Showing papers in "Phosphorus Sulfur and Silicon and The Related Elements in 1979"
TL;DR: In this paper, the reaction of carbon disulfide with sodium or potassium in dimethyl formamide yields 1,3dithiole-2-thione-4,5-dithiolate (1) and trithiocarbonate in equimolar amounts.
Abstract: Die Reaktion von Schwefelkohlenstoff mit Natrium oder Kalium fuhrt zur Bildung aquimolarer Mengen von 1.3-Dithiol-2-thion-4.5-dithiolat (1) und Trithiocarbonat. Durch Zugabe von ZnCl2 und NEt4Br last sich (1) stabilisieren. Der entstehende Zink-Komplex ermoglicht die Herstellung von 4.5-Bis(benzoylthio)-1.3-dithiol-2-thion (10), woraus durch Umsetzung mit Basen (1) in quantitativer Ausbeute wieder entsteht. Die Alkylierung von (1) fuhrt zu 4.5-Bis(alkylthio)-1.3-dithiol-2-thionen. (1) is ein neuer, schwefelreicher 1.2-Dithiolat-Ligand. Die Kristallstruktur des Bis-Chelates von (1) mit Ni(II) als (n-Bu4N)2-Salz bestatigt die fur (1) angenommene Struktur. The reaction of carbon disulfide with sodium or potassium in dimethyl formamide yields 1,3-dithiole-2-thione-4,5-dithiolate (1) and trithiocarbonate in equimolar amounts. (1) was stabilized by addition of ZnCl2 and NEt4Br. The resulting zinc complex enables the isolation of 4,5-bis(benzoylthio)-1,3-dithiole-2-thione (10). (1) can be recovered from...
408 citations
TL;DR: In this paper, twenty spirophosphoranes bearing a P-H bond have been obtained by the reaction of α-hydroxyacids or alkyl tartrates on tricoordinated phosphorus compounds.
Abstract: About twenty spirophosphoranes bearing a P–H bond have been obtained by the reaction of α-hydroxyacids or alkyl tartrates on tricoordinated phosphorus compounds. The stereochemistry is described. Intra- or extracyclic carbonyl groups, especially in the case of two identical ligands, increase the Lewis acid character of the phosphorus atom. Une vingtaine de spirophosphoranes a liaison P–H ont ete prepares en faisant reagir des α hydroxyacides ou des tartrates d'alcoyle sur des substrats a phosphore tricoordine convenables. L'etude stereochimique systematique de ces composes est decrite. La presence des groupements carbonyle a pour influence de renforcer le caractere d'acide de Lewis de l'atome de phosphore, notamment dans le cas des composes contenant deux ligands identiques, que le carbonyle soit intra ou extracyclique.
32 citations
TL;DR: In the last twenty to thirty years there has been considerable interest in the preparation of completely resolved enantiomers of tetracoordinate pentacovalent organophosphorus compounds as mentioned in this paper.
Abstract: During the last twenty to thirty years there has been considerable interest in the preparation of completely resolved enantiomers of tetracoordinate pentacovalent organophosphorus compounds. This has arisen for three main reasons:
20 citations
TL;DR: In this article, the influence of d orbitals on the stability of P4 against 2 P2 and 1/2 P8, the photoelectron spectrum, and the valence electron density is discussed.
Abstract: Experimental findings as well as quantum chemical calculations indicate that the P4 molecule has a remarkably low nucleophilicity. The P4H+ ion is predicted to have a ‘proton at apex’ configuration whereas a proton in the centre seems to be metastable. The influence of d orbitals on the stability of P4 against 2 P2 and 1/2 P8, the photoelectron spectrum, and the valence electron density is discussed.
17 citations
TL;DR: In this article, the synthesis of mono and disubstituted mononuclear carbonyls of Cr, Mo, W, Fe and Ni with the cage ligand P(NMeCH2)3CMe (2) is reported.
Abstract: The syntheses of mono and disubstituted mononuclear carbonyls of Cr, Mo, W, Fe and Ni with the cage ligand P(NMeCH2)3CMe (2) are reported. The (OC)5CrL and (OC)4FeL complexes are also described where L = As(NMeCH2)3CMe (5). Borane adducts of the complexes of (2) are reported as well as adducts of XP(NMeCH2)3CMe where X = Se and PhN. In the complexes and the selenide the BH3 group is shown from 1H nmr spectroscopy to bind to a nitrogen in a bridging group of the ligand whereas in the phenylimide it binds to the phenylimido nitrogen. Some cis and trans Pt(2)2X2 complexes are also described. The CO stretching frequencies and force constant parameters of the complexes are shown to rise in the ligand order P(NMe2)3 < (2) < (2) · BH3 and this trend is discussed in terms of constraint and inductive effects. The 31P spectra of the compounds are rationalized and 2J31P31P couplings are obtained directly from the 31P spectra of the (2) (OC) x M·(2) · BH3· complexes since the 31P nuclei are chemically nonequ...
15 citations
TL;DR: In this article, the 13C nmr spectral analysis of 1-phenyl-4-phosphorinanone 1-oxide and the corresponding sulfide was performed in a single crystal x-ray diffraction analysis.
Abstract: The 13C nmr spectral analysis has been recorded for the title compounds in DCC13, and all data appear to be in a accord with chair forms. Single crystal x-ray diffraction analysis of 1-phenyl-4-phosphorinanone 1-oxide and the corresponding sulfide revealed flattened chair forms in the solid state. Neither the solution data nor the x-ray data provided any evidence for a twist form for either compound as has been suggested for the carbon counterpart, namely, cyclohexane-1,4-dione.
15 citations
TL;DR: In this article, variable temperature nmr spectroscopy on the 1:1-adduct of cyanodiphenylphosphine and perfluorobiacetyl and on the phosphoranes formed from tetrachloro-o-benzoquinone and various 2-substituted 4,4,5,5-tetramethyl-1,3,2-dioxaphospholans has led to an order of relative apicophilicity in these phosphors of CN > C1 ∼ NCO ∼ NCS >
Abstract: Variable temperature nmr spectroscopy on the 1:1-adduct of cyanodiphenylphosphine and perfluorobiacetyl and on the phosphoranes formed from tetrachloro-o-benzoquinone and various 2-substituted 4,4,5,5-tetramethyl-1,3,2-dioxaphospholans has led to an order of relative apicophilicity in these phosphoranes of CN > C1 ∼ NCO ∼ NCS > N3 > OPh. Hexafluoroacetone and 2-(2′,4′,6′-trimethylbenzoyl)-4,4,5,5-tetramethyl-1,3,2-dioxaphospholan gave the oxide (8).
14 citations
TL;DR: In this paper, a comparative study of the P-H NMR parameters of bicyclic phosphoranes with chiral pentaco-ordinated phosphorus atoms is presented. Butler et al. proposed a configuration of the phosphorus atom of these three compounds based on a comparative analysis of the RMN parameters.
Abstract: Nous avons synthetise sept phosphoranes bicycliques nouveaux 1–7 comportant un atome de phosphore pentacoordine chiral. 5 et 6 possedent en outre un atome de carbone chiral et 7 deux atomes de carbone chiraux. Une etude comparative des parametres RMN du groupement P–H nous a permis de proposer une configuration de l'atome de phosphore de ces trois composes. Seven new bicyclic phosphoranes 1–7 bearing a chiral pentaco-ordinated phosphorus atom are described. 5 and 6 possess a chiral carbon atom and 7 two chiral carbon atoms. A configuration of phosphorus atom of these three compounds is proposed based on a comparative study of the P–H NMR parameters.
12 citations
TL;DR: In this article, it has been shown that P4S10 is a mild, effective reagent for the reduction of sulfoxides to sulfides and that this conversion can be achieved selectively in the presence of other reactive groups such as ketone, ester, amide, nitro and halogen.
Abstract: It has been shown that phosphorus pentasulfide (P4S10) is a mild, effective reagent for the reduction of sulfoxides to sulfides and that this conversion can be achieved selectively in the presence of other reactive groups such as ketone, ester, amide, nitro and halogen. This reagent can be used in similar fashion for the efficient reduction of sulfilimines (in both the N-p-toluenesulfonyl and free NH forms). Phosphorus pentasulfide also appears to be a promising reagent for reducing selenoxides but is ineffective in reducing sulfones, sulfinates, or sulfites. The mechanistic evidence presented indicates a probable four-centre (Wittig-like) intermediate or transition-state for the reduction by P4S10.
11 citations
TL;DR: In this article, it was shown that the steric environment about phosphorus changes as the carbon beta- to it in the adjacent ring changes from tetrahedral to planar geometry, rather than from a change in the degree of interaction of a carbon porbital with phosphorus.
Abstract: Naphthalenophospholenes (dihydrobenzo[e] and [g]-phosphindoles) represent a new heterocyclic type that forms in 65-80% yield on dehydrogenation with Pd–C of the corresponding dihydronaphthaleno derivatives. The latter are readily accessible from hydrolysis of cycloadducts of certain vinyldihydronaphthalenes with P(III) chlorides. Six members of this family, as well as some derived phosphines and phosphonium salts, have been prepared. A phenanthrenophospholene oxide, also a new system, was synthesized similarly. 31P nmr chemical shifts were appreciably (5-10 ppm) upfield in aromatized phosphine oxides relative to the dihydro forms. It is proposed that this shift results more from a change in the steric environment about phosphorus, as the carbon beta- to it in the adjacent ring changes from tetrahedral to planar geometry, rather than from a change in the degree of interaction of a carbon p-orbital with phosphorus. The upfield shift was even more pronounced (13 ppm) for a phosphine. Most of the new...
11 citations
TL;DR: In this article, 4-nitrobenzenethiosulfenamide (2) was isolated in the reaction of 4-chloronitrobenzene (1) with elemental sulfur in liquid ammonia at about 20°C.
Abstract: An interesting compound, 4-nitrobenzenethiosulfenamide (2) was isolated in the reaction of 4-chloronitrobenzene (1) with elemental sulfur in liquid ammonia at about 20°C. This compound yielded 4-nitrobenzenethiol (3), 4-nitroaniline (4), 4,4′-dinitrodiphenyl disulfide (5) and 4,4′-dinitrodiphenyl sulfide (6) upon further reaction in liquid ammonia. When elemental sulfur is dissolved in liquid ammonia, new nucleophile species such as H2NS-NH4 + or H2NSS-NH4 + appear to be formed and to participate in the aromatic nucleophilic reactions. These new nucleophiles, H2NS-NH4 + and H2NSS-NH4 +, would undoubtedly participate in the reactions of 4,4′-dinitrodiphenyl disulfide (5) and 4,4′-dinitrodiphenyl sulfide (6) with elemental sulfur in liquid ammonia, respectively.
TL;DR: In this article, a double pentacoordinated tetrahalogenide (5a) can be identified by NMR spectroscopy when chlorinating, and the hitherto unknown spirobromide (6b) could be synthesized independently by brominating the arylphosphite via splitting an ether-linkage under extraordinarily mild conditions.
Abstract: Bei der Halogenierung des o-Phenylenphosphits (4) bei 0°C entstehen als stabile Endprodukte Orthophosphorsaure-bis-o-phenylenesterhalogenide (6) und Orthophosphorsaure-o-phenylenester-trihalogenide (7). Bei der Chlorierung von (4) konnte ein zweifach pentakoordiniertes Tetrachlorid (5a) NMR-spektroskopisch nachgewiesen werden. Das bisher unbekannte Spirobromid (6b) konnte unabhangig auch aus dem Arylphosphit (9) gewonnen werden, wobei Etherspaltung unter ungewohnlich milden Bedingungen eintritt. The phosphite (4) gives with halogene two stable products: orthophosphoric acid bis-o-phenyleneester-halogenides (6) and orthophosphoric acid o-phenyleneester-trihalogenides (7). A double pentacoordinated tetrahalogenide (5a) can be identified by NMR spectroscopy when chlorinating (4). The hitherto unknown spirobromide (6b) could be synthesized independently by brominating the arylphosphite (9) via splitting an ether-linkage under extraordinarily mild conditions.
TL;DR: In this paper, 13C-NMR-spektroskopisch bestimmung der 1.4-Heterophosphorinane wird 13C NMR-bestimmung vorgenommen.
Abstract: Die reinen isomeren 1.4-Heterophosphorinane (5a–7a) werden durch elektrochemische Reduktion der reinen stereoisomeren Salze (2–4) in hoher Ausbeute erhalten (Gl. 3). Die entsprechenden stereoisomeren Phosphine (5b–7b) mit umgekehrter Konfiguration am Phosphor werden durch Reduktion der entsprechenden Oxide (11b–13b) mit Phenylsilan hergestellt (Gl. 5). Letzte erhalt man durch Alkalispaltung der 1.4-Heterophosphorinaniumsalze (8–10) (Gl. 4). (11b) und (12b) konnen aus dem jeweiligen Isomerengemisch durch Umkristallisieren mit hoher Isomerenreinheit isoliert werden. (13b) wird auf diese Weise nur in 80%-iger Isomerenreinheit erhalten. Die Konformations- und Konfigurations-bestimmung der 1.4-Heterophosphorinane wird 13C-NMR-spektroskopisch vorgenommen. Sowohl die vicinalen 3 J PC-als auch die 4 J PH-Kopplungskonstanten zeigen eine Abhangigkeit von der Lage des freien Elektronenpaares am Phosphor. The isomeric 1,4-hetero-phosphorinanes (5a–7a) were prepared by a cathodic cleavage of the corresponding...
TL;DR: In this article, 3-Phenyl-, 3-β-naphthyl, 3-α-thienyl- and 3α-furylthietes have been obtained, considerably more stable than simple, alkyl-substituted thietes.
Abstract: 3-Phenyl-, 3-β-naphthyl-, 3-α-thienyl- and 3-α-furylthietes have been prepared. They are considerably more stable than simple, alkyl-substituted thietes. Cobalt cyclopentadienyl complexes of 2-phenylpropenethial and its S-methyl derivative have been obtained, the latter exemplifying a new ligand.
TL;DR: In this article, the reaction between finely divided white phosphorus and several alkoxide ions in the presence of tetrachloromethane and excess of alcohol has been investigated under a variety of conditions.
Abstract: The reaction between finely divided white phosphorus and several alkoxide ions in the presence of tetrachloromethane and excess of alcohol has been investigated under a variety of conditions. High yields of trialkylphosphite are obtained when two equivalents of alkoxide are used. With one equivalent of alkoxide, dialkylphosphonate is formed in comparable yield. Maximum yields of triester are obtained within 1–3 h at room temperature. Prolonged treatment results in the conversion of trialkylphosphite to phosphate by reaction with tetrachloromethane. Phenolate ions are unreactive under the same experimental conditions. The mechanism of the reaction is discussed.
TL;DR: In this paper, the chlorohydroxybenzenesulfonyl derivatives are of interest as potential herbicides and their ir and nmr spectral characteristics are investigated as potential weedicides.
Abstract: 2,4-; 2,6-; 2,3-; 3,4-; 2,5-; and 3,5-dichlorophenols by reaction with chlorosulfonic acid were converted to the following substituted benzenesulfonyl chlorides: 3,5-dichloro-2-hydroxy-; 3,5-dichloro-4-hydroxy-; 2,3-dichloro-4-hydroxy-; 4,5-dichloro-2-hydroxy-; 2,5-dichloro-4-hydroxy-; and 2,6-dichloro-4-hydroxy-respectively. In addition o-chlorophenol gave 5-chloro-4-hydroxybenzene-1,3-bis-sulfonyl chloride. The various sulfonyl chlorides have been condensed with nucleophilic reagents, e.g. ammonia, amines, hydrazine, phenylhydrazine, N, N-dimethylhydrazine, and sodium azide. 3,5-Dichloro-2-hydroxybenzenesulfonyl azide has been reacted with norbornene, triphenylphosphine, dimethylsulfoxide, and cyclohexene. 3,5-Dichloro-2-hydroxybenzenesulfonyl chloride with phenylisocyanate gave the 2-(N-phenyl-carbamoyloxy) derivative which on heating gave a heterocyclic compound. The chlorohydroxybenzenesulfonyl derivatives are of interest as potential herbicides and their ir and nmr spectral characteristics ...
TL;DR: Pyrrolidine, morpholine, and β-hydroxyethylmorpholine have been phosphorylated with phosphorus oxychloride, phenylphosphorodichloridate, p-chlorophenylphophosphorodorodorodorodich chloridate and thiophosphoryl chloride as mentioned in this paper.
Abstract: Pyrrolidine, morpholine, and β-hydroxyethylmorpholine have been phosphorylated with phosphorus oxychloride, phenylphosphorodichloridate, p-chlorophenylphosphorodichloridate and thiophosphoryl chloride. The resultant phosphorodichloridates have been condensed with a wied range of nucleophilic reagents, e.g. amines, hydrazines, phenols and isobutanol. Piperazine with phosphorus oxychloride (2 mols) gave the N(1) N(4)-diphosphorotetrachloridate, which was characterized as the tetracyclohexylamidate. β-Hydroxyethylpiperazine was similarly phosphorylated to the N,O-diphosphorotetrachloridate which was characterized as the tetraphenylhydrazidate. Condensation of pyrrolidine (2 mols) with phosphorus oxychloride (1 mol) afforded N,N′-dipyrrolidinophosphorochloridate which was reacted with phenylhydrazide and sodium azide. The phosphoroazide with triphenylphosphine afforded the corresponding triphenylphosphinimine. N-Phenyl N′-pyrrolidinophosphorochloridate with aqueous pyridine gave the corresponding pyr...
TL;DR: The structure of triethylammonium diphenoxy-o-phenylenedioxy-1,2-bistrifluoromethylethenylenedionioxyphosphoride has been determined by x-ray crystallographic methods as discussed by the authors.
Abstract: The structure of triethylammonium diphenoxy-o-phenylenedioxy-1,2-bistrifluoromethylethenylenedioxyphosphoride, a compound with hexacoordinate phosphorus obtained by addition of triethylammonium phenoxide to the pentacoordinate phosphorus precursor, has been determined by x-ray crystallographic methods. The compound crystallizes from ether in space group P21/n of the monoclinic system. There are four formula units, (C22H14O6P)-(NC6H15)+ in the unit cell (Z=4), with one ion-pair constituting the asymmetric unit of the crystal. The cell dimensions are a=10.787(5), b=16.604(6), c=16.668(4) A; β=102.84°(3); D ctlc=1.415 g cm−3, D meas=1.412 g cm−3 (25°). Data were obtained on a CAD4 automatic diffractometer; 5310 unique non-zero reflections were collected with θ≤ 75° using (θ-2θ) scan, with a scan width of 1.0°. The phosphorus and oxygen atoms were located using the MULTAN program. All other non-hydrogen atoms were found in subsequent iterations of partial-structure phased Fourier maps. The structure ...
TL;DR: Aromatic nitro compounds were reduced with elemental sulfur in liquid ammonia and in amines, yielding the corresponding anilines as discussed by the authors, however, introduction of a substituent on the benzene ring or variation of the amine changed somewhat the pattern of this reaction.
Abstract: Aromatic nitro compounds were reduced with elemental sulfur in liquid ammonia and in amines, yielding the corresponding anilines. However, introduction of a substituent on the benzene ring or variation of the amine changed somewhat the pattern of this reaction. For example, 4-nitrotoluene (3) and 4-cyanonitrobenzene (6) were found to give not only the corresponding reduced products but also 4,4′-dicyanodiphenyl disulfide (10), formed by replacement of the nitro group, in addition to 4-cyanoaniline (9) in the reaction with elemental sulfur in liquid ammonia. Probable mechanisms of these reactions are discussed in the light of new knowledge on the similar reactions of elemental sulfur.
TL;DR: In this article, it is suggested that the potassium cation takes part in forming a transition state as a coordinating center for thienylsulfidic fragments and thus produces the matrix effect.
Abstract: Reaction of 2,5-dithiocyanatothiophene with equimolecular amounts of the dipotassium salt of cyclooctatetraene dianion in THF yields potassium 2-thiocyanato-5-thienylmercaptide. The latter converts to a cyclic tetramer with disulfide bonds—tetra [(thienylen-2,5)disulfide], whose structure was determined by x-ray analysis. In the presence of 1,4,7,10,13,16-hexaoxacyclooctadecane (“18-crown-6-ether”), the cyclic tetramer formation becomes very difficult and the main product becomes poly [(thienylen-2,5)disulfide] with linear structure. It is suggested that the potassium cation takes part in forming a transition state as a coordinating center for thienylsulfidic fragments and thus produces the matrix effect.
TL;DR: In this article, a new method to obtain aryl sulfamates has been developed from the reaction between aryls fluorosulfates and secondary aliphatic amines.
Abstract: L'action des amines aliphatiques secondaires sur les fluorosulfates d'aryle constitue une nouvelle voie de synthese des sulfamates d'aryle. A l'aide du concept HSAB (Hard and Soft Acids and Bases), nous avons montre qu'il est possible de rationaliser la difference de reactivite entre fluorosulfates et chlorosulfates d'aryle. A new method to obtain aryl sulfamates has been developed from the reaction between aryl fluorosulfates and secondary aliphatic amines. The use of HSAB concept (Hard and Soft Acids and Bases) permits us to explain the difference of the ractivity between aryl fluorosulfates and aryl chlorosulfates.
TL;DR: In this article, the absolute configuration of optically active amidophosphonium salts was deduced through further chemical reaction under known stereochemical control to products of defined absolute configuration.
Abstract: Optisch aktive Amidophosphoniumsalze, z.B. (7a) und (7b), werden elektroreduktiv unter Retention in die bisher unbekannten Phosphinigsaureamide (4a) und (4b) uberfuhrt. Die absolute Konfiguration von (4a) und (4b) wird durch chemische Korrelation mit Verbindungen bekannter absoluter Konfiguration ermittelt. Durch Umsetzung von optisch aktivem (4b) mit Trifluoressigsaure-p-kresylester erhalt man unter Retention Ethyl-phenyl-phosphinigsaure p-kresylester (13). Optically active amidophosphonium salts (e.g. 7a, 7b) may be electrochemically reduced with retention of configuration at phosphorus to the corresponding phosphinous acid amides (4a, 4b), previously unreported compounds. The absolute configuration were deduced through further chemical reaction under known stereochemical control to products of defined absolute configuration. Reaction of optically active (4b) with para-cresyl trifluoroacetate gives the ethyl–phenyl phosphinous acid para-cresyl ester (13) under retention of configuration.
TL;DR: In this paper, the synthesis and characterization of seven unsymmetrical derivatives of the type YP(NMeNMe)3PZ are reported, where Y = O or NPh: Z = S, Se, Br+ and Z = a lone pair, Z = Br+.
Abstract: The syntheses and characterization of seven new unsymmetrical derivatives of the type YP(NMeNMe)3PZ are reported. Where Y = O or NPh: Z = S, Se, Br+ and where Y = a lone pair, Z = Br+ Also reported are the new symmetrical derivatives where Y = Z = (OC)5W or (OC)3Ni and the new monovalent cage cations YP(NMeCH2)3CMe+ where Y = Ph3C and Br. Conductivity and 31P nmr evidence for the formulation of the phosphonium cations is presented. 3J31P31P couplings, obtained directly from the 31P nmr spectra of the unsymmetrical derivatives, are found to rise upon successively oxidizing the phosphorus atoms, and a rationale is offered. This coupling is also extracted from the 183W and 77Se satellite peaks in the 31P spectra of the symmetrical derivatives where Y = Z = (OC)5W and Se, respectively. A self-consistent set of assignments of the 31P chemical shifts is arrived at for YP(NMeNMe)3PZ compounds and the useful role of LIS reagents in analyzing their proton spectra is delineated. The 13C nmr spectral parame...
TL;DR: In this paper, the synthesis and photolysis of the new [2-bromo-α-oxo-phenylmethane]-diphenylphosphine (5) is described.
Abstract: Es wird die Synthese und Photolyse des neuen [2-Brom-α-oxo-phenylmethan]-diphenylphosphins (5) beschrieben. UV-Bestrahlung von (5) in Benzol liefert Produkte durch x-Spaltungen (6 und 7) und Photosubstitutionen (7 und 8) sowie das Phosphinoxid (9) durch neuartige Umlagerungsreaktion. Die Bildung von (9) wird durch photoinduzierten 1,2-Sauerstofftransfer aus der Carbonylgruppe auf den Phosphor erklart. Von (9) wird eine Rontgenstrukturanalyse vorgelegt. Synthesis and photolysis of the new [2-bromo-α-oxo-phenylmethane]-diphenylphosphine (5) is described. U. v. irradiation of (5) in benzene yields products via α-cleavages (6 and 7), and photosubstitutions (7 and 8), and the phosphine oxide (9) in a novel rearrangement reaction. The formation of (9) is interpreted by photoinduced 1,2-transfer of oxygen from the carbonyl function onto the phosphorous atom. An X-ray structure analysis of (9) is presented.
TL;DR: In this article, it has been determined that the stretching frequencies of these groups increase upon molecular constraint, and that νBH appears to be sensitive to the pi bonding nature of the phosphorus substituent at the other end of the cage in H3BP(NMeNMe)3PZ systems.
Abstract: The syntheses of the new cages P(NMeNMe)3PO, H3BP(NMeNMe)3PO, H3BP(NMeNMe)3PNPh and OP(NMeNMe)3PNPh are reported. From the ir spectra of acyclic and bicyclic aminophosphine BH3 adducts and oxides in the BH and O[dbnd]P stretching regions, respectively, it has been determined that the stretching frequencies of these groups increase upon molecular constraint. Moreover, νBH appears to be sensitive to the pi bonding nature of the phosphorus substituent at the other end of the cage in H3BP(NMeNMe)3PZ systems. Separate linear correlations of δCH 2 and 3J31P1H are observed in a series of YP(NMeCH2)3CMe compounds where the sigma accepting and sigma accepting plus pi donating Y group ranges in electronegativity. Dipole moment studies show that constraint of YP(NMe2)3 into bicyclic YP(NMeCH2)3CMe analogs results in little change in molecular moment in contrast to moments for YP(OMe)3 when compared to those of YP(OCH2)3CMe systems.
TL;DR: In this paper, the synthesis of 2.4-Dithiapentan-1-thiol (1), 2-Thiapropan- 1-thiole (2), 3-mercapto dimethyl sulfide (3), 2.
Abstract: Die Spaltung von s-Trithian, Trithioacetaldehyd, (CH2S) n und (CH2S2) n mit Natrium in flussigem Ammoniak liefert Mercaptothioether und Bis-Mercaptothioether nach einem allgemien anwendbaren Reaktionsprinzip. Beschrieben wird die Synthese von 2.4-Dithiapentan-1-thiol (1), 2-Thiapropan-1-thiol (2), 2-Mercapto-3-thiapentan (4) und Bis-mercaptodimethylsulfid (6). The cleavage of s-trithiane, trithio acetic aldehyde, (CH2S) n and (CH2S2) n by sodium in liquid ammonia leads to the formation of mercapto thioethers and bis-mercapto thioethers according to a general reaction principle. Described is the synthesis of 2.4-dithiapentane-1-thiole (1), 2-thiapropane-1-thiole (2), 2-mercapto-3-thiapentane (4) and bis-mercapto dimethyl sulfide (6).
TL;DR: The title compounds (la-c and (15a-c) as discussed by the authors are synthesized from dithianyllithium compounds and the corresponding element chlorides and react with acid chlorides either with ring opening to the S,S '-diacyl-1,3-dimercaptopropanes (3), (4) and (14) or in a simple substitution reaction to give the 2-acyl 1,3dithianes (5−13).
Abstract: The title compounds (la-c) and (15a-c) are synthesized from dithianyllithium compounds and the corresponding element chlorides. They react with acid chlorides either with ring opening to the S,S '-diacyl-1,3-dimercaptopropanes (3), (4) and (14) or in a simple substitution reaction to give the 2-acyl-1,3-dithianes (5–13). The influence of different factors on the reaction pathway is described. Die Titelverbindungen (la-c) und (15a-c) werden aus Dithianyllithium-Verbindungen und entsprechenden Element-chloriden dargestellt. Sie reagieren mit Saurechloriden entweder unter Ringoffnung zu den S,S′-Diacyl-1.3-dimercapto-propanen (3), (4) und (14) oder in einer einfachen Substitutionsreaktion zu den 2-Acyl-1.3-dithianen (5–13). Der Einfluβ verschiedener Faktoren auf den Reaktionsverlauf wird beschrieben.
TL;DR: In this article, the color determining electronic transitions of organic sulfdiimides (Sulfurdiimines) has been accounted for in terms of their constituent parts based on the more recently described PPP configuration analysis technique and the MIM-LCI method.
Abstract: The NSN group absorbs at relatively long wavelengths in the uv region. Because of its capability to release or to accept electrons, adjacent groups can produce a pronounced red shift of the color band. Based on the more recently described PPP configuration analysis technique and the MIM-LCI method the color determining electronic transitions of organic sulfdiimides (Sulfurdiimines) has been accounted for in terms of their constituent parts. The calculations revealed that the position of the color band is mainly governed by frontier orbital interactions. Symmetrical junction of the NSN unit with conjugated fragments gives rise to deeply colored heterocyclic compounds, if either their HOMO's or LUMO's have the same symmetry and undergo an effective overlap. This condition is not fulfilled, in general, for compounds which are strongly stabilized in their electronic ground states.
TL;DR: The high temperature reaction of hydrogen sulfide with chloro-and bromosubstituted aromatic and heteroaromatic compounds is a convenient method for synthesis of the corresponding thiols and sulfides as mentioned in this paper.
Abstract: The high temperature reaction of hydrogen sulfide with chloro- and bromosubstituted aromatic and heteroaromatic compounds is a convenient method for synthesis of the corresponding thiols and sulfides. The reaction of hydrogen sulfide with ortho-dihalosubstituted aromatic compounds may be directed toward the formation of thianthrene or dibenzo thiophene and their derivatives. The high temperature reaction of thiophenol with chloro- and bromoderivatives of aromatic and heteroaromatic compounds affords the corresponding mixed sulfides. The reaction with ortho-substituted halogen derivatives leads to formation of the sulfur heterocycles of the thianthrene, thioxanthene and dibenzothiophenene series. The high temperature reaction of hydrogen sulfide with vinyl chloride gives vinylthiol and thiophene. Hydrogen sulfide initiates pyrolytic transformations of thiophene, aniline and benzaldehyde into dithienyls, 5.10-dihydrophenazine and stilbene, respectively. The reaction mechanism has been discussed.
TL;DR: In this article, the authors present a suite of reactions leading to spirophosphoranes containing a P-H bond (1−4) and a P−OMe bond (5−7), the latter obtained by an oxidation reaction with iodine in basic medium via perhaps a monocyclic phosphorane containing a p−H bond.
Abstract: On presente l'ensemble des reactions conduisant a des spirophosphoranes a liaison P–H (1–4) et a liaison P–OMe (5–7); ces derniers sont obtenus par une reaction d'oxydation a l'iode en milieu basique qui peut se faire par l'intermediaire de phosphoranes monocycliques a liaison P–H. Les R-8 benzo-(2,3) trioxa-1,4,6 diaza-7,9 phosphav-5 spiro [4.4]nonene-7(3) sont suffisamment electrophiles pour donner des adduits dans des solvants peu polaires, et en particulier, l'existence de composes du phosphore hexacoordine a liaison P–OH (16) est discutee. The reactions leading to spirophosphoranes containing a P–H bond (1–4) and a P–OMe bond (5–7) are presented; the latter obtained by an oxidation reaction with iodine in basic medium via perhaps a monocyclic phosphorane containing a P–H bond. The R-8 benzo-(2,3) trioxa-1,4,6 diaza-7,9 phosphav-5 spiro [4.4]nonene-7(8) are electrophilic enough to give adducts in no polar solvents, in particular existence of hexacoordinated phosphorus compounds containing a P...