Unconventional reactivity of epichlorohydrin in the presence of triphenylphosphine: isolation of ((1,4-dioxane-2,5-diyl)-bis-(methylene))-bis-(triphenylphosphonium) chloride

Mannu, Alberto; Pietro, Maria Enrica Di; Priola, Emanuele; Baldino, Salvatore; Sacchetti, Alessandro

doi:10.1007/s11164-020-04364-9

Cited by 5 publications

(4 citation statements)

References 29 publications

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“…The 13 C chemical shifts for the methylene carbon 15 (directly attached to the phosphorus atom) are found in the range of 34.7 to 40.7 ppm ( 1 J PC between 64 and 54 Hz). For comparison, the corresponding carbon atom in similar alkyltriphenylphosphonium halides resonates at 27-18 ppm ( 1 J PC ≈ 54 Hz) [33,34]. The 31 P NMR shift (against H 3 PO 4 , 85%) of the adducts is in the range of 18.9-18.3 ppm, which is slightly shifted upfield compared to the corresponding values for the Michael acceptor derived zwitterions of 1 [28].…”

Section: Table 1 Yield and Characteristic Chemical Nmr-shifts For Zwi...mentioning

confidence: 93%

Synthesis, characterization and stability of phosphonium phenolate zwitterions derived from a (diphenylphosphino)phenol derivative and oxiranes

Steiner,

Marschner,

Baumgartner

et al. 2024

Preprint

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Phosphonium phenolate zwitterions have been synthesized from 2,4-di-tert-butyl-6-(diphenylphosphino)phenol and five different oxirane derivatives. The reaction does not proceed at a detectable rate when the two reactants are combined in dichloromethane at room temperature. Despite the substantial ring strain, the reaction proceeds only with the addition of methanol, which acts as a hydrogen transfer shuttle, allowing a slow conversion to the desired zwitterions. The compounds have been fully characterized and single crystal X-ray crystallography has been performed on the methyloxirane and the phenyl glycidyl ether-derived zwitterion. The phosphonium phenolate units exhibit an ylidic bonding situation as evidenced by spectroscopic and crystallographic analysis. Glycidyl ethers were found to react faster than alkyl and aryloxiranes. Decomposition studies of the zwitterions showed high thermal stability in solution under ambient conditions. Under forced conditions (150 °C, 6 h), decomposition to the corresponding phosphine oxide and secondary aliphatic alcohols, the formally hydrogenated oxirane derivative, was observed.

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Section: Table 1 Yield and Characteristic Chemical Nmr-shifts For Zwi...mentioning

confidence: 93%

Synthesis, characterization and stability of phosphonium phenolate zwitterions derived from a (diphenylphosphino)phenol derivative and oxiranes

Steiner,

Marschner,

Baumgartner

et al. 2024

Preprint

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show abstract

“…The ratio of rate constants of "normal" and "abnormal" flows (k n /k a ) linearly depends on the polarity of the solvent ( 10)- (11) in the coordinates of the Laidler-Eyring equation (6). The U parameter has a high negative value, which indicates a significant increase in regioselectivity with a decrease in the solvent polarity.…”

Section: Kinetics Of Ech Acetolysismentioning

confidence: 99%

“…1,2 The high reactivity of the three-membered ring provides the use of ECH to obtain di-and trifunctional organic compounds, polyfunctional polymers, and composites based on them 2,3 to develop effective methods for the synthesis of new heterocyclic and macrocyclic molecules. [4][5][6][7][8][9] The reactions of epichlorohydrin with proton-containing reagents (carboxylic acids, alcohols, phenols) are widely used for the synthesis of biologically active substances that exhibit antibacterial, antituberculous, and antimalarial properties, act as antioxidants and enzyme inhibitors, and are included to hypoglycemic drugs. 1,[10][11][12] The oxirane ring opening by carboxylic acids occurs to form two regioisomeric chlorohydrin esters (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Finding the right balance between tertiary amine steric effect and solvent polarity for the regioselectivity and kinetics of epichlorohydrin acetolysis

Yutilova,

Tkach,

Tarasenko

et al. 2023

J of Physical Organic Chem

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The asymmetric oxirane ring‐opening reaction leading to the formation of regioisomeric chlorohydrin esters was studied in the reaction series “acetic acid–epichlorohydrin–tetrahydrofuran (nitrobenzene)–trialkylamine” by kinetic methods and FT‐IR spectroscopy. The effect of solvent polarity and the structure of tertiary amines on the regioselectivity and reaction rate were studied. Tertiary amines with comparable basicity but different nucleophilicity and spatial structure were chosen as catalysts. It was shown that in solvents of different polarity, the components of the initial reaction system are present both as hydrogen‐bonded complexes and as individual substances. The reaction orders with respect to acid and amine in solvents of different polarity were established. Correlations between the reaction rate and the parameters of nucleophilicity and structure of amines as well as the polarity of the solvent were established. The regioselectivity of the reaction was studied by 1H NMR spectroscopy using the ratio of regioisomeric reaction products. It was shown that the regioselectivity and rate of catalytic acetolysis of epichlorohydrin are effectively controlled by the structure of tertiary amines and the polarity of the solvent. The scheme of reaction regio‐flows was detailed.

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“…As a rule, the interaction of oxiranes with triarylphosphines is carried out under hard conditions and often leads to the dimerization and partial polymerization of oxirane. Thus, the reaction of triphenylphosphine with epichlorohydrin, recently studied in [168], leads to the oxirane dimerization into a dioxane structure ((1,4-dioxane-2,5-diyl)-bis(methylene))bis(triphenylphosphonium)chloride. The opening of oxirane ring with the formation of triaryl (2-hydroxyalkyl) phosphonium salts occurs in the presence of acids in neutral solvents (alcohols, dichloromethane) [169][170][171][172][173] or during the triarylphosphine reaction in phenol used as the solvent [174].…”

Section: Chemistry 211 Reaction Of Triphenylphosphonium Triflate With Halomethyloxiranesmentioning

confidence: 99%

Rational Design 2-Hydroxypropylphosphonium Salts as Cancer Cell Mitochondria-Targeted Vectors: Synthesis, Structure, and Biological Properties

et al. 2021

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It has been shown for a wide range of epoxy compounds that their interaction with triphenylphosphonium triflate occurs with a high chemoselectivity and leads to the formation of (2-hydroxypropyl)triphenylphosphonium triflates 3 substituted in the 3-position with an alkoxy, alkylcarboxyl group, or halogen, which were isolated in a high yield. Using the methodology for the disclosure of epichlorohydrin with alcohols in the presence of boron trifluoride etherate, followed by the substitution of iodine for chlorine and treatment with triphenylphosphine, 2-hydroxypropyltriphenylphosphonium iodides 4 were also obtained. The molecular and supramolecular structure of the obtained phosphonium salts was established, and their high antitumor activity was revealed in relation to duodenal adenocarcinoma. The formation of liposomal systems based on phosphonium salt 3 and L-α-phosphatidylcholine (PC) was employed for improving the bioavailability and reducing the toxicity. They were produced by the thin film rehydration method and exhibited cytotoxic properties. This rational design of phosphonium salts 3 and 4 has promising potential of new vectors for targeted delivery into mitochondria of tumor cells.

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Unconventional reactivity of epichlorohydrin in the presence of triphenylphosphine: isolation of ((1,4-dioxane-2,5-diyl)-bis-(methylene))-bis-(triphenylphosphonium) chloride

Cited by 5 publications

References 29 publications

Synthesis, characterization and stability of phosphonium phenolate zwitterions derived from a (diphenylphosphino)phenol derivative and oxiranes

Synthesis, characterization and stability of phosphonium phenolate zwitterions derived from a (diphenylphosphino)phenol derivative and oxiranes

Finding the right balance between tertiary amine steric effect and solvent polarity for the regioselectivity and kinetics of epichlorohydrin acetolysis

Rational Design 2-Hydroxypropylphosphonium Salts as Cancer Cell Mitochondria-Targeted Vectors: Synthesis, Structure, and Biological Properties

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