- N-alkylation of ethylenediamine with alcohols catalyzed by CuO-NiO/γ-Al2O3
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A simple method for N-alkylation of 1, 2-diaminoethane with different alcohols in a fixed-bed reactor using cheap CuO-NiO/γ-Al2O 3 as the catalyst has been developed. The present catalytic system was applicable in the N-alkylation of 1, 2-diaminoethane with both primary and secondary alcohols. Mono-N-alkylation of 1, 2-diaminoethane with low-carbon alcohols resulted in high yields; the yields of tetra-N-alkylation of 1, 2-diaminoethane with low-carbon alcohols declined markedly with the increase of the molecular volume of alcohols.
- Huang, Jia-Min,Xu, Lu-Feng,Qian, Chao,Chen, Xin-Zhi
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Read Online
- Design, Synthesis, and Synergistic Activity of Eight-Membered Oxabridge Neonicotinoid Analogues
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Insecticide synergists are sought-after due to their potential in improving the pesticide control efficacy with a reduced dose of an active ingredient. We previously reported that a cis-configuration neonicotinoid (IPPA08) exhibited specific synergistic activity toward neonicotinoid insecticides. In this study, we synthesized a series of structural analogues of IPPA08 by converting the pyridyl moiety of IPPA08 into phenyl groups, via facile double-Mannich condensation reactions between nitromethylene compounds and glutaraldehyde. All of the oxabridged neonicotinoid compounds were found to increase the toxicity of imidacloprid against Aphis craccivora. Notably, compound 25 at 0.75 mg/L lowered the LC50 value of imidacloprid against A. craccivora by 6.54-fold, while a 3.50-fold reduction of the LC50 value was observed for IPPA08. The results of bee toxicity test showed that compound 25 display selectivity in its effects on imidacloprid toxicity against the honey bee (Apis mellifera L.). In summary, replacing the pyridyl ring with a phenyl ring was a viable approach to obtain a novel synergist with oxabridged moiety for neonicotinoid insecticides.
- Zhang, Xiao,Wang, Yiping,Xu, Zhiping,Shao, Xusheng,Liu, Zewen,Xu, Xiaoyong,Maienfisch, Peter,Li, Zhong
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p. 3005 - 3014
(2021/04/09)
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- The synthesis of asymmetric ethylenediamine derivatives catalyzed by ion-exchange resins
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The ring-opening reaction of aziridine with alkylamines over a series of ion-exchange resins was investigated. Among these catalysts, D001-CC exhibited excellent catalytic performance. The catalysts were characterized by SEM and N2 adsorption-desorption. The results indicated that the selectivity of N,N-diethylethylenediamine mainly depended on the acidity and S BET of the resins. Strong Br?nsted acid sites played an important role on the conversion of aziridine, and the distribution of acid sites on catalyst had a significant effect on the selectivity of N,N-diethylethylenediamine. The reaction parameters, such as reaction time, molar ratio, reaction temperature, and catalyst loading, were also optimized and N,N-diethylethylenediamine was obtained in an excellent yield of 97 %. Furthermore, D001-CC was efficiently recycled five times by simple treatment with large amounts of deionized water and mineral acid. Finally, a series of asymmetric ethylenediamine derivatives were successfully synthesized with this method. Therefore, a simple and versatile process for the synthesis of asymmetric ethylenediamine derivatives has been established over ion-exchange resins.
- Wang, Wenwen,Wei, Ruisong,Yin, Guohui,Tian, Jun,Duan, Yifan,Chen, Ligong,Li, Yang
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p. 4511 - 4522
(2015/06/30)
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- N-alkylation of ethylenediamine with alcohols catalyzed by CuO-NiO/?3-Al2O3
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A simple method for N-alkylation of 1,2-diaminoethane with different alcohols in a fixed-bed reactor using cheap CuO-NiO/?3-Al2O3 as the catalyst has been developed. The present catalytic system was applicable in the N-alkylation of
- Huang, Jia-Min,Xu, Lu-Feng,Qian, Chao,Chen, Xin-Zhi
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p. 304 - 307
(2015/03/03)
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- METHOD FOR PRODUCING N-MONOALKYL-SUBSTITUTED ALKYLENE AMINE
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PROBLEM TO BE SOLVED: To provide a method for producing an N-monoalkyl-substituted alkylene amine especially useful for uses such as medicine intermediates, agrochemical intermediates, urethane resin-foaming catalysts, surfactants and the like among alkyl-substituted alkylene amine compounds from an alcohol and an alkylene amine as raw materials. SOLUTION: This method for producing the N-monoalkyl-substituted alkylene amine is characterized by reacting the alkylene amine with a ≥2C alkyl alcohol in the presence of a copper-containing oxide catalyst system. The N-monoalkyl-substituted alkylenamine is produced in high conversion and in N-monoalkylation selectivity.
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Page/Page column 8
(2010/02/11)
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- Continuous chemoselective methylation of functionalized amines and diols with supercritical methanol over solid acid and acid-base bifunctional catalysts
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The selective N-methylation of bifunctionalized amines with supercritical methanol (scCH3OH) promoted by the conventional solid acids (H-mordenite, β-zeolite, amorphous silica-alumina) and acid-base bifunctional catalysts (Cs-P-Si mixed oxide and γ-alumina) was investigated in a continuous-flow, fixed-bed reactor. The use of scCH 3OH in the reaction of 2-aminoethanol with methanol (amine/CH 3OH = 1/10.8) over the solid catalysts led to a significant improvement in the chemoselectivity of the N-methylation. Among the catalysts examined, the Cs-P-Si mixed oxide provided the most efficient catalyst performance in terms of selectivity and reactivity at 300 °C and 8.2 MPa; the N-methylation selectivity in the products reaching up to 94% at 86% conversion. The present selective methylation was successfully applied to the synthesis of N-methylated amino alcohols and diamines as well as O-methylated ethylene glycol. Noticeably, ethoxyethylamine was less reactive, suggesting that the hydroxy group of the amino alcohols is a crucial structural factor in determining high reactivity and selectivity, possibly because of the tethering effect of another terminus, a hydroxo group, to the catalyst surface. The magic-angle-spinning NMR spectroscopy and X-ray diffraction analysis of the Cs-P-Si mixed oxide catalyst revealed that the acidic and basic sites originate from P2O5/SiO2 and Cs/SiO2, respectively, and the weak acid-base paired sites are attributed to three kinds of cesium phosphates on SiO2. The weak acid-base sites on the catalyst surface might be responsible for the selective dehydrative methylation.
- Oku, Tomoharu,Arita, Yoshitaka,Tsuneki, Hideaki,Ikariya, Takao
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p. 7368 - 7377
(2007/10/03)
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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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- Novel method for the preparation of piperazine and its derivatives
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A novel method for the synthesis of piperazine and its derivatives of formula 1, 1wherein R is selected from hydrogen, or a lower alkyl group having 1 to 6 carbon atoms or a phenylalkyl group the alkyl of which has 1 to 4 carbon atoms; R1 is selected from hydrogen, a methyl group, a phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms, or a phenylalkyl group the alkyl of which has 1 to 4 carbon atoms; and R2 is selected from hydrogen, or a methyl group, or a fluoromethyl group; 2comprising the steps: a. reacting an ester of formula 11 with substituted or unsubstituted ethylenediamine of formula 7 to give 3,4-dehydropiperazine-2-one and its derivatives of formula 12, wherein R, R1, R2 are as defined above and R6 is a C1 to C4 linear or branched alkyl group; and b. reacting the 3,4-dehydro-piperazine-2-one and its derivatives of formula 12 with a reducing agent to yield the piperazine and its derivatives of formula 1.
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This work is dealing with basic hydrolysis in water of allophanic esters as possible models of carboxybiotin. A complex mechanism is involved likely due to competition of nucleophilic attack on the two carbonyl groups of the substrate. The rate of hydrolysis is significantly increased by metallic cation (Mg++), a specific effect which allows to consider characterization of selectivity of bond breaking between nitrogen and carboxylate group with other nucleophiles.
- Monnier, Par E.,Klaebe,Perie
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p. 3269 - 3284
(2007/10/02)
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- KINETICS OF THE REACTION OF METAPHOS WITH ETHYLENEDIAMINE IN MICELLAR SOLUTIONS
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The kinetics and mechanism of the reaction of O,O-dimethyl O-4-nitrophenyl phosphorothioate (metaphos) with ethylenediamine in the presence of the cationic surfactant cetyltrimethylammonium bromide have been studied by a spectrophotometric method.The reaction takes place along two paths in an aqueous medium, viz., as alkylation of the amine and as nucleophilic substitution at the phosphorus atom.In the absence of micelles, alkylation of ethylenediamine mainly takes place.In a micellar solution the alkylation process is inhibited, and the reactions at the phosphorus atom are catalyzed and become predominant.This results in a sharp change in the ratio between the products of the parallel reactions in the presence of the surfactant micelles.
- Fedorov, S. B.,Bel'skii, V. E.,Kudryavtseva, L. A.,Ivanov, B. E.
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p. 1086 - 1089
(2007/10/02)
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- PROCESS FOR PREPARING 2-AMINO-2-ALKYLTHIO-1-NITROETHYLENE COMPOUNDS
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A process for preparing 2-amino-2-alkylthio-1-nitroethylene compounds by reacting a 1-lower alkylsulfinyl-1-lower alkylthio-2-nitroethylene with an amine. The products of the process are intermediates for the production of histamine H 2-antagonists.
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