- PROCESS FOR PREPARING FUNCTIONALIZED 1,2,4,5-TETRAZINE COMPOUNDS
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The present invention relates to a process for the synthesis of 3,6 functionalized 1,2,4,5-tetrazine compounds of formula (I); wherein A and B being the same; and wherein at least one of R1, R1', R2 and R2' and at least one of R10 and R10' is a halogen atom or acetate group; said process comprising reacting the corresponding 1,2,4,5-tetrazine compounds wherein at least one of R1, R1', R2 and R2' and at least one of R10 and R10' is a hydrogen atom with an oxidative reagent in presence of a catalyst.
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- Building Diversity in ortho-Substituted s-Aryltetrazines by Tuning N-Directed Palladium C-H Halogenation: Unsymmetrical Polyhalogenated and Biphenyl s-Aryltetrazines
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We report a general route for synthesizing ortho-substituted unsymmetrical biphenyl and polyaromatic s-aryltetrazines. These compounds are inaccessible by classical Pinner hydrazine condensation or by the current s-aryltetrazine aromatic core functionalization methods described up to now. We exploited multiple versatile N-directed palladium C-H activation/halogenation of s-aryltetrazine to form C-X bonds (X = I, Br, Cl, F), which collectively produced polyhalogenated unsymmetrical building blocks. We achieved a sequence of selective C-H halogenation reactions in a specific order to produce reactive aryl halides. Polyhalogenated s-aryltetrazines can then be used for controlled cross-coupling reactions toward ortho-substituted polyaromatic s-aryltetrazines. In general, this C-H functionalization route gives access to a large number of variously halogenated building blocks practical for further synthetic implementation of tetrazines (arylation, cycloaddition, etc.). Herein, we exemplified their potential by using halogen-selective Suzuki-Miyaura reactions for divergent construction of novel biphenyl s-tetrazines. Therefore, we deliver original poly(hetero)aromatic tetrazine structures, such as new typically "Z-shaped" and "T-shaped" species. We examined by DFT calculation the origin of the remarkable regioselectivity in some C-H concurrent halogenation reactions. Computations focused at free enthalpy profiles for C-H activation of aryltetrazines to form the intermediate palladacycles by CMD process. We showed that the presence of halogen substituents on aryl groups before further halogenation increases the activation barrier to form the determining C-H activation intermediate palladacycle. XRD studies of functionalized tetrazines evidenced planarity ruptures in the mutual arrangement of aromatic cycles. Finally, this methodology allowed us to deliver a unique tetrahalogenated s-aryltetrazine holding not less than four different halogens arranged in ortho-aryl positions.
- Mboyi, Clève D.,Testa, Christelle,Reeb, Sarah,Genc, Semra,Cattey, Hélène,Fleurat-Lessard, Paul,Roger, Julien,Hierso, Jean-Cyrille
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p. 8493 - 8501
(2017/12/08)
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- Ortho-Functionalized Aryltetrazines by Direct Palladium-Catalyzed C-H Halogenation: Application to Fast Electrophilic Fluorination Reactions
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A general catalyzed direct C-H functionalization of s-tetrazines is reported. Under mild reaction conditions, N-directed ortho-C-H activation of tetrazines allows the introduction of various functional groups, thus forming carbon-heteroatom bonds: C-X (X=I, Br, Cl) and C-O. Based on this methodology, we developed electrophilic mono- and poly-ortho-fluorination of tetrazines. Microwave irradiation was optimized to afford fluorinated s-aryltetrazines, with satisfactory selectivity, within only ten minutes. This work provides an efficient and practical entry for further accessing highly substituted tetrazine derivatives (iodo, bromo, chloro, fluoro, and acetate precursors). It gives access to ortho-functionalized aryltetrazines which are difficult to obtain by classical Pinner-like syntheses.
- Testa, Christelle,Gigot, élodie,Genc, Semra,Decréau, Richard,Roger, Julien,Hierso, Jean-Cyrille
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p. 5555 - 5559
(2016/05/09)
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- ACTIVE COMPOUND COMBINATIONS HAVING INSECTICIDAL AND ACARICIDAL PROPERTIES
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The novel active compound combinations comprising a compound of the formula (I-1) or (I-2) and the active compounds (1) to (26) listed in the description have very good insecticidal and acaricidal properties.
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- Synthesis, structure analysis, and antitumor activity of 3,6-disubstituted-1,4-dihydro-1,2,4,5-tetrazine derivatives
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Fourteen compounds of 3,6-disubstituted-1,4-dihydro-1,2,4,5-tetrazine derivatives were prepared and their structures were confirmed by single-crystal X-ray diffraction and the semi-empirical calculation of PM3 method. This reaction yields the 1,4-dihydro derivatives rather than the 1,2-dihydro derivatives. The central six-membered ring of 1,4-dihydro-1,2,4,5-tetrazine has a chair conformation and therefore is not homoaromatic. Their antitumor activities were evaluated in vitro by SRB method for A-549 and BEL-7402 cells, and MTT method for P-388 and HL-60 cells. The results show that there is one compound which is highly effective against P-388 cells and one compound which is highly effective against HL-60 cells. So it is a kind of compound which possesses potential antitumor activities and is worth to research further.
- Rao, Guo-Wu,Hu, Wei-Xiao
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p. 3702 - 3705
(2007/10/03)
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- Synthesis and antitumor activity of s-tetrazine derivatives
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Fifty-five compounds of s-tetrazine derivative including hexahydro-, 1,6-dihydro, 1,4-dihydro-, 1,2-dihydro- and aromatic s-tetrazine were prepared. Their antitumor activities were evaluated in vitro by MTT method for P-388 cell and SRB method for A-549 cell. The results show that there are 9 compounds which in 10-6 μM have more than 50% inhibition rate to A-549 cancer cell growth, and 7 compounds in 10-6 μM have more than 50% inhibition rate to P-388 cancer cell growth. The IC50 of compound 3q for P-388, Bel-7402, MCF-7 and A-549 are 0.6 μM, 0.6 μM, 0.5 μM and 0. 7 μM, respectively. So s-tetrazine derivative is a kind of compound which possesses potential antitumor activities and is worth to research further.
- Hu, Wei-Xiao,Rao, Guo-Wu,Sun, Ya-Quan
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p. 1177 - 1181
(2007/10/03)
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- Use of citric acid derivatives as pesticidal adjuvants
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The invention provides the use as a pesticidal adjuvant of at least one citric acid derivative and compositions containing the derivative, which has a log octanol-water coefficient (log P) of 2.6 to 11 and an equivalent hydrocarbon (EH) value of 29 to 47. The invention has been shown to enhance the efficacy of a range of pesticides.
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- Insecticidal compositions and methods of use employing imidacloprid and another insecticide
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The present invention relates to insecticidal mixtures of chloronicotinyl insecticides of the formula (I) STR1 in which R1 represents C1 -C5 -alkyl, R2 represents hydrogen or C1 -C5 -alkyl, or R1 and R2 together represent --CH2 --CH2 --; --CH2 --CH2 --CH2 -- or STR2 X represents an NH group, NCH3 group or represents sulphur, Y represents nitrogen or a CH group and Z represents cyano or nitro, with one or more of the synergists mentioned in the description.
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- Acaricidally active tetrazine derivatives
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The invention relates to novel 1,2-dihydro-1,2,4,5-tetrazine derivatives of the formula (IV) STR1 wherein means fluorine, chlorine or bromine; and Y stands for hydrogen or fluorine, as well as to a process for the preparation thereof. The compounds according to the invention have acaricidal, larvicidal and ovicidal effects.
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- Macrocyclic plant acaricides
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Compounds of the formula I STR1 in which either R is methyl and there is a double bond in the 9,10-position, or in which R is hydrogen and there is a single bond in the 9,10-position, are highly active against Acarina which damage plants.
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- 1,2,4,5-Tetrazines
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The substituted tetrazines of the formula: STR1 and of the formula: STR2 wherein: R1, R2 and R4 each represent hydrogen, phenyl, alkyl of 1 to 6 carbon atoms, or alkenyl or alkynyl of 3 to 6 carbon atoms, each of which may be unsubstituted or substituted by one or more halogen atoms, hydroxy groups, cyano groups, carboxy groups, alkoxycarbonyl groups of 2 to 5 carbon atoms, or alkoxy groups of 1 to 4 carbon atoms; or R1 and R2 together represent a single bond; R3 represents alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, phenyl or phenylalkyl of 7 to 10 carbon atoms, each of which may be unsubstituted or substituted by one or more halogen atoms, alkyl or alkoxy groups of 1 to 6 carbon atoms, nitro groups, cyano groups, mercapto groups, or alkylmercapto groups of 1 to 4 carbon atoms; and R6 represents a phenyl group substituted in at least the 2-position by fluorine, chlorine, bromine or iodine; are effective to combat acarids and their eggs.
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