50407-04-0Relevant articles and documents
Preparation of alkylated compounds using the trialkylphosphate
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Paragraph 0156-0157; 0162, (2021/11/02)
[Problem] trialkylphosphate strong base used reaction agent, a carboxylic acid, a ketone, an aldehyde, amine, amide, thiol, ester or Grignard reagent to a variety of substrates, and/or high efficiency to generate a highly stereoselective alkylation reaction, the alkylated compounds capable of producing new means. [Solution] was used as the alkylating agent in the alkylation of compound trialkylphosphate, strongly basic reaction production use. [Drawing] no
Regio- And Stereoselective (S N2) N -, O -, C - And S -Alkylation Using Trialkyl Phosphates
Banerjee, Amit,Hattori, Tomohiro,Yamamoto, Hisashi
, (2021/06/16)
Bimolecular nucleophilic substitution (S N 2) is one of the most well-known fundamental reactions in organic chemistry to generate new molecules from two molecules. In principle, a nucleophile attacks from the back side of an alkylating agent having a suitable leaving group, most commonly a halide. However, alkyl halides are expensive, very harmful, toxic and not so stable, which makes them problematic for laboratory use. In contrast, trialkyl phosphates are inexpensive, readily accessible and stable at room temperature, under air, and are easy to handle, but rarely used as alkylating agents in organic synthesis. Here, we describe a mild, straightforward and powerful method for nucleophilic alkylation of various N -, O -, C - and S -nucleophiles using readily available trialkyl phosphates. The reaction proceeds smoothly in excellent yield, and quantitative yield in many cases, and covers a wide range of substrates. Further, the rare stereoselective transfer of secondary alkyl groups has been achieved with inversion of configuration of chiral centers (up to 98% ee).
One-Pot Synthesis of Trisubstituted Triazenes from Grignard Reagents and Organic Azides
Suleymanov, Abdusalom A.,Scopelliti, Rosario,Fadaei Tirani, Farzaneh,Severin, Kay
supporting information, p. 3323 - 3326 (2018/06/11)
A simple and versatile method for the preparation of linear, trisubstituted triazenes is reported. The procedure is based on the reaction of Grignard reagents with 1-azido-4-iodobutane or 4-azidobutyl-4-methylbenzenesulfonate. These organic azides enable the regioselective formation of triazenes via an intramolecular cyclization step. The new method can be used for the preparation of aryl, heteroaryl, vinyl, and alkyl triazenes. The synthetic utility of vinyl triazenes is demonstrated by acid-induced C-N, C-O, C-F, C-P, and C-S bond-forming reactions.
Synthesis of Perhydro-1,3-diazine-2-thiones from β-Chloro Imines
Sulmon, Paul,Kimpe, Norbert De,Schamp, Niceas,Declercq, Jean-Paul
, p. 2587 - 2590 (2007/10/02)
The reaction of β-chloro imines with methanol gave rise to β-alkylamino acetals via intermediate 2-methoxyazetidines.If an aromatic β-chloro imine was used under these conditions, 1-methoxy-2-methyl-1-phenyl-1-propene was also formed.The reaction of β-chloro imines with potassium thiocyanate in methanol gave rise to perhydro-1,3-diazine-2-thiones in 10-55percent yield in addition to β-alkylamino acetals, again via methoxyazetidines.
Photochemical Reactions of Arenecarboxylic Acid Esters with Electron-Rich Alkenes: 2 + 2 Cycloaddition, Hydrogen Abstraction, and Cycloreversion
Cantrell, Thomas S.,Allen, Andrew C.
, p. 135 - 139 (2007/10/02)
The photochemical reaction of arenecarboxylic acid methyl esters and isopropyl esters with alkenes has been examined and found to afford three types of products: (a) 2-alkoxyoxetanes 3 via a direct 2 + 2 cycloaddition to the substrate alkenes; (b) β,γ-unsaturated ketones 5 via hydrogen abstraction by the carbonyl oxygen of the photoexcited ester from an allylic position of the substrate alkene; and (c) alkoxyalkenes 4, which arise via 2 + 2 cycloreversion of the oxetanes 3.The quantum yields for the formation of the various products generally fell in the range 0.005-0.03, approximately 1 order of magnitude less than those of aryl ketones and aldehydes undergoing similar reactions.
Isomerisation of 2-Alkoxycyclopropanecarboxylic Acids - An Effective Synthesis of 4-Oxo Carboxylic Acids
Kunz, Horst,Lindig, Markus
, p. 220 - 229 (2007/10/02)
(Z/E)-2-Alkoxycyclopropanecarboxylic esters 2/3 were prepared from enol ethers 1 and ethyl diazoacetate.The saponification of these esters gives the corresponding (Z/E)-2-alkoxycyclopropanecarboxylic acids 4/5, which show stereomutation in water/methanol.This isomerisation was studied in labelled solvents and interpreted for the example of (E)-2-methoxy-2-phenylcyclopropanecarboxylic acid (5a).On heating in water/methanol the compounds 4/5 are transformed quantitatively into the corresponding 4-oxo carboxylic acids 6.