bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis and X-Ray Study of a Charge-Transfer Complex of Pyrido[2,3-H]pyrrolo[1,2-a]quinoxaline - 7,7,8,8-Tetracyano-p-quinodimethane (1:1)
Authors: Viossat B , Dung NH , Daran JC , Lancelot JC , Robba M
Published: September 2010

The structure of the title complex has been determined by a three-dimensional X-ray analysis. Triclinic crystals in space group Pī have lattice parameters a 7.0912(8), b 7.692(2), c 19.119(3)Ǻ, α 87.09(2),β 84.01(1),γ 82.72(1)°, Z 2. The structure was solved by means of direct methods and refined by full matrix least squares to R 0.039 and Rw 0.035 for 1671 observed reflections. Almost parallel tetracyanoquinodimethane (tcnq ) and pyridopyrroloquinoxaline molecules are stacked alternately along the a axis. Differences in C-C distances for the complexed tcnq molecule suggest a certain amount of charge-transfer interaction between donor and acceptor molecules.
Anisatin: a Crystallographic, N.M.R. and Theoretical Conformation Study
Authors: Wong MG , Gulbis JM , Mackay MF , Craik DJ , Andrews PR
Published: September 2010

The convulsant compound anisatin has been studied by 1H n.m.r ., and X- ray crystallography, to establish its molecular geometry. The n.m.r . measurements included an analysis of proton-proton vicinal coupling constants and saturation transfer experiments which monitored exchange of the hydroxy groups of anisatin. The former analysis was used to obtain a solution conformation via the Karplus equation while the latter experiments yield information on intramolecular hydrogen bonding. The experimental geometry is compared to that obtained by several theoretical methods, including MINDO/3, MNDO, AM1 and MM2. The AM1 optimized geometry was closest to that of the crystal structure.
Rearrangements in the Molecular-Ions of Some 2,3-Dihydro-1h-1,2-Benzazaphosphole Oxides and Sulfides
Authors: Gillis RG , Porter QN
Published: September 2010

The molecular ion of 2-phenyl-2,3-dihydro-1H-1,2-benzazaphosphole oxide undergoes fission of the N-P and P-C bonds in the azaphosphole ring so that C6H5-P=O is lost giving an ion which fragments further to give C8H8N+ (m/z 118). This m/z 118 ion is common to all the compounds studied except those which are not substituted on the nitrogen atom. All the 2,3-dihydro-1H-1,2-benzazaphosphole sulfides lose SH (the oxides do not lose OH); otherwise the 2-phenyl sulfides resemble the 2-phenyl oxides, but the 2-methyl sulfides are quite different from the 2-methyl oxides.
Imidazo[1,2-B]Pyridazines. III. Syntheses and Central Nervous-System Activities of Some 6-Chloro-3-methoxy (and ethoxy)-2-aryl (and heteroaryl)imidazo[1,2-B]pyridazines
Authors: Barlin GB , Davies LP , Ngu MML
Published: September 2010

The synthesis of a series of 6-chloro-3-methoxy(and ethoxy )-2- phenyl[and (variously substituted phenyl), thienyl, and naphthalenyl ] imidazo [1,2-b] pyridazines and a 6-fluoro analogue are reported. These compounds were tested for their ability to displace [3H]diazepam bound to washed rat brain plasma membranes. Under standard assay conditions (see Experimental) and in the presence of 100 μM γ- aminobutyric acid, 6-chloro-3-methoxy-2-(p-tolyl ) imidazo [1,2- b] pyridazine was the most active compound with an IC50 value of 148 nM (cf. diazepam, with IC50 of 4.2 nM).
A Tribute to Professor Donald Richard Stranks A.O.
Authors: Lincoln SF
Published: September 2010

No Abstract Available.
The SN1CB Mechanism in Non-Aqueous Solution
Authors: Jackson WG , Angel RL
Published: September 2010

The reaction between (NH3)5Co-NCMe3+ and dimethyl sulfoxide (Me2SO) to produce (NH3)5Co-OSMe23+ and MeCN in Me2SO solvent is general base-catalysed. The rates and rate laws have been determined for 10 substituted amines. First-order kinetics are observed, and the rates show a dependence which is less than first order on base (B) concentration. These facts are rationalized in terms of a common, reactive conjugate base (NH3)4(NH2)CoNCMe2+, the solvolysis of which occurs at a rate competitive with its rate of reprotonation by BH+. Alternative mechanisms are considered. The measured rates, which span two orders of magnitude, do not correlate with base nucleophilicity, steric features of the amines, nor pKa values as measured for aqueous solution. Primary amines are very effective catalysts; secondary and especially tertiary amines are poorer catalysts. There appears to be no reaction at the bound nitrile function as there is in aqueous solution.
On the Existence and Stability of Cations of d- and f-Transition Elements in Acidic Non-Aqueous Media
Authors: Odonnell TA
Published: September 2010

Recently observed spectra
of solvated d- and f-transition element cations in superacidic media, together with spectra of aqua cations in acidic aqueous solution, are used to propose that cationic speciation is much more general in acidic solvents and melts than is usually accepted. It will be shown that cations in unusually low oxidation states are stabilized in highly acidic media, and that these cations disproportionate as the acidity of the medium is decreased and that in general these latter phenomena are independent of the chemical nature or the temperature domain of the medium.
A New Method for the Estimation of Transfer Activity Coefficients of Ions From the E.M.F. of Cells With Liquid Junction
Authors: Berne A , Popovych O
Published: September 2010

Transfer activity coefficients of the tetraalkylammonium ions, logmγR, where R+ = Me4N+, Et4N+, Pr4N+ and Bu4N+, and of the picrate ion, logmγPic, between pairs of dipolar aprotic solvents, S1 → S2, were evaluated by combining the e.m.f . of cells Ag(cryst.)|AgClO4|RX|AgClO4|Ag( cryst .)�������������������������������� S1 ������ S2with the calculated liquid-junction potentials, Ej. The salt-bridge electrolyte RX was RClO4 and R Pic for the determinations of logmγR and logmγPic, respectively, and the solvents were: acetonitrile ( MeCN ), N,N- dimethylformamide (HCONMe2), dimethyl sulfoxide (Me2SO) and propylene carbonate ( pcar ). The logmγR values showed a systematic variation with the AgClO4 concentration, apparently caused by the concentration dependence of the solvent component of the liquid-junction potential, Ej,s, neglected in the calculations. However, the above concentration dependence was virtually eliminated from the values of logmγPic when they were calculated with the aid of our concentration-dependent logmγR data. For a number of our cells it was possible to evaluate the Ej,s, with the aid of literature data. The solvent component of Ej was found to be appreciable and varied both with the AgClO4 and the RX concentration. The Ej,s, was particularly large for cells containing pcar , with a maximum of -172 mV for the pcar | MeCN junction.
Synthesis of 2-Methylpyrrolo[1,2-a]pyrazin-1(2h)-one
Authors: Brimble MA , Brimble MT , Hodges R , Lane GA
Published: September 2010

The synthesis of 2-methylpyrrolo[1,2-a]pyrazin-1(2H)-one (2) present in the insect feeding deterrent peramine (1) through oxidation of the saturated lactam (3) is described. The preparation of the related 6- methyl-1H-pyrrolo[2,3-c]pyridin-7(6H)-one (12) through a Lewis-acid- catalysed cyclization of the amide acetal (7) is also described.
Preparation and X-Ray Crystal-Structure of 4,4'-Triselenobis(pent-3-en-2-one)
Authors: Arnold AP , Cavell KJ , Edwards AJ , Hoskins BF , Peacock EJ
Published: September 2010

The title compound was prepared by the reaction of sodium hydrogen selenide with 4-chloropent-3-en-2-one. The compound appears unstable with respect to higher oligomers of the SeC (CH3)CHC(CH3)O ( seacac ) unit. X-ray crystallography reveals the unusual structure in which a central 'complexed' selenium atom is coordinated to the two selenium atoms of the seacac ligands which are in their normal cis conformations. The oxygen atoms are uncoordinated and as far removed from the coordination environment of the central selenium atom as possible. Crystals of Se( seacac )2 are orthorhombic with space group P21212, and cell dimension a 9.761(2), b 14.828(3) and c 4.6447(5)Ǻ.
The Influence of Pressure on the Infrared-Spectra of Hydrogen-Bonded Solids. VII. Deuterated Ammonium Salts
Authors: Hamann SD
Published: September 2010

The infrared stretching and
bending frequencies of isotopically dilute +NHD3 ions in predominantly +ND4 salts have been measured at pressures up to 5 GPa at 25°C. For most of the 28 salts studied, the stretching bands move to higher frequencies with increasing pressure, these results suggesting the absence of any significant hydrogen
bonding between the ammonium ions and the anions in the crystals.
Kinetic and Electron Impact Studies of the Hco+/COH+ Isomers
Authors: Harland PW , Kim ND , Petrie SAH
Published: September 2010

The ionization efficiency curve for the CHO+ ion, m/z 29, formed from the near-monochromatic electron impact ionization of CH3OH has been found to exhibit two distinct appearance energies (thresholds) which can be assigned to the formyl, HCO+, and the higher energy isoformyl, COH+, isomers. The energy separation between the appearance energies of 138 kJ mol-1 provides an estimate of the difference between the enthalpies of formation of the formyl-isoformyl isomers. Acetaldehyde undergoes dissociative ionization to yield only the lower energy, formyl, isomer. This has been confirmed from a study of the energetics of the proton transfer reaction of CHO+ on N2O over the centre-of-mass collision energy range 0.3-4 eV measured by using a drift-tube mass spectrometer.
Nitrones and Oxaziridines. XXXIX. Conversion of 1-Pyrroline 1-Oxides Into 2H-Pyrroles Through the Hetero-Cope Rearrangement
Authors: Black DSC , Strauch RJ
Published: September 2010

The 1-pyrroline 1-oxides (1) undergo a hetero-Cope rearrangement to give variously the 2H-pyrroles (2) and/or the 3-benzoyloxy-1-pyrrolines (3). The esters (3) can be hydrolysed to the corresponding alcohols (4).
Synthesis and Stability of Aryl Bis(nitrile oxides) With Potential as Curing Agents for Polysulfide Sealants
Authors: Hanhela PJ , Paul DB
Published: September 2010

Several aromatic bis( nitrile oxides) have been prepared as potential curing agents for sealants produced from thiol -terminated polysulfide liquid polymers. All were obtained by dehydrohalogenation of α-halo oximes and the requisite aldehydes were synthesized from either the dimethyl derivatives or the chloromethylated hydrocarbons. The direct chloromethylation of naphthalene which offered a convenient route to the naphthalene-1,4- and 1,5-bis(carbonitrile oxides) was re-examined. Also prepared were naphthalene-2,6-bis(carbonitri1e oxide), anthracene-9,10-bis(carbonitri1e oxide) and 4,4′-sulfonylbisbenzonitrile dioxide. The course of the reaction between naphthalene-2,3-dicarbaldehyde and hydroxylamine was established and shown to differ from that involving phthalaldehyde. Stabilities of the nitrile oxides at -15�, 4� and 25� were assessed by spectroscopic means.
Photooxidation of 2-Phenylbenzotriazoles
Authors: Amiet RG , Evans NA , Wynne PM
Published: September 2010

Irradiation, with ultraviolet light, of 2-phenylbenzotriazole in aerated solvents resulted in oxidation of the benzo ring to yield the diacid 2-phenyl-1,2,3-triazole-4,5-dicarboxylic acid. A possible intermediate, 2-phenylbenzotriazole-4,7-dione, also yielded the diacid on photooxidation . The methyl ether of the commercial photostabilizer Tinuvin P undergoes an analogous reaction to produce the corresponding diacid.
Synthetic Routes to Some Isotopically Labeled Intermediates for Diterpenoid Biosynthesis
Authors: Dawson RM , Godfrey IM , Hogg RW , Knox JR
Published: September 2010

The exo-15-hydrogen of ent-kaurene can be exchanged through a reversible ene reaction in a convenient and
efficient procedure which has the potential for giving high specific activity 3H-labelling. Copalol, the (Z)-double bond stereoisomer, and the allylic alcohol isomers ent-manool and ent-epimanool have been obtained through divergent synthetic pathways involving a 15,16-bisnor ketone intermediate. These pathways have also allowed the four compounds to be obtained with 14C-labelling. A method, involving a Wittig reaction to form a vinyl bromide intermediate, has been developed for obtaining copalol, as the trityl ether derivative, with stereospecific isotopic labelling of one or the other of the hydrogens of the exocyclic methylene group.
The Rate Constant for the Recombination of Trifluoromethyl Radicals
Authors: Arthur NL , Davis KJ
Published: September 2010

The rotating sector data reported by Ayscough for the recombination of CF3radicals have been analysed by means of a method which takes into account all first-order radical removal processes, including CF3 radical addition to CF3COCF3, the radical source. The rate constant obtained, (1.48 � 0.50)×1013 cm3 mol-1 s-l, is substantially lower than the value originally reported.
Condensations of Ethane-1,2-Diamine, Formaldehyde and Ammonia (or Nitroethane) Directed by Nickel(II) or Copper(II). Crystal Structure of (8-Methyl-8-nitro-1,3,6,10,13,15-hexaazatricyclo[13.1.1.1 13,15]octadecane)nickel(II) Perchlorate
Authors: Bernhardt PV , Curtis LS , Curtis NF , Lawrance GA , Skelton BW , White AH
Published: September 2010

Both nickel(II) and copper(II) complexes of the sterically hindered linear tetraamines 1,3,5,7-tetra-azabicyclo [3.3.l]nonane-3,7-bis( ethanamine (4) and 3,3′-(ethane-1,2-diyl)bis(1,3,5,7-tetraaza-bicyclo [3.3.1] nonane (7) have been prepared from reaction of ethane-1,2-diamine complexes with formaldehyde and ammonia or by reaction of the metal salt with the quaternary 'hexamminium' cation (8) and ammonia, respectively. Spectroscopic properties and kinetics of the acid hydrolyses of these complexes are reported. Observed pseudo-first-order rate constants are of the order of 10-1 s-1 at 25° in 1 mol dm-3 HCl/NaCl; acid dependencies are reported. In addition to (4), a further acid-stable and presumably macrocyclic compound could be produced from reaction of [cu(en)2]2+ with formaldehyde and ammonia, assigned tentatively as (9). Further reaction of the nickel(II) complex of (4) with formaldehyde and nitroethane yielded the macrocyclic complex of (10), which was characterized by a crystal structure analysis. Reduction with zinc amalgam yielded an amine-substituted macrocyclic complex from the nitro-substituted precursor. The title complex [Ni(10)](ClO4)2.H2O crystallized in the space group P21/n, a 14.367(2), b 13.099(2), c 12.325(3) � , β 101.01(1)�. The nickel(II) was located in a square plane of two secondary (Ni-N 1.92 � ) and two tertiary nitrogens (Ni-N 1.93 � ); the 'football' formed as one cap from ammonia and formaldehyde condensation was clearly defined.
Stable Negative-Ion Isomers in the Gas Phase. C7H7O- Species
Authors: Eichinger PCH , Bowie JH , Hayes RN
Published: September 2010

The C7H7O- ions formed by deprotonation of benzyl alcohol, norbornadien-7-ol and quadricyclin-7-ol are discrete species which all fragment by competitive losses of H, H2, CH2O and C6H6 on collisional activation. The isomeric ion from norbornen-2-one behaves differently undergoing retro cleavage to form HC2O- and C5H5- as product ions. The three deprotonated cresols are also distinct species. Anisole is deprotonated (by amide ion) to form both PhOCH2- and (C6H4)-OMe, ions which equilibrate prior to elimination of formaldehyde.
Reactions of Transition Metal σ-Acetylide Complexes. XIII. Alkylation and Related Reactions
Authors: Bruce MI , Humphrey MG
Published: September 2010

A series of 20 cationic vinylidene complexes of ruthenium and osmium [M(CCRR′)(L)(L′)(η- C5H5)]+ (R′ = Me, Ph, C6H4F-4, C6F5, (CH2)2C2H; R′ = Me, CH2Ph, CH2CH=CH2, CH2C2CH, (CH2hBr; L, L′=PPh3, CNBUT, dppm, dppe; not all combinations), [{Ru (CCRCH2-)(PPH3)2( η- C5H5)2]2+ and [CH2{ CPhCRu (PPh3)2(η-C5H5)]2]2+ have been obtained from reactions between the metal acetylide complexes and the appropriate organic halides.
The Oxidation of Dithiocarbamate Anion by Substitution Inert Metal Complexes
Authors: Nichols PJ , Grant MW
Published: September 2010

The kinetics of oxidation of dithiocarbamate anions to thiuram disulfides in aqueous acetone by {Fe(CN)6}3- and 11 other substitution inert metal complexes have been investigated. Outer-sphere electron transfer, resulting in the formation of dithiocarbamate thio radicals, is the rate determining step. A Marcus cross reaction treatment allows an estimate for the redox potential for the dithiocarbamate radical/anion couple. For diethyldithiocarbamate, E �(edtc/edtc-) = 425 � 33 mV v.s.c.e. and the outer-sphere electron self-exchange rate constant is log kex = 7.0 � 0.3. A comparison with thiophenolate oxidation is also given.
Eudistomins From the New Zealand Ascidian Ritterella sigillinoides
Authors: Lake RJ , Blunt JW , Munro MHG
Published: September 2010

In addition to the previously reported antiviral and antitumour compounds eudistomin K (la)and eudistomin K sulfoxide (2a), debromoeudistomin K (3a), eudistomin C (4a), eudistomin O (5a) and β-carboline (5b) have now also been isolated from the New Zealand ascidian Ritterella sigillinoides. The in vitro biological activities of these compounds are compared.
Preparation of Some 1-Alkyl-4-[1-(ethoxyimino)butyl]-3-hydroxy-5-oxocyclohex-3-ene-1-carboxylic Acid Ester and Amide Herbicides by Reductive Alkylation of 3,5-Dimethoxybenzoic Acid
Authors: Liepa AJ , Liepa AJ , Wilkie JS , Wilkie JS , Winzenberg KN , Winzenberg KN
Published: September 2010

Reductive alkylation of 3,5-dimethoxybenzoic acid with haloalkanes afforded the 1-alkyl- 3,5-dimethoxycyclohexa-2,5-diene-1-carboxylic acid derivatives (3a-e) which, upon esterification and hydrolysis, furnished methyl 1-alkyl-3-hydroxy-5-oxocyclohex-3-ene-l-carboxylate derivatives (4f-j). Reaction of (4f-j) with butyric anhydride gave methyl 1-alkyl-4-butyryl- 3-hydroxy-5-oxocyclohex-3-ene-1-carboxylate derivatives (6a-e) which were converted into methyl 1-alkyl-4-[1-( ethoxyimino )butyl]-3-hydroxy-5-oxocyclohex-3-ene-1-carbo xyate derivatives (2a-e). Similarly, the oxime O-ether derivative (2f) was prepared from the amide (41), obtained from reaction of (3b) with N,N′- carbonyldiimidazole and dimethylamine followed by hydrolysis.
Organic Curing Agents for Polysulfide Sealants. II. Additions of Thiols to Nitrile Oxides: Scope, Relative Reactivities and Application to the Cure of Polysulfide Sealants
Authors: Hanhela PJ , Paul DB
Published: September 2010

Efficient addition between various nitrile oxides and both short (C2) and long chain (C16) alkyl thiols , aliphatic dithiols and aryl thiols occurred rapidly at ambient temperature with the formation of thiohydroximic acid derivatives. Competitive experiments with bis( nitrile oxides) showed that for terephthalonitrile oxide the second addition proceeded more readily than the first whereas with anthracene-9,l0-bis(carbonitrile oxide) elevated temperatures were needed to obtain the diadduct. Relative reactivities of a number of thiols with nitrile oxides were also determined spectroscopically . Reaction between prop-2-ene-1-thiol and p-nitrobenzonitrile oxide afforded products resulting from both cycloaddition and 1,3-addition with the latter predominating. The polysulfide prepolymer LP-2 was cured effectively at ambient temperatures by both terephthalonitrile oxide and 4,4'-sulfonylbisbenzonitrile dioxide at CNO to SH ratios of 1.5 and higher giving tack-free products within 0.5 h and 90% cure in under 4 h. For the less highly cross-linked LP-32-based sealants, curing was a little slower. Unreinforced sealants produced in this manner were firm elastomers with hardness of 35-40 (Rex A). The naphthalenebis (carbonitrile oxides) afforded softer products while anthracene-9,10- bis(carbonitrile oxide) was ineffective. One-part formulations involving in situ generation of nitrile oxide from hydroximoyl chlorides and barium hydroxide (formed by action of water vapour on barium oxide) were also produced.
A Novel Route to the Dibenzofuran Ring System: Possible Applications as a Rigid Thyroid Hormone Template
Authors: Chandler CJ , Craik DJ , Waterman KJ
Published: September 2010

Photochemical cyclization reactions of iodinated diphenyl ethers to produce dibenzofuran derivatives have been studied. While U.V. irradiation of the thyroid hormone thyroxine produces a complex mixture of products, treatment of the thyroid hormone analogue 3,5-diiodo-4-(4'-methyoxphenoxy)nitrobenzene with U.V. light yielded 4-iodo-8-methoxy-2-nitrodibenzofuran (34%) in a clean reaction. The functionalized dibenzofuran framework produced in this reaction has considerable potential for the development of novel, rigid thyroid hormone analogues.
The Lead Dioxide Anode. II. The Kinetics and Participation of the Lead Dioxide Electrode in Electrochemical Oxidation Reactions in Sulfuric Acid
Authors: Randle TH , Kuhn AT
Published: September 2010

Lead dioxide is a strong oxidizer in sulfuric acid, consequently electrochemical oxidation of solution species at a lead dioxide anode may occur by a two-step, C-E process (chemical oxidation of solution species by PbO2 followed by electrochemical regeneration of the reduced lead dioxide surface). The maximum rate of each step has been determined in sulfuric acid for specified lead dioxide surfaces and compared with the rates observed for the electrochemical oxidation of cerium(III) and manganese(II) on the same electrode surfaces. While the rate of electrochemical oxidation of a partially reduced PbO2 surface may be sufficient to support the observed rates of CeIII and MnII oxidation at the lead dioxide anode, the rate of chemical reaction between PbO2 and the reducing species is not. Hence it is concluded that the lead dioxide electrode functions as a simple, 'inert' electron-transfer agent during the electrochemical oxidation of CellI and MnII in sulfuric acid. In general, it will most probably be the rate of the chemical step which determines the feasibility or otherwise of the C-E mechanism.
Studies of Australian Soft Corals. XLVII. New Halogenated Briaran Diterpenes From a Briareum Species (Octocorallia, Gorgonacea)
Authors: Bowden BF , Coll JC , Vasilescu IM , Alderslade PN
Published: September 2010

Two new halogenated briaran diterpenes (3) and (4) are reported from a Briareumspecies of soft corals from waters off Darwin, N.T. Their structures were determined by high-field n.m.r. spectroscopy including 2-D 13C-1 H-correlation experiments and COSY-45 experiments, and stereochemical features were delineated by n.0.e. difference spectroscopy. The new metabolites are (1R*,2S*,4S*,6S*,7R',8R*,9S*,10S*,11Z,14S*,17S*)-14-acetoxy-6-chloro-4,8-epoxy-9,17-dihydroxy-2-propiony10xybriar5(16,11-dien-18-one (3) and (1R*,2R*,3S*,6S*,7R*,8R*,9S*,10S*,11R*,13Z)-3,9-diacetoxy-6-chloro-8-hydroxy-2-propionyloxybriara-5(16),13-diene-12,18-dione (4). The isolation of briaran diterpenes from this specimen supports its inclusion in the genus Briareum.
(+)α-Bisabolol and (+)-Anymol. A Repetition of the Synthesis From the Limonene 8,9-Epoxides
Authors: Carman RM , Duffield AR
Published: September 2010

A repetition of Kergomard and Veschambre's determination of configuration for (4-α-bisabolol has provided further evidence for the R,R-configuration, contrary to the original report. (+)-Anymol has the 4R,8S-configuration.
Norisoprenoids in Vitis vinifera White Wine Grapes and the Identification of a Precursor of Damascenone in These Fruits
Authors: Sefton MA , Skouroumounis GK , Massywestropp RA , Williams PJ
Published: September 2010

Twenty-four norisoprenoids , which are either free volatile components of juices of Vitis vinifera cvv . Chardonnay, Semillon and Sauvignon Blanc, or are liberated by glycosidase enzyme, or acid hydrolysis of extracts of these juices, have been identified. Eleven of these norisoprenoids are reported as grape products for the first time. The hypothetical 7-oxomegastigmane precursors, grasshopper ketone (5) and
megastigm-5-en-7-yne-3,9-diol (10), as well as the related allene, 9-hydroxymegastigma-4,6,7-trien-3-one (6), have been observed for the first time, cooccurring with damascenone (1), 3-hydroxy- β- damascone (2) 3-oxo-β-damascone (3) and 3-oxo-α-damascone (4). Hydrolytic studies have shown that
megastigm-5-en-7-yne-3.9-diol (10) is a precursor of damascenone (1) and 3-hydroxy- β- damascone (2) during wine conservation.
Miniemulsions of Vinyl Stearate. II. Light-Scattering Studies During the Polymerization
Authors: Elbing E , Parts AG , Lyons CJ , Coller BAW , Wilson IR
Published: September 2010

The course of the polymerization of vinyl stearate has been followed by dilatometry and by light scattering. Kinetically stable and visually clear or at most opalescent 'miniemulsions' were used to minimize the scattering (otherwise large) by emulsion droplets. Light-scattering results demonstrate that the final particle size of the latexes may be greater or less than that of the emulsion droplets in the starting miniemulsion. This suggests that polymer particles are nucleated from the aqueous (micelle-containing) phase, and grow by transport of vinyl stearate monomer through the aqueous medium from the emulsion droplets to feed polymerization in the particles. Thus the droplets gradually decrease in size and disappear when all the monomer has been taken up by absorption into micelles or into growing particles. A previously proposed droplet-particle collision theory does not appear to be necessary.
Electronic Spectroscopy of Mixed Cyclophanes: [2.2](9,10)Anthracenometacyclophane, [2.2](9,10) and [3.3](9,10)-Anthracenoparacyclophane
Authors: Ferguson J , Puza M , Robbins RJ , Wilson GJ
Published: September 2010

The absorption and fluorescence spectra of the title compounds are reported and a simple coupled chromophore model has been used to make assignments of the absorption bands. The absorption spectra show a strong interaction between the 1Lb state of the anthracene chromophore and the 1Lb state of the benzene chromophore in both anthracenoparacyclophanes which is absent in [2.2](9,10) anthracenometacyclophane. The fluorescence comes from the 1La state of the anthracene chromophore.
Alkaloids of Cryptocarya phyllostemon
Authors: Cave A , Leboeuf M , Moskowitz H , Ranaivo A , Bick IRC , Sinchai W , Nieto M , Sevenet T , Cabalion P
Published: September 2010

The known alkaloids (-)-antofine (1), dehydroantofine (5),(-)-cryptowoline (6), (4- cryptowolidine (7), and (-)-cryptowolinol (8), were isolated from the New Caledonian lauraceous plant Cryptocarya phyllosternon, together with five new bases: two secophenanthro-indolizidines, (-)-phyllostemine (2) and (-)-phyllosteminine (3), one pyrrolidinylacetophenone, (-)-phyllostone (4), and two quaternary tetrahydrobenzylisoquinolines, (+)-phyllocryptine (9) and (+)-phyllocryptonine (10). Chemical and spectroscopic methods were used for identification and structural investigation. A synthesis of phyllocryptonine has permitted its stereostructure to be determined.
Studies of Australian Soft Corals. XLVIII. New Briaran Diterpenoids From the Gorgonian Coral Junceela gemmacea
Authors: Bowden BF , Coll JC , Konig GM
Published: September 2010

The structures of three new briaran based diterpenes are reported from the gorgonian coral Junceela gemmacea. Their structures were deduced on the basis of extensive one- and two-dimensional high-field n.m.r. experiments. The metabolites were (1R,2R,5Z,7R,8S,9R,10R,11R,14R,17S)-2,14-diacetoxy-8,17:11,20-bisepoxy-9-hydroxybriar-5-en-18-one (3), (1R,2R,5Z,7R,8S,9R,10R,11Z,14R,17S)-2,14-diacetoxy-8,17-epoxy-9-hydroxybriara-5,11-dien-18-one (4), and 1R,2R,5Z,7R,8S,9R,10R,12R,14R,17S)-2,14-diacetoxy-8,17-epoxy- 9,12-dihydroxybriara-5,11(20)-dien-18-one (5). The compounds are closely related to recently reported metabolites from Briareum species of soft corals.
The Reaction of Thiols and α,ω-Dithiols With Triphenylphosphine and Diisopropyl Azodicarboxylate
Authors: Camp D , Jenkins ID
Published: September 2010

α,ω-Dithiols in the presence of triphenylphosphine and diisopropyl azodicarboxylate are converted into a mixture of monomeric and polymeric disulfides. The product distribution is dependent on the alkyl chain length and the reaction conditions. In contrast to normal Mitsunobu reactions, disulfide bond formation is achieved with regeneration of triphenylphosphine. The mechanism of this reaction is discussed.
The Identification and Synthesis of Two New β-Orcinol para-Depsides in the Lichen Pseudocyphellaria norvegica
Authors: Elix JA , Chester DO , Wardlaw JH , Wilkins AL
Published: September 2010

The new lichen depsides, 2′-O-methylnorbarbatic acid (9) and 2′-O-methylnorobtusatic acid (12) have been detected in Pseudocyphellaria norvegica and the structures confirmed by total synthesis. In addition, the known depsides 4-O-demethylbarbatic acid (3), barbatic acid (4), diffractaic acid (5), 4-O-demethyldiffractaic acid (6), methyl 4-O-demethylbarbatate (7), methyl barbatate (8) and norobtusatic acid (II) were shown in this lichen species.
The Fragment Ion C13H9O2 m/z 197 in the Mass Spectra of 2-(2′-R-phenyl)benzoic Acids
Authors: Gillis RG , Porter QN
Published: September 2010

In the electron impact mass spectrum of 2-(2°-R-phenyl)benzoic acids where R=H, NO2, OCH3, COOH, or Br, an abundant fragment ion m/z 197 is formed by an ipso substitution in which R is expelled as a radical. The structure of the ion m/z 197 has been shown by collision-activated dissociation to be identical with that of the protonated molecule formed by methane chemical ionization of 6H-dibenzo[ b,d ]pyran-6-one.
Intramolecular Aromatic Substitution With Bisthiocarbocations. Variations of Lewis Acid, Solvent and Orthothio Substituents
Authors: Gamage SA , Gamage SA , Smith RAJ , Smith RAJ
Published: September 2010

The effects of Lewis acid, solvent and orthothio substituent have been examined with regard to intramolecular electrophilic aromatic substitution ( annulation ) with bisthiocarbocations . A suspension of silver trifluoromethanesulfonate in dichloromethane, creating bis ( arylthio ) carbocations, was found to be the most effective for annulation of six- membered rings.
Experiments Directed Towards the Synthesis of Anthracyclinones. XV. Novel Synthetic Homochiral Chloroanthracyclines From Acetal Cyclization
Authors: Brown EG , Cambie RC , Holroyd SE , Johnson M , Rutledge PS , Woodgate PD
Published: September 2010

Quinizarin (3) has been converted in seven steps into the homochiral acetal (14) in 69% overall yield, through a sequence involving reductive Claisen rearrangements of the allyl ethers (8) and (20). The acetal (15) has been converted into four novel diastereomeric 9-chloroanthracyclines (31)-(34) by an unprecedented intramolecular acetal-alkene cyclization mediated by tin(IV) chloride in N,N-dimethylformamide.
Stereocontrolled Synthesis of a Key Lactone Intermediate Required for the Synthesis of Salinomycin
Authors: Brimble MA
Published: September 2010

The stereocontrolled synthesis of lactone (1b), a key intermediate required for the synthesis of the polyether antibiotic salinomycin, is described.
A Curious By-Product in the Tipson-Cohen Reaction of a Carbohydrate Ditosylate
Authors: Engelhardt LM , Mocerino M , Stick RV , White AH
Published: September 2010

The treatment of methyl 4,6-O-benzylidene-2,3-di-O-p-toluenesulfony-β- D- galactoside , methyl 4,6-O-benzylidene-3-O-benzenesulfonyl-2-O-p- toluenesufonyl-β-D-galactoside and methyl 4,6-O-benzylidene-2-O- benzenesulfonyl-3-O-p-touenesulfonyl-β-D-galactoside under Tipson-Cohen conditions (Zn/ Nal/dimethylformamide ) gives mainly the alkene, methyl 4,6-O-benzylidene-2,3-dideoxy-β-D-threo-hex-2-enoside. However, the first two glycosides give methyl 4,6-O-benzylidene-3-deoxy-3-C-(m-methylphenyl )-β-D- galactoside, and the last, methyl 4,6-O-benzylidene- 3-deoxy-3-C-phenyl-β-D-gaactoside, as minor by-products resulting from a curious reaction of the supposed iodo sulfonate intermediate. The structure of methyl 4,6-O-benzylidene-3-deoxy-3-C-(m- methylphenyl )-β-D- galactoside was confirmed by a single-crystal X-ray structure determination of the derived p-bromobenzoate.
Radiation-Induced Gas-Phase Concurrent Dealkylation and Isomerization of ρ-Cymene
Authors: Perez G , Lilla E
Published: September 2010

D3+ ions, produced by deuterium γ-radiolysis, were allowed to react with gaseous p-cymene (p-isopropyltoluene ). The reaction leads to the formation of excited arenium ions, which, if not stabilized by collision, undergo predominantly dealkylation and, alternatively, isomerization. Dealkylation is favoured with respect to isomerization by an increase in substrate concentration, these results showing that dealkylation requires a lower activation energy.
Crystal Structures, Mössbauer Spectra and Reactivity of Sn,II Salicylideneimines
Authors: Vandenbergen AM , Cashion JD , Fallon GD , West BO
Published: September 2010

Single-crystal X-ray diffraction studies have been carried out on the tetradentate SnII complex N,N′-(4,5-dimethyl-1,2-phenylene ) bis ( salicylideneiminato )tin(II) [ Sn ( saldph )] and the tetradentate complex N-(2-oxidophenyl) salicylideneiminatotin (II) [ Sn ( salop )]. Sn ( saldph ) is a monomer and has the SnII ion 1.126(1)Ǻ above the plane of the O2N2 donors while Sn ( salop ) is dimeric with bridging between SnII ions by the oxygens of the oxidophenyl groups. SnII ions are raised above the O3N donor planes by 1.109(7)Ǻ while the molecules are bent along the bridging O-O axis with a dihedral angle between the chelate planes of 92.1°. The Mossbauer spectra of the complexes are reported. The SnII salicylideneimines react with H2O and oxygen but are inert to alkyl halides.
New Methods for the Synthesis of Troponoid Compounds
Authors: Banwell MG
Published: September 2010

The ring expansion of 7-halogenobicyclo[4.1.0] heptenones and related compounds provides a useful new method for the preparation of the seven-membered conjugated carbocyclic compounds known as tropones and tropolones. This methodology has been exploited in the synthesis of various biologically active troponoid natural products including nezukone, the thujaplicins, thujaplicinol, MY3-469 and colchicine.
A Formal Total Synthesis of 3-O-Demethylfortamine
Authors: Cambie RC , Renner ND , Rutledge PS , Woodgate PD
Published: September 2010

p-Benzoquinone has been converted into the substituted cyclohexenone (11) in five steps and 33% overall yield by a Diels-Alder cycloaddition-cycloreversion approach in which anthracene functions as a protecting and stereodirecting group. The elaboration of (11) in four steps to the known epoxide (22) constitutes a formal total synthesis of 3-O-demethylfortamine (2).
Preferred Equatorial Linkages of Hexahydropyrimidine Rings in Dodecahydro-2,2'-bipyrimidines
Authors: Black DS , Craig DC , Kassiou M , Read RW
Published: September 2010

An X-ray crystallographic study of two new dodecahydro-2,2°-bipyrimidines, prepared from condensation of meso-pentane-2,4-diamine and racemic butane-1,3-diamine with glyoxal , has been carried out, The study demonstrates for the first time that the heterocyclic rings in such underivatized dodecahydrobipyrimidines exist in chair conformations with the bond bridging the two rings arranged equatorially to both. The methyl substituents in each case lie trans to the hydrogens at C2 and C2′ and the more crystalline isomer from the butanediamine precursor is derived from combination of amines of opposite configuration.
An Improved Synthesis, Molecular-Structure, and Properties of 1,4-Dihydro-Dicyclopropa[b,g]naphthalene
Authors: Halton B , Boese R , Blaser D , Lu Q
Published: September 2010

A marked improvement in the preparation of 1,4-dihydrodicyclopropa[ b,g ]naphthalene (4) from isotetralin (7) has been achieved by selecting conditions which avoid the unwanted olefin (12). The easily available dicycloproparene (4) has C2h symmetry in the crystal lattice with the space group P21/n. The geometry is readily rationalized by the concept of 'bent bonds' that are also suggested by X-X difference electron density maps. Cheletropic biaddition of dichlorocarbene to (4) provides the dicyclobutanaphthalenes (15) and (16). Attempted Petersen olefination to mono- and di-alkylidene derivatives, e.g. (21) and (22), is foiled by a reluctance of (4) to provide an easily interceptible anion.
Preparation of Some Pyrrole-3,4-dicarboxylic Acid Derivatives and the Crystal Structure of 2-Methylpyrrolo[3,4-c]pyrrole-1,3(2H,5H)-dione
Authors: Arnold DP , Nitschinsk LJ , Kennard CHL , Smith G
Published: September 2010

A series of pyrrole-3,4-dicarboxylic acid derivatives has been prepared, and the crystal structure of one, 2-methylpyrrolo[3,4-c]pyrrole-1,3(2H,5H)- dione, has been determined by X-ray diffraction and refined to a residual R 0.049 for 1415 observed reflections. Crystals are monoclinic, space group P21/c, with Z= 8 in a cell of dimensions a 14.775(3), b 7.0692(5), c 15.151(3)Ǻ, β 118.82(8)�. Strain in the planar fused ring system is evident from the widening of the external interring angles to 143°, and from the unusual substituent effects in the 13C n.m.r. spectra.
Crystal and Molecular Structure of the Peroxo-Bridged Dimer [(trenen)CoO2Co(trenen)] (ClO4)4 Where trenen = N,N,N'-Tris(2-aminoethyl)-ethane-1,2-diamine
Authors: Gatehouse BM , Mclachlan G , Martin LL , Martin RL , Spiccia L
Published: September 2010

The preparation and crystal structure of the brown crystalline cobalt(III) dimer [( trenen )CoO2-Co( trenen )](ClO4)4 is described where the pentadentate ligand trenen is N,N,N′- tris (2-aminoethyl)ethane-1,2-diamine. The compound forms monoclinic crystals with a 13.132, b 14.214, c 8.906Ǻ and β 91.53°, and two formula units in the unit cell, in space group P21/n. The nitrogen atoms of the trenen ligand occupy five of the six slightly distorted octahedral sites about each cobalt atom with a peroxo bridge linking the two Co( trenen ) moieties through the sixth site. The Co-O-O-Co dihedral angle is 180°, the molecule possesses a centre of symmetry, and the peroxo bridging group is situated trans to the secondary nitrogen atom attached to each cobalt atom (the s,s -isomer). The electronic spectrum displays a strong (є 13700 dm3 mol-1 cm-1) absorption band at 302 nm which is typical of peroxo -bridged dicobalt complexes with a single transplanar CoO2Co bridge.
Structural and Solid-State 31P N.M.R. Studies on a Novel Fluorotris(triphenyl-phosphine)copper(I) Adduct
Authors: Healy PC , Hanna JV , Kildea JD , Skelton BW , White AH
Published: September 2010

The synthesis of the title compound as its triphenylphosphine /methanol solvate, [(PPh3)3CuF].- 4PPh3.4MeOH, is reported together with characterization by solid-state 31P CP-MAS n.m.r. and single-crystal X-ray diffraction. Crystals are trigonal, space group P3, with a 14.453(5), c 15.388(6)Ǻ. The structure refined to a final R value of 0.049 for 1926 'observed' [I> 3σ(I)] reflections. The (PPh3)3CuF molecule lies on a crystallographic threefold axis. Cu-F is 2.115(9)Ǻ, and Cu-P 2.323(3)Ǻ. The solid-state 31P n.m.r. spectrum is dominated by peaks from each of the four solvated PPh3 molecules at -1.6, -5.4, -10.6 and -14.2 ppm with respect to 85% H3PO4. The quartet of lines arising from the ligands coordinated to the copper atom shows an average chemical shift of -5 ppm and approximately equal line spacings of 1.0 kHz.
Carbocation-Mediated Rearrangements Within [n.m.1]Propellane Frameworks
Authors: Banwell MG , Ryan JH , Winkler DA
Published: September 2010

Mild thermolysis of the tetracyclic mesylate (6) in the presence of traces of mineral acid afforded a mixture of the rearrangement products (21) and (22) as well the σ-anti- bishomotetralin (20). On treatment with methanesulfonic acid in dichloromethane, compound (20) gives rise to the [5.4.1] propellene (21) which, on prolonged exposure to these reaction conditions, isomerizes to the mesyloxymethyl compound (22). Under the same conditions, the σ-anti- bishomoindan (4) is converted into the [5.3.1] propellene (3) which, in turn, slowly rearranges to the [4.3.1] propellene (23). A mechanistic rationalization of these observations is advanced which also accounts for the formation of the novel by-product (16) observed during Simmons-Smith cyclopropanation of allylic alcohol (15a).
Senkirkine Chloroplatinate, the Supposed Non-Pyrrolizidine From Senkirkine or Senecio kirkii
Authors: Culvenor CCJ , Mackay MF
Published: September 2010

The supposed non-pyrrolizidine compound prepared from senkirkine and chloroplatinic acid, and thought to be a reaction product or an impurity in the senkirkine, is shown to be senkirkine chloroplatinate by a reprocessing of the crystallographic data.
Dye-Sensitized Photooxidation of Anthracene and Its Derivatives in Nafion Membrane
Authors: Niu EP , Mau AWH , Ghiggino KP
Published: September 2010

The methylene blue (MB) sensitized photooxidations of anthracene (AN), 9,10-diphenyl-anthracene (DPA) and 2-dimethylaminoanthracene (DMA) have been studied in ethanol and in Nafion, a perfluorinated polymer with sulfonate groups. Spectroscopic studies indicate that the incorporated chromophores are heterogeneously distributed in the micelle-like polymer. The uncharged aromatic hydrocarbons are located in the non-polar polymer backbone region while the positively charged species reside at the interface of aqueous cluster regions in the membrane. The MB-sensitized photooxidations of all anthracenes are faster in Nafion than in ethanol. Furthermore the photooxidation of AN is 1.6 times higher in D2O-swollen Nafion than in H2O-swollen samples. Analysis of the photodegradation data suggests that these results can be attributed to the heterogeneous siting of the chemical species and the behaviour of singlet oxygen in the membrane.
Importance of the Halogen in the Competition Between Metal Halogen Exchange and 1,3-Elimination of 1-Halobicyclo(1.1.1)pentane
Authors: Della EW , Taylor DK
Published: September 2010

1-Iodobicyclo[1.1.1]pentane reacts cleanly with t-butyllithium by a metal-halogen exchange process to give 1-lithiobicyclo[1.1.1]pentane. Both 1-chlorobicyclo[1.1.1]pentane and the parent hydrocarbon bicyclo [1.1.1]pentane are found to be inert to t-butyllithium.
Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXI. The 1 : 1 Adducts of the Copper(I) Halides (Cl, Br, I) With Bis(2-diphenylphosphinoethyl)phenylphosphine, 'triphos'
Authors: Hart RD , Skelton BW , White AH
Published: September 2010

The 1 : 1 adducts between the copper(I) halides, CuX , X = Cl , Br, I, and the title ligand, 'triphos', Ph2P(CH2)2P(Ph)(CH2)2PPh2, have been synthesized and characterized by single-crystal X-ray structure determination. The three complexes are isomorphous : monoclinic P21/c, a ≈ 14.5, b ≈ 20.5, c ≈ 24.5 Ǻ, β ≈ 118.5°; the asymmetric unit of each structure is the binuclear [Cu2X2( triphos )2] unit (with one acetonitrile solvate). Residuals were 0.047, 0.049 and 0.065 for 6006, 4832 and 5108 'observed', independent reflections respectively. About each copper atom, the four-coordinate environment comprises a terminal halogen [Cu- Cl,Br,I , 2.305(3), 2.311(2); 2.441(2), 2.443(2); 2.614(2), 2.614(2)Ǻ], two phosphorus atoms (central and distal) from the same ligand , and one distal phosphorus atom from the other ligand.
Approaches to the Synthesis of Quassinoids
Authors: Hamilton RJ , Mander LN
Published: September 2010

A range of hydrophenanthrene methyl ethers were subjected to Birch reduction, and the products converted into the epoxides (21), (26) and (27). These were treated with diethylaluminium cyanide, but useful products were not obtained from (21) or (26). However, epoxide (27) was converted into the hydroxy nitrile (28) and thence enone (30), a potentially useful intermediate for the synthesis of quassinoids.
A New Tropane Alkaloid From Pellacalyx axillaris
Authors: Arbain D , Wiryani RD , Sargent MV
Published: September 2010

Extraction of the fresh leaves and terminal branches of Pellacalyx axillaris Korth (Rhizophoraceae) yielded 8-azabicyclo[3.2.1]oct-endo-3-yl (E)-3-phenylprop-2-enoate (nortropinyl cinnamate) (1), the structure of which followed from its spectral properties and synthesis.
Cyclization Reactions in Azole Chemistry: The Reaction of Some Azoles With o-Fluoroacetophenone, o-Fluorobenzaldehyde and o-Fluorobenzophenone
Authors: Rosevear J , Wilshire JFK
Published: September 2010

The reactions of some azoles with o-fluoro-acetophenone , -benzaldehyde and -benzophenone in dimethyl sulfoxide solution in the presence of anhydrous potassium carbonate have been investigated. In addition to the expected substitution products, cyclization reactions frequently occurred to give carbinols in the case of the reactions of o-fluoro-acetophenone and -benzophenone, and cyclic ketones in the case of the reactions with o-fluorobenzaldehyde . Fluoren-9-ol and related carbinols containing heteroaromatic nuclie are readily converted in dimethyl sulfoxide solution into the corresponding ketones by treatment with anhydrous potassium carbonate. When treated with ethanolic alkali, 2′-(benzimidazol-1′-yl) acetophenone undergoes a remarkable transformation to give 1-(2𔈊-aminophenyl)quinolin-4(1H)-one.
Preparation and Structure of Dibromobis(N,N-diethyldithiocarbamato)-thionitrosyltechnetium(III)
Authors: Baldas J , Colmanet SF , Williams GA
Published: September 2010

The title compound, [Tc (NS)(S2CNEt2)2Br2], has been prepared by the reaction of [ TcN (S2CNEt2)2] with SOBr2, and its crystal structure has been determined by single-crystal X-ray diffraction methods at 23�1°C. Crystals are orthorhombic, space group Pnma , with a 14.864(7), b 15.857(7), c 8.938(4)Ǻ, and Z 4. Full-matrix least-squares refinement gave a final R value of 0.047 for 1685 independent reflections. The technetium atom is seven-coordinate with a distorted pentagonal- bipyramidal coordination geometry. The thionitrosyl ligand and a bromo ligand occupy the axial positions, with the thionitrosyl group exerting a small trans influence with Tc-Brtrans 2.595(1) and Tc-Brcis 2.564(1)Ǻ. The coordination of the thionitrosyl group is essentially linear with Tc -N=S 177.2(7)°, Tc -N 1.754(9), and N=S 1.504(9)Ǻ.
Nitrones and Oxaziridines. XLI. Chromophoric Systems Based on 1-Pyrroline 1-Oxides and 2H-Pyrrole 1-Oxides
Authors: Black DS , Strauch RJ
Published: September 2010

1-Pyrroline 1-oxides and 2H-pyrrole 1-oxides have been shown to be suitable compounds
for the development of extended chromophoric systems. 1-Pyrroline 1-oxides (31, (5) and (7)
have conjugated systems in which a nitrone group is conjugatively linked to a dimethylamino
group. The 2H-pyrrole 1-oxides (10), (13), (14) and (19) provide cross-conjugated systems
incorporating the same structural features. The most extensive delocalization arises in the
distyryl compound (19), which on protonation gives an extended cyanine chromophore. The
bis nitrone (21) shows a chromophore with nitrone groups at each end of the conjugated
system. Some general structural principles affecting the chromophoric systems are discussed.
Synthesis of (Pyrazol-4-yl)alkanones and Alkylpyrazole-4-Carbonitriles
Authors: Mcfadden HG , Huppatz JL
Published: September 2010

1-(5-Aminopyrazol-4-yl)alkan-1-ones and 5-alkylpyrazole-4-carbonitriles were obtained by reaction of 2-(1-ethoxyalkylidene)-3-oxoalkanenitriles (acrylonitriles) with hydrazines. The ratios of the various pyrazole products depended on the solvent used, and on the nature of the substituents on both the acrylonitrile and hydrazine reactants. In general, formation of pyrazole-4-carbonitriles was favoured by the use of acetic acid whereas use of ethanol favoured the formation of 1-(pyrazol-4-yl)alkan-1-ones. The use of 3-ethylacrylonitrile gave predominantly 3-ethylpyrazole-4-carbonitriles whereas acrylonitriles unsubstituted in the 3-position gave mainly 1-(pyrazol-4-yl)alkan-1-ones. The use of hydrazine gave exclusively pyrazole-4-carbonitriles irrespective of other factors, whereas use of methyl- and phenyl- hydrazines gave mixtures of varying composition depending on the acrylonitrile 3-substituent and the solvent. This synthesis provides a convenient route using mild conditions to novel pyrazole-4-carbonitriles and 1-(pyrazol-4-yl)alkan-1-ones which may have interesting biological properties.