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1.
Russian Journal of Organic Chemistry - A number of new nitroxyadamantanes have been synthesized by nitroxylation of the corresponding substrates with nitric acid in acetic anhydride. High...  相似文献   

2.
An efficient one-pot procedure has been developed for the synthesis of cage alcohols with hydroxy groups in the bridgehead positions. The procedure includes initial nitroxylation with nitric acid or a mixture of nitric acid with acetic acid and subsequent hydrolysis in the presence of urea.  相似文献   

3.
Russian Journal of Organic Chemistry - The composition of reaction mixtures obtained by nitroxylation of 13 cage hydrocarbons with 100% nitric acid and its mixtures with acetic acid, acetic...  相似文献   

4.
Russian Journal of Organic Chemistry - A convenient method has been developed for the synthesis of 3,5-bis(hydroxymethyl)adamantan-1-ols via successive nitroxylation of...  相似文献   

5.
《Mendeleev Communications》2023,33(4):461-462
A concise safe approach for selective nitration and nitroxylation of tert-alkanes, in particular adamantane, and tert-alkyl bromides utilizing NO2 in supercritical CO2 medium has been established. Major reaction products were tert-alkyl nitro compounds and tert-alkyl nitrates depending on the reaction conditions.  相似文献   

6.
Polarographic Investigations on Symmetrical Triazacarbocyanine Dyes in Methanol The reduction mechanism of eleven symmetrical triazacarbocyanine dyes with different heterocycles in methanol (containing lithium chloride or lithium acetate/acetic acid) has been investigated by means of polarography, cyclic oscillopolarography and coulometry. The reduction occurs in a reversible to irreversible two electron transfer step, followed by an irreversible chemical step. Reduction potentials, transfer coefficients and specific currents have been measured and compared with properties measured in acetonitrile. The effect of substituents X has been studied on the compounds 1-ethyl-2-[3-(1-ethyl-6-X-1,2-dihydroquinolin-2-ylidene)-1-triazeno]-6-X-quinolinium tetrafluoroborate 1f(X) and 3-ethyl-2-[3-(3-ethyl-5-X-Δ4-1, 3-thiazolin-2-ylidene)-1-triazeno]-5-X-1, 3-thiazolium tetrafluoroborate 1g(X) , and ρ-values of 0.20 and 0.40 V, respectively, have been found.  相似文献   

7.
The electrochemical reduction of the imide complex [Mo2(cp)2(mu-SMe)3(mu-NH)]+ (1+) has been investigated in THF and MeCN electrolytes by cyclic voltammetry, controlled-potential electrolysis and coulometry. In the absence of free protons, the electrochemical reduction produces the amide derivative [Mo2(cp)2(mu-SMe)3(mu-NH2)] (2) after consumption of 1 Fmol(-1) of 1+. In THF in the presence of acid, the reduction of 1+ occurs through a two-electron process. The presence of acid also results in the shift of the equilibrium between 1+ and amide dication 2(2+) (MeCN electrolyte) or induces an isomerisation of the imide ligand (THF electrolyte). This allows the electrolysis to be conducted at a potential 600 mV less negative than the reduction potential of 1+. Controlled-potential electrolyses in the presence of acid (2 equiv HTsO) produce the ammine derivative. Ammonia is released from these compounds either by coordination of the solvent (MeCN electrolyte) or by the binding of chloride to the ammine-tosylate complex (electrolyses in THF in the presence of acid and chloride). The final products, isolated almost quantitatively (>95%), are [Mo2(cp)2(mu-SMe)3(MeCN)2]+ and [Mo2(cp)2(mu-SMe)3(mu-Cl)], respectively.  相似文献   

8.
Syntheses of Sulfonated Derivatives of 4-Amino-1, 3-dimethylbenzene and 2-Amino-1, 3-dimethylbenzene Direct sulfonation of 4-amino-1, 3-dimethylbenzene (1) and sulfonation of 4-nitro-1,3-dimethylbenzene ( 4 ) to 4-nitro-1,3-dimethylbenzene-6-sulfonic acid ( 3 ) followed by reduction yield 4-amino-1,3-dimethylbenzene-6-sulfonic acid ( 2 ). The isomeric 5-sulfonic acid ( 5 ) however is prepared solely by baking the acid sulfate salt of 1 . Reaction of sulfur dioxide with the diazonium chloride derived from 2-amino-4-nitro-1,3-dimethylbenzene ( 7 ) leads to 4-nitro-1,3-dimethylbenzene-2-sulfonyl chloride ( 8 ), which is successively hydrolyzed to 4-nitro-1,3-dimethylbenzene-2-sulfonic acid ( 9 ) and reduced to 4-amino-1, 3-dimethylbenzene-2-sulfonic acid ( 6 ). Treatment of 4-amino-6-bromo-1,3-dimethylbenzene ( 12 ) and 4-amino-6-chloro-1, 3-dimethylbenzene ( 13 ), the former obtained by reduction of 4-chloro-6-nitro-1,3-dimethyl-benzene ( 10 ) and the latter from 4-chloro-6-nitro-1, 3-dimethylbenzene ( 11 ), with oleum yield 4-amino-6-bromo-1,3-dimethylbenzene-2-sulfonic acid ( 14 ) and 4-amino-6-chloro-1,3-dimethylbenzene-2-sulfonic acid ( 15 ) respectively; subsequent carbon-halogen hydrogenolyses of 14 and 15 lead also to 6 (Scheme 1). Baking the acid sulfate salt of 2-amino-1, 3-dimethylbenzene ( 17 ) gives 2-amino-1, 3-dimethylbenzene-5-sulfonic acid ( 16 ), whereas the isomeric 4-sulfonic acid ( 18 ) can be prepared by either of the following three possible pathways: Sulfonation of 2-nitro-1,3-dimethylbenzene ( 20 ) to 2-nitro-1,3-dimethylbenzene-4-sulfonic acid ( 21 ) followed by reduction or sulfonation of 2-acetylamino-1,3-dimethylbenzene ( 19 ) to 2-acetylamino-1,3-dimethylbenzene-4-sulfonic acid ( 22 ) with subsequent hydrolysis or direct sulfonation of 17 . Further sulfonation of 18 yields 2-amino 1,3-dimethylbenzene-4,6-disulfonic acid ( 23 ), the structure of which is independently confirmed by reduction of unequivocally prepared 2-nitro- 1,:3-dimethylbenzene-4,6-disulfonic acid ( 24 )(Scheme 2).  相似文献   

9.
铁取代钨硅酸盐位壹异构体的合成、表征及电化学性质   总被引:3,自引:0,他引:3  
The four heteropoly isomers K3H2 [α-,βi-SiW11 Fe (H2O) O39]·χH2O (βi =β1,β2,β3) were prepared and Characterized by elementary analysis, IR and UV Spectroscopy. Its electrochemical behavior in aqueous solution has been discussed. The order of Polarographic half-wave potential E1/2 of heteropoly anions is as follows: β2>β1>β3>α. Its reduction process involves an one-electron reduction of Fe (Ⅲ) and a pair of two-electron reduction of W (Ⅵ). Epolidation of maleic acid with H2O2 Catalyzed by heteropoly positional isomers was studied. β3 isomers are the most active  相似文献   

10.
1-Oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octane ( 1 ) is oxidized by concentrated nitric acid to the corresponding acid 2. From the reaction of the acid chloride 3 with various phenols and aryl amines two series of new bicyclophosphates 4 and 5 have been prepared. The reduction of 4b with iron powder in HOAC gave the O→N acyl-migration product 4s. The crystal structure of 4n was determined by X-ray diffraction analysis.  相似文献   

11.
Two copper complexes, 1 and 2, with tridentate N-donor ligands, L(1) and L(2) [L(1)= (1-methyl-1H-imidazol-2-ylmethyl)-(2-pyridin-2-yl-ethyl)amine, L(2) = (2-pyridin-2-yl-ethyl)-pyridin-2 yl-methylamine] respectively, have been synthesized and characterized. On exposure to nitric oxide, the copper(II) centers in complexes 1 and 2 were found to undergo reduction in various solvents. In acetonitrile solvent the reduction was accompanied by a simultaneous N-nitrosation on the secondary amine center on the ligand frameworks. Complexes 3 and 4 were prepared with ligands L(3) and L(4), respectively. L(3) and L(4) [L(3) = 5-dimethylamino-naphthalene-1-sulfonic acid (1-methyl-1H-imidazol-2-ylmethyl)-(2-pyridin-2-yl-ethyl)-amide; L(4) = 5-dimethylamino-naphthalene-1-sulfonic acid(2-pyridin-2-yl-ethyl)-pyridin-2-ylmethyl-amide] are the dansyl derivatives of L(1) and L(2), respectively. Complex 4, due to paramagnetic quenching, does not display any fluorescence; however, on addition of nitric oxide to a methanol or water solution of complex 4, the fluorescence intensity of the fluorophore has been found to be restored. This is attributed to the reduction of the Cu(II) center by nitric oxide to diamagnetic Cu(I). The turn-on of quenched fluorescence intensity has been observed both in methanol and water media.  相似文献   

12.
The parent framework of furo[2,3-c]pyridine has been synthesized. 3-Furoic acid chloride ( 2 ) was reduced with bis(triphenylphosphine) copper(1) tetrahydroborate to afford 3-furaldehyde ( 3 ) which was condensed with malonic acid to give β-(3-furyl)acrylic acid ( 4 ). The acrylic acid 4 was converted to the acid azide ( 5 ), which in turn was cyclized to give furo[2,3-c]pyridin-7(6H)-one ( 6 ) by heating at 180° in diphenylmethane. The pyridone 6 was chlorinated with phosphorus oxychloride, followed by reduction with zinc and acetic acid to give furo[2,3-c]pyridine ( 8 ).  相似文献   

13.
The reduction of pyruvic acid in near-critical water has successfully been conducted under conditions of various temperatures, pressures, reaction time and the presence of formic acid as the reducing agent. In this work, additives (K2CO3, KHCO3, and sodium acetate) used in the reduction of pyruvic acid were also investigated. The results showed that by adding K2CO3 (25 mole %) a markedly higher lactic acid yield (70.7 %) was obtained than without additives (31.3 %) at 573.15 K, pressure of 8.59 MPa, 60 min, and in the presence of 2 mol L?1 formic acid. As a base catalyst, K2CO3 definitely accelerated the reduction of pyruvic acid. The reaction rate constants, average apparent activation energy and pre-exponential factor were evaluated in accordance with the Arrhenius equation. The reaction mechanism of the reduction was proposed on the basis of the experimental results.  相似文献   

14.
The synthesis of (2R,3R) and (2S,3S) dideuteriosuccinic acid in 63 ± 10% enantiomeric excess by reduction of the half acid ester of ethyl fumarate from (R) and (S) BINAP ruthenium (II) diacetate complex, respectively, is reported. (2R,3R) and (2S,3S)-Dideuteriosuccinic acid has also been prepared from (R)-BINAP ruthenium (II) dicarboxylate complex directly in similar optical purity by reversing the sequence of introduction of the isotopic label.  相似文献   

15.
Stereoselective Hydride Reduction of Tetronic Acid Derivatives, Synthesis of Branched-Chain Tetrofuranoses The 3-methoxymethyl derivatives of 2-methyl-D , L -threofuranose ( 10a ) and 2-deoxy-2-methyl-D ,L -erythrofuranose ( 11a ) are prepared starting from 2-methyl-tetronic acid ( 1 ). The key step is the stereoselective reduction of the 3-oxo-function of 2-chloro-2-methyl-3-oxo-γ-butyrolacton ( 2 ) by sodiumborohydride, which proceeds predominantly anti with respect to the C,Cl-bond. The configuration of the reduction products has been established by 1H- and 13C-NMR.-spectroscopy.  相似文献   

16.
Heller RL  Guyon JC 《Talanta》1970,17(9):865-871
A sensitive spectrophotometric method for the determination of nickel, based on the reduction of a complex formed between molybdophosphoric acid and Ni(II) at pH 4.3 has been developed. Excess of molybdophosphoric acid is eliminated by complexation with sodium citrate. The method is rapid and the system obeys Beer's law up to 5 ppm of Ni(II). The molar absorptivity is 1.30 x 10(3) 1.mole(-1).mm(-1). The technique compares favourably with existing photometric methods for nickel in sensitivity and is reasonably selective.  相似文献   

17.
3-硝基苯甲酸在DMSO介质中的电化学还原   总被引:2,自引:0,他引:2  
本文用循环伏安法、控制电位电解和ESR方法结合, 研究了3-硝基苯甲酸(3-NBA)在DMSO介质中, Pt电极上的电化学还原过程。结果表明, 3-硝基苯甲酸通过三电子还原生成一种亚硝基自由基。观测到了自由基ESR谱的超精细结构。确定了ESR模拟谱的参数: a_1~N=10.91G, a_2~H=1.12G, a_4~H=a_6~H=3.38G, a_5~H=3.96G. 估算了自由基衰变速度常数k=4.814×10~(-2)s~(-1).  相似文献   

18.
《Tetrahedron letters》1987,28(23):2559-2562
The four diastereomers of 1-hydroxyindolizidine have been prepared in high optical purity (>98%) by NaBH4 reduction of the (+) and (-) 3-bromocamphor-8-sulfonic acid salts of 1-oxoindolizidine followed by separation of the resulting diastereomeric alcohols by ion-exchange chromatography.  相似文献   

19.
Studies have been carried out on the solubility of Pu(III) oxalate by precipitation of Pu(III) oxalate from varying concentrations of HNO3/HCl (0.5–2.0M) solutions and also by equilibrating freshly prepared Pu(III) oxalate with solutions containing varying concentrations of HNO3/HCl, oxalic acid and ascorbic acid. Pu(III) solutions in HNO3 and HCl media were prepared by reduction of Pu(IV) with ascorbic acid. 0.01–0.10M ascorbic acid concentration in the aqueous solution was maintained as holding reductant. The solubility of Pu(III) oxalate was found to be a minimum in 0.5M–1M HNO3/HCl solutions containing 0.05M ascorbic acid and 0.2M excess oxalic acid in the supernatant.  相似文献   

20.
3,5-Disubstituted 1,2,4-triazoles containing linear and cyclic amine fragments have been synthesized by thermal cyclization of N′-(1-iminoalkyl) hydrazides prepared by condensation of imido esters with carboxylic acid hydrazides. The initial imido esters have been synthesized by the Pinner reaction, as well as by reaction of nitriles with methanol in the presence of a catalytic amount of sodium methoxide. A procedure has been developed for the synthesis of 5-substituted 3-(3-nitrophenyl)-1,2,4-triazoles which have been converted to 3-aminophenyl derivatives by reduction with hydrazine hydrate over Raney nickel.  相似文献   

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