Ringtransformationen heterocyclischer Verbindungen. XII. Neuartige Spiroindoline via Ringtransformation von 2,4,6-Triaryl-pyryliumsalzen mit 2-Methylen-indolinen

Ring Transformations of Heterocyclic Compounds. XII. Novel Spiroindolines via Ring Transformation of 2,4,6-Triarylpyrylium Salts with 2-Methyleneindolines 2,4,6-Triarylpyrylium salts 1 react with 2-methyleneindolines 2 or their salts 2 HX in the presence of triethylamine/acetic acid in ethanol by a 2,5-[C₄ + C₂] pyrylium ring transformation to give diastereomerically pure 6-aroyl-3,5-diaryl-spiro[cyclohexa-2,4-diene-1,2′-indolines] 3 , which represent a novel type of spiroindoline compounds. When the 1′-phenyl substituted spiroindolines 3 (RPh, R′H) are treated with p-toluenesulfonic acid in chloroform the 4,6-diaryl-2-[1-methyl-1-(2-phenylaminophenyl)methyl]benzophenones 4 are obtained as the result of an intramolecular amine elimination. Structural elucidation of the reaction products 3/4 is based on spectroscopic data and on an X-ray determination of the bis(4-bromophenyl) substituted spiroindoline 3i.     

Darstellung,Konfigurationen und NMR-Daten der Säuren CH3(SR)  CHCOOH (R  C6H5, CH2C6H5, CH2COOH)

Preparation, Configurations and N.M.R. Dates of the Acids CH₃(SR)CHCOOH (R  C₆H₅, CH₂C₆H₅, CH₂COOH) The cis and trans isomers of the acids CH₃(SR)CHCOOH (R  C₆H₅, CH₂C₆H₅, CH₂COOH) were prepared by addition of HSR to CH₃CCCOOH in alkaline water solution and by alkaline hydrolysis of CH₃C(SR)₂CH₂COOC₂H₅ (R  C₆H₅, CH₂C₆H₅, CH₂COOC₂H₅). The oxidation products CH₃C(SO₂R)  CHCOOH (R  C₆H₅, CH₂COOH) were also prepared. The n.m.r. dates of the acids were obtained and some relations between them were discussed.     

Efficient Access to Conjugated Dienones and Diene‐diones from Propargylic Alcohols and Enolizable Ketones: A Tandem Isomerization/Condensation Process Catalyzed by the Sixteen‐Electron Allyl‐Ruthenium(II) Complex [Ru(η3‐2‐C3H4Me)(CO)(dppf)] [SbF6]

A large variety of conjugated dienones R¹R²CCHCHC(R³)C(O)R⁴ and diene‐diones R¹R²CCHCHC{C(O)R³}C(O)R⁴ have been synthesized in high yields by reacting terminal propargylic alcohols HCCCR¹R²(OH) with enolizable ketones R³CH₂C(O)R⁴ and β‐dicarbonyl compounds R³C(O)CH₂C(O)R⁴, respectively. The process, which is catalyzed by the 16e^‐ (η³‐allyl)‐ruthenium(II ) complex [Ru(η³‐2‐C₃H₄Me)(CO)(dppf)] [SbF₆] associated with CF₃CO₂H, involves the initial isomerization of the propargylic alcohol into the corresponding α,β‐unsaturated aldehyde R¹R²CCHCHO (Meyer–Schuster rearrangement) and subsequent aldol‐type condensation.     

Noels’ vs. Grubbs’ Catalysts: Evidence for One Unique Active Species for Two Different Systems!

The catalytically active propagating species involved in the self‐metathesis of ethyl oleate obtained from the multi‐component Noels’ catalytic system {[RuCl₂(p‐cymene)(PCy₃)]+Me₃SiCHN₂} are probably the same as those of the single‐component well‐defined Grubbs’ 1st generation catalyst, [Cl₂RuCHPh(PCy₃)₂] ( 1‐Ph ). In the case of the Noels’ catalyst, it involves the de‐coordination of p‐cymene, and the redistribution of PCy₃ ligands to generate only 5–10 % of [Cl₂RuCHR(PCy₃)₂], where R=CH (CH₂)₆ CH₃ ( 1‐Oct ) and R=CH (CH₂)₆ COOEt ( 1‐E ), while 1‐Ph can generate 100 % of these species.     

Facile,Efficient Copolymerization of Ethylene with Bicyclic,Non‐Conjugated Dienes by Titanium Complexes Bearing Bis(β‐Enaminoketonato) Ligands

Copolymerizations of ethylene with 5‐vinyl‐2‐norbornene or 5‐ethylidene‐2‐norbornene under the action of various titanium complexes bearing bis(β‐enaminoketonato) chelate ligands of the type, [R¹NC(R²)CHC(R³)O]₂TiCl₂ ( 1 , R¹=Ph, R²=CF₃, R³=Ph; 2 , R¹=C₆H₄F‐p, R²=CF₃, R³=Ph; 3 , R¹=Ph, R²=CF₃, R³=t‐Bu; 4 , R¹=C₆H₄F‐p, R²=CF₃, R³=t‐Bu; 5 , R¹=Ph, R²=CH₃, R³=CF₃; 6 , R¹=C₆H₄F‐p, R²=CH₃, R³=CF₃), have been shown to occur with the regioselective insertion of the endocyclic double bond of the monomer into the copolymer chain, leaving the exocyclic vinyl double bond as a pendant unsaturation. The ligand modification strongly affects the copolymerization behaviour. High catalytic activities and efficient co‐monomer incorporation can be easily obtained by optimizing the catalyst structures and polymerization conditions.     

Über die Konfigurationen und Konformationen einiger unsymmetrisch S-substituierter 2,3-Dimercaptobernsteinsäuren

The Configurations and Conformations of Some Unsymmetrical S-Substituted 2,3-Dimercapto Succinic Acids Some acids HOOCCH(SR)CH(SR′)COOH (R/R′ = HOOCCH₂, C₆H₅, C₆H₅CH₂ and p-ClC₆H₄CH₂, R ≠ R′) were prepared from HOOCC(SR)  CHCOOH and R′SH. Their configurations and conformations were discussed.     

Convenient Modular Syntheses of Fluorous Secondary Phosphines and Selected Derivatives

Reactions of the fluorous primary phosphines R_fn(CH₂)₂PH₂ [R_fn=(CF₂)_n−1CF₃; n=6, 8, 10] and R_fn′CHCH₂ [(n′=6, 8, 10) (1 : 1; THF, reflux) in the presence of AIBN give the title compounds [R_fn(CH₂)₂][R_fn′(CH₂)₂]PH [n/n′=6/6 ( 4 , 55%), 8/8 ( 5 , 58%), 10/10 ( 6 , 53%), 8/6 ( 7 , 52%), 10/8 ( 8 , 51%)] as low-melting white solids on up to 10-g scales. The chiral tertiary phosphine [R_f6(CH₂)₂][R_f8(CH₂)₂][R_f10(CH₂)₂]P ( 9 ) is similarly prepared from 7 and R_f10CHCH₂ in the presence of VAZO (neat, 100 °C; 67%). The reaction of 5 and THF⋅BH₃ yields the phosphine borane 5 ⋅BH₃ (95%). Additions of triphosgene [(CCl₃O)₂CO] to 5 or R_f8(CH₂)₂PH₂ give [R_f8(CH₂)₂]₂PCl or R_f8(CH₂)₂PCl₂, which are characterized in situ. The CF₃C₆F₁₁/toluene partition coefficients of 4 – 9 increase with the number and lengths of the R_fn segments.     

On the Use of Non‐Symmetrical Mixed PCN and SCN Pincer Palladacycles as Catalyst Precursors for the Heck Reaction

The mixed pincer palladacycles (Me₂NCH₂(Cl)CCCH₂CH₂Y‐κN,κC,κY)PdCl ( 1 , Y=PPh₂; 2 , OPPh₂) and (t‐BuSCH₂CH₂CC(Cl)(o‐NC₅H₄)‐κS,κC,κN)PdCl 3 have been obtained in high yields by chloropalladation of heterosusbstituted alkynes Me₂NCH₂CCCH₂CH₂PPh₂, Me₂NCH₂CCCH₂CH₂OPPh₂ and t‐BuSCH₂CH₂CC(o‐NC₅H₄), respectively. The molecular structures of 1 and 3 have been ascertained by means of X‐ray diffraction analysis. The catalytic properties of these mixed donor group pincer‐type palladacycles have been evaluated in the arylation of olefins (Heck reaction). The pincer palladacycle 1 is highly active for the coupling of aryl iodides and aryl bromides with n‐butyl acrylate. In contrast it is only moderately active for the coupling of aryl chlorides substituted with electron‐withdrawing groups and inactive for the coupling of electron neutral and electron deactivated aryl chlorides.     

Organische Phosphorverbindungen. XIII. Reaktion vinyloger Chlormethylenimmoniumsalze mit Phosphorigsäuretrialkylestern

Organic Phosphorus Compounds. XIII. Reaction of Vinylogous Chloromethylene Immonium Salts with Trialkyl Phosphites 3-Chloropropenylidene immonium salts of the type Cl CArCH CHNMe₂^⊕X^⊖ don't react like chloromethylene immonium salts Cl CHNMe₂^⊕X^⊖ with trialkyl phosphites according to the classical MICHAELIS -ARBUSOV principle (RO)₃P + R′Cl → (RO)₂P(O)R′ + RCl but lead to salts of 1-dimethylaminophosphonates (RO)₂P(O) CH(NMe₂ · HX) CHCClAr the structure of which is confirmed by two independent syntheses. Some characteristic reactions of the free dimethylaminophosphonates are described.     

New organic polymers,II. Synthesis and characterization of poly[3,3′-(6,6′-bis-(2-substituted-4-quinazolonediyl)) alkylene]s

Poly[3,3′-(6,6′-bis-(2-substituted-4-quinazolonediyl))alkylene]s have been synthesized by reacting 6,6′-bis-(2-R-3,1,4-benzoxazinone) (R = Me, Ph, and ? CH₂Ph) with aliphatic diamines H₂N(CH₂)_nNH₂ with n = 0, 2, 3, 4, 6 and 8 in m-cresol. These polymers are insoluble in all common organic solvents but are fairly soluble in concentrated sulfuric acid. The polymers were characterized by IR spectral study, viscometric measurements and thermal analysis. IR spectra of the polymer samples have been compared with those of their model compounds.     

Synthesis of Ruthenium Hydride Complexes Containing beta‐Aminophosphine Ligands Derived from Amino Acids and their use in the H2‐Hydrogenation of Ketones and Imines

The new complexes RuHCl(PPh₂CH₂CHRNH₂)₂ and RuHCl(PPh₂CH₂CHRNH₂)(R‐ binap), R=H (Pgly), R=Me [(R)‐Pala] were prepared by the substitution of the PPh₃ ligands in RuHCl(PPh₃)₃ or RuHCl(PPh₃)[(R)‐binap] with beta‐aminophosphines derived from amino acids. The complex trans‐RuHCl(Pgly)[(R)‐binap] has been characterized by X‐ray crystallography. The complex trans‐RuHCl[(S)‐Ppro]₂ where (S)‐Ppro is derived from proline was also prepared and characterized by X‐ray crystallography. These were used as catalyst precursors in the presence of a base (KOPr‐i or KOBu‐t) for the hydrogenation of various ketones and imines to the respective alcohols and amines with H₂ gas (1–11 atm) at room temperature. Acetophenone was hydrogenated to (S)‐1‐phenylethanol in low ee (up to 40%) when catalyzed by the enantiomerically pure complexes. These complexes are especially active in the hydrogenation of sterically congested and electronically deactivated ketones and imines and are selective for the hydrogenation of CO bonds over CC bonds.     

Photokatalytische Systeme. XXXIV. Über die Photoreduktion von Carboxylato(cuproin)kupfer(II)-Chelaten in Alkoholen

Photocatalytic Systems. XXXIV. On the Photoreduction of Carboxylato(cuproine) Copper (II) Chelates in Alcohols In contrast to the behaviour in nonpolar aprotic solcents, the photolysis of cuproine copper(II) chelates of the type Cu(N N) (RCOO)₂ (R  CH₃, C(CH₃)₃; N N = sterically hindered heterocyclic 1, 2-diimine ligand) in alcohols does not lead to formation of free radicals. A two-step mechanism with non-radicalic intermediates is derived from e.s.r. spin trapping and microsecond flash photolysis experiments.     

Synergistic Solvent Extraction of Lanthanides(III) with Mixtures of 4-benzoyl-3-methyl-1-phenylpyrazol-5-one and Some Novel Carbamoyl- and Phosphorylmethoxymethylphosphine Oxides

The solvent extraction of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from weak acidic hydrochloric acid solutions into an organic phase containing 4-benzoyl-3-methyl-1-phenylpyrazol-5-one (HP) and neutral tridentate organophosphorus ligands R₂P(O)CH₂OCH₂C(O)NBu₂ R = Bu (I), R = Ph (II) and R₂P(O)CH₂OCH₂P(O)R¹₂ R = R¹ = Bu (III); R = Bu, R¹ = Ph (IV); R = R¹ = Ph(V) has been studied. A considerable synergistic effect was observed in the presence of HP in the organic phase containing tetraoctyldiglycolamide (TODGA) and neutral organophosphorus ligands I - V. A successive replacement of C(O)NAlk₂ groups in the diglycolamide extractant molecule by P(O)Ph₂ groups leads to an increase in the extraction efficiency of Ln(III) ions when toluene was used as diluent. Phosphoryl-containing podand I possess a higher extraction efficiency towards Ln(III) ions than TODGA. The extraction equilibrium was investigated and the equilibrium constants were calculated. It was found that the lanthanide(III) ions are extracted as LnLP₃ and LnL₂P₃ complexes with mixtures of HP and I in toluene from weak acidic solutions.     

Polyorganosiloxanes containing both ester and hydride functionalities: A detailed study by 1H and 13C NMR spectroscopy

A total of eighteen linear polysiloxanes of general formula Me₃SiO-(MeSi(E)O)_x(MeSi(H)O)_ySiMe₃ (E = —(CH₂)_nester; x+y = 40) have been prepared by the platinum catalysed addition of CH₂=CH(CH₂)_n-2 -ester to Me₃SiO-(MeSi(H)O)₄₀SiMe₃ under anhydrous conditions. Polymers containing the ester functionalities—(CH₂)₃CO₂R(R = Me, CF₃, Et, Pr, and CH₂COMe),—(CH₂)₃-CHMeCO₂Et, —(CH₂)₂CH(CO₂Me)₂, —(CH₂)₃CH(CO₂Et)₂, -(CH₂)₃CO₂CH= CHCO₂CH₂CH=CH₂ and —(CH₂)₃CO₂C₆H₄CO₂ CH₂CH=CH₂ have been characterised by analysis and ¹H and ¹³C NMR spectroscopies. Factors affecting Markownik off versus anti-Markownikoff addition of allyl acetate to this polymethylsiloxane have also been explored.     

Poly(methylphenylphosphazene)–Graft–Poly(methyl Methacrylate) Copolymers Via Atom Transfer Radical Polymerization

Atom transfer radical polymerization (ATRP) was used to graft poly(methyl methacrylate), PMMA, onto poly(methylphenylphosphazene), [(Me)(Ph)PN] _n , PMPP. A two-step process was used to convert a portion of the methyl substituents on [(Me)(Ph)PN] _n to –CH₂C(CH₃)₂OH groups and then to bromoalkyl groups, –CH₂C(CH₃)₂OC(=O)C(CH₃)₂Br, the latter of which served as initiation sites for ATRP of methyl methacrylate (MMA) in the presence of CuCl/bipyridine. Variations in the length of the grafted chains were investigated and the graft copolymers were compared to the parent polymer and blends of similar composition. The new bromoalkyl derivatives of [(Me)(Ph)PN] _n and the PMPP–graft–PMMA copolymers were characterized by elemental analysis, ¹H and ³¹P NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). We dedicate this paper to Professor Harry R. Allcock for consistently maintaining the highest standards in his creative, pioneering work in inorganic rings and polymers.     

Extraction of Lanthanides(III), U(VI), and Th(IV) from Nitric Acid Solutions with 1,5-N,N'-Bis[(diphenylphosphoryl)acetylamino]pentanes

Novel polyfunctional neutral organophosphorus ligands, namely 1,5-N,N'-bis[(diphenylphosphoryl)acetyl(alkyl)amino]pentanes [Ph₂P(O)CH₂C(O)NR]₂(CH₂)₅ (Ia, R = C₆H₁₃; Ib, R = CH₃), were studied as extractants for Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, and U from nitric acid solutions. The effect of both HNO₃ concentration in the aqueous phase and that of the extractant in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined by the slope analysis method. Compared with the related bisaminopentane [Ph2P(O)CH₂C(O)NH]₂(CH₂)₅ (Ic), the replacement of hydrogen atoms at the amide nitrogens by alkyl radicals (compounds Ia,b) leads to an increase of metal ions extraction. Bis-CMPO ligands Ia-c were found to possess higher extraction efficiency towards U(VI), Th(IV), and Ln(III) than their monophosphorylated analogue Ph₂P(O)CH₂C(O)N(C₄H₉)₂.     

Polymerized Surfactant Vesicles

Irradiation of surfactant vesicles prepared from (C₁₈H₃₇)₂ N⁺(CH₃)C₆H₄-CHCH₂p,CT⁻, 1, [C₁₅H₃₁CO₂(CH₂)₂]₂N⁺(CH₃)CH₂C₆H₄CHCH₂,CL⁻ 2, and (C₁₈-H₃₇)₂N⁺(CH₃)CH₂CH₂OCOC₆H₄CHCH₂p,Br⁻, 3, by ultraviolet light or by bursts of 266 nm laser pulses have resulted in the loss of styrene absorbances. This process has been accounted for in terms of a model which considers intravesicular surface reactions to give polymers with average chainlength of 22. Degreees of photopolymerization have been determined in vesicles prepared from 3 subsequent to separating the polystryrene, formed in the photolysis, from the surfactants. Vesicle surface photopolymerizations result in aqueous cleft formation and in enhanced stabilities. Polymerized vesicles provide media for in situ generation of colloidal catalysts and semiconductors.     

Structural characterization and thermal behaviour of block copolymers of polydimethylsiloxane and polyamide having trichlorogermyl pendant groups

Block copolymers having a pendant trichlorogermyl group as a part of polyamide segment? (CO? R′? CO? NH? Ar? NH? )_xCO? R′? CO? and polydimethylsiloxane of general formula [(? CO? R′? CO? HN? Ar? NH)_x? CO? R′? CO? NH(CH₂)₃SiO(CH₃)₂ ((CH₃)₂SiO)_ySi(CH₃)₂(CH₂)₃ NH? ]_n (where R′ = CH₂CH(GeCl₃), CH(CH₃)CH(GeCl₃), CH(GeCl₃)CH(CH₃); Ar = C₆H₄, (? C₆H₃? CH₃)₂, (? C₆H₃? OCH₃)₂, 2,5‐(CH₃)₂? C₆H₂, C₆H₄? O? C₆H₄) were prepared by a polycondensation reaction and characterized using CHN and Ge analysis, Fourier transform infrared (FTIR) and ¹H NMR spectroscopy, thermogravimetric analysis (TGA) and molecular weight determination. They have a lamellar structure with weight‐average molecular weight in the range 1.21 × 10⁵–4.79 × 10⁵ g mol^?1. These copolymers display two glass transition temperatures and have an average decomposition temperature of 489 °C. TGA, FTIR and gas chromatography/mass spectrometry studies indicate that degradation of these block copolymers results in carbon monoxide, oligomeric siloxanes and polyamide fragments. They are thermally stable due to the hydrogen bonded interlinked chains of polyamide, while they absorb water due to the presence of Ge? Cl bonding. Copyright © 2010 Society of Chemical Industry     

NMR-study of the stereochemistry and dynamic behaviour of thioacrylamides

Several model thioacrylamides, Me₂N CH = C(R) C(S) NMe₂ (R = H, Ph — 2a, b ) and (p)MeO C₆H₄ NH CHC(R) C(S) NMe₂ (R = H, Ph — 3a, b ) have been synthesized. The ¹H-n.m.r. spectra have been taken for discussing the E/Z-isomerism of the thioacrylamides and the assignment further strengthened by an added LIS-study. The 2-unsubstituted compounds have been found to exist exclusively in preferred configurations/conformations: 2a — E(s-cis); 3a — Z(s-cis); the 2-phenylsubstituted analogs are of divergent behaviour: in 2b the C(S) NMe₂ moiety is found to be twisted out of the common plane, and 3b prefers the flat s-trans conformations (E(s-trans) ⇌ Z(s-trans)). The compounds show restricted rotations about C¹, N- and C³, N-partial double bonds. The corresponding rotational barriers, determined as ΔG-values by dynamic n.m.r. spectroscopy, are discussed with respect to (i) the resonance branch at C¹, (ii) the influence of substituents, and (iii) the effect of steric hindrance in the thioacrylamide moiety generally.     

Pyryliumverbindungen. 30. C-Alkylierung von 1,3,5-Triaryl-penten-1,5-dion-Enolaten: Ein einfacher Zugang zu 3-alkylsubstituierten 2,4,6-Triaryl-pyryliumsalzen

Pyrylium Compounds. 30. C-Alkylation of 1,3,5-Triaryl-pentene-1,5-dione Enolates: A Simple Approach to 3-Alkylsubstituted 2,4,6-Triarylpyrylium Salts 1,3,5-Triaryl-pentene-1,5-dione enolates ( 10 ), obtainable in crystalline form from 2,4,6-triarylpyrylium pseudobases ( 9 ) and sodium methoxide in benzene/ether, react in dipolar aprotonic solvents (e.g. DMSO, DMF) with various types of alkyl iodides to give C-alkylation products ( 11 ) which afford 3-substituted 2,4,6-triarylpyrylium salts ( 12 ) on treatment with perchloric acid. This reaction sequence proved to be a convenient synthetic route to pyrylium salts ( 12 ) having 3-oriented substituents such as normal or branched alkyl groups C_nH_2n+1 (e.g.n = 1–5), isotopically modified alkyl groups (e.g. C[²H₃], C₂[²H₅]), allyl type substituents (e.g. CH₂CHCH₂, MeCHCHCH₂, CH₂, CH₂CMeCH₂) or benzyl groups (e. g. PhCH₂, 4-Br C₆H₄CH₂). Bifunctional alkylating agents (e.g. 1,4-diiodobutane, o-xylylenediiodide) resulted in a novel type of bispyrylium salts ( 14 ) with 3,3′-linkage. The pyrylium salts obtained were characterized by their ¹H-n.m.r. and u.v. spectra as well as, in most cases, by transformation into the corresponding pyridine derivatives ( 13 ) and bispyridines ( 15 ) respectively.