Triazole-annulated phthalocyanines and benzoporphyrazines

2006 ◽  
Vol 10 (11) ◽  
pp. 1309-1318
Author(s):  
Sergei I. Vagin ◽  
Michael Hanack
Keyword(s):  
Double Bond ◽  
Metal Complexes ◽  
Nickel Complex ◽  
Triazole Ring ◽  
Reaction Conditions ◽  
Terminal Double Bond

The application of mono-triazole-annulated phthalocyanine and benzoporphyrazine complexes for the functional unsymmetrical modification of the macrocycle's periphery is discussed. The peculiarities of the synthesis of some metal complexes with aryloxy-substituted mono-triazole-annulated Pc are described. Alkylation by ω-alkenylbromide of the triazole ring in accordingly prepared novel mono-triazole-annulated phthalocyaninato nickel, as well as in mono-benzotriazole-annulated porphyrazinato zinc, is studied. The terminal double bond in the formed derivatives could be successfully converted into acetylsulfanyl function only in the case of phthalocyaninato nickel complex due to the instability of porphyrazinato zinc under the reaction conditions.

One-pot Synthesis of Pyrazolone Sulfones by Iodine-catalyzed Sulfenylation of Pyrazolones with Aryl Sulfonyl Hydrazides Followed by Oxidation in Water

2018 ◽  
Vol 15 (3) ◽  
pp. 380-387
Author(s):  
Xia Zhao ◽  
Xiaoyu Lu ◽  
Lipeng Zhang ◽  
Tianjiao Li ◽  
Kui Lu
Keyword(s):  
Double Bond ◽  
Efficient Method ◽  
Room Temperature ◽  
Sulfonyl Chloride ◽  
Antibacterial Activities ◽  
Oxidation Reactions ◽  
Reaction Conditions ◽  
One Pot ◽  
X Ray ◽  
Amide Form

Aim and Objective: Pyrazolone sulfones have been reported to exhibit herbicidal and antibacterial activities. In spite of their good bioactivities, only a few methods have been developed to prepare pyrazolone sulfones. However, the substrate scope of these methods is limited. Moreover, the direct sulfonylation of pyrazolone by aryl sulfonyl chloride failed to give pyrazolone sulfones. Thus, developing a more efficient method to synthesize pyrazolone sulfones is very important. Materials and Method: Pyrazolone, aryl sulphonyl hydrazide, iodine, p-toluenesulphonic acid and water were mixed in a sealed tube, which was heated to 100°C for 12 hours. The mixture was cooled to 0°C and m-CPBA was added in batches. The mixture was allowed to stir for 30 min at room temperature. The crude product was purified by silica gel column chromatography to afford sulfuryl pyrazolone. Results: In all cases, the sulfenylation products were formed smoothly under the optimized reaction conditions, and were then oxidized to the corresponding sulfones in good yields by 3-chloroperoxybenzoic acid (m-CPBA) in water. Single crystal X-ray analysis of pyrazolone sulfone 4aa showed that the major tautomer of pyrazolone sulfones was the amide form instead of the enol form observed for pyrazolone thioethers. Moreover, the C=N double bond isomerized to form an α,β-unsaturated C=C double bond. Conclusion: An efficient method to synthesize pyrazolone thioethers by iodine-catalyzed sulfenylation of pyrazolones with aryl sulfonyl hydrazides in water was developed. Moreover, this method was employed to synthesize pyrazolone sulfones in one-pot by subsequent sulfenylation and oxidation reactions.

Some Analogs of 4-(2',4'-Difluorobiphenyl-4-yl)-2-methyl-4-oxobutanoic Acid: Synthesis and Antiinflammatory Activity

1995 ◽  
Vol 60 (6) ◽  
pp. 1026-1033 ◽  
Author(s):  
Miroslav Kuchař ◽  
Václav Vosátka ◽  
Marie Poppová ◽  
Eva Knězová ◽  
Vladimíra Panajotovová ◽  
...  
Keyword(s):  
Double Bond ◽  
Antiinflammatory Activity ◽  
Acid Synthesis ◽  
Reaction Conditions ◽  
Methyl Group ◽  
Oxobutanoic Acid

Analogs of 4-(2',4'-difluorobiphenyl-4-yl)-2-methyl-4-oxobutanoic acid (I, flobufen), containing a double bond (II, IV, V, VII, VIII) or a methyl group in position 3 (VI) were prepared. Their antiinflammatory activity was evaluated and compared with that of flobufen. None of the mentioned analogs reached the activity of the standard. Isomerization of the unsaturated derivatives is connected with a shift of the double bond, Z-E transformation or lactonization. Reaction conditions and spectra of the compounds prepared are described.

Double bond isomerization of ethyl linoleate and vegetable oils to conjugated derivatives over an LDH supported ruthenium catalyst

RSC Advances ◽  
2015 ◽  
Vol 5 (45) ◽  
pp. 36075-36082 ◽  
Author(s):  
Sivashunmugam Sankaranarayanan ◽  
Gobi Selvam ◽  
Kannan Srinivasan
Keyword(s):  
Double Bond ◽  
Vegetable Oils ◽  
Ethyl Linoleate ◽  
Ruthenium Catalyst ◽  
Reaction Conditions ◽  
Double Bond Isomerization

Isomerization of ethyl linoleate and vegetable oils to conjugated derivatives is achieved over an MgAl-LDH supported ruthenium catalyst under mild reaction conditions.

scholarly journals Cyclopentadienone Iron Tricarbonyl Complexes-Catalyzed Hydrogen Transfer in Water

Molecules ◽  
2020 ◽  
Vol 25 (2) ◽  
pp. 421 ◽  
Author(s):  
Daouda Ndiaye ◽  
Sébastien Coufourier ◽  
Mbaye Diagne Mbaye ◽  
Sylvain Gaillard ◽  
Jean-Luc Renaud
Keyword(s):  
Metal Complexes ◽  
Hydrogen Transfer ◽  
Low Cost ◽  
Pure Water ◽  
Free Water ◽  
Water Soluble ◽  
Tricarbonyl Complex ◽  
Reaction Conditions ◽  
Catalytic Systems ◽  
Iron Tricarbonyl

The development of efficient and low-cost catalytic systems is important for the replacement of robust noble metal complexes. The synthesis and application of a stable, phosphine-free, water-soluble cyclopentadienone iron tricarbonyl complex in the reduction of polarized double bonds in pure water is reported. In the presence of cationic bifunctional iron complexes, a variety of alcohols and amines were prepared in good yields under mild reaction conditions.

scholarly journals Silver-catalysed azide–alkyne cycloaddition (AgAAC): assessing the mechanism by density functional theory calculations

2016 ◽  
Vol 3 (9) ◽  
pp. 160090 ◽  
Author(s):  
Biswadip Banerji ◽  
K. Chandrasekhar ◽  
Sunil Kumar Killi ◽  
Sumit Kumar Pramanik ◽  
Pal Uttam ◽  
...  
Keyword(s):  
Density Functional ◽  
Click Reaction ◽  
Cycloaddition Reaction ◽  
Triazole Ring ◽  
Density Functional Theory Calculations ◽  
Dipolar Cycloaddition ◽  
Reaction Conditions ◽  
Functional Theory ◽  
Click Reactions ◽  
Counter Ions

‘Click reactions’ are the copper catalysed dipolar cycloaddition reaction of azides and alkynes to incorporate nitrogens into a cyclic hydrocarbon scaffold forming a triazole ring. Owing to its efficiency and versatility, this reaction and the products, triazole-containing heterocycles, have immense importance in medicinal chemistry. Copper is the only known catalyst to carry out this reaction, the mechanism of which remains unclear. We report here that the ‘click reactions’ can also be catalysed by silver halides in non-aqueous medium. It constitutes an alternative to the well-known CuAAC click reaction. The yield of the reaction varies on the type of counter ion present in the silver salt. This reaction exhibits significant features, such as high regioselectivity, mild reaction conditions, easy availability of substrates and reasonably good yields. In this communication, the findings of a new catalyst along with the effect of solvent and counter ions will help to decipher the still obscure mechanism of this important reaction.

Varying structural motifs in the salen based metal complexes of Co(ii), Ni(ii) and Cu(ii): synthesis, crystal structures, molecular dynamics and biological activities

2016 ◽  
Vol 45 (47) ◽  
pp. 19096-19108 ◽  
Author(s):  
Anoop Kumar Saini ◽  
Pratibha Kumari ◽  
Vinay Sharma ◽  
Pradeep Mathur ◽  
Shaikh M. Mobin
Keyword(s):  
Molecular Dynamics ◽  
Metal Complexes ◽  
Crystal Structures ◽  
Biological Activities ◽  
Biological Applications ◽  
Reaction Conditions ◽  
Structural Motifs

Four new metal complexes which demonstrates varying structural motifs from monomeric to dimeric to tetrameric complexes by slightly altering the reaction conditions and their biological applications.

A simple method of isomerization of the terminal double bond in a terpene chain

1985 ◽  
Vol 50 (10) ◽  
pp. 2174-2178 ◽  
Author(s):  
Ludvík Streinz ◽  
Zdeněk Wimmer ◽  
Georgii K. Roshka ◽  
Raisa I. Ishchenko ◽  
Miroslav Romaňuk ◽  
...  
Keyword(s):  
Double Bond ◽  
Trifluoroacetic Acid ◽  
Main Part ◽  
Simple Method ◽  
Terminal Double Bond ◽  
Quadraspidiotus Perniciosus

The utilisability of the isomerization of the terminal double bond in terpenic compounds with trifluoroacetic acid was investigated. The results obtained were used in the synthesis of the main part of the pheromone of Quadraspidiotus perniciosus COMSTOCK, i.e. (2E)-3,7-dimethyl-2,7-octadien-1-yl propionate.

Transition metal complexes of substituted alkynes. XI. The reactions of But-2-yne and Hexafluorobut-2-yne with Dicarbonyl(η-cyclopentadieny)-cobalt and -rhodium

1974 ◽  
Vol 27 (1) ◽  
pp. 61 ◽  
Author(s):  
RS Dickson ◽  
HP Kirsch
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Major Product ◽  
Reaction Conditions ◽  
A Minor ◽  
Related Reaction

The thermally initiated reaction of hexafluorobut-2-yne and (q-C5H5)C~(C0)2 gives the 1-4-q- hexakis(trifiuoromethy1)benzene complex (7-C5H5)Co [(CF3C2CF3)3] in addition to the known cyclopentadienone complex (q-C5H5)Co [(CF3C2CF3)2CO]. The related reaction of but-2-yne with (q-CjH j)Co(CO)2 gives several compounds in addition to the cyclopentadienone complex (q-C jHj)C~- [(MeC2Me)2CO] which has been isolated previously from this reaction. Thus, the duroquinone complex (q-C5H5)Co [(MeC2Me)2(C0)2], the maleoyl complex (q-C5H5)Co(MeC2Me)(C0)3, and free duroquinone have been obtained. The yields of the various products are influenced by the reaction conditions. The metallocyclopentadiene complex (q-C jH j)2Rh2(CF3C2CF3)2, which is formed in the reaction between (q-C,H,)Rh(CO), and hexafluorobut-2-yne, exhibits fluxional behaviour in solution at c. 130". Two complexes are formed in the reaction at 100-120' between (q-C5Hj)Rh- (CO)2 and but-2-yne. These are the cyclopentadienone complex (q-C5H5)Rh [(MeC2Me)2CO] and the duroquinone complex (7-CjH5)Rh [(MeC2Me)2(C0)2]. Comparison of the various reactions indicates that: (i) a cyclopentadienone complex (q-CgH5)M- [(MeC2Me)2CO] is generally formed as major product and a duroquinone complex (q-C5Hj)M- [(MeC2Me)2(C0)2] is generally formed as a minor product in reactions between (q-C5H5)M(C0)2, M = Co and Rh, and but-2-yne; and (ii) a tetrahaptobenzene complex (q-C5H5)M [(CF3C2CF3)3] is formed as major product when M = Rh and as a minor product when M = Co in reactions between (q-C5H5)M(CO)2 and hexafluorobut-2-yne.

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