- Concerted rate-limiting proton transfer to sulfur with nucleophilic attack at phosphorus - A new proposed mechanism for hydrolytic decomposition of the P=S pesticide, Diazinon, in moderately acidic sulfuric acid media
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We report herein the first kinetic study of a P=S containing organophosphorus pesticide, Diazinon (1), in the moderately concentrated acid region. Product analyses (31P NMR) show that reaction occurs only at the P centre. The rate-acidity profile (kobs vs. molarity of H 2SO4) appears as a curve in which the initial slight downward trace (molarity = 1 to ca. 5) is followed by sharper upward curve (molarity ca. 5 to 14). Using treatments involving the excess acidity (X) method, the A-1 and A-2 mechanistic possibilities were found to be inoperative over the full acidity range. A novel mechanism is proposed for the higher acidity (X ca. 2-6) region. This mechanism involves proton transfer to P=S from hydronium ion with concomitant proton transfer from water, which effectively delivers hydroxide to the P centre in a variant of the A-SE2 process. A putative A-2 mechanism in this region is supplanted by the proposed A-S E2 variant where the cyclic array results in proton transfer being efficiently coupled with nucleophilic attack involving water. This constitutes the first report of rate-limiting proton transfer at the P=S functionality in acid hydrolysis of this class of organophosphorus neutroxins. A 600 000-fold acceleration in the decomposition of Diazinon is associated with the change of medium from neutral aqueous solution to the most acidic medium studied (X ca. 6).
- Churchill, Doreen,Dust, Julian M.,Buncel, Erwin
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- Complexation of diazinon, an organophosphorus pesticide, with α-, β-, and γ-cyclodextrin - NMR and computational studies
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Complexation of the organophosphorus pesticide, diazinon, with α-, β- and γ- cyclodextrin has been investigated through NMR and computational methodologies. Binding constants (Kb) determined by 1H and 31P NMR follow the order γ-CD > α-CD = β-CD, in contrast with reported Kb data for other pesticides and thus indicative of steric encumbrance by the isopropyl group in diazinon being an important factor influencing binding constants. The interaction of diazinon with the CDs has also been investigated through computational studies via molecular dynamics - molecular mechanics (MD-MM2) and density functional theory (DFT), B3LYP/6-31G*. It is shown that the most favorable orientation in binding corresponds to the hydrophobic heterocyclic residue of diazinon being pulled deepest into the CD cavity, in agreement with the experimentally determined order of binding constants. Moreover, the computations show that it is only with γ-CD that the heterocyclic residue of diazinon and the phosphoryl residue are both largely encrypted in the CD cavity, marking a clear differentiation with α-CD and β-CD where the phosphoryl residue is located largely outside the cavity. Thus, the computational results are in essential agreement with the experimental binding constants where γ-CD stands out with the highest Kb value. Our work could point to the potential usefulness of computational studies to be undertaken in tandem with experimental work in environmental situations such as soil remediation.
- Churchill, Doreen,Cheung, Jason Chiu Fung,Park, Yong Sung,Smith, Vedene H.,VanLoon, Gary,Buncel, Erwin
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- Investigation on the acylation of heterocyclic alcoholate anions with O,O-dialkyl phosphorochloridothioate in water solvent
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The acylation of some heterocyclic alcoholate anions with O,O-dialkyl phosphorochloridothioate has been investigated. Higher yields and fewer byproducts were achieved in water at 50 °C by employing an effective phase-transfer catalyst (PTC) (benzyl triethylammonium chloride [BTEAC]), acylation catalyst (AC) (4-dimethylaminopyridine), and surfactant (sodium dodecyl sulfate), under weakly basic (pH 9.5～10) conditions. This reaction can also be applied to synthesize other insecticides with excellent yields.
- Ge, Xin,Qian, Chao,Chen, Xinzhi
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supporting information
p. 739 - 744
(2013/07/25)
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- Polymerization of Multifunctional Azides, and Polymers Therefrom
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Methods for preparing polymers from multifunctional azides and multifunctional azide-reactants are described in the present disclosure. Exemplary multifunctional azide-reactants include multifunctional alkynes and/or multifunctional α-phosphine esters. In certain embodiments, such polymers can be prepared in vivo. Such polymers can be useful in a wide variety of biomedical applications.
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- NOVEL MULTIMERIC MOLECULES, A PROCESS FOR PREPARING THE SAME AND THE USE THEREOF FOR MANUFACTURING MEDICINAL DRUGS
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The invention relates to a compound of the formula (I): in which k and j are independently 0 or 1, Y is a macrocycle in which the cycle includes 9 to 36 carbon atoms and is functionalised by three amino functions and by a chain for attaching the spacer arm Z via an X bond, Rc is a binding pattern with a receptor of the TNF superfamily, X is a chemical function for binding the Y group to the space arm, and Z is a bi-, tri- or tetra-functional spacer arm.
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- Cis-Alkoxyspiro-Substituted Tetramic Acid Derivatives
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The invention relates to novel cis-alkoxyspiro-substituted tetramic acid derivatives of the formula (I), in which A, G, X, Y and Z are as defined above, to a plurality of processes and intermediates for their preparation and to their use as pesticides and/or herbicides, and also to selective herbicidal compositions comprising firstly cis-alkoxyspiro-substituted tetramic acid derivatives and secondly a crop plant compatibility-improving compound.
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- SUBSTITUTED SPIROCYCLIC KETOENOLS
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The present invention relates to novel substituted spirocyclic ketoenols of the formula (I) in which W, X, Y, Z, A, B, D and G are as defined in the disclosure, to a plurality of processes for their preparation and to their use as pesticides, microbicides and herbicides.
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- Aryl-substituted heterocyclic enaminones
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The invention relates to novel heterocyclic enaminones of the general formula (I) in which Ar, Z, K, X, y1, Y2, Y3, Y4, Y5, Y6 and V are as defined in the description, to their use as herbicides, acaricides and insecticides, and to processes for their preparation.
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- Glyoxyl acid amides, method for producing them and their use for controlling harmful organisms
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The invention relates to novel gloyoxylic acid amides, to a process for their preparation and to their use for controlling harmful organisms.
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- Optically active 2,5-bisaryl-delta1-pyrrolines and their use as pest control agents
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Novel optically active Δ1-pyrrolines of the formula (I) in which R1, R2, R1, R4, and m are each as defined in the description, a plurality of the processes for preparing these substances and their use for controlling pests.
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- Phenyl-substituted 5,6-dihydrophyne derivatives for use as pesticides and herbicides
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The present invention relates to novel phenyl-substituted 5,6-dihydro-pyrone derivatives of the formula (I) in which W, X, Y, Z, G, A, B, Q1 and Q2 are each as defined in the description, to a plurality of processes for their preparation and to their use as pesticides and herbicides.
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- Delta1-pyrrolines used as pesticides
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Novel Δ1-pyrrolines of the formula (I) in which Ar1, Ar2 and Q are each as defined in the description, a plurality of processes for preparing these substances and their use for controlling pests.
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- Triazolopyrimidines
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The invention relates to novel triazolopyrimidines of the formula 1wherein X represents halogen, Y represents a hydrogen atom or halogen, and R has the meanings given in the disclosure, to a process for the preparation of the new compounds, and to their use as microbicides.
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- Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides(III)
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The present invention relates to novel heterocyclic fluoroalkenyl thioethers of the formula (I) in which X represents hydrogen, halogen or alkyl, m represents integers from 3 to 10, n represents 0, 1 or 2, Y represents sulphur or oxygen, R1 represents halogen, represents in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkenylthio or alkylcarbonyl, represents optionally substituted cycloalkyl, represents optionally substituted aryl or represents optionally substituted heterocyclyl and R2 represents hydrogen, halogen, represents in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkenylthio or alkylcarbonyl, represents optionally substituted cycloalkyl, represents optionally substituted aryl or represents optionally substituted heterocyclyl, ?except for compounds where R1=alkyl, Y=oxygen and X=hydrogen, and to processes for their preparation and to their use as pesticides.
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- Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides (I)
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The present invention relates to novel heterocyclic fluoroalkenyl thioethers of the formula (I) in which X represents hydrogen, halogen or alkyl, m represents integers from 2 to 10, n represents 0, 1 or 2, Y represents unsubstituted or substituted methylene and p represents 1, 2 or 3. and to processes for their preparation and to their use as pesticides.
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- Delta 1-pyrrolines used as pesticides
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Novel Δ1-pyrrolines of the formula (I) in which R1, R2, R3, m and Q have the meanings given in the description, a plurality of processes for preparing these substances and their use for controlling pests.
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- Triazolopyrimidines
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Novel triazolopyrimidines of the formula in which R1, R2, R3 and X have the meanings given in the description, a process for preparing these novel substances and their use for controlling undesirable microorganisms and animal pests. Novel amines of the formula in which R4 has the meanings given in the description, and processes for their preparation.
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- Pyrazolyl biphenyl carboxamides and the use thereof for controlling undesired microorganisms
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Novel pyrazolylbiphenylcarboxamides of the formula (I) in which R1, R2, X, m, Y and n are each as defined in the description, a plurality of processes for preparing these substances and their use for controlling undesirable microorganisms, and also novel intermediates and their preparation.
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- Sulfonylpyrroles
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Novel sulfonylpyrroles of the formula in which R1 and R2 independently of one another represent hydrogen, halogen, cyano, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl or optionally substituted heterocyclyl, R3 represents hydrogen, cyano, halogen or optionally substituted heterocyclyl, R4 represents halogen, cyano, nitro, trifluoromethyl or thiocarbamoyl and R5 represents optionally substituted heterocyclyl, a process for preparing the novel compounds and their use for controlling unwanted microorganisms.
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- Isothiazolecarboxamides and their use as microbicides
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Isothiazolecarboxamides of the formula: wherein X, Y, R1, R2, R3 and R4 have the meanings given in the specification, may be used as microbicides.
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- Isothiazolecarboxylic acid derivatives and their use as microbicides
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Novel isothiazolecarboxylic acid derivatives of the formula (I), in which A, Q, Z and k have the meanings mentioned in the specification, processes for the preparation of the new compounds and their use as microbicides.
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- Pyrazolyl benzyl ethers
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The invention relates to novel pyrazolyl benzyl ethers, to a process for their preparation and to their use for controlling harmful organisms.
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- Substituted imide derivatives
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The present invention relates to novel substituted imide derivatives of the general formula (I) in which R1 represents optionally substituted cycloalkyl, R2 represents optionally substituted alkyl or optionally substituted cycloalkyl, R3 represents alkyl, alkoxy, alkylthio, amino, alkylamino or dialkylamino and R4 represents cyano or nitro, and to processes for their preparation and to their use for controlling animal pests and as herbicides.
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- Pyrazolyl benzyl thioethers
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The invention relates to novel pyrazolyl benzyl thioethers, to two processes for their preparation and to their use for controlling harmful organisms.
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- Thienyl-pyrazoles and their use for controlling pests
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The present invention relates to compounds of the formulae (Ia) and (Ib) wherein R1represents C1-10alkyl which may be unsubstituted or substituted with halogen, or represents C2-4alkoxyalkyl, C2-4hydroxyalkyl, C3-6cycloalkyl, hydroxy, C1-9alkoxy which may be unsubstituted or substituted with halogen, or represents C3-6cycloalkoxy, C2-4alkoxyalkoxy or C3-4alkynyloxy, and R2represents hydrogen, C1-4alkoxycarbonyl, C1-3alkylcarbonyl or C2-4alkoxyalkyl, to processes for their preparation and to their use for controlling animal pests.
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- Pyrazolyl benzyl ether derivatives containing a fluoromethoxyimino group and use thereof as pesticides
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The invention relates to novel pyrazolyl benzyl ethers, to a plurality of processes for their preparation and to their use for controlling harmful organisms.
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- Phenyl substituted 4-hydroxy tetrahydroxypyridone
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The present invention relates to novel compounds of the formula (I) in which W, X, Y, Z, G, A, B, Q1, Q2 and D are each as defined in the description, to a plurality of processes for their preparation and to their use as pesticides and herbicides.
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- Active substance combinations having insecticidal and acaricidal properties
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The invention relates to insecticidal mixtures, comprising compounds of the formula (I) in which W, X, Y, Z, A, B, D and G are each as defined above and agonists or antagonists of nicotinic acetylcholine receptors for protecting plants against attack by pests.
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- Pyrazolyl benzyl ether deriviatives having a fluoromethoxy group and the use thereof as pesticides
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The invention relates to novel pyrazolyl benzyl ethers, to a process for their preparation and to their use for controlling harmful organisms.
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- Heterocylic fluoroalkenyl thioethers and the use thereof as pesticides (IV)
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The present invention relates to novel heterocyclic fluoroalkenyl thioethers of the formula (I) in which m represents integers from 3 to 10, n represents 0, 1 or 2 and Het represents the following, in each case optionally substituted, groupings: and to processes for their preparation and to their use as pesticides.
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- Heterocyclic fluoroalkenyl thioethers (II)
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The present invention relates to novel heterocyclic fluoroalkenyl thioethers of the formula (I) in which X represents hydrogen, halogen or alkyl, m represents integers from 3 to 10, n represents 0, 1 or 2, Het represents the groupings, where R1 represents hydrogen, mercapto, represents in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl or alkenyl, represents optionally substituted aryl or represents optionally substituted heterocyclyl, Y represents oxygen or sulphur, and R2 represents hydrogen, alkyl or optionally substituted aryl, and to processes for their preparation and to their use as pesticides.
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- Use of riboflavin and flavin derivatives as chitinase inhibitors
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The invention relates to the use of riboflavin and of flavin derivatives with chitinase-inhibitory action for controlling arthropods, nematodes and chitin-containing fungi.
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- SUBSTITUTED N-BENZOYL-N'(TETRAZOLYLPHENYL)-UREAS AND THEIR USE AS PEST CONTROL AGENTS
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The present invention relates to new substituted N-benzoyl-N′-(tetrazolylphenyl)-ureas of the formula (I) in which R1, R2, R3, R4 and n are as stated in the description, to processes for their preparation, and to their use as pesticides.
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- Sulphonyltriazol derivatives and their use for combating micro-organisms
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Novel sulphonyltriazole derivatives of the formula in which Hal represents fluorine, chlorine or bromine, R1represents hydrogen, alkyl, alkoxyalkyl, cycloalkyl, alkylaminocarbonyl, optionally substituted phenyl, optionally substituted phenoxy or represents optionally substituted heterocyclyl and R2represents alkyl or represents optionally substituted heterocyclyl or represents a radical of the formula in which R3represents halogen, alkyl or phenyl, R4represents hydrogen or alkyl and R5represents alkyl or optionally substituted phenyl, or R4and R5together with the nitrogen atom to which they are attached form a heterocyclic ring which may be substituted and which may also contain an additional heteroatom, a process for preparing these substances and their use for controlling undesirable microorganisms.
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- Phenyl-substituted cyclic enaminones
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The present invention relates to novel phenyl-substituted cyclic enaminones of the formula (I): in which Ar, X, Z, Y, K, n and m are each as defined in the description, to a plurality of processes and intermediates for their preparation and to their use as herbicides and pesticides.
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- Methoximinophenylacetic acid amides
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The invention relates to novel methoximinophenylacetamides, to a process for their preparation and to their use as fungicides.
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- Diphenylimidazolines
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The invention relates to novel diphenylimidazolines of the formula (I) in which Ar1, Ar2and R are each as defined in the description, and a plurality of processes for their preparation and to their use for controlling animal pests.
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- Phenylacetic acid heterocyclyl amides having an insecticidal effect
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Novel phenylacetic acid heterocyclyl amides of the formula in which R1, R2, R3, R4, A, X and n are as defined in the description, a process for preparing these novel compounds and their use for controlling undesirable microorganisms and animal pests. Novel intermediates of the formula and a plurality of processes for their preparation.
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- Arylphenyl-substituted cyclic keto-enols
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The present invention relates to novel arylphenyl-substituted cyclic ketoenols of the formula (I) in whichX represents halogen, alkyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, halogenoalkyl, halogeno-alkoxy, halogenoalkenyloxy, nitro, cyano or in each case optionally substituted phenyl, phenoxy, phenylthio, phenyl-alkoxy or phenylalkylthio,Y represents in each case optionally substituted cycloalkyl, aryl or hetaryl,Z represents hydrogen, halogen, alkyl, alkoxy, alkenyloxy, halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy, nitro or cyano,CKE represents one of the groups ?in whichA, B, D, G and Q1 to Q6 are each as defined in the description, to a plurality of processes for their use as pesticides and herbicides.
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- Sulfonyl benzazolones
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Sulphonylbenzazolones of the formula in whichR1, R2, R3, R4, R5 and Q are each as defined in the description.a process for preparing these compounds and their use as microbicides in crop protection and in the protection of materials.
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- Substituted cyclic carbonyls and derivatives thereof useful as retroviral protease inhibitors
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This invention relates to substituted cyclic carbonyls and derivatives thereof useful as retroviral protease inhibitors, to pharmaceutical compositions comprising such compounds, and to methods of using these compounds for treating viral infection. A representative compound of the invention is the compound of formula: STR1 wherein R22 and R23 are allyl.
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- Compounds and process
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A compound of formula (I): STR1 n which M is a transition metal ion; A is a counter-ion if required; r, s and t are independently 0 to 3 such that r+s+t is in the range of 1 to 3; Ra, Rb, Rc are each independently hydrogen or CH2 OR' where R' is hydrogen or an organic group; B and E are independently oxygen, CH2, NRd in which Rd is alkyl, hydrogen, alkylcarbonyl, or arylcarbonyl or SOn where n is 0 or an integer 1 or 2, with the proviso that B and E are not simultaneously CH2 and that when B is oxygen, NRd or SOn, then r cannot be 0, and when E is oxygen, NRd or SOn, then t cannot be 0; R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are independently hydrogen, alkyl or alkoxy.
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- Process to prepare diazinon
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Diazinon is prepared by coverting the starting hydroxypyrimidine to its potassium salt by reacting it with potassium carbonate in an organic solvent after removal of the water by azeotropic distillation, and reacting the resulting non-aqueous salt with diethyl thiophosphoryl chloride and recovering the diazinon formed, wherein the quantity of potassium carbonate used relative to the starting hydroxypyrimidine is less than molar and desirably of a ratio in the range of 0.55 to 0.75.
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- Diamine platinum naphthalimide complexes as antitumor agents
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The present invention provides novel bis-naphthalimides characterized by having a linker containing a heteroatom, their preparation, pharmaceutical compositions thereof, and various methods of using the bis-naphthalimides. Particularly preferred bis-naphthalimides have a linker of about 8-16 atoms where the heteroatom is oxygen, sulfur, sulfur oxide or sulfur dioxide. The bis-naphthalimides provided herein have exceptional DNA binding properties and demonstrate cytotoxicity in both in vitro and in vivo tumor models, in particular, against melanoma. Also provided a novel mono-naphthalimides linked to a DNA alkylating agent. These agents are shown to have conformational effects on double stranded DNA and to form covalent adducts after an extended incubation period.
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- Microcapsule having temperature-dependent permeability profile
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The microcapsules of the invention are comprised of crystallizable polymers which are preferably side-chain crystallizable polymers or cross-linked, side-chain crystallizable polymers having a specific first order transition point or "melt" temperature. The polymers are caused to form microcapsules and thereby encapsulate one or more compounds generally referred to herein as an active ingredient such as a herbicide, insecticide, fungicide, or fertilizer. The polymer of the microcapsule surrounds the active ingredient separating it from the outside environment. Crystallizable polymers used herein have temperature-dependent permeabilities with respect to a given component such that this component is kept out of contact with the active ingredient at a temperature below a given first order transition point and (due to increased permeability) is allowed to contact the active ingredient at a temperature at or above the transition point. The permeability of the polymer is not only temperature-dependent but reversible. The microcapsules are less than 200 microns in median diameter, more generally less than 100 microns in median diameter and preferably less than 50 microns in median diameter. By varying the polymer and reactants used in the formation of the microcapsules, the release rate and timing of the release of active ingredient from the microcapsule can be temperature controlled to obtain the various objects, advantages and features of the present invention.
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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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- 6,6'-diamino-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose
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A 6,6'-diamino-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose compound is disclosed which is useful as an intermediate compound to make water-absorbent polyamides, polyurethanes and polyamines.
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- Liquid formulations
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A pour-on formulation comprising one or more ectoparasiticides in a solvent system comprising 80 to 98% w/v of a fixed oil and 2 to 20% w/v of a volatile silicone, a method for its preparations and its use in the control of ectoparasiticides on animals.
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- Process for manufacturing diazinon
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An improved process for the production of Diazinon substantially free of toxic by-products in high yield and very high purity which involves mixing 2-isopropyl-4-methyl-6-hydroxypyrimidine with solid sodium or potassium hydroxide in a ketone or ether solvent at a temperature of about 50°-60° C. until a homogeneous mixture is formed, adding diethylthiophosphoryl chloride to the homogeneous mixture, keeping the mixture at a temperature of 55°-80° C. until the reaction is complete, and separating the Diazinon formed.
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- Bis-(1,2,3-triazol-1-yl)-derivatives
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Bis-(1,2,3,triazol-1-yl)-derivatives of the following formula (I): STR1 wherein Y is a bivalent radical selected from: STR2 and STR3 and X is a bivalent radical selected from --O--, --S--; CR2 R3 ; --NR7 --; or an α-α'-alkylenedisubstituted cycloaliphaticketone.
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