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. 2022 Dec 13;27(24):8849.
doi: 10.3390/molecules27248849.

Deamination of 1-Aminoalkylphosphonic Acids: Reaction Intermediates and Selectivity

Anna Brol  1 , Tomasz K Olszewski  1
Affiliations

Deamination of 1-Aminoalkylphosphonic Acids: Reaction Intermediates and Selectivity

Anna Brol et al. Molecules. .

Abstract

Deamination of 1-aminoalkylphosphonic acids in the reaction with HNO2 (generated "in situ" from NaNO2) yields a mixture of substitution products (1-hydroxyalkylphosphonic acids), elimination products (vinylphosphonic acid derivatives), rearrangement and substitution products (2-hydroxylkylphosphonic acids) as well as H3PO4. The variety of formed reaction products suggests that 1-phosphonoalkylium ions may be intermediates in such deamination reactions.

Keywords: 1-phosphonoalkylium ion; carbenium ion; diazotization; elimination reaction; rearrangement; substitution reaction.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
General presentation of deamination reaction carried out on 2-aminoalkanoic acids and their phosphorus analogs [34,35,36,37,49,50,51,52,53].
Scheme 2
Scheme 2
Possible structures of the 1-phosphonoalkylium ions known from the literature [54,55,56,57,58].
Figure 1
Figure 1
Structures of 1-aminoalkylphosphonic acids used in this study.
Scheme 3
Scheme 3
Preliminary experiments on the diazotization of alanine (2a) and valine (2b) and their corresponding phosphorus analogs 1a and 1b.
Scheme 4
Scheme 4
Possible mechanism of the reaction of 1-aminoalkylphosphonic acids 1 with HNO2.
Scheme 5
Scheme 5
Deamination reaction of 3-amino-3-phosphonopropanoic acid (1e) with HNO2.
Scheme 6
Scheme 6
(a) Deamination of 1-amino-2-phenylethylphosphonic acid (1g) with HNO2 and analysis of the reaction products. (b) Mechanism of phosphoric acid formation from cyclic intermediate 9″g.
Scheme 7
Scheme 7
Mechanism of H3PO4 formation in rearrangement and fragmentation reaction [64,65,66].
Scheme 8
Scheme 8
Proposed mechanisms of H3PO4 formation in the reactions of 1-phosphonoalkylium ion with nitrite ion.
Scheme 9
Scheme 9
Possible transformations of 1-phosphonoalkylium ions 9 discussed in this study.
See this image and copyright information in PMC

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