28685-60-1

Upstream product

• 79-22-1 methyl chloroformate 
• 100-61-8 N-methylaniline 
• 67-56-1 methanol 
• 2621-79-6 ethyl N-methyl-N-phenylcarbamate 
• 4285-42-1 N-phenyl-N-methylcarbamoyl chloride 
• 124-41-4 sodium methylate 
• 62-53-3 aniline 
• 616-38-6 carbonic acid dimethyl ester 
• 132431-15-3 2-(N-methylanilino)-2-phenylsulfanylacetonitrile 
• 2603-10-3 N-phenyl methyl carbamate 
• 100244-44-8 (ethoxydichloromethyl)(methylphenylcarbamoyl)disulfane 
• 6294-89-9 hydrazinecarboxylic acid methyl ester 
• 19009-45-1 N-methyl-N-phenylthiocarbamoyl chloride 
• 100244-43-7 (methoxydichloromethyl)(methylphenylcarbamoyl)disulfane 

Downstream Products

• 10252-27-4 p-Nitrophenyl-N-methyl-carbamidsaeure-methylester 
• 100-61-8 N-methylaniline 
• 88889-00-3 N-methyl-N-(methyl-d₃)aniline 
• 95569-16-7 methyl N-(2,4,6-trinitrophenyl)carbamate 
• 5882-44-0 N,N-dimethylaniline hydrochloride 
• 67-56-1 methanol 
• 93-61-8 N-methyl-N-phenylformamide 
• 121-69-7 N,N-dimethyl-aniline 

Relevant academic research and scientific papers

Copper-Catalyzed Coupling of Amines with Carbazates: An Approach to Carbamates

A new approach for the preparation of carbamatesviathe copper-catalyzed cross-coupling reaction of amines with alkoxycarbonyl radicals generated from carbazates is described. This environmentally friendly protocol takes place under mild conditions and is compatible with a wide range of amines, including aromatic/aliphatic and primary/secondary substrates.

ZINC-IMIDAZOLE COMPLEX MIXED CATALYST AND METHOD FOR PRODUCING METHYL N-PHENYL CARBAMATE USING THE SAME

Disclosed is a zinc-imidazole complex mixed catalyst. Also disclosed are a method for preparing the zinc-imidazole complex mixed catalyst and a method for producing a methyl N-phenyl carbamate in high yield with high selectivity in the presence of the catalyst. The zinc-imidazole complex mixed catalyst can be reused due to its high reaction stability. In addition, the use of the zinc-imidazole complex mixed catalyst leads to a marked improvement in the production yield of a methyl N-phenyl carbamate with high selectivity.

Formation of defect site on ZIF-7 and its effect on the methoxycarbonylation of aniline with dimethyl carbonate

The Zeolitic Imidazole Framework ZIF-7, (Zn(benzimidazole)2), is known to exhibit a unique gate-opening property depending on the temperature and pressure in the presence of guest molecules, making it useful for H2, CO2, and paraffine separation technology. Besides this distinctive gas adsorption property, ZIF-7 can be used as a catalyst because it contains a Lewis acid site on Zn, and a Lewis basic site on the benzimidazole. In this study, for the first time, we demonstrate that ZIF-7 is a very promising material as a catalyst for the methoxycarbonylation of aniline with dimethyl carbonate (DMC) to produce methyl phenyl carbamate (MPC), an isocyanate precursor. Fresh ZIF-7 showed a high aniline conversion of over 95% at 190 °C for 2 h, and the yield MPC was 60–70% due to the formation of methylated side products, such as N-methyl aniline and N,N′-dimethylaniline. However, interestingly, when the ZIF-7 was reused, the yield of MPC gradually increased and reached over 94.7% by the catalyst's 6th run. SEM and TEM images revealed the crystalline structure of ZIF-7 collapsed during the reaction due to the leaching of benzimidazole from the ZIF-7, which created defect sites on the Lewis acidic zinc center. Based on 1H NMR and XPS studies, it can be assumed that the DMC binds to the Zn defect sites on the ZIF-7, activating the carbonyl groups on DMC, resulting in the increased selectivity to methoxycarbonylation compared to methylation. Pretreating ZIF-7 with DMC at 190 °C for 6 h could directly activated the ZIF-7 for this methoxycarbonylation reaction. The activated ZIF-7 showed 91.0% MPC yield and the catalyst was reusable.

Preparation method of amide compound

The invention discloses a preparation method of an amide compound. The preparation method comprises the following steps: enabling a solution A containing a compound I to react with a solution B containing n-butyllithium at -80 to 10 DEG C, and then enabling a reaction solution to react with a solution C containing a compound II at -80 to 10 DEG C, wherein the concentration of the compound I in the solution A is 5 to 40 percent by weight, the concentration of the compound II in the solution C is 5 to 50 percent by weight, flow rates of the solution A and the solution C are respectively 0.1 to 25 L/s and 0.1 to 1.5 L/s, n is an integer of 0 to 5, and R1 is separately C1 to C6 alkyl, C1 to C6 alkoxy or substituted or un-substituted C6 to C10 aryl; R2 is hydrogen, C1 to C6 alkyl, or substituted or non-substituted phenyl, and a substituting group substituting the phenyl is C1 to C6 alkyl or C1 to C6 alkoxy; and R3 is C1 to C6 alkyl or one or more phenyl-substituted methyl.

Aniline carbamates: A versatile and removable motif for palladium-catalyzed directed c-h activation

The aniline carbamate is introduced as a new removable directing group for C-H activation. Its versatility and ability as a directing group are demonstrated by its use in the ortho-arylation of a wide variety of aniline derivatives under palladium(II) catalysis, with symmetric diaryliodonium salts as aryl donors. The reaction differs from previously reported arylations in its selectivity and its mechanism, as elucidated by kinetic and isotopic experiments. The directing group can also be easily removed under a variety of conditions.

Dimethyl carbonate as an ambident electrophile

(Chemical Equation Presented) The features of various anions having different soft/hard character (aliphatic and aromatic amines, alcohoxydes, phenoxides, thiolates) are compared with regard to nucleophilic substitutions on dimethyl carbonate (DMC), using different reaction conditions. Results are well in agreement with the Hard-Soft Acid-Base (HSAB) theory. Accordingly, the high selectivity of monomethylation of CH2 acidic compounds and primary aromatic amines with DMC can be explained by two different subsequent reactions, which are due to the double electrophilic character of DMC. The first step consists of a hard-hard reaction and selectively produces a soft anion, which, in the second phase, selectively transforms into the final monomethylated product, via a soft-soft nucleophilic displacement (yield >99% at complete conversion, using DMC as solvent).

Selective mono-N-methylation of primary aromatic amines by dimethyl carbonate over faujasite X- and Y-type zeolites

The reaction of dimethyl carbonate (DMC) with different primary aromatic amines has been investigated under batch conditions (autoclave) in the presence of Y- and X-type zeolites. Operating at 120-150°C, highly selective mono-N-methylations are observed for anilines even when they are deactivated by either electronic effects or steric hindrance (G-C6H4NH2, G = p-NO2,p-CN, o-CO2CH3 and 2,6-dimethylaniline); typical selectivities for the formation of the corresponding mono-N-methyl derivatives [ArNH(CH3)] are in the range 92-98%, at a substrate conversion of 72-93%. A synergic effect between the reactivity of DMC (acting both as a methylating and as a reversible methoxycarbonylating agent) and the dual acid-base properties of zeolites is considered to be responsible for the unusually high selectivity observed; accordingly, a reaction mechanism is discussed, involving carbamates (ArNHCO2CH3) and N-methyl-carbamates [ArN(CH3)CO2CH3] as intermediates. The reaction is an example of a synthesis with low environmental impact: it couples the use of a non-toxic methylating agent (DMC, in place of the highly toxic methyl halides or dimethyl sulfate) with eco-friendly catalysts (zeolites) in a waste-free process.

The use of dialkyl carbonates for safe and highly selective alkylations of methylene-active compounds. A process without waste production

The non-toxic compound dimethyl carbonate (DMC) can be used as a methylating and a methoxycarbonylating agent in place of methyl chloride and phosgene, respectively. We report here that DMC and other dialkyl carbonates (DAlkCs: dimethyl, diethyl and dibenzyl carbonates) allow very selective alkylations of a variety of CH2-acidic compounds. Both arylacetonitriles and alkyl arylacetates react with DAIkCs to yield the mono-C-alkylated derivatives (α-alkyl-α-arylacetonitriles and alkyl α-alkyl-α-arylacetates) with a selectivity of up to 99%, at complete conversion. Likewise, the mono-C-methylation by DMC proceeds selectively also on (aryloxy)acetonitriles and methyl (aryloxy)acetates. The reactions are carried out at temperature of 180-220°C in the presence of weak bases (usually K2CO3); under such conditions, DAlkCs efficiently replace the common and very toxic alkylating agents (dialkyl sulfates and alkyl halides). In addition to the high selectivity obtained and the intrinsic safety of the dialkyl carbonates, the reported reactions give rise to neither organic nor inorganic waste products.

2-(N-Methylanilino)-2-phenylsulfanylacetonitrile, A Reagent Tested for Electrophilic, Nucleophilic, and Radical Reactions

2-(N-Methylanilino)-2-phenylsulfanylacetonitrile 1 has been readily prepared from 2-(N-methylanilino)acetonitrile and diphenyl disulfide.Alkylation of the anion of 1 with halogenoalkanes resulted in concurrent elimination of benzenethiol to give conjugated α-aminoalkenenitriles of 2E-configuration.Autoxidation of 1 in the presence of alkoxide ions afforded alkyl N-methyl-N-phenylcarbamates.Nucleophilic substitution of 1 with Grignard reagent or appropriate silyl compounds were promoted by CuI or Lewis acids to give varied α-amino nitriles.The 4-oxo-2-aminonitriles 9 obtained by condensation of 1 and titanium enolates can be considered as derivatives of 1,3-dicarbonyl compounds with the aldehyde group being activated to give an amino nitrile umpolung.When 1 was treated with tributylstannane, the corresponding amino nitrile α-radical was formed and the self-coupling product was isolated.

Methylchloroformate synthesis via direct interaction of palladium di(methoxycarbonyl) complexes with CuCl2: utilization in the synthesis of carbonates and carbamates

ClCOOCH3 has been obtained in very good yield by reaction of (L2 = 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen)> with CuCl2.The in situ reaction of ClCOOCH3 with alcohols or amines produces carbonates or carbamates.