Isomerization of cyclic ethers having a carbonyl functional group: new entries into different heterocyclic compounds

Kanoh, Shigeyoshi; Naka, Masashi; Nishimura, Toshiaki; Motoi, Masatoshi

doi:10.1016/s0040-4020(02)00701-9

Cited by 20 publications

(8 citation statements)

References 46 publications

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“…Grosmann has demonstrated the product distribution by preparative and analytical methods [27]. The mechanism of isomerization of imides substituted with oxirane and oxetane groups on nitrogen was also described [28].…”

Section: Introductionmentioning

confidence: 99%

Hydroxyalkylation of Cyclic Imides with Oxiranes Part I. Kinetics of Reaction in Presence of Triethylamine as Catalyst

Lubczak¹

2012

OJPC

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Literature describes kinetics of reactions of alcohols, phenols, carboxylic acids, amines and amides with oxiranes such as ethylene oxide and propylene oxide. However, there is no information regarding kinetic of reaction of imides with oxiranes. In this article the kinetics of the reaction of cyclic monoimides: succinimide, phtalimide, and glutarimide, with ethylene and propylene oxides in presence of triethylamine in aprotic solvent was studied. The rate laws for those processes were established based upon on dilatometric measurements. I was said that cyclic monoimides react with oxiranes in presence of triethylamine to give N-(2-hydroxyalkyl)imides as major product. This product react further with oxiranes in consecutive reaction. The kinetics of the reaction of cyclic mono-imides with oxiranes obey the following rate law: V = k 1/2 . Based upon kinetic data the following orders of reactivity of imides and oxiranes were obtained: phtalimide ≥ succinimide > glutarimide and ethylene oxide > propylene oxide. The solvent (DMF, DMSO and dioxane) effect was also studied. From temperature dependences the thermodynamic parameters: activation energy, enthalpy and entropy from linear Eyring plots were obtained.

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Section: Introductionmentioning

confidence: 99%

Hydroxyalkylation of Cyclic Imides with Oxiranes Part I. Kinetics of Reaction in Presence of Triethylamine as Catalyst

Lubczak¹

2012

OJPC

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“…All of the reagents were purchased from commercial suppliers and were used without further purification. The following compounds: 2-allylisoindoline-1,3-dione ( 16 ) [ 31 ], 2-(but-3-en-1-yl)isoindoline-1,3-dione ( 17 ) [ 32 ], 2-(pent-4-en-1-yl)isoindoline-1,3-dione ( 18 ) [ 33 ], 2-(hex-5-en-1-yl)isoindoline-1,3-dione ( 19 ) [ 34 ], 2-(oxiran-2-ylmethyl)isoindoline-1,3-dione ( 20 ) [ 35 ], 2-(2-(oxiran-2-yl)ethyl)isoindoline-1,3-dione ( 21 ) [ 35 ], 2-(3-(oxiran-2-yl)propyl)isoindoline-1,3-dione ( 22 ) [ 35 ], 2-(4-(oxiran-2-yl)butyl)isoindoline-1,3-dione ( 23 ) [ 36 ] have been reported previously.…”

Section: Methodsmentioning

confidence: 99%

Design, Synthesis, and Biological Evaluation of 2-(Benzylamino-2-Hydroxyalkyl)Isoindoline-1,3-Diones Derivatives as Potential Disease-Modifying Multifunctional Anti-Alzheimer Agents

et al. 2018

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The complex nature of Alzheimer’s disease calls for multidirectional treatment. Consequently, the search for multi-target-directed ligands may lead to potential drug candidates. The aim of the present study is to seek multifunctional compounds with expected activity against disease-modifying and symptomatic targets. A series of 15 drug-like various substituted derivatives of 2-(benzylamino-2-hydroxyalkyl)isoindoline-1,3-diones was designed by modification of cholinesterase inhibitors toward β-secretase inhibition. All target compounds have been synthesized and tested against eel acetylcholinesterase (eeAChE), equine serum butyrylcholinesterase (eqBuChE), human β-secretase (hBACE-1), and β-amyloid (Aβ-aggregation). The most promising compound, 12 (2-(5-(benzylamino)-4-hydroxypentyl)isoindoline-1,3-dione), displayed inhibitory potency against eeAChE (IC50 = 3.33 μM), hBACE-1 (43.7% at 50 μM), and Aβ-aggregation (24.9% at 10 μM). Molecular modeling studies have revealed possible interaction of compound 12 with the active sites of both enzymes—acetylcholinesterase and β-secretase. In conclusion: modifications of acetylcholinesterase inhibitors led to the discovery of a multipotent anti-Alzheimer’s agent, with moderate and balanced potency, capable of inhibiting acetylcholinesterase, a symptomatic target, and disease-modifying targets: β-secretase and Aβ-aggregation.

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“…GTO-350RD. Polyols 1, 3 and diethanolamine 4 were purchased from Tokyo Chemical Industry Co., Ltd. Triol 2 was prepared by mono-benzoylation of pentaerythritol obtained from Tokyo Chemical Industry Co., Ltd. 2-tert-Butyl-2-hydroxymethylpropane-1,3diol (11) was prepared according to the literature. 8 Activated aluminum oxide (200 mesh) was obtained from Wako Pure Chemicals Industries, LTD. Difluoroalkylamines were prepared from the corresponding carboxylic amides according to the literature.…”

Section: Equationmentioning

confidence: 99%

Facile Synthesis of Bicyclo Orthoesters and Bicyclo Amide Acetals Using α,α-Difluoroalkylamines

Tange¹,

Fukuhara²,

Hara³

2008

Synthesis

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Bicyclo orthoesters and amide acetals were prepared from the corresponding triols or diethanolamine using -difluoroalkylamines. The reaction proceeds under milder conditions compared with the conventional methods. 4-tert-Butyl-1-(4-ethynylphenyl)trioxabicyclo[2.2.2]octane, a new class of insecticide, was prepared from a triol in 3 steps using a difluoroalkylamine.Key words: bicyclo orthoesters, bicyclo amide acetals, -difluoroalkylamines, protecting group, polymer Bicyclo orthoesters have been used by organic chemists as a protecting group for carboxylic acids.1 However, they have recently attracted the attention of a wide range of chemists because bicyclo orthoesters such as 1,4-disubstituted 2,4,6-trioxabicyclo[2.2.2]octanes have been found to be a highly potent insecticide.2 Moreover, it was found that bicyclo orthoesters polymerize reversibly to offer an environment-friendly recycling system for polymer materials.3 The bicyclo orthoesters were prepared by transetherification from the corresponding trialkyl orthocarboxylates and triols. 4 However, the reaction is reversible and is performed at high temperature over a long period to obtain the products. 4 The bicyclo orthoesters were also prepared by acid-catalyzed isomerization of the carboxylate esters of hydroxymethyloxetanes.1,5 However, severe reaction conditions are required for the preparation of the starting hydroxymethyloxetanes.5 Therefore, more facile and convenient methods are required for the synthesis of bicyclo orthoesters. Recently, we found that the reaction of -difluoroalkylamines with 2-aminoalcohols, 2-aminothiols, and 1,3-diamines proceeds rapidly to give five-membered heterocyclic compounds under mild conditions.6 During the course of the study, we found that the reaction of the difluoroalkylamines with triols proceeds quickly to give bicyclo orthoesters under mild conditions (Equation 1). Various difluoroalkylamines can be prepared from the corresponding carboxylic amides in two steps.6 When 1,1,1-tris(hydroxymethyl)ethane 1 was allowed to react with N,N-diethyl--difluorobenzylamine (DFBA) in DMF, the reaction was completed at r.t. in 2 h to give 4-methyl-1-phenyl-2,6,7-trioxabicyclo[2.2.2]octane 5 in 66% yield (Table 1). Under the same conditions, the tbutyl group substituted bicyclo orthoester 6 was obtained from 1 in 70% yield with N-(1,1-difluoro-2,2-dimethylpropyl)pyrrolidine instead of DFBA. On the other hand, a benzoyloxy group substituted triol 2 is less soluble in DMF and its reaction with DFBA was not completed under the same conditions. Therefore, the reaction was performed in CDCl 3 and was followed by NMR. Consequently, the reaction was completed in 1 h at 50 °C and the corresponding bicyclo orthoester 7 was obtained in 62% yield. Bis-bicyclo orthoester of dipentaerythritol 3 was previously prepared by transetherification using triethyl orthopropionate. The reaction was performed at high temperature (180-200 °C) for 6 h, and the desired bifunctional bicyclo orthoester was obtained in only 1.4% yield.4...

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Isomerization of cyclic ethers having a carbonyl functional group: new entries into different heterocyclic compounds

Cited by 20 publications

References 46 publications

Hydroxyalkylation of Cyclic Imides with Oxiranes Part I. Kinetics of Reaction in Presence of Triethylamine as Catalyst

Hydroxyalkylation of Cyclic Imides with Oxiranes Part I. Kinetics of Reaction in Presence of Triethylamine as Catalyst

Design, Synthesis, and Biological Evaluation of 2-(Benzylamino-2-Hydroxyalkyl)Isoindoline-1,3-Diones Derivatives as Potential Disease-Modifying Multifunctional Anti-Alzheimer Agents

Facile Synthesis of Bicyclo Orthoesters and Bicyclo Amide Acetals Using α,α-Difluoroalkylamines

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