Synthesis of 3-(4-Pyridinyl)-, 3-(2-Chloro-4-pyridinyl)- and 3-(2-Amino-4-pyridinyl)propoxymethanephosphonic Acid

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Title:Synthesis of 3-(4-Pyridinyl)-, 3-(2-Chloro-4-pyridinyl)- and 3-(2-Amino-4-pyridinyl)propoxymethanephosphonic Acid
Creators:
Krečmerová, Marcela
Holý, Antonín
Masojídková, Milena
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 60, 4, pp. 670-680

Abstract

<p>Reaction of sodium salt of 4-(3-hydroxypropyl)pyridine (<i>I</i>) with diisopropyl <i>p</i>-toluenesulfonyloxymethanephosphonate (<i>II</i>) afforded diisopropyl ester of the corresponding phosphonomethyl derivative (<i>III</i>), together with 4-cyclopropylpyridine (<i>IV</i>). The ester <i>III</i> was converted into free 3-(4-pyridinyl)propoxymethanephosphonic acid (<i>V</i>). The synthesis of 3-(2-amino-4-pyridinyl)propoxymethanephosphonic acid (<i>XVI</i>) started from 4-(3-benzoyloxypropyl)pyridine (<i>VII</i>) via the <i>N</i>-oxide <i>VIII</i> which on heating with phosphoryl chloride afforded the 2-chloro derivative <i>IX</i>. Compound <i>IX</i> was debenzoylated with sodium methoxide to give 2-chloro-4-(3-hydroxypropyl)pyridine (<i>XI</i>). Condensation of sodium salt of <i>XI</i> with tosylate <i>II</i> afforded diisopropyl 3-(2-chloro-4-pyridinyl)propoxymethanephosphonate (<i>XIII</i>) and 2-chloro-4-cyclopropylpyridine (<i>XIV</i>). Deprotection of the ester groups in <i>XIII</i> with bromotrimethylsilane gave 3-(2-chloro-4-pyridinyl)propoxymethanephosphonic acid (<i>XV</i>). The chlorine atom in position 2 was replaced by reaction of compound XV with aqueous ammonia at 200 °C under catalysis with copper(II) sulfate. This gave 3-(2-amino-4-pyridinyl)propoxymethanephosphonic acid (<i>XVI</i>) as the final product.

Title:Synthesis of 3-(4-Pyridinyl)-, 3-(2-Chloro-4-pyridinyl)- and 3-(2-Amino-4-pyridinyl)propoxymethanephosphonic Acid
Creators:
Krečmerová, Marcela
Holý, Antonín
Masojídková, Milena
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:60
Number:4
Page Range:pp. 670-680
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19950670UNSPECIFIED
ID Code:755
Item Type:Article
Deposited On:06 Feb 2009 17:03
Last Modified:06 Feb 2009 16:03

Citation

Krečmerová, Marcela; Holý, Antonín; Masojídková, Milena (1995) Synthesis of 3-(4-Pyridinyl)-, 3-(2-Chloro-4-pyridinyl)- and 3-(2-Amino-4-pyridinyl)propoxymethanephosphonic Acid. Collection of Czechoslovak Chemical Communications, 60 (4). pp. 670-680. ISSN 0010-0765

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