- Synthesis of Imidoyl Chlorides Using Phosphorus Trichloride
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Abstract: The reaction of carboxamides with phosphorus trichloride under heating at 75–80°C for 1 h in the presence of a 4-dimethylaminopyridine catalyst was used to synthesize imidoyl chlorides in yields of 63–99%.
- Nguyen, T. L.,Popov, Yu. V.,Shishkin, E. V.,Shishkin, V. E.,Vo, T. L. Q.,Zotov, Yu. L.
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p. 849 - 851
(2021/06/12)
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- Synthesis of Nitrogen-Containing Polyaromatics by Aza-Annulative π-Extension of Unfunctionalized Aromatics
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Nitrogen-containing polycyclic aromatic compounds (N-PACs) are an important class of compounds in materials science. Reported here is a new aza-annulative π-extension (aza-APEX) reaction that allows rapid access to a range of N-PACs in 11–84 % yields from readily available unfunctionalized aromatics and imidoyl chlorides. In the presence of silver hexafluorophosphate, arenes and imidoyl chlorides couple in a regioselective fashion. The follow-up oxidative treatment with p-chloranil affords structurally diverse N-PACs, which are very difficult to synthesize. DFT calculations reveal that the aza-APEX reaction proceeds through the formal [4+2] cycloaddition of an arene and an in situ generated diarylnitrilium salt, with sequential aromatizations having relatively low activation energies. Transformation of N-PACs into nitrogen-doped nanographenes and their photophysical properties are also described.
- Itami, Kenichiro,Ito, Hideto,Kawahara, Kou P.,Matsuoka, Wataru
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supporting information
p. 6383 - 6388
(2020/03/13)
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- α-Imino Iridium Carbenes from Imidoyl Sulfoxonium Ylides: Application in the One-Step Synthesis of Indoles
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Imidoyl sulfoxonium ylides are presented for the first time as potential precursors to generate α-imino metal-carbene intermediates and applied in direct C-H functionalization reactions catalyzed by [Ir(cod)Cl]2 (4 mol %) to provide 2-substituted indoles (up to 70% yield) in just one step. This class of sulfur ylide is successfully obtained from imidoyl chloride and dimethylsulfoxonium methylide (23 new examples in 45-85% yield) or by imino group formation from the corresponding β-keto sulfoxonium ylides and anilines in the presence of TiCl4 as a Lewis acid (9 examples in 33-94% yield).
- Burtoloso, Antonio C. B.,Caiuby, Clarice A. D.,De Jesus, Matheus P.
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p. 7433 - 7445
(2020/06/27)
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- Silver-Catalyzed Cascade Cyclization Reaction of Isocyanides with Sulfoxonium Ylides: Synthesis of 3-Aminofurans and 4-Aminoquinolines
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A silver-catalyzed cascade cyclization reaction of isocyanides with sulfoxonium ylides has been developed for the first time. This reaction provides a new and efficient method for the construction of highly functionalized 3-aminofurans and 4-aminoquinolines from readily available starting materials in a single step.
- Liang, Yong-Xin,Yang, Ming,He, Bo-Wen,Zhao, Yu-Long
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supporting information
p. 7640 - 7644
(2020/10/09)
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- The impact of cation structure upon the acidity of triazolium salts in dimethyl sulfoxide
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A series of triazolium salts, selected for their varying electronic and steric properties, were prepared and their pKa values were determined in DMSO at 25 °C using the bracketing indicator method. The effect of each systematic structural variation upon the acidity of the triazolium cation has been considered, in particular examining the effects of systematically altering electronic properties, quantified through the use of Hammett σ parameters. The first pKa value for an azolium salt that generates a mesionic carbene is also reported. These new data allow for the selection of appropriate bases for the deprotonation of such triazolium salts and the potential to correlate the pKa values determined herein with the nucleophilicity of the corresponding carbenes.
- Konstandaras, Nicholas,Dunn, Michelle H.,Guerry, Max S.,Barnett, Christopher D.,Cole, Marcus L.,Harper, Jason B.
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- Silver(II) oxide-mediated synthesis of 2,4-diarylquinazolines
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A single-pot procedure for the synthesis of 2,4-diarylquinazolines is described which involves a silver oxide-mediated C–H activation/C–N bond formation process. The generality of this method with respect to substituent effects is presented along with studies leading to process optimization. Mechanistic investigations provide support for the involvement of radical intermediates in the reaction process.
- Cheung, Wing,Patch, Raymond J.,Player, Mark R.
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supporting information
p. 2368 - 2371
(2018/05/25)
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- Synthesis of Quinazolines from N,N′-Disubstituted Amidines via I2/KI-Mediated Oxidative C-C Bond Formation
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An I2/KI-promoted oxidative C-C bond formation reaction from C(sp3)-H and C(sp2)-H bonds has been used to construct quinazoline skeletons from N,N′-disubstituted amidines. The required substrates are readily prepared from the corresponding acyl chlorides, anilines, and alkyl/benzylamines by sequential amidation, chlorination, and amination reactions. Under the optimal oxidative cyclization conditions, all these amidines were conveniently transformed into the expected products in moderate to good yields. This practical and environmentally benign approach works well with crude amidine intermediates and can also be carried out on a gram scale.
- Lv, Zhigang,Wang, Bingnan,Hu, Zhiyuan,Zhou, Yiming,Yu, Wenquan,Chang, Junbiao
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supporting information
p. 9924 - 9930
(2016/11/02)
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- Solvent/oxidant-switchable synthesis of multisubstituted quinazolines and benzimidazoles via metal-free selective oxidative annulation of arylamidines
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A fast and simple divergent synthesis of multisubstituted quinazolines and benzimidazoles was developed from readily available amidines, via iodine(III)-promoted oxidative C(sp3)-C(sp2) and C(sp 2)-N bond formation in nonpolar and polar solvents, respectively. Further selective synthesis of quinazolines in polar solvent was realized by TEMPO-catalyzed sp3C-H/sp2C-H direct coupling of the amidine with K2S2O8 as the oxidant. No metal, base, or other additives were needed.
- Lin, Jian-Ping,Zhang, Feng-Hua,Long, Ya-Qiu
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supporting information
p. 2822 - 2825
(2014/06/23)
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- Metal-free aminoamidiniumation employing N-iodosuccinimide: Facile syntheses of bicyclic imidazolidiniums and cyclic vicinal diamines
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NIS-mediated aminoamidiniumation has been developed for the syntheses of bicyclic imidazolidinium salts, which could be readily converted into cyclic vicinal diamines.
- Zhang, Jun,Zhang, Gengtao,Wu, Weijie,Zhang, Xuejun,Shi, Min
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supporting information
p. 15052 - 15054
(2014/12/11)
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- Parallel copper catalysis: Diastereoselective synthesis of polyfunctionalized azetidin-2-imines
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An efficient and diastereoselective synthesis of highly functionalized azetidin-2-imines has been achieved through a parallel catalysis strategy, including a copper-catalyzed azide-alkyne cycloaddition, a copper-catalyzed Csp-Csp2 cr
- Xing, Yanpeng,Zhao, Hongyang,Shang, Qiongyi,Wang, Jing,Lu, Ping,Wang, Yanguang
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supporting information
p. 2668 - 2671
(2013/07/19)
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- Investigation of ligand steric effects on a highly cis-selective Rh(i) cyclopropanation catalyst
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Four new Rh(i) complexes bearing chelating imine-functionalized N-heterocyclic carbene ligands have been synthesized and characterized. The catalytic activity of these new Rh(i) complexes has been tested in the cyclopropanation reaction between ethyl diazoacetate and styrene. One of the new complexes, having ethyl groups on the ligand N-aryl ring, exhibited a reactivity and a cis-diastereoselectivity that were comparable to our previously reported Rh(i) cyclopropanation catalyst of this type, and a higher yield and cis-diastereoselectivity were obtained at lower catalyst loadings and higher temperatures. The other new Rh(i) complexes were found to be inferior to the previously reported Rh(i) cyclopropanation catalyst. The catalytic study gave important information about the effect that changing the steric requirements of the substituents at the ligand system has on the efficiency and cis-diastereoselectivity of the complexes as cyclopropanation catalysts.
- Rosenberg, Marianne Lenes,Langseth, Eirin,Krivokapic, Alexander,Gupta, Nalinava Sen,Tilset, Mats
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scheme or table
p. 2306 - 2313
(2011/12/03)
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- Palladium-catalyzed cyclocarbonylation of o-lodoanilines with Imidoyl Chlorides to produce quinazolin-4(3H)-ones
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A wide variety of substituted quinazolin-4(3H)-ones were prepared in 63-91% yields by the palladium-catalyzed cyclocarbonylation of o-iodoanilines with imidoyl chlorides and carbon monoxide. The reaction is believed to proceed via in situ formation of an amidine, followed by oxidative addition, CO insertion, and intramolecular cyclization to give the substituted quinazolin-4(3H)-ones.
- Zheng, Zhaoyan,Alper, Howard
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supporting information; experimental part
p. 829 - 832
(2009/04/07)
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- Amides as precursors of imidoyl radicals in cyclisation reactions
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Amides have been successfully used as precursors of imidoyl radicals for radical cyclisation. The amides have been converted to imidoyl selanides via reaction with phosgene to yield imidoyl chlorides followed by reaction with potassium phenylselanide. Imidoyl selanides were reacted with tributyltin hydride (Bu3SnH) as the radical mediator with triethylborane or AIBN as initiators to yield imidoyl radicals for cyclisation reactions. Imidoyl radicals have been cyclised onto alkenes to yield 2,3-substituted-indoles and -quinolines and also onto pyrroles and indoles to give bi- and tricyclic heteroarenes.
- Bowman, W. Russell,Fletcher, Anthony J.,Pedersen, Jan M.,Lovell, Peter J.,Elsegood, Mark R.J.,Hernández López, Elena,McKee, Vickie,Potts, Graeme B.S.
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p. 191 - 203
(2007/10/03)
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- Synthesis and Biological Evaluation of 2,3,5-Substituted [1,2,4]Thiadiazoles as Allosteric Modulators of Adenosine Receptors
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A number of 2,3,5-substituted [1,2,4]thiadiazole analogues of SCH-202676 (N-(2,3-diphenyl-[1,2,4]thiadiazole-5(2H)-ylidene)methanamine, 7a) were synthesized and tested as potential allosteric modulators of adenosine receptors. All compounds were capable of displacing the binding of the radiolabeled agonist [3H]CCPA to human A1 adenosine receptors, whereas modest and varying effects were observed on the binding of [3H]DPCPX, a radiolabeled antagonist for this receptor subtype. Four compounds, 7a (SCH-202676), 7k (LUF5792), 71 (LUF5794), and 8e (LUF5789), were selected for more detailed characterization. They all proved allosteric inhibitors of agonist binding, with 7k being most potent, whereas their effects on antagonist binding were more ambiguous. Subsequently, experiments were done on human adenosine A2A and A3 receptors. Compounds 7a and 7l displayed peculiar displacement characteristics of both radiolabeled agonist and antagonist binding to A2A receptors, whereas 7a showed some activity on A3 receptors.
- Van Den Nieuwendijk, Adrianus M. C. H.,Pietra, Daniele,Heitman, Laura,G?bly?s, Anikó,IJzerman, Adriaan P.
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p. 663 - 672
(2007/10/03)
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- Amidine derived 1,3-diazabuta-1,3-dienes as potential antibacterial and antifungal agents
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Several 1-aryl-2-phenyl-4-piperidino-4-thioalkyl-1,3-diazabuta-1,3-dienes were prepared by the treatment of N-arylimino isothiocyanate with piperidine followed by S-alkylation with alkyl iodides in the presence of dry acetone and potassium hydroxide. The
- Bedi, Preet M.S.,Mahajan, Mohinder P.,Kapoor, Vijay K.
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p. 3821 - 3824
(2007/10/03)
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- N-arylbenzonitrilium ions. Photochemical generation and effect of substituents in the phenyl rings on lifetimes in water and reactivity with azide ion
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Nitrilium ions Ar-C≡N+-Ar′ have been studied by laser flash photolysis in aqueous solutions containing 20% acetonitrile. The cations were generated by photoheterolysis of benzimidate esters Ar-CZ=N-Ar′ (Z = -OC6H4-4-CN) with 4-cyanophenoxide as the photochemical leaving group. Rate constants for the reaction with water (kw), azide ion (kaz) and hydroxide (kOH) were measured. The cation Ph-C≡N+-Ph is only 50-fold shorter lived in water compared to Ph-C≡N+-iPr (2); thus the effect of replacing an N-alkyl group with N-phenyl is modest. These two cations are also shown to have similar lifetimes to iminium analogs, e.g. Ph-CH=N+ (Me)-Ph. Thus, addition of water to analogous sp and sp2 hybridized systems occurs at a similar rate, and the increased steric access to the nitrilium plays at most a modest role. For the series where substituents in Ar′ were varied with Ar equal to phenyl, the Hammett plot for log kw correlated with σ, with ρ = - 1.4. For the series where Ar was varied, the data correlated much better with σ+, although ρ+ was only -0.6. This remarkably small effect of substituents in Ar constrasts with the effects seen in benzylic carbocations, but is consistent with the nitrilium structure, with most of the positive charge located on the nitrogen. Rate constant ratios kaz:kw, including the N-alkylnitrilium ion 2, are constant at ~104, with values of kaz well below the diffusion limit, even for the most reactive nitrilium ions. This is very different behaviour from that of carbocations and arylnitrenium ions of similar lifetimes in water. For these cations the rate constants kaz would be at or at least approaching the diffusion limit.
- Ruane, Patrick H.,Ahmed, Abid R.,McClelland, Robert A.
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p. 312 - 317
(2007/10/03)
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- Synthesis and basicity of 4-amino-2-phenylquinazolines
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A new group of 6-and 7-substituted compounds of 4-amino-2-phenylquinazoline were synthesized by reaction of N-arylbenzimidoyl chlorides with cyanamide in the presence of TiCl4. The products were identified by spectroscopic methods, their dissoc
- Zielinski, Wojciech,Kudelko, Agnieszka
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p. 895 - 899
(2007/10/03)
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- Preparation of 1,5-disubstituted tetrazoles under phase-transfer conditions
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Imidoyl chlorides, obtained by common methods from a wide range of aromatic mono- and diamides, are smoothly converted to the corresponding tetrazoles in high yields by treatment with NaN3 under phase-transfer conditions.
- Artamonova,Zhivich,Dubinskii,Koldobskii
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p. 1428 - 1430
(2007/10/03)
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- Synthesis of 4-Aminoquinazoline Derivatives
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The reaction of N-phenylimidoyl chlorides (2) with cyanamide and N,N-dimethylcyanamide (4) was studied.At the first stage, linear products like 1-amino-1-chloro-3,5-diphenyl-2,4-diaza-1,3-butadienes (6) were obtained.They underwent cyclization to 4-aminoq
- Zielinski, W.,Mazik, M.
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p. 489 - 498
(2007/10/02)
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- REACTIONS OF IMIDIC ACID DERIVATIVES WITH NUCLEOPHILIC REAGENTS. THE EFFECT OF WATER ON THE AMINOLYSIS RATE OF IMIDOYL CHLORIDES IN ORGANIC MEDIA. MECHANISMS IN THE "BOUNDARY" REGIONS
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The effect of water (as a catalyst) on the rate of the reaction of N-arylbenzimidoyl chlorides C6H5CCl=NC6H4R with 4-dimethylaminopyridine in acetonitrile, propylene carbonate, γ-butyrolactone, benzonitrile, methylene chloride, dioxane (R = 4-Cl), and ace
- Saveelova, V. A.,Taran, N. A.,Drizhd, L. P.
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p. 2020 - 2030
(2007/10/02)
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- PYRAZOLO(1,5-c)PYRIMIDINES FROM PYRYLIUM SALTS AND AMIDRAZONES AND PYRIDINE IMIDOYL-N-IMIDES FROM IMIDOYL CHLORIDES
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2,4,6-Triphenylpyrylium salts react with unsubstituted amidrazones to give dihydropyrazolo(1,5-c)pyrimidines or salts of pyridine imidoyl-N-imides.Pyridine imidoyl-N-imides are conveniently prepared from N-aminopyridinium and imidoyl chlorides.
- Katritzky, Alan R.,Tomas, Alberto Tarraga
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- AMIDINES. PART IX. INFLUENCE OF SUBSTITUTION AT IMINO AND AMINO NITROGEN ATOMS ON THE BASICITY OF N,N'-DIPHENYLBENZAMIDINES
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A series of 15 unreported N1-metylo-N1,N2-diphenylbenzamidines containing two different substituents at phenyl rings have been synthesized and their pKa values in 99.8percent ethanol were determined.It was found
- Oszczapowicz, Janusz,Raczynska, Ewa,Orlinski, Ryszard
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p. 2031 - 2037
(2007/10/02)
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- THE IMINO-WITTIG REARRANGEMENT
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Iminoethers 15 are rearranged by LDA into α-aminoketones 18.
- Katritzky, Alan R.,Ponkshe, Narayan K.
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p. 1215 - 1216
(2007/10/02)
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