REACTION OF ORGANOCADMIUM REAGENTS WITH SULFONYL HALIDES III. ACTION OF ALKANESULFONYL CHLORIDES ON SELECTED DIARYLCADMIUM COMPOUNDS

Abstract

The reaction of methane- and ethanesulfonyl chloride with selected diarylcadmium compounds was investigated. In contrast with arenesulfonyl chlorides which react with diarylcadmium to give sulfones in appreciable yields, ethanesulfonyl chloride did not yield sulfones. Methane-sulfonyl chloride gave sulfones in very poor yields. The major products were haloarenes, alkane-sulfinic acids and biaryls.

Cross-over experiments revealed that the formation of biaryls involve an inter-not intra-molecular reaction (cf. eq. 4).     

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     

稀土氯化物催化作用下纳米氢化钠对芳基卤化物的还原脱卤

稀土氯化物催化作用下纳米氢化钠对芳基卤化物的还原脱卤＊张源魁廖世健＊＊徐筠余道容（中国科学院大连化学物理研究所，大连１１６０２３）沈琪（苏州大学化学化工学院，苏州２１５００６）关键词催化还原脱卤，稀土氯化物，氢化钠，双金属协同效应有机卤化物的还原脱卤...     

THE REACTIONS OF N3P3CL6 AND RELATED COMPOUNDS WITH DIFUNCTIONAL REAGENTS. COMPARISONS AND CONTRASTS

Abstract

The reactions of N₃P₃Cl₆ with a variety of difunctional reagents are discussed. NMR spectroscopic and X-ray crystallographic investigations are presented.     

THE REACTIONS BETWEEN TRIMETHOSILYL METHYL COMPOUNDS AND ELECTROPHILIC REAGENTS, WITH A DISCUSSION ON THE CONCEPT OF "SILICONIUM ION"

The reactions between trimethosilyl methyl compounds [(CH_3)_3SiCH_2X] and various typical electrophilic reagents have been studied. Unlike neopentyl compounds, the silicon analogues all gave "normal" products and no molecular rearrangement occurred. The chief results are tabulated as follows:Based on the forgoing results, the authors discussed the so-called "siliconium ion" mechanism and pointed out that "siliconium ion" is only a formal analogue of "carbonium ion". Up to present, there is no sufficient and reliable experimental basis in supporting the possibility of its existence.     

REACTIONS OF 1,3-DIOXACYCLANES WITH SULPHURY COMPOUNDS

Abstract

Saturated 1,3-dioxacyclanes under acid catalysis conditions react with thiods forming thioacetals and glycols. The effect of the type of catalysts, structure of reagents and regime parameters on the direaction and selectivity of the process was studies.     

REACTIONS OF THE SUBSTITUTED THIOUREAS WITH PLATINUM COMPOUNDS

Abstract

Thiourea and its derivatives easily form the complexes with compounds of Cu^II, Fe^III, Pt^IV etc. By the formation of complexes as a rule redoxprocess proceeds to give an appropriate thiourea disulphide. It has been shown, that redoxprocess goes on prejudice on the derivatives of thiourea in that case when the thion-thiol tautomerism is possible.     

REACTIONS OF PHOSPHORUS MONOTHIO ACIDS WITH ALIPHATIC DIAZO COMPOUNDS

Abstract

Reactions of phosphorus monothio acids with diazomethane, diazoacetone, diphenyldiazomethane, and diazofluorene have been studied. The ratio of the yields of the S- and O-derivatives Q_S/Q_O has been found to be dependent on three factors: i) the nature of substituents at phosphorus - with electron-donor substituents raising the O-derivative yield and the quantity log (Q_S/Q_O) varying as εσ of the substituents; (ii) stability of alkyldiazonium and carbocation - with Q_O increasing with the carbocation stability; and (iii) polarity of the medium - the O-derivative yield rises with dielectric permeability of the medium and Q_S/Q_O has been found to be a linear function of 1/D. The most probable mechanism has been established as proton transfer from the acid to the diazocompound followed be formation of the S-derivative and the O-derivative. The former results from an S_N2 reaction of the alkyldiazonium cation with the thiol-thione anion within the ion pair. The O-derivative arises from the thiol-thion anion and the carbocation; the latter resulting from decomposition of the alkyldiazonium cation within the ion pair.     

SOME INTERESTING REACTIONS OF AN N－BROMOMETHYL QUATERNARY AMMONIUM SALT WITH HALOPHILIC REAGENTS

ＳＯＭＥＩＮＴＥＲＥＳＴＩＮＧＲＥＡＣＴＩＯＮＳＯＦＡＮＮ－ＢＲＯＭＯＭＥＴＨＹＬＱＵＡＴＥＲＮＡＲＹＡＭＭＯＮＩＵＭＳＡＬＴＷＩＴＨＨＡＬＯＰＨＩＬＩＣＲＥＡＧＥＮＴＳ￥ＧｕｏＦｅｎｇＨＵＡＮＧａｎｄＸｉａｏＴｉａｎＬＩＡＮＧ（Ｉｎｓｔｉｔｕｔｅｏ...     

OCCURRENCE OF LIGAND COUPLING IN THE REACTIONS OF VARIOUS SULFOXIDES WITH GRIGNARD REAGENTS

Abstract

Ligand coupling reactions take place not only between benzyl and 2-pyridyl groups and two 2-pyridyl groups in the treatment of benzyl, alkyl and aryl 2-pyridyl sulfoxides with Grignard reagents, but also between such groups as p-benzenesulfonylphenyl, 4-pyridyl, 2-quinolyl and 2-pyrimidyl, and the benzyl group. There are cases in which ligand exchange precedes ligand coupling, especially with 2-heteroaryl groups. In addition, even some alkyl groups were found to couple with the 2-pyridyl group. The ease of coupling seems to be associated with the electronegativity of the coupling carbon atom of the ligand, when one compares the ¹³C NMR chemical shifts.     

REACTIONS OF 1,3-OXAZOLIDINE-2-THIONE WITH ZINC(II), CADMIUM(II) AND MERCURY(II) HALIDES

Abstract

The reactivity of 1,3-oxazolidine-2-thione towards II B group metals is considered. Cadmium halides, mercury chloride and bromide react to give coordination compounds, whose stereochemistry is tentatively assigned by their i.r. spectra.

Otherwise zinc halides and mercury iodide induce a ring opening.     

PHOTOINDUCED S_(RN)1 REACTIONS OF ARYL HALIDES WITH CARBAZOLYL NITROGEN ANION

The photoinduced reactions of aryl halides with carbazolyl nitrogen anion,in dimethyl sulfoxide,yield the corresponding N-arylated products.These reactions are suggested in terms of the S_RNl mechaism of nucleophilic substitution.     

两种含氟三氮烯显色剂FNDAA与FFDAA的合成及其与镉显色反应的研究

报道了两种新显色剂 4 氟 4′ 硝基苯基重氮氨基偶氮苯 (FNDAA)和 4 氟 4′ 氟苯基重氮氨基偶氮苯 (FFDAA)的合成、性质及其与Cd(Ⅱ )的显色反应。在弱碱性介质中 ,TritonX 10 0存在下两种试剂均与Cd(Ⅱ )形成络合比为 3∶1的橙红色络合物。对FNDAA ,ε4 92 =1.5 4× 10 5 L·mol- 1·cm- 1,对FFDAA ,ε4 90 =1.17× 10 5 L·mol- 1·cm- 1。镉量分别在 0 15和 0 2 5 μg/2 5ml范围内遵守比耳定律。FNDAA有较好的选择性 ,用于测定环境水标样中镉含量 ,结果满意。     

THE REACTIONS OF N3P3CL6 WITH POLYFUNCTIONAL REAGENTS

Abstract

The reactions of N₃P₃Cl₆ with polyfunctional reagents, such as glycerol, are reported. NMR spectroscopic and X-ray crystallographic studies will be presented.     

铁系元素冠醚配合物的研究--Ⅰ.铁系氯化物与4''-硝基-苯并15-冠-5配合物的合成和性质

本文报导铁系氯化物,FeCl_3、CoCl_2和NiCl_2(均为水合物)与4—硝基—苯并—15—冠—5(L)固态配合物的合成和性质。 合成的FeCl_3·L·2H_2O是一种新的冠醚配合物。经元素分析、红外光谱,紫外光谱、热谱及X—射线衍射分析证明是1:1型,非溶剂化、含有两个结晶水的固态配合物,并且研究了其他有关性质。 在同样条件下,CoCl_2和NiCl_2皆不与4′—硝基—苯并—15—冠—5配体生成配合物。从中可望得到铁系元素分离的新方法和新途径。     

PREPARATION AND REACTIONS OF METHYLTHIOMETHYL-SUBSTITUTED PHOSPHORUS HALIDES1

Abstract

Methylthiomethylphosphonous dichloride, MeSCH₂PCI₂ (1), is synthezised by the reaction of MeSCH₂SnBuⁿ, with phosphorus trichloride. Substitution reactions to give MeSCH₂PX₂ (X=NEt₂, OPrⁱ, F, Ph) are described. The phosphorus(III) compounds are readily converted to the corresponding phosphonyl and thiophosphonyl derivatives, MeSCH₂P(Z)X₂ (Z=O, S), and the phosphorane, MeSCH₂PF₄, respectively. Chlorination of the methylene group to give compounds of the type MeSCHCIP(O)X₂ and MeSCCI₂P(O)X₂ is reported.     

超声辐射下某些含官能团化合物与二氯卡宾的反应

超声辐射在有机反应中的应用日趋广泛。我们曾报道了超声辐射与相转移催化相结合产生二氯卡宾和二溴卡宾的方法及其与烯烃加成反应的结果。该法比单纯使用相转移催化剂或超声辐射更为可取。本文进一步将它用于二氯卡宾与某些含官能团化合物的反应,考察超声辐射的影响。反应是在固-液两相条件下进行的,即以粉末状氢氧化钠为碱,氯仿过量兼作溶剂。结果表明,超声辐射对各类化合物反应的影响有相当明显的差异。     

NONCONVENTIONAL FRIEDEL-CRAFTS CHEMISTRY II. ON THE CATALYTIC ACTION OF TRIFLIC ACID AND ALUMINIUM CHLORIDE ON SELECTED ARYL THIOESTERS

Abstract

The catalytic action of triflic acid and/or aluminium chloride on seven selected aryl thioesters (1-7) gave in all cases aryl thiols, diaryl sulfides, diaryl disulfide, and thianthrene derivatives in addition to the corresponding aryl carboxylic acids. Thioester 5 gave thiochromanone derivatives in good yield under the same conditions. Plausible mechanisms were suggested to rationalize the obtained results.