36926-15-5

Upstream product

• 100-52-7 benzaldehyde 
• 141-43-5 ethanolamine 
• 7127-19-7 2-phenyl-1,3-oxazoline 
• 463962-26-7 thiobenzoyl 2-(5,5-dimethyl-2-thiono-1,3,2-dioxaphosphorinanyl)sulfide 
• 13522-38-8 thiobenzoic acid O-(4-nitrophenyl) ester 
• 157841-96-8 benzoyl 2-(5,5-dimethyl-2-thiono-1,3,2-dioxaphosphorinanyl)sulfide 
• 693-06-1 (2-hydroxyethyl)-formamide 
• 98-91-9 thiobenzoic acid 
• 23405-15-4 benzoic acid N-hydroxysuccinimide ester 
• 65-85-0 benzoic acid 
• 98-88-4 benzoyl chloride 
• 115231-72-6 2-phenylthioamidoethyl acetate 
• 92367-87-8 2-(benzoylamino)ethyl Acetate 
• 18838-10-3 N-(2-hydroxyethyl)-benzamide 

Downstream Products

• 66867-07-0 2-phenyl-2,5-dihydrothiazole 
• 7127-19-7 2-phenyl-1,3-oxazoline 
• 75-08-1 ethanethiol 
• 2722-34-1 2-phenylthiazoline 
• 16180-99-7 2-benzamidoethyl benzoate 
• 26385-07-9 N-(2-chloro-ethyl)-benzamide 
• 96159-97-6 3-Ethyl-2-phenyl-4,5-dihydro-thiazol-3-ium; iodide 

Relevant academic research and scientific papers

Ynamide-Mediated Thionoester and Dithioester Syntheses

A novel ynamide-mediated synthesis of thionoesters and dithioesters is described. The selective addition reactions of various monothiocarboxylic acids with ynamide furnish α-thioacyloxyenamides, which undergo transesterification with nucleophilic -OH or -SH species to afford thionoesters and dithioesters, respectively. The broad substrate scope, mild reaction conditions, and excellent yields make this method an attractive synthetic approach to thionoesters and dithioesters.

Microwave-Assisted Synthesis of 2-Substituted 2-Thiazolines and 5,6-Dihydro-4 H -1,3-thiazines

An efficient and general method for the synthesis of 2-substituted thiazolines and 5,6-dihydro-4 H -1,3-thiazines is developed via microwave-assisted ring closure of ω-thioamidoalcohols promoted by ethyl polyphosphate (PPE). The cyclization reaction involves an S N 2-type mechanism and features the advantages of very short reaction times, high yields and a predictable stereochemical outcome. The acyclic precursors are prepared in high overall yields by an improved diacylation-thionation-saponification sequence from commercially available ω-amino alcohols. The whole process is metal-free and operationally simple.

Aqueous Compatible Protocol to Both Alkyl and Aryl Thioamide Synthesis

An efficient aqueous synthesis of thioamides through aldehydes, sodium sulfide, and N-substituted formamides has been developed. Both alkyl and aryl aldehydes are amenable to this protocol. N-Substituted formamides are essential for this transformation. Readily available inorganic salt (sodium sulfide) serves as the sulfur source in water, which makes this method much more practical and efficient. Furthermore, the late-stage modification of bioactive molecules and derivatives through this protocol has been established.

Selective thioacylation of amines in water: A convenient preparation of secondary thioamides and thiazolines

Primary thioamides have been utilised directly in water, without any derivatisation, to selectively thioacylate primary amines. By employing 2-hydroxyethylamines, the reaction can be extended to the preparation of 2-thiazolines via formation of β-hydroxythioamides.

A mild and efficient synthesis of 2-oxazolines via transamidation- cyclodehydrosulfurisation of thioamides with 2-aminoethanol

Transamidation of thioamides with 2-aminoethanol, followed by cyclodehydrosulfurisation of the resultant N-(β-hydroxyethyl)thioamides, has been utilised for the mild and efficient synthesis of 2-oxazolines. The developed protocol was found to be of general applicability. Georg Thieme Verlag KG Stuttgart · New York.

Synthesis of S-thioacyl dithiophosphates, efficient and chemoselective thioacylating agents

Easily available acyl dithiophosphates are not stable and isomerise reversibly to O-thioacyl monothiophosphates, especially when subjected to heating. Much slower but probably irreversible isomerisation to S-thioacyl monothiophosphates occurs. Since equilibrium states are established and S-thioacyl (mono)thiophosphates form slowly, reaction mixtures contain generally both thioacylating and acylating agents, and consequently cannot be used for efficient thioacylation. On the other hand, treatment of a mixture of isomeric anhydrides with an excess of a dithiophosphoric acid leads to exclusive formation of S-thioacyl dithiophosphates. They appear to be excellent thioacylating agents: relatively stable, inert towards water and oxygen and therefore easy to handle. Reactions with nitrogen or sulfur nucleophiles proceed very rapidly under ambient conditions, yielding respective thioacyl derivatives. Isolation of the products is very simple. Due to the low reactivity of S-thioacyl dithiophosphates towards oxygen nucleophiles they can be used for direct thioacylation of multifunctional nucleophiles with unprotected hydroxy groups. Respective thioacyl derivatives cannot readily be obtained using other methods.

Effect of amine nature on reaction mechanism: Aminolyses of O-4-nitrophenyl thionobenzoate with primary and secondary amines

Pseudo-first-order rate constants (kobs) have been measured spectrophotometrically for reactions of O-4-nitrophenyl thionobenzoate (2) with a series of primary and acyclic secondary amines. The plots of kobs vs amine concentration are linear for the reaction of 2 with primary amines. The slope of the Bronsted-type plot for the reaction of 2 with primary amines decreases from 0.77 to 0.17 as the amine basicity increases, indicating that the reaction proceeds through a zwitterionic addition intermediate in which the rate-determining step changes from the breakdown of the intermediate to the reaction products to the formation of the intermediate as the amine basicity increases. On the other hand, for reactions with all the acyclic secondary amines studied, the plot of kobs vs amine concentration exhibits an upward curvature, suggesting that the reaction proceeds through two intermediates, e.g., a zwitterionic addition intermediate and an anionic intermediate. The microscopic rate constants (k1, k-1, k2, and k3 where available) have been determined for the reactions of 2 with all the primary and secondary amines studied. The k1 value is larger for the reaction with the primary amine than for the reaction with the isobasic acyclic secondary amines, while the k-1 value is much larger for the latter reaction than for the former reaction. The k3 value for the reaction with secondary amine is independent of the amine basicity. The small k2/k-1 ratio is proposed to be responsible for the deprotonation process observed in aminolyses of carbonyl or thiocarbonyl derivatives.

New, efficient and chemoselective method of thioacylation, starting from carboxylic acids

S-Acylation of dithiophosphoric acids yields mixed anhydrides 3; they readily isomerize to O-thioacyl 4 and S-thioacyl monothiophosphates 5, which treated with the excess of dithiophosphoric acid 2 can be easily converted into thioacyl dithiophosphates 6, excellent thioacylating reagents.

Research on radioprotective agents: Δ-2 Thiazolines and homologous derivatives

Compounds derived from Δ-2 thiazoline, Δ-2 thiazolinium iodoalkylate and 4,5-dihydro-1,3 thiazine have been prepared and evaluated as potential antiradiation agents in mice. They generally have a low toxicity and significant radioprotective activity.