bluuebunny/crossref_metadata_2025 huggingface dataset:
Electron impact studies. CVIII. Negative-ion mass spectra of the oxime group
Authors: Bowie JH , Janposri S
Published: September 2010

Molecular anions derived
from Ar-CH=NOH systems fragment by the process [MI-
→ [M-H2O]- to yield pronounced peaks corresponding to [ArCN]-. Molecular anions from Ar(CH2)nC(NOH)Ph (n = 0-2) also eliminate H2O,
but the mechanisms are often complex. Possible mechanisms for some of these
eliminations are suggested after consideration of the + E spectra of
non-decomposing [M?H2O]- ions. A characteristic cyclization/retro
process of o-O2NC6H4-CH=CH-C(NOH)R molecular
anions produces CHO-CR=N-O- as the major product anion.
The application of the Hammett equation to 13C N.M.R. spectroscopy: correlations in the β-nitrostyrenes
Authors: Happer DAR
Published: September 2010

A series of 33 β-nitrostyrenes
has been prepared and their 13C N.M.R. spectra have been determined
in dimethyl sulphoxide and in deuterochloroform (where soluble). Hammett
correlations between substituent and the chemical shift of both the para ring
carbons and the α-carbon of the ethenyl group have been shown to be only
approximate. In contrast, an excellent correlation has been observed between
the chemical shift of the β-carbon of the ethenyl group and Hammett σ+
constants in all cases except those involving para substituents capable of
exerting a - R effect. Possible reasons for this are considered. The system
appears to be the first reported one where 13C measurements for both
meta- and para-substituted compounds give rise to correlations in which agreement
lies well inside the limits of experimental error, and shows promise as a
convenient method for calculating substituent constants and studying their
variation with solvent.
Reactions of π-allylpalladium compounds with 1,3-dipolar species
Authors: Ashraf MC , Burrowes TG , Jackson WR
Published: September 2010

Reactions of π-allylpalladium
compounds with the 1,3-dipolar species, benzonitrilioanilide and benzonitrile
N-oxide, give low yields of five- membered ring heterocyclic compounds. It is
proposed that the π- allylpalladium compounds decompose to give allylic
halides which then react with the dipolar species to give heterocyclic
products.
Electron impact studies of 4a-Methyl-4,4a-dihydrophenanthren-2(3H)-one and related phenanthrones
Authors: Njau E
Published: September 2010

The mass spectra of
4a-methyl-4,4a-dihydrophenanthren-2(3H)-one and closely related phenanthrenones
have been studied. The suggested fragmentation processes, substantiated by
high-resolution mass measurements and appropriate metastable peaks, are shown
to be characteristic of compounds with the same hydro-oxo-phenanthrene
chromophore. 2-Cinnamylidene-6-methyl-cyclohexanone possessing a similar
chromophore is also shown to exhibit a comparable fragmentation pattern.
The thermal decomposition of alkali metal chlorochromates, MCrO3Cl
Authors: Foster JJ , Hambly AN
Published: September 2010

A systematic study of the
thermal decomposition of potassium chlorochromate, KCrO3Cl, has been
made, and less complete studies with the corresponding lithium, rubidium and
caesium compounds. Three major processes occur, characterized by the formation
of chromyl chloride, the mixed oxides, MCr308, and of
chromium(III) oxide. In each case there is simultaneous production of
dichromate and alkali chloride. ��� Chromyl chloride formation increases with
rising temperature but decreases as the cationic radius increases. It is the
major reaction when KCr3OCl is heated under vacuum at 400°C. Decomposition
with the formation of M2Cr2O7 and MCr3O8
in equimolar amounts occurs below the melting point of KCrO3Cl, but,
as the temperature of decomposition is raised, a reaction producing these
products in the molar ratio 1 : 2 becomes more important. In the presence of
air and alkali halide MCr3O8 can oxidize slowly to form
dichromate, or at higher temperatures decompose to dichromate, chromium(III)
oxide and oxygen. It can also react with alkali halide to form dichromate,
chlorochromate and chromium(III) oxide. Decomposition with the formation of
chromium(III) oxide is a secondary reaction involving the preliminary formation
of MCr3O8 or chromyl chloride. ��� The temperatures and enthalpy increases for
the solid state transitions and the fusion of KCrO3Cl, RbCrO3Cl
and CsCrO3Cl are reported.
The Lewis-acidity of square-planar nickel(II) complexes. II. A kinetic investigation of the addition of substituted phenanthrolines to Bis(O,O-diethylphosphorodithioato-S,S')nickel(II), Bis(O-ethylxanthato)nickel(II) and Bis(4-mercaptopent-3-en-2-onato)nickel(II) in toluene
Authors: Fayyaz MU , Grant MW
Published: September 2010

The rates of the addition
reaction between substituted phenanthrolines and the square-planar nickel
complexes bis(O,O-diethyl phosphorodithioato-S,S')nickel(II),
Ni(dtp)2, bis(O-ethylxanthato)-nickel(II), Ni(xan)2, and
bis(4-mercaptopent-3-en-2-onato)nickel(II), Ni(sacac)2,
have been measured in toluene by the stopped-flow technique. For Ni(xan)2, the second-order rate constants, kf,
are in the range (1- 8)×105 l. mol-1 s-1,
ΔHf‡ is 16�2 kJ mol-1 and there is a
significant substituent effect. For Ni(dtp)2,
kf is (1-3)×104 l. mol-1 s-1,
ΔHf‡ is 24�2 kJmol-1 and there is a minor
substituent effect. For Ni(sacac)2, kf
is about 5‡102 l. mol-1 s-1, ΔHf‡
is 50 kJ mol-1 and there is no substituent effect. The results are
discussed in terms of the relative importance of Ni-N bond formation and
displacement of the in-plane ligands in the transition state.
Synthesis of 2-Oxo-3-phenylimidazolidine-1-carbonyl chloride
Authors: Maclaren JA
Published: September 2010

The reaction of phosgene
with N-methyl-N-phenylethane-1,2-diamine, with N-phenylethane-1,2-diamine and with
1-phenylimidazolidin-2-one, gives in each case 2-oxo-3-phenylimidazolidine-1-carbonyl
chloride. This acid chloride reacts with ammonia to form 1,1'-carbonylbis(3- phenylimidazolidin-2-one).
Reactions of N-Aryl-4-chlorobenzamides in sulphuric acid
Authors: O'Conner CJ , Ramage RE
Published: September 2010

Rate constants of reaction
of 4-chloro-N-phenylbenzamide at 353 and 373 K, and of
N-benzyl-4-chlorobenzamide at 373 K have been studied in aqueous sulphuric
acid. The rate acidity profiles in <40% w/w H2SO4 show
the typical bell shape normally observed for the A2 hydrolysis of amides. However,
with increasing acidity there is competition from sulphonation on the N-aryl
substituent and subsequent A 2 hydrolysis of the sulphonated intermediates. At
>75% w/w H2SO4, sulphonated 4-chloro- N-phenylbenzamide is charred. At >52% w/w H2SO4,
sulphonation of N- benzyl-4-chlorobenzamide ceases and is replaced by A 1
hydrolysis of the substrate.
Iron complexes of pyridylimidazole derivatives
Authors: Baker AT , Goodwin HA
Published: September 2010

Complexes of iron(II) with
2-(2-pyridyl)benzimidazole (pbi) and 2-(6-
methyl-2-pyridyl)benzimidazole (mpbi) have been
characterized. [Fe(pbi)3] [BF4]2
undergoes a temperature-induced spin transition the course of which is
determined by the extent of hydration. [Fe(mpbi)3]
[ClO4]2 is high-spin and the differences in the
properties of the two complexes are correlated with electronic spectral data.
[Fe(pbi)2(CN)2] is low-spin. Iron(III)
complexes of deprotonated pbi and 2-(2- pyridyl)imidazole (pyim), [Fe(pbi-H)3] and [Fe(pyim-H)3],
result when the cationic iron(II) complexes are treated with base. Magnetic and
Mossbauer effect data show that these complexes, which display strong π
→ t2 charge-transfer absorption, are low-spin.
Electron impact studies. CXIII. Aromatic nucleophilic substitution in the gas phase. The dinitrobenzenes. An ion cyclotron resonance study
Authors: Bowie JH , Stapleton BJ
Published: September 2010

The negative ion mass
spectra derived from the three dinitrobenzenes show NO2-,
[M-?-NO?]- and M-? as major ions.
The i.c.r. spectrum of o- dinitrobenzene shows the
formation of the adducts [M+NO2-]-, [M+(M-?-NO?)-
]- and 2M-?, but the m- and p-dinitrobenzenes only
produce the adduct [M+NO2-]-. The nucleophile Cl- adds to each of the three dinitrobenzene neutrals
in the abundance ratio o >> m ≈ p. Evidence is presented which
suggests that the neutral products formed by the reaction between NO2-
and o-dinitrobenzene are dinitro- and trinitro-benzenes, whereas those resulting
from the interaction of Cl- with o-dinitrobenzene
are chloronitrobenzene and a chloro-dinitrobenzene.
Cyclophanes. VII. Naphthalene and phenanthrene cyclophanes for the synthesis of coronene
Authors: Jessup PJ , Reiss JA
Published: September 2010

A coupling reaction between
3,6-bis(bromomethyl)phenanthrene and p- xylene-α,α?-dithiol
gave 2,11-dithia[3,3](3,6)phenanthroparacyclophane
(4). Ring-contraction of the sulphonium salt (5)proceeded in low yield.
However, a corresponding dimethyl cyclophane (12) reacted efficiently togive the desired ring-contracted [2,2]cyclophane (13).
Wittig rearrangement of the cyclophane (4) gave a high yield of compound (7)
which in turn was oxidized to the disulphoxide (8). Thermal elimination of
methylsulphenic acid produced the diene (9) which could be photochemically
cyclized to coronene. A similar series of reactions with
2,13-dithia[3,3](2,7)naphthalenophane (14) was effected. Oxidation,
halogenation and photochemical reactions of both the naphthalene- and phenanthrene-based
cyclophanes are reported.
Thermodynamics of molecular association in binary methanol solutions
Authors: Singh PP , Sharma BR , Sidhu KS
Published: September 2010

This paper deals with
isothermal total vapour pressure measurements on methanol (B)+pyridine (A),
methanol (B)+β-picoline (A), methanol (B)+N,N-dimethylformamide (A) over
the whole range of composition at 303.15 K and the excess Gibbs free energies
are evaluated. The data have been analysed in terms of a r-mer-r-mer
model of interaction. The equilibrium constants for the various association
reactions are evaluated and the enthalpy changes ΔH�l involved
in the ABx and A2B molecular species of A and B have also
been computed.
Electron impact studies. CXV. Release of kinetic energy during negative ion decompositions. C-O bond cleavage reactions
Authors: Klass G , Bowie JH
Published: September 2010

Kinetic energy release
values T(50%) for the collision-induced formation of the p-nitrobenzoate and
p-nitrophenoxide anions from the molecular anions of p-O2NC6H4COOC6H4R-p
and p-O2NC6H4- OC6H4R-p
respectively are small and relatively insensitive to the nature of the
substituent R.T (50%) values for the elimination of R? (R = alkyl) from O2NC6H4OR
molecular anions range from 0.4 to 0.01 eV, and are dependent upon the nature
of R and upon its number of active oscillators.
Complexes of carbohydrates with metal cations. IX. Synthesis of the methyl D-tagatosides, D-psicosides, D-apiosides and D-erythrosides
Authors: Angyal SJ , Bodkin CL , Mills JA , Pojer PM
Published: September 2010

All the methyl glycosides
of the sugars mentioned in the title were synthesized by Fischer glycosidation
in the absence or in the presence of calcium chloride; addition of the salt
improved the yield of some of the furanosides. The glycosides were separated on
a cation-exchange resin in its calcium form. The anomeric equilibria of methyl
furanosides are discussed.
The kinetics and mechanism of the oxidation of mercaptoethanol by riboflavin
Authors: Holden JW , Main L
Published: September 2010

Kinetic study of the
oxidation of mercaptoethanol (RSH) by riboflavin (FlH)
over the pH range 8.5-10.5 establishes that the rate is given by the term
0.036[FlH][RSH][RS-]]2 mol-2
s-1, there being no buffer catalysis. Any reactivity of the N
3-ionized riboflavin species (Fl-) is sufficiently low to be
kinetically undetected. The kinetic form and lack of general acid catalysis are
consistent with a nucleophilic (thiolate) 4a-addition-elimination mechanism
previously proposed, but a possible alternative mechanism involving a flavin
semiquinone (radical) intermediate is suggested.
Depsidone synthesis. X. Methoxy- and Hydroxy-colensoic acids
Authors: Djura P , Sargent MV , Clark PD
Published: September 2010

The synthesis of the lichen
depsidones 8-hydroxy-3,4-dimethoxy-11-oxo- 1,6-dipenty1-11H-di-benzo[b,e][1,4]dioxepin-7-carboxylic acid (methoxycolensoic acid)
(1) and 4,8-dihydroxy-3-methoxy-11-oxo-1,6- dipentyl-11H-dibenzo[b,e][1,4]dioxepin-7-carboxylic acid (hydroxycolensoic acid)
(2) is described. An abortive attempt to synthesize depsidones of the lobaric
acid-type is also reported.
Metal complexes of thiosemicarbazide: Vibrational analysis of nickel(II) thiosemicarbazide complexes and their deutero isotopomers
Authors: Geetharani K , Sathyanarayana DN
Published: September 2010

The assignments of the
in-plane vibrations of the ionic and neutral nickel(II) thiosemicarbazide
complexes, Ni(Htsc)2Cl2 and Ni(tsc)2, and their deuterated molecules have been
made with the aid of normal coordinate treatments. The out-of-plane vibrations
have been assigned empirically. The results of the coordinate treatments have
been discussed by referring to the spectra of related molecules. The changes in
the infrared bands of thiosemicarbazide on complex formation are also
discussed.
Crystal structure of Hydroxyimino(N,N'-dimethyl)malonamide
Authors: Hall SR , Raston CL , White AH
Published: September 2010

The crystal structure of
the title compound, namely hydroxyimino(N,N?- dimethyl)malonamide (MeNHCOC(=NOH)CONHMe), has been
determined by single-crystal X-ray diffraction with diffractometer data at 295
K. The structure was solved by direct methods and refined by least squares to a
residual of 0.055 for 1477 observed reflections. ��� Crystal data: monoclinic, P21/n,
a 15.508(3), b 10.544(2), c 9.377(1) Ǻ, β 103.15(2)�, Z 8. ��� The two crystallographically independent
molecules exhibit little conjugation throughout the C-C-C skeleton (
1.50 Ǻ), the molecule being non-planar.  is 1.234,
 1.443,  1.323,
1.278 and (N-O) 1.375 Ǻ. The geometry is compared
with those observed for several related derivatives.
Crystal structure of Iodobis(1,10-phenanthroline)copper(II) iodide octasulphur
Authors: Hambley TW , Raston CL , White AH
Published: September 2010

The crystal structure of
the title compound, [Cu(C12H8N2)2I]I,S8,
has been determined by X-ray diffraction at 295(1) K and refined by least
squares to R 0.066 (2031 ?observed? reflections). ��� Crystal data: orthorhombic, Pbcb, a 7.984(5), b 16.690(4), c 22.986(12) Ǻ, Z 4. ��� The structure comprises five-coordinate
trigonal bipyramidal [Cu(phen)2I]+ cations
(I equatorial) lying on the 2 axes parallel to a which pass through the Cu-I
bonds, together with iodide anions, and lattice S8 molecules, also
lying on 2 axes but parallel to b. In the cation, Cu-I is 2.672(3), Cu-N
(equatorial) 2.10(1) and Cu-N (axial) 2.00(1) Ǻ. S-S ranges from 2.004(7)
to 2.059(7). There appears to be no significant interaction between the
octasulphur molecules and any other species.
Analysis of oxidized layers on pyrite surfaces by X-ray emission spectroscopy and cyclic voltammetry
Authors: Michell D , Woods R
Published: September 2010

X-Ray emission
spectroscopic analysis of the surface of the iron sulphide mineral, pyrite, has
demonstrated the presence of an oxygen- containing layer. Differences between
the quantity of oxygen detected after grinding the pyrite on 600 grade silicon
carbide paper and polishing it to the 10 μm or
0.25 μm diamond stage are considered to be due
to differences in surface roughness. Triangular potential sweep voltammograms
display current peaks which have been identified with the oxidation and
reduction of the oxide layer between iron(II) and iron(III) valence states. The
quantities of oxide on the surface determined from the charge passed on a
potential sweep correlate with the X-ray emission measurements for the three
surface preparations.
Electrochemical synthesis of amino acids by reductive amination of keto acids. I. Reduction at mercury electrodes
Authors: Jeffery EA , Meisters A
Published: September 2010

Racemic
2-amino-2-phenylacetic acid, monoammonium glutamate, 2-aminobutyric
acid, α-alanine and ammonium 5-amino-5-phenylvalerate have been prepared
by electrochemical reductive amination of the corresponding keto acids in
aqueous ammonia/ammonium chloride solution at a mercury electrode. The yields
ranged from 24% for ammonium 5-amino-5-phenylvalerate to 88% for
2-amino-2-phenylacetic acid. The current efficiency and yield of
2-amino-2-phenylacetic acid from reductive amination of 2-oxo-2-phenylacetic
acid increased with increase in ammonia concentration. Also, decreasing the
reduction potential from -1.10 to -1.30 V (with respect to a saturated calomel
electrode) in 2 M ammonia raised the initial current density from c. 2 mA/cm2
to c. 7 mA/cm2 but halved the yield of 2-amino-2-phenylacetic acid.
Studies of Australian soft corals. IV. A novel bicyclic diterpene from Lobophytum hedleyi
Authors: Bowden BF , Coll JC , Liyanage N , Mitchell SJ , Stokie GJ , Altena IAV
Published: September 2010

A new bicyclic diterpene,
(3E,5E)-2-methyl-6-[(2'R*,4a'S*,8a'R*)-4a'-methyl-8'-methylene-trans-perhydronaphthalen-2'-yl]hepta-3,5-dien-2-ol
(1), is reported as the major terpenoid component from Lobophytum hedleyi. It
represents the first non-cembranoid diterpene to be reported from soft corals. A
minor component in the coral is tentatively identified as the 7-hydroxy
derivative of (1). Evidence for the structure of (1) is mainly spectroscopic
but final proof rests on degradation and conversion into a known compound.
The synthesis and preliminary biological testing of some bicyclic guanidine derivatives
Authors: Freeman CG , Turner JV , Ward AD
Published: September 2010

Condensation of
2-amino-2-imidazoline with α,β-unsaturated
esters yields an imidazo[1,2-a]pyrimidin-7-one system whereas reaction with an
acetylenic ester or β-keto esters gives the corresponding unsaturated
imidazo[1,2-a]pyrimidin-5-one product. In some cases a non-cyclized product is
obtained under milder reaction conditions. Cyclization of ω- (imidazolin-2-ylamino)
acids yields fused bicyclic products for the acetic and propionic acid
derivatives whereas the butyric acid analogue cyclizes to yield an N-substituted
pyrrolidone. Representative examples of all these compounds do not show
mutagenic properties in a modified Ames test and are mainly inactive when
tested for central nervous system activity.
Enthalpy of the isotopic exchange reaction H2O + D2O → 2HDO
Authors: Fenby DV , Chand A
Published: September 2010

The enthalpy of the
reaction
������������������������ H2O(l)+D2O()
→ 2HDO(l)
at 298 K is calculated from
the statistical-mechanical enthalpy of the corresponding gas-phase reaction and
recent vapour-pressure isotope effect results. Enthalpies of the same reaction
obtained from calorimetric results by assuming that the H2O + HDO +
D2O liquid mixture is an ideal solution agree, to within the
estimated uncertainities, with the calculated value. It is concluded that any
'physical' contributions are less than 20% of the measured enthalpy changes.
Molar excess enthalpies of D2O(l)+H2O(l) at 298.15 K are
reported and compared with earlier studies. Enthalpies of reaction obtained
from our excess enthalpies show a systematic variation with mole fraction.
The infrared matrix isolation spectra of ND3 and NH3 in an argon matrix in the v2 bending region
Authors: Cugley JA , Liberts S , Pullin ADE
Published: September 2010

The spectra of NH3
and ND3 in an argon matrix have been obtained in the v2
(bending fundamental) region. The v2 region of ND3 has
been interpreted in terms of a gas-phase model, with slightly altered
rotational constants. Thus for the matrix an effective value of (B'+B') = 9.85
is required compared with 10.25 cm-1 for the gas phase. This
represents a smaller fractional change than for NH3. The inversion
splitting of ND3 in the argon matrix has been clearly resolved and a
value of 2.0�0.1 cm-1 deduced. However, there are extra lines in the
spectrum of ND3 which we cannot assign on the basis of a gas-phase
model. For NH3 some vib-rotor 'lines' have
been shown to be composite, in particular Q(11+) and Q(11-)
are close triplets.
Mononuclear oxo thiolato compounds of molybdenum(V)
Authors: Boyd IW , Dance IG , Murray KS , Wedd AG
Published: September 2010

The intensely blue salts B+
[MoO(SAr)4]- (B+ = quaternary cation; Ar =
phenyl, p-tolyl) have been isolated. Magnetic susceptibility, e.s.r.,
conductance and electronic spectral data indicate that the complexes are
essentially mononuclear both in the solid state and in solution. The solution
electronic spectra exhibit an intense maximum at 598 nm, which is tentatively
assigned to a sulphur-to-molybdenum charge- transfer transition.
Activity coefficients in the system NaCl-DL-Alanine-H2O at 298.15 K from E.M.F. measurements
Authors: Phang S
Published: September 2010

The activity coefficients
of NaCl in the ternary system NaCl-DL-
alanine-H2O have been measured at 298.15 K by the e.m.f. method with
sodium-ion-selective glass electrodes. Measurements were made over the concentration
range 0.1-6.0 mol kg-1 NaCl and 0.1-1.0
mol kg-1 DL- alanine. The dipole moment of DL-alanine was found to
be 12.3 D from Kirkwood's equations. The difference in behaviour between
DL-alanine and β-alanine in a similar system is also discussed.
Crystal structure of Tris(pyrrolidine-1-carbodithioato)iron(III)
Authors: Mitra S , Raston CL , White AH
Published: September 2010

The crystal structure of
the title compound, [Fe{CS2N(CH2)4}3]
(a new phase prepared from chloro-form/toluene solutions), has been determined
by single-crystal X-ray diffraction at 295 K and refined to a residual of 0.059
for 5651 'observed' reflections. Crystals are monoclinic, P21/a, a
18.033(6), b 9.398(2), c 13.176(6) Ǻ, β 100.80(3)°, Z 4. The compound
is a purely high-spin derivative, the iron atom being in the usual pseudo-D3
environment with  very long (2.456 Ǻ).
Crystal and molecular structure of polymeric MeSHgO2CMe and MeSHgO2CMe,C5H5N and the tetranuclear complex (ButS)4Cl4Hg4(C5H5N)2
Authors: Canty AJ , Raston CL , White AH
Published: September 2010

Crystals of methanethiolatomercury(II) acetate are monoclinic, P 21/c,
with a 5.292(2), b 15.912(7), c 7.086(2) Ǻ, β 92.96(3)°, Z 4, and its
pyridine complex MeSHgO2CMe,C5H5N is
monoclinic, P21/n, with a 10.093(3), b 7.026(2), c 15.350(5) Ǻ,
β 105.01(3)°, Z4. Both structures are based on a polymeric chain (-Hg-SMe-)n with coordinated acetate groups. In
MeSHgO2CMe the chains are linked into sheets by bridging acetate
groups, and in the pyridine complex the chains are isolated with pyridine and
acetate coordination at each mercury. Crystals of (ButS)4Cl4Hg4(C5H5N)2
are triclinic, Pī, with a 14.399(6), b 9.893(6),
c 9.597(5) Ǻ, α 121.82(1), β 102.52(4), γ 102.94(4)°, and Z
1. The structure is based on a tetranuclear grouping of mercury atoms bridged
by chloride and thiolate species and centrosymmetric about the origin. There
are two mercury environments 'Hg(μ-SBut)2ClN'
and 'Hg(μ-SBut)2(μ-Cl)2' with the dichloro bridge linking two
equivalent mercury atoms on opposite sides of an (-Hg-SBut-)4
ring.
Long range proton-proton coupling in endo-3,4-Disubstituted bornanones
Authors: Brown FC , Fraser RK , Jemison RW , Morris DG , Murray AM , Stephen JD
Published: September 2010

The coupling constant 4Jexo.H
3exo-H 5 of 3,4-disubstituted bornanones increases or decreases depending
on the point of attachment of substituents.
Volatility studies of metal chelates. III. Thermal and gas chromatographic properties of the volatile copper(II) and nickel(II) chelates of the isomeric tetradentate β-keto enamines formed in the reaction of 1,1,1-Trifluoro-5,5-dimethylhexane-2,4-dione with Ethane-1,2-diamine
Authors: Dilli S , Patsalides E
Published: September 2010

The Schiff base,
6,6,6,6',6',6'-hexafluoro-2,2,2',2'-tetramethyl-5,5'-(ethane-1,2-diyldiimino)bis(hex-4-en-3-one),
as normally prepared by the condensation of
1,1,1-trifluoro-5,5-dimethylhexane-2,4-dioneand ethane-1,2-diamine is only one
of two isomeric forms which give distinct isomers with copper(II)and nickel(II),
readily separated on columns of silica gel. The isomeric chelates have large
volatility differences and display greater volatility than other tetradentate
β- keto enamine complexes. The excellent gas chromatographic behaviour of
the chelates leads to detection limits of about 2 picograms metal with the
electron-capture detector.
Temperature dependence of chlorine-35 N.Q.R. in 2,6-Dichlorophenol
Authors: Chandramani R , Basavaraju SP , Devaraj N
Published: September 2010

Chlorine n.q.r, in 2,6-dichlorophenol has been investigated at
temperatures from 77 K to room temperature. Two resonance lines due to
chemically inequivalent sites have been observed throughout this temperature
range. Torsional frequencies of the molecule have been calculated at
temperatures from 77 to 300 K according to Bayer's theory and Brown's method.
Also the temperature coefficients of the torsional frequencies have been
calculated.
Proton-deuterium isotope shifts in 59Co N.M.R.
Authors: Bendall MR , Doddrell DM
Published: September 2010

An isotope shift of 5 ppm per deuterium atom has been observed for the 59Co
resonance of tris(ethylenediamine)cobalt(III) chloride ([Co(en)3]Cl3)
and hexaamminecobalt(III) chloride([Co(NH3)6]Cl3)
after exchange of hydrogen for deuterium. The upfield direction of the shift
can be readily understood as changes in the ligand-field strength causing
changes in the nuclear paramagnetic screening.
Preparation and characterization of hexamethylenetetramine N-oxide and some acid adducts
Authors: Lam Y , Mak TCW
Published: September 2010

Hexamethylenetetramine N-oxide (4) was isolated from the reaction of hexamethylenetetramine (1)
with 30% aqueous hydrogen peroxide. With the two reactants in molar ratio 1 : 2, a 1 : 1 : 1
crystalline adduct (5) of (4) with hydrogen peroxide and water was obtained at temperatures around
10°C, and a 1 : 1 adduct (6) of (4) with formic acid upon warming the reaction mixture to above 30°C.
Information pertaining to the nature of compounds (4), (5) and (6) was derived from p.m.r, and
X-ray determination of unit cells and space groups. Several 1 : 1 acid adducts similar to (6) were
prepared by adding the corresponding acid to an ethanolic solution of (4).
Depsidone synthesis. XII. Some exploratory synthetic routes to highly functionalized depsidones
Authors: Sala T , Sargent MV
Published: September 2010

Attempts to synthesize the
depsidones virensic acid (1), physciosporin (2), and pannarin (3) by routes
based on the Ullmann ether condensation and the Hems
reaction are described. Selective functionalization of highly substituted
p-xylenes by photobromination is reported.
Pyrimidine reactions. XXVII. Syntheses, reactivities and mass spectra of some 2-isopropylpyrimidine derivatives
Authors: Brown DJ , .Waring P
Published: September 2010

Syntheses of
2-(1'-bromo-1'-methylethyl)-4-chloropyrimidine (1c) and its 4-fluoro analogue
(1f) are described. Rates for solvolysis of these and similar bromo compounds
in 50% aqueous methanol at pH 7.0 are recorded at several temperatures. These
data and some unusual facets of the mass spectra shown by 2-isopropylpyrimidines,
and their α-bromo or α-methoxy derivatives, are discussed.
Carbonyl halides of the Group VIII transition metals. VII. Reactions of palladium(I) halocarbonyls with Bis(diphenylphosphino)methane and Bis(diphenylarsino)methane and the crystal and molecular structures of these derivatives
Authors: Colton R , McCormick MJ , Pannan CD
Published: September 2010

The reactions of Pd(CO)X (X
= Cl, Br) with bis(diphenylphosphino)methane (dpm) and its arsenic analogue, dam, have been investigated.
The iodo complexes were prepared indirectly. Ligand dpm gives complexes of the formula [Pd(dpm)X]2.
With dam, the nature of the product depends upon the identity of the halogen;
with X = Cl, Br the products are [Pd(dam)X]2CO,
but the iodo derivative is [Pd(dam)I]2.
N.m.r. spectroscopy suggests that [Pd(dam)I]2 has a structure
different to the dpm complexes. ��� [Pd(dam)Cl]2CO,3C6H14
is tetragonal, space group P4I, a 22.0458(1), c 14.4345(1) Ǻ
containing four dimer units per unit cell. The structure was refined to R 0.096
and Rw 0.097 for 1698 independent reflections. The crystals are
molecular being composed of discrete dimeric molecules of the complex and
solvent. The palladium coordination is approximately square planar with two
trans arsenic atoms, terminal halogen and the bridging carbonyl group which is
common to both metal environments. There is no twist about the Pd-Pd axis so
the Pd,As, unit is planar. The Pd-Pd distance of
3.274(8) Ǻ is too long for a direct metal-metal bond. However, the
compound is diamagnetic so spin pairing must occur through the unusual carbonyl
bridge.
The Lewis-acidity of square-planar nickel(II) complexes. III. A kinetic study of the effects of substituents on the addition of 1,10-Phenanthroline to Bis(monothioacetylacetonato)nickel(II) and Bis(dithiophosphato)nickel(II) complexes in toluene
Authors: Fayyaz MU , Grant MW
Published: September 2010

The second-order rate
constants and activation parameters for the addition of 1,10-phenanthroline to bis(dialkyldithiophosphato)nickel(II) complexes and substituted
bis(monothioacetylacetonato)-nickel(II) complexes in
toluene have been measured. Rate constants are in the range 102-108
1. mol-1 s-1 at 25°C, while ΔH‡ is in the
range 10-50 kJ mol-1 and ΔS‡ is in the range from
-30 to -110 J mol-1 K-1. The higher rate constants,
smaller ΔH‡ and more negative ΔS‡ values are associated
with complexes with electron- withdrawing substituents. The results are related
to the thermo- dynamics of adduct formation, the inductive effects of the
substituents and the pKa of the ligands.
Annellation of tricarbonylcyclobutadieneiron to the cycloheptatrienyl (tropylium) cation and to Cyclohepta-2,4,6-trienone (tropone). Synthesis of some derivatives of (1,7,8,9-η-Bicyclo[5,2,0]nonatetraene)tricarbonyliron
Authors: Stringer MB , Wege D
Published: September 2010

The compounds
(1,7,8,9-η-bicyclo[5,2,0]nonatetraenyl hexafluorophosphate)tricarbonyliron
(9), (1,7,8,9-η-bicyclo[5,2,0]nona- 1(7),2,5,8-tetraen-4-one)tricarbonyliron
(10), and (1,7,8,9-η-bicyclo- [5,2,0]nona-1(7),3,5,8-tetraen-2-one)tricarbonyliron
(11) have been prepared. The cation (9) undergoes nucleophilic capture at C2,
the position α to the coordinated cyclobutadiene ring. Oxidative removal
of the tricarbonyliron group from the symmetrical tropone derivative (10)
generates bicyclo-[5,2,0]nona-1(7),2,5,8-tetraen-4-one, which can be trapped as
a Diels-Alder adduct with cyclopentadiene.
Colour effects with the Nitrobenzyll Esters of Dimethylaminobenzoic acids
Authors: Stewart FHC
Published: September 2010

Nitrobenzyl esters of
dimethylaminobenzoic acids are strongly coloured in the solid state but not in
solution. The operation of electron donor-acceptor interaction within the
crystal lattice is indicated. One of the compounds, o-nitrobenzyl
m-dimethylaminobenzoate, formed two differently coloured polymorphic
modifications.
Conformational analysis of coordination compounds. IX. 1H N.M.R. study of diamagnetic complexes of (R)-1-Phenylethane-1,2-diamine
Authors: Hawkins CJ , McEniery ML
Published: September 2010

The conformational analyses
of the complexes [Co(CN)4L]-, [Co(NH3)4L]3+,
[Mo(CO)4L], and [PtL2]2+, where L is
(R)-1-phenylethane-1,2-diamine, have been carried out by a method based on the
vicinal proton coupling constants of the CHCH2 fragment. In the three
octahedral complexes, the phenyl showed a similar preference for the equatorial
orientation with nλ values of 0.87�0.05, 0.84�0.11, and 0.77�0.01,
respectively. For the bis(diamine)platinum(II) complex, the λλ
and δλ configurations were found to be equally
populated, with the δδ configuration 3.4 kJ
mol-1 less favoured.
The anodic oxidation of hydrogen on sodium tungsten bronzes
Authors: Smith JH , Fredlein RA
Published: September 2010

The anodic oxidation of
hydrogen has been studied on Na0.72WO3 electrodes in H2SO4
solutions over the potential range 0.35-1.34 V (s.h.e.).
Only one mechanism, which involves the rate-determining dissociation (H2(ad)→2H(ad))
with Temkin adsorption of H2, has been
found to be consistent with the experimental data.
The crystal and molecular structure of 1α,9β-Dichloro-2,2,10,10-tetramethoxy[2,2](2,6)pyridinophane
Authors: Taylor D
Published: September 2010

Crystals of the title
compound, C18H20Cl2N2O4,
are monoclinic, a 14.706(1), b 17.168(1), c 7.269(1) Ǻ, β 92.72(1)°,
space group P21/c with Z = 4. The structure was solved from
diffractometer data by direct methods. Block-diagonal least-squares refinement
converged at R 0.037, Rw 0.045 for 2103 reflections with I ≥
3σ(I) which had been corrected for absorption (μ 34.0 cm-1).
The asymmetric unit is comprised of two independent half-molecules, each
molecule being centrosymmetric. The pyridine rings are distorted from
planarity, with a maximum deviation of 0.10 Ǻ at the nitrogen atoms, as a
consequence of the short intramolecular N...N contacts of 2.476(4) and 2.473(5)
Ǻ.
Colouring Matters of the Aphidoidea. XLIV. A Survey of Long-Chain Acid Derivatives From Aphid Lipids Compared With Those of Related Insects. Glycerides of Octa-2,4,6-Trienoic Acid
Authors: Addae-Mensah I , Cameron DW
Published: September 2010

A comprehensive survey of
lipids representing all families of the Aphidoidea and several related families
supports the chemotaxonomic separation of aphids and coccids from the remainder
of the Hemiptera. Aphid glycerides are based chiefly
on myristate, palmitate and sorbate as noted earlier; octa-2,4,6-trienoate
residues are reported for the first time.
Crystal structure of fac-Tris(pentane-2,3,4-trione 3-oximato)cobalt(III)
Authors: Figgis BN , Raston CL , Sharma RP , White AH
Published: September 2010

The crystal structure of
the title compound has been determined by single-crystal X-ray diffraction at
295 K and refined by least squares to a residual of 0.058 for 2363 'observed'
reflections. Crystals are triclinic, Pī, Z 4, a
15.517(8), b 11.772(7), c 11.282(7) Ǻ, α 112.10(4), β 94.80(3),
γ 90.60(4)°. | distances are 1.883, 1.925
Ǻ respectively, the disposition of the three bidentate ligands within each
of the two independent molecules being fac.
Radical reactions of p-nitrobenzylidene halides with aci-nitronate ions
Authors: Freeman DJ , Norris RK , Woolfenden SK
Published: September 2010

The radical SRN1
and subsequent ERC1 reactions of p-nitrobenzylidene dibromide (2b)
and bromide chloride (2c) with the lithium salt (1a) and the tetrabutylammonium
salt (1b) (under phase-transfer conditions) of 2-nitropropane are discussed and
compared with the reactions of the dichloride (2a). The SRN1 and ERC1
sequence occurs in rapid succession in the reaction of (2b), in contrast to the
reactions of (2a) and (2c) which give isolable amounts of the SRN1
product, p-NO2C6H4CH(Cl)-CMe2NO2
(3a). The monobromide p-NO2C6H4CH(Br)CMe2NO2
(3b) cannot be detected in the SRN1-ERC1 sequence
leading from (2b) to β,β-dimethyl-p-nitrostyrene
(5). The ERC1 reaction of the monobromide (3b) is also studied and
shown to take place more slowly than the combined SRN1-ERC1
sequence for (2b). ��� The phase-transfer technique is shown to be
a convenient method for the preparation of C-alkylated derivatives like (3a),
but not (3b), in both-the o- and p-nitrobenzylic systems. The dibromide p- NO2C6H4CH(Br)CMe2Br
(7) was shown to undergo competitive ERC1 and E2(H) reactions with
(1a) to give the styrene (5) and p-NO2C6H4C(Br)=CMe2
(8) respectively. Iodide ion reacts with (7) to give the styrene (5) by an
E2(Br) mechanism at a rate which is several orders of magnitude slower than the
radical process. Alkoxide ions gave E2(H) reactions on dibromide (7) and
monochloride (3a) with elimination of the elements of hydrogen bromide and
nitrous acid respectively. The catalytic effect of white light, the inhibitive
effect of oxygen and p-dinitrobenzene, and the effect of concentration on the
radical processes are discussed.
A low-temperature matrix isolation infrared study of the interaction between phosphine and zerovalent copper, nickel and chromium
Authors: Bowmaker GA
Published: September 2010

The infrared spectrum of
the matrix produced by co-deposition of copper vapour with neat phosphine at 60
K showed new bands at c. 2245, 1057, 1005, 997, 593 and 512 cm-1.
These bands shifted to 1635, 766, 742, 733, 450, 370 cm-1 when PD3
was used in place of PH3. When nickel or chromium were used in place
of copper, new bands were observed at 2280, 1004 cm-1 and 2250, 1025
cm-1 respectively. The infrared spectrum of the matrix produced by
co-deposition of copper vapour with a dilute mixture of phosphine in krypton at
12 K showed new bands at 2250, 970, 968 and 958 cm-1. Experiments
involving variation of the PH3 : Kr ratio and replacement of PH3
by a 1 : 1 PH3/PD3 mixture suggest that the latter three
bands are due to Cu(PH3)n with n = 1, 3 and 2 respectively.
A redetermination of the crystal structure of 'Thorium(IV) Tetrakis(trifluoroacetylacetonate)': Stereochemistry of the system [M(bidentate ligand)4(unidentate ligand)x±
Authors: Hambley TW , Kepert DL , Raston CL , White AH
Published: September 2010

The structure of '[Th(CF3COCHCOCH3)4]' has
been redetermined from diffractometer data and shown to be [Th(CF3COCHCOCH3)4(H2O)].
The stereochemistry is in agreement with that determined for the [M(bidentate
ligand)4(unidentate ligand)]x� system by a calculation
based on a repulsion model.
Kinetic Resolution in the Reaction of (2R,3R)-2,3-Diacetoxy- and (2R,3R)-2,3-Dibenzoyloxy-succinic Anhydrides with Racemic Alcohols
Authors: Bell KH
Published: September 2010

The stereoselectivity in
the reaction of various racemic alcohols with (2R,3R)-2,3-diacetoxy-and
(2R,3R)-2,3-dibenzoyloxy-succinic anhydrides has been studied. Kinetic
resolution values ranged up to 48%. A correlation between the absolute
configuration of the more reactive enantiomeric alcohol with that of the chiral
anhydride has been obtained. Attempted regeneration of the alcohols from the
derived half-esters in the above reaction leads to partial racemization.
The Use of Sodium Dithionite for the Reduction of Imines and the Cleavage of Oximes
Authors: Pojer PM
Published: September 2010

Sodium dithionite reduces a
variety of imines to secondary amines. Oximes are cleaved by the reagent to the
parent carbonyl compound.
Volatility Studies of Metal Chelates. IV*Thermal Behaviour of Copper(II) Chelates of Aryl β-Diketones
Authors: Dilli S , Robards K
Published: September 2010

The thermal stability and volatility of the copper (II)
chelates of 38 aryl β-diketones have been
examined by combined thermogravimetry and
differential thermal analysis. Volatility is characterized by fluorine
substitution (in R and R' of RCOCH2COR?), particularly in the alkyl
(R) moiety of the β-diketone. When chlorine,
bromine and methyl substituents are introduced into the aromatic ring (R'),
there is a significant reduction in volatility. If R is CH3, thermal
stability is markedly affected, especially when R' is C6F5.
Immutable and Variable Transition State Structures
Authors: Poh B
Published: September 2010

A variation in reaction
rates that is caused by replacing a reactant with a member of a closely related
series, or by replacing a solvent with a closely related one, does not lead to
any variation in the transition state structure. A variation in reaction rates
that is caused by replacement of reactants, or solvents, with others not
closely related leads to a variation in the transition state structure.
4-Aminochroman-3-ols-Cyclic Analogues of 1-Amino-3-aryloxypropan-2-ols, the Potent β-Adrenergic Blocking Agents
Authors: Lap BV , Williams LR , Lim CH , Jones AJ
Published: September 2010

cis- and trans-4-Aminochroman-3-ols have been prepared and their configurations
have been established by stereospecific reactions. The configurations of the cis and trans isomers of both 4-amino-chroman-3-ols and 3-aminochroman-4-ols
were confirmed by analysis and iterative refinement of the 270-MHz proton
N.M.R. spectra.
Synthetic Plant Growth Regulators. III. The Preparation of Further Tricyclic Helminthosporic Acid Analogues with Gibberellin-like Properties
Authors: Cossey AL , Mander LN , Pyne SG
Published: September 2010

7-Methyl-7,8-dihydro-4a,7-methano-4aH-benzocycloheptene-2,6(9H,5H-dione
(6) was prepared and reduced to a 3 : 7 mixture of the trans- and cis-decalin
derived ketones (8) and (15). Each compound was further elaborated to the
plant-growth-promoting acids (13), (14), (16) and (17). Dienone (5) was also
reduced (NaBH4, hydrogenation) to a 7 : 3 mixture of the cis- and trans-decalin derivatives (11) and (9). The stereochemistry of (11),
and by inference (12), was determined by correlation with the known ketone (7).
Molecular Reorientation in the Plastic Crystalline Phase of Tris
Authors: Wasylishen RE , Barron PF , Doddrell DM
Published: September 2010

Carbon-13 N.M.R.
spectra of tris(hydroxymethyl)aminomethane
(Tris) have been measured between 407 and 461 K. Proton-decoupled 13C
N.M.R. spectra of solid Tris between
407 K and its melting point are relatively sharp (v� < 30 Hz)
indicating rapid overall molecular reorientation in this temperature range. It
was not possible to detect a 13C N.M.R, signal for Tris below 407 K.
The observed 13C N.M.R. spin-lattice relaxation times appear
continuous across the solid ↔ liquid phase transition. From the
temperature dependence of T1, a rotational activation energy of 51.6
� 6 kJ mol-1 is calculated, which indicates that the molecules must
expend considerable energy in reorienting. The N.M.R. results are discussed in
relation to previous differential scanning calorimetry
and X-ray diffraction data which indicate that Tris undergoes a solid ↔ solid
transition at 407 K.
Nuclear Quadrupole Resonance in Coordination Chemistry. Identification of Bridging and Terminal Chlorines in the Mercuric Chloride-4-picoline N-Oxide Complex
Authors: Ramakrishnan L , Soundararajan S , Sastry VSS , Ramakrishna J
Published: September 2010

The temperature dependence
of the chlorine-35 n.q.r. in the mercuric chloride-4-picoline
N-oxide complex has been studied from
77 K to room temperature, and the results are used to assign the observed
frequencies to terminal and bridging chlorines.
Reactions of Methyl Radicals. II. Hydrogen Abstraction from Methyl Trifluoroacetate
Authors: Arthur NL , Newitt PJ
Published: September 2010

Hydrogen abstraction from
CF3COOCH3 and CH3COCH3 by
CH3 radicals
CF3 + CF3COOCH3 → CH4 +
CF3COOCH2 (1)
CF3 + CF3COOCH3 → CH4 +
CH3COCH2 (3)
has been studied
in the temperature range 117-244�. The rate constants, based on the value of 1013.34
cm3 mol-1 s-1 for the recombination of CH3
radicals, are given by (k in cm3
mol-1 s-1 and E
in J mol-1) :
logk1 = (10.39 �
0.11)- (37680 � 880)/19.145T
logk3 = (11.53 �
0.02)- (40590 � 170)/19.145T
CF3COOCH3
is less susceptible to attack by CH3 radicals than by CF3
radicals by a factor of 2.8 at 400 K, due mainly to a difference in A factors, since the activation energies
of the two reactions are almost identical. These results can be rationalized in
terms of intermolecular polar repulsion between the CF3 radical and
CF3COOCH3.
Solution Chemistry in Fused Phenol. III. Conductance Studies of the Solutions of Acids, Bases and Salts in Fused Phenol
Authors: Malhotra KC , Mahajan VP , Sud RG
Published: September 2010

Conductance measurements of
protonic acids, Lewis acids, bases and quaternary
ammonium and inorganic salts have been carried out in fused phenol at 50 � 0.1°C.
The possibility of triple ion formation has been ruled out: however, an
extensive ion pair formation in the solution is supported by results from plots
of Λc against log√C
Λ0 values have been determined for these solutes. A possibility
of the estimation of weak bases, in fused phenol, has been explored, fluorosulfuric
acid being used as a titrant.
Condensation of α- and β-Acetylnaphthalenes with Dimethyl Diglycollate
Authors: El-Newaihy MF , Salem MR , Enayat EI , El-Bassiony FAA
Published: September 2010

α-and β-Acetylnaphthalenes condense with dimethyl oxydiacetate (dimethyl diglycollate)
in the presence of sodium hydride to give good yields of the corresponding
half-esters, the (Z)-isomers (2a) and (2b) being predominant. The structure and
configuration of the half-esters were established by chemical and spectroscopic
evidence.
The Infrared Matrix Isolation Spectra of Water Species in a Deuterium Matrix
Authors: Murby EJ , Pullin ADE
Published: September 2010

The spectra of matrices of
deuterium at c.7 K containing water species derived from D2O, H2O
and mixtures of D2O and H2O have been obtained in the
region 4000-1000 cm-1. Six bands have been assigned to the
fundamentals of (H2O)2, of (D2O)2
and of deuterium-bonded HDO dimeric species.A preference for HDO to
form HO-D. . .O (deuterium) bonds rather than DO-H. . .O (hydrogen)bonds has
been observed. The spectra in matrices of deuterium are closely similar to
those observed in nitrogen matrices and support an open, rather than a cyclic,
structure for the water dimer.
Diterpene Chemistry. X. Synthesis of Perfumery Compounds from Labda-8(17),14-dien-13-ol (Manool)
Authors: Grant PK , Liau HTL , Temple WA
Published: September 2010

The syntheses of
intramolecular acetals related to known perfumery
compounds and of an ambreinolide ester are reported.
A Study of Chemical Reactions in Molten Sodium-Potassium Bisulfate Eutectic. I. The Reactions of Metals
Authors: Meehan BJ , Tariq SA
Published: September 2010

The reactions of 18 metals
with molten sodium-potassium bisulfate eutectic were studied. Results obtained
isothermally at 200�C indicated that Al, V and Au did not react with the melt;
Na, Mg, Mn and Zn reacted to produce H2; Co, Ni, Cu, Ag, Sn, Hg and Pb produced SO2
and H2O; while Ti, Cr, Fe and Cd produced
H2, H2O and SO2. Reactions in general were
slow and, due to formation of a protective coating on the surface, metals
reacted only partly, with the exception of Na, Cu, Ag and Zn which reacted and
dissolved in the melt completely. Due to partial reactions mostly qualitative
or semi-quantitative results were obtained and possible reaction
stoichiometries have been suggested.
Diterpene Chemistry. XI. Synthesis of Perfumery Compounds from Labda-8(17),14-dien-13-ol (Manool)
Authors: Grant PK , Rowan DD
Published: September 2010

The potentially odiferous
isomeric acetals
8,13:8,14-diepoxy-15,16,17-trinorlabdanes have been synthesized from manool. A
Tanabe-Eschenmoser fragmentation provided the crucial intermediate.
The Preparation and Low-Frequency Vibrational Spectra of Some Copper(I) and Silver(I) Alkane- and Arene-monothiolate Complexes
Authors: Bowmaker GA , Tan L
Published: September 2010

A number of different
methods for preparing anionic Group 1B metal thiolate complexes have been
investigated. The compounds [Me4N] [CU2(SMe)3]
and [Et4N] [Ag5(SBut)6] are
reported for the first time, and new methods for preparing the previously known
compounds [Et4N] [Cu5(SBut)6], [Me4N]2
[CU5(SPh)7] and [Et4N]2 [Cu5(SPh)7]
are described. The far-infrared spectra of the above compounds, and of CuSMe,
CuSBut, AgSBut, [Me4N]2 [CU4(SPh)6]
and [Me4N]2 [Ag5(SPh)7] have been
obtained, and metal-sulfur stretching bands are assigned in the 150-350 cm-1
region. The low-frequency Raman spectra have also been obtained for some of
these compounds. Possible structures for the new compounds are considered in
the light of the low-frequency vibrational spectra.
The Chemistry of Aryllead(IV) Tricarboxylates. Reaction with β-Diketones
Authors: Pinhey JT , Rowe BA
Published: September 2010

Dimedone (1) and p-methoxyphenyllead triacetate (2) react
in chloroform containing pyridine at 40� to give 2,2-bis(p-methoxyphenyl)-5,5-dimethylcyclohexane-,3-dione (3) in high
yield. This arylationreaction of β-diketones has been examined with
2-methylcyclohexane-1,3-dione, 2-methylcyclopentane-1,3-dione, acetylacetone
and 2-acetyl-3,4-dihydronaphthalen-l(2H)-one,
and in all cases synthetically useful yields of arylated products were
obtained. The vinylogous β-diketone,
6β-acetylcholest-4-en-3-one,
also underwent the reaction to give a mixture of 6β-acetyl-6α-(p-methoxypheny1)-cholest-4-en-3-one
(21) and the corresponding 6β-aryl
compound (22).