- OCCURRENCE OF β-D-GALACTOPYRANOSYL UNITS ESTERIFIED AT O-6 WITH 2-AMINOETHYLPHOSPHONIC ACID IN THE D-GALACTAN OF ALBUMEN GLANDS OF THE SNAIL MEGALOBULIMUS PARANAGUENSIS
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The albumen glands of the snail Megalobulimus paranaguensis were previously found to contain a branched β-D-galactopyranan consisting mainly of nonreducing end-groups and 3,6-di-O-substituted residues with smaller proportions of 3-O- and 6-O-substituted units. (13)C-n.m.r. spectroscopy has now shown that 2-aminoethylphosphonic acid (1) is an additional component and its presence was confirmed by cellulose-plate chromatography.Furthermore, the 2-aminoethyl-phosphonic acid-substituted oligosaccharides, formed on partial hydrolysis of the polysaccharide, were isolated, examined by fast-atom-bombardment mass spectrometry, and found to have molecular weights consistent with monophosphonic esters of 1.The (13)C-n.m.r. spectrum of this mixture indicated substitution of D-galactopyranosyl units at O-6 with esters of 1, and this was confirmed by spectral examination of a monosubstituted D-galactose isolated after strong acid hydrolysis of the polymer.The snail D-galactan contained one ester of 1 every 34 residues, it was free of other components such as protein, lipid, and nucleic acid, and is the first polysaccharide of this type has been identified.
- Fontana, Jose D.,Duarte, Jose H.,Gallo, Ciro B. H.,Iacomini, Marcello,Gorin, Philip A. J.
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- A new simple route to N-substituted 2-aminoethylphosphonic acids
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2-Aminoethylphosphonic acid (AEPA) and its N-substituted compounds were prepared by one step reaction using 2-chloroethylphosphonic acid with ammonia and amines (H2NMe, HNMeMe, HNEtEt, H2NPr-n, H2NCH2ph,H2NCH2CH2NH2 and H2N(C=NH)NH2 in a dilute alkaline solution below 20 °C with simple work- up and easy purification. The reaction was accelerated by catalytic amount of potassium iodide. The yield for the reaction products were 35.6 to 48.6% for the KI absence and 78.2 to 88.0% for the KI presence.
- Fu, Xiangkai,Gong, Chengbin,Ma, Xuebing,Wen, Shuying
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p. 2659 - 2664
(2007/10/03)
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- ORGANOPHOSPHORUS COMPOUNDS AS POTENTIAL FUNGICIDES. PART II. AMINOALKANE-, GUANIDINOALKANE-, AND THIOUREIDOALKANE-PHOSPHONIC ACIDS: PREPARATION, SPECTROSCOPY, AND FUNGICIDAL ACTIVITY
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A range of α-amino-, ω-amino-, α-guanidino-, and ω-guanidinoalkanephosphonic acids has been prepared for the purpose of studying their spectroscopic features and fungicidal activity.In addition, α-thioureido-octanephosphonic acid and thioureylene-1,1-bis(1-octanephosphonic acid) were isolated during the preparation of α-guanidino-octanephosphonic acid. 31P, 1H, and 13C nmr spectral data which were obtained for solutions of the amino- and guanidino-compounds in D2O or D2O/D2SO4, and for the thioureido compounds in DMSO-d6, are discussed together with previouslyreported data for the aminophosphonic types.FAB mass spectrometry generally gives strong pseudomolecular ions + for the zwitterionic amino- and guanidino-compounds with relatively simple fragmentations.Fungicidal activity of the α-aminophosphonic acids was found to be greater than for the ω-amino compounds, with maximum activity at a chain length of three carbon atoms when used as a seed dressing for the control of Drechslera spp.Moderately good activity was shown by the thioureido compounds against a number of fungal organisms in vitro but the guanidino-compounds exhibited low activity.Key words: Organophosphorus; fungicides; aminophosphonic acids; guanidinophosphonic acids; NMR spectroscopy; FAB mass spectroscopy.
- Cameron, David G.,Hudson, Harry R.,Pianka, Max
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- BIOSYNTHESIS OF NATURAL PRODUCTS WITH A P-C BOND: INCORPORATION OF D-GLUCOSE INTO 2-AMINOETHYLPHOSPHONIC ACID IN TETRAHYMENA THERMOPHILA AND OF D-GLUCOSE AND L-METHIONINE INTO FOSFOMYCIN IN STREPTOMYCES FRADIAE
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D-Glucose was fed to Tetrahymena thermophila and to Streptomyces fradiae producing 2-aminoethylphosphonic acid and fosfomycin, respectively.The labelled products isolated indicate that the phosphoenol pyruvate mutase catalyzes the stereospecific transfer of the phospho group of (Z)-phosphoenol pyruvate from oxygen to carbon from the si-face.The methyl group of L-methionine is transferred intact to a precursor for fosfomycin.
- Hammerschmidt, Friedrich
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p. 111 - 114
(2007/10/02)
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- Biosynthesis of Naturally Products with a P-C Bond. Part 6. Preparation of Deuterium- and Carbon-13-Labelled L-Alanyl- and L-Alanyl-L-alanyl-(2-aminoethyl)phosphonic Acids and their Use in Biosynthetic Studies of Fosfomycin in Streptomyces fradiae
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(2-Aminoethyl)phosphonic acid (AEP) is not taken up by Streptomyces fradiae in the biosynthesis of fosfomycin.Attachment of L-alanine or L-alanyl-L-alanine to the amino group of deuteriated AEP affords di- and tri-peptides 4 and 5 which are transported into the cell. AEP is synthesized from Na(13)CN and the tosyloxymethylphosphonate 7.It is transformed into dipeptide 4d, which acts as a carrier for AEP which is incorporated into fosfomycin with an enrichment of 2 percent.
- Hammerschmidt, Friedrich,Kaehlig, Hanspeter,Mueller, Norbert
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p. 365 - 369
(2007/10/02)
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- Borane Reduction of Dialkoxyphosphorylcarboxamides as a New Route to Aminoalkylphosphonic Acids
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A new, simple method for the synthesis of aminoalkylphosphonic acids is based on the reduction of dialkoxyphosphorylcarboxamides with the borane-dimethyl sulfide complex.
- Wasielewski, Czeslaw,Dembkowski, Leszek,Topolski, Marek
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- CONVERSION OF AMINO ACIDS AND DIPEPTIDES INTO THEIR PHOSPHONIC ANALOGS; Aminoalkylphosphonic acids and peptides II.
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Acylamino carboxylic acids were degradated by the Hunsdiecker-reaction; the bromo-derivatives were reacted with NaPO(OC2H5)2.Aminophosphonic acids were obtained by acidic hydrolysis, and half-blocked derivatives by the selective removal of masking substituents.Two phosphonopeptides were also prepared by this route.
- Oesapay, George,Szilagyi, Ildiko,Seres, Jenoe
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p. 2977 - 2984
(2007/10/02)
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- PREPARATION OF OPTICALLY ACTIVE 2-AMINOALKYLPHOSPHINIC AND PHOSPHONIC ACIDS
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The reaction of sodium alkylphosphinates or sodium dialkylphosphonates with tosylamino tosylates of amino alcohols derived from 1-aminoalkylcarboxylic acids gives high yields of optically active 2-tosylaminoalkylphosphinic or phosphonic esters.
- Duggan, Mark E.,Karanewsky, Donald S.
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p. 2935 - 2938
(2007/10/02)
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- Aminobenzylation d'aldehydes phosphoniques: preparation d'acides aminoalkylphosphoniques
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The reaction of phosphonic aldehydes with benzylamine in presence of NaBH3CN yields benzylaminoalkylphosphonates which, submitted to catalytic hydrogenation, lead to phosphonic amino esters.When reductive amination is carried out with H2/Pd reduction and debenzylation are observed simultaneously.In the absence of reducing agent the enaminobenzylphosphonate can be isolated and N-alkylated.Hydrolysis of phosphonic amino-esters with dilute HCl gives phosphonic amino acids.The order of occurence of each operation, as well as the choice of the catalyst is discussed.
- Fabre, Genevieve,Collignon, Noel,Savignac, Philippe
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p. 2864 - 2869
(2007/10/02)
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- AMINATION REDUCTRICE D'ALDEHYDES PHOSPHONIQUES. Un Reexamen
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The reactivity of diethyl-2-oxo ethyl- and 3-oxo propylphosphonates with ammonia, methyl and dimethylamine at pH 7 in the presence of sodium cyanohydridoborate via reductive amination of the carbonyl group has been reexamined.Reactions of diethyl-2-oxoethyl- and 3-oxopropylphosphonates with ammonia give imino-bis-(alkylphosphonates); methyl and dimethylamine give monocondensation products thus permitting the synthesis of N-substituted aminoalkylphosphonates.
- Collignon, N.,Fabre, G.,Varlet, J. M.,Savignac, Ph.
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