673-41-6

Upstream product

• 74317-29-6 18-crown-6/p-chlorobenzenediazonium tetrafluoroborate complex 
• 106-47-8 4-chloro-aniline 
• 7632-00-0 sodium nitrite 
• 7664-39-3 hydrogen fluoride 
• 11113-50-1 boric acid 
• 13755-29-8 sodium tetrafluoroborate 
• 109-63-7 boron trifluoride diethyl etherate 
• 540-80-7 tert.-butylnitrite 
• 110-46-3 isopentyl nitrite 

Downstream Products

• 69065-69-6 N',N'''-bis-(4-chloro-phenyl)-N,N''-(4-cyclohexyl-1-methoxy-1-phenyl-1λ⁵-phosphinine-2,6-diyl)-bis-diazene 
• 51459-98-4 4-[3-(4-chloro-phenylazo)-5-phenyl-furan-2-yl]-morpholine 
• 58296-84-7 cis-1-(4-Chlorphenyl)-3-(3-methyl-benzthiazolin-2-yliden)triazen 
• 56184-18-0 1-Chloro-4-((E)-4-ethoxy-but-2-enyl)-benzene 
• 100376-68-9 (4-chloro-phenylazo)-phosphonic acid dimethyl ester 
• 57604-54-3 1-(4-chloro-phenyl)-1-methoxy-2,4,6-triphenyl-1λ⁵-phosphinine 
• 117769-04-7 3-(p-chlorophenylazo)-1,3-thiazolidine 
• 17221-37-3 2-(4-chlorophenyl)furan 
• 40133-23-1 2-(4-chlorophenyl)thiophene 
• 5969-83-5 2-(4-chlorophenyl)pyridine 
• 5957-96-0 4-(4-chlorophenyl)pyridine 
• 5957-97-1 4-(3'-pyridinyl)-1-chlorobenzene 
• 80228-03-1 (4-chlorophenyl)isopropyldiazene 
• 94144-24-8 2-(4-Chloro-phenyl)-4-(4-chloro-phenylsulfanyl)-5,6-dihydro-2H-2aλ⁴,3-dithia-1,2-diaza-cyclopenta[cd]pentalene 

Relevant academic research and scientific papers

Metal-Free Visible-Light Synthesis of Arylsulfonyl Fluorides: Scope and Mechanism

The first metal-free procedure for the synthesis of arylsulfonyl fluorides is reported. Under organo-photoredox conditions, aryl diazonium salts react with a readily available SO2 source (DABSO) to afford the desired product through simple nucleophilic fluorination. The reaction tolerates the presence of both electron-rich and -poor aryls and demonstrated a broad functional group tolerance. To shed the light on the reaction mechanism, several experimental techniques were combined, including fluorescence, NMR, and EPR spectroscopy as well as DFT calculations.

Matsuda-Heck arylation of itaconates: A versatile approach to heterocycles from a renewable resource

Itaconic acid esters and hemiesters undergo Pd-catalyzed coupling reactions with arene diazonium salts in high to excellent yields. The coupling products of ortho-nitro arene diazonium salts can be converted in one or two steps to benzazepine-2-ones.

Aqueous and Visible-Light-Promoted C-H (Hetero)arylation of Uracil Derivatives with Diazoniums

Direct C5 (hetero)arylation of uracil and uridine substrates with (hetero)aryl diazonium salts under photoredox catalysis with blue light was reported. The coupling proceeds efficiently with diazonium salts and heterocycles in good functional group tolerance at room temperature in aqueous solution without transition-metal components. A plausible radical mechanism has been proposed.

Comparison of the Thermal Stabilities of Diazonium Salts and Their Corresponding Triazenes

A range of diazonium salts and their corresponding triazenes have been prepared in order to directly compare their relative thermal stabilities (via initial decomposition temperature) from differential scanning calorimetry (DSC) data. A structure-stability relationship has been explored to investigate trends in stability, depending on the aromatic substituent and the structure of the secondary amine component of the diazonium salts and triazenes. All of the triazenes investigated show significantly greater stability (many are stable above 200 °C) compared with the corresponding diazonium salts, which show varying stabilities.

Copper-mediated tandem ring-opening/cyclization reactions of cyclopropanols with aryldiazonium salts: Synthesis of: N -arylpyrazoles

A general method for the synthesis of structurally diverse N-arylpyrazoles from readily available cyclopropanols and aryldiazonium salts is disclosed. The reaction was conducted at room temperature within minutes with a broad substrate scope and excellent regioselectivity.

Discovery and structure-activity relationship studies of 1-aryl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione derivatives as potent dual inhibitors of indoleamine 2,3-dioxygenase 1 (IDO1) and trytophan 2,3-dioxygenase (TDO)

Indoleamine 2,3-dioxygenase 1 (IDO1) and tryptophan 2,3-dioxygenase (TDO), which mediate kynurenine pathway of tryptophan degradation, have emerged as potential new targets in immunotherapy for treatment of cancer because of their critical role in immunosuppression in the tumor microenvironment. In this investigation, we report the structural optimization and structure-activity relationship studies of 1-phenyl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione derivatives as a new class of IDO1/TDO dual inhibitors. Among all the obtained dual inhibitors, 1-(3-chloro-4-fluorophenyl)-6-fluoro-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione (38) displayed the most potent IDO1 and TDO inhibitory activities with IC50 (half-maximal inhibitory concentration) values of 5 nM for IDO1 and 4 nM for TDO. It turned out that compound 38 was not a PAINS compound. Compound 38 could efficiently inhibit the biofunction of IDO1 and TDO in intact cells. In LL2 (Lewis lung cancer) and Hepa1-6 (hepatic carcinoma) allograft mouse models, this compound also showed considerable in vivo anti-tumor activity and no obvious toxicity was observed. Therefore, 38 could be a good lead compound for cancer immunotherapy and deserving further investigation.

Transition-Metal- A nd Light-Free Directed Amination of Remote Unactivated C(sp3)-H Bonds of Alcohols

Due to the great value of amino alcohols, new methods for their synthesis are in high demand. Abundant aliphatic alcohols represent the ideal feedstock for the method development toward this important motif. To date, transition-metal-catalyzed approaches for the directed remote amination of alcohols have been well established. Yet, they have certain disadvantages such as the use of expensive catalysts and limited scope. Very recently, transition-metal-free visible-light-induced radical approaches have emerged as new powerful tools for directed remote amination of alcohols. Relying on 1,5-HAT reactivity, these methods are limited to β-or δ- A mination only. Herein, we report a novel transitionmetal- A nd visible-light-free room-temperature radical approach for remote β-, γ-, and δ-C(sp3)-N bond formation in aliphatic alcohols using mild basic conditions and readily available diazonium salt reagents.

σ-Bond initiated generation of aryl radicals from aryl diazonium salts

σ-Bond nucleophiles and molecular oxygen transform aryl diazonium salts into aryl radicals. Experimental and computational studies show that Hantzsch esters transfer hydride to aryl diazonium species, and that oxygen initiates radical fragmentation of the diazene intermediate to produce aryl radicals. The operational simplicity of this addition-fragmentation process for the generation of aryl radicals, by a polar-radical crossover mechanism, has been illustrated in a variety of bond-forming reactions.

Dual palladium-photoredox catalyzed chemoselective C-H arylation of phenylureas

A highly chemoselective C-H arylation of phenylureas has been accomplished using dual palladium-photoredox catalysis at room temperature without any additives, base or external oxidants. Regioselective C-H arylation ofN,N'-diaryl substituted unsymmetrical phenylureas has also been accomplished by a careful choice of aryl groups.

Visible-Light-Mediated Ru-Catalyzed Synthesis of 3-(Arylsulfonyl)but-3-enals via Coupling of α-Allenols with Diazonium Salts and Sulfur Dioxide

The first coupling of α-allenols, sulfur dioxide, and arenediazonium salts is presented. The three-component reaction which is promoted by visible light can be easily accomplished using DABSO as a sulfur dioxide surrogate in the presence of a photoredox catalyst. In this manner, a broad range of electron-rich and electron-deficient aryl substituents are well accommodated in the sulfonylation-rearrangement cascade to afford the 2,2-disubstituted 3-(arylsulfonyl)but-3-enals in reasonable yields. Based on control experiments, a radical mechanism which does imply 1,2-aryl migration has been proposed.