Synthesis of vinyl ether compounds by pyrolysis of dimethyl perfluoro-2,7-dimethyl-3,6-dioxa-1,8-octanedioate

Takata, Kuniaki; Takesue, Masahiro; Iseki, Yuji; Sata, Toshikatsu

doi:10.1016/0022-1139(95)03316-1

Cited by 6 publications

(4 citation statements)

References 12 publications

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“…For a practical synthesis of the target compounds, we established that mono‐ P ‐fluorophosphonates were accessible directly from the phosphonic acids 1 – 3 using oxalyl fluoride as a powerful and efficient reagent (Scheme ) . Oxalyl fluoride was superior to other fluorinating reagents like diethylaminosulfur trifluoride (DAST) and fluoride–chloride exchange reactions because it delivered pure products by evaporation of the excess of volatile reagent and byproducts.…”

Section: Resultsmentioning

confidence: 99%

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Benzyl Mono‐P‐Fluorophosphonate and Benzyl Penta‐P‐Fluorophosphate Anions Are Physiologically Stable Phosphotyrosine Mimetics and Inhibitors of Protein Tyrosine Phosphatases

Wagner

Accorsi

Rademann

2017

Chemistry A European J

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α,α-Difluoro-benzyl phosphonates are currently the most popular class of phosphotyrosine mimetics. Structurally derived from the natural substrate phosphotyrosine, they constitute classical bioisosteres and have enabled the development of potent inhibitors of protein tyrosine phosphatases (PTP) and phosphotyrosine recognition sites such as SH2 domains. Being dianions bearing two negative charges, phosphonates, however, do not permeate membranes and thus are often inactive in cells and have not been a successful starting point toward therapeutics, yet. In this work, benzyl phosphonates were modified by replacing phosphorus-bound oxygen atoms with phosphorus-bound fluorine atoms. Surprisingly, mono-P-fluorophosphonates were fully stable under physiological conditions, thus enabling the investigation of their mode of action toward PTP. Three alternative scenarios were tested and mono-P-fluorophosphonates were identified as stable reversible PTP1B inhibitors, despite of the loss of one negative charge and the replacement of one oxygen atom as an H-bond donor by fluorine. In extending this replacement strategy, α,α-difluorobenzyl penta-P-fluorophosphates were synthesized and found to be novel phosphotyrosine mimetics with improved affinity to the phosphotyrosine binding site of PTP1B.

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Section: Resultsmentioning

confidence: 99%

“…Oxalyl fluoride : Oxalyl fluoride was prepared according to literature . Deviant from the existing preparation instructions, multiple distillation of oxalyl fluoride could not be accomplished without significant loss of the product.…”

Section: Methodsmentioning

confidence: 99%

Benzyl Mono‐P‐Fluorophosphonate and Benzyl Penta‐P‐Fluorophosphate Anions Are Physiologically Stable Phosphotyrosine Mimetics and Inhibitors of Protein Tyrosine Phosphatases

Wagner

Accorsi

Rademann

2017

Chemistry A European J

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“…NaCl + X 2+ (in Na 2 CO 3 ) (11) X 2+ (in Na 2 CO 3 ) + CO 3 2-(in Na 2 CO 3 ) f XO + CO 2 (12) X 2+ (in Na 2 CO 3 ) + CO 3 2-(in Na 2 CO 3 ) f X + 1 / 2 O 2 + CO 2 (13) Na + (in Na 2 CO 3 ) + C 6 H 5 Cl f NaCl + C 6 H 5 + (in Na 2 CO 3 ) (14) the JMU-NSF-REU program, and the NSF-ILIP program for supporting this project.…”

Section: Resultsmentioning

confidence: 99%

“…Because sodium oxalate thermally decomposes to form sodium carbonate in this temperature region (10,11), sodium carbonate may have contributed to the reaction and may also react with chlorofluorocarbons in this temperature range. Molten sodium carbonate has been reported to react with chlorocarbons (12) and to remove fluorine from dimethylperfluoro-3,6-dioxa1,7-1,8octanedioate (13).…”

Section: Introductionmentioning

confidence: 99%

Reaction between Chlorocarbon Vapors and Sodium Carbonate

Parrett

Sumner

Devore

1999

Environ. Sci. Technol.

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The kinetics of the reactions between tetrachloromethane (CCl4), 1,2-dichloroethane (C2H4Cl2), or chlorobenzene (C6H5Cl) and sodium carbonate were investigated using evolved gas analysis−Fourier transform infrared spectroscopy. Sodium carbonate reacted with CCl4 between 600 and 900 K to form over 90% carbon dioxide (CO2) and less than 10% tetrachloroethene (C2Cl4). This reaction followed the three-dimensional diffusion mechanism and had an activation energy of 105 ± 10 kJ/ mol and a steric factor of 5000 ± 3000 min-1. The reaction between C2H4Cl2 and sodium carbonate produced CO2, ethanal (C2H4O), water (H2O), vinyl chloride (C2H3Cl), ethene (C2H4), and ethyne (C2H2) between 600 and 900 K from at least two different pathways. The product temperature profiles indicated that CO2, C2H4O, and C2H3Cl were formed initially and that approximately 10% of the product is C2H4 at 900 K. The reaction kinetics followed the Ginstling−Brounshtein diffusion mechanism and had an activation energy of 100 ± 10 kJ/ mol and a steric factor of approximately 104 min-1. Benzene was produced from the reaction between chlorobenzene and sodium carbonate at temperatures above 800 K. This reaction followed the three-dimensional diffusion mechanism and had an activation energy of 80 ± 10 kJ/mol and a steric factor of approximately 500 min-1.

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Functions Incorporating a Halogen and a Chalcogen

Geraghty

2005

Comprehensive Organic Functional Group Transformations II

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Synthesis of vinyl ether compounds by pyrolysis of dimethyl perfluoro-2,7-dimethyl-3,6-dioxa-1,8-octanedioate

Cited by 6 publications

References 12 publications

Benzyl Mono‐P‐Fluorophosphonate and Benzyl Penta‐P‐Fluorophosphate Anions Are Physiologically Stable Phosphotyrosine Mimetics and Inhibitors of Protein Tyrosine Phosphatases

Benzyl Mono‐P‐Fluorophosphonate and Benzyl Penta‐P‐Fluorophosphate Anions Are Physiologically Stable Phosphotyrosine Mimetics and Inhibitors of Protein Tyrosine Phosphatases

Reaction between Chlorocarbon Vapors and Sodium Carbonate

Functions Incorporating a Halogen and a Chalcogen

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