bluuebunny/crossref_metadata_2025 huggingface dataset:
Micellar catalysis of organic reactions. XII. Basic hydrolysis of some alkyl and aryl N-(4-Nitrophenyl)carbamates
Authors: Broxton TJ
Published: September 2010

The basic hydrolysis of a
number of alkyl and aryl N-(4-nitrophenyl)carbamates in the presence and
absence of micelles of cetyltrimethylammonium bromide (ctab) are reported. In
water the stable product at 26�C was N-(4-nitrophenyl)carbamate ion (3). At higher
temperatures this carbamate ion slowly decomposed to 4-nitroaniline. In ctab
the decarboxylation of the N-(4-nitrophenyl)carbamate ion was strongly
catalysed (× 45) and thus the observed final product even at 26�C was
4-nitroaniline. Kinetic studies in water and in ctab were consistent with
decomposition of the methyl carbamate (la) by a BAC2 mechanism and
the 2,2,2-trifluoroethyl carbamate (lc) by an E1cB mechanism. The extent of ionization of the substrate
carbamates to nitranion (4) was enhanced in ctab as was the rate of spontaneous
decomposition of the nitranion. This is in contrast to other E1cB reactions reported in the
literature, for which the rate of spontaneous decomposition of the carbanion
was inhibited by ctab. For compounds reacting by the BAC2 mechanism,
the tetrahedral intermediate (2) partitioned in favour of C-OR bond breaking
rather than C-N bond breaking observed previously for some N-methyl derivatives.
The nitration of some substituted 4-methylphenols; X-ray crystal structure of (Z)-3-Bromo-5-(bromonitromethylene)furan-2(5H)-one
Authors: Gray MJ , Hartshorn MP , Penfold BR , Vaughan J
Published: September 2010

The nitrations
of 2-substituted 4-methyl-6-nitrophenols (1a),(l1b) and (1c) give 6-substituted
3-methyl-2-nitro-1,4-benzoquinones (2a), (2b) and (2c). Similar reaction of
2,3-dibromo-4-methyl- 6-nitrophenol (5) gives
2,3-dibromo-5-methyl-6-nitro-1,4-benzoquinone (7) and the 4-nitratocyclo-
hexa-2,5-dienone (12). In contrast, 2,3,6-tribromo-(4a) and 2,6-dibromo-(4b)
4-methylphenols give 1,4-benzoquinones with loss of the methyl group. Lactone
(18) was formed in the nitration of the 2,6-dibromophenol (4b) and its
structure was determined by single-crystal X-ray analysis.
Synthesis and evaluation of diaryl oxalate esters for low-intensity chemiluminescent illumination
Authors: Dowd CD , Paul DB
Published: September 2010

Various diaryl
oxalate esters have been prepared from oxalyl
chloride and substituted salicylates. A number of
intermediates and byproducts were obtained from chlorinations
of salicyclic acid and their mechanistic significance
has been discussed. The chemiluminescent emission
from the oxalates in the presence of hydrogen peroxide has been examined in the
search for low-intensity illumination of at least 10 h duration.
Bis(2-alkoxycarbonyl-4,6-dinitrophenyl) oxalates were too unstable while the chemiluminescence of the
bis(6-alkoxycarbonyl-2,4,5-trichloropheny) oxalates could not be adjusted
suitably. Some bis(6-alkoxycarbonyl-2,4-dichlorophenyl) oxalates were prepared
and, by treatment with various combinations of potassium salicylate
and oxalic acid, satisfactory low-intensity light emission could be achieved.
The chemistry of pyrrolic compounds. LIV. The chemistry of rhodins, verdins and related compounds
Authors: Clezy PS , Mirza AH , Ravi BN , Thuc LV
Published: September 2010

Coprorhodin II trimethyl ester has
been prepared and its chemical and spectroscopic properties examined.
Autoxidation of coprorhodin yields coproverdin while reduction with sodium borohydride
affords a secondary alcohol which readily dehydrates under aerobic conditions
to furnish a benzo-chlorin. The chemistry of these derivatives of coprorhodin
has been studied.
Complexes of the dicyclohexylphosphinodithioformate anion involving the nickel triad metals: the crystal and molecular structures of the platinum(II) and palladium(II) derivatives
Authors: Dakternieks D , Hoskins BF , Tiekink ERT
Published: September 2010

The crystal and molecular
structures of bis (dicyclohexylphosphinodithioformato-S,P)M,
M[S2CP-(C6Hl1)2]2 where
M = Pt (1) and Pd (2), have been determined by single-crystal three-dimensional
X-ray diffraction methods. The isomorphous crystals
are monoclinic, of space group P21/c with four molecules per unit
cell which has dimensions for (1) a 14.732(4),
b 15.11 8(4), c 16.000(3) � and β 120.90(2)� and for (2) a 14.721(2), b 15.142(2), c 15.986(2) �
and β 120.80(1)�. The structures were solved by normal Fourier methods and
were refined with anisotropic thermal parameters. A full-matrix least-squares
method was used, involving 3454 and 5052 statistically significant reflections
for (1) and (2) respectively with final R and Rw values of 0.058 and 0.055 for
(1) and 0.038 and 0.039 for (2). The complexes are isostructural.
The ligand coordinates in a bidentate manner to the central atom through the
phosphorus atom and one of the sulfur atoms with the metal atom in a cis-planar
environment.
Peracid oxidation of 1-pyrroline 1-oxides
Authors: Bapat JB , Durie A
Published: September 2010

Peracid oxidation of twelve 1-pyrroline 1-oxides (a class of
cyclic nitrones) has been carried out.� Those
compounds without a substituent in position 2 yielded the corresponding hydroxamic acids.�2-Phenyl-substituted
1-pyrroline 1-oxides gave nitro ketones, whereas 2-alkyl substituted
1-pyrroline 1-oxides gave nitroso ketones (as dimers) or nitro ketones. 2,4,4-Trimethyl-1-pyrroline
1-oxide gave an abnormal oxidation product, 2,4,4-trimethyl-1-pyrrolin-5-ol
1-oxide. Possible mechanisms of these reactions are discussed.
Constituents of Boesenbergia sp. Isolation and crystal structure of crotepoxide ([1R-(1α,2α,4α,5β,6α,7α,)]-4-[(Benzoyloxy)methyl]-3,8-dioxatricyclo[5, 1,0,02,4]octane-5,6-diyl diacetate)
Authors: Pancharoen O , Patrick VA , Reutrakul V , Tuntiwachwuttikul P , White AH
Published: September 2010

The crystal structure of crotepoxide, isolated from the rhizomes of Boesenbergia sp.,
has been determined by single crystal X-ray diffraction methods at 295 K, being
refined to a residual of 0.059 for 682 independent
'observed' reflections. Crystals are orthorhombic, P212121,
a 23.53(2), b 10.59(1),c, 6.99(1)�, Z
4.
Studies of Australian soft corals. XXXIV. A new substituted pyrrole from a soft coral-sponge association
Authors: Bowden BF , Clezy PS , Coll JC , Ravi BN , Tapiolas DM
Published: September 2010

5-Nonylpyrrole-2-carbaldehyde
has been isolated from a soft coral-sponge association. The structure was
determined spectroscopically and confirmed by synthesis.
Oxomolybdenum(V) complexes with Quinolin-8-olato, Quinoline-8-thiolato and Quinolin-8-aminato ligands
Authors: Boyd IW , Wedd AG
Published: September 2010

The mononuclear complexes
[MoVOXL2] (X = Cl, Br; LH = quinolin-8-ol,
quinoline-8-thiol) have been synthesized from the reaction of (pyH)2 [MoOCl5] and (pyH) [MoOBr4] with quinolin-8-ol or
8-mercaptoquinolinium chloride and bromide in the presence of NEt3 or
NaOMe. Bromine superhyperfine
coupling [A(79,81Br) 7 × 10-4
cm-1] is observed in the e.s.r. spectra of
[MoOBrL2]. The reaction of (pyH)2
[MoOCl5] with quinolin-8-amine (LH) and water produces binuclear [Mo2O3Cl2L2].
The chemistry of pyrrolic compounds. LV. 13C chemical shift data for the isomeric protoporphyrins
Authors: Abraham RJ , Clezy PS , Thuc Lv
Published: September 2010

The 13C n.m.r, spectra of the 15 isomeric protoporphyrin
dimethyl esters have been determined. Measurements were made on the zinc
chelate derivatives of the porphyrins in the presence of pyrrolidine and
assignments are given for the side chain and methine carbon
atoms.
The rearrangements of the nitrones of simple cyclic conjugated ketones
Authors: Prager RH , Raner KD , Ward AD
Published: September 2010

The ring expansions of
N-methyl nitrones formed from cyclic conjugated ketones have been investigated.� Low yields of cyclic amides were obtained. In
general, the best conditions for the rearrangementinvolved using p-toluenesulfonyl chloride and polyphosphoric
acid in tetrahydrofuran. The parent ketone and, in some cases, an N-aryl sulfonamide were also obtained;
mechanisms for their formation are discussed.
(1'RS,2'SR,6'RS)-(2,6-Dihydroxy-4-methoxyphenyl)-[3'-methyl-2'-(3''-methylbut-2''-enyl)-6'-phenyl-cyclohex-3'-enyl]methanone (panduratin A)-a Constituent of the Red Rhizomers of a variety of Boesenbergia pandurata
Authors: Tuntiwachwuttikul P , Pancharoen O , Reutrakul V , Byrne LT
Published: September 2010

Spectroscopic studies have
established the structure (l'RS,2'SR,6'RS)-(2,6-dihydroxy-4-methoxy-
phenyl)[3'-methyl-2'-(3''-methylbut-2''enyl)-6'-phenylcyclohex-3'-enyl]methanone
for panduratin A which, together with pinostrobin and two known chalcones,
boesenbergin A and rubranine, has been isolated from the red rhizomes of a
variety of Boesenbergia pandurata (Roxb.) Schltr. A synthesis of rubranine, in
moderate yield, has also been achieved.
Wavelength controlled production of SO4- radicals in the ultraviolet photolysis of ceric sulfate solutions
Authors: Matthews RW
Published: September 2010

Solutions of cerium(III)/(IV)
and formic acid in 0.4 M sulfuric acid have been photolysed
under 254 nm and 365 nm light. Marked differences in the reaction kinetics and
quantum yields are observed at the two different wavelengths. At 365 nm, the
reactions leading to cerium(IV) reduction are caused almost exclusively by the
SO4- radical. The ratio of rate constants, k(SO4-
+ CeIII)/ k(SO4- + HCOOH), is 116 � 11 and the
quantum yield of sulfate radicals, ф(SO4-), is
0.023 � 0.002. At 254 nm, the reactions leading to cerium(IV) reduction are
caused mainly by the OH radical, but approximately 35% of the oxidizing
radicals formed in the primary photochemical reaction are SO4-.
Cerium(III) species, excited at 254 nm, transfer energy to cerium(IV) and this
results in an additional yield of OH and SO4- radicals.
Fluorescence measurements confirmed the efficiency of the energy transfer
reaction. The ratio of rate constants, k(OH+CeIII)/k(OH+HCOOH), is
2.22 � 0.18 and ф(CeIV*)
and ф(CelIII*) giving oxidizing radicals are 0.116 � 0.010 and
0.0083 � 0.0008 respectively. Thus about 5 times more total oxidizing radicals
are produced from excited cerium(IV) species at 254 nm than at 365 nm.
Organolanthanoids. VI. Syntheses of cyclopentadienyllanthanoids by transmetallation reactions between thallous cyclopentadienides and lanthanoid elements
Authors: Deacon GB , Koplick AJ , Tuong TD
Published: September 2010

Cyclopentadienyllanthanoids (C5H5)3M(thf) (M = Ce, Nd,
Sm, Gd or Er; thf = tetrahydrofuran), (C5H5)3M
(M = Er or Yb), (MeC5H4),M
(M = Nd, Sm or Gd), (C5H5)2Yb, (C5H5)2Yb(dme) (dme = 1,2-dimethoxyethane),
and (MeC5H4)2Yb(thf),
have been synthesized in satisfactory-to-good yield by reaction of the lanthanoid elements with the thallous
cyclopentadienides (RC5H4)TI (R
= H or Me) in tetrahydrofuran or 1,2-dimethoxyethane. The outcome of the
reaction of ytterbium with thallous cyclopentadienide [(C5H5),Yb; n = 2 or 3] depends on the stoichiometry;
it has been shown that (C5H5),Yb
is reduced by ytterbium metal to (C5H5),Yb and that the divalent compound is oxidized to (C5H5),Yb by thallous cyclopentadienide. Addition of mercury metal aids
initiation of transmetallation, but it is not
essential for reaction to occur.
Nitrones and oxaziridines. XXXII. Some reactions of bicyclic 1-pyrroline 1-oxides
Authors: Black DSC , Johnstone LM
Published: September 2010

Oxidation of the bicyclic
nitrone (2) with nitric acid gave the nitro diketone (3). Bridgehead
hydroxylation was achieved by conversion of the nitrones (1), (2) and (8) into
the imino-benzoates (4), (5) and (9) respectively with benzoyl chloride and
subsequent base hydrolysis to give the hydroxy-imines (6), (7) and (10)
respectively. Photoirradiation of the bicyclic
nitrone (2) gave the oxaziridine (14), which on
further irradiation gave the fused azetidine (15) and
the fused pyrroline (16).
Nitrones and oxaziridines. XXXIV. Synthesis of medium-sized oxo-lactams by ring-opening of fused tricyclic oxaziridines
Authors: Black DSC , Johnstone LM
Published: September 2010

The medium-sized oxo
lactams (9)-(11), (22)-(25), containing eight-to eleven-membered rings, have
been synthesized by a three-atom condensative ring expansion of the related
cyclic ketones. The key step involves the cleavage of a common ring-fusing bond
brought about by the ring-opening of a structurally suitable oxaziridine. These
oxaziridines were derived either from the corresponding hydroxy nitrones (13),
(14), (18)-(21) or hydroxy imines (3), (9, (7).
The stereochemistry of some Polychlorocyclohex-3-enones; X-ray crystal structures of trans-2,2,3,4,5,6-Hexachloro-6-methylcyclohex-3-enone, cis-2,4,5,6,6-Pentachloro-2-methylcyclohex-3-enone and r-2,4,t-5,c-6-Tetrachloro-2,3,6-trimethylcyclohex-3-enone
Authors: Hartshorn MP , Martyn RJ , Vaughan J
Published: September 2010

X-ray crystal structures of
trans-2,2,3,4,5,6-hexachloro-6-methylcyclohex-3-enone, cis-2,4,5,6,6-penta-chloro-2-methylcyclohex-3-enone, and r-2,4,t-5, c-6-tetrachloro-2,3,6-trimethylcyclohex-3-enone are reported. The
stereochemistry and probable conformations of some further
polychlorocyclohex-3-enones are established from considerations of
spectroscopic data.
The identification of further new depsidones in the lichen Parmelia notata
Authors: Elix JA , Lajide L
Published: September 2010

Two new depsidones,
8-hydroxy-3-methoxy-1,6-dimethyl-11-oxo-11 H-dibenzo[b,e][1,4]dioxepin-7- carboxylic acid (subnotatic
acid) (5) and 8-hydroxy-3-methoxy-1,6,9-trimethyl-11-oxo-11 H- dibenzo[b,e][1,4]dioxepin-7-carboxylic
acid (isonotatic acid) (7), have been detected in
strains of the lichen Parmelia notata Kurok. and isolated and characterized as the corresponding
methyl esters. The structures of the latter compounds have been confirmed by
synthesis.
Synthesis of Thieno[2,3-g][1,4]oxazonine and Thieno[2,3-h][1,5]oxazecine derivatives by cyanogen-bromide-induced ring expansion
Authors: Bremner JB , Browne EJ , Chohan V , Yates BF
Published: September 2010

4-Phenyl-4,6,7,8,9,10-hexahydrothieno[2,3-g][1,4]oxazonine-8-carbonitrile
(5a) and the analogous 4-phenyl-6,7,8,9,10,11-hexahydro-4H-thieno[2,3-h][1,5]oxazecine-9-carbonitrile
(5b) were preparedin moderate yields by
cyanogen bromide-induced ring expansion of the appropriate ω-(tetrahydrothieno[3,2-c]pyridyl)alkan-1-ol
precursors (3). N-Methyl derivatives of these new fused medium-ring heterocyclic
systems were prepared by standard methods.
Potential Antimalarials. I. 1,8-Naphthyridines
Authors: Barlin G , Tan W
Published: September 2010

A number of 1,8-naphthyridines
including 8-aza analogues of chloroquine and amodiaquine,
and similar 1,8-naphthyridines with 2- and 7-methyl substituents have been
prepared. These compounds showed minimal antimalarial activity in a preliminary
in vivo screen against Plasmodium vinckei vinckei.
Constituents of Eupomatia species. IX. N.M.R. evidence for the structure of eupolauramine and hydroxyeupolauramine
Authors: Taylor WC
Published: September 2010

The 1H and 13C
n.m.r. spectra of eupolauramine, 6-methoxy-5-methylbenzo[h]pyrrolo[4,3,2-de]-quinolin-4(5H)-one (3), have been assigned. Hydroxyeupolauramine was shown to
be the 10-hydroxy derivative (4). The biogenesis of eupolauramine and
eupolauridine (2) is discussed.
Crystal structure of Diaqua(1,10-phenanthroline)copper(II) sulfate
Authors: Healy PC , Patrick JM , White AH
Published: September 2010

The crystal structure of
the title compound, [Cu(OH2)2(phen)] (SO4)
(phen = 1,10-phenanthroline), has been determined by single-crystal X-ray
diffraction methods at room temperature, being refined by full matrix
least-squares methods to a residual of 0.033 for 1445 'observed' reflections.
Crystals are monoclinic, C2/c, a
14.883(8), b 13.843(9), c 7.019(4) �, β 108.60(4)�, Z 4. As
in a number of other copper(II) and nickel(II) derivatives with (CuL4)(SO4)
stoichiometry, the pseudo-square planar copper
environments [Cu-N,O: 2.009(2), 1.970(2) � in the present case] are bridged
through the two axial coordination positions by sulfate groups: O.SO2.O[Cu(OH2)2(phen)]O.SO2.0,
etc. to give a linear polymeric array [Cu-O(SO4), 2.468(3) �]; a
crystallographic twofold axis passes through the copper atom.
Pyrimidine N-oxides. VI. The ionization constants of Pyrimidine-2,4-diamine N-oxides
Authors: Cowden WB , Jacobsen NW
Published: September 2010

The ionization constants of
some pyrimidine-2,4-diamines and their N-oxides,
including the drugs 'trimethoprim' and 'minoxidil', are reported. The syntheses of several
pyrimidine-2,4-diamine N-oxides are
described.
An application of the Nenitszescu reaction to the synthesis of 1,2-annulated indoles and Benz[g]indoles
Authors: Parr RW , Reiss JA
Published: September 2010

The Nenitszescu reaction
has been investigated as a means of preparing several indoles, benz[g]-indoles
and 1,2-annulated indoles (3),(9),(13),(17) and (18) and a number of their
derivatives.Reactions between
benzoquinone and enaminones to form Michael addition products (15) and (16), major
intermediates in the Nenitszescu reaction, and the acetic acid induced
cyclization of (16) to (22) are recorded. Attempts to produce functionalized
5-hydroxyindoles as possible precursors to the mitomycin structure are discussed.
Constituents of Eupomatia species. X. The synthesis of 6-Methoxy-5-methylbenzo[h]pyrrolo[4,3,2-de]quinolin-4(5H)-one (eupolauramine)
Authors: Karuso P , Taylor WC
Published: September 2010

Two syntheses of
6-methoxy-5-methylbenzo[h]pyrrolo[4,3,2-de]quinolin-4(5H)-one (eupolauramine) starting from 4-methoxynaphthylamine are
described. One synthesis is highly efficient.
The addition of benzyne to benzofuran. A ready route to Benz[e]acephenanthrylene
Authors: Anthony IJ , Wege D
Published: September 2010

The title reaction affords
the 2+2 cycloadduct cis-4b,9b-dihydrobenzo[3,4]cyclobuta[1,2-b]benzofuran (13) together with the bis-adduct (4aα,8bα,9β,13b
β)-8b,9-dihydro-9,13b-epoxy-13bH-
benzo[3,4]cyclobuta[l,2-k]phenanthrene (14) in a ratio of c. 1 : 8. The mechanism of
formation of these adducts is suggested to occur through a non-concerted
pathway. Treatment of (14) with acid results in rearrangement and dehydration
to give benz[e]acephenanthrylene in good yield.
Aqua and perfluoro anion (BF4-, AsF6-) coordination isomers of manganese and rhenium carbonyls
Authors: Horn E , Snow MR
Published: September 2010

Pentacarbonyl- and tricarbonyl-rhenium bromide complexes react with AgAsF6 and AgBF4 in
dichloromethane to form the respective aqua species, [Re(CO)5(OH2)]+ Y- (where, Y = AsF6-,
BF4-) and [Re(CO)(L2)(OH2)]+ BF4- [where L2 = bpy, dppe, P(OPh)3].* A variable-temperature
19F nuclear magnetic resonance study of the [Re(CO),3(tmen)(OH2)]+ BF4- system establishes
that an equilibrium exists between the coordinated and 'free' tetrafluoroborate anion in solution
(CD2Cl2):
Re(CO)3(tmen)FBF3 + H2O ℰ [Re(CO)3(tmen)(OH2)]+ + BF4-
This equilibrium is forced to the right by low temperature (c. -10°C) and by removing the water
with phosphorus pentoxide. Thus, under controlled reaction conditions (c. - 10°C, dry nitrogen
atmosphere), AsF6- and BF4- are seen by infrared spectra to be coordinated in the complexes
Re(CO)3(bpy)FAsF5.δ(H2O) and Re(CO)3(tmen)FBF3.δ(H2O). The species [Re(CO)3(L2)(OH2)]+
Y- [where (i), L2 = 2CO, Y = AsF6-; (ii), L2 = tmen, Y = AsF6-, BF4-] have been characterized
by their crystal structures. Crystals of [Re(CO)5(OH5)]+ AsF6- are monoclinic, space group C2/c
with a 27.085(5), b 7.208(1), c 13.404(3) Ǻ and β 105.50(1)°. A full-matrix least-squares refinement
when using the absorption corrected data converged with R = 0.027 and R, = 0.028. The species
[Re(CO)3(tmen)(OH2)] + AsF6- crystallizes in the monoclinic space group P2, with a 7.858(1),
b 15,68(1), c 7.887(2) Ǻ and β 117.11(1)°. The final full-matrix refinement converged with
R = 0.021 and Rw = 0.022. [Re(CO)3(trnen)(OH2)]+ BF4- crystallizes in themonoclinic space group
C2/m with a 14.134(4), b 16.010(4), c 7.729(1) Ǻ and β 113.16(2)°. In these structures the water
molecule coordinates to the rhenium(1) at an average distance of 2,246(5) Ǻ. This is significantly
larger than the rhenium-fluoride bond length of 2.040(4) Ǻ.
Similar manganese aqua complexes, [Mn(CO)3 {P(OPh)3}2(H2O)]+ Y- (where, Y- = AsF6-,
BF4-), also exhibit the same infrared features characteristic of coordinated water [i.e. the presence
of sharp δ(H-O-H) bending absorption near 1600 cm-1]. This feature is absent from all the species
which only have lattice water and a coordinated fluoro anion.
Fluorine magnetic resonance studies. VI. Fluorine-fluorine coupling over four bonds in α-Fluoro- and α,α-Difluoro-toluenes
Authors: Rae ID , Burgess DA , Bombaci S , Baron ML , Woolcock ML
Published: September 2010

The 4J fluorine-fluorine coupling over four bonds involving an sp3
carbon and two sp2 carbons has been studied by using constrained
structures to calibrate the dependence of the size of coupling on the dihedral
angle (8). Both CF and CF2 groups follow the pattern established for
CF3, with the largest couplings (38, 62 and 86 Hz respectively)
arising from closest approaches of two fluorines (θ = 0�)
and the zero couplings resulting from θ = 180�.
Fused heterocycles from pyrrolethiols
Authors: Harris RLN , Mcfadden HG
Published: September 2010

Pyrrolethiols are highly
reactive bidentate nucleophiles which give a wide variety of fused heterocyclic
ring systems on reaction with acylating and alkylating agents via S-substituted
intermediates that are in most instances themselves isolable. Representative
syntheses of thieno[2,3-b]pyrroles, pyrrolo-[1,2-b]thiazoles, thiopyrano[2,3-c]pyrrol-4(6H)-ones
and thiopyranopyrrole salts are described.
The nitration of pentamethylphenol
Authors: Hartshorn MP , Robinson WT , Vaughan J , White JM , Whyte AR
Published: September 2010

Nitration of pentamethylphenol (1) with nitrogen dioxide in benzene gives the four possible
2,5,6-trinitrocyclohex-3-enones (6), (7), (8) and (9), three 4,5,6-trinitrocyclohex-2-enones (10), (11)
and [(12) or (13)], the 2-hydroxy-5,6-dinitrocyclohex-3-enone (14), quinone (17) and the 4-nitro
dienone (3). The fuming nitric acid nitration of pentamethylphenol (1) for 90 h gives most of these
products, except that 4-nitratomethyl-2,5,6-trinitrocyclohex-3-eones (21), (22), (23) and (24) are
isolated. X-ray crystal structures are reported for compounds (6), (7), (8), (10), (11), (14) and (21).
The crystal structure of Tris(1,10-phenanthroline)osmium(II) Bis(perchlorate) monohydrate and its implications for electron-pair repulsion theory
Authors: Goodwin HA , Kepert DL , Patrick JM , keltn BW , White AH
Published: September 2010

The crystal structure of
the title compound, [Os(phen)3](ClO4)2.c. 1H2O,
has been determined by single-crystal X-ray diffraction methods at 295 K, being
refined to a residual of 0.043 for 3477 'observed' independent reflections.
Crystals are monoclinic, C2/c, a
35.94(2), b 16.020(5), c 12.370(5) �, β 102.38(3)�, Z 8,
and are isostructural with the copper(II) analogue.
Osmium-nitrogen distances range from 2.066(7) to 2,082(7) � (mean, 2.075 �).
Departures of the stereochemistry of tris- (α, α'-diimine)metal
systems from the expectations of electron-pair repulsion theory are examined.
Synthetic applications of intramolecular insertion in arylcarbenes. VI. Ylid rearrangements in pyrolysis of o-alkylthiophenylcarbenes
Authors: Crow WD , Pang YT
Published: September 2010

Low-pressure thermal
generation of a range of o-alkylthiophenylcarbenes
produces, in addition to the normal insertion products, styrenes
and 1,3-dihydrobenzo[c]thiophens-clearly arising from
rearrangement. The main features of their mechanism of formation are
established by deuterium-labelling studies: in both cases participation by
S-ylids is implicated.
Some more transition metal acetylides
Authors: Bruce MI , Humphrey MG , Matisons JG , Roy SK , Swincer AG
Published: September 2010

Routes developed for the syntheses of σ-acetylide complexes of
tungsten, iron, nickel, copper and silver include reactions of metal halide
complexes with alk-1-ynes in organic amines, with copper(I) halides as
catalysts, or in methanol in the presence of sodium methoxide.
Yields range from good to excellent, and the reactions are generally simpler to
carry out than previous methods.
The chlorination of some 2,6-substituted 4-chlorophenols; X-ray crystal structure of (E)-(2RS,5RS)-2,4,5,6,6-Pentachloro-2-methyl-6-nitrohex-3-enoic acid
Authors: Hartshorn MP , Martyn RJ , Vaughan J
Published: September 2010

Chlorination of
4-chloro-2-methyl-6-nitrophenol (4) with chlorine in acetic acid containing
concentrated hydrochloric acid gives the epimeric acyclic carboxylic acids (6)
and (7). The structure of compound (6) was determined by X-ray crystal
structure analysis. No such acyclic compounds are formed in similar chlorinations of 2,4-dichloro-6-nitrophenol (13a) or
2,4-dichloro-6-methylphenol (13b). The mode of formation of compounds (6) and
(7) is discussed.
Isotopic volume differences: the possible influence of pressure on the distribution of sulfur isotopes between sulfide minerals
Authors: Hamann SD , Shaw RM , Lusk J , Batts BD
Published: September 2010

Theoretical calculations have been made,
with the aid of the Debye model, of the differences
in molar volumes between different isotopic forms of simple crystals. Where
comparisons are possible, the agreement with experimentally determined (X-ray)
volume differences is fairly good. The theory has been applied to predict the
differences between the molar volumes of the 32S and 34S
forms of the minerals sphalerite, ZnS,
galena, PbS, and pyrite, FeS2, and hence
to estimate the possible influence of pressure on the partitioning of sulfur
isotopes between pairs of those minerals. This partitioning has been used in
the past as an isotopic 'geothermometer', with an
assumption that it depends upon temperature but not pressure. It turns out that
for the conditions that generally apply in practical isotope geothermometry (pressure ≤ 800 MPa, temperature ≤ 1100 K), the calculated pressure effects are
considerably less than the uncertainties in experimental fractionation factors.
The base hydrolysis of coordinated fluorophosphate
Authors: Creaser II , Dubs RV , Sargeson AM
Published: September 2010

[(NH3)5CoO3PF]+
undergoes base hydrolysis in 0.1-0.3 M NaOH, � = 1.0,
at 25�C to generate free FPO32-, F- and [(NH3)4Co(OH)(NH2PO3)]
with a second-order rate constant k2 3.3 × 10 mol-1 s-1
where k2 is the composite rate constant for FPO32-
release and hydrolysis of F- with the two products being formed in
approximately equal amounts. The measured rate constitutes an estimated
enhancement of about 1010 over the base hydrolysis of the
uncoordinated FPO32- ion under the same conditions when
the concentration of the coordinated nucleophile is
taken into account.
Reactions of (E)-1-Methoxy-1-trimethylsiloxyprop-1-ene with acyl isocyanates and acyl isothiocyanates
Authors: Cambie RC , Davis PF , Rutledge PS , Woodgate PD
Published: September 2010

Reaction of aryl acyl, and
alkyl acyl isocyanates with
(E)-1-methoxy-1-trimethylsiloxyprop-1-ene affords high yields of various methyl
3-acylamino-2-methyl-3-oxopropanoates. The corresponding acyl isothiocyanates give a variety of products depending on the
structure of the isothiocyanate.
Phenanthrene synthesis: The synthesis of effusol a 9,10-Dihydrophenanthrene from the marsh grass Juncus effusus
Authors: Carvalho CF , Sargent MV , Stanojevic E
Published: September 2010

The synthesis of
5-ethenyl-1-methyl-9,10-dihydrophenanthrene-2,7-diol (effusol)
(1), a natural product isolated from the marsh grass, Juncus effusus, is described. The key step was
the intramolecular Ullmann reaction of methyl
2-bromo-3-[2'-(6''-bromo-3''-methoxy-2-methylphenyl)ethyl]-5-methoxybenzoate (19).
Potential antimalarials. II. N4-Substituted 2-Methoxy(and 2-hydroxy)-1,5-naphthyridin-4-amines
Authors: Barlin GB , Tan W
Published: September 2010

Several new N4-substituted
2-methoxy(and 2-hydroxy)-1,5-naphthyridin-4-amines have been prepared from
ethyl 3-aminopyridine-2-carboxylate. 2,4-Dichloro-1,5-naphthyridine with methanolic sodium methoxide gave
4-chloro-2-methoxy-1,5-naphthyridine but with methanolic
hydrogen chloride afforded 4-chloro-1,5-naphthyridin-2-ol. The N4-substituted
1,5-naphthyridin-4-amines showed no significant antimalarial activity compared
to chloroquine or primaquine in a preliminary in vivo screen against Plasmodium vinckei vinckei
in mice.
Fused heterocycles from pyrrolethiols. 1,3-Dithiolo[4,5-b]pyrroles,1,3-Dithiolo[4,5-c]pyrroles and 1,3-Dithiolo[4,5-b]indoles
Authors: Harris RLN , Mcfadden HG
Published: September 2010

S-(Pyrrolyl)dithiocarbamates, prepared by addition of in situ-generated pyrrolethiols
to isothiocyanates, cyclize
on treatment with bromine to fused 1,3-dithiolopyrrole ring systems, provided
the pyrrole ring is unsubstituted in the position adjacent to the dithiocarbamate group. S-(3-Indolyl)- dithiocarbamates
cyclize to give analogous 1,3-dithiolo[4,5-b]indoles.
Some aspects of the structure and reactivity of these new heterocycles are
discussed.
Synthesis of precursors of C4 and C5 cumulenones
Authors: Brown RFC , Coulston KJ , Eastwood FW , Gatehouse BM , Guddatt LW , Pfenninger M , Rainbow I
Published: September 2010

Bicyclo[2.2.l]hept-5-en-2-one
was condensed with 2,2-dimethyl-1,3-dioxan-4,6-dione in the presence of
titanium tetrachloride/pyridine to yield
5-(bicyclo[2.2.1]hept-5'-en-2'-ylidene)-2,2-dimethyl-1,3- dioxan-4,6-dione (6a)
which on pyrolysis at 520-560�/0.01 mm gave acetone, carbon dioxide, cyclopentadiene and butatrienone.
In the same way 5-(7'-oxabicyclo[2.2.1]hept-5'-en-2'-ylidene)-2,2-
dimethyl-1,3-dioxan-4,6-dione (6b) was prepared from
7-oxabicyclo[2.2.1]hept-5-en-2-one and on pyrolysis at 570�/0.01 mm it gave
acetone, carbon dioxide, furan and butatrienone.
Alkylation of 2-trimethylsiloxybicyclo[2.2.1]hepta-2,5 with phenylthiomethyl
chloride with titanium tetrachloride as catalyst followed by condensation with
2,2-dimethyl-1,3-dioxan-4,6-dione gave an endo/exo mixture of
5-(3'-phenylthiomethylbicyclo[2.2.1]hept-5'-en-2'-ylidene)-2,2-dimethy 1-1,3-dioxan-
4,6-dione. The structure of the endo isomer was established by X-ray crystallography.
Oxidation of the phenylthiomethyl compound with
m-chloroperbenzoic acid yielded the sulfoxide which was converted by boiling in
carbon tetrachloride into 5-(3'-methylenebicyclo[2.2.l]hept-5'-en-2'-ylidene)-
2,2-dimethyl-1,3-dioxan-4,6-dione (8). Preliminary studies on the fragmentation
of compound (8) have shown that at 450�/0.01 mm it is converted into acetone,
carbon dioxide and products showing ketene absorption at 2140 cm-1.
The formation of pentatetraenone has not been
established with certainty. The 3'-phenylsulfonylmethyl, phenylselenyl
and methyl derivatives of (6a) are also described.
Phenoxathiins and (o-Hydroxyphenyl)phenyl sulfides from 1-Oxaspiro[2.5]octa-5,7-dien-4-ones
Authors: Cacioli P , Reiss JA
Published: September 2010

A series of halogenated phenoxathiins (10a-c),(11a,b),
and a 1-azaphenoxathiin (13) have been prepared satisfactorily by the reaction
between l-oxaspiro[2.5]octa-5,7-dien-4-ones (6-spiroepoxy-
2,4-cyclohexadienones) (9a-c) and the appropriate halogenated thiophenolate anion. The method described provides a novel
synthetic pathway to highly substituted phenoxathiins.
Several (O-hydroxyphenyl)phenyl sulfides (14a-d) were also prepared with the
anion of p-chlorothiophenol.
Formation of the diphenyl sulfide (14b) with concomitant trapping of
formaldehyde as a dimedone derivative (19) enabled a
reaction pathway to be proposed.
Crystal structure of panduratin A: (1'RS,2'SR,6'RS)-(2,6-Dihydroxy-4-methoxyphenyl)[3''-methyl-2'-(3'-methylbut-2'-enyl)-6'-phenylcyclohex-3'-enyl]methanone
Authors: Pancharoen O , Reutrakul V , Skelton BW , Taylor WC , Tuntiwachwuttikul P , White AH
Published: September 2010

Single-crystal X-ray
structure determination of the title compound, C26H30O4,
confirms the stoichiometry, connectivity and
stereochemistry recently assigned spectroscopically.
Crystals are monoclinic, P21/n, a
10.140(5), b 24.85(1), c 9.4134) � β 90.69(4)�,Z 4; the
structure was refined to a residual of 0.055 for 1701 'observed' independent
reflections.
The formation and some reactions of a spirocyclic chroman derived from a 1-Oxaspiro[2.5]octa-5,7-dien-4-one
Authors: Cacioli P , Reiss JA
Published: September 2010

Reaction between the
5-hydroxymethyl-l-oxaspiro[2.5]octa-5,7-dien-4-one (1) and chlorotrimethylsilane
gave the spirocyclic chroman (2) in consistently good
yields. The spirocyclic chroman (2) reacted with the
sodium salt of p-chlorothiophenol
(4) to produce the corresponding (p-chloropheny1)
thiomethoxy derivative (3). Evidence is presented for
a ring-opened product (5) obtained from the reaction of compound (2) with
sodium methoxide. 1H and 13C
n.m.r. data are reported for the spirocyclic structures (2) and (3) and
compound (5) and suggestions as to their mode of formation are presented.
5-Isopropyl-3-methylbenzene-1,2-diol
Authors: Carman RM , van Dongen JMAM
Published: September 2010

5-Isopropyl-3-methylbenzene-1,2-diol,
obtained by thermal degradation of the diterpenoid
3,10-dihydroxydielmentha-5,11-diene-4,9- has been synthesized.
Substituent Effects in the Crystal Structures of Isoxindigos [(E)-3,3'-Bibenzofuranylidene-2,2'-diones]
Authors: Becker H , Raston CL , Skelton BW , White AH
Published: September 2010

Single-crystal X-ray structure determinations of the parent isoxindigo (1),
C16H8O4, together with those of derivatives substituted in both benzene rings with ( i ) t-butyl groups in the 5- and 7-positions [derivative (2)] and (ii) methoxy and t-butyl groups in the 5- and 7- positions respectively [two polymorphs, (3α,8)] have been determined in order to examine the possibility of distortion of molecular planarity by substituent steric effects, and the spectroscopic consequences thereof. Crystals of (1) are monoclinic, P21/n, a 17.69(1), b 5.690(3), c5.693(3)Ǻ, β 100.52(5)�, Z 2; after least-squares refinement, a residual R 0.067 was obtained for No 385 ?observed? Independent reflections. For (2), C32H40O4, crystals are monoclinic, P21/n, a 16.402(8), b 12.313(6), c 13.913(8)Ǻ, β
96.75(4)�, Z4; R 0.088 for No 1261. For (3), C26H28O6 (α-form), crystals are orthorhombic, Pcab , a 10.449(4), b 12.477(4), c 17.825(6)Ǻ, Z 4; R 0.058 for No 959; in the case of the β-form of (3), crystals are monoclinic, P21/n, a 6.828(2), b 15.464(3), c 10.770(3) Ǻ, β 98.58(4)�, Z 2. In (1) and
(3α,β), the molecules all lie disposed about crystallographically imposed symmetry elements, with one-half of the molecule, with a substantially planar fused-ring skeleton, comprising the asymmetric unit. In (2), the full molecule is the asymmetric unit; the fused-ring skeletons are substantially planar also, but the molecule exhibits a substantial twist about the bond connecting the two halves, with an interplanar dlhedral angle of 16.8°. This is ascribed to the steric effect of the large and more numerous t-butyl substituents.
Polyhalogenated Monoterpenes of the New Zealand Marine Red Alga Plocamium cartilagineum
Authors: Blunt JW , Bowman NJ , Munro HG , Parsons MJ , Wright GJ , Yeow Kok Kon.
Published: September 2010

A series of polyhalogenated monoterpenes have been isolated from the New Zealand marine red alga Plocamium cartilagineum (L.) Dixon. These findings are in contrast to the previously reported finding of a hydroxy bisnor monoterpene from a morphologically similar sample of P. cartilagineum collected from the same area.
On the Synthesis of 2,12-Dimethoxy-6,7,8,9-tetrahydro-5H-dibenz[d,f]azonine-3,11-diol and the Other Bridged Biphenyldiols and the E.S.R. of Their Oxidation Products in Relation to the Biosynthesis of Erythrina Alkaloids
Authors: Hewgill FR , Pass MC
Published: September 2010

An improved synthesis in described for the dibenzazonine precursor of erysodienone . Other biphenyl-4,4′-diols, bridged by two, three and five atoms, were also prepared. E.s.r. examination of the oxidation of these compounds produced spectra of the 9,10-dihydrophenanthrene-4,4′- semiquinone system, hitherto unrecorded, but semiquinone spectra could not be obtained from the other diols.
Pregnane Derivatives from Two Soft Corals of the Genus Capnella
Authors: Blackman AJ , Heaton A , Skelton BW , White AH
Published: September 2010

The steroids from two soft corals of the genus Capnella have been determined. Capnella sp. nov . afforded the novel pregnane derivatives 3-methoxy-19-norpregna-1,3,5(10),20-tetraen-4-ol (8) and 19-norpregna- 1,3,5(10),20-tetraen-3-ol (10) while Capnella erecta yielded the previously described pregna-1,20-dien-3-one (13).
Synthesis of Urushiol Derivatives by the Fries Rearrangement
Authors: Jefferson A , Wangchareontrakul S
Published: September 2010

The photo- and thermal-induced Fries rearrangement reactions of some unsaturated aliphatic esters of benzene-1,2-diol (catechol) have been studied. Photorearrangement and thermal rearrangement favoured products correspond to ortho and para migration respectively, but the thermal rearrangement may be accompanied by indanones, chromanones and other products which were formed through subsequent side reactions of the double bond. Photoinduced Fries rearrangement of 2-hydroxy-phenyl oleate followed by reduction of the carbonyl group gave monosubstituted catechol derivatives with an unsaturated C18 side chain in either the 3- or the 4-position. These alkenylcatechol derivatives are related in
structure to chemical components isolated from oriental lacquer trees, such as urushiol from Rhus verniciflua or thitsiol from Melanorrhoea usitata.
Influencing of Ring Size on Germinal Interproton Coupling Constants in Exocyclic Methylene Groups
Authors: Spear RJ , Sternhell S
Published: September 2010

In systems where substituent effects are constant, there is a well defined trend in the magnitude of geminal interproton coupling constants in exocyclic methylene groups with ring size. Reduction of ring size from six to five to four results in a monotonic reduction in the magnitude of Jgem. These trends apply to methylenecycloalkanes , methylenebenzocycloalkenes and α- methylenecycloalkanones . There is an indication that the trend does not continue for methylenecyclopropanes. A number of new exocyclic-methylene compounds have been designed and synthesized to provide specific experimental data.
Mechanism of Acetal Cleavage with Methylmagnesium Iodide
Authors: Abell AD , Massy-Westropp RA
Published: September 2010

The reaction of methylmagnesium iodide with methyl (1R,3S,5R)-1-(furan- 3′-yl)-5-methyl-2,8-dioxabicyclo[3.2.1]octane-3-carboxylate (2) gives products arising from regioselective carbon-oxygen bond fission and intermolecular transfer of the methyl group of the Grignard reagent to the intermediate oxocarbonium ion, in addition to the usual tertiary alcohol.
Lewis-Base Adducts of Group 1B Metal(I) Compounds. XXII. Crystal Structure of 'Bis(pyridine)silver(I) Perchlorate
Authors: Dyason JC , Healy PC , Engelhardt LM , White AH
Published: September 2010

Determination of the crystal structure of 'bis (pyridine)silver(I) perchlorate' by single-crystal X-ray methods shows it to be of 2.4:1 pyridine:silver (I) perchlorate stoichiometry , the structure being refined by least squares to a residual of 0.054 for 1142 'observed' reflections. Crystals are tetragonal, I4, a 21.95(1), c 7.684(3) Ǻ. The structure comprises perchlorate anions of two types of I and 4 symmetry, together with two types of complex cation: [Ag( py )2]+, with 1 symmetry, and [Ag( py )4]+ with 4 symmetry. For the two types of cation Ag-N are 2.15(1), 2.16(1) and 2.30(1) Ǻ.
Reactions of 4-Methyl-2,6-diphenylphenol and 4-Nitro-2,6-diphenylphenol with Nitrogen Dioxide
Authors: Hartshorn MP , Martyn RJ , Robinson WT , Sutton KH , Vaughan J , White JM
Published: September 2010

Reaction of 4-methyl-2,6-diphenylphenol (11a) with nitrogen dioxide in benzene solution gives the polysubstituted cyclohex-2-enones (14), (15), (16), (17) and (18) via the 4-nitro dienone (13). The reversibility of the 4-nitro dienone (13)/4-hydroxy dienone (19) conversion under these reaction conditions is demonstrated. Reaction of 4-nitro-2,6-diphenylphenol (11b) with nitrogen dioxide in benzene solution gives the C2-epimeric 2,6-dihydroxy-4,5-dinitrocyclohex-3- enones (32) and (33) via the 6-nitro-6-phenyl dienone (12b). X-ray crystal structure analyses are reported for compounds (14), (15), (16), (17), (18) and (33).
Platinum Silicide/n-Silicon Photoelectrodes: Dependence on the Conditions of 'Platinum Silicide' Formation
Authors: Pham DK , Hope GA
Published: September 2010

The photoelectrochemical efficiency and ideality of platinum silicide /n-silicon (1 1 1 ) electrodes were investigated for dependence on silicide growth parameters. A thermal fabrication process was chosen and variation to the following three variables was made individually: the thickness of the deposited platinum, the reaction temperature and the reaction time. The silicide surface layers investigated were PtSi , Pt2Si, and combinations of these compounds, in a single thermally grown product layer. The electrode efficiency was found to be most dependent upon the thickness of the silicide layer, increasing with layer thickness over the range studied, from 5 to 75 nm. Sputtering of the surface with 4 keV argon ions was found to reduce the photoelectrochemical response to a very low level. Solid state photocells could be constructed with efficiencies similar to the photoelectrochemical devices. These cells were also affected by sputtering the surface. For sputtered samples, both in solution and solid state, white light illumination produced a larger photocurrent than a He/ Ne laser. Shining a laser onto the sample when illuminated with white light reduced the photocurrent, indicating that the sputtering altered the silicon near the silicide interface. � Corrosion measurements produced Tafel corrosion rates of a low magnitude, near 10-2 mpy .
Synthesis of Further Divarinol and Olivetol Lichen Para-Depsides
Authors: Elix JA , Parker JL , Tearne PD , Wardlaw JH
Published: September 2010

The lichen depsides 2-O-methyldivaricatic acid (1), 3-chlorodivaricatic acid (2), 4-O-demethyl-stenoporic acid (3), 2-O-methylstenosporic acid (4), 4-O-demethylimbricaric acid (5) and 3,5-dichloro-2′-O- methylanziaic acid (6) have been prepared by unambiguous synthesis for the first time.
Effects of Substituents on the Barriers to Rotation in Phenyl and Benzyl Carbamates
Authors: Yamagami C , Takao N , Takeuchi Y
Published: September 2010

The free energy of activation for rotation about the C-N bond (ΔG‡Tc) in substituted phenyl and benzyl N,N- dimethylcarbamates was determined by the 13C dynamic n.m.r. method. The ΔG‡Tc value depended linearly on Hammett's σ with positive p. We have separated the substituent effects into inductive and resonance effects by using dual substituent parameter ( d.s.p .) analysis, and found that the resonance effect is more important than the inductive effect for para derivatives, and vice versa for meta derivatives. General trends of electronic substituent effects on barriers to rotation in carbamates and structurally related amides are also discussed. The ortho steric effect was small.
Intramolecular Diels-Alder Additions of Benzynes to Furans. Application to the Total Synthesis of Biflorin, and the Mansonone-E, I and F
Authors: Best WM , Wege D
Published: September 2010

Benzynes, generated either by the debromination of an appropriately substituted (o-dibromobenzene, or by the thermolysis of a substituted diazotized anthranilic acid, have been trapped intramolecularly by an attached furan moiety. One such adduct (41) has been transformed into 6,9-dimethylnaphtho[1,8-bc]pyran-3(2H)-one (43), which served as the key intermediate for the total synthesis of the title compounds, all of which are derivatives of 6,9-dimethylnaphtho[1,8-bc]pyran-7,8-quinone.
New Depsidones From the Lichen Genus Erioderma
Authors: Elix JA , Jenie UA , Arvidsson L , Jorgensen PM , James PW
Published: September 2010

The depsidones norpannarin (4) and norargopsin (5) have been prepared by unambiguous synthesis and shown to co-occur with nordechloropannarin (7), pannarin (3) and argopsin (2) in Erioderma chilense.
An Unusual Cleavage and Macrocyclization in the Zinc-Aqueous Acid Reduction of [2-Methyl-2-Nitro-N,N'-Bis(Pyridin-2-Ylmethyl)-Propane-1,3-Diamine]Coppe R(II) Cation - Crystal-Structure of the (6,13-Dimethyl-1,4,8,11-Tetraazacyclotetradecane-6,13-Diamine)Copper(II) Perchlorate Product
Authors: Lawrance GA , Skelton BW , White AH , Comba P
Published: September 2010

Reduction of [2-methyl-2-nitro-N,N?-bis(pyridin-2-ylmethyl)propane- 1,3-diamine]copper(II) with zinc in aqueous hydrochloric acid and subsequent recomplexation yields the macromonocyclic complex (6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine)copper(II) perchlorate as the major product, apparently by cleavage of both pyridine rings from the precursor ligand and direct recombination of two saturated residues. Catalytic reduction of the nitro group in the precursor compound can be achieved cleanly over palladium-carbon with hydrogen. The macrocyclic complex crystallized in the space group P21/c, a 8.031(4), b 17.45(1), c 8.436(5) Ǻ, β 117.87(4)°, Z 2; for a single-crystal X-ray structure determination R was 0.078 for 1378 'observed' reflections. The complex is centrosymmetric, the macrocycle having pendant amines on opposite sides of the macrocyclic plane, while perchlorate oxygen atoms occupy the axial sites with Cu-O at 2.59 Ǻ. Observed Cu-N distances of 2.022(6) and 1.996(7) Ǻ are longer than usual for copper(II) amines. Electron spin resonance and electronic spectroscopy define an essentially square-planar geometry in solution, with only weak axial interactions.
Abstraction by Cyanide of Thio Ligand From [MoVIOS] and Related Centers: The Crystal and Molecular-Structure of cis-Oxobis[piperidine N-oxido(1-)-O,N]-selenomolybdenum(VI)
Authors: Traill PR , Tiekink ERT , Oconnor MJ , Snow MR , Wedd AG
Published: September 2010

cis -[ MoOS (C5H10NO)2] reacts with cyanide in CDCl3 solution to produce cis -[MoO2(C5H10NO)2](50-60%) and SCN- (65-85%). Free C5H10NH and C5H10NOH are formed as well, these results suggesting piperidine N- oxido ligand as the source of oxidizing equivalents in the system. Under the same conditions, cis -[MoS2(C5H10NO)2] and cis -[ MoOSe (C5H10NO)2] also form cis - [MoO2(C5H10NO)2]. The molecular structure of the title compound reveals Mo-Se and Mo-O ( oxo ) bond lengths of 2.299(1) and 1.719(4) Ǻ, and an O-Mo-Se bond angle of 115.3(1)°. The structure is related closely to that of [ MoOS (C5H10NO)2], and detailed differences are those expected for substitution of a thio ligand by the larger seleno congener. Crystal data: a 6.977(1), b 21.469(3), c 9.791(2) Ǻ, β 91.50(2)°; P21/n; Z 4.
Halogenated Terpenoids. XXIV. The Bromocineoles
Authors: Carman RM , Fletcher MT
Published: September 2010

The bromination of cineole under a range of conditions is reported. Various bromocineoles and their properties are discussed.
Structural Studies of Technetium Complexes. X. The Crystal-Structure of Tetraphenylarsonium Hexakis(Isothiocyanato)Technetate(IV)-Dichloromethane (1/1)
Authors: Williams GA , Bonnyman J , Baldas J
Published: September 2010

The crystal structure of [AsPh4]2 [ Tc (NCS)6].CH2Cl2 has been determined by single-crystal X-ray diffraction methods at 23 � 1�C . Crystals are tetragonal, space group I4/m, with a 11.523(5), c 22.43(2) �, and Z 2. Diffraction data from two different crystals were analysed and in both cases disorder was present in the crystal lattices. Full-matrix least-squares refinement gave a final R value of 0.073 for 1188m independent reflections. The [TC(NCS)6]2- anion has an octahedral structure with the technetium(1V) atom situated on a site of 4/m symmetry. The Tc -N bond lengths are 2.00(1) and 2.01(1) Ǻ with N- Tc -N angles of exactly 90�. Two of the Tc -NCS groups are constrained by the crystal symmetry to be perfectly linear, while for the remaining four Tc -NCS groupings the Tc -N-C and N-C-S angles are 175.9(9)� and 175.3(10)� respectively.
Metal Template Reactions. XXIV. Synthesis of Macrocyclic Amide and Ester Complexes Via Substituted 1,1'-Oxalylbisisatins and the Deesterification of Some Ester Complexes
Authors: Black DS , Moss GI
Published: September 2010

The 5-substituted phenylglyoxylic esters (3) and amides (4) have been prepared via the
corresponding 1,1′-oxalylbisisatins (2). The nickel(11) macrocyclic amide complexes (7) have been prepared but the related ester complexes (5) were found to undergo deesterification (hydrolysis and decarboxylation) to provide a convenient route to the proto-complexes (6).