex mixture of keto
acids. Ascorbic acid was converted to dehydroascorbic acid and an unidentified
acid.

The reactions offer possible explanations
for the formation of sulphate and the loss of bisulphite observed during
storage of foods treated with sulphur dioxide. An oxidative mechanism has been
suggested for the inhibition of non-enzymic browning by sulphur dioxide.
Some Studies in Inorganic Complexes. VIII. Cobalt(II) and Cobalt(III) with 2-Picolylamine
Authors: Sutton GJ
Published: September 2010

Complexes of cobalt(II) and (III) with the
chelating ligand 2-picolylamine have been prepared and studied. Those of
cobalt(II) are Copic3(ClO4)2
and CopicI2.2H2O, where pic is
the ligand 2-picolylamine. Measurements of magnetic susceptibility have shown
that in both of these the cobalt atom is spin-free, giving rise to momenta of
4.8 and 4.9B.M. respectively. By means of conductance measurements in water,
methanol, nitromethane, and nitrobenzene, it has been shown that the former is
an octahedral complex and the latter, whilst probably octahedral, could be
tetrahedral. The cobalt(III) complexes described include [Copic3](ClO4)3,
[Copic2Cl2]Cl.HCl,
[Copic2Cl2]Cl, [Copic2(NO2)2]NO3.�H2O,
[Copic2(NO2)2]NO2,
and [Copic2(H2O)2](ClO4)2.
By means of the above measurements it has been shown that all the latter are
diamagnetic octahedral complexes. A study of absorption spectra in the visible
region, in the above solvents where possible, has also been made and the
results correlated to solution stability. Attempts to resolve the Copic33+
complex into its enantiomorphs were unsuccessful.
Sugar-Cane Wax. II. An Examination of the Constituents of Sugar-Cane Cuticle Wax by Gas Chromatography
Authors: Kranz ZH , Lamberton JA , Murray KE , Redcliffe AH
Published: September 2010

Sugar-cane cuticle wax previously found to
consist of long-chain aldehydes, alcohols, acids, and hydrocarbons (Lamberton
and Redcliffe 1960) has been re-examined by gas chromatography to identify and
estimate the individual constituents. The aldehydes, alcohols, and acids, all
straight chain, are principally of even carbon number in each instance with the
C28 member predominant, but appreciable amounts of odd carbon
homologues are also present. The hydrocarbons are also of odd and even carbon
number but with the odd members in greater amounts and n-heptacosane as the
major hydrocarbon constituent.
Degradation of Carbohydrates. II. The Action of Acid and Alkali on 3-Deoxyhexosones
Authors: Anet EFLJ
Published: September 2010

The two
3-deoxy-D-hexosones, 3-deoxy-D-erythrohexosone and 3-deoxy-D-threohexosone, were
quantitatively converted by acid to 5-(hydroxymethyl)-2-furaldehyde.The
mechanism of the formation of 2-furaldehyde from sugars is discussed.

Calcium hydroxide
rapidly converted 3-deoxy-D-erythrohexosone to α- and β-glucometasaccharinic
acids, and 3-deoxy-D-threohexosone to α- and β-galactometasaccharinic
acids.
A Possible Physical Distinction between Isomeric α- and β-Aldoximes
Authors: Le Fevre RJW , Pierens RK
Published: September 2010

Five pairs of geometrically isomeric
aldoximes show consistent differences when examined as solutes in the
near-infrared (0.7 to 2.6 μ) region. Whereas α-oximes exhibit two
absorption peaks, at 2.010-2.030 μ and at 2.065-2.085 μ, β-oximes
exhibit only one, at 2 046-2.060 μ.
The Reaction of Alkali Metal Derivatives of Group IV Metal Alkyls with Bis(cyclopentadienyl)titanium(IV) Dichloride
Authors: Dickson RS , West BO
Published: September 2010

The reactions of
bis(cyclopentadienyl)titanium(IV) dichloride with sodium lead triethyl and with
lithium tin triethyl have been investigated. Unstable solid products are
formed. The reaction of liquid ammonia with bis(cyclopentadienyl)titanium(IV)
dichloride has also been studied.
The polarography of glycine metal complexes and the determination of stepwise formation constants
Authors: Mellor DP , McKenzie HA
Published: September 2010

The polarography of metal-glycine
complexes has been studied with a view to assessing its usefulness in measuring
the stability of metal complexes, especially the stepwise formation constants.
It is shown that the equation derived by De Ford and Hume (1951) may be
transformed in a way that makes possible the calculation of both overall and
stepwise stoichiometric constants from experimental data obtained with
solutions of constant ionic strength. Problems in the use of maximum
suppressors and buffer ions are considered.

Stoichiometric stepwise stability
constants for the glycine complexes of copper(II) and cadmium(II) have been
determined : (i) polarographically and (ii) by the pH- titration method of
Irving and Rossotti (1954a, 1954b). The values obtained by the two methods
agree reasonably well. Problems of hydrolysis and precipitation arise with t8he
lead(II) complexes. The zinc(II) complexes exhibit anomalous polarographic behaviour.
The reasons for this behaviour are briefly discussed.

Although the polarographic technique is
capable of yielding values for step constants in substantial agreement with
those obtained by the pH-titration technique, there is evidence that it in not
so generally applicable as the latter.
Some Aspects of the Oxidation of Sugars and Inisitols by Periodate: The Formation of Intermediary Esters
Authors: Angyal SJ , Klavinsm J.E.
Published: September 2010

Evidence, obtained mainly by determining
the amount of intermediary esters formed during the oxidation of aldoses by
periodate, indicates that aldoses are pre- dominantly attacked in their
original cyclic form ; that the oxidation of the intermediary aldoses is faster
than their cyclization ; and that the oxidation of the intermediary hemiacetals
is faster than their hydrolysis. Inositols are oxidized to tartron-aldehyde
which undergoes " overoxidation " ; 0-methylinositols are degraded to
methyl glyoxylate.
Volume Changes on Mixing. I. Alcohol + Benzene Solutions
Authors: Brown I , Smith F
Published: September 2010

Direct measurements have been made at 25,
35, and 45 �C of the volume changes on mixing of benzene with each of the
following alcohols : methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,
2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-hexanol, and 1-octanol.

These systems have positive values of VM,
the volume change on mixing per mole of mixture, with maxima at mole fractions
of alcohol from 0.15 to 0.35 for the normal alcohol systems and from 0.34 to
0.54 for the secondary and tertiary alcohol systems. The systems containing the
three lower normal alcohols also show at 25 �C small negative values of VM
with minima at mole fractions of from 0.85 to 0.98.

Values of VM increase with the
molecular weight of the alcohol and with an increase in temperature. For a
given alcohol molecular weight the values of VM increase with
alcohol type in the order primary, iso, secondary, tertiary.
Cathode Ray Oscillography in A.C. Polarography and Tensammetry
Authors: Biegler T
Published: September 2010

Applications of the cathode ray
oscilloscope in a.c. polarography and tensammetry are described. The instrument
is used to enable observation of the waveform of the alternating current and of
the relationship between alternating current and time during the growth of a
mercury drop. Some typical results are presented and it is shown that the
method can provide useful information about electrode processes.
Deuterium Exchange Reactions with Substituted Aromatics. III. Heterocyclics and Polycyclic Hydrocarbons
Authors: Garnett JL , Sollich WA
Published: September 2010

Platinum-catalysed deuterium exchange
reactions between heavy-water and polycyclic aromatics and heterocyclics have
been investigated. The results confirm a charge-transfer-no-bond adsorption
mechanism for catalytic chemisorption. Degree of catalyst poisoning increases
with decreasing ionization potential for aromatic molecules of similar
complexity, e.g., anthracene and phenanthrene. As the number of nodal planes in
the bonding orbitals of the more complex polycyclic aromatics increases, a
decrease is observed in catalyst poisoning. Exchange of pyridine is slower than
benzene and this is attributed to an additional interaction of the pyridine
molecule with the catalyst through its lone-pair of electrons. The reactivity
of n-octane supports extension of the authors' π-complex chemisorption
theory to molecules possessing only σ-electrons. Anisole, cyclohexane,
nitrobenzene, cyclohexene, and phenyl cyanide exchange in an anomalous manner.
Electrochemical Studies on Eriochrome Violet B and Its Lanthanide Complexes. I. Behaviour of Eriochrome Violet B and Its Lanthanide Complexes at the Dropping Mercury Electrode: D.C., A.C., and Cathode Ray Polarography
Authors: Florence TM , Aylward GH
Published: September 2010

The polarographic behaviour of Eriochrome
Violet B (5-sulpho-2-hydroxybenzene-azo-2-naphthol) and its lanthanide
complexes has been investigated in some detail. Earlier workers found the dye
to be reduced at the dropping mercury electrode in (I two-electron step to a
stable hydrazo compound. The present work shows, however, that four electrons
are involved in the reduction, and that the amines are the final reduction
products. To explain the apparently anomalous polarographic behaviour of
Eriochrome Violet B, a mechanism involving the disproportionation of an
unstable hydrazo intermediate is proposed for the reduction. A diffusion
current constant of 5 77 � 0.09 and a diffusion coefficient of 0.57 X cm2
sec-1 were found for the free dye in an ammonia buffer at 26 �C.

The lanthanides combine with Eriochrome
Violet B in a 1 : 2 ratio. These complexes produce discrete reduction steps
which are separated from the free-dye step by a potential difference (ΔE) which depends on the atomic number of
the lanthanide. In an ammonia buffer of pH 9.5 the ΔE values vary from 45 mV for lanthanum to 234 mV for lutetium.
Studies in Mass Spectrometry. I. Structures and Reactions of Ions from Benzyl Alcohol, ortho-, meta-, and para-Hydroxybenzyl Alcohols, and their 0-Deuterated Derivatives
Authors: Shannon JS
Published: September 2010

The work described in the present paper, which was undertaken in the course of
investigations into the mass spectra of coal and coal fractions, led the author to propose
mechanisms of dissociation and rearrangement reactions of ions derived from benzyl
alcohol and from o-, m-, and p-hydroxybenzyl alcohol on the basis of a study of;
(i) the mass spectra of these latter compounds, including comparable features
in the mass spectra of 1,4-cyclohexadiene and O-deuterated o- and p-cresols;
(ii) the mass spectra of the corresponding 0-deuterated benzyl and hydroxybenzyl
alcohols;
(iii) meta-stable transitions.
π-Complex structures may play an important role in the dissociation of some of
the ions-for example, in the loss of D2O from molecular ions of m- and p-hydroxybenzyl
alcohols.
The Structure of Polygodial: A New Sesquiterpene Dialdehyde from Polygonum hydropiper L
Authors: Barnes CS , Loder JW
Published: September 2010

A pungent substance, polygodial, isolated
from Polygonum hydropiper L. is shown to be drim-7-en-11,12-dial
(I), a new dialdehyde structurally related to sesquiterpene lactones from Drimys
species.
The formation of sulphonic acids from the reactions of reducing sugars with sulphite
Authors: Ingles DL
Published: September 2010

β-Sulphopropionic acid has been
isolated from the reaction of glucose or fructose with sodium sulphite. The
source of this acid has been studied by using glucose-1-, -2-, and -6-[14C].

A sulphonic acid, probably
3,4-dideoxy-4-sulpho-D-hexosone, has been isolated from the reaction of glucose
with sulphite at pH 6.5. The mechanism of the formation of this acid is
discussed.
The Behaviour of Lead in Iodide Medium at the Dropping Mercury Electrode. II. A.C. Polarographic Study
Authors: Srinivasan VS , Sundaram AK
Published: September 2010

An a.c.
polarographic study of the lead-iodide system is described. Three peaks are
obtained. The second and third peaks are proved to be due to a combined
tensammetric-polarographic process.
Metal Complexes of 6-Hydroxymethylpyridine-2-carboxylic Acid
Authors: Green RW , Ooi GKS
Published: September 2010

Spectrophotometric and pH-titration
methods have been used to determine the stability constants at 25 �C of
complexes between transition metal ions and the anion of
6-hydroxymethylpyridine-2-carboxylic acid. This anion is found to be a weaker
base and a weaker complexing agent than the pyridine-2-carboxylate ion. There
is some evidence for steric hindrance of tris complexes.
The extent of reduction of wool proteins by thiols
Authors: Maclaren JA
Published: September 2010

The extent of reduction of disulphide
groups in Merino wool by dilute solutions of thiols in aqueous alcohols at 20 �C
has been studied by carboxymethylation of the reduced wool and estimation of
the residual disulphide in the product. The wool fibres remain intact
throughout the process. Under these conditions toluene-ω-thiol was the
most effective agent giving 93% reduction in 2 days, and more than 99%
reduction by repeated reduction-carboxymethylation cycles. With Lincoln wool
100% reduction was achieved.
The Fine Structure of Cytosine
Authors: Brown DJ , Lyall M
Published: September 2010

The ionization constants and ultraviolet
spectra of cytosine, of its appropriately methylated derivatives, and of
related compounds are used to indicate that its pre- dominant tautomeric form
in aqueous solution is 4-amino-1,2-dihydro-2-oxopyrimidine.
This is in sharp contrast to its recent formulation as a zwitterion on the
grounds of its nuclear magnetic resonance spectrum.
The Chemistry of the Western Australian Rutaceae. II. The Structure of Eriostemoic Acid
Authors: Duffield AM , Jefferies PR
Published: September 2010

Eriostemon tomentellus contains an acid,
eriostemoic acid whose structure has been shown to be (II). The same acid has
been isolated from Geleznowia verrucosa and E. thryptomenoides. Evidence is
presented for intramolecular charge-transfer complexes in eriostyl and
eriostemyl 3,5-dinitrobenzoates.

The structure of franklinone has been
confirmed by a synthesis of tetrahydro-franklinone.
Discophoridin, A New Coumarin from Velleia discophora F. Muell
Authors: Bottomley W
Published: September 2010

A new coumarin, discophoridin, isolated from Velleia discophora F. Muell.,
has been shown almost certainly to have structure (I). This conclusion isbasedmainly
on evidence from nuclear magnetic resonance spectroscopy.
Pschorr Reactions with Sulphonamides derived from N-Benzyl-o-phenylenediamine: A New Route to Phenanthridine, and a New Type of Molecular Rearrangement
Authors: Huppatz JL , Sasse WHF
Published: September 2010

The preparation in three steps of
N-benzyl-N-benzenesulphonyl-o-phenylenediamine (Va), of N-benzyl-N-p-toluenesulphonyl-o-phenylenediamine
(Vb), and of N-benzyl-N-methanesulphonyl-o-phenylenediamine (Vc) from
o-nitroaniline is described. The copper-catalysed decomposition of diazonium
salts of each of these amines in acetic acid-sulphuric acid has been examined.
Compound (Va) gave N-benzyl-2-aminobiphenyl (IXa),
5-benzenesulphonyl-5,6-dihydrophenanthridine (VIa), N-
benzyl-2-aminobiphenyl-2'-sulphonic acid sultam (Xa),
N-benzenesulphonyl-2-amino-biphenyl (XIIa), and phenanthridine. Compound (Vb)
gave N-benzyl-2-amino-4'-methylbiphenyl (IXb),
6-p-toluenesulphonyl-5,6-dihydrophenanth (VIb), a compound C20H17NO2S
thought to be N-benzyl-2-amino-5'-methylbiphenyl-2'-sulphonic acid sultam (Xb),
N-benzyl-N-p-toluenesulphonylaniline (XIb), N-p-
toluenesulphonyl-2-aminobiphenyl (XIIb), and phenanthridine.

Compound (Vc) gave
5-methanesulphonyl-5,6-dihydrophenanthri (VIc),
N-benzyl-N-methanesulphonylaniline (XIc), N-methanesulphonyl-2-aminobiphenyl
(XIIc), and phenanthridine. It has been found that the yields of most of these
products depend inter alia on the excess of sodium nitrite present during the
diazotization prior to cyclization. It is suggested that this effect is caused
by changes in the concentration of cuprous ions present during the cyclization.
Heterolytic and homolytic processes may be involved in the formation of the
dihydrophenanthridines and sultams. The formation of the biphenyl derivatives (IX)
and (XII) is postulated to proceed via the spirane intermediates (XIX) or (XX).�The
conversion of the sulphonamides of dihydrophenanthridine (VI) to phenanthridine
in c. 70% yield completes new syntheses of this ring system.
Polynuclear Heterocyclic Systems. XV. Dihydroquinoxalino[2,3-b]quinoxalines
Authors: Badger GM , Nelson PJ
Published: September 2010

Fluoflavin has been found to have an
absorption spectrum very similar to that of 5,12-dimethylquinoxalino[2,3-b]quinoxaline
(I; R = R' = CH3), and is assigned the structure
5,12-dihydroquinoxalino[2,3-b]quinoxaline (I; R = R' = H). Attempts to prepare
5,12-dimethylquinoxalino[2,3-b]quinoxaline from 2,3-dihydroxyquinoxaline and
NN'-dimethyl-o-phenylenediamine resulted in the loss of a methyl group, and
5H-12-methylquinoxalino[2,3-b] was obtained. The same compound was also
isolated following attempts to prepare 5,11-dimethylquinoxalino- [2,3-b]quinoxaline (II; R =
R' = CH3). The latter compound has not been obtained.
Geminal H,D spin-spin coupling and isotope effects in partially deuterated methyl-aromatic compounds
Authors: Macdonald CG , Shannon JS , Sternhell S
Published: September 2010

Seventeen methyl-aromatic compounds were
selectively, partially deuterated by catalytic hydrogen exchange. The proton
magnetic resonance (p.m.r.) spectra of the partially deuterated compounds
showed that the geminal H,D coupling constant is approximately 2.2 c/s and that
it does not vary significantly with the type of substitution in the ring. The
deuterium isotope effect on the chemical shift of the remaining protons in the
methyl group is approximately 0.7-1.1 c/s in the upfield direction for the introduction
of one deuterium atom.
Synthesis of colensan-1-one
Authors: Grant PK , Hill NR
Published: September 2010

Colensan-I-one (I), an isomer of the
naturally occurring norditerpene, colens-14-en-2-one, has been synthesized from
2-oxomanoyl oxide (II).
Kinetics of the gas-phase oxidation of methanol catalysed by nitric oxide
Authors: Batten JJ
Published: September 2010

The oxidation of methanol catalysed by nitric oxide has been studied in a
static system in the temperature range 300-400°. The kinetics and product
distribution were compared with previously published data on the uncatalysed
reaction and shoum to dlffer significantly. The reaction vessel was of Pyrex glass
and the maximum rate was found to be sensitive to the condition of its surface. The
rate of pressure change was shown to be a valid measure of the reaction rate which
accelerated rapidly to a maximum, remained constant for some time, and then
decreased slowly.
The overall activation energy was about 8 kcal mole-1 in the range 300-330°,
and 25 kcal mole-1 between 360 and 400°. At 310°
(d(Δp)/dt)max. ∝ [CH3OH]00.4[O2]0-1 [NO]01.7
and at 380°
(d(Δp)/dt)max. ∝ [CH3OH]00.75[O2]0-1 [NO]00.75
provided that [O2]0 < [CH3OH]0 = 100 mmHg. At [O2]0 > [CH3OH]0, the maxi-
mum rates were approximately independent of [O2]0 The pressure of the product,
formaldehyde, always rose to a maximum and then decayed in the later stages of an
experiment. Oxides of nitrogen appear to participate in the chain reaction.
The kinetics of the oxidation of ammonia by nitrous oxide
Authors: Bell TN , Hedger JW
Published: September 2010

Ammonia is oxidized by nitrous oxide
smoothly and homogeneously at temperatures between 658 and 730� and total
pressures up to 250 mm. The products of reaction, nitrogen, water, and
hydrazine are accounted for by a free-radical mechanism initiated by oxygen
atoms which result from the thermal decomposition of nitrous oxide. Ammonia
labelled with the 15N-isotope was used to distinguish between the nitrogen
formed from the nitrous oxide and that from the ammonia.

The kinetics follow an empirical rate
equation, ������������� Rate = k'[N2O]1.56
+ k"[N2O]0.61[NH3]. This is of a form which
shows the importance of the ammonia molecule participating in the activation of
nitrous oxide through bimolecular collision. Assigning a collisional efficiency
of unity for like N2O-N2O collisions, the efficiency of
ammonia in the process ������������ NH3 + N2O →
NH3 + N2O* is determined as 0.85.
Paper ionophoresis of amino compounds. Formation of carbamates, and related reaction
Authors: Frahn JL , Mills JA
Published: September 2010

Carbamates (N-carboxy derivatives) are
formed when solutions of primary or secondary amino compounds in strong alkali
are exposed on paper strips to carbon dioxide, and may be separated by paper
ionophoresis and detected as additional, anionic components. The formation of
mono-, di-, tricarbamates, and so on, from a polyamino compound occurs concurrently,
and when an amino compound containing n reactive groups is submitted to paper
ionophoresis in 0.lN sodium hydroxide at 18-20� after exposure to carbon
dioxide, it affords n additional spots. Most primary and secondary amino groups
in saturated compounds, and some aromatic amino groups, are reactive, but
highly hindered amino groups are not. Some unreactive groups become reactive
when the ionophoresis is conducted at 1-2�. The procedure is analytically
useful, and may be used to gain information about the structure of amino
compounds.

The conditions favouring the formation of
carbamates have been defined by paper ionophoresis. The primary reaction in the
formation of carbamates is the addition of carbon dioxide to the amino nitrogen
atom; carbamates are not formed directly from the carbonate ion. The rate of
reaction with carbon dioxide and the stability of the carbamates may be
correlated with the steric and electronic environment of the amino groups. Low
temperature and high alkalinity are essential for the stability of carbamates
in solution.�The
"basic mercury carbamates" described by Neuberg and Kerb (Biochem.
Z., 1912, 40, 498) do not seem to have the structure assigned by these authors.

Dithiocarbamates obtained by reaction of
amines with carbon disulphide in alkaline solution are easily identified by
paper ionophoresis, but they cannot readily be formed on the paper strip.
Attempts to prepare N-sulphinates by reaction of amino compounds with sulphur
dioxide on paper strips have been unsuccessful.
Mono- and Bis-(2,2'-bipyridine) and (1,10-phenanthroline) chelates of ruthenium and osaium. III. Mono chelates of bivalent, tervalent, and quadrivalent osmium
Authors: Buckingham DA , Dwyer FP , Goodwin HA , Sargeson AM
Published: September 2010

Osmium complexes of the type (BH)[OsX4B], K[OsX4B], [OSX4B]0,
[OsX3pyB]0, [OsX3H2OB]0, [OspysB]+/2+, [Ospy4B]2+/3+,
[OsX3py3]0, [OsX2py4]0, [OsX2acaB]0, [Osaca2B]0/+,
[OsX2glyB]0, [Osgly2B]+, and [OsBen2]2+
have been prepared, where B = 1,10-phenanthroline or 2,2'-bipyridine, py = pyridine, aca = acetylacetonate, gly = glycinate, en = ethylenediamine, and X = Cl or Br. They are
generally inert to dissociation of their ligands and to disproportionation. The
existence of the possible isomeric forms among the complexes is discussed.
Synthetical applications of activated metal catalysts. XXII. The desulphurization of 2,5-Diphenyl-1,4-dithiin
Authors: Badger GM , Cheuychit P , Sasse WHF
Published: September 2010

The desulphurization of 2,5-diphenyl-1,4-dithiin
(II) with a hydrogen-poor Raney nickel (W-7J Raney nickel) has been shown to
give 2,4-diphenylthiophen together with three hydrocarbons, viz. cis- and
trans-1,3-diphenylbuta-1,3-diene, and 1,3-diphenylcyclobut-1-ene. In another
experiment with a Raney nickel having a higher hydrogen content, the
hydrocarbon fraction was found to be 1,3-diphenylbut-2- ene. It has been
concluded that chemisorption via one sulphur atom leads to
2,4-diphenylthiophen, but that chemisorption via both sulphur atoms leads to
the intermediate diradicals (VI) which subsequently react further to give the
observed hydrocarbon products.
Potentially tautomeric pyridines. IV. Ethyl 2-, 3-, and 4-pyridyl acetate
Authors: Jones RA , Katritzky AR
Published: September 2010

Ultraviolet and infrared spectral
comparisons of the isomeric pyridylacetic esters with the anhydro bases derived
from the corresponding N-methyl derivatives show that the title compounds exist
predominantly in the pyridine form. Basicity measurements provided a
quantitative estimation of the tautomeric ratios.
Effect of surface on the gas-phase oxidation of methanol catalysed by nitric oxide
Authors: Batten JJ
Published: September 2010

A study has been made of the effect of the
surface-to-volume ratio of the reaction vessel and of coatings of various
inorganic substances on the vessel walls on the gas-phase oxidation of methanol
catalysed by nitric oxide. The results show that, whereas packing the vessel
does not have a marked effect on the rate, the kinetics of the reaction are
profoundly influenced by the nature of the surface.

The results suggest that the
methanol-oxidation chains are initiated at the surface by reaction between
methanol and nitrogen dioxide, and that HO2 radicals play an
important role in the subsequent chain reaction.
The analysis of the proton magnetic resonance spectra of heteroaromatic systems. II. Quinoline and its mononitroderivatives
Authors: Black PJ , Heffernan ML
Published: September 2010

The nuclear magnetic resonance spectra of
quinoline, as a pure liquid and as a dilute solution in carbon tetrachloride
and acetone, and of the 3-, 5-, 6-, 7-, and 8-nitroquinolines, all as dilute
solutions in acetone, have been investigated at 100 Mc/s. Field sweep double
resonance experiments, as well as chemical considerations, have been used to
assign the spin multiplets to individual protons. The spectral parameters for
these systems have been obtained by the iterative technique of Swalen and Reilly.
The modifications to the proton chemical shifts and the coupling constants
caused by the nitro substituent in various positions around the molecule are
discussed in the light of previous related investigations.
Nuclear magnetic resonance spectra, stereochemistry, and conformation of flavan derivatives
Authors: Clark-Lewis JW , Jackman LM , Spotswood TM
Published: September 2010

Chemical-shift and coupling-constant data
for protons in 68 flavan derivatives are reported.

Coupling-constant data for interactions
involving the 2-, 3-, and 4-protons have been used to define the configuration
of the 2-, 3-, and 4-substituents and the conformation of the heterocyclic
ring. It is shown that chemical-shift data for protons of the heterocyclic ring
and of 3- and 4-acetoxyl groups are of little value in stereochemical studies.

Analysis of the absorptions of the
aromatic protons shows that N.M.R. is useful for determining the oxygenation
pattern in rings A and B.
Porphyrins. II. The synthesis of porphyrins from 2-aminomethylpyrroles
Authors: Badger GM , Ward AD
Published: September 2010

Benzyl
5-formyl-3,4-dimethylpyrrole-2-carboxylate oxime (VI; R = COOCH2Ph)
has been reduced and treated with cupric acetate to yield copper
octamethylporphin in 20% yield. Copper octaethylporphin was obtained in similar
yield from 2-formyl-3,4-diethylpyrrole oxime (VII). The porphyrins are also
obtained, in much smaller yield, following acid-catalysed condensation; a by-
product formed under these latter conditions is probably a biladiene.

Attempts to prepare meso-substituted
porphyrins by similar treatment of the oximes of 2-acetyl- and
2-benzoyl-pyrroles were unsuccessful.
Porphyrins. V. Studies on the cyclization of linear tetrapyrroles
Authors: Badger GM , Harris RLN , Jones RA
Published: September 2010

Condensation of
3-acetyl-2,4-dimethylpyrrole with the bis(methoxymethyl)-dipyrromethene (IV)
has given the tetrapyrrene (I; R = Ac). This has been cyclized to
1,2-diacetyl-3,4,5,6,7,8-hexamethylporphin by heating with copper acetate in
methanol. The yield was not as good as that reported for fully alkylated
tetrapyrrenes, but the acetyl groups survived the reaction conditions.
Similarly, condensation of 3-cyano-2,4-dimethylpyrrole with the
bis(methoxymethyl)dipyrromethene (IV), gave the tetrapyrrene (I; R = CN).
Cyclization under the same conditions gave two porphyrins, presumably
1-cyano-3,4,5,6,7,8-hexamethylporphin and
1,2-dicyano-3,4,5,6,7,8-hexamethylporphin, in poor yield.
199Hg-1H Spin-spin coupling in vinyl and ethynyl mercurials
Authors: Wells PR , Kitching W
Published: September 2010

The proton magnetic spectra of cis and
trans-2-chlorovinylmercuric chloride, bis(trans-2-chlorovinyl)mercury, and
methylethynylmercury have been determined. Large variations in the 199Hg-1H
spin-spin coupling constants are observed for different hybridization states
and different geometries.
Experiments in artificial coalification
Authors: Sternhell S
Published: September 2010

Lignin derived from conifer wood was
converted by the action of boiling 6N hydrochloric acid into a material closely
resembling Victorian brown coals. The mechanism of this conversion and its
implication for the theories of coal genesis are discussed.

Morwell brown coal was converted, by
treatment with alkali at 230� followed by decarboxylation with
copper/quinoline, into a material resembling a more mature coal.
Dimedone (5,5-Dimethylcyclohexane-1,3-dione) as a protecting agent for amino groups in peptide synthesis
Authors: Halpern B , James LB
Published: September 2010

The reaction of dimedone
(5,5-dimethylcyclohexane-1,3-dione) with amino-acid "active" esters
leads to optically pure enamine derivatives. The dimedone derivatives of amino
acid esters could also be converted by way of their hydrazides to the corresponding
azides. The thiophenyl ester and azide derivatives have been used directly for
peptide synthesis. The protecting group can easily be removed from the
N-protected peptides by means of aqueous bromine, with the formation of
2,2-dibromodimedone and the hydrobromide of the corresponding peptide ester.
Phenanthridines. III. Syntheses of 9-bromophenanthridine and 7-bromophenanthridine by Pschorr reactions with sulphonamides derived from N-p-bromobenzyl- and N-o-bromobenzyl-o-phenylenediamines, and a new route to N-sulphonylcarbazoles
Authors: Huppatz JL , Sasse WHF
Published: September 2010

9-Bromophenanthridine (Ic) has been
prepared by oxidative hydrolysis of
9-bromo-5-p-toluenesulphonyl-j,8-dihydrophenanthridine (IIc), which is one of
the products of the copper-catalysed decomposition of diazotized
N-p-bromobenzy1.N-p- toluenesulphonyl-o-phenylenediamine (IIIc).
7-Bromophenanthridine (Ie) was similarly synthesized from
N-o-bromobenzyl-N-methanesulphonyl-o-phenylenediamine (IIIe) by way of
9-bromo-5-methanesulphonyl-5,6-dihydrophenanthridine (IIe). The decomposition
of diazotized o-bromobenzyl-N-p-toluenesulphonyl-o- phenylenediamine (IIId) did
not yield the corresponding phenanthridine derivative (IId). By-products formed
in the cyclization of (IIIc) include 2-p-bromobenzylamino-4'-methylbiphenyl
(Vc), 4-bromo-2'-p-toluenesulphonamidobiphenyl (VIc), and
N-p-bromobenzyl-2-amino-5'-methylbiphenyl-2'-sulphonic acid sultam (IVc). The
amine (IIId) gave 2-o-bromobenzylamino-4'-methylbiphenyl (Vd),
2-bromo-2'-p-toluenesulphonamidobiphenyl (VId),
N-o-bromobenzyl-2-amino-5'-methylbiphenyl- 2'-sulphonic acid sultam (IVd), and
AT-p-toluenesulphonylcarbazole (VIIa). The amine (IIIe) gave also
2-bromo-2'-methanesulphonamidobiphenyl (VIe) and N-methanesulphonylcarbazole
(VIIb). The relative yields of these products depend inter alia on the amount
of sodium nitrite used during the inverse diazotization prior to the addition
of copper. Under the influence of cuprous compounds the
2-amino-2'-bromobiphenyls (VId) and (VIe) are converted in high yields to the
carbazoles (VIIa) and (VIIb), respectively.
Pigments of marine animals. III. The synthesis of some substituted polyhydroxy-anthraquinones
Authors: Low TF , Park RJ , Sutherland MD , Vessey I
Published: September 2010

Synthetic specimens of
1,3,6,8-tetramethoxyanthraquinone and its 4-methoxy and 4-methoxycarbonyl
derivatives have been prepared for comparison with products derived from the
degradation of the pigments of the crinoids, Comatula pectinata and C. cratera.
Phenanthridines. IV. Pschorr reactions with sulphonamides derived from N-o-aminobenzylaniline: Synthesis of 4-bromophenanthridine and formationof 6-Phenyl-7H-dibenzo[d,f]-[1,2]-thiazepine-5-dioxide
Authors: Huppatz JL , Sasse WHF
Published: September 2010

The copper-catalysed decomposition of
diazotized N-o-aminobenzyl-N-benzenesulphonylaniline (IIIb) yielded
5-benzenesulphonyl-5,6-dihydrophenanthri. dine (IIa) in lower yield than the
Pschorr cyclization of N-benzenesulphonyl-N-benzyl-o-phenylenediamine (IIIa)
previously studied. However, only one major by-product,
6-phenyl-7H-dibenzo[d,f]-[1,2]-thiazepine-5-dioxide (VIa) was formed from
(IIIb). Pschorr cyclization of
N-o-aminobenzyl-N-p-toluenesulphonyl-o-bromoaniline (IIIc) gave
4-bromophenanthridine (Ic) and 6-(2-bromophenyl)-2-methyl-7H-dibenzo[d,f]-[1,2]-thiazepine-5-dioxide
(VIc). When this cyclization was carried out after diazotization with 30%
excess sodium nitrite, N-benzyl-N-p-toluenesulphonyl-o-bromoaniline (IIIg) was
also formed.
The diffusion of monocarboxylic acids in aqueous solution at 25°
Authors: Dunn LA , Stokes RH
Published: September 2010

The diffusion of the monocarboxylic acids
formic, propionic, and n-butyric in aqueous solution at 25� over the range
0.06-2.00M is studied by the Gouy interferometric method. The results, together
with Vitagliano's and Lyons's results for acetic acid, are corrected to allow
for the effects of ionization. A treatment of the effects of molecular
association on the experimental diffusion coefficients is proposed, and applied
with moderate success to acetic acid, propionic acid, and n-butyric acid. Mobilities
of the undissociated acid molecules at infinite dilution are found to be
greater than the limiting mobilities of the corresponding anions. Association
constants of the monocarboxylic acids over the concentration range studied are
calculated from existing activity data.
The analysis of the proton magnetic resonance spectra of heteroaromatic systems. IV. Benzofuran, indole, and related compounds
Authors: Black PJ , Heffernan ML
Published: September 2010

The proton magnetic resonance spectra of
benzofuran, dibenzofuran, indole, 7-azaindole, carbazole, and 4-azacarbazole (α-carboline)
have been investigated at 100 Mc/s, and the spectral parameters for these
molecules have been obtained. The presence of cross-ring coupling constants
involving the NH proton of indole and carbazole is reported.
Pyrrole studies. IV. The electronic spectra of alkyl- and ethoxycarbonyldipyrromethenes
Authors: Guy RW , Jones RA
Published: September 2010

The NH stretching frequency and the
electronic spectra of 8 alkyl- and 12 ethoxycarbonyl-dipyrromethenes have been
measured and the results correlated with the electronic and steric effects of
the substituents. It is postulated that there is steric interaction between the
two ethoxycarbonyl groups of 3,3'-diethoxycarbonyl.
4,5,4',5'-tetramethyldipyrromethene. The electronic effect of substituents in
the 4,4'-positions of 3,5,3',5'-tetramethyldipyrromethenes is discussed.
Peptides of L-leucine and glycine via N-chloroacetyl intermediates
Authors: Beecham AF
Published: September 2010

The synthesis is described of some N-chloroacetyl-peptide
intermediates and of the peptides derived from them, including
glycyl-L-leucylglycylglycyl-L-leucylglycylglycyl-L-leucylglycylglycyl-L-leucylglycine.
Apparent molar volumes in dilute aqueous propanol solutions
Authors: Alexander DM , Hill DJT
Published: September 2010

Apparent molar volumes of propan-2-ol have
been determined in dilute aqueous solution from 0� to 80�. Structural volume
changes in propan-1-ol and propan-2-ol solutions are discussed and related to compressibilities.
Organic semiconductors: Effect of substituents and metal ions on electrical conductivity of Schiff bases
Authors: Gooden EW
Published: September 2010

The effect of substituents on the
electrical conductivity of some crystalline anils of salicylaldehyde is
reported. A correlation exists between specific conductivity (log K) and the
Hammett substituent constant (σ) for both the meta and para series of
substituents, and between the activation energy of conduction (Δє) and σ for the para series. In each case
the relationship between conductivity and temperature can be described by the
equation K = K0exp(-Δє/2kT).��� Certain current questions as to the validity
of measurements ~f electrical resistivities of polycrystalline pellets and of
the application of band theory considerations to organic crystals are
discussed.

The effect of chelating Schiff bases with
divalent metal ions is to lower the conductivity considerably. Copper(II)
chelates are less conductive than the corresponding nickel(II) chelates. The
conductivity of the anils increases abruptly by several orders of magnitude at
the melting point, and Δєc values
appropriate to the super- cooled liquids are much lower than the solid state
values.
Schiff base equilibria. II. Beryllium complexes of N-n-butylsalicylideneimine and the hydrolysis of the Be2+ ion
Authors: Green RW , Alexander PW
Published: September 2010

The Schiff base,
N-n-butylsalicylideneimine, extracts more than 99.8% beryllium into toluene
from dilute aqueous solution. The distribution of beryllium has been studied in
the pH range 5-13 and is discussed in terms of the several complex equilibria in
aqueous solution. The stability constants of the complexes formed between
beryllium and the Schiff base are log β1 11.1 and log β2
20.4, and the distribution coefficient of the bis complex is 550. Over most of
the pH range, hydrolysis of the Be2+
ion competes with complex formation and provides a means of measuring the
hydrolysis constants. They are for the reactions: Be(H2O)42+
↔ 2H+ + Be(H2O)2(OH)2, log*β2
- 13.65; Be(H2O)42+ ↔ 3H+ + Be(H2O)(OH)3-,
log*β3 -24.11.
The reaction of N-t-Butyl-2,4,6-trinitrobenzamide with sodium hydroxide. A unimolecular nucleophilic aromatic substitution
Authors: Hutchison PJ , Martin RJL
Published: September 2010

N-t-Butyl-2,4,6-trinitrobenzamide
undergoes a nucleophilic substitution with hydroxyl ions to form nitrite ions.
The amide is stable during this reaction and will only undergo hydrolysis under
the more drastic conditions of higher hydroxyl ion concentrations at higher
temperatures. The observed rate of the nucleophilic substitution is inversely
proportional to the hydroxyl ion concentration. In the presence of alkali, the
amide is in equilibrium with a red anionic complex and the equilibrium constant
has been calculated from the kinetic data. When allowance has been made for
this equilibrium, it is found that the formation of nitrite ions from the amide
is zero order with respect to the hydroxyl ion concentration.
Degradation of carbohydrates. VI. Isolation and structure of some Glycos-2-enes
Authors: Anet EFLJ
Published: September 2010

The action of lime-water on 2,3-di-O-methyl-D-glucose
has yielded crystalline 3-deoxy-2-O-methyl-β-D-erythro-hexofuranos-2-ene,
which showed a complex muta-rotation involving the α-furanosene and the α-pyranosene
forms. Acetylation gave 1,4,6-tri-O-acetyl-3-deoxy-2-O-methyl-α-D-erythro-hexopyranos-2-ene.
Crystalline products shown to have the α-pyranosene form were obtained
from 2,3,4-tri-O-methyl-D-glucose, 2,3,4,6-tetra-O-methyl-D-glucose, and
2,3,4-tri-O-methyl-D-galactose. The ring forms, anomeric configurations, and
conformations of the products were determined, largely, by nuclear magnetic
resonance spectroscopy.
Reduction of the alkali and alkaline earth halides in high-frequency discharges. I. Hydrogen discharge
Authors: McTaggart FK
Published: September 2010

The halides of the alkali and alkaline
earth metals have been reduced in a hydrogen discharge at 2450 Mc/s. The
alkaline earth halides appear to react according to the overall equation MCl2
+ H → MCl + HCl, and the monohalide subsequently disproportionates to an
equimolar mixture of dihalide and metal. However, this reaction is not always
in accord with thermodynamic predictions, which suggests that further
elaboration of the reducing species is necessary.

Halides of the alkali metals are reduced
to metal, and the relative reaction rates range from 86 for lithium iodide to 1
for potassium bromide. Although for each metal, with the exception of
potassium, the rate is least for the fluoride and greatest for the iodide as
might be expected from the heats of formation, neither heat of formation nor
bond energy appears to be the major factor involved in the rate of reduction,
and an interesting relationship with the dimerization tendency of the halides
is suggested.

The role of halide sublimation rate and
the distribution of energies in the active species are also discussed.
Catalytic deuterium exchange reactions with organics. XIII. Characteristic reactions of the Group VIII transition metals
Authors: Garnett JL , Sollich WA
Published: September 2010

Activation procedures and hydrogen
exchange reactions with six Group VIII transition metal catalysts (Pt, Pd, Ru, Rh, Ir,
Ni) are reported for three characteristic reaction systems: (i) deuterium oxide/benzene,
(ii) deuterium oxide/naphthalene, and (iii) deuterium oxide/n-octane. Results
of these exchange reactions indicate that both π-complex adsorption and
the dissociative π-complex substitution mechanism previously established
for platinum are applicable to other Group VIII transition metal catalysts. For
general catalytic labelling with isotopic hydrogen, platinum was found to be the
most efficient of the catalysts investigated.
Extractives of Australian timbers. VI. Ebelin lactone
Authors: Eade RA , Rossler LP , Simes HV , Simes JJH
Published: September 2010

Ebelin lactone, formed by hydrolysis of a
saponin, is a carbotricyclic triterpene with a novel carbon skeleton. Chemical
evidence leading to the structure (I) for ebelin lactone is now presented in
detail. Ebelin lactone, C30H46O3, possesses a
secondary, equatorial hydroxyl group shown to be the 3β-hydroxyl group
located in a typical triterpene ring A (III). Spectroscopic and chemical
results show that the remaining two oxygen atoms are present in a γ-lactone
ring (XIII). The side- chain has been subjected to oxidative degradations; an
examination of the volatile fragments, and the isolation and characterization
of the non-volatile C22 octanor compounds indicate that the
side-chain has one of four possible structures (XVII). Structure (XVIII) is
preferred on biogenetic grounds. The side-chain is attached equatorially; the
conjugated triene system is allotted the trans arrangement of the double bonds
on spectroscopic evidence. The biogenesis of ebelin lactone is discussed.
Molecular polarizability. The optical anisotropies of certain aromatic molecules as solutes
Authors: Aroney MJ , Le Fevre RJW , Saxby JD
Published: September 2010

Estimates of the molecular optical
anisotropies (relative to benzene as standard) have been made from electric
birefringence data for a large number of aromatic compounds. The values so
derived are shown to be generally in accord with those determined directly from
light scattering techniques.
1,10-Phenanthroline and 2,2'-bipyridine chelates of higher-valent manganese
Authors: Goodwin HA , Sylva RN
Published: September 2010

Interaction of 1,10-phenanthroline or
2,2'-bipyridine in strongly acidic solution with the solution obtained by
treating potassium permanganate with concentrated hydrochloric acid results in
the separation of NN'-dihydrophenanthrolinium or NN'-dihydrobipyridinium
pentachloromanganate(III). In solutions of lower acidities
trichloroaquophenanthrolinemanganese(III) and trichloroaquobipyridinemanganese(III)
are formed. These complexes are notable for their stability. In addition,
tetrachlorobipyridinemanganese(IV) has been obtained. This decomposes when
heated to a bridged manganese(111) complex, [Mn(bipy)Cl3]2,
which has an anomalously low magnetic moment. The same complex and the
corresponding phenanthroline complex were also isolated from the product of interaction
of manganese dioxide and hydrochloric acid.