132401-91-3

Upstream product

• 75-44-5 phosgene 
• 1613-88-3 4-chloro-N-hydroxybenzamide 
• 122-01-0 4-chloro-benzoyl chloride 
• 10507-69-4 4-methoxybenzohydroxamic acid 
• 530-62-1 1,1'-carbonyldiimidazole 
• 1126-46-1 Methyl 4-chlorobenzoate 
• 10364-95-1 1-(4-chloro-benzoyl)-1H-imidazole 
• 74-11-3 para-chlorobenzoic acid 

Downstream Products

• 128258-86-6 4-methyl-5-methoxy-2-(4-chlorophenyl)-2-oxazoline 
• 54573-19-2 4,4-dimethyl-5-methoxy-2-(4-chlorophenyl)-2-oxazoline 
• 104-12-1 p-chlorphenylisocyanate 
• 1581756-86-6 4-chloro-N-[2-(pyridin-2-yl)phenyl]benzamide 
• 83800-99-1 2-(4-chlorophenyl)-4-methoxyquinazoline 
• 1967-26-6 N-(4-chlorophenyl)-N'-phenylurea 
• 18600-52-7 2-(4-chlorophenyl)-4H-benzo[d][1,3]oxazin-4-one 
• 1239778-88-1 6-(4-chlorophenyl)indolo[1,2-c]quinazoline 
• 52072-95-4 3-(4-chlorophenyl)-1-methyl-1-phenylurea 
• 150-68-5 monuron 

Relevant academic research and scientific papers

Rhodium(iii)-catalyzed diamidation of olefins: Via amidorhodation and further amidation

Rh(iii)-catalyzed synthesis of vicinal diamides has been realized via elaboration of an authenticated Rh-C(sp3) species generated via initial intramolecular amidorhodation of olefins. The second amidation was achieved using both electrophilic and nucleophilic amidating reagents. The reactions proceeded under mild conditions with good yield, broad substrate scope, and excellent functional-group tolerance.

Site-Selective C–H Amidation of Azobenzenes with Dioxazolones under Rhodium Catalysis

The rhodium(III)-catalyzed amidation reaction of azobenzenes with dioxazolones is described. This strategy allows the facile and efficient construction of highly substituted ortho-amidated azobenzenes by direct C–H cleavage approach. A wide range of substrates, excellent levels of chemoselectivity as well as high functional-group tolerance were observed. In addition, this protocol was used to generate an array of ortho-amidated ketazines. Further synthetic transformation of amidated azobenzenes furnished a facile construction of benzimidazole and benzotriazole derivatives.

Cu(II)-Catalyzed C-H Amidation/Cyclization of Azomethine Imines with Dioxazolones via Acyl Nitrenes: A Direct Access to Diverse 1,2,4-Triazole Derivatives

We report a Cu(II)-catalyzed C-H amidation/cyclization of azomethine imines with dioxazolones as acyl nitrene transfer reagents under additive-and ligand-free conditions. An array of 1,2,4-triazolo[1,5-a]pyridine derivatives were afforded in moderate to good yields with excellent functional group tolerance. In addition, scale-up reaction and photoluminescence properties were discussed.

1,4,2-Dioxazol-5-ones as Isocyanate Equivalents: An Efficient Synthesis of 2-Quinolinones via β-Keto Amides

Under thermal conditions, 1,4,2-dioxazol-5-ones are known to undergo decarboxylation followed by Lossen's rearrangement to yield isocyanates. Described herein is the in situ trapping of the resulting isocyanates with carbon nucleophiles to synthesize β-keto amides. Furthermore, a general and mild method for the conversion of the resulting β-keto amides into quinolin-2-ones is reported.

Silver-Catalyzed Acyl Nitrene Transfer Reactions Involving Dioxazolones: Direct Assembly of N-Acylureas

Dioxazolones and isocyanides are useful synthetic building blocks, and have attracted significant attention from researchers. However, the silver-catalyzed nitrene transfer reaction of dioxazolones has not been investigated to date. Herein, a silver-catalyzed acyl nitrene transfer reaction involving dioxazolones, isocyanides, and water was realized in the presence of Ag2O to afford a series of N-acylureas in moderate to good yields.

Thioether-Directed NiH-Catalyzed Remote γ-C(sp3)-H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones

A NiH-catalyzed thioether-directed cyclometalation strategy is developed to enable remote methylene C-H bond amidation of unactivated alkenes. Due to the preference for five-membered nickelacycle formation, the chain-walking isomerization initiated by the NiH insertion to an alkene can be terminated at the γ-methylene site remote from the alkene moiety. By employing 2,9-dibutyl-1,10-phenanthroline as the ligand and dioxazolones as the reagent, the amidation occurs at the γ-C(sp3)-H bonds to afford the amide products in up to 90% yield (>40 examples) with remarkable regioselectivity (up to 24:1 rr).

Direct synthesis of benzoxazinones via Cp*Co(III)-catalyzed C–H activation and annulation of sulfoxonium ylides with dioxazolones

A highly novel and direct synthesis of benzoxazinones was developed via Cp*Co(III)-catalyzed C–H activation and [3 + 3] annulation between sulfoxonium ylides and dioxazolones. The reaction is conducted under base-free conditions and tolerates various functional groups. Starting from diverse readily available sulfoxonium ylides and dioxazolones, a variety of benzoxazinones could be synthesized in one step in 32%-75% yields.

Interweaving Visible-Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones

Herein, visible-light-driven iron-catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp3)-N, N=S, and N=P bond formation are described. These reactions occur with exogenous-ligand-free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C?H amidations strategies, an intermolecular regioselective C?H amidation via visible-light-induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via a radical pathway. Computational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone-bounding iron species to quartet spin state via visible-light irradiation.

Chemical Upcycling of Waste Poly(bisphenol A carbonate) to 1,4,2-Dioxazol-5-ones and One-Pot C?H Amidation

Chemical upcycling of poly(bisphenol A carbonate) (PC) was achieved in this study with hydroxamic acid nucleophiles, giving rise to synthetically valuable 1,4,2-dioxazol-5-ones and bisphenol A. Using 1,5,7-triazabicyclo[4.4.0]-dec-5-ene (TBD), non-green carbodiimidazole or phosgene carbonylation agents used in conventional dioxazolone synthesis were successfully replaced with PC, and environmentally harmful bisphenol A was simultaneously recovered. Assorted hydroxamic acids exhibited good-to-excellent efficiencies and green chemical features, promising broad synthetic application scope. In addition, a green aryl amide synthesis process was developed, involving one-pot depolymerization from polycarbonate to dioxazolone followed by rhodium-catalyzed C?H amidation, including gram-scale examples with used compact discs.

METHOD FOR THE SYNTHESIS OF 3-R-1,4,2-DIOXAZOL-5-ONES TECHNICAL FIELD

Provided are methods of preparing 3-R-1,4,2-dioxazol-5-one compounds using convenient and efficient methods. Also provided are 3-R-1,4,2-dioxazol-5-one compounds produced using the methods described.