Carbon dioxide: a renewable feedstock for the synthesis of fine and bulk chemicals

The syntheses of carbon dioxide (CO₂) based industrially important chemicals have gained considerable interest in view of the sustainable chemistry and “green chemistry” concepts. In this review, recent developments in the chemical fixation of CO₂ to valuable chemicals are discussed. The synthesis of five-member cyclic carbonates via, cycloaddition of CO₂ to epoxides is one of the promising reactions replacing the existing poisonous phosgene-based synthetic route. This review focuses on the synthesis of cyclic carbonates, vinyl carbamates, and quinazoline-2,4(1H,3H)-diones via reaction of CO₂ and epoxide, amines/phenyl acetylene, 2-aminobenzinitrile and other chemicals. Direct synthesis of dimethyl carbonate, 1,3-disubstituted urea and 2-oxazolidinones/2-imidazolidinones have limitations at present because of the reaction equilibrium and chemical inertness of CO₂. The preferred alternatives for their synthesis like transesterification of ethylene carbonate with methanol, transamination of ethylene carbonate with primary amine and transamination reaction of ethylene carbonate with diamines/β-aminoalcohols are discussed. These methodologies offer marked improvements for greener chemical fixation of CO₂ in to industrially important chemicals.     

Use of carbon dioxide as feedstock for chemicals and fuels: homogeneous and heterogeneous catalysis

CO₂ is considered to play a key role in an eventual climate change, due to its accumulation in the atmosphere. The control of its emission represents a challenging task that requires new ideas and new technologies. The use of perennial energy sources and renewable fuels instead of fossil fuels and the conversion of CO₂ into useful products are receiving increased attention. The utilization of CO₂ as a raw material for the synthesis of chemicals and fuels is an area in which scientists and industrialists are much involved: the implementation of such technology on a large scale would allow a change from a linear use of fossil carbon to its cyclic use, mimicking Nature. In this paper the use of CO₂ as building block is discussed. CO₂ can replace toxic species such as phosgene in low energy processes, or can be used as source of carbon for the synthesis of energy products. The reactions with dihydrogen, alcohols, epoxides, amines, olefins, dienes, and other unsaturated hydrocarbons are discussed, under various reaction conditions, using metal systems or enzymes as catalysts. The formation of products such as formic acid and its esters, formamides, methanol, dimethyl carbonate, alkylene carbonates, carbamic acid esters, lactones, carboxylic acids, and polycarbonates, is described . The factors that have limited so far the conversion of large volumes of CO₂ are analyzed and options for large‐scale CO₂ catalytic conversion into chemicals and fuels are discussed. Both homogeneous and heterogeneous catalysts are considered and the pros and cons of their use highlighted. © 2013 Society of Chemical Industry     

精细化学品选择性催化合成的机遇与趋势

评述了当前精细化工生产中的环境导向趋势，在原子利用率与E-因子(副产物kg/产物kg)基础上对替换工艺作了比较讨论。应用替代铬的分子筛作为循环使用的固体催化剂用于苄基与烯丙基氧化，氧化仲醇为酮，以及烃基过氧化物的选择性分解。介绍了沸石包裹金属铬合物作为氧化一还原固体催化剂的新进展，在水为介质中钯(O)三磺酸三苯膦络合物作为羰基化催化剂的应用，以及支载水相催化剂在包括对映选择性氢化反应在内的各种工艺中的应用。     

叔丁胺的催化合成及其在精细化工中的应用

综述了国内外叔丁胺的生产工艺和催化合成方法的研究进展。指出固体酸催化甲基叔丁基醚的氨化是值得开发的绿色化工技术。介绍了叔丁胺在医药、农药、橡胶促进剂等精细化工领域的应用。     

低级焦油酚下游精细化学品产业链技术进展

焦油酚产业链技术开发和相关产业向高端、精细化发展,是传统煤化工产业转型的方向。以低级焦油酚为基础的甲基酚合成具有催化体系近似、工艺过程通用、多产物共生的特点。开发单系统甲基酚多联产技术,有助于减少投资,增强市场适应能力。2,3,5-三甲基氢醌是该产业链走向高端化的重要产品路线。2,3,6-三甲基苯酚催化空气氧化-催化加氢还原法是氢醌合成技术方向,但需解决氧化催化剂效率与易分离性的矛盾,以及相关中间及最终产品的分离效率问题。     

Synthesis of p-cymene from limonene, a renewable feedstock

Highly selective limonene conversions to p-cymene in short reaction times were achieved under “solvent free” conditions over mesoporous silica–alumina supports heated by microwave irradiation. An increase in the silica content of these mixed oxides led to increases in the specific surface area, porosity (pore size and volume) and the surface acidity. The conversion and selectivity of limonene to p-cymene under microwave irradiation was also found to rise as the silica content in these mixed oxides was increased. By careful choice of the solid and reaction parameters the activities for the conversion of limonene and selectivity to p-cymene (used as an intermediate in fine chemical syntheses) could be fine tuned. Results are presented under both dry media and reflux conditions.     

Solid catalysts for the production of fine chemicals: the use of ALPON and hydrotalcite base catalysts for the synthesis of arylsulfones

α#x2010;phenylsulfonylcinnamononitrile and derivatives as well as α-phenylsulfonylchalcone have been obtained by condensation of phenylsulfonylacetonitrile and phenylsulfonylacetophenone with benzaldehyde and 4-substituted benzaldehydes, using solid base catalysts with different basic strengths. Cs-exchanged X zeolite showed low activity for the above reactions, while high-surface-area MgO and MgO–Al₂O₃ mixed oxides derived from hydrotalcite were active and selective catalysts. An optimum basicity was observed with MgO–Al₂O₃ with the atomic ratio Al/(Al+Mg) between 0 and 0.20, showing the increase in basicity when introducing Al in the MgO structure. Nitridation of a high-surface-area aluminophosphate gives active and selective catalysts for the above reactions. The activity per unit surface area for the less demanding reaction between sulfonylacetonitrile and benzaldehyde is directly proportional to the level of nitridation. However, formation of α-phenylsulfonylchalcone, which is a more demanding reaction, does not increase linearly but goes through a maximum with the nitrogen content of the solid, showing the heterogeneity of active sites on ALPONs and the decrease in the activity coefficient of the basic sites when the density of N atoms increases. This revised version was published online in July 2006 with corrections to the Cover Date.     

Immobilized fungal biocatalysts for the production of cellulase complex hydrolyzing renewable plant feedstock

We discuss characteristics of the directional formation of samples of heterogeneous biocatalysts based on immobilized cells of different microscopic fungi that are characterized by high productivity of cellulases with different substrate specificities (endoglucanases, exoglucanases, and beta-glucosidases). Samples of immobilized cells characterized by maximum productivity of the enzymes of cellulase complex are selected based on our study of the catalytic and operating characteristics of the designed biocatalysts. It is found that a biocatalyst based on Aspergillus terreus spores immobilized in polyvinyl alcohol cryogel is the best of the ones available. It is shown for the first time that the developed biocatalyst retains a high level of productivity for the full complex of cellulases when using various substrate inducers of enzyme biosynthesis, such as birch and oak sawdust, and rice and wheat straw. We demonstrate the possibility of efficiently using cellulase complexes obtained as a result of the functioning of immobilized cells in the saccharification of various cellulose-containing agricultural wastes and the conversion of the obtained sugars to organic solvents (ethanol, butanol) considered to be promising alternative fuels. The concentrations of organic solvents in media with immobilized cells are considerably higher than those found for free cells of the same microorganisms.     

4,4-二甲氧基-2-丁酮的合成方法及应用开发

介绍了4,4二甲氧基2丁酮的合成工艺,并提出了一些具有发展前景的后续精细化工产品,如2氯3氨基4甲基吡啶、3羟基异戊醛缩二甲醇、2巯基4甲基嘧啶等,这些产品采用4,4二甲氧基2丁酮工艺路线合成,能大大简化生产工艺,降低生产成本。     

Catalysis for fine chemicals: towards specificity with polyphasic media

Three examples of the work undertaken at the Institut de Recherches sur la Catalyse for the selective preparation of fine chemicals in polyphasic media are presented and discussed:

1. diastereoselective hydrogenation of 1,2-disubstituted arenes to cyclohexyl derivatives,

2. chemoselective oxidation of anilines, and

3. regioselective alkoxycarbonylation of styrene derivatives to 2-arylpropionic esters.

Factors influencing the selectivity of these reactions are discussed in the light of concepts from molecular chemistry.