208664-53-3

Upstream product

• 864512-14-1 2-iodophenyl 4-chlorobenzenesulfonate 
• 68-12-2 N,N-dimethyl-formamide 
• 100-61-8 N-methylaniline 
• 62-53-3 aniline 
• 91-40-7 2-(phenylamino)benzoic acid 
• 88-67-5 2-Iodobenzoic acid 
• 121-69-7 N,N-dimethyl-aniline 
• 95888-33-8 2-((N-phenyl)amino)benzaldehyde 
• 74-88-4 methyl iodide 
• 552-82-9 benzhydrylidene(methyl)amine 
• 73323-82-7 2-(N-Methyl-N-phenylamino)-benzoic acid 
• 208664-59-9 C₂₁H₂₁N₃O₃S 
• 117296-15-8 (2-(methyl(phenyl)amino)phenyl)methanol 
• 118-91-2 ortho-chlorobenzoic acid 

Downstream Products

• 260-94-6 acridine 
• 2622-60-8 1-phenyl-1H-benzoimidazole 
• 602-56-2 9-phenylacridine 
• 1859-76-3 2-(methylamino)benzophenone 
• 209412-43-1 [2-(methylanilino)phenyl](phenyl)methanone 
• 209412-61-3 [1-[2-(Methyl-phenyl-amino)-phenyl]-meth-(E)-ylideneaminooxy]-acetic acid 
• 209412-73-7 [1-[2-(Methyl-phenyl-amino)-phenyl]-meth-(E)-ylideneaminooxy]-ethaneperoxoic acid tert-butyl ester 
• 1416427-14-9 2-((N-methyl-N-phenyl)amino)styrene 
• 719-54-0 10-methyl-9, 10-dihydro-9-acridinone 
• 1428865-53-5 C₁₄H₇⁽²⁾H₄NO 
• 30713-65-6 9-hydroxy-9,10-dihydro-10-methylacridine 
• 64236-22-2 10-methyl-N-phenylacridine-9(10H)-imine 

Relevant academic research and scientific papers

Substrate-Controlled Selectivity Switch in the Three-Component Coupling Involving Arynes, Aromatic Tertiary Amines, and CO2

The transition-metal-free multicomponent coupling involving arynes, aromatic tertiary amines, and CO2 is reported. The reaction exhibits switchable selectivity depending on the electronic nature of the aromatic amines used. With amines bearing electron-releasing/neutral groups as the nucleophilic trigger, the reaction afforded 2-arylamino benzoates via a nitrogen to oxygen alkyl group migration. Employing electron-deficient amines in the reaction furnished 2-aminoaryl benzoates proceeding via the aryl to aryl amino group migration resembling a Smiles rearrangement.

PhI(OAc)2-mediated intramolecular oxidative aryl-aldehyde C sp 2-C sp 2 bond formation: Metal-free synthesis of acridone derivatives

A metal-free protocol for direct aryl-aldehyde Csp2-Csp 2 bond formation via a PhI(OAc)2-mediated intramolecular cross-dehydrogenative coupling (CDC) of various 2-(N-arylamino)aldehydes was developed. The novel methodology requires no need of preactivation of the aldehyde group, is applicable to a large variety of functionalized substrates, and most of all provides a convenient approach to the construction of biologically important acridone derivatives.

Sc(OTf)3-catalyzed dehydrogenative cyclization for synthesis of N-methylacridones

A novel method has been developed for the synthesis of substituted N-methylacridones from 2-(N-methyl-N-phenylamino)benzaldehydes via dehydrogenative cyclization. This transformation involves two primary processes: the aldehyde first coordinates with Sc(OTf)3 and induces the aromatic electrophilic substitution (SEAr) reaction to form the active intermediate N-methyl-acridin-9-ol, which is then quickly oxidized in situ to afford the acridones. Furthermore, the procedure involved is both environmental friendly and atom efficient; H2O is the only byproduct in this reaction.

Ruthenium-based metathesis catalysts and precursors for their preparation

The invention is directed to ruthenium-based metathesis catalysts of the Hoveyda-Grubbs type. The new N-chelating diarylamino-based ruthenium catalysts described herein are stable in solid state and in solution and reveal rapid initiation behavior. Further, the corresponding N-substituted styrene precursor compounds are disclosed. The catalysts are prepared in a cross-metathesis reaction starting from N-substituted styrene precursors. The new Hoveyda-Grubbs type catalysts are suitable to catalyze ring-closing metathesis (RCM), cross metathesis (CM) and ring-opening metathesis polymerization (ROMP). Low catalyst loadings are sufficient to convert a wide range of substrates via metathesis reactions.

RUTHENIUM-BASED METATHESIS CATALYSTS AND PRECURSORS FOR THEIR PREPARATION

The invention is directed to ruthenium-based metathesis catalysts of the Hoveyda-Grubbs type. The new N-chelating diarylamino-based ruthenium catalysts described herein are stable in solid state and in solution and reveal rapid initiation behavior. Further, the corresponding N-substituted styrene precursor compounds are disclosed. The catalysts are prepared in a cross-metathesis reaction starting from N-substituted styrene precursors. The new Hoveyda-Grubbs type catalysts are suitable to catalyze ring- closing metathesis (RCM), cross metathesis (CM) and ring-opening metathesis polymerization (ROMP). Low catalyst loadings are sufficient to convert a wide range of substrates via metathesis reactions.

Fast olefin metathesis at low catalyst loading

Reactions of the Grubbs 3rd generation complexes [RuCl2(NHC) (Ind)(Py)] (N-heterocyclic carbene (NHC)=1,3-bis(2,4,6- trimethylphenylimidazolin)-2-ylidene (SIMes), 1,3-bis(2,6- diisopropylphenylimidazolin)-2-ylidene (SIPr), or 1,3-bis(2,6- diisopropylphenylimidazol)-2-ylidene (IPr); Ind=3-phenylindenylid-1-ene, Py=pyridine) with 2-ethenyl-N-alkylaniline (alkyl=Me, Et) result in the formation of the new N-Grubbs-Hoveyda-type complexes 5 (NHC=SIMes, alkyl=Me), 6 (SIMes, Et), 7 (IPr, Me), 8 (SIPr, Me), and 9 (SIPr, Et) with N-chelating benzylidene ligands in yields of 50-75 %. Compared to their respective, conventional, O-Grubbs-Hoveyda complexes, the new complexes are characterized by fast catalyst activation, which translates into fast and efficient ring-closing metathesis (RCM) reactivity. Catalyst loadings of 15-150 ppm (0.0015-0.015 mol %) are sufficient for the conversion of a wide range of diolefinic substrates into the respective RCM products after 15 min at 50 °C in toluene; compounds 8 and 9 are the most catalytically active complexes. The use of complex 8 in RCM reactions enables the formation of N-protected 2,5-dihydropyrroles with turnover numbers (TONs) of up to 58 000 and turnover frequencies (TOFs) of up to 232 000 h-1; the use of the N-protected 1,2,3,6-tetrahydropyridines proceeds with TONs of up to 37 000 and TOFs of up to 147 000 h-1; and the use of the N-protected 2,3,6,7-tetrahydroazepines proceeds with TONs of up to 19 000 and TOFs of up to 76 000 h-1, with yields for these reactions ranging from 83-92 %. The tortoise and the hare: The use of diphenylalkylamino-based instead of phenyldialkylamino-based styrenes (see figure) leads to rapidly initiating precatalysts that enable very fast ring-closing metathesis reactions with turnover numbers of up to 58 000 and turnover frequencies of up to 232 000 h-1. Copyright

Preparation of functionalized aryl magnesium reagents by the addition of magnesium aryl thiolates and amides to arynes

(Chemical Equation Presented) Reactive arynes, which are readily generated by the reaction of ortho-iocloarylsulfonates with iPrMgCl, undergo the smooth addition of various magnesium nucleophiles like magnesium thiolates, selenides, and amides. In all cases the resulting functionalized aryl magnesium species can be trapped by an electrophile leading to highly functionalized aromatic compounds (see scheme).

Gas-phase cyclisation reactions of 1-(2-arylaminophenyl)alkaniminyl radicals

Flash vacuum pyrolysis (FVP) of the oxime ethers 9-11 at 650°C (10-2-10-3 Torr) gives products such as the nitrile 17, carbazoles 19 and 20 and acridines 18 and 21 derived from the corresponding iminyl radicals 13-15. The mechanism proposed for the formation of the acridines involves a key hydrogen abstraction by the iminyl of the adjacent N-H atom. When this route is blocked by an N-methyl group, as in 12, alternative cyclisations ensue, yielding the dihydroquinazoline 26 (via another hydrogen abstraction process) and the benzimidazole 25 (via an iminyl-imidoyl interconversion).

Thermal decomposition of tert-butyl o-(phenoxy)- and o-(anilino)-phenyliminoxyperacetates

Some o-phenoxy- and o-anilino-substituted aryliminyl radicals have been generated by thermal decomposition of suitable tert-butyl iminoxyperacetates. The iminyls show no disposition to give 7-membered cyclisation on the phenyl group. In some cases, products have been found that can be rationalised through a 1,6-spirocyclisation of the iminyl radicals followed by homolytic 1,5-migration of the phenyl group from the aminic to the iminic nitrogen: this seems to be the first instance of such a process. Evidence has been found for the formation of imines through hydrogen abstraction by the iminyls; with two o-phenoxy-substituted peresters these imines have been unexpectedly isolated. The reactions have also afforded significant - in some cases major - amounts of other products (acridine, quinazolinone and indole derivatives) presumably deriving from carbon radicals: mechanisms are suggested to account for the formation of these compounds. The structure of the quinazolinone compound has been determined by X-ray crystallographic analysis.