Synthesis and physico-chemical studies of some polynuclear mixed carboxylate complexes of nickel(II)

A number of polynuclear mixed carboxylates of nickel(II) with the general composition [Ni(OOCCH₃)_2–n (OOCR) _n ] _x (whereR=C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅ and C₂₁H₄₃ andn=1 or 2) have been synthesized by the transacylation reactions of anhydrous nickel acetate with higher carboxylic acids in refluxing toluene. On recrystallization from benzene-alcohol mixtures, mono-alcoholate complexes, Ni(OOCCH₃)_2–n (OOCR) _n ·ROH (whereR=CH₃ and C₂H₅) have been isolated. All these derivatives have been characterized by the molecular weight determinations, infra-red and electronic reflectance spectra and magnetic susceptibility measurements.

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Synthese und Eigenschaften einiger gemischter Carboxylat-Komplexe von Nickel(II)

Zusammenfassung Komplexe des Typs [Ni(OOCCH₃)_2–n (OOCR) _n ] _x (mitR=C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅ und C₂₁H₄₃,n=1 oder 2) wurden aus wasserfreiem Nickelacetat mit höheren Carbonsäuren in siedendem Toluol erhalten. Bei der Kristallisation aus Benzol-Alkohol-Mischungen wurden Monoalkoholate Ni(OOCCH₃)_2–n (OOCR) _n ·ROH (mitR=CH₃ und C₂H₅) isoliert. Die Charakterisierung der Komplexe erfolgte mittels Molekulargewichtsbestimmung, Infrarot- und Elektronenspektren und der Messung der magnetischen Susceptibilität.

     

New (1R,4R)-2-arylidene-p-menthan-3-ones with a bridging ester group in the arylidene fragment. Synthesis and behavior in liquid-crystalline systems

(1R,4R)-2-(4-Hydroxybenzylidene)- and (1R,4R)-2-(4"-hydroxybiphenyl-4-yl)methylene-p-menthan-3-ones were synthesized by condensation of (–)-menthone with O-tetrahydropyran-2-yl derivatives of 4-hydroxybenzaldehyde and 4"-hydroxy-4-formylbiphenyl, respectively, in a DMSO—base medium followed by the removal of the protective group. The reactions of these hydroxy derivatives with 4-alkylbenzoic, 4-alkyloxybenzoic, trans-4-alkylcyclohexane-4-carboxylic, and 4"-alkylbiphenyl-4-carboxylic acids afforded three series of new chiral esters. Compounds containing the arylidene moiety with three benzene rings were found to exhibit liquid-crystalline properties. The characteristic features of these compounds are discussed based on the results of studies by polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. It was found that the mesomorphic compounds under study can form a smectic A mesophase, twist grain boundary mesophases (TGBA), and blue phases in a wide temperature range. Upon dissolution of certain of chiral compounds in 4"-cyano-4-pentylbiphenyl, a rather high twisting power and the thermal stabilizing effect on mesophases were observed.     

Optisch aktive aromatische Spirane, 18. Mitt.: Darstellung von optisch aktiven 4,4′-disubstituierten 2,2′-Spirobi-s-hydrindacenen

Summary All optically active title compounds were obtained from the 4,4-diacetyl-spiro compound2; (+)- and (–)-2 were accessible by chromatography on triacetyl cellulose in ethanol. The enantiomeric purities were established from chromatographic data. The chirality (–)-(2R) was deduced for all new compounds on the basis of the CD spectra of (–)-2 and (–)-2,2-spirobi-(5,6,7,8-tetrahydrobenzo[f]indane). From the molar rotations of these 4,4-disubstituted 2,2-spirobiindanes (empirical) ligand parameters were determined (using the so-called shortened approach). Generally, the values of in these compounds are higher than those of the analogous tetrahydrobenzoindane derivatives.

Herrn Prof. Dr.F. Sauter mit besten Wünschen zum 65. Geburtstag gewidmet     

Synthese von substituierten 2-(Ethoxycarbonyl-formyl-methylen)-2H-benzopyranen und ihre Überführung in Polymethinderivate

Summary 3-Chloro-2-ethoxycarbonyl crotonic aldehydeC reacts with several 2-hydroxybenzene carbaldehydes and 2-hydroxy-naphthalene-1-carbaldehyde, respectively, to give 2-(ethoxycarbonyl-formyl-methylene)-2H-benzopyrans1a–h under mild conditions. With exception of1c and1d these compounds are mixtures ofE–Z isomers.1a–h easily undergo reactions, e.g. with aniline and derivatives to give2a–e, with various CH-acidic compounds to give3a–h and with 2-alkyl-4,6-diphenyl pyrylium salts to give4a–e. In the presence of alcoholic hydrochloric acid, compounds1 are converted into symmetrical 2,2-benzopyrylotrimethine salts5a–e which exhibit longwave absorptions from 640–705 nm. These polymethine dyes with ester groups in the methine chain exhibit a remarkable thermal stability.

     

2,5,6,7,8-Pentasubstituted (S)- and (R)-[2-chroman-2-yl]ethanols as intermediates for the synthesis of α-tocopherol and its chiral analogs

In the presence of lipase from the yeast Candida cylindracea, partial acetylation of (±)-2-[6-benzyloxy-2,5,7,8-tetramethylchroman-2-yl]ethanol with vinyl acetate gives S-(+)-acetate whose alkaline hydrolysis affords (S)-(–)-alcohol. Repeated enzymatic acetylation of the residual alcohol up to 39% conversion afforded the R-enantiomer. The enantiomeric alcohols were oxidized to (S)- or (R)-aldehydes having the same sign of []_D as the original alcohols. These alcohols were converted into S-(+)- and R-(–)-enantiomers of the antioxidant MDL-73404, a hydrophilic analog of -tocopherol.     

A new synthesis ofE- andZ(-)(1R,3S)-2,2-dimethyl-3-(3,3,3-trifluoro-2-chloropropen-1-yl)cyclopropanecarboxylic acids from (+)-3-carene

A new synthesis ofE- andZ(-)(1R,3S)-2,2-dimethyl-3-(3,3,3-trifluoro-2-chloropropen1-yl)cyclopropanecarboxylic acids from (+)-3-carene in 21 % total yield was carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 517–518, March, 1995.     

New approach to the synthesis of(<Emphasis Type="Italic">R</Emphasis>)-3-methyl-γ-butyrolactone

Optically active pure (R)-3-methyl--butyrolactone was synthesized from (R)-4-menthenone.Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 396–397, September–October, 2004.     

Kinetics of ferrocenoylacetonato substitution from (1,5-cyclooctadiene)(ferrocenoylacetonato)rhodium(I) with 2,2′-dipyridyl and derivatives of 1,10-phenanthroline

Treatment of MeOH solutions of [Rh(cod)(fca)] (cod = 1,5-cyclooctadiene, fca = ferrocenoylacetonato) with seven derivatives of 1,10-phenanthroline (N,N), as well as with the (N,N) ligand 2,2-dipyridyl, gave [Rh(cod)(N,N)]⁺. The kinetics of these reactions follow the rate law: Rate = k[Rh(cod)(fca)[N,N] The temperature dependence of all the studied substitutions resulted in activation entropies, S , more negative than –100 J K^–1 mol^–1 which is indicative of associative mechanisms. The pK _a's of the incoming phenanthroline derivatives were between 3.03 and 6.31 but did not influence the reaction rate to any significant extent. This implies that the rate determining step during the substitution involves Rh—O bond breaking and not Rh—N bond formation. Substitution of fca with 2,2-dipyridyl was slightly faster (k = 118 dm³ mol^–1 s^–1) than with the 1,10-phenanthroline derivatives (k _average = 14.2 dm³ mol^–1 s^–1) and may be attributed to the free rotation capability of the two pyridyl rings about the 1-1 carbon–carbon axis in 2,2-dipyridyl. 1,10-Phenanthroline cannot rotate about the corresponding carbon axis.     

Schiff base complexes of dioxouranium(VI). VII. Dioxouranium(VI) acetate complexes with monobasic bidentate and bibasic tridentateSchiff bases

11 and 12 molar reactions of dioxouranium(VI) acetate dihydrate with the monobasic bidentateSchiff bases,o-HOC₆H₄CH=NR oro-HOC₁₀H₆CH=NR (R=C₂H₅,n-C₃H₇,n-C₄H₉ or C₆H₅) and bibasic tridentateSchiff bases,o-HOC₆H₄CH=NR(OH) oro-HOC₁₀H₆CH=NR(OH) (R=–CH₂CH(CH₃)- or —CH₂CH₂CH₂–) have been studied and derivates of the type UO₂(OAc)₂(SBH), UO₂(OAc)₂(SBH)₂, UO₂(OAc)₂(SBH ₂) and UO₂(OAc)₂(SBH ₂)₂ (whereSBH andSBH ₂ represent monobasic bidentate and bibasic tridentateSchiff base molecules respectively) have been isolated. These have been characterized by elemental analysis, conductance measurements and IR spectral studies.

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UO₂ ²⁺-Komplexe von Schiff-Basen. VII. Uranylacetat-Komplexe mit monobasischen zweizähnigen und bibasischen dreizähnigen Schiff-Basen

Zusammenfassung Es wurden in 1:1- und 1:2-molaren Reaktionen von UO₂(OAc)₂·2H₂O mitSchiff-Basen (L) Komplexe des Typs UO₂(OAc)₂ L bzw. UO₂(OAc)₂ L ₂ isoliert. Die Komplexe wurden mittels Elementaranalyse, Leitfähigkeitsmessungen und IR-Spektren untersucht.

     

Reaktionen mit phosphororganischen Verbindungen, 17. Mitt.: Zur Oxydation von β-Oxophosphoniumrhodaniden mit Bleitetraacetat

Zusammenfassung Die Oxydation von Phosphoniumrhodaniden (C₆H₅)₃P–CH (Alkyl) CO–CHR₁R₂ SCN mitPbTA liefert in Abhängigkeit von den Resten R₁ und R₂ Verbindungen des Typs R₁R₂C=C=C (SCN) (Alkyl) und die daraus durch 1,3-Umlagerung resultierenden Senföle R₁R₂C(NCS)–CC-Alkyl. Für R₁=R₂=H und R₁=Cl, R₂=C₂H₅ entsteht fast nur die Allenverbindung. Für R₁=H und R₂=Alkyl isoliert man ein Gemisch aus Allenrhodanid und Acetylenverbindung. Wenn R₁=R₂=(–CH₂–CH₂–CH₂–) oder CH₃ darstellen, kommt es zur ausschließlichen Bildung des Acetylensenföls.Aus -Methoxyphosphoniumrhodaniden (C₆H₅)₃P–CH (OCH₃)CH–CHR₁R₂ SCN erhält man bei der Umsetzung mitPbTA R₁R₂CH–CO–CH(OCH₃) (NCS) und R₁R₂CH–CO–CH(OCH₃) (S–CO–CH₃).

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The oxidation of phosphoniumrhodanides (C₆H₅)₃P–CH (Alkyl)CO–CHR₁R₂ SCN with lead tetraacetate results in the formation of R₁R₂C=C=C=(SCN) (alkyl) type compounds, dependent on the substituents R₁ and R₂ sometimes followed by a 1,3-rearrangement to mustard oils R₁R₂C(NCS)–CC–alkyl. The case R₁=R₂=H and R₁=Cl, R₂=C₂H₅ yields almost exclusively the allenic compound. With R₁=H and R₂-alkyla mixture of allene rhodanide and the acetylenic compound is isolated. If R₁ and R₂ stand for –CH₂–CH₂CH₂– or CH₃, only the mustard oil with an acetylenic group is produced.Upon the oxidation of (C₆H₅)₃P–CH(OCH₃)CO–CHR₁R₂ SCN^– we observed formation of R₁R₂CH–CO–CH(OCH₃) (NCS) and R₁R₂CH–CO–CH(OCH₃) (S–CO–CH₃).

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Mit 5 Abbildungen

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Herrn Prof. Dr.L. Schmid zum 70. Geburtstag gewidmet.

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16. Mitt.:Elisabeth Werner undE. Zbiral, Angew. Chem.79, 899 (1967).     

Tin(IV) complexes ofSchiff bases derived from salicylaldehyde and aminoalcohols

11 and 12 molar reactions of tin(IV) chloride with theSchiff bases, HO–C₆H₄CHNROH [where R=–(CH₂)₂–, –CH₂–, –CH(CH₃)–, –(CH₂)₃–, and –CH(C₂H₅)CH₂–] have been studied in different stoichiometric ratios and derivatives of the type SnCl₄(SBH₂) and SnCl₄(SBH₂)₂ (whereSBH₂ represents theSchiff base molecule) have been isolated. These have been characterised by elemental analysis, conductivity measurements and I.R. spectral studies.     

Phosphorylformonitrile oxides as spin traps for carbon-centered free radicals: co-formation with radicals in the generation of nitrile oxides from <Emphasis Type="Italic">C</Emphasis>-phosphorylformohydroximoyl halides in the presence of alcohols or ethers

One-electron oxidation of the oximes R₂P(=O)C(=NOH)X (X = Cl or Br) generates the nitrile oxides R₂P(=O)C⁺=NO⁻, which serve as spin traps for unstable carbon-centered radicals.The latter are generated upon addition of PbO₂ to a mixture of formohydroximoyl halide with an alcohol or an ether of the general formula R¹OCHR²R³ under the action of atomic chlorine (bromine) released during the generation of nitrile oxide. This gives rise to new, more persistent C phosphoryliminoxyls R₂P(=O)C(=NO^·)C(OR¹)R²R³ (R¹, R², R³ = H, Alk). When primary alcohols (R¹ = R² = H) are used, acyl radicals generated at the initial step of the reaction are also trapped by nitrile oxides to give C-acyl-C phosphoryl iminoxyl radicals R₂P(O)C(=NO^·)C(=O)R³. Hyperfine coupling constants for more than 20 C-phosphoryl-iminoxyls existing in solutions as mixtures of Z- and E-isomers were determined.The effect of the structure of the primary radical (length of the carbon chain, degree of branching, the presence of a ring, and its size) on the radiospectroscopic characteristics of new C-phosphoryliminoxyl radicals was studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 336–341, February, 2005.     

Synthesis and structural characterization of camphanates of (−)-(2S3S,3S) and (+)-(2S,3R)-4-Phenyl-3-bromo-2-butanol diastereoisomers

The X-ray crystal structures of (–)-syn-4-phenyl-3-bromo-2-butyl camphanate (I) and (+-anti-4-phenyl-3-bromo-2-butyl camphanate (II) have been determined. Thesyn diastereoisomer of bromohydrin has the (2S,3S) absolute configuration whereas theanti diastereoisomer has the (2S,3R) absolute configuration. The crystallized derivatives I and II have been obtained by the reaction of each stereoisomer of bromohydrin, synthesized by reduction with baker's yeast, with (1S)-camphanic chloride. Crystal data: (I) C₂₀H₂₅BrO₄:M _w: 409.32; orthorhombic,P2₁2₁2₁;a=11.245(3),b=12.086(1),c=14.512(4) å; Z=4; finalR=0.053 for 1819 observed reflections. (II) C₂₀H₂₅BrO₄;M _w=409.32; monoclinic, P2₁;a=11.352(1),b=6.378(1),c=14.255(2) å,=110.38(1);Z=2; finalR=0.045 for 1672 observed reflections.     

New hetero-annelation reactions using N-[bis-(methylthio)-methylene]-amino and related reagents

Summary Reaction of acyclic (B _1–3) and cyclic (R _4–5)BMMA (=N-[b is-(methylthio)-methylene]-amino) reagents withGewald-type thiophene derivatives (2,3) led to annelation of pyrimidine moieties. Thus, linear thiazolo- or thiazino- and pyrrolo-, pyrido- or azepino-fused thiopyrano[4,3:4,5]thieno-[2,3-d]pyrimidines (5 and6) as well as the angular imidazo-fused thiopyrano[4,3:4,5]thieno-[2,3-d]pyrimidine8 were easily obtained from one-pot reactions in good yields.on leave from Chemistry Department, Minia University, El-Minia, Egypt     

Synthesis, reactions and X-ray crystal structures of metallacrown ethers with unsymmetrical bis(phosphinite) and bis(phosphite) ligands derived from 2-hydroxy-2′-(1,4-bisoxo-6-hexanol)-1,1′-biphenyl

Chlorodiphenylphosphine and 2,2′-biphenylylenephosphorochloridite react with 2-hydroxy-2′-(1,4-bisoxo-6-hexanol)-1,1′-biphenyl to yield the new α,ω-bis(phosphorus-donor)-polyether ligands, 2-Ph₂PO(CH₂CH₂O)₂–C₁₂H₈-2′-OPPh₂ (1) and 2-(2,2′-O₂C₁₂H₈)P(CH₂CH₂O)₂–C₁₂H₈-2′-P(2,2′-O₂C₁₂H₈) (2). These ligands react with Mo(CO)₄(nbd) to form the monomeric metallacrown ethers, cis-Mo(CO)₄{2-Ph₂PO(CH₂CH₂O)₂–C₁₂H₈-2′-OPPh₂} (cis-3) and cis-Mo(CO)₄{2-(2,2′-O₂C₁₂H₈)P(CH₂CH₂O)₂–C₁₂H₈-2′-P(2,2′-O₂C₁₂H₈)} (cis-4), in good yields. The X-ray crystal structures of cis-3 and cis-4 are significantly different, especially in the conformation of the metal center and the adjacent ethylene group. The very different ¹³C-NMR coordination chemical shifts of this ethylene group in cis-3 and cis-4 suggest that the solution conformations of these metallacrown ethers are also quite different. Both metallacrown ethers undergo cis–trans isomerization in the presence of HgCl₂. Although the cis–trans equilibrium constants for the isomerization reactions are nearly identical, the isomerization of cis-3 is more rapid. Phenyl lithium reacts with cis-3 to form the corresponding benzoyl complexes but does not react with either trans-3 or cis-4. Both the slower rate of cis–trans isomerization of cis-4 and its lack of reaction with PhLi are consistent with weaker interactions between the hard metal cations and the carbonyl oxygens in both trans-3 and cis-4.     

ESR study of adducts of diisopropylphosphoryl radicals with C60C[P(O)(OEt)2]2 2 isomers

The radical adducts of the P^·(O)(OPrⁱ)₂ (R^·) radicals with C₆₀C[P(O)(OEt)₂]_{2 2} fullerene derivatives were studed by ESR spectroscopy. The number of stable regioisomers of phosphorylfullerenyl radicals formed by addition of the phosphoryl radicals to the C₆₀C[P(O)(OEt)₂]_{2 2} isomers depends on the mutual position of the organophosphorus groups and decreases in the series trans-2 > trans-3 trans-4 > e. The rate constants for addition of the R^· radicals to the trans-3 regioisomer (k = 1.7·10⁸ L mol^–1 s^–1) were determined.     

Products and kinetics of the thermal decomposition of (l-(−)-menthyl)[2,2′-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphite ozonide

Two conformers (chair, boat) of [l-(–)-menthyl)]-[2,2-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphite ozonide have been obtained by the low temperature ozonization (–80 °C) of [l-(–)-menthyl)]-[2,2-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphite. It was determined that decomposition of the ozonide is first order with the rate constant logk ₀ = (10.92±1.10)–(14.02±1.25)/gq ( = 2.303RT, kcal mol^–1), leading to [l-(–)-menthyl)]-[2,2-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphate and oxygen (including singlet oxygen). Conformational transitions (chair-boat) for [l-(–)-menthyl)]-[2,2-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphate have been registered by³¹P NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1758–1761, October, 1994.This work was supported by Russian Foundation for Basic Research (Project No. 93-03-532l).     

Asymmetric alkylation catalyzed by chiral alkali metal alkoxides of TADDOL. Synthesis of α-methyl amino acids

It is shown that sodium alkoxides formed from (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-bis(diphenylmethanol) ((R,R)-TADDOL) and some of its derivatives can be used as chiral catalysts for enantioselective alkylation of Schiff's bases derived from alanine with reactive alkyl halides. Acid hydrolysis of the reaction products affords (R)-α-methylphenyl-alanine, (R)-α-allylalanine, and (R)-α-methylnaphthylalanine in 61–93% yields and withee 69–94%. When (S,S)-TADDOL is used, the (S)-amino acid is formed. A mechanism explaning the observed features of the reaction is proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 926–932, May, 1999.     

Zur Kenntnis der Reaktionsfähigkeit des unsubstituierten Thiomorpholins und alkylsubstituierter Thiomorpholine. 3. Mitt

A new synthesis of thiomorpholine by ring closure of -chloro--aminodiethylene-sulfide with potassium hydroxide is reported. Numerous reactions of thiomorpholine (1) and, especially, 2-methyl-3-ethyl-thiomorpholine (2) are described such as acylation, diacylation (3–43), reactions with sulfonic acid chlorides (44–52), isocyanates (53–61, 70–75), diisocyanates (62–66, 76–78) and isothiocyanates (67–69, 79–82), alkylation reactions (83–111) and the synthesis of thiomorpholino-dithiocarbamates (112–121).

Teil der Dissertation,E. Wilms, Techn. Hochschule Aachen, 1971.     

Tin(IV) and organotin(IV) derivatives of novel β-diketones: Part IV. Triorganotin(IV) complexes of fluorinated 4-acyl-5-pyrazolones. Crystal structure of (1-(4-trifluoromethylphenyl)-3-methyl-4-acetylpyrazolon-5-ato)triphenyltin(IV)

The synthesis of three 1-(4-trifluoromethylphenyl)-3-methyl-4-R¹(C=O)-5-pyrazolone proligands LH (L¹H; R¹=C₆H₅: L²H; R¹=CH₃: L³H; R¹=CF₃) and their interaction with R₃Sn(IV) acceptors (R=Me, Buⁿ, Ph) are reported. When R=Me or Buⁿ, aquo (4-acylpyrazolonate)SnR₃(H₂O) derivatives are obtained and the anionic donors 4-acylpyrazolonate (L⁻) act in the O–monodentate form. These triorganotin complexes are not stable in chlorohydrocarbon solvents and decompose to R₄Sn and bis(4-acyl-5-pyrazolonate)₂SnR₂. When R=Ph, stable (4-acyl-5-pyrazolonate)SnPh₃ derivatives, both in solution and in the solid state, are obtained. The crystal structure of (1-(4-trifluoromethylphenyl)-3-methyl-4-acetylpyrazolon-5-ato)triphenyltin(IV) shows a five-coordinate tin atom in a strongly distorted cis-bipyramidal trigonal environment (axial angle=161.2(2)°) with the acylpyrazolonate donor acting as an asymmetric O₂–bidentate species (Sn–O(1)=2.081(6) Å: Sn–O(2)=2.424(5) Å). Electronic effects are responsible for the different behavior shown by these trialkyl and triphenyl derivatives.