Reconfigurable system for automated optimization of diverse chemical reactions

Science ◽  
2018 ◽  
Vol 361 (6408) ◽  
pp. 1220-1225 ◽  
Author(s):  
Anne-Catherine Bédard ◽  
Andrea Adamo ◽  
Kosi C. Aroh ◽  
M. Grace Russell ◽  
Aaron A. Bedermann ◽  
...  
Keyword(s):  
Chemical Synthesis ◽  
High Performance ◽  
Smartphone Application ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Reaction Conditions ◽  
Unit Operations ◽  
Electronic File ◽  
Automated Optimization ◽  
Error Optimization

Chemical synthesis generally requires labor-intensive, sometimes tedious trial-and-error optimization of reaction conditions. Here, we describe a plug-and-play, continuous-flow chemical synthesis system that mitigates this challenge with an integrated combination of hardware, software, and analytics. The system software controls the user-selected reagents and unit operations (reactors and separators), processes reaction analytics (high-performance liquid chromatography, mass spectrometry, vibrational spectroscopy), and conducts automated optimizations. The capabilities of this system are demonstrated in high-yielding implementations of C-C and C-N cross-coupling, olefination, reductive amination, nucleophilic aromatic substitution (SNAr), photoredox catalysis, and a multistep sequence. The graphical user interface enables users to initiate optimizations, monitor progress remotely, and analyze results. Subsequent users of an optimized procedure need only download an electronic file, comparable to a smartphone application, to implement the protocol on their own apparatus.

Deuterated Aryl Alkyl Ethers Synthesis via Nucleophilic Etherification of Aryl Alkyl Ethers and Thioethers with Deuterated Alcohols

Synlett ◽  
2019 ◽  
Vol 30 (15) ◽  
pp. 1805-1809
Author(s):  
Shuai Li ◽  
Xia Wang ◽  
Xin-Ge Yang ◽  
Gui-Quan Yu ◽  
Xue-Qiang Wang
Keyword(s):  
Transition Metal ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Metal Free ◽  
Wide Range ◽  
Alkyl Ethers

A transition-metal-free etherification protocol that is capable of synthesizing deuterated ethers is described. A wide range of aryl alkyl ethers and thioethers were suitable for this transformation owing to the mild reaction conditions. Besides, a series of sterically bulky deuterated alcohols were successfully incorporated into cyano-substituted arenes. The results of mechanistic studies suggested this reaction might take place via nucleophilic aromatic substitution pathway.

scholarly journals N-[4-(1-Methyl-1H-imidazol-2-yl)-2,4′-bipyridin-2′-yl]benzene-1,4-diamine

Molbank ◽  
10.3390/m1030 ◽  
2018 ◽  
Vol 2018 (4) ◽  
pp. M1030 ◽  
Author(s):  
Dhafer Zinad ◽  
Dunya AL-Duhaidahaw ◽  
Ahmed Al-Amiery ◽  
Abdul Kadhum
Keyword(s):  
Mass Spectrometry ◽  
Nuclear Magnetic Resonance ◽  
High Performance ◽  
Nucleophilic Aromatic Substitution ◽  
Gas Chromatography Mass Spectrometry ◽  
Aromatic Substitution ◽  
Target Compound ◽  
Chromatography Mass Spectrometry ◽  
Snar Reaction ◽  
Layer Chromatography

N-[4-(1-Methyl-1H-imidazol-2-yl)-2,4′-bipyridin-2′-yl]benzene-1,4-diamine was synthesized with a good yield by the reaction of 2′-chloro-4-(1-methyl-1H-imidazol-2-yl)-2,4′-bipyridine with 4-phenylenediamine. The functionalization of the pyridine was accomplished by a nucleophilic aromatic substitution (SNAr) reaction that afforded the target compound. The synthesized compound was characterized by chemical analysis, which includes nuclear magnetic resonance (NMR) (1H-NMR and 13C-NMR), Thin Layer Chromatography-Mass Spectrometry (TLC-MS), high- performance liquid chromatography (HPLC), Gas Chromatography-Mass Spectrometry (GC-MS), and elemental analysis.

Modification of Polyfluoro-Containing 3-(Ethoxycarbonyl)flavones by Biogenic Amines and Amino Acids

2018 ◽  
Vol 15 (5) ◽  
pp. 707-714 ◽  
Author(s):  
Konstantin V. Shcherbakov ◽  
Yanina V. Burgart ◽  
Victor I. Saloutin ◽  
Oleg N. Chupakhin
Keyword(s):  
Amino Acids ◽  
Biogenic Amines ◽  
Nucleophilic Aromatic Substitution ◽  
Gamma Aminobutyric Acid ◽  
Aromatic Substitution ◽  
Substitution Product ◽  
Reaction Conditions ◽  
Pyrone Ring ◽  
Beta Alanine ◽  
Ir Spectroscopic

Aim and Objective: The objective of our work was to study the peculiarities of transformations of fluorine-containing flavone-3-carboxylates with N-nucleophiles, including biogenic amines and amino acids. Materials and Methods: 6,7,8-Trifluoro and 5,6,7,8-tetrafluoroflavone-3-carboxylates were involved in interactions with a number of N-nucleophiles, such as pyrrolidine, morpholine, proline, arginine, gammaaminobutyric acid, beta-alanine, histamine, dopamine and amantadine under different reaction conditions. All synthesized compounds were characterized by NMR 1H, 19F, (NMR 13C for some compounds) and IR spectroscopic data, and elemental analysis. Results: 3-(Ethoxycarbonyl)polyfluoroflavones react with morpholine, pyrrolidine and L-proline to form 7- monosubstituted flavone-3-carboxylates. For the reactions of tetrafluoroflavone with pyrrolidine and morpholine, the formation of 5,7-disubstituted products is also possible. Interaction with gamma-aminobutyric acid leads to the 4-{[3-ethoxy-2-(2-hydroxypolyfluorobenzoyl)-3-oxo-1-phenylprop-1-enyl]amino}butanoic acids as a result of the pyrone ring opening. In reactions with dopamine, histamine, L-arginine and β-alanine, polyfluoroflavone-3-carboxylates underwent a chromone-coumarin rearrangement. 3-(Ethoxycarbonyl)tetrafluoroflavone forms with amantadine the nucleophilic aromatic substitution product, while trifluoro-substituted analog gives the chromone-coumarin rearrangement product. Conclusion: This work showed possibilities of chemical modification of polyfluorinated flavones in the reactions with amines depending on the structure of the nucleophilic reagent. Synthesized compounds are of interest for biological testing.

scholarly journals Nucleophilic Aromatic Substitution Reactions under Aqueous, Mild Conditions Using Polymeric Additive HPMC

2021 ◽  
Author(s):  
Niginia Borlinghaus ◽  
Tharique N. Ansari ◽  
Leon Hendrik H. Braje ◽  
Deborah Ogulu ◽  
Sachin Handa ◽  
...  
Keyword(s):  
Hydroxypropyl Methylcellulose ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Reaction Conditions ◽  
Polymeric Additive ◽  
Mild Conditions

The use of the inexpensive, benign, and sustainable polymer, hydroxypropyl methylcellulose (HPMC), in water enables nucleophilic aromatic subsitution (SNAr) reactions between various nucleophiles and electrophiles. The mild reaction conditions facilitate...

Resistive memory devices based on novel functionalized poly(aryl ether)s with pendant azobenzene

2018 ◽  
Vol 31 (3) ◽  
pp. 273-281
Author(s):  
Hejing Sun ◽  
Haibo Zhang ◽  
Jinhui Pang ◽  
Zheng Chen ◽  
Yuntao Han ◽  
...  
Keyword(s):  
Data Storage ◽  
High Performance ◽  
Nucleophilic Aromatic Substitution ◽  
Future Application ◽  
Memory Devices ◽  
The Novel ◽  
Aromatic Substitution ◽  
Aryl Ether ◽  
Good Thermal Stability ◽  
Memory Mechanism

We designed and synthesized two novel azobenzene functionalized poly(aryl ether)s (PAEs), PAE-azo-1 and PAE-azo-2, from a new azobenzene monomer via nucleophilic aromatic substitution polycondensation. This direct polymerization approach via azobenzene monomer has the advantages of controlling the distribution and amount of the azobenzene chromophores in the polymer. Both of the polymers showed very good thermal stability and excellent solubility for future application in the electronics industry. These polymers were fabricated as films by simple spin-coating and both of them were then prepared as sandwich memory devices. PAE-azo-1 and PAE-azo-2 exhibit write-once-read-many-times-type memory behavior, which can be encoded as “0” and “1,” and possess the low operation voltage below −3.0 V. The memory mechanism was investigated through ultraviolet–visible optical absorption spectrum and the cyclic voltammetry. These obtained results indicate that the novel azobenzene functionalized PAEs are a promising candidate for low power consumption and high-performance materials for data storage.

scholarly journals Machine learning meets mechanistic modelling for accurate prediction of experimental activation energies

2021 ◽  
Author(s):  
Kjell Jorner ◽  
Tore Brinck ◽  
Per-Ola Norrby ◽  
David Buttar
Keyword(s):  
Machine Learning ◽  
Activation Energies ◽  
Accurate Prediction ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Mechanistic Modelling

Hybrid reactivity models, combining mechanistic calculations and machine learning with descriptors, are used to predict barriers for nucleophilic aromatic substitution.

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