1943-87-9

Usage

Uses

Used in Pesticide Industry:
Methyl (4-nitrophenyl)carbamate is used as an insecticide for controlling various pests due to its ability to inhibit the activity of acetylcholinesterase, an enzyme essential for the proper functioning of the nervous system in insects.
Used in Insecticide Formulations:
Methyl (4-nitrophenyl)carbamate is used as an active ingredient in insecticide formulations to target and eliminate pests, providing protection to crops and reducing damage caused by insects.

InChI:InChI=1/C8H8N2O4/c1-14-8(11)9-6-2-4-7(5-3-6)10(12)13/h2-5H,1H3,(H,9,11)

Upstream product

• 67-56-1 methanol 
• 100-28-7 4-Nitrophenyl isocyanate 
• 142-96-1 dibutyl ether 
• 121-44-8 triethylamine 
• 100-25-4 para-dinitrobenzene 
• 1620457-77-3 N-p-nitrophenyl-N',N'-bis(pyridin-2-ylmethyl) urea 
• 124-41-4 sodium methylate 
• 124-38-9 carbon dioxide 
• 100-01-6 4-nitro-aniline 
• 132755-73-8 methyl N-(4-nitrophenyl)-N-(phthalimidomethyl)carbamate 
• 619-80-7 4-nitrobenzamide 
• 79-22-1 methyl chloroformate 
• 681-84-5 tetramethylorthosilicate 
• 198763-89-2 1,1-diisopropyl-3-(4-nitrophenyl)urea 

Downstream Products

• 67-56-1 methanol 
• 74401-81-3 N-(4-nitrophenyl)carbamate ion 
• 29111-81-7 methyl N-(2,4-dinitrophenyl)carbamate 
• 100-28-7 4-Nitrophenyl isocyanate 
• 53558-25-1 1-(pyridin-3-ylmethyl)-3-(4-nitrophenyl)urea 
• 1430217-39-2 (S)-methyl 4-(1,2,3,4-tetrahydroisoquinoline-1-carboxamido)phenylcarbamate 
• 1430217-38-1 (S)-(9H-fluoren-9-yl)methyl 1-((4-((methoxycarbonyl)amino)phenyl)carbamoyl)-3,4-dihydroisoquinoline-2(1H)-carboxylate 
• 1597575-44-4 methyl 4-(2-((1r,4r)-4-(aminomethyl)cyclohexanecarbonyl)-1,2,3,4-tetrahydroisoquinoline-1-carboxamido)phenylcarbamate trifluoroacetate 
• 1309945-86-5 C₂₀H₂₀N₄O₄ 
• 587-90-6 bis-N,N'-(4-nitrophenyl)urea 
• 132755-77-2 methyl N-(2,4-dinitrophenyl)-N-(phthalimidomethyl)carbamate 
• 5433-04-5 dimethyl N,N′-(1,4-phenylene)dicarbamate 
• 132755-69-2 methyl N-<4-nitro-2-(phthalimidomethyl)phenyl>carbamate 
• 132755-73-8 methyl N-(4-nitrophenyl)-N-(phthalimidomethyl)carbamate 

Relevant academic research and scientific papers

N-Aryl and N-Alkyl Carbamates from 1 Atmosphere of CO2

We have successfully isolated and characterized the zinc carbamate complex (phen)Zn(OAc)(OC(=O)NHPh) (1; phen=1,10-phenanthroline), formed as an intermediate during the Zn(OAc)2/phen-catalyzed synthesis of organic carbamates from CO2, amines, and the reusable reactant Si(OMe)4. Density functional theory calculations revealed that the direct reaction of 1 with Si(OMe)4 proceeds via a five-coordinate silicon intermediate, forming organic carbamates. Based on these results, the catalytic system was improved by using Si(OMe)4 as the reaction solvent and additives like KOMe and KF, which promote the formation of the five-coordinated silicon species. This sustainable and effective method can be used to synthesize various N-aryl and N-alkyl carbamates, including industrially important polyurethane raw materials, starting from CO2 under atmospheric pressure.

Methoxycarbonylation of Alkyl-, Cycloalkyl-, and Arylamines with Dimethyl Carbonate in the Presence of Binder-Free Zeolite

Abstract: Methyl N-alkyl-, N-cycloalkyl-, and N-arylcarbamates were synthesized by reaction of the correspondingamines with dimethyl carbonate in the presence of binder-free FeHY zeolite. Theoptimal conditions (reactant ratio, amount of the catalyst, temperature,reaction time) were found to afford the target products with high yields.

Preparation of a novel bromine complex and its application in organic synthesis

Although molecular bromine (Br2) is a useful brominating reagent, it is not easy to handle. Herein, we describe the preparation of a novel air-stable bromine complex prepared from 1,3-dimethyl-2-imidazolidinone (DMI) and Br2, which was identified to be (DMI)2HBr3 by spectral and X-ray techniques. This complex was then used to brominate olefins, carbonyl compounds, and aromatics, as well as in the Hofmann rearrangement. Yields of reaction products using this complex were almost the same or superior to those using other bromine alternatives.

PRODUCTION METHOD OF CARBAMIC ACID ESTER

A method of production of carbamic acid ester has a high yield and high selectivity and is superior in economy. The method of production of a carbamic acid ester includes reacting an amine, carbon dioxide, and an alkoxysilane compound in the presence of a catalyst containing a zinc compound or an alkali metal compound or in the presence of an ionic liquid. A carbamic acid ester is produced, for example by reacting aniline, carbon dioxide, and tetramethoxysilane at a temperature of 150 to 180° C. in the presence of zinc acetate and 2,2′-bipyridine.

Phosgene-free synthesis of carbamates using co2 and titanium alkoxides

A facile one-pot, phosgene-free method for the synthesis of N-phenylcarbamates is developed. Using this method, various aromatic carbamates could be prepared from aromatic amines, CO2 and metal alkoxides. Aniline reacted with titanium methoxide (Ti(OMe)4)) in the presence of CO2 (5 MPa) to give methyl N-phenylcarbamate in 85% yield, in 20min. Titanium residue could be regenerated by reaction with dimethyl carbonate at 220 °C for 16 h.

Metal-Free Synthesis of Unsymmetrical Ureas and Carbamates from CO2 and Amines via Isocyanate Intermediates

A mild and metal-free synthesis of aryl isocyanates from arylamines under an atmosphere of CO2 was developed. The carbamic acid intermediate, derived from the arylamine starting material and CO2 in the presence of DBU, is dehydrated by activated sulfonium reagents to generate the corresponding isocyanate. The latter can be detected by in situ IR and trapped by various amines and alcohols to make unsymmetrical ureas and carbamates, respectively. Dicarbamates can also be prepared in good yields via the mild dehydration of the corresponding dicarbamic acids.

Direct synthesis of carbamate from CO2 using a task-specific ionic liquid catalyst

A superbase-derived protic ionic liquid (IL, [DBUH][OAc]) catalyst was used to directly synthesize carbamate from an amine, CO2, and a silicate ester. This IL catalyst was easily prepared using its precursors, DBU, and acetic acid. Using 10 mol% of the catalyst under a CO2 pressure of 5 MPa in acetonitrile at 150 °C, carbamate was isolated in up to 96% yield. Specifically, aliphatic and aromatic amines were activated even though aromatic amines exhibited low activities because of their low pKa values. Other functional groups in amines were barely activated, affording exclusive chemoselectivity for amine activation. Isotope labeling experiments indicated that the proton in the counter cation is crucial in the catalytic cycle to produce water. In addition, a chemical shift corresponding to a mixture of aniline and [DBUH][OAc] was observed in the 1H NMR spectrum, related to the formation of hydrogen bonds between aniline and basic acetate anions. The experimental results indicated that the designed IL catalysts require a protonated cation and a basic anion.

A Simple Zinc Catalyst for Carbamate Synthesis Directly from CO2

Several zinc salts were employed as catalysts for the synthesis of carbamates directly from aromatic amines, CO2, and silicate esters. Zn(OAc)2 offered the best performance among the salts tested. The addition of an N-donor ligand such as 1,10-phenanthroline increased the yield. The best catalytic performance of Zn(OAc)2 can be explained by carboxylate-assisted proton activation. The interaction between the substrate and the catalyst can be observed by chemical shifts in 1H and 15N NMR spectra. Isocyanate was a key intermediate, which was generated from amine and CO2. Silicate ester was finally converted to siloxane, which was determined by 29Si NMR. The commercially available catalyst system could be reused. The yield of isolated carbamate could reach up to 96 % with various substrates, and the catalytic reaction was amine-selective in the presence of other functional groups.

Synthesis of carbamates from carbon dioxide promoted by organostannanes and alkoxysilanes

A cooperative methoxy transfer between orthosilicate esters and organotin oxides was developed for the synthesis of various N-alkyl and N-aryl carbamates from carbon dioxide in up to 97% isolated yield. The reaction is highly selective and N-alkylated amines are not observed. Density functional theory calculations of the reaction were performed and, together with NMR observations, a plausible mechanism featuring the catalytic regeneration of dialkyltin dialkoxide is proposed.

N-Methylation of poorly nucleophilic aromatic amines with dimethyl carbonate

Abstract: Dimethyl carbonate (DMC), an environmentally friendly methylation agent, is a substitute for traditional methylation agents such as methyl halides (CH3X, X?=?I, Br, Cl) or dimethyl sulfate. An efficient, convenient, and green method has been developed for N-methylation of poorly nucleophilic aromatic amines with DMC. It was found that the couple PEG400/K2CO3 provides good selectivity for the N-methylation product. Finally, the mechanism for reaction of amines with DMC was investigated, and a plausible multistep mechanism proposed and verified. Graphical Abstract: [Figure not available: see fulltext.]