bluuebunny/crossref_metadata_2025 huggingface dataset:
The structure and properties of Unsymmetrical-Facial 2,3-Bis[(2-aminoethyl)(methyl)-aminoethyliminol-1-methylpiperazinecobalt(III) perchlorate monohydrate, u-fac-[Co(amam)] (ClO4)3,H2O
Authors: Horn EO , Lincoln SF , Searle GH , Snow MR
Published: September 2010

X-ray crystallographic
analysis of the title complex, which was formed spontaneously from aqueous s-fac-[Co(medien)2]3+ [medien = 2,2?- methyliminodi(ethylamine)] in the presence of charcoal and
oxygen, shows that it has the u-fac geometry of the
[Co(medien)2]3+ moiety. Two coplanar en-type rings of
this moiety are bridged by a new planar ring which is fused through a
di-amidine grouping to a piperazine ring. The close planarity of this linked
ring system, which results from the conjugated unsaturation and resonance in
the di-amidine grouping, provides a powerful force in stabilizing the u-fac geometry. The crystals are monoclinic, spacegroup P21/c
with a 10.700(6), b 13.38(6), c 20.076(5) Ǻ, β 98.58(13)�. The
structure was refined to an R-factor (on F) of 0.077 by blocked-matrix least-squares
techniques. The complex has an acidic amidine proton (pKa
10.3 at 20�) located on the piperazine nitrogen. The 13C n.m.r,
spectra of the complex and its deprotonated form are interpreted and indicate
that the predominant solution tautomer is the same as that in the solid state.
The existence of this complex indicates that it might be possible to prepare
the unstable u- fac-[Co(medien)2]3+
isomer.
Three new diterpenes from the sea pen Scytalium tentaculatum
Authors: Ravi BN , Marwood JF , Wells RJ
Published: September 2010

Three new diterpenes,
related to briarein A, have been isolated from the sea pen Scytalium
tentaculatum. The structures and relative stereochemistries were obtained by
spectral evidence and chemical degradations.
Further stereoselective reductions of 3-O-hexofuranosyl S-methyl dithiocarbonates with tributyltin deuteride. A comment on mechanism
Authors: Fuller TS , Stick RV
Published: September 2010

The reduction of
1,2:5,6-di-O-isopropylidene-3-O- (methylthio)thiocarbonyl-β-D-altrose,
-mannose and -(3-2H)mannose with tributyltin deuteride and hydride
leads to highly stereoselective syntheses of
3-deoxy-1,2:5,6-di-O-isopropylidene-β-D-(3-2H)altrose and -(3-2H)mannose.
In addition, the reduction of a pair of diastereomeric dithiocarbonates with
virtually no stereochemical constraints leads to the same diastereomeric
mixture of reduced products, indicating a common radical intermediate for the
reduction.
Studies in the tricyclooctane series. V. Dehydrohalogenation of the Bis-dihalocarbene adducts of some methoxycyclohexadienes
Authors: Banwell MG , Halton B
Published: September 2010

The bis-dichloro and
bis-dibromo carbene adducts (1c-h) of 1-methoxy-, 1,4-dimethoxy- and 1,5-dimethoxy-cyclohexa-1,4-diene
undergo regiospecific dehydrohalogenation by strong base to the 4,8,8- trihalomethoxybicyclo[5,1,0]octa-2,4-dienes (7c-h), in
contrast to the 1,7-dimethoxytricyclooctane(1i) and its methyl derivatives (1j-m),
which are unchanged. The dienes (7c-h) are resistant to further
dehydrohalogenation.
Kinetics of the pinacol rearrangement of Propane-1,2-diol
Authors: Herlihy KP
Published: September 2010

The pinacol
rearrangement of propane-1,2-diol in aqueous acid gives propanal.
The rate of loss of optical activity (kα)
is greater than the loss of diol (kre)
over the range of acid concentrations investigated. Also the ratio kα/kre decreases with the increasing
acidity. A value of c. 0.5 has been
obtained for the relative rates of oxygen exchange to racemization. Relative
rates for the partitioning of a proposed carbocation intermediate have been
calculated from these data.
Isobenzofulvenes. VII. Regio- and site-selective cycloadditions and their potential in anthraquinone synthesis
Authors: Russell RAVEG , Warrener RN
Published: September 2010

The regiochemistry of the
cycloaddition of the 4-methoxyisobenzofulvene (8a) with 5- and 6-chloro-
2-methyl-1,4-benzoquinones has been evaluated. The resulting cycloadducts have
been converted into the known 5-methyl ethers of islandicin and digitopurpone.
The concept and value of a 'ghost' substituent in controlling the
regiochemistry of a cycloaddition is discussed in general and evaluated for a
specific case.
The stereochemistry of organometallic compounds. XX. The stereochemistry of formation of (1-3-η)-PdCl complexes from Deutero-substituted1-acetyl-4-t-butylcyclohex-1-enes
Authors: Coller BAW , Jackson WR , Stragalinou A , Strauss JUG
Published: September 2010

The preparation and
assignment of stereochemistry of some deutero-substituted
1-acetyl-4-t-butyl- cyclohex-1-enes is described. The formation of (1-3-η)-PdCl
complexes from these compounds is accompanied by a non-stereoselective
loss of H and D, in agreement with a mechanism of formation which involves an
initial palladium-assisted enolization of the ketone.
Cyclopentadienyl-ruthenium and -osmium chemistry. XIII. Some complexes containing isonitrile ligands
Authors: Bruce MI , Wallis RC
Published: September 2010

Reactions between isonitriles and RuCl(PPh3)2(η-C5H5) have
given RuCl(CNR)(PPh3)(η-C5H5)(R = But, c-C6H11,
CH2S02C6H4Me-p or C6H40Me-p) and RUCl(CNBut)2(η-C5H5); in
the presence of NH4PF6, cationic complexes [RU(CNR)(PPh3)2(η-C5H5)]PF6
(R = But, c-C6H11 or CH2SO2C6H4Me-p) and [RU(CNBut)2(PP~h3)(η-C5H5)]PF6
were obtained. Protonation of Ru(CN)- (PPh3)2(η-C5H5) gives
the hydrogen isocyanide derivative [Ru(CNH)(PPh3)2(η-C5H5)]PF6; tri- alkyloxonium salts alkylate the cyano complex affording [Ru(CNR)(PPh3)2(η-C5H5)]PF6
(R = Me or Et).
Nucleophilic alkenes. VIII. Addition of an ethene-1,1-diamine to quinones and related compounds
Authors: Cameron DW , Feutrill GI , Thiel JM
Published: September 2010

The nucleophile N,N�-dimethyl-N,N�-diphenylethene-1,1-diamine (3) reacted with simple
1,4-quinones and related compounds to give highly conjugated enediamines. These
products resultedfrom 1 : 1-addition
processes under conditions where reactions of 1,1-dialkoxyethenes proceeded by
1 : 2-addition.
A 195Pt and 15N N.M.R. study of the anticancer drug, cis-diammine-dichloroplatinum(II), and its hydrolysis and oligomerization products
Authors: Boreham CJ , Broomhead JA , Fairlie DP
Published: September 2010

195Pt and 15N n.m.r, spectra for aqueous
solutions of the anti-cancer drug cis-diamminedichloroplatinum(II)
and its hydrolysis and oligomerization products are reported. In the blood
substituteHanks medium, conversion of
cis-[Pt(15NH3)2(H20)2](NO3)2
into cis[PtCl2(15NH3)2],
cis-[PtCl(H20)(15NH3)2]+,[Pt(15NH3)2OH]33+
and [Pt(15NH3)2OH]22+
has been observed, the reaction taking several hours at 30�C. In 0.15 M sodium
chloride, both [Pt(NH3)2OH]33+ and[Pt(NH3)2OH]22+
are converted overnight into cis-[PtCl(H2O)(NH3)2]+.
The infrared bands at 546 and 522 cm-1 in [Pt(NH3)2OH]2SO4
and at 520 cm-1 in [Pt(NH3)2OH]2(SO4)3
have been reassigned to Pt-N modes.
The preparation of some 2-nitroacridines and related compounds
Authors: Rosewear J , Wilshire JFK
Published: September 2010

The reaction of 2-fluoro-5-trobenzaldehyde
with a wide variety of arylamines gives, in general, mixtures of the
corresponding 2-arylamino-5-nitrobenzaldehydes and their related anils. Both
aldehydes and anils readily underwent acid-catalysed cyclization to give the
corresponding 2-nitro-acridines. The effect of substituent on the rate of
cyclization of these aldehydes and of some related anilino-benzaldehydes and
-acetophenones has been studied in trifluoroacetic acid solution by means of 1H
n.m.r. spectroscopy. A solution of 2-(N-methylanilino)-5-nitrobenzaldehyde
in trifluoroacetic acid appears to contain a substituted acridinium ion;
treatment of this solution with alkali gave 10-methyl-2-nitroacridone. 1H
n.m.r. data for a wide variety of substituted 2-nitro-acridines are discussed.
The preparation of a stable 8-oxatricyclo[4,3,0,07,9]nona-2,4-diene and an evaluation of its potential as a source for the photochemical generation of oxiren
Authors: Warrener RN , Russell RA , Tan RYS
Published: September 2010

The synthesis of
2-methyl-3,4,5-triphenyl-8-oxatricyclo[4,3,0,07,9]nona-2,4-diene
(14) is described, the first stable member of this ring system. Preparation of
(14) was achieved by reacting dibenzyl diazenedicarboxylate with
2-methyl-3,4,5-triphenylbicyclo[4,2,0]octa-2,4,7-triene (29) to form the adduct
(30a), which was selectively epoxidized at the cyclobutenyl double bond with
3-chloroperbenzoic to yield the epoxide (32a). Removal of the benzyl groups (H2/Pd)
from the hydrazo bridge of (32a), followed by oxidation (red mercuric oxide or
hydrogen peroxide) yielded the putative azo compound (33) which spontaneously
lost dinitrogen, even at -78�, to yield (14) as a crystalline solid, m.p. 128�.
While (14) has the potential to undergo 1,2-photoaromatization to yield oxiren
(4a), this is not realized and ring-opening to the cyclic epoxide (34) is the
major photochemical reaction observed under various ultraviolet irradiation
conditions. Isomerization of (14) into (34) also occurs under thermal
conditions. The 1H n.m.r, spectra of (14) as well as its trapping
with dienophiles is discussed.
Phyllocladan-16β-ol (13β-Kauran-16β-ol)
Authors: Carman RM
Published: September 2010

The title compound has been
synthesized from phyllocladene and found to be different from the compound
previously claimed to occur naturally.
Empirical polarity parameters for some binary solvent mixtures
Authors: Balakrishnan S , Easteal AJ
Published: September 2010

Values of the empirical
solvent polarity parameters ET
and Z have been determined as a function of composition for the binary solvent
systems 1,2-dibromoethane + 1,2-dibromopropane, acetone + chloroform, acetone +
ethanol, ethanol + chloroform and acetone + dichloromethane. For the 1,2-dibromoethane
+ 1,2-dibromopropane system both ET
and Z are accurately linear (i.e. additive) functions of composition. For the
other systems both parameters vary with composition in a strongly non-additive
manner, and the deviations from additivity are
interpreted in terms of intermolecular interactions. For these systems, in
general ET and Z are not
highly correlated, and neither parameter is highly correlated with other
macroscopic properties or parameters derived from them.
Synthetic applications of intramolecular insertion in arylcarbenes. V o-Benzyl, phenylamino, phenoxy and phenylthio phenylcarbenes
Authors: Crow WD , McNab H
Published: September 2010

The 2-(XC6H4)-substituted
phenylcarbenes in which X = CH2, NH, O and S have been generated and
pyrolysed in the gas phase at low pressure. When X = CH2 or NH, the
main reaction is simple insertion into the adjacent o-position of the XC6H5 ring to give dihydroanthracenes
and dihydroacridines respectively. The use of substituents shows that no spiro
diene rearrangement is involved in the case X = NH. For X = O or S, on the
other hand, the carbene inserts into the π-system ofthe XC6H5
ring and expansion occurs to give benzo[b]cyclohepta[d]furans and thiophens.
Central nervous system active compounds. VIII. New syntheses of phthalide isoquinolines
Authors: Prager RH , Tippett JM , Ward AD
Published: September 2010

Isoquinoline methiodides
react with phthalides in the presence of sodium methoxide to give intermediates
which may be reduced to phthalide isoquinolines with hydrogen or sodium
cyanoborohydride. The predominant isomer formed is the erythro, which is also the more active compound when tested for
central nervous system activity. The direct coupling of phthalides with dihydroisoquinoline
methiodides under these conditions fails to occur.
Constituents of Eupomatia species. VIII. The structures of eupodienone-4, -5,-6 and -7
Authors: Read RW , Taylor WC
Published: September 2010

On the basis of
spectroscopic evidence structures (4), (5), (7) and (8) respectively are
assigned to the neolignans eupodienone-4, -5, -6 and -7 isolated from Eupomatia
laurina R.Br. The products of dienone-phenol and dienol-benzene rearrangement
of the substances are characterized.
The reaction of 2-Alkyl-1,1-dichlorocyclopropanes with lithium naphthalene
Authors: Watanabe S , Fujita T , Suga K , Kasahara K
Published: September 2010

2-Alkyl-1,1-dichlorocyclopropanes
react with lithium naphthalene to give a mixture of dechlorinated
alkylcyclopropanes and unsaturated hydrocarbons. For example, a mixture of
octylcyclopropane and undec-1-yne was obtained from the reaction of
1,1-dichloro-2-octylcyclopropane and lithium naphthalene.
Pressure studies on the intramolecular isomerization reactions of (Diethylenetriamine)(methyldiethylenetriamine)cobalt(III) and Bis(diethylenetriamine)cobalt(III) cations
Authors: Keene FR , Mcdonald IAS , Searle GH
Published: September 2010

The homogeneous
intramolecular isomerization reactions of all the isomers of [Co(dien)2] (ClO4)3 and [Co(dien)(medien)] (ClO4)3 (dien, diethylenetriamine; medien, 4-methyldiethylenetriamine)
have been studied at 90°C under atmospheric pressure and conditions of high
pressure. The isomerization reactions are retarded by an increase in pressure,
and for a given starting isomer of each system: the various isomerization
processes are affected uniformly. For each system, the same equilibrium isomer
distribution was obtained regardless of starting isomer or of the pressure
conditions of the experiment. The results are interpreted on the basis of a common
mechanism for all isomerizations, involving Co-N bond-rupture followed by
rearrangement of the resultant five-coordinate species.
A carbon-13 nuclear magnetic resonance study of protonation in Imidazo[4,5-c]pyridines
Authors: Barlin GB , Fenn MD
Published: September 2010

A carbon-13 n.m.r. study of
protonation in various imidazo[4,5- c]pyridines has revealed that
imidazo[4,5-c]pyridine and its 1- and 3- methyl derivatives are protonated at
N5; 6-chloroimidazo-[4,5- c]pyridine and its 1-methyl derivative are protonated
at N 3 but the 3- methyl analogue protonates at N 1; and
2-methylthioimidazo[4,5- c]pyridine (and also its 5-methyl derivative)
protonate at both N 1 and N 3, but 1- and 3-methyl-2-methylthioimidazo[4,5-c]pyridine
protonate at N 5.
Temperature dependence of tryptophan and tyrosine luminescence in poly(vinyl alcohol) films
Authors: Sakurovs R , Ghiggino KP
Published: September 2010

The temperature dependence
of the fluorescence and phosphorescence from tyrosine and tryptophan in
poly(vinyl alcohol) films has been studied over the temperature range 90-295 K.
A kinetic scheme is proposed which allows the calculation of activation energies
for excited singlet and triplet state deactivation processes. A single
temperature-dependent radiationless process from the singlet state is observed
for tyrosine and tryptophan, with activation energies of 5.2�0.4 and 7.1�0.6 kJ
mol-1 respectively. However,
two distinct temperature transitions have been detected for triplet-state
relaxation at 180 and 255 K. The role of polymer phase transitions in
determining excited state relaxation pathways of embedded luminescent probes is
discussed.
Methyleneketenes and methylenecarbenes. XVI. The formation of Diphenylfuran-2-ones and 3-Phenylphthalide as minor products of the pyrolysis of diphenylmethyl propiolate
Authors: Brown RFC , Eastwood FW , Chaichit N , Gatehouse BM , Pfeiffer JM , Woodroffe D
Published: September 2010

The formation of a mixture
of lactones as a minor product of the flash vacuum pyrolysis of diphenyl-methyl
propiolate (1) has been investigated further. ��� The diphenylfuran-2-ones (3), (4), and (5)
are shown to be formed through an intramolecular insertion reaction of the methylenecarbene (2), formed from (1) at 640°, which leads
to 5,5-diphenyl-furan-2(5H)- one (3) as the primary product. ��� 3-Phenylphthalide (8) is apparently formed
by intramolecular Diels-Alder addition of the
C≡C bond of (1) to one phenyl ring which acts as the diene component,
followed by loss of acetylene from an intermediate barrelene derivative (10).
This is confirmed by a deuterium labelling experiment. ��� 1-Phenyl-2-benzoxepin-3(1H)-one (7),
considered at first as a possible intermediate in the pyrolysis of (1), is
synthesized in six steps from 2-aminobenzophenone, and its X-ray structure
determination is reported. On pyrolysis at 640°/0.07 mm (7) decarbonylates
smoothly to give 2-vinylbenzophenone.
Synthesis of haemofluorone B trimethyl ether
Authors: Feutrill GI , Whitelaw ML
Published: September 2010

The revision of the
structure of haemofluorone B to 5,8,9-trihydroxy- 3H-naphtho[2,1,8-mna]xanthen-3-one
is confirmed by the synthesis of its trimethyl ether
by photochemical oxidative cyclization of 9-(3,4- dimethoxyphenyl)-4-hydroxy-2-methoxy-1H-phenalen-1-one.
The conventional process for conjugate arylation of phenalenones has been
improved by the use of aryllithium reagents.
Synthesis and evaluation of fluorescent materials for colour control of peroxyoxalate chemiluminescence. I. The phenylethynylation of anthraquinone
Authors: Hanhela PJ , Paul DB
Published: September 2010

The synthesis of
9,10-bis(phenylethynyl)anthracene has been examined in detail prior to the
synthesis of a series of phenylethynyl substituted aromatic compounds which are
of interest as fluorescent materials for peroxyoxalate chemiluminescence.
Reductions of the 9,10- bis(phenylethynyl)-9,10-dihydroanthracene-9,10-diol
precursor by stannous chloride and by sodium hypophosphite-potassium iodide
both gave a series of byproducts, in addition to 9,10- bis(phenylethynyl)anthracene.
The formation of these compounds is interpreted in terms of a free-radical
process. The interaction of 10-hydroxy-10-(phenylethynyl)anthrone with both
the reducing systems has been rationalized and the reaction with concentrated
sulfuric acid reinterpreted.
Synthesis and evaluation of fluorescent materials for colour control of peroxyoxalate chemiluminescence. II. Violet and blue emitters
Authors: Hanhela PJ , Paul DB
Published: September 2010

Synthetic approaches to
efficient blue fluorescent compounds suitable for use in peroxyoxalate
chemiluminescence systems are described. Various
bis(phenylethynyl)-naphthalenes and -phenan-threnes were obtained but these
were shown to produce purple fluorescence and chemiluminescence. Ring
substitution of 9,10-diphenylanthracene, however, afforded a number of
satisfactory blue fluorescent emitters. The structure and derivation of several
byproducts is also discussed.
The synthesis of 5-Alkylidenefuran-2(5H)-ones
Authors: Babidge PJ , Massy-Westropp RA
Published: September 2010

5-Alkylidenefuran-2(5H)-ones
can be synthesized efficiently from S- methyl 5-oxo-2,5-dihydro-furanylidenealkanethioates
by treatment with Raney nickel. The ylidenealkanethioates are prepared from the
Wittig reactions between cyclic anhydrides and (methylthio)carbonylmethylenetriphenyl-phosphorane
or its alkylated derivative. The decarbonylation-desulfurization
process proceeds largely with retention of configuration about the double bond.
It is considered that the reaction proceeds by loss of carbon monoxide to give
a thioenol ether which is subsequently hydrogenolysed to the 5- alkylidenefuran-2(5H)-one.
Stereochemistry in the Bis(1,4,7-triazacyclodecane)cobalt(III) system and force field calculations
Authors: Dwyer M , Searle GH
Published: September 2010

An analysis of the stereochemical possibilities for the [Co(tacd)2]3+ complex is presented (tacd = 1,4,7-triazacyclodecane). Stereochemical
variables are cis (chiral) and trans
relative dispositions of the two six-membered rings,
combinations of alternative conformations for the six chelate rings in the
complex, and alternative configurations R or S about one secondary amine
nitrogen in each coordinated ligand. Energy minimization calculations have been
carried out on a number of the possible isomers, from which it is deduced that
the most stable conformational arrangements in the trans geometry are {λδ chair,A 6 chair} and {I. 6 chair,6 6 chair), and those in
the cis geometry are { λδ chair δδ chair}, { λδ
chair δδ chair } and { λδ
chair δδ chair skew). The calculations give
the trans-cis energy difference as
9.3 kJ mol-1, to be compared with the experimental free energy
difference of 8 � 1 kJ mol-1.
The crystal and molecular structure of oxovanadium(V) orthophosphate dihydrate, VOPO4,2H2O
Authors: Tietze HR
Published: September 2010

The structure of a
tetragonal crystal of the title compound was determined by X-ray diffraction.
The space group was found to be P4/nmm
with a 6.202(2) and c 7.410(1) � and Z 2. The structure
consists of infinite sheets of distorted VO6 octahedra
and PO4 tetrahedra linked by shared oxygen
atoms. Shared water molecules link these sheets together. A short V-O(4) bond,
1.567(5) �, indicates the presence of the cation VO3+.
Synthesis and characterization of Tris[(S)-1-dithiocarboxypyrrolidine-2-carboxylato(2 -)-S,S']cobalt(III), a complex derived from the (S)-proline residue
Authors: Woon T , O'Conner MJ
Published: September 2010

The ammonium salt of
(S)-1-dithiocarboxypyrrolidine-2-carboxyic acid and its tris-chelated cobalt(III) complex have been prepared and
characterized. The ammonium salt of the complex anion is soluble in water
whereas the fully protonated form is soluble in some
organic solvents. These diamagnetic cobalt(III) compounds and the corresponding
neutral methyl ester complex are shown by 13C n.m.r. spectroscopy to
have the facial geometrical structure. The complex anion was successfully
separated into diastereomeric Δ(SSS) and λ(SSS) forms (S refers to
the asymmetric carbon atom in each of the proline moieties) by using Sephadex
DEAE anion-exchange resin with aqueous ammonium chloride eluent. The more
easily eluted species has the Δ absolute configuration at the dissymmetric
cobalt atom as assigned from its circular dichroism
spectrum.
Synthesis of analogues of GABA. VI. Stereoisomers of cis-3-Aminocyclohexanecarboxylic acid
Authors: Allan RD , Johnston GAR , Twitchin B
Published: September 2010

The syntheses are described
of (1R,3S)- and (1S,3R)-3-aminocyclohexanecarboxylic acids
via unsaturated intermediates suitable for tritium labelling.
The absolute stereochemistry was determined by an alternative synthesis
of the (1R,3S) isomer from (R)-3-oxocyclohexanecarboxylic acid. The (1S,3R)
isomer showed a similar potency to GABA as an inhibitor of the uptake of
radioactive GABA by rat brain slices whereas
the (1R,3S) isomer was at least 20 times less potent.
Conjugate addition of the anion derived from 3-(Phenylsulfinyl)prop-1-ene to Cyclopent-2-en-1-one
Authors: Binns MR , Haynes RK , Houston TL , Jackson WR
Published: September 2010

The title anion in
tetrahydrofuran containing one equivalent of hexamethylphosphoric triamide at -
78� undergoes a rapid conjugate addition reaction with cyclopent-2-en-1-one. The
sole product obtained, in 73% yield, is (E)-3-[3-(phenylsulfinyl)prop-2-enyl]cyclopentan-1-one.
Central nervous system active compounds. IX. Cinnolinylisobenzofuranones [1-(3-Phthalidyl)cinnolin-4(1H)-ones]
Authors: Marshall PA , Mooney BA , Prager RHWAD
Published: September 2010

The synthesis and central
nervous system activity of a number of cinnolinylisobenzofuranones are
described. The compounds are prepared in moderate yield by the reaction of the
sodium salt of a cinnolin-4-one with the appropriate 3-bromophthalide. 1H,
13C n.m.r., and infrared spectral evidence for the structure of the
compounds is presented. The compounds cause a loss of muscular control in mice.
Synthesis of analogues of GABA. VII. (Z)- and (E)-4-Amino-3-(4-chlorophenyl)-but-2-enoic acids as unsaturated baclofen derivatives
Authors: Allan RD , Tran H
Published: September 2010

(Z)- and
(E)-4-Amino-3-(4-chlorophenyl)but-2-enoic acids have been synthesized from
4-chloroacetophenone as conformationally restricted analogues of baclofen. The
corresponding unsaturated lactam (4) has been catalytically reduced and
hydrolysed to baclofen to demonstrate the suitability of (4) as a precursor for
radiolabelled baclofen of high specific activity.
Studies of Australian soft corals. XXVI. Tetraprenylbenzoquinone derivatives from a Nephthea species of soft coral (Octocorallia, Alcyonacea)
Authors: Bowden BF , Coll JC
Published: September 2010

5-Methyl-2-tetraprenyl-p-benzoquinone (4) and its cyclized 2H-1- and 3,4-dihydro-2H-1-benzopyran derivatives (5) and (6)
have been isolated from the soft coral Nephthea sp. Structures were assigned on the basis of
spectroscopic evidence and the nature of the side chain in (4) and (5) was
confirmed by micro-ozonolysis.
Chemistry of the Podocarpaceae. LVIII. An improved preparation of 12-Methoxypodocarpa-5,8,11,13-tetraen-19-ol
Authors: Cambie RC , Robertson JD , Rutledge PS , Woodgate PD
Published: September 2010

An improved method for
reducing methyl 12-methoxy-7-oxopodocarpa-5,8,11,13-tetraen-19-oate (1) to
12-methoxypodocarpa-5,8,11,13-tetraen-19-ol(2) with aluminium hydride is
described. Reductions of 19-hydroxy-12-methoxypodocarpa-5,8,11,13-tetraen-7-one
(3) and its methyl ether (4) are also examined.
New furano-sesquiterpenes from the sponge Dysidea herbacea
Authors: Dunlop RW , Kazlauskas R , March G , Murphy PT , Wells RJ
Published: September 2010

Eight new sesquiterpenes, (ll), (12), (14)-(16), (18), (20) and (21),
have been isolated from four separate small collections of the sponge Dysidea herbacea. The
structures of these compounds, all of which contain a furan group, were derived
by comparison of their spectral properties with those of known sesquiterpenes.
A series of new diterpenes from the brown alga Dilophus marginatus (Dictyotaceae)
Authors: Ravi BN , Wells RJ
Published: September 2010

The dichloromethane extract
of the brown alga Dilophus marginatus
has yielded 17 new diterpenes. Nine of these metabolites were found to possess
a new bicyclic diterpene skeleton which we have named secospatane, five had the
recently reported spatane skeleton whilst three compounds had a new tricyclic
diterpene skeleton.
The nitration of 4,5-Dichloro-, 4,5-Dichloro-6-nitro-, 4,6-Dichloro- and 4,5,6-Trichloro-2-methylphenols ; the formation of substituted Cyclohex-3-enones
Authors: Hartshorn MP , Ing HT , Richards KE , Thompson RS , Vaughan J
Published: September 2010

Nitration of 4, 5-dichloro- and 4, 5-dichloro-6-nitro-2-methylphenols (la) and (lb) gives the gem-dinitrocyclohex-3-enone (6), and
nitration of 4, 6-dichloro- and 4, 5, 6-trichloro-2-methylphenols(2)
and (1c) gives the dinitrocyclohex-3-enones (8a) and (8b) respectively. Compounds (6) and (8b) yield α-diketone
(9b), and compound (8a) yields α-diketone (9a) on heating in tetrachloroethylene. Some reactions of α-diketones (9a) and (9b) are described.
Organophosphorus intermediates. VIII. The synthesis of some 2,6-dioxo-1,2,3,4,6,7,8,8a-octahydro-2λ5-isophosphinoline derivatives
Authors: Gallagher MJ , Honegger H , Sussman J
Published: September 2010

Methyl
1-methoxy-1,4-dioxo-1λ5-phosphorinan-3-carboxylate
(3) adds readily to but-3-en-2-one to give an adduct (5) which cyclizes under mild non-aqueous conditions to the novel
tricyclic compound(6). Substance (5) may be cyclized to mixtures of bicyclic derivatives
with either acid or base but the combination LiL/LiOH
affords 2-hydroxy-1,2,3,4,8,8a-hexahydroisophosphinolin-6(7H)-one 2-oxide (7a) in an overall yield
of 65%. 1H, 13C and 31P n.m.r., and mass
spectra are reported and discussed.
Synthesis of 1,3,5-risubstituted 2,4-dithiobiurets: Their conversion into 4-Alkyl-3,5-di(substituted imino)-l,2,4-dithiazolidines and to related benzothiazolylthioureas
Authors: Joshua CP , Thomas SK
Published: September 2010

The interaction of alkyl
and aryl isothiocyanates with an equimolar quantity of 1,3-dialkyl- and
1-alkyl-3-aryl-thioureas in the presence of a strong alkali has been found to
yield 1-alkyl-or aryl-3-alkyl-5-alkyl- or aryl-2,4-dithiobiurets in excellent
yield. The 2,4-dithiobiurets so obtained were easily converted into
1,2,4-dithiazolidine derivatives by oxidation with iodine or bromine in a non-
polar medium. The 4-alkyl-3-alkylimino-5-arylimino-1,2,4-dithiazolidine salts
were found to undergo a facile thermal rearrangement to the related
N-benzothiazol-2-ylthioureas.
Proton N.M.R. of the muramyl dipeptide adjuvant in dimethyl sulfoxide
Authors: Chapman BE , Batley M , Redmond JW
Published: September 2010

The active principle of
complete Freund's adjuvant, N-acetylmuramyl-L-alanyl-D-isoglutamine,
was studied in the α-anomeric form in dimethyl sulfoxide solutions by 1H
n.m.r, at 200 MHz. All resonances except those of the nonanomeric sugar protons
were assigned. Temperature dependences of the chemical shifts of the amide
protons indicated that the alanyl NH is involved in hydrogen bonding. The
isoglutamine β-CH2 protons showed large chemical-shift
nonequivalence, an effect consistent with a hydrogen bond to the side chain
carboxyl of this residue.
Heterocyclic ambident nucleophiles. III. The alkylation of sodium adenide
Authors: Rasmussen M , Hope JM
Published: September 2010

The alkylation of sodium
adenide in HCONMe2 (30�) with various alkylating agents was analysed
by 1H n.m.r. spectroscopy. Widely varying N3 : N7 : N9 alkylation
patterns were observed, depending on the alkylating agent. These patterns are
interpreted in terms of the electrostatic, thermodynamic and steric factors
involved in the different SN2 transition states appropriate to each
alkylating agent. Hydrogen bonding association between the 6-amino group and
certain carbonyl containing alkylating agents is proposed to explain the
enhanced N7-alkylation in some cases. Support for this latter proposal was
obtained from a comparison of the adenine alkylation results with the
corresponding alkylation patterns of 6-pivaloylamino- and 6-chloro-purine.
Constituents of Endiandra species. II. (E)-4-(6'-Phenyltetracyclo[5,4,2,03,13,010,12]-trideca-4',8'-dien-11'-yl)but-2-enoic acid from Endiandra introrsa (Lauraceae)
Authors: Bandaranayake WM , Banfield JE , Black DSC
Published: September 2010

The structure (5) of the
title compound, a vinylog of endiandric
acid, is proposed on the basis of chemical and spectroscopic evidence.
The reaction of N-dichloromethylene-N,N-dimethylammonium chloride (Viehe's salt) with some carbohydrate diols
Authors: Copeland C , Stick RV
Published: September 2010

The reaction of Viehe's salt
(Me2N+=CCl2Cl-) with various
carbohydrate diols (manno, allo) in
the presence of a base is reported, the products being, after hydrolysis,
either carbonate (with pyridine) or the carbamate (with triethylamine). A
rationalization of the two different types of product formed is given in terms
of the stereoelectronic control proposal by Deslongchamps.
Chemistry of the Podocarpaceae. LX. The preparation of homologues of Ambrox and Isoambrox from podocarpic acid
Authors: Cambie RC , Palmer BD
Published: September 2010

Derivatives of podocarpic
acid (5) have been converted into the homologues (22), (23), (24), (26), (27)
and (28) of the cyclic ethers Ambrox (25) and Isoambrox (29). All possess
ambergris-like odours.
Insect moulting hormones. LIV. The synthesis and biological acitvity of some alkylated ecdysone analogues
Authors: Horn DHS , Kelly BA , Kinnear JF , Martin M , Middleton EJ , Willing RI
Published: September 2010

A number of ecdysone analogues were prepared, with alkyl substituent
groups projecting above and below the plane of the A-ring of the analogue (37),
to gain an insight into the steric requirements for the binding of ecdysteroids to the hormone receptor. Moulting
hormone activities of these analogues, determined with the Calliphora bioassay, revealed
that the β-face is more sensitive to projecting alkyl groups than the α-face.
It is concluded that binding of the hormone to the receptor probably takes
place on both sides of the A-ring but that a close fit is more important on the
β-face than the α-face.
Cotton-Mouton and Kerr constants of twelve non-dipolar tri- and hexa-substituted benzenes
Authors: Ritchie GLD , Vrbancich J
Published: September 2010

Measurements of the
infinite-dilution molar Cotton-Mouton and Kerr constants of 12 non-dipolar
1,3,5-tri- and hexa-substituted benzenes as solutes
in carbon tetrachloride at 298 K are reported. Some of the experimental results
are in notable disagreement with earlier determinations made on equipment of
much lower sensitivity. Although the magnetic anisotropies derived for the tri-substituted
benzenes are concordant with other observed or predicted values, those for the hexa-substituted benzenes are generally very much larger
than expected. It is suggested, in explanation, that relatively large and
strongly anisotropic atomic polarizabilities may
cause the ratio of the static to the high-frequency polarizability
anisotropy to be considerably smaller in the hexa-substituted
benzenes than in benzene; in addition, there may be significant temperature
independent contributions to the magnetic birefringences
of these molecules.
An analysis of the 1H N.M.R. spectra and conformation of fructofuranoside derivatives in solution
Authors: Guthrie RD , Jenkins ID , Yamasaki R
Published: September 2010

The 1H n.m.r.
spectra of a number of D-fructofuranosides and related compounds, including
3,4-oxiran derivatives, are reported. The conformation of D-fructofuranosides
in solution is discussed.
Unfused heterobicycles as amplifiers of phleomycin. V. A range of pyridinylpyrimidines with strongly basic side chains
Authors: Brown DJ , Cowden WB
Published: September 2010

The condensation of
3-aminocrotonamide with ethyl pyridine-2-carboxylate or a related ester gave
6-methylpyrimidin-4(3H)-ones, each bearing at its 2-position a pyridin-2'-yl,
pyridin-3'-yl, pyridin- 4'-yl, furan-2'-yl, furan-3'-yl, thien-2'-yl or
pyrazin-2'-yl substituent. Of these, the pyridinyl derivatives (1a), (2a) and
(3a) were converted into their 4-chloro analogues and thence by nucleophilic
displacement into the corresponding β-dimethylaminoethylthio, β-dimethylaminoethylamino,
β-dimethylaminoethoxy and γ-dimethylaminopropylamino derivatives. The
activities of these compounds as amplifiers of phleomycin against Escherichia coli are reported.
Deuterium isotope effects in liquid-liquid phase diagrams : methanol + n-hexane systems
Authors: Khurma JR , Fenby DV
Published: September 2010

Liquid-liquid phase
diagrams have been measured for the systems CH3OH+n-C6H14,
CH3OH + n-C6D14, CH3OD + n-C6HI4
and CH3OD + n-C6D14. The upper critical
solution temperatures of these systems are 306.70, 304.30, 307.59 and 304.84 K,
respectively. The results are in accord with the qualitative predictions of the
Rabinovich theory, which considers hydrogen bond and
London dispersion interactions.
Methyleneketenes and methylenecarbenes. XVIII. A pyrolytic synthesis of aniline from trimethylsilyl (E,E)-2-Cyanohexa-2,4-dienoate
Authors: Besida J , Brown RFC
Published: September 2010

Flash vacuum pyrolysis of trimethylsilyl (E,E)-2-cyanohexa-2,4-dienoate(α-cyanosorbate) (4) gives
N-trimethylsilylaniline through O-to-N silyl transfer with decarboxylation, followed by rearrangement
of intermediate N-silylketenimines (5) and (6). After hydrolysis, aniline is obtained in 53% yield
from the α-cyano acid (3).
A synthesis of alkylated 3-aminoisoquinolines and related compounds
Authors: Liepa AJ
Published: September 2010

N,N-Dialkyl
derivatives of 3-aminoisoquinoline have been prepared by reaction of nitriles
with various arylacetic acid tertiary amides in the presence of phosphoryl
chloride. The synthesis has been extended to include a benzoisoquinoline and
annulated isoquinolines by the selection of appropriate amide and nitrile
precursors.
Plant growth regulators in Eucalyptus grandis. V. Synthesis of the G-regulators
Authors: Bolte ML , Crow WD , Yoshida S
Published: September 2010

Problems associated with
earlier synthetic approaches to the G-regulators have been overcome by the use
of the Mannich reaction in aprotic media. Under these conditions the Mannich
base formed from the reaction of 1,3-diketones and aldehydes is stabilized by
internal hydrogen bonding and can be isolated in high yield. In aqueous acid
rapid elimination occurs to give the 2-methylene 1,3-diketones, which first
enolize then add oxygen to generate the G-regulator structure. The steric
limitations of the reactions are examined.
Plant growth regulators in Eucalyptus grandis. VI. Reaction of the G-regulators with nucleophiles
Authors: Bolte ML , Crow WD , Yoshida S
Published: September 2010

The formation of Michael
adducts from the G-regulators and analogues with amines is described. Such
adducts are, in general, unstable zwitterionic compounds and are decomposed by
the action of acid into the parent G-regulator and the related 2-aminomethylene
1,3-diketone. Analogies are drawn with the natural storage and release in vivo.
Synthetic studies on 5-(3,4-dimethoxyphenyl)-5,6-dihydrophenanthridin-6-ol,an analogue of perloline
Authors: Clarke SI , Prager RH
Published: September 2010

Two independent syntheses
of the title compound (2), an analogue of perloline, are described.
9-(3,4-Dimethoxyphenyl)fluoren-9-ol reacted with hydrazoic acid in
polyphosphoric acid to give 6-(3,4-dimethoxyphenyl)phenanthridine, the N-oxide of which was photolysed to
5-(3,4-dimethoxy-phenyl)phenanthridin-6-one (8) which was reduced to the title
compound directly with sodium bis(2-methoxyethoxy)aluminium hydride ('Redal'),
or by reduction to 5-(3,4-dimethoxypheny1)-5,6- dihydrophenanthridine followed
by oxidation with N-bromosuccinimide.
The phenanthridinone (8) was also synthesized by photolysis of the nitrone of
3,4-dimethoxy-N-fluorenylideneaniline.
Chemistry of the Podocarpaceae. LXIV. Studies in the ambergris odorant field
Authors: Cambie RC , Hayward RC , Palmer BD , Robertson JD , Rutledge PS , Woodgate PD
Published: September 2010

The cyclic ethers
17-nor-16-oxa-l3β-kaurane (8) and 15,16-epoxy-17-nor-15,16-seco-8β,13β-kaurane
(11) have been prepared from 13 β-kaur-15-ene ('isophyllocladene')(1)
and 13 β-kaur-16-ene ('phyllocladene') (2),
respectively. The derivative (8), but not (11), possesses an ambergris-type odour. Preparation of the 8 β,12-epoxides (30),(31),(33)
and (34) from 12-hydroxypodocarpa-8,11,13-trien-19-oic acid ('podocarpic acid') (3) indicates that substitution of the 4β-methyl
group destroys their potentially odoriferous nature. An attempt to prepare epimers of the C8 demethyl
analogue of the known ambergris-type odorant (45) is reported; a mixture of the
C13 epimers of (45) is readily prepared from the unsaturated
ketone (41).
Pulse length measurement in N.M.R. spectroscopy: a convenient digital method using second-dimension transformation
Authors: Lawn DB , Jones AJ
Published: September 2010

A standardized procedure for the accurate measurement (1%
error) (in reasonable time (10-20 min)) of critical pulse
lengths is recommended. It uses the 2d-n.m.r. scheme:
[t1t2] →
[f1t2] [t2] →
[f2 ≡
θ]
where
t2 is an incremental
time, f1 is made to
vanish by selection of a single point region and f2 is equivalent to pulse length (angle θ). Pulse
imperfections are readily detected. To make the method totally general sources
of these imperfections should be corrected. Applications to T1 and
2d-J n.m.r, measurements are
outlined.
Conformational analysis of coordination compounds. XIV. Proton, carbon-13, cobalt-59 and platinum-195 n.m.r. spectra of six-membered diamine chelaterings
Authors: Hawkins CJ , Holm RH , Palmer JA , Traficante DD
Published: September 2010

The conformations adopted by six-membered diamine chelate rings in complexes of the types
[Co(NH3),L]3+, [Co(CN)4L]-, [Pt(bpy)L]2+, [Pt(NH3)2L]2+ and [CoL3]3+ have been studied by
n.m.r. techniques. The ligands (L) used in the study were meso- and (+)-pentane-2,4-diamine,
butane-1,3-diamine, propane-1,3-diamine and 2-methylpentane-2,4-diamine. It has been found that
for most complexes of meso-pentane-2,4-diamineth e diequatorial chair conformation predominates,
although for the bipyridineplatinum(II) complex it is unclear whether the skew-boat conformation
is significantly populated or the chair structure is unusually distorted. For (+)-pentane-2,4-diamine
chelates, which normally adopt the skew-boat conformation in octahedral complexes, the chair
conformation with an axial and an equatorial methyl group has a mole fraction of 0.5 and 0.7
for the bipyridine- and diammine-platinum(II) complexes, respectively. In tetraammine(butane-1,3-
diamine)cobalt(III) the chelate ring is in the chair conformation with the methyl equatorial.
Initiation mechanisms in radical polymerizations : Reaction of cumyloxy radicals with methyl methacrylate and styrene
Authors: Rizzardo E , Serelis AK , Solomon DH
Published: September 2010

Cumyloxy (1-methyl-1-phenylethoxy) radicals have been
generated by thermolysis (60�) of dicumyl
hyponitrite in methyl methacrylate and styrene. The
carbon-centred radicals formed by interaction of cumyloxyl with the respective monomers were trapped as stable
adducts of 1,1,3,3-tetramethyl-isoindolin-2-yloxyl. Extensive hydrogen atom
abstraction and methyl radical generation as well as double-bond addition were
observed in methyl methacrylate. Styrene underwent
only double-bond addition by both cumyloxy and methyl
radicals. Some possible implications of these results for polymer structure are
discussed. A kinetic study of the decomposition of dicumyl
hyponitrite in cyclohexane at various temperatures gave
k=7.7 × 1014exp(-13600/T) s-1
for the rate constant. Rate
constants for the addition of cumyloxyl to methyl methacrylate (k ≈ 2 × 104 dm3
mol-1 s-1) and styrene (k≈2 × 105 dm3
mol-1 s-1) at 60�have been estimated.
The stereochemistry of organometallic compounds. XXI. Asymmetric addition of hydrogen cyanide to alkenes catalysed by zerovalent metal compounds
Authors: Elmes PS , Jackson WR
Published: September 2010

[(+)-(diop)]2Pd
and [(+)-(diop)]2Ni have been prepared and
used as catalysts for the asymmetric addition of hydrogen cyanide to alkenes.
The corresponding complex of platinum with diop has also been prepared and
found to be less useful as a catalyst as were the complexes of these three
metals with other chelating diphosphines.
Crystal structure of 3-Phenylazo-1H-4,1,2-benzothiadiazine (a redetermination)
Authors: Pakawatchai C , White AH
Published: September 2010

The crystal structure of
3-phenylazo-1H-4,1,2-benzothiadiazine, C13H10N4S,
an oxidation product of 'dithizone', has been redetermined by using
diffractometer data, the 1001 'observed' reflections being refined to a
residual of 0.030. Crystals are orthorhombic P212121,
a 15.15(1), b 12.008(7), c 6.756(6) �,
Z 4. The molecule is substantially planar, with a number of angular distortions
arising from ring substituent interactions.
Constituents of Endiandra species. IV. Isolation of 2-(8'-[(E,E)-5'-phenylpenta-2',4''-dien-1''-yl]bicyclo[4,2,0]octa-2',4'-dien-7'-yl)acetic acid, a biogenetically predicted metabolite of Endiandra introrsa (Lauraceae) and its structure determination by means of 1D and 2D N.M.R. spectroscopy
Authors: Banfield JE , Black DSC , Johns SR , Willing RI
Published: September 2010

The structure (6a) is
proposed for the title compound, on the basis of chemical and spectroscopic
data. In particular, a combination of one- and two-dimensional n.m.r.
techniques has led to this assignment. Compound (6a) is relatively unstable and
its isolation requires a careful extraction process.
Systemic fungicides. The synthesis of certain pyrazole analogues of carboxin
Authors: Huppatz JL
Published: September 2010

Methods are described for
the synthesis of 1,3-dimethyl-N-phenylpyrazole-4-carboxamid (3) and the
isomeric 1,5-dimethyl compound (4), structural analogues of the systemic
fungicide carboxin. Evidence confirming the structural assignment of the
compounds is presented, and a convenient method for the removal of the amino
group from some aminopyrazoles is described.
1,2-Dihydroisoquinolines. XXII. Benzo[b]quinolizine derivatives
Authors: Dyke SF , Spray CR , Kilminster RA
Published: September 2010

Some time ago it was
reported that 4,6,11,11a-tetrahydro-1H-benzo[b]quinolizin-2(3H)-ones are
produced when N-benzylaminoacetaldehyde dialkyl acetals react with methyl vinyl
ketone in acid solution. These structures have now been confirmed, the scope of
the reaction broadened and the conformations of the products investigated. Some
of these ketones have been treated with phenyl- magnesium bromide, but no
useful central nervous system activity has been found for any of the tertiary
alcohols produced.
The structure of a diterpene with a new carbocyclic ring skeleton from the soft coral Efflatounaria sp. nov.
Authors: Burns KP , Englert G , Kazlauskas R , Murphy PT , Schonholzer P , Wells RJ
Published: September 2010

The structure of a diterpene with a new bicarbocyclic
ring skeleton has been solved by analysis of the 400-MHz 1H n.m.r.
spectrum, and confirmed by a single-crystal X-ray analysis.
Photolysis of cerium/thallous solutions. Enhanced reduction rate in the presence of titanium dioxide
Authors: Matthews RW
Published: September 2010

Aqueous suspensions of
titanium dioxide (anatase) in dilute sulfuric acid
solution containing ceric and thallous
ions have been photolysed. The presence of TiO2
enhances the reduction rate by at least 40%. The observations are consistent
with the formation of an additional yield of oxidizing radicals in the presence
of the TiO2 which react with the same characteristics as the
hydroxyl radical. The additional oxidizing radicals generated in the presence
of TiO2 cannot be formed via hydrogen peroxide as an intermediate.
A reinvestigation of the reaction between Prop-2-en-1-ol and chloramine-T in hydrochloric acid medium
Authors: Herlihy KP
Published: September 2010

Contrary to a previous
report the reaction of prop-2-en-1-ol with chloramine-T
in 1 M HCl gives 2,3-dichloropropan-1-ol not
prop-2-en-1-al. For HCl concentrations of 0.075 M and
higher the reaction is of first order each with respect to the concentration of
chloramine-T, H+ and Cl- ions,
but independent of the alcohol. As chloroamines in
these conditions are known to give chlorine, it is proposed that the reaction
involves the addition to the unsaturated alcohol of molecular chlorine which is
produced by a prior, rate-determining reaction between H+ and Cl-
ions with chloramine-T.
Phenylimido complexes of tungsten(VI) and tungsten(V). The crystal and molecular structure of Trichloro(phenylimido)bis(trimethylphosphine)tungsten(V)
Authors: Nielson AJ , Waters JM
Published: September 2010

Tetrachloro(phenylimido)tungsten(VI)
is reduced by trimethylphosphine in tetrahydrofuran
solution to give the tungsten(V) complex PhNWCl3(Pme3)2
in which the phenylimido multiple bond remains
intact. The complex reacts with oxygen to form the phosphine oxide complex PhNWCl3
(OPMe3)2. Pyridine and alkyl cyanides do not reduce
tetrachloro(phenylimido)tungsten(V1)
but give the adducts PhNWCl4.L (L = py, MeCN, EtCN). The crystal and
molecular structure of the title complex has been determined from single-crystal
X-ray diffractometer data. The crystals are monoclinic with a 14.903, b 10.221, c 14.380Š β 116.05�, space group P21/c,
Z 4. The structure has been solved by Patterson and Fourier methods and refined
to R 0.030 for the 1566 observed data. Distorted octahedral coordination
geometry is found with two trans trimethylphosphine and two trans chloride ligands; a third chloride is trans to the phenylimido group. The W-N(imido) bond length is 1.731 �.
The stability of allylic and vinylic deuterium atoms during the lithium/ammonia reduction of some styrenoid systems
Authors: Collins DJ , Molinski TF , Sjovall J
Published: September 2010

Reduction of
2-(p-methoxyphenyl)cyclohexan-1-one (8) with lithium aluminium deuteride
followed by acetylation gave trans-l-acetoxy-2-(p-methoxyphenyl)(1-2H1)cycohexane
(10b). Base-catalysed deuteration of 2-(p-methoxypheny1)cyclohexan-1-one (8)
afforded the corresponding trideuterated ketone (11a) which upon hydride
reduction and acetylation yielded trans-1-acetoxy-2-(p-methoxy-
phenyl)(2,6,6-2H3)cyclohexane (15b). Pyrolysis of the
acetate (10b) at 600�/1.0 mm gave 1-(p-methoxyphenyl)(2-2H1)cyclohex-1-ene
(16) which was separated from the unconjugated isomer (13) by preparative g.l.c.
1-(p-Methoxyphenyl)(3,3-2H2)cyclohex-1-ene (18) was
similarly obtained by pyrolysis of the trideutero acetate (15b).
Lithium/ammonia reduction of the deuterated styrenoid compounds (16) and (18)
proceeded in each case without any detectable loss or redistribution of the
deuterium atoms.