Diborheterocyclen: Oxadiborolan – Oxadiborinan – Diazadiborinan

Diboron Heterocyclic Compounds: Oxadiborolane – Oxadiborinane – Diazadiborinane The diboryl compounds R(Cl)B(CH₂)_nB(Cl)R (R ? Cl or CH₃; n = 2, 3) and the silylated or stannylated starting materials [(CH₃)₃Y]₂X (Y ? Si or Sn; X ? S, NCH₃, O, NCH₃? NCH₃) were used for (5+1)- and (4+2)-cyclocondensation reactions. Dimethylether was an additional starting molecule. While no thiadiborinanes could be isolated, the nitrogen or oxygen containing heterocycles were formed in varying yields. Synthesis and properties of these compounds are described.     

Synthesis of N-[chloro(diorganyl)silyl]anilines

A series of N-[chloro(diorganyl)silyl]anilines RR′Si(NR″Ph)Cl (R, R′ = Me, Ph, CH₂=CH, ClCH₂, Cl(CH₂)₃; R″ = H, Me) was prepared via the reaction of diorganyldichlorosilanes with aniline or N-ethylaniline in the presence of triethylamine.     

Darstellung und Eigenschaften von Tris-(β-chloräthyl) phosphinoxid und Bis-(β-chloräthyl)-(chlormethyl)-phosphinoxid. 43. Mitteilung über organische Phosphorverbindungen [1]

The oxidative degradation of [(HOCH₂CH₂)₃PCH₂OH]⁺Cl^? ( 1 ) with Cl₂ yields, dependent on the pH used, either (HOCH₂CH₂)₃P?O ( 2 ) or (HOCH₂CH₂)₂ (HOCH₂) P?O ( 3 ). Chlorination of 2 and 3 with PCl₅ produces the corresponding chlorides (ClCH₂CH₂)₃P?O ( 4 ) and (ClCH₂CH₂)₂ (ClCH₂)P?O ( 5 ), respectively. Acetylation of 2 and 3 gives the corresponding esters (CH₃CO₂CH₂CH₂)₃P?O ( 6 ), and (CH₃CO₂CH₂CH₂)₂ (CH₃CO₂CH₂)P?O ( 7 ), respectively. Reaction of 7 with HBr results in the formation of (BrCH₂CH₂)₂ (BrCH₂)P?O. Nucleophilic substitution of the chlorine atoms in 4 and 5 with alkoxide or mercaptide gives e.g., 9 , 10 , 11 or 11a , while treatment with tertiary amines yields the vinyl compounds (CH₂?CH)₃P?O ( 12 ) and (CH₂?CH)₂ (CH₂Cl)P?O ( 13 ). 4 and 5 also undergo an Arbuzov type reaction with tertiary phosphites to give 14 and 15 , respectively, which on hydrolysis with conc. HCl give the corresponding acids 16 and 17 , respectively.     

3‐Rhoda‐1,2‐diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From CN Functionalization of Ethylene

Rh‐containing metallacycles, [(TPA)Rh^III(κ²‐(C,N)‐CH₂CH₂(NR)₂‐]Cl; TPA=N,N,N,N‐tris(2‐pyridylmethyl)amine have been accessed through treatment of the Rh^I ethylene complex, [(TPA)Rh(η²‐CH₂CH₂)]Cl ([ 1 ]Cl) with substituted diazenes. We show this methodology to be tolerant of electron‐deficient azo compounds including azo diesters (RCO₂N?NCO₂R; R=Et [ 3 ]Cl, R=iPr [ 4 ]Cl, R=tBu [ 5 ]Cl, and R=Bn [ 6 ]Cl) and a cyclic azo diamide: 4‐phenyl‐1,2,4‐triazole‐3,5‐dione (PTAD), [ 7 ]Cl. The latter complex features two ortho‐fused ring systems and constitutes the first 3‐rhoda‐1,2‐diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N–N coordination followed by insertion of ethylene into a [Rh]?N bond. In terms of reactivity, [ 3 ]Cl and [ 4 ]Cl successfully undergo ring‐opening using p‐toluenesulfonic acid, affording the Rh chlorides, [(TPA)Rh^III(Cl)(κ¹‐(C)‐CH₂CH₂(NCO₂R)(NHCO₂R)]OTs; [ 13 ]OTs and [ 14 ]OTs. Deprotection of [ 5 ]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end‐on coordinated diazene [(TPA)Rh^III(κ²‐(C,N)‐CH₂CH₂(NH)₂‐]⁺ [ 16 ]Cl, a hitherto unreported motif. Treatment of [ 16 ]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)Rh^III(κ²‐(C,N)‐CH₂CH₂(NAc)₂‐]⁺, [ 17 ]Cl. Treatment of [ 1 ]Cl with AcN?NAc did not give the Rh?N insertion product, but instead the N,O‐chelated complex [(TPA)Rh^I ( κ²‐(O,N)‐CH₃(CO)(NH)(N?C(CH₃)(OCH?CH₂))]Cl [ 23 ]Cl, presumably through insertion of ethylene into a [Rh]?O bond.     

Cyclische Ester von Phosphin- und Thiophosphinsäuren

Zusammenfassung Chlormethyl-methyl-phosphinsäurechlorid (ClCH₂)(CH₃)P(O)Cl und Chlormethyl-methyl-thiophosphinsäurechlorid (ClCH₂)(CH₃)-P(S)Cl reagieren mit aromatische 1,2-Diolen wie Brenzcatechin, mit o-Aminophenol, o-Aminothiophenol und Toluol-3,4-dithiol unter Substitution der beiden Chloratome zu den entsprechenden Benzophosphorinanen.

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(ClCH₂)(CH₃)P(O)Cl and (ClCH₂)(CH₃)P(S)Cl react with aromatic diols like catechol, o-aminophenol, o-aminothiophenol and toluene-3,4-dithiol with the formation of benzophosphorinanes.

     

Organische Phosphorverbindungen XXXVIII. Darstellung und Eigenschaften von Tris-(dialkoxyphosphonyl-methyl)-, Tris-(alkoxyphosphinyl-methyl)-und Tris-(oxophosphoranyl-methyl)-phosphinsäureestern sowie der entsprechenden Säuren [1]

Tris-chloromethyl-phosphine oxide, (ClCH₂₎₃ P?O(I), is obtained by chlorination of (HOCH₂₎₃P?O with PCl₅ or (C₆H₅₎₃PCl₂, and also by oxidation of (CICH₂₎₃P?O and (ClCh₂₎₂(CH₃)P?O. High yields of tris-(dialkyloxyphosphonly-methyl)-phosphine oxides, [RO₂(O)PCH_2]2P?O (II) (R?CH₃, C₂H₅, iso-C₃H₇, n-C₄H₉, 2- ethyl-hexyl), tris (alkyloxyphosphinyl-methyl)-phosphine oxides, [R₂(O)PCH_2]3P?O(R = C₆H₅, CH₃) are obtained by heating tris-chloromethyl-phosphine oxides, [(RO) (R′) (O)PCH_2]3P?O (R = C₄H₉, R′? C₆H₅) and tris-(oxophosphoranyl-phosphine oxides with phosphites, phosphonites and phosphinites, respectively, at 170–180°C for several hours. Compounds II possess an extraordinarily high absorption capacity. Thus a warm. 2% solution of II (R = C₂H₅) in benzene solidifies completely on cooling so that no benzene can be poured off. Tris-dihydroxyphosphonyl-methyl)-phosphine oxide, [(HO)₂(O)PCH_2]3P?O, obtained by hydrolysis of II (R ? C₂H₅) with refluxing conc. HCl or by thermal decomposition of II (R ? iso-C₃H₇) at 190°, titrates in aqueous solution as a hexabasic acid with breaks at pH = 4,4 (three equivalents) and pH = 10,7 (three equivalents). It forms crystalline salts with amines, alkali and alkaline earth metals, and is an excellent chelating agent. The ¹H- and ^31?P-NMR. spectra of all the compounds prepared are discussed.     

Synthesis of sulphonated aminomethylphosphines and some nickel(II), palladium(II), platinum(II) and rhodium(I) complexes. Crystal structure of [Et3NH][(Ph2PCH2)2 N(CH2)2SO3]

Summary Aminoalkanesulphonic acids H₂N(CH₂) _n SO₃H, (n = 1, 2 or 3) react with phosphonium salts [R₂P(CH₂OH)₂]Cl (R = Ph or Cy, Cy = cyclohexyl) in the presence of Et₃N to give the sulphonated aminomethylphosphines [Et₃NH] [(R₂PCH₂)₂N(CH₂) _n SO₃] (R = Ph, n = 1, 2 or 3; R = Cy, n = 1). The single crystal X-ray structure of [Et₃NH] [(Ph₂PCH₂)₂N(CH₂)₂SO₃] has been determined. Some Ni^II, Pd^II, Pt^II and Rh^I complexes of the phosphines have been prepared.     

Organische Phosphorverbindungen 44 Darstellung und Eigenschaften von Bis-(ß-chloräthyl)-phosphinsäure-Derivaten [1]

Reaction of ClCH₂CH₂PCl₂ with ethylene oxide gives the phosphonous acid ester ClCH₂CH₂P (OCH₂CH₂Cl)₂ which on heating to 120° rearranges to the phosphinic acid ester (ClCH₂CH₂)₂P(O)OCH₂CH₂Cl ( 3 ). Chlorination of 3 with PCl₅ in CCl₄-solution yields the phosphinic chloride (ClCH₂CH₂)P(O)Cl ( 4 ), which on treatment with P₂S₅ at 170° produces the thioderivative, (ClCH₂CH₂)₂P(S)Cl, (₅). Treatment of 4 and 5 with alcohols, mercaptanes, or amines in the presence of an acid binding agent leads to the corresponding phosphinic and thiophosphinic acid derivatives, (ClCH₂CH₂) P (X)Y, (X = O, S; Y = OR, SR, NR₂) ( 6 ). Reaction of 6 with excess base yields the corresponding divinylphosphinic and divinylthiophosphinic acid derivatives (CH₂ = CH)₂P (X) Y (X = O, S; Y = OR, SR, NR₂) ( 7 ). Bis-(ß-chloroethyl)-phosphinates, e. g. (ClCH₂CH₂)₂P (O) OEt, undergo a Michaelis-Arbuzov reaction when heated with phosphites to 160–170° to give bis-(phosphonylethyl)-phosphinates, e.g. (EtO) (O)P[CH₂CH₂CH₂P(O)(OEt)₂]₂ ( 8 ), which on hydrolysis with conc. HCl under reflux yield the corresponding acid HO₂P(CH₂CH₂PO₃H₂)₂.     

Mono- and bis-alkoxides of tris(3,5-dimethylpyrazolyl)borato molybdenum and tungsten nitrosyls

The complexes [ML^*(NO)Cl(OR)] {L^* = HB(3,5-Me₂C₃HN₂)₃; M= Mo, R = CH₂CH₂X, X = Cl, OMe or OEt; (CH₂)_nOH, n = 2, 5, 6; M = W, R = CH₂CH₂X, X = Cl, OMe or OEt; (CH₂)_nOH, n = 2–6; CH₂(CF₂)₃CH₂OH; CHMeCH₂CMe₂OH} and [ML^*(NO)(OR)₂] {M = Mo, R = CH₂CH₂X, X = Cl, OMe or OEt; (CH₂)_nOH, n = 2–6; M = W,R = CH₂CH₂X, X= Cl, OMe or OEt; (CH₂)_nOH, n = 2,4–6; CH₂(CF₂)₃CH₂OH} have been prepared from [ML^*(NO)Cl₂] and the appropriate alcohol in the presence of NEt₃ or NaCO₃, and have been characterized by IR, ¹H NMR and mass spectroscopy.     

Fluordiazadiphosphetidine, 14. Mitt.: Nucleophile Substitutionsreaktionen von 1-Chlormethyl-2,2,2,4,4,4-hexafluor-3-methyl-1,3,2λ5,4λ5-diazadiphosphetidin und 1,3-Bis(chlormethyl)-2,2,2,4,4,4-hexafluor-1,3,2λ5,4λ5-diazadiphosphetidin mit ausgewählten metallorganischen Reagentien

Photochemical chlorination of (CH₃NPF₃)₂ yields ClCH₂(NPF₃)₂CH₃(I) and ClCH₂(NPF₃)₂CH₂Cl (II). By reaction with organometallics unsymmetric N-substituted hexafluorodiazadiphosphetidines are synthesized. Depending on the nucleophilic strength of the used organometallic the chlorine atom of the N-CH₂Cl group can be selectively substituted versus an organic substituent without side-reaction at the phosphorus atom.

     

Polymerization of phenylacetylene catalysed by RhTp(cod) and RhBp(cod) in ionic liquids: effect of alcohols and of tetraammonium halides

RhTp(cod) ( 1 ) and RhBp(cod) ( 2 ), almost inactive in CH₂Cl₂, became good catalysts of phenylacetylene polymerization in ionic liquids ([bmim]Cl, [bmim]BF₄: bmim = 1‐butyl‐3‐methylimidazolium, [mokt]BF₄: mokt = 1‐methyl‐3‐oktylimidazolium, [bumepy]BF₄: 1‐butyl‐4‐methylpyridinium) and in CH₂Cl₂ in the presence of tetraammonium halides ([R₄N]X, R = Bu, Et; X = Cl, Br). The highest yields of polyphenylacetylene with catalyst 1 were obtained in [bmim]Cl at 65°C (64% after 2 h) and in [mokt]BF₄ at 20°C (56% after 24 h). In alcohols (CH₃OH, (CH₃)₂CHOH, (CH₃)₃COH) as solvents, up to 100% of the polymer was produced. When a mixture of an ionic liquid and CH₃OH was used as the reaction medium, the polymer yield was similar to the yield achieved in an ionic liquid only, but the molecular weight increased remarkably. Tetraammonium salts, [R₄N]X, are co‐catalysts for 1 , and the yield of the polymer increased in the order [Et₄N]Br < [Bu₄N]Br < [Et₄N]Cl < [Bu₄N]Cl. Polymers with molecular weights from 6900 to 38 800 Da were obtained with catalyst 2 in [R₄N]Br or [R₄N]Cl, whereas in ionic liquids ([bmim]Cl, [bmim]BF₄) the corresponding molecular weights were higher, from 51 300 to 60 300 Da. Copyright © 2004 John Wiley & Sons, Ltd.     

Syntheses and rearrangements of tris(hydroxymethyl)phosphine and tetrakis(hydroxymethyl)phosphonium salts

Abstract

Tetrakis(hydroxymethyl)phosphonium (HOCH₂)₄P⁺ salts, particularly the chloride (THPC) and sulfate (THPS), are among the most accessible organophosphorus compounds that can be made quantitatively from PH₃ and formaldehyde in aqueous media under ambient conditions. These phosphonium salts are air-stable, and are widely used as reactants in organic syntheses, as well as in textile or oil industries. Synthesis of tris(hydroxymethyl)phosphine (THP), an active component of the salts, is more complicated because direct synthesis from PH₃ and CH₂O requires either pressure and high temperature, at which THP rearranges into bis(hydroxymethyl)methylphosphine oxide, CH₃P(O)(CH₂OH)₂, or a metal catalyst that is usually difficult or impossible to recover. Syntheses of THP based on neutralization of the salts are more convenient but require pH control and additional steps to separate THP from CH₂O. This review summarizes literature data on syntheses and purification of the salts and THP, and side reactions such as thermal rearrangement and oxidation.     

Fluordiazadiphosphetidine. 8. Mitt. Die photochemische chlorierung von 2,2,2,4,4,4-Hexafluoro-1,3-dimethyl-1,3,2λ5,4λ5-diazadiphosphetidin

Chlorination of (CH₃NPF₃)₂ with Chlorine under UV-radiation yields the new compounds CH₃(NPF₃)₂CH₂Cl and (ClCH₂NPF₃)₂.

     

Neue Synthesewege für Organohalogenstibane

New Methods for Synthesis of Organohalogenostibanes Organohalogenostibanes RSbX₂ (R = CH₃, C₆H₅; X = Cl, Br) and R₂SbX (R = C₆H₅; X = Cl) are received in good yields by alkylation or arylation of the corresponding antimony halides with Pb(CH₃)₄, Sn(CH₃)₄, Sb(CH₃)₃, or Sb(C₆H₅)₃. These methods are better than those, described in the literature for preparation of the compounds.     

α,ω-Disubstituted polymethylpolyphosphonates and polyphenylpolyphosphonates from condensation polymerization

Condensation polymerization of phosphonates through formation of P? O? P linkages has been achieved by (1) volatilization of methyl chloride from mixtures of CH₃P(O)Cl₂ with CH₃P(O)(OCH₃)₂; (2) volatilization or chemical removal of water from CH₃P(O)(OH)₂; and (3) volatilization of HCl from mixtures of CH₃P(O)Cl₂ with CH₃P(O)(OH)₂ or C₆H₅P(O)Cl₂ with C₆H₅P(O)(OH)₂. Depending on the proportions of the reagents, the polymerization products consist of various mixtures of chain molecules of the type \documentclass{article}\pagestyle{empty}\begin{document}${\rm X \hbox{--} P}({\rm O})({\rm R})\rlap{--}[{\rm O \hbox{--} P}({\rm O})({\rm R})\rlap{--}]_n {\rm X}$\end{document} for R = CH₃ and X = OCH₃, Cl, or OH, or for R = C₆H₅, x = Cl or OH. ³¹P nuclear magnetic resonance (NMR) was used to investigate both the polymethylpolyphosphonates and the polyphenylpolyphosphonates; and ¹H NMR of the CH₃P and CH₃O moieties was also used to study the polymethylpolyphosphonates. In the methoxyl-terminated polymethylpolyphosphonates, which was the system studied most extensively, no detectable amounts of cyclic molecules were found at equilibrium, but a crystalline methylphosphonic anhydride, CH₃PO₂, exhibited some ring structures. The equilibrium size distributions gave evidence that the sorting of the mono- and difunctional phosphorus-based units making up the oligomeric chains is affected by neighboring units. Kinetic measurements demonstrated that the condensation polymerization is a complicated process involving considerable scrambling of terminal groups with bridging oxygen atoms.     

Generation and dissociation of oxygen‐ and chloride‐bridged iron(III) and manganese(III) tetraphenylporphyrin dimer ions in the gas phase

Electrospray ionization mass spectrometry (ESI/MS) has allowed the discovery of novel dimer ions emerging from solutions of metalloporphyrin salts and their investigation by collision‐induced dissociation (CID) with N₂ molecules. ESI mass spectra have been recorded for the formation of the oxygen or chloride‐bridged dimer ions [(FeTPP)₂OH]⁺, [(MnTPP)₂OH]⁺, [(FeTPP)₂Cl]⁺ and [(MnTPP)₂Cl]⁺ derived from various solutions of FeTPPCl and MnTPPCl salts. The CID of [(FeTPP)₂OH]⁺ proceeds mainly by neutral loss of (FeTPP)OH to form [FeTPP]⁺ and, to a minor extent, to form the charge‐reversed products. The CID of [(MnTPP)₂OH]⁺ exhibits exclusively the product ion [MnTPP]⁺ by loss of neutral (MnTPP)OH. [(FeTPP)₂Cl]⁺ and [(MnTPP)₂Cl]⁺ dissociate by loss of (Fe/MnTPP)Cl to give rise to [Fe/MnTPP]⁺. [(FeTPP)₂O]⁺ and [(FeTPP)₂OH]⁺ were generated from a solution of the dimer, (FeTPP)₂O. Dissociation of [(FeTPP)₂O]⁺ yields two product ions, [FeTPP]⁺ and [(FeTPP)O]⁺, with higher onsets compared to the equivalent fragments formed from [(FeTPP)₂OH]⁺. Copyright © 2009 John Wiley & Sons, Ltd.     

Exergonic and Spontaneous Production of Radicals through Beryllium Bonds

High‐level ab initio calculations show that the formation of radicals, by the homolytic bond fission of Y?R (Y=F, OH, NH₂; R=CH₃, NH₂, OH, F, SiH₃, PH₂, SH, Cl, NO) bonds is dramatically favored by the association of the molecule with BeX₂ (X=H and Cl) derivatives. This finding is a consequence of two concomitant effects, the significant activation of the Y?R bond after the formation of the beryllium bond, and the huge stabilization of the F^. (OH^., NH₂^.) radical upon BeX₂ attachment. In those cases where R is an electronegative group, the formation of the radicals is not only exergonic, but spontaneous.     

Cyclization of N-alkyldithiocarbamates in alkaline media,a counter example of well-known chemistry – an experimental and theoretical study

In strong alkaline media, the reaction of 2-(tert-butylamino)ethanol (3: R?=?Bu^t) with CS₂ at 0°C produced a cyclic dithiocarbamate, 3-tert-butylthiazolidine-2-thione (1: R?=?Bu^t), rather than alkaline metal or ammonium salts of [S₂CN(Bu^t)CH₂CH₂OH]^?. This is in contrast to isolation of stable alkaline metal or ammonium salts of [S₂CN(R)CH₂CH₂OH]^? (R?=?Me, Et, Pr, or CH₂CH₂OH) obtained in analogous reactions. The use of Ni(OAc)₂, both as a source of Ni(II) and a weaker base, in a one-pot reaction with (3: R?=?Bu^t) and CS₂, successfully gave the first reported metal complex of [S₂CN(Bu^t)CH₂CH₂OH]^?, namely [Ni{S₂CN(Bu^t)CH₂CH₂OH}₂] (2: R?=?Bu^t). Compounds 1 and 2 have been fully characterized by infrared and NMR spectroscopies, and by X-ray crystallography. DFT calculations on the cyclization and stabilities of [S₂CN(R)CH₂CH₂OH]^? (R?=?Pr and Bu^t) have been carried out.     

Reactions of trialkylalanes with cyclic acetals and orthoformates in CH2Cl2 and ClCH2CH2Cl as solvents

Under mild conditions, trialkylalanes (Et₃Al and Buⁱ ₃Al) in chlorine-containing solvents (CH₂Cl₂ or ClCH₂CH₂Cl) react with cyclic acetals and orthoformates to form glycol monoethers and dialkylacetals, respectively, in high yields. The ¹H NMR spectroscopic data demonstrate that CH₂Cl₂ or ClCH₂CH₂Cl interacts with Buⁱ ₃Al.     

On the Existence of Two New Mixed-Alkali Cyclohexaphosphates: Li3Na3P6O18 · 12 H2O and Li3K3P6O18 · H2O

Reaction of (CH₃)₂ Te with CF₃I: Preparation and Properties of [(CH₃)₂TeCF₃]I The irradiation of a mixture of (CH₃)₂ Te and CF₃I at low temperature yields [(CH₃)₂TeCF₃]I. From the thermal decomposition as well as in polar solvents CH₃TeCF₃ and CH₃I are formed. Attempts to prepare bis- or tris(trifluoromethyl)tellurium compounds from these reactions failed. [(CH₃)₂TeCF₃]I reacts with salts or acids to form many new derivatives of the composition [(CH₃)₂TeCF₃]X (X = Cl, NO₃, 1/2 SO₄, OCOCH₃, OCOCF₃, B(C₆H₅)₄, OC₆H₂(NO₂)[₃].