Synthesis of Aromatic Urea Herbicides by the Selenium-assisted Carbonylation using Carbon Monoxide With Sulfur

Commercially useful aromatic urea herbicides were synthesized in good yields from lithium amides of aromatic amines with thiocarbamates, which were prepared by the selenium-assisted carbonylation of secondary amines with carbon monoxide and sulfur under mild conditions.     

Achieving functional group diversity in parallel synthesis: solution-phase synthesis of a library of ureas, carbamates, thiocarbamates, and amides using carbamoylimidazolium salts

A convenient protocol for the parallel solution-phase synthesis of a library of thiocarbamates, ureas, carbamates, and amides from carbamoylimidazolium salts has been developed. The crystalline carbamoylimidazolium salts are readily synthesized from secondary amines, CDI and iodomethane, and act as stable carbamoylation reagents. A common set of reaction conditions and a straightforward non-chromatographic liquid-liquid extraction purification protocol were developed for reactions with thiols, amines, phenols, and carboxylic acids, giving the products with high purities and yields. The resultant library incorporates diversity arising from the choice of reaction partners and the functional group linkage generated in the couplings.     

Straightforward and highly efficient catalyst-free one-pot synthesis of dithiocarbamates under solvent-free conditions

[Structure: see text] A highly efficient and simple synthesis of dithiocarbamates is possible based on the one-pot reaction of amines, CS2, and alkyl halides without using a catalyst under solvent-free conditions. The mild reaction conditions, high yields, and broad scope of the reaction illustrate the good synthetic utility of this method. The reaction is a highly atom-economic process for production of S-alkyl thiocarbamates and successfully can be used in high quantities in the pharmaceutical or agrochemical industries.     

Carbamoylimidazolium salts as diversification reagents: an application to the synthesis of tertiary amides from carboxylic acids

An efficient method for the preparation of tertiary amides from carbamoylimidazolium salts and carboxylic acids is described. The transformation occurs at room temperature and under relatively mild conditions. The carbamoylimidazolium salts are obtained from the reaction of secondary amines with N,N′-carbonyldiimidazole, followed by methylation with methyl iodide. The utility of this reaction was demonstrated in the formation of Weinreb amides and in a short synthesis of fused bicyclic amides. The introduction of this reaction now permits carbamoylimidazolium salts to be utilized in the formation of tertiary amides, ureas, carbamates and thiocarbamates under a single set of conditions.     

A synthesis of N-alkyl and N,N-dialkyl O-ethyl thiocarbamates from diethyl dixanthogenate using different oxidants

Abstract  

A novel synthesis of N-alkyl and N,N-dialkyl O-ethyl thiocarbamates from diethyl dixanthogenate and primary and secondary amines, using three oxidizing systems, has been developed on the laboratory scale, and the method using sodium hypochlorite has been applied on a semi-industrial scale. The effect of the oxidizing agents, sodium hypochlorite, in-situ-generated peracetic acid, and the manganese(II) acetate/oxygen system on product purity and yield was studied. The results obtained by use of these three methods were compared with those obtained by reaction of sodium ethyl xanthogenacetate and amines, and of sodium ethyl xanthate with amines in the presence of sulfated nickel zeolite catalyst. The reaction mechanism of sodium hypochlorite oxidation has been established on the basis of isolation of reaction intermediates and determination of their structure by use of Fourier-transform infrared, ¹H and ¹³C NMR, and mass spectrometric methods. The suggested sodium hypochlorite and manganese(II) acetate/oxygen systems have many advantages in comparison with commercial and catalytically promoted synthetic methods, because they are new ecologically friendly syntheses.     

Carbamoylimidazolium and thiocarbamoylimidazolium salts: novel reagents for the synthesis of ureas, thioureas, carbamates, thiocarbamates and amides

Carbamoylimidazolium salts act as efficient N,N-disubstituted carbamoylating reagents. These salts are readily prepared by the sequential treatment of secondary amines with N,N′-carbonyldiimidazole (CDI) and iodomethane. The carbamoylimidazolium salts are more efficient carbamoyl transfer reagents than the intermediate carbamoylimidazoles, as a result of the ‘imidazolium’ effect. Kinetic studies on the base promoted hydrolysis of both carbamoylimidazoles and carbamoylimidazolium salts reveal over a hundred-fold rate acceleration. The salts react with amines, thiols, phenols/alcohols, and carboxylic acids in high yields, without the need for subsequent chromatographic purification of the products, producing ureas, thiocarbamates, carbamates, and amides, respectively. Analogous thiocarbamoylimidazolium salts were also synthesized from secondary amines and N,N′-thiocarbonyldiimidazole (TCDI), followed by methylation with iodomethane.     

Facile synthesis of urea derivatives under mild conditions

Urea derivatives were readily synthesized in good yields under quite mild conditions, i.e., at ambient pressure and room temperature by sulfur-assisted carbonylation of primary amines with carbon monoxide followed by oxidation of the resulting ammonium thiocarbamates with molecular oxygen.     

Synthesis of Sulfonylurea Derivatives Used as Oral Antidiabetics by the Selenium-Assisted Carbonylation Using Carbon Monoxide with Sulfur

Sulfonylurea derivatives including useful antidiabetics (Tolbutamide, Chlorpropamide) were synthesized in good yields from benzene-sulfonamides with thiocarbamates in the presence of DBU. Thiocarbamates were prepared by the selenium-assisted carbonylation of primary amines with carbon monoxide, sulfur, and methyl iodide under mild conditions.     

Reactivity of 2-deoxy-2-iodoglycosyl isothiocyanates with O-, S-, and N-nucleophiles. Synthesis of glycopyranoso-fused thiazoles

The reactivity of 2-deoxy-2-iodoglycosyl isothiocyanates toward O- and S-nucleophiles gives an easy access to 2-deoxy-2-iodoglycopyranosyl thiocarbamates and dithiocarbamates. Internal nucleophilic displacement of the iodine by the sulfur atom in these compounds allows the preparation of glycopyranoso[1,2-d]-1,3-thiazoles and glycopyranoso[1,2-d]-1,3-thiazolidin-2-one or -2-thione. Reaction with amines or polyamines as N-nucleophiles led directly to 2-aminoglycopyranoso[1,2-d]-1,3-thiazoles without isolation of the intermediate thioureas. Methyl 2-deoxy-2-iodoglycopyranosyl thiocarbamates also allow the synthesis of 2-deoxyglycopyranosyl thiocarbamates or 2-deoxy-2-iodoglycopyranosyl carbamates.     

A convenient synthesis of some α-oxoketene-N,S- and N,N-acetals

Some α-oxoketene-N,S- and N,N-acetals were selectively synthesized in good to excellent yields by the reaction of 1,1-dimethoxy-4,4-di(methylthio)-3-buten-2-one with primary and secondary amines under moderate conditions. Secondary amines in reaction with α-oxoketene dithioacetal yielded double-substitution products exclusively, whereas primary amines under the same conditions yielded the mono-substituted products as exclusive or main products.     

An eco-friendly protocol for synthesis of thiourea derivatives: 1-benzoyl-3-benzylguanidine and 1-benzoyl-3-benzyl-O-ethylisourea. A possible non-purely thermal microwave assisted reaction

1-Benzoyl-3-benzylguanidine and 1-benzoyl-3-benzyl-O-ethylisourea were synthesized in good yields (68 and 76%, respectively) from 1-benzoyl-3-benzylthiourea and benzoyl-ethylthiocarbamate in dry media conditions using KF-Al₂O₃ under microwave irradiation. Strong nucleophilic amines promoted the sulfur elimination by attack on the thiocarbonyl group in both thiourea and thiocarbamates to afford guanidines and isourea, respectively. Transesterification products were obtained from p-TsOH catalyzed reaction of thiocarbamate with alcohols under MW-solvent-free conditions. Very important non-purely thermal MW specific effects were evidenced and attributed to stabilization by coulombic interactions between materials and waves.     

Direct electrochemical imidation of aliphatic amines via anodic oxidation

Direct electrochemical synthesis of sulfonyl amidines from aliphatic amines and sulfonyl azides was realized with good to excellent yields. Traditional tertiary amine substrates were broadened to secondary and primary amines. The reaction intermediates were observed and a reaction mechanism was proposed and discussed.     

Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines

Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.     

Study of CuI catalyzed coupling reactions of aryl bromides with imidazole and aliphatic amines under microwave dielectric heating

Amination of a variety of functionalized aryl bromides with imidazole and primary and secondary amines was accomplished using a CuI/amino acid catalyst system under microwave heating. Application of microwave irradiation shortened the reaction time from 25–40 h to 6–20 min. Good to very good yields of the corresponding coupling products were obtained when imidazole and secondary amines were used as starting materials. In case of primary amines, the outcome of the reaction was dependent on the character of the substituent on aryl bromide.     

Acid-free, aminoborane-mediated Ugi-type reaction leading to general utilization of secondary amines

A variety of secondary amines have become utilized in the Ugi reaction by using aminoborane 1 as an iminium ion generator. Aldehydes, secondary amines, and isocyanides are coupled in the presence of 1 at room temperature, giving the corresponding alpha-amino amides in good yields. The nonacidic reaction conditions are beneficial for unique chemoselectivity, where the aldimine functionality is left intact in the present Ugi-type reaction.     

Thiol on silica as a ‘catch and release’ support for isocyanates to afford ureas

Silica-bound thiocarbamates were prepared by Curtius rearrangement of carboxylic acids in the presence of thiol on silica gel. The solid supported thiocarbamates were found to be stable isocyanate equivalents, which upon treatment with amines efficiently afforded di- and tri-substituted ureas. The urea products released from the catch and release support were, in the majority of cases, greater than 95% pure and required no further work up.     

Three-component synthesis of N-sulfonylformamidines in the presence of magnetic cellulose supported N-heterocyclic carbene-copper complex,as an efficient heterogeneous nanocatalyst

A cellulose based magnetic nanocomposite possessing NHC-Cu Complex has been synthesized and characterized. It was then applied as a highly active catalyst in one-pot three-component reaction of sulfonyl azides, secondary amines and triethylamine to afford N-sulfonylformamidines. Copper catalyzed oxidative transformation of C-N bond of triethylamine is a key step to give desired products. In contrast with the good reactivity of the conventional secondary amines, aromatic amines and NH containing heteroaromatics had no activity in these reactions. Moreover, the used nanocatalyst which could be recovered by external magnet, showed reasonable catalytic activity for several times.     

Synthesis of Unsymmetrical Ureas and S‐Thiocarbamates under Catalyst‐free Conditions in a [BMIM]BF4 Ionic Liquid

Unsymmetrical ureas and S‐thiocarbamates were prepared in good to excellent yields by direct condensation of phenylurea with amines and thiols in 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIM]BF₄) without the addition of any additives. The [BMIM]BF₄ ionic liquid is a mild medium and can be recycled and reused several times.     

Intramolecular vinylation of secondary and tertiary organolithiums

Deprotonation of benzylic ureas, carbamates, and thiocarbamates bearing N'-alkenyl substituents generates carbanions which undergo intramolecular migration of the alkenyl group to the carbanionic center. Solvolysis of the urea products generates α-alkenylated amines. With an enantiomerically pure starting urea, migration proceeds stereospecifically, generating in enantiomerically enriched form products containing allylic quaternary stereogenic centers bearing N. Computational and in situ IR studies suggest that the reaction, formally a nucleophilic substitution at an sp(2) carbon atom, proceeds by a concerted addition-elimination pathway.     

cis-Fused bicyclic sugar thiocarbamates. Reactivity towards amines

1,2-cis-Fused bicyclic sugar thiocarbamates of gluco and manno configurations have been prepared by treatment of the corresponding O-unprotected amino sugars and glycopyranosyl amines with thiophosgene. The reactivity of these compounds towards amines has been studied in order to determine whether these compounds could act as latent isothiocyanates; it is shown that 1,2-cis-fused bicyclic sugar thiocarbamates are more stable than their trans analogues, and are not transformed into thioureas upon treatment with amines. An unprecedented isomerization of a peracetylated glucopyranoso[2,1-d]oxazolidine-2-thione into a glucopyranoso[2,1-d]thiazolidin-2-one in DMF is also reported. The structure of this thiazolidin-2-one was confirmed by X-ray crystallography.