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New methods and reagents for small scale synthesis of phosphor organic compounds with focus on the phosphonic acids and their analogues
Umeå University, Faculty of Science and Technology, Chemistry.
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The development of a synthetic method of radiolabelled methylphosphono-fluoridates on a milligram scale is presented. The aim of this method is, besides affording high yield, to choose reaction pathways and reagents so that handling and transfer of labelled toxic substances is minimised, thereby reducing the risk of exposure as much as possible. The only substituent that is stable enough to be labelled is the methyl group, directly bonded to phosphorus. A drawback when labelling the methyl group is that it requires the label to be introduced early in the synthesis since the carbon-phosphorus bond of the methyl substituent usually has to be synthesized a few steps ahead of the final product.

Two new classes of reagents for halogenation of phosphorus oxyacids have been developed. Firstly, four different analogues of α-chloroenamines and α-fluoroenamines were evaluated. Secondly, cyanuric fluoride was assessed in solution, but more importantly, as a resin-bound reagent. The reagents are evaluated for halogenation of phosphinic, phosphonic and phosphoric acids. Cyanuric fluoride is also successfully loaded on a polystyrene resin and used as a solid-phase reagent. The reagents produce high yields and low levels of impurities on a milligram scale.

Furthermore, a new method for the preparation of mono-alkylated phosphonic acids on a small scale has been developed. The new method utilises the crystal water bound to certain salts to liberate limited amounts of water in a controlled manner. Phosphonic dichlorides are in this way reacted with water to form anhydrides. The anhydride is then cleaved with an appropriate alcohol to produce mono-alkylated phosphonic acids.

Place, publisher, year, edition, pages
Umeå: Kemiska institutionen, Umeå universitet , 2010. , 74 p.
Keyword [en]
micro scale, phosphorus oxyacids, solid phase, chlorination, fluorination, radiolabelling
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-32904ISBN: 978-91-7264-991-0 (print)OAI: oai:DiVA.org:umu-32904DiVA: diva2:306626
Public defence
2010-04-23, KBC-huset, Stora hörsalen, KB3B1, Umeå universitet, Umeå, 10:00 (English)
Opponent
Supervisors
Note
Rikard Norlin = Rikard WärmeAvailable from: 2010-04-01 Created: 2010-03-30 Last updated: 2010-04-06Bibliographically approved
List of papers
1. Synthesis of 14C Sarin
Open this publication in new window or tab >>Synthesis of 14C Sarin
2003 (English)In: Journal of labelled compounds & radiopharmaceuticals, ISSN 0362-4803, E-ISSN 1099-1344, Vol. 6, 599-604 p.Article in journal (Refereed) Published
Abstract [en]

Synthetic routes for the synthesis of [14C] sarin and related nerve agents are described. Triethyl phosphite and [14C] methyl iodide are reacted in the Michaelis-Arbusov reaction to produce diethyl methyl phosphonate which is converted to methylphosphonic acid by hydrolysis. After chlorination and subsequent fluorination the final product is formed by reaction with the appropriate alcohol.

Place, publisher, year, edition, pages
Wiley Interscience, 2003
Keyword
synthesis, o-isopropyl methylphosphonofluoridate, [14C] sarin synthesis, chemical warfare agents, O-isopropyl methyl phosphono fluoridate
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:umu:diva-32899 (URN)10.1002/jlcr.699 (DOI)
Note
Rikard Norlin = Rikard WärmeAvailable from: 2010-03-30 Created: 2010-03-30 Last updated: 2017-12-12Bibliographically approved
2. a-Haloenamines as reagents for the conversion of phosphorus oxyacids to their halogenated analogues
Open this publication in new window or tab >>a-Haloenamines as reagents for the conversion of phosphorus oxyacids to their halogenated analogues
2005 (English)In: Synthesis (Stuttgart), ISSN 0039-7881, E-ISSN 1437-210X, no 11, 1765-1770 p.Article in journal (Refereed) Published
Abstract [en]

Phosphorus oxyacids are converted to their halogenated analogues under mild conditions. α-Haloenamines are shown to be effective halogen transfer reagents affording good to high yields of the desired products at reaction times, in some cases, less than one minute.

Place, publisher, year, edition, pages
Stuttgart: Georg Thieme Verlag, 2005
Keyword
phosphorus, α-haloenamines, halogenation, fluorine, chlorine
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:umu:diva-32901 (URN)10.1055/s-2005-865363 (DOI)
Note
Rikard Norlin = Rikard WärmeAvailable from: 2010-03-30 Created: 2010-03-30 Last updated: 2017-12-12Bibliographically approved
3. A new microscale method for the conversion of phosphorus oxyacids to their fluorinated analogues, using cyanuric fluoride in solution and on solid support
Open this publication in new window or tab >>A new microscale method for the conversion of phosphorus oxyacids to their fluorinated analogues, using cyanuric fluoride in solution and on solid support
2010 (English)In: Phosphorus Sulfur and Silicon and the Related Elements, ISSN 1042-6507, E-ISSN 1563-5325, Vol. 185, no 12, 2402-2408 p.Article in journal (Refereed) Published
Abstract [en]

Cyanuric fluoride, in solution or loaded onto a Wang resin, is successfully used as a fluorinating agent for phosphorus oxy acids. The reaction is very efficient with high yields and easy workup procedures, thereby in general generating products in quantitative yields. The cyanuric fluoride is proven suitable for micromolar scale synthesis of analytical standards, particularly in its resin-bound form.

Place, publisher, year, edition, pages
Abingdon: Taylor & Francis, 2010
Keyword
Cyanuric fluoride, micro scale, phosphorus fluoridates, solid phase synthesis
National Category
Organic Chemistry
Identifiers
urn:nbn:se:umu:diva-32902 (URN)10.1080/10426501003671445 (DOI)000284418300002 ()
External cooperation:
Note

Rikard Norlin = Rikard Wärme

Available from: 2010-03-30 Created: 2010-03-30 Last updated: 2017-12-12Bibliographically approved
4. A new one-pot microscale synthesis of alkyl alkylphosphonic acids utilizing water release of inorganic salts
Open this publication in new window or tab >>A new one-pot microscale synthesis of alkyl alkylphosphonic acids utilizing water release of inorganic salts
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:umu:diva-32903 (URN)
Note
Rikard Norlin = Rikard WärmeAvailable from: 2010-03-30 Created: 2010-03-30 Last updated: 2010-04-06Bibliographically approved

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