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Vinyl nosylates derived from 1,3-dicarbonyl compounds could be engaged in Suzuki-Myaura cross coupling reactions with aryl-, vinyl- and methylboronic acids or trifluoborate derivatives at room temperature in the presence of 2mol% of [1,1?-bis(diphenylphosphino)ferrocene]dichloropalladium(II) [PdCl2(dppf)]. One-pot procedures have been set up for practical and efficient nosylation-cross-coupling reactions. Nosylate, as a cheap novel pseudo-halide, gives very stable compounds and is very efficient in Suzuki-Myaura cross coupling reactions (21 examples, 44-99%).

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BACKGROUND: Spiromesifen and spirotetramat are novel insecticides belonging to the chemical class of tetronic and tetramic acid derivatives. Both compounds have proven very effective against field populations of Bemisia tabaci around the world. However, several growers have recently reported control failures in Spain. Therefore, we studied the resistance level to these insecticides in field populations reporting control failures. In addition, we further selected a spiromesifen-resistant strain to study the mechanisms involved and the cross-resistance pattern. RESULTS: All the new field populations collected were significantly more resistant to spiromesifen than the susceptible population, confirming the presence of resistance. Several populations showing high levels of resistance to spiromesifen (>10 000-fold), exhibited cross-resistance to spirotetramat, but resistance ratios were much lower (130-fold). The spiromesifen laboratory-selected strain was very resistant to spiromesifen (LC50 > 30 000 mg L?1) and spirotetramat (LC50 = 368.1 mg L?1), but lacks any cross-resistance to other insecticides, thus providing options for resistance management. None of the synergists tested significantly restored the susceptibility of B. tabaci to either spiromesifen or spirotetramat. CONCLUSION: This is the first report of resistance to spiromesifen and spirotetramat in B. tabaci, and such high levels of resistance have not been reported before in any field collected pest. Our results suggest that enhanced detoxification does not critically contribute to resistance to ketoenols in B. tabaci. The obvious lack of a metabolic resistance mechanism either suggests a target-site resistance mechanism or a metabolic mechanism insensitive to the synergists tested.

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Milk and dairy products continue to raise concerns with regard to contamination with mycotoxins, most of which have a likely or confirmed carcinogenic status. Such concerns are more serious for certain cheeses due to their frequent contamination with high concentrations of mycotoxins from various sources, including the milk used as a raw material and moulds found as contaminants or purposely added for ripening. Different control measures have been suggested to prevent the formation or to remove mycotoxins in dairy products once formed therein. However, these methods either provide an insufficient degree of protection or are onerous to implement. This review surveys the main mycotoxins associated with dairy products and discusses their health significance. Attention is drawn to the lack of knowledge on the emerging and masked mycotoxins with relevance to dairy products. Known control measures are discussed from the perspective of their application while presenting their strengths and weaknesses.

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Substituted ethyl 2-amino-3-cyano-2?,5-dioxo-5?-phenyl-1?,2?,5,7-tetrahydrospiro[furo[3,4-b]pyran-4,3?-pyrrole]-2?-carboxylates were synthesized by one-pot reaction of ethyl 2-phenyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-3-carboxylates with malononitrile and furan-2,4(3H,5H)-dione.

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Unexpected and green synthesis of azapodophyllotoxin derivatives via microwave-assisted multicomponent reactions in ammonia water

An unexpected and green synthesis of azapodophyllotoxin derivatives was realized via microwave-assisted multicomponent reactions of dimedone, tetronic acid, and aromatic aldehydes in ammonia water. This protocol has the advantages of environmental friendliness, short reaction time, good yields, low cost, and easy operation.

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Synthesis of new 5-alkylidene-4-chloro-5h-1,2,3-dithiazoles and their stereochemistry

A variety of 5-alkylidene-4-chloro-5H-1,2,3-dithiazoles (9-25) have been prepared from 4-chloro-5H-1,2,3-dithiazolium chloride, active methylene compounds, and pyridine. The reactions with ethyl nitroacetate ((Z) > (E)), ethyl 3-nitrobenzoylacetate ((E) > (Z)), ethyl 2-fluorobenzoylacetate ((E) > (Z)), and tetronic acid ((Z) > (E)) gave a mixture of (E)- and (Z)-isomers, whereas those of benzoylnitromethane (Z), 5,6-dihydro-4-hydroxy-6-methyl-2H- pyran-2-one (E), 4-hydroxy-6-methyl-2-pyrone (E), 4-hydroxycoumarin (E), 6- chloro-4-hydroxycoumarin (E), and 6-bromo-4-hydroxycoumarin (E) afforded only single stereoisomers. The reactions with 4-hydroxy-1-methyl-2(IH)-quinolone, 2-hydroxy-1,4-naphthoquinone and homophthalic anhydride gave only single stereoisomers whose stereochemistry is uncertain. It appears that geometrically more rigid cyclic 1,3-dicarbonyl compounds give better yields of dithiazol-5-ylidenes than the corresponding acyclic compounds.

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Systemic and non-systemic pesticides in apples from Kazakhstan and their impact on human health

Understanding the behavior of pesticides used during fruit cultivation is important for effectively and safety applying to minimize the risk exposure of consumer. The aim of this study was estimated the level of pesticide in 80 apple samples collected from the South Kazakhstan. Additionally, the peel and pulp was investigated. Around 50% samples contained 24 pesticides, ranging 0.006?0.62, 0.005?0.46 and 0.02?1.38 mg/kg in whole apples, pulp and peel, respectively. The penetration factor pesticide peel/pulp was calculated and ranged 1.7?10.9 for kresoxim methyl and triazophos, respectively. Acute (aHI) and cumulative (cHQ) exposure health risks associated with consuming these pesticides in whole fruit, pulp and skin were estimated. The triazophos, chlorpiryfos and cyhalothrin exceeded safety ARfD: 830, 136 and 112% for adults, whereas for infants 4514, 742 and 609%. The cHQ exposure were the highest in peel for AChE inhibitors: 999%, and sodium channel modulators 123% for adults.

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Recent Advances in the Synthesis of Cyclobutanes by Olefin [2 +2] Photocycloaddition Reactions

The [2 + 2] photocycloaddition is undisputedly the most important and most frequently used photochemical reaction. In this review, it is attempted to cover all recent aspects of [2 + 2] photocycloaddition chemistry with an emphasis on synthetically relevant, regio-, and stereoselective reactions. The review aims to comprehensively discuss relevant work, which was done in the field in the last 20 years (i.e., from 1995 to 2015). Organization of the data follows a subdivision according to mechanism and substrate classes. Cu(I) and PET (photoinduced electron transfer) catalysis are treated separately in sections 2 and 4, whereas the vast majority of photocycloaddition reactions which occur by direct excitation or sensitization are divided within section 3 into individual subsections according to the photochemically excited olefin.

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A simple synthesis of furo[3?,4?:5,6]pyrido[2,3-d]pyrimidine derivatives through multicomponent reactions in water

A series of furo[3?,4?:5,6]pyrido[2,3-d]pyrimidine and indeno[2?,1?:5,6]pyrido[2,3-d]pyrimidine derivatives were synthesized by three-component reactions involving an aldehyde, 2,6-diaminopyrimidine-4(3H)-one, and either tetronic acid or indane-1,3-dione in water, under microwave irradiation and traditional heating conditions, without use of any catalyst. This protocol has the advantages of higher yields, lower cost, reduced environmental impact, and convenience of procedure. The synthesis of a class of important compounds in aqueous medium has been achieved. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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[4+2+1] domino cyclization in water for chemo- and regioselective synthesis of spiro-substituted benzo[b]furo[3,4-e][1,4]diazepine derivatives

New regio- and chemoselective [4+2+1] domino cyclization consisting of the formation of two spiro rings and five sigma bonds has been developed for the synthesis of spiro-substituted benzo[b]furo[3,4-e][1,4]diazepine derivatives. The reaction is a multicomponent domino green process and can be readily performed by reacting inexpensive starting materials of benzene-1,2-diamines, tetronic acid and 2,2-dihydroxy-2H-indene-1,3-dione in aqueous solution under microwave irradiation. The present synthesis shows attractive characteristics, such as the use of water as reaction media, convenient one-pot operation, short reaction periods of 10-18 min and reduced waste production without the use of any strong acids or metal promoters. This synthesis serves as a nice addition to GAP (Group-Assistant-Purification) chemistry in which purification via chromatography and recrystallization can be avoided, and the pure products were obtained simply by washing the crude products with 95% EtOH.

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