Synthesis of methyl N-phenyl carbamate from dimethyl carbonate and 1,3-diphenyl urea under mild conditions

Synthesis of methyl N-phenyl carbamate from dimethyl carbonate and 1,3-diphenyl urea was investigated under atmospheric pressure. The results showed that homogenous catalyst sodium methoxide had the excellent activity to efficiently catalyze the synthesis of methyl N-phenyl carbamate under atmospheric pressure.

Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO_2 and Methanol

Methyl N-phenyl carbamate(MPC), an important organic chemical, can be synthesized from aniline,CO2 and methanol. Catalyst Cu-Fe/ZrO2-SiO2 was first prepared and its catalytic performance for MPC synthesis was evaluated. Then the influence of solvent on the reaction path of MPC synthesis was investigated. It is found that the reaction intermediate is different with acetonitrile or methanol as a solvent. With acetonitrile as a solvent,the synthesis of MPC follows the reaction path with diphenyl urea as the intermediate, while with methanol as a solvent the reaction occurs via the reaction path with dimethyl carbonate as the intermediate. The catalytic mechanism of cooperative catalysis comprising metal sites, Lewis acid sites and Lewis base sites is proposed according to different reaction intermediates.

Isobaric vapor–liquid equilibrium for binary system of aniline+methyl-N-phenyl carbamate

In this study,the quasi-static ebulliometric method was used to measure both of the vapor pressures of methyl N-phenyl carbamate(MPC),and the isobaric vapor–liquid equilibrium(VLE) data of the aniline and MPC binary system.The measured vapor pressure data of MPC,at different temperature ranging from 369.60 to 389.54 K,fitted well with the Antoine equation.The VLE data for the aniline and MPC system at(2.00,4.00,6.00,7.00 and 8.00) k Pa were correlated by both of nonrandom two-liquid(NRTL) and Wilson models.The parameters of the two models were obtained by regressing the experimental data,with the absolute temperature deviations of 0.54 K and 0.53 K,respectively.The relative volatility of the binary system calculated was all far more than 1,which gives the conclusion that the high purity MPC can be separated from aniline and MPC binary system by rectification or distillation technology.

A Novel Non-phosgene Process for the Synthesis of Methyl N-Phenyl Carbamate from Methanol and Phenylurea: Effect of Solvent and Catalyst

A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selec- tivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied.

Studies on the Purification and Characterization of Soybean Esterase,and Its Sensitivity to Organophosphate and Carbamate Pesticides

Soybean esterase, a cholinesterase-like enzyme, was purified by differential centrifugation firstly, then, ammonium sulfate precipitation, dialysis, and finally, DEAE-cellulose-32 ion-exchange chromatography after extracting it from soybean seeds with phosphate buffer （0.3 mol L^-1, pH 7.0）. The extract recovery rate of the purified enzyme was 8.18% and purification fold was 91.58. The soybean esterase appeared as two bands on the denaturing SDS-PAGE with molecular weights of 24 and 37.2 kDa, respectively, which proved that it is a dimer protein consisting of two subunits. The result of nondenaturing PAGE revealed that the soybean esterase is a single band with cholinesterase-like activity using α- naphthyl acetate as the substrate and fast blue B salt as coloring agent. The esterase showed very high sensitivity to 18 kinds of organophosphate pesticides and 6 kinds of carbamate pesticides with the lowest detective limits of 0.03125- 0.0625 and 0.03125-0.25 mg kg^-1, respectively, and can meet the demands of MRL specified by the most countries.

Novel method for the determination of five carbamate pesticides in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography

A novel method for the determination of five carbamate pesticides （metolcarb, carbofuran, carbaryl, isoprocard and diethofencard） in water samples was developed by dispersive liquid-liquid microextraction （DLLME） coupled with high performance liquid chromatography-diode array detector （HPLC-DAD）. Some experimental parameters that influence the extraction efficiency were studied and optimized to obtain the best extraction results. Under the optimum conditions for the method, the calibration curve was linear in the concentration range from 5 to 1000 ng mL^-1 for all the five carbamate pesticides, with the correlation coefficients （r^2） varying from 0.9984 to 0.9994. Good enrichment factors were achieved ranging from 80 to 177- fold, depending on the compound. The limits of detection （LODs） （S/N = 3） were ranged from 0.1 to 0.5 ng mL^-1. The method has been successfully applied to the analysis of the pesticide residues in environmental water samples.

Selective protection of ribostamycin by cyclic carbamates

Aim To develop a novel selective protection strategy for the synthesis of ribostamycin cyclic carbamate derivatives. Methods Ribostamycin protected by carbobenzoxy group was treated with Nail, to give different protected intermediates under respective controllable cyclization reaction conditions. New ribostamycin derivative was obtained after the cleavage of carbobenzoxy groups. Result The novel selective protection of ribostamycin was achieved by the synthesis of protected intermediates. New ribostamycin derivative was obtained, but showed no expected antibacterial activity. Conclusion Several ribostamycin cyclic carbamate derivatives were obtained by novel selective protection strategy, which shows the practicability and convenience of the protection strategy. But these new ribostamycin derivatives containing cyclic carbamates structure may not be an ideal leading compound for antibiotic activity.

Probit Analysis of Carbamate-Pesticide-Toxicity at Soil-Water Interface to N_2-Fixing Cyanobacterium Cylindrospermum sp.

Toxicity-data of two carbamate insecticides, carbaryl and carbofuran, and three fungicides, ziram, zineb and mancozeb with rice-field N2-fixing cyanobacterium Cylindrospermum sp., obtained by in vitro growth and at soil-water interface, were analyzed by the probit method. Growth enhancing concentration, no-observed effective concentration, minimum inhibitory concentration, the highest permissive concentration and lethal concentration100 （LCloo） were determined experimentally. The LC^o values of carbaryl, carbofuran, ziram, zineb and mancozeb in N2-fixing liquid medium were 56.2, 588.8, 0.07, 4.2 and 3.4 IJg/mL, respectively, whereas the corresponding LCloo values were 100.0, 1500.0, 0.17, 25.0 and 9.0 IJg/mL, respectively. The LC50 values of these pesticides in succession in N2-fixing agar medium were 44.7, 239.9, 0.07, 1.8 and 2.3 IJg/mL, respectively, whereas the corresponding LC100 values were 100.0, 600.0, 0.17, 10.0 and 7.0 IJg/mL, respectively. Similar results with nitrate supplemented liquid and agar media indicated that nitrate supplementation had toxicity reducing effect. The LCso and LC^oo values of toxicity in the N2-fixing liquid medium at soil-water interface were 91.2 and 200.0 IJg/mL for carbaryl, 2 317 and 6 000 pg/mL for carbofuran, 0.15 and 0.50 pg/mL for ziram, 16.4 and 50.0 pg/mL for zineb, and 7.2 and 25.0 pg/mL for mancozeb, respectively. Each LC^oo value at soil- water interface with a pesticide was significantly higher than its corresponding LCloo value at liquid/agar media. It can be concluded that, under the N2-fixing conditions, the cyanobacterium tolerated higher levels of each pesticide at soil-water interface.

Carbamate Synthesis from Aromatic Amines and Dimethyl Carbonate Using Lead Acetate as Catalyst

Carbamates are important intermediates in the syntheses of pesticides, herbicides, drugs, polyurethane-based polymers, and other fine and commodity chemicals.

Enzyme Inhibition Rate Method for Rapid Detection of Organophosphorus and Carbamate Pesticides in Cowpea

[Objectives ] The paper was to explore enzyme inhibition rate method for rapid detection of organophosphorus and carbamate pesticides in cowpea. [ Methods ] Acetylcholinesterase （ACHE） was added to cowpea extract, to determine the inhibition rate of extract against enzyme. The influences of different sampiing methods and sampling parts on detection results were compared. [ Results] The positive rate of standard sampling was 18.18% higher than that of non-stand- ard sampling, and the positive rate of samples collected from cowpea tail was 16.67% higher than that collected from other parts. [ Condmions] Enzyme inhibi- tion rate method is suitable for rapid detection of organophosphorus and carbamate pesticides in cowpea.

Vapor Pressure, Vaporization Enthalpy, Standard Enthalpy of Formation and Standard Entropy of n-Butyl Carbamate

The vapor pressures of n-butyl carbamate were measured in the temperature range from 372.37 K to 479.27 K and fitted with Antoine equation. The compressibility factor of the vapor was calculated with the Virial equation and the second virial coefficient was determined by the Vetere model. Then the standard enthalpy of vaporization for n-butyl carbamate was estimated. The heat capacity was measured for the solid state(299.39–324.2 K) and liquid state(336.65–453.21 K) by means of adiabatic calorimeter. The standard enthalpy of formation ΔfH[crystal(cr),298.15 K] and standard entropy S(crystal,298.15 K) of the substance were calculated on the basis of the gas-phase standard enthalpy of formation ΔfH(g,298.15 K)and gas-phase standard entropy S(g,298.15 K), which were estimated by the Benson method. The results are acceptable, validated by a thermochemical cycle.

A Novel Synthesis of N-Methyl-N-aryl Carbamates from Aromatic Amines and Dimethyl Carbonate Catalyzed by K_2CO_3/Bu_4NBr

A facile synthesis of N-methyl-N-aryl carbamates from aromatic amines and dimethyl carbonate (DMC) has been achieved with high yields in the presence of potassium carbonate (K2CO3)and tetrabutylammonium bromide (Bu4NBr) under solvent-free conditions.

Synthesis and herbicidal activities of pyridyl sulfonylureas:More convenient preparation process of phenyl pyrimidylcarbamates

Four 4-monosubstituted pyrimidine pyridyl sulfonylureas were synthesized from pyridinesulfonamide and phenyl pyrimidylcarbamate and screened for herbicidal activities. We also reported a convenient preparation process of phenyl pyrimidylcarbamates from pyrimidineamine and phenyl chloroformate.

An Efficient and Novel Synthesis of Carbamate Esters from the Coupling of Amines, Halides and Carbon Dioxide in the Presence of Basic Resin

A convenient, efficient, one-pot, novel process has been developed for the synthesis of carbamates from corresponding alkyl halides and amines using basic resin/CO2 system.

Determination of Neurotoxin β-ODAP and Non-protein Amino Acids in Lathyrus Sativus by High-Performance Liquid Chromatography with Precolumn Derivatization with 6-Amino quinolyl-N-hydroxysuccinimidyl Carbamate (AQC)

A new method was developed for the quantitative determination of the neurotoxic nonprotein amino acid, 3-N-oxalyl-L-2,3-diaminopropioni acid (β-ODAP), its nontoxic α-isomer and other non-protein amino acids in the plant samples of Lathyrus sativus after derivatization with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) by reversed-phase high-performance liquid chromatography (HPLC). 2-Amino butyric acid (ABA) was used as an internal standard.The RP HPLC detection limit for both isomers is 1.8 ng with good response linearity. The results are compared with a colorimetric method.

Recent advances in fixation of CO_(2) into organic carbamates through multicomponent reaction strategies

Carbon dioxide(CO_(2)) is the main greenhouse gas and also an ideal C1 feedstock in organic synthesis because it is abundant,nontoxic,nonflammable,and renewable.The synthesis of organic carbamates using CO_(2) as a phosgene alternative has attracted extensive attention because of the importance of carbamates in organic synthesis and in the pharmaceutical and agrochemical industries.In recent decades,many multicomponent reaction strategies have been designed for constructing different types of organic carbamate molecules.Most of these methods rely on the in situ generation of carbamate anions from CO_(2) and amines,followed by reactions with other coupling partners.Synthetic strategies for acyclic carbamates include nucleophile‐electrophile coupling,nucleo‐phile‐nucleophile oxidative coupling,difunctionalization of unsaturated hydrocarbons,and C–H bond functionalization.Strategies for the synthesizing cyclic carbamates include carboxylative cyclization of in situ‐generated unsaturated amines and difunctionalization of unsaturated amines with CO_(2) and other electrophilic reagents.This review summarizes the recent advances in the synthesis of organic carbamates from CO_(2) using different multicomponent reaction strategies.Future perspectives and challenges in the incorporation of CO_(2) into carbamates are also presented.

Carbamate synthesis from amines and dialkyl carbonate over inexpensive and clean acidic catalyst—Sulfamic acid

Sulfamic acid has been proved to be the most efficient and recyclable catalyst in carbamate synthesis from alkylamine and dialkyl carbonate.High selectivity,cost-efficiency and simple product separation were the advantageous features obtained in this process.Sulfamic acid could be reused several times and keep its initial activity in the recycle runs.In addition,sulfamic acid has also exhibited the potential catalytic ability for alkylation of aromatic amines.

Inhibition Mechanism of Cholinesterases by Carbamate: A Theoretical Study

The density functional theory at the B3LYP/6-311G（d, p） level was applied to exploring the inhibition mechanism of cholinesterases by carbamate. The results indicate that the inhibition reactions with or without the catalytic effect of the catalytic triad in eholinesterases underwent a two-step addition-elimination mechanism, which is in good agreement with the proposed mechanism. The solvent has a strong effect on the inhibition reactions and the reaction with the catalytic triad in the solvent phase is close to the real reaction under biological condition.

Deconvolution Method for Determination of the Nitrogen Content in Cellulose Carbamates

Cellulose carbamates (CC) were synthesized with microcrystalline cellulose as raw materials. The Fourier transform infrared spectra of CC with different nitrogen content were recorded. The accurate results of the nitrogen content for CC can be obtained by using the deconvolution method when the nitrogen content is less than 3.5%. The relationship between the nitrogen content and the absorption intensity ratio of the corresponding separated absorption peaks in FTIR spectra has been expressed bg an equation precisely.