Isopropyl N-phenylcarbamate Research Articles

Techno-economic, environmental, and exergetic evaluation of a novel isopropyl n-phenylcarbamate production process through non-reductive conversion of CO2

The conversion of carbon dioxide (CO2) into valuable chemicals has emerged as a prominent research field. This study attempts to uncover the rigorous design and comprehensive analysis of an innovative process that produces Isopropyl N-phenylcarbamate (IPPhCM) through direct synthesis involving CO2, 2-Propanol (IPA), and phenylamine (PHAM). The reaction system utilizes CeO2 as a catalyst and 2-Cyanopyridine (2-CP) as a chemical dehydrant. In general, this work presents alternative designs in a rigorous manner, with different combinations of conversion and yield. It also evaluates various strategies, such as heat integration, thermal coupling, and the addition of a co-reactant, to enhance the efficiency of the system. Based on the results, the configuration designed with a 92% yield of IPPhCM and incorporating both dividing-wall columns and direct heat integration was determined to be the best scenario. The corresponding minimum required selling price (MRSP) for IPPhCM is 1.996 USD/kg (at a 15% internal rate of return, measured without considering the cost of 2-CP), and the amount of CO2 emission per unit amount of product formed is + 0.075 kg/kg. However, the overall exergy efficiency of this process is only 42.7%. The main reason is the formation of mixtures that are difficult to separate, involving side products such as isopropyl picolinate (IPP), diisopropyl carbonate (DIPC), and others. To enhance the scheme, retrofitting it by adding ammonia to the reaction section enables the conversion of IPP and DIPC into valuable and separable by-products, namely 2-picolinamide (2-PA) and isopropyl carbamate (IPCM). This arrangement significantly enhances the exergy efficiency to 71.8% and reduces the MRSP to 1.759 USD/kg, at the cost of a slight increase in CO2-e to 0.118 kg/kg. With these results, the regeneration of byproducts can make the entire process more appealing and sustainable.

Effect of flue gas impurities in carbon dioxide from power plants in the synthesis of isopropyl N-phenylcarbamate from CO2, aniline, and 2-propanol using CeO2 and 2-cyanopyridine

Current CO2 utilization technologies generally start with purification of CO2, which requires considerable energy input. Using CO2-containing flue gases as a feedstock in chemical conversions of CO2 can help simplify pre-treatment of CO2 and reduce the carbon footprint of the process, however, study of the effects of other components in the flue gases in chemical reactions using CO2 is limited. Our previous study demonstrated that the combination catalyst system of CeO2 and 2-cyanopyridine was effective for the reaction of pure CO2, aniline, and 2-propanol to afford isopropyl N-phenylcarbamate, which is a promising precursor for polyurethane, in over 90% yield. In this study, the addition effect of other components in CO2-containing flue gases namely N2, O2, SO2 (ppm-order) and NO2 (ppm-order) on the reaction was investigated. The addition of N2 and NO2 had almost no influence on the catalytic performance, however, that of O2 and SO2 had some negative effects. The addition of O2 decreased the selectivity and yield to the target carbamate due to the formation of aniline-derived byproducts such as aniline-coupling products and aniline-oligomers. The increase of the amount of 2-cyanopyridine and 2-propanol was effective for the suppression of the aniline-derived byproducts, providing a similar yield of the isopropyl N-phenylcarbamate to the case without any additives. The catalyst system was strongly poisoned by addition of SO2, and the activity of CeO2 was not recovered even by calcination treatment.

Screening of CO2 utilization routes from process simulation: Design, optimization, environmental and techno-economic analysis

This work aims at evaluating potential direct CO2 conversion processes through systematic screening and process simulation. Fifteen direct routes converting CO2 to carbonates or carbamates, with in situ chemical dehydration using 2-cyanopyridine (2-CP) are focused. The work covers an extensive examination (and supplement) on the physical properties, selection of promising routes, process simulation, optimization, environmental, and techno-economic evaluation. Firstly, three promising routes were selected, producing dimethyl carbonate (DMC), dipropyl carbonate (DPC), and Isopropyl N-phenylcarbamate (IPPhCM), based on three criteria: azeotropic search, product selectivity and reacting conditions. Next, the corresponding processes were simulated, optimized, heat-integrated, and systematically compared with the previously-proposed diethyl carbonate (DEC) process through environmental and economic analysis. From environmental analysis, the CO2 emission rate (CO2-e, in kg/kg-product) was 0.067, 0.088, −0.040 and −0.154 for producing DMC, DPC, IPPhCM and DEC, respectively. By reducing the excess ratio used for reaction (i.e. 2-CP/alcohol or amine/alcohol), the CO2-e improved to −0.122, −0.086, and −0.117 for producing DMC, DPC and IPPhCM, respectively. Finally, the minimum required selling prices (MRSP) at 15 % internal rate of return (IRR) were determined, with the unit price of 2-CP, 2-picolinamide (2-PA), and the reactor residence time regarded as uncertainties. The MRSPs for DMC, DPC, IPPhCM and DEC are found in the range of 1.50–4.96, 2.29–4.24, 2.07–4.06 and 1.12–2.81 (all in USD/kg), respectively. Future studies exploring the commercial availability and the regeneration of 2-CP, and the feasibility of reducing the excess ratio and the reaction residence time are considered helpful.

Sugar-Starch Metabolism and Antioxidant Potential in Potato Tubers in Response to Different Antisprouting Agents During Storage

Single applications of different antisprouting agents like hot water treatment, spearmint oil and clove oil were carried out on potato cultivar “Lady Rosetta” to compare their efficacy with that of synthetic chloro isopropyl N-phenyl carbamate (CIPC). The tubers were stored at ambient storage conditions (25 ± 2 °C) for 81 days to assess changes in their sugar-starch concentrations and antioxidant potential. Antioxidant potential in the tubers was assessed as their total phenolic concentrations and radical scavenging activities. In addition, the enzymatic activities were also determined in order to evaluate the possible depletion of these antioxidants as substrate during storage. Results revealed significant response of stored potatoes to all antisprouting agents compared with the control (P ≤ 0.05). CIPC and clove oil applications maintained tuber dormancy almost twice as long (81 days) as observed in the control (45 days). Application of spearmint oil and hot water treatment maintained tuber dormancy for almost 2 months. However, it was associated with an increased percentage sprouting during the last weeks of storage. At the end of storage, the highest starch (16.83%) and lowest sugar (0.99%) concentrations were estimated after CIPC application and maximum total phenolic concentration (143.57 mg gallic acid equivalent (GAE)/100 g), and highest antioxidant activity (39.73%) were found after clove oil application. Enzymatic activities were not statistically different between CIPC and clove oil application during most of the storage period. Results showed that efficient replacement of CIPC with clove oil in the premium potato cultivar might be useful; this may avert related food safety and environmental issues and would also ensure organic potato storage.

Effects of the herbicide isopropyl‐N‐phenyl carbamate on microtubules and MTOCs in lines of Nicotiana sylvestris resistant and sensitive to its action

To clarify the mechanism of isopropyl-N-phenyl carbamate (IPC) action on higher plant cells the sensitivity of microtubules (cortical network and mitotic arrays) and microtubule organizing centers to IPC treatment (30 microM) in IPC-resistant and sensitive Nicotiana sylvestris lines was studied. It was clearly demonstrated that IPC does not depolymerize plant MTs but causes the MTOC damage in cells, which results in MTOC fragmentation, splitting of the spindle poles and in abnormal division spindle formation. It was also found that IPC-resistance of mutant N. sylvestris line correlates not with tubulin resistance to IPC action but possibly with resistance of one of the proteins involved in MTOC composition.

Nicotiana sylvestris L. mutants resistant to isopropyl N-phenyl carbamate possess microtubule organizing centers of heightened stability

N. sylvestris mutants resistant to isopropyl N-phenyl carbamate (IPC), a herbicide belonging to the phenyl carbamate series, are obtained by means of in vitro selection using gamma radiation. A concentration of 30 μM IPC was found to be the maximum concentration at which mutants of the N. sylvestris line capable of regeneration and rooting under conditions of selection pressure could be selected. IPC resistance in the mutants obtained was confirmed by a number of tests, in particular, tests that measure the capacity of leaf explants of the mutant lines to regenerate plants and the ability of their callus cells to survive in media with a selective IPC concentration, as well as by means of genetic, morphometric, cytological, and immunofluorescent analyses. The results of these studies attest to increased resistance of the mutant plants to this antimitotic substance by comparison with a control. It is shown that resistance to IPC is based on the heightened resistance of the microtubule organizing centers of the cells of these lines. It is established that the acquired resistance trait inherited in the F1 and F2 generations of the mutants is a dominant nuclear trait.

Early PCD events in male gametophyte development of isopropyl-N-phenyl carbamate resistant Nicotiana sylvestrismutant lines

Background Microtubules provide structural support for cells and play a key role in mitosis and meiosis. They also play a key role in plant cell differentiation, new tissue and organ formation through a coordinated program of symmetric or asymmetric cell division. It is well known that microtubule-damaging agents suppress microtubule dynamics, leading to disruption of the mitotic spindle in dividing cells, cell cycle arrest at M-phase, and the late apoptosis [1]. A better understanding of the processes coupling microtubule damage to the onset of apoptosis will help to find out in process of higher plants development. Recently, the mutant Nicotiana lines with high resistance to antimitotic herbicide isopropyl-N-phenyl carbamate (IPC) were produced [2,3]. Detailed analysis of IPC-resistant Nicotiana sylvestris plants revealed some abnormalities in microsporogenesis leading to partial pollen sterility. Here we report that these mutant N. sylvestris lines conferring resistance to IPC demonstrate clearly programmed cell death (PCD) events in male gamethophyte formation and development.

Development of a New Fungicide, Diethofencarb

Diethofencarb [isopropyl N-(3, 4-diethoxyphenyl)carbamate] is a new carbamate fungicide developed by Sumitomo Chemical Co., Ltd. This compound has an outstanding activity against benzimidazole-resistant gray mold of fruit trees, grapes, and vegetables caused by Botrytis cinerea. One of the most effective ways to cope with resistance of plant pathogens is considered to be the use of fungicides to which resistant strains show negatively correlated cross-resistance. Through extensive investigations to search for N-phenylcarbamates with a potent fungicidal activity against benzimidazole-resistant fungi, we synthesized an isopropyl N-phenylcarbamate having 3, 4-diethoxy substituents on the benzene ring, named diethofencarb, to which the resistant strains of B. cinerea exhibited negatively correlated cross-resistance. Diethofencarb controled benzimidazole-resistant strains of B. cinerea curatively as well as preventively and showed systemic activity in plants. This fungicide did not inhibit germination of conidia of the benzimidazole-resistant B. cinerea, but the germ tubes were distored and swollen. Their abnormal morphology was quite similar to that of the wild type isolates treated with a benzimidazole fungicide, carbendazim. In field trials, the combination of diethofencarb with carbendazim (Sumico®), another benzimidazole fungicide, thiophanatemethyl (Gtter®), or a dicarboximide fungicide, procymidone (Sumiblend®) showed excellent performance for control of gray mold diseases where benzimidazole-resistant strains and the wild type ones coexisted.

The perturbation of the endomembrane network of the chlamydomonad alga Gloeomonas by the herbicide isopropyl N‐phenyl carbamate (IPC)

Abstract. The highly complex and symmetric endomembrane network of the chlamydomonad alga, Gloeomonas kupferri, can be disrupted by the herbicide, isopropyl N‐phenyl carbamate (IPC). Upon incubation with IPC for between 30 min and 1 h, curling of the dictyosomes, proliferation of small vesicles from the trans face and swelling of the peripheral vacuolar complex takes place. Longer treatments result in degeneration of dictyosome cisternae into vesicular masses and the formation of supervacuolar complexes. Enzyme cytochemistry revealed that endomembrane ‘marker’ enzymes are altered/inhibited by IPC. A second but striking I PC‐induced effect is the production of branched, fibrillar inclusions in the cell nucleus. A discussion of I PC‐induced affects on ion regulation and microtubule/MTOC distribution in the cell is presented.

Anomalies in mineralization of low concentrations of organic compounds in lake water and sewage.

The rates of mineralization of nitrilotriacetic acid (NTA), 2,4-dichlorophenoxyacetic acid (2,4-D), p-nitrophenol, aniline, and isopropyl N-phenylcarbamate (IPC) at one or more concentrations ranging from 100 pg/ml to 1.0 microgram/ml were proportional to chemical concentrations in samples of three lakes. The rates at 100 pg of NTA, 2,4-D, p-nitrophenol, and aniline per ml in samples of one or more lakes were less than predicted, assuming the rates were linearly related to the concentration. Neither NTA nor 2,4-dichlorophenol at 2.0 ng/ml was mineralized in some lake waters, but higher levels of the two chemicals were converted to CO2 in samples of the same waters. In samples from two lakes, little or no mineralization of IPC or 2,4-D occurred at 1.0 microgram/ml, but 10 ng/ml or lower levels of the herbicides were mineralized. The mineralization in sewage of 1.0 microgram of NTA per ml was biphasic; about 20% of the substrate was mineralized in 20 h, and mineralization was only reinitiated after a period of 130 h. The biphasic transformation was not a result of the accumulation of organic products, and it was still evident if protozoan activity was inhibited. NTA also underwent a biphasic mineralization in lake waters, and the biphasic pattern was not altered by additions of growth factors and inorganic nutrients. From 40 to 60% of the carbon of aniline added to lake water at levels of 100 pg/ml to 1.0 microgram/ml was mineralized, but more than 90% of the carbon of NTA, 2,4-D, or p-nitrophenol added to lake water at 10 ng/ml or 1.0 microgram/ml was mineralized.(ABSTRACT TRUNCATED AT 250 WORDS)

Microbial transformations: Part 4(1) Regioselective para hydroxylation of aromatic rings by the fungus [formula omitted][formula omitted] the metabolism of isopropyl n-phenyl

A specific para hydroxylation of the aromatic ring of isopropyl N-phenyl carbamate 1 by the fungus Beauveria sulfurescens has been achieved. Studies of the deuterium labelled compound show high retention (NIH shift) for this transformation, a fact uhich indicates that the mechanism implied is consistent which the intermediate formation of an arene oxide. Also, formation of a glucoside conjugate of the phenol has been observed.

Acceleration of the Cleavage in Sea Urchin Eggs by Treatments with Local Anesthetics (II) Treatments with Some Other Local Anesthetics than Procaine*: (acceleration of cleavage/local anesthetics/caffeine/sea urchin eggs).

Unfertilized sea urchin eggs were exposed to sea water solutions of local anesthetics, such as caffeine, tetracaine and ethyl urethane, and the herbicide, isopropyl N-phenyl carbamate (IPC) for 10min and returned to normal sea water. Then they were inseminated 5min later. When eggs were pre-treated with 1-2 mM caffeine, 0.02-0.05 mM tetracaine, 50-100 mM ethyl urethane and 2% saturated sea water of IPC, respectively, they could cleave and hatch earlier than the control eggs. However, when fertilized eggs were continuously post-treated with solutions of the agents except IPC at the same concentrations as those in the case of the pre-treatments, the fertilized eggs could not cleave or were retarded in development. The possible mechanisms of the cleavage acceleration by pre-treatments with local anesthetics were discussed.

Effect of Substrate Concentration and Organic and Inorganic Compounds on the Occurrence and Rate of Mineralization and Cometabolism

Isopropyl N-phenylcarbamate (IPC) at 400 pg and 1 mug/ml was mineralized in samples of sewage, but only the lower concentration was mineralized in lake water samples in a 50-day period. IPC at 1 mug/ml disappeared from lake water, but it was converted to organic products. Mineralization of IPC at 400 pg/ml in lake water was enhanced by additions of inorganic nutrients or a mixture of nonchlorinated water pollutants but not by yeast extract or mixtures containing aromatic compounds or excretions of primary producers. The mineralization of 200 pg of 2,4-dichlorophenoxyacetate per ml of lake water was not affected by additions of low levels of yeast extract or compounds excreted by primary producers but was enhanced by low concentrations of mixtures of water pollutants. It is suggested that some chemicals that are found to be converted only to organic products, presumably by cometabolism, in tests using the concentrations commonly employed in laboratory evaluations may be mineralized at the lower concentrations prevailing in natural waters.

Spindle sensitivity to isopropyl-N-phenyl-carbamate and griseofulvin of common wheat plants carrying different doses of the Ph1 gene

Lines of common wheat cv. 'Chinese Spring' carrying different doses of the Ph1 gene, located on the long arm of chromosome 5B were treated with the antimitotic agents griseofulvin and isopropyl-N-phenyl-carbamate (IPC). Treatments with low griseofulvin concentrations and IPC resulted mainly in the production of a high percentage of cells exhibiting spindle disorganization at metaphase and multipolar cells at anaphase–telophase. These treatments did not differentially affect the tested genotypes. On the other hand, higher griseofulvin concentrations induced the appearance of frequent C-metaphases and C-anaphases because of complete disruption of the spindle microtubules; in such cases, more pronounced sensitivity was observed in a line lacking the Ph1 gene than in lines disomic and tetrasomic for chromosome 5B. From this evidence it can be concluded that subcellular structures regulating microtubule organization and orientation, which are apparently the target of IPC and low griseofulvin concentrations, are not related to the action of the Ph1 gene. Rather, tubulin–microtubules equilibrium, which is affected by colchicine and high griseofulvin concentrations, is influenced by the action of this gene. Thus, the Ph1 gene product may correspond to a tubulin or a microtubule-associated protein which in turn stabilizes microtubule structure. In either case, the equilibrium tubulin–microtubules would be shifted towards microtubules in plants containing two doses of Ph1 and even more in plants containing an extra dose of this gene.Key words: spindle, Triticum, microtubules, antitubulins, griseofulvin.

Structural alterations inEuglena gracilis exposed to the herbicide isopropyl-N-phenylcarbamate (IPC)

Ultrastructural abnormalities of various kinds and severity appeared inEuglena gracilis green cells after a 48-hour exposure to 4 × 10−4M of isoprophyl-N-phenylcarbamate (IPC), a widely used herbicide thought to affect microtubules and/or microtubule organizing centers in susceptible plant and animal species.

Microtubule‐dependent transport of secretory granules during stalk secretion in a peritrich ciliate

AbstractThe role of microtubules in secretory granule translocation was studied during stalk secretion in the peritrich ciliate, Zoothamnium arbuscula. In each cell, the release of stalk‐forming secretory materials is restricted to a specialized region of the cytoplasm, the scopula. Many of the membrane‐bound secretory granules that dominate the scopular cytoplasm appear to be aligned along cortical microtubules that converge on the scopular surface. This arrangement is consistent with the hypothesis that microtubules transport granules relative to the sites of exocytosis. To establish the role of microtubules in stalk secretion, telotrochs were exposed to agents with different disruptive effects on microtubule function. Exocytosis itself is not prevented by these drugs, and granules positioned for secretion prior to treatment are released. Maytansine and isopropyl‐n‐phenyl carbamate (IPC) completely inhibit stalk elongation. In maytansine‐treated cells, microtubules are absent from the scopular cytoplasm, and granules are absent from the scopular surface. Microtubules are present in IPC‐treated cells, but the granules are misdirected to the cytoplasm lateral to the scopula where no secretory sites exist. Even though the rate of stalk secretion is decreased by deuterium oxide (D2O), a control length stalk is eventually produced. In D2O‐treated cells microtubules are present and in their normal orientation. The inhibition of secretion when microtubules are absent (maytansine) or misdirected (IPC) and the retardation of secretion when microtubule turnover is reduced (D2O) supports a mechanism of granule transport based on the directional turnover of microtubule subunits.

Effect of microtubule inhibitors on the tubulin system ofDictyostelium discoideum

Indirect immunofluorescence with antibodies to microtubular proteins has been used to investigate the microtubule system of Dictyostelium discoideum vegetative amoebae and the action of several compounds that interfere with that system. All the inhibitors tested show an antimicrotubular effect. Colchicine, vinblastine, nocodazole, thiabendazole, and isopropyl-N-phenyl-carbamate (IPC) seem to act mainly by destroying microtubules leaving the appearance of nuclei associated organelles (NAOs) undisturbed. On the other hand griseofulvin also affects NAOs which disappear in treated cells.

Effect of microtubule inhibitors on the tubulin system of Dictyostelium discoideum

AbstractIndirect immunofluorescence with antibodies to microtubular proteins has been used to investigate the microtubule system of Dictyostelium discoideum vegetative amoebae and the action of several compounds that interfere with that system. All the inhibitors tested show an antimicrotubular effect.Colchicine, vinblastine, nocodazole, thiabendazole, and isopropyl‐N‐phenyl‐carbamate (IPC) seem to act mainly by destroying microtubules leaving the appearance of nuclei associated organelles (NAOs) undisturbed. On the other hand griseofulvin also affects NAOs which disappear in treated cells.

Cell Expansion Patterns and Directionality of Wall Mechanical Properties in Nitella.

As a means of assessing the extent to which deformation of isolated walls relates to in vivo cell expansion, the directionality of wall mechanical properties was examined in Nitella. Measurements were made of plastic and elastic deformation and creep under both uniaxial and multiaxial stress conditions. Walls of different structural characteristics were obtained from control, isopropyl N-phenylcarbamate (IPC)-treated and IPC recovery cells. Although microfibrils in the inner portion of the wall were transverse for control and recovery cells but random for IPC cells, all walls had similar over-all microfibrillar orientations. Consequently, differences in wall mechanical properties should reflect structural differences in the inner wall. It is the action of the prevailing stress pattern on the inner, not overall, wall microfibrillar organization which dictates the directionality of growth in Nitella. The results indicate that the directional character of expansion is preserved to a large extent in the mechanical properties of isolated walls, and that most, but not all, of the deformation is determined by the inner wall. In addition, directional differences in the threshold for acid-induced extension varied in accord with the pattern of inner wall microfibrils.

Isolation of tobacco protoplasts in the presence of isopropyl N-phenylcarbamate and their culture and regeneration into plants

Mutagenized tobacco protoplasts were plated in the presence of isopropyl N-phenyl-carbamate (IPC) in an attempt to isolate IPC resistant cells. A high proportion of the plants regenerated in the presence of IPC were sterile. Only one «mutant» plant produced protoplasts which are more resistant to IPC than the parental «Xanthi».