98407-14-8

Upstream product

• 100-51-6 benzyl alcohol 
• 1972-28-7 diethylazodicarboxylate 
• 100-52-7 benzaldehyde 
• 65-85-0 benzoic acid 

Downstream Products

• 21816-80-8 2-phenyl-4-ethyl-1,3,4-oxadiazol-5(4H)-one 
• 1199-02-6 5-phenyl-3H-[1,3,4]oxadiazol-2-one 

Relevant academic research and scientific papers

A reusable and heterogeneous Ti(IV) anchored MCM-41 catalyzed hydroacylation and hydroamination reactions

An efficient, mild and reusable catalytic hydroacylation and hydroamination reactions have been developed by using heterogeneous Ti(IV) anchored MCM-41 catalyst from various aryl, heteroaryl, aliphatic aldehydes as well as aryl and aliphatic amines with d

Direct Observation and Analysis of the Halo-Amino-Nitro Alkane Functional Group

Conventional amide synthesis is a mainstay in discipline-spanning applications, and it is a reaction type that historically developed as a singular paradigm when considering the carbon-nitrogen bond-forming step. Umpolung amide synthesis (UmAS) exploits the unique properties of an α-halo nitroalkane in its reaction with an amine to produce an amide. The “umpolung” moniker reflects its paradigm-breaking C–N bond formation on the basis of evidence that the nucleophilic nitronate carbon and electrophilic nitrogen engage to form a tetrahedral intermediate (TI) that is an unprecedented functional group, a 1,1,1-halo-amino-nitro alkane (HANA). Studies probing HANA transience have failed to capture this (presumably) highly reactive intermediate. We report here the direct observation of a HANA, its conversion thermally to an amide functionality, and quantitative analysis of this process using computational techniques. These findings validate the HANA as a functional group common to UmAS and diverted UmAS, opening the door to its targeted use and creative manipulation. Functional groups are the “cities” on a map of mechanistic pathways (the “roads”), and chemists use functional groups as pivot points to valuable chemical intermediates. Functional groups are defined by a collection of atoms, and variations on these atoms can define a group's behavior, especially its stability and reaction trajectory. Once recognized as a distinct arrangement of atoms connected by a discrete pathway to a specific product, new opportunities are presented to manipulate its conversion to new outcomes. Herein, we prepare and characterize an intermediate containing halogen (F), amine (N), and nitro (NO2) at an alkane (C-sp3) carbon and establish it as a precursor to both amide and oxadiazole products, thereby codifying two key mechanistic pathways united by the HANA functional group. A computationally driven study of the pathway connecting these species identifies additional diversion points, and the HANA itself might be targeted with novel entry points. Preparation and characterization of a new functional group, HANA, is described. A study of its thermal conversion to amide provides direct evidence for its role as a TI in UmAS, and this interconversion along several possible pathways is studied by computational analysis. The experimental and energy landscape outlined by these studies illustrates that the HANA can be manipulated to acyclic and heterocyclic products, setting the stage for future rational reaction design.

Efficient Method to Synthesize Benzhydrazides by in Situ Oxidation/Coupling of Benzylic Alcohols with Azodicarboxylates

An efficient synthesis of benzhydrazides has been achieved through the direct acylation of azodicarboxylates with benzylic alcohols in moderate to high yields. The method represents the first practical approach to amides containing a hydrazine structural unit from benzylic alcohols.

Lewis- and Bronsted-acid cooperative catalytic radical coupling of aldehydes and azodicarboxylate

An efficient radical coupling reaction of aldehydes and azodicarboxylate was developed by using the strategy of merging Lewis- and Bronsted- acid catalysis. This journal is the Partner Organisations 2014.

The use of a Mitsunobu reagent for the formation of heterocycles: A simple method for the preparation of 3-alkyl-5-aryl-1,3,4-oxadiazol-2(3H)-ones from carboxylic acids

The reaction of carboxylic acids with Mitsunobu reagents, prepared by the reaction of triphenylphosphine with dialkyl azodicarboxylates, followed by heating at 180-190 °C under solvent-free conditions, afforded 3-alkyl-5-aryl-1,3,4-oxadiazol-2(3H)-ones. This facile and convenient method readily provides the 1,3,4-oxadiazolone ring systems in good yields using a one-pot protocol starting from the corresponding carboxylic acids. It was also demonstrated that the presence of a catalytic base facilitates the final ring closure forming the 1,3,4-oxadiazol-2(3H)-one.