REACTIONS OF TETRAPHOSPHORUS DECASULFIDE AND LAWESSON'S REAGENT WITH SILANES CONTAINING A FEW Si-O BONDS

Abstract

The reactions of tetraphosphorus decasulfide and Lawesson's reagent with tetra-, tri- and dialkoxysilanes were studied. On the basis of these reactions, new S-silyl esters of phosphorus(V) thioacids have been prepared. The prepared compounds were identified by IR, ¹H, and ³¹P NMR and mass spectra as well as elemental analyses.     

SULFENAMIDES AND SULFINAMIDES VI. REACTIONS OF ARYL SULFENAMIDES WITH DIPHENYLPICRYLHYDRAZYL FREE RADICAL

Abstract

Hydrogen abstraction may be postulated as the first step in reactions of aryl sulfenamides with the stable diphenylpicrylhydrazyl free radical. Differences in the reactivity of the sulfenamides are controlled by steric and electronic effects of the substituents, with attention drawn to the capacity of the divalent sulfur atom to relay these effects. Origins of decomposition products are discussed.     

MASS SPECTRA OF SULFUR COMPOUNDS. ASSESSMENT OF 1, X (X=2,3,4,5) HYDROGEN TRANSFER IN DIALKYL SULFIDES AND DISULFIDES UNDER ELECTRON IMPACT. A NOVEL 1,5-H SHIFT

Abstract

The transfer of hydrogen atoms from the gamma carbon of dialkyl disulfides upon electron impact is presented and its occurrence is formally shown by the electron ionization mass spectrum of 1-(2′,2′-dideuteriocyclohexyl)-2,3-dithiapent-1,1′-ene (4b). Also, the spectrum of 1-(2′,2′-dideuteriocyclohexyl)-2-thiahex-1-ene (3b) is analyzed in terms of hydrogen/deuterium transfer, where it is absent. This result is compared with selected mass spectral data of eighteen other dialkylthianes. Evidence is put forth to indicate that dialkyl sulfides are prone to undergo only 1,3-H shift upon electron inpact, whereas in dithianes 1,3- and 1,5-Hydrogen transfer take place. The evidence collected suggests that neither 1,2- nor 1,4-hydrogen transfer occurs in both sulfur derivatives.     

SELECTIVE AND CONVENIENT OXIDATION OF THIOLS TO DISULFIDES USING n-BUTYLTRIPHENYLPHOSPHONIUM DICHROMATE (Bu n PPh3)2Cr2O7 IN SOLUTION,UNDER SOLVENT-FREE CONDITIONS AND MICROWAVE IRRADIATION

A variety of aliphatic, aromatic, and heteroaromatic thiols were rapidly and cleanly converted to their corresponding disulfides in excellent yields using n-butyltriphenylphosphonium dichromate (BTPPDC) in acetonitrile solution under solvent-free conditions and microwave irradiation. Selective oxidation of thiols in the presence of other oxidizable functional groups, such as alcohol and sulfide, is a noteworthy advantage of this method.     

REDUCTION OF NITROGEN FUNCTIONAL GROUPS WITH ELEMENTAL SULFUR IN LIQUID AMMONIA AND AMINES

Abstract

Nitrosobenzene and phenylhydroxylamine were reduced with elemental sulfur in liquid ammonia and amines to give aniline as the major product. Although hydrazobenzene was obtained by the reactions of azoxybenzene and azobenzene with elemental sulfur in liquid ammonia and amines, the expected aniline was not obtained. The utilities of elemental sulfur in liquid ammonia and amines as reductant is discussed.     

SYNTHETIC,N.M.R. SPECTROSCOPIC AND X-RAY CRYSTALLOGRAPHIC INVESTIGATIONS ON THE PRODUCTS OF THE REACTIONS OF PHENYL (METHYL) PHOSPHONOTHIOIC DICHLORIDE AND THIOPHOSPHORYL CHLORIDE AND PSCL3 WITH PRIMARY AMINES

Abstract

The syntheses in solution of (i) 2,4-dialkylamino-, (ii) 2,4-dimethyl-, and (iii) 2,4-diphenyl-2,4-dithio-cyclodiphosph(V)azanes, [R′P(S)NR]₂ (R′ = NHR, Ph, or Me; R = alkyl), derived from thiophosphoryl trichloride, methylphosphonothioic and phenylphosphonothioic dichlorides and primary alkylamines are described. N.m.r. spectroscopic properties for these cyclodiphosph(V)azanes and their monomeric precursors, R′P(S)(NHR)₂ (R′ = NHR, Ph, or Me; R = alkyl), are presented and structural inferences are drawn from this data. The X-ray crystal structure of [PhP(S)NBuⁱ]₂ is reported.     

MECHANISM OF THE REACTION OF DIPHENYL N-BROMOSULFILIMINE WITH SULFIDES,PHOSPHINES AND TERTIARY AMINES

Abstract

The mechanism of the reactions of diphenyl N-bromosulfilimine (I) with such nucleophiles as sulfides, phosphines and tertiary amines was investigated. In the presence of water, (I) reacts with sulfides or phosphines to afford the corresponding sulfoxides or the phosphine oxides in moderate yields; however, the reaction with tertiary amine gave only the N-t-aminosulfilimine derivative. The effect of ring size in the reaction with cyclic sulfides suggests that the reaction proceeds via initial bromine transfer from the nitrogen atom to the sulfur atom of the cyclic sulfides followed by S_N2 type substitution of bromide on the sulfur atom of the cyclic sulfide with the sulfilimino group. The phosphine oxide obtained in the reaction of (I) with optically active methyl n-propyl phenyl phosphine was racemized but retained a small portion of the optical activity. In the case of tertiary amines, even 1,4-diazabicyclo-(2,2,2)-octane (DABCO), in which the back side of the nitrogen atom is blocked, reacted smoothly to afford the corresponding ammonium salts, suggesting the reaction to be of S_N2 type on the nitrogen atom of the sulfilimine.     

PHOSPHORUS-NITROGEN COMPOUNDS. PART 64.1 THE REACTIONS OF HEXACHLOROCYCLOTRIPHOSPHAZATRIENE WITH 2, 2-DIMETHYLPROPANE-1, 3-DIOL. NUCLEAR MAGNETIC RESONANCE STUDIES OF THE PRODUCTS

Abstract

The reactions of hexachlorocyclotriphosphazatriene, N₃ P₃ CI₆, with 2, 2-dimethylpropane-1, 3-diol yield monospiro-, N₃ P₃ Cl₄ [(OCH₂)₂ CMe₂, dispiro-, N₃ P₃ Cl₄((OCH₂)₂CMe₂|₂, and trispiroderivatives, N₃ P₃ ((OCH₂)₂, CMe₂]₃. An ansa, N₃ P₃ CI₄ [(OCH₂)₂ CMe₂]₂ and a spiro-ansa, N₃ P₃ Cl₂- ((OCH₂), CMe₂,]₂ and a doubly-bridged compound, (N₃ P₃ Cl₄,)₂[(OCH₂)]₂ were also isolated. Product types and relative yields were compared with those arising from propane-1, 3-diol. The yields of ansa products from the reactions of the dimethyl diol seem to be considerably enhanced relative to those of its unmethylated analogue. ³¹P and ¹H n.m.r. spectra are reported.     

固相配位化学反应研究 LV.FeCl_2·4H_2O,CoCl_2·6H_2O,NiCl_2·6H_2O,CuCl_2·2H_2O与邻菲咯啉的低热固相化学反应研究

邻菲咯啉(Phen)与过渡金属离子在液相中的反应速度很快,瞬间即可完成,形成稳定的配合物。过渡金属氯化物在水溶液中反应时,一般是以水合离子[M(H_2O)_6]~(2+)的形式参加反应。而在固相中参加反应物质的形式是其物质本身的凝聚态分子。因此,尽管是同一反应物,但在固相,液相反应中,参加反应物质的形式不同,可能产生两种不同的反应结果。为了比较固、液相反应的差别,寻找固相反应的规律性。我们研究了FeCl2_·4H_2O,CoCl_2·6H_2O,NiCl_2     

OCTAHEDRAL METAL CARBONYLS. XXVIII.1 KINETICS AND MECHANISM OF OXIDATIVE ELIMINATION REACTIONS OF SUBSTITUTED GROUP VI-B METAL CARBONYLS WITH TIN- AND GERMANIUM-CONTAINING OXIDIZING AGENTS

Abstract

The kinetics and mechanism of reactions of (2,2′-dipyridyl)W(CO)₄ with SnCl₄, (C₆H₅)SnCl₃, (n-C₄H₉)SnCl₃ and (C₆H₅)₂SnCl₂, and of (o-phenanthroline)Mo(CO)₄ with GeI₄ have been investigated employing stopped flow and conventional kinetic techniques. The oxidizing agent-dependent rate laws are encompassed in a mechanism which involves reversible addition of two successive molecules of the oxidant to the substrate, followed by other, rapid, steps. For the reaction of (C₆H₅SnCl₂ with (dipy)W(CO)₄ at 95–115°, a parallel reaction path probably involving rate-determining dissociation of CO was also observed. Rates were found to be very sensitive to the nature of the substituents bonded to the Group IV-A metal, being greatest for electron-withdrawing substituents. Different rate laws were observed for reactions which yielded products of different stereochemistries.     

COMPARATIVE STUDY OF THIOPHENIC COMPOUNDS IN SUNNILAND OILS AND SOURCE ROCKS VERSUS OTHER OILS IN U. S. A.

This paper analyzed thiophenic compounds in Sunniland oils and source rock extractsfrom the South Florida Basin, USA using GC-MS, and compared them with those of oilsfrom shales. We found that oils derived from carbonates versus shales have different distribu-tions of thiophenic compounds. Used in conjunction with such other geochemical parametersas n--alkane, sterane and terpane compositions, thiophenic compounds will be a useful toolfor oil--oil and oil--source correlations.     

HETEROCYCLES SYNTHESIS THROUGH REACTIONS OF NUCLEOPHILES WITH ACRYLONITRILES,PART 5, SYNTHESIS OF SEVERAL NEW THIAZOLE AND THIAZOLO[2,3-a]PYRIDINE DERIVATIVES

Abstract

Several new thiazole and thiazolo[2,3-a]pyridine derivatives were prepared by reaction of the thiazolin-4-one derivatives 2 (synthesised from α-cyano-2-ethylacetanilide and thioglycollic acid) with acrylonitriles 1a-h.     

CONVENIENT HETEROCYCLIZATION REACTIONS WITH ETHYL 2-AMINO-4,5,6,7-TETRAHYDROBENZO[b] THIOPHENE-3-CARBOXYLATE: SYNTHESIS OF PYRAZOLE,ISOXAZOLE AND PYRIDAZINE

Abstract

The ethyl 2-diazo-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate 2 reacts with ethyl acetoacetate to give the hydrazone derivative 4. The reactivity of 4 towards a number of different reagents including active methylene compounds as well as the use of 4 to synthesize fused heterocyclic systems is described.     

希土发光配合物研究──Ⅰ．希土与邻菲罗啉－N－氧化物及丙烯酸三元配合物的合成、表征和荧光性质

合成了邻菲罗啉－Ｎ－氧化物（Ｌ１）及丙烯酸（ＨＬ２）与部分希土的三元配合物［ＲＥ（Ｌ１）（Ｌ２）３］（ＲＥ＝Ｌａ－Ｎｄ．Ｓｍ－Ｔｂ）．通过元素分析、红外光谱、紫外光谱、摩尔电导、热分析对该系列配合物进行了表征．研究了Ｅｕ（Ⅲ）、Ｓｍ（Ⅲ）配合物的荧光性质，讨论了阴离子对Ｅｕ（Ⅲ）配合物荧光性质的影响．