bluuebunny/crossref_metadata_2025 huggingface dataset:
The Structures of the Decaphenylmetallocenium Cations of Chromium and Cobalt
Authors: Field Leslie D. , Hambley Trevor W. , He, Taian , Masters Anthony F. , Turner Peter
Published: August 2004

Decaphenylchromocenium and decaphenylcobaltocenium cations
[M(η5-C5Ph5)2]+,
M = Cr and Co, were synthesized by oxidation of the corresponding
neutral decaphenylchromocene and decaphenylcobaltocene respectively with
nitrosyl tetrafluoroborate. The complexes are air-stable and were fully
characterized; decaphenylchromocenium tetrafluoroborate (1) and
decaphenylcobaltocenium tetrafluoroborate (2) were structurally characterized
by X-ray crystallography. Crystals of (1) (as a water/methylene chloride
solvate),
C70·5H50BClCrF4O0·5,
M 1079·42, are triclinic, space group
P -1 (No. 2),
a 13·634(5), b
17·424(5), c 13·298(4) Å, α
106·45(2), β 101·83(3), γ 74·56(2)°,
Z 2. Crystals of (2) (as a water/methylene chloride
solvate),
C70·5H50BClCoF4O0·5,
M 1086·36, are triclinic, space group
P-1 (No. 2),
a 13·633(2), b
17·683(3), c 13·255(3) Å, α
107·95(1), β 102·71(1), γ 73·23(1)°,
Z2.
Epiphorellic Acid 3, a New Lichen Diphenyl Ether
Authors: Elix John A. , McCaffery Leslie F.
Published: August 2004

The diphenyl ether epiphorellic acid 3
[6-hydroxy-3-(5′-hydroxy-2′-methoxycarbonyl-3′-propylphenoxy)-4-methoxy-2-pentylbenzoic
acid] (3) has been prepared by unambiguous synthesis, and has been
detected in the lichen Coelopogon abraxas by
chromatographic and spectroscopic comparisons.
Synthesis and Activity of Some Antimalarial Bisquinolinemethanols
Authors: Cowman, Alan F. , Deady, Leslie W. , Deharo, Eric , Desneves José , Tilley Leann
Published: August 2004

A new type of bisquinoline antimalarial, containing the basic side chain of
the cinchona alkaloids, has been evaluated. Five bis ethers, from
10,11-dihydrocupreine linked through the 6′-hydroxy group by
-(CH2)2n- bridges
(n = 2-5) (series A), and six bis amides, from
8′-amino-10,11-dihydrocinchonidine linked by
-CO(CH2)2nCO- bridges
(n = 1-6) (series B), were synthesized and
screened against chloroquine-sensitive and -resistant strains and a
mefloquine-resistant strain of
Plasmodium falciparum in vitro. Two analogues of series
B (n= 4; 5), with a
2-(dibutylamino)-1-hydroxyethyl side chain (series C), were also included.
Compounds within series A were generally least active. Among the rest were
compounds as active as mefloquine, with diminished cross-resistance to the
mefloquine-resistant strain. The most potent (series B,
n = 4) was highly active against
chloroquine-sensitive, chloroquine-resistant and mefloquine-resistant
parasites. Invivo testing, however, showed the compound
to be too toxic for further development
Some Chemistry of Ru3(µ-H)(µ3-CMeCHCMe)(CO)9: Reactions with Diphenylethyne and Characterization of a Digold Derivative
Authors: Bruce Michael I. , Gulbis Jacqueline M. , Humphrey Paul A. , Surynt Richard J. , Tiekink Edward R. T.
Published: August 2004

The complex
Ru3(µ3-CEtCMeCPhCPh)(CO)7{Au2(PPh3)2}
(3) has been shown by a single-crystal X-ray structure determination to
contain a
C4Au2Ru3
cluster with an unusual geometry, consisting of the Au2
unit interacting with a C4Ru3
pentagonal bipyramid. Complex (3) was obtained from
[O{Au(PPh3)}3]
[BF4]/[ppn]
[Co(CO)4] and the product (2) obtained from
C2Ph2 and
Ru3(µ-H)-(µ3-CMeCHCMe)(CO)9,
previously assumed to have a CMeCEtCPhCPh ligand.
New Depsides from the Lichen Neofuscelia depsidella
Authors: Elix John A. , Wardlaw Judith H.
Published: August 2004

The new depsides decarboxydivaricatic acid (3),
decarboxy-2′-O-methyldivaricatic acid (4), de-
carboxynorstenosporic acid (5), decarboxynorimbricaric acid (6),
decarboxystenosporic acid (7),
decarboxy-2′-O-methylnorimbricaric acid (8),
decarboxyanziaic acid (9) and decarboxyperlatolic acid (10), and the novel
tridepsides depsidellin A (23), depsidellin B (27) and depsidellin C (29) have
been detected in the lichen Neofuscelia depsidella and
their structures determined by total synthesis
'Soft' Calixarenes–Structural Aspects of Calixarene Allyl Ethers and of Thiacalixarene Synthesis
Authors: Delaigue Xavier , Harrowfield Jack M. , Hosseini M. Wais , Mocerino Mauro , Skelton Brian W. , White Allan H.
Published: August 2004

Syntheses and room-temperature single-crystal X-ray structure determinations
are recorded for an array of
p-t-butylcalix[n]arenes,
n = 4 or 6, diversely functionalized at the
phenolic oxygen atoms: the 1,3-diallyl 2,4-dimethyl ether for
n = 4 (1), the hexaallyl ether for
n = 6 (2), and the 1,3-dibenzyl
2,4-bis(dimethylthiocarbamoyl) derivative for n =
4 (3), with a view to establishing ligand baseline conformations for
subsequent metal complexation studies, and for exploring any inclusion
properties. Compound (1) is monoclinic,
P21/c,
a 16·751(9), b
20·772(7), c 27·91(1) Å, β
99·39(4)°, Z = 8, conventional
R on |F| being
0·060 for No 4396
'observed' (I >
3σ(I )) reflections. Compound (2) is triclinic,
P-1, a
19·63(2), b 14·57(2),
c 14·188(9) Å, α 107·84(8),
β 93·26(7), γ 99·48(10)°, Z
= 2, R 0·067 for
No 7315. Compound (3), as its
methanol monosolvate, is triclinic,
P-1, a
15·592(4), b 15·17(3),
c 14·31(2) Å, α 88·8(1), β
64·3(1), γ 75·7(1)°, Z = 2,
R 0·076 for
No 3802. The conformation of (1)
is similar to that previously established for an analogue in which two of the
t-butyl groups were absent; the conformation of (2) is that of a flattened
1,2,3-alternate form, the asymmetric unit being a pair of half
(centrosymmetric) dimers; the conformation of (3) is 1,3-alternate.
Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. IV [Acid Salts] of the 4-Nitrophenoxides of Group 1
Authors: Harrowfield Jack M. , Sharma Raj Pal , Skelton Brian W. , White Allan H.
Published: August 2004

Room-temperature single-crystal X-ray studies are recorded for a number of
‘acid salts’ formed between Group 1 salts of 4-nitrophenol,
M(4-np), and the parent ligand 4-npH, variously hydrated. The 1 : 1 salts
M(4-np)(4-npH).x H2O are found for
all of M = Li, Na, K, Rb and Cs. The lithium adduct (tetrahydrate) is
monoclinic, C2/c,
a 19·438(4), b
11·207(2), c 7·421(2) Å, β
91·38(2)°, Z = 4, conventional
R on |F| being
0·043 for 1369 independent ‘observed’
(I > 3σ(I))
diffractometer reflections. The sodium adduct (dihydrate) is monoclinic,
C2, a 2·174(3),
b 3·674(2), c
10·358(1) Å, β 117·21(1)°, Z
= 2, R 0·035 for
No 1092; the potassium adduct
(monohydrate) is monoclinic, C
2/c, a 22·10(1),
b 3·798(3), c
21·270(6) Å, β 120·97(4)°, Z
= 4, R 0·050 for
No 1065. The isomorphous rubidium
and caesium monohydrates are triclinic,
P-1, a ≈
11·9, b ≈ 10·2,c
≈ 6·3 Å, α ≈ 90, β ≈ 92, γ ≈ 112°,
Z = 2, R 0·042,
0·028 for No 2340, 3053
respectively. For M = Rb, a 1 : 3 adduct Rb(4-np).3(4-npH) is also
obtained (with an isomorphous thallium counterpart recorded elsewhere):
a 12·143(5), b
11·50(1), c 11·36(1) Å, α
114·38(9), β 110·54(6), γ 96·73(6)°,
Z = 2, R 0·034 for
No 3945. The lithium salt may be
represented as
[Li(OH2)4]+
(4-npH.4-np)½-. The cation lies disposed about a
crystallographic 2 axis; the anion, close to an axis,
confronts its rotational image, with the associated hydrogen atom modelled as
disordered between them, rather than located on the 2
axis. The sodium salt is a sheet structure, the six-coordinate sodium atoms
being disposed on a crystallographic 2 axis and linked
up that axis ...
Na(µ-O)2Na(µ-O)2Na ...
by bridging water molecule oxygen atoms, while symmetry-related trans
O-nitrophenoxide moieties are bridged by confronting
phenoxide oxygen atoms about an associated hydrogen atom provisionally
disposed on a 2 axis also. The potassium salt structure
is developed from this array, modelled with disordered potassium atoms, now
lying off the 2 axis, 0·922(2) Å apart. In
the rubidium/caesium structure, columns of oxygen-bridged metal ions are
disposed about c, crosslinked by
O-nitro-bonded phenoxide moieties, with confronting
phenoxide oxygen atoms about a shared associated hydrogen.
Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. VI 4-Nitrophenoxides of Group 2
Authors: Harrowfield Jack M. , Sharma Raj Pal , Skelton Brian W. , Venugopalam Paloth , White Allan H.
Published: August 2004

Room-temperature single-crystal X-ray structure determinations are recorded
for 4-nitrophenolate (4-np-) salts of Group 2 metal
ions, variously hydrated,
M(4-np)2.xH2O,
M = Mg, Ca, Sr, Ba.
Mg(4-np)2.8H2 O is monoclinic,
P21/c,
a 12·402(3), b 6·673(7),
c 11·833(6) Å, β 93·70(3)°,
Z = 2; conventional R on
|F| was 0·041 for
No 1995 independent
‘observed’ (I >
3σ(I)) reflections.
Ca(4-np)2.4H2O is monoclinic,
P21/c,
a 13·109(8), b
3·644(1), c 21·181(8) Å, β
125·55(3)°, Z= 2,
R 0·050 for No 1371.
Sr(4-np)2.8H2O is monoclinic,
P21/n, a
7·934(1), b 10·658(1),
c 23·602(2) Å, β 91·36(1)°,
Z = 4, R 0·038 for
No 2050.
Ba(4-np)2.8H2O is monoclinic
P21/c,
a 15·990(8), b
6·337(3), c 25·634(8) Å, β
126·1(3)°, Z = 4,
R 0·021 for
No 3115. The magnesium salt is
ionic with
[Mg(OH2)6]2+
cations and interleaved anion stacks up b. The calcium
salt is a one-dimensional polymer with ...
Ca(µ-O)2Ca(µ-O)2Ca ...
spine, the bridges being phenolic oxygen
atoms.trans-Coordinated water molecules make up
six-coordination about the calcium, the anion planes stacking at the
b spacing. The strontium adduct is also a
one-dimensional polymer with a similar spine, but with water molecule oxygen
atoms bridging, the nine-coordinate strontium environment being made up by a
chelating nitro group and three unidentate water molecules. Coordinated anions
stacked up a are interleaved by free anions. The barium
salt is simply
[Ba(4-np)(OH2)8]+
(4-np-), the ligand anion (semi)chelated through the
nitro pair of oxygen atoms, again with interleaving anion/ligand stacking.
Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. VII Acid Salts of the 4-Nitrophenoxides of Group 2
Authors: Harrowfield Jack M. , Sharma Raj Pal , Skelton Brian W. , White Allan H.
Published: August 2004

Room-temperature single-crystal X-ray structure determinations are recorded
for a number of Group 2 4-nitrophenoxide acid salts, variously hydrated
M(4-np)2.x(4-npH).yH2O.
Ca(4-np)2.2(4-npH).8H2O is
monoclinic, P
21/n, a 30·52(1), b
10·027(1), c 23·65(2) Å, β 116·3(5)°,
Z = 8, conventional R on
|F| being 0·058 for
No 5092 independent
‘observed’ (I >
3s(I)) reflections.
Sr(4-np)2.2(4-npH).8H2O, based on
a subcell of the former, is monoclinic, P
21/c, a
15·576(5), b10·081(6),
c 24·20(2) Å, β 117·99(5)° ,
Z = 4, R 0·054 for
No 2908.
Ba(4-np)2.2(4-npH).4H2O is
orthorhombic, Fdd2, a
28·01(1), b 19·90(1),
c 10·692(7)Å, Z
= 8, R 0·028 for
No 1967. The strontium array (and
that of the calcium salt developed from it) may be represented as
[(H2O)6Sr(4-npH.4-np)]
(4-npH.4-np), a neutral ligand being unsymmetrically chelated to the strontium
through the nitro group, with a quasi-parallel counter ion hydrogen-bonded to
it by phenoxide confrontation. The other two 4-np residues make up a similar
phenoxide-confronting pair (4-npH.4-np), the hydrogen being more intimately
associated with one moiety. The barium salt is also an interesting array: the
10-coordinate barium lies on a crystallographic 2 axis,
in an environment of two pairs of symmetry-related nitro-chelating ligand
anions, and a pair of nitro-O coordinating neutral 4-npH
ligands; the whole
[(H2O)4Ba(4-np)2(4-npH)2]
array may be envisaged as a single neutral (super)molecule. Hydrogen bonds
between confronting phenoxides of the neutral 4-npH components of the parent
and the 4-np- components of neighbouring molecules link
the whole into a three-dimensional array.
Substituent Effects in the Preparation of Quinazolinones by Rhodium-Catalysed Hydroformylation Reactions of 2-(Allylamino)benzamides
Authors: Campi Eva M. , Jackson W. Roy , Trnacek Andrew E.
Published: August 2004

Rhodium-catalysed reactions of 2-(allylamino)benzamides with 4-chloro,
5-methyl and 5-nitro substituents in the arene ring give varying yields of
pyrrolo[1,2-a]quinazolinones together with
branched chain aldehydes.
Pigments of Fungi. XLV The Cardinalins 8 - 12, Unique Pre-naphthoquinone Dehydro Dimers from the New Zealand Toadstool Dermocybe cardinalis
Authors: Buchanan, Malcolm S. , Gill Melvyn , Yu Jin
Published: August 2004

Five new pre-naphthoquinone dehydro dimers (3)–(7) belonging to the
unique cardinalin class of pyranonaphthoquinonoid natural products have been
isolated and characterized from the ethanolic extracts of the fruit bodies of
the New Zealand toadstool Dermocybe cardinalis. Four
other cardinalin derivatives (8) and (10)–(12) are believed to be
artefacts of the purification procedure. The structures and relative
stereochemistry of these new cardinalins are deduced from spectroscopic data.
Neutron Powder Diffraction Study of Sr2SnO4 and Ba2SnO4
Authors: Kennedy Brendan J.
Published: August 2004

The structures of Sr2SnO4
(I 4/mmm,
a 4·0528(1), c
12·5852(5) Å) and
Ba2SnO4 (I
4/mmm, a 4·1428(1),
c 13·2993(4) Å) have been refined from
neutron powder diffraction data by the Rietveld method. The results show the
SnO6 polyhedra are not regular octahedra but are either
elongated or compressed along the c direction depending
on the dimension of the AO layer in these
A2SnO4-type compounds.
Formation of Cyclopent[a]indene and Acenaphthylene from Allyl Esters of Biphenyl Mono- and Di-carboxylic Acids and from Biphenyl Dicarboxylic Anhydrides on Flash Vacuum Pyrolysis at 1000 - 1100°C
Authors: Bapat, Jayant B. , Brown Roger F. C. , Bulmer, Glenn H. , Childs, Trevor , Coulston Karen J. , Eastwood Frank W. , Taylar Dennis K.
Published: August 2004

Flash vacuum pyrolysis at 1000-1100°C of the allyl esters of the three
isomeric biphenylcarboxylic acids, of the allyl esters of the 12
biphenyldicarboxylic acids and of the three biphenyldicarboxylic anhydrides
gave pyrolysates which were examined by 1H n.m.r.
spectroscopy at temperatures below -50°C. In all cases the spectra showed
the presence of cyclopent[a]indene and
acenaphthylene together with other products. Possible mechanisms for these
ring contraction and cyclization processes are discussed and the results of
pyrolyses of [2,3-13C2]
biphenyl-2,3-dicarboxylic anhydride, and
[3,4-13C2]- and
(2-2 H1)-biphenyl-3,4-dicarboxylic
anhydrides are reported.
Crystal Structures of the Pentacoordinate Bromo, Isocyanato, Iodo, Acetato and Isothiocyanato Complexes of the meso-Tetraphenylporphyrinatomanganese Cation
Authors: Turner Peter , Gunter Maxwell J. , Skelton Brian W. , White Allan H.
Published: August 2004

The room-temperature single-crystal X-ray diffraction determined structures of the Mn(tpp)Br.C7H8, Mn(tpp)(NCO), Mn(tpp)I.C7H8, Mn(tpp)(CO2CH3).0·5C7H8, and Mn(tpp)(NCS).0·5C7H8 complexs are described. The monoclinic P21/c unit cell of Mn(tpp)(NCO) has a 14·82(1), b 17·136(5), c 14·576(5) Å, β 111·41(5)°, V 3446(3) Å3, Z 4. The refinement converged with conventional R(|F|) 0·053 for No 3199 (I > 3·0σ(I)) ‘observed’ reflections. The monoclinic P 21/m unit cell of Mn(tpp)Br.C7H8 has a 9·984(1), b 15·453(6), c 13·583(3) Å, β 103·99(2)°, V 2033(1) Å3, Z 2, R 0·039 for No 2668. The Mn(tpp)I.C7H8 structure is triclinic, P-1, with a 22·28(1), b 14·466(4), c 13·555(6) Å, α 76·32(3), β 81·74(4), γ 74·75(3)°, V 4079(3) Å3, Z 4, R 0·050 for No 9039. The triclinic P-1 crystal structures of the Mn(tpp)(CO2CH3).0·5C7H8 and Mn(tpp)(NCS).0·5C7H8 complexes are isomorphous. The Mn(tpp)(CO2CH3).0·5C7H8 structure has a 26·18(1), b 13·503(3), c 12·074(6) Å, α 66·08(4), β 81·36(4), γ 86·71(5)°, V 3858(3) Å3, Z 4, R 0·075 for No 6388. Solvate disorder, requiring a rigid body model, islargely responsible for the relatively high residuals. The Mn(tpp)(NCS).0·5C7H8 structure has a 25·442(6), b 13·746(3), c 12·182(5) Å, α 66·97(3), β 78·59(3), γ 87·90(2)°, V 3839(2) Å3, Z 4, R 0·061 for No 5506. The asymmetric units of the iodo, acetato and isothiocyanato structures each contain two crystallographically independent complex molecules that are sensitive to crystal packing forces. The metal ion displacements from the least-squares planes formed by the pyrrole nitrogen atoms are 0·299(1) and 0·274(1) Å for the Mn(tpp)(NCO) and Mn(tpp)Br.C7H8complexes, and 0·240(1) and 0·252(1), 0·281(1) and 0·278(1), and 0·243(1) and 0·244(1) Å for the independent (a) and (b) complex molecules of Mn(tpp)I.C7H8, Mn(tpp)(CO2CH3).0·5C7H8, and Mn(tpp)(NCS).0·5C7H8 respectively. The axial Mn–X bond lengths are 2·029(5) and 2·490(1) Å for the Mn(tpp)(NCO) and Mn(tpp)Br.C7H8 complexes, and 2·767(1) and 2·730(1), 2·028(5) and 2·010(5), and 2·067(6) and 2·072(5) Å for the (a) and (b) complex molecules of Mn(tpp)I.C7H8, Mn(tpp)(CO2CH3).0·5C7H8, and Mn(tpp)(NCS).0·5C7H8. One of the independent complex molecules in the Mn(tpp)(CO2CH3).0·5C7H8 structure appears to exhibit acetate coordination through a carbonyl oxygen.
Syntheses of Angucyclinones Related to Ochromycinone
Authors: Rozek Tomas , Janowski Wit , Hevko John M. , Tiekink Edward R. T. , Dua Suresh , Stone David J. M. , Bowie John H.
Published: August 2004

Two synthetic approaches have been investigated for the syntheses of model
angucyclinones related to ochromycinone. The first involves a
Diels–Alder/Friedel–Crafts strategy in which the
Diels–Alder adduct formed between dimethyl acetylenedicarboxylate and
3-ethenyl-5,5-dimethylcyclohex-2-en-1- one was converted into
6,6-dimethyl-8-oxo-5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic anhydride,
which was then reacted with benzene in a Friedel–Crafts reaction.
Acid-catalysed cyclization of the Friedel–Crafts products gave
3,3-dimethyl-3,4-dihydrobenz[a]anthracene-1,7,12(2H)-trione
(3) in poor yield. Angucyclinones related to (3) are formed (in
40–50% overall yield) by aromatization of the adduct formed
between the appropriate 1,4-naphthoquinone and
3-[(E)-2-methoxyethenyl]-
5,5-dimethylcyclohex-2-en-1-one (this dienone reacts with itself by a
Diels–Alder process to yield an adduct which decomposes to
3,3,8,8-tetramethyl-3,4,7,8-tetrahydroanthracene-1,6(2H,5H)-dione).
When the substituted 1,4-naphthoquinone is unsymmetrical, a boron triacetate
assisted Diels–Alder reaction gives a single regioisomer (e.g. X-ray
investigations indicate that
8-hydroxy-3,3-dimethyl-3,4-dihydrobenz[a]anthracene-1,7,12(2H)-trione
is the product from 5-hydroxy-1,4-naphthoquinone). An X-ray structural study
of the Diels–Alder adduct in the above reaction confirms the operation
of an endo cyclization.
The Synthesis of a Diastereoisomer of Methyl Acarviosin
Authors: McAuliffe Joseph C. , Stick Robert V. , Tilbrook D. Matthew G. , Watts Andrew G.
Published: August 2004

In model studies, a fully protected D-galactopyranoside 4-triflate and two
6-deoxy analogues were shown to alkylate cyclohexylamine, leading to
4-cyclohexylamino-4-deoxy- and 4,6-dideoxy-D-glucopyranosides as the major
products in satisfactory yield, accompanied by alkenes resulting from
elimination of triflic acid. Coupling of
tetra-O-benzyl-1-epivalienamine with methyl
3-O-benzoyl-6-deoxy-4-O-
trifluoromethylsulfonyl-β-D-galactoside gave a diastereoisomer of methyl
acarviosin in protected form. Deprotection completed the first synthesis of
methyl
4,6-dideoxy-4-[(1′R,4′R,5′S,6′S)-4′,5′,6′-trihydroxy-3′-(hydroxymethyl)cyclohex-2′-enyl]amino-β-D-glucoside,
a potential β-glycosidase inhibitor.
Pigments of Fungi. XLVII. Cardinalic Acid, a New Anthraquinone Carboxylic Acid from the New Zealand Toadstool Dermocybe cardinalis and the Synthesis and X-Ray Crystal Structure of Methyl 1,7,8-Tri-O-methylcardinalate
Authors: Gill Melvyn , Morgan Peter M. , Yu Jin , White Jonathan M.
Published: August 2004

Cardinalic acid
(1,7,8-trihydroxy-6-methoxy-3-methyl-9,10-dioxoanthracene-2-carboxylic acid)
(4) and the known anthraquinone carboxylic acids endocrocin (1), dermolutein
(2) and cinnalutein (3) have been isolated from the New Zealand toadstool
Dermocybe cardinalis. Methyl
1,7,8-tri-O-methylcardinalate (5) has been prepared both
by permethylation of the natural product (4) and from
2,6-dichloro-1,4-benzoquinone by two consecutive regioselective
Diels–Alder cycloaddition reactions. A single-crystal X-ray structure
analysis of the ester (5) corroborates the structure of the natural product
(4) and confirms the outcome of both cycloaddition reactions.
Sulfonamide Analogues of Creatinine. The Synthesis of 3-Amino-4,5-dihydro-1,2,4-thiadiazole 1,1-Dioxides from Base-Induced Cyclization Reactions
Authors: Fares Fares A. , Ridley Damon D. , Yin Ping
Published: August 2004

We report the preparation of 3-amino-4,5-dihydro-1,2,4-thiadiazole 1,1-dioxide
and of its 4-methyl derivative which are of interest as potential analogues of
creatinine. The thiadiazoles are obtained from chloromethylsulfonylation
ofS-benzylisothiourea, followed by cyclization of the
chloromethanesulfonamide under basic conditions in the presence of
2-(t-butoxycarbonyloxyimino)-2-phenylacetonitrile or of methyl iodide.
Anion Effects on the Structural Properties of Bis(triphenylphosphine)copper(I) Carboxylate Complexes, [(PPh3)2CuO2CR]
Authors: Hart Robert D. , Healy Peter C. , Peake Michelle L. , White Allan H.
Published: August 2004

The crystal and molecular structure of the 2 : 1 triphenylphosphine copper(I)
benzoate complex
[(PPh3)2CuO2CC6H5]
have been determined by a room-temperature single-crystal X-ray study. The
complex is isomorphous with the dithiobenzoate analogue, crystallizing in the
orthorhombic space group
P212121 with
a 20·094(5), b
16·929(9), c 10·659(8) Å,
Z 4; conventional R on
|F| was 0·039 for 4261 independent
‘observed’ (I >
3σ(I)) reflections. Comparison of structural data
for this and other
[(PPh3)2CuO2CR]
complexes shows that the P–Cu–P angle and the anion coordination
are dependent on both the donor strength of the anion and on steric
interactions between the anion and the triphenylphosphine ligands. The
structure of the analogous nitrate complex
[(PPh3)2CuNO3]
has also been redetermined.
A New One-Dimensional Bimetallic Complex: Cu(en)2Fe(CN)5(NO). Synthesis, Crystal Structure and Magnetic Behaviour
Authors: Kou Hui-Zhong , Wang Hong-Mei , Liao Dai-Zheng , Cheng Peng , Jiang Zong-Hui , Yan Shi-Ping , Huang Xiao-Ying , Wang Geng-Lin
Published: August 2004

The nitrosyl cyanide
Cu(en)2Fe(CN)5(NO) was prepared by
the reaction of Cu(en)2Cl2 and
Na2
[Fe(CN)5(NO)].2H2O in
aqueous solution. Single-crystal X-ray structure analysis revealed that the
complex assumes a cyanide-bridged chain structure in which iron(II) is
coordinated by five cyanide ligands and a nitrosyl group, and copper(II) is
coordinated by two ethylenediamine ligands and two bridging cyanide ligands.
The copper centres display a typical Jahn–Teller distortion
characteristic of octahedral copper complexes with bond distance deviations in
lattice symmetry from octahedral ideality: Cu-N(equatorial, mean)
2·010(3) Å and Cu-N(axial, mean) 2·569(3) Å.
Infrared and ultraviolet studies shed light on the above molecular structure.
A magnetic investigation showed the presence of a weak antiferromagnetic
interaction (J = -1·06
cm-1) between the copper atoms within each chain through
the diamagnetic Fe(CN)5(NO)2-
ions.
The Ground State in Tris(acetylacetonato)ruthenium(III) from Low-Temperature Single-Crystal Magnetic Properties
Authors: Reynolds Philip A. , Figgis Brian N. , Moubaraki Boujemaa , Murray Keith S.
Published: August 2004

The magnetic susceptibilities of tris(acetylacetonato)ruthenium(III) have been
measured between 2·5 and 300 K along the a,
b, c, and
a* axis directions, together with the magnetizations
along the same directions up to a magnetic field of 5 T. There is a small
amount of magnetic exchange interaction apparent below 10 K, with Weiss
constants up to –0·35 K and the magnetization is fitted with
exchange integrals up to –0·38 K in magnitude. A pathway for
magnetic exchange in terms of a pair of symmetry-related Ru(acac) rings lying
parallel and close is obvious from the structure. The susceptibility results
above 10 K have been interpreted in terms of a four-parameter ligand field
model (CF1) operating on the ground
2T2g term of the
d5 configuration. The t2g orbitals
are found to be split by 475 cm-1 by a dominant trigonal
symmetry component and then by –50 cm-1 by a
subsidiary rhombic component. The single-electron spin-orbit coupling constant
is 875 cm-1 and the orbital angular momentum reduction
parameter is 0·7. The g-values deduced for the
ground Kramers doublet are not in good agreement with those from e.s.r.
experiments, but rather better agreement is found for closely allied ligand
field parameter sets (CF2) which can fit the susceptibilities at particular
temperatures but do not reproduce their temperature dependence well.
Consideration of the variation of structural details with temperature indicate
that, in fact, the CF2 sets may be more realistic.
Reactions of RuCl(C=CHBut)(PPh3)(hC5Me5) with Tertiary Phosphites: Molecular Structure of RuCl{P(OPh)3} 2(h;-C5Me5)
Authors: Bruce Michael I. , Hall Ben C. , Tiekink Edward R. T.
Published: August 2004

Reactions between
RuCl(C=CHBut)(PPh3)(η-C5Me5)
and tertiary phosphites result in displacement of both vinylidene and tertiary
phosphine ligands to give
RuCl{P(OR)3}2(η-C5Me5)
(R = Me, Ph). The crystal and molecular structures of
RuCl{P(OPh)3}2(η-C5Me5)
are reported.
New Multifunctional Polar Silanes for Polymer Modification
Authors: Hewitt David G. , Jing Lin
Published: August 2004

New trifunctional carbosilanes containing hydroxy, alkenyl, chloro and cyano
groups have been synthesized in good yields. A useful synthesis of these
polymer precursors from dichlorosilanes was developed after it was found that
hydrosilation of functionalized alkenes by a dihydrosilane,
2-cyanoethylmethyldihydrosilane, failed to give the expected dialkylsilanes.
Preparation and X-Ray Crystal Structures of Tetrahydrofuran-Complexed Rare Earth Chlorides — a Structurally Rich Series
Authors: Deacon Glen B. , Feng Tiecheng , Junk Peter C. , Skelton Brian W. , Sobolev Alexander N. , White Allan H.
Published: August 2004

Anhydrous lanthanoid metal chlorides
LnCl3(thf)n (Ln = La, Ce,
Nd, Sm, n = 2; Ln = Tb, Ho,
n = 2·5; Ln = Dy, Tm,
n= 2·7; Ln = Gd, Yb, Lu,
n = 3; Ln = Er, n
= 3·5) have been prepared in excellent yield by the direct
reaction of the lanthanoid metal powders with hexachloroethane in
tetrahydrofuran (thf), and (Ln = Eu, n =
0·8; Ln = La, n = 1·7; Ln
= Pr, n = 2; Ln = Gd,
n = 2·5; Ln = Er,
n = 3) in good yield except for
EuCl3(thf)0·8 from bulk metal.
[YbCl3(thf)2]2
was prepared by prolonged treatment of solid
YbCl3(thf)3 with pentane. The
X-ray crystal structures of
[LnC3(thf)2] (Ln
= La, Ce or Pr),
[LnCl3(thf)3.5] (Ln
= Gd or Er),
[YbCl3(thf)3] and
[LaCl3(thf)(H2O)] have
been determined. For
[LaCl3(thf)2], a square
antiprismatic single-stranded polymer, ...
La(-Cl)3(thf)3La(-Cl)3(thf)2
..., is the first eight-coordinate
LnCl3(thf)n complex. The metal is
surrounded by two sets of three bridging chlorines and cis thf oxygens.
[LnCl3(thf)2] (Ln
= Ce, Pr) have seven-coordinate structures with doubly chloride-bridged
linear chains, ...
LnCl(µ-Cl)3(thf)2LnCl(µ-Cl)2(thf)2
... where the lanthanoid atom exists in a pentagonal bipyramidal environment,
the pentagonal bipyramidal plane being defined by four chloride atoms and one
oxygen atom of the thf ligand, and the axial positions being occupied by a
chloride and a thf oxygen atom.
[LnCl3(thf)3.5] (Ln
= Gd, Er) crystallize as discrete ion pairs,
[LnCl2(thf)5]+
[LnCl4(thf)2]¯. The
lanthanoid atom in the cation displays pentagonal bipyramidal geometry with
two apical chloride atoms and five equatorial thf ligands while the anion has
quasi-regular octahedral stereochemistry with trans thf ligands.
[LaCl3(thf)(H2O)]
displays an eight-coordinate two-dimensional polymeric array with six bridging
chlorides per lanthanum atom. Far-infrared spectra have been recorded for a
number of products and used as a basis for structural proposals, particularly
for products with fractional thf.
The Asymmetric Dihydroxylation of Some Alkenyl 2-Acetylamino-2-deoxy-β-D-glucopyranosides: the Preparation of Optically Pure Epoxides as Putative Inhibitors of Chitinases
Authors: Fairweather Jon K. , Stick Robert V. , Tilbrook D. Matthew G.
Published: August 2004

Various alkenyl 2-acetylamino-2-deoxy-β-D-glucopyranosides have been
subjected to the Sharpless asymmetric dihydroxylation protocol to yield the
corresponding diols, albeit with somewhat disappointing stereoselectivity. An
alternative, more traditional approach has yielded the optically pure
epoxyalkyl 2-acetylamino-2-deoxy-β-D-glucopyranosides as putative
inhibitors of chitinases. As well, an epoxypropyl chito-bioside and -trioside
have been prepared, each as mixtures of two diastereoisomers.
cis-3-Hydroxy-N-methyl-L-proline: a New Amino Acid from a Southern Australian Marine Sponge, Dendrilla sp.
Authors: Capon Robert J. , Ovenden Simon P. B. , Dargaville Tim
Published: August 2004

A specimen of the sponge Dendrilla sp. collected during
commercial trawling operations in the Great Australian Bight, Australia,
analyses for a very high natural abundance of the new amino acid
cis-3-hydroxy-N-methyl-L-proline
(1). The complete stereostructure for (1) was determined by spectroscopic
analysis and chemical derivatization.
Two New Clerodane Glycosides from Gleichenia microphylla
Authors: Wada Hiroshi , Shimizu Yasufumi , Hakamatsuka Takashi , Tanaka Nobutoshi , Cambie Richard C. , Braggins John E.
Published: August 2004

From the fronds of Gleichenia microphylla, two new
clerodane glycosides were isolated. Their structures were determined to be
(6S,13S)-6-[O-α-L-rhamnopyranosyl-(1→6)-O-β-D-glucopyranosyl-(1→3)-α-L-rhamnopyranosyloxy]-13-[O-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranosyloxy]cleroda-3,14-diene
and
(6S,13S)-6-[O-α-L-rhamnopyranosyl-(1→6)-O-β-D-glucopyranosyl-(1→3)-α-L-rhamnopyranosyloxy]-13-[O-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranosyloxy]cleroda-3,14-diene
on the basis of their spectroscopic data and chemical evidence.
Synthesis of Some 1,2,3,8-Tetrasubstituted Naphthalenes
Authors: Comber Mark F. , Morris Jonathan C. , Sargent Melvyn V.
Published: August 2004

Effcient methods for the synthesis of 3,4,5-trimethoxynaphthalene-2-carboxylic
acid (7) and 2,8-dimethoxy-3-methylnaphthalene-1-carboxylic acid (25) are
described.
Synthesis of 7-Methoxy-3′,4′,5′,6′-tetrahydrospiro-[isobenzofuran-1(3H),2′-pyran]-3-one and 5,7-Dimethoxy-3′,4′,5′,6′-tetrahydrospiro[isobenzofuran-1(3H),2′-pyran]-3-one
Authors: Brimble Margaret A. , Chan Seng H.
Published: August 2004

The synthesis of novel aryl spiroketals, which contain a similar substitution
pattern to that present in the antifungal agents the papulacandins, is
described. Thus, spiroketal (7) was obtained from acid-catalysed cyclization
of the keto alcohol (13), and spiroketal (8) was obtained from acid-catalysed
cyclization of keto alcohols (12) and (19). Keto alcohols (12), (13) and (19)
in turn were prepared by ortho-directed lithiation of
amides (10), (11) and oxazoline (17) respectively, followed by reaction with
δ-valerolactone. Substitution of the aromatic ring occurred at the
sterically hindered position ortho to both the methoxy
and ortho-directing metalation group. In an alternative
approach to the synthesis of the desired spiroketals, two
palladium(0)-catalysed coupling strategies were examined. The Stille coupling
between the aryl stannane (24) and iodoglucal (25) resulted in a low yield of
the aryl C-glycoside (21). Likewise, a low yield for the
same coupled product (21) was achieved by a Suzuki coupling between the
arylboronic acid (26) and iodoglucal (25).
The Chemistry of 5-Oxodihydroisoxazoles. XX Photolysis of 2,4-Diphenylisoxazol-5(2H)-one: Evidence for Singlet and Triplet Pathways
Authors: Ang Kiah H. , Prager Rolf H.
Published: August 2004

2,4-Diphenylisoxazol-5(2H)-one (2) has been photolysed
in the presence of alcohols, amines and in inert solvents, and the products
are shown to arise by two competitive singlet state photolytic processes. The
minor pathway involves loss of carbon dioxide to give an imino carbene which
is captured by nucleophiles: the major pathway involves isomerization to a
ketene which is rapidly decarbonylated, and the resultant carbene captured by
solvent. The presence of acetone or other triplet sensitizers induces a third
competitive pathway involving triplet states.
Chemistry of Fijian Plants. XIV An Unsaturated Aryl Keto Acid from Xylocarpus moluccensis
Authors: Bercich M. Gabrielle , Cambie Richard C. , Lal Allick R. , Sidwell David
Published: August 2004

A new unsaturated aryl keto acid (1) and its methyl ester (2) have been
isolated from the wood of FijianXylocarpus moluccensis
and their structures determined by spectroscopic examination.
The Chemistry of 5-Oxodihydroisoxazoles. XXI Amidines and Pyrimidin-4-ones from the Reaction of Isoxazol-5(2H)-ones with Amines
Authors: Baradarani Mehdi M. , Clark Adrian , Prager Rolf H.
Published: August 2004

While isoxazol-5(2H)-ones substituted with heterocycles
at C2 but unsubstituted at C3 react with amines to give either amidines or
malonamides, their reaction at low temperatures with lithium dialkylamides is
a preparatively useful procedure for obtaining the amidines in most cases.
Longer reaction times may lead to formation of pyrimidin-4-ones when ester
groups are present at C4 of the isoxazolone.
Molecular Cocrystals of Carboxylic Acids. XXXI Adducts of 2-Aminopyrimidine and 3-Amino-1,2,4-triazole with Heterocyclic Carboxylic Acids
Authors: Lynch Daniel E. , Latif Tariq , Smith Graham , Byriel Karl A. , Kennard Colin H. L. , Parsons Simon
Published: August 2004

A series of molecular adducts of 2-aminopyrimidine and 3-amino-1,2,4-triazole
with heterocyclic carboxylic acids have been prepared and characterized by
using X-ray powder diffraction and in four cases by single-crystal X-ray
diffraction methods. These four compounds are the (1 : 1) adducts of
2-aminopyrimidine with indole-3-acetic acid
[(C4H5N3)(C10H9NO2)],
N-methylpyrrole-2-carboxylic acid
[(C4H5N3)(C6H7NO2)]
and thiophen-2-carboxylic acid
[(C4H5N3)(C5H4O2S)],
and the (1 : 1) adduct of 3-amino-1,2,4-triazole with thiophen-2-carboxylic
acid
[(C2H4N4)(C5H4O2S)].
Other compounds described are the (1 : 1) adducts of 3-amino-1,2,4-triazole
with indole-3-acetic acid and
N-methylpyrrole-2-carboxylic acid.
Acyl Transfer Isomerization of Glycerol 1,2-Dibutyrate and Propane-1,2-diol 1-Butyrate
Authors: O'Connor Charmian J. , Barton Richard H.
Published: August 2004

The speciation of mixed butyrylglycerols (glycerol butyrates) and propanediol
butyrate esters in the product mix from lamb pregastric lipase-catalysed
hydrolysis of tributyrylglycerol and propane-1,2-diol dibutyrate has been
examined by 13C n.m.r. spectroscopy. Samples from the
quenched reaction mixture were extracted and allowed to stand in emulsion
systems made up in bis tris propane buffer or water, pH 7·0, and in the
absence of enzyme. There is clear evidence of uncatalysed conversion of
rac-1,2-dibutyrylglycerol into the 1,3-isomer to form an
equilibrium mixture containing c. 60–67%
1,3-isomer, and of conversion of propane-1,2-diol 1-butyrate into
propane-1,2-diol 2-butyrate to form an equilibrium mixture containing
c. 67% 2-monoester. Conversion kinetics to reach
equilibrium are first order. Rate constants for acyl transfer of the
diacylglycerol are 0·48 h-1 (in water) and
0·68 h-1 (in buffer) at 50°C, while those for
acyl transfer of the 1-monoester are 0·72 h-1
(50°C) and 0·35 h-1 (35°C).
Oxidative Decarboxylation of Podocarpic Acid Derivatives
Authors: Cambie Richard C. , Davy Perry K. , Mitchell Lorna H. , Rickard Clifton E. F. , Rutledge Peter S.
Published: August 2004

The radical decarboxylation–sulfoxide cycloelimination of
2′-pyridylthio esters formed from a series of podocarpic acid
derivatives gives Δ4(18) -alkenes in high yield.
An exception is the 13-nitro acid (2) which affords a thiohydroxamic ester
(28), the relative stability of which is attributed to inhibition of the
radical chain reaction by the nitro group. The stereochemistry of the pyridyl
sulfide (18) has been confirmed by X-ray crystallography.
Preparation and Structure of [Ru(CO)2(PPh3)(η-C5Me5)][Fe3(µ3-C2But)(CO)9]
Authors: Bruce Michael I. , Zaitseva Natasha N. , Skelton Brian W. , White Allan H.
Published: August 2004

The reaction between
RuCl(C=CHBut)(PPh3)(η-C5Me5)
and Fe2(CO)9 afforded the salt
[Ru(CO)2(PPh3)-(η-C5Me5)]
[Fe3(µ3-C2But)(CO)9],
which has been characterized by a single-crystal X-ray structure
determination. The cation has a piano-stool structure, while the anion
contains a CCBut ligand sitting on a triangular
Fe3 cluster.
Probing the Ground-State δ Effect of Group 14 Metal Substituents. X-Ray Structures of cis- and trans-4-Trimethylmetal-Substituted Cyclohexyl p-Nitrobenzenesulfonates
Authors: Green Alison J. , Van Victor , White Jonathan M.
Published: August 2004

Accurate low-temperature X-ray structural studies on
trans-4-trimethylsilylcyclohexyl
p-nitrobenzene- sulfonate (31) and
cis- and
trans-4-trimethylstannylcyclohexyl
p-nitrobenzenesulfonates (32) and (33) failed to
demonstrate the presence of any significant structural effects due to a
σM-C-σC-C-σ*C-O
through-bond interaction between the C–M σ donor orbital and the
σ*C-ONs acceptor orbital.
Synthesis of Chiral Diazanedicarboxylates
Authors: Brimble Margaret A. , Duckworth Matthew S. , Lee Connie K. Y.
Published: August 2004

The potential of di-(–)-isobornyl diazenedicarboxylate (2) to act as a
chiral azo-enophile in asymmetric ene reactions was investigated. Azo-enophile
(2) was treated with trans-hex-3-ene and cyclohexene in
the presence of tin(IV) chloride affording the ene adducts (4) and (5)
respectively; however, no diastereoselectivity was observed. The synthesis of
the novel chiral diazanedicarboxylates (12), (17) and (19) and the
unsuccessful attempts to transform them into the chiral azo-enophiles (11),
(16) and (19) bearing chiral oxazolidinone, diacetone-D-glucose and
pantolactone chiral auxiliaries are also described.
Indirect Monobromination of the Cubane Nucleus. The Synthesis of Dimethyl 2-Bromocubane- 1,4-dicarboxylate
Authors: Bliese Marianne , Gable Robert W. , Fanning Lisa-Ann , Lowe David A. , Tsanaktsidis John
Published: August 2004

The preparation of dimethyl 2-bromocubane-1,4-dicarboxylate (3) is described
starting from the readily available
(3aα,4β,7α,7aα)-2,4-dibromo-3a,4,7,7a-tetrahydro-4,7-methano-1H-indene-1,8-dione
8-ethylene ketal (4).
Isolation and Structure of Some Constituents of the Australian Medicinal Plant Tinospora smilacina ('Snakevine')
Authors: Hungerford Natasha L. , Sands Donald P. A. , Kitching William
Published: August 2004

The structures of a number of compounds isolated from the stems of
Tinospora smilacina (known as ‘snakevine’)
have been determined. The known clerodane-type compound columbin is a major
component, and two new minor compounds incorporate a heavily oxygenated
tetrahydrofuran ring in place of the furan ring of columbin. The lignan
isolariciresinol is also shown to be a minor component, along with
dihydrosyringenin. The traditional medicinal use of the vine, particularly in
countering snake venom, may be associated primarily with the presence of
columbin.
Pyrolytic Electrocyclization of Arylmethylidene Derivatives of Glutacononitrile; Synthesis of Dihydroaromatic 1,3-Dinitriles
Authors: Banciu Mircea D. , Brown Roger F. C. , Coulston Karen J. , Eastwood Frank W. , Macrae Tamara
Published: August 2004

Condensation of seven aromatic aldehydes (1a–g) with glutacononitrile
(2) gave 4-(arylmethylidene)pent-2-enedinitriles (3a–g). Flash vacuum
pyrolysis of the dinitriles (3a–g) at 750°/0·
02–0·03 mm gives annulated dihydroaromatic 1,3-dicarbonitriles by
electrocyclic ring closure of (3). Fully aromatized products formed by
secondary loss of H2 or HCN are also obtained.
Aggregation-Induced Linear and Non-Linear Optical Properties of Four Hydroxy-Substituted Analogues of 2,4-Bis[4-(dibutylamino)phenyl]squaraine
Authors: Ashwell Geoffrey J. , Williamson Patricia C. , Green Andrew , Bahra Gurmit S. , Brown Christopher R.
Published: August 2004

Langmuir films of the title compound,
2,4-bis[4-(dibutylamino)phenyl]squaraine, Sq0, and its substituted
analogues, Sq1 (monohydroxy) to Sq4 (tetrahydroxy), exhibit three well defined
phases at the air–water interface: λmax
525–550 nm (H-aggregate); 660–670 nm (intermediate); 760–770
nm (J-aggregate). The monolayer spectra are influenced by the surface pressure
and the number of hydroxy substituents and, when the monolayers are
transferred to a solid substrate, there is a correlation between the linear
and non-linear optical behaviour of the Langmuir-Blodgett films.
Second-harmonic generation has been observed even though the unit molecular
structures of two analogues, Sq0 and Sq4, are centric. The behaviour is
aggregation-induced and there is evidence that the dyes associate in dilute
solution. The electrospray ionization mass spectra exhibit peaks with high
mass/charge (m/z) ratios; the data conform to the
dimeric aggregate and, for solutions of two or more squaraines, corroborate
the existence of heteromolecular associates.
Triplex Formation by an Oligonucleotide Containing the Novel Modified Nucleoside 2′-Deoxy-N4-phenylcarbamoylcytidine
Authors: Guzzo-Pernell Nancy , Lawlor John M. , Tregear Geoffrey W. , Haralambidis Jim
Published: August 2004

2′-Deoxy-N4-phenylcarbamoylcytidine
(Pc) was designed for triplex
recognition of the cytosine{guanine base pair at physiological pH values
to assist in the development of triplex-forming oligomers. Thermal
denaturation of a triplex mixture in which the third strand incorporated
Pc as a central nucleoside showed
that, at pH 6·1, Pc binds
selectively—though weakly—to the target cytosine—guanine and
also to guanine—cytosine; but the gel mobilities of the same mixtures
indicate the possibility of specificity for the target cytosine-guanine base
pair at pH values higher than 6·1. The result may provide leads useful
in the development of improved triplex-forming oligomers.
Regioselective Alkylation of β-Cyclodextrin
Authors: Bansal Paramjit S. , Francis Craig L. , Hart Noel K. , Henderson Scott A. , Oakenfull David , Robertson Alan D. , Simpson Gregory W.
Published: August 2004

Methodology for preparation of
heptakis(2,6-di-O-alkyl)-β-cyclodextrins,
heptakis(2-O-alkyl)-β- cyclodextrins, and
heptakis(6-O-alkyl)-β-cyclodextrins in substantially
purified form has been developed. Treatment of β-cyclodextrin (1) with
sodium or barium hydroxide and various alkyl halides in dimethyl sulfoxide or
a mixture of dimethyl sulfoxide and
N,N-dimethylformamide provided the corresponding
heptakis(2,6-di-O-alkyl)-β-cyclodextrins. Treatment
of heptakis(6-O-t-butyldimethylsilyl)-β-cyclodextrin
(5) with sodium hydroxide and several haloalkanes in dimethyl sulfoxide
followed by desilylation provided
heptakis(2-O-alkyl)-β-cyclodextrins. Protection of
the secondary hydroxy groups of the t-butyldimethylsilyl-β-cyclodextrin
(5) as benzyl ethers, followed by desilylation, alkylation, and debenzylation
afforded several
heptakis(6-O-alkyl)-β-cyclodextrins. Analytical
methodology has been developed to characterize all of these compounds, with
the homogeneity of the pattern of substitution verified by h.p.l.c. analysis,
f.a.b.–mass spectrometry and n.m.r. spectroscopy.
Invited Review. Combinatorial Synthesis: A Heterocyclic Chemist's Perspective
Authors: Loughlin Wendy A.
Published: August 2004

An overview of the combinatorial synthesis of heterocyclic compounds is
presented. Recent developments and innovations in the solid and solution phase
combinatorial synthesis of heterocyclic compounds are discussed.
Two New Clerodane Diterpenes from the New Zealand Marine Sponge Raspailia sp.
Authors: West Lyndon M. , Northcote Peter T. , Battershill Chris N.
Published: August 2004

Two new cis-ring fused clerodane diterpenes,
raspailenone (1) and raspailol (2), have been isolated from a
Raspailia species collected from subtidal waters of the
South Island of New Zealand. The structures of the two compounds have been
established by spectroscopic methods.
The Alkaloids of Uncaria cf. glabrata
Authors: Arbain Dayar , Afrida  , Ibrahim Satria , Sargent Melvyn V. , Skelton Brian W. , White Allan H.
Published: August 2004

Extraction of the aerial part of Uncaria cf.
glabrata D.C. (Rubiaceae) has yielded
(2R,3S)-(+)-catechin (1),
14α-hydroxyrauniticine (2) and rauniticine (3) which were identified by
their spectroscopic properties. A single-crystal X-ray structure determination
is reported for rauniticine (3).
Mechanochemical Reaction Between Sulfur and Ilmenite
Authors: Welham Nicholas J.
Published: August 2004

An ilmenite (FeTiO3) concentrate has been milled with
sulfur in a laboratory-scale ball mill for 100 h under a variety of
conditions. X-Ray diffraction and thermal processing have shown that
reaction occurs within the mill forming pyrite (FeS2)
and rutile (TiO2). The reaction was of greatest extent
in a mill run under 400 kPa of inert gas; some reaction occurred in a mill
under 10-2 Pa, whereas little reaction was observed when
either water or air was present. Annealing of the product powders showed that
reaction to TiO2 and FeS2 could be
achieved in a closed system after 1 h at 400C but with the evolution of
SO2, whereas annealing at 800C also gave
TiO2 and FeS2, but without
formation of SO2 which was thought to have
disproportionated to form iron sulfate(VI). Closed-tube annealing of unmilled
sulfur and milled ilmenite showed the same reactions as milled powders but of
much greater extent.
Synthesis of the Pentasubstituted Lichen p-Terphenyls Butlerins A, B and C
Authors: Ernst-Russell Michael A. , Chai Christina L. L. , Hockless David C. R. , Elix John A.
Published: August 2004

Total syntheses of the p-terphenyls butlerin A (1)
(3′,4,4′′,6′-tetramethoxy[1,1′:4′,1′′-terphenyl]-2′-yl
acetate), butlerin B (2)
(3′,4,4′′,5′-tetramethoxy[1,1′:4′,1′′-terphenyl]-2′-yl
acetate) and butlerin C (3)
(3′,4,4′′-trimethoxy[1,1′:4′,1′′-terphenyl]-2′,6′-diyl
diacetate), previously isolated from the lichen
Relicina connivens, are reported.
A Diastereomer of an ortho-Palladated R)-α-Methylbenzylamine Complex Containing an (R,R)-Tetra(tertiary phosphine) in Which the Two Organometallic Rings Have Opposite Helicities
Authors: Skelton Brian W. , Swiegers Gerhard F. , White Allan H. , Wild S. Bruce
Published: August 2004

The bis(palladium(II)–(R)-a-methylbenzylamine)
diastereomers of the
(R*,R*)-(±)-form of
the lin- ear tetra(tertiary phosphine)
1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane,
(RC)(RP,RP)-
and
(RC)(SP,SP)-(4),
are readily separated because of a large difference in their solubilities in
moderately polar solvents. The single-crystal X-ray structure of
(RC)(SP,SP)-(4),
along with published data on
(RC)(RP,RP)-(4),
suggests that the ease of separation is due to conformational differences in
the two organometallic rings present in each diastereomer (δδ or
δλ) in the solid state.
Studies on the Synthesis of Benzimidazo[2,1-a]isoquinolines
Authors: Deady Leslie W. , Loria Paul M. , Rodemann Thomas
Published: August 2004

The reaction of the isocoumarin derivative
1-acetylimino-3-methyl-1H-2-benzopyran-4-carbonitrile
(1a) with aromatic ortho diamines provides entry to the
benzimidazo[2,1-a]isoquinoline and related
systems. Various conversions of the methyl and cyano groups in the tetracycles
into amide, aldehyde and acid functions have been carried out, along with
studies of electrophilic nitration.
From IUPAC.
Compilation and Critical Evaluation of Structure-Reactivity Parameters and Equations. II Extension of the Hammett s Scale Through Data for the Ionization of Substituted Benzoic Acids in Aqueous Organic Solven
Authors: Shorter John
Published: August 2004

Data have been compiled for the pK values in certain
aqueous organic solvents at 25°C of about 70 meta-
or para-substituted benzoic acids, with a view to
proposing values of Hammett constants, σ, in the case of substituents
for which values cannot be based on the ionization of substituted benzoic
acids in water (Part I). The emphasis of the work is on the use of data for
the apparent pK values of the acids in 1 : 1
EtOH–H2O, i.e. a solvent made up of equal volumes
of ethanol and water. A calibration equation is derived relating substituent
effects measured in this solvent to those measured in water. On the basis of
this equation s values are proposed for 25 substituents, although some of the
values are subject to caveats, and several further substituents are also
discussed.