Bis Trichloromethyl Carbonate Research Articles

One-Pot Synthesis of 4-Chloroquinolines via Bis(trichloromethyl) Carbonate and Triphenylphosphine Oxide-Mediated Cascade Reactions of N-Aryl Enaminones.

A novel method for synthesizing substituted 4-chloroquinolines has been devised, utilizing a cascade reaction of N-aryl enaminones promoted by bis(trichloromethyl) carbonate (BTC) and triphenylphosphine oxide (TPPO). This approach features accessible starting materials, a broad substrate range, extensive functional group compatibility, gentle reaction conditions, and straightforward operation. Its versatility is evidenced by its facile scalability and suitability for late-stage derivatization. A plausible mechanism involving α-carbonylation, 6π-azaelectrocyclization, and dehydroxychlorination sequence is proposed.

Efficient Phosphorus-Free Chlorination of Hydroxy Aza-Arenes and Their Application in One-Pot Pharmaceutical Synthesis

The chlorination of hydroxy aza-arenes with bis(trichloromethyl) carbonate (BTC) and SOCl2 has been effectively performed by refluxing with 5 wt % 4-dimethylaminopyridine (DMAP) as a catalyst. Vari...

Synthesis and physiochemical property evaluation of carbamate derivatives of scutellarin methyl ester

A series of carbamate prodrugs of scutellarin methyl ester (4a–4e) were prepared in the presence of bis(trichloromethyl) carbonate (BTC) with scutellarin methyl esters and l-amino acid tert-butyl ester hydrochloride as starting materials. In vitro stability and aqueous solubility of target compounds were evaluated. The results indicated that compounds 4d and 4e have higher solubility and in vitro stability than scutellarin respectively.

A novel and efficient strategy for the synthesis of various carbamates using carbamoyl chlorides under solvent-free and grinding conditions using microwave irradiation

Abstract We present an efficient, fast and simple strategy of generating the intermediate carbamoyl chlorides from secondary amines using stoichiometric amounts of bis(trichloromethyl)carbonate (BTC) in solution and solvent-free conditions with excellent yields. The results obtained showed the yield increasing on whether a base was used. Finally, an efficient and rapid synthesis of variety carbamate derivatives was developed by the reaction with a high variety of different alcohols, phenols, diols and this intermediate at room temperature with grinding and in solvent-free conditions under microwave irradiation. The presence of various safe bases is shown to be effective in reducing the reaction times, increasing the yields and easing purification. The present method does not involve any hazardous phosgene.

Ring Expansion of 2‐(1‐Hydroxyalkyl)azetidines to 4‐(2‐Chloroethyl)oxazolidinones

Abstract2‐(1‐Hydroxyalkyl)azetidines react with bis(trichloromethyl) carbonate (BTC) after basic treatment to afford 4‐(2‐chloroethyl)oxazolidinones. The scope of this rearrangement was examined in detail and its efficiency was shown to depend on the class of the reacting alcohol and on the substitution pattern on the azetidine ring.

Efficient Synthesis of a New Type of Baylis–Hillman Adducts and Their Stereoselective Bromination

A new type of Baylis–Hillman adducts derived from chlorovinyl aldehydes were prepared via Vilsmeier reaction of ketones with a bis(trichloromethyl) carbonate (BTC)/DMF system to construct chlorovinyl aldehydes, followed by sonochemical Baylis–Hillman reaction under solvent-free conditions. The stereoselective bromination of these new compounds with a Br2-Ph3P system has been achieved efficiently with good to excellent yields under mild conditions.

Stereoselective Chlorination of New Type Baylis-Hillman Adducts by bis(Trichloromethyl)carbonate with the Aid of Catalytic Amount of Triphenylphosphine Oxide

The chlorination of the new type Baylis-Hillman adducts by bis(trichloromethyl)carbonate (BTC) with the aid of catalytic amount of triphenylphosphine oxide (Ph3PO) was achieved with high yields and high stereoselectivities. A plausible mechanism is presented. Keywords: New type Baylis-Hillman adducts, chlorination, triphenylphosphine oxide, bis(trichloromethyl)carbonate, stereoselectivity

Acylchloride Reaction of Organic Acids with Bistrichloromethylcarbonate Catalyzed by Yb(OTf)3

Compared to traditional acylchloride reagent, bistrichloromethylcarbonate (BTC) is an excellent acylchloride reagent. Aromatic acids and aliphatic acids react with it to afford the corresponding acylchloride compounds in high yields (99%). In addition, Yb(OTf)3 catalyzed efficiently the desired process.

One-Pot Synthesis of New Type Aza- Baylis–Hillman Adducts from Chlorovinyl Aldehydes under Solvent-Free Condition

A series of new type aza- Baylis–Hillman adducts were prepared in moderate yields by one-pot treatment of chlorovinyl aldehydes, benzenesulfonamides and activated olefins under solvent-free condition. The chlorovinyl aldehydes were obtained via chloroformylation of ketones using bis(trichloromethyl)carbonate(BTC)/DMF system.

Synthesis of Cationic Surfactant Intermediates 3-(dimethylamino)-propane-1,2-di-alkylcarbamate

Abstract Two cationic surfactant intermediates were synthesized by improved method. The alkyl isocyanates, dodecyl isocyanate (1a) and tetradecyl isocyanate (1b), were synthesized by corresponding alkyl amines and bis(trichloromethyl) carbonate (BTC) in anhydrous toluene. The yield of 1a–b reached 86%, the product was colorless liquid and the purity was measured more than 98% by GC. The target products, 3-(dimethylamino)propane-1,2-di-dodecylcarbamate (2a) and 3-(dimethylamino)propane-1,2-di-tetradecylcarbamate (2b) were synthesized by 1-dimethylamino-2,3-propanediol and alkyl isocyanates with triethylamine as catalyst, the yield of 2a–b was 65%.

Novel Synthesis of 2,4-Dihydro-5-amino[1,2,4]triazol-3-ones from 1,3-Disubstituted Thioureas

A facile two-step synthesis of 2,4-dihydro-5-amino-[1,2,4]triazol-3-ones is described. Firstly, 1,3-disubstituted thioureas reacted with bis(trichloromethyl) carbonate (BTC) in the presence of a base such as NaHCO3 to form the intermediate 4-(arylimino)-1,3-thiazetidin-2-ones almost quantitatively. Then the intermediates were treated with hydrazine monohydrate to give 2,4-dihydro-5-amino[1,2,4]triazol-3-ones in high yields. In the case of highly sterically hindered thioureas, carbodiimides were unexpectedly obtained in high yields under the same conditions.

Use of N‐Methylpiperazine for the Preparation of Piperazine‐Based Unsymmetrical Bis‐Ureas as Anti‐HIV Agents

Substituted piperazines are common motifs in a large number of compounds with biological activity. Furthermore, N-urea and N,N’-bis-urea piperazine derivatives have interesting antiviral properties as well as attributes for other therapeutic indications. Unsymmetrical substituted piperazine derivatives require monoprotected piperazines, which can be tedious to prepare and expensive. Furthermore, their use calls for an additional deprotection step. Herein we propose N-methylpiperazine for the preparation of unsymmetrical derivatives containing at least one N-urea moiety as a substitute of the piperazine core. The methyl group acts as protecting group of one of the nitrogen atoms of the piperazine and is concomitantly removed during the formation of a synthetic intermediate. In one of our ongoing research programs devoted to the development of novel proton acceptor immonium-type coupling reagents, we address the preparation of aminium chlorides, shown in Figure 1. Although the reaction of N,N-dimethylmorpholine-4-carboxamide and N,N-dimethylthiomorpholine-4carboxamide with bistrichloromethyl carbonate (BTC) or phosgene rendered the corresponding oxygenand sulfur-containing aminium salts, this result was not achieved if N,N-4-trimethylpiperazine-1-carboxamide was used. Thus, reaction of this compound with BTC followed by the addition of potassium benzotriazolate (KOBt) or potassium 7-azabenzotriazolate (KOAt) (Figure 1, left), a pure white solid was obtained. This product showed a H NMR spectrum similar to that expected (aromatic region from the OBt/OAt and protons from the piperazine cycle and dimethylamino group), but with a distinct molecular weight, as determined by MS, and with extra C NMR signals (2 carbonyls) and one missing CH3 (N-CH3). Xray crystallography (Figure 2) confirmed that the product was active carbamate piperazine 1.

Highly efficient intramolecular cyclizations of 2′‐hydroxychalcones to 4‐chloro‐2H‐chromenes under vilsmeier conditions

Abstractmagnified imageHighly efficient intramolecular cyclization and of 2′‐hydroxychalcones to 4‐chloro‐2H‐chromenes under Vilsmeier conditions have been developed. In comparison with the reported methods, studies carried out indicate that Vilsmeier reagent generated in situ from DMF and bis(trichloromethyl) carbonate (BTC) provides excellent chemselectivity, higher yields and avoids the formation of inorganic phosphorus salts.

An efficient method for the synthesis of dialkyl chlorophosphates from trialkyl phosphites using bis(trichloromethyl) carbonate

A mild and simple method for the synthesis of dialkyl chlorophosphates is described, bis(trichloromethyl) carbonate (BTC) is used as the effective reagent for the conversion of dialkyl phosphites to their corresponding dialkyl chlorophosphates under mild conditions.

First Catalytic and Green Synthesis of Aryl-(Z)-vinyl Chlorides and Its Plausible Addition−Elimination Mechanism

Via a catalytic cycle in the presence of scandium triflate (2 mol %)/DMF (1 mol %)/benzoyl chloride (5 mol %), aromatic ketones were treated with bis(trichloromethyl) carbonate (BTC) to afford aryl-(Z)-vinyl chlorides. All metal triflates tested in the reaction showed highly catalytic activity. A plausible addition-elimination mechanism was proposed. The present work describes the first catalytic and green route to the synthesis of aryl-(Z)-vinyl chlorides. [reaction: see text]

A One‐Pot Preparation of Isothiocyanates from Amines Using Two Phosgene Substitutes: Bis‐(trichloromethyl) Carbonate and Trichloromethyl Chloroformates.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A One-pot Preparation of Isothiocyanates from Amines Using Two Phosgene Substitutes: Bis-(trichloromethyl) Carbonate and Trichloromethyl Chloroformates

A series of isothiocyanates have been prepared in high yields in a one-pot reaction from commercial amines and carbon disulfide under mild conditions using bis(trichloromethyl)carbonate (BTC) and trichloromethyl chloroformate (TCF) as reagents in the presence of base.

Preparation of Chloroformates Using Bis(trichloromethyl)carbonate.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A Practical Synthesis of Carbamates Using an “in‐situ” Generated Polymer‐Supported Chloroformate.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Preparation of Chloroformates Using Bis(Trichloromethyl)Carbonate

The synthesis of eight chloroformates using bis(trichloromethyl)carbonate(BTC) is reported. It has been found that the yields by this BTC method are improved over the earlier phosgene method, and sodium hydroxide is better than pyridine as catalyst for the preparation of phenyl chloroformate.