Intramolecular-catalyzed hydrolysis of sulfonamides. 10. Intramolecular nucleophilic catalysis by the neighboring hydroxyl group in acid- and base-catalyzed hydrolysis of aromatic sulfonamides and sultones. Mechanism of intramolecular nucleophilic substitution at sulfonyl sulfur

1988 ◽  
Vol 53 (4) ◽  
pp. 768-772 ◽  
Author(s):  
Anno Wagenaar ◽  
Jan B. F. N. Engberts
Keyword(s):  
Nucleophilic Substitution ◽  
Hydroxyl Group ◽  
Nucleophilic Catalysis ◽  
Intramolecular Nucleophilic Substitution ◽  
Acid And Base ◽  
Hydrolysis Of

ChemInform Abstract: Broensted Acid-Catalyzed Intramolecular Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer.

ChemInform ◽  
2015 ◽  
Vol 46 (38) ◽  
pp. no-no
Author(s):  
Anon Bunrit ◽  
Christian Dahlstrand ◽  
Sandra K. Olsson ◽  
Pemikar Srifa ◽  
Genping Huang ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Hydroxyl Group ◽  
Chirality Transfer ◽  
Intramolecular Nucleophilic Substitution ◽  
Acid Catalyzed

scholarly journals SYNTHESIS 7-O-CARBOXYMETHYL-3’,4’-DIMETHOXYISOFLAVONE

2012 ◽  
Vol 12 (3) ◽  
pp. 242-246
Author(s):  
Andi Hairil Alimuddin ◽  
Sabirin Matsjeh ◽  
Chairil Anwar ◽  
Mustofa Mustofa
Keyword(s):  
Melting Point ◽  
Nucleophilic Substitution ◽  
Substitution Reaction ◽  
Ester Group ◽  
Nucleophilic Substitution Reaction ◽  
Hydroxyl Group ◽  
Hydrolysis Of

Synthesis of 7-O-carboxymethyl-3',4'-dimethoxyisoflavone from 7-hydroxy-3',4'-dimethoxyisoflavone derived from eugenol had been done. 7-hydroxy-3',4'-dimethoxyisoflavone was first converted into 7-O-ethoxycarbonylmethyl-3',4'-dimethoxyisoflavone via substitution of hydroxyl group at 7-O position by ethyl-2 chloro acetate through bimolecular nucleophilic substitution reaction (SN2). Hydrolysis of ester group of 7-O-ethoxycarbonylmethyl-3',4'-dimethoxyisoflavone using KOH produce 7-O-carboxymethyl-3',4'-dimethoxyisoflavone in 93.4% yield as a white solid with melting point of 155-159 °C.

Intramolecular Nucleophilic Substitution in the Hydrolysis of Bis(4-Nitrophenyl) Phosphate Ester Catalyzed by the Metallomicelle

2012 ◽  
Vol 554-556 ◽  
pp. 345-348
Author(s):  
Min Wang ◽  
Li Qin Xu ◽  
Ci Li ◽  
Bing Ying Jiang ◽  
Jia Qing Xie
Keyword(s):  
Nucleophilic Substitution ◽  
Absorption Spectra ◽  
Catalytic Efficiency ◽  
Phosphate Ester ◽  
Catalytic Hydrolysis ◽  
Characteristic Absorption ◽  
Intramolecular Nucleophilic Substitution ◽  
Nitrophenyl Phosphate ◽  
Hydrolytic Reaction ◽  
Hydrolysis Of

A macro-cyclic Schiff base ligand and the corresponding Cu (II) and Ni (II) complexes were synthesized and characterized. And the catalytic efficiency of the metallomicelles made of these complexes and noninonic micelle Brij35, as mimetic hydrolytic metalloenzyme, was investigated in the catalytic hydrolysis of bis(p-nitrophenyl) phosphate (BNPP) in this paper. The results show that the rate of the BNPP hydrolysis in the metallomicelles is about 106 -fold faster than that of the BNPP spontaneous hydrolysis in aqueous solution at the same conditions. The analysis of the characteristic absorption spectra of the hydrolytic reaction systems indicates that the key intermediate, composing of BNPP and Ni(II) or Cu(II) complexes, has been formed and the catalytic hydrolysis of BNPP is an intramolecular nucleophilic substitution reaction. Based on the results of characteristic absorption spectra, the mechanism of BNPP catalytic hydrolysis has been proposed and also the corresponding kinetic mathematical model has been established.

Kinetics of Hydrolysis of an Activated Phosphate Ester in Brij35 Micelle Containing a Macrocyclic Complex of Cu(II) OR Ni(II)

2008 ◽  
Vol 33 (4) ◽  
pp. 349-361 ◽  
Author(s):  
Zhang Yi ◽  
Xie Jia-qing ◽  
Li Ci ◽  
Shang Hong-li ◽  
Wang Min
Keyword(s):  
Mathematical Model ◽  
Nucleophilic Substitution ◽  
Absorption Spectra ◽  
Macrocyclic Complex ◽  
Phosphate Ester ◽  
Specific Absorption ◽  
Intramolecular Nucleophilic Substitution ◽  
Kinetics Of Hydrolysis ◽  
Kinetics Of ◽  
Hydrolysis Of

A macrocyclic ligand and its corresponding Cu(II) and Ni(II) complexes were synthesized and characterized. The kinetics of hydrolysis of bis( p-nitrophenyl) phosphate (BNPP, an activated phosphate diester) in Brij35 micelle containing each macrocyclic complex was investigated. The metallomicelles made up of the macrocyclic metal complex and micelle, as a mimic hydrolytic metalloenzyme, display higher catalytic activity although they do not attain the catalytic efficiency of enzymes. The analysis of specific absorption spectra show that the course of the catalytic BNPP reaction is different from that of the spontaneous hydrolysis of BNPP, and is an intramolecular nucleophilic substitution reaction. Based on the analytical results of the specific absorption spectra, an intramolecular nucleophilic substitution mechanism for the catalytic hydrolysis of BNPP is proposed, a correlative kinetic mathematical model is established, and the corresponding thermodynamic and kinetic constants are calculated. The validity of the mechanism and the proposed mathematical model is confirmed by the results of this study.

scholarly journals Synthesis of Carbohydrate Based Macrolactones and Their Applications as Receptors for Ion Recognition and Catalysis

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3394
Author(s):  
Surya B. Adhikari ◽  
Anji Chen ◽  
Guijun Wang
Keyword(s):  
Nucleophilic Substitution ◽  
Supramolecular Chemistry ◽  
Copper Sulfate ◽  
Substitution Reaction ◽  
Biological Properties ◽  
Anion Binding ◽  
Nucleophilic Substitution Reaction ◽  
Binding Properties ◽  
Intramolecular Nucleophilic Substitution ◽  
Leaving Groups

Glycomacrolactones exhibit many interesting biological properties, and they are also important in molecular recognitions and for supramolecular chemistry. Therefore, it is important to be able to access glycomacrocycles with different sizes and functionality. A new series of carbohydrate-based macrocycles containing triazole and lactone moieties have been designed and synthesized. The synthesis features an intramolecular nucleophilic substitution reaction for the macrocyclization step. In this article, the effect of some common sulfonate leaving groups is evaluated for macrolactonization. Using tosylate gave good selectivity for monolactonization products with good yields. Fourteen different macrocycles have been synthesized and characterized, of which eleven macrocycles are from cyclization of the C1 to C6 positions of N-acetyl D-glucosamine derivatives and three others from C2 to C6 cyclization of functionalized D-glucosamine derivatives. These novel macrolactones have unique structures and demonstrate interesting anion binding properties, especially for chloride. The macrocycles containing two triazoles form complexes with copper sulfate, and they are effective ligands for copper sulfate mediated azide-alkyne cycloaddition reactions (CuAAC). In addition, several macrocycles show some selectivity for different alkynes.

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