铪催化合成聚3-羟基丙酸

以3-羟基丙酸(3-HP)为单体,金属铪(Ⅳ)催化合成了高纯度的聚3-羟基丙酸[P(3-HP)]。3-HP和P-(3-HP)的结构经NMR,FT-IR和GPC等表征。     

Synthesis of benzopyran derivatives,XV Preparation of arylsulfonyloxy-2,2-dimethyl-2H-chromenes

Summary Arylsulfonyloxy-2,2-dimethyl-2H-chromenes (26–35) have been synthesized by reduction of arylsulfonyloxy-2,2-dimethyl-4-chromanones (6–15) followed by dehydration.

---

Synthese von Benzopyranderviaten. 15. Mitt.: Darstellung von Arylsulfonyloxy-2,2-dimethyl-2H-chromenen

Zusammenfassung Reduktion von Arylsulfonyloxy-2,2-dimethyl-4-chromanonen (6–15) und anschließende Dehydratisierung liefert Arylsulfonyloxy-2,2-dimethyl-2H-chromene (26–35).

     

Darzens synthesis of 2,2-dichloro-3-(2-furyl)-3-hydroxypropionic acid derivatives

Esters and amides of 2,2-dichloro-3-(2-furyl)-3-hydroxypropionic acid were prepared by the reaction of furfural with dichloroacetic acid derivatives under the conditions of the Darzens condensation. The structures of the reaction products were confirmed by their¹H NMR and IR spectra and chemical transformations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1444–1448, August, 1994.     

Synthesis of 2,2-dimethylchromans by the hydrogenation of 2,2-dimethyl-2H-chromenes

Summary 2,2-Dimethylchromans19–36 have been synthesized by the hydrogenation of 2,2-dimethyl-2H-chromenes1–18 in acetic acid solution in the presence of 10% Pd-C catalyst.Dedicated to Prof. Dr. W. Fleischhacker on the occasion of his 60th birthday     

Asymmetric reduction of 2,2-dimethyl-6-(2-oxoalkyl/oxoaryl)-1,3-dioxin-4-ones and application to the synthesis of (+)-yashabushitriol

The asymmetric transfer hydrogenation of a series of 2,2-dimethyl-6-(2-oxoalkyl)-1,3-dioxin-4-ones and 2,2-dimethyl-6-(2-oxoaryl)-1,3-dioxin-4-ones was achieved in high enantiomeric excess using a Ru(II) catalyst. The aryl substrates were most compatible with the methodology and this process facilitated a total synthesis of enantiomerically pure (+)-yashabushitriol.     

Electro-generation of TGA by Ni-mSA-mCS bipolar membrane

Ni-mSA-mCS bipolar membrane (BM) was prepared by sodium alginate (SA) and chitosan (CS),which were modified by Ca~(2 ) and glutaraldehyde as linking reagents,respectively,mSA-mCS membrane was characterized by FTIR,SEM,TG and used as a separator in the electrolysis cell to produce thioglycolic acid (TGA).The experiment results show that TGA was prepared effectively by electro-reduction of dithiodiglycolic acid (DTDGA) with the mixture of TGA and DTDGA in the cathodic chamber.The current efficiency was up to 66.7% at the room temperature (25℃) during the current density of 10 mA/cm~2.Compared with the traditional metal reduction method,the electro-reduction technology saves the zinc powder and eliminates the pollution to environment. (?)2007 Zhen Chen.Published by Elsevier B.V.on behalf of Chinese Chemical Society.All rights reserved.     

ReCl(CO)5-catalyzed cyclocondensation of phenols with 2-methyl-3-butyn-2-ol to afford 2,2-dimethyl-2H-chromenes

A direct one-pot route for the synthesis of 2,2-dimethyl-2H-chromenes by Re(CO)₅Cl-catalyzed cyclocondensation of phenols with 2-methyl-3-butyn-2-ol has been developed. The easy availability of starting materials, mild reaction conditions, high atom-efficiency, and the use of a recoverable catalyst are advantages of this procedure.     

New reaction of the sodium salt of 2-nitroethanol. X-ray analysis of the sodium salt of 2-oxo-3-hydroxypropionic acid oxime, 2-bromo-2-nitropropane-1,3-diol,and the model 2,2-dinitropropane-1,3-diol

A novel reaction of the sodium salt of 2-nitroethanol in aqueous ammonia resulted in the sodium salt of 2-oxo-3-hydroxypropionic acid oxime (1) has been found. Bromination of1 affords 2-bromo-2-nitropropane-1,3-diol (2) with a previously unknown molecular conformation. The formation mechanisms of compounds1 and2 were suggested. X-ray analysis of products1,2 and that of the model compound, 2,2-dinitropropane-1,3-diol, was performed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1217–1221, May, 1996.     

Synthesis,characterization, and crystal structure determination of Cu(II) coordination compounds with 2,2′-dimethyl-4,4′-bithiazole

[{CuCl(dm4bt)}₂ μ-Cl)₂] (1) (dm4bt = 2,2′-dimethyl-4,4′-bithiazole) was prepared from the reaction of CuCl₂ · 2H₂O with 2,2′-dimethyl-4,4′-bithiazole in methanol; [Cu(dm4bt)₂NO₃](NO₃) (2) was prepared from the reaction of Cu(NO₃)₂ · 3H₂O with 2,2′-dimethyl-4,4′-bithiazole in methanol. Both complexes were characterized by IR, UV–Vis spectroscopy, and single-crystal structure. The structure of 1 consists of centrosymmetric dimeric [{CuCl(dm4bt)}(μ-Cl)], in which two chloro ligands bridge the coppers forming a four-membered ring; a terminal chloride and a bidentate chelating bithiazole complete five coordination at each Cu(II) in a highly distorted trigonal-bipyramidal geometry. The mononuclear structure 2 consists of a Cu(II), two 2,2′-dimethyl-4,4′-bithiazoles, one monodentate nitrate and one uncoordinated nitrate in a highly distorted square pyramid.     

Three-compartment bipolar membrane electrodialysis for splitting of sodium formate into formic acid and sodium hydroxide: Role of diffusion of molecular acid

Bipolar membrane electrodialysis is used in a three-compartment configuration to regenerate formic acid and sodium hydroxide from sodium formate. A previous study showed that the diffusion of molecular formic acid induces the loss of acid current efficiency. The present study shows the following results: the diffusion of molecular formic acid through the bipolar membrane explains quantitatively the presence of sodium formate in the sodium hydroxide solution. The loss of acid current efficiency is only due to diffusion of molecular acid through both anion-exchange and bipolar membranes. The sodium hydroxide current efficiency is determined by acid diffusion through the bipolar membrane and OH⁻ leakage through the cation-exchange membrane. The flux of acid diffusion through the membranes is proportional to acid concentration and depends on sodium hydroxide concentration for bipolar membrane and on sodium formate concentration for anion-exchange membrane. The flux rates vary with temperature.     

Modifying bipolar membranes with palygorskite and FeCl3

To explore a more function-stable and energy-efficient bipolar membrane, palygorskite and FeCl₃ were added at the intermediate layer as water-splitting catalysts. As proven, the two materials have a synergetic effect on water splitting. Particularly, the bipolar membrane modified with 5 g dm⁻³ palygorskite and 0.005 mol dm⁻³ FeCl₃ can achieve a voltage drop of 0.68 V at 100 mA cm⁻² and loses only 14.7 μg of Fe after an electrodialysis operation at 100 mA cm⁻² for 660 min. Obviously, palygorskite can protect ferric ions from significant loss, which makes the membrane stable in the performance of water splitting. Nevertheless, how palygorskite immobilizes ferric ions is still under investigation.     

Stereochemistry of the Reactions of Cyclic Ketones with Lithium Aluminum Hydride and Methyllithium. IV. The Stereochemistry of the Reactions in 2,2-Dimethyl-4-t-Butylcyclohexanone Systems

Previous publication showed that the stereochemistry of lithium aluminum hydride reduction of cyclic ketones can be evaluated by the use of an empirical equation, . This paper reports further test of this relationship in the new system of 2,2-dimethyl-4-t-butyl-cyclohexanone. Lithium aluminum hydride reduction of this ketone yields 95.6% trans-alcohol (lit., 95.9%) corresponding to D?(D?G*)_H of 1.67 Kcal/mol. With methyllithium, the ketone formed 77.5% of trans-alcohol (D?(D?G*)_D?fs = 0.67 Kcal/mol). These data give a calculated D?G* = 0.74 Kcal/mol which agrees well with the literature value of 0.87 or 0.28 Kcal/mol. Structural assignments of 2,2-dimethyl-4-t-butylyclohexanone, 1,2,2-trimethyl-cis- and trans-4-t-butylcyclohexanols by pmr spectroscopic method are also given.     

Efficient One-Pot Synthesis of 2,2-Dimethyl-2H-chromenes via Pd(II)-Catalyzed Coupling and SiO2-Promoted Condensation of o-Halophenols with 2-Methyl-3-buten-2-ol

An efficient synthesis of 2,2-dimethyl-2H-chromenes was accomplished by Pd(II)-catalyzed coupling and SiO₂-promoted condensation of o-halophenols with 2-methyl-3-buten-2-ol (1,1-dimethylallyl alcohol) in one pot. The method is very general and can be useful for the synthesis of some natural 2,2-dimethyl-2H-chromenes.     

Heat Capacities and Thermodynamic Properties of 3-（2,2-Dichloroethenyl）-2,2-dimethylcyclopropanecarboxylic Acid

The heat capacities of 3 - (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid ( a racemic mixture,molar ratio of cis-/trans-structure is 35/65) in a temperature range from 78 to 389 K were measured with a precise automatic adiabatic calorimeter. The sample was prepared with a purity of 98.75% ( molar fraction). A solid-liquid fusion phase transition was observed in the experimental temperature range. The melting point, Tm, enthalpy and entropy of fusion, △fusHm, △fusSm, of the acid were determined to be ( 331.48 ± 0.03 ) K, ( 16. 321 ± 0.031 ) kJ/mol,and (49.24 ± 0.19) J/( K·mol), respectively. The thermodynamic functions of the sample, HT - H298.15, ST -S298.15 and GT - G298.15, were reported at a temperature intervals of 5 K. The thermal decomposition of the sample was studied using thermogravimetric (TG) analytic technique, the thermal decomposition starts at ca. 418 K and ends at ca. 544 K, the maximum decomposition rate was obtained at 510 K. The order of reaction, preexponential factor and activation energy are n =0.23, A =7. 3 × 107 min -1, E =70.64 KJ/mol, respectively.     

Synthesis, characterization and crystal structure determination of zinc (II) and mercury (II) complexes with 2,2′-dimethyl-4,4′-bithiazole

The 2,2′-dimethyl-4,4′-bithiazole ligand (1), (dm4bt), and its Zn and Hg complexes have been prepared. A conformational property calculation at the DFT level for the ligand shows the anti conformation is energetically more stable by about 22.83 kJ/mol and the rotational barrier is about 32.01 kJ/mol for the anti → syn conversion, a phenomena happening during complex formation. The complexes [Zn(dm4bt)Cl₂] (2) and [Hg(dm4bt)Cl₂] (3) have spectral properties typical for d¹⁰ metal diimine systems. The structures of the ligand and the two complexes have been determined by the single crystal diffraction method. The X-ray structure determinations show that both complexes are four coordinated by two chloride atoms and one bidentate dm4bt. In the Hg complex one of the two chlorides is set at a semi-bridging position.     

Innovative beneficial reuse of reverse osmosis concentrate using bipolar membrane electrodialysis and electrochlorination processes

Reverse osmosis (RO) is a widely used and rapidly growing desalination technology. A major disadvantage of this process is that the concentrate from the RO process, which could be as much as 25% of the feed stream, represents a polluting stream. This waste stream could pose a significant challenge to the implementation of this process, particularly for inland communities which do not have the option of ocean disposal. An excellent environmentally benign approach to disposal could be beneficial reuse of the waste stream. This study presents two innovative beneficial reuse strategies for RO concentrate produced by an integrated membrane system (IMS) from a wastewater reclamation facility. The technologies evaluated in this study included bipolar membrane electrodialysis (BMED) for conversion of RO concentrate into mixed acid and mixed base streams, and electrochlorination (EC) for onsite chlorine generation. Bench-scale studies conducted with BMED demonstrated that RO concentrate could be desalted while producing mixed acids and mixed bases with concentrations as high as 0.2N. Similarly, the EC process was capable of producing a 0.6% hypochlorite solution from RO concentrate. The acids and bases as well as the hypochlorite produced could be directly applied to the RO process as well as upstream pre-treatment processes. A preliminary economic evaluation of the viability of these two approaches was conducted by conducting rough order of magnitude cost estimates based on the bench-scale performance of these processes on RO concentrate. A comparison of the overall costs of an Integrated Membrane System utilizing these innovative reuse strategies with conventional disposal options and thermal zero liquid discharge treatment is presented. This comparison indicates that a reuse approach might be economically viable for inland wastewater reuse facilities that utilize RO membranes and have limited options for concentrate disposal.     

Preparation and properties of polyarylates both from 2,2′-bibenzoyl chloride and bisphenols and from biphenyl-2,2′-diol and aromatic dicarboxylic acid chlorides

Polyarylates having inherent viscosities up to 1.02 dL/g were synthesized both by the phase-transfer catalyzed two-phase polycondensation of 2,2′-bibenzoyl chloride with various bisphenols and by the high-temperature solution polycondensation of biphenyl-2,2′-diol with aromatic dicarboxylic acid chlorides. All the polyarylates were amorphous and soluble in a variety of organic solvents including N,N-dimethylformamide, N-methyl–2-pyrrolidone, chloroform, m-cresol, and pyridine. Transparent and flexible films of these polymers could be cast from the chloroform solutions. These polyarylates had glass transition temperatures in the range of 120–250°C and began to lose weight at around 380°C in air. © 1992 John Wiley & Sons, Inc.     

Preparation of 2,2-disubstituted 1,2-dihydro-3H-indol-3-ones via oxidation of 2-substituted indoles and Mannich-type reaction

A novel preparative method for 2,2-disubstituted 1,2-dihydro-3H-indol-3-ones through the oxidation of 2-arylindoles followed by a Mannich-type reaction with carbon nucleophiles is described.     

One-pot synthesis of 5,5′-dibromo-2,2′-dipyridylacetylene and its boronic acid derivative

5,5′-Dibromo-2,2′-dipyridylacetylene was prepared from 2,5-dibromopyridine and (trimethylsilyl)acetylene via the new one-pot synthesis approach using a regioselective palladium-catalyzed coupling reaction with a 60% yield. Several protocols of lithium-halogen exchange were then attempted to synthesize 6,6′-(1,2-ethynediyl)bis[3-pyridylboronic acid] from 5,5′-dibromo-2,2′-dipyridylacetylene. The former was successfully obtained with a 54% yield by a reverse addition method using toluene and THF and it showed potential as a useful building block for cross-coupling reactions in the formation of carbon-carbon bonds.