大取代茂钛,锆,铪,铁化合物的合成与结构分析

通过芳基锂与6,6-二烷基富烯发生环外双键的加成反应,形成的取代环戊二烯基阴离子与FeCl_2、MCl_4(M=Ti,Zr,Hf)及(CpTiCl_2)_2络合,合成出16个含或不含手性碳取代茂金属化合物。对其~1H NMR光谱进行了研究。     

Syntheses and Structures of Sil abridged Hafnocene Dichlorides

The present paper covers three silabridged hafnocene dichlorides(1, 2 and 3) prepared by sequential reactions of α, ω-dichloropermethyl polysilane with cyclopentadienyl sodium, n-butyl lithium and hafnium tetrachloride. Their structures were characterized by elemental analyses, UV, 1H(13C) NMR and MS. Furthermore the crystal and molecular structures of 1 and 2 were determined by X-ray diffraction method. The crystal of 1 is monoclinic, space group C2/c with a=1. 3401(4), b=0. 9977(3), c = 1. 0922(4) nm; β=94. 07(1)° V=3. 6342 nm3, Z = 2, Dc = 2.155 g·cm-3. The final deviation factor R = 0. 064. The crystal of 2 is monoclinic, space group P21/c with a=0.0847(1), b=1.5181(1), c=2.9824(2) nm; β= 94. 07(1)°? V=3.634 nm3; Dc= l. 805 g·cm-3. The final deviation factor R = 0. 033. The relationship between the silabridged structure and spectral properties is also discussed.     

大位阻取代环戊二烯基钛,锆化合物的合成及光谱性质

通过１－环己烯基锂与６，６－二烷基富烯发生环外双键的加成反应形成大位阻取代茂锂盐；后者再与ＭＣｌ４（Ｍ＝Ｔｉ，Ｚｒ）反应，合成了７个含或不含手性碳的大位阻取代茂金属有机化合物，并研究了它们的１ＨＮＭＲ、ＥＩＭＳ和ＩＲ．     

新型大位阻取代茂钛,锆化合物的合成及其谱学性质

通过１－环庚烯基锂与６，６－二烷基富烯发生环外双键的加成反应形成的大取代茂锂试剂与ＭＣｌ４（Ｍ＝Ｔｉ，Ｚｒ）反应，合成了１２个含或不含手性碳的大位阻取代茂金属有机化合物，并研究了它们的１ＨＮＭＲ，ＥＩＭＳ和ＩＲ．     

Reactions of Carbon Monosulfide with Geminal Disulfenyl Dichlorides

Unlike vicinal disulfenyl dichlorides whose carbon monosulfide diinsertion products readily cyclize with loss of thiophosgene, geminal disulfenyl dichlorides diinsert carbon monosulfide to form stable gem-bis(chlorodithioformates).     

Reactions of Late First-Row Transition Metal (Fe-Zn) Dichlorides with a PGeP Pincer Germylene

The reactivity of the PGeP germylene 2,2’-bis(di-isopropylphosphanylmethyl)-5,5’-dimethyldipyrromethane-1,1’-diylgermanium(II), Ge(pyrmPiPr₂)₂CMe₂, with late first-row transition metal (Fe-Zn) dichlorides has been investigated. All reactions led to PGeP pincer chloridogermyl complexes. The reactions with FeCl₂ and CoCl₂ afforded paramagnetic square planar complexes of formula [MCl{κ³P,Ge,P-GeCl(pyrmPiPr₂)₂CMe₂}] (M=Fe, Co). While the iron complex maintained an intermediate spin state (S¹; μ_eff=3.0 μ_B) over the temperature range 50–380 K, the effective magnetic moment of the cobalt complex varied linearly with temperature from 1.9 μ_B at 10 K to 3.6 μ_B at 380 K, indicating a spin crossover behavior that involves S^1/2 (predominant at T<180 K) and S^3/2 (predominant at T>200 K) species. Both cobalt(II) species were detected by electron paramagnetic resonance at T<20 K. The reaction of Ge(pyrmPiPr₂)₂CMe₂ with [NiCl₂(dme)] (dme=dimethoxyethane) gave a square planar nickel(II) complex, [NiCl{κ³P,Ge,P-GeCl(pyrmPiPr₂)₂CMe₂}], whereas the reaction with CuCl₂ involved a redox process that rendered a mixture of the germanium(IV) compound GeCl₂(pyrmPiPr₂)₂CMe₂ and a binuclear copper(I) complex, [Cu₂{μ-κ³P,Ge,P-GeCl(pyrmPiPr₂)₂CMe₂}₂], whose metal atoms are in tetrahedral environments. The reaction of the germylene with ZnCl₂ led to the tetrahedral derivative [ZnCl{κ³P,Ge,P-GeCl(pyrmPiPr₂)₂CMe₂}].     

Reactions of benzonitrile oxide with fluoroketones and their imines

Conclusions Fluoroketones (I) and their imines (III) enter into a noncatalyzed addition reaction with benzonitrile oxide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1916–1918, August, 1968.     

Reactions of zinc oxide with molten diacids and their anhydrides

The reactions of some organic diacids and their anhydrides with powdered ZnO were studied. The products are salts of approximately 1:1 mole composition. Their thermal stability is rather high, in comparison with their organic components. They are insoluble and usually cannot be recrystallized. It is suggested that anhydrides react with ZnO via their parent diacids, resulting initially in a half salt, as an intermediate product, followed by the formation of the normal salt.     

Reactions of pyrimidinophanes and their acyclic analogs with electron-deficient substrates

Acyclic and macrocyclic compounds having different numbers of pyrimidine fragments and nitrogen atoms in the polymethylene bridges or in substituents at the pyrimidine rings reacted with 2,3,5,6-tetrachloro-1,4-benzoquinone and 1,4-benzoquinone according to the charge transfer scheme to give products with an ionic structure. The reaction was accompanied by protonation of nitrogen atoms in the polymethylene bridges or in substiuents at the pyrimidine rings and reduction of 2,3,5,6-tetrachloro-1,4-benzoquinone or 1,4-benzoquinone to 2,3,5,6-tetrachlorobenzene-1,4-diol or benzene-1,4-diol, respectively. The isolated products are dielectrics.     

Reactions of polyfluorocarbonyl compounds and their trifluoroacetylimines with fused heterocycles

C-Hydroxy- andC-aminoalkylation of iminodibenzyl, iminostilbene, phenoxazine, and phenothiazine with hexafluoroacetone, methyl trifluoropyruvate, and their trifluoroacetylimines were investigated. The substitution occurred at one or severalpara- andortho-positions to the N atom of the heterocycles. In the case of methyl trifluoropyruvate and its derivative the substitution in theortho-position was accompanied by the formation of lactams.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1239–1242, May, 1996.     

Reactions of Quinazoline Alkaloids and their Derivatives with Electrophilic Reagents

Nitration of deoxypeganine (DOP), deoxyvasicinone (DOV), 2,3-tetramethylene-, 2,3-pentamethylene-, and 3,4-dihydroquinazol-4-ones and their 1,2-dihydro derivatives was studied. It was shown that the reaction pathway changed depending on the presence of a carbonyl on C-4 and an N=C bond in these compounds. Only the H atom on C-6 was subject to nitration if both functional groups were present, for example DOV and its homologs. Substitution of the H atom of either the 6-position (DOP, 1,2-dihydro-DOV, and their homologs) or the 6- and 8-positions simultaneously (DOP and its homologs) was enhanced if one of these functional groups was missing depending on the substrate:nitrating agent ratio. The bromination and nitration reactions of 1,2-dihydro-DOV and its analogs in a 1:2 ratio were accompanied by oxidation of the N¹H-CH bond with formation of 6,8-dibromo- and 6,8-nitro-DOV and their homologs. The difference in the behavior of these compounds was due to the different nucleophilicity of the benzene rings in them. The reaction of 1,2-dihydro-DOV and its homologs with isocyanates and p-nitro- and p-methylbenzoic acid chlorides was studied. 6-Nitro- and 6,8-dinitro-DOP and 6,8-dibromo- and 6,8-dinitro-DOV and their homologs and 6-bromo- and 6-nitro-1,2,3,4-tetrahydro-2,3-polymethylenequinazol-4-ones and their 1-alkyl(aryl)-carbamoyl and p-nitro(methyl)-benzoyl derivatives were synthesized. The molecular structures of 1-ethyl-and 1-(o-chlorophenyl)-carbamoyl-1,2-dihydrodeoxyvasicinones and 6,8-dinitro-2,3pentamethylene-3,4-dihydroquinazol-4-one were established. UDC 547.944/945 547.856.1 Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 387-393, July-August, 2008. Original article submitted May 5, 2008.     

Synthesis and Structure of an Extremely Air‐Stable Binuclear Hafnocene Perfluorooctanesulfonate Complex and Its Use in Lewis Acid‐Catalyzed Reactions

Stable complexes : An extremely air‐stable μ²‐hydroxy‐bridged binuclear hafonocene perfluorooctanesulfoante complex shows high catalytic efficiency in Lewis acid‐catalyzed reactions, such as esterification, Friedel–Crafts acylation, the Mukaiyama aldol reation, and the allylation of aldehyde (see scheme).

     

Reactions of aromatic aldehydes and their acetals with phosphorous acid esters

Russian Journal of General Chemistry -     

Reactions of Isocyanide Dihalides and their Derivatives

The readily obtainable isocyanide dichlorides can be used as starting materials for the preparation of many types of substances. Exchange reactions yield numerous derivatives of formic and carbonic acids, while heterocyclic products have been obtained by reaction with bifunctional partners. The present article deals not only with reactions that are known from the literature but also with the author's own work, some of which has not been published before.     

Reactions of N-substituted diazoles and their halo derivatives with naphthyllithium and naphthylsodium

1-Methylimidazole and halo derivatives of some 1-substituted imidazoles and pyrazoles react with naphthyllithium(sodium) to give organolithium(sodium) compounds. 1-Benzyl-3, 5-dimethylpyrazole undergoes debenzylation on reaction with naphthyllithium.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 392–395, March, 1975.     

混合二烃基二氯化锡与水杨醛缩苯胺类Schiff碱1∶1配合物的合成和表征

由混合二烃基二氯化锡（ＲＲ＇ＳｎＣｌ＿２）与水杨醛缩苯胺类Ｓｃｈｉｆｆ碱（２－ＨＯＣ＿６Ｈ＿４ＣＨ＝ＮＡｒ）反应，合成了１４种新的有机锡配合物。经元素分析、ＩＲ、ＮＭＲ和ＴＧ－ＤＳＣ测定，确定配合物的组成是有机锡与Ｓｃｈｉｆｆ碱的１：１配合物，配体以酚羟基氧原子与锡原子配位，摩尔电导率测定表明配合物均为非电解质。     

Reactions of α-trifluoromethyl-β-chloroethylsulfenyl chloride with phenols and their derivatives

In the absence of a catalyst, -trifluoromethyl--chloroethylsulfenyl chloride reacts electrophilically with ortho-para-substituted phenols bearing substituents of the first type. The reaction conditions are determined by the C-nucleophilic properties of the phenol, and the selectivity by solvent effects. These -trifluoromethyl--chloroethylthiolated phenols are shown to be highly prone to dehydrochlorination.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 832–837, April, 1990.