Ion Neda

Calix[4]arene‐based Bis‐phosphonites, Bis‐phosphites, and Bis‐O‐acyl‐phosphites as Ligands in the Rhodium(I)‐catalyzed Hydroformylation of 1‐Octene

New calix[4]arene-based bis-phosphonites, bis-phosphites and bis-O-acylphosphites were synthesized and characterized. Treatment of these P-ligands with selected rhodium and platinum precursors led to mononuclear complexes that were satisfactorily characterized. The solid state structure of the dirhodium(I) complex 14 has been determined by X-ray diffraction. The two rhodium centres are bridged by two chloro ligands; one rhodium atom is further coordinated by calix[4]arene phosphorus atoms and the other by cyclooctadiene. The new calix[4]arene P-ligands were tested in the Rh(I) catalyzed hydroformylation of 1-octene. All Rh(I) complexes catalyzed the reaction leading to high chemoselectivity with regard to the formation of aldehydes. Yields and n/iso-selectivities depended on the reaction conditions. Average yields of 80 % and n/iso-ratios of about 1.3 to 1.5 were observed. High yields of aldehydes can be achieved using the methoxy substituted P-ligands at low Rh:ligand ratios. Auf Calix[4]arenen basierende Bis-phosphonite, Bis-phosphite und Bis-O-acyl-phosphite als Liganden in der rhodium(I)-katalysierten Hydroformylierung von 1-Octen Neue auf Calix[4]arenen basierende Bis-phosphonite, Bis-phosphite und Bis-O-acyl-phosphite wurden synthetisiert und charakterisiert. Die Umsetzung dieser Phosphorliganden mit ausgewahlten Rhodium- und Platinvorstufen fuhrte zu mononuklearen Komplexen, die vollstandig charakterisiert wurden. Durch eine Rontgenstrukturanalyse konnte die Struktur des Dirhodium( I)-Komplexes 14 im festen Zustand bestimmt werden. Die beiden Rhodiumzentren sind durch zwei Chlorliganden verbruckt, wobei das eine Rhodiumatom an die Phosphoratome des Calix[4]-arens und das andere Rhodiumatom durch das Cyclooctadien koordiniert ist. Die neuartigen phosphorhaltigen Calix[4]aren-Liganden wurden in der Rhodium(I)-katalysierten Hydroformylierung von 1-Octen getestet. Alle Rh(I)-Komplexe katalysierten die Reaktion bei hoher Chemoselektivitat, bezogen auf die Bildung von Aldehyden. Ausbeuten und n/iso-Selektivitaten waren dabei von den Reaktionsbedingungen abhangig. Durchschnittliche Ausbeuten von 80 % und n/iso-Verhaltnisse von 1.3 bis 1.5 wurden beobachtet. Hohe Ausbeuten an Aldehyden bei geringen Rhodium:Ligand-Verhaltnissen konnten durch den Einsatz von methoxysubstituierten Phosphorliganden erzielt werden.

VERBINDUNGEN MIT DEM 1,3,2-BENZODIAZAPHOSPHORINAN-4-ON GRUNDGERÜST: SYNTHESE VON NEUARTIGEN, N,N-DIMETHYLAMINO- UND BIS-2-CHLORETHYLAMINO-SUBSTITUIERTEN DERIVATEN MIT DREI-, VIER- UND FÜNFFACH KOORDINIERTEM PHOSPHOR

Abstract The reaction of 1,3-dimethyl-2-chloro-1,3,2-benzodiazaphosphorinan-4-one 1 with sodium fluoride furnished 2. The reaction of 1 with Me3SiNMe2 3 yielded the product 4. The 1,3-dimethyl-2-(2-chloroethyl)amino- and 1,3-dimethyl-2-[bis(2-chloroethyl)amino]-1,3,2-benzodiazaphosphorinan-4-one derivatives 5 and 6 were prepared by the reaction of 4 with 2-chloroethylamine and with bis(2-chloroethyl)-amine. Oxidative addition of elemental sulfur at the λ3 P atom of 4 and 6 gave the λ4 P-thiophosphoryl compounds 9 and 10, whereas the reaction of 4 with tetrachloro-o-benzoquinone and hexafluoroacetone, respectively, furnished the spirophosphoranes 11 and 12. The reaction of 4 with p-nitrobenzoyl azide led to the p-nitrobenzoylphosphorinane imide 13. The structures of 6 and 12 were confirmed by single-crystal X-ray analysis. The heterocyclic ring of 6 displays a flattened 1,3-diplanar conformation. The phosphorus atom of 12 has distorted trigonal-bipyramidal coordination geometry, with both rings subtending ...

N,N′,N′-trimethylethylenediamine as a substituent group at main group centers: intramolecular donor-acceptor interactions and unusual modes of coordination in compounds of silicon and phosphorus and their transition metal complexes

Abstract This review is concerned with the role of the N , N ′, N ′-trimethylethylenediamine group as a substituent at phosphorus atoms in different coordination and/or oxidation numbers. A few examples for silicon are also presented. Intramolecular donor-acceptor interactions between the nitrogen atom of the dimethylamino group and Si or P as the central atom were first noted in some N , N ′, N ′-trimethylethylenediamine-substituted fluorosilanes (LSiF 3 , PhSiF 2 L) and P(III)Cl systems, e.g. LPCl 2 and PhP(Cl)L (L = N , N ′, N ′-trimethylethylenediamine group). These observations gave rise to a more detailed study of the coordinating behavior, especially of further phosphorus compounds of different substitution pattern. Spontaneous intramolecular coordination with formation of salt-like products was observed, especially, for compounds in which a phosphorus-bonded halogen atom is available to dissociate as an anion. A dependence both on the nature of the halogen atom and on the nature of other ligands at P(III) [or P(V)] was noted and will be discussed. Through the action of Lewis acids, e.g. AlCl 3 of PF 5 , or in the reaction with tetraphenylborate as a non-coordinating anion, halide abstraction and consequent formation of the Me 2 N → P coordinative bond from cyclic N , N ′, N ′-trimethylethylenediamine-substituted halophosphines or trimethylethylenediamine-substituted fluorophosphoranes could be induced. No such Me 2 N → P coordination took place during oxidation of N , N ′, N ′-trimethylethylenediamine-substituted phosphorus(III) compounds with oxidizing agents, e.g. sulfur, selenium, o -quinones or hexafluoroacetone. Numerous oxidation reactions were conducted on intramolecularly stabilized phospholidin-1-ium salts. They furnished the expected oxidation/addition products. This was accompanied in some cases (depending on the nature of the substituents at P(III)) by a scission of the coordinative Me 2 N → P bond. The reaction of phospholidin-1-ium salts with phenyl azide, dimethyl sulfoxide and sulfur furnished phosphonic acid diamides and substituted λ 4 -phospholidin-1-ium salts, as well as substituted diazadiphosphetidines, as a result of the dimerization of PN species. Intramolecular donor-acceptor interaction in N , N ′, N ′-trimethylethylenediamine-substituted fluorophosphoranes was only observed in the presence of the Lewis acid, phosphorus pentafluoride leading to the formation of hexafluorophosphate salts. The reaction of dialkylamino-substituted tetrafluorophosphoranes with N , N ′, N ′-trimethylethylenediamine took an unusual course. Instead of the expected PF cleavage and formation of an N , N ′, N ′-trimethylethylenediamine-substituted dialkylaminotrifluorophosphorane, cyclic tetrafluorophosphates with a λ 6 P atom, and dialkylaminotrimethylsilane were formed. The reaction of phosphorus(III)- N , N ′, N ′-trimethylethylenediamine compounds with transition metal compounds [Fe(0), Cr(0), Mo(0), Pt(II)] furnished mono-, di- or trisubstituted coordination compounds, depending on the nature of the metal. The P(III) ligand was bonded in some cases via P(III) only (as a monodentate ligand) and in other cases as a chelating ligand coordinated via P(III) and N. A variety of variable-temperature NMR experiments have examined the dynamic processes occurring at room temperature in solution, and X-ray single-crystal structure determinations have been conducted in many cases to characterize these new and unusual compounds.

VERBINDUNGEN MIT DEM 1,3,2- BENZODIAZAPHOSPHORINAN-4-ON GRUNDGERÜST: SYNTHESE VON NEUARTIGEN N,N′,N′- TRIMETHYLETHYLENDIAMINSUBSTITUIERTEN DERIVATEN MIT DREI- UND VIERFACH KOORDINIERTEM PHOSPHOR

Abstract The reaction of N,N′-dimethylanthranilic amide with phosphorus trichloride furnished 3, the first compound of P(III), involving the 1,3,2-benzodiazaphosphorinanone ring system. In the reaction of 3 with N-trimethylsilyl-N,N′,N′-trimethylethylenediamine 2 the product 4 was formed. The possibility of in tramolecular donor-acceptor-interaction between the nitrogen atom of the (CH3)2N group and the λ3P atom was investigated by 1H n.m.r. studies. No interaction was observed. Oxidative addition of elemental sulfur at the λ3P atom of 4 gave the λ4P-thiophosphoryl compound 5 while the reaction of 4 with methyl iodide and bromine, in an unusual reaction, furnished the ammonium salts 6 and 7. The N-Br bond in 7 was established by IR-spectroscopy. In the reaction of 4 with C7H8Cr(C0)4 (C7H″ = norbornadiene) a substitution product 8, involving intramolecular coordination of 4 to Cr(O) via λ3P and the nitrogen atom of the (CH3)2N grouping was formed. By contrast, the reaction of C7118Mo(CO)3 (C7H8 = cyclohept...

Synthesis and characterization of novel bioactive 1,2,4-oxadiazole natural product analogs bearing the N-phenylmaleimide and N-phenylsuccinimide moieties

Summary Taking into consideration the biological activity of the only natural products containing a 1,2,4-oxadiazole ring in their structure (quisqualic acid and phidianidines A and B), the natural product analogs 1-(4-(3-tert-butyl-1,2,4-oxadiazol-5-yl)phenyl)pyrrolidine-2,5-dione (4) and 1-(4-(3-tert-butyl-1,2,4-oxadiazol-5-yl)phenyl)-1H-pyrrole-2,5-dione (7) were synthesized starting from 4-(3-tert-butyl-1,2,4-oxadiazol-5-yl)aniline (1) in two steps by isolating the intermediates 4-(4-(3-tert-butyl-1,2,4-oxadiazol-5-yl)phenylamino)-4-oxobutanoic acid (3) and (Z)-4-(4-(3-tert-butyl-1,2,4-oxadiazol-5-yl)phenylamino)-4-oxobut-2-enoic acid (6). The two natural product analogs 4 and 7 were then tested for antitumor activity toward a panel of 11 cell lines in vitro by using a monolayer cell-survival and proliferation assay. Compound 7 was the most potent and exhibited a mean IC50 value of approximately 9.4 µM. Aniline 1 was synthesized by two routes in one-pot reactions starting from tert-butylamidoxime and 4-aminobenzoic acid or 4-nitrobenzonitrile. The structures of compounds 1, 2, 4, 5 and 6 were confirmed by X-ray crystallography.

BENZODIAZA-, BENZOXAZA-, AND BENZODIOXAPHOSPHORINONES - FORMATION, REACTIVITY, STRUCTURE, AND BIOLOGICAL ACTIVITY

Abstract Although diverse phosphorus-containing heterocycles had been synthe-sized during the late nineteenth century already, work was still sparse in this area as recently as 1950[1,2]. The realization, around 1950, of the importance of phosphorus-containing substances in biological processes resulted in intense activity in preparative organophosphorus chemistry, and in an upsurge of research on structural and mechanistic problems [3–6].

SUBSTITUTIONSREAKTIONEN DES 4,5-BENZO-2-CHLOR-3-METHYL-6-OXO-1,3,2-OXAZAPHOSPHINANS; MOLEKÜLSTRUKTUREN VON γ3P-DERIVATEN

Abstract The previously known precursor 4,5-benzo-3-methyl-6-oxo-1,3,2-oxazaphosphinane 1 was additionally characterized by single crystal X-ray structure analysis. The reaction of 1 with excess dry sodium fluoride furnished 2. The reaction of 1 with bromotrimethylsilane and iodotrimethylsilane, respectively, led to the products 3 and 4. The reaction of 1 with dimethylaminotrimethylsilane yielded the dimethylamino derivative 5. The derivatives 6–8 were prepared in a similar fashion via the appropriate trimethylsilyl precursors. The δ(31P) values of the halogen derivatives 1–4 increase with halogen size. The hydrolytic stability decreases in the order 2–1–3–4. The structures of 2 and 8 were confirmed by single-crystal X-ray structure analysis. 1, 2 and 8 all show envelope conformation with an exposed phosphorus atom.

Darstellung von Bis-(2-chlorethyl)amino-substituierten Diazaphosphorinonen. Reversible oxidative Addition von Hexafluoraceton an σ3λ3-Phosphor-Verbindungen. Synthese von σ5λ5-Spirophosphoranen und deren Zersetzung

Durch Umsetzung von 1-Methyl-pyrido[3,2-e]-3,1-oxazin-2,4-dion (1) mit Benzylaminen wurden die Aminonicotinsaureamide 2–4 gebildet. Die anschliesende Umsetzung mit Phosphortrichlorid lieferte die P-Chlor-pyridodiazaphosphorinone 5–7, die durch Umsetzung mit Bis-(2-chlorethyl)ammoniumchlorid/Triethylamin in die entsprechenden P-bis-(2-chlorethyl)amino-substituierten Pyridodiazaphosphorinone 8–10 uberfuhrt wurden. Das P-Chlor-benzodiazaphosphorinon 11 wurde mit 2-Chlorethylammoniumchlorid/Triethylamin zum 2-Chlorethylamino-substituierten Derivat 12 umgesetzt. Durch Oxidation der σ3Diazaphosphorinone 8, 9, 12 und 13 mit dem Harnstoff-Wasserstoffperoxid-(1 : 1)-Addukt wurden die entsprechenden Phosphorylderivate 14–17 erhalten. Die oxidative Addition von Hexafluoraceton (HFA) an das σ3-Diazaphosphorinon 18 fuhrte unter Abspaltung von Methylchlorid zu dem tricyclischen Phosphoran 19 b. Die Spirophosphorane 21–23 wurden durch Reaktion der Verbindungen 8, 9 und 13 mit HFA gebildet. Es wurden NMR-Untersuchungen hinsichtlich der Zersetzung der bicyclischen Phosphorane 20 a, 22 und 23 unternommen. Die oxidative Addition von HFA an Diazaphosphorinone stellte sich dabei als reversibel heraus. Von den Verbindungen 17 und 19 b wurden Rontgenstrukturanalysen angefertigt, die die erwartete Konnektivitat bestatigen. Verbindung 17 weist kurze C–H…O-Wasserstoffbrucken auf (H…O 234 pm). Verbindung 19 kristallisiert mit zwei unabhangigen Molekulen, die sich u. a. in der Ausrichtung der Chlorethylgruppen unterscheiden. Synthesis of Bis-(2-chloroethyl)amino-substituted Diazaphosphorinones. Reversible Oxidative Addition of Hexafluoroacetone to σ3λ3-Phosphorus Compounds. Synthesis of σ5λ5-Spirophosphoranes and their Decomposition The reaction of 1-methyl-pyrido[3,2-e]-3,1-oxazin-2,4-dione (1) with benzylamines led to the aminonicotinic acid amides 2–4. Their reaction with phosphorus trichloride furnished the P-chloro-pyridodiazaphosphorinones 5–7, which, upon reaction with bis-(2-chloroethyl) ammonium chloride/triethylamine, were converted into the P-bis-(2-chloroethyl)amino-substituted pyridodiazaphosphorinones 8–10. The P-chloro-benzodiazaphosphorinone 11 was allowed to react with 2-chloroethylammonium chloride/triethylamine to form the 2-chloroethylamino-substituted derivative 12. The σ3-diazaphosphorinones 8, 9, 12 and 13 were oxidized with the urea-hydrogen peroxide-(1 : 1)-adduct to the corresponding phosphoryl derivatives 14–17. The oxidative addition of hexafluoroacetone (HFA) to the σ3-diazaphosphorinone 18 led, with abstraction of methyl chloride, to the tricyclic phosphorane 19 b. The spirophosphoranes 21–23 were formed by reaction of compounds 8, 9 and 13 with HFA. NMR-studies were made on the decomposition of the bicyclic phosphoranes 20 a, 22 and 23. The oxidative addition of HFA to diazaphosphorinones was found to be reversible. Single crystal X-ray determinations were conducted on compounds 17 and 19 b. They confirm the expected connectivity. Compound 17 was found to exhibit short C–H‥ O-hydrogen bonds (H…O 234 pm). Compound 19 crystallises as two independent molecules which differ, e. g., in the orientation of the chloroethyl groups.

UMSETZUNGEN VON 4-CHLOR-1,3,5,7-TETRAMETHYL-1,3,5,7-TETRAAZA-4λ5- PHOSPHASPIRO[3,3]HEPTAN-2,6-DION, BIS(TRIMETHYLSILYL)- TRIMETHYLBIURET UND BIS(2-CHLORETHYL)- AMINOPHOSPHORSÄUREDICHLORID MIT Me2NCH2CH2N(Me)SiMe3; STUDIUM INTRAMOLEKULARER P-N-WECHSELWIRKUNGEN

Abstract A study of possible donor-acceptor interactions in N,N′,N′-trimethylethylenediamine-substituted phosphorus compounds has been conducted. Neither the trimethylethylenediamine-substituted λ5P-spirophosphorane 3 nor compound 6, a λ3P-trimethylethylenediamine-substituted derivative of trimethylbiuret, showed any evidence for intramolecular interaction (1H n.m.r. spectroscopy). In the case of the bis(2-chloroethyl)amino-substituted compounds 9 and 10 dynamic behaviour was observed by n.m.r. spectroscopy. By 31P n.m.r. spectroscopy three isomers (a-c) were established. The dimerization of isomer a with formation of two dioxaphosphetidine structures (b and c) is suggested to occur, as are cis and trans isomers, b and c. No reaction occurred between N,N′-dimethylanthranilic acid amide and bis(2-chloroethyl)aminophosphoric acid dichloride, in contrast to the analogous reaction with methylphosphonic acid dichloride. Electronic reasons are thought to be responsible for the lack of reactivity of bis(2-chloro...

Derivate der 5,6-benzo-1,3-dialkyl-2-oxo-1,3,2λ4-diazaphosphorinan-4-one: Umsetzung mit ketonen (hexafluoraceton und trifluoracetophenon); Einkristall-röntgenstrukturanalysen von konstitutionsisomeren

Abstract 5,6-Benzo-1-methyl-3-(2-chloroethyl)-2-hydro-2-oxo-1,3,2 λ 4 -diazaphosphorinan-4-one ( 2 ) reacts with p -benzoquinone in a 1:1 molar ratio in the presence of triethylamine as a catalyst to give as the sole addition product 5,6-benzo-1-methyl-3-(2-chloroethyl)-2-(2,5-dihydroxyphenyl)-2-oxo-1,3,2 λ 4 -diazaphosphorinan-4-one ( 3 ). No reaction occurred betwwen 2 and acetone, methyl t-butylketone or acetophenone in the presence of triethylamine, even at elevated temperature. The reaction of the 5,6-benzo-1,3-diorgano-2-hydro-2-oxo-1,3,2 λ 4 -diazaphosphorinan-4-ones 1 and 2 with hexafluoroacetone furnished the 2-hexafluoroisoproposy-substituted compounds 4a and 5a . In both cases, the 2-bis(trifluoromethyl)hydroxymethyl-substituted structural isomers 4b and 5b were formed in low yield. Analogous reactions of 1 and 2 with trifluoroacetophenone, catalysed by triethylamine, furnished as the main products the 2-trifluoromethylphenylmethoxy-substituted compounds 6a and 7a , together with small amounts of the 2-trifluoromethylphenylhydroxymethyl-substituted isomers 6b and 7b . The unusual reaction of the acetylaminophosphorinanone 8 with hexafluoroacetone in a 1:2 molar ratio led to the formation of the 2-hexafluoroisopropoxy-substituted compound 4a with N-acetyl-bis(trifluoromethyl)imine ( 11 ) as a by-product. A pathway for the formation of 4a is proposed. Characterization of 3 and 4a–7a was based on 1 H, 13 C, 19 F and 31 P NMR and mass spectra. The existence of 4a, 5a, 4b and 5b as enantiomeric pairs was established mainly by 19 F NMR spectroscopy. The diasteromeric pairs 6a and 7a, 6b and 7b were not observed in the 19 F and 31 P NMR spectra. X-ray structure analyses were carried out for 4a, 5b and 7a . Compound 7a crystallizes with two independent molecules, which are however closely similar. Intermolecular hydrogen bonds of the form P(:O)…H are observed for all compounds, leading to centrosymmetrical dimers. In 4a the two trifluoromethyl substituents presumably make the carbon H atom more positive. The existence of hydrogen bonds is confirmed by infrared spectroscopic studies. In all structures the phosphorus atom exhibits a distorted tetrahedral coordination. The six-membered heterocycle of 4a displays an envelope conformation with the phosphorus atom out of plane.