scholarly journals Development of Efficient and Selective Processes for the Synthesis of Commercially Important Chlorinated Phenols

Organics ◽  
2021 ◽  
Vol 2 (3) ◽  
pp. 142-160
Author(s):  
Keith Smith ◽  
Gamal A. El-Hiti

para-Selective processes for the chlorination of phenols using sulphuryl chloride in the presence of various sulphur-containing catalysts have been successfully developed. Several chlorinated phenols, especially those derived by para-chlorination of phenol, ortho-cresol, meta-cresol, and meta-xylenol, are of significant commercial importance, but chlorination reactions of such phenols are not always as regioselective as would be desirable. We, therefore, undertook the challenge of developing suitable catalysts that might promote greater regioselectivity under conditions that might still be applicable for the commercial manufacture of products on a large scale. In this review, we chart our progress in this endeavour from early studies involving inorganic solids as potential catalysts, through the use of simple dialkyl sulphides, which were effective but unsuitable for commercial application, and through a variety of other types of sulphur compounds, to the eventual identification of particular poly(alkylene sulphide)s as very useful catalysts. When used in conjunction with a Lewis acid such as aluminium or ferric chloride as an activator, and with sulphuryl chloride as the reagent, quantitative yields of chlorophenols can be obtained with very high regioselectivity in the presence of tiny amounts of the polymeric sulphides, usually in solvent-free conditions (unless the phenol starting material is solid at temperatures even above about 50 °C). Notably, poly(alkylene sulphide)s containing longer spacer groups are particularly para-selective in the chlorination of m-cresol and m-xylenol, while, ones with shorter spacers are particularly para-selective in the chlorination of phenol, 2-chlorophenol, and o-cresol. Such chlorination processes result in some of the highest para/ortho ratios reported for the chlorination of phenols.

2011 ◽  
Vol 239-242 ◽  
pp. 161-167
Author(s):  
Xiao Zhen Wang ◽  
Yi Feng Zhu ◽  
Xiao Nian Li

A 2 wt % Pd/C catalyst has been prepared by chemical impregnation and used to catalyze the hydrogenation of o-chloronitrobenzene (o-CNB) to o-chloroaniline (o-CAN) in solvent-free conditions. The effects of reaction temperature, H2 pressure, and stirring intensity on the hydrogenation kinetics have been investigated. The hydrogenation reaction showed very high selectivity with dehalogenation side products as low as 0.3% of total yield. The favorable reaction conditions were found to be temperature T = 383 K, stirring speed = 900 rpm, and feeding ratio CNB/catalyst = 200/1 (m/m). The recycled Pd/C still retained more than 98% of its original selectivity after 12 repeat used, indicating the catalyst had strong potentials for commercial application at industrial scale.


2020 ◽  
Vol 501 (1) ◽  
pp. L71-L75
Author(s):  
Cornelius Rampf ◽  
Oliver Hahn

ABSTRACT Perturbation theory is an indispensable tool for studying the cosmic large-scale structure, and establishing its limits is therefore of utmost importance. One crucial limitation of perturbation theory is shell-crossing, which is the instance when cold-dark-matter trajectories intersect for the first time. We investigate Lagrangian perturbation theory (LPT) at very high orders in the vicinity of the first shell-crossing for random initial data in a realistic three-dimensional Universe. For this, we have numerically implemented the all-order recursion relations for the matter trajectories, from which the convergence of the LPT series at shell-crossing is established. Convergence studies performed at large orders reveal the nature of the convergence-limiting singularities. These singularities are not the well-known density singularities at shell-crossing but occur at later times when LPT already ceased to provide physically meaningful results.


Climate ◽  
2021 ◽  
Vol 9 (2) ◽  
pp. 20
Author(s):  
Kleoniki Demertzi ◽  
Vassilios Pisinaras ◽  
Emanuel Lekakis ◽  
Evangelos Tziritis ◽  
Konstantinos Babakos ◽  
...  

Simple formulas for estimating annual actual evapotranspiration (AET) based on annual climate data are widely used in large scale applications. Such formulas do not have distinct compartments related to topography, soil and irrigation, and for this reason may be limited in basins with high slopes, where runoff is the dominant water balance component, and in basins where irrigated agriculture is dominant. Thus, a simplistic method for assessing AET in both natural ecosystems and agricultural systems considering the aforementioned elements is proposed in this study. The method solves AET through water balance based on a set of formulas that estimate runoff and percolation. These formulas are calibrated by the results of the deterministic hydrological model GLEAMS (Groundwater Loading Effects of Agricultural Management Systems) for a reference surface. The proposed methodology is applied to the country of Greece and compared with the widely used climate-based methods of Oldekop, Coutagne and Turk. The results show that the proposed methodology agrees very well with the method of Turk for the lowland regions but presents significant differences in places where runoff is expected to be very high (sloppy areas and areas of high rainfall, especially during December–February), suggesting that the proposed method performs better due to its runoff compartment. The method can also be applied in a single application considering irrigation only for the irrigated lands to more accurately estimate AET in basins with a high percentage of irrigated agriculture.


2020 ◽  
Vol 11 (1) ◽  
pp. 168
Author(s):  
Hyeonu Im ◽  
Jiwon Yu ◽  
Chulung Lee

Despite the number of sailings canceled in the past few months, as demand has increased, the utilization of ships has become very high, resulting in sudden peaks of activity at the import container terminals. Ship-to-ship operations and yard activity at the container terminals are at their peak and starting to affect land operations on truck arrivals and departures. In response, a Truck Appointment System (TAS) has been developed to mitigate truck congestion that occurs between the gate and the yard of the container terminal. The vehicle booking system is developed and operated in-house at large-scale container terminals, but efficiency is low due to frequent truck schedule changes by the transport companies (forwarders). In this paper, we propose a new form of TAS in which the transport companies and the terminal operator cooperate. Numerical experiments show that the efficiency of the cooperation model is better by comparing the case where the transport company (forwarder) and the terminal operator make their own decision and the case where they cooperate. The cooperation model shows higher efficiency as there are more competing transport companies (forwarders) and more segmented tasks a truck can reserve.


Biologia ◽  
2016 ◽  
Vol 71 (8) ◽  
Author(s):  
Amin Golpour ◽  
Mohammad Abdul Momin Siddique ◽  
Diógenes Henrique Siqueira-Silva ◽  
Martin Pšenička

AbstractInterest in reproductively sterile fish in aquaculture has prompted research into their production. Several methods are available for inducing sterility and optimizing its application in the global fishery industry. Sterilization can potentially be accomplished through irradiation, surgery, or chemical and hormonal treatment. Alternative approaches include triploidization, hybridization, and generation of new lines via advanced biotechnological techniques. Triploids of many commercially important species have been studied extensively and have been produced on a large scale for many years. Novel approaches, including disruption of gonadotropin releasing hormone signalling and genetic ablation of germ cells, have been developed that are effective in producing infertile fish but have the disadvantage of not being 100% reliable or are impractical for large-scale aquaculture. We review currently used technologies and recent advances in induction of sterility in fish, especially those intended for use in germ cell transplantation. Knowledge of the implications of these approaches remains incomplete, imposing considerable limitations.


2017 ◽  
Vol 19 (22) ◽  
pp. 5396-5402 ◽  
Author(s):  
Zhi Tang ◽  
Qiutao Jiang ◽  
Lifen Peng ◽  
Xinhua Xu ◽  
Jie Li ◽  
...  

A highly efficient way for the direct (trans)esterification of acyl acids (esters) and alcohols in a strict 1 : 1 ratio using a zirconocene complex (1, 1 mol%), a strong Lewis acid of good water tolerance, as a catalyst under solvent-free conditions has been developed.


Author(s):  
Gang Zheng ◽  
Yawei Lei ◽  
Xuesong Cheng ◽  
Xiyuan Li ◽  
Ruozhan Wang

Collapses of braced or tied-back excavations have frequently occurred. However, the influence of the failure of some retaining structure members on the overall safety performance of a retaining system has not been studied. Model tests of failures of retaining piles, struts or anchors were conducted in this study, and the load transfer mechanisms underlying these conditions were analysed. When failures or large deformations occurred in certain piles, the increasing ratios of the bending moments in adjacent piles were much larger in the braced retaining system than in the cantilever system and more easily triggered progressive failure. When the strut elevation was lower or the excavation depth was greater, the degree of influence and range of pile failures became larger. When certain struts/anchors failed, their loads transferred to a few adjacent struts/anchors, possibly leading to further strut/anchor failure. The influence mechanisms of strut or anchor failure on piles were different from those of pile failure. As the number of failed struts or anchors increases, the bending moments of the piles in the failure zone first decrease and then increase to very high values. Therefore, the progressive failure path extends from struts/anchors to piles and will lead to large-scale collapse.


2021 ◽  
Vol 9 (1) ◽  
pp. 01-12
Author(s):  
Charvia Ismi Zahrani ◽  
Setia Pramana

AbstractCOVID-19 is a serious problem that faced by almost all countries in the world. Since announced as a pandemic by WHO on March, the number of positive COVID-19 cases in Indonesia has reached 287,008 patients until the end of September 2020. COVID-19 cases dispersion depends on the local government policies and the awareness of the public to obey. About 60 percent of positive cases and 65 percent of death cases were in Java. Therefore, the aim of this study is to analyze the growth of the COVID-19 case in Java from March to September 2020 in relation to the local government policies. The results showed that six provinces in Java had the same pattern. The large-scale social restriction (PSBB), which was implemented since April 10 2020, seen to be able to contain the dispersion of cases because from April to June the positive cases did not increase significantly. A very high increase occurred in August and September, this was probably due to the easing of the PSBB become new-normal where various public places and facilities have been reopened. Meanwhile, death cases, the number is very high in mid-April and June and late July to September 2020. For cured cases, there was a significant increase in late August to September 2020. The importance of information about the growth of the COVID-19 cases can help government to formulate strategies and policies to prevent the dispersion of COVID-19.Keyword: COVID-19, Pandemic, Java, cases growth AbstrakCOVID-19 merupakan suatu masalah serius yang sedang dihadapi oleh hampir seluruh negara. Sejak diumumkan sebagai pandemi oleh WHO pada Maret lalu, jumlah kasus positif COVID-19 di Indonesia mencapai 287.008 pasien hingga akhir September. Penyebaran kasus COVID-19 sangat bergantung pada kebijakan yang ditetapkan oleh pemerintah serta kesadaran masyarakat untuk mematuhinya. Sebesar 60 persen kasus positif dan 65 persen kasus meninggal berada di Pulau Jawa. Oleh karena itu, tujuan penelitian ini adalah menganalisis perkembangan kasus COVID-19 di Pulau Jawa sejak Bulan Maret-September 2020 dikaitkan dengan kebijakan pemerintah setempat. Hasil penelitian menunjukkan bahwa keenam provinsi memiliki pola yang sama. Pembatasan Sosial Berskala Besar (PSBB) yang dilakukan sejak 10 April 2020 terlihat dapat menahan penyebaran kasus karena pada bulan April-Juni 2020 kasus positif tidak mengalami kenaikan yang signifikan. Kenaikan yang sangat tinggi terjadi pada bulan Agustus dan September 2020, hal ini mungkin disebabkan oleh dilonggarkannya kebijakan PSBB menjadi PSBB Transisi dimana berbagai tempat dan fasilitas umum telah dibuka kembali. Sementara untuk kasus meninggal, angka tertinggi terjadi pada pertengahan April dan Juni serta akhir Juli hingga September 2020. Untuk kasus sembuh, terjadi peningkatan yang signifikan pada akhir Agustus hingga September 2020. Pentingnya informasi tentang perkembangan kasus COVID-19 ini dapat membantu pemerintah daerah untuk membuat strategi dan kebijakan untuk mencegah penyebaran rantai virus COVID-19.Kata Kunci: COVID-19, Pandemi, Jawa, perkembangan kasus 


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