Showing papers in "Phosphorus Sulfur and Silicon and The Related Elements in 1984"
TL;DR: The synthesis and properties of N-methyl-phosphonic acid derivatives are described in this article. But none of these compounds showed herbicidal or plant growth regulator properties. And none of them showed any herbicidal properties.
Abstract: The synthesis and the chemical, physical and spectral properties of glycino-N-methylphosphonic acid derivatives, i.e., 1-(N-carbethoxymethyl)-aminocyclopropan-1-phosphonic acid (5), 2-dihydroxyphosphonyl-N-carboxymethylpyrrolidine (10), 5-dihydroxyphosphonylproline (13), 2-carboxy-6-dihydroxy-phosphonyl-piperidine (16), N-(dihydroxyphosphonylmethyl)-proline (18a), N-(dihydroxyphosphonyl-methyl)-piperidin-2-carbonic acid (18b), N-phosphonomethylsubstituted-1-aminocyclopropyl-1-carbonic acid derivatives (21, 22, 23, 24), and 1-(N-dihydroxyphosphonylmethyl)-aminocyclohexan-1-carbonic acid (26) are described. None of these compounds showed herbicidal or plant growth regulator properties. 1-Aminocyclopropyl-1-phosphonic acid (3c) releases ethylene in the presence of oxidizing agents.
39 citations
TL;DR: In this article, the synthesis of bridged dibenzo[d,f][1,3,2]dioxaphosphepin and Dioxaphosphocin ring systems is described.
Abstract: The syntheses of novel bridged dibenzo[d,f][1,3,2]dioxaphosphepin and dibenzo[d,g][1,3,2]dioxaphosphocin ring systems are described. The 1H NMR spectral data of the eight-membered bridged dioxaphosphocins suggest the observation of a single conformational isomer. The 1H NMR spectrum of the dibenzo[d,g][1,3,2]dioxaborocin 5 requires that either a single nonplanar conformation is being observed or that ring inversion is slow on the NMR time scale. A lower limit of δG ‡ for ring inversion of 5 has been calculated to be 14.4 Kcal/mole. The 1H NMR of the C-12 methyl substituted dioxaphosphocins 4h-i showed the presence of a cis-trans isomer mixture.
36 citations
TL;DR: In this article, the reactions of substituted 6-chloro-12H-dibenzo[d,g][1,3,2]dioxaphosphocins with primary, secondary and tertiary alkanolamines are described.
Abstract: The reactions of substituted 6-chloro-12H-dibenzo[d,g][1,3,2]dioxaphosphocins and 6-chlorodibenzo[d,f][1,3,2]dioxaphosphepins with primary, secondary and tertiary alkanolamines are described. The primary and sec-aminoalkyl phosphites prepared show no IR or NMR spectroscopic evidence for formation of their tautomeric pentacoordinate form.
24 citations
TL;DR: In this paper, the synthesis of 2-phosphorin from 1-benzylphosphole by reaction with benzoyl chloride, followed by sulfurization and pyrolysis with nickel powder at around 170-200°C is described.
Abstract: On decrit la preparation de la phenyl-2-phosphorine a partir du benzyl-1-phosphole par extension de cycle au chlorure de benzoyle, sulfuration et pyrolyse sur nickel vers 170–200°C. Dans le but de preparer des phosphorines acylees sur la position 4, on etudie la fonctionnalisation des sulfures de dihydro-1,6-phosphorines par metallation au butyllithium suivie d'une attaque des anions obtenus par divers electrophiles. Les essais de preparation des phophorines fonctionnelles correspondantes ont echoue. La derniere partie est consacree a la preparation de phosphorines heteroarylees a partir du phenyl-1-dimethyl-3,4-phosphole et des chlorures de furoyle et de thenoyle. The synthesis of 2-phenylphosphorin from 1-benzylphosphole by reaction with benzoyl chloride, followed by sulfurization and pyrolysis with nickel powder at around 170–200°C is described. In order to prepare some unknown 4-acylphosphorins, we have also studied the metalation of 1,6-dihydrophosphorin sulfides. Our attempts have been unsu...
21 citations
TL;DR: In this paper, the As[dbnd]C derivative 1a is attacked by methyl iodide and CCl4 to give λ5- and (δ3-dihydro)benzoxarsoles, respectively.
Abstract: The title compounds show low reactivity towards electrophiles. Under forced conditions, however, the As[dbnd]C derivative 1a is attacked by methyl iodide and CCl4 to give λ5- and (δ3-dihydro)benzoxarsoles, respectively. Nucleophilic additions take place with “soft” bases while “hard” bases fail to react, thus indicating some aromaticity of the heterocycles. Me3SnH is smoothly added by a radical way. Die Titelverbindungen sind gegenuber Elektrophilen wenig reaktiv. Unter encrgischen Bedingungen setzt sich das As[dbnd]C-Derivat 1a jedoch mit Methyliodid und CCl4 zu δ5- bzw. (δ3-Dihydro)benzoxarsolen um. Nucleophile Additionen gelingen mit “weichen” Basen, wahrend “harte” Basen nicht reagieren. Dies verweist auf gewisse aromatische Stabilisierung der Heterocyclen. Me3SnH wird leicht radikalisch addiert.
19 citations
TL;DR: Etude de la composition des produits de sulfonation juste apres la consommation de SO 3 and quelques jours plus tard a l'aide d'une etude thermochimique et d'un etude cinetique de l'evolution of sulfonations (β-sultones puis isomerisation en acides alcenesulfoniques et γ- et δ-sults) as mentioned in this paper.
Abstract: Etude de la composition des produits de sulfonation juste apres la consommation de SO 3 et quelques jours plus tard a l'aide d'une etude thermochimique et d'une etude cinetique de l'evolution des produits de sulfonation (β-sultones puis isomerisation en acides alcenesulfoniques et γ- et δ-sultones)
19 citations
TL;DR: In this paper, the substitution nucleophilic substitution between the sodium anion of diethylphosphite and several halogenated substrates like: iodo-anilines, Iodo-nitrobenzenes, bromo-and iodopyridines, and Bromoquinoline.
Abstract: Our aim was to study the aromatic nucleophilic substitution between the sodium anion of diethylphosphite and several halogenated substrates like: iodo-anilines, iodo-nitrobenzenes, bromo- and iodopyridines, bromoquinoline. Two coupling processes have been evaluted. The first one is the photostimulated nucleophilic substitution (SRN1), the second the promoted arylation by transition metals. We obtain good results with the first method which is efficient and simple; by contrast the second one has given only few positive results. We describe five aromatic aminophosphonic acids. Nous avons etudie la substitution nucleophile aromatique entre le diethylphosphite sode et plusieurs substrats halogenes tels que iodo-anilines, iodonitrobenzenes, bromo- et iodo-pyridines, bromo-quinoleine. Deux methodes de couplage ont ete evaluees. L'une est la substitution nucleophile sous photostimulation (SRN1), l'autre l'assistance par les metaux de transition. La premiere donne de bons resultats dans la majorite des c...
18 citations
TL;DR: In this paper, an Abramow reaction was used to transform diisopropylidene mannofuranose and dimethylphosphite into diasteromeric δ-phostones, which were then transformed into their crystalline tosylates.
Abstract: Diisopropylidene mannofuranose (1) and dimethylphosphite react under base catalysis in an Abramow reaction with subsequent internal transesterification to yield the diasteromeric δ-phostones 2, which are also transformed into their crystalline tosylates 3. Surprisingly, these compounds adapt a boat conformation, however, after change of the protecting groups a flat chair conformation (of 8 and 9) results. The δ-phostone formation (7) turned out to be the preferred reaction course even when the cyclic phosphite 6 is applied to react with 1. In basic medium the tosylate 3 does not undergo a ring contraction to a glycosyl phosphonate, however, the 2-desoxy mannonic acid ester 10 is obtained; this is discussed and a mechanism proposed. Starting with the ribofuranose derivative 12 the corresponding δ-phostones 14 are prepared. In the reaction of the glucopyranose compound 16 a competition between the formation of δ-phostones 19 and the open-chain phosphonates 21 is observed.
18 citations
TL;DR: In this article, the ESR spectra of R2C2S2 with R = [sbnd]C(CH3)3, [SBnd]CH3]2[sbnd], CH2[SBND]CH2[ SBnd] CH2]2, CH3]3 and CH3)2 are shown to exhibit 33S satellites in the SS bridge of the four-membered ring.
Abstract: Novel 1,2-dithiete derivatives R2C2S2 with R = [sbnd]C(CH3)3 and [sbnd]C(CH3)2[sbnd]CH2[sbnd]CH2[sbnd]CH2[sbnd]C(CH3)2[sbnd] are readily oxidized by the one-electron transfer system AlCl3/H2CCl2 to their radical cations. The single line ESR spectra, on high amplification, exhibit 33S satellites in natural abundance. Both the ESR data, i.e. rather large g values and 33S hyperfine coupling constants as well as MNDO closed and open shell calculations for the parent molecule H2C2S2 illustrate that spin and positive charge are predominantly located in the SS bridge of the four-membered ring.
17 citations
TL;DR: Cyclodextrins are naturally occurring doughnut-shaped molecules composed of 6,7 and 8 D-glucose units and are known to be able to form inclusion complexes with a wide variety of molecules as mentioned in this paper.
Abstract: Cyclodextrins are naturally occurring doughnut-shaped molecules composed of 6,7 and 8 D-glucose units and are known to be able to form inclusion complexes with a wide variety of molecules.1–3 Due to these properties cyclodextrins (CD) have been widely used as a model of enzymes because they form molecular complexes with substrates prior to chemical transformations. From the point of view of stereochemistry it is interesting to point out that cyclodextrins are chiral molecules and show enantioselection in many reactions. This feature has been utilized for the optical resolution of racemic compounds and in asymmetric synthesis, although the application of CDs as chiral catalysts or reagents for asymmetric synthesis has been limited to a small number of reactions as yet.4
17 citations
TL;DR: In this article, the stereochemistry in solution of 16-to 20-membered metacyclophanes having mesitylene units connected by methylene, sulphide, and/or disulphide linkages was investigated by means of 1H n.m. spectroscopy.
Abstract: The stereochemistry in solution of 16- to 20-membered metacyclophanes having mesitylene units connected by methylene, sulphide, and/or disulphide linkages, has been investigated by means of 1H n.m.r. spectroscopy. Depending upon the size of the ring system, saddle or crown conformation is preferred. Remarkably, within the crown conformation adopted by the 18-membered metacyclophanes with alternating disulphide and methylene or sulphide linkages, the single bridged dimesityl moieties approach the butterfly configuration.
TL;DR: In this paper, two N,N-diethyl derivatives of phosphinamides in the 3-phospholene series were used as models to develop techniques for reduction to P(III) derivatives.
Abstract: Two N,N-diethyl derivatives of phosphinamides in the 3-phospholene series were used as models to develop techniques for reduction to P(III) derivatives. The products from the reduction with HSiCl3 in the presence of pyridine depended on the molar ratio of the participants. A 1 : 1 : 1 amide-HSiCl3-pyridine mixture after 2 h in refluxing benzene provided the phosphinous chlorides in preparatively useful (55–65%) yield. A 1 : 1.5 : 1.5 mixture led to coupling at phosphorus to give the diphosphine, also in good yield (60–65%). The diphosphines also resulted from refluxing a 1 : 1 mixture of the amide with phenylsilane. However, heating a 2 : 1 amide–silane mixture at 100° gave only the product of deoxygenation (65%). A 1-benzylaminophosphetane oxide was also reduced successfully. The conditions with HSiCl3 and C6H5SiH3 were applied to a noncyclic phosphinamide (C6H5)2PO(NEt2); reaction rates were considerably slower than for the cyclic amides, but similar P(III) products were formed. 13C and 31P NMR...
TL;DR: In this article, a novel synthesis of 1,3-dioxoles by the action of diphenylmethylenetriphenylphosphorane (1) and fluorenylidenetrivenetriptonylphophosphoranes (2) on tetrahalo-o-benzoquinones (5) is reported.
Abstract: A novel synthesis of 1,3-dioxoles (6a), (6b) and (7a-d) by the action of diphenylmethylenetriphenylphosphorane (1) and fluorenylidenetriphenylphosphoranes (2) on tetrahalo-o-benzoquinones (5) is reported. A possible reaction mechanism is considered and the structural assignments are supported by chemical and physical evidence.
TL;DR: Trimesitylphosphaethene (MesP[dbnd]CMes2, If) is of interest as a sterically protected and presumably very stable phosphaalkene as mentioned in this paper.
Abstract: Trimesitylphosphaethene (MesP[dbnd]CMes2, If) is of interest as a sterically protected and presumably very stable phosphaalkene. Its synthesis was attempted along three different routes. The first two routes were modelled after the well-documented syntheses by phosphaalkenes by base catalyzed elimination of hydrogen chloride from MesPCICHMes2 (3). In the first approach, 3 could not be obtained from the precursor MesP(NEt2)CHMes2 (4) by treatment with hydrogen chloride. Instead, the phosphonium salt [MesPH(NEt2)CHMes2]⊕Cl⊖ (2) was formed; (2) is of interest as a “frozen” intermediate in the acid catalyzed nucleophilic substitution at phosphorus(III). The mechanistic implications of its formation and the reasons for its lack of reactivity are discussed. In the second approach, 3 was obtained from the reaction of MesPCl2 (8) with α-potassiodimesityl-methane. However, several attempts to eliminate hydrogen chloride from 3 were unsuccessful. Similarly, the third route, aimed at the preparation of CIP[...
TL;DR: The 2H-1,2,3-diazaphospholes 1a and b undergo 1,2-addition with tert-butyllithium onto the P/C-double bond under the formation of the lithium derivatives as discussed by the authors.
Abstract: The 2H-1,2,3-diazaphospholes 1a and b undergo 1,2-addition with tert-butyllithium onto the P/C-double bond under the formation of the lithium derivatives 6a and b, which are transformed into 3-tert-butyl-3,4-dihydro-1,2,3-diazaphospholes with formic acid (6 → 7) or tert-butylchloride (6 → 8 → 7). The lithium compound 6b may be methylated, silylated or carboxylated in the 4-position under the formation of trans-substitution products [10a(A). 10b(A) and 11a(A)]. Some 3,4-dihydro-1,2,3-diazaphospholes are oxidized at the phosphorus atom with hydrogen peroxide or oxygen, sulfur and selenium (12a-g). Die 2H-1,2,3-Diazaphosphole 1a und b gehen mit tert-Butyllithium 1,2-Addition an die P/C-Doppelbindung unter Bildung der Lithiumderivate 6a und b ein, die mit Ameisensaure (6 → 7) oder tert-Butylchlorid (6 → 8 → 7) in 3-tert-Butyl-3,4-dihydro-1,2,3-diazaphosphole umgewandelt werden konnen. Die Lithiumverbindung 6b last sich in 4-Position methylieren, silylieren und carboxylieren, wobei trans-Substitutions...
TL;DR: Sterically protected tris(tertiarybutyl)phenylphosphine reacts with sulfur, giving rise to the corresponding sulphide which reacts further to produce bis[tris(tris[trtiary butyl]trithiodiphosphinate] as mentioned in this paper.
Abstract: Sterically protected tris(tertiarybutyl)phenylphosphine reacts with sulfur, giving rise to the corresponding sulphide which reacts further to produce bis[tris(tertiarybutyl)phenyl]trithiodiphosphinate. This last compound finally affords the first stable metadithiophosphonate.
TL;DR: In this article, the SH-selectivity of triphenyl-vinylphosphonium bromide was investigated in Konkurrenzversuchen with RXH (X=O, S, NH) and diphenylvinyl-phosphine oxide.
Abstract: As a result of competition reactions triphenylvinylphosphonium bromide 1 is SH-selective. But the reactivity is significantly reduced in comparison to the vinyl sulfones. The elimination reaction (b) is also slowed down compared with the cleavage of the corresponding sulfones. In diphenylvinylphosphine oxide 2 the SH-selectivity is preserved. The rate of the reactions (a) and (b) is so extremely slow that 2 has no chance as a SH-protective reagent. Triphenyl-vinylphosphoniumbromid 1 reagiert in Konkurrenzversuchen mit RXH (X=O, S, NH) SH-selektiv bei deutlich reduzierter Reaktivitat im Vergleich zu den Vinylsulfonen. Auch die Eliminierung nach (b) verlauft langsamer als bei analogen Sulfonen. Beim Diphenyl-vinylphosphinoxid 2 ist die SH-Selektivitat noch erhalten. Die Reaktionen (a) und (b) verlaufen jedoch so extrem langsam, das 2 als SH-Schutzgruppe praktisch ausscheidet.
TL;DR: In this article, the synthesis of compounds containing both a phosphonic end group and a chlorofluorinated chain is achieved by means of a redox reaction using cuprous chloride as catalyst.
Abstract: The synthesis of compounds containing both a phosphonic end group and a chlorofluorinated chain is achieved by means of a redox reaction using cuprous chloride as catalyst. By a redox catalysis system monoadducts are obtained. The taxogens involved are diethyl vinylphosphonate and diethyl allylphosphonate. The telogens are CF3[sbnd]CCl3 and CCl3[sbnd](CF2[sbnd]CFCl) n [sbnd]Cl. The resulting products contain a C[sbnd]P bond. Their structure has been determined by 1H NMR. The hydrolysis of phosphonic esters is carried out with concentrated hydrochloric acid and leads to the corresponding acids and salts.
TL;DR: In this paper, the ortho-lithiation of R-rsp is used for the synthesis of the Verbindungstypen in the context of the title compounds.
Abstract: Schlusselreaktion fur die Synthese der im Titel genannten Verbindungstypen ist die ortho-Lithiierung von R-bzw. S-1-Phenyl-ethyl-N,N-dimethylamin. Mit geeigneten Verbindungen, z.B. R,NEt2,PCl (R=Me, Ph) wird nach (1) in die ortho-Position zur Seiteniette der Phosphorrest eingefuhrt. Durch Grignardierung der Verbindungen 1 und 2 erhalt man die tertiaren Phosphine 3 bis 6. Uber die Phosphinoxide 7 bis 10 gelingt die Trennung in die Diastereomeren, die mit PhSiH3 in die tertiaren Phosphine 3 bis 6 mit unbekannter Konfiguration am Phosphor uberfuhrt werden. Nach (3a) und (3b) erhalt man die bis-chiralen Triarylphosphine 12 bis 15, die jedoch nicht in die Diastereomeren aufgetrennt werden konnten. Die Bis-N,P-Chelate 16, 17, 18 und 21 sind nach (4) und (5) zuganglich. Nur die Verbindungen 17 und 18 konnten in die Diastereomeren mit unbekannter Konfiguration am Phosphor aufgetrennt werden. For the synthesis of the title compounds the key reaction is the ortho-lithiation of R-rsp. S-1-phenyl-ethyl-N,N-d...
TL;DR: In this article, the authors showed that fluorescent compounds of type A are fluorescent if the donator groups, such as NMe2, OMe, SMe and PR2, and acceptor groups, like R′P(O)X, SO2R′ and CO2R'', are linked to different nuclei of the naphthalin ring system.
Abstract: Compounds of type A are fluorescent, if the donator groups, like NMe2, OMe, SMe and PR2, and the acceptor groups, like R′P(O)X, SO2R′ and CO2R′, are linked to different nuclei of the naphthalin ring system
TL;DR: The nucleophilic attack of alkyl and aryl-lithium compounds at the sulfenyl sulfur atom in thiosulfonic S-esters performs a convenient synthesis of aromatic sulfides which are obtained cleanly and in generally excellent yields.
Abstract: The nucleophilic attack of alkyl- and aryl-lithium compounds at the sulfenyl sulfur atom in thiosulfonic S-esters performs a convenient synthesis of aromatic sulfides which are obtained cleanly and in generally excellent yields. Considering that recently we have reported a ready preparation of thiosulfonic S-esters from sulfonyl chlorides, this sulfidation reaction completes an interesting general procedure for converting the latters to any symmetrical or unsymmetrical sulfides.
TL;DR: In this paper, the synthesis of N-chlorosulfonyl carbamates derived from seven hindered phenols is described, as well as their hydrolysis giving a high yield of the corresponding simple carbamate, the selective substitution of their chlorine atom by the anilino radical, and their thermolysis which takes places differently depending on the starting phenol substituents.
Abstract: The synthesis of the N-chlorosulfonylcarbamates derived from seven hindered phenols is described, as well as their hydrolysis giving a high yield of the corresponding simple carbamates, the selective substitution of their chlorine atom by the anilino radical (with formation of a new family of N-substituted carbamates) and their thermolysis which takes places differently depending on the starting phenol substituents and hence on the sensitivity of the latter to oxidation.
TL;DR: In this paper, a comparison of the infrared spectra of benzazole-2-selenone compounds with the thionic isologue is presented, showing that they differ in the low frequency region, while they are very similar in the finger-print region.
Abstract: Several benzazole-2-selenone compounds have been prepared and the syntheses are discussed together with those of the corresponding azolidine-2-selenones. The comparisons of the infrared spectra of each selenonic compound with the thionic isologue differ in the low frequency region, while they are very similar in the finger-print region. This similarity can be used as a diagnostic aid in confirming the analogy in structure between sulphur and selenium compounds.
TL;DR: A phosphorus ozonides series was obtained by reaction of ozone on various phosphites (1a-13a) as mentioned in this paper, and the oxidative addition of ozone leads to trioxophosphetane ring formation branched on pentacoordinated (1b-9b) or hexacoordination (10b-13b) phosphorus.
Abstract: A phosphorus ozonides series was obtained by reaction of ozone on various phosphites (1a-13a). The oxidative addition of ozone leads to trioxophosphetane ring formation branched on pentacoordinated (1b-9b) or hexacoordinated (10b-13b) phosphorus. The stability and stereochemistry of these compounds were studied.
TL;DR: Several synthetic schemes have been devised starting from [N,N-diethyl phenylphosphinamide]pentacarbonyltungsten 1.5.
Abstract: Several synthetic schemes have been devised starting from [N,N-diethyl phenylphosphinamide]pentacarbonyltungsten 1. Metalation of the P[sbnd]H bond of 1 by butyllithium followed by reaction with al...
TL;DR: In this paper, a structural isomer of tetrathiafulvalene, exhibits a low first ionization potential of only 7,47 eV and, therefore, can also be oxidized to a radical cation by AlCl3 in H2CCl2.
Abstract: 1,4,5,8-Tetrathiatetralin, a structural isomer of tetrathiafulvalene, exhibits a low first ionization potential of only 7,47 eV and, therefore, can also be oxidized to a radical cation by AlCl3 in H2CCl2. The photoelectron spectrum, fan-shaped in the low energy region, and the one-line electron spin resonance spectrum are assigned and discussed based on MNDO calculations. For the structures both of the neutral molecule and of its radical cation an easy bending along the S … S axes is calculated. 1,4,5,8-Tetrathiatetralin, ein Strukturisomeres des Tetrathiafulvalens, weist eine niedrige erste Ionisierungsenergie von nur 7.47 eV auf und last sich daher mit AlCl3 in H2CCl2 ebenfalls zum Radikalkation oxidieren. Das im Bereich niedriger Energie aufgefacherte Photoelektronen-Spektrum und das Einlinien-Elektronenspinresonanz-Spektrum werden anhand von MNDO-Rechnungen zugeordnet und diskutiert. Fur die Strukturen des Neutralmolekuls sowie seines Radikalkations wird leichte Abknickbarkeit entlang der S …...
TL;DR: In this paper, the sulfone group deactivation for cyclialkylation and cycliacylation reactions in the presence of Friedel-Crafts catalysts was demonstrated in a number of aryl chlorlalkylsulfones (1-8) and arylsulfonylacyl chlorides (17a-22a), respectively.
Abstract: The sulfone group deactivation for cyclialkylation and cycliacylation reactions in the presence of Friedel-Crafts catalysts was demonstrated in a number of aryl chlorlalkylsulfones (1–8) and arylsulfonylacyl chlorides (17a-22a), respectively. As expected, the corresponding arylchloralkyl sulfides (9–16) and arylmercaptoacyl chlorides (13a-28a) underwent ring-closure reaction in most cases under the same conditions. The ease of cyclization was governed by the ring size, the stability of the attacking carbocation and the nucleophilicity of the aryl moiety. Also the behaviour of benzyl sulfones (29, 31a, and 32a) and sulfides (33, and 36a) was inconsistent. Noteworthy, the Friedel-Crafts cyclization reaction is thus considered an accessible method for the synthesis of compound 37–41 and 45,51.
TL;DR: In this paper, a new synthetic pathway was exploited for the preparation of several Umpolung reagents, including 1,3-dithiane, and an efficient isolation of sodium trithiocarbonate was described.
Abstract: Cyclic trithiocarbonates can be desulfurized with diisobutylaluminium hydride (DIBAL) to form the corresponding thioacetals. This new synthetic pathway was exploited for the preparation of several Umpolung reagents, including 1,3-dithiane. An efficient isolation of sodium trithiocarbonate is described.
TL;DR: In this paper, the influence of hydrocarbon substituent in the electrophilic sulfur on the reaction road has been investigated in detail, and the reaction of 3,3-disubstituted allenylphosphonic dichlorides with sulfenyl chlorides in the presence of sulfur dioxide proceeds with formation of mixtures of 2,5-dihydro-1,2-oxaphospholes and 1, 2-adducts.
Abstract: The reaction of 3,3-disubstituted allenylphosphonic dichlorides with sulfenyl chlorides in the presence of sulfur dioxide proceeds with formation of mixtures of 2,5-dihydro-1,2-oxaphospholes and 1,2-adducts. The influence of hydrocarbon substituent in the electrophilic sulfur on the reaction road has been investigated in detail.
TL;DR: The metalation of benzylmethyl sulfide with n-butyllithium in hexane and in the presence of TMEDA has been investigated in this article, and the results show that metalation occurs only at the benzylic position with no Wittig type rearrangement, cleavage of thioether bond and aliphatic or aromatic substitution.
Abstract: The metalation of benzylmethyl sulfide with n-butyllithium in hexane and in the presence of TMEDA has been investigated. The results show that metalation occurs only at the benzylic position with no Wittig type rearrangement, cleavage of thioether bond and aliphatic or aromatic substitution. The lithium derivative has been allowed to react with some electrophiles.