Cycloaddition of C60 fullerene to stable 2-RSO2-benzonitrile oxides

The interaction of stable 2-RSO₂-benzonitrile oxides1a−c (R=Ph, Bu^t, or PhMeN) with C₆₀ fullerene proceeds at the double (6,6)-bond of fullerene as the [3+2] cycloaddition to form the corresponding isoxazolines2a−c. The molecular structure of compound2b was established by X-ray structural analysis. The interaction of C₆₀ fullerene with 2-(5-methyl-4-nitrothiophene)carbonitrile sulfide, which was obtained by thermolysis of 5-(5′-methyl-4′-nitro-2′-thienyl)1,3,4-oxathiazol-2-one, affords only unstable products. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 118–126, January, 1997.     

取代吡唑-5-酰基杂环衍生物的合成、结构与生物活性

为了寻求新的含吡唑双杂环先导化合物. 用4-取代-1-甲基-3-乙基-5-吡唑甲酰氯与2-噻唑烷酮、2-噻唑硫酮、2-噁唑烷酮等含氮杂环反应得到了12个含吡唑环的双杂环化合物. 化合物结构用IR, ¹H NMR, MS和元素分析进行了表征. 并用X射线单晶衍射法测定了化合物3-(1-甲基-3-乙基-4-硝基-5-吡唑甲酰基)-噁唑烷-2-酮(3k)的晶体结构. 晶体为单斜晶系, P2₁/n (#14)空间群, a＝1.52175(3) nm, b＝0.52970(1) nm, c＝1.58185(3) nm, β＝104.893(4), V＝1.2323(4) nm³, Z＝4, D_c＝1.45 g/cm³, F(000)＝560.00, R₁＝0.064, wR₂＝0.193. 初步生物活性实验结果表明, 在25 mg/L浓度下, 3-(1-甲基-3-乙基-4-硝基-5-吡唑甲酰基)-噻唑烷-2-酮(3c), 3-(1-甲基-3-乙基-4-硝基-5-吡唑甲酰基)-噻唑烷-2-硫酮(3g)对水稻稻瘟病菌(Pyricularia oryzae)的抑制活性达到40%. 在500 mg/L浓度下, 3-(1-甲基-3-乙基-4-溴-5-吡唑甲酰基)-噻唑烷-2-酮(3d), 3-(1-甲基-3-乙基-4-溴-5-吡唑甲酰基)-噁唑烷-2-酮(3l)对稻黑尾叶蝉(Nephotettix cinc-ticeps)的抑制活性达到53.37%.     

Stereochemie von Metallocenen, 43. Mitt.: Torsionsisomere Biphenyl-tricarbonylchrom-Komplexe: Darstellung,Konformationsanalyse und Kinetik der Interkonversion

Complexation of methyl 3-nitro-2-(o-tolyl)-benzoate (2, ano-trisubstituted biphenyl) with hexacarbonyl chromium gave the isomeric Cr(CO)₃ complexes3 and4 both existing as two torsional isomersa andb, as seen by nmr. For the main product3 the preferred conformations of the two torsional isomersa andb were deduced by the lanthanide induced shift (LIS) technique. The activation energy for the interconversion process could be determined from kinetic measurements and especially from¹H-nmr coalescence temperature of the methylsignals. The barrier of 91±1.5 kJ/mol (21.7±0.3 kcal/mol) in3 reflects the interaction of theo-H-atom of the benzene ring passing the Cr(CO)₃ moiety of the benchrotrene ring during the interconversion.A partial optical resolution of3 was achieved by asymmetric reduction with a chiral lithium-aluminium hydride yielding (+)-3 with [] _D ²⁰ +30° (benzene) and the levorotatory alcohol (–)-7.

42. Mitt.:K. Schlögl undR. Schölm, Mh. Chem.109, 1227 (1978).     

Generation of diazo-2-methylenecyclopropane and its 1,3-dipolar cycloaddition to acrylates

N-(2-Methylenecyclopropyl)-N-nitrosourea (2) was synthesized for the first time (yield 70%) and its decomposition induced by bases was studied. In particular, treatment with MeONa/MeOH at-30°C in the presence of methyl methacrylate gives the corresponding I-pyrazoline stereoisomers, the products of [3+2]-cycloaddition of diazo-2-methylene-cyclopropane (1) generatedin situ. Decomposition of2 on treatment with K₂CO₃ at 0–5°C in the presence of acrylonitrile also proceeds as [3+2]-cycloaddition: however, the expected 2-pyrazoline easily isomerizes into 5(3)-isopropenyl-3(5)-cyanopyrazole. Buta1,2,3-triene is the main product of base-induced decomosition of2 in the absence of unsaturated substrates. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1210–1214, July, 2000.     

3,1-苯并噁嗪化合物的合成及晶体结构

报道了一种用5-硝基-2-胺基苯甲腈为原料, 在二氯化锌催化下与环酮反应环化合成3,1-苯并噁嗪类化合物的新方法, 并用此方法合成了6-硝基-1,2-二氢-2,2-(1,5-亚戊基)-4-亚胺-4H-3,1-苯并噁嗪(4a). 产物经元素分析、红外光谱、核磁共振氢谱和碳谱进行了表征, 用X射线单晶衍射法测定了其晶体结构. 晶体属单斜晶系, P2₁/c空间群, a＝0.66339(13) nm, b＝2.5329(5) nm, c＝0.73756(15) nm, β＝91.85(3)°, V＝1.2387(4) nm³, Z＝4, D_c＝1.401 g/cm³, F(000)＝552, µ＝0.102 mm^－1, R＝0.0994, wR＝0.3001.     

Electrochemical oxidative ring opening of 1-methylcyclobutanol

The manganese(III) acetate-mediated electrooxidative ring opening of 1-methylcyclobutanol (1) in acetic acid affords pentane-2-one (2) as the major product. The reaction of 1-methylcyclobutanol with Mn(OAc)₃-LiCl gives 5-chloropentane-2-one (4.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1306–1307, May, 1996     

Synthesis and reactivity of furazanyl- and furoxanyldiazonium salts

Diazotization of aminofurazans (1) and 4-aminofuroxans (2) with nitrosylsulfuric acid in a mixture of conc. H₂SO₄ and H₃PO₄ has been studied and offered as a general method for preparing furazanyl- (3) and furoxanyldiazonium (4) salts. It has been shown that reactions with the retention of the N-N-group (azo coupling, formation of triazenes and azides) are typical of salts3 and4, while elimination of the N₂ molecule (Sandmeyer reaction, hydrolysis, reduction) is not typical.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1949–1953, November, 1993.     

Hydrothermal synthesis,crystal structure and fluorescence of a cyclic dimer copper compound constructed by 2-nitrobenzenedicarboxylate

The reaction of 2-nitro-1,4-benzenedicarboxylic acid (H₂nbdc) and 2,2′-bipyridine (2,2′-bipy) with CuCl₂ under hydrothermal conditions gives rise to a cyclic dimer [Cu(nbdc)(2,2′-bipy)(H₂O)]₂ · 2H₂O (1). X-ray structural analysis revealed that 1 crystallizes in a monoclinic space group P2₁/c with a = 7.3801(13) Å, b = 15.305(3) Å, c = 16.333(3) Å, β = 92.951(4)°, V = 1842.5(6) ų, and Z = 2. Compound 1 represents the first cyclic dimeric example with 1,4-benzenedicarboxylate or its derivatives, in which two carboxylates of the nbdc are nearly perpendicular due to the steric effect by the nitro group. Compound 1 also displays strong fluorescent emission in the solid state.     

Polar bonds in π-complexes. Preparation and crystal structures of cyclopentadienylcarbonyl iron(II) and ruthenium(II) benzoates andp-fluorobenzoates

Complexes of Fe(II) and Ru(II) of the general formula Cp(OC)₂MOC(O)C₆H₄X-p, where M=Fe, X=H, F (1, 2) or M=Ru, X=H, F (3, 4) have been prepared by reactingp-XC₆H₄COOAg with [CpFe(CO)₂]₂ or CpRu(CO)₂I. The crystal structures of complexes1–3 have been determined using X-ray diffraction. Compounds1 and3 are isomorphous. The COO group in1–3 is coordinated as a monodentate ligand. As the latter and the CO ligands are electronically non-equivalent, the coordination of the Cp ligand to the metal is slightly asymmetric.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 395–399, February, 1993.     

Zur Synthese von 4-Aminochinolinen durch intramolekulareFriedel—Crafts-Reaktion

Treatment of arylaminomethylene-malononitriles,-cyanoacetamides and--cyanoacetophenones with AlCl₃ yields substituted 4-aminoquinolines2, while quinolin-4-ones3 are obtained from ethyl arylaminomethylene cyanoacetates. N--naphthylcyanoacetamide reacts in the presence of AlCl₃ to form 1-amino-3-benzo[f]quinolinone (6). Isothiazolo[4,3–c]quinolines (10) and pyrimido[5,4–c]quinolines (11, 12) can be obtained from2. 4-Aminoquinoline-3-carboxylic acids derived from2, can be decarboxylated.3 are cyclized to form oxazino[5,6–c]-quinolinones (4).     

Silicon-containing esters of α-cyanoacrylic acid: synthesis and properties

A number of cyanoacetates have been synthesized: cyanoacetoxymethyitrimethylsilane (1), cyanoacetoxymethylpentamethyldisiloxane (2), cyanoacetoxyetoxymethylpentamethyldisiloxane (3). They were converted by the Knoevenagel reaction to novel esters of a-cyanoacrylic acid (4–13) containing silicon atoms in the ester groups and having the general formula RCH=C(CN)COOCH₂X (where R=H, 4-MeOC₆H₄, MeCH=CH, 2-furyl; X=SiMe₃, SiMe₂OSiMe₃, CH₂OCH₂SiMe₂OSiMe₃). These compounds are capable of copolymerization with esters of cyanoacrylic acid which are the precursors to adhesives for cold curing.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 949–952, May, 1993.     

Nitropyrazoles

A method of synthesizing nitro derivatives of lH,4H-pyrazolo[4,3-c]pyrazole is developed, and some of its transformations are studied. 3-Methyl-6-nitro-, 3-carboxy(methoxy-carbonyl, carbamoyl)-6-nitro-, 3-amino-6-nitro-, 3-nitro-, 3,6-dinitro-, 1,4-diacetonyl-3,6-dinitro-, and lH,4H-3-aminopyrazolo[4,3-c]pyrazoles were obtained from 1H,4H-3 -methylpyrazolo[4,3-c]pyrazole. Unsubstituted 1H,4H-pyrazolo[4,3-c]pyrazole, the first member of this series, was obtained for the first time. The compounds prepared were characterized by¹H,¹³C,¹⁴N, and¹⁵N NMR spectroscopy. NH-Acidity and basicity of the series of pyrazolo[4,3-c]pyrazoles synthesized is studied and the effect of the fused pyrazole ring on these properties is examined.Deceased March 18, 1989.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1108–1113, June, 1993.     

The synthesis of 4-(2,6,10-trimethyl-1,3,5,9-undecatetraenyl)benzoic acid based on alkoxy alkene-acetal condensation

4-(2,6,10-Trimethyl-1,3,5,9-undecatetraenyl)benzoic acid (1) was synthesized starting from ethyl 4-formylbenzoate (2) and linalool. The key intermediate, ethyl 4-(2-methyl-3-oxo-1-propenyl)benzoate (5), was obtained by the addition of diethyl acetal (3), prepared from2, to ethyl 1-propenyl ether (EPE) followed by the hydrolysis of the resulting adduct.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 914–915, May, 1993.     

Reactions ofo-tosylaminobenzaldehyde withp-aminobenzenesulfonamides. Synthesis and structures of 13-(4-aminosulfonylphenyl)-6,12-epimino-5,11-ditosyl-5,6,11,12-tetrahydrodibenzo[b,f]-1,5-diazocine and itsN-substituted derivatives

The reactions ofo-tosylaminobenzaldehyde (1) withp-aminobenzenesulfonamides (2a-c) yielded 13-(p-RNHSO₂C₆H₄)-6,12-epimino-5,11-ditosyl-5,6,11,12-tetrahydrodibenzo[b f]-1,5-diazocines (3a-c) (R=H (a); 2-thiazolyl (b); or 2,6-dimethoxy-4-pyrimidinyl 2,6-dimethoxy-4-pyrimidinyl (c). The structure of compound3c was confirmed by X-ray diffurction study. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2035–2039, November, 1997.     

Polyfluorinated hydrazones in organic synthesis

The oxidation of 1,1,1,5,5,5-hexafluoro-4-trifluoromethylpentane-2,3-dione bishydrazone (1) with SeO₂, HgO, and Hg(OAc)₂ was studied. The use of selenium dioxide leads to 1,1,1,5,5,5-hexafluoro-4-trifluoromethylpent-2-ene (2) and C₁₂H₄F₁₈Se₂. 1,1,1,5,5,5-Hexafluoro-4-trifluoromethylpent-2-yne (4) and C₆H₂F₉HgC₆H₂F₉ were obtained by the oxidation of bishydrazone1 with mercuric oxide. The oxidation of compound1 with mercuric acetate in diglyme affords 1,1,1,5,5,5-hexafluoro-4-trifluoromethylpenta-2,3-diene (6). Alkyne4 is isomerized to allene6 at 130 °C. For Part 3, see Ref. 1 Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 677–680, April, 1998.     

OH−-induced β-elimination reactions with 1-(2-Xethyl)-4-nitrobenzene substrates in solvent mixture H2O/CH3CN and H2O/DMSO: Reactivity and mechanism

The behaviour of 1-(2-bromoethyl) 4-nitrobenzene (1), N,N,N-triethyl-2-(4-nitrophenyl)ethanaminium bromide (2) and N,N-diethyl-N-[2-(4-nitrophenyl)ethyl]octan-1-aminium bromide (3) in the OH⁻-induced elimination reactions with formation of 1-nitro-4-vinylbenzene in mixtures of DMSO/H₂O or CH₃CN/H₂O has been investigated. With all three substrates an increase in dipolar aprotic solvent content implies a limited increase of the second-order rate constant k _OH up to ≅605, and then an exponential increase is observed. The variation of activation parameters ΔH ^# and dGS ^#, measured in DMSO/H₂O mixtures, is parallel for 1 and 2. This similar behaviour of 1 and 2 with respect to variation in solvent composition is evidence that it is not possible to use this technique of solvent effect for the mechanistic diagnosis of elimination reactions.     

Novel transformations of nitraminodiol diacetates

A novel scission reaction of nitraminodiol diacetates of the formula AcO[CH₂N(NO₂) _x CH₂OAc (x = 1–4) in concentrated sulfuric acid to form formaldehyde, nitramide, and 2-nitro-2-azapropane-1,3-diol disulfate was found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 3, pp 761–762, March, 1996.     

On the [4+2]-cycloaddition reaction of levoglucosenone with piperylene

The Diets-Alder reaction of levoglucosenone with piperylene catalyzed by ZnCl₂ proceeds regio- and stereoselectively to give thesin-cis-adduct3; the thermal reaction yields an epimeric mixture of compound3 withsin-trans-adduct4 in the ratio of 4 : 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2584–2585, October, 1996.     

Synthesis and crystal structure of triphenyl[tris(tetrahydrofuran)]ytterbium, Ph3Yb(THF)3

Triphenyl[tris(tetrahydrofuran)]ytterbium, Ph₃Yb(THF)₃ (1), was synthesized in high yields by the reaction of Yb with an excess of Ph₂Hg or Ph₃Bi in the presence of catalytic amounts of YbI₂(THF)₄ as well as by the reaction of Ph₂Yb(THF)₂ (2) with Ph₂Hg or Ph₃Bi. The crystal structure of complex1 was studied by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 163–166, January, 1998.