1019770-60-5Relevant articles and documents
Synthesis of N-Protected 1-Aminoalkylphosphonium Salts from Amides, Carbamates, Lactams, or Imides
Adamek, Jakub,Ziele?ny, Paulina,Erfurt, Karol
, p. 5852 - 5862 (2021)
This report describes the development and optimization of the one-pot method for the synthesis of N-protected 1-aminoalkylphosphonium salts based on the three-component coupling of aldehydes and either amides, carbamates, lactams, imides, or urea in the presence of triarylphosphonium salts. The proposed strategy is very efficient and easy to carry out even on a larger scale (20 g) in any typical laboratory. Most reactions occur at temperatures between 50 and 100 °C in a short time (1-2 h) without requiring any catalyst, and simple workup procedures afford good to excellent yields. The exceptions are condensations with imides, which require much higher temperatures (150-170 °C) and longer reaction times (even 30 h). The possibility of carrying out the synthesis under solvent-free conditions (neat reactions) is also demonstrated. It is especially important for less reactive substrates (imides), and reactions required high temperature (or generally harsher conditions). Finally, we prove the developed one-pot methodology can be successfully applied for the synthesis of structurally diverse N-protected 1-aminoalkylphosphonium salts. Mechanistic studies showed the intermediate products of described couplings are 1-hydroxyalkylphosphonium salts, not N-hydroxyalkylamides, -imides, etc., as initially expected.
Thermogravimetrical investigations of the dealkoxycarbonylation of N-acyl-α-triphenylphosphonioglycinates
Adamek, Jakub,Mrowiec-Bia?on?, Julita,Pa?dzierniok-Holewa, Agnieszka,Mazurkiewicz, Roman
experimental part, p. 22 - 27 (2011/02/26)
Thermogravimetrical experiments revealed that immediately after the endothermic process of the melting of N-acyl-α- triphenylphosphonioglycinates 1, an exothermic demethoxycarbonylation of phosphonioglycinates commenced, accompanied by the release of CO2. The residues contained the corresponding N-acylaminomethyltriphenylphosphonium salts 2 (18.3-49.5%), methyltriphenylphosphonium salts 7 (21.8-67.9%), and the corresponding 1,2-di(N-acylamino)fumaric acid dimethyl ester 6 (2.1-26.0%). When the reaction was carried out in the presence of Ph3P and the corresponding triphenylphosphine hydrobromide, hydroiodide, or tetrafluoroborate, N-acyl-α-triphenylphosphoniumglycinate bromides and iodides 1a-f underwent demethoxycarbonylation to form the corresponding N-acylaminomethyltriphenylphosphonium salts 2a-f at 95-130 °C in good to excellent yields (79-100%). On the other hand, tetrafluoroborates 1g-i underwent corresponding reactions at about 170-175 °C to give phosphonium tetrafluoroborates 2g-i in much lower yields (34-67%). Plausible mechanisms of the investigated reaction are discussed. It was also demonstrated that the obtained crude α-(N-acylamino)alkyltriphenylphosphonium salts 2 could be applied as valuable α-amidoalkylating agents in spite of their contamination with inert methyltriphenylphosphonium salts 7.
N-Acyl-α-triphenylphosphonio-α-amino acids: Synthesis and decarboxylation toα-(N-Acylamino)alkyltriphenylphosphonium salts
Mazurkiewicz, Roman,Pazdzierniok-Holewa, Agnieszka,Grymel, Mirosawa
experimental part, p. 1017 - 1027 (2009/12/07)
4-Phosphoranylidene-5(4H)-oxazolones 1 undergo hydrolysis in THF in the presence of HBF4 at room temperature to give N-acyl-α- triphenyphosphonioglycines 3 (R2 = H) in very good yields. 4-Alkyl-4- triphenylphosphonio-5(4H)-oxazolones 2 react with water in CH2Cl 2/THF solution without any acidic catalyst at 0-5°C in a few days yielding N-acyl-α-triphenylphosphonio-α-amino acids 3 (R 2 = Me) or α-(N-acylamino)alkyltriphenylphosphonium salts 4 (R2 = alkyl, other then Me).-Triphenylphosphonio-α-amino acids 3 upon heating to 105-115°C under reduced pressure (5 mm Hg) or upon treatment with a Hunig base in CH2Cl2 at 20°C undergo decarboxylation to give the corresponding α-(N-acylamino)-alkyltriphenylphosphonium salts 4, usually in very good yields.
