1,1,1-Trifluoro-3-(2-thenoyl)acetone in Reactions with Hydrazines

Properties of 1,1,1-trifluoro-3-(2-thenoyl)acetone and its reactions with hydrazine hydrate, 2,4-dinitrophenylhydrazine, and 1,1-dimethylhydrazone are studied.     

Photolysis of 2-phenylethyl and 4-phenyl-1-butyl halides in alcoholic solvents

Photolysis of 2-phenylethyl bromide in the lower alcohols gave the corresponding carbinols and ethers as the main products. With 2-phenylethyl iodide, the products were almost exclusively of the latter type, while 4-phenyl-1-butyl halides gave n-butylbenzene, 4-phenyl-1-butene and tetralin.It is shown chac each of these produtes may be assigned to an ionic or radical pathway and that both the nature of the solvent and the structure of the substrate affect the course of photolysis. There is a substrate dependent preference for specific reactions along pathways of both the radical and ionic types. The variations in product composition and distribution are rationalized in terms of the relative efficiencies furnished in these pathways for the relaxation of high energy intermediates produced in the initial stages of photolysis. Intervention by the phenyl group is more pronounced in the case of 2-phenylethyl halides than In the case of the higher homologues and more effective in the ionic pathway.     

3-三氟-2-羟基/氨基-1-氟代丙基膦酸酯的合成

Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6Z in 1 ： 1 ratio. Upon hydrolysis, this reaction mixture gave solely 1,3,3,3-tetrafluoro-2-dioxypropanephosphonate （9）. Reaction of 3 with DBU provided only 6, in which the ratio of E/Z forms was dependent on the reaction conditions. Aqueous hydrolysis of 6 led to 9. Catalytic hydrogenation and hydrogenolysis of 6 gave geometric isomers of 11 as expected. The reaction mechanism involved was discussed.     

四种苯甲酰丙酮合铜和1，1，1-三氟-3-(2-噻吩基)丙酮合铜的偶氮二吡啶长链配合物的热分析研究

用热重法(TG)研究了4种苯甲酰丙酮合铜和1，1，1-三氟-3-(2-噻吩基)丙酮合铜的偶氮二吡啶一维长链聚合配位化合物在动态氮气气氛下的热行为，结合元素分析和能谱技术，确定了各步分解的组分，并讨论了其晶体结构与热性质的关系。应用新的非线性等转化率法，并结合其他方法考察了各步分解反应的属性，进行了动力学分析，并试对传统动力学方法的适用性进行了讨论。     

2-取代-1,1,1-三氯-3-硝基丙烷新型杀菌剂的合成

报道了46个2-羟基-、2-胺基-、2-肼基和2-氮杂环基-1,1,1-三氯-3-硝基丙烷衍生物的合成方法。初步生物试验表明它们呈现良好的抑菌活性,其中以2-苯肼基-1,1,1-三氯-3-硝基丙烷的活性最高。     

Formylation of 2-phenyl- and 3-phenyl-5-hydroxybenzofuran derivatives

The Vilsmeier formylation of 2-phenyl- and 3-phenyl-5-hydroxybenzofuran derivatives was studied. It is shown that 2-phenyl-5-methoxybenzofuran is formylated in the 4 position, whereas 3-phenyl-5-methoxybenzofuran is formylated in the 2 position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1023–1024, August, 1976.     

Cyclopalladation of 3-methoxyimino-2-phenyl-3H-indoles

The direct cyclopalladation of 3-methoxyimino-2-(4-chlorophenyl)-3H-indole (1a) and 3-methoxyimino-2-phenyl-3H-indole (1b) results in the regioselective activation of the ortho σ[C(sp², phenyl)-H] bond affording (μ-OAc)₂[Pd{κ²-C,N-C₆H₃-4R-1-(C₈H₄N-3′-NOMe)}]₂ (2) {R = Cl (2a) or H (2b)} that contain a central “Pd(μ-OAc)₂Pd” core. Compounds 2a and 2b reacted with triphenylphosphine (in a molar ratio PPh₃:2 = 2) giving [Pd{κ²-C,N-C₆H₃-4R-1-(C₈H₄N-3′-NOMe)}(OAc)(PPh₃)] (3) {R = Cl (3a) or H (3b)}. Treatment of 2a or 2b with a slight excess of LiCl in acetone produced the metathesis of the bridging ligands and the formation of (μ-Cl)₂[Pd{κ²-C,N-C₆H₃-4R-1-(C₈H₄N-3′-NOMe)}]₂ (4) {R = Cl (4a) or H (4b)} with a central “Pd(μ-Cl)₂Pd” moiety. The reactions of 4a or 4b with deuterated pyridine (py-d₅) or triphenylphosphine gave the monomeric derivatives [Pd{κ²-C,N-C₆H₃-4R-1-(C₈H₄N-3′-NOMe)}Cl(L)] with R = Cl or H and L = py-d₅ (5) or PPh₃ (6). The crystal structure of 6b·1/2CH₂Cl₂ confirmed the mode of binding of the ligand, the nature of the metallated carbon atom and a trans-arrangement of the phosphine ligand and the heterocyclic nitrogen. Theoretical calculations on the free ligands are also reported and have allowed the rationalization of the regioselectivity of the cyclopalladation process.     

New example of acyl cleavage of benzoyl-1,1,1-trifluoroacetone in a three-component synthesis of 4-aryl-2-thioxo-6-phenyl-1,2-dihydropyridine-3-carbonitriles

A three-component condensation of aromatic aldehydes, cyanothioacetamide, and benzoyl-1,1,1-trifluoroacetone, involving the acyl cleavage of the latter, results in 4-aryl-2-thioxo-6-phenyl-1,2-dihydropyridine-3-carbonitriles. Their alkylation was studied.     

铟参与的4-溴-1,1,1-三氟-2-丁烯与a-烷氧基醛亚胺的烯丙化反应:4,4,4-三氟-y-羟基缬氨酸的合成

铟参与的4-溴-1,1,1-三氟-2-丁烯与a-烷氧基醛亚胺的烯丙化反应以中等的产率和高非对映选择性生成了高烯丙基胺3.从甘油醛亚胺和4-溴-1,1,1-三氟-2-丁烯反应制备的高烯丙基胺3g出发,以7步反应24%的总产率合成了4,4,4-三氟-y-羟基缬氨酸11.     

Ultraviolet spectra of 2-phenyl-4- and 2-phenyl-5-azaindan-1, 3-diones

The UV spectra of 2-phenyl-4-azaindan-1, 3-dione (I), 2-phenyl-5-azaindan-1, 3-dione (II), and their N-methylbetaines are investigated. 2×10^–5 M aqueous alcoholic solutions of 2-phenyl-4-azaindan-1, 3-dione (I) contain the anionic form (IA), and in solutions of 2-phenyl-5-azaindan-1, 3-dione (II) the betaine form (IIB) is also in equilibrium with the anion (IIA). Solutions of I and II in 0.1 M sulfuric acid are characterized by a wide and rather intense absorption band at about 500 m, indicating the presence of a betaine form (IB and IIB). In 2M hydrochloric acid solution 2-phenylazaindan-1, 3-diones and their N-methylbetaines (III and IV) are protonated at the oxygen atom, giving the enol forms of the N-protonated or corresponding N-methylated 2-phenylazaindandiones.     

Hyperconjugation in the 2-butyl cation

A comparison of the optimized geometries of the hydrogen-bridged ethyl and 2-butyl cations suggest the contribution of hyperconjugation to the stability of the latter to be 10 kcal/mole. An examination of the barrier to rotation of a methyl group is in accord with the phenomenon of hyperconjugation.