- A New and Practical Synthesis of Indolones
-
A variety of indolones can be obtained from α-haloanilides through a radical cyclisation mediated by a combination of nickel powder and acetic acid.
- Boivin, Jean,Yousfi, Mohammed,Zard, Samir Z.
-
-
Read Online
- Synthesis and Mechanistic Insights of the Formation of 3-Hydroxyquinolin-2-ones including Viridicatin from 2-Chloro- N,3-diaryloxirane-2-carboxamides under Acid-Catalyzed Rearrangements
-
N-Benzyl-2-chloro-N,3-diaryloxirane-2-carboxamides, easily obtained from aromatic aldehydes and anilides of dichloroacetic acid under Darzens condensation conditions, proved to be excellent starting compounds for the synthesis of 3-hydroxyindolin-2-ones, cyclohepto[b]pyrrole-2,3-diones, and 1-azaspiro[4.5]deca-3,6,9-triene-2-ones via the C(sp2)-C(sp2) bond formation in the first case and C(sp2)-C(sp3) bond formation in the second and third cases. Under optimized reaction conditions, 3-hydroxyindolin-2-ones are obtained in a one-pot process, which involves the treatment of N-benzyl-2-chloro-N,3-diaryloxirane-2-carboxamides with CF3CO2H or AcOH/H2SO4. In the case of intramolecular cyclization, the detailed reaction channels depend strongly on the substituents present in the anilide component and in the aromatic ring of the aldehyde component of N-benzyl-2-chloro-N,3-diaryloxirane-2-carboxamides, as well as the temperature and duration of the reaction. A combined experimental and DFT mechanistic study of the formation of 1-benzyl-3-hydroxy-4-arylquinolin-2(1H)-ones showed that there are three competing reaction channels: (a) ring-closure via the ipso site, (b) ring-closure via the 1,2-Cl shift, and (c) ring-closure via the ortho site. Such mechanistic insights enabled an effective one-pot gram-scale synthesis of viridicatin from benzaldehyde and 2,2-dichloro-N-(4-methoxybenzyl)-N-phenylacetamide.
- Mamedov, Vakhid A.,Mamedova, Vera L.,Qu, Zheng-Wang,Zhu, Hui,Galimullina, Venera R.,Korshin, Dmitry E.,Khikmatova, Gul'Naz Z.,Litvinov, Igor A.,Latypov, Shamil K.,Sinyashin, Oleg G.,Grimme, Stefan
-
p. 13514 - 13534
(2021/09/28)
-
- Synthesis of 3-Hydroxy-4-arylquinolin-2-ones Including Viridicatol via a Darzens Condensation/Friedel-Crafts Alkylation Strategy
-
The new efficient synthesis of biologically important 3-hydroxy-4-arylquinolin-2-ones through the Darzens condensation (epoxidation) of dichloroacetanilides with aromatic aldehydes followed by one-pot dechlorative epoxide-arene cyclization is described. T
- Mamedov, Vakhid A.,Mamedova, Vera L.,Kadyrova, Saniya F.,Galimullina, Venera R.,Khikmatova, Gul'Naz Z.,Korshin, Dmitry E.,Gubaidullin, Aidar T.,Krivolapov, Dmitry B.,Rizvanov, Il'Dar Kh.,Bazanova, Olga B.,Sinyashin, Oleg G.,Latypov, Shamil K.
-
p. 13132 - 13145
(2018/10/31)
-
- Investigation of the Potential of Molybdenum(VI) Hydrazido(2-) Complexes as Sources of Nitrenium Ions: Cleavage of the N-N Bond and Incorporation of the β-Nitrogen Group into Solvent Molecules
-
Photolyis or thermolysis of bis(N,N-dimethyldithiocarbamato)bismolybdenum(VI) complexes in 1,1,2,2-tetrachloroethane results predominantly in transfer of the hydrazido group to the solvent with formation of dichloroacetohydrazides.A small amount of the corresponding dichloroacetamides are produced by N-N cleavage and N(R)Ph transfer.In contrast, the latter process dominates the reaction of dichlorobis(N,N-dimethyldithiocarbamato)mono-molybdenum(VI) complexes with silver nitrate in alcohols occuring concomitantly with ring methoxylation and nitration and N-nitrosation.Neither transfer of N(R)Ph appears to involve free nitrenium ions.
- Baum, Marc M.,Smith, Edward H.
-
p. 2513 - 2520
(2007/10/02)
-
- HYDRODEHALOGENATION OF TRICHLOROACETAMIDES DURING THERMOCATALYTIC DECOMPOSITION OF SODIUM TRICHLOROACETATE
-
N-Substituted trichloroacetamides are reduced to the corresponding dichloroacetamides during the thermal decomposition of sodium trichloroacetate in chloroform in the presence of benzyltriethylammonium chloride as phase-transfer catalyst.The relative reac
- Khlebnikov, A. F.,Kostik, E. I.,Novikov, M. S.,Kostikov, R. R.
-
p. 1468 - 1471
(2007/10/02)
-
- THE REACTION OF DICHLOROCARBENE WITH TETRTIARY CARBOXAMIDES. PREPARATION OF α-CHLOROMETHYLENELACTAMS AND (E)-CHLOROACRYLAMIDES
-
An easy method is described for the preparation of (E)-3-chloroacrylamides and α-chloromethylenelactams which is based on the simple treatment of tertiary carboxamides and lactams with dichlorocarbene.
- Marcos, Manuel,Castro, Jose L.,Castedo, Luis,Riguera, Ricardo
-
p. 649 - 654
(2007/10/02)
-
- Substituted chloroacylanilides
-
The invention concerns a process for the preparation of substituted chloroacylanilides of the general formula: SPC1 Wherein R1 represents an alkyl group having from 1 to 4 carbon atoms or a phenyl group; R2 represents a hydrogen atom or halogen atom; R3 represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms and X1 and X 2 , which may be the same or different, represent a hydrogen atom, a halogen atom, a methyl group or an ethyl group. The process comprises acylating a substituted aniline of the general formula: SPC2 Wherein R1, X1 and X2 are as above defined, in the presence of phosphoryl chloride under substantially anhydrous conditions with a chlorocarboxylic acid of the general formula: EQU1 wherein R2 and R3 are as above defined. Particularly suitable compounds of general Formula II are N-methyl aniline and N-isopropyl aniline, and particularly suitable compounds of general Formula III are chloroacetic acid, dichloroacetic acid and α-chloropropionic acid and α-chlorobutyric acid. The compounds of general Formula I have phytotoxic effects and some are active herbicides.
- -
-
-