2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成

详细研究了2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成方法。由苯基二硝基甲烷钾盐经羟甲基化，磺酰酯化和叠氮化得到目标化合物：3-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4b)，4-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4c)，m-二(2-叠氮基-1,1-二硝基乙基)苯(10)和p-二(2-叠氮基-1,1-二硝基乙基)苯(15)。     

Mass-spectrometric fragmentation of <Emphasis Type="Italic">N,N</Emphasis>-dimethyl-4-methoxy-6-polynitromethyl-1,3,5-triazin-2-amines

Mass-spectrometric fragmentation of N,N-dimethyl-4-methoxy-6-X-1,3,5-triazin-2-amine (X = fluorodinitromethyl, chlorodinitromethyl, bromodinitromethyl, trinitromethyl, 1,1-dinitroethyl, 2-hydroxy-1,1-dinitroethyl) under electron impact was studied. The stability of the molecular ion and the main fragmentation pathways are discussed.     

High-energy 4(10)-2-fluoro-2,2-dinitroethyl and 4(10)-2,2-dinitropropyl derivatives of polynitrohexaazaisowurtzitanes

Russian Chemical Bulletin - Methods for the syntheses of a series of high-energy 4(10)-2-fluoro-2,2-dinitroethyl and 4(10)-2,2-dinitroethyl derivatives of polynitrohexaazaisowurtzitanes were...     

Synthesis and thermochemical properties of some fluorine-containing formals

Fluorination of bis(2-fluoro-2,2-dinitroethyl) and bis(2,2,2-trinitroethyl) thionocarbonates by elemental fluorine gave bis(2-fluoro-2,2-dinitroethyl) and bis(2,2,2-trinitroethyl) difluoroformals. The reaction of 2,2,2-trinitroethyl nitrate with 2-fluoro-2,2-dinitroethyl chloromethyl ether gave 2-fluoro-2,2-dinitroethyl 2,2,2-trinitroethyl formal. The standard heats of combustion and formation of the synthesized formals were determined by combustion in a calorimetric bomb. Increments of substitution of the trinitromethyl group by the fluorodinitromethyl group and of the H atom by F in the methylene group for formals were calculated and recommended for rough calculations. It was shown that it is possible to evaluate Hf⁰ of the formals by the method of increments and group contributions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2513–2517, November, 1991.     

Synthetic utility of 3-(perfluoro-1,1-dimethylbutyl)prop-1-ene. Part VI. A free-radical addition of CCl4 and CBr4 and dehydrohalogenation of the adducts

Heating the title compound 1 in excess CCl₄ and in the presence of a free-radical initiator (t-butyl peroxide) at 120 °C afforded 1,1,1,3-tetrachloro-4-(perfluoro-1,1-dimethylbutyl)butane (2) as the main product together with considerable amounts of cyclic dimer, 1,4-bis(perfluoro-1,1-dimethylbutyl)cyclohexane (3). Reaction of 1 with CBr₄ at 120 °C gave 1,1,1,3-tetrabromo-4-(perfluoro-1,1-dimethylbutyl)butane (4) as the sole product while at 220 °C a mixture of 1,2-dibromo-3-(perfluoro-1,1-dimethylbutyl)propane (5) and 1,1-dibromo-4-(perfluoro-1,1-dimethylbutyl)buta-1,3-diene (6) was formed. Treatment of adducts 2 and 4 with methanolic potassium hydroxide at ambient temperature gave mixtures of 1,1,3-trihalo-4-(perfluoro-1,1-dimethylbutyl)but-1-enes (7) or (8) and 1,1-dihalo-4-(perfluoro-1,1-dimethylbutyl)buta-1,3-dienes (9) or (6) in ratios depending on the adduct to base ratio and on the reaction conditions. Using an excess of the base and reflux temperature, adduct 4 and diene 6 were converted into methyl 4-(perfluoro-1,1-dimethylbutyl)buten-3-oate (10).     

Diborane(4) compounds with bidentate diamino groups

The reaction between B(2)(NMe(2))(4) and 1,2-(NH(2))(2)-4-Bu(t)C(6)H(3) affords the diborane(4) compound 1,2-B(2){1,2-(NH)(2)-4-Bu(t)C(6)H(3)}(2) as the exclusive product whilst the reaction between rac-1,2-(NH(2))(2)C(6)H(10) and B(2)(NMe(2))(4) also affords only the 1,2-isomer, i.e. 1,2-B(2){1,2-(NH)(2)C(6)H(10)}(2), which is shown to be the more stable isomer by computational methods. The previously reported compounds 1,1-B(2){1,2-(NH)(2)C(6)H(4)}(2) and 1,2-B(2){1,2-(NH)(2)C(6)H(4)}(2) both react with four equivalents of Bu(n)Li to give what are presumed to be tetra-anions which react further with MeI, SnClMe(3) or SnClPh(3) to give the tetrasubstituted products 1,1-B(2){1,2-(NMe)(2)C(6)H(4)}(2), 1,1-B(2){1,2-(NSnMe(3))(2)C(6)H(4)}(2) and 1,2-B(2){1,2-(NSnPh(3))(2)C(6)H(4)}(2) respectively. The compound 1,1-B(2){1,8-(NH)(2)C(10)H(6)}(2) has also been prepared from the reaction between B(2)(NMe(2))(4) and 1,8-diaminonaphthalene. Lithiation and subsequent reaction with SnClMe(3), SnCl(2)Me(2) or SnCl(2)Ph(2) affords 1,1-B(2){1,8-(NSnMe(3))(2)C(10)H(6)}(2), 1,1-B(2){1,8-(N(2)-μ-SnMe(2))C(10)H(6)}(2) and 1,1-B(2){1,8-(N(2)-μ-SnPh(2))C(10)H(6)}(2) respectively. All new compounds have been characterised by X-ray crystallography.     

Synthesis, structure, and biological activity of ferrocenyl carbohydrate conjugates

Seven ferrocenyl carbohydrate conjugates were synthesized. Coupling reactions of monosaccharide derivatives with ferrocene carbonyl chloride produced {6-N-(methyl 2,3,4-tri-O-acetyl-6-amino-6-deoxy-alpha-D-glucopyranoside)}-1-ferrocene carboxamide (3), {1-O-(2,3,4,6-tetra-O-benzyl-D-glucopyranose)}-1-ferrocene carboxylate (4), and {6-O-(1,2,3,4-tetra-O-acetyl-beta-D-glucopyranose)}-1-ferrocene carboxylate (5). Similarly, 1,1'-bis(carbonyl chloride)ferrocene was coupled with the appropriate sugars to produce the disubstituted analogues bis{6-N-(methyl 2,3,4-tri-O-acetyl-6-amino-6-deoxy-alpha-D-glucopyranoside)}-1,1'-ferrocene carboxamide (8), bis{1-O-(2,3,4,6-tetra-O-benzyl-D-glucopyranose)}-1,1'-ferrocene carboxylate (9), and bis{6-O-(1,2,3,4-tetra-O-acetyl-beta-D-glucopyranose)}-1,1'-ferrocene carboxylate (10). {6-N-(Methyl-6-amino-6-deoxy-alpha-D-glucopyranoside)}-1-ferrocene carboxamide monohydrate (12) was synthesized via amide coupling of an activated ferrocenyl ester with the corresponding carbohydrate. All compounds were characterized by elemental analysis, 1H NMR spectroscopy, and mass spectrometry. X-ray crystallography confirmed the solid-state structure of three ferrocenyl carbohydrate conjugates: 2-N-(1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-D-glucopyranose)-1-ferrocene carboxamide (1), 1-S-(2,3,4,6-tetra-O-acetyl-1-deoxy-1-thio-D-glucopyranose)-1-ferrocene carboxylate (2), and 12. The above compounds, along with bis{2-N-(1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-D-glucopyranose)}-1,1'-ferrocene carboxamide (6), bis{1-S-(2,3,4,6-tetra-O-acetyl-1-deoxy-1-thio-D-glucopyranose)}-1,1'-ferrocene carboxylate (7), and 2-N-(2-amino-2-deoxy-D-glucopyranose)-1-ferrocene carboxamide (11) were examined for cytotoxicity in cell lines (L1210 and HTB-129) and for antimalarial activity in Plasmodium falciparum strains (D10, 3D7, and K1, a chloroquine-resistant strain). In general, the compounds were nontoxic in the human cell line tested (HTB-129), and compounds 4, 7, and 9 showed moderate antimalarial activity in one or more of the P. falciparum strains.     

Synthesis of annulated oligothiophenes

Reactions of 1,1-di(2-naphthyl)-2,2-dichloroethene and 1,1-di(2-benzothienyl)-2,2-dichloroethene with sulfur at 220–225 °C resulted in hitherto unknown oligothiophenes. Tetrathio[6]helicene was synthesized from 1,1-di(3-benzothienyl)-2,2-dichloroethene. Preparative pathway to helicene involving intramolecular ring closure of dithiol derived from 1,1-di-(3-benzothienyl)-2,2-dichloroethene was developed as an alternative to high temperature synthesis.     

Synthesis and structures of (R)-cyclopentadienyl-binaphthoxy titanium(IV) complexes and catalytic properties for olefin polymerization

Two new chiral pre-ligands, (R)-3,3'-bis(tetramethylcyclopentadienyl)-2,2'-bismethoxy-1,1'-bisnaphthalene (1) and (R)-3-tetramethylcyclopentadienyl-2,2'-bismethoxy-1,1'-bisnaphthalene (2), were synthesized by reaction of (R)-3,3'-dilithium-2,2'-bismethoxy-1,1'-bisnaphthalene with 2,3,4,5-tetramethyl-2-cyclopentenone at room temperature. Treatment of the pre-ligands 1 and 2 with butyllithium and Me(3)SiCl first, and subsequently with TiCl(4) (2 and 1 equiv for 1 and 2, respectively) afforded a binuclear complex (R)-3,3'-bis[(tetramethylcyclopentadienyl)trichlorotitanium]-2,2'-bismethoxy-1,1'-bisnaphthalene (3) and a mononuclear complex (R)-3-(tetramethylcyclopentadienyl)trichlorotitanium-2,2'-bismethoxy-1,1'-bisnaphthalene (4) in moderate yields. Complexes 3 and 4 were further converted into constrained geometry complexes (R)-1,1'-bis{2,2'-naphthoxy-3,3'-bis[(tetramethylcyclopentadienyl)dibromotitanium]} (5) and (R)-1-(2-naphthoxy)-1'-(2'-naphthol)-3-(tetramethylcyclopentadienyl)dibromotitanium (6) by treatment with BBr(3). The pre-ligands 1 and 2 were characterized by (1)H and (13)C NMR and high resolution mass spectroscopy (HRMS), and the new titanium complexes 3-6 were characterized by (1)H and (13)C NMR and elemental analyses. Molecular structures of 4, 5, and 6 were determined by single-crystal X-ray diffraction analysis. Complexes 4, 5, and 6 all have a pseudo-octahedral coordination environment and adopt a three-legged piano stool geometry around the titanium atom in their solid state structures. When activated with Al(i)Bu(3) and Ph(3)CB(C(6)F(5))(4), the chiral complexes 5 and 6 show moderate catalytic activities for propylene, 1-hexene, and 5-ethylidene-2-norbornene (ENB) polymerization and ethylene/1-hexene copolymerization. The polymers produced by the chiral 5/(i)Bu(3)Al/Ph(3)CB(C(6)F(5))(4) catalyst system from the 1-hexene, and ENB polymerization and ethylene/1-hexene copolymerization with high comonomer contents exhibit optical activity.     

Absolute configuration and predominant conformations of 1,1-dimethyl-2-phenylethyl phenyl sulfoxide

The absolute configuration of the (+)-1,1-dimethyl-2-phenylethyl phenyl sulfoxide is determined to be (R), using three different chiroptical spectroscopic methods, namely vibrational circular dichroism (VCD), electronic circular dichroism (ECD) and specific rotation. Four solution conformations are identified for 1,1-dimethyl-2-phenylethyl phenyl sulfoxide. In each of the methods used, experimental data for the enantiomers of 1,1-dimethyl-2-phenylethyl phenyl sulfoxide were measured in the solution phase and concomitant quantum mechanical calculations of corresponding properties were carried out using density functional theory with B3LYP functional and 6-31G* and 6-31+G basis sets. Additional VCD and ECD calculations were also undertaken with 6-311G(2d,2p) basis set. A comparison of theoretically predicted data with the corresponding experimental data has allowed us to elucidate the absolute configuration and predominant conformations of (+)-1,1-dimethyl-2-phenylethyl phenyl sulfoxide.     

手性联萘基-2,2'-联吡啶及其衍生物的合成及其在不对称合成中的应用

利用Kröhnke方法,以芳基乙酮为原料一锅法简洁地合成了6-芳基-6'-溴-2,2'-联吡啶2b~2d。 通过(R)-3-(4,4,5,5-四甲基-1,3,2-二噁唑硼烷基)-2,2'-乙氧基-1,1'-联萘((R)-1)与6-溴-2,2'-联吡啶及其衍生物2a~2d的Suzuki偶联, 合成了4种手性6-[3-((R)-2,2'-二乙氧基-1,1'-联萘)基]-2,2'-联吡啶(R)-3a~3d。 将配体(R)-3a~3d应用于苯乙酮的不对称氢转移反应中,配体(R)-3a给出92%的转化率和4%的对映体过量(ee)值。     

β-三氯锗基丙酸及β-三苯锗基丙酸与苯基溴化镁的反应

三氯锗基丙酸(1a)和三苯锗基丙酸(2a)与过量苯基溴化镁起反应时,这两个分子中的羧基表现出一些奇特性质。当1a和2a与不同浓度的苯基溴化镁起反应时,都能生成相应的酮(3a)和醇(4a)。在稀盐酸作用下,4a极易脱水生成1,1-二苯基-3-三苯锗基丙烯-1(5a)。当1a与苯基溴化镁起反应,然后再用稀盐酸处理也同样得到5a。5a的Ge-C键能被LiAlH~4高选择性地切断,生成三苯基锗烷(6a)和1,1-二苯基丙烯(6b)。     

Scope and limitations of the double [4+3]-cycloadditions of 2-oxyallyl cations to 2,2'-methylenedifuran and derivatives

The reactivity of various 2-oxyallyl cations toward 2,2'-methylenedifuran (1b), 2,2'-(hydroxymethyl)difuran (1c), 2,2'-(trimethylsilylmethylene)difuran (1d), and di(2-furyl)methanone (1e) has been explored. Difuryl derivatives 1c, 1d, and 1e refused to undergo formal double [4+3]-cycloadditions. Conditions have been found to convert 1b into meso-1,1'-methylenedi[(1R,1'S,5S,5'R)- (3) and (+/-)-1,1'-methylenedi[(1RS,1'SR,5SR,5'RS)-8-oxabicyclo[3.2.1]oct-6-en-3-one] (4) that do not require CF(3)CH(OH)CF(3) as solvent. High yields of meso-1,1'-methylenedi[(1R,1'S,2S,2'R,4R,4'S,5S,5'R)- (5) and (+/-)-1,1'-methylenedi[(1RS,1'RS,2SR,2'SR,4RS,4'RS,5SR,5'SR)-2,4-dimethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one] (6) have been obtained when 1b was reacted with 2,4-dibromopentan-3-one (7h) and NaI/Cu.     

Prenylindoles from Tanzanian Monodora and Isolona species

6-(3-Methyl-but-2-enyl)-1,3-dihydro-indol-2-one, annonidine F [3-[6-(3-methyl-but-2-enyl)-1H-indolyl]-6-(3-methyl-but-2-enyl)-1H-indole], 1H-indole-5-carbaldehyde, 6-(3-methyl-2-butenyl)-1H-indole, 6-(3-methyl-buta-1,3-dienyl)-1H-indole, 6-(4-oxo-but-2-enyl)-1H-indole and 3-geranylindole were isolated from Monodora angolensis (Annonaceae) while 3-(1,1-dimethyl-but-2-enyl)-5-(3-methyl-but-2-enyl)-1H-indole (caulidine A), 4-[3-(1,1-dimethyl-but-2-enyl)-1H-indol-5-yl]-but-3-en-2-one (caulidine B), 5-(3-methyl-2-butenyl)-1H-indole and 5-(3-methylbuta-1,3-dienyl)-1H-indole were obtained from Isolona cauliflora (Annonaceae); structural determination by spectroscopic analysis. Some of the prenylindoles had antifungal and antimalarial activities.     

1,1-Dimethyl-1-(trialkoxysilylmethyl)hydrazinium and 1,1-Dimethyl-1-(silatranylmethyl)hydrazinium Halides

Formerly unknown 1,1-dimethyl-1-(trialkoxysilylmethyl)- and 1,1-dimethyl-1-(silatranylmethyl)hydrazinium halides were prepared by reaction of 1,1-dimethylhydrazine with (halomethyl)trialkoxysilanes XCH₂Si(OR)₃ (X = Cl, I; R=Me, Et) and 1-(halomethyl)silatranes XCH₂Si(OCH₂CH₂)₃N (X = Cl, Br). 1,1-Dimethyl-1-(silatranylmethyl)hydrazinium chloride and iodide were also obtained by transetherification of corresponding 1,1-dimethyl-1-(trimethoxysilylmethyl)hydrazinium halides with tris(2-hydroxyethyl)amine.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 915–919.Original Russian Text Copyright © 2005 by Sorokin, Voronkov.     

Synthesis and structure of o-bis(2-fluoro-2,2-dinitroethyl)-nitromethyl ester of 2′-fluoro-2′, 2′-dinitroethyl-2″-fluoro-2″-nitroethylenecarboxime

Conclusions The product of conversion of O-bis(2-fluoro-2,2-dinitroethyl)nitromethylbis(2-fluoro-2,2-dinitroethyl)carboxime in methanol or ether is O-bis(2-fluoro-2,2-dinitroethyl)nitromethyl-2-fluoro-2,2-dinitroethyl-2'-fluoro-2-nitroethylenecarboxinie, the structure of which has been established by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2019–2021, September, 1987.     

Kinetics of radical heterolysis reactions forming alkene radical cations

Rate constants for heterolytic fragmentation of beta-(ester)alkyl radicals were determined by a combination of direct laser flash photolysis studies and indirect kinetic studies. The 1,1-dimethyl-2-mesyloxyhexyl radical (4a) fragments in acetonitrile at ambient temperature with a rate constant of k(het) > 5 x 10(9) s(-1) to give the radical cation from 2-methyl-2-heptene (6), which reacts with acetonitrile with a pseudo-first-order rate constant of k = 1 x 10(6) s(-1) and is trapped by methanol in acetonitrile in a reversible reaction. The 1,1-dimethyl-2-(diphenylphosphatoxy)hexyl radical (4b) heterolyzes in acetonitrile to give radical cation 6 in an ion pair with a rate constant of k(het) = 4 x 10(6) s(-1), and the ion pair collapses with a rate constant of k < or = 1 x 10(9) s(-1). Rate constants for heterolysis of the 1,1-dimethyl-2-(2,2-diphenylcyclopropyl)-2-(diphenylphosphatoxy)ethyl radical (5a) and the 1,1-dimethyl-2-(2,2-diphenylcyclopropyl)-2-(trifluoroacetoxy)ethyl radical (5b) were measured in various solvents, and an Arrhenius function for reaction of 5a in THF was determined (log k = 11.16-5.39/2.3RT in kcal/mol). The cyclopropyl reporter group imparts a 35-fold acceleration in the rate of heterolysis of 5a in comparison to 4b. The combined results were used to generate a predictive scale for heterolysis reactions of alkyl radicals containing beta-mesyloxy, beta-diphenylphosphatoxy, and beta-trifluoroacetoxy groups as a function of solvent polarity as determined on the E(T)(30) solvent polarity scale.     

Dinuclear and octanuclear Mn(II) complexes with mu2-C, mu2-N(pyrrolide), and mu-eta1:eta5-(pyrrolide) bridges: a structural and magnetic study

Reaction of the dinuclear [(CH2SiMe3)(mu-CH2SiMe3)Mn(THF)]2 (1) with an equivalent amount of 1,1-dipyrrolylcyclohexane afforded two compounds depending on the solvent employed. Reaction carried out in THF afforded the dinuclear ([1,1-(mu-C4H3N)(C4H3N)C6H10]Mn(THF)2)2.2(THF) (2) while reaction in toluene yielded the octanuclear and cyclic cluster ([1,1-(mu,eta1:eta5-C4H3N)2C6H10]Mn)8.4(toluene) (3). The magnetism in all three cases is dominated by intramolecular antiferromagnetic exchange with strong coupling in 1 (J=-85 cm(-1)), and in 2 (J=-23.2 cm(-1)), whereas substantially weaker coupling through the sigma/pi-bonded dipyrrolide bridges (J=-3.3 cm(-1)) was observed within the cyclic and octameric 3.     

Ru(eta3-2-C3H4Me)(CO)(dppf)][SbF6]: a mononuclear 16e - ruthenium(II) catalyst for propargylic substitution and isomerization of HC[triple bond]CCPh2(OH)

The 16e(-) derivative [Ru(eta3-2-C3H4Me)(CO)(dppf)][SbF6] catalyzes: (i) the propargylic substitution reaction of 1,1-diphenyl-2-propyn-1-ol with alcohols to produce propargylic ethers, and (ii) the formal isomerization of 1,1-diphenyl-2-propyn-1-ol into 3,3-diphenyl-2-propenal.     

Polymeric mesoions, 3. Synthesis of polymeric mesoionic 1,3-diazinium-olates via polymer analogous modification of a polythiourea from m-phenylenediamine and p-phenylene diisothiocyanate

Mesoionic poly(1,1′-(1,3-phenylene)-3,3′-(1,4-phenylene)-bis(5-decyl-2-decylthio-4,6-dioxo-1,3-diazine)) ( 6 ) was prepared by cyclisation of the isothiourea component of poly(1,1′-(1,3-phenylene)-3,3′-(1,4-phenylene)-bis(2-decylisothiourea)) ( 4 ) with decylmalonic acid (5) by use of dicyclohexylcarbodiimide (DCC). Polymer 4 was obtained by polymer analogous alkylation of poly(1,1′-(1,3-phenylene)-3,3′-(1,4-phenylene)-bisthiourea) ( 3 ). For comparison of spectroscopic data, 5-butyl-2-propylthio-4,6-dioxo-1,3-diphenyl-1,3-diazine ( 9 ) was synthesized as low molecular weight model compound.