Pd-Catalyzed Cross-Coupling Reactions of Hydrazones: Regioselective Synthesis of Highly Branched Dienes

The regioselective formation of highly branched dienes is a challenging task. Design and exploration of alternative working models to achieve such a regioselectivity to accomplish highly branched dienes is considered to be a historical advancement of Heck reaction to construct branched dienes. On the basis of the utility of carbene transfer reactions, in the reaction of hydrazones with Pd(II) under oxidative conditions, we envisioned obtaining a Pd-bis-carbene complex with alpha-hydrogens, which can lead to branched dienes. Herein, we report a novel Pd-catalyzed selective coupling reaction of hydrazones in the presence of t-BuOLi and benzoquinone to form the corresponding branched dienes. The utility of the Pd catalyst for the cross-coupling reactions for synthesizing branched conjugated dienes is rare. The reaction is very versatile and compatible with a variety of functional groups and is useful in synthesizing heterocyclic molecules. We anticipate that this Pd-catalyzed cross-coupling reaction will open new avenues for synthesizing useful compounds.

Regioselective Synthesis of 4-Substituted Indoles via C-H Activation: A Ruthenium Catalyzed Novel Directing Group Strategy

A highly regioselective functionalization of indole at the C-4 position by employing an aldehyde functional group as a directing group, and Ru as a catalyst, under mild reaction conditions (open flask) has been uncovered. This strategy to synthesize 4-substituted indoles is important, as this class of privileged molecules serves as a precursor for ergot alkaloids and related heterocyclic compounds.

Oxy-steam gasification of biomass for hydrogen rich syngas production using downdraft reactor configuration

The paper focuses on the use of oxygen and steam as the gasification agents in the thermochemical conversion of biomass to produce hydrogen rich syngas, using a downdraft reactor configuration. Performance of the reactor is evaluated for different equivalence ratios (ER), steam to biomass ratios (SBR) and moisture content in the fuel. The results are compared and evaluated with chemical equilibrium analysis and reaction kinetics along with the results available in the literature. Parametric study suggests that, with increase in SBR, hydrogen fraction in the syngas increases but necessitates an increase in the ER to maintain reactor temperature toward stable operating conditions. SBR is varied from 0.75 to 2.7 and ER from 0.18 to 0.3. The peak hydrogen yield is found to be 104g/kg of biomass at SBR of 2.7. Further, significant enhancement in H-2 yield and H-2 to CO ratio is observed at higher SBR (SBR=1.5-2.7) compared with lower range SBR (SBR=0.75-1.5). Experiments were conducted using wet wood chips to induce moisture into the reacting system and compare the performance with dry wood with steam. The results clearly indicate the both hydrogen generation and the gasification efficiency ((g)) are better in the latter case. With the increase in SBR, gasification efficiency ((g)) and lower heating value (LHV) tend to reduce. Gasification efficiency of 85.8% is reported with LHV of 8.9MJNm(-3) at SBR of 0.75 compared with 69.5% efficiency at SBR of 2.5 and lower LHV of 7.4 at MJNm(-3) at SBR of 2.7. These are argued on the basis of the energy required for steam generation and the extent of steam consumption during the reaction, which translates subsequently in the LHV of syngas. From the analysis of the results, it is evident that reaction kinetics plays a crucial role in the conversion process. The study also presents the importance of reaction kinetics, which controls the overall performance related to efficiency, H-2 yield, H-2 to CO fraction and LHV of syngas, and their dependence on the process parameters SBR and ER. Copyright (c) 2013 John Wiley & Sons, Ltd.

Scientific and technological aspects of fixed bed biomass gasification

In recent years new emphasis has been placed on problems of the environmental aspects of waste disposal, especially investigating alternatives to landfill, sea dumping and incineration. There is also a strong emphasis on clean, economic and efficient processes for electric power generation. These two topics may at first appear unrelated. Nevertheless, the technological advances are now such that a solution to both can be combined in a novel approach to power generation based on waste-derived fuels, including refuse-derived fuel (RDF) and sludge power (SP) by utilising a slagging gasifier and advance fuel technology (AFT). The most appropriate gasification technique for such waste utilisation is the British Gas/Lurgi (BGL) high pressure, fixed bed slagging gasifier where operation on a range of feedstocks has been well-documented. This gasifier is particularly amenable to briquette fuel feeding and, operating in an integrated gasification combined cycle mode (IGCC), is particularly advantageous. Here, the author details how this technology has been applied to Britain's first AFT-IGCC Power Station which is now under development at Fife Energy Ltd., in Scotland, the former British Gas Westfield Development Centre.

Experiments and analysis of propagation front under gasification regimes in a packed bed

The paper analyses the results of experiments on the propagation rate in a fuel bed under gasification conditions in a co-current reactor configuration. Experiments using wood chips with different values of moisture content have been conducted under gasification conditions. The influence of air mass flux on the propagation rate, peak temperature and gas quality is investigated. It is observed from the experiments that the flame front propagation rate initially increases as the air mass flux increased, reaching a peak propagation rate, and further increase in the air mass flux results in a decrease in the propagation rate. However, the bed movement increases with the increase in air mass flux. The experimental results provide an understanding on influence of the fuel properties on propagation front. The surface area per unit volume of the particles in the packed bed plays an important role in the propagation rate. It has been argued that the flaming pyrolysis contributes towards the flame propagation as opposed to the overall combustion process in a packed bed. The calorific value of the producer gas generated is nearly the same over the entire range of air mass flux for bone-dry and 10% moist wood. (C) 2014 Elsevier B.V. All rights reserved.

Copper-Catalyzed Oxidative Transformation of Secondary Alcohols to 1,5-Disubstituted Tetrazoles

A mild and convenient oxidative transformation of secondary alcohols to 1,5-disubstituted tetrazoles is uncovered by employing trimethylsilyl azide (TMSN3) as a nitrogen source in the presence of a catalytic amount of copper(II) perchlorate hexahydrate Cu(ClO4)(2)(.)6H(2)O] (5mol%) and 2,3-dichloro-5,6-dicyano-para-benzoquinone (DDQ) (1.2equiv.) as an oxidant. This reaction is performed under ambient conditions and proceeds through CC bond cleavage.

Influence of surface area to volume ratio of fuel particles on gasification process in a fixed bed

The paper addresses the effect of particle size on tar generation in a fixed bed gasification system. Pyrolysis, a diffusion limited process, depends on the heating rate and the surface area of the particle influencing the release of the volatile fraction leaving behind residual char. The flaming time has been estimated for different biomass samples. It is found that the flaming time for wood flakes is almost one fourth than that of coconut shells for same equivalent diameter fuel samples. The particle density of the coconut shell is more than twice that of wood spheres, and almost four times compared with wood flakes; having a significant influence on the flaming time. The ratio of the particle surface area to that of an equivalent diameter is nearly two times higher for flakes compared with wood pieces. Accounting for the density effect, on normalizing with density of the particle, the flaming rate is double in the case of wood flakes or coconut shells compared with the wood sphere for an equivalent diameter. This is due to increased surface area per unit volume of the particle. Experiments are conducted on estimation of tar content in the raw gas for wood flakes and standard wood pieces. It is observed that the tar level in the raw gas is about 80% higher in the case of wood flakes compared with wood pieces. The analysis suggests that the time for pyrolysis is lower with a higher surface area particle and is subjected to fast pyrolysis process resulting in higher tar fraction with low char yield. Increased residence time with staged air flow has a better control on residence time and lower tar in the raw gas. (C) 2014 International Energy Initiative. Published by Elsevier Inc. All rights reserved.

Copper-Catalyzed Decarboxylative Sulfonylation of alpha,beta-Unsaturated Carboxylic Acids

Copper-catalyzed, ligand-promoted decarboxylative coupling of readily available a,fi-unsaturated acids with sodium aryl sulfinates is presented. This method provides a new avenue for the synthesis of vinyl sulfones via a decarboxylative radical coupling strategy by employing a catalytic amount of Cu(ClO4)(2)center dot 6H(2)O, TBHP in decane as an oxidant, and 1,10-phenanthroline as a ligand. The salient feature of this method is that it furnishes exclusively the (E)-isomer.

First and second law thermodynamic analysis of air and oxy-steam biomass gasification

Gasification is an energy transformation process in which solid fuel undergoes thermochemical conversion to produce gaseous fuel, and the two most important criteria involved in such process to evaluate the performance, economics and sustainability of the technology are: the total available energy (exergy) and the energy conserved (energy efficiency). Current study focuses on the energy and exergy analysis of the oxy-steam gasification and comparing with air gasification to optimize the H-2 yield, efficiency and syngas energy density. Casuarina wood is used as a fuel, and mixture of oxygen and steam in different proportion and amount is used as a gasifying media. The results are analysed with respect to varying equivalence ratio and steam to biomass ratio (SBR). Elemental mass balance technique is employed to ensure the validity of results. First and second law thermodynamic analysis is used towards time evaluation of energy and exergy analysis. Different component of energy input and output has been studied carefully to understand the influence of varying SBR on the availability of energy and irreversibility in the system to minimize the losses with change in input parameters for optimum performance. The energy and exergy losses (irreversibility) for oxy-steam gasification system are compared with the results of air gasification, and losses are found to be lower in oxy-steam thermal conversion; which has been argued and reasoned due to the presence of N-2 in the air-gasification. The maximum exergy efficiency of 85% with energy efficiency of 82% is achieved at SBR of 0.75 on the molar basis. It has been observed that increase in SBR results in lower exergy and energy efficiency, and it is argued to be due to the high energy input in steam generation and subsequent losses in the form of physical exergy of steam in the product gas, which alone accounts for over 18% in exergy input and 8.5% in exergy of product gas at SBR of 2.7. Carbon boundary point (CBP), is identified at the SBR of 1.5, and water gas shift (WGS) reaction plays a crucial role in H-2 enrichment after carbon boundary point (CBP) is reached. Effects of SBR and CBP on the H-2/CO ratio is analysed and discussed from the perspective of energy as well as the reaction chemistry. Energy density of syngas and energy efficiency is favoured at lower SBR but higher SBR favours H-2 rich gas at the expense of efficiency. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Gold Catalyzed Plasma Assisted Growth of Germanium Nanoneedles

A systematic study of Gold catalyzed growth of Ge nanoneedles by PECVD at low temperatures (<400 degrees C) is presented. Morphology, growth rate and aspect ratio of the needles are studied as a function of power, gas flow rate and chamber pressure. Nanoneedles were grown at pre-defined positions with catalytic particles obtained by e-Beam Lithography and lift off. This opens up the possibility of using Ge Nano needles in photovoltaic, nanoelectronics and nanosensor device applications.

BIOMASS GASIFICATION TO SUBSTITUTE FOSSIL FUEL IN FOOD INDUSTRY

Food industries like biscuit and confectionary use significant amount of fossil fuel for thermal energy. Biscuit manufacturing in India is carried out both by organized and unorganized sector. The ratio of organized to unorganized sector is 60 : 40 (1). The total biscuit manufacturing in the organized sector India in 2008 was about 1.7 million metric tons (1). Accounting for the unorganized sector in India, the total biscuit manufacturing would have been about 2.9 million metric tons/annum. A typical biscuit baking is carried in a long tunnel kiln with varying temperature in different zones. Generally diesel is used to provide the necessary heat energy for the baking purpose, with temperature ranging from 190 C in the drying zone to about 300 C in the baking area and has to maintain in the temperature range of +/- 5 C. Typical oil consumption is about 40 litres per ton of biscuit production. The paper discusses the experience in substituting about 120 lts per hour kiln for manufacturing about 70 tons of biscuit daily. The system configuration consists of a 500 kg/hr gasification system comprising of a reactor, multicyclone, water scrubbers, and two blowers for maintaining the constant gas pressure in the header before the burners. Cold producer gas is piped to the oven located about 200 meters away from the gasifier. Fuel used in the gasification system is coconut shells. All the control system existing on the diesel burner has been suitably adapted for producer gas operation to maintain the total flow, A/F control so as to maintain the temperature. A total of 7 burners are used in different zones. Over 17000 hour of operation has resulted in replacing over 1800 tons of diesel over the last 30 months. The system operates for over 6 days a week with average operational hours of 160. It has been found that on an average 3.5 kg of biomass has replaced one liter of diesel.

Copper-Catalyzed Direct Transformation of Secondary Allylic and Benzylic Alcohols into Azides and Amides: An Efficient Utility of Azide as a Nitrogen Source

A mild and convenient method for the synthesis of amides has been explored by using secondary alcohols, Cu(ClO4)(2)6H(2)O as a catalyst, and trimethylsilyl azide (TMSN3) as a nitrogen source in the presence of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) at ambient temperature. This method has been successfully adapted to the preparation of azides directly from their corresponding alcohols and offers excellent chemoselectivity in the formation of -halo azides and the azidation of allylic alcohols in the presence of a benzyl alcohol moiety. In addition, this strategy provides an opportunity to synthesize azides that can serve as precursors to -amino acids.

Ru (II)-Catalyzed C-H Activation: Ketone-Directed Novel 1,4-Addition of Ortho C-H Bond to Maleimides

A 1,4-addition with the nucleophilic center generated at the ortho carbon atom of an aromatic ketone in the presence of the highly reactive alpha-C-H bond, using a directing group strategy, is presented. The reaction yields pharmaceutically useful 3-arylated succinimide derivatives. In order to gain understanding of this redox neutral reaction, despite the presence of copper acetate, and to substantiate the lack of Heck-type products, DFT calculations have been carried out.

Site-Selective Addition of Maleimide to Indole at the C-2 Position: Ru(II)-Catalyzed C-H Activation

Synthesis of 3-(indol-2-yl)succinimide derivatives is presented using a directing group strategy. Selective functionalization of C-2 in the presence of highly reactive C-3 in indole derivatives has been achieved. A conjugate addition product instead of Heck-type product has been brought about by careful selection of the alkene partner (maleimides and maleate esters) such that a beta-hydride elimination is avoided.