bluuebunny/crossref_metadata_2025 huggingface dataset:
Catalytic deuterium exchange reactions with organics. LXXI. Homogeneous platinum catalysed deuteration of the long-chain alkylbenzenes. Relationship toalkane exchange
Authors: Garnett JL , Kenyon RS
Published: September 2010

The long-chain alkylbenzenes out to nonylbenzene have been exchanged with D2O in the
presence of homogeneous platinum, deuteration
occurring in both ring and side chain. ortho-Deactivation
in the ring is observed, consistent with a mechanism involving a π-dissociative
process. Total isotope incorporation in a particular compound decreases with
increase in length and degree of branching of the side chain. In the side chain
α and terminal positions deuterata
predominantly, degree of isotope incorporation in these positions decreasing
gradually down the series to nonylbenzene. For butylbenzene and higher homologues, deuteration
of methylene positions is low.

Orientation of isotope in the side chain of l',l?-dimethylpropylbenzene is
unique and is used as a basis for a novel terminal abstraction π-complex
(TAPC) mechanism proposed to explain terminal exchange in the

alkylbenzenes. Concepts involving 'inner' and
'outer' π-complexes are shown to be of value in discussing mechanisms of
exchange in other positions of these compounds. The data may be related to
mechanisms for simple alkane exchange using this same catalyst.
Cobalt(III) ammine complexes containing acetylpyruvic acid derivatives. I. Preparation and characterization of the complexes
Authors: Hughes JG , O'Conner MJ
Published: September 2010

When the [Co(en)2(H2O)2]3+
ion is allowed to react with the sodium salt of acetylpyruvic acid or its
methyl ester in aqueous solution at 80�C, hydrolysis of the β-diketone
occurs and [Co(en)2(ox)]I2 is isolated by the addition of
potassium iodide. The method of preparation and characterization of [Co(en)2(ap)]I
and [Co(en)2(map)]I2 are described. Reactions involving
the corresponding tetraammine and cis-α-triethylenetetramine
cobalt(111) complexes are also described.
Thio derivatives of β-Diketones and their metal chelates. XV. Mass spectra of cobalt(III) and rhodium(III) chelates of some fluorinated Monothio-β-diketones
Authors: Das M , Livingstone SE
Published: September 2010

The mass spectra of the
cobalt(111) and rhodium(111) chelates of the fluorinated monothio-β-diketones
RC(SH)=CHCOCF3 (R = Ph, p-MeC6H4,
p-BrC6H4, p-FC6H4, and 2-thienyl)
and of the cobalt(111) chelate of CH3C(SH)=CHCOCF3 have
been obtained. The cobalt chelates do not give a peak for the molecular ion
because of thermal degradation to the cobalt(11) complex CO(RCS=CHCOCF3)2,
which then undergoes reactions in the mass spectrometer. Fluorine migration
occurs with cobalt but not with rhodium. The cobalt complexes give rise to more
metal-containing fragments than their rhodium analogues. Mechanisms are
proposed for the reactions involving the metal-containing fragments. Cobalt
undergoes valency changes to give cobalt(11) and cobalt(1) complex ions,
whereas rhodium undergoes a valency change to the bivalent state only.
Conformational analysis about the N-N bond by N.M.R. spectroscopy: N'-sulphonyl derivatives of N-Aminobicyclo[2,2,1]hept-5-ene-endo-2,3-dicarboximide
Authors: Verma SM , Koteswara Rao C
Published: September 2010

A series of N'-sulphonyl and N'-acyl derivatives of N-aminobicyclo[2,2,1]hept-5-ene-endo-2,3-dicarboximide
have been synthesized and their conformations have been investigated by N.M.R.spectroscopy. The effect of
the sulphonyl group at the exocyclic nitrogen on the conformational process
about the N-N bond has been studied.
Existence of non-planar ground states about the N-N bond in the N',N?-disulphonyl and N'-sulphonyl-N'-acyl
derivatives has been demonstrated.Temperature-dependent
spectral changes have been related to the conformational changes about the N-N bond. It has been shown that the N'-tosyl substituent assumes a preferred
conformation about the N-SO2 bond; the aryl part of the tosyl group
lies exo to the cage-moiety. The N'-tosyl-N'-aroyl derivatives also show a preferred conformation about the N'-aroyl bond, the aryl part of the aroyl
group lying endo to the cage-moiety.
The N'-acetyl-N'-aroyl derivatives have been shown toexhibit low rotational
barriers about the N'-aroyl bond.
Studies on intramolecular alkylation. VI. ortho-Alkylation in phenolic diazoketones: the preparation of intermediates containing the Cyclohexa-2,4-dienonemoiety suitable for gibberellin synthesis
Authors: Johnson DW , Mander LN
Published: September 2010

Simple efficient syntheses
of 8-hydroxy- and 8-methoxy-2-tetralones (9) and (10), 1,2,3,4-tetrahydro-8-
hydroxy-2-naphthoic acid (5),
1,2,3,4-tetrahydro-2-hydroxy-8-methoxy-2-naphthoic acid (8),
1,2,3,4-tetrahydro-2,s-dihydroxy-2-naphthoic acid (7) and 1,2,3,4-tetrahydro-5-hydroxy-2-naphthoic
acid (20) are described. The acid-catalysed reactions of the diazoketones derived from (5) and (20) gave good yields of tricyclic ketones (3) and (4) incorporating a
cyclohexa-2,4-dienone moiety. The potential of (3) for gibberellin
synthesis is examined.
Chemistry of the Podocarpaceae. XLVII. Steroidal analogues from 12-Hydroxypodocarpa-8,11,13-trien-19-oic acid
Authors: Cambie RC , Denny WA , Fullerton TJ , Hayward RC
Published: September 2010

Attempts to utilize the
ketones (10) and (11) for the preparation of steroidal analogues are described.
The ketone (10) has been converted into the octahydrochrysene (26) and to the
benzindene derivative (29). The diketone (16) has been converted into the de-A
pregnane derivative (27) and by auto-cyclization to the ketol (8) and the
ketone (34).
Fungal metabolites. III. The synthesis of a derivative of a 1,4-naphthoquinone fungal pigment
Authors: Coombe RG
Published: September 2010

The synthesis of
2-acetonyl-3-hydroxy-5,7-dimethoxy-1,4-naphthoquinone, the 5-methoxy derivative
of a pigment obtained from Cylindrocarpon sp. C.M.I. 127996, is described.
Organophosphorus compounds. XIV. A new synthesis of 3-pyridylphosphonic acid
Authors: Collins DJ , Hetherington JW , Swan JM
Published: September 2010

The reaction of
3-pyridyllithium with diethyl phosphorochloridate at ?
80� gave 36% of pure diethyl 3-pyridylphosphonate, hydrolysis of which afforded
3-pyridylphosphonic acid. Treatment of diethyl 3-pyridylphosphonate with
aqueous dimethylamine at 150� for 3h afforded 78% of ethyl
3-pyridylphosphonate, characterized as the crystalline cyclohexylamine salt.
Conformations of higher acditols
Authors: Mills JA
Published: September 2010

Analysis of stereomodels of alditols shows
several conformational features in heptitols and
higher members that are not readily apparent from published experimental
studies on pentitols and hexitols.
There are severe restrictions on possible conformations of higher alditols that contain segments of ribo or allo configuration. The higher members of the stereoregular
series that starts with xylitol and iditol can have non-planar conformations free of serious
non-bonded interactions. A conformational nomenclature is proposed for acyclic
carbohydrates, which can be used to describe the arrangement of either the
hydroxyl groups or the carbon chain, or both, and can also be used to describe
conformations of segments of a chain.
Organoboranes in organic synthesis. I. The reaction with α,α'-dibromo ketones in the presence of base
Authors: Prager RH , Tippett JM
Published: September 2010

α,α?-Dibromocycloalkanones react with organoboranes
in the presence of base to give products dependent on the amount and type of
base used. Small alkoxides yield mainly the reduced cycloalkanone; one equivalent of more hindered alkoxides also leads to reduction, but two equivalents of
hindered alkoxides afford monoalkylcycloalkanones.
Unsymmetrical dibromo ketones give alkylation
exclusively on the least hindered side.
Nitrones and oxaziridines. XII. Vinylogous hydroxamic acid structures of the reduction products from γ-nitro (o- and p-hydroxyphenyl) ketones
Authors: Bapat JB , Black DSC , Newland G
Published: September 2010

Vinylogous hydroxamic acid structures (4) and (5) are assigned to the
products of the zinc and ammonium chloride reduction of the γ-nitro (o- and p-hydroxyphenyl) ketones (lc) and (1d) respectively. Similar reduction of the related
γ-nitro (m-hydroxyphenyl)
ketone (le) afforded the nitrone (2e).
The mechanism of lead tetraacetate decarboxylation. I. Tertiary carboxylic acids
Authors: Beckwith ALJ , Cross RT , Gream GE
Published: September 2010

The reactions of cis- and trans-decalin-9-carboxylic acid, 2,2,3-trimethylbutanoic acid, and
adamantane-1-carboxylic acid with lead tetraacetate in benzene and, in some
cases, acetic acid have been studied. In each case the nature and distribution
of the products is consistent with the hypothesis that the reaction mechanism
involves the initial generation of tertiary radicals which are subsequently
converted into the related cations either by one-electron oxidation by lead
species, or via organolead intermediates which
undergo heterolysis. The change in product distribution which occurs when the
reactions are conducted in the presence of copper salts indicates that tertiary
radicals react rapidly with cupric species to afford organocopper
intermediates from which olefins are derived by a cis-elimination process, and acetates by SNi
or heterolytic mechanisms.
Reactions of some carbanions generated with lithium aluminium hydride
Authors: Collins DJ , Hobbs JJ
Published: September 2010

Treatment of erythro-2,3-bis(p-methoxyphenyl)butyronitrile with lithium aluminium hydride in
tetrahydrofuran gave the stable 2-anion, protonation of which gave a 2.3 : 1 erythro : threo mixture of the nitrile; in air, 1,2-bis(p-methoxyphenyl)propan-1-ol was formed by oxygenation of the anion.
The same anion was produced rapidly and quantitatively from 2,3-bis(p-methoxyphenyl)crotononitrile with
LiAlH4 in tetrahydrofuran. Some reactions of carbanions generated
similarly from α,α? -dicyanostilbene, 9-benzylidenefluorene,
fluoren-9-ylidenemalononitrile and 1,l-diphenylethylene are described.
2,3-Bis(pmethoxyphenyl)butadiene was reduced with LiAlH4 in
tetrahydrofuran to give a mixture of (Z)- and (E)-2,3-bis(p-methoxyphenyl)but-2-ene and 2,3-bis(p-methoxypheny1)but-l-ene, probably via organoaluminium
intermediates.
Organophosphorus compounds. XV. Synthesis of 2-Ethoxy-1-methyl-1,2-azaphospholidine 2-oxide
Authors: Collins DJ , Hetherington JW , Swan JM
Published: September 2010

The reaction of diethyl
3-bromopropylphosphonate with phosphorus pentachloride
in carbon tetrachloride gave ethyl 3-bromopropylphosphonochloridate, which upon
reaction with anhydrous methylamine at -15� gave ethyl N-methyl-P-3-bromopropylphosphonamidate.
Treatment of this phosphonamidate with sodium hydride
in boiling xylene gave 2-ethoxy-1-methyl-l,2-azaphospholidine 2-oxide. Some
other possible routes to this compound were investigated.
Synthesis of para-olivetol depsides
Authors: Elix JA
Published: September 2010

The unambiguous synthesis
of the lichen depsides, anziaic,
perlatolic, 2'-O-methylanziaic,
2-O- methylperlatolic,
2'-O-methylperlatolic, 4-O-demethylplanaic, planaic,
imbricaric and stenosporic
acids is reported. Where necessary the phenolic and carboxy
groups of the intermediate phenols were protected by O-benzylation until after the depside-ester bond formation had been achieved by treatment
with trifluoroacetic anhydride. Catalytic hydrogenolysis of the depside esters so formed subsequently gave the natural
acids.
Dye sensitized photooxidation of 1,3-Diphenyl-2-pyrazoline
Authors: Evans NA , Leaver IH
Published: September 2010

Dye sensitized photooxidation of 1,3-diphenyl-2-pyrazoline in methylene
chloride yields 1,3-diphenyl- pyrazole and in
methanol yields 1,3-diphenylpyrazole and β,β-dimethoxypropiophenone.
The formation of 1,3-diphenylpyrazole is quenched by the singlet oxygen
quencher β-carotene, whereas the formation of β-dimethoxypropiophenone
does not appear to be affected. The photooxidation in
methanol shows a large deuterium isotope effect, the rate being approximately
ten times faster in methanol[D4] than in methanol. Under anaerobic
conditions, 1,3-diphenyl-2-pyrazoline quenches the phosphorescence of eosin Y
and rose bengal B with quenching rate constants 1.0 x
108 and 3.0 x 108 1, mol-1 s-1,
respectively. Photobleaching of the dyes is shown to
occur by reduction to the semi-reduced dye radicals.
Substituent effects by carbon-13 nuclear magnetic resonance: Concerning the π-inductive effect
Authors: Adcock W , Aurangzeb M , Kitching W , Smith N , Doddrell D
Published: September 2010

13C Substituent chemical shifts (scs) data for the C4
and C10 carbon atoms in 1-x-naphthalenes and 9-x-anthracenes respectively do
not corroborate the proposal that the meso
disposition in anthracene is a suitable model for the detection of the π-inductive
or inductomesomeric effect.
An electron spin resonance study of dimeric oranotitanium(III) carboxylates
Authors: Coutts RSP , Looney FD , Martin RL , Wailes PC
Published: September 2010

The e.s.r. spectra of a
series of binuclear titanium(111) carboxylates, [CpTi(O2CR)2]2, both in
toluene solution or in a polycrystalline state, are characteristic of a triplet
(S = 1) state. The zero-fieldsplitting parameter D lies
in the range D = 0.055 � 0.004 cm-1 whereas E is close to zero. The
g values for five R-substituents are g/=1.94 � 0,02 and g// = 2.00 � .03; the
forbidden ΔM = 2 resonance occurs at gav
= 3.96 � 0.09. Pairs of titanium atoms (electron configuration 3d1)
arebelieved to be strongly
coupled antiferromagnetically through a dxy(Ti1) // π(carboxy1ate)//dxy(Ti2) superexchange
pathway.
Electron impact studies. LXXXVIII. formation of an adduct between the trifluoroacetate anion and perfluoroacetic anhydride by ion cyclotron resonance
Authors: Bowie JH , Williams BD
Published: September 2010

The gas phase reaction
between the trifluoroacetate anion and perfluoroacetic anhydride produces a 1 :
1 adduct. The decompositions of this adduct suggest a tetrahedral species
rather than a loose association complex. If this is so, this constitutes the first
direct observation of the formation of a tetrahedral intermediate produced by
anionic displacement at a carbonyl centre.
Chemistry of the Podocarpaceae. XLVIII. Photo-sensitized oxidations of unsaturated ring-c aromatic diterpenoids
Authors: Cambie RC , Hayward RC
Published: September 2010

Photo-sensitized oxidation
of the 6,7-dehydro ring-c aromatic diterpenoids (5),
(8) and (38) affords high yields of the corresponding 5-ene-7-ones (62), (63)
and (69). Similar oxygenation of 13-methoxy- totara-6,8,11,13-triene (21) gives
a hydroperoxide (74) which undergoes a facile
rearrangement to a naphthyl derivative (80) in the
presence of acid. Photo-sensitized oxidation of the enol
acetates derived from the 7-oxo diterpenoids,
however, provides a general method for preparation of the corresponding 5-ene-7-one.
Reduction of the enone (62) with lithium aluminium hydridealuminium
chloride gives a mixture of the 5,8,11,13-tetraene (66) and the
6,8,11,13-tetraene (9) while reduction with sodium borohydride and treatment of
the resulting alcohols (61) and (67) with acid gives a mixture of the tetraenes (5) and (68). Photo-oxygenation of the latter
mixture provides a convenient method for isolating the tetraene
(68). Similar reductions of 13-methoxytotara-5,8,11,13-tetraen-7-one (76) have
been examined and products from the action of m-chloroperbenzoic acid on the enol acetates (19), (20) and (7) are reported.
Thermodynamics of metal-ligand bond formation. XV. Adducts of mercury(II) halides with bidentate bases
Authors: Farhangi Y , Graddon DP
Published: September 2010

Thermodynamic data are
reported for the reaction of mercury(11) halides with a range of potentially
bidentate bases in benzene solution. The enthalpy data show that in 1 : 1
adducts with tetramethyl-alkanediamines and bis(diphenylphosphino)ethane both donor atoms are coordinated,
the mercury being four-coordinate with two Hg-N or Hg-P bonds, each of
comparable strength to those in 1 : 1 adducts with unidentate
bases. N-Methylmorpholine
and dioxan are almost certainly unidentate.
1,10-Phenanthroline, 2,2'-bipyridine and N,N'-dimethylpiperazine gave 1 : 1 adducts of higher stability
than those of unidentate bases, but the enthalpies of
adduct formation were similar or smaller; the most satisfactory explanation of
this seems to be that both nitrogen atoms arecoordinated
but that the two Hg-N bonds are unusually weak because of steric misfitting of the bidentate base with the mercury atom.
Comparative study of methods of computer-matching mass spectra
Authors: Mathews RJ , Morrison JD
Published: September 2010

The performance of
different methods of computer-matching mass spectra has been examined, using a
library of terpene mass spectra. The matching of from six to eight of the most
intense peaks in each spectrum yielded the best results. A discrimination level
of 10.0 to 12.5% of base peak gave the best results when using the 1-Bit
encoding method, a result significantly different from a previous finding.
The acid-catalysed rearrangement of two Benzo-p-quinols
Authors: Woodgate PD , Fitchett CR
Published: September 2010

Treatment of the phenyl p-quinol (7a)
with acetic anhydride-sulphuric acid yields the naphthalene- 1,3-diol
derivative (8a), whereas the methyl p-quinol (7b) gives 4-acetoxymethyl-2,6-di-t-butyl-1- naphthyl acetate (15).
Simple pyrimidines. XV. The synthesis, piperidinolysis and hydrolysis of simple 2- and 4-(Halogenomethyl)pyrimidines
Authors: Brown DJ , Waring P
Published: September 2010

The 2-and 4-bromomethyl-, dibromomethyl- and (impure) tribromomethyl-pyrimidines,
as well as their chloro analogues, were made by direct halogenation
of 2- or 4-methylpyrimidine (3m) and (3e) with the appropriate N-halogenosuccinimide.
Rates were measured spectrometrically for piperidinolysis and alkaline hydrolysis of the monohalogenomethylpyrimidines which reacted much more
rapidly than 2- and 4-halogenopyrimidines. 4,6-Dimethylpyrimidin-2-ylmethanol
and 2,6-dimethyl- pyrimidin-4-ylmethanol were made by reduction of the
corresponding esters (1 and 2; R = CO2Et). The u.v.,
n.m.r, and mass spectra of the compounds are discussed.
The triterpenes of Faradaya splendida (Verbenaceae)
Authors: Eade RA , Harper P , Simes JJH
Published: September 2010

Extraction of the roots of Faradaya splendida F. Muell, has yielded 3-O-acetyloleanolic
aldehyde, 3-O-acetylerythrodiol and a
very small amount of the potassium salt of a new polyhydroxy triterpene diacid,
C30H46O11, named faradoic
acid.
Hydrolysis of Monothio-β-diketones. I. Monothioacetylacetone and monothiobenzoylacetone
Authors: Leban M , Fresco J , Livingstone SE
Published: September 2010

The hydrolysis of
monothioacetylacetone (4-mercaptopent-3-en-2-one) and monothiobenzoylacetone
(3-mercapto-1-phenylbut-2-en-1-one) in acid solution has been studied
spectrophotometrically. The half-lives were found to be 50�2 min and 124�5 min
at 25� for monothioacetylacetone and monothiobenzoylacetone, respectively. The
corresponding pseudo first- order rate constants are 1.39�0.05 x 10-2
and 5.59�0.14 x 10-3 min-1. The enthalpy of activation
for the hydrolysis of monothiobenzoylacetone was determined as 79.5 � 4 kJ/mol.
Zinc dissolution in Leclanche electrolyte
Authors: Matthews DB , Capps PG
Published: September 2010

The rate and morphology of
zinc dissolution were studied in a Leclanche
electrolyte of composition 0.5 mol dm-3 ZnCl2 and 5 mol
dm-3 NH4Cl. A gelled electrolyte layer 2 x 10-3
m thick on the zinc surface was found to reduce the corrosion rate by an order
of magnitude and to promote even dissolution. The corrosion results are
interpreted in terms of a diffusion-controlled cathodic reaction involving O2
dissolution and metallic impurity deposition.
The reaction between Hexafluorobut-2-yne and a ferrole complex
Authors: Bruce MI , Kuc TA
Published: September 2010

The reaction between C2(CF3)2
and C4H2(OH)2Fe2(CO)6
affords the diether complex, C4H2-[OC(CF3)=CH(CF3)-(Z)]Fe2(CO)6.
The non-stoichiometry of pink zinc oxide
Authors: Norman VJ
Published: September 2010

A highly coloured pink zinc
oxide, having a total nitrogen content of 0.054%, has been prepared by heating
white zinc oxide and ammonium carbamate in an atmosphere of ammonia and carbon
dioxide at 200�. The preparation results in a marked increase in the specific
surface area of the zinc oxide. ��� The non-stoichiometry of the pink zinc
oxide has been determined, and it is shown that the amount of reactive oxygen
chemisorbed on the surface increases with time. The maximum chemisorption
amounted to 52 p.p.m. by weight (1.1 x 1025
ion m-3) after exposure for 35 days in a controlled environment. The
surface concentration of interstitial zinc has been estimated indirectly from
the reactive oxygen results. The concentration of the non-stoichiometric
species in pink zinc oxide is more than an order higher than that of the white
zinc oxide from which it was prepared. The results support the mechanism
tentatively proposed by previous workers for the incorporation of nitrogen in
zinc oxide.
The reactions of linear conjugated diynes with Dicarbonyl(η-cyclopentadienyl)- cobalt and -rhodium
Authors: Dickson RS , Michel LJ
Published: September 2010

The reactions of (η-C5H5)Co(CO)2
with the diynes hexa-2,4-diyne and 1,4- diphenylbutadiyne
give three isomers of the cyclopentadienone complexes (C5H5)Co[(RC2C2R)2CO],
R = Me or Ph, and two isomers of the tris-alkyne complexes (C5H5)2Co2(RC2C2R)3CO,
R = Me or Ph. Organic products of formula (RC2C2R)3,
R = Me or Ph, (MeC2C2Me)5, and (PhC2C2Ph)3CO
have been isolated also. Two isomers of (RC2C2R), were
separated and were identified as the 1,2,4-(R)3-3,5,6-(C2R)3-
and the 1,3,5-(R)3-2,4,6-(C2R)3-benzenes. The
compound (PhC2C2Ph)3CO is believed to be tris(phenylethynly)triphenylcycloheptatrienone,
and (MeC2C2Me)5 is probably a polycyclic aromatic
compound. Thermal degradation of the complexes (C5H5)2CO2(RC2C2R)3CO
gives the substituted benzenes (RC2C2R)3. ��� The reaction of (η-C5H5)Rh(CO)2 and hexa-2,4-diyne gives the
cyclopentadienone complex(C5H5)Rh[(MeC2C2Me)2CO]
and the cycloheptatrienone complex (C5H5)Rh[(MeC2C2Me)3CO].Two
isomers of the substituted benzene (MeC2C2Me)3
were obtained also.
The magnetic properties of hexaureatitanium(III) and vanadium(III) salts at very low temperatures
Authors: Baker J , Figgis BN
Published: September 2010

The magnetic susceptibility
of the perchlorate and iodide salts of the hexaureatitanium(III) and
hexaureavanadium(III) cations have been measured to temperatures as low as 4 K
in the former and 1.5 K in the latter cases. The results were interpreted to
deduce the three parameters of the simplest theory for the splitting of the
ground T term for each ion. The parameter sets agree only fairly well with
results from the magnetic susceptibility and anisotropy data at higher
temperatures.
Thio derivatives of β-diketones and their metal chelates. XVIII. Mass spectra of some metal chelates of the monothio derivatives of benzoylacetone anddibenzoylmethane
Authors: Das M , Livingstone SE
Published: September 2010

The mass spectra of the
iron(III), cobalt(III), nickel(II) and zinc(II) complexes of the
monothio-β-diketones RC(SH)=CHCOPh (R = Me, Ph)
have been obtained. The iron and cobalt complexes of 3-mercapto-1-phenylbut- 2-en-1-one
(R = Me) do not give a peak for the molecular ion due to thermal degradation to
the bivalent metal complex Met(MeCS=CHCOPh)2 (Met = Fe, Co), which then undergoes
reactions similar to those undergone by the nickel and zinc complexes. The most
interesting feature of the spectra is the loss of hydrogen sulphide which does
not occur with the free ligand or with metal complexes of fluorinated monothio-8-diketones
RC(SH)=CHCOCF3. ��� The zinc complex of
3-mercapto-1,3-diphenylprop-2-en-1-one (R = Ph) undergoes fragmentation in the
mass spectrometer to produce inter alia [ZnC6H5]+.
However, the iron(III), cobalt(III), nickel(II) and palladium(II) complexes
undergo thermal degradation in the mass spectrometer but the mass spectra of
these four complexes give metal-free ions with m/e greater than m/e for L, due
to fragmentation of the ion 2L.
Isolation of unstable alkaloids from Erythrophleum chlorostachys (Leguminosae)
Authors: Falkiner MJ , Faux AF , Loder JW , Nearn RH
Published: September 2010

Unstable 2-methylaminoethyl
esters from E. chlorostachys can be isolated with
careful pH control and then manipulated as their stable hydrochlorides. A
large-scale extraction and counter- current distribution separated two new
crystalline alkaloid hydrochlorides, namely norerythrostachaldine
hydrochloride, C23H37NO5,HCl, and a second
salt, C24H37NO7,HCl. Four new monoacetates are
tentatively identified as the 3β-acetoxy derivatives of the two new
alkaloids, norerythrostachamine, and norerythrophlamine. Norerythrophlamine
has been isolated for the first time as its crystalline hydrochloride.
The effect of pressure on the rates of some substitution reactions of alkyl halides
Authors: Hamann SD
Published: September 2010

Measurements have been made
of the influence of hydrostatic pressure on the rates of three kinds of
bimolecular substitution reactions of alkyl halides in solution. They are
reactions with (a) halide ions in acetone solution (Finkelstein reactions), (b)
silver nitrate in aqueous ethanol and (c) mercuric nitrate in aqueous dioxan. ��� The Finkelstein reactions were
unsymmetrical with respect to the halogen atoms, for instance I- + PrCl → PrI+Cl-.
They were all accelerated by an increase of pressure, in contrast to the sym-
metrical exchange I*- + PrI → PrI* + I-, which is known to be retarded by an
increase of pressure. This fact supports Gonikberg's
view of the role of partial desolvation in the symmetrical reactions. Reactions
involving LiCl as the source of halide ions were
accelerated much more than those involving KI, simply because an increase of
pressure enhances the dissociation of unreactive LiCl
ion pairs. ��� Reactions of the types (6) and (c) were
also accelerated by an increase of pressure, a fact which argues against a
suggestion that the attacking species might be ion pairs.
1,3,4-Thiadiazole-2,5-dithiol as a complexing agent. Complexes of RuIII, RuII, RhIII, PdIV IrIII and PtIV
Authors: Gajendragad MR , Agarwala U
Published: September 2010

Complexes of RuIII, RuII,
RhIII, PdIV,
IrIII and PtIV
with 1,3,4-thiadiazole- 2,5-dithiol have been prepared. Probable structures for
the complexes have been proposed on the basis of chemical analyses, magnetic
susceptibility and electronic and infrared spectral data. Crystal field
parameters have been calculated which are in accordance with the structures
proposed. In every complex the ligand behaves as a unidentate towards two metal
ions.
Copper complexes of 4,7-Diphenyl-1,10-phenanthroline
Authors: Lip HC , Plowman RA
Published: September 2010

4,7-Diphenyl-1,10-phenanthroline
(dph) forms mono-, bis- and tris- complexes with
copper(II). The mono- and tris-complexes appear to be octahedral, the
bis-complexes five-coordinate. Although dph readily
forms complexes with copper(II), the isolation of copper(I) complexes is more
difficult.
Studies on the application of the quinhydrone electrode in formamide. III. The ionization constants and related thermodynamic quantities of phthalic acid frome.m.f. measurements at different temperatures
Authors: Dash UN , Nayak B
Published: September 2010

The first and second
ionization constants of phthalic acid have been determined, in formamide, at
temperatures ranging from 5� to 45�C at 5� intervals, with the help of cells
without liquid junction using quinhydrone and silver-silver chloride
electrodes. By means of the Bjerrum equation, the
distance r between the acidic groups has been estimated in formamide at
different temperatures.
Nickel-catalysed conjugate addition of trimethylaluminium to 3-Oxo-Δ4-steroids
Authors: Bagnell L , Meisters A , Mole T
Published: September 2010

Nickel-catalysed addition
of trimethylaluminium to 3-oxo-Δ4-steroids (cholest-4-en-3-one,
testosterone propionate and progesterone) in ether gives the corresponding
5β-methyl saturated ketones in moderate yields. Lithium dimethylcuprate
gives similar results.
One-electron bonds as intermolecular bonds for molecular complexes involving Mulliken n-electron donors and as-electron acceptors
Authors: Harcourt RD
Published: September 2010

For 1 : 1 molecular
complexes involving an n-type electron donor and an aσ-type
electron acceptor, it is proved that the simplest Mulliken
description, ΨN ≈ Ψ(D,A)+λΨ(D+-A-),
is equivalent to using a one-electron bond as the intermolecular bond between
the donor (D) and the acceptor (A). The theory is illustrated with reference to
the Hassel compound Me3N...I2,
and the charge-transfer aspects of hydrogen bonding for the water dimer.
The synthesis of 2-Phenyl-2-imidazoline via a dithionamide intermediate
Authors: Ewin G , Hill JO
Published: September 2010

2-Phenyl-2-imidazoline is
prepared by the reaction between N,N?- ethylenebisthiobenzamide
and ethylenediamine in the presence of mercuric oxide. Some new crystalline
derivatives (I-, NCS-,Co(NCS)42-
and Zn(NCS)42-) have been prepared and characterized.
Beyeren-19-ol from Helipterum craspedioides
Authors: Dennison NR , Mirrington RN
Published: September 2010

The resinous coating on
Helipterum craspedioides consists mainly of the
succinate ester (2) of (+)-beyeren-19-ol (1) (monogynol,
erythroxylol A).
Synthesis of para-β-orcinol depsides
Authors: Elix JA , Norfolk S
Published: September 2010

The unambiguous syntheses
of the lichen depsides norobtusatic acid, obtusatic acid, 4-O-demethyl-barbatic
acid, barbatic acid, diffractaic acid, chloroatranorin, baeomycesic acid and
squamatic acid are reported.
Thio derivatives of β-diketones and their metal chelates. XIX. Metal chelates of two new fluorinated Monothio-β-diketones and their mass spectra
Authors: Livingstone SE , Saha N
Published: September 2010

The nickel(II),
palladium(II), platinum(II), copper(II), zinc(II) and rhodium(III) chelates of
the new fluorinated monothio-β-diketones RC(SH)=CHCOCF3 (R = Pri,
Bui) and the iron(III), ruthenium(III) and cobalt(III) chelates of
PriC(SH)=CHCOCF3 have been prepared. The mass spectra of
all but the two copper chelates have been obtained. The novel features of the
spectra are the occurrence of the ions M-(R-H), M-R, and M-LH and the loss of H2S
from the ions M-LH and M-L.
The synthesis of a phenolic sesquiterpene isolated from Elvira bifora (Compositae)
Authors: Dennison NR , Mirrington RN , Stuart AD
Published: September 2010

The proposed structure for
a phenolic sesquiterpene, 2-(11,5?- dimethylhex-4?-enyl)-4-methylphenol (1),
previously isolated from Elvira biflora, has been
confirmed by synthesis of its racemate in 3 steps from 3-bromo-4-methoxytoluene
and 6-methylhept-5-en-2-one. A structural isomer, 4-(1?,5?-di-methylhex-4?-enyl)-2-methylphenol
(4), has also been synthesized for spectral comparison, since the natural
product and the synthetic racemate (1) were only able to be compared by N.M.R.
spectroscopy.
Structure of the Acid-Stable Core-Polysaccharide Derived From the Seed Mucilage of Ocimum Basilicum
Authors: Tharanathan RN , Anjaneyalu YV
Published: September 2010

Partial acid hydrolysis of
the mucilage gave an acid-stable core- polysaccharide composed of glucose and
mannose (10 : 2). Repeated methylation of the core-polysaccharide by the usual
techniques gave chloroform-soluble and -insoluble fractions. Hakomori methylation of the two fractions, hydrolysis,
conversion of the sugar derivatives into alditol acetates and their
identification by g.l.c.revealed that the soluble
fraction is a glucomannan-type polymer while the
insoluble fraction is of the glucan type. Combined g.l.c.-m.s.
of the derived alditol acetates indicated that the glucan fraction is a
degraded cellulose material while the glucomannan-type
fraction is a linear polymer with sugar residues linked by (1→4)-β-glycosidic
bonds terminated at the non-reducing end by a unit of D-glucose and/or D- mannose.
The presence of contiguous glucose as well as glucose and mannose units was
indicated by isolation of the corresponding oligosaccharides from the core-polysaccharide.
Thus, the core- polysaccharide was found to be a composite aggregate of
degraded cellulose and glucomannan-type polymers.
Acridone studies. XIV. The selective demethylation of 2,3-Dimethoxy-10-methyl-9-oxoacridine-1,4-quinone by base
Authors: Cowan JR , Hodgeman DKC , Prager RH
Published: September 2010

The selective demethylation
of 2,3-dimethoxy-10-methyl-9-oxoacridine- 1,4-quinone by sodium hydroxide has
been studied by following the change in product composition with hydroxide
concentration, by measuring the relative extent of exchange at C2 and C3 with
sodium methoxide[T], and by following the kinetics of the reaction in alkali.
Reaction pathways are proposed to rationalize the observation that the C2
methoxyl group is replaced more readily in dilute alkali or on warming, but the
C 3 methoxyl group is replaced in more concentrated alkali.
Behaviour of silver-silver oxalate and mercury-mercurous oxalate electrodes in formamide at different temperatures
Authors: Dash UN , Nayak B
Published: September 2010

The e.m.f. values of the
cells:

Pt, H2|H2C2O4(m)|Ag2C2O4-Ag
(A) Pt, H2|H2C2O4(m)|HgC2O4-Hg
(B) Hg-Hg2C2O4|H2C2O4(m)|Ag2C2O4-Ag
(C)

have been measured in
formamide at nine temperatures ranging from 5 to 45�C. Values of the standard
potentials (E�m) of silver-silver oxalate and mercury-mercurous
oxalate electrodes and values of the e.m.f. of cell (C) can be expressed as
equations obtained by using the least squares method:

(A) E�m =
0.44642-1.042x10-3(t-25)+4.150x10-6(t-25)2 (B) E�m =
0.39438-1.040x10-3(t-25)+4.500x10-7(t-25)2 (C) E�celt =
0.05255-9.750x10-5(t-25)+8.750x10-7(t-25)2

The standard thermodynamic
quantities ΔG�, ΔH� and ΔSo associated with the
corresponding cell reaction have been evaluated for different temperatures.
Ionization constants and related thermodynamic quantities of (CH2)n(CO2H)2 (n = 0, 1, 2, 3 or 4) from e.m.f. measurements in HCONH2
Authors: Dash UN , Nayak B
Published: September 2010

The first and second
ionization constants of the dicarboxylic oxalic, malonic, succinic, glutaric
and adipic acids in formamide have been determined at nine temperatures ranging
from 5 to 45�, using cells of type:

�������������������� Pt, H2|H2A(m1),
KHA(m2), KCl(m3)|AgCl-Agand�������������������� Pt, H2|KHA(m1),
K2A(m2), KCl(m3)|AgCl-Ag

respectively, where H2A
stands for dicarboxylic acids, KHA for mono- potassium salts and K2A
for potassium salts of dicarboxylic acids. These values have been utilized to
evaluate the standard thermodynamic quantities ΔG�, ΔH� and ΔS�
associated with the first and second ionization processes at 25�.
The vibrational spectra of Dewar benzene and benzvalene
Authors: Griffith DWT , Kent JE , O'Dwyer MF
Published: September 2010

Complete assignment of the
fundamental vibrations of the two benzene valence isomers, Dewar benzene
(bicyclo[2,2,0]hexa-2,5-diene) and benzvalene (tricyclo[3,1,0,02,6]hex-3-ene)
based on infrared and Raman spectra are reported. Both molecules exhibit abnormal
C=C stretching frequencies indicative of σ-π interaction between the
strained bridge bond(s) and the π-bonds. The ?wing flapping? mode of Dewar
benzene occurs at 381 cm-1.
Bonding in d10 transition metal complexes. III. Infrared, Raman and N.Q.R. studies of some trimethylphosphine sulphide and trimethylarsine sulphide copper(I) complexes
Authors: Bowmaker GA , Whiting R , Ainscough EW
Published: September 2010

The infrared, Raman and n.q.r. (63Cu, 65Cu) spectra of
tris(trimethylphosphine sulphide)copper(I) perchlorate, [Cu(Me3PS)3]
ClO4, cyclo-tris-μ(trimethylphosphine sulphide)-tri(chlorocopper(I)), (Me3PSCuCl)3, the
trimethylarsine sulphide compounds [Cu(Me3AsS)3] ClO4,
(Me3AsSCuCl)n (n = an integer), and the bromo and iodo
compounds (Me3PSCuBr)n, (Me3PSCuI)n
have been studied with the aim of finding out more about the structure and
bonding in these complexes. The infrared and Raman spectra indicate that the trimethylarsine
sulphide compounds are probably isostructural with the corresponding
trimethylphosphine sulphide compounds. The origin of the electric field
gradient responsible for the copper nuclear quadrupole coupling in these
compounds is discussed, and it is shown that the copper n.q.r.
results can be explained in terms of a bonding scheme involving 3d-4s orbital
mixing.
The reaction of hexaaquanickel(II) with hydroxide ion
Authors: Clare BW , Kepert DL
Published: September 2010

The reaction of a large
excess of nickel(II) sulphate and perchlorate with hydroxide ions has been
studied using a stopped flow spectrophotometer. The concentrations of
nickel(II) were relatively high (⁄<0.2M). A
series of hydroxo-nickel polymers are formed immediately on mixing (< 2 ms),
which increase in size with increasing hydroxide ion concentration and
decreasing nickel ion concentration. These polymers then react with the excess hexaaquanickel(II) ion to form the product Ni4(OH)44+.
Bistetrachloronitrophenylmercury compounds
Authors: Deacon GB , Miller JM , Taylor BSF
Published: September 2010

The bistetrachloronitrophenylmercurials
R2Hg (R = o-, m- or p-O2NC6Cl4)
have been prepared by mercuration of the appropriate tetrachloronitrobenzenes
with mercuric trifluoroacetate under forcing conditions. Bis(2,3,5,6-tetrachloro-4-nitrophenyl)mercury
could not be obtained analytically pure by this method, but pyrolysis of
mercuric 2,3,5,6-tetrachloro-4-nitrobenzenesulphonate gave the pure mercurial.
Sodium 2,3,5,6-tetrachloro-4-nitrobenzenesulphonate was prepared by reaction of
2,3,5,6- tetrachloro-1,4-dinitrobenzene with sodium sulphite, and was converted
into the mercuric salt via the barium salt and free sulphonic acid. Cleavage of
the bistetrachloronitrophenylmer- curials
with iodine in N,N-dimethylformamide gave the corresponding tetrachloroiodonitrobenzenes.
When the mercurials were cleaved with triiodide ions, the resulting tetrachloroiodonitrobenzenes contained impurities, e.g. tetrachloronitrobenzenes or tetrachlorodiiodobenzenes,
which were formed by reaction of iodide ions (derived from I3-)
either with the mercurials or with their cleavage products.
Methyleneketenes and methylenecarbenes. V. Condensation of ketones with isopropylidene malonate catalysed by titanium tetrachloride and synthesis of a dibenzofuran
Authors: Baxter GJ , Brown RFC
Published: September 2010

The TiCl4/pyridine/tetrahydrofuran
reagent of Lehnert will effect direct condensation of some aromatic ketones
with isopropylidene malonate (Meldrum's acid). The synthetic value of this reaction
is explored in a synthesis of 7-methoxy-9-methyldibenzofuran-3-ol involving two
pyrolytic steps and using only aliphatic precursors. A 1,9-dimethyldibenzofuran
related to strepsilin could not be obtained in the same way.
Mixed ligand complex formation by copper ion: Stability constants of copper-oxalate-malonate, copper-oxalate-succinate and copper-oxalate-maleatecomplexes
Authors: Khurana SC , Nigam IJ , Saxena SP , Gupta CM
Published: September 2010

The mixed ligand complex
formation by copper ion with some dicarboxylic acids has been investigated
polarographically. The reduction of all the three systems under
investigation(copper-oxalate-malonate, copper- oxalate-succinate and
copper-oxalate-maleate) has been found to involve a two-electron reversible
diffusion controlled wave. It has been shown that steric effects are
considerable apart from statistical considerations. Electrostatic effects are,
however, negligible.
Solvent structure. The use of internal pressure and cohesive energy density to examine contributions to solvent-solvent interactions
Authors: Dack MRJ
Published: September 2010

Internal pressures,
(∂U/∂V)T, have been obtained at 25� for the solvents dimethyl
sulphoxide, propylene carbonate, formamide, dimethylformamide, acetonitrile,
methanol and hexamethyl-phosphoramide by measurement
of the thermal pressure coefficients. Data in the literature suggest that
values of the internal pressure and the cohesive energy density, (ΔU/Vm),
are similar for a non-polar solvent. The observed divergence of the two
properties in the polar solvents under investigation is discussed in terms of
the nature of the solvent-solvent interactions.
Autoxidation and photochromism of aryl aldehyde arylhydrazones
Authors: Lewis GE , Spencer GL
Published: September 2010

Aerial oxidation of
aldehyde arylhydrazones has been shown to result in the formation of bright red
formazans in varying yields. A mechanism proposed for this reaction involves
the decomposition of an intermediate arylazo hydroperoxide to an aryldiazonium ion
and subsequent coupling of the latter with another molecule of the
arylhydrazone.��� The irreversible formation of
1,3,5-triphenylformazan from benzaldehyde phenylhydrazone satisfactorily
accounts for the ?photochromism? (light-induced coloration) of the latter
compound; the apparent reversibility of the photochromism is attributed to the
subsequent aerial oxidation of the red formazan to the corresponding colourless
tetrazolium ion.
The C6H5N energy surface. III. Isomerization processes and intramolecular trapping in picolylcarbenes
Authors: Crow WD , Khan AN , Paddon-Row MN
Published: September 2010

The synthesis is reported
of a series of 5-(methyl-2-, -3- and -4- pyridyl)tetrazoles from the corresponding
picolinecarbonitriles. These compounds are used as
gas phase generators for the corresponding picolylcarbenes at 600�/0.05 mm. The
normal isomerization process in arylcarbenes are interrupted in some cases by
intramolecular trapping by the methyl groups, resulting in the first reported
syntheses of cyclobuta-[b] and -[c]pyridines. The major process competing with
this is that of nitrogen-extrusion to give tolylnitrenes, which then undergo ring
contraction to form methyl-cyclopentadienecarbonitriles.
The relative yields from these and other processes are used to deduce the
preferred isomerization pathways in picolylcarbenes. In methyl-2- pyridylcarbenes there is almost exclusive insertion into
the 2,3-bond, leading to the tolylnitrenes. The 3- and 4-pyridylcarbenes,
however, show a tendency for the carbene centre to oscillate over the 3-, 4-
and 5-positions of the ring with slower leakage to the 2-position.
The C6H5N energy surface. V. Isomerization of pyridylcarbenes to phenylnitrene - a 13C-labelling study
Authors: Crow WD , Khan AN , Paddon-Row MN , Sutherland DS
Published: September 2010

5-(2-, 3- and 4-Pyridyl)tetrazoles
have been synthesized with a 13C- label at the 5-position and
pyrolysed at 500-600� under reduced pressure to generate the corresponding
pyridylcarbenes. Analysis of the aniline which results from their isomerization
to phenylnitrene has been carried out by pulsed Fourier transform 13C
N.M.R. The results show that, although both the cycloperambulatory (CP) and
insertion-extrusion (IEP) mechanisms are operative, the latter predominates to
a very great extent. As in the case of tolylcarbenes, this result is ascribed
to a kinetic effect, i.e. the (largely irreversible) nitrogen extrusion step
which generates phenylnitrene. The preferred modes of isomerization in the
pyridylcarbenes are discussed.
Indole alkaloids from Ervatamia orientalis. III. The configurations of the ethyl side chains of dregamine and tabernaemontanine and some further chemistry of the vobasine group
Authors: Knox JR , Slobbe J
Published: September 2010

Evidence is presented to
show that the configurations of the ethyl side chains of dregamine and
tabernaemontanine are the reverse of the original assignments, i.e. the correct
structures are (2) and (3) respectively. Dregamine readily forms the 16-epimer
(6) from treatment with sodium methoxide; two neutral products from similar
treatment of tabernaemontanine are assigned the epimeric structures (7) and
(8). Evidence for the mode of formation of the methine products of Hofmann
degradation of dregamine and vobasine (1) is presented and the stereochemistry
of these products is assigned on the basis of chemical correlations with
taberpsychine (23).
Chromium(III) complexes in dipolar aprotic solvents. VIII. Solvolysis of hexaisothiocyanatochromate(III) and solvent exchange, substitution and anation of the pentaisothiocyanato(solvento)chrornate(III) complex, [Cr(NCS)5(sol)]2-
Authors: Lo STD , Watts DW
Published: September 2010

The displacement of the
coordinated Me2SO from [Cr(NCS)5(Me2SO)]2-
by NCS- and pyridine has been studied in the solvent tetramethylene
sulphone (sulpholane). The results are consistent with a limiting dissociative
mechanism. The solvolysis reactions:

�� ��������������[Cr(NCS)6]3-
+ sol → [Cr(NCS)5(sol)]2- + NCS-

have been studied in the
solvents (sol) Me2SO, HCONMe2 and MeCONMe2.
The transition states for these solvolysis reactions are compared with a
dissociative model

������������������������ [Cr(NCS)5(3-)+(∂+)...NCS∂-]

by means of solvent
transfer activity coefficients. Kinetic and activation data are recorded for a
number of solvent interchange reactions:

����������� [Cr(NCS)5(sol1)]2-
+ sol2 → [Cr(NCS)5(sol2)]2- +
sol1
Solvent interactions with dithiocarbamatoiron(III) complexes
Authors: Golding RM , Kok LL , Lehtonen K , Nigam RK
Published: September 2010

The interaction of a polar
molecule in a solvent with the iron(III) dithiocarbamates has been examined and
a linear relationship derived for the variation of the reduction potential, E1/2
with the mole fraction of the specific polar molecule. Experimental results of
E1/2 from voltammetry measurements of several iron(III)
dithiocarbamates in acetone water mixtures support the theoretical model. The
effect of this solvent interaction on the n.m.r, spectra of these compounds is
discussed briefly.
The thermolysis of some μ-Alkyne-bis(tricarbonylcobalt) complexes
Authors: Dickson RS , Michel LJ
Published: September 2010

Thermolysis of the μ-alkyne-bis(tricarbonylcobalt) complexes Co2(CO)6(C6F5C2C6F5), Co2(CO)6.
(C6H5C2C6F5), Co2(C6H2C2H) , and [ Co2( CO)6]2(C6H5C2C2C6H5) has given a wide range
of products. The substituents on the alkyne affect the nature of the products formed in these reactions,
and small changes in the thermolysis conditions have a significant effect on the yields of particular
products.
Major products formed in the thermal degradation of Co2(CO)6(C6F5C2C6F5) are the free
alkyne C6F5C≡CC6F5 and the cyclopentadienone C4(C6F5)4CO. The degradation of CO2(CO)6-
(C6H5C2C6F5) gives two isomers of the cyclopentadienone C4(C6H5)2(C6F5)2CO and one isomer
of the benzene C6(C6H5)3(C6F5)3. Organometallic complexes of probable formula Co2(CO)6
(C6H5C2C6F5)3 and Co(C6H5C2C6F4)[C4(C6H5)2(C6F5)2CO] are also formed in this decomposition
reaction. Thermolysis of the terminal alkyne complex Co2(CO)6(C6H5C2H) gives 1,2,4-triphenyl-
benzene and several complexes of general formula Co3(CO)9CY. One of these is the new complex
Co3(CO)6C3H2C6H5 which has been separated into two isomers. Degradation of the diyne complex
[Co2(CO)6]2(C6H5C2C6H5) has given the monoalkyne complex Co2(CO)6(C6H5C2C6H5) which
degrades further to form tetraphenylcyclopentadienone and hexaphenylbenzene. When this
degradation is conducted in the presence of some diphenylacetylene, an additional arene of formula
C6(C6H5)5(C2C6H5) can be isolated.
Self-radiation induced exchange between tritiated water and organic compounds. The labelling of L-chiro-inositol, myo-inositol and Hexa-O-methyl-L-chiro-inositol
Authors: Fong DHT , Bodkin CL , Long MA , Garnett JL
Published: September 2010

The stereochemistry of the
tritiation of L-chiro-inositol, myo-inositol
and hexa-O-methyl-L-chiro-inositol by self-radiation
induced exchange with tritiated water of high specific activity has been
investigated. Predominance of configurational retention was found to accompany
tritium labelling in the two inositols, while
substantial configurational inversion occurred in the hexa-O-methyl
derivative. Tritiation occurred predominantly at C 1 in L-chiro-inositol,
with slight inversion at this position alone accompanying the labelling.
Comparison with Wilzbach T2 gas exposure
results indicates the HTO method yields less by-products, myo-inositol
having a radiochemical purity of 97%.