bluuebunny/crossref_metadata_2025 huggingface dataset:
Photochemical syntheses. V. The photo-addition of heterocyclic diarylacetylenes to naphthalene and 1-methylnaphthalene
Authors: Teitei T , Collin PJ , Sasse WHF
Published: September 2010

Eight heterocyclic diarylacetylenes derived from pyridine, furan, thiophen,
and thiazole have been irradiated in the presence of naphthalene.
Phenyl(4-pyridyl)- acetylene gave the compounds (2a) and (2b), phenyl(3-pyridyl)acetylene
gave the compounds (3a) and (3b), and phenyl(2-pyridyl)acetylene compounds (4a)
and (4b). From 1-methylnaphthalene and phenyl(3-pyridyl)acetylene the adducts
(5a) and (5b) have been isolated and two adducts which formed by addition to
the unsubstituted ring were detected. From phenyl(2-thiazolyl)acetylene
and naphthalene probably only one isomeric adduct (6b) was isolated. The
methiodides of all the new adducts except (6b) have been prepared. The
structures proposed for these photo-adducts are based on their p.m.r., mass, and ultraviolet absorption spectra. Factors
influencing the isomer distribution and overall yields are discussed in terms
of a mechanism previously proposed for the addition of diphenylacetylene
to naphthalene.
The vibrational and electronic spectra of 3,4-dimethylenecyclobutene
Authors: Griffith DWT , Kent JE , O'Dwyer MF
Published: September 2010

The infrared spectrum of
3,4-dimethylenecyclobutene (dmcb) as a vapour, glass, and polycrystalline
film has been investigated from 4000 to 250 cm-1. The Raman spectrum
of liquid dmcb and the infrared spectrum of
1,2-dideutero-3,4-dimethylenecyclobutene vapour have also been investigated. On
the basis of these results a partial assignment of the spectrum has been made. A study of the electronic spectrum of dmcb from the visible to the vacuum ultraviolet at 169 nm
has also been undertaken and the spectrum has been found to be very diffuse in
all bands. Assignments are discussed in the light of theoretical calculations.
Circular dichroism spectra of some complexes with the CoN4Cl2 chromophore
Authors: Hawkins CJ , Stark JA , Wong CL
Published: September 2010

The preparations and circular dichroism spectra of an optical isomer of
cis-[Co(en)(NH,),Cl2]+, and some of the isomers of [Co(R-pn)(NH3)2Cl2]+ are reported.
To facilitate the interpretation of the c.d, spectra, the absorption spectra of these
complexes and a series of closely related complexes with the CoN4Cl2 chromophore
were analysed to give the position of the tetragonal components of the 1A1g →1T1g
cubic absorption bands. The absolute configurations of the isomer of cis-[Co(en)-
(NH3)2Cl2]+ and of (+)-[Co(en)(NH3)2CO3]+, from which the dichloro compound
was prepared, were determined by a comparison of the c.d. spectrum of the carbonato
complex with that of D(+)-[Co(en)2CO3]+.
Cyclic phosphines and arsines. IV. Perfluoroalkyl-substituted cyclic phosphines
Authors: Ang HG , Redwood ME , West BO
Published: September 2010

Diiodopentafluoroethylphosphine and iodobispentafluoroethylphosphine have
been prepared. Reaction of these compounds with silver chloride and silver cyanide
leads to replacement of the iodide to give chloro and cyano phosphines.
Reaction of RPI2 (R = CBF5, C3F7) with mercury gives the cyclic phosphine
(PR)4,5. Conversion of (PC2F5)5 into(PC2F5)4 occurs irreversibly a t room temperature
on standing for several days and can be followed by n.m.r. No analogous rearrange-
ment was found for (PC3F7)5. Both 31P and 19F n.m.r. spectra for the cyclic
phosphine are discussed and compared with those for (PCF3)4,5.
Reactions of trifluoromethyl radicals. I. Hydrogen abstraction from dimethyl sulphide
Authors: Arthur NL , Yeo KS
Published: September 2010

Hydrogen atom abstraction
from (CH3)2S by CF3 radicals has been studied in the temperature range
79-167�:

(1)

CF3 + CH3SCH3 ←→ CF3H
+ CH3SCH2

(-1)

The rate constant, based on
Ayscough's value of 1013.36cmS
mol-l s-l for the recombination of CF3 radicals,
is given by (k1 in cm3 mol-1 s-l, E in J mol-l):

Logk1 = (12.05 � 0.02)-(28710
� 130)/2.303RT
Combination of these
results with thermochemical data gives a calculated value of

log k-1 = 12.2 - 62600/2.303RT

for the rate constant of
the reverse reaction.

ΔH�f(CH3SCH2) and S�(CH3SCH2)
are estimated to be 155.6 kJ mol-l and 290 J K-l mol-1
respectively.
Chemistry of the Podocarpaceae. XXXVII. Oxidative degradations of phyllocladene and isophyllocladene : conversion of isophyllocladene into (+)-Podocarp-8(14)-en-13-one
Authors: Cambie RC , Hayward RC
Published: September 2010

The ozonolysis of phyllocladene (2) and isophyllocladene
(12) has been carried out under a number of different conditions and the ozonide (34) of isophyllocladene
has been isolated and characterized. Conversion of phyllocladene
(2) into the diacid (20) has been accomplished by several routes from the norketone (3).

Isophyllocladene (12) has been converted into
(+)-podocarp-8(14)-en-13-one (1), an optically active relay which is useful in
synthesis. The route involves ozonolysis of isophyllocladene,
Baeyer-Villiger oxidation of the keto aldehyde (25),
lithium aluminium hydride reduction of the ester (27), and chromium trioxide-pyridine
oxidation of the resulting keto aldehyde (32) which gives the keto acid (30) in
26% overall yield. Oxidative decarboxylation then affords the enone (1) in 14%
yield.
Carbon and hydrogen scrambling in the ions C(9+n)H(9+2n)+. Rearrangements of cyclooctatetraene derivatives
Authors: Bowie JH , Gream GE , Mular M
Published: September 2010

Carbon and hydrogen
scrambling occurs either prior to, or during, the decompositions of the ions C9H9+,
CllH13+, and C12H15+ in the first
field-free region of the mass spectrometer. The ions may be produced from
various substrates, and the decompositions of CllH13+ may
be interpreted in terms of a decomposing ion in which some, but not all, of the
C-H bonds have broken and reformed. The ions C9H9+ and C10H11+
may be produced by complex hydrogen rearrangement in the side-chain of
particular bromo-and hydroxy-alkylcyclooctatetraene
derivatives.
Monocyclopentadienyltitanium(III) compounds. II. Complexes of nitrogen containing ligands
Authors: Coutts RSP , Martin RL , Wailes PC
Published: September 2010

The complexes cpTiCl2,
bipy, cpTiCl2,phm, cpTiCl2,2py,
and cpTiCl2,2pic (bipy
= bipyridyl, phm = o-phenylenediamine,
py = pyridine, pic = α-picolylamine,
cp = π-cyclopentadienyl) have been prepared by
allowing the appropriate nitrogen base to react with cpTiCl2.
Spectroscopic, magnetic, and conductivity data are consistent with either
non-ionic, six-coordinate dimeric species with pseudooctahedral
symmetry or five-coordinate monomeric species. A complex of the type cpTiCl2,1.5en
(en = ethylenediamine) was also formed. Possible
structures are discussed.
Oxidation of carbohydrates with chromium trioxide in acetic acid. III. Synthesis of the 3-hexuloses
Authors: Angyal SJ , Evans ME
Published: September 2010

The D-arabino, L-lyxo, and L-xylo
isomers of 3-hexulose have been synthesized by oxidation, with chromium
trioxide in acetic acid, of fully acetylated derivatives of
3,4-0-ethylidene-D-mannitol, 3,4-0-ethylidene-L-iditol, and 2,4-O-benzylidene-D-glucitol, respectively.
The D-ribo isomer has been obtained from the L-lyxo compound by inversion at C5. The
3-hexuloses were characterized as their crystalline di-O-isopropylidene derivatives: the
arabino-
and ribo-hexuloses
each give three diacetals. The stereochemistry of
these derivatives, and of the spiro-acetals of
ketoses in general, is discussed.
Complexes of 8-Amino-2-methylquinoline with cobalt(II)
Authors: Power LF , King JA
Published: September 2010

The bidentate ligand
8-amino-2-methylquinoline (maq) forms complexes with
cobalt(11) of the type Co(maq)X2,nH2O where X = Cl, Br, or I,
and Co(maq) 2X2nH2O where X = Cl, Br, I, or
NO3. Evidence suggests that the mono-chelated complexes are
tetrahedral in the solid state and in acetone and nitrobenzene solution but
octahedral in methanol solution. The bis-compounds are octahedral in the solid
state and in methanol solution but are tetrahedral in nitrobenzene.
Phosphorous and hypophosphorous acid derived radicals and their reactionsùan E.P.R. study
Authors: Beckwith ALJ
Published: September 2010

The radicals HPO2-,
HPO3-, and PO32- can be generated in aqueous solution by interaction of
Ti111 and hydrogen peroxide with hypophosphorous
and phosphorous acids in the flow cell of an e.p.r.
spectrometer. Their spectral parameters indicate that each of these radicals
has a pyramidal structure. Radicals formed by addition of HPO2-, HPO3-,
and PO32-, to unsaturated compounds are characterized by
large 31P hyperfine splitting constants. The delocalization of the
unpaired electron is tentatively
attributed to interaction of the half-filled p-orbital with phosphorus 3d orbitals. Reduction of iodo and bromo compounds with HPO2-, HPO3-,
and PO32- gives high stationary concentrations of alkyl
radicals. Benzenediazonium ion is similarly reduced
to phenyl radical, and biacetyl to its semidione.
The chemistry of pyrrolic compounds. XX. Bilenes-b as intermediates in the synthesis of porphyrins related to protoporphyrin IX. meso-Pyrrolylporphyrins
Authors: Clezy PS , Liepa AJ , Webb NW
Published: September 2010

α-Formyl-α'-methyldipyrrylmethanes
have been shown to react with α,α'-

dicarboxydipyrrylmethanes to give hexapyrrenes which
cyclize with copper acetate in pyridine to yield meso-pyrrolylporphyrins.
However, if an α,α'-dicarboxydipyrrylmethane
is decarboxylated in N,N-dimethylformamide and the product converted into its monoimmonium salt (Vilsmeier-Haack
intermediate) with benzoyl chloride this salt with an
α-formyl-α'-methyldipyrrylrnethane affords
a bilene-b which with copper acetate-pyridine
gives a normal porphyrin. This latter procedure has been adapted to prepare tetrapyrroles of the protoporphyrin IX type. A synthesis of
pemptoporphyrin dimethyl ester is reported.
Halogen nuclear quadrupole resonance and structural relationships in some complex halides of zinc and copper
Authors: Asker WJ , Scaife DE , Watts JA
Published: September 2010

X-ray diffraction and
halogen nuclear quadrupole resonance (n.q.r.) methods
show that Rb3ZnBr5, (NH4)3ZnBr5,
and CsZnI5 are isostructural with
orthorhombic (NH4)3ZnCl5, and that Rb3ZnCl5
has the tetragonal Cs3CoCl5 structure. ZnI2,2NH3
is isomorphous with the corresponding chloride and bromide diammines.
Rb2ZnBr4 and (NH4)2ZnBr4
have structures of Cs2ZnBr4 type, although the rubidium
salt shows some stacking faults. In the complex chlorides 35Cl
n.q.r. frequencies are grouped about 9 MHz, while the
bromides have 81Br frequencies grouped around 60 MHz. The � →
3/2 transitions of 127I in the iodides are in the region of 76 MHz.
The diammine compounds ZnBr2,2NH3
and ZnI2,2NH3 have frequencies close to the mean values
for the ZnBr42- and ZnI42- ions
respectively, but in the hydrates ZnCl2,l⅓H2O,ZnBr2,2H2O,
β-KZnBr3,2H2O, and KZnI3,2H2O
the halogen frequencies are increased.

N.q.r. and X-ray data are also reported for the compound
Cs3CuCl5, formed by quenching the melt. This compound
slowly disproportionates at room temperature into Cs2CuCl4
and CsCl.
γ-Radiolysis of chloranil in benzene
Authors: Wilson JG
Published: September 2010

Γ-Radiolysis of
chloranil in benzene gave four products: the quinones 3,6-di-chloro-2,5-diphenyl-1,4-benzoquinone
(11) and 2-chloro-3,5,6-triphenyl-1,4-benzo-quinone (12),
and small amounts of 2,3,5-trichloro-6-phenylhydroquinone
(10) and 1,3,4-trichloro-2-hydroxydibenzofuran (14; R
= H). The last compound only was formed when radiolysis was carried out in the
presence of oxygen. Syntheses of 2,3,5-trichloro-6-phenylhydroquinone (10), 2,3,6-trichloro-6-phenyl-1,4-benzoquinone (9), and
2-chloro-3,5,6-triphenyl-1,4-benzoquinone (12)are
described.
Reactions of pyrazine radical anions in solution. II. Oxidation reduction equilibrium between radical anions of pyrazine and anthracene
Authors: Hay RS , Pomery PJ
Published: September 2010

The relative electron
affinity of pyrazine (pz) and anthracene (A) has been
determined in 1,2-dimethoxyethane (dme) solution. Electron spin resonance and spectrophotometric
methods were employed to study the equilibrium:

(pz-,K+) + A ←→ pz + (A-,K+)

The equilibrium constant
for this reaction has been calculated, after consideration of other reactions
of the pyrazine radical anions in the solution, and modified for the case of
the equilibrium reaction of the unassociated radical anions. The resultant value
has been used to calculate the relative solution electron affinity of pyrazine,
which was determined to be of the order of 0.09 eV
smaller than that of anthracene in dme. The free energies of solvation of the radical anions
of pyrazine and anthracene have been estimated and a
value of the gaseous electron affinity of pyrazine calculated.
Diazabenzenes. I. Synthesis of some t-butylpyrazines and their N-oxides
Authors: Evans RF , Mewett KN
Published: September 2010

Steric hindrance prevented
formation of tetra-t-butylpyrazine either when pivaloin was heated with
ammonium acetate or when pivalil monooxime was reduced with zinc and alkali.
Diminution of the steric hindrance of the t-butyl groups by masking them by
incorporation into a seven-membered ring containing sulphur was of no avail.
2,5-Di-t- butylpyrazine resulted from the analogous reduction of t-butyl-glyoxal
dioxime and could be converted into its N-oxide and N,N?-dioxide. t- Butyl-lithium
reacted with the pyrazine and the mono-N-oxide to give a mixture of products
including 2,3,5-tri-t-butylpyrazine whose spectroscopic properties suggested a buckling
of the pyrazine ring. Benzonitrile and diphenylacetylene reacted independently
in the presence of iron pentacarbonyl and gave, inter alia, 2,4,6-triphenyl-
1,3,5-triazine and hexaphenylbenzene respectively. ��� The most prominent features of the low
resolution mass spectra of these pyrazines and some of their precursors are
discussed and rationalized.
Single photon decay spectroscopy.
Authors: Knight AEW , Selinger BK
Published: September 2010

Fluorescence lifetimes of
low pressure gaseous systems are necessary for the understanding of electronic
relaxation in an isolated molecule. A detailed experimental and theoretical
analysis of the technique of single photon decay spectroscopy is presented.
This includes the construction of nanosecond light sources, the detection and
timing of single photons, and a statistical analysis of the results. Standards
for time calibration and detection sensitivity are suggested. ��� This paper provides the basis for
subsequent studies of the fluorescence decay of aromatic vapours.
Nucleophilic cleavage of diaryl disulphides
Authors: Happer DAR , Mitchell JW , Wright GJ
Published: September 2010

The rates of cleavage of 14
symmetrically substituted diaryl disulphides by
cyanide ion have been measured in 60% aqueous t-butyl alcohol at pH 9.2. A plot
of log k against σ� shows that while the reaction rate is accelerated by
inductive electron withdrawal from the benzene rings, substituents capable of
conjugative interaction are not correlated by their σ� parameters. +R
substituents cause reaction to occur much faster than predicted on the basis of
their σ� values, while -R substituents react more slowly than predicted.
Measurement of rates of cleavage of three series of unsymmetrically substituted
disulphides by cyanide or hydroxide shows that these unusual substituent
effects arise from substituents in the thiocyanate-forming aryl ring. This
behaviour is explained in terms of a change in the electronic behaviour of the thio- cyanate-forming sulphur atom from -I, + R in the
disulphide to -I,-R in the rate-determining transition state for the reaction.
The study does not show whether the cleavage involves an SN2 process
or rapid equilibrium formation of a pentacovalent intermediate.
Two new methylnickel compounds
Authors: Jeffery EA
Published: September 2010

Tris(dimethylphenylphosphine)dimethylnickel(II) and bis(dimethylphenyl-
phosphine)methylphenoxynickel(II) have been prepared
and characterized.
Reaction between 4-Nitrobenzoyl chloride and 1-Ethyl-4-methoxycarbonylpyridinyl radical
Authors: Mohammad M
Published: September 2010

Rates of reaction between
benzoyl chloride and its 4-nitro derivative with
1-ethyl-4-methoxycarbonylpyridinyl radical in acetonitrile and
1,2-dimethoxyethane were measured. The reduction potential for 4- nitrobenzoyl
chloride was also measured.
The reactions of some 5,6-Dihalogenocyclohex-2-ene-1,4-diones (1,4-Benzoquinone dihalides) in boron trifluoride diethyl etherate
Authors: Norris RK , Sternhell S
Published: September 2010

Treatment of five
1,4-benzoquinone dihalides in boron trifluoride etherate gives very high yields
of isomeric dihalogenohydroquinones. With the exception of the conversion of
5,6-dichlorocyclohex-2-ene-1,4- dione into 2,3-dichlorohydroquinone, which is a
true keto-enol isomerization, these products arise through elimination of
hydrogen halides followed by re-addition.
Terpenoid chemistry. XXI. ( - )-Epingaione, ( - )-Dehydrongaione, ( - )-Dehydroepingaione, and ( - )-Deisopropylngaione, toxic furanoid sesquiterpenoid ketones from Myoporum deserti
Authors: Hamilton WD , Park RJ , Perry GJ , Sutherland MD
Published: September 2010

The isolation and
properties of four furanoid sesquiterpene ketones from various specimens of the
stock-poisoning shrub Myoporum deserti are described. (-)-Epingaione [(-)-(1S,4S)-β-(4,8-dimethyl-6-oxo-1,4-
epoxynonyl)furan] may be epimerized to (-)-ngaione either thermally or by base.
(-)-Dehydrongaione [(-)-(1S,4R)-β-(4,8-dimethyl-6-oxo-1,4-
epoxynon-7-enyl)-furan] is hydrogenated to (-)-ngaione and is equilibrated
either thermally or by base with the unconjugated isopropenylic non-8-enyl
isomer and (-)-dehydroepingaione [the (1S,4S)- diastereomer], which is
hydrogenated to (-)-epingaione. Treatment of dehydrongaione and its epimer with
aqueous alkali yields (-)- deisopropylngaione and its epimer by a retroaldol
reaction. ��� The argument used by Matsuura1
to deduce the absolute stereochemistry of (+)-ngaione (ipomeamorone) is invalid
since, contrary to the literature report, the ipomic lactone obtained from the
oxidation of ngaione is not optically active. ��� Specimens of M. deserti have been found
which yield essential oils containing each of the four furanoid ketones
(-)-ngaione, (-)- epingaione, (-)-dehydrongaione, and (-)-dehydroepingaione
free or virtually free from the others. The presence of a few percent of (-)- deisopropylngaione
in one (dehydrongaione-rich) M. deserti oil has been demonstrated. ��� (+)-Ngaione, (-)-epingaione, and a mixture
of (-)-dehydrongaione and (-)-dehydroepingaione all cause the typical
(-)-ngaione liver pathology when injected intraperitoneally into mice. M.
deserti plants containing the latter three ketones must be regarded as potentially
capable of inducing M. deserti poisoning in stock. A mixture of (-)- deisopropylngaione
and (-)- deisopropylepingaione causes both kidney and liver lesions.
The photochemistry of papaverine N-oxide
Authors: Bremner JB , Wiriyachitra P
Published: September 2010

Ultraviolet irradiation of papaverine N-oxide (2) in methanol gave papaverine
(1) and 6,7-dimethoxy-2-(3',4'-dimethoxybenzyl)isocarbostyril (3). Irradiation of (2)
in acetone resulted in the isolation of 7,8-dimethoxy-2-(3',4'-dimethoxybenzyl)-l,3-benz-
oxazepine (4) by crystallization of the photolysate, and of 5,6-dimethoxy-2-(3',4'-di-
methoxybenzy1)benzofuran-3-carboxaldehyde (6), 5,6-dimethoxybenzofuran-3-yl-
3',4'-dimethoxybenzyl ketone (7), 5,6-dimethoxy-2-(3',4'-dimethoxybenzyl)benzofuran
(8), and papaverine by preparative thin-layer chromatography on silica gel. Evidence is
presented in support of the formation of (6) and (7) from the valence tautomer (5) of
the oxazepine (4), by acid-catalysed hydrolysis and rearrangement.
Thermodynamic properties of alcohol +alkane mixtures. I. Theoretical results for the hydrogen bond contribution to the excess energies.
Authors: Smith FBI
Published: September 2010

Using molecular models with
the hydrogen bond as the only contributing interaction, the results from
existing theories for the excess energies of mixtures with an associating
component are compared with each other and with the experimental results for alcohol
+ alkane systems. After excluding the Redlich-Kister
theory as inappropriate, these comparisons are made very effectively using
plots of mixture property against composition parameter as then, for each of
the Kretschmer-Wiebe or Barker models, one curve
gives to a good approximation the mixing property for all systems for any
values of the hydrogen bond free energy and enthalpy parameters. The results
from the Kretschmer-Wiebe model are essentially the
same as those from one of the two Barker models considered. ��� For a given temperature and alkane solvent
the experimental excess free energies can also be approximately summarized by
one parent mixture property curve. As shown previously this is also true for
the excess enthalpies so that comparison of theory and experiment is made very
easy by this approach as the results for individual systems do not have to be
considered. The theoretical results are in qualitative agreement with the
experimental results but give poor values for the excess energies. As deduced
from excess enthalpies the extent of hydrogen bonding as a function of alcohol
concentration differs from that deduced by i.r.
measurements, as discussed fully in the following paper, but the theoretical
results cannot be made to agree with either of these results. Reported results
for more complex models also appear to reflect the quantitative failings of the
simple models.
Catalysed gas phase decompositions. XXV. 2,2-Dimethoxypropane and acetic acid
Authors: Kairaitis DA , Stimson VR , Tilley JW
Published: September 2010

Acetic acid catalyses the
decomposition of 2,2-dimethoxypropane into methyl isopropenyl ether and
methanol in the temperature range 314- 400�. The reaction is first order in the
pressure of each reactant, and the variation of rate with temperature is given
by the Arrhenius equation:

������������ k2 = 1012.90�0.15exp(-30830�420/1.987T)
s-1 ml mol-1

The reaction is believed to
be homogeneous and molecular. This is the first example of this series where
the catalyst has been other than a hydrogen halide.
Extractives of Australian Timbers. XIV. Triterpene Glycosides of Acacia myrtifolia
Authors: Eade RA , McDonald FJ , Simes JJH
Published: September 2010

Extraction of Acacia myrtifolia has yielded quercitrin and three triterpene
glycosides, named myrtifoliosides A, B, and C. Myrtifolioside A, a minor
crystalline component, gave erythrodiol and L-arabinose and D-glucose on
hydrolysis. Myrtifolioside B (7), C48H80O17,H2O,
the major crystalline glycoside, formed erythrodiol, D- glucose, and
D-galactose on hydrolysis. Hydrolysis of the methyl ester of the amorphous
myrtifolioside C gave methyl oleanolate, D-glucose, and D-galactose. The three
glycosides were readily separated on silica gel by elution with a solvent
containing sodium acetate.
Studies of oxidations by fenton's reagent using redox titration. V. Effect of complex formation on reaction mechanism
Authors: Ingles DL
Published: September 2010

The effect of complex
formation on the oxidation of substrate in the Fe2+-H2O2
system has been studied. t-Butyl alcohol which is normally oxidized to the
dimer, 2,5-dimethylhexane-2,5-diol, by Fenton's reagent has been used as a
probe for the presence of free hydroxyl radical. ��� It is shown that when suitable complexes
are formed substrates are not oxidized by free hydroxyl radical. Instead, new
mechanisms involving one- and two-electron transfers within a substrate-ferrous
ion-peroxide complex are proposed.
Annelated furans. XIII. Methylation of 3-Acylbenzofuran-2(3H)-ones
Authors: Elix JA , Ferguson BA
Published: September 2010

Methylation of
3-acylbenzofuran-2(3H)-ones with diazomethane generally led to a mixture of
3-acyl-2-methoxybenzofuran and 3-(α- methoxy)alkylidenebenzofuran-2(3H)-one.
These reactions provided the first evidence for the existence of 3-acylbenzo-
furan-2(3H)-ones in the 3-acyl-2-hydroxybenzofuran tautomeric form as well as
the widely accepted 3-(or-hydroxy)alkylidenebenzofuran-2(3H)one form. In
general, methylation of the title compounds with methanol and sulphuric acid
gave initially the corresponding 3-(α-methoxy)alkylidenebenzofuran-
2(3H)one while prolonged reaction led to the formation of methyl 2- alkylbenzofuran-3-carboxylates.
The mechanism of this acid-catalysed rearrangement and the rearrangement of
3-acetyl-2-methoxybenzo- furan were studied. ��� The reaction of
3-acetylbenzofuran-2(3H)-one with methyl iodide and potassium carbonate gave a
mixture of 3,3-dimethylbenzo-furan-2(3H)-one and 3-methylbenzofuran-2(3H)-one.
These products were also obtained by methylating
benzofuran-2(3H)-one under similar conditions.
6-Methyl-2,2'-methylenedipyridine from aα-picoline under the influence of trimethylaluminium
Authors: Meisters A , Mole T
Published: September 2010

6-Methyl-2,2?-methylenedipyridine
is formed in c. 60% yield from α- picoline under the influence of
trimethylaluminium at 200�.
A reinvestigation of a possible route to 1,2-Benzisothiazoles: The reaction between N-benzyl-substituted sulphonamides and trichloromethanesulphenyl chloride in the presence of base
Authors: Davis M , Homfeld E
Published: September 2010

The reaction between
N-benzyl-substituted sulphonamides (1) and trichloromethanesulphenyl chloride
in the presence of base afforded the expected N-trichloromethanesulphenyl
derivatives (4); the previously reported 1,2-benzisothiazolines (2) were not
obtained. Treatment of the derivatives (4) with base under various conditions
gave no indication of cyclization to 1,2-benzisothiazolines (2).
Cleavage of anisole by hydrogen chloride in non-aqueous media in presence of inorganic catalysts
Authors: Walvekar SP , Halgeri AB
Published: September 2010

Anisole is cleaved and
rearranged with HCl and Al2O3 or Cr2O3
catalysts, but is rearranged without cleavage by HCl-SiO2 or by
catalysts alone. A mechanism is proposed.
Oxidative dimerization of methyl (E)-sinapate
Authors: Wallis AFA
Published: September 2010

Oxidation of methyl
(E)-sinapate (1c) with 1 equiv. of ferric chloride in aqueous acetone gave the
tetralols (2a) and (2b), the dihydronaphthol(3a), and the lactone (4), all of
which result from C-C coupling, and an unidentified oil. The configurations of tetralols
(2a) and (2b) were ascertained by their conversion into (�)-lyoniresinol
dimethyl ether (5c) of known stereochemistry, and by p.m.r,
spectroscopy. The dimethyl ether (3b) of compound (3a) was identified as
thomasidioic acid dimethyl ether dimethyl ester. Reaction of phenol (1c) with
other one-electron oxidants is briefly discussed.
Spontaneous and stimulated emission from dyes. Spectroscopy of the neutral molecules of acridine orange, proflavine, and rhodamine B
Authors: Ferguson J , Mau AWH
Published: September 2010

The absorption and fluorescence
spectra of acridine orange, proflavine, and rhodamine B have been studied with
particular attention being paid to the acid-base properties of these dyes in
polar and non-polar solvents. These studies show that the neutral acridine dyes
do not form dimers but they are readily protonated even in non-polar solvents
due to traces of water which are difficult to remove. Attempts to achieve laser
emission form the acridine dyes were unsuccessful, probably because of their
low fluorescence quantum yields. Suggestions are made for optimizing the laser
efficiency of rhodamine B in various alcohol solutions at low temperatures.
The C7H6 energy surface: phenylcarbene and 2-Methylene-3,5-cyclohexadienylidene - A duality of mechanism
Authors: Crow WD , Paddon-Row MN
Published: September 2010

The conversion of
phenylcarbene (1) into fulvenallene (17) and ethynylcyclo-pentadiene (18) on
gas-phase pyrolysis has been examined by 13C-tracer techniques.
Complete randomization of all seven carbon atoms has been shown to precede ring
contraction. The result is consistent with a pool of intermediates
[cycloheptatrienylidene (19) and bicyclo[4,1,0]hepta-2,4,6-triene (21)],
interconverting rapidly through tautomerism and concomitant H-shifts.
Dimerization, intramolecular trapping, and ring contraction constitute the
major exits from this pool. ��� Gas-phase thermolysis of indazole generates
the same products (17)/(18) and in this case the mechanism has been
investigated by the intramolecular trapping in 1-deutero-3-methylindazole to
yield deuterostyrenes. Two pathways are revealed, proceeding respectively
through phenylcarbene and 2-methylene-3,5-cyclohexadienyl-idene (36); factors
affecting the latter pathway are discussed.
Transition metal complexes of substituted alkynes. X. The formation of disubstituted cyclopentadienone complexes from terminal alkynes and (η-C5H5)Co(CO)2
Authors: Dickson RS , Kirsch HP
Published: September 2010

The reaction at 160� of
dicarbonyl(η-cyclopentadienyl)cobalt with each of the terminal alkynes
phenylacetylene, t-butylacetylene, propyne, and 3,3,3-trifluoropropyne has been
studied. The reactions give p(disubstituted cyclopentadienone)-η-cyclopenta-dienylcobalt
complexes as the major products; two or three isomers of each cyclo-
pentadienonecobalt complex are formed. The arrangement of the substituents in
each isomer has been assigned on the basis of electronic, infrared, nuclear
magnetic resonance, and mass spectral data. Attempts to rationalize the
distribution of isomers are based on considerations of electronic and steric
effects.
Halogenated terpenoids. VIII. The halogenation of some axial α-Bromo-p-menthanones. Boat conformers of halogenated cyclohexanones
Authors: Carman RM , Venzke BN
Published: September 2010

The structures of some
halogenated p-menthan-2-ones and p-menthan-3- ones are determined. Some
cyclohexanones with α-axial bromine and α?- equatorial bromine substituents
exist in a boat conformation provided an additional attractive halogen→carbonyl interaction is available to
stabilize the boat through a five-membered bridging ring. Some profound
differences in the conformations of bromo- and chloro-cyclohexanones are noted.
The α?-bromination of α-bromocyclohexanones
is discussed. The configurations of the new compounds are determined chemically
and the conformations are determined chiefly by p.m.r.
spectroscopy.
Mechanism of alkaline degradation of sucrose. A study of some model compounds
Authors: O'Donnell GW , Richards GN
Published: September 2010

Alkaline degradation of
sucrose proceeds by a slow first stage to yield reactive intermediates (perhaps
glucose and fructose) which degrade rapidly to acids (predominantly lactic
acid). In an attempt to determine the mechanism of the first stage of the reaction,
the rates of alkaline degradation of sucrose and some model compounds have been
determined unequivocally by measuring their rates of disappearance by paper or
gas chromatography. Selective blocking of hydroxyl groups in sucrose by
methylation, indicates that the alkaline degradation probably involves free
hydroxyl groups (presumably via the derived anions) on both glucose and
fructose components of sucrose. It is unlikely that the hydroxyls at C 6 of the
glucose moiety or C 1? of the fructose moiety are involved.
Electric dipole moments and molar Kerr constants of Phenyl- and Diphenylpyridylmethanes
Authors: Chiu KK , Huang HH
Published: September 2010

The difference in total
polarization (ΔP) or dipole moment (ΔP) of 2- benzyl-pyridine,
4-benzylpyridine, diphenyl-2-pyridylmethane, diphenyl- 3-pyridylmethane, or
diphenyl-4-pyridylmethane in carbon tetrachloride relative to benzene solution
provides evidence of weak interaction between these amines and the former
solvent. The molar Kerr constants of the amines in the two solvents for
4-benzylpyridine and diphenyl-4- pyridylmethane are analysed to yield the
preferred angles of orientation of the phenyl and 4-pyridyl rings in these two
molecules.
The magnetic behaviour of some polynuclear methoxide complexes of iron(III) alkanoates
Authors: Kokot E , Mockler GM , Sefton GL
Published: September 2010

The magnetic
susceptibilities in the temperature range 80-350 K are reported for iron(III)
complexes of the type FeL(OMe)2, where L is alkanoate. The magnetic
behaviour and the presence of a single C-O methoxide stretching band at 1038-1052
cm-1 are interpreted in terms of a tetrameric structure involving
trigonal prismatic antiferromagnetically interacting iron atoms arranged in a
planar cluster and equivalent, bridging methoxo groups.
Photochemical syntheses. VII. The formation of 1,2-Diaryl-8b-methoxy-2a,8b-dihydrocyclobuta[a]naphthalenes in photoadditions involving 1-methoxy-naphthalene and heterocyclic diarylacetylenes
Authors: Teitei T , Wells D , Sasse WHF
Published: September 2010

The diarylacetylenes (2),
(3), (4), (9, (6), and (7) react with 1- methoxynaphthalene
on ultraviolet irradiation to give 1,2-diaryl-8b- methoxy-2a,8b-dihydrocyclobuta[a]-naphthalenes
(d) and/or (d?). Phenyl(4-pyridyl)acetylene (2), phenyl(3-pyridyl)-acetylene
(3), di(3- pyridyl)acetylene (5) and phenyl(2-furyl)acetylene
(6) also give tetracyclic photoadducts (c) and/or (c?). The major product of
the reaction with (2) is a benzo[h]isoquinoline which is formed by photodehydrocyclization of (2d) and for which structure
(2f) is proposed on spectral grounds. Similarly (3) gives a benzo[f]-quinoline
(3g) and two benzo[h]quinolines (3h) and (3h?). ��� Thermolysis of (3c) and (3c?) gives (3e)
and (3e?), respectively. These isomerizations are quantitatively reversed by
ultraviolet irradiation but irradiation of (3d) and (3d?) gives mixtures
containing (3h), (3h?), (3c), and (3c?). Di(3-pyridyl)acetylene
(5) forms with naphthalene the photoadduct (5a).
The rearrangement of 8-Phenyl-2-quinolyl nitrene at 530°
Authors: Brown RFC , Irvine F , Smith RJ
Published: September 2010

8-Phenyl-2-quinolyl
nitrene, generated by pyrolysis of 9- phenyltetrazolo[1,5-a]-quinoline at 530�/0.2
mm, rearranged to form a single product, 7H-pyrido[2,3,4-gh]-phenanthridine
(82%). The formation of this product is consistent with rearrangement by ring
expansion of 8-phenyl-2-quinolyl nitrene followed by ring contraction to give
8- phenyl-1-isoquinolyl nitrene.
Phenolic Constituents of Grevillea robusta (Proteaceae). The Structure of Robustol, a Novel Macrocyclic Phenol
Authors: Cannon JR , Chow PW , Fuller MW , Hamilton BH , Metcalf BW , Power AJ
Published: September 2010

Rutin, 2,5-dihydroxycinnamic acid (5), methyl
4-hydroxycinnamate (6), and a mixture of novel macrocyclic phenols have been
isolated from the leaves of Grevillea robusta A. Cunn. The major
macrocyclic phenol, robustol, has been shown to have the structure (8) by the
application of physical methods and by degradation of robustol trimethyl ether
(9) to give 3-[14?-(3?,5?-dimethoxyphenyl)tetradec-1?-yl]-5-methoxy-phenol
(34). Three of the minor macrocyclic phenols have been assigned tentative structures
(11), (12), and (13).
The synthesis of potential anti-tumour compounds
Authors: Lahey FN , Stick RV
Published: September 2010

2,2-Dimethylchromens
containing a nitrogen function at C6 [compounds (6), (8), and (10)] have been
synthesized from the appropriate chromanone by sodium borohydride reduction and
dehydration of the resultant alcohol mixture with acid.
Nitrones and oxaziridines. VIII. Cycloaddition reactions of nitrones with isothiocyanates
Authors: Black DSC , Watson KG
Published: September 2010

Whereas nitrones undergo
cycloaddition to the C=N double bond of phenyl isothiocyanate, predominant
addition to the C=S double bond of substituted phenyl isothiocyanates, methyl
isothiocyanate and benzoyl isothiocyanate occurs. However, these cycloadducts are
not stable but undergo fragmentation usually with the formation of thioamides
and isocyanates.
Nitrones and oxaziridines. XI. Reactions of oxaziridines with ferrous ions
Authors: Black DSC , Watson KG
Published: September 2010

Ferrous-ion-catalysed
reactions of five oxaziridines are described. The mono-cyclic oxaziridines (1)
and (2) were converted into N-t- butylformamide and N-t-butyl-acetamide
respectively. The bicyclic oxaziridines (3) and (12) both afforded the
pyrrolidin-2-one (5) and the bicyclic oxaziridine (4) yielded the
pyrrolidin-2-one (6) together with other products. Also, the bicyclic
oxaziridines (13)-(15) have been found to undergo deoxygenation to afford the
corresponding 1- pyrrolines, on treatment with a molar equivalent of ferrous
sulphate.
Thermodynamics of metal-ligand bond formation. VIII. Pyridine adducts of zinc(II) β-diketonates
Authors: Dakternieks DR , Graddon DP
Published: September 2010

Equilibrium constants and
enthalpies in benzene solution are reported for the formation of 1 : 1-adducts
of pyridine with four zinc(II) complexes of β-diketones, determined by
calorimetric titration. Adduct formation constants at 30�C fall in the range
300-2000 and enthalpies of formation lie between -15 and - 34 kJ mol-1.
Though the enthalpies of formation differ little from those of corresponding
copper(II) complexes, the adducts are about a hundred times more stable. The
pyridine adduct of bis(2,2,6,6-tetramethylheptane-3,5-dionato)zinc(II)
is entropy-stabilized relative to those of other complexes. No evidence was
obtained for the addition of a second molecule of pyridine under the
experimental conditions used.
Long-range proton-fluorine spin-spin coupling. Further evidence for a 'direct' mechanism
Authors: Adcock W , Rizvi SQA
Published: September 2010

A variable temperature p.m.r. study of outho- and peri-acetyl substituted fluoro-naphthalenes (including
o-fluoroacetophenone) has been carried out. Further, 1-fluoro-
8-methylnaphthalene (previously unknown) has been synthesized and its p.m.r. spectra has been measured at various temperatures.
The data, together with 19F substituent chemical shifts (SCS) for
ortho-substituted cyanofluoronaphthalenes, provide further strong support for a
through-space coupling mechanism (JMe,F).
Carbon dioxide as a quencher of fluorescence
Authors: McDonald RJ , Selinger BK
Published: September 2010

Carbon dioxide is found to
form a reversible quench complex with the excited singlet states of certain
amines. No separate exciplex emission could be observed and the complexation
was not dependent on solvent polarity. Irradiation leads to photochemical products.
The nature of the complexes of zinc(II), cadmium(II) and mercury(II) halides with benzoin
Authors: Malhotra KC , Chaudhry SC
Published: September 2010

Zinc(11) halides react with
benzoin (bnH) in benzene to
form adducts of composition ZnX2(bnH) at
room temperature and [ZnX(bn)]2
when refluxed. Zinc acetate forms chelates Zn(bn)2
with benzoin in boiling methanol. Cadmium(11) halides
form adducts CdX2(bnH), [CdX(bn)(bnH)]2,
[Cd(bn)2(bnH)]2
and Cd(bn)2 under similar conditions.
Mercury(11) halides form compounds of composition HgX2(bnH)z only.
The synthesis and reactions of some polychloroaromatic azides, sulphonyl azides and sulphonohydrazides
Authors: Bernard IRA , Chivers GE , Cremlyn RJW , Mootoosamy KG
Published: September 2010

Azidopentachlorobenzene (2)
and 4-azidotetrachloropyridine (4) react with norbornene to give the aziridines
(6) and (7); with cyclohexene the enamines (10) and (11) are formed.
1,2,3,4-Tetrachlorobenzene reacts with chlorosulphonic acid to give 2,3,4,5-tetrachlorobenzenesulphonyl
chloride (14), but the reported chlorosulphonation of
1,2,4,5-tetrachlorobenzene could not be effected, and under drastic conditions
the reaction afforded hexachlorobenzene. The sulphonyl chloride (14) reacts
with hydrazine to give the sulphonohydrazide (15). However, in contrast to
previous work, reaction of polychloroaromatic sulphonyl chlorides with ammonia
and phenylhydrazine gave only the normal sulphonamides and N'-phenyl sulphonohydrazides.
Single-crystal 57Fe Mössbauer studies of the site positions in cordierite
Authors: Duncun JF , Johnson JH
Published: September 2010

Mossbauer (57Fe) absorption spectra of different
orientations of single crystals of cordierite (Mg,Fe)2AI3
[Si5AIO18] have been determined. The variation of the
ratio of the peak areas of the quadrupole split lines with orientation has
enabled the determination of the electric field gradient directions, and the
site positions and occupancies of the Fe2+ and Fe3+ ions.
Of a total iron content of 1.85% w/w, 79% is present as Fe2+
replacing Mg2+ in the octahedral sites; 19% as Fe2+
occupying the larger of two channel sites; and 1% as Fe3+ replacing
Al3+ in the larger of the two tetrahedral sites. A possible
interpretation of the observed pleochroism in terms
of Fe2+-Fe2+ and Fe2+-Fe3+ electranic interactions along the directions of the
electric field gradients of these ions is suggested.
The camphenehydro (methylcamphenilyl) and isobornyl (bornyl) cations. II. Anodic oxidations of carboxylic acids
Authors: Gream GE , Pincombe CF
Published: September 2010

The anodic oxidation of exo- and endo-1,7,7-trimethylnorbornane-2-carboxyc acid (exo- and endo- bornane-2-carboxylic acid) and exo- and endo-2,3,3-trimethylnorbornane-2-carboxyic
acid in methanol containing sodium methoxide at platinum and carbon electrodes
gives an equilibrium mixture of the 1,7,7-trimethylnorborn-2-yl [isobornyl (bornyl)] and 2,3,3-trimethylnorborn-2-yl (camphenehydro) cations having properties similar to that
formed by methanolysis of the respective chlorides. Under the same conditions of
electrolysis, α-campholenylcarboxylic acid
[3-(2',2',3'- trimethylcyclopent-3'-enyl)propanoic acid] gives very low yields
of products, including cyclized ones, the nature of which depends markedly on
the type of anode used.
The influence of π-bonding and steric factors on helahalogeno-metallates
Authors: Fergusson JE , Heveldt PF
Published: September 2010

A comparison of the
asymmetric stretching frequency v3 and unit cell length a0
for a series of hexahalogeno-metallates A2MX6
[A = K+, Rb+, Cs+
and NH4+, M = Ru, Os, Sn and Te
and X = Cl,Br] has been made. Trends observed for the
tellurium and tin compounds may be related to stericfactors whereas possible M →
X dπ-pπ bonding may
explain the opposite trend found for ruthenium and osmium compounds.
Solvation of ions. Some applications. I. Electrorefining of silver by means of silver sulphate solutions in mixtures of water with 3-hydroxypropionitrile
Authors: Parker AJ , Diggle JW , Avraamides J
Published: September 2010

High purity, adherent,
non-dendritic, porous cathodes can be produced at 100-300 MV by electrolysing
at > 98% efficiency a silver anode at 30-35�C for 48 h in a simple vertical
cell without diaphragm at a current density of 100-150 A/m2. The
electrolyte solution contains water, 150 g/l. 3-hydroxypropionitrile, 140 g/l.
sulphuric acid and 0.2M silver sulphate.
Some pyrazine derivatives from the Argentine ant, Iridomyrmex humilis
Authors: Cavill GWK , Houghton E
Published: September 2010

3-Isopentyl-2,5-dimethyl-,
and the (Z)- and (E)-isomers of
2,5-dimethyl-3-styryl-pyrazine, have been fully characterized from the
Argentine ant, I. humilis.
A facile conversion of the (E)- into
the (Z)-styryl
derivative is noted. These pyrazines comprise 70 and 200 p.p.m,
of the body weight of the insect. Mass spectrometric data suggests a further
pyrazine, the 2,5-dimethyl-3-propyl derivative, is present at approximately 5 p.p.m.
The decomposition of permanganate in molten alkali-metal nitrates
Authors: Temple RB , Thickett GW
Published: September 2010

The decomposition of MnO4-
has been studied in molten (K/Li)NO3 eutectic at temperatures
between 150� and 200�C. The rate of decomposition in a Pyrex vessel increased
in the presence of traces of NO2-, Br- and CN-
and of the manganate(1V) precipitate produced in the
decomposition. Various transition and heavy metal ions were also found to
accelerate the decomposition of MnO4- : the rate law
appears to be

-d[MnO4-]/dt
= k[Mn+]2/n[MnO4-]

where n = oxidation state
of metal ion M which was added to the melt solution of MnO4-
(in the presence of a fixed weight of insoluble reaction product). Nickel and
cobalt(11) ions are oxidized by MnO4- to insoluble nickel(111)
and cobalt(111) manganates(1V). Whilst NO2-
produced by the thermal decomposition of NO3- appears to
be the active reductant in (K/Li)NO3
melts, the reaction is complicated by being partly heterogeneous. The method of
preparation of the reaction product critically affects the rate constant k.
Complexes of Pyridine-2-carbaldehyde S-Methylthiosemicarbazone with nickel(II) and copper(II)
Authors: Malik MA , Phillips DJ
Published: September 2010

New complexes of
pyridine-2-carbaldehyde S-methylthiosemicarbazone
(pmts) with nickel(11) and copper(11) are reported, together with magnetic
moments, infrared and electronic spectra. The pale yellow bis-ligand complexes
with nickel perchlorate, tetrafluoroborate and
nitrate have the ionic structures [Ni(pmts)2] X2, with
six-coordinate nickel(11) and tridentate ligands. Thiocyanate co-ordination and
bidentate pmts appear to be present in the six-coordinate orange-brown complex
Ni(pmts)2(NCs)2. The complexes,
Ni(pmts)X2 (X = Cl, Br), are
halogen-bridged and six-coordinate. The complexes Cu(pmts)X2 (X = Cl, Br, NO3) do not appear to be five
coordinate, and may be six coordinate.
The preparation of stable dimercury(I)-nitrogen donor complexes
Authors: Kepert DL , Taylor D
Published: September 2010

A series of dimercury(1) complexes of the type [Hg2L2]
[ClO4]2 has been prepared with heterocyclic nitrogen
donor ligands. Complexes with 2-ethylpyridine and 4-benzylpyridine were of the
form [Hg2L3.7] [ClO4]2 and [Hg2L4]
[ClO4]2 respectively. The formation of a stable complex
is found to be dependent on the effective base strength of the ligand.
The periodate oxidation of some Cycloalk[b]indoles and their N-methyl derivatives: Effect of ring size on the spectral and chemical properties of the resultant lactams
Authors: Gale DJ , Wilshire JFK
Published: September 2010

The sodium periodate oxidation of several cycloalk[b]indoles and their N-methyl derivatives gave a
series of lactams, the ring size of which varied from 8 to 11 members. The effect of ring size on the
spectral (ultraviolet, infrared and proton magnetic resonance) properties of these lactams and on
their behaviour towards alkali (the Camps reaction), acid and heat is discussed.
Oxidation of 1,2,3-trimethylindole with periodate gave N-methyl-o-acetamidoacetophenone which
exists in solution as a mixture of the exo and endo conformers. Solvent shift [δl(CDCl3) - δ(C6H6)]
data were useful in assigning structures not only to these conformers but also to the conformers of
several related N-methyl-o-substituted acetanilides.
The ultraviolet and proton magnetic resonance spectra (including solvent shift data) of several
related quinol-2(1H)- and -4(1H)-ones (obtained by the alkaline treatment of the above lactams)
are discussed.
Hydroxamic acids. V. The alkylation of O-alkylarylhydroxamic acids
Authors: Beart PM , Ward AD
Published: September 2010

The reactions of O-alkylarylhydroxamic
acids with a variety of alkylating agents, to yield mixtures of the N,O-dialkyl
and 0,O'-dialkyl products, are
described. Spectral data and independent synthesis allow the unambiguous
assignment of structure to these isomeric products. Substituents on the aryl
ring exert an electronic influence on the ratio of the two products; the extent
of this influence varies with the alkylating agent. Diazomethane, triethyloxonium tetrafluoroborate
and methyl fluorosulphonate give largely, but not
exclusively, the 0,O'-dialkyl
product. Methyl fluorosulphonate, in the presence of
a base, reacts further to form an unstable salt which appears also to function
as an alkylating agent.
Organoboranes in organic synthesis. II. The mechanism of the reaction of α,α'-dibromo ketones with organoboranes in the presence of base
Authors: Prager RH , Tippett JM
Published: September 2010

The mechanism of the
reaction of α,α-dibromocyclohexanones with organoboranes has been
investigated, and is suggested to occur by attack of base on bromine in the
ketone-borane adduct, followed by rate-determining alkyl group transfer from
boron to carbon. Labelling studies show that the extra proton in the products
comes from the solvent, tetrahydrofuran.