Synthesis of Glycerol-1,3-diphosphonic Acid

1973 ◽  
Vol 51 (8) ◽  
pp. 1203-1205 ◽  
Author(s):  
Ranga Robinson ◽  
Erich Baer
Keyword(s):  
Acid Hydrolysis ◽  
Phosphonic Acid ◽  
Hydrobromic Acid ◽  
Condensation Product ◽  
Triethyl Phosphite ◽  
Phosphate Esters ◽  
Glyceric Acid ◽  
Diphosphonic Acid ◽  
Naturally Occurring ◽  
Acid Analogue

The synthesis of glycerol-1,3-diphosphonic acid, the phosphonic acid analogue of the naturally occurring glycerol-1,3-diphosphoric acid, is described. The phosphonic acid analogue was obtained in an overall yield of 29.7%, by heating a mixture of 1,3-dibromo-2-hexadecanoyloxypropane and triethyl phosphite to 140° for 48 h, distilling off in vacuo the excess of triethyl phosphite, hydrolyzing the condensation product, 1,3-bis(diethylphosphono)-2-hexadecanoyloxypropane, with 2 N hydrobromic acid at 100° for 5 h, and isolating the glycerol-1,3-diphosphonic acid in form of the dibarium salt. The glycerol-1,3-diphosphonate differs from glycerol-1,3-diphosphate and other phosphate esters of glycerol and glyceric acid by its greater stability towards acid hydrolysis. The glycerol-1,3-diphosphonic acid is readily distinguished from glycerol-1,3-diphosphoric acid and glycerol-1,2-diphosphoric acid by paper chromatography.

PHOSPHONOLIPIDS: XI. SYNTHESIS OF PHOSPHONOLIPID METABOLITES. L-α-GLYCERYL-(2-TRIMETHYLAMMONIUMETHYL)PHOSPHONATE

1967 ◽  
Vol 45 (11) ◽  
pp. 1747-1754 ◽  
Author(s):  
Erich Baer ◽  
Ranga Robinson
Keyword(s):  
Acid Hydrolysis ◽  
Phosphonic Acid ◽  
Cadmium Chloride ◽  
Condensation Product ◽  
Hydrolysis Product ◽  
Chloride Complex ◽  
Acid Analogue ◽  
Benzene Removal

The synthesis of a possible intermediate in phosphonolipid metabolism, viz. L-α-glyceryl-(2-trimethylammoniumethyl)phosphonate, a phosphonic acid analogue of L-α-glycerylphosphorylcholine, is described. The compound was obtained by condensation of D-acetone glycerol with (2-bromoethyl)metaphosphonate in boiling benzene, removal of the acetone group of the condensation product by acid hydrolysis, treatment of the hydrolysis product in dimethylformamide with trimethylamine at 60–62° for 3 days, isolation of L-α-glyceryl-(2-trimethylammoniumethyl)phosphate as cadmium chloride complex. Removal of the cadmium chloride was effected with a mixture of Amberlites IR-45 and IRC-50. A procedure for the preparation of (2-bromoethyl)metaphosphonate is reported.

Synthesis of 2,3-Diphosphono-DL-glyceric Acid, a Racemic Analogue of 2,3-Diphospho-D-glyceric Acid, the Cofactor of both Phosphoglyceric Acid Mutase and Hemoglobin

1971 ◽  
Vol 49 (3) ◽  
pp. 300-305 ◽  
Author(s):  
Erich Baer ◽  
Ranga Robinson
Keyword(s):  
Hydrobromic Acid ◽  
Methyl Esters ◽  
Acid Methyl Ester ◽  
Triethyl Phosphite ◽  
Glyceric Acid ◽  
Acid Methyl ◽  
Acid Analogue ◽  
Phosphoglyceric Acid ◽  
Major Reaction Product ◽  
Major Reaction

2,3-Diphosphono-DL-glyceric acid, a racemic phosphonic acid, analogue of 2,3-diphospho-D-glyceric acid, the cofactor of phosphoglyceric acid mutase and hemoglobin, has been synthesized. It was obtained by treating the methyl esters of either β-chlorolactic acid, β-bromolactic acid, or glyceric acid with triethyl phosphite at 140–145° for 48 h, hydrolyzing the major reaction product tetraethyl 2,3-diphosphono-DL-glyceric acid methyl ester with concentrated hydrobromic acid at 140° for 24 h, and isolating 2,3-diphosphono-DL-glyceric acid as pentabarium or tricyclohexylammonium salt. 2,3-Diphosphonoglyceric acid and 2,3-diphosphoglyceric acid are readily distinguished from each other by chromatographic and chemical as well as by spectroscopic methods.

Phosphonic acid analogues of carbohydrate metabolites. I. Synthesis of L- and D-dihydroxypropylphosphonic acid

1969 ◽  
Vol 47 (10) ◽  
pp. 955-960 ◽  
Author(s):  
Erich Baer ◽  
Hemendra Basu
Keyword(s):  
Propylene Glycol ◽  
Phosphonic Acid ◽  
Cold Water ◽  
Condensation Product ◽  
Triethyl Phosphite ◽  
Hot Water ◽  
Diethyl Ester ◽  
Mineral Acids ◽  
Optical Rotations ◽  
Carbohydrate Metabolites

A synthesis of the phosphonic acid analogues of L-α- and D-α-glycerophosphoric acid, viz. L- and D-dihydroxypropylphosphonic acid, is described. The L-dihydroxypropylphosphonic acid was obtained by treating acetone α-iodo-L-propylene glycol with triethyl phosphite at 120–125° for 24 h, hydrolyzing the condensation product acetone L-dihydroxypropylphosphonic acid diethyl ester with 2 N sulfuric acid at 100° for 48 h, and isolating the L-dihydroxypropylphosphonic acid as barium salt. The D-dihydroxypropylphosphonic acid was prepared in the same manner from acetone α-iodo-D-propylene glycol. The barium salts are readily soluble in cold water, much less soluble in hot water, and insoluble in the more common organic solvents. Dihydroxypropylphosphonic acid and α-glycerophosphoric acid can be distinguished from each other by their different behaviors towards hot mineral acids, and by the infrared spectra, n.m.r. spectra, and optical rotations of their barium salts.

PHOSPHONOLIPIDS: XII. Synthesis of Phosphonolipid Metobolites. L-α-Glyceryl-(2-aminoethyl) phosphonate

1967 ◽  
Vol 45 (11) ◽  
pp. 1755-1761 ◽  
Author(s):  
Erich Baer ◽  
G. Raghupati Sarma
Keyword(s):  
Phosphonic Acid ◽  
Condensation Product ◽  
Acid Analogue

The synthesis of L-α-glyceryl-(2-phthalimidoethyl)phosphonic acid and of L-α-glyceryl-(2-aminoethyl)phosphonate, the latter a phosphonic acid analogue of L-α-glycerylphosphorylethanolamine and a possible intermediate in phosphonolipid metabolism, is described. The compounds were obtained by condensing D-acetone glycerol with (2-phthalimidoethyl)metaphosphonate in boiling benzene, and freeing the condensation product, viz. acetone L-α-glyceryl-(2-phthalimidoethyl)phosphonic acid, of its acetone group to obtain L-α-glyceryl-(2-phthalimidoethyl)phosphonic acid, or of its phthaloyl and acetone groups to give L-α-glyceryl-(2-aminoethyl)phosphonate.A procedure for the preparation of (2-phthalimidoethyl)metaphosphonate is reported.

Phosphonolipids. XXVI. Mixed-Acid Phosphonocephalins: Synthesis of α′-Stearoyl- β-oleoyl-L-α-glyceryl-(2-aminoethyl)phosphonate

1974 ◽  
Vol 52 (7) ◽  
pp. 570-574 ◽  
Author(s):  
Erich Baer
Keyword(s):  
Fatty Acid ◽  
Phosphonic Acid ◽  
Glycerol Moiety ◽  
Mixed Acid ◽  
New Class ◽  
Naturally Occurring ◽  
Acid Analogue

The synthesis of α′-stearoyl-β-oleoyl-L-α-glyceryl-(2-aminoethyl)phosphonate is reported. It is a member of a new class of phosphonolipids containing two dissimilar fatty acid substituents, one of which is unsaturated and occupies the 2 or β position of the glycerol moiety. The mixed-acid phosphonolipid, a phosphonic acid analogue of naturally occurring L-(α-stearoyl-β-oleoyl)cephalin, was obtained by phosphonylating D-α-stearoyl-β-oleoylglycerol with (2-phthalimidoethyl) phosphonic acid monochloride and triethylamine, and freeing the resulting α-stearoyl-β-oleoyl-L-α-glyceryl-(2-phthalirnidoethyl)phosphonate of its protective phthaloyl group by hydrazinolysis.

scholarly journals Copper(II) Complexes of Organophoshonic Acids-A Comparative Study

2011 ◽  
Vol 8 (s1) ◽  
pp. S271-S281
Author(s):  
B. Venkateswara Rao ◽  
D. M. Puri
Keyword(s):  
Phosphonic Acid ◽  
Octahedral Geometry ◽  
Spectral Studies ◽  
Diphosphonic Acid ◽  
Paramagnetic Resonance ◽  
Diethylene Triamine ◽  
Coordination Sites ◽  
Infrared Spectral ◽  
Electron Paramagnetic ◽  
Derivatives Of

Polynuclear copper(II) derivatives of 1-hydroxyethylidenediphosphonic acid (HEDP), 1-aminoethylidenediphosphonic acid (AEDP, H4L),α-aminobenzylidene diphosphonic acid (ABDP, H4L), 1-amino-2-carboxyethane- 1,1-diphosphonic acid (ACEDP, H5L), 1,3 diaminopropane-1,1,3,3-tetra-phosphonic acid (DAPTP, H8L), Ethylenediamine-N,N'-bis (dimethyl-methylenephosphonic) acid (EDBDMPO, H4L),o-phenylene-diamine-N,N'-bis (dimethylmethylenephosphonic) acid (PDBDMPO, H4L), diethylene triamine –N,N,N',N',N"N-penta (methylene phosphonic) acid (DETAPMPO, H10L) and diethylene triamine –N,N"-bis (dimethyl methylene phosphonic) acid (DETBDMPO, H4L) have been prepared in aqueous medium. The general formula of derivatives from elemental analysis was found to be Cu2L.XH2O (in case of AEDP, ABDP, EDBDMPO, PDBDMPO, DETBDMPO), Cu5L2.XH2O (in case of ACEDP) Cu4L.XH2O, Cu2H4L. XH2O (in case of DAPTP) and Cu5L.XH2O (in case of DETAPMPO). The electronic spectra have shown them to be six coordinated with slight distortion from octahedral geometry. Antiferromagnetism was inferred from magnetic moment data. Infrared spectral studies were carried out to determine coordination sites. EPR (Electron Paramagnetic Resonance) spectra that supports the presence of tetragonal distortion and antiferromagnetic behaviour, have also been studied.

Isosteres of natural phosphates. 11. Synthesis of a phosphonic acid analogue of an oligonucleotide

Tetrahedron ◽  
1984 ◽  
Vol 40 (20) ◽  
pp. 3949-3956 ◽  
Author(s):  
Adam Mazur ◽  
Burton E. Tropp ◽  
Robert Engel
Keyword(s):  
Phosphonic Acid ◽  
Acid Analogue

scholarly journals Interactions of C-reactive protein with the complement system. II. C-reactive protein-mediated consumption of complement by poly-L-lysine polymers and other polycations.

1975 ◽  
Vol 142 (3) ◽  
pp. 709-721 ◽  
Author(s):  
J Siegel ◽  
A P Osmand ◽  
M F Wilson ◽  
H Gewurz
Keyword(s):  
Inflammatory Response ◽  
Potential Role ◽  
Egg White ◽  
Phosphate Esters ◽  
C Reactive Protein ◽  
Cationic Proteins ◽  
Reactive Protein ◽  
Naturally Occurring ◽  
The Complement System

Cationic homopolymers of poly-L-lysine were found to activate complement (C) via C-reactive protein (CRP) and deplete C3 and C5 as well as early-acting C components. Maximum C consumption was obtained with polymers of 2,000-8,000 daltons; polymers of 1,700, 11,000, and 23,000 daltons were intermediate in reactivity, while L-lysine, lysyl-L-lysine, tetra-L-lysine, and polymers of 70,000-400,000 daltons lacked significant C-consuming activity. Naturally occurring polycations which consumed C in the presence of CRP included myelin basic proteins, cationic proteins of rabbit leukocytes, and both lysine- and arginine-rich histones; poly-L-arginine polymers of 17,000 but not 65,000 daltons also were C-consuming. Polycations without such reactivity included poly-L-orithine (5,000 and 165,000 daltons), egg white and human lysozymes, and Polybrene. The polycations which failed to induce C consumption via CRP, inhibited its consumption by both active polycations and by C-polysaccharide (CPS). The relative inhibitory capacity of phosphorylcholine and polycations in CPS- and polycations-CRP systems was consistent with the concept that phosphate esters and polycations react at the same or an overlapping combining site. The ability of certain polycations to activate C via CRP increases the potential for initiation of host reactions via C. The capacity of other polycations to inhibit C activation via CRP introduces a potential for physiologic or pharmacologic manipulation. These considerations would seem to expand the potential role of CRP in the initiation and modulation of the inflammatory response.

scholarly journals The borohydride-reducible compounds of human aortic elastin. Demonstration of a new cyclic amino acid in alkali hydrolysate, and changes with age and in patients with annulo-aortic ectasia including one with Marfan syndrome

1985 ◽  
Vol 232 (1) ◽  
pp. 169-175 ◽  
Author(s):  
T Halme ◽  
M Jutila ◽  
T Vihersaari ◽  
P Oksman ◽  
N D Light ◽  
...  
Keyword(s):  
Acid Hydrolysis ◽  
Marfan Syndrome ◽  
Aldol Condensation ◽  
Condensation Product ◽  
Hydrolysis Product ◽  
Exchange Chromatography ◽  
Spectrometric Analysis ◽  
Cross Link ◽  
Aortic Ectasia ◽  
And Control

Human aortic elastin reduced with [3H]borohydride was analysed by ion-exchange chromatography after alkali or acid hydrolysis. Alkali hydrolysates of elastins contained a radioactive peak that was eluted between proline and leucine. This peak was not present in foetal elastin, but its proportion increased steadily during aging. Aortic samples from patients with annulo-aortic ectasia (aneurysm of the ascending aorta), including one with classical Marfan syndrome, contained less elastin (CNBr-insoluble material) than did the age-matched controls. The proportion of radioactivity in the new peak of all these aortas was low when compared with age-matched controls. Gas-chromatographic/mass-spectrometric analysis suggested that it contained a cyclic derivative of a hydrated aldol-condensation product. The concentration of the cross-link precursors, lysine aldehyde and aldol-condensation product (estimated from the acid-hydrolysis product 6-chloronorleucine and the acid-degradation product of reduced aldol-condensation product) was high in very young aortas but remained quite stable after childhood. No differences were observed in cross-link profiles of acid hydrolysates between pathological and control aortas. A low proportion of radioactivity in the new peak may indicate the presence of young or immature elastin in the pathological aortas.

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