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Chemistry of 2-aryl-1-cyano-1-nitroethenes. Part II. Chemical transformations

Woliński P., Kącka-Zych A.

Technical Transactions

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2018

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Vol. 115, iss. 2

123--139

EN

This work is a continuation of our study on the chemistry of 2-aryl-1-cyano-1-nitroethenes. In this paper, we describe the reactivity of 2-aryl-1-cyano-1-nitroethenes as a key component in [2+3] and [2+4] cycloaddition reactions, and in other transformations.

PL

Praca stanowi kontynuację studiów dotyczących chemii 2-arylo-1-cyjano-1-nitroetenów. W jej ramach dokonaliśmy przeglądu transformacji 2-arylo-1-cyjano-1-nitroetenów jako komponentów [2+3], [2+4] cykloaddycji oraz w innych reakcjach.

2

Termodynamika cykloaddycji (e)-3,3,3-trichloro-1-nitroprop-1-enu do (z)-c-antrylo-n-fenylonitronu w świetle obliczeń b3lyp/6-31g(d)

Goliasz G., Jasiński R.

Czasopismo Techniczne. Chemia

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2012

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R. 109, z. 1-Ch

13--18

PL

W artykule zbadano termodynamikę cykloaddycji (E)-3,3,3-trichloro-1-nitroprop-1-enu do (Z)-C-antrylo- N-fenylonitronu.

EN

The thermodynamics of cycloaddition reaction of (E)-3,3,3-trichloro-1-nitroprop-1-ene to (Z)-C-anthryl- N-phenylnitrone were carried out.

3

Reaction of 1,2-Di(1-adamantyl)-2-thioxoethanone with Diazomethanes; 1,3- versus 1,5-Dipolar Electrocyclization of a Sterically Crowded Thiocarbonyl S-Methylide

Mlostoń G., Urbaniak K., Nomura T., Nakayama J., Heimgartner H.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 11

1945-1951

EN

The reaction of 1,2-di(1-adamantyl)-2-thioxoethanone (4c) with diazomethane and 2-diazopropane yielded 2-acylthiiranes 6a and 6b, respectively, and no 1,3-oxathioles of type 7 were formed. The reaction course is explained via [2+3]-cycloaddition, elimination of N2, and 1,3-dipolar electrocyclization of the in ter me di ate acyl-substituted thiocarbonyl ylides of type 1. The fail ure of the competitive 1,5-dipolar electrocyclization is a result of the sterically unfavor able conformation 1a.

4

Synthesis and Properties of Azoles and Their Derivatives. Part LXII. Secondary Deuterium Kinetic Isotope Effects in [2+3] Cycloaddition of (E)-2-Phenylnitroethene to (Z)-C,N-Diphenylnitrone

Barański A., Lyubimtsev A., Jasiński R., Kwiatkowska M.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 5

1037-1042

EN

SKIE analysis of [2+3] cycloaddition of (E)-2-phenylnitroethene to (Z)-C,N-diphenyl - nitrone suggests that for both stereoisomeric reaction paths (Scheme 1), the O1-C5 bond of the adduct forms faster than the corresponding C3-C4 bond. Never the less, both stereo isomers are formed by an one-step mechanism. According to Hammond's terminology, the transition states in volved in the reaction mechanism can be classified as asynchronous early states.

5

Synthesis and Properties of Azoles and Their Derivatives. Part LXIV. [2+3] Cycloaddition of trans-1-Nitropropene-1 to C,C,N-Triphenylnitrone in the Light of AM1/COSMO Calculations

Jasiński R., Barański A.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 5

1043-1049

EN

Quantum-chemical simulations of [2+3] cycloaddition of trans-1-nitropropene with triphenylnitrone in nitromethane and formamide have been carried out using AM1/COSMO algorithm. The results suggest that the reaction leading to 2,3,3- tri - phenyl-4-methyl-5-nitroisoxazolidine occurs by a concerted mechanism, while the alternative reaction leading to regioisomeric 2,3,3-triphenyl-4-ni tro-5- methyl isoxazolidine occurs by anionic mechanism.

6

Synthesis and Properties of Azoles and Their Derivatives. Part LXV*. Kinetic Study on the [2+3] Cycloaddition of Triphenylnitrone to trans-1-Nitroprop-1-ene

Jasiński R., Barański A.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 11

2125-2131

EN

The [2+3] cycloaddition of triphenylnitrone to trans-1-nitroprop-1-ene proceeds according to concerted mechanism, in spite of pi-deficient character of dipolarophile and strongly shielded one of the reaction centers in molecule of 1,3-dipole. This mechanism is indicated by the obtained values of activation parameters and weak kinetic solvent effect.

7

Regionoselektywność [2+3] cykloaddycji nitroetenu z Z-C,N-diarylonitronami w świetle teorii FMO

Jasiński R., Mikulska M., Pawlik H., Barański A.

Czasopismo Techniczne. Mechanika

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2008

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R. 105, z. 2-M

121-127

PL

Na podstawie danych obliczeń kwantowochemicznych przeprowadzono analizę pierwotnych efektów orbitalnych oraz coulombowskich w reakcjach [2+3] cykloaddycji diarylonitronów z nitroetenem. Ustalono, że efekty te generalnie sprzyjają powstawaniu odpowiednich 4-nitroizoksazolidyn.

EN

Using quantum-chemical calculations we have carried out an analysis of frontier molecular orbital interactions in the [2+3] cycloaddition reactions of nitroethene with diarylnitrones. In all cases the primary orbital effects and coulombic interactions favored the corresponding 4-nitroisoxazolidines.

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Termodynamiczne aspekty [2+3] cykloaddycji C-m,m,p-trimetoksyfenylo - N-p - metylofenylonitronu z E-3,3,3-trichloro-1-nitropropenem-1

Szczepanek A., Jasiński R.

Czasopismo Techniczne. Chemia

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2008

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R. 105, z. 1-Ch

143-147

PL

Zbadano termodynamikę [2+3] cykloaddycji C-m,m,p-trimetoksyfenylo-N-p-metylofenylonitronu z E-3,3,3-trichloro-1-nitropropenem-1. Ustalono, że czynniki termodynamiczne najsilniej sprzyjają powstawaniu 3,4-trans-2-p-metylofenylo-3-m,m,p-trimetoksyfenylo-4-trichlorometylo- 5-nitroizoksazolidyny.

EN

The thermodynamics of [2+3] cycloaddition reaction of C-m,m,p-trimethoxyphenyl-N-pmethylophenylnitrone with E-3,3,3-trichloro-1-nitropropene-1 were carried out. The thermodynamics effects indicate that 3,4-trans-2-p-methylophenyl-3-m,m,p-trimethoxyphenyl-4- -trichloromethylo-5-nitroisoxazolidines in this reaction are favored.

9

Synthesis and Properties of Azoles and Their Derivatives. Part LVIII. DFT Study on [2+3] Cycloaddition of trans-Nitroethenes to Z-C,N-Diphenylnitrone

Jasiński R., Barański A.

Polish Journal of Chemistry

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2007

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Vol. 81, nr 8

1441-1447

EN

DFT calculations indicate that the transition states of [2+3] cycloaddition of trans-2- phenylnitroethene to Z-C,N-diphenylnitrone led to 3,4-cis and 3,4-trans 4-nitroisoxazolidines are almost perfectly symmetrical. Asymmetry of the transition states appears for the reaction with more -deficient trans-2-(trichloromethyl)-nitroethene. Nevertheless, in both cases the formation of azolidine rings occurs in one step. The calculational results correlate well with experimental data.

10

Studia nad regioselektywnością [2+3] cykloaddycji C,C,N-trifenylonitronu z ε-β-cyjanonitroetylenem

Jasiński R.

Czasopismo Techniczne. Chemia

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2007

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R. 104, z. 1-Ch

27-31

PL

[2+3] Cykloaddycja trifenylonitronu z β-cyjanonitroetylenem nie prowadzi do trwałych cykloadduktów. Powstająca 4-nitroizoksazolidyna ulega dekompozycji do nitronu i nitroalkenu, zaś 5-nitroizoksazolidyna konwertuje do β-laktamu.

EN

[2+3] Cycloaddition of triphenylonitrone with β-cyanonitroethene does not lead to stable cycloadducts. 4-nitroisoxazolidine decomposes easily to nitrone and nitroalkene, while 5-nitroisoxazolidine converts to β-lactam.

11

Synthesis and Properties of Azoles and Their Derivatives. Part LVI. Mechanistic Aspects on the [2+3] Cycloaddition of Z-C,N-Diphenylnitrone with trans-1-Nitropropene-1 and trans-3,3,3-Trichloro-1-nitropropene-1

Jasiński R., Barański A.

Polish Journal of Chemistry

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2006

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Vol. 80, nr 9

1493-1502

EN

The [2+3] cycloaddition reactions of diphenylnitrone with trans-1-nitropropene-1 and trans-3,3,3-trichloro-1-nitropropene-1 occur via a concerted mechanism despite high -deficient character of dipolarophiles. This mechanism is indicated by cis-stereospecificity of the cycloaddition, the obtained values of activation parameters and weak solvent effect on the reaction kinetics.

12

New Thiocarbonyl Ylides Derived from 3,3-Dichloro-2,2,4,4-tetramethylcyclobutanethione; Generation and Reactions

Woźnicka M., Rutkowska M., Mlostoń G., Majchrzak A., Heimgartner H.

Polish Journal of Chemistry

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2006

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Vol. 80, nr 10

1683-1693

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Synthesis and Properties of Azoles and Their Derivatives. Part LV*. Mechanism of c,C,N-Triphenylnitrone [2+3]-Cycloaddition with (E)-3,3,3-Trichloro-1-nitropropene-1 in the Light of AM1 and AM1/COSMO Calculations

Jasiński R., Brandel E., Barański A.

Polish Journal of Chemistry

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2004

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Vol. 78 / nr 1

83-88

EN

AM1 calculations suggest that the [2+3]-cycloaddition of C,C,N-triphenylnitrone (1) to (E)-3,3,3-trichloro-1-nitropropene-1 (2) in gas phase occurs in concerted manner. Kinetic factors favour the formation of cycloadduct with nitrogen group in position C4 of the isoxazolidine ring (path A). Introduction of toluene as a dielectric medium does not alter this preferable. However, the character of the energy profile for path A undergoes a critical change. In this case, two transition states and intermediate with zwitterionic character were localized by means of AM1/COSMO method.

14

Reakcje [2+3] cykloaddycji sprzężonych nitroalkenów z nitronami

Barański A., Jasiński R.

Wiadomości Chemiczne

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2002

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[Z] 56, 9-10

829-854

EN

The work is an attempt of systematizing of the literature data concerning the regio- and stereoselectivity of [2+3] cycloadditions of conjugated nitroalkenes to nitrones. In most cases these reactions are regiospecyfic leading to the corresponding 4-nitro-isoxasolidines. In the reactions with trans-b-arylnitroethylenes, trans-configuration of the substituents at C-3 and C-4 positions of the heterocyclic ring is always favored. However, in the case of trans-b-alkylnitroethylenes, usually the 3,4-cis-isomers are formed in majority. If steric effects do not affect significantly the reaction course, the observed regioselectivity can be well explained in the terms of FMO or HSBA theory. The reaction stereoselectivity is hard to predict in advance. It seems that it depends on the equilibrium between the two complementary interactions in the reaction transition state: the attractive secondary overlaps of the reactants pz-orbitals, and the repulsive steric interactions of the reactants substituents. In some cases, the possibility of (Z)-(E) isomerisation of nitrones under reaction conditions has to be taken into account. Chemical properties of the cycloadducts resulting from the presence of nitro group in the isoxazolidine ring have also been discussed.

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Synthesis and Properties of Azoles and Their Derivatives : XLIII. Regio- and Stereoselectivity of [2+3] Cycloaddition Reaction of E-B-Nitrostyrene to Z-C-Aryl-N-phenylnitrones

Barański A.

Polish Journal of Chemistry

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2000

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Vol. 74, nr 6

767-775

EN

E-B-Nitrostyrene (1) reacts with Z-C-acryl- N-phenylnitrones (2a-h) exclusively to give trans- and cis-2,5-diphenyl-3-aryl-4-nitroisoxazolidines (3a-h, 4a-h) in high yield. The molar ratio of trans and cis stereoisomers is affected by substituent in phenyl ring of the parent nitrone (2c). The reaction is found by AM1 calculations to be controlled bt the interactions of the HOMO of nitrone with the LUMO of nitrostyrene.

16

Synthesis and Properties of Azoles and Their Derivatives : Part XLI : Stereoselectivity and Kinetic Study of the [2+3]Cycloaddition of E-B-Nitrostyrene to Z-C,N-Diphenylnitrone

Barański A.

Polish Journal of Chemistry

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1999

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Vol. 73, nr 10

1711-1717

EN

Stereoselectivity and the kinetics of the reaction of E-B-nitrostyrene to Z-C,N-diphenylnitrone at different temperatures and in several solvents have been studied. From the results obtained, it is evident that the reaction shows the properties of a one-step concerted process, so that it can be considered a typical [2+3]cycloaddition process.